Lesson 1: Introduction to Petroleum Refining and Crude Oil

Composition
 Lesson 1 Overview
 Market Drivers for the Refining Industry
 An Overview of Refinery Products and Processes
 Chemical Constitution of Crude Oil
 Summary and Final Tasks

1.1. Overview

Petroleum provides the largest fraction of primary energy supply in the U.S. and in the
world [Figure 1.1,eia1]. Resource consumption patterns shown in Figure 1.1 reflect major
epochs in human history, such as The Industrial Revolution ushering in the rapid
increase in coal consumption. Petroleum trace, for example, marks the mass production
of automobiles with the introduction of Model T by Ford, world wars, supply crises of
1973 and 1979 and the economic recession in 2008.Transportation of people and goods in
many parts of the world depends almost completely on petroleum fuels, such as gasoline,
jet fuel, diesel fuel, and marine fuel. Apart from the fuels, materials that are necessary for
operating the combustion engines of cars, trucks, planes, and trains also come from
petroleum. These materials include lubricating oils (motor oils), greases, tires on the
wheels of the vehicles, and asphalt to pave the roads for smooth rides in transportation
vehicles. All petroleum fuels and many materials are produced by the processing of
crude oil in petroleum refineries. Petroleum refineries also supply feedstock to the
petrochemicals and chemical industry for producing all consumer goods from rubber
and plastics (polymers) to cosmetics and medicine. Only ten percent of petroleum
consumption, the portion that is not used for transportation or other energy outlets, is
sufficient to manufacture all the materials used in human economy with the exception of
those derived from wood or minerals.

Figure 1.1. History of energy use in the United States. 1 Quadrillion (10 15) Btu = 1.05 ×
1018 Joules.
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Source: U.S. Energy Information Administration.

The petroleum industry consists of two separate operations: Upstream and Downstream
Operations. Upstream operations involve exploration of new oil reserves, development
of oil fields, constructing the well-head and crude oil production facilities. Downstream
operations cover processing of crude oil in petroleum refineries to produce liquid and
gaseous fuels and materials for the market. This course addresses petroleum refining to
review how a variety of physical processes and chemical reactions in separate refinery
units are integrated to process compliant fuels and materials.

Learning Outcomes

By the end of this lesson, you will be able to:

 recognize the significance of petroleum fuels in the U.S. energy supply;

 express the overall objectives of petroleum refining;
 identify the economic and environmental drivers of petroleum refining;
 describe the overall approach to petroleum refining and categorize refinery
processes and products;
 portray chemical constitution of petroleum.

What is due for Lesson 1?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignment page within this lesson.

This table contains the readings and assignments for Lesson 1.

J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 1, pp. 1-12; Chapter
Readings
3, pp. 62-65

For your information, review the most recent supply of petroleum fuels
from the data given at U.S. Energy Information
Assignments Administration [2] (eia.gov) and research how petroleum refining
addresses the environmental concerns from the combustion of
petroleum fuels in internal combustion engines.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

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Composition > Market Drivers for the Refining Industry

1.2. Market Drivers for the Refining Industry

Market Drivers for the Refining Industry

Markets and demand for refinery products depend on the dynamics of a global economy.
It is generally agreed that oil and gas will continue to be the primary energy resource in
the U.S. and world economies for decades to come. Because of the projected increase in
the production of oil in tight formations, the United States is expected to become an
exporter of petroleum products and crude oil after decades of being an importer (Figure
1.2, EIA Annual 2013, eia.gov). Petroleum fuels will continue to dominate the
transportation sector, but the following trends should be noted:

 increasing fuel economy of vehicles (offset by increasing number of vehicles and

miles driven);
 more strict environmental regulations with demand for cleaner fuels;
 biofuels as additives (e.g., ethanol, biodiesel) or alternative fuels in niche markets
(jet fuel from algae);
 demand for high-quality, high-performance fuels.

Figure 1.2. U.S. domestic crude oil production by source, 1990-2040 (million barrels per
day)
Source: EIA Annual 2013, US Energy Information Administration [1].
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Competitive forces in the global economy lead to joint ventures and mergers and shutting
down of inefficient refineries, or shutting down of processing units with low efficiency
within refineries. Figure 1.3 shows the changes in the refinery capacity and number of
refineries in the U.S. since 2000. The increasing refining capacity, with the decreasing
number of refineries, results in the closing down of small inefficient refineries while
expanding the large refineries.

Figure 1.3. Number and capacity of operable refineries in the United States.
Source: EIA Annual 2013, US Energy Information Administration.

Regarding the global competition, the technological advancement addresses the

degrading quality of crude oils to produce cleaner and higher quality petroleum fuels.
On the supply side, there is the increasing abundance of natural gas liquids (ethane,
propane, n-butane, and iso-butane) due to increased shale gas production in the U.S. and
elsewhere. These liquids enter refineries as new feedstock in addition to crude oil supply.

Refineries need process improvements to advance their capabilities to deal with the
changing crude oil base and changing environmental regulations. These improvements
in refinery processes would need to create and use, for example:

 new catalysts and new chemistry;

 more sophisticated process modeling and computational methods;
 more effective use of computers in refinery management;
 online monitoring and property measurements;
 new materials to reduce maintenance and extend the useful life of equipment.

Concerns for efficiency include running a refinery efficiently and producing fuels that
will burn efficiently in the combustion engines, as follows:

 Efficiency of refinery processes

o Minimize waste and optimize the yield and properties of the refinery
products to obtain maximum value from the crude oil.
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 o Increase the energy efficiency of each unit in the refinery.
 Fuel economy in internal combustion engines
o Produce high-performance fuels for efficient operation of combustion
engines.

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Composition > An Overview of Refinery Products and Processes

1.3. An Overview of Refinery Products and Processes

An Overview of Refinery Products and Processes

Considering the market drivers just reviewed along the small profit margins that are
often usually associated with petroleum refinery products, refineries should carefully
select the crude oil feedstock and configure the refinery processes such that they
produce the desirable petroleum products at the lowest cost.

In the U.S. refineries, a principal focus is on the production of gasoline because of high
demand. Diesel fuel is the principal refinery product in most other parts of the world.
Figure 1.4 shows a typical distribution of products from a barrel of crude oil in a U.S.
refinery. Distillation process separates the crude oil into boiling point fractions. The
liquefied petroleum gas (LPG) constitutes the lowest boiling point (most volatile)
product from a refinery and higher boiling fractions lead to most desirable distillate
liquids, such as gasoline, jet fuel, diesel fuel, and fuel oil in the increasing order of boiling
points, while asphalt is made from the residual fraction remaining after distillation.

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Figure 1.4: A typical distribution of products made from crude oil in a U.S. refinery.

Click here for text description of Figure 1.4

Source: U.S. Department of Energy

The following animation shows a refinery flow chart indicating some of the major
refinery processes and refinery products. Note that the distillation process (Fractionation
Tower) separates crude oil into a number of distillate fractions that are sent as feedstocks
to different processes, some of which are interconnected. It is also important to recognize
that petroleum refining not only produces transportation fuels and fuels for space
heating or industrial furnaces but also produces materials needed for the operation of the
combustion engines and paving the roads for vehicles to travel on.

A refinery flow chart for converting crude oil to fuels and materials.

Click here for transcript of FSC Refinery Flow Chart.

Source: 1995 Amoco Corp.

Figure 1.5 indicates that chemical constitution and physical properties of crude oils are
important parameters that guide the refinery configurations. The refining processes can
be divided into four groups, as indicated. While the separation processes involve just
physical phenomena, the conversion, finishing, and support processes require chemical
changes, i.e., breaking chemical bonds to modify the molecular structure of the
feedstocks. These changes are necessary to produce the fuels and materials in accordance
with industrial/commercial specifications.

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Figure 1.5. Classification of refining processes and types of refinery products.

Source: Dr. Semih Eser

Figure 1.6 shows a more detailed refinery block diagram to show how different processes
are integrated for producing the desired fuels and materials.

Figure 1.6. A flow diagram integrating the four types of processes in a petroleum
refinery.

Source: Dr. Semih Eser

Separation processes, such as distillation, dewaxing, and deasphalting make use of the
differences in the physical properties of crude oil components to separate groups of
hydrocarbon compounds or inorganic impurities, whereas conversion processes cause
chemical changes in the hydrocarbon composition of crude oils. For example, Fluid
Catalytic Cracking process breaks chemical bonds in long-chain alkanes to produce
shorter chain alkanes to produce gasoline from higher boiling gas oil fractions. Finishing
processes involve hydrotreating to remove heteroatoms (S, N, and metals) and product
blending to produce fuels and materials with desired specifications and in compliance
with environmental and government regulations. Finally, supporting processes provide
the recovery of the removed heteroatoms or heteroatom compounds, production of the
hydrogen necessary for conversion and hydrotreating processes, and effluent water
treatment systems.
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Please take a few minutes to answer the question below. Click "Check My Answer" to see
some feedback.

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Composition > Chemical Constitution of Crude Oil

1.4. Chemical Constitution of Crude Oil

Chemical Constitution of Crude Oil

Crude oil contains organic compounds, heteroatom compounds (S,N,O), hydrocarbons

(C, H), metals and organic (Ni, V, Fe) and inorganic (Na+, Ca++, Cl-) compounds as listed
in Figure 1.7. Compounds that contain only elements of carbon and hydrogen are called
hydrocarbons and constitute the largest group of organic compounds found in
petroleum. There might be as many as several thousand different hydrocarbon
compounds in crude oil. Hydrocarbon compounds have a general formula of C xHy,
where x and y are integer numbers.

Figure 1.7. Constituents of crude oil.

Source: Dr. Semih Eser

Hydrocarbons are generally divided into four groups: (1) paraffins, (2) olefins, (3)
naphthenes, and (4) aromatics (Figure 1.8). Among these groups, paraffins, olefins, and
naphthenes are sometimes called aliphatic compounds, as different from aromatic
compounds. The lightest hydrocarbon found as a dissolved gas is methane (CH4), the

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main component of natural gas. Olefins are not usually found in crude oils, but produced
in a number of refining processes.

Figure 1.8. Chemical bonding in hydrocarbons.

Source: Dr. Semih Eser

1.4.a. Aromatic Hydrocarbons

Aromatic hydrocarbons are an important series of hydrocarbons found in almost every

petroleum mixture from any part of the world. Aromatics are cyclic but unsaturated
hydrocarbons with alternating double bonds (Figure 1.12). The simplest aromatic
hydrocarbon is benzene (C6H6). The name “aromatic” refers to the fact that such
hydrocarbons are commonly fragrant compounds. Although benzene has three carbon-
carbon double bonds, it has a unique arrangement of electrons with resonance structures
of the double bonds (aromaticity) that allow benzene to be relatively stable. However,
benzene is known to be a cancer-inducing compound. For this reason, the amount of
benzene allowed in petroleum products such as gasoline or fuel oil is limited by
government regulations in many countries. Under standard conditions, benzene,
toluene, and xylene are in liquid form whereas higher aromatics such as naphthalene
occur as solids in isolation, but dissolve to form a liquid solution with simple aromatics.

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Figure 1.12. Simple aromatic compounds, benzene, toluene, xylene (BTX) and isomers of
xylene.

Source: Dr. Semih Eser

Knowledge Check

Please take a few minutes to answer the questions below. When you are ready, click
Check to see the solution.

1.4.b. Polyaromatic and Hydroaromatic Compounds

Some of the common aromatics found in crude oil and petroleum products are benzene
derivatives with attached methyl, ethyl, propyl, or higher alkyl groups. This series of
aromatics is called alkylbenzenes, and compounds in this homologous group of
hydrocarbons have the general formula of CnH2n-6 (where n ≥ 6). Generally, an aromatic
series with only one benzene ring is also called mono- aromatics or mononuclear
aromatics. However, heavy petroleum fractions and residues contain unsaturated
multirings with many benzene and naphthene rings attached to each other. Such
aromatics that exist as solids in isolation are also called polyaromatic hydrocarbons
(PAHs) or polynuclear aromatics (PNAs) (Figure 1.13). Heavy crude oils usually contain
more aromatics than light crudes. It is common to have compounds with naphthenic and
aromatic rings side by side (hydroaromatics, or naphthenoaromatics, Figure 1.13)
especially in heavy fractions.

Figure 1.13 shows examples of PAHs, such as anthracene, phenathrene, and pyrene. The
configuration of rings in PAHs strongly influences the physical and chemical properties
of these compounds. For example, three-ring aromatics anthracene and phenanthrene
have significantly different properties. In petroleum, PAHs exist mostly as alkyl
substituted ring systems such that the substitutent alkyl groups (e.g., methyl, ethyl)
replace (substitute for) the hydrogen atoms on the rings.

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Figure 1.13. Polyaromatic and hydroaromatic compounds in crude oils.

Source: Dr. Semih Eser

Normally, high-molecular-weight polyaromatics contain several heteroatoms such as

sulfur, nitrogen, or oxygen, but these compounds are still called aromatic compounds
because their electronic configurations maintain the aromatic character.

Sulfur is the most important heteroatom found in crude oil and refinery products
petroleum and it can be found in cyclic (e.g., thiophenes) and noncyclic compounds such
as mercaptans (R-S-H) and sulfides (R-S- R′), where R and R′ are alkyl groups. Sulfur in
natural gas is usually found in the form of hydrogen sulfide (H2S). Figure 1.14 shows the
types of sulfur compounds in crude oils. The amount of sulfur in a crude oil may vary
from 0.05 to 6 % by weight. The presence of sulfur in finished petroleum products is not
desirable. For example, the presence of sulfur in gasoline can promote corrosion of engine
parts and produce sulfur oxides upon combustion, contributing to air pollution.

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Figure 1.14. Types of sulfur compounds found in crude oil.

Source: Dr. Semih Eser

Normally, the concentration of the other heteroatom compounds (nitrogen, oxygen, and
metals) in crude oils is usually lower than that of the sulfur compounds. Figure 1.15
shows the nitrogen compounds that may be found in crude oils.

Generally, in heavier crude oils the proportions of carbon, sulfur, nitrogen, and oxygen
compounds are higher at the expense of hydrogen content. Heavier crude oils also
contain organometallic compounds of commonly nickel and vanadium (Figure 1.16).
These compounds are highly corrosive and toxic and should be removed in the refinery.
Nickel, vanadium, and copper can also severely affect the activities of catalysts and result
in lower quality products. Organometallic compounds tend to concentrate in heavy, or
residual fractions of crude oils.

Figure 1.15. Types of nitrogen compounds found in crude oil.

Source: Dr. Semih Eser

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Figure 1.16. Oxygen and organometallic compounds that may be found in crude oils.

Source: Dr. Semih Eser

Knowledge Check

Please take a moment to answer the question below. Click Check when you are ready to
see the solution.

1.4.c. Paraffins

Paraffins are also called alkanes and have the general formula of CnH2n+2, where n is the
number of carbon atoms in a given molecule. Paraffins are divided into two groups of
normal and isoparaffins. Normal paraffins or normal alkanes are simply written as n-
paraffins or n-alkanes, and they are open, straight-chain saturated hydrocarbons. The
second group of paraffins is called isoparaffins, which are branched-type hydrocarbons,
and they begin with isobutane (also called methylpropane), which has the same closed
formula as n-butane (C4H10). Compounds of different structures with the same closed
formula are called isomers (Figure 1.9). For example, the open formula for n-butane, n-
C4, can be shown as CH3-CH2-CH2-CH3, based on the quadrivalency of the carbon atom,
and for simplicity, only the carbon-carbon bonds are drawn and most C-H bonds are
omitted, as shown in Figure 1.7 and 1.8 on the previous page. Paraffins are the largest
series of hydrocarbons found in petroleum and beginning with the simplest compound,
methane.

Under standard conditions of temperature and pressure (STP), the first four members of
the alkane series (methane, ethane, propane, and butane) are in gaseous form, and
compounds starting from C5H12 (pentane) to n-heptadecane (C17H36) are liquids
(constituting large fractions of hydrocarbons found in liquid fuels (e.g., gasoline, jet fuel,
and diesel fuel), whereas n-octadecane (C18H38) or heavier compounds exist in isolation
as wax-like solids at STP. These heavier paraffins are soluble in lighter paraffins or other
hydrocarbons and can be found in diesel fuel and fuel oils. Paraffins from C 1 to
C40 usually appear in crude oil (heavier alkanes in liquid solution, not as solid particles)
and represent up to 20% of crude by volume.

Figure 1.10 shows the statistically possible number of isomers of paraffins that increase
exponentially with carbon number, starting with just one isomer for butane, reaching
approximately 60,000 for C18 paraffins. Note that the branching in hydrocarbons causes
significant changes in physical properties (e.g., boiling point and density, Figure 1.11)
and chemical behavior (e.g., octane number, Figure 1.10) of paraffins with the same
carbon number. Note in Figure 1.10 that the removal of an H atom from alkanes generates
free radicals (reactive species containing unpaired electrons) that are called alkyl species
(e.g., methyl formed from methane and ethyl formed from ethane by removing a
hydrogen atom) also a radical with an unpaired electron. Also note the nomenclature

13
using alkyl groups to specifically name isoalkanes (e.g., 2,2,4-trimethylpentane to
designate a specific iso-octane).

Figure 1.9. Normal and isoparaffins (as isomers) and the effect of molecular structure on
boiling points of paraffins.

Source: Dr. Semih Eser

Figure 1.10. Isomers of paraffins and the formation of alkyl groups.

Source: Dr. Semih Eser

Naphthenes or cycloalkanes are rings or cyclic saturated hydrocarbons with a general

formula of CnH2n5H10), cyclohexane (C6H12), and their derivatives such as n-
alkylcyclopentanes are normally found in crude oils.

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Figure 1.11. Cycloalkanes (naththenes) and the effect of cyclic structures on physical
properties of alkanes.

Source: Dr. Semih Eser

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1.5. Summary and Final Tasks

Summary
Petroleum, the most important crude oil, consists of a mixture of hydrocarbon
compounds including paraffinic, naphthenic, and aromatic hydrocarbons with small
amounts of impurities including sulfur, nitrogen, oxygen, and metals. The first process
in petroleum refining operations is the separation of crude oil into its major constituents
using distillation to separate the crude oil constituents into common boiling-point
fractions. Other separation processes include deasphalting to remove the heaviest
fraction of crude oil, asphalt, and dewaxing to remove long-chain n-paraffins called wax.

To meet the demands for high-octane gasoline, jet fuel, and diesel fuel, heavier
components of crude oils are converted to gasolines and other distillate fuels. Among the
conversion processes are cracking, coking, and visbreaking that are used to break large
petroleum molecules into smaller ones. Polymerization and alkylation processes are used
to combine molecules smaller than those in gasoline into larger ones to make more
gasoline in the refinery. Isomerization and reforming processes are applied to rearrange
and reform the structure of hydrocarbons to produce higher-value gasoline components
of a similar molecular size.

Finishing processes in a refinery processes stabilize and upgrade petroleum products by

hydrogenation and remove undesirable elements, such as sulfur and nitrogen by
hydrotreating processes. Blending of many product streams, to come up with

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commercial refinery products with the required specifications, also belong to the
category of finishing processes.

Lesson Objectives
You should now be able to:

 recognize the significance of petroleum fuels in the U.S. energy supply;

 express the overall objectives of petroleum refining;
 identify the economic and environmental drivers of petroleum refining;
 describe the overall approach to petroleum refining and categorize refinery processes
and products;
 portray chemical constitution of petroleum.
Reminder - Complete all of the Lesson 1 tasks!
You have reached the end of Lesson 1! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 2. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignment below can be found within this lesson.

This table contains the readings and assignments for Lesson 1.

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 1, pp. 1-12;

Chapter 3, pp. 62-65

Assignments For your information, review the most recent supply of petroleum
fuels from the data given at The U.S. Energy Information
Administration website(link is external) (eia.gov) and research how
petroleum refining addresses the environmental concerns from
combustion of petroleum fuels in internal combustion engines.
Questions?
If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

16
Lesson 2: Properties and Classification of Crude Oil
 Lesson 2 Overview
 API Gravity
 Viscosity
 Pour Point
 Concentration of Various Contaminants
 Distillation and Boiling Points
 Crude Assay
 Characterization Factors
 Elemental Analysis and Ternary Classification of Crude Oils
 Summary and Final Tasks

2. 1. Overview
Physical properties and composition of crude oil provide critical information for the
optimum operation of a petroleum refinery. This information does not only help predict
the physical behavior of crude oil in refinery units but also gives insight into its chemical
composition. Therefore, the physical properties can be related to chemical properties of
crude oil and its fractions and the characteristics of the resulting refinery products. The
most important properties of crude include density, viscosity, boiling point distribution,
pour point, and the concentration of various contaminants.

Learning Outcomes
By the end of this lesson, you should be able to:

 define the significant properties of crude oil, including density, viscosity, average
boiling point, sulfur, and salt content;
 understand the significance of crude oil properties in terms of refinery objectives, and
describe crude oil assay;
 define and interpret the classification factors (Watson, UOP, VGC, and BMCI) as they
relate to the hydrocarbon composition of crude oils;
 calculate average boiling points for crude oils using different averaging techniques
and differentiate Watson and UOP characterization factors;
 analyze the elemental composition of crude oils and outline ternary classification of
crude oils with respect to hydrocarbon composition, i.e., aromatics, paraffins, and
naphthenes;
 assess the use of ternary classification of crude oils to estimate the refinery product
yields.
What is due for Lesson 2?

17
This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignments page within the Lesson.

This table contains the reading and assignments for Lesson 2.

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 3, pp. 57-61, 65-70 and
the course material from this site

Assignments Exercise 1 - Submit to the Exercise 1 Assignment in the Lesson 2 Module.

 Calculation of API gravity of crude oil blends

 Calculation of Watson and UOP characterization factors for
hydrocarbons and crude oil fractions
Quiz 1: Assessment of learning outcomes in Lessons 1 and 2. Quiz 1 is
found in the Lesson 2 folder.
Questions?
If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

2.2. API Gravity

Density is defined as mass per unit volume of a fluid. The density of crude oil and liquid
hydrocarbons is usually reported in terms of specific gravity (SG) or relative density,
defined as the density of the liquid material at 60°F (15.6°C) divided by the density of
liquid water at 60°F. At a reference temperature of 15.6°C, the density of liquid water is
0.999 g/cm3 (999 kg/m3), which is equivalent to 8.337 lb/gal (U.S.). Therefore, for a
hydrocarbon or a petroleum fraction, the SG is defined as:

SG( 60 ∘F / 60 ∘F ), or ( 15.6 ∘C / 15.6 ∘C )=(Density of liquid at 60 ∘F in g/ cm 3 )/(0.99

9g/ cm 3 )

In the early years of the petroleum industry, the American Petroleum Institute (API)
adopted the API gravity (°API) as a measure of the crude oil density. The API gravity is
calculated from the following equation:

The API scale for gravity was adapted from the Baumé scale, developed in late 18th
century to be used in hydrometers for measuring even small differences in the specific
gravity of liquids, using water as a reference material in these devices. A liquid with SG
of 1 (i.e., water) has an API gravity of 10. One can note from Eq. 1 that liquid

18
hydrocarbons with lower SGs have higher API gravities. The API of crude oils varies
typically between 10 and 50, with most crude oils falling in the range of 20-45. Using API
gravity, the conventional crude oils can be generally considered as light (°API>30),
medium (30>°API>22), and heavy (°API<22).

Note that the relationship between °API and specific gravity is not linear. Therefore, the
°API gravity of crude blends cannot be calculated by linear averaging of the component
°APIs. Specific gravities of the components can be averaged, though, to determine the
specific gravity of the resulting blend. In practice, averaging °APIs is usually accepted
because the error involved in averaging is small.

Among the hydrocarbons, aromatic hydrocarbons have higher SG (lower °API) than
paraffinic hydrocarbons with the same number of carbon atoms. For example, benzene
has an SG of 0.883 (°API of 28.7), whereas n-hexane has an SG of 0.665 (°API of 81.3).
Therefore, the heavy (high-density) crude oils tend to have high concentrations of
aromatic hydrocarbons, whereas the light (low-density) crude oils have high
concentrations of paraffinic hydrocarbons.

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2.3. Viscosity
Viscosity
Viscosity, commonly depicted by the symbol μ, is a physical property of a fluid that
describes its tendency/resistance to flow. A high-viscosity fluid has a low tendency to
flow, whereas low-viscosity fluids flow easily. Newton’s Law of Viscosity provides a
physical definition of viscosity. Power requirement to transport (e.g., to pump) a fluid
depends strongly on the fluid’s viscosity. Interestingly, the viscosity of liquid decreases
with increasing temperature, while viscosity of gases increases with increasing
temperature. Among petroleum products, viscosity constitutes a critically important
characteristic of lubricating engine oils. Viscosity of liquids is usually measured in terms
of kinematic viscosity, which is defined as the ratio of absolute (dynamic) viscosity to
absolute density (ν = μ/ρ). Kinematic viscosity is expressed in units of centistokes (cSt),
Saybolt Universal seconds (SUS), and Saybolt Furol seconds (SFS). Values of kinematic
viscosity for pure liquid hydrocarbons are usually measured and reported at two
reference temperatures, 38°C (100°F) and 99°C (210°F) in cSt. However, different
reference temperatures, such as 40°C (104 °F), 50 °C (122 °F), and 60 °C(140 °F), are also
used to report kinematic viscosities of petroleum fractions. The viscosity of crude oils can
be measured using a standard method (ASTM D2983).

2.4. Pour Point

Pour Point

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The pour point of a crude oil, or a petroleum fraction, is the lowest temperature at which
the oil will pour or flow when it is cooled, without stirring, under standard cooling
conditions. Pour point represents the lowest temperature at which oil is capable of
flowing under gravity. It is one of the important low-temperature characteristics of high-
boiling fractions. When the temperature is less than the pour point of a petroleum
product, it cannot be stored or transferred through a pipeline. Standard test procedures
for measuring pour points of crude oil or petroleum fractions are described in the ASTM
D97 (ISO 3016 or IP 15) and ASTM D5985 methods. The pour point of crude oils relates
to their paraffin content: the higher the paraffin content, the higher the pour point.

2.5. Concentration of Various Contaminants

Concentration of Various Contaminants
In addition to hydrocarbons, crude oil contains hetroatom (S, N, metals) species that need
to be removed if their concentrations are higher than the specified thresholds. Other
impurities in crude oil include salt and sediment and water. The acidity of crude oil is
also important particularly for concerns of corrosion in pipes or other process units.
Carbon residue of a crude oil indicates the tendency to generate coke on heter tubes or
rector surfaces. All of these contaminants and properties of crude oils are measured using
standard methods, as described in this section.

 Sulfur and Nitrogen Content

 Metals Content and Total Acid Number
 Carbon Residue, Basic Sediment and Water, and Salt Content

2.5.a. Sulfur and Nitrogen Content

Sulfur Content
Sulfur content of crude oils is the second most important property of crude oils next to
API gravity. Sulfur content is expressed as weight percent of sulfur in oil and typically
varies in the range from 0.1 to 5.0%wt. The standard methods that are use to measure the
sulfur content are ASTM D129, D1552, and D2622, depending on the sulfur level. Crude
oils with more than 0.5%wt sulfur need to be treated extensively during petroleum
refining. Using the sulfur content, crude oils can be classified as sweet (<0.5%wt S) and
sour (>0.5% %wt S). The distillation process segregates sulfur species in higher
concentrations into the higher-boiling fractions and distillation residua. Removing sulfur
from petroleum products is one of the most important processes in a refinery to produce
fuels compliant with environmental regulations.

2.5.b. Nitrogen Content

Nitrogen content of crude oils is also expressed as weight percent of oil. Basic nitrogen
compounds are particularly undesirable in crude oil fractions as they deactivate the

20
acidic sites on catalysts used in conversion processes. Some nitrogen compounds are also
corrosive. Crude oils with nitrogen contents greater than 0.25%wt need treatment in
refineries for nitrogen removal.

2.5.c. Metals Content and Total Acid Number

Metals Content
Most common metals that are found in crude oil are included in organometallic
compounds like nickel, vanadium iron and copper, ranging in concentration from a few
ppm up to 1000 ppm by weight, depending on the source of crude oil. Similar to sulfur
species, the metallic compounds tend to concentrate in the higher-boiling fraction of
crude oil. Higher metal contents also require treatment during petroleum refining
because of the corrosion activity of some metals and their tendency to accumulate on
catalyst surfaces, thus deactivating the catalysts in a number of refinery processes. Metal
content can be measured using a standard EPA Method 3040.

2.5.d. Total Acid Number

Acidity of crude oil is measured by titration with potassium hydroxide (KOH), using the
standard method ASTM D664. The measured acidity is expressed as the Total Acid
Number (TAN) that is equivalent to milligrams of KOH required to neutralize 1 gram of
oil. This number is particularly important to control corrosion in the distillation columns
through selection of corrosion-resistant alloys for surfaces that come into contact with
oil.

2.5.e. Carbon Residue, Basic Sediment and Water, and Salt Content
Carbon Residue
Carbon residue (as % wt of crude oil, or crude oil fraction) is determined as the weight
of solid residue remaining after heating crude oil to coking temperatures (700-800°C).
Two standard tests with slightly different procedures are used to measure carbon
residue: ASTM D524 Ramsbottom Carbon Residue (RCR) and ASTM D189 Conradson
Carbon Residue (CCR). Carbon residue relates to asphalt (or asphaltenes) content of oil
and indicates the tendency of fouling in heater tubes and catalyst deactivation. Higher
the carbon residue, higher is the coking (fouling) propensity of crude oil.

2.5.f. Basic Sediment and Water (BS&W)

The standard method ASTM D4007 is used to measure the amount of suspended
inorganic solid particles and water (BS&W) in crude oils. These contaminants are mixed
with the oil during production, and high concentration of BS&W causes operational
problems in a refinery.

2.5.g. Salt Content

Salt content of crude oils can be measured using the standard method ASTM D3230 and
reported as lb NaCl/1000 bbl. Desalting (removing the salt) is necessary when NaCl

21
content is greater than 10 lbs/1000 bbl. Such high salt contents lead to corrosion in
distillation towers and other equipment.

2.6. Distillation and Boiling Points

Distillation and Boiling Points
The boiling point of a pure compound in the liquid state is defined as the temperature at
which the vapor pressure of the compound equals the atmospheric pressure or 1 atm.
The boiling point of pure hydrocarbons depends on carbon number, molecular size, and
the type of hydrocarbons (aliphatic, naphthenic, or aromatic) as discussed in Lesson 1.
Figure 2.1 shows the boiling points of n-alkanes as a function of carbon number.

Figure 2.1. Boiling points (°C) of n-alkanes as a function of carbon number.

Source: M. R. Riazi and S. Eser, “Properties, Specifications, and Quality of Crude Oil and
Petroleum Products,” In Petroleum Refining and Natural Gas Processing, Editors: M. R. Riazi, S.
Eser, J. L. Peña, ASTM International, West Conshohocken, PA, 2013, p. 80.

Complex mixtures such as crude oil, or petroleum products with thousands of different
compounds, boil over a temperature range as opposed to having a single point for a pure
compound. The boiling range covers a temperature interval from the initial boiling point
(IBP), defined as the temperature at which the first drop of distillation product is
obtained, to a final boiling point, or endpoint (EP) when the highest-boiling compounds
evaporate. The boiling range for crude oil may exceed 1000 °F.

The ASTM D86 and D1160 standards describe a simple distillation method for measuring
the boiling point distribution of crude oil and petroleum products. Using ASTM, D86
boiling points are measured at 10, 30, 50, 70, and 90 vol% distilled. The points are also
frequently reported at 0%, 5%, and 95% distilled. ASTM D1160 is carried out at reduced
22
pressure to distill the high-boiling components of crude oil. As an alternative method,
distillation data can be obtained by gas chromatography (GC), in which boiling points
are reported versus the weight percent of the sample vaporized. This test method
described in ASTM D2887 is called simulated distillation (SimDis).

2.6.a. Average Boiling Points

Average boiling points are useful in predicting physical properties and for
characterization of complex hydrocarbon mixtures. The key here is to represent a mixture
of compounds with a range of boiling points by a single characteristic boiling point. Since
this is a formidable task, there are five different “average boiling points” that are used in
different correlations. They are:

1. VABP (Volume Average Boiling Point)

2. MABP (Molal Average Boiling Point)
3. WABP (Weight Average Boiling Point)
4. CABP (Cubic Average Boiling Point)
5. MeABP (Mean Average Boiling Point)=(MABP+CABP)/2
1, 2, and 3 can be defined for a mixture of n components as:

(Vol, Mol, or Weight) ABP=∑ x i T bi

where ABP is is expressed as VABP, MABP, or WABP and xi is the corresponding
volume, mole, or weight fraction of component i, and Tbi is the normal boiling point of
component i. Cubic average boiling point (CABP) and Mean Average Boling Points
(MeABP) can be calculated as follows.
CABP= ∑ x ivolume T bi 1/3 3MeABP= MABP+CABP /2
For petroleum streams, volume, weight, or mole fractions of the components are not
usually known. In this case, VABP is calculated from standard distillation (ASTM D86
Method) data, and empirical relationships (charts, or equations) are used to calculate the
other average boiling points.

Here is the procedure:

Equation 1 (Ts are ASTM D86 temperatures for 10, 30, 50, 70, and 90% volume distilled,
respectively):
VABP=( T 10% + T 30% + T 50% + T 70% + T 90% )/5
Along with VABP, the slope of the ASTM D86, SL, is used for converting VABP to other
average boiling points.

Equation 2:
SL=( T 90% − T 10% )/80
The following empirical equations can, then, be used to obtain the temperature difference
(ΔT) between VABP and other average boiling points (ABP) [2] :

23
Equation 3:
In −Δ T Weight Average =−3.64991−0.02706 (VABP−273.15) 0.6667 +5.163875S L 0.25
Equation 4:
In Δ T Molal Average =−1.15158−0.01181 (VABP−273.15) 0.6667 +3.70612S L 0.333
Equation 5:
In Δ T Cubic Average =−0.82368−0.08997 (VABP−273.15) 0.45 +2.456791S L 0.45
Equation 6:
In Δ T Mean Average =−1.53181−0.0128 (VABP−273.15) 0.6667 +3.646064S L 0.333
and

Equation 7:
(Weight, Molal, Cubic, or Mean) ABP=VABP−Δ T (weight, molal, cubic, or mean)
The temperature unit used for VABP, SL, and ΔT in these correlations is Kelvin.
The following script can be used to calculate VABP, MeABP by entering the distillation
temperatures in the table.

You may also use the charts in Figure 4.1a and Figure 4.1b (p. 39) of your textbook [3] to
obtain MeABP and MABP, respectively, from VABP. Note that the slope of the
distillation curve used in those charts refers to True Boiling Point (TBP) distillation (not
to ASTM distillation), and it is calculated as (T70% -T10%)/60.

2.6.b. Crude Assay

Crude oil assay consists of a compilation of data on properties and composition of crude
oils. The assay provides critical information on the suitability of crude oil for a particular
refinery and estimating the desired product yields and quality. It also indicates how
extensively a given crude oil should be treated in a refinery to produce fuels that are in
compliance with environmental regulations. A typical crude assay should include the
following major specifications:

 API Gravity
 Total Sulfur (% wt)
 Pour Point (°C)
 Viscosity @ 20°C (cSt)
 Viscosity @ 40°C (cSt)
 Nickel (ppm)
 Vanadium (ppm)
 Total Nitrogen (ppm)
 Total Acid Number (mgKOH/g)
 Distillation Data
 Characterization factor KUOP, KW
24
2.6.c. Characterization Factors
Since the early days of the petroleum industry, some physical properties of crude oil were
used to define characterization factors for classification of crude oil with respect to
hydrocarbon types [4] as shown in Equation 8.
where: Tb = volume, or mean average normal boiling point in R (degree Rankine) and
SG = specific gravity at 15.6°C (60°F). To calculate KUOP or KW,volume average boiling
point (VABP) or mean average boiling point is used, respectively. Depending on the
value of the Watson characterization factor, crude oils are classified as paraffinic (Kw =
11-12.9), naphthenic (Kw =10-11), or aromatic (Kw <10).

Watson Characterization Factor Animation

Another parameter defined in the early years of petroleum characterization is the

viscosity gravity constant (VGC). This parameter depends on viscosity expressed in
Saybolt Universal Seconds (SUS) and specific gravity. According to a standard method
(ASTM D2501), VGC can be calculated at a reference temperature of 100°F as follows
in Equation 9:
where V(100°F) is the viscosity in SUS and SG is the specific gravity at 15.6°C (60°F). VGC
varies between 0.74 to 0.75 for paraffinic, 0.89 and 0,94 for naphthenic, and 0.95 and 1.13
for aromatic hydrocarbons.

The U.S. Bureau of Mines Correlation Index (BMCI) or (CI) is useful for characterization
of crude oil fractions. CI is defined in terms of Mean Average Boiling Point (Tb) and
specific gravity (SG) at 60°F as shown in Equation 10:
According to this CI scale, all n-paraffins have a CI value of 0, while cyclohexane (the
simplest naphthene), has a CI value of 50, and benzene has a CI value of 100. Using the
CI values, crude oils can be classified as follows:

25
 Table 2.1

paraffinic CI<29.8

naphthenic CI<57.0

aromatic CI>75.0

[4] K. M. Watson, E. F. Nelson , George B. Murphy, “Characterization of Petroleum

Fractions,” Ind. Eng. Chem., 1935, 27 (12), pp 1460–1464

2.6.d. Elemental Analysis and Ternary Classification of Crude Oils

Despite a wide variety of crude oil found in different parts of the earth, the elemental
composition of most crude oils changes in narrow ranges, as shown in Table 2.2.

Table 2.2: Elemental Composition of Crude Oils

Element % Wt

C 84-86%

H 11-14%

S 0-6%

N 0-1%

O 0-2%

With such narrow ranges of change in elemental contents, elemental composition does
not have much utility for classification of crude oil. Instead, variations in hydrocarbon
composition (paraffins, naphthenes, and aromatics) are used to classify crude oils, using
a ternary diagram, shown in Figure 2.2. Each apex of the triangle represents 100 percent
weight of the corresponding compounds, and 0% of this particular type of hydrocarbons
on the side of the triangle across from the apex. For example, the side at the bottom of
the triangle (across from the apex of 100% aromatics) represents binary mixtures of
paraffins and naphthenes.

26
Figure 2.2. A ternary diagram for classification of crude oils

Source: Dr. Semih Eser

If you need to refresh your memory on reading ternary diagrams, you may
check “Reading a Ternary Diagram”(link is external), or consult other sources. The list
below shows the six classes of crude oil that are defined using a ternary diagram. These
classes are shown as areas on the ternary diagram for paraffins, below. It is generally
accepted that Class 1 (rich in paraffins) represents the most desirable type of crude oil
because refining these crudes would readily lead to high yields of light and middle
distillates that constitute the fuels such as gasoline, diesel fuel, and jet fuel which are in
high demand. Extensive refining would be required to produce high yields of distillate
fuels from aromatic crudes (e.g., Class 4-6). Class 1 crudes tend to have high °API and
low sulfur contents and tend to be more expensive than the other types of crude oils.

Ternary Classification of Crude Oils

1. Paraffinic Crudes
paraffins + naphthenes > 50%
paraffins > naphthenes
paraffins > 40%
2. Naphthenic Crudes
paraffins +naphthenes > 50%
naphthenes > paraffins
naphthenes > 40%
3. Paraffinic-Naphthenic Crudes
Aromatics < 50%
paraffins < 40%
naphthenes < 40%
4. Aromatic-Naphthenic Crudes
Aromatics > 50%
naphthenes > 25%
paraffins < 10%
5. Aromatic-Intermediate Crudes
Aromatic > 50%
paraffins > 10%
6. Aromatic-Asphaltic Crudes
Naphthenes < 25%
paraffins < 10%

Video: Lesson 2 Paraffins (2:47)

Placement of Class 1 Paraffinic Crudes on the ternary diagram.

27
Click here for transcript of Lesson 2 Paraffins

Credit: Dutton Institute

Video: Lesson 2 Aromatics (2:34)

Placement of Class 4, 5, and 6 Crudes on the ternary diagram.

Click here for transcript of Lesson 2 Aromatics

Credit: Dutton Institute(link is external)

‹ Cha

2.7. Summary and Final Tasks

Lesson 2 Summary
Selected properties of crude oil provide information on its quality and the conditions for
optimum operation of a petroleum refinery for processing the crude oil to produce the
desired fuels. Readily measurable physical properties of crude oil (such as density,
boiling point, and viscosity) not only help predict the physical behavior of crude oil
during refining but also give insight into the chemical composition of the oil. Therefore,
physical properties can be used in developing characterization factors that relate to the
chemical behavior of crude oil and the characteristics of the resulting refinery products.
In addition to using characterization factors, crude oils are classified using ternary
diagrams reflecting the hydrocarbon composition in terms of paraffins, naphthenes, and
aromatics.

Learning Outcomes
By the end of this lesson, you should be able to:

 define the significant properties of crude oil, including density, viscosity, average
boiling point, sulfur, and salt content;
 understand the significance of crude oil properties in terms of refinery objectives, and
describe crude oil assay;
 define and interpret the classification factors (Watson, UOP, VGC, and BMCI) as they
relate to the hydrocarbon composition of crude oils;
 calculate average boiling points for crude oils using different averaging techniques,
and differentiate Watson and UOP characterization factors;
 analyze the elemental composition of crude oils and outline ternary classification of
crude oils with respect to hydrocarbon composition, i.e., aromatics, paraffins, and
naphthenes;
 assess the use of ternary classification of crude oils to estimate the refinery product
yields.
Reminder - Complete all of the Lesson 2 tasks!
28
You have reached the end of Lesson 2! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 3. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignment below can be found within this lesson.

This table contains the reading and assignments for Lesson 2.

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 3, pp. 57-61, 65-70

and the course material from this site

Assignments Exercise 1 - Submit to the Exercise 1 Assignment in the Lesson 2

Module.
 Calculation of API gravity of crude oil blends

 Calculation of Watson and UOP characterization factors for

hydrocarbons and crude oil fractions
Quiz 1: Assessment of learning outcomes in Lessons 1 and 2. Quiz 1 is
found in the Lesson 2 module.
Questions?
If you have any questions, please post them to our Help Discussion Forum (not email),
located in Canvas. I will check that discussion forum daily to respond. While you are
there, feel free to post your own responses if you, too, are able to help out a classmate.

29
Lesson 3: Overall Refinery Flow
 Lesson 3 Overview
 Desalting and Distillation
 Light Ends Unit
 Catalytic Reformer
 Catalytic Hydrotreatment
 Conversion of Heavy Gas Oil
 Conversion and Processing of Vacuum Gas Oils
 Processing and Conversion of Vacuum Distillation Residue
 Paths for Upgrading Heavy Oil
 Summary and Final Tasks

3.1. Overview

Selected properties of crude oil provide information on its quality and the conditions for
the optimum operation of a petroleum refinery for processing the crude oil to produce
the desired fuels. Readily measurable physical properties of crude oil (such as density,
boiling point, and viscosity) not only help in predicting the physical behavior of crude
oil during refinery but also give insight into the chemical composition of the oil.
Therefore, physical properties can be used in developing characterization factors that
relate to the chemical behavior of crude oil and the characteristics of the resulting refinery
products. In addition to using characterization factors, crude oils are classified using
ternary diagrams reflecting the hydrocarbon composition in terms of paraffins,
naphthenes, and aromatics.

As introduced in Lesson 1, petroleum refining integrates four types of processes:

separation, conversion, finishing, and supporting processes. This lesson involves a quick
walk through a simple refinery in the U.S. to see what happens to a barrel of crude oil,
and to provide more detail on how different processes are sequenced for optimum
operation. The simple animation below shows a simplified diagram of processing
network to maximize gasoline yield and produce the other distillate fuels (jet fuel, diesel
fuel, and fuel oil) in high yield.

The first sequence of processes in a refinery makes use of physical separation to wash the
salt out and to fractionate the desalted crude into different boiling ranges in a distillation
column. Following the distillation, these fractions are subjected to further separation
processes, such as those in Light Ends Unit (LEU) dewaxing and deasphalting units; to
finishing processes, such as hydrotreatment; and to conversion processes, such as
catalytic cracking, hydrocracking, visbreaking, and delayed coking. As shown in the
animation below, the final products from these processes include Liquefied Petroleum

30
Gas (LPG), lubricating oil base stock, asphalt, jet fuel and diesel fuel, gasoline, fuel oil,
and petroleum coke. Some fractions from LEU are sent to finishing processes (blending
and hydrotreatment) and further to a conversion process (reforming) to produce
additional gasoline. Light products from catalytic cracking are subjected to further
conversion in the alkylation process to produce more gasoline. Finally, supporting
processes, hydrogen production and sulfur recovery, help remove the major heteroatom
contaminant, sulfur, from the petroleum fuels through hydrotreatment [1].

This refinery scheme is typical in U.S. refineries where the premium product is gasoline,
as one could tell from the number of processes that lead to gasoline as the major product.
The gasoline streams from different processes are blended in sophisticated linear and
non-linear programming schemes to produce the three grades of gasoline sold in the U.S.,
regular, intermediate, and premium grades defined in reference to octane number.
Elsewhere in the world, there is more emphasis on producing diesel fuel rather than
gasoline, since the transportation systems are not as heavily dependent on gasoline-
powered passenger vehicles. Diesel fuel is preferred for mass transport options (e.g.,
buses and trains), as diesel engines (with compression-ignition) can deliver more power
than spark-ignition gasoline engines.

In the following sections, each major process group in a refinery network will be
introduced in sequence. We will discuss how they fit in the “industrial ecology” of
petroleum refining for the overall economic goal of maximizing profit in the prevailing
markets for crude oil and the refined petroleum products. The video below presents a
flow diagram integrating the four types of processes in a petroleum refinery.

Video: FSC 432 Simple Refinery Flow (4:36)

Simple Refinery Flow

Click here for transcript of Simple Refinery Flow

Credit: Dutton Institute

Learning Outcomes

By the end of this lesson, you should be able to:

 illustrate the refinery processes with examples for each category of processes;
 distinguish and evaluate the functions of different refinery processes to control
refinery product yield and composition;
 evaluate the principles behind the major refinery processes and examine the products
from each process from Distillation to Hydrocracking;
 formulate strategies for upgrading heavy oil.

31
 What is due for Lesson 3?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignments page within this lesson.

Lesson 3

Readings: J. H. Gary, G. E. Handwerk, & Mark J. Kaiser, Chapter 1, pp. 32-36;

Chapter 2, pp. 41-55 and the course material from this site

Assignments: Exercise 2: Using ternary classification to characterize crude oil blends

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

[1] Petroleum Refining, by J. H. Gary and G. E. Handwerk, 5th Edition, CRC Press NY, 2007,
Chapter 1.

3.2. Desalting and Distillation

Desalting and Distillation

Although distillation is usually known as the first process in petroleum refineries, in

many cases, desalting should take place before distillation (Figure 3.1). Salt dissolved in
water (brine) enters the crude stream as a contaminant during the production or
transportation of oil to refineries. If salt is not removed from crude oil, serious damage
can result, especially in the heater tubes, due to corrosion caused by the presence of Cl.
Salt in crude oil also causes reduction in heat transfer rates in heat exchangers and
furnaces.

The three stages of desalting are:

1. adding dilution water to crude;

2. mixing dilution water with crude by a mixer;
3. dehydration of crude in a settling tank to separate crude and sediment and water
(S&W).

32
Figure 3.1. Desalting and fractional distillation of crude oil.

Source: Dr. Semih Eser

Desalting can be performed in a single-stage or two-stage units. Amount of water wash

and temperature of the mixing process depend mainly on the crude API gravity [2].

Distillation separates hydrocarbon compounds into distillate fractions based on their

boiling points or volatility. More volatile compounds (with low boiling points) tend to
vaporize more readily than heavy compounds, and this forms the basis of separation
through distillation. In a distillation column, light components are removed from the top
of the column, and the heavier part of the mixture appears in the bottom. For a crude that
is a mixture of thousands of hydrocarbons, some very light compounds such as ethane
and propane only appear in the top product, while extremely heavy and non-volatile
compounds such as asphalts only appear in the bottom. Figure 2 shows a simple diagram
of atmospheric and vacuum distillation units and the fractional separation of the crude
oil into different boiling fractions with the indicated boiling ranges. The lightest
compounds found in crude oil come out from the top of the distillation column (referred
33
 to as overhead distillate, or full-range naphtha) and are sent to the Light Ends Unit (LEU)
for further separation into LPG and naphtha, as discussed later. The side streams
separated in the atmospheric distillation column give fractions that include the “straight-
run” products called kerosene, and light and heavy gas oils. The residue from the
atmospheric distillation column generates two side streams, light and heavy vacuum gas
oils, and vacuum residue from the bottom. All of these distillation products are subjected
to subsequent processing to produce light and middle distillate fuels and non-fuel
products, as described in the following sections starting with LEU.

[2] S. Eser and M. R. Riazi, “Crude Oil Refining Processes,” In Petroleum Refining and
Natural Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, ASTM International, West
Conshohocken, PA, 2013, pp 103-104.

3.3. Light Ends Unit

Light Ends Unit

As shown in Figure 3.2, the Light Ends Unit consists of a sequence of distillation
processes to separate the overhead distillate product from the atmospheric distillation
column into five streams consisting of methane and ethane (C2 and lighter), to propane
(C3), butane (C4), light naphtha, and heavy naphtha. The fraction C2 and lighter is used
as fuel gas in the refinery to provide heat or generate steam. Propane and butane are sold
as liquefied petroleum gas (LPG) after removing H2S. Light naphtha fraction that consists
of C5 and C6 paraffins (pentane and hexane) is sent to the gasoline blending pool as
straight-run gasoline, while the heavy naphtha fraction (rich in cycloalkanes, or
naphthenes) is sent to a catalytic reforming process to produce gasoline with a high
octane number.

34
Figure 3.2. Separations in light ends unit.

Source: Dr. Semih Eser

3.4. Catalytic Reformer

Catalytic reforming converts low-octane straight run naphtha fractions (particularly

heavy naphtha that is rich in naphthenes) into a high-octane, low-sulfur reformate, which
is a major blending product for gasoline (Figure 3.3). The most valuable byproduct from
catalytic reforming is hydrogen, which is needed in refineries with increasing demand
for hydrotreating and hydrocracking processes. Most reforming catalysts contain
platinum supported on alumina, and some may contain additional metals such as
rhenium and tin in bi-, or tri-metallic catalyst formulations. Early reforming processes
were called platforming in reference to reforming with a platinum catalyst. In most cases
for catalytic reforming, the naphtha feedstock needs to be hydrotreated before reforming,
to protect the platinum catalyst from poisoning by sulfur or nitrogen species. The
principal reactions in catalytic reforming include dehydrogenation of naphthenes to
aromatics (with significant quantity of hydrogen as byproduct) and
cracking/isomerization of n-paraffins into i-paraffins. The principal product from
catalytic reforming is called reformate, consisting of C4 to C10hydrocarbons. Reformate
has a high octane number because of high concentration of aromatic compounds
(benzene, toluene, and xylene) produced from naphthenes. With the more stringent
requirements on benzene and total aromatics limit in US and Europe (less than 1%
benzene, 15% total aromatics), the amount of reformate that can be used in gasoline
blending has been limited, but the function of catalytic reforming as the only internal
source of hydrogen continues to be important for refineries.
35
Figure 3.3. Catalytic reforming.

Source: Dr. Semih Ese

3.5. Catalytic Hydrotreatment

Catalytic Hydrotreatment

As seen with the catalytic reforming in the previous section, catalytic hydrotreatment can
be used as a pretreatment step to protect catalysts from crude oil contaminants such as
heteroatom (S, N, O) compounds, as well as metals (mainly Ni, V). Hydrotreatment is
also used as a major finishing process in a petroleum refinery. Shifting to the side stream
products from the distillation column, kerosene and light gas oil fractions can be
hydrotreated to remove the heteroatoms to produce the final products of jet fuel, and
diesel fuel, as shown in Figure 3.4. Particularly strict sulfur limits are imposed on diesel
fuels so that the particulate emissions from diesel engines can be reduced. In the U.S., the
government regulations [3] require that highway and non-road locomotive and marine
(NRLM) use diesel fuel that meets a maximum specification of 15 parts per million (ppm)
sulfur by 2014, with a full compliance for highway use and non-road diesel fuel since
December of 2010. Note in Figure 5 that typical catalysts used for hydrotreating are Co
and Mo compounds supported on alumina (Al2O3). Jet fuel consists of C10 to
C15 hydrocarbons, and diesel fuel consists of C15 to C20 hydrocarbons. Analogous to
octane number for gasoline, a performance parameter for diesel fuel is cetane number (n-
C16H34, n-hexadecane) that measures, in contrast to octane number, the tendency (not
resistance) of diesel fuel to ignite upon compression with air. As a side note, light gas oil
fraction is not typically used in the U.S. for producing diesel fuel, but sent to catalytic
cracking to make gasoline.

36
 Figure 3.4. Catalytic hydrotreatment of jet fuel and diesel fuel.

Source: Dr. Semih Eser

[3] Electronic Code of Federal Regulations, PART 80—REGULATION OF FUELS AND

FUEL ADDITIVES, Subpart I—Motor Vehicle Diesel Fuel; Nonroad, Locomotive, and
Marine Diesel Fuel; and ECA Marine Fuel, accessed on April 9, 2014.

3.6. Conversion of Heavy Gas Oil

Conversion of Heavy Gas Oil

Moving down on the side streams of the distillation column, heavy gas oil constitutes the
next fraction in line. Some generic conversion processes for the heavy distillates, such as
heavy gas oil (consisting of C20 to C25 hydrocarbons), are shown in Figure 3.5. These
processes, aimed at reducing the molecular size or the boiling point of gas oil
compounds, involve thermal cracking or catalytic cracking. A mild thermal cracking
process, called visbreaking, is applied to reduce the viscosity of the feedstock, and it is
more frequently applied to residual fractions, such as vacuum distillation residue. A
more severe thermal cracking of heavy gas oil can be used to produce LPG and ethylene
and light and middle distillates from heavy gas oil. A highly aromatic byproduct from
thermal cracking is called ethylene tar. Ethylene is an important petrochemical feedstock,
while ethylene tar can be used as feedstock to produce carbon blacks. Catalytic cracking
is more frequently used for conversion of heavy gas oil to gasoline.

37
Figure 3.5. Conversion of heavy gas oil.

Source: Dr. Semih Eser

A particular process of catalytic cracking, Fluid Catalytic Cracking, is almost exclusively

used worldwide in heavy gas oil and light vacuum gas oil conversion. This process
produces high octane gasoline primarily, with important byproducts, including LPG,
light olefins and i-alkanes, light cycle oil (LCO), heavy cycle oil (HCO), and clarified
slurry oil (also called decant oil), as shown in Figure 3.6. LCO is used in the U.S. to
produce diesel oil by hydrocracking, and decant oil can be used as fuel oil, feedstock for
carbon black manufacturing, and to produce a special type of petroleum coke called
needle coke. Needle coke has a microstructure that makes it a good precursor to graphite
electrodes that are used in electric-arc furnaces to recycle scrap iron and steel. The
manufacturing of graphite electrodes, using a byproduct from FCC used to produce
gasoline, is considered a principal interface between petroleum refining and the iron and
steel industry.

38
Figure 3.6. Fluid Catalytic Cracking (FCC) of heavy gas oil.

3.7. Conversion and Processing of Vacuum Gas Oils

Conversion and Processing of Vacuum Gas Oils

Moving to the vacuum distillation column, the vacuum distillates, light vacuum gas oil
(LVGO) and heavy vacuum gas oil (HVGO) can be processed by some advanced FCC
processes. However, hydrocracking is more frequently used to convert LVGO and
HVGO into light and middle distillates, using particular catalysts and hydrogen. Similar
to LCO, the LVGO and HVGO fractions from vacuum distillation tend to be highly
aromatic. Catalytic hydrocracking combines hydrogenation and cracking to handle
feedstocks that are heavier than those that can be processed by FCC, because of excessive
coke deposition on the catalyst in the absence of hydrogen. Middle distillates (e.g.,
kerosene and diesel fuel) are the principal products of hydrocracking. In addition to light
and middle distillates, hydrocracking also produces light distillates and LPG, as shown
in Figure 3.7.

HVGO can also be used as a feedstock to produce lubricating oil base stock, through a
sequence of solvent extraction processes to remove aromatic hydrocarbons by furfural
extraction, and to remove long-chain paraffins by dewaxing (Figure 3.8).

Figure 3.7. Hydrocracking of light vacuum gas oil.

Source: Dr. Semih Eser

Figure 3.8. Solvent extraction and processing heavy vacuum gas oil.
39
Source: Dr. Semih Eser

3.8. Processing and Conversion of Vacuum Distillation Residue

Processing and Conversion of Vacuum Distillation Residue

The heaviest and the most contaminated component of crude oil is the vacuum
distillation residue (VDR), also referred to as the bottom-of-the-barrel. There are multiple
processing paths to upgrade VDR into usable products. One process is called
deasphalting, which removes the heaviest fraction of VDR as asphalt that is used mainly
to pave roadways. The lighter fraction obtained in the deasphalting process, deasphalted
oil (DAO), can be used as fuel oil after hydrotreatment (Figure 3.9).

Figure 3.9. Deasphalting of vacuum distillation residue.

Dr. Semih Eser

Thermal processes, such as visbreaking and coking, also provide options for upgrading
VDR, which is normally a solid at ambient temperature. As shown in Figure 3.10, the
visbreaking operation involves mild thermal cracking, with the primary purpose of
producing a relatively low grade fuel oil (with a much lower pour point than VDR) and
byproducts such as middle and light (naphtha) distillates and LPG. The yield of these
byproducts would normally not exceed 10%wt of VDR. As a general rule in refinery
conversion processes, producing a lighter product with a higher H/C ratio (e.g., fuel oil,
middle distillates, LPG) from a feedstock (e.g., VDR) would require the simultaneous
formation of a heavier product (e.g., coke) with a lower H/C ratio than the feedstock.
Clearly, this compensation is dictated by the hydrogen balance, or hydrogen distribution
among the products. With no external hydrogen entering the conversion unit (as it would
in hydrogenation, or hydrocracking reactions), making a product(s) with a higher H/C
ratio than that of the feed would require making other product(s) with a lower H/C ratio
than that in the feedstock. In the case of visbreaking, what enables the production of
lighter (or lower viscosity) fuel oil and other products from VDR is the formation of small
quantities of coke with an extremely low H/C ratio. Hence, the
termdisproportination describes this unequal distribution of C or H in the conversion
products, or losing (rejecting) C in the coke that accumulates on reactor tubes and is
periodically burned out to clean the reactor tubes.

40
Figure 3.10. Thermal processing of VDR by visbreaking, or coking processes.

Source: Dr. Semih Eser

As different from visbreaking, coking involves severe thermal cracking with intentional
production of coke with a low H/C, so that lighter fuels can be obtained from VDR (by
disproportionation), as can also be seen in Figure 3.10. The product coke obtained from
VDR with relatively low heteroatom concepts, termed sponge coke, can be used in
manufacturing carbon anodes that are used in electrolysis of alumina (Al2O3) to produce
aluminum metal. This is another important interface between petroleum refining and
metals industries, similar to the coke produced from decant oil used for making needle
coke for manufacturing graphite electrodes to operate electric-arc furnaces, as mentioned
before.

3.9. Paths for Upgrading Heavy Oil

It should be clear from this quick tour of a refinery, that the most valuable products from
a refinery include light distillates (gasoline) and middle distillates (jet fuel and diesel).
These products are mostly paraffinic and contain relatively short paraffin chains, or small
molecules, or, in other words, high H/C ratios. In this context, one could summarize the
overall goal of petroleum refining as managing the H/C ratio of the products for the
optimum distribution of hydrogen into products to maximize profits. Controlling the
H/C ratio of the products would require either lowering the C content of the products
(i.e., carbon rejection), or increasing the H content (i.e., hydrogen addition). The
animation below depicts these two major paths for upgrading heavy oil (or crude oil)
with some examples for each path. The processes, coking, solvent extraction (e.g.,
deasphalting), visbreaking, and catalytic cracking reject carbon in the coke
(carbonaceous) product so that lighter products (with high H/C) ratios can be obtained
in these processes. Carbon in the coke, or in the heavier product is considered to have
41
been rejected (and potentially lost) since the carbonaceous byproducts have much lower
value in comparison to those of the lighter products. In contrast, hydrogen addition, as
in the processes of hydrogenation and hydrocracking, enables the conversion of all the
carbon present in heavy oil (or crude oil) to high value products without rejecting, or
sacrificing, any. One might ask, then, why would any refinery carry out any carbon
rejection process instead of hydrogen addition? A short answer to this question involves
basic refinery economics; the hydrogen addition processes cost much more than carbon
rejection processes, because producing hydrogen and the catalysts used in hydrogen
addition processes are very expensive.

Video: FSC 432 Upgrading Heavy Oil (3:48)

Heavy oil upgrading strategies: Carbon Rejection and Hydrogen Addition

Click here for transcript of Upgrading Heavy Oil

Credit: Dutton Institute

3.10. Summary and Final Tasks

Petroleum refining may be considered as the most sophisticated scheme of integrated
physical and chemical processes to meet the market demand for a number of fuels and
materials in the economy. In addition to satisfying the performance specifications
required by combustion engines, the composition of the produced fuels such as gasoline,
jet fuel, and diesel fuel, should be in compliance with environmental regulations.
Considering that crude oil is a natural material that displays a wide range variability in
hydrocarbon composition and the distribution of heteroatom species, it is vital to practice
an optimum sequence of the four types of processes that make up petroleum refining:
separation, conversion, finishing, and support. These processes are integrated as an
example of industrial ecology, such that every drop of crude oil ends up as a marketable
product, including the contaminants such as sulfur. The U.S. refineries are configured to
maximize the yield of gasoline (a light distillate) as the major product, along with jet fuel
and diesel fuel (middle distillates). A number of processes produce different gasoline
streams that are blended in sophisticated linear and non-linear programming schemes to
produce the three grades of gasoline sold in the U.S. for profit. A quick walk through the
network of refinery processes reveals the two general strategies that are in place to create
the most value in the operation: carbon rejection and hydrogen addition. The balance
between these two strategies hangs in the refinery economics and the markets for crude
oil and refined petroleum products.

Learning Objectives

You should now be able to:

42
 illustrate the refinery processes with examples for each category of processes;
 distinguish and evaluate the functions of different refinery processes to control
refinery product yield and composition;
 evaluate the principles behind the major refinery processes and examine the products
from each process from Distillation to Hydrocracking;
 formulate strategies for upgrading heavy oil.

Reminder - Complete all of the Lesson 3 tasks!

You have reached the end of Lesson 3! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 4. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignment below can be found within this lesson.

Lesson 3

Readings: J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 1, pp. 32-36;

Chapter 2, pp. 41-55 and the course material from this site

Assignments: Submit Exercise 2 as a PDF, or Excel file to the Exercise 2 assignment

in the Lesson 3 Module.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

43
Lesson 4: Separation Processes 1
 Lesson 4 Overview
 Atmospheric and Vacuum Distillation Units
 Distillation Methods
 Distillation Terminology
 Summary and Final Tasks

4.1. Overview

As introduced in Lesson 3, distillation is a key separation process that fractionates crude

oil into a number of streams with specific boiling point ranges, or distillation cuts.
Removing salt from crude oil usually precedes the distillation process to protect the
downstream units from corrosion caused by Cl¯. Desalting process could also remove
metals (e.g., Fe, Ni, V) and other inorganic solids and sediments that may deactivate
catalysts used in conversion and finishing units. Depending on the specific gravity and
the amount of salt present in a crude oil, refineries conduct from one up to three stages
of desalting [1]. Heavy and crudes may require three stages of desalting, using processes
such as gravity settling, electrostatic coalescence, and packed column separation [2].
Figure 4.1 shows a simple desalting process that uses gravity settling to separate brine
(NaCl +H2O) from crude oil after diluting the crude with water and adding de-
emulsifiers (chemical additives) to facilitate phase separation.

Learning Outcomes

By the end of this lesson, you should be able to:

 compare and evaluate different distillation methods;

 define boiling point ranges (TBP) of distillation fractions of crude oil;
 identify and exemplify distillation terminology, including cut points and product
yields in distillation ranges;
 illustrate the crude fractionation in Atmospheric Distillation and calculate the extent
of separation between the distillation fractions;
 illustrate Vacuum Distillation and assess the application of Watson Characterization
Factor to select the temperature in Vacuum Distillation Tower.

What is due for Lesson 4?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignment below can be
found on the Assignments page within this lesson.

44
 Lesson 4

Reading J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 4 (Crude Distillation)

Assignments Exercise 3: Appraisal of the degree of separation between distillation

fractions
Quiz 2: Will cover the material in Lessons 3-4.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 1, pp.32-36.
[2] S. Eser and M. R. Riazi, “Crude Oil Refining Processes,” In Petroleum Refining and Natural
Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, ASTM International, West
Conshohocken, PA, 2013, pp 103-104.

4.2. Atmospheric and Vacuum Distillation Units

Atmospheric and Vacuum Distillation Units

Distillation of crude oil is carried out in two units, first in an Atmospheric Distillation
Unit (also known as Crude Distillation Unit, CDU), with further processing of the residue
from atmospheric distillation in the Vacuum Distillation Unit (VDU), as illustrated in
Figure 4.2. For sake of simplicity, Figure 4.2 does not include the network of heat
exchangers and pump around loops to pre-heat the desalted crude before it is fed into
the fired furnace. In the furnace, the crude is heated to the desired temperatures (700-
750° F) such that all the distillate fraction and roughly 10-20% of the bottom product are
evaporated, depending on the volatility of crude oil. The two-phase mixture is then
introduced into the CDU flash zone for separation of vapor and liquid streams where
vapor fraction rises toward the top of the column and the liquid fraction is subjected to
stripping with steam to recover the low-boiling distillate components dissolved in
heavier liquid before sending the bottom product (i.e., atmospheric distillation residue)
to the vacuum distillation unit.

45
Figure 4.1. Desalting by using gravity settling to separate brine from crude oil.

Source: S. Eser and M. R. Riazi, “Crude Oil Refining Processes” In Petroleum Refining and
Natural Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, ASTM International, West
Conshohocken, PA, 2013, p. 105.

Figure 4.2. An overall flow for fractional distillation of crude oil.

Source: Dr. Semih Eser

A temperature gradient is established in the column by removing heat from the overhead
vapor. The column condenses the naphtha fraction and sends a portion of the liquid
naphtha, as reflux, to the column to achieve a good separation of the distillate products
drawn from the side of the distillation column, such as kerosene, LGO, and HGO, as seen
in the diagram. Steam strippers on the side of the column also provide reflux to the main
46
column to help with clean separation of the distillate products. Additional reflux is
provided to the main column by pump around loops associated with heat exchangers
(see Figure 4.3, below, and Figure 4.8 in the textbook) for preheating the crude. Counter-
current flow of vapor and liquid streams through the contact stages (e.g., trays) in the
main column, enabling good separation of the distillate fractions. The temperature at the
bottom of CDU is limited to 700-750° F to prevent cracking – breaking of the chemical
bonds between carbon atoms in the aliphatic hydrocarbons constituting the crude oil.
Cracking would cause coking (accumulation of carbonaceous solids) on the metal
surfaces in the column and interferes with fractionation in distillation. Vacuum
distillation is necessary to fractionate the heavy distillates because further increase in
temperature would cause thermal cracking of the feed components. In HYSYS Project
1 assignment, you will learn how to introduce crude assay data to a distillation simulator
and calculate the yields of naphtha, kerosene, diesel, atmospheric gas oil, and residue for
different crudes.

Figure 4.3. A schematic diagram of atmospheric distillation unit illustrating the feed
heat exchangers, pump around loops, and side steam strippers (adapted from [3]).

Source: Dr. Semih Eser

As shown in Figure 4.4, below (and in Figure 4.10 in the textbook), the atmospheric
residue is reheated in a fired furnace to 730-850° F before introduction into the vacuum
distillation unit (VDU). Furnace outlet temperature is selected depending on the thermal
reactivity (or coking propensity of crude oil, as will be discussed further) and the desired
level of separation in the column. Steam ejectors, or, more recently, vacuum pumps, are
47
used to create vacuum for evaporation of the light vacuum gas oil and heavy vacuum
gas oil fractions. The temperature and pressure in VDU also depend on whether steam
is introduced, or the separation is carried out without the steam addition in “dry” towers,
varying between 10 to 30 mmHg at the bottom of the tower. Lower pressures and higher
temperatures are used in dry towers. To minimize the pressure difference between the
bottom and top of the column, some special packing materials are used (see, for example,
Figure 4.5) instead of trays for providing contact between liquid and vapor streams to
improve fractionation.

Figure 4.4. Vacuum distillation unit and processing paths for the vacuum distillates.

Source: Dr. Semih Eser

Figure 4.5. Examples of packing materials to achieve low-pressure drop in vacuum

distillation columns [4].

Source: [4]Tower Packing(link is external). Retrieved on April 16, 2014

The heavy distillates (light vacuum gas oil and heavy vacuum gas oil) separated in VDU
are further processed in downstream separation and conversion units to produce
lubricating oil base stocks, or as feedstock for hydrocracking to produce light and middle

48
 distillates. The residue from vacuum distillation (VDR) can be upgraded into marketable
products and fuels using processes such as visbreaking, deasphalting, and coking, as will
be discussed in later sections.

[3] Refining Overview - Petroleum, Products and Processes, AIChE, 2000, p. 10-4.

[4] Tower (link is external)Packing(link is external). Retrieved on April 16, 2014

4.2.a. Selecting the Right Temperature

Selecting the Right Temperature

Selecting the right temperature in the vacuum distillation column is critical to control the
risk of coking in the column. The Watson Characterization Factor (Kw) may be used to
estimate the upper temperature limit for vacuum distillation to avoid coking. Figure 4.6
shows an empirical correlation between Kw and the temperatures above which
significant thermal decomposition could take place. This region is labeled as the
decomposition zone in Figure 4.6. Because of the complex variability in crude
oil composition as it relates to coking propensity, one could draw a band of temperatures
below which coking risk is negligible, and the area within the band represents
uncertainty in terms of the probability of coking. To be on the safe side, the temperature
in the column should be lower than the lower temperature line of the band. Figure 4.6
also shows that crudes with high Kw (paraffinic) should be heated to lower temperatures
in the column than crudes with lower Kw (less paraffinic). Hydrocarbon composition is
closely related to thermal reactivity, since paraffins could be more readily cracked than
naphthenes, whereas aromatic compounds are the most stable hydrocarbons. To sum up,
vacuum distillation temperatures should be selected with particular care for paraffinic
crudes because of the relative ease of cracking of paraffins that leads to the formation of
coke on surfaces.

Figure 4.6. Use of KW factor to select the operating temperatures in VDU.

Source: Dr. Semih Eser

49
Severe cases of coking can plug the flow paths in the distillation column and require
shutting down the unit. Shutting down a distillation unit would be catastrophic, as it
would require shutting down the whole refinery that must run around the clock except
for the scheduled maintenance period.

4.3. Distillation Methods

Distillation Methods

Three different distillation methods are commonly used to generate laboratory data on
crude oil:

1. True Boiling Point Distillation (TBP)

2. ASTM Distillation (ASTM)
3. Equilibrium Flash Vaporization (EFV)
The degree of separation between the distillation fractions obtained in these methods
decreases significantly as one moves down the list from TBP through ASTM to EFV. Each
method and the associated distillation data have different applications in the refinery
practice.

 True Boiling Point Distillation (TBP)

 ASTM Distillation (ASTM)
 Equilibrium Flash Vaporization (EFV)
 TBP, ASTM, and EFV Compared

4.3.a. True Boiling Point Distillation (TBP)

True Boiling Point Distillation (TBP)

This method, described in Figure 4.7a and b, uses a batch distillation operation that
incorporates more than 100 theoretical plates and a high reflux ratio (R/P) of 100, as
described in Figure 4.7a. This is an idealized method to achieve the best possible
separation in distillation, made possible by a large number of theoretical plates (stages)
for liquid vapor contact in the column and an extremely high reflux ratio. As an example,
consider distillation of a binary mixture of compounds A (70% by volume) and B (30%
by volume), with boiling points Ta and Tb, respectively. Figure 4.7b illustrates the
distillation curve that would be obtained if this mixture were distilled using the TBP
method, with perfect separation of A and B as pure compounds. Because of the TBP
distillation conditions, first the lower boiling component A is distilled off without any
contamination with B, and following the complete vaporization of A, B is distilled off as
a pure compound. Note that because a large number of plates and a high reflux ratio in
50
the column, temperature remains constant during evaporation of A until all of this
compound is boiled off, as would be seen in the distillation of a pure compound.

Figure 4.7a. TBP distillation apparatus

Source: Dr. Semih Eser

Figure 4.7b. Distillation curve for perfect separation of the components A and B in a
binary mixture.

Source: Dr. Semih Eser

4.3.b. ASTM Distillation (ASTM)

ASTM Distillation (ASTM)

ASTM distillation also uses a batch operation, but in contrast to TBP, it operates without
the presence of a contact plate and a reflux ratio (R/P, or RR) of zero, as shown Figure
4.8a. There may be a slight unintentional reflux because of the condensation of the vapor
on the tube that connects the flask to the condenser.

51
Figure 4.8a. ASTM distillation apparatus.

Source: Dr. Semih Eser

Figure 4.8b. Distillation curve for ASTM distillation of the binary mixture A and B.

Source: Dr. Semih Eser

Figure 4.8c. TBP distillation curve for distillation of the same binary mixture.

Source: Dr. Semih Eser

4.3.c. Equilibrium Flash Vaporization (EFV)

Equilibrium Flash Vaporization (EFV)

Equilibrium flash vaporization involves heating a flowing feed and the separation of the
liquid and vapor in a flash drum. A distillation curve may be obtained by conducting
this distillation at varying heater outlet temperatures. Figure 4.9 shows the diagram of
an EFV set up and compares the distillation curves from the three methods, TBP, ASTM,
and EFV. From the comparison of the curves and the relationship between IBP and EP
52
obtained in each case, one concludes that EFV gives the lowest degree of separation
between A and B, even lower than that given by the ASTM distillation.

Figure 4.9. Equilibrium Flash Vaporization (EFV) and comparison of distillation

curves for EFV, ASTM, and TBP distillation of the binary mixture A and B.

Source: Dr. Semih Eser

4.3.d. TBP, ASTM, and EFV Compared

TBP, ASTM, and EFV Compared

The TBP, ASTM, and EFV distillation methods achieve different levels of separation for
a given sample, as related to the different techniques used in these analyses. Figure 4.10
shows TBP, ASTM, and EFV curves for a middle distillate fraction crude oil, showing
significant differences in IBP and EP of the three curves [6]. Note that three curves
converge near 50% volume distilled. TBP distillation achieves a higher degree of
separation than ASTM and ASTM achieves better separation than EFV, as can be seen in
the curves in Figure 4.10. Empirical correlations have been developed to convert one set
of distillation data to another [7].

53
 Figure 4.10: TBP, ASTM, and EFV curves for a middle distillate fraction crude oil.

Source: Refining Overview - Petroleum, Products and Processes, AIChE, 2000.

Each distillation method discussed in this section has an application in petroleum

refining. TBP distillation is used to characterize crude oils and constitute a significant
component of crude essay. ASTM methods are usually used for refinery products and
property calculations and correlations for distillate fractions. EFV provides useful data
for flashing operations in the refinery.

There are no standard methods for TBP distillation, but ASTM D-2892 method is used to
approximate the TBP distillation. This method is also referred to as 15-5 distillation,
because of 15 theoretical plates and a reflux ratio of 5 used in the distillation. A simulated
distillation method described in ASTM D2887 may also be used to obtain TBP data for
crude oils.

ASTM D86 (atmospheric distillation) and ASTM D1160 (vacuum distillation) are used for
low-boiling, and high-boiling fractions, respectively.

[6] Refining Overview - Petroleum, Products and Processes, AIChE, 2000.

[7] Riazi, M.R., “Characterization and Properties of Petroleum Fractions,” MNL5, ASTM
International, West Conshohocken, PA, 2005.
‹ Equilibrium Flash Vaporization (EFV)

4.4. Distillation Terminology

Distillation Terminology

It is important to use the correct terms to clearly represent the fractionation of crude oil
by distillation. The distillation temperatures, or cut points, are used to delineate the
distiilate fractions and define commercial fuels and solvents.

 Cut Points
 Separation in Fractional Distillation

4.4.a. Cut Points

Using a crude TBP curve, cut points are defined as the temperatures that represent the
limits of a distillate fraction, as illustrated in Figure 4.11. For example, for kerosene,
fraction Ta represents the lower cut point, and Tb represents the upper cut point in Figure
4.11.

54
Figure 4.11. Cut points and definition of distillate products as boiling ranges.

Source: Dr. Semih Eser

Boiling ranges between the cut points represent distillate products, such as naphtha,
kerosene, light gas oil, etc. The difference between the cumulative volume percent at
upper and lower cut points is reported as the yield (in volume %) for the particular
distillate fraction. For example, for the crude represented in Figure 4.11, the kerosene
yield can be calculated as 40%(at Tb) -20% (Ta) = 20% by volume. Table 4.1 shows the
TBP cut points for crude oil distillate fractions.

Table 4.1 TBP cut points for crude oil distillate fractions.

Distillate Product Boiling Range

Butanes and Lighter

Light SR Naphtha 90 - 190o F (32-88o C)

Heavy Naphtha 190 - 380o F (88 - 193o C)

Kerosene 380 - 520o F (193 - 271o C)

Light Gas Oil 520 - 610o F (271 - 321o C)

Heavy Gas Oil 610 - 800o F (321 - 425o C)

Light Vacuum Gas Oil 800 - 950o F (425 - 510o C)

Heavy Vacuum Gas Oil 950 - 1050o F (510 - 564o C)

Vacuum Residue > 1050o F (>565o C)

55
4.4.b. Separation in Fractional Distillation

Separation in Fractional Distillation

The quality of separation in fractional distillation can be calculated using the designated
cut points (at 5%voland 95%vol) for the two adjacent fractions, termed as light and heavy.
As shown below, the difference in temperature (ΔT) between 5% vol temperature of the
heavy fraction and 95%vol temperature of the light fraction is used to define the quality
of separation. A positive value of ΔT(termed ASTM gap) indicates good separation, while
a negative value of ΔT (termed ASTM overlap) points to a bad separation.

ASTM distillation temperatures and separation in a distillation process

Fractionation
What defines a good separation?

The relationship between the ASTM distillation temperatures at 95% vol and 5% vol of
two adjacent fractions, light and heavy, respectively.
ASTM 5% volT (heavy fraction) - 95% volT (light fraction) = ∆T
(e.g., LGO) (e.g., kerosene)

if ∆T >0, called ASTM gap (good separation)

if ∆T<0, called ASTM overlap (bad separation)

4.5. Summary and Final Tasks

Summary

Distillation, a key separation process in petroleum refining, is considered as a gateway

to all refinery processes. Fractionation of crude oil by distillation into a number of
streams generates feedstocks for all the subsequent separation, conversion, and finishing
processes that lead to the refinery

products. Prior to distillation, crude oil is subjected to desalting to remove in particular

the Cl¯ion to prevent corrosion in downstream processes. Both atmospheric and vacuum
distillation processes are used to separate the desired fractions from crude oil which has
a boiling range of over a 1000° F. Three different distillation methods used in laboratory
include True Boiling Point distillation, used for characterization of crude oils, ASTM
distillation for product characterization, and Equilibrium Flash Vaporization for
conducting efficient flash operations in the refinery. The performance of an atmospheric

56
distillation column can be monitored through using the ASTM distillation data obtained
for the distillate products. The three parameters that control the performance of a
distillation column in terms of the quality of separation achieved in the process are
number of plates, reflux ratio, and the amount of steam used in the operations. Empirical
correlation relates these three factors to control the quality of separation in an operating
distillation column or help design a new distillation column.

Learning Outcomes

You should now be able to:

 compare and evaluate different distillation methods;

 define boiling point ranges (TBP) of distillation fractions of crude oil;
 identify and exemplify distillation terminology, including cut points and product
yields in distillation ranges;
 illustrate the crude fractionation in Atmospheric Distillation and calculate the extent
of separation between the distillation fractions;
 analyze the vapor-liquid equilibrium and evaluate the application of Fenske Equation
to distillation in Light Ends Unit;
 illustrate Vacuum Distillation and assess the application of Watson Characterization
Factor to select the temperature in Vacuum Distillation Tower.

Reminder - Complete all of the Lesson 4 tasks!

You have reached the end of Lesson 4! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 5. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignments below can be found within this lesson.

Lesson 4 tasks

Reading J. H. Gary and G. E. Handwerk, Chapter 4 (Crude Distillation)

Assignments Exercise 3: Submit your answers to the Exercise 3 assignment in the

Lesson 4 Module. Quiz 2: Will cover the material in Lessons 3 and 4.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

57
Lesson 5: Separation Processes 2
 Lesson 5 Overview
 Fractionation in Light Ends Unit (LEU)
 Deasphalting
 Gradient Solubility Model
 Deasphalting Process
 Dewaxing
 Summary and Final Tasks

5.1. Overview

Overview

This section will continue to discuss the separation processes that are carried out on the
distillate products obtained from the atmospheric and vacuum distillation units, and the
residue from the vacuum distillation unit, as introduced in Section 4. Light Ends Unit
(LEU) fractionates the lightest fraction of crude oil obtained as overhead distillate from
the atmospheric column in a series of distillation towers to produce LPG as a refinery
product and straight-run light, and heavy naphtha for further processing in finishing and
conversion units to produce gasoline streams for the blending pool (Section 3). Vacuum
distillation residue (VDR) can be fractionated using solvent extraction (deasphalting) to
produce an insoluble (asphalt) and a soluble fraction, deasphalted oil (DAO). DAO can
be further processed by freezing point separation in a suitable solvent to separate wax.
The remaining dewaxed oil is used as base stock for producing lubricating oil. Heavy
vacuum gas oil (HVGO) can also be used as a feedstock for dewaxing.

Learning Outcomes

By the end of this lesson, you should be able to:

 analyze the vapor-liquid equilibrium and evaluate the application of Fenske Equation
to distillation in Light Ends Unit;
 describe the principles of solvent fractionation as a separation technique;
 place the Deasphalting Process in the refinery and interpret the significance of this
process for refining;
 interpret the gradient solubility model that explains the solution of asphaltenes in
resin and oil fractions and analyze the structure of asphaltenes;
 analyze the process parameters for deasphalting and assess the anti-solvent effect;
 evaluate the unit operations of deasphalting and assemble the process flow diagram;

58
 explain the purpose of dewaxing and examine the physical and chemical dewaxing
processes.

What is due for Lesson 5?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignments page within this lesson.

Lesson 5 Checklist

Readings J. H. Gary and G. E. Handwerk, Mark J. Kaiser, Chapter 15 (Lubricating Oil

Feedstocks)

Assignments Exam 1 will cover the material in Lessons 1-5. Exam 1 is found in the Exam 1
Module.

Exercise 4:

1. Use of Fenske Equation to evaluate the performance of a distillation

column
2. Qualitative evaluation of process parameters to estimate product yields
from deasphalting

Questions?

If you have any questions, please post them to our Help Discussion Forum (not email),
located in Canvas. I will check that discussion forum daily to respond. While you are
there, feel free to post your own responses if you, too, are able to help out a classmate.

5.2. Fractionation in Light Ends Unit (LEU)

Fractionation in Light Ends Unit (LEU)

Because of the low molecular weight and high volatility of the constituents in the
overhead distillate, the feedstock to LEU can be analyzed on a molecular basis, using, for
example, a gas chromatograph. The hydrocarbon range in overhead distillate (over a
boiling point of gas to 380°F mid-boiling point) covers carbon numbers C1 through C10.
Because of the relatively simple composition of this feed, the quality of separation in LEU
units can be defined in terms of the concentrations of selected hydrocarbon compounds
such as propane, butane, and i- butane. Remember that one needs to use the distillation
data to define the quality of separation (in terms of ASTM gap, or ASTM overlap)

59
between the adjacent cuts obtained from the side of atmospheric distillation column
(Lesson 4).
Figure 5.1 shows the separation scheme in light end towers where the feed is separated
into the distillate (low-boiling point) and bottom (high-boiling point) fractions.
Considering a depropanizer unit, the distillate will consist mainly of propane and lighter
compounds, whereas the bottoms will contain butane and heavier hydrocarbons. To
determine the degree of separation in the light end towers, the first step is to select the
key components, which may be real compounds (such as butane, or i-butane), or a
pseudo component which is defined by the mid-boiling point of the a boiling range (i.e.,
temperature at which 50%vol of the selected component is evaporated). Two key
components (light key and heavy key) must be selected using the two selection rules, as
shown in Figure 5.1.

Figure 5.1. Distillation in the light end towers.

Source: Dr. Semih Eser

The key component selection rules are:

1. Light key and heavy key should be adjacent compounds (in terms of boiling points)
in the feed stream.
2. Both light key and heavy key must be present in the distillate and bottom fractions.
Once the key components are selected, their concentrations in the distillate and bottom
fractions and their respective vapor liquid equilibrium coefficients (K values) can be used
in the Fenske Equation to calculate the number of theoretical plates (including a reboiler)
needed in the distillation column under the ideal condition of total reflux (100% reflux).
Figure 5.2 shows the Fenske Equation and defines all the terms used in the equation. The
ideal conditions assumed for using the Fenske Equation include 100% plate efficiency
(for perfect separation in a plate) and total reflux in the column where no product is
drawn as distillate. Total reflux means the whole overhead product is refluxed back to
the column. Obviously, to get data on an actual (not an ideal) case of distillation, one
needs to make two corrections to obtain the actual number of plates from the number of
60
theoretical plates used in, or calculated by the Fenske Equation: 1) by assuming an actual
plate efficiency to correct for 100% plate efficiency), 2) by assuming a correction factor to
correct from total reflux (or infinite reflux ratio to the operational (actual) reflux
conditions).

Figure 5.2. Fenske Equation and the definition of all terms in the equation.

Source: Dr. Semih Eser

It is common to use an actual plate efficiency of 75% (for plate efficiency correction), and
a correction factor of 1.5 (for reflux ratio correction) for the operation under a finite
(actual) reflux ratio from the total reflux condition. Therefore, these corrections could be
made as follows:

# [actual plates (at 75% efficiency) at total reflux] = [theoretical # plates (at 100%
efficiency)]/0.75

# [actual plates (at normal reflux)] = 1.5 x [actual plates (at 75% efficiency) at total reflux]

In other words, making both corrections from #theoretical plates used in Fenske equation
to #actual plates after both corrections (for plate efficiency and reflux conditions) would
give:

# actual plates = ([#theoretical plates used in Fenske Equation]/0.75) x 1.5

5.2.a. Exercise

Using the problem definition given in Figure 5.3, calculate n-C4 flow rate in the distillate
product, if the debutanizer column has 18 (actual) plates.

Constraint:

61
The concentration of i- C5 should be <1 mole% of total C4’s and lighter compounds in the
distillate product.

Given:

Column efficiency =75%, Reflux correction factor =1.5

Mean tower conditions: 210°F and 110 psig

Select appropriate light and heavy keys, and use the K values for the corresponding key
compounds using the chart given in Figure 5.4 at the mean tower conditions.

Instructions for Submitting Your Answers:

Once you have calculated your answer, post it in the Exercises Dropbox inside the Lesson
5 folder in Canvas.

If possible, submit a Microsoft Word, or Excel document, showing all the steps in your
calculations, indicate the K values you read from the nomograms, and assumptions, if
any. You may submit scanned images or clear handwritten pages as a pdf that is less than
2 MB in size.

Figure 5.3. Debutanizing full-range naphtha.

Click here for text description of Figure 5.3.

Source: Dr. Semih Eser

62
Figure 5.4a. K values for light hydrocarbons at low temperatures (DePriester Chart).

Figure 5.4b. K values for light hydrocarbons at high temperatures (DePriester Chart).

63
5.2.b. Deasphalting

While distillation achieves separation/fractionation of the feed components with

respect to differences in their boiling point, deasphalting (as a solvent extraction process)
fractionates the feedstock, atmospheric, or more often vacuum distillation residue (VDR),
with respect to solubility/insolubility of molecular components in a given solvent. Figure
5.5 shows a solvent fractionation scheme used in laboratories to separate VDR into
fractions that are defined based on the solubility behavior. VDR, which could be a solid
at ambient temperature, is completely dissolved in aromatic solvents such as benzene
and toluene. The highest molecular weight components of VDR classified as
“asphaltene” can be separated by precipitation (as solid material) when a light paraffin
solvent is mixed with VDR solubilized in an aromatic solvent (e.g., toluene). The paraffin
solvent used (e.g., n-heptane) defines the identity of the separated asphaltenes (e.g.,
toluene soluble and n-heptane insolubles). The portion of VDR that is soluble in the
paraffin solvent is called maltenes, but also labeled with respect to the solvent used in
the separation, i.e., n-heptane maltenes. As can be seen in Figure 5.5, the n-heptane
solubles can further be separated using n-pentane (a lighter and a weaker solvent) into
insoluble (hard resin) and soluble (n-pentane solubles) fractions. The n-pentane solubles
can also be separated using a lighter solvent yet (propane) to soft resin and oil products.
In refinery practice, only one stage of separation is used using the lightest solvent (e.g.,
propane) to produce asphalt and deasphalted oil (DAO) fractions, as discussed later in
this section.

Asphaltenes consist of high-molecular weight compounds with strong aromatic

character and contain highest concentrations of heteroatom (S, N, and metal) species.
Because of the low H/C ratio of asphaltenes and resins, the deasphalting process can be
considered as a “carbon rejection” process, yielding a high H/C ratio product (i.e., oil)
after removing the asphaltenes and resins, as, typically, lower value byproducts.

Figure 5.5. Solvent fractionation of vacuum distillation residue (VDR).

Source: Dr. Semih Eser

64
5.2.c. Gradient Solubility Model

Because of the large disparity in structure and properties of asphaltenes and oil fractions
in VDR, it is surprising that VDR appears as a solution (one-phase material) rather than
a suspension of discrete asphaltene particles in VDR. A commonly accepted hypothesis
to explain the single phase observed with VDR is known as the gradient solubility model,
illustrated in Figure 5.6. The model claims that asphaltene molecules (depicted as dark
spheres in Figure 5.6a) can be dissolved in resins (light spheres) and the resulting solution
can be dissolved in oil (wiggly lines), thus producing a single phase solution. Some model
molecular structures proposed for asphaltenes are shown in Figures 5.6b and 5.6c. There
is a more widespread acceptance of the smaller molecular structures shown in 6c, as
better representatives of asphaltenes molecules among the asphaltene researchers.

Figure 5.6a. Gradient-solubility model to explain dissolution of asphaltenes in crude

oil.

Source: Dr. Semih Eser

Figure 5.6b. Proposed molecular structures for asphaltene molecules.

Source: Dr. Semih Eser

Figure 5.6c. Proposed molecular structures for asphaltene molecules.

65
 Source: Dr. Semih Eser

The gradient solubility model offers an explanation of how asphaltenes can be forced out
of the solution in VDR by solvent extraction. Briefly, the solubility of a compound in a
given solvent depends on the strength of the solvent that is measured by Hildebrand
Solubility Parameters (HSP) for non-polar solvents. The two definitions of HSP are given
in Figure 5.7, indicating the dependence of the parameter values on surface tension and
molar volume of the solvent (1st Hildebrand parameter), or on the energy of vaporization
(heat necessary to evaporate the solvent under constant volume conditions) and molar
volume (2nd Hildebrand Parameter), respectively. These parameters correlate well with
one another, and each can be used without any preference to express the dissolving
power of a solvent. A discussion of the Solution Theory is beyond the scope of this course,
but it would suffice to consider that solubility parameter increases with the increasing
density (decreasing molar volume) and increasing surface tension, or increasing latent
heat of vaporization. This explains why aromatic solvents have higher solvent power
than aliphatic hydrocarbons, and why the solvent power of paraffins decreases with the
decreasing carbon number.

It is now possible to explain that using a large volume of a paraffin solvent, added to
dissolved VDR in a laboratory experiment, effectively disrupts the gradient solubility of
asphaltenes, and as a result, asphaltenes precipitate as solid particles and can be filtered
out for recovery. In refinery deasphalting process, however, e.g., in propane
deasphalting [1], lower quantities of solvent (or lower solvent to resid (S/R) ratio) is used
to separate asphalt (asphaltenes + resins) and deasphalted oil (DAO).

Figure 5.7. Hildebrand solubility parameters for non-polar solvents.

Source: Dr. Semih Eser

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 15, pp.311-312.

66
5.3. Deasphalting Process

Deasphalting Process

Figure 5.8 places the deasphalting process in a refinery flow scheme as an intermediate
process between vacuum distillation and dewaxing processes, for producing the refinery
output streams as asphalt deasphalted oil (DAO), which can be directed to another
separation process, dewaxing, to produce lubricating oil base stock and wax,or can be
sent to conversion units such as hydrocracking to produce light and middle distillate
fuels. It is important to note that the deasphalting process is an upgrading process to
transform VDR into marketable products, and/or convert it to distillate fuels that
command high demands.

Figure 5.8. Configuration of deasphalting and dewaxing processes in a petroleum

refinery.

Source: Dr. Semih Eser

The two objectives of the deasphalting process are:

1. Produce asphalt - as final product.

2. Remove asphaltenes to prevent coke, or metal buildup on catalyst in further
processing of DAO.
Depending on the properties of the VDR and prevailing markets, the emphasis could be
placed on one of these objectives. Remember that aromatic asphaltic crudes are more
expensive to convert into distillate fuels. Such crudes could be processed readily into
making high yields of asphalt and serve the asphalt market. With lighter crudes, the
principal focus could be on removing the asphaltenes from VDR so that DAO produced
can be used in conversion processes with a lower extent of problems caused by
asphaltenes such as coke buildup, or metals buildup on catalysts in, for example,
hydrotreating or hydrocracking reactions.

 Simplified Flow Diagram of a Deasphalting Process

 Asphaltene Yield
 Solubility Parameter of the Solvent
67
 5.3.a. Simplified Flow Diagram of a Deasphalting Process

Figure 5.9 shows a simplified flow diagram of a propane deasphalting process.

See a more detailed flow diagram in your textbook along with a description of the
operating conditions in the commercial process. As the first step in deasphalting, residue
(feedstock) is mixed with four to eight times the volume of liquid propane. Heavier
residua require a higher solvent to residue (S/R ) ratio for effective separation of asphalt.
Following the precipitation of asphalt, DAO and asphalt are separated, and each stream
is purified and flashed to recover and recycle the propane solvent, as shown in Figure
5.9.

Figure 5.9. A deasphalting process [1].

Source: Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 15, pp.311-312.

The four-unit operations of deasphalting illustrated in the process flow diagram are:

1. Flocculation (& precipitation) of asphaltenes

2. Asphalt decanting - separation
3. Asphalt washing - to remove entrained oil
4. Solvent recovery and recycle
[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 15, pp.311-312.

5.3.b. Asphaltene Yield

68
 Independent variables in the deasphalting process include the solvent used,
pressure, temperature, S/R, and contact time. These variables can be controlled to obtain
the optimum conditions for the desired separation in deasphalting. One of the important
dependent variables in the process is the asphaltene yield. Figure 5.10 shows, in
qualitative plots, how asphaltene yield varies as a function of the process parameters

Figure 5.10a. Effect of solubility parameter on asphaltene yield.

Source: Dr. Semih Eser

Figure 5.10b. Effect of molecular weight on asphaltene yield.

Source: Dr. Semih Eser

Figure 5.10c. Effect of temperature on asphaltene yield.

Source: Dr. Semih Eser

69
Figure 5.10d. Effect of contact time on asphaltene yield.

5.3.c. Solubility Parameter of the Solvent

Solubility parameter of the solvent is a key a variable that affects asphaltene yield.
Asphaltene is completely soluble in toluene which has a high solubility parameter.
Therefore, the asphaltene yield with toluene will be zero (Figure 5.10a). Propane (C3,)
which has the lowest solubility parameter among the solvents given in the plot, will give
the highest asphaltene yield.
Figure 5.10b shows that asphaltene yield increases with the increasing solvent/residue
ratio used in the process. This is an unusual behavior for solvent extraction because,
typically, the yield of an insoluble fraction would decrease with the increasing quantity
of solvent used in the extraction behavior. The unusual behavior seen in Fig. 5.10b is
termed as the “anti-solvent effect.” This relates to the gradient theory of asphaltene
solubility in crude oil (or in VDR) such that larger quantities of paraffin solvent used in
the process more effectively disrupt the gradient solubility by removing more oils from
VDR, forcing the asphalt fraction (asphaltene+resin) to separate out. One should point
out here that the molecular composition of the asphaltenes would vary significantly
along with the yield of asphaltenes in the plot shown in Figure 5.10b. As the yield of
asphaltenes increases with the increasing S/R, lower molecular weight asphaltenes
would be progressively included in the separated asphaltenes. In other words, for a given
process, low yields of asphaltenes (obtained at low S/R) would contain the highest
molecular weight and highly aromatic compounds, whereas asphaltenes obtained at
high yield with high SR ratio would include a broader range of molecular weight and
aromaticity in the separated asphaltenes.

The consideration of variable asphaltene composition would also apply to the

asphaltenes separated with different paraffin solvents as shown in Figure 5.4b. In this
case, lower yields of asphaltenes obtained with C7 (n-heptane) will be associated with
heavier and more aromatic asphaltenes than those obtained with propane (C3). These
observations relate to the absence of a precise molecular definition to express the complex
of asphaltenes, but the need to use an operational definition on the basis of
solubility/insolubility in a given solvent. It should, therefore, be remembered that the
composition of the asphaltenes, or asphalt produced in a refinery would not only depend
on the properties and composition of the parent crude oil, but also on the solvent, as well
as the S/R ratio used in the process among other factors, such as temperature and
pressure as they affect the solubility parameters of the solvent. Figure 5.10c shows the
dependence of asphaltene yield on temperature, as explained by the decreasing solubility
parameter of the solvent used in this case with the increasing temperature. A sufficient

70
amount of contact time with paraffin is necessary for good asphaltene separation. The 8-
10 h contact time refers to batch experiments in laboratory. In flow systems of commercial
deasphalting, the contact time necessary for the desired separation of asphalt is much
shorter.

5.4. Dewaxing

Dewaxing

Another important separation process in petroleum refining is removal of wax. The

process of dewaxing is introduced and discussed in the next sub-section.

Figure 5.11 locates the dewaxing process in the refinery landscape. The feedstocks to
dewaxing include DAO from deasphalting, and HVGO from vacuum distillation as
shown in Figure 5.11 along with some compositional characteristics of the feedstock and
the dewaxing product. Note that wax (long-chain paraffins) obtained in dewaxing is a
marketable by-product. Lubricating oil base stock is the principal product of interest. The
main purpose of dewaxing is to remove hydrocarbons that solidify readily (i.e., wax) for
making lubricating oil base stock with low pour points (-9 to 14°F).

Figure 5.11. Feedstock for dewaxing and hydrocarbon composition of the feed and the
products.

Source: Dr. Semih Eser

In addition to low pour points, other important properties of lube oil base stocks include:

71
1. Volatility – should be low to keep oil in the liquid phase during engine operation.
Vapors are not good lubricants.
2. Viscosity– important to control because of lubrication and heat transfer
considerations. Moderate viscosities are desired. Low viscosity may not provide the
required lubrication and lead to high friction between metal parts. High viscosity
causes loss of energy.
3. Viscosity Index (change in viscosity with temperature) – small change in viscosity is
desired over a wide temperature oil, i.e., high viscosity index (HVI). HVI ensures that
the lube oil functions well at both cold start and at high temperatures generated by
the engines.
4. Thermal Stability – High thermal stability (or small degree of thermal degradation at
high temperatures) is necessary to minimize viscosity loss and coke deposition on
metal surfaces.
All of these properties depend on the molecular composition of the hydrocarbons
constituting the lubricating oil base stocks. Commercial engine oils and other commercial
lube oils are formulated with chemical additives that would enhance the performance of
the base stocks.

Two commercial methods of dewaxing are:

1. Solvent dewaxing - physical process; separation of wax by freezing and solvent

transport.
2. Catalytic dewaxing - chemical process; removal of wax by selective reaction of long
chain n-alkanes (wax).

5.4.a. Solvent Dewaxing

Figure 5.12 shows a general scheme of solvent dewaxing that uses stage-wise
refrigeration of the feedstock after it is mixed with the solvent. The lowest temperature
used in the refrigeration cascade depends on the desired pour point of the lube oils base
stock product. Upon refrigeration, wax compounds solidify to form crystals. Wax
crystals are carried in the solvent to a rotary filter where wax is separated on a filter cloth
covering the rotating drum. The layer of wax (filter cake) on the drum is scraped from
the filter by a blade and carried away in a solvent stream to a steam-stripping unit to
recover and recycle the solvent separated from the wax product. The wax product, called
slack wax, can be used to make paraffin wax for candles, microwax used in the cosmetics
industry, and petrolatum for petroleum jelly. The dewaxed oil from the filtration unit is
also steam stripped to recover the solvent to produce the lube oil base stock.

72
 Figure 5.12. Solvent dewaxing process.

Source: Dr. Semih Eser

The two principal solvents used in solvent dewaxing units are methyl ethyl ketone
(MEK) and propane. Although the majority of dewaxing units in the U.S. refineries use
MEK), some advantages of using propane as a solvent compared to MEK include the
following [2]:

 Propane is used both as a diluent and as a refrigerant

 Lower capital investment
 Refrigeration energy savings
 Higher filtration rates
 Rejection of asphaltenes and resins in the feed
 Higher VI than ketone dewaxing
[2] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 15, pp.318-321.

5.4.b. Catalytic Dewaxing

Although included under the separation processes, catalytic dewaxing is actually a low-
severity conversion process involving a selective catalytic cracking of n-paraffins.
Because of removing wax (long chain n-paraffins) by chemical reaction, the process is
called dewaxing. The selective cracking of n-alkanes takes place in the pores of molecular
sieve catalysts (zeolites) with pore openings in the order of 0.6nm, which keep i-paraffins
out because of their larger size due to branching in the hydrocarbon skeleton, as shown
in Figure 5.13. This selective cracking increases the ratio of i-paraffins to n-paraffins in
the product and lowers its pour point. Hydrogen is introduced along with the feed to

73
prevent coking on the catalyst surfaces (Figure 5.14). The cracking of n-paraffins
produces distillate fuels such as gasoline as a by-product from catalytic dewaxing.

The advantages of catalytic dewaxing include [3]:

 production of lube base stock with lower pour point and in higher yield compared to
the product obtained from solvent dewaxing. Low yield from solvent dewaxing
results from the difficulty of separating the oil from the wax;
 lower capital investment;
 good product stability;
 flexibility to produce both lube oil base stock and light distillates.

Figure 5.13. Chemistry of catalytic dewaxing inside molecular sieving zeolites, e.g.,
mordenite, the structure of which is shown in the figure.

Source: Dr. Semih Eser

74
 Figure 5.14. Catalytic dewaxing process.

Source: Dr. Semih Eser

[3] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 15, pp.321-322.

5.5. Summary and Final Tasks

Summary

Separation of the lowest-boiling fraction of the crude oil is carried out in Light Ends Unit
using distillation columns that may yield almost pure products, such as propane and
butane. Because of the simple molecular composition of the light ends, it is possible to
use the data on vapor liquid equilibrium coefficients of pure compounds. On the heaviest
end of the crude oil, Vacuum Distillation Residue can be processed using solvent
extraction to separate asphalt from the residue to produce deasphalted oil for further
treatment either by dewaxing to produce lubricating oil base stock, or by conversion
reactions to produce distillate fuels from the deasphalted oil.

Learning Outcomes

You should now be able to:

 analyze the vapor-liquid equilibrium and evaluate the application of Fenske Equation
to distillation in Light Ends Unit;
 describe the principles of solvent fractionation as a separation technique;

75
 place the Deasphalting Process in the refinery and interpret the significance of this
process for refining;
 interpret the gradient solubility model that explains the solution of asphaltenes in
resin and oil fractions and analyze the structure of asphaltenes;
 analyze the process parameters for deasphalting and assess the anti-solvent effect;
 evaluate the unit operations of deasphalting and assemble the process flow diagram;
 explain the purpose of dewaxing and examine the physical and chemical dewaxing
processes.

Reminder - Complete all of the Lesson 5 tasks!

You have reached the end of Lesson 5! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 6. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignments below can be found within this lesson.

Lesson 5 tasks

Readings J. H. Gary and G. E. Handwerk, Chapter 15 (Lubricating Oil

Feedstocks)

Assignments Exam 1: Will cover the material in Lessons 1-5. Exam 1 is found in the

Exercise 4:

1. Use of Fenske Equation to evaluate the performance of a

distillation column
2. Qualitative evaluation of process parameters to estimate product
yields from deasphalting

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

76
Lesson 6: Thermal Conversion Processes
 Lesson 6 Overview
 Chemistry of Thermal Cracking
 Thermal Reactivity Considerations in Processing
 Visbreaking
 Coking
 Summary and Final Tasks

6.1. Overview

Thermal cracking is the first commercial conversion process developed in the

early 1900s principally to produce more motor gasoline from crude oils and produce
high-octane gasoline for aircraft use, initiating an attempt to change the composition of
crude oil in petroleum refinery. The purpose of thermal cracking is to make light middle
distillates from heavier ends by pyrolysis, or thermolysis. With the advent of catalytic
cracking in the 1930s and 1940s and its capability to produce higher yields of gasoline
with higher octane number, thermal cracking of gas oils has ceased to be an important
process for gasoline production in modern refineries. In countries where the principal
petroleum fuel with a high demand is diesel fuel, thermal cracking is still important in
fuel refineries. A principal application of thermal cracking of distillate fractions in current
refineries is limited to naphtha cracking for the purpose of producing ethylene (C2H4) for
the petrochemical industry. However, thermal cracking of residual fractions, particularly
VDR, is still practiced in association with visbreaking and coking processes in the
refineries. The chemistry of thermal cracking and thermal cracking processes is discussed
in this section.

Learning Outcomes

By the end of this lesson, you should be able to:

 summarize the chemistry of thermal cracking and free radical chain reactions;
 apply thermal cracking of gas oil to produce lighter distillates and examine how
thermal reactivity affects process configuration;
 appraise thermal cracking for upgrading of residual fractions (visbreaking and
coking) and interpret thermal severity to compare visbreaking processes;
 analyze and compare different coking processes: Delayed Coking, Fluid Coking and
Flexicoking.

What is due for Lesson 6?

77
This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignments page within this lesson.

Lesson 6 Tasks

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 5

Assignments Exercise 5: A coil visbreaker operates at 500°C for 1 min. How long will it
take to achieve the same thermal severity at 450°C in a soaker visbreaking
process? An apparent Arrhenius activation energy for thermal cracking is
given as 50 kcal/mol.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

6.2. Chemistry of Thermal Cracking

Chemistry of Thermal Cracking

Thermal cracking produces shorter straight chain alkanes from longer straight chains
found in gas oils or other crude oil fractions. Free radicals (reactive species with unpaired
electrons, but no electronic charge) are the active species that govern thermal cracking
reactions. Because of the free radical chemistry, thermal cracking of gas oil would
produce gasoline with relatively low octane numbers, as will be discussed later in this
section.

Figure 6.1 lists the three steps of free radical chain reactions as initiation, propagation,
and termination. In the figure, R-H represents a paraffin chain which can be expanded
such as (H3-(CH2)n – H) where n represents the number of carbon atoms in the alkane. In
other words, R represents a radical with an unpaired electron that becomes an alkane (R-
H) when combined with a hydrogen atom. A Hydrogen atom with one proton and one
electron is the simplest radical.
The free radical chain reaction starts with breaking the weakest C-C bond in the reactant
alkane (R-H) to form two free radicals R1 and R2, each with one unpaired electron
resulting from the homolysis of the C-C bond (initiation). Once formed by the initiation
step, each free radical can go through two different propagation reactions:
1. Hydrogen abstraction
2. Beta (β) scission
78
Figure 6.1. Free radical chain reactions.

Source: Dr. Semih Eser

In a hydrogen abstraction reaction, for example, the radical R1 removes (abstracts) a

hydrogen atom from an alkane (R-H) to produce a shorter chain alkane product (R1-H)
and a new radical R (hydrogen abstraction), thus propagating the free radical chain.
Alternatively, the radical R1, (or R2) can go through a β scission reaction to produce an
olefin (ethylene) as a product, and a radical R to propagate the chain. The β scission refers
to the breaking of covalent bond in the β position relative to the position of the unpaired
electron as shown below:

Figure 6.1b. The β scission

Note that the initiation step produces two free radicals, the propagation step produces a
reaction product and one radical to continue the chain. The last step in the chain reaction,
the termination step, removes two radicals to produce one or two stable compounds
depending on the termination reaction, as seen in Figure 6.1. The principal end result of
the free radical chain reactions in thermal cracking is to produce from long chain alkanes
shorter-chain alkanes, light olefins, and some aromatic compounds. One important
feature of free radical reactions is that isomerization reactions, e.g., shifting of the
unpaired electron site from an edge atom of a molecule to the interior atoms (as shown
in Figure 6.1), are not favored reactions. In other words, isomerization reactions take
place at a slower rate than other propagation reactions, e.g., β scission reaction. The
critical importance of this observation is that the thermal cracking reactions produce
shorter straight-chain alkanes and olefins without any significant formation of branched-
chain (or iso-alkanes). This is the reason why catalytic cracking processes have virtually
replaced thermal cracking processes to produce high octane number gasoline, as will be
discussed in the next section on catalytic cracking.

79
6.3. Thermal Reactivity Considerations in Processing

Thermal Reactivity Considerations in Processing

Management of thermal reactivity is important in thermal cracking processes for

optimum conversion of the feeds with a wide boiling range. Figure 6.2 shows an example
of a thermal cracking process to convert a heavy gas oil fraction primarily to light gas oil
(LGO). Typically, lighter products (gasoline and gas) and the heavier product (fuel oil)
are considered by-products in this process. A heavy gas oil feedstock with a wide boiling
range is fed to a fractionator to separate the feed into a light oil and a heavy oil fraction
depending on the desired cut points. Light oil (which would have a relatively low
thermal reactivity) is heated in a separate furnace to higher temperatures so that the
cracking takes place in a vapor phase. Heavy oil fraction (with a high thermal reactivity)
is heated to a lower temperature for cracking in the liquid phase. The heated feed streams
are combined in a soak drum to provide sufficient time for the completion of the cracking
reactions. After the soaker, the products are sent to a flash separator to separate the heavy
end as a side product (fuel oil) and the lighter products are sent to the fractionator for
separation into LGO, gasoline and the gaseous products. Separating the feed into two
fractions will avoid heating the reactive longer alkane chains to high temperatures to
keep coke formation and gas production under control to maximize the LGO yield. In
naphtha cracking for ethylene production, all reactions are carried out in vapor phase at
low pressures to promote β scission reactions for high ethylene yields. Coking of reactor
tubes creates a major maintenance problem in naphtha cracking for ethylene production.

Figure 6.2. Thermal cracking process configuration.

Source: Dr. Semih Eser

6.4. Visbreaking
80
Visbreaking

Visbreaking is a mild thermal cracking process applied to reduce the viscosity of VDR to
produce fuel oil and some light products to increase the distillate yield in a refinery [1].
Depending on the feedstock properties and thermal severity in the reactor, the process
will typically achieve 10–25% of conversion of the heavy ends to gas, gasoline, and
distillates while producing fuel oil with the desired specifications. Carbon rejection in
small quantities on the reactor surfaces during thermal cracking helps reduce the
viscosity of the fuel oil product (Figure 6.3). The process decreases the demand for a
cutter stock used as diluent (e.g., kerosene) that might otherwise be used to reduce the
viscosity of the heavy ends to meet the fuel oil specifications. Adding a diluent may still
be needed depending on the sulfur content of the product and the fuel oil specifications.
Although the principal objective of visbreaking is to reduce viscosity, some refineries
may use this mild cracking process to convert fuel oil into lighter distillates.

Figure 6.3. Overall chemistry of visbreaking – breaking up long chains of

hydrocarbons.

Source: Dr. Semih Eser

As in all chemical reactions, conversion in visbreaking depends primarily on temperature

and time. As a measure of “thermal severity” under reactions conditions, one can use a
thermal severity index (TSI) as a function of temperature and time that is shown in Figure
6.4. The exponential dependence of TSI on temperature relates to the general exponential
term that constitutes the chemical reaction rate constants. The chemical conversion in
visbreaking reactions can be expressed as the reduction in concentration (cA) of long-
chain alkane (or high-molecular weight compounds) in the feedstocks. One can see from
Figure 6.4 that the conversion in the visbreaking reaction can be expressed by the integral
in Figure 6.4, assuming an apparent first-order kinetics for the reaction. It can also be
seen, in Figure 6.4, that the conversion that can be related to the extent of visbreaking
depends on (kt); and the TSI to establish the interchangeability of T and t for a given
conversion relates to (e(-Ea/RT)t), where Ea is the apparent activation energy of the
reaction, R is the universal gas constant, T is the temperature, and t is time. In using the

81
 TSI for comparing thermal severity of different T and t combinations as major operating
variables of visbreaking, care should be taken to use the right units for R and T. As a
general convention, an apparent activation of energy of 50 kcal/mol is assumed for
thermal cracking reactions involving the homolysis of C-C bonds to produce free
radicals.
Higher visbreaking severity would produce a higher reduction in viscosity. Thermal
severity is limited by the reactivity of the feedstock and the storage stability of the
residual fuel in accordance with the desired conversion level and desired reduction in
viscosity. Asphaltene content and concarbon of the feedstocks are important factors to
consider when selecting an appropriate thermal severity for the process to prevent
excessive coking in the visbreaking reactor.

Figure 6.4. A definition of thermal severity index as a function of temperature (T) and
time (t) in a visbreaker.

Source: Dr. Semih Eser

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 5, pp.111-116.

6.4.a. Visbreaking Processes

There are two types of visbreaking processes: coil or soaker visbreaking. Figure 6.5a
shows a schematic diagram of the coil visbreaking process. For visbreaking, the feedstock
is introduced into the coil heated in the furnace where the thermal cracking reactions take
place. At the furnace outlet, the reaction products are immediately quenched using a
portion of the gas oil product from the fractionator to stop the thermal cracking reactions.
The quenched products are sent to the fractionator for separation into gas, gasoline, light
gas oil, and visbroken residue streams. A steam stripper can be used with the fractionator
for better separation of the visbreaking products. In the soaker visbreaking process, a
soak drum is placed after the furnace, Figure 6.5b. Most of the thermal cracking reactions
in this case take place in the soaker drum.

82
Depending on the process objectives and feedstock characteristics, reaction temperatures
range from 450°C to 485°C and pressures range from 3 to 10 bar. Higher temperatures
and lower residence times are used in the coil visbreaking process.

Figure 6.5a. Coil Visbreaking Process

Source: Dr. Semih Eser

Figure 6.5b. Soaker Visbreaking Processes

Source: Dr. Semih Eser

Residence times can vary from 1 min (associated with high temperatures in coil
visbreaking) to 10 min (for lower temperatures used in soaker visbreaking).

Similar to deasphalting and distillation, the environmental impact of visbreaking is

associated with burning fuel in the furnace to provide energy for thermal cracking, and,
to a lesser extent, burning off the coke deposited in the coil or soaker drum leading to
emissions of CO2, oxides of nitrogen (NOx), and oxides of sulfur (SOx) in the flue gases.

83
6.5. Coking

Coking

Despite the development of catalytic cracking processes, coking processes have survived
as a popular refining process all over the world to refine the heavy end of crudes or heavy
oils through carbon rejection as coke. Coking is the most severe thermal process used in
the refinery to treat the very bottom-of-the-barrel of crude oil, i.e., vacuum residue.

Because of the high severity of thermal cracking during coking, the residue feed is
completely converted to gas, light and medium distillates, and coke with no production
of residual oil. Three different coking processes are used in the refineries: delayed coking,
fluid coking, and flexi-coking (a variation of fluid coking). The common objective of the
three coking processes is to maximize the yield of distillate products in a refinery by
rejecting large quantities of carbon in the residue as solid coke, known as petroleum coke.
Complete rejection of metals with the coke product provides an attractive alternative for
upgrading the extra-heavy crude and bitumen, and that is particularly useful for initial
processing of tar (or oil) sands for liberating the hydrocarbons from the sand that is left
behind with the coke. Finding markets for the coke product as fuel or as filler for
manufacturing anodes for the electrolysis of alumina (possible only with petroleum coke
from delayed coking) makes the economics of coking more attractive by creating value
for the rejected carbon. Sulfur and metal contents of the petroleum coke, as determined
by the sulfur and metal contents of the residue feed, are two important factors that affect
the commercial value of petroleum coke. Of the two coking processes, delayed coking is
the preferred approach in many refineries that process heavy crudes.

6.5.a. Delayed Coking

Figure 6.6 shows a flow scheme in a delayed coking progress and a photograph of a
delayed coking unit. The derricks above the drums that contain the drill stems are used
to drill out the coke from the coke drums at the end of the coking cycle.

84
 Figure 6.6. Delayed coking process and a photograph of a delayed coking unit.

Source: Dr. Semih Eser

As shown in Figure 6.6, the residue feed is introduced to the fractionator after being
heated in the heat exchangers with the coker gas oil products. The bottoms from the
fractionator, including the heavy ends of the vacuum residue feed with heavy coker gas
oil recycle, are mixed with steam and sent to the tubular heater in the furnace to be heated
to approximately 475°C at a pressure of 10-30 psi. Steam is added to prevent coking in
the heater and the heated feed is introduced from the bottom of one of the coke drums.
The coking takes place in the insulated coke drum as the drum fills up for a period of 16–
18 h. While drum A is being filled up, drum B is decoked by using hydraulic cutters and
the drilling stem and the coke is removed from the bottom of the drum. As the coking in
drum A is completed, drum B should be decoked, sealed, heated, and prepared for
switching the feed. The coking cycle is controlled such that the vacuum residue is
continuously fed to the unit (because the vacuum column works around the clock) and
the fluid products are recovered continuously, while coke is removed intermittently in a
semi-continuous process scheme. Therefore, there are at least two coke drums in every
delayed coking unit, and some units have more than two drums. All of the heat necessary
for coking is provided in the heater, whereas coking takes place in the coke drum; hence,
the process is called “delayed coking.”

The hot product vapors and steam from the top of the drum are quenched by the
incoming feed in the fractionator to prevent coking in the fractionator and to strip the
lighter components of the vacuum residue feed. The fractionator separates the coking
products into gasses, coker naphtha, coker light gas oil, and coker heavy gas oil. A side-
steam stripper is used with the fractionator to ensure a good separation between the
coker naphtha and light gas oil streams [2].

The delayed coking operating variables include heater outlet temperature, pressure,
recycle ratio, and cycle time. These variables are selected based on feed properties such
as the characterization factor, asphaltene content, and Conradson Carbon Residue (CCR
) to ensure that coking in tubular heaters is minimized and liquid product yield is
maximized. The recycle ratio, which is typically 3–5%, is used to control the endpoint of
the coker heavy gas oil. The coke yield can vary from 20% to 30% depending on the feed
properties and coking conditions. In the textbook, you may find some proposed
equations to predict coke and other product yields on the basis of the CCR of the vacuum
residue and estimates of the distribution of sulfur in the feed among the coking products,
suggesting that up to 30 wt% of the sulfur in the feed ends up in the coke, 30 wt% in the
gas product, and 20 wt% in the coker heavy gas oil.

[2] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 5, pp.97-111.

85
Two Kinds of Coke

There are two kinds of coke produced by delayed coking of VDR: high-density shot coke,
and porous sponge coke. Figure 6.7 shows the appearances of shot coke consisting of
aggregates of ~5 mm diameter spherical particles (resembling buckshots) and sponge
coke (with a porous structure resembling a sponge). The formation of shot coke is usually
troublesome because of difficulties in removing the coke from the drums and problems
with grinding, although shot coke has some niche applications such as in titanium
dioxide (TiO2) production. Sponge coke is used as solid fuel, and manufacturing anodes
for aluminum production, if its sulfur and metal concentrations are sufficiently low.

Figure 6.7. Photographs of shot coke and sponge coke.

Source: Dr. Semih Eser

Among the delayed coking products, needle coke is a specialty coke produced mostly
from coking of a highly aromatic FCC decant oil. The major properties of the needle coke
include a low coefficient of thermal expansion, a low puffing (sudden volume
expansion) tendency during graphitization because of lower nitrogen and sulfur
contents, and high mechanical strength. The anode coke has limits on metal
contaminants, requiring less than 500 ppm of Ni and V in the coke. The price of fuel coke
depends on its carbon purity (S, N, and metal contaminants); however, the fuel coke is
traded at a price comparable to that of coal.

6.5.b. Fluid and Flexi-Coking

Fluid coking and flexi-coking are fluid-bed processes developed from the basic principles
of FCC, with close integration of endothermic (cracking, coking, or gasification) and
exothermic (coke burning) reactions. In fluid coking and flexi-coking processes, part of
the coke product is burned to provide the heat necessary for coking reactions to convert
vacuum residua into gasses, distillate liquids, and coke. Flexi-coking, as a variation of
fluid coking, provides the options of partial or complete gasification of the coke product
to produce a fuel gas with some or no coke in the product slate. Different from the bulk
liquid-phase coking in delayed coking, coking takes place on the surface of circulating
coke particles of coke heated by burning the surface layers of accumulated coke in a
separate burner. Figure 6.8 shows a schematic flow diagram of the fluid coking process.
The preheated vacuum residue is sprayed onto the hot coke particles heated in the burner
by partial combustion of coke produced in the previous cycle. Using fluid beds in the
reactor and burner provides efficient heat transfer and fast coking on a collectively large

86
surface area of the small coke particles circulating between the reactor and burner. The
products of coking are sent to a fractionator (similar to that used in delayed coking after
recovery of fine coke particles). Steam is also added at the bottom of the reactor (not
shown in the figure) in a scrubber to strip heavy liquids sticking to the surface of coke
particles before they are sent to the burner. This steam also provides fluidization of coke
particles in the reactor. The reactor and the burner operate at temperatures of 510–570°C
and 595–675°C, respectively.

Higher temperatures and short residence times in the reactor lead to higher liquid and
lower coke yields compared with those of delayed coking. Coke is deposited layer by
layer on the fluidized coke particles in the reactor. Air is injected into the burner to burn
15–30 % of the coke produced in the reactor, part of the particles are returned to the
reactor, and the remainder is drawn out as the fluid coke product. Fluid coking can
process heavier VDR and gives a higher distillate yield (and lower coke yield) than
delayed coking.

Figure 6.9 shows a schematic diagram of flexi-coking. A gasifier is added for conversion
of some or all coke produced in the coker in reaction with air and steam to produce a
synthesis gas. The hot coke particles from the combustor are circulated back to the coking
reactor to provide the heat necessary for coking. The distillate products from the coker
are sent to the fractionator, as is done in the fluid coking process. On the gasifier outlet,
after removing the fine particles from the gas by cyclones, the gas is cooled in a direct-
contact cooler to condense the sour water and recover the flexi-gas. The product gas can
be used as fuel gas in the refinery. Depending on the demand, the flexi-coking process
can produce both fluid coke and fuel gas, or gasify all the coke to produce only fuel gas.

Figure 6.8. Fluid-coking process.

87
Source: Dr. Semih Eser

Figure 6.9. Flexi-coking process.

6.6. Summary and Final Tasks

Physical separation of crude oil was not sufficient to meet the demand for motor fuels
that had increased significantly with the increasing number of automobiles. Thermal
cracking was therefore introduced as the first conversion process to produce more
distillate fuels from petroleum refining. Thermal cracking, starting typically with
breaking the C-C bonds in alkanes, proceeds with free radical chain reactions. One of the
common outcomes of thermal cracking is to make light or medium distillates from the
heavier fractions of the crude oil. Visbreaking, a mild (low-severity) thermal cracking
process, reduces the viscosity of the VDR by rejecting a small quantity of coke as deposits
on reactor surfaces. The principal product of visbreaking from VDR is a heavy fuel oil.
On the other end of the thermal conversion spectrum, coking, the most severe thermal
cracking process, converts VDR to light distillates and gaseous products by rejecting
carbon in large quantities in the form of petroleum coke. If the sulfur and metal contents
of VDR are sufficiently low, the petroleum coke can be a valuable by-product that is used
for producing anode coke for electrolysis of alumina to produce metallic aluminum.

Learning Outcomes

You should now be able to:

 summarize the chemistry of thermal cracking and free radical chain reactions;

88
 apply thermal cracking of gas oil to produce lighter distillates and examine how
thermal reactivity affects process configuration;
 appraise thermal cracking for upgrading of residual fractions (visbreaking and
coking) and interpret thermal severity to compare visbreaking processes;
 analyze and compare different coking processes: Delayed Coking, Fluid Coking and
Flexicoking.

Reminder - Complete all of the Lesson 6 tasks!

You have reached the end of Lesson 6! Double-check the to-do list on the Lesson
6 Overview page to make sure you have completed all of the activities listed there before
you begin Lesson 7.

Lesson 6 tasks

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapter 5

Assignments Exercise 5: A coil visbreaker operates at 500°C for 1 min. How long will
it take to achieve the same thermal severity at 450°C in a soaker
visbreaking process? An apparent Arrhenius activation energy for
thermal cracking is given as 50 kcal/mol.

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

89
Lesson 7: Catalytic Conversion Processes Part 1
 Lesson 7 Overview
 Chemistry of Catalytic Cracking
 Catalytic Cracking Processes
 Catalytic Hydrocracking
 Summary and Final Tasks

7.1. Overview

Catalytic conversion processes became important in petroleum refining after the Second
World War. Catalytic cracking has been developed to produce high yields of gasoline
with high octane # from high-boiling stocks using catalysts. As different from thermal
cracking, catalytic cracking

 uses a catalyst;
 takes place at lower temperature and lower pressure;
 is more selective and flexible.
One particular catalytic cracking process, Fluid Catalytic Cracking (FCC), has captured
universal acceptance in the refining industry because of its feed flexibility, ability to
modify product yields through minor changes in the process operating conditions. FCC
is used to produce high-octane gasoline mainly from straight-run atmospheric gas oil
and light vacuum gas oil (LVGO) [1]. This process involves breaking up long chains of
n-alkanes into shorter chains of branched alkanes (isoalkanes), cycloalkanes
(naphthenes), and aromatics by using acidic catalysts. In addition to high-octane
gasoline, catalytic cracking produces LPG, cycle oils, and olefin-rich light hydrocarbons
(C3, C4). The olefins are used as petrochemical feedstocks, or as reactants in alkylation
and polymerization reactions, to produce higher molecular weight branched alkanes and
olefins to contribute to the high-octane gasoline pool.

Hydrocracking processes have been introduced for upgrading heavier crude oil fractions
such as heavy vacuum gas oil (HVGO) and vacuum distillation residue VDR. The
heaviest fractions of crude oil, HVGO and VDR, may not be easily processed by FCC
because of potential problems with excessive coking on the catalysts. For upgrading these
high-boiling and aromatic-rich feedstocks, hydrogen is introduced in the hydrocracking
process, along with bi-functional catalysts systems, to keep coking under control while
upgrading the heavy fractions to light and middle distillates.

Learning Outcomes

By the end of this lesson, you should be able to:

90
 distinguish the chemistry of catalytic cracking from chemistry of thermal cracking
and illustrate the formation of carbocations and IUPAC terminology for classification
of carbocations;
 categorize the formation of different carbocations on active sites of cracking catalysts
and assess the classification of acid sites (Lewis vs Bronsted) on catalyst surfaces;
 compare, with examples, how the product yields and composition obtained from
catalytic differ from those from thermal cracking;
 analyze the thermodynamics of carbocation formation and evaluate how ionic chain
reactions produce hydrocarbons with high octane numbers;
 appraise the historical evolution of catalytic cracking processes and formulate the
driving forces that have shaped this evolution in reactor design and catalyst
development;
 locate the hydrocracking process and hydroprocessing in the refinery flow diagram,
illustrate hydrocracking processes and evaluate different process objectives.

What is due for Lesson 7?

This lesson will take us less than one week to complete. Please refer to the Course
Syllabus for specific time frames and due dates. Specific directions for the assignments
below can be found on the Assignments page within this lesson.

Lesson 7 tasks

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapters 7 (Catalytic

Hydrocracking) and Chapter 8 (Hydroprocessing and Resid
Processing)

Assignments Exercise 6

Quiz 3. Will cover material in Lessons 6 and 7. Check the Syllabus, or

Course Calendar for Quiz 3 schedule.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

91
7.2. Chemistry of Catalytic Cracking

Chemistry of Catalytic Cracking

As opposed to thermal cracking governed by free radicals, catalytic cracking proceeds

through the formation of ionic species on catalyst surfaces, and produces shorter, but
branched-chain (not straight-chain) alkanes by cracking the long straight-chain alkanes.
The formation of branched-chain alkanes, or iso-alkanes, leads to the production of
gasoline with high octane numbers. This is the fundamental reason why catalytic
cracking has replaced thermal cracking as the central process in a refinery geared to
maximize gasoline production. A high octane number of gasoline is needed for current
spark-ignition engines to run at high compression ratios without knocking. High
compression ratios in spark-ignition engines translate to high power and high efficiency.

Figure 7.1 introduces the two types of ionic species, carbocations, that are active in
catalytic cracking reactions as carbenium, and carbonium ions, using the IUPAC
terminology. Carbocations are the positively charged ions made from hydrocarbons.
Figure 7.1 shows that removing a hydride ion (H-, a hydrogen atom with an additional
electron) from an alkane (e.g., methane) produces carbenium ions (path 1a). Also, adding
a proton (H+, a hydrogen atom without the electron) to an olefin (e.g., ethylene) can
produce carbenium ions, as shown in path 1b.

Figure 7.1. Definition and formation of carbocations from hydrocarbons.

Source: Dr. Semih Eser

Analogous to the terminology used for free radicals, C+H3 is called methyl carbenium
ion, and C2+H5 is called an ethyl carbenium ion. Carbonium ions are produced by adding
a proton to an alkane, say methane, as shown in Figure 7.1. The resulting ion C +H5 is
called methanium. Note that there is some confusion in the literature about naming the
carbocations. Carbenium ions used to be called carbonium ions in some sources,
including your textbook [2]. All references to carbonium ions in Section 6.3 Cracking
Reactions in the textbook should be corrected as carbenium ions.
 Bronsted and Lewis Acid Sites
 Distribution of Products

92
 Comparison of Products by Type of Hydrocarbon
 Ionic Chain Reactions

7.2.a. Bronsted and Lewis Acid Sites

Carbocations are formed from hydrocarbons on two different acid sites: Bronsted acid
sites and Lewis acid sites. You should remember that Bronsted acid sites donate protons,
while Lewis acid sites accept electrons to form carbocations from hydrocarbons. Figure
7.2 illustrates how an olefin (e.g., ethylene, C=C) produces an ethyl carbenium ion
(C+2H5) by reacting with a proton donated from Bronsted acid site. Alternatively, also
seen in Figure 7.2, a Lewis acid site accepts an electron (or a hydride ion, H -) from an
alkane (e.g., ethane, C-C) to produce the same ethyl carbenium ion (C+2H5). These two
reactions that take place on the acid sites of catalysts, along with the formation of
carbonium ions by protonation of hydrocarbons on Bronsted sites, function as the
initiation steps in the ionic chain reactions that lead to the products obtained from
catalytic cracking.

Figure 7.2. Formation of carbocations on different acid sites of catalysts.

Source: Dr. Semih Eser

7.2.b. Distribution of Products

Figure 7.3 compares the distribution of products from thermal cracking (free radical
chain reactions) and catalytic cracking (ionic chain reactions). Short chain paraffins
constitute the principal products in both cases with one important difference – an
abundance of iso-alkanes (branched-chain alkanes) in catalytic cracking products. One
can also note in Figure 7.3 that catalytic cracking products contain higher concentration
of aromatic compounds. High octane number of gasoline produced by catalytic cracking
can be attributed to high concentrations of i-alkanes and relatively more abundant
aromatics present in the crackate (catalytic cracking product). Having no olefins larger
than butylene (C4) from catalytic cracking processes, also distinguishes catalytic cracking
products from thermal cracking products obtained from gas oil.
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Figure 7.3. Differences in distribution of hydrocarbons obtained from thermal and
catalytic cracking reactions.

Source: Dr. Semih Eser

7.2.c. Comparison of Products by Type of Hydrocarbon

Table 7.1 compares the products of thermal cracking and catalytic cracking of different
type of hydrocarbons. Notably, high yields of C1 and C2 gaseous products (methane,
ethane and ethylene) from thermal cracking are contrasted with high yields of C3- C6,
with small quantities of methane and essentially no olefins heavier than butylene, from
catalytic cracking. Significant for the octane number of the gasoline fraction from the
catalytic cracking of aliphatic hydrocarbons are the abundance of i-alkanes and
significant concentration of aromatic compounds (BTX) that increase the octane number.
Table 7.1: Catalytic Cracking vs. Thermal Cracking
Hydrocarbons Thermal Cracking Catalytic Cracking

C2 is major product
n-alkanes (e.g., C3-C6 are major light prods
C1 in large quantities
C16) C1 in small quantities
C4-C15 olefins in moderate
No olefins > C4
abundance
Significant aromatization
Little aromatization at 500ºC
Aliphatic No branched – chain alkanes
Abundance of branched –
present
chain alkanes

Slow double bond isomerization Rapid isomerization

n-0lefins
Little skeletal isomerization C=C–C–C → C–C=C–C

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 Table 7.1: Catalytic Cracking vs. Thermal Cracking
Hydrocarbons Thermal Cracking Catalytic Cracking

Rapid skeletal isomerization

C–C=C–C → C= C C | –C

Alkylaromatics ß – scission α – scission (dealkylation)

Crack more slowly than n- Crack at comparable rates

Naphthenes
paraffins with n-paraffins

As discussed in Lesson 6, the slow isomerization of free radicals (moving the unpaired
electron from an edge atom to the interior atoms) results in the production of shorter
straight-chain alkanes and straight-chain olefins in thermal cracking, thus leading to low
octane numbers of the gasoline product. In contrast to free radicals, the isomerization of
carbocations is very fast because of the thermodynamic driving force, shown in Table 7.2.
One can see in Table 7.2 that the isomerization of a primary propyl carbenium ion to a
secondary propyl carbenium ion releases (19.1- 1.5) = 17.6 kcal/mol. This is a very large
thermodynamic driving force for the isomerization of primary ion to a secondary ion,
and further to a tertiary ion with even a larger driving force. Isomerization of the
secondary propyl ion to the tertiary propyl ion, releases 1.5 kcal/mol of energy. It is,
therefore, clear that the initiation and propagation of carbocations in catalytic cracking
chain reactions on the catalyst surfaces will be dominated by the formation of secondary
and tertiary carbocations. The reactions of these carbocations lead to the formation of
branched-chain alkanes and olefins with high octane numbers.

Table 7.2: ΔHf of Carbenium Ions

Carbenium Ions ΔHf (relative) (kcal/mol)

C1+ primary
C–C– C | | ⊕ 19.1

C2+ secondary
C– C ⊕ –C 1.5

C3+ tertiary
C– C ⊕ C | –C 0

Another important feature of carbocation formation is the differences in the enthalpy of

formation which favors the formation of carbocations > C3 versus C1 and C2 ions (Table

95
7.3), because C1 and C2 ions are primary ions. This explains the low yields of C1 and
C2 species obtained from catalytic cracking.
Table 7.3: ΔHf of Carbenium Ions
Carbenium Ions ΔHf (relative) (kcal/mol)

CH3 ⊕ 258

C2H5 ⊕ 225

n-C3H7 ⊕ 218

i-C3H7 ⊕ 198

n-C4H9 ⊕ primary 211

t-C4H9 ⊕ tertiary 174

7.2.c. Ionic Chain Reactions

Ionic Chain Reactions

Figure 7.4 illustrates the ionic chain reactions that govern catalytic cracking of
hydrocarbons. The initiation step includes the formation of a carbonium ion by proton
donation from a Bronsted acid site and/or the formation of a carbenium ion through
hydride ion abstraction by a Lewis acid site. In a propagation step, the carbonium ion
goes through cracking to produce an alkane product and a carbenium ion, while the
carbenium ion produced on the Lewis acid site goes through a β-scission to produce an
olefin product and another carbenium ion. In additional propagation reactions,
carbenium ions (secondary, or tertiary) react with alkanes to produce i-alkane products
and other carbenium ions, which can go through isomerization reactions generating
more stable ions. Finally, in termination steps, carbenium ions donate a proton to restore
a Bronsted acid site and produce an olefin as final product, or they abstract a hydride ion
to restore a Lewis acid site producing an i-alkane product, and the ionic chain reaction
continues. Other reactions during catalytic cracking include dehydrocyclization and
dehydrogenation reactions to produce aromatic compounds. One should note that
thermal cracking reactions also take place during catalytic cracking because of the
sufficiently high temperatures used in the process. Some claim that initial thermal
cracking of alkanes to produce olefins should also be considered as an initiation step in
ionic chain reactions [2].

96
Figure 7.4. Carbocationic chain reactions in catalytic cracking.

Source: Dr. Semih Eser

7.3. Catalytic Cracking Processes

Catalytic Cracking Processes

Increasing demand for gasoline, along with the need to produce high-octane gasoline for
increasingly more powerful spark ignition engines, led to the development and
maturation of catalytic cracking processes just before and during World War II.
Following the development of a fixed-bed (Houdry process, 1936) and a moving-bed
(Thermafor Catalytic Cracking, 1941) catalytic cracking process, fluid-bed catalytic
cracking (FCC, 1942) became the most widely used process worldwide because of the
improved thermal efficiency of the process and the high product selectivity achieved,
particularly after the introduction of crystalline zeolites as catalysts in the 1960s.

The list below shows a timeline for the development of the catalytic cracking processes.
The evolution of catalytic cracking processes is an exemplary showcase in chemical
engineering for discussing the advancement of reactor configuration, driven by energy
conservation and process kinetics. The evolution of these processes is discussed in the
following subsections.

Historical Time-Line for Catalytic Cracking Processes

1. McAfee (1915)
o Batch reactor catalytic cracking to produce light distillates
o Catalyst: A1Cl3 – A Lewis acid, electron acceptor

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 o Alkane – electron(abstracted by A1Cl3)→ a carbocation(+)→ ionic chain reactions
to crack long chains
2. Houdry (1936) - a commercial process
o Continous feedstock flow with multiple fixed-bed reactors
o Cracking/catalyst regeneration cycles
o Catalyst: clays, natural alumina/silica particles
3. Thermafor Catalytic Cracking (TCC) (1942)
o Continues feedstock flow with moving-bed catalysts
o Catalyst: synthetic alumina/silica particles
o Higher thermal efficiency by process integration
4. Fluid Catalytic Cracking (FCC) (1942)
o Continuous feedstock flow with fluidized-bed catalysts
o Catalyst: synthetic alumina/silica+zeolites (1965)
 Houdry Catalytic Cracking
 Thermafor Catalytic Cracking (TCC)
 Fluid Catalytic Cracking (FCC)

7.3.a. Houdry Catalytic Cracking

The first catalytic cracking process was developed as a batch process (McAfee, 1915)
shortly after the development of a thermal cracking process. The process used Lewis acid
catalysts (e.g., AlCl3) for cracking. These catalysts were expensive and corrosive. In
addition to these impediments, use of a batch reactor in the McAfee process did not allow
large-scale commercialization of this process. The first full-scale commercial process, the
Houdry Catalytic Cracking, used much less expensive catalysts, such as clays, and
natural alumina and silica particles. Figure 7.5 shows the configuration of the Houdry
Catalytic Cracking process. For cracking, gas oil feed was heated to 800°F and fed to a
fixed-bed reactor packed with the catalyst particles. Cracking products are sent to a
fractionator to be separated into gas, gasoline, light cycle oil (LCO) and heavy cycle oil
(HCO) products.

Video: Houdry Catalytic Cracking (5:03)

Houdry Catalytic Cracking

Click here for transcript of Houdry Catalytic Cracking.

Credit: Dutton Institute(link is external)

98
Figure 7.5. Houdry catalytic cracking process configuration.

Source: Dr. Semih Eser

A series of swing reactors were needed to switch the feed flow from one reactor to
another after approximately 10 minutes of operation. The switch to a swing reactor was
necessary because of rapid coking on catalysts which, being natural materials, had a wide
range of activity. Rapid coking on silica/alumina particles deactivated these catalysts
and led to plugging of the reactors. After the flow was switched to another reactor, the
isolated reactor was stripped with steam for five minutes to remove the liquid products
adsorbed on catalyst particles. After stripping with steam, the deactivated catalysts were
regenerated by burning off the coke on catalysts with hot air introduced to the reactor.
Catalyst regeneration also takes approximately 5 minutes before the reactor with
regenerated catalyst is ready to accept the feed again. By this time, the second reactor
would be ready for the 10-minute cycle of steam stripping and catalyst regeneration.
Having a third reactor in the plant would help deal with any delays/problems in reactor
preparation. Considering that catalytic cracking is an endothermic process, the heat
generated from burning the coke off the catalyst could be used partially to heat the
catalyst particles for the endothermic reaction. A large portion of the heat in the flue gases
from coke combustion was not available for the process. Therefore, the thermal efficiency
of the Houdry Process was low.

7.3.b. Thermafor Catalytic Cracking (TCC)

Thermafor (also referred to as “thermofor” in some sources) Cracking Process was

introduced for better integration of thermochemistry (endothermic cracking and
exothermic catalyst regeneration) by introducing a moving-bed configuration, rather
than a fixed-bed, as shown in Figure 7.6. Catalysts used in this process were synthetic
alumina/silica beads that have more homogeneous and consistent properties (e.g.,
activity) than the natural minerals. Catalysts particles and the feed are introduced from
the top of the reactor and the catalyst particles move downward with gravity as the
cracking reactions take place on the catalyst surfaces. Steam is injected from the bottom

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of the reactor to carry the cracking products to the fractionator for recovery. As the
particles move down the reactor, they are deactivated by coke build-up on active sites.
The deactivated catalysts removed from the bottom of the reactor are sent to a
regenerator unit where the coke on catalysts surfaces are burned off and the heated
catalysts particles are recycled to the top of the reactors by bucket elevators. Hot catalyst
particles provide most of the heat necessary for the cracking reactions in the reactor.
Although the thermal efficiency of TCC is higher than that of the Houdry process, there
was still a significant amount of heat loss during transport of heated catalyst particles by
bucket elevators.

Video: Thermafor (3:53)

Click here for transcript of Thermafor

Credit: Dutton Institute(link is external)

Figure 7.6. Process configuration for Thermafor Catalytic Cracking (TCC) process.

Source: Dr. Semih Eser

7.3.c. Fluid Catalytic Cracking (FCC)

Fluid Catalytic Process, also introduced in 1942, offered an excellent integration of the
cracking reactor and the catalyst regenerator that provides the highest thermal efficiency,
as shown in Figure 7.7. In FCC, a fluidized-bed (or fluid-bed) of catalyst particles is
brought into contact with the gas oil feed along with injected steam at the entrance (called
the riser) of the reactor. The hot catalyst particles coming from the regenerator unit
evaporate the feed gas oil upon contact in the riser, and the cracking starts as the gas oil
vapors and the catalyst particles move upward in the reactor. The temperature of the
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catalyst particles drops as the evaporation of gas oil and endothermic cracking reactions
proceed during the upward movement. Cracking reactions also deposit a significant
amount of coke on the catalysts, leading to the deactivation of the catalyst. After
removing the adsorbed hydrocarbons by steam stripping, the coked catalyst is sent to the
regeneration unit to burn off the coke with air. Heat released from burning the coke
deposit increases the temperature of the catalyst particles that are returned to the riser to
complete the cycle. Burning off the rejected carbon (coke) in the regenerator provides the
energy necessary for cracking without much loss, thus increasing the thermal efficiency
of the process. The cracking products are sent to the fractionator for recovery after they
are separated from the catalyst particles in the upper section of the reactor [3].

In the reactor, the cracking reactions initiate on the active sites of the catalysts with the
formation of carbocations and the subsequent ionic chain reactions produce branched
alkanes and aromatic compounds to constitute the crackate (cracked gasoline with high
octane number), light olefins, cycle oils, and slurry oil that are sent to the fractionator. A
carbon-rich byproduct of catalytic cracking, termed “coke,” deposits on catalyst surfaces
and blocks the active sites. FCC is considered a carbon rejection process because the coke
deposited on the catalyst surface and eventually burned off for heat is rich in carbon and
thus enables the production of large quantities of a light distillate (crackate) in the process
without the addition of hydrogen.

Two different configurations of the commercial FCC processes exist depending on the
positions of the reactor and the regenerator: they can be side by side or stacked, where
the reactor is mounted on top of the regenerator. Major licensor companies that offer FCC
processes with different configurations include Kellogg Brown & Root, CB&I Lummus,
ExxonMobil Research and Engineering, Shell Global Solutions International, Stone &
Webster Engineering Corporation, Institut Francais du Petrole (IFP), and UOP. Figure 7.8
shows examples of Exxon and UOP designs [1,4]. The UOP design of high-efficiency two-
stage regenerator units offer advantages of uniform coke burn, higher conversion of CO
to CO2 and lower NOxemissions among others. Another modification to FCC plants
could be the installation of a catalyst cooler, which may provide better control of the
catalyst/oil ratio; the ability to optimize the FCC operating conditions, increase
conversions, and process heavier residual feedstocks; and better catalyst activity and
catalyst maintenance [3].
In the link below (external link), the animation of an explosion in an FCC unit in 2015
(7:12 minute long) provides a good review of the FCC process, and points out the
potential hazards of working with hydrocarbons exposed to high temperatures in
refinery units:

Animation of 2015 Explosion at ExxonMobil Refinery in Torrance, CA(link is external)

Video: Fluid Catalytic Cracking (5:08)

101
Click here for transcript of Fluid Catalytic Cracking

Credit: Dutton Institute(link is external)

Figure 7.7. Process configuration for Fluid Catalytic Cracking (FCC) process.

Source: Dr. Semih Eser

102
Figure 7.8. Different configurations of the FCC Units [4].

Source: Dr. Semih Eser

7.3.c.1. Zeolite Catalysts

One of the significant developments in FCC practice was the introduction of zeolite
catalysts in 1965. Catalysts and additives play a major role in the selectivity and flexibility
of FCC processes. FCC catalyst consists of a fine powder with an average particle size of
60–75 μm and a size distribution ranging from 20 to 120 μm. Four major components
make up the catalysts: zeolite, active matrix, filler, and binder. Each of these constituents
has a unique role to play, but zeolite is the key component that is more active and
selective for high-octane number gasoline production [4]. Table 7.4 compares the octane
numbers of some refinery products and FCC gasoline.

103
Figure 7.9. Components of FCC catalyst [4].

Source: Dr. Semih Eser

Table 7.4: Gasoline Octane Number

RON MON
Product
(600 rpm) (900 rpm)

Regular - Premium Gasoline 90-100 80-90

Straight Run Gasoline 60-68 60-68

FCC Gasoline (light) 93 82

FCC Gasoline (heavy) 95 85

7.4. Catalytic Hydrocracking

Catalytic Hydrocracking

Catalytic hydrocracking is one of the latest additions to petroleum refining processes,

with the first modern commercial unit started up by Chevron in 1958. The interest in
hydrocracking has been attributed to the increasing demand for light and middle
distillates, the availability of byproduct hydrogen in large quantities from catalytic
reforming, and the environmental regulations limiting sulfur and aromatic hydrocarbons
in motor fuels [5]. The advantages of hydrocracking include its ability to handle a wide
range of feedstocks that may be difficult to process by catalytic cracking and its flexibility
in selectivity between light and middle distillates. The principal objective of

104
hydrocracking is to decrease the molecular weight and boiling point of heavy oils to
produce saturated hydrocarbons (diesel and jet fuel) from highly aromatic feedstocks
(e.g., LCO from FCC) and distillation residua.

The hydrocracking process has two dimensions: Hydrogenation of aromatic rings and
cracking of aliphatic compounds, as shown in Figure 7.10, using naphthalene as an
example for an aromatic ring system. One should note that that the aromatic rings cannot
be cracked before they are saturated with hydrogen. With hydrocracking it is possible to
convert an aromatic compound to a paraffinic compounds without any loss of carbon, as
shown in Figure 7.10. As a hydrogen-addition process, hydrocracking provides high
yields of valuable distillates without producing low-grade byproducts (e.g., heavy oils,
gas, or coke) as experienced in carbon rejection processes such as coking.

Figure 7.10. Reactions of hydrocracking.

Source: Dr. Semih Eser

7.4.a. Reaction Systems

The two different reaction systems in hydrocracking, hydrogenation and cracking, are
supported by bi-functional catalyst formulations, as illustrated in Figure 7.11.
Hydrogenation reactions are promoted by the metal component of the catalysts (e.g., Ni,
Co, Mo), and the cracking takes place on catalyst support consisting of silica/alumina.
Highly active noble metals (e.g., Pt, and Pd) can be used for hydrogenation of
hydrocarbons with extremely low sulfur contents as the noble metals are susceptible to
sulfur poisoning.

105
Figure 7.11. Functions of hydrocracking catalysts.

Source: Dr. Semih Eser

Hydrocracking processes most commonly include two reaction stages: Hydrotreating to

remove heteroatom (S, N, O) species and Hydrocracking to increase the H/C ratio of the
hydrocarbons in the feeds by hydrogenation and to decrease their molecular weight by
cracking. In most cases, the hydrotreating reactor (HT) packed with cobalt-molybdenum
catalysts precedes the hydrocracking (HC) reactor typically packed with nickel-tungsten
catalysts (for hydrogenation) supported on alumina/silica (for cracking). Figure 7.12
shows different configurations of hydrocracking processes, depending on the
heteroatom content of the feeds. For feeds with very low heteroatom contents,
hydrocracking without hydrotreating may be applied, but this is very rare. Other process
configurations include single stage with dual catalysts, two-stage dual and triple
catalysts, as shown in Figure 7.11. The hydrocracking reactions are performed at 300–
400°C and 8–15 MPa of hydrogen pressure.

7.4.b. Uses of Hydrocracking

In a refinery, hydrocracking complements catalytic cracking by taking on the more

aromatic feedstocks that resist cracking, including the byproducts of FCC, such as light
cycle oil (LCO). Hydrocracking can also be used to upgrade residual fractions using
different reactor configurations and catalysts depending on the complexity of the
upgrading tasks, as shown in Figure 7.12. As shown in Figure 7.13, for hydrocracking a
relatively light feedstock (e.g., atmospheric residue), a fixed-bed configuration and
relatively large-size catalyst particles can be used. In extreme cases with very heavy
vacuum residue, an expanded bed configuration is used in which very fine catalyst
particles are entrained in the feed at high hydrogen pressures (high hydrogen/oil ratio).

106
These extreme reaction conditions are necessary to prevent extensive coking on catalysts
that could shut down the process. For intermediate cases, an ebullated (fluidized) bed
configuration can be used, as shown in Figure 7.13.

In the United States, hydrocracking of LCO (from FCC) provides a large proportion of
the diesel fuel production because straight-run LGO is a preferred stock for FCC to
produce gasoline as the principal product. The major licensors of hydrocracking
processes include Chevron, UOP, ExxonMobil Research and Engineering, BP, Shell, and
BASF-IFP.

Figure 7.12. Configuration of hydrocracking process with respect to feed properties.

Source: Dr. Semih Eser

107
Figure 7.13. Hydrocracking of heavy residua.

Source: Dr. Semih Eser

Hydrocracking vs. Catalytic Cracking

HYDRCRC
FCC
 hydrogen addition
 carbon rejection
 exothermic
 endothermic
 metal catalyst on acid support
 acid catalyst
 less gas
 more gas
 less coke
 more coke
 costly process ($$$)
 Hydrocracking involves C-C bond cleavage to produce lighter HC's
 More liquid yield with HYDRCRC
 More hydrogenated products
o Cracking is less severe
o Secondary cracking reactions are minimized by stabilization of active species by
hydrogen
 Hydrocracking is more flexible w.r.t. the feedstock
o Refractory feedstocks (i.e. aromatics) can be processed
o C-C bond breaking after saturation with hydrogen

108
Above, we compare catalytic cracking (FCC - a carbon rejection process) with
hydrocracking (HYDRCRC) with respect to the major attributes of both projects. Clearly,
in a flexible refinery with a wide range of crude oil feedstocks, both processes are needed
for the optimum conversion of the crude oil into desirable refinery products.

7.5. Summary and Final Tasks

Summary

Catalytic processes constitute the core of the petroleum refineries to accomplish a

number of conversion and finishing tasks. Catalytic cracking has been developed to
produce high yields of gasoline with high octane # from high-boiling stocks using
catalysts. Compared to thermal cracking, catalytic cracking takes place at lower
temperatures and pressures and proceeds through carbocationic active species produced
on acidic sites on catalyst surfaces. Fluid Catalytic Cracking (FCC) has become universal
refining process because of its high efficiency and feed flexibility. This process involves
breaking up long chains of n-alkanes into shorter chains of branched alkanes (isoalkanes),
cycloalkanes (naphthenes), and aromatics in high yields. Although the main product
from FCC is high-octane number gasoline, it also produces LPG, cycle oils, and olefin-
rich light hydrocarbons (C3, C4). The olefins are used as petrochemical feedstocks, or as
reactants in alkylation and polymerization reactions, to produce higher molecular weight
branched alkanes and olefins to contribute to the high-octane gasoline pool.
Hydrocracking processes have been introduced for upgrading heavier crude oil fractions
such as heavy vacuum gas oil (HVGO) and vacuum distillation residue VDR. The
heaviest fractions of crude oil, HVGO and VDR, may not be easily processed by FCC
because of potential problems with excessive coking on the catalysts. For upgrading these
high-boiling and aromatic-rich feedstocks, hydrogen is introduced in the hydrocracking
process, along with bi-functional catalysts systems, to keep coking under control while
upgrading the heavy fractions to light and middle distillates.

Learning Outcomes

You should now be able to:

 distinguish the chemistry of catalytic cracking from the chemistry of thermal cracking
and illustrate the formation of carbocations and IUPAC terminology for classification
of carbocations;
 categorize the formation of different carbocations on active sites of cracking catalysts
and assess the classification of acid sites (Lewis vs Bronsted) on catalyst surfaces;
 compare with examples how the product yields and composition obtained from
catalytic processes differ from those from thermal cracking processes;

109
 analyze the thermodynamics of carbocation formation and evaluate how ionic chain
reactions produce hydrocarbons with high octane numbers;
 appraise the historical evolution of catalytic cracking processes and formulate the
driving forces that have shaped this evolution in reactor design and catalyst
development;
 locate the hydrocracking process and hydroprocessing in the refinery flow diagram,
illustrate hydrocracking processes, and evaluate different process objectives.

Reminder - Complete all of the Lesson 7 tasks!

You have reached the end of Lesson 7! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 8. Please
refer to the Course Syllabus for specific time frames and due dates. Specific directions
for the assignments below can be found within this lesson.

Lesson 7 Tasks

Readings J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapters 7 (Catalytic

Hydrocracking) and Chapter 8 (Hydroprocessing and Resid
Processing

Assignments Exercise 6: The dry air flow rate to the regenerator is given as
593 SCMM (standard cubic meters per minute). Considering that
a significant portion of coke is carbon, calculate the carbon
burning rate in the regenerator in kg/min. Remember: (1 kgmole
at STP = 22.4 m3).

Quiz 3. Will cover material in Lessons 6 and 7. Check the

Syllabus, or Course Calendar for Quiz 3 schedule.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

110
Lesson 8: Catalytic Conversion Processes Part 2
 Lesson 8 Overview
 Catalytic Reforming
 Chemistry of Catalytic Reforming
 Catalytic Reforming Processes
 Alkylation
 Polymerization
 Isomerization
 Summary and Final Tasks

8.1. Overview

Among the catalytic conversion processes developed just before and during the Second
World War are included, in addition to catalytic cracking, polymerization processes that
were introduced in the mid- to late 1930s, and alkylation and isomerization processes
that were developed in the early 1940s. The principal impetus for developing these
processes was to meet the demand for high-octane-number gasoline required by the high
compression gasoline engines, including those used in the aircraft. Catalytic reforming
and catalytic isomerization were developed in the 1950s to increase the high-octane-
number gasoline yields from refineries. These processes are still important in current
refineries that are directed to maximize gasoline yield from the crude oil feedstock. By-
products from some of these processes, such as LPG and hydrogen, have gained
significance because of the increasing demand in modern refineries for LPG recently used
as automobile fuel and for hydrogen to supply the increasing demand for hydrotreating
and hydrocracking processes.

Learning Outcomes

By the end of this lesson, you should be able to:

 locate the catalytic reforming process in the refinery flow diagram, summarize the
process objectives and evaluate the chemical reactions that take place in catalytic
reforming to realize the process objectives;
 identify the catalysts used for catalytic reforming, evaluate the reaction network and
the activity of catalysts, and illustrate the desirable reactions with specific examples;
 outline the principles of thermodynamics, kinetics, and transport phenomena to
formulate limits on reaction conditions for controlling desirable and undesirable
reactions in catalytic reforming;
 assess the commercial catalytic reforming processes and compare catalyst
regeneration practice in each process;
111
 place the alkylation process in the refinery flow diagram particularly in relation to
FCC process and describe the purpose of alkylation;
 demonstrate alkylation reaction mechanisms and evaluate the use of concentrated
acid catalysis of alkylation;
 demonstrate polymerization reaction mechanisms and compare alkylation and
polymerization reactions and catalysis.

What is due for Lesson 8?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignments below can be
found on the Assignments page within this lesson.

Lesson 8 Tasks

Readings: J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapters 10 (Catalytic

Reforming and Isomerization)and 11(Alkylation and Polymerization)

Assignments: Exercise 7

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

8.2. Catalytic Reforming

Catalytic Reforming

Catalytic reforming converts low-octane, straight-run naphtha fractions, particularly

heavy naphtha that is rich in naphthenes, into a high-octane, low-sulfur reformate, which
is a major blending product for gasoline. The most valuable byproduct from catalytic
reforming is hydrogen to satisfy the increasing demand for hydrogen in hydrotreating
and hydrocracking processes. Most reforming catalysts contain platinum as the active
metal supported on alumina, and some may contain additional metals such as rhenium
and tin in bi- or tri-metallic catalyst formulations. In most cases, the naphtha feedstock
needs to be hydrotreated before reforming to protect the platinum catalyst from
poisoning by sulfur or nitrogen species. With the more stringent requirements on
benzene and the total aromatics limit for gasoline in the United States and Europe, the
amount of reformate that can be used in gasoline blending has been limited, but the

112
function of catalytic reforming as the only internal source of hydrogen continues to be
important for refineries.

Figure 8.1 locates the catalytic reforming process in a refinery. The feedstock for catalytic
reforming is straight-run (directly from the crude oil) heavy naphtha that is separated in
the naphtha fractionator of the Light Ends Unit, as discussed in Lesson 4. Light naphtha
from the naphtha fractionator, inherently a low-octane-number fraction, can be sent
directly to blending in gasoline pool after hydrotreating, if necessary, or sent to an
isomerization process to increase its octane number. As discussed in Lesson 3,
hydrotreating heavy naphtha is often necessary before catalytic reforming to protect the
noble metal catalyst (e.g., Pt) used in the reforming process. The intended product from
catalytic reforming is the high-octane-number reformate and the most significant by-
product is hydrogen gas.

Figure 8.1. Placement of catalytic reforming process in a refinery.

Source: Dr. Semih Eser

8.3. Chemistry of Catalytic Reforming

Chemistry of Catalytic Reforming

The general categories of the desired reactions in catalytic reforming are identified in list
below, along with the catalysts used in the process. Considering that the main purpose
of the process is to increase the octane number of heavy naphtha, conversion of
naphthenes to aromatics and isomerization of n-paraffins to i-paraffins are the most
important reactions of interest. Under the right reaction conditions, aromatics in the feed,
or those produced by dehydrogenation naphthenes should remain unchanged. The
reforming reactions produce large quantities of hydrogen, and one should remember that
the dehydrogenation catalysts used in reforming can also catalyze hydrogenation and
hydrocracking of aromatics during catalytic reforming. It is, therefore, important to keep
these side reactions to a minimum by controlling the reactor conditions such as
temperature and hydrogen pressure, as discussed in more detail later in this section.

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The catalysts used in reforming contains platinum (Pt), palladium (Pd), or, in some
processes, bimetallic formulations of Pt with Iridium or Rhenium supported on alumina
(Al2O3).

Catalytic Reforming Reactions and Catalysts

Reactions of Interest
1. naphthenes → aromatics
2. paraffins are isomerized
3. aromatics are unchanged
Catalysts Used
Platinum catalyst on metal oxide support (platforming)

Pt/Al2O3
Bimetallic – Iridium or Rhenium

Pt-Re/Al2O3

The information above shows the ranges of composition for feedstock heavy naphtha
and the reformate product (high-octane gasoline). Comparing the compositions of the
feedstock and the product, one can see that the largest change in feedstock composition
is a substantial increase in the aromatics content of the feedstock, with attendant
decreases in naphthene and paraffin contents to constitute the product.

Catalytic Reforming Feedstock and Product

Feedstock: Heavy Naphtha Product: High Octane Gasoline

Paraffins ⇒ 45-55% Paraffins ⇒ 30-50%

Naphthenes ⇒ 30-40% Naphthenes ⇒ 5-10%

Aromatics ⇒ 5-10% Aromatics ⇒ 45-60%

Low severity (relatively low octane) → low paraffin conversion

High severity → high paraffin conversion

Lean naphtha → high n-paraffinic content - difficult to process

Rich naphtha → low n-paraffinic (high naphthene) content - easy to process

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The information above also defines some specific terms for catalytic reforming related to
the feedstock composition (lean, or rich naphtha), or to the extent of n-paraffin
conversion in the process (low-, or high-severity). One could conclude from these terms
that reforming of heavy naphtha that contains higher n-paraffin content requires more
severe conditions in the reactor.

 Desirable Chemical Reactions

 Undesired Reactions
 Reaction Network

8.3.a. Desirable Chemical Reactions

Figure 8.2 illustrates more specifically the desirable chemical reactions of catalytic
reforming including:

 dehydrogenation of naphthenes to aromatics,

 dehydroisomerization of alkyl-C5-naphthenes,
 dehydrocyclization of n-paraffins to aromatics, and
 isomerization of n-alkanes to i-alkanes.
All of these reactions significantly increase the octane number (research octane number
[RON] from 75 to 110 in Reaction 1, from 91 through 83 [cyclohexane] to 100 in Reaction
2, from 0 to 110 in Reaction 3, and from –19 to 90 in Reaction 4).

Figure 8.2: Desirable chemical reactions in of catalytic reforming reactions.

Source: Dr. Semih Eser

Reaction conditions that promote the desirable reactions are also listed in Figure 8.2. As
can be seen in Figure 8.2, aromatic compounds and large quantities of by-product H2 are
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produced in the highly endothermic Reactions 1–3. High temperatures, low hydrogen
pressures, low space velocity (SV), and low H2/HC ratio strongly promote the
conversion in Reaction 1-3. Although maintaining a low hydrogen pressure is needed for
promoting equilibrium conversion in Reactions 1-3, it is, however, necessary to maintain
a sufficiently high hydrogen pressure in the reactors to inhibit coke deposition on the
catalyst surfaces.

8.3.b. Undesired Reactions

Hydrocracking is an undesired side reaction in catalytic reforming because it consumes

hydrogen and decreases the reformate yield by producing gaseous hydrocarbons.
Hydrocracking reactions are exothermic, but they can still be kinetically favored at high
temperatures, and favored, obviously, by high hydrogen pressures. Below lists the heat
of reactions for catalytic reforming reactions. Typically, reformers operate at pressures
from 50 to 350 psig (345–2415 kPa), a hydrogen/feed ratio of 3–8 mol H2/mol feed, and
liquid hourly space velocities of 1–3 h-1[1]. These conditions are chosen to promote the
desired conversion reactions and inhibit hydrocracking while limiting coke deposition
on the catalyst surfaces.

Undesired Reactions in Catalytic Reforming

Hydrocracking
n-C10+H2 → n-C6+n-C4
to inhibit this reaction, use

1. high T
2. high SV
3. Low H2P
Catalytic reformers are normally run at low H2 pressure to inhibit hydrocracking!
Heats of Reactions:

paraffin to naphthene → 44 kJ/mol H2 - endothermic

naphthenes to aromatics → 71 kJ/mol H2 - endothermic
hydrocracking → -56 kJ/mol H2 - exothermic

8.3.c. Reaction Network

A reaction network for catalytic reforming is shown in Figure 8.3 [2], indicating the role
of metallic (M) and the acidic (A) sites on the support in catalyzing the chemical reactions.
The surfaces of metals (e.g., Pt) catalyze dehydrogenation reactions, whereas the acid
sites on the support (e.g., alumina) catalyze isomerization and cracking reactions. Metal
and acid sites are involved in the catalysis of hydrocracking reactions. Achieving the
principal objective of catalytic reforming—high yields and high quality of reformate—
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can be achieved, to a large extent, by controlling the activity of the catalysts and the
balance between acidic and metallic sites to increase the selectivity to desirable reactions
in the reaction network.

Figure 8.3: Reaction network of catalytic reforming.

Source: Dr. Semih Eser

8.4. Catalytic Reforming Processes

Catalytic Reforming Processes

Even in the presence of hydrogen during reforming reactions, catalysts are deactivated
by coke deposition. Commercial catalytic cracking processes are classified based on how
catalysts are regenerated, as shown below, as semi-regenerative, cyclic, and continuous
reforming processes. The first commercial catalytic reforming process was introduced by
UOP in 1949 as the PlatformingTM process that used three fixed-bed reactors. Figure 8.4
(on next page), shows a process with two reactors. The reactors operate in series with
furnaces placed before each reactor to heat the feedstock and the reactor effluents to 500–
530°C before entering each reactor because the predominant reforming reactions are
highly endothermic. These units, called “semi-regenerative catalytic reformers,” need to
be shut down once every 6–24 months for the in-situ regeneration of catalysts that are
deactivated by coke deposition. Later designs included an extra reactor (a swing reactor)
to enable isolation of one reactor at a time to undergo catalyst regeneration, whereas the
other three reactors are running (Cyclic). This configuration enables longer on-stream
times (up to 5 years) before scheduled shutdowns for catalyst regeneration, but it has not
become popular. In the HYSYS Project 2, you will be comparing the performance of the
three different configurations of catalytic reforming processes.

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Catalytic Reforming Processes

Catalytic Reforming Processes Based on Catalyst Regeneration

1. Semi-regenerative (1949) – unit taken off-stream anywhere from every 3 to 24 months
2. Cyclic (1960) – involves swing reactor. Basically, operate 3 out of 4 and use extra
reactor to take one offline.
3. Continuous (1971) – catalyst is removed and replaced during the operation.
Maintains high activity. Expensive.
Licenced Processes (differences in catalysts and reactor configurations)
1. Platforming (UOP process) (1949)
2. Powerforming (Exxon)
3. Ultraforming (Amoco)
4. Catalytic Reforming (Engelhard)
5. Magnaforming (Arco)
6. Reforming (IEP)
7. Rheniforming (Chevron)

8.4.a. Continuous Catalyst Regeneration

A continuous catalyst regeneration (CCR) scheme for reforming came on stream in 1971.
Figure 8.5 shows a flow diagram for the CCR process. The reactors are stacked with a
moving bed of catalyst trickling from the top reactor to the bottom reactor by gravity.
Partially deactivated catalyst from the bottom of the reactor stack is continuously
withdrawn and transferred to the CCR regenerator. The regenerated catalyst is re-
injected to the top of the first reactor to complete the catalyst circulation cycle.
Hydrotreated naphtha feed is combined with recycled hydrogen gas and heat exchanged
with the reactor effluent. The combined feed is then raised to the reaction temperature in
the charge heater and sent to the first reactor section. Because the predominant reforming
reactions are endothermic, an inter-reactor heater is used to reheat the charge to the
desired reaction temperature before it is introduced to the next reactor. The effluent from
the last reactor is heat exchanged with the combined feed, cooled, and separated into
vapor and liquid products in a separator.

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Figure 8.4. A semi-regenerative catalytic reforming process.

Source: Dr. Semih Eser

The vapor phase is rich in hydrogen gas, and a portion of the gas is compressed and
recycled back to the reactors. Recycling hydrogen is necessary to suppress coking on the
catalysts. The hydrogen-rich gas is compressed and charged together with the separator
liquid phase to the product recovery section. The performance of the unit (i.e., steady
reformate yield and quality) depends strongly on the ability of the CCR regenerator to
completely regenerate the catalyst. In addition to UOP’s Platforming process, the major
commercial catalytic reforming processes include PowerformingTM (ExxonMobil),
UltraformingTM and MagnaformingTM (BP), Catalytic Reforming (Engelhard), Reforming
(IFP), and RheniformingTM (Chevron).

Figure 8.5. A continuous catalytic reforming process.

Source: Dr. Semih Eser

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8.5. Alkylation

Alkylation

The alkylation process combines light iso-paraffins, most commonly isobutane, with C3–
C4 olefins, to produce a mixture of higher molecular weight iso-paraffins (i.e., alkylate)
as a high-octane number blending component for the gasoline pool. Iso-butane and C3–
C4 olefins are produced as by-products from FCC and other catalytic and thermal
conversion processes in a refinery. The alkylation process was developed in the 1930s
and 1940s to initially produce high-octane aviation gasoline, but later it became
important for producing motor gasoline because the spark ignition engines have become
more powerful with higher compression ratios that require fuel with higher octane
numbers. With the recent restrictions on benzene and the total aromatic hydrocarbon
contents of gasoline by environmental regulations, alkylation has gained favor as an
octane number booster over catalytic reforming. Alkylate does not contain any olefinic
or aromatic hydrocarbons.
Alkylation reactions are catalyzed by strong acids (i.e., sulfuric acid [H2SO4] and
hydrofluoric acid [HF]) to take place more selectively at low temperatures of 70°F for
H2SO4 and 100°F for HF. By careful selection of the operating conditions, a high
proportion of products can fall in the gasoline boiling range with motor octane numbers
(MONs) of 88–94 and RONs of 94–99 [15]. Early commercial units used H2SO4, but more
recently, HF alkylation has been used more commonly in petroleum refineries. HF can
be more easily regenerated than H2SO4 in the alkylation process, and HF alkylation is
less sensitive to temperature fluctuations than H2SO4 alkylation [3]. In both processes,
the volume of acid used is approximately equal to the volume of liquid hydrocarbon
feed. Important operating variables include acid strength, reaction temperature, iso-
butane/olefin ratio, and olefin space velocity. The reactions are run at sufficiently high
pressures to keep the hydrocarbons and the acid in the liquid phase. Good mixing of acid
with hydrocarbons is essential for high conversions.
Some examples of desired alkylation reactions (combination of iso-paraffins with olefins)
are given in Figure 8.6. These occur through ionic chain reactions (Figure 8.7) initiated by
donation of a proton from the acid catalyst to an olefin to produce a carbocation that
reacts with iso-butane to form a tert-butyl cation. Subsequent propagation reactions
involve the reactions of a tert-butyl cation with olefins to form larger iso-paraffin cations
that lead to final products through reactions with iso-butane to form a new tert-butyl
cation to sustain the chain reaction [3]. The alkylation reaction is highly exothermic;
therefore, cooling the reactor contents during alkylation is important.

120
Figure 8.6. Principal alkylation reactions.

Source: Dr. Semih Eser

Figure 8.7. Acid catalyzed alkylation reactions.

Source: Dr. Semih Eser

8.5.a. UOP HF Alkylation Process

Figure 8.8 shows a flow diagram for a UOP HF alkylation process [4]. Olefin and iso-
butane feed streams are dried to remove water before they are mixed with the iso-butane
recycle stream. The mixture is fed to the reactor, where it is highly dispersed into an
incoming stream of acid catalyst. Conversion of reactants to high-quality alkylate takes
place quickly, and the mixture flows up to the settling zone. In the settler, the catalyst is
separated out as a bottom phase and flows, by gravity, through the catalyst cooler and
returns to the reactor. The hydrocarbon phase from the settler, which contains propane,
recycled iso-butane, normal butane, and alkylate, is charged to the main fractionator.
High-purity propane is sent overhead to pass through the HF- propane stripper, de-
fluorinator, and potassium hydroxide (KOH) treater before it is recovered. Recycled iso-
butane is drawn from the side of the fractionator and returned to the entrance of the
reactor after it is mixed with the dried olefin and isobutane feed. The n-butane product
is taken from the side of the fractionators as vapor, condensed and KOH- treated before
recovery. The alkylate product is obtained from the bottom of the fractionator. The HF
catalyst is regenerated onsite in the regeneration section where heavy oils (tars) are
removed from the catalyst.

121
Figure 8.8. UOP HF Alkylation Process [4].

Source: Dr. Semih Eser

Transporting and working with concentrated acids pose safety risks. In particular, HF
tends to form a vapor cloud that is difficult to disperse. The major licensor of the HF
alkylation processes is UOP, whereas ExxonMobil and Stratford Engineering
Corporation license H2SO4 alkylation processes. A newly designed alkylation process by
UOP uses a solid catalyst called Alkylene®. Advantages of this new process over
traditional HF alkylation processes (liquid acid technology) include no acid
transportation, no acid spills, no corrosion, and reduced maintenance cost. Efforts to
develop alternative processes that use solid acid catalysts instead of concentrated HF and
H2SO4 for alkylation are underway.

8.6. Polymerization

Polymerization

The polymerization process combines propenes and butenes to produce higher olefins
with high-octane numbers (97 RON and 83 MON) for the gasoline pool. The
polymerization process was used extensively in the 1930s and 1940s, but it was replaced
to a large extent by the alkylation process after World War II. It has gained favor after
phasing out the addition of tetraethyl lead (TEL) to gasoline, and the demand for
unleaded gasoline has increased. Typical polymerization reactions are shown in Figure
8.9 [5].

The most commonly licensed polymerization process is the UOP polymerization process,
which uses phosphoric acid as catalyst. IFP licenses a Dimersol® process that produces
dimers from propene or butene using a homogeneous aluminum alkyl catalyst.
122
Figure 8.9. Typical polymerization reactions [5].

Source: Dr. Semih Eser

8.7. Isomerization

Isomerization

Isomerization processes have been used to isomerize n-butane to iso-butane used in

alkylation and C5 /C6n-paraffins in light naphtha to the corresponding iso-paraffins to
produce high-octane number gasoline stocks after the adoption of lead-free gasoline.
Catalytic isomerization processes that use hydrogen have been developed to operate
under moderate conditions. Typical feedstocks for isomerization process include
hydrotreated light straight-run naphtha, light natural gasoline, or condensate. The fresh
C5/C6 feed combined with make-up and recycled hydrogen is directed to a heat
exchanger for heating the reactants to reaction temperature. Hot oil or high-pressure
steam can be used as the heat source in this exchanger. The heated feed is sent to the
reactor. Typical isomerate product (C5+) yields are 97 wt% of the fresh feed, and the
product octane number ranges from 81 to 87, depending on the flow configuration and
feedstock properties.

8.8. Summary and Final Tasks

Summary

Catalytic reforming, alkylation and polymerization processes aim at increasing the yield
of high-octane-number gasoline in the refineries. Catalytic reforming uses naphthene-
rich, straight-run heavy naphtha as feedstock and produces a high-octane number
reformate for the gasoline blending pool in a refinery. Principal catalytic reactions that
take place on noble metals (e.g., Pt) and on acidic catalyst supports (e.g., Al2O3) produce
high yields of aromatic hydrocarbons and i-alkanes, respectively, to result in a high-
octane number product. A valuable by-product from catalytic reforming is hydrogen gas
for which the demand is increasing in the refineries, particularly for finishing processes,
such as hydrotreatment. Alkylation and polymerization reactions take shorter chains of
C3, C4 alkanes and olefins and combine them to get branched C7, C8 alkanes in alkylate,
and polymerate, respectively, to increase the yield of high-octane gasoline. Isomerization
123
processes convert n-butane to i-butane to be used as feed in alkylation processes, or
isomerize n-C5 and n-C6 to the corresponding i-alkane to produce, again, high-octane-
number gasoline stock.

Learning Outcomes

You should now be able to:

 locate the catalytic reforming process in the refinery flow diagram, summarize the
process objectives and evaluate the chemical reactions that take place in catalytic
reforming to realize the process objectives;
 identify the catalysts used for catalytic reforming, evaluate the reaction network and
the activity of catalysts, and illustrate the desirable reactions with specific examples;
 outline the principles of thermodynamics, kinetics and transport phenomena to
formulate limits on reaction conditions for controlling desirable and undesirable
reactions in catalytic reforming;
 assess the commercial catalytic reforming processes and compare catalyst
regeneration practice in each process;
 place the alkylation process in the refinery flow diagram particularly in relation to
FCC process and describe the purpose of alkylation;
 demonstrate alkylation reaction mechanisms and evaluate the use of concentrated
acid catalysis of alkylation;
 demonstrate polymerization reaction mechanisms and compare alkylation and
polymerization reactions and catalysis.

Reminder - Complete all of the Lesson 8 tasks (Blog 8 and Quiz 4)!

You have reached the end of Lesson 8! Double-check the to-do list in the table below to
make sure you have completed all of the activities listed there before you begin Lesson
9. Please refer to the Course Syllabus for specific time frames and due dates. Specific
directions for the assignment below can be found within this lesson.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

Lesson 8 Tasks

124
 Readings: J. H. Gary, G. E. Handwerk, Mark J. Kaiser, Chapters 10
(Catalytic Reforming and Isomerization)and 11(Alkylation and
Polymerization)

Assignments: Exercise 7

Lesson 9: Finishing Processes

 Lesson 9 Overview
 Hydrogenation
 Hydrotreatment
 Hydrodesulfurization
 Hydrodenitrogenation
 Hydrodemetallation
 Hydrotreatment Processes
 Product Blending
 Summary and Final Tasks

9.1. Overview

Following our discussion on separation and conversion processes, this lesson will cover
the third type of refining processes – finishing processes. Finishing processes include
hydrogenation for stabilization of petroleum products, hydrotreating to remove
heteroatoms (S, N, and metals) and product blending to attain the product specifications
and assure compliance with environmental and government regulations on petroleum
fuels and materials. The finishing step is the last stage before the hydrocarbon streams
from different units leave the refinery as commercial fuels and materials. Therefore, the
challenges involved both hydrotreatment and blending operations are diverse and
125
complex. The constraints on the commercial fuels that need to be satisfied simultaneously
range from composition and performance specifications to seasonal fluctuations in
demand for different fuels and materials. A brief overview of only the basic concepts in
finishing operations is presented in this lesson.

Learning Outcomes

By the end of this lesson, you should be able to:

 compare hydrogenation and hydrotreatment with respect to process goals, catalysis,

and chemistry;
 categorize and evaluate HDS, HDN, and HDM processes;
 assess hydrotreatment catalysts, kinetics and process configurations;
 demonstrate procedures to calculate critical properties of blended products, e.g.,
octane number, pour point, and viscosity.

What is due for Lesson 9?

Please refer to the Course Syllabus for specific time frames and due dates. Specific
directions for the assignments below can be found in this lesson.

Lesson 9 Tasks

Readings: Petroleum Refining, by J. H. Gary and G. E. Handwerk, Chapter 9

(Hydrotreating) and Chapter 12 (Product Blending)

Assignments: Exercise 8

Exam 2. Will cover material in Lessons 6-9. Exam 2 is found in the Exam
2 Module.

Questions?

If you have any questions, please post them to our Help Discussion Forum (not email),
located in Canvas. I will check that discussion forum daily to respond. While you are
there, feel free to post your own responses if you, too, are able to help out a classmate.

9.2. Hydrogenation

Hydrogenation

126
 Hydrogenation, or adding hydrogen to unsaturated hydrocarbons, is used for
stabilization of petroleum products and aromatic reduction [1]. One particular
application of hydrogenation is to saturate unstable olefins and di-olefins that are
implicated in producing gums (high-molecular-weight sticky semi-solid material)
during the storage of fuels, such as gasoline and jet fuel. Gum formation is detrimental,
particularly, to the operation of fuel injectors in combustion engines. Narrow passages
found in fuel injectors can be partially or completely plugged with
deposition/accumulation of gums on flow surfaces causing engine failures. Figure 9.1 on
the next page shows examples of hydrogenation of an aromatic compound (alkylated
naphthalene) and an olefin. The objective of hydrogenation is just adding hydrogen to
unsaturated hydrocarbons using precious metal (Pt, Pd) or Ni catalysts at low
temperatures to avoid cracking or other chemical changes.

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 9, Hydrotreatment, pp. 195-203.

9.3. Hydrotreatment

Hydrotreatment

As a natural substance, crude oil contains heteroatom (S, N, and O) compounds as well
as metals (mainly Ni and V) in addition to hydrocarbons. The sulfur content of crude oils
normally ranges from 0.05 to 6 wt %, nitrogen content varies from 0.1 to 1 wt %, oxygen
from 0.1 to 2.0 wt %, and metals from 10 to 1000 ppm. Once crude is fractionated by
distillation, the heteroatoms (particularly S, N, and metal compounds) are distributed in
the products. Heteroatom compounds are mainly associated with the higher boiling
fractions and the residues that are rich in aromatic compounds. The presence of
heteroatom compounds in petroleum products is undesirable because they reduce fuel
stability, contribute to the emission of pollutants, and damage engines. Heteroatom
compounds in refinery streams (e.g., basic nitrogen compounds, sulfur compounds, and
metals) can deactivate catalysts and promote coke formation [2].

127
 Figure 9.1. Hydrogenation of unsaturated hydrocarbons for stabilization.

Source: Dr. Semih Eser

The light products such as LPG and naphthas have low concentrations of sulfur and
require minimal treatment, such as absorption in alkaline solvents (e.g., H2S or
mercaptan sulfur) or conversion of mercaptans to sulfides to eliminate odor. For
example, the UOP MeroxTM process is widely used to remove H2S and mercaptan sulfur
(Merox extraction) or to convert mercaptan sulfur to less-objectionable disulfides (Merox
sweetening) [2]. The Merox process can be used to treat liquids such as LPG, naphtha,
and kerosene. Removing sulfur from higher molecular weight and more complex
molecules requires hydrotreatment processes that use hydrogen.
[2] S. Eser and M. R. Riazi, “Crude Oil Refining Processes” In Petroleum Refining and Natural
Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, ASTM International, West
Conshohocken, PA, 2013, p. 119.

9.4. Hydrodesulfurization

Hydrodesulfurization

Desulfurization of fuels is commonly achieved by catalytic hydrodesulfurization (HDS),

in which the organic sulfur species are converted to H2S and the corresponding
hydrocarbon, as in the following reaction: R-SH + H2 → R-H + H2S. Here R represents an
alkyl group, such as methyl (CH3–), or ethyl (C2H5–). Figure 9.2 shows the type and
relative reactivity of different sulfur species in HDS reactions. The reactivity of R-SH
(mercaptan, or thiol) compounds is higher than that of disulfides (R-S-S-R). The H2S is
easily removed from the desulfurized oil by absorption in a gas treatment unit and
subsequently converted to elemental sulfur by the Claus process, as will be discussed in
Lesson 10.

128
Figure 9.2. Types of sulfur compounds found in crude oil and their relative reactivity
in HDS reactions.

Source: Dr. Semih Eser

Some HDS reactions are shown in Figure 9.3. Note that the objective of hydrotreatment
reactions is to take the heteroatom out with minimum hydrogen consumption. The ideal
scenario is to get the hydrogen atoms to break the carbon-sulfur bonds and to remove
sulfur as H2S. This may not always be possible because of problems with the accessibility
of sulfur atoms to hydrogen atoms. Sulfur ring compounds such as methylated
dibenzothiophenes have the lowest reactivity in HDS reactions because they are planar
compounds, and in some methylated DBTs the S atom is shielded by the methyl groups
(See Figure 9.4). Removing sulfur from these compounds requires more hydrogen
consumption in order to saturate the aromatic rings in dibenzothiophene (DBT) to form
non-planar compounds. Remember that, as opposed to aromatic compounds,
cycloalkanes are not planar compounds. Therefore, saturation of the aromatic rings in
methylated DBTs eliminates the steric hindrance (shielding) of methyl groups to make
the S atom accessible to active sites on the catalyst surface for removal as H 2S. The
geometry of this proposition is better understood when one looks at the configuration of
active sites on the HDS catalysts shown in Figure 9.5.

129
Figure 9.3. Hydrodesulfurization reactions.

Source: Dr. Semih Eser

Figure 9.4. Numbering of sites in the 4,6 DMDBT- a challenging compound for HDS.

Source: Dr. Semih Eser

9.4.a. HDS catalysts

The HDS catalysts consist of sulfided molybdenum supported on Al 2O3. Sulfided

molybdenum surfaces have vacancies (with missing S atom in the sequence) that act as
active sites on the catalyst surface (Figure 9.5). In addition to Mo, HDS catalysts also
contain other metals, such as cobalt (Co) as promoters, the main function of which is
believed to dissociate H2 to atomic species that readily react with S. The HDS mechanism
involves inviting the sulfur atom at the HDS target to sit in the vacancy and once the S is
in the vacancy, dispatching H atoms to clip C-S atoms to make H2S that will leave the
vacancy and make it available for the next action. You can see that this scenario would
get into trouble if S cannot sit in the vacancy, as would happen with the compound 4,6
dimethyldibenzothiophene (Figure 9.4 on the previous page and Figure 9.5 below). This
calls for saturating the aromatic rings to twist the methyl groups aside to make the S atom
fit in the vacancy to be taken away as H2S. The list below lists the relative HDS reactivities
of methylated DBT compounds relative to HDS of unsubstituted DBT.

130
Figure 9.5. Hydrodesulfurization catalysts and the configuration of active sites
(vacancies).

Source: Dr. Semih Eser

Reactivity in HDS (k methylated DBT/k DBT)

1. 4, 6 dimethylIDBT → 0.1
2. 3,7 dimethylIDBT → 1.5
3. 2,8 dimethylIDBT → 2.6
4. 4-methyl-DBT → 0.2
One can see above that the HDS reactivity of 4,6 dimethyldibenzothiophene (4,6
dimethylDBT) is one-tenth of unsubstituted dibenzothiophene (DBT), because of the
shielding of the S atom by methyl groups as discussed above. Moving the methyl groups
away from the sulfur atom to 3,7 positions (See Figure 9.4) increases the HDS reactivity
15- fold to 1.5 times of DBT. Interestingly, having methyl groups away from the S atom
(as in 3,7 and 2,8 positions) increases the HDS reactivity relative to that of DBT. Methyl
substitution on DBT away from the S atom increases the HDS reactivity by promoting
adsorption of the compounds on the catalyst surface and may weaken the C-S bonds on
DMDBTs. In contrast, even one methyl group shielding the S atom (4-
methyldibenzothiphene in list above) reduces the reactivity of the methylatedDBT to
one-fifth of the reactivity of DBT.

9.5. Hydrodenitrogenation

Hydrodenitrogenation

Hydrodenitrogenation (HDN) is a similar process to HDS in which hydrogen is used to

remove nitrogen, and for this reason during HDS the nitrogen content of fuels is also
reduced. Figure 9.6 shows different types of nitrogen-containing compounds in crude oil
and refinery unit products. In addition to reducing the N content in fuels as a finishing
process, basic nitrogen compounds such as pyridine and quinoline shown in Figure 9.6
should also be removed as a pretreatment step to protect the acidic catalysts used in
processes such as FCC. This is similar to HDS being an important pretreatment process

131
for feedstocks that would be exposed to noble metal catalysts (such as Pt in catalytic
reforming process) that are poisoned by sulfur compounds. Figure 9.7 shows examples
of HDN reactions and catalysts used for HDN. Similar to HDN reactions for quinoline,
shown in Figure 9.7, pyridine (C5H5N) can be reduced to pentane (C5H12) and ammonia
(NH3) by adding 5 molesH2 in three steps. The overall HDN reaction for pyridine is
C5H5N + 5H2 → C5H12 + NH3.

Figure 9.6. Types of nitrogen containing compounds found in crude oil.

Source: Dr. Semih Eser

Figure 9.7. HDN reactions and catalysts.

Source: Dr. Semih Eser

9.6. Hydrodemetallation

Hydrodemetallation

Similar to HDS and HDN, hydrodemetallation (HDM) is carried out: 1) as a pretreatment

operation to remove metals (mostly nickel and vanadium) to protect the catalysts in
subsequent conversion reactions, and 2) for removing metals in petroleum fuels to

132
 prevent corrosion in furnaces and toxic emissions from combustion engines. As
mentioned in Lesson 1, metals (Ni, V) are mostly incorporated in the cage-like structures
of highly stable organometallic compounds called porphyrins. As seen in Figure 9.8, to
remove the metals, the cage structure of porphryins needs to be broken up. Similar to
HDS and HDN, hydrotreatment on a Mo/Al2O3 catalyst first breaks up the chemical
bonds in porphyrins to free the metals. The metals are then reacted with H 2S and
precipitated as metal sulfides, e.g., NixSy, on catalyst surfaces. Note that this is different
from HDS and HDN where the heteroatoms are removed as gas (H2S and NH3,
respectively). [Think: What would be the significance of removing metals as metal
sulfides as far as the morphology of the HDM catalysts is concerned? Save your
answer for the Self-Check question later in this lesson. ] Metals Ni and V deposited on
the catalysts can be recovered by post treatment of the used catalysts.

Figure 9.8. Hydrodemetallation reactions.

Source: Dr. Semih Eser

In addition to HDS, HDM, and HDN, there may be a need for hydrodeoxygenation and
hydrodehalogenation processes to remove O, or Cl in petroleum products [1].

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 9, Hydrotreatment, pp. 195-203.

9.7. Hydrotreatment Processes

Hydrotreatment Processes

Process objectives, conditions, and configurations are similar for all hydrotreatment
processes [1]. As an example, HDS list below, lists the project objectives and selected
conditions for HDS processes. Minimization of cracking (or any other chemical change
133
that is not needed for removing heteroatoms) and minimization of hydrogen
consumption are the two principal objectives of hydrotreatment processes for reducing
the heteroatom concentrations to the desired levels in the reaction products. These
objectives are achieved by careful selection of process conditions that need to be adjusted
based on the chemical composition of the feedstock. You can see in HDS list, that more
severe reaction conditions (e.g., higher reaction temperatures, higher hydrogen/feed
ratios, and lower space velocities) are necessary for treating heavy residue compared to
treating light distillates. Catalysts have shorter lives in residue treatment processes, as
well, because of harsh reaction conditions and more excessive deposition on catalysts
during the treatment of heavy residue.

HDS (Hydrodesulfurization)

Objectives

 minimizing cracking
 minimizing hydrogen consumption
Light Distillate Heavy Residue
300-400 340-425
Process Conditions
 Temperature, ºC
2-10 0.2-1
 LHSV, h-1
 H2/Oil, scf/bbl 300-2000 2000-10000
o Catalyst life, years
10 ~1

Note: LHSV (Liquid Hourly Space Velocity) – the volumetric flow rate of liquid reactant
passing through a reactor divided by the volume of the catalyst in the reactor, measured
in units of h-1. Lower LHSV (i.e., longer exposure to catalyst in the reactor) is needed for
more challenging hydrotreatment tasks.
Figure 9.9 shows a process flow diagram for HDS. The feed is introduced into a fixed-
bed catalytic reactor along with hydrogen and the products are sent to a high-pressure
separator to separate H2 and H2S gases from the hydrocarbons. The gases are sent to a
scrubber with a basic solution (containing ethanol amine or diethanol amine) to remove
H2S that is sent to the sulfur recovery unit and H2 is recycled to the treatment reactor.
Desulfurized products are sent to a fractionator to separate C3 and C4 alkanes (LPG) and
the liquid products.

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Figure 9.9. HDS Process Configuration.

Source: Dr. Semih Eser

For HDS, HDN and HDM sequential reactors can be configured with different catalysts
optimized for the targeted heteroatom removal. Figure 9.10 shows staging of the HDM
and HDS operations. The first step in a series of reactors is always HDM because of the
unique removal mechanism of the metals (Ni and V), as solid materials on catalyst
surfaces, catalysts with large pores in the support materials are needed so that the
problems with reactor plugging can be avoided. Following the removal of metals, HDS
and HDN can be conducted on medium-pore and small-pore catalysts, in some cases
simultaneously in the same reactor or the same catalyst bed.

Figure 9.10. Staging of hydrotreatment processes.

Source: Dr. Semih Eser

135
 Increasing sulfur contents of the crude oils available for the U.S. refineries on one hand,
and decreasing sulfur contents of regulated fuels on the other, have increased the sulfur
production in the U.S. refineries as a by-product to 40,000 tons/day [4]. This is sufficient
capacity to meet all sulfur demand for the chemical industry, particularly for
H2SO4 production used in many chemical industries. One should note that this quantity
of sulfur comes only from desulfurization of the fuels that are subject to sulfur regulation.
A significant fraction of sulfur in crude oil (>60%) is concentrated in the heavy ends (e.g.,
residual fuel oil, asphalt) that are not regulated for sulfur content.

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 9, Hydrotreatment, pp. 195-203.
[4] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 12, Product Blending, pp.257-270

9.8 Product Blending

Product Blending

Product blending plays a key role in preparing the refinery products for the market to
satisfy the product specifications and environmental regulations. The objective of
product blending is to assign all available blend components to satisfy the product
demand and specifications to minimize cost and maximize overall profit [5]. Almost all
refinery products are blended for the optimal use of all of the intermediate product
streams for the most efficient and profitable conversion of petroleum to marketable
products. For example, typical motor gasolines may consist of straight-run naphtha from
distillation, crackate (from FCC), reformate, alkylate, isomerate, and polymerate, in
proportions to make the desired grades of gasoline and the specifications.

Basic intermediate streams can be blended into different finished products. For example,
naphthas can be blended into gasoline, or jet fuel streams, depending on the demand.
Until the 1960s, the blending was performed in batch operations. With computerization
and the availability of the required equipment, online blending operations have replaced
blending in batch processes. Keeping inventories of the blending stocks along with cost
and physical data has increased the flexibility of and profits from online blending
through optimization programs. In most cases, the components blend nonlinearly for a
given property (e.g., vapor pressure, octane number, cetane number, viscosity, pour
point), and correlations and programming are required for reliable predictions of the
specified properties in the blends [3].

136
[3] U.S. Refinery Sulfur Production Capacity(link is external)
[5] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 12, Product Blending, p.267.
 Octane Number Blending
 Pour Point Blending

9.8.a Octane Number Blending

Octane numbers are blended on a volumetric basis using the blending octane numbers
of the components. True octane numbers do not blend linearly, thus it is necessary to use
blending octane numbers in calculating the octane number of the blend. Blending octane
numbers can be estimated from empirical correlations that have been developed over the
years. Blending octane numbers, when added on a volumetric average basis, will give
the true octane of the blend, as can be obtained from standard test using CFR test engines.

(True Octane Number of a blend) ON = Σ xi∗ ONi

Where xi is the volume fraction of component i in the blend, and ONi is the blending
octane number of component i.

For example, if you have

 a light naptha stream with a blending octane number = 75

 a reformate with a blending octane number = 86
and would like to get a gasoline of ON = 83, what would be the volume fraction of
reformate (x) in the blend?

 ON = x(86) + (1-x)(75) = 83
 x = 0.73
So, you need 73% by volume of reformate in your blend. Additive concentration may be
calculated the same way and ON for multicomponent blends can be calculated the same
way for research or motor octane numbers.

9.8.b. Pour Point Blending

Pour point is an important property for diesel and fuel oil blends. Pour point blending is
also non-linear, and pour point blending indices were developed to enable reliable
calculation of the pour points of the blends. Pour point blending indices for some
distillate fuels are given in Table 12.7 of the textbook, and copied in Figure 9.11, where
the blending indices are tabulated as a function of ASTM 50% temperature, °F (first
horizontal listing) and Pour Point, °F (first vertical listing). For example, pour point
blending index for a distillate that has and ASTM 50% temperature of 500°F and a pour

137
point of 40°F would be 36. This index can be used in calculating the pour point of blends
using this distillate as a component.

Figure 9.11. Pour Point Blending Indices [5].

By arrangement with Chevron Research Company

As an example of using blending indices to calculate the pour point of a blend, consider
blending a straight-run gas oil (50% ASTM T = 470°F and pour point = -6°F) and a
hydrotreated heavy gas oil (50% ASTM T = 620°F and pour point = 40°F). What would
be the pour point of a binary blend that consists of 68.7 % vol of straight-run gas oil and
31.3% vol of hydrotreated heavy gas oil?

The procedure used to calculate the pour point of the blend (shown Figure 9.12) can be
summarized as follows:

1. Read pour point blending indices for the two distillates in the table (PPI column)
shown in Figure 9.11, and list it in the table (Figure 9.12). Straight- run gas oil PPBI
=6.3 (using double interpolation), and Hydrotreated heavy gas oil PPBI = 26.
2. Multiply PPBI for individual distillates with their respective volume fraction to
calculate the Pour Factor. For example the Pour Factor for straight-run gas oil = 0.687
x 6.3 = 4.33. Add the pour factors for each component, to calculate the blending index
for the blend = 12.47.

138
3. Calculate blend 50% ASTM temperature (linearly additive) of the blend by
multiplying the volume fraction with ASTM 50% T of each component and adding
them together (0.687x470 +0.313x620 = 517).
4. Using the blend ASTM 50% just calculated (517) and the blending index for the blend
from the pour factors (12.47), interpolate/read the pour point of the blend from the
table in Figure 9.11, as 15°F.
Note that if you would assume linear addition of the pour points, you would calculate a
blend pour point as = 0.687x(-6) +0.313x40 = 8.4°F. A serious underestimation of the pour
point! Thinking that your diesel fuel has a pour point 8.4 °F, you may try to start your
diesel truck on a 12°F day, to no avail, not knowing that your fuel tank has a gel, and not
a liquid that can be easily pumped to the combustion cylinder.

Similar to pour point, the viscosity of blends can also be calculates using blending index
numbers, or plots developed for this purpose. For the same blend, we can use the
Viscosity Blending Index Numbers in Table 12. 3. of your textbook [6], and the procedure
shown in Figure 9.13 to calculate the viscosity of the blend. Try to verify the numbers
given in Figure 9.13, and calculate a viscosity of the blend if viscosities were linearly
additive to compare with the value calculated in Figure 9.13. Post your questions, if any,
and comments in the Help Discussion Forum.

Figure 9.12. Calculating the pour point of a binary blend.

Source: Dr. Semih Eser

139
 Figure 9.13. Calculating the viscosity of a binary blend.

Source: Dr. Semih Eser

[6] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 12, Product Blending, p.263.

9.9. Summary and Final Tasks

Summary

Finishing processes make sure that the refinery products fully comply with the
commercial specifications and environmental regulations. Hydrotreatment removes
heteroatoms from intermediate refinery products to protect the catalysts in the
subsequent processes, or from final products to be sent out to the market. A particular
challenge for hydrotreatment is that while the crude oil slate is getting more
contaminated, the demand for cleaner fuels is mandated by the increasingly stringent
environmental regulations. Major hydrotreatment processes include
hydrodesulfurization, hydrodenitrogenation, and hydrodemetallation, all using
hydrogen and specially designed catalysts to remove heteroatoms with minimal change
to the hydrocarbon constitution of petroleum products. Product blending as a major
finishing process takes up the challenge of the optimum allocation of many intermediate
streams in the refinery to make up the refinery products to satisfy all performance
parameters and environmental mandates. Product blending is carried out using linear
and non-linear programming techniques for online blending.

Learning Outcomes

 compare hydrogenation and hydrotreatment with respect to process goals, catalysis,

and chemistry;
 categorize and evaluate HDS, HDN, and HDM processes;
 assess hydrotreatment catalysts, kinetics and process configurations;
140
 demonstarate procedures to calculate critical properties of blended products, e.g.,
octane number, pour point, and viscosity.

Reminder - Complete all of the Lesson 9 tasks

You have reached the end of Lesson 9! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 10.

Lesson 9 Tasks

Readings: Petroleum Refining, by J. H. Gary and G. E. Handwerk, Chapter 9

(Hydrotreating) and Chapter 12 (Product Blending)

Assignments: Exercise 8
Exam 2. Will cover material in Lessons 6-9. Exam 2 is found in the Exam
2 Module.

Questions?

If you have any questions, please post them to our Help Discussion Forum (not email),
located in Canvas. I will check that discussion forum daily to respond. While you are
there, feel free to post your own responses if you, too, are able to help out a classmate.

141
Lesson 10: Supporting Processes
 Lesson 10 Overview
 Gas Processing Unit
 Sulfur Recovery
 Hydrogen Production
 Wastewater Treatment
 Environmental Regulation of Refineries
 Summary and Final Tasks

10.1. Overview

The fourth type of refining processes constitutes the supporting processes. Figure 10.1
lists the supporting role of these processes as:

1. acid gas removal to separate and concentrate H2S and other acid gases produced in
hydrotreatment and conversion operations;
2. sulfur recovery from H2S captured in acid gas removal unit;
3. hydrogen production for hydrocracking and hydrotreatment processes; and
4. wastewater treatment.
Although these processes and units are not involved directly in hydrocarbon fuels
production, their roles are essential for the operation of a refinery.

Figure 10.1. Refinery supporting processes.

Source: Semih Eser

142
 Learning Outcomes

By the end of this lesson, you should be able to:

 outline and assess the processes for acid gas removal and elemental sulfur recovery
from H2S;
 discuss and illustrate sources of hydrogen and hydrogen production processes;
 assess primary water toxicants and waste water characterization parameters, and
outline waste water treatment processes.

What is due for Lesson 10?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignment below can be
found in this lesson.

Lesson 10 Assignments

Reading: J. H. Gary and G. E. Handwerk, Chapter 13 (Supporting Processes)

Assignments: Exercise 9

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

10.2. Gas Processing Unit

Gas Processing Unit

The gas streams produced in refinery units such as catalytic crackers, cokers,
hydrocrackers, and reformers are sent to the Gas Processing Unit [1] in order to:

1. recover C3-C6 hydrocarbons for LPG production (C3 and C4) and feedstocks (C5 and
C6) for isomerization (light naphtha) and reformer (heavy naphtha) units;
2. separate H2S in a sour gas stream that also contains C1 and C2 gases.
In some refineries, Gas Processing Units also function as Light End Units.

[1] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 13, Supporting Processes, pp. 278-280.

143
 10.2.a. Acid Gas Removal

Sour gas separated in the Gas Processing unit is sent to the Amine Unit for acid gas
removal using chemical solvents such as monoethanolamine (MEA), or diethanolamine
(DEA), as shown in Figure 10.2.

Figure 10.2. Acid gas removal by absorption in chemical solvents, such as MEA, or
DEA.

Source: Semih Eser

As shown in Figure 10.2, the sour gas is pumped from the bottom of an absorption
column to get in contact with the basic solution (typically 15-30wt% diethanolamine) to
capture H2S (and other acidic gases such as CO2) in the solution. The rich solution
containing the acid gases is sent to a flash drum to recover the C 1and C2 hydrocarbons
from the rich solution to be used as fuel gas in the refinery to generate process heat, or
steam in fired furnaces. The rich solvent is then sent to a regenerator still to remove the
acid gases that are sent to the sulfur recovery unit. The remaining solvent is cooled in a
heat exchanger and recycled to the absorption unit to close the loop [2].

[2] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 13, Supporting Processes, pp. 280-283.

10.3. Sulfur Recovery

Sulfur Recovery

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 As indicated in Figure 10.3, the objective of the sulfur recovery process is to convert H2S
to elemental sulfur. Sulfur recovery takes place in a series of two steps: Claus Process and
SCOT Process [3]. In the Modified Claus Process, partial combustion of H2S takes place
to generate SO2 that is reacted with the remaining H2S to recover sulfur as elemental
sulfur. The Modified Claus Process, once-through burner operation, works only with
acid gases that contain more than 50% H2S by volume. In the process, hydrogen in H2S
is converted to H2O. The second stage, the SCOT Process, functions as a tail gas clean-up
operation to remove the sulfur compounds produced in the side reactions of the Claus
Process, i.e., carbonyl sulfide (COS) and carbon disulfide (CS2).

Figure 10.3. Sulfur recovery processes.

Source: Semih Eser

[3] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 13, Supporting Processes, pp. 283-290.

10.3.a. Modified Claus Process

Figure 10.4 shows the configuration of the multi-step Modified Claus Process that
includes two kinds of reactors: a burner reactor and a converter reactor. In the burner
reactor, H2S is burned with compressed air to SO2 and H2O. Two critically important
variables of the burner reactor are the oxygen to H2S ratio and the reactor temperature.
The O2/H2S ratio needs to be one-third of the stoichiometric ratio for complete
combustion of H2S. The significance of the O2/H2S will be discussed further in the next
section. The temperature in the burner reactor must be maintained typically at 1850°F to
make sure that any ammonia present in the feed gas is completely destroyed to protect
the catalysts in the converter reactor. The effluent gas from the burner reactor is cooled
to 450°F (above the dew point of S) in the waste heat boiler as it enters the converter
reactor for catalytic conversion of H2S and SO2 to elemental sulfur and water. The
converter effluent is introduced into a condenser unit to obtain elemental sulfur as a
liquid product. Small quantities of S produced in the burner reactor may also be
recovered after the waste heat boiler. Typically, three sets of converter-condenser units
in series are needed to achieve 95% recovery of S in the Modified Claus Process.

145
Figure 10.4. The Modified Claus Process.

Source: Semih Eser

Figure 10.5 shows the principal reactions in the Modified Claus Process in the burner and
converter-reactor sections. In the burner, H2S is partially oxidized to produce H2O and
SO2. In the reactor converter, the burner product SO2 reacts with the remaining H2S to
produce elemental sulfur (the intended product in the sulfur recovery process) along
with the side product water. Ideally, the final products should consist only of elemental
sulfur and water with no H2S or SO2 present. The only way to achieve the intended
product mix is to control the O2/H2S ratio in the burner. As can be seen, the
stoichiometric ratio of O2/H2S for complete conversion of H2S to SO2 is 3/2 which would
effectively convert all H2S to SO2. In order to reserve part of the feed H2S to react with
the burner product so that no H2S or SO2 remains in the final product from the converter,
the O2/H2S ratio should be controlled at 1/3 of the stoichiometric ratio, that is
(1/3)(3/2)=1/2. As a self-check exercise, explain with chemical equations why the
desired oxygen/hydrogen sulfide ratio in the feed to the Burner in the Claus Process
should be 1/3 of the stoichiometric oxygen/hydrogen sulfide ratio (for complete
combustion of hydrogen sulfide). The answer to this exercise is given at the end of the
lesson.
As seen in Figure 10.5, the side reactions in the burner produce COS and CS2 which
cannot be converted in the catalytic reactions that take place in the converter reactor.
Therefore, a tail gas clean-up process, or SCOT Process, is needed to reduce the
concentration of these side products to less than 20 ppm by volume in the outlet.

146
Figure 10.5. Chemical reactions in the Modified Claus Process.

Source: Semih Eser

10.3.b. SCOT Process

Figure 10.6 illustrates how the SCOT Process is integrated with the Claus Unit to convert
COS, CS2 and any remaining SO2 by reacting with H2 in the catalytic reactor back to H2S
to be recycled to the Claus Unit to close the loop. The hydrogenating catalysts used in
SCOT contain nickel or tungsten on alumina support and the reaction takes place at 480-
570°. By coupling Claus and SCOT processes, more than 99% of sulfur entering the Claus
unit can be recovered as elemental sulfur to be sold as a refinery product.

Figure 10.6. The Shell Claus Off-gas Treatment (SCOT) process.

Source: Semih Eser

10.4. Hydrogen Production

147
Hydrogen Production

Although refineries produce a significant quantity of hydrogen needed for hydrotreating

and hydroconversion processes, in most cases, additional hydrogen is needed
particularly for refining the sour crudes. Therefore, a Hydrogen Plant is needed on site
to provide the additional hydrogen demand. As seen in Figure 10.7, steam reforming of
natural gas is most commonly used in the U.S. to produce hydrogen, whereas partial
oxidation of heavy hydrocarbons is preferred in Europe [4].

For partial oxidation process, a heavy hydrocarbon fraction, typically fuel oil, is reacted
at high pressures (1300-1800 psig) with pure oxygen supplied in strictly controlled
quantities for partial oxidation of hydrocarbons to carbon monoxide and hydrogen, as
shown in Figure 10.7. Carbon monoxide produced in the reaction is converted to
hydrogen by catalytic shift reaction with steam. In the purification step, CO2produced in
the shift reaction is removed by absorption in a basic solvent such as potassium
carbonate.

Figure 10.7. Hydrogen demand and additional hydrogen production on site in the US
and European refineries.

Source: Semih Eser

Figure 10.8 illustrates the reactions in steam reforming of natural gas (CH 4) to produce
hydrogen in the U.S. refineries. In the reforming reaction, CH4 is converted to H2 and CO
on a NiO/SiO2-Al2O3 catalyst at temperatures of 760-816°C. Reforming is followed by the
water gas shift reaction at 343°C to shift CO to H2and CO2 on a Cr2O3 and Fe2O3 catalyst
in multiple catalyst beds with external cooling to control the temperature to achieve high
conversion in the exothermic reaction. The product gas is purified by absorption of
CO2 in an Amine Unit. In the final step of methanation, residual CO and CO2 is removed
by hydrogenation on a Ni/Al2O3 catalyst at 370-427°C.

148
 Figure 10.8. Steam reforming of CH4 for hydrogen production.

Source: Semih Eser

[4] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 13, Supporting Processes, pp. 273-278.

10.5. Wastewater Treatment

Wastewater Treatment

Considering the vast amounts of water used in a refinery, wastewater treatment

constitutes a very significant supporting process for safe operation. Figure 10.9 lists the
different types of wastewater, pollutants involved in wastewater streams, and the major
refinery units that generate significant amounts of wastewater. The four types of refinery
wastewater include cooling water, process water and steam, storm water, and sanitary
sewage water. Among these, the most heavily polluted wastewater stream that requires
serious treatment is the process water and steam that come into direct contact with
petroleum fractions. Storm water may be contaminated because of incidental exposure
to pollutant sources on refinery surfaces and accidental spills. Cooling water and sanitary
sewage water may not require much treatment before they are sent to public water
treatment facilities. One rule of thumb is to avoid mixing different types of wastewater
streams to reduce the load on the treatment units.

Pollutants found in the wastewater streams include hydrocarbons with particular

concern for toxic aromatic compounds, such as benzene; heteroatom compounds, such
as mercaptans, amines, phenols, and cyanides; dissolved gases such as H2S and NH3, and
acids, such as H2SO4 and HF; and suspended and dissolved solids. The refinery units that
149
 generate the most significant amount of wastewater are desalting, distillation, thermal
and catalytic cracking, coking, as well as heat exchangers and storage tanks [5].

Figure 10.9. Refinery wastewater, water pollutants, and refinery units.

Source: Semih Eser

[5] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 13, Supporting Processes, pp. 290-293.

10.5.a. Wastewater characterization

Standard measurements used for wastewater characterization are listed in Figure 10.10.
Biochemical Oxygen Demand (BOD) measures the amount of oxygen consumed by
microorganisms in decomposing organic matter, whereas Chemical Oxygen Demand
(COD) measures the total oxygen consumption by organic and inorganic chemicals
present in water. Both measurements relate to the level of contamination in wastewater,
and they are used to gauge the effectiveness of the wastewater treatment processes. Other
water quality parameters include the amount of suspended solids, hydrocarbon content,
nitrogen content, phenols content, and acidity.

150
Figure 10.10. Measurements for characterization of wastewater.

Source: Semih Eser

10.5.b. Primary and secondary treatment processes

Figures 10.11 and 10.12 illustrate the primary (physical) and secondary (biological)
treatment processes, respectively. The primary treatment of sour water contaminated
with oils and solid particles involve the stripping of dissolved H2S using steam,
float/sink density separation for skimming the floating oil, and the settling tanks to
separate heavier oil and solids, usually in multiple stages, before the treated water can
be directed to public treatment facilities. The secondary treatment uses micro-organisms
to further remove organic contaminants.

Figure 10.11. Primary Treatment of Wastewater

151
 Figure 10.12. Secondary treatment of wastewater.

Source: Semih Eser

10.6. Environmental Regulation of Refineries

Environmental Regulation of Refineries

Air pollutant emissions from the refinery processes are also controlled. Figure 10.13 lists
the major legislations and regulations that affect the environmental impact of refineries
in the U.S. [6].

 Clean Water Act (CWA)

 Safe Drinking Water Act
 Clean Air Act of 1963
 Clean Air Act of 1970 (CAA) and regulations
 Clean Air Act Amendments of 1977 and 1990 (CAAA) and regulations thereunder
 Clear Skies Act of 2003
 Resource Conservation and Recovery Act (RCRA)
 Superfund: Comprehensive Environmental Response, Compensation, and Liability
Act (CERCLA)
 Emergency Planning and Community Right-to-Know (EPCRA)
 Occupational Saftey and Health Act (OSHA)
 Toxic Substances Control Act (TSCA)
 Oil Pollution Act
 Spill Prevention Control and Countermeasure Plans
Figure 10.13. U.S. Federal and state legislations and regulations that affect the
environmental im
[6] C. S. Khor and A. Elkamel, “Environmental Issues Related to the Petroleum Refining
Industry” In Petroleum Refining and Natural Gas Processing, Editors: M. R. Riazi, S.
Eser, J. L. Peña, ASTM International, West Conshohocken, PA, 2013, pp. 701-716.

10.7. Summary and Final Tasks

Summary

Supporting processes are essential to the operation of a refinery. These processes have
become more important as the crude oil base has become more sour. The demand for
hydrogen has increased to support the required finishing processes for heteroatom
removal and recovery of sulfur and metals. Refineries have become major producers of
elemental sulfur for the chemical industry.

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Learning Outcomes

You should now be able to:

 outline and assess the processes for acid gas removal and elemental sulfur recovery
from H2S;
 discuss and illustrate sources of hydrogen and hydrogen production processes;
 assess primary water toxicants and waste water characterization parameters, and
outline waste water treatment processes.

Reminder - Complete all of the Lesson 10 tasks.

You have reached the end of Lesson 10! Double-check the to-do list below to make sure
you have completed all of the activities listed there before you begin Lesson 11.

Please refer to the Course Syllabus for specific time frames and due dates. Specific
directions for the assignments below can be found within this lesson.

Lesson 10 Tasks

Reading: J. H. Gary and G. E. Handwerk, Chapter 13 (Supporting Processes)

Assignments: Exercise 9

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Lesson 11: Past and Future of Petroleum Refining
 Lesson 11 Overview
 Refinery Evolution
 Future Trends in Petroleum Refining
 Summary and Final Tasks

11.1. Overview

In the roughly 150-year history of petroleum refining, remarkable changes have taken
place in refining processes and refinery configurations. These changes were driven by
transitions and developments in combustion engines, the wars (World War I and, most
notably, World War II), variations in the crude oil slate available for refining, and the
environmental regulations. This historical evolution has taken place with the
introduction of new processes more or less in the order of the four refinery processes that
we have discussed: separation, conversion, finishing, and support. The new petroleum
refining processes were developed and incorporated into the refinery to control the yield
and properties of the desired fuels and refineries. Through the stages of the refinery
evolution, it is interesting to note that the demand for even the same petroleum product
has changed not only in the desired composition, as it is linked to properties, but also in
its application to a particular commercial sector. In this regard, kerosene provides a good
example of this change from being primarily a source of light in lamps (as a replacement
for whale oil which allegedly saved the sperm whales from extinction) in the 1850s to
becoming an established base fuel for jet aircraft since the end of World War II. Kerosene
has also been used as a fuel for domestic heating and cooking in many parts of the world,
long after the introduction of electric lamps.

This lesson will provide an overview of the historical evolution of the petroleum refinery
and discuss some current developments in crude oil supply and in related energy
technologies to catch a glimpse of what the near future could bring to the refinery
practice. The overview and discussions will often reflect on specific aspects of different
refinery processes that have been introduced in previous lessons.

Learning Outcomes

By the end of this lesson, you should be able to:

 review, illustrate, appraise, and critique discrete stages in the history of petroleum
refining;
 evaluate driving forces that could impact the future of petroleum refineries and
propose scenarios for responding to the driving forces.

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 What is due for Lesson 11?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignment below can be
found in this lesson.

Lesson 11 Tasks

Readings: F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum,

Processes and Products, AIChE CD-ROM, 2000.

Assignment: Exercise 10: Refinery Flow Diagrams

Quiz 4. Will cover material in Lessons 10-11. Check the Syllabus or Course
Calendar for Quiz 4 schedule.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

11.2. Refinery Evolution

Refinery Evolution

The configuration and complexity of a petroleum refinery has evolved from one-pot
batch distillation to produce kerosene as the major product (1850s) to the complex
refinery of the day [1] that produces a multitude of fuels and petrochemical feedstocks
from a wide range of crude oils, as discussed in Lessons 1 and 2. Different stages of this
evolution, in tune with the changing demand for petroleum products as well as the
changing crude oil base over time, are presented in the following sections listed below
and in your menu.

[1.] Petroleum Refining, by J. H. Gary, G. E. Handwerk, M. J. Kaiser, 5th Edition, CRC Press
NY, 2007, Chapter 1.

 Batch Fractionation (1855-1880)

 Continuous Fractionation (1880-1910)
 The Thermal Refinery (1910-1940)
 The Catalytic Refinery (1940-1970)
 Heavy Ends Conversion Refinery (1970-)

11.2.a.Batch Fractionation (1855-1880)

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In the first refineries of the United States, Pennsylvania crude was easily distilled to
produce kerosene for lamps (which burned cleanly without producing much smoke
because of the paraffinic composition of Penn crude) and lubricating oil for steam
engines. Lighter fractions obtained from distillation such as naphtha, propane, and
butane were largely considered a nuisance and were flared for disposal because of their
high vapor pressure and low flash points that would cause difficulties with storage.
Figure 11.1 shows a typical batch distillation process in early refineries of the 1850s used
primarily to produce kerosene, labeled as “product” from the separator in the diagram.
For the distillation process, crude oil feed was filled into a kettle heated by burning gas,
or other fuels in a fire box and the residual tar was removed after the distillation was
over. The Dephlegmator Tower worked as a distillation column and as the crude boiled
in the still, the vapor fraction from the dephlegmator was condensed and sent to the
separator [2]. The separated kerosene fraction often went through a second distillation
process to control the flash point for the safe use of fuel in lamps and reduce odor. The
residue fraction was also distilled using vacuum to produce lubricating oil and grease
for the steam engines and wax for making candles.

Charging the kettle with crude oil and emptying the residue left over from distillation
took a lot of time and effort, making the batch distillation highly inefficient. In most cases,
the recovered overhead fraction was fed back to the same still to drive off more hydrogen
sulfide and lighter fractions to control the flammability (flash point) of kerosene. Driving
off hydrogen sulfide and other light sulfur species also reduced the odor of kerosene and
of the products obtained from burning kerosene in gas lamps. As the demand increased
for kerosene, the refiners began to use two stills, one for the first fractionation of a
kerosene cut and the second one to redistill the kerosene for purification. Using two stills
in series marked the beginning of the continuous stills [2].

Fig 11.1 An early batch distillation process to produce primarily kerosene as product [2].

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[2.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and
Products, AIChE, 2000, Chapter 4.

11.2.b. Continuous Fractionation (1880-1910):

Continuous fraction with multiple stills replaced batch operations in the

refineries, enabling increased throughputs and the production of multiple distillate
fractions as products from a refinery [2]. As shown in Figure 11.2, a series of stills could
operate continuously by taking an overhead fraction from the crude oil in the first still
by flashing and moving the remaining liquid to a still drum while continuously
introducing more fresh feed to the first still. The second still operates at a higher
temperature to produce a higher boiling distillate. The reflux to the column with bubble
trays was adjusted from the color of the overhead stream, utilizing a “look box,” shown
in the diagram in Figure 11.2, to improve separation.

The demand for kerosene as a source of light declined with the invention of the electric
light bulb in 1879. However, the first powered airplane flight in 1903 and mass
production of an automobile (Model T) in 1908 ushered in a large demand for gasoline
that cannot be met by simple distillation. Thermal cracking provided means to increase
gasoline supply. This was the beginning of a new era in petroleum refining,
incorporating a conversion process with separation processes.

Figure 11.2. Continuous fractionation process using two stills in series.

11.2.c. The Thermal Refinery (1910-1940):

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Incorporating thermal cracking of gas oil into the refinery increased the yield of light and
middle distillates, i.e., gasoline, kerosene, and diesel fuel, from crude oil. Although the
electric light made the kerosene lamps obsolete, there was still continued demand for
kerosene in rural regions because of slow electrification outside the urban areas. The
evolution of refinery in the three decades between 1910 and 1940 was driven largely by
the development of thermal cracking processes, although finishing (or chemical treating)
processes also started to become important in this era to stabilize and purify the products
of thermal cracking.

Figure 11.3 shows a simple schematic diagram of the Burton-Clark batch thermal
cracking process. The process employed tubular heating similar to those used in a steam
boiler. The series of tubes in the firebox circulate the hot gas oil back to the drum by
thermal convection for more uniform heating. The hot gases from the coal-fired furnace
are directed up over the high end of the tubes and down over the low end of the slanted
bundle. Feed is introduced in the low end of the tubes and tar is withdrawn from the
bottom set of tubes. The products of thermal cracking are fractionated in the Bubble Tray
Tower and in the high-pressure and low-pressure separators. In the high-pressure
separator are the gaseous products hydrogen, methane, and ethane, and in the low-
pressure separator are the gases ethane and propane and the liquid products gasoline
and kerosene.

Figure 11.3. Burton-Clark Batch Thermal Cracking Process to increase distillate yields
[3].

Figure 11.4 shows the configuration of different processes in the thermal refinery. As
different from the thermal processes in a current refinery, the thermal refinery includes
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processes such as Thermal Polymerization, making gasoline from the light olefins
propene and butene; Thermal Reforming, to make relatively high octane number
gasoline from straight-run naphtha; and gasification of heavy gas oil with steam, to
produce town gas (CO+H2) which predates the use of natural gas in cities for domestic
heating and cooking.

Figure 11.4. The configuration of the thermal refinery [3].

The essential driver of the Thermal Refinery was the shift in demand to gasoline from
kerosene because of the introduction of the automobile, the airplane, and electricity. The
demand for gasoline rapidly increased when the U.S. declared war on Germany in 1917
and became a party in World War I. Thermal refinery processes, thermal cracking,
thermal reforming, and thermal polymerization enabled the expansion of gasoline
supply [3]. With the introduction of tetraethyl lead (TEL) as an octane number boosting
additive in 1923, a growing interest was directed to production of high-performance
gasoline which would be defined later as a high-octane number-gasoline after the
introduction of a test method to measure the octane number of gasoline as an anti-knock
property in 1931. Because of the toxicity of lead, TEL concentration was limited to 3
milliliters per gallon of finished gasoline (approximately 800 ppm by volume). The
addition of lead to motor gasoline continued until the 1970s in the United States when
the mandate for adding catalytic converters to automobiles took effect in accordance with
the Clean Air Act to reduce tailpipe emissions, and the unleaded gasoline was

159
 introduced. Lead is still added to aviation gasoline used in turboprop aircraft in
quantities 0.3-0.56 g/L in a range of avgas grades, and efforts are underway to remove
lead from the aviation gasoline as well in the near future.

Up through 1924, even with the rapid introduction of various thermal cracking processes,
only 20% of the gasoline produced in the U.S. came from thermal processes. But after the
introduction of TEL, the contribution of gasoline produced by thermal cracking has
steadily increased to reach over 50% of the gasoline pool by the end of the age of the
Thermal Refinery in 1940. For reasons discussed in Lessons 6 and 7, the Catalytic Refinery
arrived in the scene of brutal competition of making high-performance gasoline and
other petroleum fuels in the period leading to and during World War II.

[3.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and
Products, AIChE, 2000, Chapter 5.

11.2.d. The Catalytic Refinery (1940-1970):

As discussed in Lessons 6 and 7, the development of catalytic processes has

changed the chemistry of petroleum refining from free radical to ionic reactions. World
War II provided the stimulus to urgently develop catalytic technologies that were being
investigated in the late thirties. The catalytic age of refining which could be bracketed
between1940 and 1970 also brought the advent of the petrochemical industry.

Figure 11.5 shows a configuration of the catalytic refinery which resembles, to a large
extent, the current day refineries focused on making high yields of gasoline. The
introduction of catalytic cracking, reforming, alkylation, polymerization has
revolutionized the ways of making high octane number gasoline. Development of
hydrotreatment processes was also an important asset of the catalytic refinery.
Hydrotreatment was essential to protect the platinum catalyst used in reforming from
sulfur and as a versatile finishing process to replace the chemical treatments used in the
thermal refinery to finish fuels.

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Figure 11.5. The configuration of the catalytic refinery [4].

One should note in Figure 11.5 that the catalytic refinery also incorporated new thermal
processes such as delayed coking and visbreaking, and separation processes, such as
deasphalting. Principles of chemical engineering have found great applications in the
development of the catalytic refinery with particular emphasis on designing different
catalytic process configurations (remember Fixed-Bed, Moving-Bed, and Fluid-Bed
Catalytic Cracking), catalyst development, thermal efficiency (e.g., FCC) and product
yield and selectivity. The catalytic refinery produced large quantities of LPG (for reasons
discussed in Lesson 7) and witnessed the increasing demand for kerosene, now as jet
fuel. The time-line for the development of refining processes shown in Table 11.1 shows
the intense activity of process development particularly during World War II.

The age of catalytic refining may be considered to have ended in 1970s, not because new
chemistry was introduced as it happened in the transition from thermal to catalytic
refinery or the development of new process concepts. The oil crises of the 1970s
highlighted the significance of refinery flexibility with respect to the diversity of crude
oil slates. Further, the concerns for environmental pollution by the combustion of
petroleum fuels have brought emphasis on more effective finishing processes. These
factors lead to the development of the modern refinery focused on processing the heavy
ends of petroleum and making cleaner fuels.

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Year Process Name Purpose Byproducts, etc.

1849 Canadian geologist Abraham Gesner distills kerosine from crude oil

1859 An oil refinery is built in Baku (Azerbaijan)

1860- Oil refineries are built near Oil Creek, Pennsylvania; Petrolia, Ontario, Canada; and Unio
1861 County, Arkansas

1862 Atmosphere distillation Produce kerosine Naphtha, tar, etc.

Lubricants (original) cracking Asphalt, residual coke

1870 Vacuum distillation feedstocks
feedstocks (1930s)

1913 Thermal Cracking Increase gasoline Residual, bunker fuel

1916 Sweetening Reduce sulfur and odor Sulfur

1930 Thermal reforming Improve octane number Residual

1932 Hydrogenation Remove sulfur Sulfur

1932 Coking Produce gasoline base stocks Coke

Improve lubricant viscosity

1933 Solvent extraction Aromatics
index

1935 Solvent dewaxing Improve pour point Waxes

Improve gasoline yield and Petrochemical

1935 Catalyst polymerization
octane number feedstocks

Petrochemical
1937 Catalytic cracking Higher octane gasoline
feedstocks

1939 Visbreaking Reduce viscosity Increased distillate, tar

Increase gasoline octane and High-octane aviatio

1940 Alkylation
yield gasoline

1940 Isomerization Produce alkylation feedstock Naphtha

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 Increase gasoline yield and Petrochemical
1942 Fluid catalytic cracking
octane feedstocks

1950 Deasphalting Increase cracking feedstock Asphalt

1952 Catalytic reforming Convert low-quality naphtha Aromatic

1954 Hydrodesulfurization Remove sulfur Sulfur

1956 Inhibitor sweetening Remove mercaptan Disulfides

Convert to molecules with high

1957 Catalytic isomerization Alkylation feedstocks
octane number

Improve quality and reduce

1960 Hydrocracking Alkylation feedstocks
sulfur

1974 Catalytic dewaxing Improve pour point Wax

Increase gasoline yield from

1975 Residual hydrocracking Heavy residuals
residual

The phaseout of tetraethyl lead

1975 Catalytic converter Cleaner air
begins

SCANfining (Exxon),
Reformulated gasoline and low-
1990s OCTGAIN (Mobil), Prime G Low sulfur fuel
sulfur diesel
(Axens), and S Zorb (Phillips)

Deep or ultra-deep Decrease sulfur level in diesel (2

2000 Sulfur
desulfurization (ULSD) ppm0

Table 11.1. Historical time-line for petroleum refining processes [6].

[4.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and
Products, AIChE, 2000, Chapter 6. [6.] M.R. Riazi, S. Eser2, J. L. Peña Díez, and S. S.
Agrawal, “Introduction” In Petroleum Refining and Natural Gas Processing, Editors: M.
R. Riazi, S. Eser, J. L. Peña, S. S. Agrawal, ASTM International, West Conshohocken, PA,
2013, p.6

11.2.e. Heavy Ends Conversion Refinery (1970-):

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 Oil crises of 1973 and 1979, which created crude oil price shocks, contributed to an
increasing emphasis on energy efficiency and independence. These events along with the
stricter environmental regulations set up the evolution of the End of the Century Refinery
(or Heavy Ends Conversion Refinery) which has focused on efficient processing of heavy
crudes as well as the heavy ends of crude oils to produce higher yields of distillate fuels.
Producing cleaner fuels and cleaner operation of refining processes have been mandated
by environmental regulations.

Figure 11.6 shows the configuration of the Heavy Ends Conversion refinery with
emphasis on processes marked with the red rectangle in Figure 11.6. These processes
include hydrotreating of heavy gas oils before catalytic cracking to remove sulfur that
contaminates downstream catalysts and to saturate aromatic C-C bonds to produce
higher yields of fuel products from catalytic cracking. With better protection from sulfur
contamination, FCC units can use modified catalysts to increase gasoline yield and
reduce coke yield.

HECR offers four primary heavy oil or residue processing technologies as options for
processing heavy crudes or “bottom-of-the barrel” processing. These processes have
become more important as the world crude slate becomes heavier and more
contaminated with sulfur and other heteroatom species, as sulfur limits become more
stringent with environmental regulations.

Hydrocracking of heavy oils removes downstream catalyst contaminants and saturate

aromatic compounds to produce higher yields of fuel products. Hydrocracking offers
flexibility to choose between gasoline, jet fuel, and diesel fuel by coordinating the
operations of fluid catalytic cracking and hydrocracking.

Other options for residue processing include coking, visbreaking, and deasphalting.
Coking followed by catalytic upgrading of coking products (naphtha and gas oils) by
hydrogenation, or hydrocracking generates high-quality distillates from residua that are
not suitable for catalytic processes due to large concentrations of asphaltenes and
heteroatom compounds (sulfur, nitrogen, oxygen, metals). Visbreaking and deasphalting
removes the highly reactive compounds and asphaltenes from residua making the
visbroken and deasphalted oils attractive feedstocks for catalytic hydroprocessing to
produce distillate fuels

The End of the 20th Century Refinery (the present-day refinery) is much more complex
and versatile than its predecessor The Catalytic Refinery. In addition, there are
differences that are not so visible in conventional descriptions and flow sheets, such as
computerized control of the operations and on-line measurements of product
composition and properties.

164
 Figure 11.6. The heavy ends conversion refinery (or the End of the 20th Century
Refinery) [5]

[5.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and
Products, AIChE, 2000, Chapter 7.

11.3. Future Trends in Petroleum Refining

Future Trends in Petroleum Refining

Speculation about the future of refining is risky at best, but some trends are described as
to be more certain by Self, Ekholm, and Bowers [5], as follows:

 Computers will increasingly be used for research, design, control and operation,
maintenance, information handling, supply chain management, marketing execution,
and distribution. As a result, research will broaden and manufacturing facilities will
become more complex.
 The sophistication of competitors and customers, both domestic and international,
will drive more transparent and efficient markets.

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  Consumers will continue to search for energy sources that are reliable and
independent of political forces, sustainable, environmentally acceptable, simple to
generate and store and distribute, and inexpensive. Consequently, companies will
hasten to reconcile the position of fossil fuels within emerging energy alternatives.
Meanwhile, fuel formulations and usage will evolve, particularly for better
performance and pollution prevention. This will progress despite the apparent trend
of heavier crudes with increased sulfur, metals, solids, and water.
 Sensitivity will spread for the concerns and desires of consumers, communities,
investors, and other stakeholders in all aspects of refining. Interaction with all
stakeholders will be critical.
 Strategic consolidation of the size, number, and ownership of facilities and companies
will continue. New partnerships will form among customers, competitors and
suppliers. Companies will attempt to maximize their return on assets, optimize
allocation of capital, and reduce operating costs. In particular, efforts at hazard
elimination and pollution prevention will intensify to reduce operational and liability
costs.
 Factors that may influence the future of petroleum refining
 Considerations for the Future Refinery

11.3.a. Factors that may influence the future of petroleum refining:

Figure 11.7 lists four factors that may influence the future of petroleum refining,
including product demand, crude supply, environmental regulations, and new
technology development. It is expected that in the near future the demand for distillate
fuels will keep increasing, while the conventional crude oil slate will become heavier and
more contaminated. This conflict between the trends in supply and demand that is
aggravated by more strict environmental regulations on the purity of fuels can be
mitigated by new and more effective technologies (processes and catalysts). Although
the conventional crude oils are becoming heavier (Figure 11.8), non-conventional liquids
such as synthetic crude oil from oil sands in Canada and shale gas liquid by-products are
lighter than the conventional crude oils and could be used as blend components to dilute
the heavy crudes. Natural gas liquids and coal-derived liquids may also be used as
alternative feedstocks for refining. The diversity in crude oil supply calls out the need to
plan/operate a more flexible and versatile refinery.

166
 Figure 11.7. Some predictions on future trends in petroleum Refining.

Figure 11.8. Gravity and sulfur contents of the U.S. crudes [1].

[1.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and
Products, AIChE, 2000, Chapter 1.

11.3.b. Considerations for the Future Refinery:

Figure 11.9 recaps some considerations for the future refinery, as discussed above, and
lists the future challenges that include the need to process heavier and more

167
contaminated crude oils to produce cleaner products than before. Production of diesel
from highly aromatic by-product from FCC (LCO) remains a concern for the cost and
quality of diesel fuel produced in the U.S. refineries. Also, extensive hydrotreatment to
comply with the limits on heteroatom levels in fuels would negatively affect the octane
numbers of gasoline because during hydrotreatment, olefins and aromatic compounds
may be hydrogenated, thus reducing the octane number. No such conflict exists for diesel
fuel, because cetane number of diesel actually increases with hydrogenation. It is clear
that the hydrogen demand for the future refinery will keep increasing, and refineries will
build or expand the existing hydrogen production capacity.

Figure 11.9. Considerations for future refineries.

11.4. Summary and Final Tasks

Summary

The evolution of petroleum refinery can be considered to have taken in four stages from
being just a separation refinery (distillation and dewaxing) to a conversion refinery in
accordance with the demand for petroleum products. The conversion refinery evolved
first as a thermal refinery with the development of thermal cracking, reforming, and
polymerization, and transitioned into the catalytic refinery during World War II, with
the development of processes such as catalytic cracking, catalytic reforming, alkylation,
and catalytic hydrotreatment to define the finishing processes. The next stage of
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evolution after the catalytic refinery, high end conversion refinery, has kept all the
catalytic processes and added hydrocracking with emphasis on processing the heavy
crude oils and production of cleaner fuels in compliance with environmental regulations.
The increasing demand for hydrogen for hydrocracking and hydrotreatment operations
and the need to recover increasing quantities of elemental sulfur highlighted the
requirement of supporting processes for the operation of this refinery.

Learning Outcomes

 Comprehension of discrete stages in the history of petroleum refining and the driving
forces that ushered in these stages.
 Evaluation of the driving forces that could impact the future of petroleum refineries
and consideration of different scenarios for responding to the driving forces.
Reminder - Complete all of the Lesson 11 tasks!

Lesson 11 Tasks

Readings: F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum,

Processes and Products, AIChE CD-ROM, 2000.

Assignment: Exercise 10: Construct refinery flow diagrams.

Quiz 4. Will cover material in Lessons10-11. Check the syllabus and

course calendar for Quiz 4 schedule.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.

169
Lesson 12: Natural Gas Processing
 Lesson 12 Overview
 Shale Gas
 Natural Gas Liquids
 Natural Gas Composition and Specifications
 Natural Gas Processing
 Summary and Final Tasks

12.1. Overview

Natural gas has become a very significant fossil fuel in the U.S. because of a sharp
increase in shale gas production starting in 2006.The U.S. Energy Information
Administration projects that the U.S. natural gas production will increase 44% from 23.0
trillion cubic feet in 2011 to 33.1 trillion cubic feet in 2040 [1]. Almost all of this increase
in domestic natural gas production is due to projected growth in shale gas production,
which is projected to grow from 7.8 trillion cubic feet in 2011 to 16.7 trillion cubic feet in
2040. It is interesting to note that before the shale gas boom (that has taken place largely
in Pennsylvania), the U.S. was planning to import liquefied natural gas (LNG) from
countries as far as Peru with the planned construction of LNG ports in California and
other states. Currently, there are prospects of exporting LNG overseas in the near future.
One particular aspect of the natural gas boom that concerns the petroleum refining
industry is the increased production of natural gas liquids (NGL) that are co-produced
with natural gas. NGL consist of light hydrocarbons, and they have become an important
non-conventional feedstock for refineries contributing mainly to gasoline production.
This new input to refineries along with the increased domestic oil production by the new
drilling technology has helped small inland refineries that do not have easy access to
imported crude oil as, for example, Gulf Coast refineries.

This lesson will provide an overview of the natural gas processing that employs the same
techniques and processes as we have covered in petroleum refining operations, such as
in Light Ends Unit for fractionation of light hydrocarbons, and recovering H2S, as well
as its conversion to S. Brief introductions to shale gas and natural gas liquids will be
presented before discussing the natural gas processing.

Learning Outcomes

By the end of this lesson, you should be able to:

 appraise different natural gas reserves (conventional, tight, and shale) and assess the
contribution of natural gas to energy supply;

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  illustrate and evaluate the different stages of natural gas processing, including
condensate removal, acid gas removal, water removal, fractionation of natural gas
liquids.

What is due for Lesson 12?

This lesson will take us one week to complete. Please refer to the Course Syllabus for
specific time frames and due dates. Specific directions for the assignment below can be
found in this lesson.

Lesson 12 Tasks

Readings: Natural Gas

Assignments: Review the US DOE web page on shale gas(link is external). The material in the
section on Shale Gas Basics is included in the coverage of the final exam.

Questions?

If you have any questions, please post them to our Help Discussion (not email), located in
Canvas. I will check that discussion forum daily to respond. While you are there, feel free
to post your own responses if you, too, are able to help out a classmate.
[1.] US DOE EIA Annual Energy Outlook 2013 Early Release

12.2. Shale Gas

Shale Gas

Shale gas refers to natural gas that is trapped within shale formations, as different from
conventional natural gas resources, such as associated (produced with crude oil), or non-
associated (without crude oil) natural gas that is found mostly in sandstone formations.
Shales are fine-grained sedimentary rocks that can be rich sources of petroleum and
natural gas. Over the past decade, the combination of horizontal drilling and hydraulic
fracturing has allowed access to large volumes of shale gas that were previously
uneconomical to produce. The production of natural gas from shale formations has
invigorated the natural gas industry and the small inland refineries in the United States.

Figure 12.1 shows the EIA data and projections on dry natural gas production in the U.S.,
indicating the surge in shale gas production, while the conventional associated and non-
associated gas production are expected to decline [3]. Dry natural gas refers to natural
gas that consists, essentially, of methane without any significant concentration of

171
 condensable hydrocarbons, such as propane and butane, that are present in natural gas
liquids.

Figure 12.1. History and projections of dry natural gas production in the U.S. [2].

Source: U.S. Energy Information Administration, Annual Energy Outlook Early Release

[2.] Natural Gas Overview(link is external)

[3.] What are Natural Gas Liquids?

12.3. Natural Gas Liquids

Natural Gas Liquids

Natural gas liquids (NGLs) are composed of hydrocarbons, including ethane, propane,
butane, isobutane, pentane, and higher alkanes. Although ethane cannot be readily
liquefied by pressure at ambient temperature such as propane and butane (LPG) it is
considered a component of NGL. There are many uses for NGLs, as summarized in Table
12.1 [3]. NGLs are extracted from the natural gas production stream in field processing
plants, using techniques discussed related to petroleum refining operations.

NGL field production is growing in the United States, representing an important part of
the supply picture.

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 Table 12.1: NGL Attribute Summary (EIA)

Natural Chemical Applications End Use Products Primary

Gas Formula Sectors
Liquid

Ethane C2H6 Ethylene for plastics Plastic bags; Industrial

production; petrochemical plastics; anti-
feedstock freeze; detergent

Propane C3H8 Residential and commercial Home heating; Industrial,

heating; cooking fuel; small stoves and Residential,
petrochemical feedstock barbeques; LPG Commercial

Table 12.2: NGL Attribute Summary (EIA)

Natural
Chemical End Use
Gas Applications Primary Sectors
Formula Products
Liquid

Ethylene for plastics

C2H6 Plastic bags;
production;
Ethane plastics; anti- Industrial
petrochemical
freeze; detergent
feedstock

Residential and
C3H8 commercial heating; Home heating; Industrial,
Propane cooking fuel; small stoves and Residential,
petrochemical barbeques; LPG Commercial
feedstock

Petrochemical
C4H10 Synthetic rubber
feedstock; blending Industrial,
Butane for tires; LPG;
with propane or Transportation
lighter fuel
gasoline

Alkylate for
C4H10 Refiner feedstock;
gasoline;
Isobutane petrochemical Industrial
aerosols;
feedstock
refrigerant

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Table 12.2: NGL Attribute Summary (EIA)

Natural
Chemical End Use
Gas Applications Primary Sectors
Formula Products
Liquid

C5H12 Natural gasoline; Gasoline;

Pentane blowing agent for polystyrene; Transportation
polystyrene foam solvent

Blending with vehicle

Mix Gasoline; ethanol
Pentanes fuel; exported for
of C5H12 and blends; oil sands Transportation
Plus* bitumen production in
heavier production
oil sands

C indicates carbon, H indicates hydrogen; Ethane contains two carbon atoms and six
hydrogen atoms

*Pentanes plus is also known as "natural gasoline." Contains pentane and heavier
hydrocarbons.

Table 12.2. Some components and applications of natural gas liquids [3].

Source: US Energy Information Administration

[3.] What are Natural Gas Liquids?

12.4. Natural Gas Composition and Specifications

Natural Gas Composition and Specifications

Natural gas as recovered at the wellhead consists of mostly methane (C1), but it contains
other hydrocarbons, principally ethane (C2), propane (C3), butanes (C4), and pentanes
C5 that constitute the natural gas liquids, as discussed in the previous section. Raw
natural gas also contains water vapor, hydrogen sulfide (H2S), carbon dioxide, nitrogen,
helium, and other impurities, such as mercury. Table 12.3 gives some examples of the
composition of natural gas produced in three different locations, to give an example that
methane content of natural gas can be as low as 65%. One can also note in Figure 12.2 that
some natural gas streams may contain high concentrations of H2S and N2. Some natural
gas streams could be a commercial source for helium [4]. One of the important objectives
of natural gas processing is to remove the corrosive and toxic gas H2S and convert it to

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elemental sulfur, as will be discussed later. Important impurities, including those shown
in Table 12.3, that need to be removed from natural gas are listed below [5].
Table 12.3: Composition of Natural Gas in Different Locations

Canada Kansas Texas

C1 77.1 73.0 65.8

C2 6.6 6.3 3.8

C3 3.1 3.7 1.7

C4s 2.0 1.4 0.8

C5s+ 3.0 0.6 0.5

H2S 3.3 0.0 0.0

CO2 1.7 0.0 0.0

N2 3.2 14.7 25.6

He 0.0 0.5 1.8

Important impurities found in natural gas [5].

 Water: Most gas produced contains water, which must be removed. Concentrations
range from trace amounts to saturation.
 Sulfur species: If the hydrogen sulfide (H2S) concentration is greater than 2 to 3%,
carbonyl sulfide (COS), carbon disulfide (CS2), elemental sulfur, and mercaptans may
be present.
 Mercury: Trace quantities of mercury may be present in some gases; levels reported
vary from 0.01 to 180 μg/Nm3. Typically, the mercury level in pipeline gas should be
reduced to 0.01 μg/Nm3.
 Diluents: Although the gases shown in Figure 12.2 are typical, some gases have
extreme amounts of undesirable components. For example, some wells in Colorado
contain as much as 92% carbon dioxide. High hydrogen sulfide contents (e.g., in
Alberta, Canada), and nitrogen contents (e.g., in Texas) have also been observed.
 Oxygen: Some gas-gathering systems in the United States operate below atmospheric
pressure. As a result of leaking pipelines, open valves, and other system
compromises, oxygen is an important impurity to monitor. A significant amount of
corrosion in gas processing is related to oxygen contamination.

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 Considering that the principal transportation of natural gas over land is by pipeline,
natural gas specifications for pipeline transmission have been developed. Table
12.4 gives the natural gas specifications that need to be satisfied for pipeline
transportation. Note that in addition to the specified impurity levels for the
contaminants, the specifications include the heating value of natural gas (950 -1150
Btu/scf) which depends on the composition, particularly the concentration of inert gases
(e.g., N2 and CO2) and other diluents.
Table 12.4. Specifications for pipeline quality natural gas [6].

Click for a text description of Table 12.4

[4.] A. J. Kidnay and W. R. Parrish, Fundamentals of Natural Gas Processing, CRC Press, Boca
Raton, FL, 2006, p.9.
[5.] A. J. Kidnay and W. R. Parrish, Fundamentals of Natural Gas Processing, CRC Press, Boca
Raton, FL, 2006, p.10.

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[6.] A. J. Kidnay and W. R. Parrish, Fundamentals of Natural Gas Processing, CRC Press, Boca
Raton, FL, 2006, p.16.

12.5. Natural Gas Processing

Natural Gas Processing

A comparison of Table 12.1 and Table 12.2 illustrates the significance of natural gas
processing for purification of the raw natural gas to obtain a pipeline quality gas. In
general, natural gas processing includes the following steps:

 Condensate and Water Removal

 Acid Gas Removal
 Dehydration – moisture removal
 Mercury Removal
 Nitrogen Rejection
 NGL Recovery, Separation, Fractionation, and Treatment of Natural Gas Liquids
In addition to these processes, it is often necessary to install scrubbers and heaters at or
near the wellhead. The scrubbers remove sand and other large-particle impurities. The
heaters ensure that the temperature of the natural gas does not drop too low and form a
hydrate with the water in the gas stream. Natural gas hydrates are crystalline ice-like
solids or semi-solids that can impede the passage of natural gas through valves and
pipes.

A generalized natural gas flow diagram is shown in Figure 12.2 [7]. After initial
scrubbing to remove particles, the first step in natural gas processing is the removal of
condensate (oil) and water that is achieved by controlling the temperature and pressure
of the inlet stream from the well, as shown in Figure 12.4. Gas separated in this unit is
sent to acid gas recovery; the condensate or the oil recovered is usually sent to a refinery
for processing, while water is disposed, or treated as wastewater.

177
Figure 12.2. A generalized natural gas processing flow diagram [7].

Figure 12.3. Condensate and water removal [6].

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Acid gases (H2S and CO2) are separated usually by absorption in an amine solution, as
discussed for H2S recovery in a petroleum refinery in Lesson 10. The recovered H2S is
sent to a combined Claus-SCOT (Tail Gas Treating) unit to be converted to elemental
sulfur, as was also discussed in Lesson 10. After removing the acid gases, the natural gas
stream is sent to a dehydration unit to remove water typically by absorption in a glycol
unit, followed by mercury removal (by adsorption on activated carbons or other
sorbents), and nitrogen rejection either cryogenically, or by adsorption, or absorption
depending on the nitrogen concentration. The last step in the processing sequence is the
Natural Gas Liquids (NGL) extraction, fractionation, and treatment, as described in
Figure 12.4.

Figure 12.4: Separation and Fractionation of Natural Gas Liquids [6]

Natural gas liquids (NGLs) have a higher value as separate products.

Two basic steps: 1) Extraction, 2) Fractionation

1. NGL Extraction
Absorption Method
o Similar to using absorption for dehydration, using a different absorbing oil for
hydrocarbons.
Cryogenic Expansion Process
o Dropping the temperature of the gas stream to around -120°F by expansion and
external refrigeration
2. Natural Gas Liquid Fractionation - works like Light Ends Unit
o Deethanizer - separates ethane from the NGL stream
o Depropanizer - separates propane.
o Debutanizer - boils off the butanes
o Butane Splitter or Deisobutanizer - separates iso and n-butanes.
NGL extraction can be carried out by absorption in oil that selectively absorbs
hydrocarbons heavier than methane, or by a cryogenic expansion and external
refrigeration to condense NGL.

Following the NGL extraction, the treated natural gas stream that is, now, mostly
methane, or a gas compliant with the natural gas specifications is sent to the pipeline for
transmission to the point of use. The extracted NGL, on the other hand, is sent to a
fractionation unit that operates like Light Ends Unit in a refinery, as discussed in Lesson
5, separating ethane, propane, butane, and naphtha (>C5, natural gasoline). Note that the
fractionation unit may also include a butane splitter or deisobutanizer to separate n-
butane and iso-butane. You may remember from Lesson 8 that iso-butane is a feedstock
to alkylation to produce high-octane gasoline when reacted with C3 and C4 olefins. NGL

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 from highly sour gases may need additional treatment to remove mercaptans and other
sulfur species before NGL leaves the processing plant.
[6. ]A. J. Kidnay and W. R. Parrish, Fundamentals of Natural Gas Processing, CRC Press, Boca
Raton, FL, 2006, p.16.
[7.] M.R. Riazi, S. Eser, J. L. Peña Díez, and S. S. Agrawal, “Introduction” In Petroleum
Refining and Natural Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, S. S. Agrawal,
ASTM International, West Conshohocken, PA, 2013, p.12.

12.6. Summary and Final Tasks

Summary

Natural gas has gained prominence in the energy scene as a rising fossil fuel following
the development of new drilling technology that set up a boom in shale gas production.
As crude oil, natural gas contains wide-ranging impurities in addition to the main
component, methane. Natural Gas Processing removes the contaminants in the raw gas
and recovers some valuable byproducts, such as natural gas liquids. A number of
separation and recovery processes used in a petroleum refinery can also be used for
natural gas processing.

Learning Outcomes

By the end of this lesson, you should be able to:

 appraise different natural gas reserves (conventional, tight, and shale) and assess the
contribution of natural gas to energy supply;
 illustrate and evaluate the different stages of natural gas processing, including
condensate removal, acid gas removal, water removal, fractionation of natural gas
liquids.

Reminder - Complete all Lesson 12 tasks!

Lesson 12 Tasks

Readings: Natural Gas

Assignments: Review the US DOE web page on shale gas(link is external). The material
in the section on Shale Gas Basics is included in the coverage of the final
exam.

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