Petroleum Refining Engineering-II

(CHE425PG 2 credit hours)

2014-Mid-term







Dr. Muhammad Rashid Usman
Institute of Chemical Engineering and Technology
University of the Punjab, Lahore.
Crude oil refining
Iamge taken from: http://heatexchanger-design.com/2011/10/06/heat-exchangers-6/ Dated: 17-Jan-2012
3
Course outline

1. Simplified overall crude oil refinery picture
2. Major refinery products and tests: Brief description
3. Separation process: Atmospheric and vacuum
distillations, lube oil extraction, dewaxing, deasphalting,
and clay treatment.
4. Catalysts used in refinery operations
5. Conversion processes: Brief description of alkylation,
polymerization, isomerization of light paraffins,
hydrotreating, catalytic reforming, catalytic cracking,
hydrocracking, visbreaking of resids, and coking.
5. Material and energy balances for refinery processes:
Simulation of refinery processes
6. Design guidelines for the selected refinery equipment
4
Evaluation


Mid term exam: 35 Marks
Final term exam: 40 Marks
Assignment: 25 Marks

May be one mid-mid term and one mid-final term
exams bearing no marks. The assignment may include
attendance marks, theoretical or experimental problems,
quizzes, etc.

Communication with the instructor will be through
email only. Please see your emails regularly.
Instructor email: [email protected]

5
Text books

Gary, J.H.; Handwerk, G.E. 2001. Petroleum refining: Technology
and economics. 4
th
ed. Marcel Dekker, Inc.
Fahim, M.A.; Al-Sahhaf, T.A.; Elkilani, A. 2010. Fundamentals of
petroleum refining. Elsevier.
6
Suggested books

[1] Gary, J.H.; Handwerk, G.E. 2001. Petroleum refining:
Technology and economics. 4
th
ed. Marcel Dekker, Inc.
[2] Fahim, M.A., AlSahhaf, T.A. and Elkilani, A. 2010.
Fundamentals of petroleum refining. Elsevier.
[3] Parkash, S. 2003. Refining processes handbook. Gulf
professional publishing, Elsevier. Singapore.
[4] Wauquier, J.-P. (ed.). 1998. Petroleum refining: Separation
processes. Vol. 2. Technip.
[5] Meyers, R.A. 2004. Handbook of petroleum refining
processes. 3
rd
ed. McGraw-Hill.
7











Overall refinery flow [2]
8
Crude oil distillation: Atmospheric

9
Crude oil distillation: Vacuum

Approximate ranges of crude
distillation products [2]


Conversion and separation processes

Separation processes:
Crude distillation (atmospheric distillation and vacuum
distillation), solvent extraction, solvent deasphalting,
solvent dewaxing, and clay treatment.

Conversion processes:
Catalytic reforming, hydrotreating, hydrocracking,
catalytic cracking, alkylation, isomerization, delayed
coking, flexicoking, and visbreaking.

Refinery processes

12
Separation processes

Atmospheric distillation: Desalted crude oil is flashed in the
atmospheric distillation unit and the crude oil is fractionated into
various fractions. Light gases, light and heavy naphthas,
kerosene, light and heavy gas oils, and atmospheric residuum
may be the principal fractions.
Vacuum distillation: The atmospheric residue is vacuum
fractionated and vacuum gas oil and vacuum residuum may be
the products.
Solvent deasphalting: A solvent usually liquid propane is
employed to remove asphaltenes from heavy crude fractions such
as vacuum resid.
Solvent dewaxing: Paraffins of high molecular weight (wax) are
removed from the lube oil stock to adjust the pour point.
13
Separation processes

Solvent extraction: Lube oil stock is treated with a solvent and
aromatics are removed.
Clay treatment: Lube oil stocks are subjected to clay treatment
to remove impurities to better stabilize and to improve the color.




14
Conversion processes
Hydrotreating: It is carried out to remove impurities such as
sulfur, nitrogen, halides etc.
Isomerization: For example, n-butane is isomerized to isobutane
to feed the alkylation plant. n-hexane is isomerized to branched
alkanes to produce a high octane rating product.
Catalytic reforming: It is used to process low grade (octane
number) fraction such as straight run gasoline and naphthas to
produce high grade gasoline range products. Dehydrogenation,
isomerization, and hydrocracking may occur during the course of
catalytic reforming.
Alkylation: As an example, it is the addition of isobutane to
butenes to produce high grade gasoline range product (alkylate).
15
Conversion processes
Catalytic cracking: The catalytic cracking of heavy oil fractions
to produce mainly of gasoline range products.
Hydrocracking: The cracking of heavy oil fractions to produce
low boiling products in the presence of hydrogen and catalyst.
Coking: It is severe thermal cracking that results in light gases,,
coker naphtha, and solid coke.
Visbreaking: It stands for viscosity breaking. Liquid phase mild
thermal cracking of heavy feedstocks.

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Conversion and separation processes


The crude oil is heated in a furnace and flash-charged to an
atmospheric distillation tower (ADU). Here, it is separated into
light wet gases, unstabilized light naphtha, heavy naphtha,
kerosene, light and heavy atmospheric gas oils, and atmospheric
reduced crude.
The atmospheric reduced crude enters the vacuum reduced
distillation column (VDU) and separated into vacuum gas oil
streams and vacuum reduced crude.
The vacuum reduced crude is sent to a coker where it is
thermally cracked to produce wet gas, gasoline and gas oil range
products and solid coke.
The gas oil ranged products from the ADU and VDU and gas oil
from the coking process are subjected to catalytic and
hydrocracking. The purpose is usually to produce products of
gasoline and diesel range.
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Conversion and separation processes


The light naphtha streams from the crude tower, coker and
cracking units are sent to an isomerization unit to convert
straight-chain paraffins to isomers that have higher octane
numbers [1].
The heavy naphtha streams from the crude tower, coker and
cracking units are fed to the catalytic reformer to improve their
octane numbers [1].
The wet gases streams from the crude units, coker, and
cracking units are separated in the vapor recovery section (gas
plant) into fuel gas, liquefied petroleum gas (LPG), unsaturated
hydrocarbons (propylene, butylenes, and pentenes), normal
butane, and isobutane. The fuel gas is burned as a fuel in refinery
furnaces and normal butane is blended into gasoline or LPG. The
unsaturated hydrocarbons and isobutane are sent to the alkylation
unit for processing [1].
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Conversion and separation processes


In some refineries, the heavy vacuum gas oil and reduced
crude from paraffinic or naphthenic base crude oils are processed
into lubricating oils [1].
The vacuum gas oils and deasphalted stocks are first solvent-
extracted to remove aromatic compounds and then dewaxed to
improve the pour point. They are then treated with special clays
or high-severity hydrotreating to improve their color and stability
before being blended into lubricating oils [1].
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Optimum refinery operation

Each refinery has its own unique processing scheme which is
determined by the process equipment available, crude oil
characteristics, operating costs, and product demand. The
optimum flow pattern for any refinery is dictated by economic
considerations and no two refineries are identical in their
operation. [1]
20
Some crude oils of Pakistan
(From thesis of my student Ahmad)


21
Refining facility in Pakistan

Byco 35,000 bbl/day
ARL 40,000 bbl/day
PRL 50,000 bbl/day
NRL 65,000 bbl/day
PARCO 100,000 bbl/day

Byco has added nearly 120,000 bbl/day capacity in its new
installation.

In the past, further new installations were expected including KCR,
Indus, and Trans Asia.
22
General refinery products


Refinery fuel gas
Liquefied petroleum gas
Solvent naphtha
Gasoline
Kerosene
Jet fuel or gas turbine fuel
Diesel fuel
Fuel oil
Residual fuel oil
Lubricating oil or lube oil
Wax
Asphalt
Petroleum coke




23
Refinery products: Brief description[2]

24
Tests on petroleum fraction


Pour point: A lower pour point means paraffinic content is low.
It is a measure of ease or difficulty of a fraction to be pumped in
cold conditions.
Viscosity: It is usually measured in centi Stokes or Saybolt
seconds at 37.8 and 99 C. These two points are used to find
viscosity index of the fraction.
Aniline point: It is an indication of the amount of the aromatic
content in a given fraction.
Flash point: It is important for gasoline and naphtha.
Octane number: Motor octane number (MON) is the test carried
out at high speed (900 rpm). Research octane number (RON) is
measured at low speed (600 rpm). PON (posted octane number is
the arithmetic average of RON and MON).
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Tests on petroleum fraction


Reid vapor pressure: Vapor pressure determined in a volume of
air four times the liquid volume at 37.8 C (100 F). It indicates
vapor lock characteristics and explosion hazards.
Carbon residue:
Smoke point: It is a measure of the burning qualities of kerosene
and jet fuels. It is measured in terms of the maximum height in
mm of a smokeless flame of fuel.
Refractive index: It is the ratio of the velocity of light in vacuum
to the velocity of light in the oil. It is a used to characterize a
petroleum fraction.
Cetane number: It measures the ability for autoingnition in
diesel (compression ignition) engines. It is the percentage of pure
cetane (n-hexadecane) in a blend of cetane and alpha methyl
naphthalene which corresponds to the ignition characterstics of a
given diesel sample.
26
Tests on petroleum fraction


Freezing point: It is the temperature at which the hydrocarbon
liquid solidifies at atmospheric pressure. It is one of the important
property specifications for kerosene and jet fuels due to the low
temperatures encountered at high altitudes in jet planes.
Sediments: These are solid materials that are not soluble in the
hydrocarbon or water and can be comprised of sand, drilling
mud, rock or minerals, particles from erosion of metal pipes,
tanks, and other process equipments.
27
Separation processes


Generally, separation processes may be classified as
either mechanical-physical separation processes or mass
transfer operations.

o Mechanical-physical separation processes
(do not require a mass transfer gradient for the
separation)
o Mass transfer operations
(based on diffusion and require a mass transfer
gradient for the separation)
28
Separation processes


Examples of mechanical-physical separation processes
are:
Size reduction
Size enlargement (not crystallization)
Size separation (screening, etc.)
Filtration
Some and not all membrane separation processes
Sedimentation (Thickening and clarification)
Elutriation
Floatation
Centrifugation

29
Separation processes

Examples of mass transfer operations are:
Distillation
Drying
Liquid-liquid extraction
Leaching or lixiviation
Gas absorption
Membrane separation
(Not all membrane separation processes)
Humidification
Adsorption


30
Atmospheric distillation unit
(ADU)



What is distillation?

Why do we need distillation of
a crude oil?




31
Atmospheric distillation unit (ADU)[3]





32
Atmospheric distillation unit (ADU)






The column operates generally at a pressure greater than
atmospheric pressure. This may be done for pressure drop
considerations, to flow the vapors from one location to the
desired location, and/or cooling water to be used for the
overhead condenser. A higher pressure increases the
bubble point.

What is the criteria for setting pressure in the
overhead condenser (column)?

33
Atmospheric distillation unit (ADU)






Nearly 5060% of the crude oil is vaporized in the flash
zone of the tower [3].
A preflash tower is sometimes added before the
atmospheric column, if the crude oil contains appreciable
amounts of lighter products.
How is this advantageous?
The bottom temperature is bounded in the range of 700-
750 F [3]. This is done avoid cracking.
The superheated steam required to boil off the crude
bottoms is usually at about 600 F [3].
The steam consumption is usually 510 lb/bbl of
stripped product [3].
34
References

[1] Gary, J.H. and Handwerk, G.E. 2001. Petroleum refining:
Technology and economics. 4
th
ed. Marcel Dekker, Inc.
[2] Fahim, M.A., AlSahhaf, T.A. and Elkilani, A. 2010.
Fundamentals of petroleum refining. Elsevier.
[3] Parkash, S. 2003. Refining processes handbook. Gulf
professional publishing, Elsevier. Singapore.
[4] Wauquier, J.-P. (ed.). 1998. Petroleum refining: Separation
processes. Vol. 2. Technip.
[5] Myers, R.A. 2004. Handbook of petroleum refining
processes. 3
rd
ed. McGraw-Hill.
[6] Stan Jones, D.S.J. and Pujad, P.R. 2006. Handbook of
petroleum processing. Spinger.