27

A.SOLVENT EXTRACTION AND DEWAXING.

1.Description. Solvent treating is a widely used method of refining lubricating oils as
well as a host of other refinery stocks. Since distillation (fractionation) separates
petroleum products into groups only by their boiling-point ranges, impurities may
remain. These include organic compounds containing sulfur, nitrogen, and oxygen;
inorganic salts and dissolved metals; and soluble salts that were present in the crude
feedstock. In addition, kerosene and distillates may have trace amounts of aromatics and
naphthenes, and lubricating oil base-stocks may contain wax. Solvent refining processes
including solvent extraction and solvent dewaxing usually remove these undesirables at
intermediate refining stages or just before sending the product to storage.

2.Solvent Extraction.

a. The purpose of solvent extraction is to prevent corrosion, protect catalyst in
subsequent processes, and improve finished products by removing unsaturated, aromatic
hydrocarbons from lubricant and grease stocks. The solvent extraction process separates
aromatics, naphthenes, and impurities from the product stream by dissolving or
precipitation. The feedstock is first dried and then treated using a continuous
countercurrent solvent treatment operation. In one type of process, the feedstock is
washed with a liquid in which the substances to be removed are more soluble than in the
desired resultant product. In another process, selected solvents are added to cause
impurities to precipitate out of the product. In the adsorption process, highly porous solid
materials collect liquid molecules on their surfaces.
b. The solvent is separated from the product stream by heating, evaporation, or
fractionation, and residual trace amounts are subsequently removed from the raffinate by
steam stripping or vacuum flashing. Electric precipitation may be used for separation of
inorganic compounds. The solvent is then regenerated to be used again in the process.

c. The most widely used extraction solvents are phenol, furfural, and cresylic acid. Other
solvents less frequently used are liquid sulfur dioxide, nitrobenzene, and 2,2'-
dichloroethyl ether. The selection of specific processes and chemical agents depends on
the nature of the feedstock being treated, the contaminants present, and the finished
product requirements.
TABLE. SOLVENT EXTRACTION PROCESS
Feedstock From Process Typical products . . . To

Naphthas,
distillates,
kerosene
Atm.
tower
Treating/
blending
High octane gasoline . . Storage
Refined fuels . . . . . . . . Treating and blending
Spent agents . . . . . . . . Treatment and blending
28
FIGURE AROMATICS EXTRACTION







IV.Solvent Dewaxing. Solvent dewaxing is used to remove wax from either distillate or
residual basestocks at any stage in the refining process. There are several processes in use
for solvent dewaxing, but all have the same general steps, which are: (1) mixing the
feedstock with a solvent, (2) precipitating the wax from the mixture by chilling, and (3)
recovering the solvent from the wax and dewaxed oil for recycling by distillation and
steam stripping. Usually two solvents are used: toluene, which dissolves the oil and
maintains fluidity at low temperatures, and methyl ethyl ketone (MEK), which dissolves
little wax at low temperatures and acts as a wax precipitating agent. Other solvents that
are sometimes used include benzene, methyl isobutyl ketone, propane, petroleum
naphtha, ethylene dichloride, methylene chloride, and sulfur dioxide. In addition, there is
a catalytic process used as an alternate to solvent dewaxing.
29

TABLE SOLVENT DEWAXING PROCESS
Feedstock From Process Typical products . . To

Lube
basestock
Vacuum
tower
Treating Dewaxed lubes . . . . . Hydrotreating
Wax . . . . . . . . . . . . . Hydrotreating
Spent agents . . . . . . Treatment or recycle

FIGURE. SOLVENT DEWAXING


D. THERMAL CRACKING.
1. Description.

a. Because the simple distillation of crude oil produces amounts and types of products
that are not consistent with those required by the marketplace, subsequent refinery
processes change the product mix by altering the molecular structure of the
hydrocarbons. One of the ways of accomplishing this change is through "cracking," a
process that breaks or cracks the heavier, higher boiling-point petroleum fractions into
more valuable products such as gasoline, fuel oil, and gas oils. The two basic types of
cracking are thermal cracking, using heat and pressure, and catalytic cracking.


30
b. The first thermal cracking process was developed around 1913. Distillate fuels and
heavy oils were heated under pressure in large drums until they cracked into smaller
molecules with better antiknock characteristics. However, this method produced large
amounts of solid, unwanted coke. This early process has evolved into the following
applications of thermal cracking: visbreaking, steam cracking, and coking.
2. Visbreaking Process. Visbreaking, a mild form of thermal cracking, significantly
lowers the viscosity of heavy crude-oil residue without affecting the boiling point range.
Residual from the atmospheric distillation tower is heated (800-950 F) at atmospheric
pressure and mildly cracked in a heater. It is then quenched with cool gas oil to control
overcracking, and flashed in a distillation tower. Visbreaking is used to reduce the pour
point of waxy residues and reduce the viscosity of residues used for blending with lighter
fuel oils. Middle distillates may also be produced, depending on product demand. The
thermally cracked residue tar, which accumulates in the bottom of the fractionation
tower, is vacuum flashed in a stripper and the distillate recycled.
TABLE VISBREAKING PROCESS.
Feedstock From Process Typical products . . . . . To

Residual Atmospheric
tower &
Vacuum
tower
Decompose Gasoline or distillate . . Hydrotreating
Vapor . . . . . . . . . . . . Hydrotreater
Residue . . . . . . . . . . . Stripper or recycle
Gases . . . . . . . . . . . . Gas plant
FIGURE VISBREAKING.

3.
31
4. Steam Cracking Process. Steam cracking is a petrochemical process sometimes used
in refineries to produce olefinic raw materials (e.g., ethylene) from various feedstock for
petrochemicals manufacture. The feedstock range from ethane to vacuum gas oil, with
heavier feeds giving higher yields of by-products such as naphtha. The most common
feeds are ethane, butane, and naphtha. Steam cracking is carried out at temperatures of
1,500-1,600 F, and at pressures slightly above atmospheric. Naphtha produced from
steam cracking contains benzene, which is extracted prior to hydrotreating. Residual from
steam cracking is sometimes blended into heavy fuels.
1. Coking Processes. Coking is a severe method of thermal cracking used to upgrade
heavy residuals into lighter products or distillates. Coking produces straight-run gasoline
(coker naphtha) and various middle-distillate fractions used as catalytic cracking
feedstock. The process so completely reduces hydrogen that the residue is a form of
carbon called "coke." The two most common processes are delayed coking and
continuous (contact or fluid) coking. Three typical types of coke are obtained (sponge
coke, honeycomb coke, and needle coke) depending upon the reaction mechanism, time,
temperature, and the crude feedstock.

a. Delayed Coking. In delayed coking the heated charge (typically residuum from
atmospheric distillation towers) is transferred to large coke drums which provide the long
residence time needed to allow the cracking reactions to proceed to completion. Initially
the heavy feedstock is fed to a furnace which heats the residuum to high temperatures
(900-950 F) at low pressures (25-30 psi) and is designed and controlled to prevent
premature coking in the heater tubes. The mixture is passed from the heater to one or
more coker drums where the hot material is held approximately 24 hours (delayed) at
pressures of 25-75 psi, until it cracks into lighter products. Vapors from the drums are
returned to a fractionator where gas, naphtha, and gas oils are separated out. The heavier
hydrocarbons produced in the fractionator are recycled through the furnace. After the
coke reaches a predetermined level in one drum, the flow is diverted to another drum to
maintain continuous operation. The full drum is steamed to strip out uncracked
hydrocarbons, cooled by water injection, and decoked by mechanical or hydraulic
methods. The coke is mechanically removed by an auger rising from the bottom of the
drum. Hydraulic decoking consists of fracturing the coke bed with high-pressure water
ejected from a rotating cutter.

b. Continuous Coking. Continuous (contact or fluid) coking is a moving-bed process
that operates at temperatures higher than delayed coking. In continuous coking, thermal
cracking occurs by using heat transferred from hot, recycled coke particles to feedstock in
a radial mixer, called a reactor, at a pressure of 50 psi. Gases and vapors are taken from
the reactor, quenched to stop any further reaction, and fractionated. The reacted coke
enters a surge drum and is lifted to a feeder and classifier where the larger coke particles
are removed as product. The remaining coke is dropped into the preheater for recycling
with feedstock. Coking occurs both in the reactor and in the surge drum. The process is
automatic in that there is a continuous flow of coke and feedstock.

32
TABLE : COKING PROCESSES.
Feedstock From Process Typical products . . . To

Residual . . . . Atmospheric &
vacuum catalytic
cracker
Decompo-
sition
Naphtha, gasoline . . Distillation
column,blending
Clarified oil . .
Tars . . . . . .
Wasteater
(sour) . . . . .
Gases . . . . .
Catalytic cracker
Various units

Treatment
Gas plant
Coke . . . . . . . . . . . Shipping, recycle
Gas oil . . . . . . . . . . Catalytic cracking

FIGURE DELAYED COKING.

CATALYTIC CRACKING.
Description.
a. Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to
increase the quality and quantity of lighter, more desirable products and decrease the
amount of residuals. This process rearranges the molecular structure of hydrocarbon
compounds to convert heavy hydrocarbon feedstock into lighter fractions such as
kerosene, gasoline, LPG, heating oil, and petrochemical feedstock.

b. Catalytic cracking is similar to thermal cracking except that catalysts facilitate the
conversion of the heavier molecules into lighter products. Use of a catalyst (a material
that assists a chemical reaction but does not take part in it) in the cracking reaction
increases the yield of improved-quality products under much less severe operating
conditions than in thermal cracking. Typical temperatures are from 850-950 F at much
lower pressures of 10-20 psi. The catalysts used in refinery cracking units are typically
solid materials (zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth,
bauxite, and silica-alumina) that come in the form of powders, beads, pellets or shaped
33
materials called extrudites.

c. There are three basic functions in the catalytic cracking process:
1. Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons;
2. Regeneration: Catalyst is reactivated by burning off coke; and
3. Fractionation: Cracked hydrocarbon stream is separated into various products.

d. The three types of catalytic cracking processes are fluid catalytic cracking (FCC),
moving-bed catalytic cracking, and Thermofor catalytic cracking (TCC). The catalytic
cracking process is very flexible, and operating parameters can be adjusted to meet
changing product demand. In addition to cracking, catalytic activities include
dehydrogenation, hydrogenation, and isomerization.
TABLE: CATALYTIC CRACKING PROCESS
Feedstock From Process Typical products . . . . To

Gas oils . . . . Towers, coker
visbreaker
Decomposition,
alteration
Gasoline . . . . . . . . . Treater or blend
Gases . . . . . . . . . . Gas plant
Deasphalted
oils . . . . . . .

Deasphalter
Middle distillates . . .Hydrotreat, blend, or recycle
Petrochem feedstock . . Petrochem or other
Residue . . . . . . . . . . . Residual fuel blend
E. FLUID CATALYTIC CRACKING.
1. Description.

a. The most common process is FCC, in which the oil is cracked in the presence of a
finely divided catalyst which is maintained in an aerated or fluidized state by the oil
vapors. The fluid cracker consists of a catalyst section and a fractionating section that
operate together as an integrated processing unit. The catalyst section contains the reactor
and regenerator, which, with the standpipe and riser, forms the catalyst circulation unit.
The fluid catalyst is continuously circulated between the reactor and the regenerator using
air, oil vapors, and steam as the conveying media.

b. A typical FCC process involves mixing a preheated hydrocarbon charge with hot,
regenerated catalyst as it enters the riser leading to the reactor. The charge is combined
with a recycle stream within the riser, vaporized, and raised to reactor temperature (900-
1,000 F) by the hot catalyst. As the mixture travels up the riser, the charge is cracked at
10-30 psi. In the more modern FCC units, all cracking takes place in the riser. The
"reactor" no longer functions as a reactor; it merely serves as a holding vessel for the
cyclones. This cracking continues until the oil vapors are separated from the catalyst in
the reactor cyclones. The resultant product stream (cracked product) is then charged to a
fractionating column where it is separated into fractions, and some of the heavy oil is
34
recycled to the riser.

c. Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the
process. Spent catalyst flows through the catalyst stripper to the regenerator, where most
of the coke deposits burn off at the bottom where preheated air and spent catalyst are
mixed. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking
process.
FIGURE : FLUID CATALYTIC CRACKING.

2. Moving Bed Catalytic Cracking. The moving-bed catalytic cracking process is
similar to the FCC process. The catalyst is in the form of pellets that are moved
continuously to the top of the unit by conveyor or pneumatic lift tubes to a storage
hopper, then flow downward by gravity through the reactor, and finally to a regenerator.
The regenerator and hopper are isolated from the reactor by steam seals. The cracked
product is separated into recycle gas, oil, clarified oil, distillate, naphtha, and wet gas.
3. Thermofor Catalytic Cracking. In a typical thermofor catalytic cracking unit, the
preheated feedstock flows by gravity through the catalytic reactor bed. The vapors are
separated from the catalyst and sent to a fractionating tower. The spent catalyst is
regenerated, cooled, and recycled. The flue gas from regeneration is sent to a carbon-
monoxide boiler for heat recovery.
F. HYDROCRACKING.
1. Description.

a. Hydrocracking is a two-stage process combining catalytic cracking and
hydrogenation, wherein heavier feedstocks are cracked in the presence of hydrogen to
produce more desirable products. The process employs high pressure, high temperature, a
35
catalyst, and hydrogen. Hydrocracking is used for feedstocks that are difficult to process
by either catalytic cracking or reforming, since these feedstocks are characterized usually
by a high polycyclic aromatic content and/or high concentrations of the two principal
catalyst poisons, sulfur and nitrogen compounds.

b. The hydrocracking process largely depends on the nature of the feedstock and the
relative rates of the two competing reactions, hydrogenation and cracking. Heavy
aromatic feedstock is converted into lighter products under a wide range of very high
pressures (1,000-2,000 psi) and fairly high temperatures (750-1,500 F), in the presence
of hydrogen and special catalysts. When the feedstock has a high paraffinic content, the
primary function of hydrogen is to prevent the formation of polycyclic aromatic
compounds. Another important role of hydrogen in the hydrocracking process is to
reduce tar formation and prevent buildup of coke on the catalyst. Hydrogenation also
serves to convert sulfur and nitrogen compounds present in the feedstock to hydrogen
sulfide and ammonia.

c. Hydrocracking produces relatively large amounts of isobutane for alkylation
feedstock. Hydrocracking also performs isomerization for pour-point control and smoke-
point control, both of which are important in high-quality jet fuel.
2. Hydrocracking Process.

a. In the first stage, preheated feedstock is mixed with recycled hydrogen and sent to the
first-stage reactor, where catalysts convert sulfur and nitrogen compounds to hydrogen
sulfide and ammonia. Limited hydrocracking also occurs.

b. After the hydrocarbon leaves the first stage, it is cooled and liquefied and run through
a hydrocarbon separator. The hydrogen is recycled to the feedstock. The liquid is charged
to a fractionator. Depending on the products desired (gasoline components, jet fuel, and
gas oil), the fractionator is run to cut out some portion of the first stage reactor out-turn.
Kerosene-range material can be taken as a separate side-draw product or included in the
fractionator bottoms with the gas oil.

c. The fractionator bottoms are again mixed with a hydrogen stream and charged to the
second stage. Since this material has already been subjected to some hydrogenation,
cracking, and reforming in the first stage, the operations of the second stage are more
severe (higher temperatures and pressures). Like the outturn of the first stage, the second
stage product is separated from the hydrogen and charged to the fractionator.
36

TABLE HYDROCRACKING PROCESS.
Feedstock From Process Typical products . . . . To

High pour
point
Catalytic
cracker,
atmospheric
& vacuum
tower
Decomposition,
hydrogenation
Kerosene, jet fuel . . . .Blending
Gas oil Vacuum
tower,
coker
Gasoline, distillates . . Blending
Hydrogen Reformer Recycle, reformer gas . . Gas plant

FIGURE : TWO-STAGE HYDROCRACKING.



37
F. CATALYTIC REFORMING.
1. Description.

a. Catalytic reforming is an important process used to convert low-octane naphthas into
high-octane gasoline blending components called reformates. Reforming represents the
total effect of numerous reactions such as cracking, polymerization, dehydrogenation,
and isomerization taking place simultaneously. Depending on the properties of the
naphtha feedstock (as measured by the paraffin, olefin, naphthene, and aromatic content)
and catalysts used, reformates can be produced with very high concentrations of toluene,
benzene, xylene, and other aromatics useful in gasoline blending and petrochemical
processing. Hydrogen, a significant by-product, is separated from the reformate for
recycling and use in other processes.

b. A catalytic reformer comprises a reactor section and a product-recovery section. More
or less standard is a feed preparation section in which, by combination of hydrotreatment
and distillation, the feedstock is prepared to specification. Most processes use platinum as
the active catalyst. Sometimes platinum is combined with a second catalyst (bimetallic
catalyst) such as rhenium or another noble metal.

c. There are many different commercial catalytic reforming processes including
platforming, powerforming, ultraforming, and Thermofor catalytic reforming. In the
platforming process, the first step is preparation of the naphtha feed to remove impurities
from the naphtha and reduce catalyst degradation. The naphtha feedstock is then mixed
with hydrogen, vaporized, and passed through a series of alternating furnace and fixed-
bed reactors containing a platinum catalyst. The effluent from the last reactor is cooled
and sent to a separator to permit removal of the hydrogen-rich gas stream from the top of
the separator for recycling. The liquid product from the bottom of the separator is sent to
a fractionator called a stabilizer (butanizer). It makes a bottom product called reformate;
butanes and lighter go overhead and are sent to the saturated gas plant.

d. Some catalytic reformers operate at low pressure (50-200 psi), and others operate at
high pressures (up to 1,000 psi). Some catalytic reforming systems continuously
regenerate the catalyst in other systems. One reactor at a time is taken off-stream for
catalyst regeneration, and some facilities regenerate all of the reactors during
turnarounds.
G. CATALYTIC HYDROTREATING.
1. Description. Catalytic hydrotreating is a hydrogenation process used to remove about
90% of contaminants such as nitrogen, sulfur, oxygen, and metals from liquid petroleum
fractions. These contaminants, if not removed from the petroleum fractions as they travel
through the refinery processing units, can have detrimental effects on the equipment, the
catalysts, and the quality of the finished product. Typically, hydrotreating is done prior to
processes such as catalytic reforming so that the catalyst is not contaminated by untreated
feedstock. Hydrotreating is also used prior to catalytic cracking to reduce sulfur and
improve product yields, and to upgrade middle-distillate petroleum fractions into finished
38
kerosene, diesel fuel, and heating fuel oils. In addition, hydrotreating converts olefins and
aromatics to saturated compounds.
2. Catalytic Hydrodesulfurization Process. Hydrotreating for sulfur removal is called
hydrodesulfurization. In a typical catalytic hydrodesulfurization unit, the feedstock is
deaerated and mixed with hydrogen, preheated in a fired heater (600-800 F) and then
charged under pressure (up to 1,000 psi) through a fixed-bed catalytic reactor. In the
reactor, the sulfur and nitrogen compounds in the feedstock are converted into H
2
S and
NH
3
. The reaction products leave the reactor and after cooling to a low temperature enter
a liquid/gas separator. The hydrogen-rich gas from the high-pressure separation is
recycled to combine with the feedstock, and the low-pressure gas stream rich in H
2
S is
sent to a gas treating unit where H
2
S is removed. The clean gas is then suitable as fuel for
the refinery furnaces. The liquid stream is the product from hydrotreating and is normally
sent to a stripping column for removal of H
2
S and other undesirable components. In cases
where steam is used for stripping, the product is sent to a vacuum drier for removal of
water. Hydrodesulfurized products are blended or used as catalytic reforming feedstock.
3. Other Hydrotreating Processes.

a. Hydrotreating processes differ depending upon the feedstock available and catalysts
used. Hydrotreating can be used to improve the burning characteristics of distillates such
as kerosene. Hydrotreatment of a kerosene fraction can convert aromatics into
naphthenes, which are cleaner-burning compounds.

b. Lube-oil hydrotreating uses catalytic treatment of the oil with hydrogen to improve
product quality. The objectives in mild lube hydrotreating include saturation of olefins
and improvements in color, odor, and acid nature of the oil. Mild lube hydrotreating also
may be used following solvent processing. Operating temperatures are usually below
600 F and operating pressures below 800 psi. Severe lube hydrotreating, at temperatures
in the 600-750 F range and hydrogen pressures up to 3,000 psi, is capable of saturating
aromatic rings, along with sulfur and nitrogen removal, to impart specific properties not
achieved at mild conditions.

c. Hydrotreating also can be employed to improve the quality of pyrolysis gasoline
(pygas), a by-product from the manufacture of ethylene. Traditionally, the outlet for
pygas has been motor gasoline blending, a suitable route in view of its high octane
number. However, only small portions can be blended untreated owing to the
unacceptable odor, color, and gum-forming tendencies of this material. The quality of
pygas, which is high in diolefin content, can be satisfactorily improved by hydrotreating,
whereby conversion of diolefins into mono-olefins provides an acceptable product for
motor gas blending.
39

TABLE : HYDRODESULFURIZATION PROCESS
Feedstock From Process Typical products . . To

Naphthas,
distillates
sour gas
oil,
residuals
Atmospheric
& vacuum
tower,
catalytic &
thermal
cracker
Treating,
hydrogenation
Naphtha . . . . . . . Blending
Hydrogen . . . . . . Recycle
Distillates . . . . . . Blending
H
2
S, ammonia . . Sulfure plant, treater
Gas . . . . . . . . . . Gas plant


FIGURE DISTILLATE HYDRODESULFURIZATION.

1. Description.

a. Isomerization converts n-butane, n-pentane and n-hexane into their respective
isoparaffins of substantially higher octane number. The straight-chain paraffins are
converted to their branched-chain counterparts whose component atoms are the same but
are arranged in a different geometric structure. Isomerization is important for the
conversion of n-butane into isobutane, to provide additional feedstock for alkylation
units, and the conversion of normal pentanes and hexanes into higher branched isomers
for gasoline blending. Isomerization is similar to catalytic reforming in that the
hydrocarbon molecules are rearranged, but unlike catalytic reforming, isomerization just
converts normal paraffins to isoparaffins.

b. There are two distinct isomerization processes, butane (C
4
) and pentane/hexane
(C
5
/C
6
). Butane isomerization produces feedstock for alkylation. Aluminum chloride
catalyst plus hydrogen chloride are universally used for the low-temperature processes.
40
Platinum or another metal catalyst is used for the higher-temperature processes. In a
typical low-temperature process, the feed to the isomerization plant is n-butane or mixed
butanes mixed with hydrogen (to inhibit olefin formation) and passed to the reactor at
230-340 F and 200-300 psi. Hydrogen is flashed off in a high-pressure separator and
the hydrogen chloride removed in a stripper column. The resultant butane mixture is sent
to a fractionator (deisobutanizer) to separate n-butane from the isobutane product.

c. Pentane/hexane isomerization increases the octane number of the light gasoline
components n-pentane and n-hexane, which are found in abundance in straight-run
gasoline. In a typical C
5
/C
6
isomerization process, dried and desulfurized feedstock is
mixed with a small amount of organic chloride and recycled hydrogen, and then heated to
reactor temperature. It is then passed over supported-metal catalyst in the first reactor
where benzene and olefins are hydrogenated. The feed next goes to the isomerization
reactor where the paraffins are catalytically isomerized to isoparaffins. The reactor
effluent is then cooled and subsequently separated in the product separator into two
streams: a liquid product (isomerate) and a recycle hydrogen-gas stream. The isomerate is
washed (caustic and water), acid stripped, and stabilized before going to storage.
TABLE ISOMERIZATION PROCESSES
Feedstock From Process Typical products . . . To

n-Butane Rearrangement Isobutane . . . . . . . Alkylation
n-Pentane Isopentane . . . . . . Blending
n-Hexane
Various
Processes
Isohexane . . . . . . . Blending
Gas . . . . . . . . . . . Gas Plant
41

FIGURE. C
4
ISOMERIZATION.


42
FIGURE C
5
AND C
6
ISOMERIZATION.



POLYMERIZATION.
Description.

a. Polymerization in the petroleum industry is the process of converting light olefin gases
including ethylene, propylene, and butylene into hydrocarbons of higher molecular
weight and higher octane number that can be used as gasoline blending stocks.
Polymerization combines two or more identical olefin molecules to form a single
molecule with the same elements in the same proportions as the original molecules.
Polymerization may be accomplished thermally or in the presence of a catalyst at lower
temperatures.

b. The olefin feedstock is pretreated to remove sulfur and other undesirable compounds.
In the catalytic process the feedstock is either passed over a solid phosphoric acid catalyst
or comes in contact with liquid phosphoric acid, where an exothermic polymeric reaction
occurs. This reaction requires cooling water and the injection of cold feedstock into the
reactor to control temperatures between 300 and 450 F at pressures from 200 psi to
1,200 psi. The reaction products leaving the reactor are sent to stabilization and/or
fractionator systems to separate saturated and unreacted gases from the polymer gasoline
product.
43

NOTE: In the petroleum industry, polymerization is used to indicate the production of
gasoline components, hence the term "polymer" gasoline. Furthermore, it is not essential
that only one type of monomer be involved. If unlike olefin molecules are combined, the
process is referred to as "copolymerization." Polymerization in the true sense of the word
is normally prevented, and all attempts are made to terminate the reaction at the dimer or
trimer (three monomers joined together) stage. However, in the petrochemical section of
a refinery, polymerization, which results in the production of, for instance, polyethylene,
is allowed to proceed until materials of the required high molecular weight have been
produced
TABLE POLYMERIZATION PROCESS

Feedstock From Process Typical products . . . . . . To

Olefins Cracking
processes
Unification High octane naphtha . . Gasoline blending
Petrochem. feedstock . . Petrochemical
Liquefied petro. gas . . . Storage
FIGURE. POLYMERIZATION PROCESS.

ALKYLATION.
1. Description. Alkylation combines low-molecular-weight olefins (primarily a
mixture of propylene and butylene) with isobutene in the presence of a catalyst,
either sulfuric acid or hydrofluoric acid. The product is called alkylate and is
composed of a mixture of high-octane, branched-chain paraffinic hydrocarbons.
44
Alkylate is a premium blending stock because it has exceptional antiknock
properties and is clean burning. The octane number of the alkylate depends
mainly upon the kind of olefins used and upon operating conditions.
2. Sulfuric Acid Alkylation Process.

a. In cascade type sulfuric acid (H
2
SO
4
) alkylation units, the feedstock
(propylene, butylene, amylene, and fresh isobutane) enters the reactor and
contacts the concentrated sulfuric acid catalyst (in concentrations of 85% to 95%
for good operation and to minimize corrosion). The reactor is divided into zones,
with olefins fed through distributors to each zone, and the sulfuric acid and
isobutanes flowing over baffles from zone to zone.

b. The reactor effluent is separated into hydrocarbon and acid phases in a settler,
and the acid is returned to the reactor. The hydrocarbon phase is hot-water washed
with caustic for pH control before being successively depropanized,
deisobutanized, and debutanized. The alkylate obtained from the deisobutanizer
can then go directly to motor-fuel blending or be rerun to produce aviation-grade
blending stock. The isobutane is recycled to the feed.
3. Hydrofluoric Acid Alylation Process. Phillips and UOP are the two common
types of hydrofluoric acid alkylation processes in use. In the Phillips process,
olefin and isobutane feedstock are dried and fed to a combination reactor/settler
system. Upon leaving the reaction zone, the reactor effluent flows to a settler
(separating vessel) where the acid separates from the hydrocarbons. The acid
layer at the bottom of the separating vessel is recycled. The top layer of
hydrocarbons (hydrocarbon phase), consisting of propane, normal butane,
alkylate, and excess (recycle) isobutane, is charged to the main fractionator, the
bottom product of which is motor alkylate. The main fractionator overhead,
consisting mainly of propane, isobutane, and HF, goes to a depropanizer. Propane
with trace amount of HF goes to an HF stripper for HF removal and is then
catalytically defluorinated, treated, and sent to storage. Isobutane is withdrawn
from the main fractionator and recycled to the reactor/settler, and alkylate from
the bottom of the main fractionator is sent to product blending.
4. The UOP process uses two reactors with separate settlers. Half of the dried
feedstock is charged to the first reactor, along with recycle and makeup isobutane.
The reactor effluent then goes to its settler, where the acid is recycled and the
hydrocarbon charged to the second reactor. The other half of the feedstock also
goes to the second reactor, with the settler acid being recycled and the
hydrocarbons charged to the main fractionator. Subsequent processing is similar
to the Phillips process. Overhead from the main fractionator goes to a
depropanizer. Isobutane is recycled to the reaction zone and alkylate is sent to
product blending.
45

TABLE. ALKYLATION PROCESS
Feedstock From Process Typical products . . . . To

Petroleum
gas
Distillation
or cracking
Unification High octane gasoline . . Blending
Olefins Cat. or hydro
cracking
n-Butane & propane . . . Stripper or blender
Isobutane Isomerization


FIGURE SULFURIC ACID ALKYLATION.


FIGURE HYDROGEN FLUORIDE ALKYLATION.



46
SWEETENING AND TREATING PROCESSES
1.Description.
a. Treating is a means by which contaminants such as organic compounds containing
sulfur, nitrogen, and oxygen; dissolved metals and inorganic salts; and soluble salts
dissolved in emulsified water are removed from petroleum fractions or streams.Petroleum
refiners have a choice of several different treating processes, but the primary purpose of
the majority of them is the elimination of unwanted sulfur compounds. A variety of
intermediate and finished products, including middle distillates, gasoline, kerosene, jet
fuel, and sour gases are dried and sweetened. Sweetening, a major refinery treatment of
gasoline, treats sulfur compounds (hydrogen sulfide, thiophene and mercaptan) to
improve color, odor, and oxidation stability. Sweetening also reduces concentrations of
carbon dioxide.

b. Treating can be accomplished at an intermediate stage in the refining process, or just
before sending the finished product to storage. Choices of a treating method depend on
the nature of the petroleum fractions, amount and type of impurities in the fractions to be
treated, the extent to which the process removes the impurities, and end-product
specifications. Treating materials include acids, solvents, alkalis, oxidizing, and
adsorption agents.
2.Acid, Caustic, or Clay Treating. Sulfuric acid is the most commonly used acid
treating process. Sulfuric acid treating results in partial or complete removal of
unsaturated hydrocarbons, sulfur, nitrogen, and oxygen compounds, and resinous and
asphaltic compounds. It is used to improve the odor, color, stability, carbon residue, and
other properties of the oil. Clay/lime treatment of acid-refined oil removes traces of
asphaltic materials and other compounds improving product color, odor, and stability.
Caustic treating with sodium (or potassium) hydroxide is used to improve odor and color
by removing organic acids (naphthenic acids, phenols) and sulfur compounds
(mercaptans, H
2
S) by a caustic wash. By combining caustic soda solution with various
solubility promoters (e.g., methyl alcohol and cresols), up to 99% of all mercaptans as
well as oxygen and nitrogen compounds can be dissolved from petroleum fractions.
3.Drying and Sweetening. Feed stocks from various refinery units are sent to gas
treating plants where butanes and butenes are removed for use as alkylation feedstock,
heavier components are sent to gasoline blending, propane is recovered for LPG, and
propylene is removed for use in petrochemicals. Some mercaptans are removed by water-
soluble chemicals that react with the mercaptans. Caustic liquid (sodium hydroxide),
amine compounds (diethanolamine) or fixed-bed catalyst sweetening also may be used.
Drying is accomplished by the use of water absorption or adsorption agents to remove
water from the products. Some processes simultaneously dry and sweeten by adsorption
on molecular sieves.
47
FIGURE MOLECULAR SIEVE DRYING AND SWEETENING.

7. Sulfur Recovery. Sulfur recovery converts hydrogen sulfide in sour gases and
hydrocarbon streams to elemental sulfur. The most widely used recovery system is the
Claus process, which uses both thermal and catalytic-conversion reactions. A typical
process produces elemental sulfur by burning hydrogen sulfide under controlled
conditions. Knockout pots are used to remove water and hydrocarbons from feed gas
streams. The gases are then exposed to a catalyst to recover additional sulfur. Sulfur
vapor from burning and conversion is condensed and recovered.
8. Hydrogen Sulfide Scrubbing. Hydrogen sulfide scrubbing is a common treating
process in which the hydrocarbon feedstock is first scrubbed to prevent catalyst
poisoning. Depending on the feedstock and the nature of contaminants, desulfurization
methods vary from ambient temperature-activated charcoal absorption to high-
temperature catalytic hydrogenation followed by zinc oxide treating.