VALERO ENERGY,

BENICIA
-ONKAR KOTPALLIWAR

SHIVAM SINGH
VALERO ENERGY
OVERVIEW

2
VALERO ENERGY CORPORATION

• Valero Energy Corporation is a Fortune 500 international manufacturer and

marketer of transportation fuels, other petrochemical products, and power. It is
headquartered in San Antonio, Texas, United States.
• Valero was created on January 1, 1980.
• Largest independent refiner in North America
– 16 refineries throughout the United States, Canada, and United Kingdom
– 3 million barrels per day (BPD) of capacity
– Refineries geographically diversified among four key regions
• One of the USA’s largest retail fuel marketers with nearly 6,800 branded
marketing sites
– Company‐owned/operated sites: approximately 1,000 in U.S. and 400 in
Canada including leased sites

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• One of the largest ethanol companies in U.S.
– 11 large‐capacity plants with total of 1.2 billion gallons/year (78,000 BPD) of
production capacity
– All plants located in resource‐advantaged corn belt
• Other investments in alternative energy
– 50 megawatt wind farm in Texas Panhandle
– Seed investments in next generation ethanol and biodiesel
• Approximately 10,015 employees

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Valero’s Geographically Diverse Operations

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BENICIA REFINERY

• The Benicia Refinery is an oil refinery located near the San Francisco Bay Area city
of Benicia, California. Located on 800 acres on the Carquinez Strait, a tributary of
San Francisco Bay
• The refinery was built in 1968 for ExxonMobil. Valero purchased the property in
2000.

• Currently, the refinery processes domestic crude from the San Joaquin Valley in
California and the Alaska North Slope, along with foreign sour crudes.
• Total feedstock throughput capacity of 170,000 barrels per day
• Strategic position allowing refinery to receive feedstocks by both ship and
pipeline

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• Products include propane, butane, CARB gasoline, ultra-low-sulfur diesel (ULSD),
jet fuel, fuel oil, residual oil and asphalt
• Approximately 70 percent of the refinery’s product slate is California Air
Resources Board (CARB) gasoline, California’s clean-burning fuel i.e. without lead
& methyl-tertiary-butyl-ether.

• The refinery also has significant asphalt production capabilities and produces 35
percent of the asphalt supply in northern California.
• Produces 10 percent of the clean-burning CARB gasoline used in California and
25 percent of the CARB used in the San Francisco Bay Area
• Employs approximately 480 personnel

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BENICIA FEEDSTOCKS

 Crude slate includes Alaska North Slope (ANS), San Joaquin Valley (SJV) and
a wide variety of other crudes
• 80% received by ship across Refinery docks
• 20% received by pipeline
 Shifting crude slate
• When acquired in 2000, 80% of Benicia’s crude was ANS
• Today, less than 40% ANS
 Versatile, high-conversion facility with ability to process heavy, sour crudes
• 35% heavy sour, 47% medium/light sour, 2% acidic sweet, 16% other
 Capable of processing imported intermediate feedstocks
 Primary utilities used include natural gas, electric power and fresh water

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PROCESS
OVERVIEW

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BASIC REFINING CONCEPTS
Intermediates Final Products
< 90°F Propane, Butane and • Refinery fuel gas
C1 to C4 lighter • Propane
• NGLs
90–220°F Straight Run More
Gasoline (low • Gasoline (high octane)
C5 to C8 processing
octane)
Crude oil
220–315°F More • Gasoline (high octane)
Naphtha
Distillation C8 to C12 processing • Jet fuel
Tower
(Crude • Kerosene
Unit) 315–450°F More • Jet fuel
Kerosene
C12 to C30 processing • Diesel
• Fuel oil

More • Gasoline (high octane)

450–650°F Light Gas Oil
Furnace • Diesel
processing
C30 to C50+ • Fuel oil

More • Gasoline (high octane)

650–800°F Heavy Gas Oil • Diesel
Vacuum C 30 to C50+ processing • Fuel oil
Unit
• Gasoline (high octane)
800+°F Residual Fuel More • Diesel
Oil/Asphalt processing • Fuel oil
C50 to C100+
• Lube stocks 22
BENICIA REFINERY FLOW DIAGRAM

Fuel Gas
Propane
Propane
Off Gas Light Ends Dimersol
Butane 5 MBPD
5MBPD Gasoline

LPG

Naphtha
Naphtha/Jet Naphtha
Hydrotreaters
Jet Fuel/Kero 45.3 MBPD
Alkylation Gasoline
Isobutane
20 MBPD
20MBPD
Jet Fuel/Kero
Refinery
Crude Crude
Crude
Gas Oil P/P
Distillation
Distillation
Asphalt Gas Oil
FCCU B -B
134
134 MBPD
MBPD Gas Oil Hydrogen
72 MBPD Gasoline
Catalytic
LPG
Reformer
FCC Feed
FCCFeed Slurry 35 MBPD
35MBPD
Hydrotreater Gasoline
39 MBPD
39 MBPD
ULSD ULSD
LPG
ATBs Diesel 16 MBPD

Naphtha

Gas Oil Gas Oil Hydrocracker Gasoline

Vacuum
Distillation Naphtha/Diesel 36 MBPD
72 MBPD
MBPD Diesel
72
Coker
Resid 28 MBPD FCC
Gasoline
Low Sulfur Gasoline
Hydrotreater
45 MBPD
Coke 11
REFINING PROCESS

• Crude pre-treatment: Preparation of crude oil for distillation.

• Fractionation (distillation) is the separation of crude oil in atmospheric and
vacuum distillation towers into groups of hydrocarbon compounds of differing
boiling-point ranges called "fractions“.

• Conversion Processes change the size and/or structure of hydrocarbon molecules.

These processes include:
– Decomposition (dividing) by thermal and catalytic cracking;
– Unification (combining) through alkylation and polymerization; and

– Alteration (rearranging) with isomerization and catalytic reforming.

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• Treatment Processes: To prepare hydrocarbon streams for additional processing
and to prepare finished products. Treatment includes removal or separation of
aromatics and naphthenes, impurities and undesirable contaminants. It involves
chemical or physical separation e.g. dissolving, absorption, or precipitation using
a variety and combination of processes including drying, hydro-desulfurizing,
solvent refining, sweetening, solvent extraction, and solvent dewaxing.
• Formulating and Blending is the process of mixing and combining hydrocarbon
fractions, additives, and other components to produce finished products with
specific performance properties.

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OUTLINE

1. Crude Characteristics
2. Crude Pre-treatment
3. Physical Processes (Distillation)
4. Thermal Processes (Delayed Coking)
5. Catalytic Processes (FCC, Dimersol, Hydrotreating, Catalytic Reforming,
Alkylation)
6. Blending

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CRUDE OIL CHARACHTERISTICS

 Crudes are classified and priced by density and sulfur content

 Crude density is commonly measured by API gravity
• API gravity provides a relative measure of crude oil density
• The higher the API number, the lighter the crude
 Light crudes are easier to process
 Heavy crudes are more difficult to process
 Crude sulfur content is measured as a percentage
• Less than 0.7% sulfur content = sweet
• Greater than 0.7% sulfur content = sour
• High sulfur crudes require additional processing to meet regulatory specs
 Acid content is measured by Total Acid Number (TAN)
• Acidic crudes highly corrosive to refinery equipment
• High acid crudes are those with TAN greater than 0.7
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PRETREATMENT OF CRUDE OIL

• Crude oil often contains water, inorganic salts, suspended solids, and water-
soluble trace metals. STEP 0 in the refining process is to remove these
contaminants so as to reduce corrosion, plugging, and fouling of equipment and
to prevent poisoning catalysts in processing units.
• PRETREATMENT TAKES PLACE IN TWO WAYS:
– Field separation
– Crude desalting
• Field separation is the first step to remove the gases, water and dirt that
accompany crude oil coming from the ground. The field separator is often no
more than a large vessel, which gives a quieting zone to permit gravity separation
of three phases: gases, crude oil and water (with entrained dirt).

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• The two most typical methods of crude-oil desalting are chemical and
electrostatic separation, and both use hot water as the extraction agent.
• In chemical desalting, water and chemical surfactant are added to the crude,
which is heated so that salts and other impurities dissolve or attach to the water,
then held in a tank to settle out.

• Electrical desalting is the application of high-voltage electrostatic charges to

concentrate suspended water globules in the bottom of the settling tank.
Surfactants are added only when the crude has a large amount of suspended
solids

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PHYSICAL
PROCESS

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DISTILLATION

• Distillation is defined as:

– a process in which a liquid or vapor mixture of two or more substances
is separated into its component fractions of desired purity, by the application and
removal of heat.
• Distillation is the most common separation technique and it consumes enormous
amounts of energy, both in terms of cooling and heating requirements.
• Distillation can contribute to more than 50% of plant operating costs.
• STEP 1 in the refining process is the separation of crude oil into various fractions
or straight-run cuts by distillation in atmospheric (crude) and vacuum towers. The
main fractions or "cuts" obtained have specific boiling point ranges and can be
classified in order of decreasing volatility into gases, light distillates, middle
distillates, gas oils, and residuum.

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CRUDE DISTILLATION UNIT

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ATMOSPHERIC DISTILLATION

• The desalted crude feedstock is preheated using recovered process heat. The
feedstock then flows to a direct-fired crude charge heater then into the vertical
distillation column just above the bottom, at pressures slightly above
atmospheric and at temperatures ranging from 340-370°C (above these
temperatures undesirable thermal cracking may occur). All but the heaviest
fractions flash into vapor.
• As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil or
asphalt residue is taken from the bottom. At successively higher points on the
tower, the various major products including lubricating oil, heating oil, kerosene,
gasoline, and uncondensed gases (which condense at lower temperatures) are
drawn off.

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VACUUM DISTILLATION

• To further distill the residuum or topped crude from the atmospheric tower
without thermal cracking, reduced pressure is required. The process takes place
in one or more vacuum distillation towers.
• The principles of vacuum distillation resemble those of fractional distillation
except that larger diameter columns are used to maintain comparable vapor
velocities at the reduced pressures.

• A typical vacuum tower may produce gas oils, lubricating oil base stocks, and
heavy residual for propane deasphalting. While, tower operating at lower
vacuum may distill surplus residuum from the atmospheric tower, which is not
used for lube-stock processing, and surplus residuum from the first vacuum
tower not used for deasphalting.
• Vacuum towers are typically used to separate catalytic cracking feedstock from
surplus residuum. 22
THERMAL
PROCESSES

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DELAYED COKING

• 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 completely
reduces hydrogen so that the residue is a form of carbon called "coke."
• 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.
• Heavy feedstock is fed to a fractionator.

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• The bottoms of the fractionator are fed to cooker drums via a furnace where the
hot material (440°-500°C ) is held approximately 24 hours (delayed) at pressures
of 2-5 bar, 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 de-coked 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. 26
BENICIA REFINERY FLOW DIAGRAM

Fuel Gas
Propane
Propane
Off Gas Light Ends Dimersol
Butane 5 MBPD
5MBPD Gasoline

LPG

Naphtha
Naphtha/Jet Naphtha
Hydrotreaters
Jet Fuel/Kero 45.3 MBPD
Alkylation Gasoline
Isobutane
20 MBPD
20MBPD
Jet Fuel/Kero
Refinery
Crude Crude
Crude
Gas Oil P/P
Distillation
Distillation
Asphalt Gas Oil
FCCU B -B
134
134 MBPD
MBPD Gas Oil Hydrogen
72 MBPD Gasoline
Catalytic
LPG
Reformer
FCC Feed
FCCFeed Slurry 35 MBPD
35MBPD
Hydrotreater Gasoline
39 MBPD
39 MBPD
ULSD ULSD
LPG
ATBs Diesel 16 MBPD

Naphtha

Gas Oil Gas Oil Hydrocracker Gasoline

Vacuum
Distillation Naphtha/Diesel 36 MBPD
72 MBPD
MBPD Diesel
72
Coker
Resid 28 MBPD FCC
Gasoline
Low Sulfur Gasoline
Hydrotreater
45 MBPD
Coke 27
CATALYTIC
PROCESSES

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CATALYTIC CRACKING

• Main incentive for catalytic cracking is the need to increase gasoline production.
Its feedstocks are typically vacuum gas oil.
• Cracking is catalyzed by solid acids which promote the rupture of C-C bonds. The
crucial intermediates are carbocations (+ve charged HC ions) formed by the
action of the acid sites on the catalyst.

• Besides C-C cleavage many other reactions occur:- isomerization, protonation

and deprotonation, alkylation, polymerization, cyclization and condensation.
• Catalytic cracking comprises a complex network of reactions, both intra-
molecular and inter-molecular.
• The formation of coke is an essential feature of the cracking process & this coke
deactivates the catalyst.

• Catalytic cracking was the first large-scale application of fluidized beds which
explains the name fluid catalytic cracking (FCC). 29
FLUID CATALYTIC CRACKING

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FLUID CATALYTIC CRACKING

• 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, form 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.
• Preheated feed is mixed with hot, regenerated catalyst in the riser and combined
with a recycle stream, vaporized, and raised to reactor temperature (485-540°C)
by the hot catalyst.
• As the mixture travels up the riser, the charge is cracked at 0.7-2 bar.
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• In modern FCC units, all cracking takes place in the riser and the "reactor" merely
serves as a holding vessel for the cyclones. Cracked product is then charged to a
fractionating column where it is separated into fractions, and some of the heavy
oil is recycled to the riser.
• 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.

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BENICIA REFINERY FLOW DIAGRAM

Fuel Gas
Propane
Propane
Off Gas Light Ends Dimersol
Butane 5 MBPD
5MBPD Gasoline

LPG

Naphtha
Naphtha/Jet Naphtha
Hydrotreaters
Jet Fuel/Kero 45.3 MBPD
Alkylation Gasoline
Isobutane
20 MBPD
20MBPD
Jet Fuel/Kero
Refinery
Crude Crude
Crude
Gas Oil P/P
Distillation
Distillation
Asphalt Gas Oil
FCCU B -B
134
134 MBPD
MBPD Gas Oil Hydrogen
72 MBPD Gasoline
Catalytic
LPG
Reformer
FCC Feed
FCCFeed Slurry 35 MBPD
35MBPD
Hydrotreater Gasoline
39 MBPD
39 MBPD
ULSD ULSD
LPG
ATBs Diesel 16 MBPD

Naphtha

Gas Oil Gas Oil Hydrocracker Gasoline

Vacuum
Distillation Naphtha/Diesel 36 MBPD
72 MBPD
MBPD Diesel
72
Coker
Resid 28 MBPD FCC
Gasoline
Low Sulfur Gasoline
Hydrotreater
45 MBPD
Coke 33
DIMERSOLTM

• An approach based on the Ziegler-Natta catalyzed oligomerization using

organometallic catalysts. Because of the nature of catalyst, this process can be
tailored to specific highly selective applications that have been identified by
various names:
– Dimerization of ethylene to n-butene

– Dimerization of ethylene to 1-butene

– Dimerization of propylene and butene, separately or combined
• The Dimersol process uses an organometallic catalyst consisting of a nickel salt in
combination with an alkylaluminum compound. Various modalities available are:
– Dimersol G - for dimerization of propylene to isohexenes used in Gasoline.

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– Dimersol E - for oligomerization of ethylene and propylene olefins contained in
FCC gases.
– Dimersol X - for selective dimerization of propylene and butenes for the
production of heptenes or for the dimerization of n-butenes for production of
octenes.

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DIMERSOL PROCESS (IFP)

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• The Dimersol Process proceeds as follows: olefinic feedstock and liquid catalyst, is
charged to the reactor where soluble catalyst is added in low concentration.
• The reaction occurs at essentially ambient temperature, allowing for the
exothermic heat of reaction, at a pressure sufficient to maintain a liquid phase.

• The effluent from reactor enters a drum where ammonia injection neutralizes
the catalyst, forming salts; subsequent water injection dissolves the salts,
removing them from the system. The scale of this washing operation is small
because the catalyst concentration is low - with only about 15 gpm of process
water required for 1000 BPSD of isohexenes product.
• The depropanizer operates to separate the isohexenes from product mixture.
• The level of conversion and the distribution of dimers and oligomers depend on
the number of reactors used in series, the residence time, and the concentration
of catalyst
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HYDROTREATING

• Catalytic hydrotreating is a hydrogenation process used to remove about 90% of

contaminants such as nitrogen, sulfur, oxygen, and metals from liquid petroleum
fractions.
• If these contaminants are not removed from the petroleum fractions they can
have detrimental effects on equipment, 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 kerosene,
diesel fuel, and heating fuel oils.
• In addition, hydrotreating converts olefins and aromatics to saturated
compounds.
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HYDRO DESULFURIZATION

• Hydrotreating for sulfur removal is called hydro desulfurization.

• In a typical catalytic hydro desulfurization unit, the feedstock is deaerated and
mixed with hydrogen, preheated in a fired heater (315°- 425° C) and then
charged under pressure (up to 70 bar) through a trickle-bed catalytic reactor.

• In the reactor, the sulfur and nitrogen compounds in the feedstock are converted
into H2S and NH3.
• 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 H2S is sent to a gas treating unit where H2S is removed.

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• 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 H2S and other undesirable components.
• In cases where steam is used for stripping, the product is sent to a vacuum drier
for removal of water.

• Hydro desulfurized products are blended or used as catalytic reforming

feedstock.

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CATALYTIC REFORMING

• Catalytic reforming is an important process used to convert low-octane naphtha's

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 benzene, toluene, xylene,
(BTX) 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.

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• A catalytic reformer comprises a reactor and product-recovery section. There is a
feed preparation section comprising a combination of hydro treatment and
distillation.
• Most processes use Pt as the active catalyst. Sometimes Pt is combined with a
second catalyst (bimetallic catalyst) such as rhenium or another noble metal.

• Some reformers operate at low pressure (3-13 bar), others at high pressures (up
to 70 bar). Some 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.

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• 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 fractionators
called a stabilizer (butanizer). It makes a bottom product called reformate;
butanes and lighter go overhead and are sent to the saturated gas plant.

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ALKYLATION

• 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 highoctane,
branched-chain paraffinic hydrocarbons.

• 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.

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BLENDING

• Blending is the physical mixture of a number of different liquid hydrocarbons to

produce a finished product with certain desired characteristics.
• Products can be blended in-line through a manifold system, or batch blended in
tanks and vessels.
• In-line blending of gasoline, distillates, jet fuel, and kerosene is accomplished by
injecting proportionate amounts of each component into the main stream where
turbulence promotes thorough mixing.
• Additives including octane enhancers, anti-oxidants, anti-knock agents, gum and
rust inhibitors, detergents, etc. are added during and/or after blending to provide
specific properties not inherent in hydrocarbons.
• Here, isohexene formed through Dimersol are blended with gasoline to obtain
high-octane gasoline

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IMAGES

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ADU-VDU AND REFORMER

Reactor

Heater

Crude Atmospheric Tower Vacuum Tower Reformer

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FCC AND HYDROCRACKER REACTORS
Fluidized Catalytic Cracker
Reactor Hydrocracker Reactors

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Main Column Regenerator

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COKERS & DIMERSOL
DELAYED COKER
Superstructure holds the drill and drill stem
Dimersol - Benicia
while the coke is forming in the drum

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AERIAL VIEW OF BENICIA REFINERY

BENICIA INDUSTRIAL
MAIN PROCESS PARK
AREA

SOUTHAMPTON
ASPHALT PLANT

CRUDE
TANKAGE

BENICIA INDUSTRIES

OLD TOWN

BENICIA INDUSTRIES DOCK

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THANK YOU