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Course № O-3001
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FUNDAMENTALS OF PETROLEUM REFINING
by Kevin A. Giles, P.E.
Introduction
Imagine, for just a moment, how your lifestyle would be changed if you
had no access to transportation via automobiles, trucks, motorcycles, planes, or
any other equipment powered by internal combustion engines. How would you
commute to work or to shop for consumer goods? Would you walk, ride a
bicycle—or ride a horse? Imagine how the selection of goods available to you at
local retailers would be negatively impacted by similar constraints. For example,
you would have limited or no access to fresh fruits and vegetables except during
the local growing season. The costs of goods produced other than locally would
be appreciably higher. The lifestyle that we take for granted is made possible
through the usage of the fuels (i.e., motor gasolines, diesel fuels, jet fuels,
aviation gasolines, heating oils, heavy fuel oils, etc.) and specialty products (i.e.,
lubricants, waxes, asphalts and solvents), as well as the petrochemical industry
feedstocks produced by the petroleum refining industry from crude oils.
Fuel Gas
A Propane
Light Ends
Normal Butane
Distillation
IsoButane
B
Crude
Oil Coker Naphtha
C Light Naphtha
Naphtha
Naphtha
HDS Heavy Reformate
Catalytic Gasoline
Naphtha
Reforming
D Alkylate
Kerosene C5
Kerosene
Atmospheric HDS
Distillation
Diesel
Jet Fuel
HDS E
A
C 3/C 4 /C 5
Isobutane
B
Atm os pheric
Alkylation
C ata ly tic N aphth a
Gas
R es idu um
Heavy Oil
Gas Oil HDS
C 3/C 4 C5
Diesel /
Heating Oil
Fluidized
Catalytic
L ig ht C a tay tic
Cracker
Light
Vacuum
G a s O il
Vacuum
Gas Oil Catalytic Bottoms
Distillation
Heavy
Heavy Coker Gas Oil Delayed
Vacuum
Gas Oil Coker Fuel Oil
C
Vacuum Residuum Light Coker Gas Oil
Hydro-
Cracking
Naphtha D E
Jet Fuel
The process units that constitute a refinery are continuous operations that
run 24 hours per day, 365 days per year. Refinery process operations personnel
typically work 12-hour shifts around-the-clock to operate the process equipment.
A process unit run-length is usually 1 to 5 years before it is shutdown for several
weeks of turnaround maintenance. As a result, a refinery process unit’s service
factor (i.e., availability) is well above 90%. The turnaround timing is scheduled
based upon catalyst activity requiring a catalyst change out (if applicable) or
based on predictive maintenance techniques applied to the critical process
equipment.
Crude Oils
In almost all cases, crude oils have no inherent value without a petroleum
refining industry to process them into usable specification products. The rare
exceptions are very light crude oils or condensates that may be burned as low
quality fuels in locations with very loose or non-existent environmental
restrictions. However, as a result of the refining industry, crude oil is one of the
most significant categories among the commodities in the world.
Crude oils are named and grouped into broad categories typically based
on the geographic location of origin, along with the level of sulfur contained in the
crude and/or density of the crude oil. For example, West Texas Intermediate
(WTI) and West Texas Sour (WTS) are two families of crude oils produced in the
oilfields of West Texas—WTI is a light, sweet (i.e., low levels of sulfur relative to
high sulfur “sour” crude oils) crude oil when compared to the heavier, higher
sulfur content WTS. Higher sulfur crude oils are more corrosive than lower sulfur
crude oils. To ensure a reasonable life expectancy for equipment processing the
higher sulfur crude oils, refiners specify that such equipment be built from more
expensive alloys with a higher corrosion resistance.
The American Petroleum Institute (API) has developed the term Degrees
API Gravity (°API) which is widely used as another general characterization of
the density of crude oils. The relationship is as follows:
Therefore, when comparing two crude oils, the higher density crude (i.e., the one
with the highest specific gravity) will have a correspondingly lower °API. For
example, the 34.5°API West African crude oil Bonny Light is heavier than the
40.4°API North Sea crude oil Forties.
Unfortunately, the boiling point curve for most crude oils does not match
that of the products demanded. The United States demand for the lighter
petroleum products boiling below 650°F (motor gasolines, diesel fuels, and jet
fuels) represents roughly 85% by volume of the crude oil processed in the U.S.
However, an average crude mix (as exemplified by the Strategic Petroleum
Reserve crude oil assays in Appendix 2 showing only 54-62% by volume of the
crude oil boiling below 650°F) has a much lower volumetric yield of hydrocarbons
in the desired boiling range. Refinery process operations split the crude oils into
fractions by boiling range and then convert some of the unwanted fractions (i.e.,
low demand and low value) into higher value, specification products.
Fractionation
Distillation concentrates the lower boiling point material towards the top of
the tower. The lowest boiling point product is the tower overhead vapors which
are condensed as distillate. Progressively higher boiling point material is present
further down the tower. Gravity forces the liquid phase to flow down the tower.
Additional intermediate boiling range streams may be withdrawn at various levels
from the tower as side-stream products. The highest boiling range material is the
liquid product withdrawn from the bottom of the tower.
Active Area
(Sieve Tray)
Slotted Liquid
Distibutor
Downcomer
Downcomer
Liquid
Distributors
Tray Deck
Bed of
Packing
Downcomer
Legend
Liquid Path
Vapor Path
The first refinery process unit that a crude oil or mixture of crude oils is
charged to is a Crude Distillation unit (commonly referred to as a pipe still), which
consists of an Atmospheric Distillation tower and typically also includes a
Vacuum Distillation tower. The crude oil or mixture of crude oils that represents
the feed to a Crude Distillation unit is pumped from crude oil storage tanks into
banks of heat exchangers which pre-heat the crude oil to approximately 250°F by
cross exchanging heat with various product streams. Most crude oils contain
appreciable levels of inorganic salts which would cause downstream corrosion
and equipment fouling. The crude oil is then desalted by emulsifying the crude
oil with water. The salts are dissolved in the water and the brine phase is then
separated from the oil phase and withdrawn. The crude oil is further preheated
to the maximum possible temperature (typically about 500-550°F) through heat
exchange with distillation product streams. Finally, the crude oil is heated to
approximately 750°F in a direct-fired furnace and fed to the Atmospheric
Distillation tower.
Crude
Atmospheric Reflux Drum
Tower
250 0F
Preheat Reflux
Sour Water
Desalter Pump Around
Naphtha
(Cooling)
Pump Around
Brine Kerosene
(Cooling)
550 0 F
Steam
Atmospheric Residuum
To Steam
Vacuum
Jet Ejectors
Vacuum
Tower
Steam Oily Water
Light
Vacuum
Gas Oil
Pump Around
(Cooling)
Heavy
Vacuum
750 0 F Flash Gas Oil
Zone
20mm
Hg
Vacuum Furnace
Steam
Vacuum
Residuum
Typical primary fractions and TBP cut-point ranges from Crude Oil
Distillation (i.e., both Atmospheric and Vacuum tower products) are presented in
the table below. The actual cut-point target within the range for individual
fractions is predicated upon downstream processing objectives and product
specifications.
Treating
Hydrotreating
In the HDS reaction, the bond between the carbon and sulfur atoms is
broken, and the sulfur atom is replaced with a hydrogen atom. The sulfur atom
combines with additional hydrogen to form the toxic gas hydrogen sulfide (H2S).
The general chemical formula for the HDS reaction occurring is:
Similarly, in the HDN reaction, the bond between the carbon and nitrogen
atoms is broken, and the nitrogen atom is replaced with a hydrogen atom. The
nitrogen combines with additional hydrogen to form ammonia (NH3).
Generally, the process flow for a Hydrotreater process unit is that the
hydrocarbon feedstock and hydrogen streams are both preheated through heat
exchange with reactor effluent, then combined either before or after the final
heating from a direct-fired furnace and then the mixed hydrocarbon and
hydrogen stream is passed through the reactor, flowing from top to bottom. The
reactor effluent (hydrogen, light hydrocarbons, H2S and NH3) is cooled through
heat exchange with unit feed followed by separation of the vapor and liquid
phases.
The liquid stream is sent to a stripper tower in which steam (or nitrogen in
some cases) is employed to “strip” the hydrogen sulfide and any naphtha and
lighter boiling components generated in the reactor from any higher boiling range
product streams. Since the resulting naphtha stream contains light ends
components, it is referred to as unstabilized naphtha or “wild naphtha”. The
stripped liquid product stream is then further cooled prior to disposition to storage
tanks for additional refinery processing or finished product blending.
Hydrogen Recycle
Compressor
(If Applicable) Sour Fuel
Gas
Wild
Naphtha
Separator
Sour Water
Hydrogen
Make-up Stripper Tower
Gas
Hydrocarbon
Feed
Furnace
Fixed
Bed
Catalytic
Reactor
Stripping Steam
Hydrotreater Product
The activity of the reactor catalyst bed is reduced over time as coke (i.e.,
essentially pure carbon) and metals attach to the individual catalyst surface and
block active catalyst surface area from the oil being processed. To compensate
for this catalyst deactivation, the reactor temperature is gradually increased as
required to meet product specifications over the life of the catalyst bed. Upon
reaching the maximum operating reactor temperature (typically 750°F) the unit
will be scheduled for a shutdown to allow the catalyst bed to be replaced with
either fresh or regenerated catalyst. Depending on the catalyst, feedstock and
processing severity requirements, typical run lengths for catalyst beds are
anywhere from one to four years.
Many fuels products are treated as a finishing step prior to being shipped
as “finished” products. Treating removes impurities which cause objectionable
odors, unwanted colors or corrosivity of the product. Hydrogen sulfide (H2S) and
other sulfur compounds such as mercaptans are examples of such impurities.
Jet fuels which have not been hydrotreated are typically caustic washed to
neutralize naphthenic acids. Jet fuels may also be clay treated by passing the
fuel through a fixed bed of clay to remove any surfactants as well as color
bodies.
Upgrading
Catalytic Reforming
Reformate
Naphtha
900-940 0 F
The FCC process cracks the heavy gas oils by breaking carbon-to-carbon
bonds in the large molecules comprising the gas oils and splitting them into
multiple smaller molecules which boil at a much lower temperatures. The FCC
may achieve conversions of 70-80% of the feed hydrocarbons boiling above the
gasoline range (i.e., 430°F) to products boiling below 430°F. The lower density
of the FCC products relative to the gas oil feedstocks has the added benefit of
producing a volume gain in which the combined volume of the liquid product
streams is greater than the volume of the unit feed stream. Since most
petroleum products are bought and sold on a volume basis, the volume gain
aspect of the FCC process is a key aspect in how it enhances refinery
profitability. The resulting FCC product hydrocarbons are highly olefinic (i.e.,
unsaturated). Virgin is a term used to distinguish straight-run (i.e., crude
distillation and possibly hydrotreated only) hydrocarbons stocks from those that
are products of conversion units such as the FCC.
The gas oil feed to the FCC is preheated via heat exchange with reactor
products and then a direct-fired furnace before being mixed with the hot (1,200-
1,350°F) regenerated catalyst. The hot catalyst vaporizes the gas oil and heats
the oil to the reactor temperature. To prevent “overcracking” which produces
excessive light ends at the expense of gasoline yield, the contacting time
between the oil and catalyst is minimized. The bulk of the cracking reactions
occur in the transfer line from the initial point of contact between the catalyst and
gas oil feed and the “reactor” vessel. The primary purpose of the FCC reactor
Atmosphere
Regenerator Reactor
Cyclone Cyclone
Separators Separators
Catalytic
Naphtha
Light
Catalytic
Gas Oil
Cycle Oil
Fractionator
0 (Simplified)
950-1020 F
Slide Valve
Transfer
Line
Spent Catalyst Catalytic
Bottoms
Regenerated
Catalyst Slide Valve
Air
700-750 0 F
Air Blower
Gas Oil
Pre-Heat
Furnace
Hydrocracking
Typical Hydrocracking feedstocks are the light catalytic gas oil from the
FCC (which is very unsaturated), the light coker gas oil and virgin, light gas oils.
The heavy naphtha produced from Hydrocracking makes an excellent Catalytic
Reformer feedstock due to the significant presence of naphthenes created by
saturating aromatics in the gas oil feedstock with hydrogen. Hydrocracking also
produces an excellent blendstock for jet fuels. The yields across a
Hydrocracking unit may exhibit liquid volume gains of as much as 20-25 percent!
Hydrogen Furnace
Hydrogen Compressor
650-750 0F 650-750 0 F
1500-2500 psi
H y dr o cra ckin g R e acto r F i rst S ta g e
High Pressure
Separator
Light Ends
Low Pressure
Separator
Light
Gasoline
Fractionator
HDS/HDN
Reactor
650-750 0F Naphtha
Quench Hy drogen
H yd ro cr ack in g R eac tor Se co n d Stag e
Preheat
Light
Gas
Oil
Jet Fuel
Diesel
(or 100%
Recycled)
Hydrocracking units are configured for either a single stage or two stages
of Hydrocracking reactors. The second stage reactor enables the overall unit
conversion of light gas oils into lower boiling range components to be increased.
This is accomplished by recycling (depending on economics, “recycling to
extinction”) the diesel oil boiling range stream from the fractionator tower bottoms
back to the second stage Hydrocracking reactor where it is converted into lighter
boiling range material.
Alkylation
DePropanizer
Refrigeration Cycle
Chiller
Isobutane
Compressor
Isobutane Recycle
Vapors
35-60 0F
Caustic
Wash
Normal
Butane
Isobutane Feed
Dryer
C 3,C 4 ,C 5 Feed
(50+% Olefins)
Alkylate
Chiller Acid Settling
Dryer
Acid Recycle
Coking
With the exception of the Coking process, the formation of coke (i.e.,
essentially pure carbon) is an undesirable result of refinery processing operations
because coke formation fouls equipment and reduces catalyst activity. However,
in the Coking process, coke is intentionally formed to maximize the conversion of
the bottom of the barrel vacuum residuum from low value fuel oils to higher value
products.
800 0 F
Coker
Naphtha
Light
Coke Coker
Drums Gas Oil
Heavy
Coker
Gas Oil
Rec irculated W ater
Fractionater
(Simplified)
Steam
925 0F
Furnace
Coke Pit
The coker fractionator distills the unit feed and coking reaction product
stream into gas, coker naphtha, light and heavy coker gas oils, and bottoms.
The bottoms stream is recycled to extinction via the heater and coke drums. The
Delayed Coker fractionated products are very highly olefinic (i.e., unsaturated
with carbon to carbon double bonds), even containing diolefins (molecules with
two carbon to carbon double bonds). Coker naphtha may be routed to Catalytic
Reforming (after Hydrotreating to remove sulfur and saturate the diolefins) or
Hydrocracking, depending on current economics. Light coker gas oil may be
routed to Hydrocracking or to FCC. Heavy coker gas oil is typically routed to the
FCC via Hydrotreating. Coker gas oils may alternatively be routed to fuel oil
product blending--possibly after Hydrotreating for sulfur removal.
Ancillary Processes
Hydrogen Production
Zinc
Oxide
Bed
Reformer
Furnace
Steam
1500 0F
Hydrogen
(95% purity)
Separator
Steam
Water
Shift
Converter Carbon
Dioxide
Carbon
Dioxide
Still
Potassium Carbonate
The Steam Reforming reactor products are then cooled by heat exchange
to generate waste heat and more steam is added prior to entering the Shift
Conversion reactor. The Shift Conversion reaction takes place in a fixed-bed
reactor consisting of an iron or iron/chromium catalyst. The Shift Conversion
reaction converts the carbon monoxide to carbon dioxide and produces
additional hydrogen according to the following reaction:
CO + H2O ! CO2 + H2
Since carbon monoxide (CO) and carbon dioxide (CO2) are poisons to the
catalysts of some of the hydrogen consuming refinery processes, Methanation is
employed as the final step to remove any remaining CO and CO2 in the hydrogen
stream. The Methanation reaction takes place in a fixed-bed reactor consisting
of a nickel-based catalyst. The resulting hydrogen product stream is typically
approximately 95% hydrogen and the balance methane with only trace amounts
of CO and CO2. The Methanation reactions are:
Sulfur Conversion
Hydrogen sulfide (H2S) is a highly toxic gas that originates in crude oils
and is also produced in the Hydrotreating, Hydrocracking, FCC, and Delayed
Coking process reactions. Simply burning H2S as a fuel gas component is
precluded by safety and environmental considerations since one of the
combustion products is sulfur dioxide (SO2), which is also toxic. Special
operating and maintenance procedures are in place for any refinery process
equipment containing H2S in concentrations above 50 parts per million. H2S is
typically removed from the refinery light ends gas streams through amine
Tail Gas
2/3 Incinerator
Treater
Waste
Heat
2000-
1/3 2500 0F
Acid Thermal
Gas Reactor
Tail
450 0F
Gas
Air
First
Converter
Air
Blower Waste
Heat
Second
Converter
Waste
Heat
Third
Converter
Waste
Heat
Condensed
Sulfur
Sulfur Pit
The Sulfur Conversion process takes the acid gas stream and converts
the toxic H2S into the benign products of elemental sulfur and water. The Sulfur
Conversion process utilized in most modern refineries is a variant of the process
first invented by Claus in the late 19th century—hence the name ”Claus process”.
In general, the Claus process entails combusting one-third of the H2S to sulfur
dioxide (SO2) and then reacting the SO2 with the remaining H2S in the presence
of a fixed bed of activated alumina, cobalt molybdenum catalyst to form
elemental sulfur. The combustion and conversion chemical reactions occurring
are:
Product Blending
Summary
This course has provided the student with an overview of the fuels
processes typically employed in the modern petroleum refinery to accomplish its
objectives. Primary distillation of the crude oils into the hydrocarbon fractions for
subsequent processing occurs in the Crude Distillation process. Hydrotreating is
utilized to reduce or remove the sulfur and nitrogen compounds that are poisons
to the catalysts in downstream processes. The Hydrogen Generation process
produces additional hydrogen, if needed, to meet the overall refinery hydrogen
demand. Catalytic Reforming and Alkylation provide high-octane components for
gasoline blending. Delayed Coking, Fluidized Catalytic Cracking and
Hydrocracking convert undesirable higher boiling range hydrocarbon into the
more desirable gasoline, jet fuel, and diesel fuel products.