Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed
Hydrogen
Delayed Coker Catalytic Cracker Alkylation Hydrotreating Blending
Distillation Plant
(FCC)

Crude and Vacuum Distillation is the first unit in this seven-step overview of Refining

Overview of Crude and VacuumDistillation

The crude stills are the first major processing units in a refinery. They are used to separate the crude oils by distillation into fractions
according to boiling point, so that each of the processing unitsfollowing will have feedstocksthat meet their particular specifications.
Higher efficiencies and lower costs are achieved ifthe crude oil separation is accomplished in two steps: first by fractionating the total
crude oil at essentially atmospheric pressure; second by feedinghigh-boiling bottoms fraction (topped or atmospheric reduced crude)
from the atmospheric still to a second fractionator operated at a high vacuum. The vacuum still is employed to separate the heavier
portion of the crude oil into fractions because the high temperatures necessaryto vaporize the topped crude at atmospheric pressure
cause thermal cracking to occur.

Before the crude enters the atmospheric distillation tower, it normally requires desalting. This is necessary to minimize fouling and
corrosion caused by salt deposition on heat transfer surfaces and acids formed bydecomposition of the chloride salts. The salt in crude
oil is in the form of dissolved or suspended salt crystals in water emulsified with the crude oil. The basic principle is to wash the salt
fromthe crude oil with water.

After desalting, the crude oil is pumped through a seriesof heatexchangers and its temperature is raised to about 550°F (288°C) by heat
exchange with product and refluxstreams. It is then further heated to about 750°F (399°C) in a furnace and charged to the flash zone of
the atmospheric fractionators. The furnace discharge temperature is sufficiently high to cause vaporization of all products withdrawn
above the flash zone plus about 10 - 20% of the bottoms products. Reflux is provided by condensing the tower overhead vapors and
returninga portion of the liquid to the top of the tower,and by pump-around streams lower in the tower.
The bottoms fromthe atmospheric crude tower feed the vacuumtower. Distillation is carried out with absolute pressures in the tower
flash zone area of 25 to 40 mm Hg. To improve vaporization, the effective pressure is lowered even further (to 10 mmHg or less) by
the addition of steamto the furnace inletand at the bottomof the vacuumtower. The vacuumtower products are used as FCC charge
stocks or lube oil stocks.

Crude and Vacuum Distillation Keyfactors affecting the

Process Diagram distillation effectiveness:

- Feed temperature and

Composition

- Feed/ Reflux Ratio

- Pump-around, reboiler
and condenser duties

- Column temperature
profile (top to bottom
temperature cascade)

- Tower pressure

- Product draw-off rates

Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed
Alkylation Hydrotreating Hydrogen Blending
Distillation
Delayed Coker Catalytic Cracker
(FCC) Plant

Delayed Coker is the second unit in this seven-step overview of Refining

Overview of Delayed Coker Process

The delayed coker is one of the keyprocesses inthe refinery where heavier crudes arebeing processed.Optimizing this process
is becoming increasingly important, and good measurementis a key factorto be able to effectively evaluate coker operations.
The most common methodof upgrading the heavy,high sulfur, low quality “bottomofthe barrel”is by converting itinto lighter
products in a delayed coker. The coking unit converts heavy feedstocks into solid coke and lower boiling hydrocarbon products
which are suitable as feedstocks to other refinery units forconversionintohighervaluetransportation fuels.
The delayed coking process is a thermal process and consists of fired heaters, coke drums and a main fractionator. The cracking
and coking reactions are initiated in the fired heater under controlled time-temperature-pressure conditions. High velocities are
maintained in theheaters in orderto prevent significantcoke formation. Thereactions continue as theprocess streammoves to
the coke drums. Being highly endothermic, the coking reaction rate drops dramatically as coke-drum temperature decreases.
Coke is depositedin the cokedrums. Thevaporis routed to thefractionator, where itis condensed andfractionatedintoproduct
streams – typically fuelgas, LPG,naphtha,distillate, and gas oil.
When one pair of coke drums is fullof coke, the heater outlet streamis directedto the othercoke drum.The fulldrum is taken
offline, cooled with steam and water and opened. The coke is removed by hydraulic cutting. The empty drum is then closed,
warmed-up andmadereadyto receivefeed while the otherdrum becomes full.

Delayed Coker
Process Diagram
The challenges to the
Delayed Coker Process
are detailed on the
next page.
Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed Hydrogen
Delayed Coker Cataly tic Crac ker Alkylation Hydrotreating Blending
Distillation Plant
(FCC)

Fluidized-bed Catalytic Cracker (FCC) is the third unit in this seven-step overview of Refining

Overview of Fluidized-bed Catalytic Cracker (FCC)

The primary function of the Fluid Catalytic Cracking (FCC) unit is to “crack”the gas oil fraction of the crude oil to produce more gasoline
and distillate fuels. The FCC was developed as the amount of naphtha available in the crude oil is insufficient to meet the demand for
gasoline per barrelof crude oil. The FCC is often the most profitable operation in the refinery.

The cracking process produces carbon (coke) which remains on the catalyst particle and rapidly lowers its activity. To maintain the catalyst
activity at a useful level, it is necessary to regenerate the catalyst by burning off this coke with air. As a result, the catalyst is continuously
moved from reactor to regenerator and back to reactor. The cracking reaction is endothermic and regeneration reaction exothermic.

The FCC processemploysa catalyst in the formof veryfine particles which behave as a fluid when aerated with a vapor. The fluidized
catalyst is circulated continuously between the reaction zone and the regeneration zone and acts as a vehicle to transfer heat fromthe
regenerator to the oil feed and reactor.

The FCC unit has a lot of flexibility in the type of feedstocks it can process. Typical FCC Feedstocks include atmospheric gas oil, vacuum
tower bottoms, and Coker gas oils. The hot oil feed is contacted with the catalyst in either the feed riser line or the reactor. As the
cracking reaction progresses, the catalyst is progressivelydeactivated by the formation of coke on the surface of the catalyst. The catalyst
and hydrocarbon vapors are separated mechanicallyand oil remaining on the catalyst is removed by steamstripping before the catalyst
entersthe regenerator. The oil vapors are taken overheadto a fractionation tower for separation into streams having the desired boiling
ranges. The major products include alkylation unit feedstocks (Propylene, Isobutane and butylenes), gasoline, and diesel fuel or heating oil.
The spent catalyst flows into the regenerator and is reactivated by burning off the coke depositswith air.Regeneratortemperatures are
carefully controlled to prevent catalyst deactivation byoverheatingand to provide the desired amount of carbon burn-off. This is done
by controlling the air flow to give a desired CO2/CO ratio in the exit flue gases or the desired temperature in the regenerator. The flue
gas and catalyst are separatedby cyclone separators and electrostatic precipitators.

FCC Process Diagram

Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed Hydrogen
Delayed Coker Catalytic Cracker Alkylation Hydrotreating Blending
Distillation Plant
(FCC)

Alkylation is the fourth unit in this seven-step overview of Refining

Overview ofAlkylation
The alkylation process in a refinery is often part of the same operating area as the FCC unit because the two units are closely linked.
The primary function of the alkylation unit is to re-combine some of the smaller molecules formed via cracking in the FCC unit into the
gasoline size range. Alkylation produces a very high quality gasoline blendingcomponent because it has a high octane rating, contains
no benzene or other aromatics, no olefins, and little or no sulfur. It is a product very much in demand because of its “cleanliness”.
Alkylation is the reaction of low-molecular weight olefinswith an isoparaffin to formhigher-molecular-weight isoparaffins. The alkylation
process takes place at low temperatures in the presence of either liquid sulfuric acid or hydrofluoric acid as the catalyst. M any licensors
and engineeringcompanieshave been trying to develop an economical solid bed alkylation catalyst but there hasbeen limited success.
The two alkylation processes, hydrofluoric or sulfuric, are quite different. There are two primary licensors of the HF alkylation process,
which are UOP and Phillips. Because of the dangersof exposure to HF acid,there are few if any new HF alkylation processes being built,
but there are a large number of units running around the world. Because Micro Motion doesnot have metallurgy compatible with
HF acid, we will concentrate mainly on the sulfuric acid alkylation process in this document.
The primary sulfuric acid alkylation technology is DupontTM STRATCO® Effluent-Refrigerated Alkylation technology. The plants include
the followingsections:
• feed treating
• reaction section
• refrigeration section
• effluent treating
• fractionation
The units are designed to process a mixture of propylene, butylenes, and amylenes. There are a number of different configurations,
but there are generally between three and six ContactorTM and acid settler combinations. The feed streams generally flow through
one ContactorTM, with three to sixoperating in parallel, while the acid streams flow in series fromthe first Contactor TM to the last. The
alkylation reaction takes place in the Contactor TM, and that mixture flows to an acid settler,where the acid and hydrocarbon separate.

Alkylation Process Diagram

Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed Hydrogen
Delayed Coker Catalytic Cracker Alkylation Hydrotreating Blending
Distillation Plant
(FCC)

Hydrotreating is the fifth unit in this seven-step overview of Refining

Overview of Hydrotreating
Hydrotreatingis a process to catalytically stabilize petroleumproducts and remove objectionable elements fromproducts or feedstocks
by reacting them with hydrogen. Stabilization usually involves converting unsaturated hydrocarbons such as olefins and gum-forming
unstable diolefins to paraffins. Objectionable elements removed by hydrotreating include sulfur, nitrogen, oxygen, halides, and
trace metals. Hydrotreating is applied to a wide range of feedstocks fromnaphtha to reduced crude. When the process is employed
specifically for sulfur removal it is usually called hydrodesulfurization or HDS. To meet environmental objectives it also may be
necessary to hydrogenate aromatic rings to reduce aromatic content by convertingaromatics to paraffins.

Hydrotreating Process Diagram

Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed
Delayed Coker Alkylation Hydrotreating Hydrogen Blending
Distillation Catalytic Cracker
(FCC) Plant

H ydrog en Plant is the sixth unit in this seven-step overview of Refining

Overview of Hydrogen Plant Process

The need for deeper hydrotreating, because of lower and lower sulfur levels in transportation fuels, and for the processing of
heavier and higher sulfurcrude slates is driving the demand forhydrogen. Allhydrotreating processes to removesulfur fromthe
products require hydrogen. The major source of hydrogen in the refinery is normally the catalytic reformer off gas, which is rich
in hydrogen. As sulfur removal increases though, most refiners find they need additional sources of hydrogen. Many refiners
have either built an on-site hydrogen plant, or have a hydrogen plant on-site which is operated by one of the major commercial
gas suppliers.
A hydrogen plant ata refinery often consists of a SteamMethane Reformer (SMR)and a hydrogen purificationsystem, normally a
PSA (PressureSwing Adsorption)unit.
This process involves introducing preheated natural gas (or another hydrocarbon stream such as Refinery Off Gas) with steam
across a catalyst to produce a 75–80% hydrogen streamcomposed primarily of hydrogen and carbon monoxide,then purifying
this effluent, using either an MEA scrubberor a PSA unit,to produce 99%+ hydrogen.
Two reactions occur inthe SMR:
• First, the reforming reaction thatconverts hydrocarbonfeedstock to carbon oxides and H 2
CnHm + nH 2O + heat  n CO + (n/2 +n) H 2
• Second,the shiftreaction thatconverts CO produced during the reforming reaction to carbon dioxideand additionalH 2
CO + H 2O  CO2 + H 2 + heat
The second part of the process, hydrogen purification, is based on advanced pressure swing adsorption (PSA) technology.
Polybed PSA units contain 4 to 14 adsorber vessels. One or more vessels are on the adsorption step while the others arein
various stages ofregeneration. Purified H 2 is delivered at essentially feed pressure. Purity canbe 99.99mol%.

Hydrogen Plant
Process Diagram
The challenges to the
process are detailed on
the nextpage.
Process Solutions Guide

Refining
Crude and Vacuum Fluidized-bed
Delayed Coker Alkylation Hydrotreating Hydrogen
Distillation Catalytic Cracker Blending
(FCC) Plant

Blending is the seventh unit in this seven-step overview of Refining

Overview of Blending Process

The major refinery products produced by the product blending process aregasoline,jet fuels,heating oils,and diesel fuels.
The objective of product blending is to allocate the available blending components in such a way as to ensure all product
demands and specifications aremet atthe least cost and to produce products which maximize overallprofit.
Gasoline blending is a refinery operation that blends different component streams into various grades of gasoline. Typical
grades include83 octane (blendedlaterwith an oxygenated fuelsuch as ethanol), regular 87 octaneand premium92 octane.
The Ried Vapor Pressure (RVP) is set depending on the average temperature of the location the gasoline will be used (cold
temperatures require higher RVP than warmer climates). These two specifications are the most significant and they are
documented with each blend, to minimizethepotential for octane giveaway.
If the octane specification is 87.0, each0.1octaneoverthis target valuecosts the refinermoney. In the United States,this
cost calculates to approximately $1,000,000per 0.1octanegiveaway per 100,000 bpd crude capacity.
The RVP is slightly different.Refiners aim to blend as much low valuenormal-butane(component RVP of 52.0 psi) into the
final blend without going overthe specification. For example (note,these values change over time),the cost ofn-butaneis
$7 per barrel that can be sold as gasoline at$25 per barrel just by blending. The$18 per barrelprofitis significant to the
refiner, making RVP economics important.
Distillate fuel blending has otherspecifications thatmust be met.Distillate blending includes jet fuels,diesel fuels, kerosene
and No.1 and No.2 fueloils. Dieselfuelproperties thataremeasured includeCetane number (analogous to octanenumber
for the gasoline engine); Flash point (relates to fire hazard in storage); Low temperature properties, including cloud point;
and pour point Sulfurcontent.
In blending some products,such as residualfueloils or asphalt, viscosity is one of thespecifications that must be met.

Blending Process
Diagram
The challenges to the
Blending Process are
detailed on the nextpage.