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C H A P T E R O N E

c0010
Introduction

s0010 1.1. Introduction

p0135 Petroleum refining plays an important role in our life. Most transpor-
tation vehicles are powered by refined products such as gasoline, diesel,
aviation turbine kerosene (ATK) and fuel oil. The recent price rise of crude
oil between $50 and $150 per bbl for the last 2 years has affected the refining
industry in three ways: (1) search for fuel products from non-fossil sources
such as biodiesel and alcohols from vegetable sources, (2) considering the
development of better methods to process tar sand, coal gasification and
synthesis of fuels by Fischer–Tropsch (FT) technology and (3) initiation of
long-term plans to look for regenerative energy sources. However, crude
oil prices are still a cheap source for transportation fuels and petrochemicals.
p0140 On the other hand stricter environment regulations have raised the cost
of producing clean fuels. This motivated the search for producing clean fuels
by non-conventional methods such as ambient desulphurization by liquid
oxidants. Olefin alkylation and Fischer–Tropsch were suggested to produce
clean fuels. New technology and better design of refinery equipment are
being developed to produce clean and less expense fuels.
p0145 In the modern refinery, the refining processes are classified as either
physical separation processes or chemical conversion processes. Examples
for each class are given in Table 1.1.

s0015 1.2. Refining Processes

s0020 1.2.1. Physical Separation Processes
s0025 1.2.1.1. Crude Distillation
p0150 Crude oils are first desalted and then introduced with steam to an atmo-
spheric distillation column. The atmospheric residue is then introduced to a
vacuum distillation tower operating at about 50 mmHg, where heavier
products are obtained. Typical products from both columns and their
boiling points range are listed in Table 1.2.

Fundamentals of Petroleum Refining # 2009 Elsevier B.V.

DOI: 10.1016/B978-0-444-52785-1.00001-2 All rights reserved.

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2 Chapter 1

t0010 Table 1.1 Major refining processes in modern refinery

Chemical conversion
Physical separation Catalytic Thermal
Distillation Reforming Delayed coking
Solvent deasphalting Hydrotreating Flexicoking
Solvent extraction Hydrocracking Visbreaking
Solvent dewaxing Alkylation
Isomerization

t0015 Table 1.2 Crude distillation products (Gary and Handwerk, 2001)

Yield (wt%) True boiling temperature (
C)

Atmospheric distillation
Refinery gases (C1  C2) 0.10 –
Liquid petroleum gases 0.69 –
(LPG)
Light straight run (LSR) 3.47 32–82 (90–180
F)
Heavy straight run (HSR) 10.17 82–193 (180–380
F)
Kerosene (Kero) 15.32 193–271 (380–520
F)
Light gas oil (LGO) 12.21 271–321 (520–610
F)
Heavy gas oil (HGO) 21.10 321–427 (610–800
F)
Vacuum distillation
Vacuum gas oil (VGO) 16.80 427–566 (800–1050
F)
Vacuum residue (VR) 20.30 þ566 (þ1050
F)
The yields quoted here depend on feed composition and properties. In this case feed API was 26.3.

s0030 1.2.1.2. Solvent Deasphalting

p0155 This is the only physical process where carbon is rejected from heavy
petroleum fraction such as vacuum residue. Propane in liquid form (at
moderate pressure) is usually used to dissolve the whole oil leaving asphal-
tene to precipitate. The deasphalted oil (DAO) has low sulphur and metal
contents since these are removed with asphaltene. This oil is also called
‘‘Bright stock’’ and is used as feedstock for lube oil plant. The DAO can also
be sent to cracking units to increase light oils production.

s0035 1.2.1.3. Solvent Extraction

p0160 In this process lube oil stock is treated by a solvent, such as N-methyl
pyrrolidone (NMP), which can dissolve the aromatic components in one
phase (extract) and the rest of oil is another phase (raffinate). The solvent is
removed from both phases and the raffinate is dewaxed.

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Introduction 3

s0040 1.2.1.4. Solvent Dewaxing

p0165 The raffinate is dissolved in a solvent (methyl ethyl ketone, MEK) and the
solution is gradually chilled where high molecular weight paraffin (waxes)
is crystallized and the remaining solution is filtered. The extracted and
dewaxed resulting oil is called ‘‘lube oil’’. In some modern refineries
removal of aromatics and waxes is carried out by catalytic processes in ‘‘all
hydrogenation process’’.

s0045 1.2.2. Chemical Catalytic Conversion Processes

s0050 1.2.2.1. Catalytic Reforming
p0170 In this process special catalyst (platinum metal supported on silica or silica
base alumina) is used to restructure naphtha fraction (C6–C10) into aromatics
and isoparaffins. The produced naphtha reformate has much higher octane
number than the feed. This reformate is used in gasoline formulation and as a
feedstock for aromatic production (benzene–toluene–xylene, BTX).

s0055 1.2.2.2. Hydrotreating

p0175 This is one of the major processes for cleaning of petroleum fractions from
impurities such sulphur, nitrogen, oxy-compounds, chloro-compounds,
aromatics, waxes and metals using hydrogen. The catalyst is selected to
suit the degree of hydrotreating and type of impurity. Catalysts such as
cobalt and molybdenum oxides on alumina matrix are commonly used.

s0060 1.2.2.3. Catalytic Hydrocracking

p0180 For higher molecular weight fractions such as atmospheric gas oils and
vacuum gas oils (VGOs), cracking in presence of hydrogen is required to
get light products. In this case dual function catalyst is used. It is composed
of zeolite base acid catalyst for the cracking function and rare earth metals
supported on alumina for the hydrogenation function. The main feed here
is VGO and the main products are kerosene, jet fuel, diesel and fuel oil.

s0065 1.2.2.4. Catalytic Cracking

p0185 Fluid catalytic cracking (FCC) is the main player for the production of
gasoline. The catalyst in this case is zeolite base for the cracking function.
The main feed to FCC is VGO and the product is gasoline, but some gas oil
and refinery gases are also produced.

s0070 1.2.2.5. Alkylation

p0190 Alkylation is the process in which isobutane reacts with olefins such as
butylene (C¼ 4 ) to produce gasoline range alkylate. The catalyst in this case is
either sulphuric acid or hydrofluoric acid. The hydrocarbons and acid react
in liquid phase. Isobutane and olefins are collected mainly from FCC and
delayed coker.

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4 Chapter 1

s0075 1.2.2.6. Isomerization

p0195 Isomerization of light naphtha is the process in which low octane number
hydrocarbons (C4, C5, C6) are transformed to a branched product with the
same carbon number. This process produces high octane number products.
One main advantage of this process is to separate hexane (C6) before
entering to the reformer and thus preventing the formation of benzene
which produces carcogenic products on combustion with gasoline. The
main catalyst in this case is Pt-zeolite base.

s0080 1.2.2.7. Thermal Chemical Conversion Processes

p0200 These processes are considered as upgrading processes for vacuum residue.

s0085 1.2.2.8. Delayed Coking

p0205 This process is based on thermal cracking of vacuum residue by carbon
rejection forming coke and lighter products such as gases, gasoline and gas
oils. Three types of coke can be produced: sponge, shot and needle. The
vacuum residue is heated in a furnace and flashed into large drums where
coke is deposited on the walls of these drums and the rest of the products are
separated by distillation.

s0090 1.2.2.9. Flexicoking

p0210 In this thermal process most of the coke is gasified into fuel gas using steam
and air. Burning of coke by air will provide the heat required for thermal
cracking. The products are gases, gasoline and gas oils with very little coke.

s0095 1.2.2.10. Visbreaking

p0215 This is a mild thermal cracking process used to break the high viscosity and
pour points of vacuum residue to the level which can be used in further
downstream processes. In this case the residue is either broken in the furnace
coil (coil visbreaking) or soaked in a reactor for few minutes (soaker vis-
breaker). The products are gases, gasoline, gas oil and the remainder of the
residue.
p0220 A schematic diagram of modern refinery containing most of these
processes is given in Fig. 1.1 (Gary and Handwerk, 2001).

s0100 1.3. Refinery Configuration

p0225 The refinery configuration can range from single topping for crude
distillation to high conversion refinery for petro-refinery. This will depend
on the following factors ( Jones and Pufado, 2005):

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Gas
LPG
Gas Gas Plant Polymerization
Separation
Introduction

n-Butane Aviation
Gasoline
Alkylate
Light crude oil Alkylation
Distillate Catalytic
Isomerization Automotive
Light SR Naphtha Light SR Naphtha
gasoline
Heavy SR Naphtha Hydrodesulfuri Catalytic Reformate
Crude Oil Reforming
-zation/Trating

Gasoline (Naphtha)
Solvents

Sweetening & Blending

Kerosene

Desalting
Middle Distillate Catalytic
Hydrocracking
Hydro- Jet fuel
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Atmospheric Distillation
desulfurization Kerosene
Gas Oil
Solvents
Distillate

Distillate fuel oils

Diesel fuel oils
Lt Vacuum Distillate Catalytic
Sweetening & Blending

Cracking
Vacuum
Atmospheric Hvy Vacuum Distillate
Dist.

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Residue
Solvent

Distillate fuel oils

Vacuum Solvent
Residual

Coking Visbreaking
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Residue Deasphalting
Residue
Asphalt Coke Vacuum Residue
Sweetening & Blending

Atmospheric Residue
Lubricants
Solvent Solvent Dewaxed oil
Lube feedstock Greases
Extraction Dewaxing
Hydro-
Blending
treating &

Deoiled wax Waxes

f0010 Figure 1.1 Modern refinery.

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6 Chapter 1

4 LPG C Refinery Coke

Hydrogen/Carbon Atom

VR Vacuum Residue
3
Hydrogenation AR Atmospheric Residue
Crude Oil
Ratio

Gaso CR Crude Oil

2 JF
GO
CR AR GO Gas Oil
VR
1 JF Jet Fuel/Diesel
Cracking C Gaso Gasoline
0 LPG Liquefied PG
0 10 20 30 40 50
Average Carbon Number (Atoms per Molecule)

f0015 Figure 1.2 Petroleum products (Speight,1999).

s0105 1.3.1. Type of Products

p0230 In this case, refining is carried out by increasing hydrogen/carbon (H/C)
ratio. This can be achieved either by hydrogenation processes such as
hydrotreating, hydrocracking or by carbon rejection processes such as ther-
mal cracking (coking) and FCC. The products of such processes are shown in
Fig. 1.2 (Speight, 1999).
p0235 Some products can also be produced by special refining operations such
as catalytic reforming, isomerization and alkylation. In Fig. 1.2, the products
are classified in terms of average carbon number and H/C ratios.

s0110 1.3.2. Environmental Regulation

p0240 Modern regulations in many countries require low level of contaminants
such as sulphur. This requires the change of severity or design of hydro-
conversion units which can produce ultra low sulphur products. Clean fuels
are gaining great interest, and completely new refineries configuration is
now introduced to produce clean fuels from new refinery feeds and con-
figurations. Additional units have been added to existing refineries to handle
untreated gas emissions and refinery waste water due to change of environ-
mental regulations.

s0115 1.3.3. Crude Assay and Quality

p0245 The crude quality is getting heavier worldwide. Existing refineries which
are designed to handle normal crudes are being modified to handle heavy
crude. New technology for upgrading is used to obtain clean and light
products from cheaper feeds. The crude assay will determine the yields of
different cuts and consequently the refinery configuration. A high conver-
sion cracking-coking refinery is shown in Fig. 1.3 (Jones and Pufado, 2005).

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Light Ends Fuel Gas

Introduction

Butane LPG
Lt Naphtha
Gasoline
Hvy Naphtha
Hydrotreater & Reformer

Kerosene Jet Fuel/Stove Oil

Hydrotreater FCC Gasoline

Crude
Alkylate
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Gas Oil Diesel/Heating Oil

Atmospheric Distillation
Hydrotreater

Vac Gas Oil VGO HDT

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FCC/Hydrocracker
Atmospheric Resid Alkylation

Vac Dist.
Light Crude Oil
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Slurry

Vac Resid
Coker
Coke

f0020 Figure 1.3 High conversion refinery.

7
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C3 LPG

C4 LPG

Splitter

Stabilizer
C5/C6 Isomerate Acetone
LSRN
Isom Acetone

HSRN HDS Bis-

Cumene Phenol Phenol A Bis-Phenol A
Cat Ref
Crude Air Phenol
Kerosene
HDS Kerosene

Crude Dist.
Diesel Polypropylene Polypropylene
AGO HDS H2 Diesel
Off -Gas
VGO C3/C4
Olefins Ethylene Ethylene Ethylene
Purer Cracking Oxide Glycol Glycol
Ethylene
FCC Fuel

Splitter
Splitter
Oxide

C3 Splitter
Gas

Debutanizer
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Vacuum Dist.
C4’s
C4’s Gasoline
Gasoline
MTBE Alkylation Blending
iC4 MTBE

Methanol

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Resid
Cooling & Syn Gas Methanol
Gasification Methanol
Shift RX
Oxygen Carbon
Oxide
CO2 CO2
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Recovery Hydrogen Hydrogen

Combined
Electric Power
Cycle
Cogen Stream
Synthesis Gas to Petrochemical
Derivatives Plants Units
Chapter 1

f0025 Figure 1.4 Refinery-petrochemical integration.

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Introduction 9

s0120 1.3.4. Refinery-petrochemical Integration

p0250 The growth of petrochemical industry has put pressure on refineries to
either change their configuration or operating conditions to produce more
aromatics and gases. FCC has been developed to petro-FCC which pro-
duces high yield of gases. The phasing out of the idea of increasing the
octane number by increasing aromatic content has changed the role of
catalytic reformer to produce high yield of aromatics as BTX feedstock.
The addition of gasification units to process vacuum residue has opened
the way for the addition of a variety of petrochemicals. Such refinery-
petrochemical configuration is shown in Fig. 1.4 (Crawford et al., 2002).

s0125 1.3.5. Development of New Technology

p0255 If a new technology is developed to give better yields, save energy, meet
environmental regulations and product specifications, then this technology
might replace old technology in existing and new refineries depending on
the economics. Other factors, which might influence the refinery configu-
ration, are feedstock availability, product markets and company strategic
objectives.

REFERENCES
Crawford, C. D., Bharvani, P. R., and Chapel, D. G. (2002). Integrating petrochemicals
into the refinery. Hydrocarbon Process 7, 35–38.
Gary, J. H., and Handwerk, G. E. (2001). ‘‘Petroleum Refining Technology and Econom-
ics.’’ 4th ed. Marcel Dekker, New York.
Jones, D. S. J, and Pufado, P. R. (2005). ‘‘Handbook Of Petroleum Processing.’’ Springer,
Berlin.
Speight, J. G. (1999). ‘‘The Chemistry and Technology of Petroleum,’’ 3rd ed. Marcel
Dekker, New York.

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