Petroleum Refinery Process Design &

Naphtha Methaforming - Simulation

Using Aspen HYSYS
Specialized Scientific Programs
Gas & Petrochemicals Program
(10th Term) Spring 2019
Project II

Abdelhadi Nasr Al Yassin 3711

Bahaa eldin Hany Mohamed 3539
Mennatallah Saad Morsi 3098
Mayar Essam Osman 3564
Malak Tarek Mohamed 3710

Instructor Dr. Yehia Elshazly

July 2019
 Acknowledgment

We would like to thank Prof. Dr. Yehia El Shazly for his great help and communication with us!
This work would have never been done without his guide, availability and the great knowledge he
provided us with! Nevertheless, his spirit, motivation and constant advice were vital to our success
and top-level work. We wish him the best of luck in his life!

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 Table of Contents

List of Figures

Abstract 1

Chapter (-1-) Introduction to Petroleum Refining 2-22

1.1 – Background & History 2

1.2 – Crude Oil (Structure, Classification & Economy) 4
1.3 – Refinery Classification 12
1.4 – Petroleum Supply Chain 20

Chapter (-2-) Petroleum Refinery Processing 23-65

2.1 – Petroleum Emulsion & Dehydration 24

2.2 – Desalting, Preheating & Flashing 29
2.3 – Separation in Distillation Tower 36
2.4 – Products of Distillation Tower 44
2.5 – Vacuum Column 55
2.6 – Storage of Petroleum Products 58

Chapter (-3-) Naphtha Processing 66-88

3.1 – Cracking 66
3.2 – Steam Cracking 68
3.3 – Catalytic Cracking 72
3.4 – Methaforming 77
 Petroleum Refinery &
Chapter (-4-) Naphtha Methaforming 89-170
Simulation
4.1 – Introduction 89
4.2 – Crude Oil Data Generation 92
4.3 – Preheating, Preflashing & Heating Units 103
4.4 – Atmospheric Distillation Tower Unit 115
4.5 – Vacuum Tower Unit 132
4.6 – Naphtha Methaforming Unit 146

Chapter (-5-) Sensitivity Analysis 171-181

..
5.1 – Introduction 171
5.2 – Application in the Proposed Plant 174

References 182
 List of Figures

Fig Name Page Fig Name Page

1.1 Energy Consumption Growth by Energy Source 2 2.35 Tank Agitators 64
1.2 Total Primary Energy Supply (TPES), 2015 3 2.36 Tank Thief Hatch 64
1.3 Important Classes of HCs in Crude Oil 5 2.37 Tank Thief 65
1.4 Natural Yields of Light and Heavy Crude Oils 6 2.38 Tank Pressure Relief Valve 65
1.5 Price Volatility for a crude oil 11 3.1 Refinery Processing Process 66
1.6 Typical Petroleum Supply Chain 21 3.2 Crude Oil Products Processing Processes 68
1.7 Upstream, Midstream &Downstream Activities 22 3.3 Feedstock Comparison for Ethylene Production 69
2.1 Notional (Very) Complex Refinery 23 3.4 Steam Cracking Process Products Uses 69
2.2 Crude Oil Distillation & Downstream Processing 24 3.5 Steam Cracking Process Flowsheet 70
2.3 Crude Oil Overall Refinery Process 25 3.6 Heating System in Cracking Furnace 71
2.4 Crude Oil Desalting Process 30 3.7 Real Life Steam Cracking Unit 72
2.5 Electric Desalting of Crude 30 3.8 Energy Saving in Catalytic Cracking 73
2.6 Electrostatic Desalting of Crude 32 3.9 Catalytic Cracking Process 74
2.7 Electrostatic Desalting of Crude CSV 32 3.10 Catalytic Cracking Vs Catalytic Reforming 75
2.8 Typical Furnace Components 34 3.11 Real Life Catalytic Reforming Reactors 76
2.9 Typical Flow of feed inside Furnaces 34 3.12 Different Cracking Processes 77
2.10 Crude oil distillation with a preflash unit 35 3.13 Methaforming Unit 78
2.11 Fractional Distillation fractions with BP & uses 36 3.14 Methaforming Playing Roles 79
2.12 Fractional Distillation Illustration 37 3.15 Light Naphtha Processing Processes 81
2.13 Fractionation Column Sections 38 3.16 Dehydration and Dehydrogenation Reactions 83
2.14 Typical Tray Layout 39 3.17 Methaforming Illustrative Flow Diagram 84
2.15 Bubble caps, Sieves & Valves Types of Trays 39 3.18 Economical Benefits Compared to Alternatives 86
2.16 Flow in Bubble caps Tray 40 3.19 Reduced Reactions in Methaforming 87
2.17 Flow in Sieve Tray 40 3.20 Methaforming Unit Utilities 88
2.18 Flow in Valve Tray 41 4.1 Overall Plant Design 90
2.19 Downcomer and Weir Work 42 4.2 Overall Plant Design Sectioned 91
2.20 Crude Oil Products 44 4.3 Defining Components List 92
2.21 Real Life Company Vacuum Column 55 4.4 Components List Options 93
2.22 Vacuum distillation unit and processing paths 56 4.5 Fluid Property Package 93
2.23 Classification of Petroleum Liquids to be stored 58 4.6 Crude Oil Assay Data 94
2.24 Storage Tanks Parts 59 4.7 Oil Manager 95
2.25 Underground Storage Tanks 60 4.8 Oil Manager Input Assay 95
2.26 Domed Coned Aboveground Storage Tanks 60 4.9 Light Crude Distillation Input Data 96
2.27 Breathing losses in fixed roofs tanks 61 4.10 Light Crude Light Ends Input Data 96
2.28 External & Internal Floating Roof Tanks 61 4.11 Density Input Data 97
2.29 Tank dike 62 4.12 Light Crude Input Data 97
2.30 Tank Spray Nozzles 62 4.13 User Properties 98
2.31 Tank Sumps 63 4.14 Basic User Properties Definitions 98
2.32 Tank Risers 63 4.15 User Properties Sulfur Input 99
2.33 Tank Siphons 63 4.16 Sulfur Distribution 99
2.34 Tank Spreader 64 4.17 User Curves 99
 4.18 Output Blend 100 4.68 Atmospheric Tower Monitor 127
4.19 Installing Blends 100 4.69 Atmospheric Tower Connections 128
4.20 Components List-1 101 4.70 Atmospheric Tower Output Compositions 128
4.21 Unit Sets 101 4.71 Light Gas Conditions 129
4.22 Units of Measure 102 4.72 Naphtha Conditions 129
4.23 Display Units 102 4.73 Kerosene Conditions 130
4.24 Display Units Pressure Alteration 103 4.74 Diesel Conditions 130
4.25 Overall Units Design 103 4.75 AGO Conditions 131
4.26 Feed Preheating Unit Design 104 4.76 Atm Residue Conditions 131
4.27 Preheater1 Connections 104 4.77 Vacuum Tower Unit Design 132
4.28 Crude Oil Conditions 105 4.78 Vacuum Tower Environment 132
4.29 Preheater1 Conditions 106 4.79 Mixer Connections 133
4.30 Desalter Water Conditions 106 4.80 Steam Conditions 134
4.31 Desalter Water Conditions Molar Flow 107 4.81 Furnace Vacuum Connections 134
4.32 Desalter Water Compositions 107 4.82 Furnace Vacuum Conditions 135
4.33 Mixer Connections 108 4.83 Absorber Column Input 135
4.34 Mixer Conditions-1 108 4.84 Pumparound Inputs 136
4.35 Mixer Conditions-2 108 4.85 Side Operations Input 136
4.36 Mixer Renaming 109 4.86 Pumparound Specs 137
4.37 Preflashing Unit Design 109 4.87 Pumparound Pressure Specs 137
4.38 Preflash Connections 110 4.88 Vacuum Column Efficiencies 138
4.39 Preflash Design Parameters 110 4.89 Vacuum Column Profiles 138
4.40 Separator Unit Design 111 4.90 Vacuum Column Specs Summary 139
4.41 Separator Connections 111 4.91 LVGO Rate 139
4.42 Separator Conditions 112 4.92 Column Specification Types 140
4.43 Heating Unit Design 112 4.93 Vacuum Column Compositions 140
4.44 Furnace Connections 113 4.94 Vacuum Column Conditions 141
4.45 Furnace Parameters 113 4.95 Column LVGO & HVGO specs 142
4.46 Furnace Conditions 114 4.96 Column Liquid Flow Spec 142
4.47 Furnace Design 114 4.97 Vacuum Column Output Compositions 143
4.48 The Full Unit Output Conditions 114 4.98 Vacuum Gases Conditions 144
4.49 Atmospheric Unit Overall Design 115 4.99 LVGO Conditions 144
4.50 Atmospheric Tower Environment 116 4.100 HHGO Conditions 145
4.51 Distillation Column Inputs 118 4.101 Vacuum Reaid Conditions 145
4.52 Refluxed Absorber Pressure Inputs 118 4.102 Naphtha Methaforming Unit Design 146
4.53 Refluxed Absorber Temperature Inputs 119 4.103 Naphtha Mixing Unit Design 146
4.54 Refluxed Absorber Distillate Rate Inputs 119 4.104 Mixer Connections 147
4.55 Side Operations Inputs 120 4.105 Mixer Conditions 147
4.56 Pumparounds Inputs 120 4.106 Mixing Conditions 148
4.57 Side Products Inputs 121 4.107 Pump Connections 148
4.58 Pump-Around Specs 121 4.108 Pump Parameters 148
4.59 Atmospheric Tower Efficiencies 122 4.109 Pump Conditions 149
4.60 Atmospheric Tower Efficiencies Cont’d 123 4.110 Heater Connections 149
4.61 Atmospheric Tower Conditions 124 4.111 Heater Conditions 150
4.62 Atmospheric Tower Conditions Cont’d 124 4.112 Heater Parameter 150
4.63 Atmospheric Tower Compositions 125 4.113 Furnace Design 151
4.64 Atmospheric Tower Specs Summary 125 4.114 Furnace Connections 151
4.65 Column Specification Types 126 4.115 Furnace Conditions 151
4.66 Atmospheric Tower Design Specs 126 4.116 Methanol Reaction Design 152
4.67 Specs Parameters 127 4.117 Model Palette Options 152
4.118 Methanol Material Stream Conditions 152 4.144 Gasoline Conditions 165
4.119 Methanol Material Stream Compositions 153 4.145 LPG Conditions 166
4.120 Pump Connections 153 4.146 Water Conditions 166
4.121 Pump Conditions 154 4.147 Methaforming Units Outputs Compositions 167
4.122 Methanol Heater Connections 154 4.148 Column Properties Vs Tray Position 167
4.123 Methanol Heater Conditions 155 4.149 Component Ratio Vs Tray Position 168
4.124 Methanol Vaporization Design 155 4.150 Flow Vs Tray Position 168
4.125 Methanol Furnace Connections 155 4.151 Composition Vs Tray Position 169
4.126 Methanol Furnace Conditions 156 4.152 Pressure Vs Tray Position 169
4.127 Methaforming Reactor Connections 156 4.153 Temperature Vs Tray Position 170
4.128 Methaforming Reactor Conditions 157 5.1 Excel Data Generation 174
4.129 Stabilized Feed Conditions 157 5.2 Europe&North America Crudes Analysis Bar Chart 175
4.130 Stabilized Feed Compositions 158 5.3 Europe&North America Crudes Analysis Bar Chart 2 175
4.131 Reboiler Configuration 159 5.4 Excel Data Generation 176
4.132 Reboiler Inputs 159 5.5 Middle East & Asia Crudes Analysis Bar Chart 177
4.133 Reboiler Reflux Ratio 160 5.6 Middle East & Asia Crudes Analysis Bar Chart 177
4.134 Debutanizer Efficiencies 160 5.7 Excel Data Generation 178
4.135 Condenser Connections 161 5.8 Africa Crudes Analysis Bar Chart 179
4.136 Condenser Conditions 161 5.9 Africa Crudes Analysis Bar Chart 2 179
4.137 Reboiler Connections 162 5.10 Crude Oils Prices Compared to API Bar Chart 180
4.138 Reboiler Conditions 162
4.139 Methaformate Stabilizer Monitor 163
4.140 Methaformate Stabilizer Profiles 163
4.141 Methaformate Stabilizer Spec Summary 164
4.142 Methaformate Stabilizer Conditions 164
4.143 Methaformate Stabilizer Properties 165
 List of Tables

Table Name Page

1.1 Crude Oil Classes based on API & Sulfur Content 8
1.2 °API Gravity and Sulfur Levels of Some Important Crude Oils 8
1.3 Properties of some types of crude oils 9
1.4 Average Regional and Global Crude Oil Quality: 2008 (Actual) and 2030 (Projected) 11
1.5 Refinery Classification Scheme 12
1.6 Refinery Classes and Characteristic Yield Patterns 14
1.7 Important Classes of Refining Processes 15
2.1 Comparison between Trays 43
3.1 Light Naphtha Supply & Demand 80
3.2 Heavy Naphtha Supply & Demand 81
3.3 Material Balance of a Methaformer with Full Range Naphtha as a Feed 82
3.4 Typical Properties of Naphthas That Were Successfully Processed by Methaforming 82
3.5 Example of the Aromatic Shift 83
3.6 Properties of the Catalyst 85
3.7 Methaforming Unit Utilities Requirements 88
4.1 Atmospheric Column Conditions 117
4.2 Vacuum Column Conditions 133
4.3 Methaformate Stabilizer Column Conditions 158
5.1 Europe & North America Crude Oils Products Comparison 174
5.2 Middle East & Asia Crude Oils Products Comparison 175
5.3 Africa Crude Oils Products Comparison 178
5.4 Some Crude Oils API & Prices 180
 Abstract

Petroleum industry has a major share in the world energy and industrial markets. In the recent
years, petroleum industry has grown increasingly complex as a result of tighter competition,
stricter environmental regulations and lower-margin profits. It is facing a challenging task to
remain competitive in a globalized market, the fluctuating demand for petroleum products and the
current situation of fluctuating high petroleum crude oil prices is a demonstration that markets
and industries throughout the world are impacted by the uncertainty and volatility of the
petroleum industry.
These factors and others forced petroleum companies for a greater need in the strategic planning
optimization and sensitivity analysis in order to make decisions that satisfy conflicting multi-
objective goals of maximizing expected profit while simultaneously minimizing risk. These
decisions have to take into account uncertainties and constraints in factors such as the source and
availability of raw material, production and distribution costs and expected market demand.

This book discusses the full aspects concerning the Petroleum Refinery starting from its history
reaching a plant design for the products refinery processes and naphtha processing with the help
of an industrial simulation programs such as Aspen HYSYS. It covers refinery classification, crude
oil structure and economics, in addition to the refinery processing line from the beginning of the
handling of the feed introduced to plant units passing through the desalting, preheating, flashing
units till reaching the separation processes in distillation towers producing the refinery products,
vacuum tower distillation and the naphtha processing using the modern technique Methaforming
that are all discussed theoretically and simulated for a real-life Petroleum Plant Production Units
using the industrial simulating programs.

This finally demonstrate the full image of the petroleum refinery processes importance to the local
and international world of petroleum and petrochemical industries and human’s life.
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 Chapter (1)
Introduction to Petroleum Refining

(1.1) Background & History [1]

Petroleum refining is a unique and critical link in the petroleum supply chain, from the wellhead to the pump. The
other links add value to petroleum mainly by moving and storing it (e.g., lifting crude oil to the surface; moving
crude oil from oil fields to storage facilities and then to refineries; moving refined products from refinery to
terminals and end-use locations, etc.). Refining adds value by converting crude oil (which in itself has little end-use
value) into a range of refined products, including transportation fuels. The primary economic objective in refining
is to maximize the value added in converting crude oil into finished products.

Supply and demand for crude oil and petroleum products are the key factor in determining the status of world
economy. Petroleum is a vital source of energy that has, since 1990, met over 30% of the world’s energy demand
(the five other main sources of energy are natural gas, nuclear energy, hydroelectricity, renewables and coal)
(Cohen, 2016). It has contributed to the world’s economic, industrial and technological development with
applications that span from powering vehicles and electricity generation to construction and the manufacture of
plastics and other synthetics.

Figure 1.1 Energy Consumption Growth by Energy Source

Today, the world is heavily dependent on petroleum, and demand continues to rise steadily year on year. According
to the International Energy Agency 2015, oil and natural gas accounted for 36.1% and 26% respectively in 2015 of
the total global energy consumptions in the world. Oil accounted for the largest share of energy consumption since
1990, followed by Coal and natural gas as indicated in Figure 1.2. A rising global population and continued
economic growth mean that worldwide demand for petroleum products will remain high. If it is to meet this
demand, the petroleum industry must plan strategically and invest heavily in optimization tools.

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 Figure 1.2 Total Primary Energy Supply (TPES), 2015

All this depends on a supply chain (SC) made up of complex and expensive processes. The huge level of investment
required to plan and operate the chain has driven organizations to look for safe, cheap and efficient ways of
meeting customers' needs while ensuring things are done right the first time. This is important as errors in this
context may not only necessitate extra spending on correction (depending on the stage of the project), but may also
result in environmental damage and even fatal accidents. The petroleum industry is a material flow intensive. Since
supply chain cost amounts to 40% of total refining and distribution cost, effective management and optimization of
the chain are critical.

Historically, the modern petroleum industry began in 1859, when Edwin Drake drilled the first successful oil wells
in Pennsylvania, US. Prior to that time, petroleum was only available in very small quantities via the natural
seepage of subsurface oil in various areas throughout the world. With the discovery of ''rock oil'' in north-western
Pennsylvania, crude oil became available in sufficient quantities to allow the development of large-scale processing
systems.

During the 1930s and World War II, sophisticated refining processes involving the use of catalysts led to further
improvements in the quality of transportation fuels and further increased their supply. These improved processes—
including catalytic cracking of heavy oils, alkylation, polymerization, and isomerization—enabled the petroleum
industry to meet the demands of high-performance combat aircraft and, after the war, to supply increasing
quantities of transportation fuels.

The earliest refineries employed simple distillation units, or “stills,” to separate the various constituents of
petroleum by heating the crude oil mixture in a vessel and condensing the resultant vapors into liquid fractions.
Initially the primary product was kerosene, which proved to be a more abundant, cleaner-burning lamp oil of more
consistent quality than whale oil or animal fat.

The lowest-boiling raw product from the still was “straight run” naphtha, a forerunner of unfinished gasoline
(petrol). Its initial commercial application was primarily as a solvent. Higher-boiling materials were found to be
effective as lubricants and fuel oils, but they were largely novelties at first.

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The perfection of oil-drilling techniques quickly spread to Russia, and by 1890 refineries there were producing large
quantities of kerosene and fuel oils. The development of the internal-combustion engine in the later years of the
19th century created a small market for crude naphtha. But the development of the automobile at the turn of the
century sharply increased the demand for quality gasoline, and this finally provided a home for the petroleum
fractions that were too volatile to be included in kerosene. As demand for automotive fuel rose, methods for
continuous distillation of crude oil were developed.

More than 660 refineries, in 116 countries, are currently in operation, producing more than 85 million barrels of
refined products per day. Each refinery has a unique physical configuration, as well as unique operating
characteristics and economics. A refinery’s configuration and performance characteristics are determined primarily
by the refinery’s location, vintage, availability of funds for capital investment, available crude oils, product demand
(from local and/or export markets), product quality requirements, environmental regulations and standards, and
market specifications and requirements for refined products.

Most refineries in North America are configured to maximize gasoline production, at the expense of the other
refined products. Elsewhere, most of the existing refining capacity and virtually all new capacity is configured to
maximize distillate (diesel and jet fuel) production and, in some areas, petrochemical feedstock production, because
these products are enjoying the fastest demand growth in most regions of the world.

(1.2) Crude Oil – Structure, Classification & Economy [2][3]

Refineries exist to convert crude oil into finished petroleum products. Hence, to understand the fundamentals of
petroleum refining, one must begin with crude oil.

➢ The Chemical Constituents of Crude Oil

Hundreds of different crude oils (usually identified by geographic origin) are processed, in greater or lesser
volumes, in the world’s refineries.

Each crude oil is unique and is a complex mixture of thousands of compounds. Most of the compounds in crude oil
are hydrocarbons (organic compounds composed of carbon and hydrogen atoms). Other compounds in crude oil
contain not only carbon and hydrogen, but also small (but important) amounts of other (“hetero”-) elements –
most notably sulfur, as well as nitrogen and certain metals (e.g., nickel, vanadium, etc.). The compounds that make
up crude oil range from the smallest and simplest hydrocarbon molecule – CH4 (methane) – to large, complex
molecules containing up to 50 or more carbon atoms (as well hydrogen and hetero-elements).

The physical and chemical properties of any given hydrocarbon species, or molecule, depends not only on the
number of carbon atoms in the molecule but also the nature of the chemical bonds between them. Carbon atoms
readily bond with one another (and with hydrogen and hetero- atoms) in various ways – single bonds, double
bonds, and triple bonds – to form different classes of hydrocarbons, as illustrated in Figure 1.3 in the next page.

Paraffins, aromatics, and naphthenes are natural constituents of crude oil, and are produced in various refining
operations as well. Olefins usually are not present in crude oil; they are produced in certain refining operations that
are dedicated mainly to gasoline production. As Exhibit 1 indicates, aromatic compounds have higher carbon-to-
hydrogen (C/H) ratios than naphthenes, which in turn have higher C/H ratios than paraffins.

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The heavier (more dense) the crude oil, the higher its C/H ratio. Due to the chemistry of oil refining, the higher the
C/H ratio of a crude oil, the more intense and costly the refinery processing required to produce given volumes of
gasoline and distillate fuels. Thus, the chemical composition of a crude oil and its various boiling range fractions
influence refinery investment requirements and refinery energy use, the two largest components of total refining
cost.

The proportions of the various hydrocarbon classes, their carbon number distribution, and the concentration of
hetero-elements in a given crude oil determine the yields and qualities of the refined products that a refinery can
produce from that crude, and hence the economic value of the crude. Different crude oils require different refinery
facilities and operations to maximize the value of the product slates that they yield.

Figure 1.3 Important Classes of Hydrocarbon Compounds in Crude Oil

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 ➢ Characterizing & Classifying Crude Oils
Assessing the refining value of a crude oil requires a full description of the crude oil and its components, involving
scores of properties. However, two properties are especially useful for quickly classifying and comparing crude oils:
API gravity (a measure of density) and sulfur content.

• API Gravity (Density)

The density of a crude oil indicates how light or heavy it is, as a whole. Lighter crudes contain higher proportions of
small molecules, which the refinery can process into gasoline, jet fuel, and diesel (for which demand is growing).
Heavier crudes contain higher proportions of large molecules, which the refinery can either (1) use in heavy
industrial fuels, asphalt, and other heavy products (for which the markets are less dynamic and in some cases
shrinking) or (2) process into smaller molecules that can go into the transportation fuels products.

The classifications of crude oils as light or heavy depend on its density and specific gravity. American Petroleum
Institute (API) gravity is the common measure of crude oil density; the heaviness of the crude oil is measured in
comparison to water. It is calculated by the formula: API gravity = (141.5/SG) – 131.5 Where SG = Specific gravity
of oil.

In the refining industry, the density of an oil is usually expressed in terms of API gravity, a parameter whose units
are degrees (o API) – e.g., 35o API. API gravity varies inversely with density (i.e., the lighter the material, the higher
its API gravity). By definition, water has API gravity of 10o.

Figure 1.4 indicates the quality of a typical light crude (35°API) and a typical heavy crude (25°API), in terms of their
natural yields of light gases, gasoline components, distillate (mainly jet fuel and diesel) components, and heavy
oils. The exhibit also shows the average demand profile for these product categories in the developed countries.

Figure 1.4 Typical Natural Yields of Light and Heavy Crude Oils

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The natural yields of the heavy oils from both the light and the heavy crudes exceed the demand for heavy
refined products, and the natural yield of heavy oil from the heavy crude is more than twice that of the light
crude. These general characteristics of crude oils imply that (1) refineries must be capable of converting at least
some, and perhaps most, of the heavy oil into light products, and (2) the heavier the crude, the more of this
conversion capacity is required to produce any given product slate.

• Sulfur Content
Of all the hetero-elements in crude oil, sulfur has the most important effects on refining.
Sufficiently high sulfur levels in refinery streams can (1) deactivate (“poison”) the catalysts that promote desired
chemical reactions in certain refining processes, (2) cause corrosion in refinery equipment, and (3) lead to air
emissions of sulfur compounds, which are undesirable and may be subject to stringent regulatory controls.
Sulfur in vehicle fuels leads to undesirable vehicle emissions of sulfur compounds and interferes with vehicle
emission control systems that are directed at regulated emissions such as volatile organic compounds, nitrogen
oxides, and particulates.

Consequently, refineries must have the capability to remove sulfur from crude oil and refinery streams to the
extent needed to mitigate these unwanted effects. The higher the sulfur content of the crude, the greater the
required degree of sulfur control and the higher the associated cost.

The sulfur content of crude oil and refinery streams is usually expressed in weight percent (wt%) or parts per
million by weight (ppmw). In the refining industry, crude oil is called sweet (low sulfur) if its sulfur level is less
than a threshold value (e.g., 0.5 wt% (5,000 ppmw)) and sour (high sulfur) if its sulfur level is above a higher
threshold. Most sour crudes have sulfur levels in the range of 1.0–2.0 wt%, but some have sulfur levels > 4 wt%.

Within any given crude oil, sulfur concentration tends to increase progressively with increasing carbon number.
Thus, crude fractions in the fuel oil and asphalt boiling range have higher sulfur content than those in the jet and
diesel boiling range, which in turn have higher sulfur content than those in the gasoline boiling range. Similarly,
the heavier components in, say, the gasoline boiling range have higher sulfur content than the lighter
components in that boiling range.

Table 1.1 shows a widely-used scheme for classifying crude oils on the basis of their API gravity and sulfur
content. Each crude class is defined by a range of API gravity and a range of sulfur content; the names of the
categories indicate these ranges in qualitative terms.

Table 1.2 lists some important crude oils in the world oil trade and indicates the API gravity/sulfur classification
for each of these crudes.

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 Property Range

Crude Oil Class Gravity Sulfur

(°API ) (wt.%)

Light Sweet 35-60 0-0.5

Light Sour 35-60 > 0.5

Medium Medium Sour 26-35 0-1.1

Medium Sour 26-35 > 1.1

Heavy Sweet 10-26 0-1.1

Heavy Sour 10-26 > 1.1

Table 1.1 – Crude Oil Classes based on API & Sulfur Content

Properties
Country of
Crude Oil Crude Oil Class
Origin Gravity Sulfur
(°API ) (wt.%)

Brent U.K. 40.0 0.5

Light Sweet
West Texas Intermediate U.S.A. 39.8 0.3

Arabian Extra Lt. Export Saudi Arabia Light Sour 38.1 1.1

Daqing China 33.0 0.1

Medium Medium Sour
Forcados Export Nigeria 29.5 0.2

Arabian Light Export Saudi Arabia 34.0 1.9

Medium Sour
Kuwait Export Blend Kuwait 30.9 2.5

Marlim Export Brazil 20.1 0.7

Heavy Sweet
Cano Limon Colombia 25.2 0.9

Oriente Export Maya Ecuador 25.0 1.4

Heavy Sour
Heavy Export Mexico 21.3 3.4

Table 1.2 – °API Gravity and Sulfur Levels of Some Important Crude Oils

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 • Paraffinic/Naphthenic/Aromatic Crude Oils
Crude oil may be paraffinic, naphthenic and aromatics depending on the relative proportion of hydrocarbons that
are present. Paraffin or Alkanes are presented by general formula (Cn H2n+2), the simplest compound of Alkanes
is Methane (CH4). Other types of saturated hydrocarbons are Naphthalene or Cycloalkanes. These have at least
one ring of carbon and are denoted by the general formula Cn H2n). A common example is Cyclohexane (C6H12)
Roussel and Boulet (1995b). Aromatics are unsaturated compounds classics according to Benzene rings. Light
petroleum fractions contain mono- aromatics which have one benzene ring such as toluene (CH3). The heaviest
portion of the crude oil contains asphaltenes which are condensed Polynuclear aromatic compounds of complex
structure.
Crude Source Paraffin Naphthenic Aromatics Sulphur API

% vol. % vol. % vol. % wt. gravity

(˚API)
Light Crudes
Saudi Light 63 18 19 2.0 34
South Louisiana 79 45 19 0.0 35

Bery1 47 34 19 0.4 37
North Sea Brent 50 34 16 0.4 37

Lost Hills Light 50% 50 0.9 > 38

Aliphatic
Mid-range Crudes
Venezuela Light 52 34 14 1.5 30

Kuwait 63 20 24 2.4 31
USA West 46 32 22 1.9 32
Texas Sour
Heavy Crudes
Prudhoe Bay 27 36 28 0.9 28
Saudi Heavy 60 20 15 2.1 28
Venezuela Heavy 35 53 12 2.3 24

Table 1.3 - Properties of some types of crude oils

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 ➢ Crude Oil Refining Economics

World oil production grew steadily from about 400,000 barrels a day in 1900 to over 86 million barrels a day in
2013. The International Energy Agency (2013) expects this to rise to about 96 million barrels a day by 2035.

Crude Oil Quality Influences Crude Oil Pricing

The popular press often refers to “the price of crude oil,” as though all crude oils were priced the same. In fact,
they are not. The higher the crude quality, the higher the market price relative to the prevailing average price for
all crude oil. In other words, light sweet crudes carry a price premium relative to medium and heavy sour crudes.
Light sweet crudes have higher refining value than heavier, more sour crudes, because (1) light crudes have higher
natural yields of the components that go into the more valuable light products, and (2) sweet crudes contain less
sulfur. Hence, light sweet crudes require less energy to process and call for lower capital investment to meet given
product demand and quality standards than heavier, more sour crudes.
Refiners therefore face a key economic choice in meeting product demand and quality standards. They can either
pay a price premium for higher quality crudes to capture their economic benefits or incur higher investment in
refinery capital stock and higher refining costs to take advantage of the relatively lower prices of lower quality
crudes.
Light sweet/heavy sour price differentials fluctuate over time and vary from place to place, due to the interplay of
many technical and economic factors. These factors include crude quality differentials, crude supply/demand
balances, local product markets and product specifications, and local refining capacity and upgrading capabilities.
However, in general, the light sweet/heavy sour price differential tends to (1) increase (in absolute terms) with
increasing world oil price level and (2) range from about 15% to 25% of the average price of light sweet crude.

Average Crude Oil Quality is Trending Down

The average API gravity and sulfur content of aggregate refinery crude slates varies by region; some regions process
lighter, sweeter crude slates than others. However, over time, the average quality of the global crude slate has been
declining gradually. Average API gravity has been decreasing, but slowly. Average sulfur content has been
increasing more rapidly, a trend likely to continue for the foreseeable future.

Illustrating this trend, Table 1.4 shows estimated crude quality, in terms of API gravity and sulfur content, in
various regions of the world for 2008 (actual) and 2030 (projected),

10
 2008 (Actual) 2030 (Projected)
Region
Gravity Sulfur Gravity Sulfur
(°API) (wt%) (°API) (wt%)

North America 31.2 1.21 28.7 1.66

Latin America 25.1 1.59 23.5 1.57

Europe 37.1 0.37 37.4 0.38

Commonwealth of Independent States 32.5 1.09 35.1 0.97

Asia-Pacific 35.4 0.16 35.7 0.16

Middle East 34.0 1.75 33.9 1.84

Africa 36.5 0.31 37.1 0.26

World Average 33.0 1.1 32.9 1.3

Table 1.4 - Average Regional and Global Crude Oil Quality: 2008 (Actual) and 2030 (Projected)

Also, the volatility of oil prices has a direct impact on the prices of petroleum products, which in turn have a
negative impact on other goods and services. For example, in the United States, the cost of crude oil account for
53% of retail price of gasoline. Figure 1.5 shows the volatility of prices for a type of crude oil. Oil price fluctuation
considered a source of uncertainty affecting the cost of an essential input; this creates uncertainty regarding
company profitability and valuations, which can have a knock-on effect on investment.

Figure 1.5 Price Volatility for a crude oil

11
 (1.3) Refinery Classification [4] [5]

▪ Classifying Refineries by Configuration and Complexity

Each refinery’s configuration and operating characteristics are unique. They are determined primarily by the
refinery’s location, vintage, preferred crude oil slate, market requirements for refined products, and quality
specifications (e.g., sulfur content) for refined products.
In this context, the term configuration denotes the specific set of refining process units in a given refinery, the size
(throughput capacity) of the various units, their salient technical characteristics, and the flow patterns that connect
these units.

Although no two refineries have identical configurations, they can be classified into groups of comparable
refineries, defined by refinery complexity.
In this context, the term complexity has two meanings. One is its non-technical meaning: intricate, complicated,
consisting of many connected parts. The other is a term of art in the refining industry: a numerical score that
denotes, for a given refinery, the extent, capability, and capital intensity of the refining processes downstream of
the crude distillation unit (which, by definition, has complexity of 1.0). The higher a refinery’s complexity, the
greater the refinery’s capital investment intensity and the greater the refinery’s ability to add value to crude oil by
1. Converting more of the heavy crude fractions into lighter, high-value products and
2. Producing light products to more stringent quality specifications (e.g., ultra-low sulfur fuels).

Broadly speaking, all refineries belong to one of four classes, defined by process configuration and refinery
complexity, as shown in Table 1.5.

Complexity

Configuration Ranking Range

Topping Low <2

Hydroskimming Moderate 2 -- 6

Conversion High 6 -- 12

Deep Conversion Very high > 12

Table 1.5 - Refinery Classification Scheme

12
 Topping refineries have only crude distillation and basic support operations. They have no capability to alter
the natural yield pattern of the crude oils that they process; they simply separate crude oil into light gas and
refinery fuel, naphtha (gasoline boiling range), distillates (kerosene, jet fuel, diesel and heating oils), and
residual or heavy fuel oil. A portion of the naphtha material may be suitable for very low octane gasoline in
some cases. Topping refineries have no facilities for controlling product sulfur levels and hence cannot
produce ULSF.
 Hydroskimming refineries include not only crude distillation and support services but also catalytic
reforming, various hydrotreating units, and product blending. These processes enable
(1) upgrading naphtha to gasoline and (2) controlling the sulfur content of refined products. Catalytic
reforming upgrades straight run naphtha to meet gasoline octane specification and produces by-product
hydrogen for the hydrotreating units. Hydrotreating units remove sulfur from the light products (including
gasoline and diesel fuel) to meet product specifications and/or to allow for processing higher-sulfur crudes.

Hydroskimming refineries, commonplace in regions with low gasoline demand, have no capability to alter
the natural yield patterns of the crudes they process.

 Conversion (or cracking) refineries include not only all of the processes present in hydroskimming refineries
but also, and most importantly, catalytic cracking and/or hydrocracking. These two conversion processes
transform heavy crude oil fractions (primarily gas oils), which have high natural yields in most crude oils,
into light refinery streams that go to gasoline, jet fuel, diesel fuel, and petrochemical feedstocks.
Conversion refineries have the capability to improve the natural yield patterns of the crudes they process as
needed to meet market demands for light products, but they still (unavoidably) produce some heavy, low-
value products, such as residual fuel and asphalt.

 Deep Conversion (or coking) refineries are, as the name implies, a special class of conversion refineries.
They include not only catalytic cracking and/or hydrocracking to convert gas oil fractions, but also coking.
Coking units “destroy” the heaviest and least valuable crude oil fraction (residual oil) by converting it into
lighter streams that serve as additional feed to other conversion processes (e.g., catalytic cracking) and to
upgrading processes (e.g., catalytic reforming) that produce the more valuable light products.
Deep conversion refineries with sufficient coking capacity destroy essentially all of the residual oil in their crude
slates, converting them into light products.

Almost all U.S. refineries are either conversion or deep conversion refineries, as are the newer refineries in Asia,
the Middle East, South America, and other areas experiencing rapid growth in demand for light products. By
contrast, most refining capacity in Europe and Japan is in hydroskimming and conversion refineries.

In the U.S. and in many other countries, including Brazil, China, India, and Mexico, conversion and deep
conversion refineries constitute more than 95% of total crude running capacity, and essentially 100% of crude
running capacity in refineries with > 50 K Bbl/day of crude distillation capacity.

13
 Table 1.6 summarizes the salient features of the different refinery classes and indicates their characteristic
product yield patterns at constant crude oil quality.

Product Yield
Profile (vol%)
Refinery Category Characteristic Processes Comments
Diesel &
Gasoline
Jet
 Product sulfur levels same as crude fraction
sulfur levels
Topping Crude distillation 31 30  Product yields and quality determined solely by
crude properties
 Gasoline has low octane
 Product sulfur levels controllable by hydrotreating
Crude distillation
Hydroskimming Reforming 28 30  Some capability to improve product yields and
quality
Hydrotreating
 Gasoline octane improved by reforming
Crude distillation
FCC and/or hydrorcracking  Product sulfur levels controllable by hydrotreating
Conversion Reforming 44 32  Substantial capability for yield and quality
Alkylation & other upgrading improvement
Hydrotreating
Crude distillation
Coking  Product sulfur levels controllable by hydrotreating
Deep Conversion FCC and/or hydrorcracking  Maximum yields of high-value refined products
47 42
Reforming  Maximum capability for quality improvement
Alkylation & other upgrading  Essentially all residual oil "destroyed"
Hydrotreating

Table 1.6 - Refinery Classes and Characteristic Yield Patterns

▪ Classes of Refining Processes

The physical and chemical transformations that crude oil undergoes in a refinery take place in numerous distinct
processes, each carried out in a discrete facility, or process unit. Large modern refineries comprise as many as fifty
distinct processes, operating in close interaction. However, for tutorial purposes, these processes can be thought
of in terms of a few broad classes, shown in Table 1.7.

14
 Class Function Examples

 Separate crude oil charge into boiling range fractions for  Atmospheric distillation
Crude Distillation
further processing  Vacuum distillation

 Break down ("crack") heavy crude fractions into lighter  Fluid catalytic cracking (FCC)
Conversion ("Cracking")
refinery streams for further processing or blending  Hydrocracking

 Rearrange molecular structures to improve the properties  Catalytic reforming

Upgrading
(e.g., octane) and value of gasoline and diesel components  Alkylation, Isomerization
 FCC feed hydrotreating
 Remove hetero-atom impurities (e.g., sulfur) from refinery  Reformer feed hydrotreating
Treating streams and blendstocks  Gasoline and distillate
 Remove aromatics compounds from refinery streams hydrotreating
 Benzene saturation
 Separate, by physical or chemical means, constituents of  Fractionation (numerous)
Separation
refinery streams for quality control or for further processing  Aromatics extraction

 Combine blendstocks to produce finished products that  Gasoline blending

Blending
meet product specifications and environmental standards  Jet and diesel blending
 Refinery fuel, power, and steam supply; sulfur recovery; oil  Power generation
Utilities movements; crude and product storage; emissions control;
etc.  Sulfur recovery

Table 1.7 - Important Classes of Refining Processes

These categories are discussed briefly below.

▪ Crude Distillation
Crude oil distillation is the front end of every refinery, regardless of size or overall configuration. It has a unique
function that affects all the refining processes downstream of it.
Crude distillation separates raw crude oil feed (usually a mixture of crude oils) into a number of intermediate
refinery streams (known as “crude fractions” or “cuts”), characterized by their boiling ranges (a measure of their
volatility, or propensity to evaporate). Each fraction leaving the crude distillation unit (1) is defined by a unique
boiling point range (e.g., 180o–250o F, 250o–350o F, etc.) and (2) is made up of hundreds or thousands of distinct
hydrocarbon compounds, all of which have boiling points within the cut range. These fractions include (in order of
increasing boiling range) light gases, naphthas, distillates, gas oils and residual oil.

The naphthas are gasoline boiling range materials; they usually are sent to upgrading units (for octane
improvement, sulfur control, etc.) and then to gasoline blending. The distillates, including kerosene, usually
undergo further treatment and then are blended to jet fuel, diesel and home heating oil. The gas oils go to
conversion units, where they are broken down into lighter (gasoline, distillate) streams. Finally, the residual oil (or
bottoms) is routed to other conversion units or blended to heavy industrial fuel and/or asphalt. The bottoms have
relatively little economic value – indeed lower value than the crude oil from which they come.

15
Most modern refineries convert, or upgrade, the low-value heavy ends into more valuable light products (gasoline,
jet fuel, diesel fuel, etc.). Because all crude oil charged to the refinery goes through crude distillation, refinery
capacity is typically expressed in terms of crude oil distillation throughput capacity.

▪ Conversion (Cracking) Processes

Conversion processes carry out chemical reactions that fracture (“crack”) large, high-boiling hydrocarbon
molecules (of low economic value) into smaller, lighter molecules suitable, after further processing, for blending
to gasoline, jet fuel, diesel fuel, petrochemical feedstocks, and other high-value light products. Conversion units
form the essential core of modern refining operations because they (1) enable the refinery to achieve high yields of
transportation fuels and other valuable light products, (2) provide operating flexibility for maintaining light
product output in the face of normal fluctuations in crude oil quality, and (3) permit the economic use of heavy,
sour crude oils.

The conversion processes of primary interest are fluid catalytic cracking (FCC), hydrocracking, and Coking.

Fluid Catalytic Cracking

FCC is the single most important refining process downstream of crude distillation, in terms of both industry-wide
throughput capacity and its overall effect on refining economics and operations.

FCC offers (1) high yields of gasoline and distillate material (in the range of 60–75 vol% on FCC feed), (2) high
reliability and low operating costs, and (3) operating flexibility to adapt to changes in crude oil quality and refined
product requirements. In a large, transportation fuels oriented refinery, the FCC unit accounts for more than 40%
of the total refinery output of gasoline and distillate fuels (e.g., diesel).

FCC also produces significant volumes quantities of light gases (C1 to C4), including olefins. Light olefins are highly
reactive chemicals that are valuable either as petrochemical feed stocks or as feedstocks to the refinery’s upgrading
processes (which produce high-octane, low-sulfur gasoline blend stocks). With suitable catalyst selection, FCC units
can be designed to maximize production of gasoline blend stock (FCC naphtha), distillate blend stock (light cycle
oil), or petrochemical feedstocks.

Sulfur is a “poison” to FCC catalysts; that is, contact with sulfur reduces the effectiveness of FCC catalysts. To
alleviate this problem, many refineries have desulfurization units in front of the FCC that remove much of the
sulfur from the FCC feed. Even with such units in place, the refinery streams produced by the FCC unit still contain
some of the sulfur that was present in the FCC feed. Indeed, untreated FCC products (FCC naphtha and light cycle
oil) are the primary sources of sulfur in gasoline and diesel fuel.

16
Hydrocracking
Hydrocracking, like FCC, converts distillates and gas oils from crude distillation (as well as other heavy refinery
streams), primarily to gasoline and distillates. Hydrocracking is a catalytic process that operates at moderate
temperature and high pressure. It applies externally-generated hydrogen to crack distillate and heavy gas oil feeds
into light gases, petrochemical feedstocks, and gasoline and diesel fuel blend stocks.

Like FCC, hydrocracking offers high yields of light products and extensive operating flexibility. Product yields from
hydrocracking depend on how the unit is designed and operated. At one operating extreme, a hydrocracker can
convert essentially all of its feed to gasoline blend stocks, with yields ≈100vol% on feed. Alternatively, a
hydrocracker can produce jet fuel and diesel fuel, with combined yields of 85% to 90vol%, along with small
volumes of gasoline material.

Hydrocracking has a notable advantage over FCC; the hydrogen input to the hydrocracker not only leads to
cracking reactions but also to other reactions that remove hetero-atoms –especially sulfur –from the hydrocracked
streams. These “hydrotreating” reactions yield hydrocracked streams with very low sulfur content and other
improved properties.

Coking
Coking is a thermal, non-catalytic conversion process that cracks residual oil, the heaviest residue from crude
distillation, into a range of lighter intermediates for further processing. Coking is the refining industry’s primary
(but not sole) means of converting residual oil –the “bottom of the crude barrel” –into valuable lighter products.

The cracked products from coking comprise light gases (including light olefins), low quality naphtha (coker
naphtha) and distillate streams (coker distillate) which must be further processed, and large volumes of coker gas
oil and of petroleum coke (≈25–30 wt% on feed).

The coker gas oil is used primarily as additional FCC feed. However, coker gas oil contains high levels of sulfur and
other contaminants, which make it a less valuable FCC feed than straight run gas oils.

▪ Upgrading Processes
Upgrading processes carry out chemical reactions that combine or re-structure molecules in low-value streams to
produce higher-value streams, primarily high-octane, low sulfur gasoline blend stock. The upgrading processes of
primary interest all employ catalysts, involve small hydrocarbon molecules, and apply to gasoline production.
The most important of the many upgrading processes are catalytic reforming, alkylation, isomerization,
polymerization, and etherification.

Catalytic Reforming
Catalytic reforming (or, simply, “reforming”) is the most widely used upgrading process, particularly in U.S.
refineries. Reforming units process various naphtha streams (primarily, but no exclusively, straight run naphthas
from crude distillation). Reformers carry out a number of catalytic reactions on these naphtha streams that
significantly increase the octane of these streams (in some instances by as much as 50 octane numbers). The
reformer output (called reformate) is premium, high-octane gasoline blend stock. Catalytic reforming is a core
refining process. It is both the primary refinery source of incremental octane for gasoline and the primary means of
regulating the octane of the gasoline pool.

17
Alkylation
Alkylation combines light olefins (primarily C4s, and some C3) with iso-butane (see Exhibit 1) to produce a high-
octane (≈90–94RON) gasoline blend stock (alkylate). The light olefins and most or all of the iso-butane come from
the refinery FCC unit.8Hence, alkylation units are found only in refineries having FCC units. Due to the nature of
the alkylation process, alkylate contains no aromatics and no sulfur, making it a premium gasoline blend stock.

Polymerization
Polymerization combines two or three light olefin molecules (C3 or C4) to produce a high-octane, olefinic gasoline
blend stock (poly gasoline) component. Polymerization is a relatively inexpensive process. But it is not widely used,
because poly gasoline is a relatively undesirable gasoline blend stock. It is highly olefinic, and olefins are unstable in
gasoline (they tend form gum in storage).

Etherification
Etherification combines C4 and/or C5 olefins produced by FCC plants with a purchased alcohol (methanol or
ethanol) to produce an ether (a class of oxygen-containing organic compounds). Ethers are premium gasoline blend
stocks, with very high octane and other desirable blending properties. The most common etherification process
combines methanol with iso-butene (a C4 olefin) to produce methyl tertiary butyl ether (MTBE).

▪ Treating (Hydrotreating) Processes

Treating processes carry out chemical reactions that remove hetero-atoms (e.g., sulfur, nitrogen, heavy metals)
and/or certain specific compounds from crude oil fractions and refinery streams, for various purposes. The most
important purposes are (1) meeting refined product specifications (e.g.; sulfur in gasoline and diesel fuel, benzene
in gasoline, etc.) and (2) protecting the catalysts in many refining processes from deactivation (“poisoning”)
resulting from prolonged contact with hetero-atoms.

By far the most widely-used of the various treating technologies is catalytic hydrogenation, or hydrotreating.
Hydrotreaters remove hetero-atoms by reacting the refinery streams containing the hetero-atom(s) with hydrogen
in the presence of a catalyst. The hydrogen combines with the hetero-atom(s)to form non-hydrocarbon molecules
that are easily separated from refinery streams.10Hydrotreating has many forms and degrees of severity; as a
result, it goes by many names in the refining industry and in the literature.

Hydrotreating focused on sulfur removal is often referred to as hydro-desulfurization; hydrotreating focused on

nitrogen removal is called hydro-denitrification; and so on. Hydrotreating conducted at high severity (i.e., high
temperature, pressure, and hydrogen concentration) often involves some incidental hydrocracking as well. Deep
hydrotreating of this kind is called hydro-refining. Hydrotreating conducted at low severity is used to modify
certain characteristics of specialty refined products (e.g., various lubricating oil properties) to meet specifications.
Mild hydrotreating is often called hydro-finishing.

18
 ▪ Separation Processes
Virtually all refinery streams are mixtures of hydrocarbon compounds. Separation processes use differences in the
physical and chemical properties of these compounds to separate one refinery stream into two or more new ones.

Distillation, or fractionation, the most common separation process, uses differences in boiling point temperatures
to effect separations into relatively lighter (lower boiling) and relatively heavier (higher boiling) mixtures.
Distillation employs well-established technology and is doubtless the most widely used refining process; distillation
units (fractionators) are ubiquitous in refineries.

Distillation units require significant inputs of thermal energy, to boil the more volatile components of the mixture
being separated. Consequently, a refinery’s distillation units, including crude distillation, collectively account for a
significant fraction of the refinery’s total energy use.

Extraction, another common separation process, uses differences in the relative solubilities of different compounds
in a liquid solvent to remove specific compounds from hydrocarbon mixtures. The most common refining
application of extraction is aromatics extraction, which selectively removes certain aromatics compounds from the
highly aromatic reformate stream produced in catalytic reforming. The extracted aromatics (benzene, toluene, and
xylenes) are primary petrochemical feedstocks.

▪ Utilities and Support Operations

Refineries encompass many additional process units of varying complexity and purpose. Some produce specialty
products (waxes, lubricants, asphalt, etc.); others control emissions to air and water; and still others provide
support to the mainline processes discussed above.

The primary support facilities include

 Hydrogen production and recovery,

 Sulfur recovery (from desulfurization processes)
 Light gas handling and separation,
 Wastewater treatment
 Oil movement and storage
 Electricity and steam generation

Hydrocrackers and hydrotreaters require substantial inputs of hydrogen. As noted above, some of the refinery
hydrogen requirement (about 45% of the total in U.S. refineries) is met by by-product hydrogen produced in the
reformer. The rest of the hydrogen requirement is met by on-purpose hydrogen production units in the refinery
or (in some locales) by purchases of hydrogen from near- by merchant hydrogen plants. These units produce
hydrogen from natural gas. Because on- purpose hydrogen is expensive, regardless of its source, most refineries
also have facilities for recovering and recycling the spent hydrogen in hydrocracking and hydrotreating effluent
streams.

19
Refinery processes use fuel and steam to heat and/or boil process streams and to provide the energy needed to
drive chemical reactions, and they use electricity for running pumps and compressors. Some refineries purchase
fuel (natural gas), electricity, and/or steam; others generate some or all of their utilities on-site. On-site generation
involves traditional steam boilers and power generation facilities, or co-generation. Co-generation is the integrated
production of electricity and steam, at very high thermal efficiency, using either purchased natural gas or refinery-
produced light gas as fuel.

▪ Product Blending
Product blending, the operation at the back end of every refinery, regardless of size or overall configuration, blends
refinery streams in various proportions to produce finished refined products whose properties meet all applicable
industry and government standards, at minimum cost. The various standards pertain to physical properties (e.g.,
density, volatility, boiling range); chemical properties (e.g., sulfur content, aromatics content, etc.), and
performance characteristics (e.g., octane number, smoke point).

Production of each finished product requires multi-component blending because (1) refineries produce no single
blend component in sufficient volume to meet demand for any of the primary blended products such as gasoline,
jet fuel, and diesel fuel,(2) many blend components have properties that satisfy some but not all of the relevant
standards for the refined product into which they must be blended, and (3) cost minimization dictates that refined
products be blended to meet, rather than exceed, specifications to the extent possible. Typically, gasoline is a
mixture of ≈6–10 blend stocks; diesel fuel is a mixture of ≈4–6 blend stocks.

Gasoline blending is the most complex and highly automated blending operation. In mod ern refineries, automated
systems meter and mix blend stocks and additives. On-line analyzers (supplemented by laboratory analyses of
blend samples) continuously monitor blend properties. Computer control and mathematical models establish blend
recipes that produce the required product volumes and meet all blend specifications, at minimum production cost.
Blending of other products usually involves less automation and mathematical analysis.

(1.4) Petroleum Supply Chain [6]

Supply chain management (SCM) is a term that has been defined as the planning and flow of materials and
products to deliver goods and services to end consumers. Christopher and Gattorna (2005) define the supply chain
as: “The network of organizations that are involved, through upstream and downstream linkages, in the different
processes and activities that produce value in the form of products and services delivered to the ultimate
consumer”.

20
Management of the supply chain involves planning the flow of materials and products so as to ensure that these
products and services are delivered to end consumers in a timely and cost-efficient way. Christopher (2010) defines
SCM as: “the management of upstream and downstream relationships with suppliers and customers with the aim
of delivering superior customer value at less cost to the SC as a whole”. Lambert and Cooper (2000) add that it is:
“the integration of key business processes from original supplier through to end user that provides products,
services, and information that add value for customers and other stakeholders".

The definitions characterize the SC as an integrated process in which a number of distinct business entities (e.g.
customers, suppliers, manufacturers, distributors and retailers) collaborate to: (1) obtain raw materials, (2) process
these raw materials into the required final products and (3) deliver these products to retailers/customers. Materials
usually flow forwards along the chain, while information flow backwards (Beamon, 1998).

A typical petroleum supply chain involves oil exploration, oil production, oil transportation, crude oil storage (tanks
are connected to the refinery by a network of pipelines), refinery operations, inventory of the finished products
and distribution (via distribution centers). Strategic, tactical and operational decision making is required at all
stages of the chain. Figure 1.6 displays the typical petroleum industry supply chain, from exploration and petroleum
production, through processing and storage, to distribution and marketing of the refined products to consumers.

Figure 1.6 Typical Petroleum Supply Chain

21
As in any other industry, the petroleum supply chain comprises multiple entities performing multiple functions.
These functions may be classified as upstream, midstream and downstream, according to their position within the
chain as shown in Figure 1.7. Upstream activities include all exploration activities (e.g. seismic, geophysical and
geological investigations) and oil extraction operations such as drilling, production, facility engineering and
reservoir maintenance. This is the highest level of the chain as activities at this stage have a significant influence
on the operation of the SC as a whole. The midstream consists of the infrastructure used to transport crude oil and
gas to refineries for conversion, along with the storage tanks.

Finally, the downstream comprises the processing, transportation, marketing and distribution of petroleum
products to end users. The recovered crude oil is transformed into higher value products such as gasoline, kerosene,
diesel and naphtha in the refinery. These products are transported to distribution centers via pipeline, ships or rail,
with trucks then being used for the last stage of the journey from the distribution center to the retailer. Some
petroleum companies are fully integrated; operating at all three levels of the chain, while others may be active at
just one or two levels.

Figure 1.7 Upstream, Midstream, and Downstream Activities

22
 Chapter (2)
Petroleum Refinery Processing

Fundamentals of Refinery Processing [7]

Petroleum refineries are large, capital-intensive, continuous-flow manufacturing facilities. They transform crude
oils into finished, refined products (most notably LPG, gasoline, jet fuel, diesel fuel, petrochemical feedstocks, home
heating oil, fuel oil, and asphalt) by (1) separating crude oils into different fractions (each with a unique boiling
range and carbon number distribution) and then (2) processing these fractions into finished products, through a
sequence of physical and chemical transformations.

Figure 2.1 is a simplified flow chart of a notional (typical) modern refinery producing a full range of high-quality
fuels and other products. It is intended only to suggest the extent and complexity of a refinery’s capital stock, the
number of process units in a typical refinery, and the number of co- products that a refinery produces. An
appreciation of this complexity is essential to a basic understanding of the refining industry.

Figure 2.1 Notional (Very) Complex Refinery

23
Several aspects of refining operations suggested by Exhibit 7 merit comment. Refineries produce dozens of refined
products (ranging from the very light, such as LPG, to the very heavy, such as residual fuel oil). They do so not
only because of market demand for the various products, but also because the properties of crude oil and the
capabilities of refining facilities impose constraints on the volumes of any one product that a refinery can produce.
Refineries can – and do – change the operations of their refineries to respond to the continual changes in crude oil
and product markets, but only within physical limits defined by the performance characteristics of their refineries
and the properties of the crude oils they process. Finally, the complexity of refinery operations is such that they
can be fully understood and optimized, in an economic sense, only through the use of refinery-wide mathematical
models. Mathematical models of refinery operations are the only reliable means of generating achievable (i.e.,
feasible) and economic (i.e., optimal) responses to changes in market environment and to the introduction of new
(usually more stringent) product specifications.

Figure 2.2 is a simpler schematic representation of a petroleum refinery, more useful for purposes of this tutorial.
This exhibit illustrates, in schematic form, the separation of crude oil into specific boiling range (carbon number)
fractions in the crude distillation process, shows standard industry names for these crude fractions, and indicates
the subsequent refinery processing of these streams to produce a standard slate of finished refined products.

Figure 2.2 Crude Oil Distillation and Downstream Processing

24
 Figure 2.3 Crude Oil Overall Refinery Process

(2.1) Petroleum Emulsion & Dehydration [8]

Origin:

The most accepted theory about origin of petroleum is the organic theory. According to this theory,
petroleum and gas form from organic matter scattered in the sedimentary rock. The remains of marine
animals and plants to which remains of the world animals and plants were added are considered to be the
main organic material accumulating in sedimentary rock.

In the top layers of the sediments, the buried organic matter is subjected to the action of oxygen and
bacteria and decomposes to a considerable extent to form gases (CO2, N2, NH3, CH4, etc...) and liquid
products soluble in water. The most stable part of the initial organic matter as regards to chemical and
bacterial action remains in the precipitate.

Subsequently, as it submerges into the body of the sedimentary rock, this organic matter during millions
of years at a depth of 1.5 -3.0 km and more, already in a reducing medium, experiences the action of
elevated temperatures (approximately up to 120-150 °C and less often to 200 °C) and of a pressure of 10 -
30 Mpa, as well as, the catalytic influence of the enclosing rock (mainly clays). As a result of the thermal
and thermo-catalytic process the organic matter transforms into the hydrocarbons of petroleum.

25
The crude is found associated with water in the form of emulsion; this water is saturated with different
salts such as NaCl, MgCl2 CaSO4, MgSO4 etc.... This water content of the crude ranges from about 2 – 20
% by volume, in some rare cases it may reach up to 60 %.

Before transporting the crude to the refineries, this water should be separated by emulsions breaking
methods. The presence of water and salts in petroleum delivered for refining harmfully affects the
operation of the refinery.

When water content is high, the pressure in the petroleum distillation column increases, its productivity
decreases and excessive heat is spent to heat and evaporate the water. Also, water increase the corrosion
rate in pipelines, tanks and refinery equipment besides it causes the fouling of refinery equipment due to
the deposition of mineral salts originally dissolved in formation water.
Salts mainly chlorides, have a more adverse effect. They are deposited in the tubes of the heat exchanges
and tube stills, which requires frequent cleaning of the tubes and lowers the heat transfer coefficient.
Calcium and magnesium chlorides hydrolyze with the formation of HCl, the latter corrodes the metal of
the technological equipment. Finally, the salts accumulating in the residual petroleum products, e.g. fuel
oil and tar (residual stock) detract from their quality.

Petroleum Emulsion:

By an emulsion is meant such a system of two mutually insoluble or not completely soluble liquids in which
one of them is contained in the other one in the suspended state in the forms of an enormous number of
microscopic droplets (globules). The liquid in which the globules are distributed is called the dispersing
medium and the second liquid distributed in the dispersing medium in the dispersed phase.

Petroleum emulsions are colored from light yellow to dark brown. They are mostly emulsions of the water
in oil type, in which petroleum is the dispersing medium and water is the dispersed phase.

▪ Hydrophobic.
▪ Float in water.
▪ Uniformly distributed in naphtha or other solvents.

Oil in water type in which water is the dispersing medium is less frequent

▪ Hydrophilic.
▪ Uniformly distributed in water.
▪ Sink in gasoline or naphtha.

26
Types of oil/water emulsions:
Any emulsion is composed essentially of the following components:
1. A continuous (or external) phase composed of a fluid A
2. A fluid B, essentially immiscible in fluid A and dispersed through it. Fluid B is called the dispersed (or
internal) phase.
3. A film of an emulsifying agent at the interfaces around the dispersed phase.

In case of oil and water, the water is always the dispersed phase and oil is the continuous phase. The type
of emulsion depends on the properties of the emulsifying agents. Naturally occurring emulsifying agents
in oil/water emulsions are: asphalenes, waxes, organic acids, fine clays, and some types of salts.

Formation of oil/water emulsions:

Oil and water are flowing in the porous medium of the reservoir rock as two continuous phase flow. Once
this stream of oil and water enters the well and flow through the components of production facilities,
emulsion starts to form. To better understand what really happens, one has to remember that any liquid
due to its surface tension tends to attain a form where the surface area for a given mass is minimum. There
is naturally occurring energy at the surface of the liquid which always cause different droplets of the liquid
to attract each other and unite in bigger ones. This energy is called surface energy.

Now, in order to split a liquid body into droplets, and thus create, a new surface area, an external energy
has to be given to the system to overcome the surface energy. If the new droplets were subjected to further
external energy, they will be divided into smaller and smaller sizes, whereby the total surface area
increases.

Consequently, any energy given to the oil/water stream will cause the water phase to break down and divided into
smaller and smaller droplets. Why the water and not the oil? Apparently, because the surface tension of water is
much less than that of the oil.

The sources of the external energy could be:

1. The turbulence and mixing of the stream in tubing, chokes and flow lines especially when there is a
free gas concurrently flowing with the oil and water.
2. Any pressure drop across any restriction or valve.
3. Energy provided by the pumps to the system

Once the water is so divided, the natural emulsifying agents will start to migrate through the oil phase and
coat the water droplets with a film of their own molecules. This film, if conditions permit, can grow in
thickness by time. It is believed that this film has similar electrical charges on the different droplets, which
cause the latter to repulse each other and prevent their coalescence.

27
Factors affecting stability of oil/water emulsions:
1. Size of the dispersed droplets. Small droplets have less tendency to segregate.
2. Aging of the emulsion. Longer times will cause thicker film of the emulsifying agent to coat the
dispersed phase.
3. Viscosity of the oil. The viscous the oil the more stable is the emulsion.
4. The difference in densities between the oil and water. The smaller this difference the more stable is
the emulsion.

Breaking oil/water emulsions:

The breaking of the oil /water emulsions is accomplished through two basic operations:

a. Weakening and destroying the protective films of the emulsifying agents which are coating the
dispersed water droplets.
b. Getting the dispersed water droplets into contact with each other to coalesce and unite into bigger
and bigger droplets and fall by gravity.

The first operation is done by:

1. Adding certain chemicals called demulsifies, and
2. Applying heat.

The exact way how the emulsifier destroys the emulsifier film is still unclear. One theory explains the mechanism
this way:

- The demulsifiers have the tendency to convert the water-in-oil emulsion into inverted- type emulsion. In doing so,
the charge on the water droplets is neutralized and heat will help to break the emulsifier film.

- Other theory claims that when the demulsifier comes into contact with the emulsifier film it changes its thermal
properties. The coefficient of expansion of the film will decrease and becomes much less than that of water. Upon
heating, the water droplets expand and break the coating film and emulsion breaks down.

Even when the emulsion is broken, the droplet size is still far small from being capable to settle down in short time.
Heat has the effect of reducing the oil viscosity and increasing (D2- D1). to increase R, some means has to be
applied to increase the collision between the different droplets to encourage their coalescence into bigger and
bigger droplets of water. An effective method is to apply external electrical current.

- Effect and limitations of chemical demulsifier application.

- Effect and limitations of heat application.

28
Summary: dehydration of crude oil usually achieved by the application of:

1- Chemical demulsifiers
2- Heat
3- Electrical current

Principles of electrical dehydration:

Water droplet is composed of a number of water molecules. The water droplet is not dipolar, and it is spherical in
shape. However, when a water droplet is placed in an electrical field, it becomes an induced dipole and ellipsoidal in
form.

Due to the opposite charges on the droplets at their close ends, a force of attraction is created, this force increases
by increase of the droplet radius and by the decrease of the distance between the droplet centers. It increases with
the increase of the electrical gradient.

Summary: two factors will cause the water droplets to coalesce when subjected to electric field:

1. Distortion and weakening of the coating emulsifier film due to the elongation of the water droplets
2. Attraction force between the water droplets due to the opposite charges on their facing ends.

Through proper oil dehydration, it can significantly extend the life of the equipment components, minimize
downtime, optimize efficiency, and increase overall profitability.

(2.2) Desalting, Preheating & Flashing [9]

CRUDE OIL PRETREATMENT

* DESALTING
o Crude oil contains water, inorganic salts, suspended solids, and water-soluble trace metals.
o First step in the refining process is to remove salt and solids to reduce corrosion, plugging, and fouling of
equipment and to prevent poisoning of the catalysts in processing units.
o contaminants must be removed by desalting.
o If the salt content of the crude is greater than 10 lb/1000 bbl (expressed as NaCl), the crude requires desalting to
minimize fouling and corrosion caused by salt deposition on heat transfer surfaces and acids formed by
decomposition of chloride salts. (<1000 lb/bbl)

29
 Figure 2.4 Crude Oil Desalting Process

Most typical methods of crude-oil desalting:

o Chemical and Electrostatic separation: Washing of the salt from crude oil with
water oil and water phases are separated in a settling tank by adding chemicals to
assist in breaking up emulsion or by the application of electrostatic field to collapse
the droplets of saltwater more rapidly.
o Chemical desalting: Water and chemical surfactant (demulsifiers) are added to the
crude, heated so that salts and other impurities dissolve into the water or attach to
the water, and then held in a tank where they settle out.
o Electric desalting: Under charge condition polar molecules get oriented and get
separated. More than 90% of salt can be removed in just less than half an hour.

Figure 2.5 Electric Desalting of Crude

30
Electric Desalting

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

suspended water globules in the bottom of the settling tank. Either AC or DC fields may be used
and potentials from 12,000 to 35,000 volts are used to promote coalescence.
o Surfactants are added if the crude has a large amount of suspended solids.
o The feedstock crude oil is heated to between 150 and 350oF to reduce viscosity and surface
tension for easier mixing and separation of the water.
o The temperature is limited by the vapor pressure of the crude-oil feedstock.

o The dual field electrostatic process provides efficient water separation at temperatures lower
than the other processes and as a result, higher energy efficiencies are obtained.
o The salts are dissolved in the wash water and the oil and water phases separated in a settling
vessel either by adding chemicals to assist in breaking the emulsion or by developing a high-
potential electrical field across the settling vessel to coalesce the droplets of salty water more
rapidly.

o Desired pH <6, at higher pH emulsion forms.

o Ammonia is used to reduce corrosion. Caustic or acid may be added to adjust the pH of the
water wash.
o Wastewater and contaminants are discharged from the bottom of the settling tank to the
wastewater treatment facility.
o The desalted crude is continuously drawn from the top of the settling tanks and sent to the
crude distillation (fractionating) tower.

Wash water and Temperature requirement in Desalter:

o (3-4vol%, T 240-260oF (API >30), to 7-10 vol%, T 280-300o F for API<30)

o For single-stage desalting units 90 to 95% efficiencies are obtained and two-stage processes
achieve 99% or better efficiency.
o Efficiencies of up to 99% water removal in a single stage are claimed for the dual field process.
About 90% of desalters use AC field separation only.
o Heavy naphthenic crudes form more stable emulsions than other crudes. Higher temperature is
required.

31
 Figure 2.6 Electrostatic Desalting of Crude

Figure 2.7 Electrostatic Desalting of Crude CSV

32
* Preheating and flashing

In petrochemical industries, furnaces are used to heat petroleum feedstock for fractionation, thermal cracking, and
high-temperature processing. Usually, these furnaces are fired by oil or gas. They have to be designed to ensure
that the fluid receives the correct amount of heat and has sufficient residence time within hot zone. While at the
same time excess temperatures have been avoided. These excess temperatures lead to degeneration of the product
or damage to the furnace. The balance is achieved by appropriate disposition of the tubes carrying the fluid within
the furnace, and careful control of firing rate and fluid flow.

An industrial furnace or direct fired heater is equipment used to provide heat for a process or can serve as reactor
which provides heats of reaction. Furnace designs vary as to its function, heating duty, type of fuel and method of
introducing combustion air. However, most process furnaces have some common features. Fuel flows into the
burner and is burnt with air provided from an air blower. There can be more than one burner in a particular
furnace which can be arranged in cells which heat a particular set of tubes. Burners can also be floor mounted,
wall mounted or roof mounted depending on design.

The flames heat up the tubes, which in turn heat the fluid inside in the first part of the furnace known as the
radiant section or firebox. In this chamber where combustion takes place, the heat is transferred mainly by
radiation to tubes around the fire in the chamber. The heating fluid passes through the tubes and is thus heated
to the desired temperature. The gases from the combustion are known as flue gas. After the flue gas leaves the
firebox, most furnace designs include a convection section where more heat is recovered before venting to the
atmosphere through the flue gas stack. (HTF=Heat Transfer Fluid.

Industries commonly use their furnaces to heat a secondary fluid with special additives like anti-rust and high
heat transfer efficiency. This heated fluid is then circulated round the whole plant to heat exchangers to be used
wherever heat is needed instead of directly heating the product line as the product or material may be volatile or
prone to cracking at the furnace temperature.)

The radiant section is where the tubes receive almost all its heat by radiation from the flame. In a vertical,
cylindrical furnace, the tubes are vertical. Tubes can be vertical or horizontal, placed along the refractory wall, in
the middle, etc., or arranged in cells. Studs are used to hold the insulation together and on the wall of the furnace.
The tubes are a distance away from the insulation, so radiation can be reflected to the back of the tubes to
maintain a uniform tube wall temperature. Tube guides at the top, middle and bottom hold the tubes in place.
The convection section is located above the radiant section where it is cooler to recover additional heat. Heat
transfer takes place by convection, and the tubes are finned to increase heat transfer.

The first two tube rows in the bottom of the convection section and at the top of the radiant section is an area of
bare tubes (without fins) and are known as the shield section, so named because they are still exposed to plenty
of radiation from the firebox and they also act to shield the convection section tubes, which are normally of less
resistant material from the high temperatures in the firebox. The area of the radiant section just before flue gas
enters the shield section and into the convection section called the bridge zone. Crossover is the term used to
describe the tube that connects from the convection section outlet to the radiant section inlet.

33
 Figure 2.8 Typical Furnace Components

Figure 2.9 Typical Flow of feed inside Furnaces

34
The different preflash devices can be grouped in two main typologies: preflash drums and preflash
towers/columns. The choice between the two types depends on the scope of the revamping work and on the space
constrictions of the plant. Usually preflash drums are preferred when it is necessary to increase the capacity of the
plant, while preflash towers are preferred to improve the naphtha-kerosene separation, in some cases both can
improve the heat integration of the plant. [13]

The preflash drum is the simplest device to separate light crude compounds before the feed inlet to the main
column. This device consists of a simple vessel sized for a mean residence time of about 15-20 minutes to assure a
good separation between the liquid and the vapor phase. Particular attention is required during the design to avoid
the entrainment of the unflashed liquid crude in the vapor stream. [13]

The preflash column, differently from the preflash drum, realizes an effective separation and it is possible to set
the cut point of the desired product. There are some reported cases of refineries which use a preflash column in
their plant or consider this device in a revamping project to unload the atmospheric furnace, to eliminate
vaporization at the furnace inlet control valves, to increase the naphtha production, decrease heat duty and to
debottleneck the crude column overhead system. [13]

The main problems of the preflash column are related to the presence of only a few plates between the inlet and the
withdrawn and to the high reflux ratio flow rate. Another aspect to consider is the naphtha reduction in the top of
the main column. So, if we want to keep the same end point for the naphtha stream, the top temperature decreases
with possible condensation phenomena and consequent corrosion possibility. Usually it is better to assure a
sufficient column top temperature to avoid corrosion and a long-time running apparatus. [13]

Figure 2.10 Crude oil distillation system with a preflash unit

35
 (2.3) Separation in Distillation Tower [10][11]

Distillation is a widely used method for separating mixtures based on differences in the conditions required to
change the phase of components of the mixture. To separate a mixture of liquids, the liquid can be heated to force
components, which have different boiling points, into the gas phase. The gas is then condensed back into liquid
form and collected. Repeating the process on the collected liquid to improve the purity of the product is called
double distillation. Although the term is most commonly applied to liquids, the reverse process can be used to
separate gases by liquefying components using changes in temperature and/or pressure. A plant that performs
distillation is called a distillery. The apparatus used to perform distillation is called a still.

Figure 2.11 Fractional Distillation fractions with their boiling points & uses

36
The fractional distillation of crude oil carries out several steps:

1. Heating the mixture of the substances of crude oil (liquids) with different boiling points to a high temperature.
Heating is usually done with high pressure steam to temperatures of about 1112 degrees Fahrenheit / 600 degrees
Celsius.

2. The mixture boils, forming vapor (gases); most

substances go into the vapor phase.

3. The vapor enters the bottom of a long column

(fractional distillation column) that is filled
with trays or plates. The trays have many holes
or bubble caps (like a loosened cap on a soda
bottle) in them to allow the vapor to pass
through. They increase the contact time
between the vapor and the liquids in the column
and help to collect liquids that form at various
heights in the column. There is a temperature
difference across the column (hot at the bottom,
cool at the top).

4. The vapor rises in the column.

5. As the vapor rises through the trays in the
column, it cools.

6. When a substance in the vapor reaches a height where

the temperature of the column is equal
to that substance's boiling point, it will condense to form
a liquid. (The substance with the
lowest boiling point will condense at the highest point in
the column; substances with higher
boiling points will condense lower in the column)

7. The trays collect the various liquid fractions.

8. The collected liquid fractions may pass to condensers,

which cool them further, and then go to
storage tanks, or they may go to other areas for further
chemical processing. Figure 2.12 Fractional Distillation Illustration

37
 Figure 2.13 Fractionation Column Sections

Distillation Column Trays Components & Types [14]

Components:
1. Bubbling Area
2. Downcomer Backup
3. Downcomer Bottom Area
4. Downcomer Seal Area
5. Downcomer Top Area
6. Fraction Hole Area
7. Free Hole Area
8. Hole Area

38
 Figure 2.14 Typical Tray Layout

There are three types of distillation trays:

1- Bubble caps Tray
2- Sieve Tray
3- Valve Tray

Figure 2.15 Bubble caps, Sieves & Valves Types of Trays

39
 1. Bubble caps Tray
A bubble cap tray has riser or chimney fitted over each hole, and a cap that covers the riser. The cap is mounted so
that there is a space between riser and cap to allow the passage of vapor. Vapor rises through the chimney and is
directed downward by the cap, finally discharging through slots in the cap, and finally bubbling through the liquid
on the tray.

Figure 2.16 Flow in Bubble caps Tray

2. Sieve Tray
Sieve trays are simply metal plates with holes in them. Vapor passes straight upward through the liquid on the
plate. The arrangement, number and size of the holes are design parameters.

Figure 2.17 Flow in Sieve Tray

40
 3. Valve Tray
In valve trays, perforations are covered by liftable caps. Vapor flows lifts the caps, thus self creating a flow area for
the passage of vapor. The lifting cap directs the vapor to flow horizontally into the liquid, thus providing better
mixing than is possible in sieve trays.

Figure 2.18 Flow in Valve Tray

Downcomers
They are used to guide liquid flow from an upper tray to a lower tray. The most common is the segmental-type,
which can be either straight or sloped (angled). ... Inadequate downcomer area will lead to downcomer choking,
whereby liquid backs up the downcomer into the tray above and eventually flood the column.

The straight, segmental, vertical downcomer is widely used as it provides good utilization of column area for
downflow and has cost and simplicity advantage.

Sloped downcomer can be used if vapor-liquid disengagement is difficult due to foaming, it also provid a slightly
larger active area for vapor-liquid contact, but it is also more expensive.

A weir on the tray ensures that there is always some liquid (holdup) on the tray and is designed such that the
holdup is at a suitable height, e.g. such that the bubble caps are covered by liquid.
Being lighter, vapor flows up the column and is forced to pass through the liquid, via the openings on each tray.
The area allowed for the passage of vapor on each tray is called the active tray area.

41
 Figure 2.19 Downcomer and Weir Work

Selection of Tray Type

1- Cost
2- Capacity
3- Operating range
4- Maintenance
5- Pressure drop

42
1- Cost

Bubble caps trays are appreciably more expensive than sieve or valve trays. The relative cost will depend on the
material of construction used.

2- Capacity

There is little difference in the capacity rating for the three types (the diameter of the column required for a given
flow-rate) the ranking is: sieve, valve and bubble-cap

3- Operating range

This is the most significant factor.

By operating range is meant the range of vapor and liquid rates over which the plate will operate satisfactory (the
stable operating range)

Bubble caps trays have a positive liquid seal and can therefore operate efficiently at very low vapor rates.

Sieve trays rely on flow of vapor through the holes to hold the liquid on the tray and cannot operate at very low
vapor rate, but with good design, sieve trays can be designed to give a satisfactory operating range; Typically, from
50 %to 120% of design capacity.

Valve trays are intended to give greater flexibility than sieve trays at a low cost than bubble caps.

4- Maintenance

For dirty services, bubble caps are not suitable as they are most susceptible to plugging. Sieve trays are the easiest
to clean.

5- Pressure drop

The pressure drop over the trays can an important design consideration, particularly for vacuum columns. The
trays pressure drop will depend the detailed design of the trays but in general sieve plates give the lowest pressure
drop, followed by valves, while bubble-cap is the highest.

Table 2.1 - Comparison between Trays

43
 (2.4) Products of Distillation Tower [12]

Figure 2.20 Crude Oil Products

Some Common Products from Petroleum Crude:

1. Petroleum Gases
2. Gasoline & Naphtha
3. Kerosene
4. Gas Oil (Diesel Fuel)
5. Fuel Oil (Mazot)
6. Lubricating Oils, Lubricating greases & Paraffin wax
7. Asphalt

1. Petroleum Gases

Based on the origin of the gases, they may be classified as:

a. Natural gas.
b. Refinery gas.

44
 a. Natural Gas:

May be found in reservoirs either alone or associated with petroleum crude.

Natural gas consists mainly of methane with progressively decreasing amounts of the higher homologues C2 up to
C5, C6, C7.

If the natural gas consists mostly of CH4 with very small amounts of other H.Cs. is known as dry natural gas i.e.
free from condensable HCs

If it contains condensable H.Cs. it is called wet natural gas.

Natural gas usually contains other non H.C. gases e.g H2S, N2, CO2, etc.

b. Refinery Gas:

Refinery gas indicates that this gas is obtained from the various operations in the refinery. If the refinery gas is
obtained by distillation of the crude, it is expected to have a composition similar to the natural gas.

On the other hand, if it is obtained from cracking and reforming processes, they are expected to have appreciable
amounts of olefinic H.Cs. e.g. ethylene, propene, pentene.

Uses of Petroleum Gases:

a. Fuel:
• For Industrial and domestic purposes.
• LPG (Liquefied Petroleum Gas)

It is a special type of petroleum gases consisting mainly of propane and butane which have been well fractionated
from the lower H.Cs. (C2 and lower) and the higher H.Cs. (C5)

C2 is undesirable because of difficulty in liquefaction at atmospheric conditions, and C5 is undesirable because they
have high boiling point and therefore, appreciable quantities will remain as liquid at atmospheric conditions.

Small amounts of ethyl or methyl mercaptan are added as a warning if leakage takes place.

b. Petrochemical:

Petroleum gases are used as a raw material for petrochemical industries.

2. Gasoline

Gasoline is the lightest liquid fraction of petroleum. It is used as a fuel for internal combustion engines of the-
spark-ignition type.

45
A commercial gasoline may be a mixture of two or more of the following types of gasoline:

a. Natural Gasoline:

Is obtained from wet natural gas by separating the C4 heavier H.Cs.

Natural gasoline is important as a blending agent in commercial gasolines to increase its volatility.

b. Straight-Run Gasoline:

This gasoline is obtained from the crude by distillation (separation without change in composition, or modification
of the structure).

c. Cracked Gasoline:

Gasoline obtained from a cracking process. Low value product → more value product.

d. Reformed Gasoline:

It is obtained by modifying the structure of the H.Cs. in straight run gasoline or naphtha.

Low quality → high quality.

e. Polymer Gasoline (poly gasoline):

It is prepared by polymerization of two olefinic H.Cs.

3. Naphtha (Jet Fuel)

It is important to note that jet engines operate on the principle that whenever there is an action, there is also an
opposite and equal reaction.

In principle, the fuel in a jet engine burns producing hot flue gases which are directed to the jet opening at high
velocity.
This reaction provides the necessary force which drives the jet engine forward. Accordingly, the jet fuel should
meet the following requirements:

1. It should have a high calorific value (both per unit mass and per unit volume).
2. It should have a low volatility so that it would not vaporize at the low pressure of high
altitudes.
3. It should not solidify at the extremely low temperature of the high altitudes (the
temperature at 30.000 ft. is bout - 50°C).
4. It should have a low viscosity which remains reasonably low at these low temperatures.

46
According to the above requirements, the best fuel satisfying these conditions is the petroleum fraction between
gasoline and kerosene. This fraction is usually called "Naphtha" and when specially prepared for use as a jet fuel, it
is simply called "jet fuel"

The best jet fuels are those obtained from paraffinic crudes. The amount of jet fuel which could be obtained from
any crude is usually small, the percentage increases when the crude is of paraffinic nature. Furthermore, it is
common to treat jet fuels with concentrated H2SO4 in order to remove olefins, aromatic, and other impurities.

4. Kerosene

Uses:

1. In illumination.
2. Heating purpose.
3. Source of power:

▪ Power kerosene.
▪ Tractors spark ignition.
▪ Jet fuel.

4. As a solvent, pesticides, paint, dry cleaning.

- The kerosene cut falls in the range 140 to 300°C.

- The properties of the kerosene depend on the use of the product.

a. Sulfur Content:

Specification limits the S content in the various kerosene's.

b. Smoke Point:

This test is used for kerosene used in illumination.

The smoke point is the maximum height in mm of a flame without giving smoke in lamp.

Aromatics are undesirable because they have low smoke point (a low flame height without giving smoke). Special
treatments are known; which remove aromatics from kerosene.

c. Flash Point:

The flash point is the minimum temperature at which the fuel forms enough vapors to form an explosive mixture
with the air in a special test apparatus and it will give a flash when subjected to a test flame.
This test has no direct relation with performance, but it is a characteristic for safe storage.

47
 d. Ignition Quality:

The octane number of kerosene as a fuel in tractors of the spark ignition type should be high that is aromatics are
desirable in this type of kerosene.

In this type of engines cold starting begins using gasoline then after warming up the fuel is shifted to kerosene.

e. Freezing Point:

This is very important characteristic in jet fuels.

A very low freezing point is required because the fuel is used in very high altitudes where the weather is very cold.
Freezing point may reach -60°C or - 75° C for some military uses.

The freezing point can be lowered by:

a. Removing selectively the straight chain hydrocarbons (highest freezing point).

b. Modern technology uses either molecular sieves or urea adducts (complex).

5. Fuel Oil

Fuel oil is the name given to the furnace fuel as "Mazot".

Uses:

▪ The main domestic use of F.O is in central heating.

▪ The main industrial use in steam generation-as a fuel for heating kilns or furnaces.
▪ The heaviest types of F.O. are used in ships and these are known as "bunker fuels".

No economic methods are known for refining fuel oils and consequently they are sold as produced. The main
properties of F.O. are:

a. Viscosity:

These are specified according to the facilities available to the customer.

Viscous fuels require special methods for atomization in order to be efficiently burned. They also require special
heating in order to be pumped.

In Egypt the mazot has a maximum specified viscosity of 1500 sec Red I in winter and 2000 sec Red I in summer.

b. Carbon Residue:

This is limited to avoid coke deposits on the burner nozzle. No method is known to reduce, economically, the
carbon residue, if this value is high, it is blended with another fuel of low carbon residue. Invariably, cracked fuel
oils have higher carbon residues than straight run oils.

48
 c. Sulfur Content:

As a rule, the S-content of straight run fractions increases with increase in molecular weight.

F.O. is therefore expected to have the highest S-content of all petroleum fractions. The common limit of the S-
content of fuel oils is about 4 %. As with C -residue, the only method for obtaining low S content F.O. is by
"blending".

d. Pour Point:

In many cases the pour point of F.O. is specified according to the minimum weather temperature. This specification
is not important for

F.O. since it has to be heated anyway to facilitate its pumping.

e. Flash Point:

Sometimes this is specified to serve as an indication of or guarantee against concentration with light fractions.

The common limit on the flash point is 150°F.

f. Calorific Value:

The range of CV for F.O. is small (18000-19000 Btu/Ib). The heavier fuels have the lower CV values.

In general, the CV of F.O. is not specified being the residual product from atmospheric crude distillation units.

6. Gas Oil & Diesel Oil

These are fuels, which are used in internal combustion engine of the diesel type.

The difference between the two is that gas oil can be almost vaporize completely at atmospheric pressure,

Diesel oil is heavier than gas oil.

Gas oil is prepared by the atmosphere distillation of the diesel oil.

Gas oil is used for high speed and medium speed diesel engines while diesel oil is used in lower speed diesel
engines.

Compression ratio in the engine is much higher than in the spark ignition engine reach about 21: 1.

The ignition of the diesel fuel requires a high pressure fuel pump (allowance for the plunger of the pump = 0.0001
inch to prevent leakage), this require good lubrication for the plunger and the walls of the pump.

The diesel fuel is a lubricant therefore the diesel fuel should have a suitable viscosity.
Also, the viscosity of the diesel fuel is also important for good atomization and good penetration of the atomized
fuel into the hot compressed air.

49
Some Important Properties of Diesel Fuel
a. Ignition Quality:

A good diesel fuel should be easily self-ignited and this can be attained by an appreciable content of straight chain
H.Cs. with minimum branching and smaller content of cyclic H.Cs.

Aniline point is the minimum temperature at which equal volumes of aniline and the sample under the test are
completely miscible.

The aniline point is low for diesel fuels rich in aromatic and cyclic compounds.

A low aniline point indicates the presence of appreciable quantities of aromatics, while on the other hand a high
aniline point indicates a higher percentage of paraffins.

A good diesel fuel should have a high aniline point.

b. Flash Point:

As a specification is used (required) for safe storage, it also an indication of contamination with lighter products.

c. Viscosity:

This is an important property for diesel fuels. A suitable viscosity for diesel fuels is required. A very low viscosity is
undesirable because it causes a very high degree of atomization and poor penetration of the fuel. Furthermore, a
low viscosity diesel fuel will not give good lubrication for the moving parts in the high pressure fuel pump

On the other hand, a diesel fuel with a high viscosity will not be easily atomized and at the same time will need
longer periods for injection through the atomizer.

d. Carbon Residue:

It is an important property of diesel fuel because it gives an indication of the possibility of carbon deposition on the
atomizer holes. A good diesel fuel should have a low carbon residue, especially in high- speed diesel engines.

e. Pour Point:

It is the minimum temperature below which the material will not act as a liquid.

7. Lubricating Oils

Function:

Their function is to lower the friction between the solid surfaces of the moving parts of various mechanisms,
machine tools, engines, motors and machines, and to prevent wear of the material of these moving parts.

Lubricating oils play the role of a coolant, which absorbs the heat generated due to friction.

50
The function of lubricating oils is achieved by replacing dry friction of metallic surfaces, when a lubricating is
introduced, with friction of the layers of a viscous liquid between each other. The force of cohesion between the
molecules of the moving parts and those of the lubs. exceed the force of mutual cohesion between the layers of the
oil itself consequently a strong lubricating layer forms on the surface of the metal that excludes any possibility of
dry friction and greatly reduces mechanical wear of the components.

Preparation:

Lubricating oils are obtained by vacuum distillation of the residue from atmospheric distillation. The side streams
of the vacuum distillation are called wax distillates. It's used for manufacturing of L.O. after various refining
treatments. The residue from the vacuum distillation of a paraffin base is also good stock for production of heavy
L.O. It is called cylinder stock.

The residue from vacuum distillation of some mixed base crude may be treated to produce cylinder stock.

After dewaxing treatment of cylinder stock we got the so called bright stock. Wax distillate and bright stock can
prepare neutral oils after some refining treatment.

Some Additives to Lube Oils

a. Pour Point Depressant:

E.g. Ca. Alkylphenolate. They are used to improve the pumping properties of L.O. at low temperature, they are also
sometimes used for jet and diesel fuel.

The addition of these additives to L.O. and fuel makes it possible to lower their pour point by 20-30°F and more.

There is no single opinion on this action, they are not able to prevent the initial crystallization of paraffin wax but
their action apparently is represented in that they hinder the growth of the wax crystals, and destroy the lattice
structure. Thus, shifts the temperature of the loss of the mobility to the region of low temperature.

b. Viscosity Index Improver:

These are substances which when mixed with low viscosity oil substantially increase their viscosity at above zero
temperature and don't affect it appreciably at below zero ones. Consequently, the addition of it makes it possible to
transform low viscosity oils into high-viscosity oils that are also characterized by a gently sloping viscosity -
temperature curve. A variety of highly viscous polymer is used as viscosity Index improvers. Poly isobutylene is the
most common one, it has a molecular weight ranging from 15,000 to 25,000. The ones with a higher M.wt. have a
better solubility in oil and higher thermal stability. Polymer of methaacrylaite M.wt. range (2700-3700 and 12000-
17000) is also used.

The disadvantage of polymer additives is their thermal and mechanical stability is insignificant.

51
 c. Corrosion Inhibitors:

They are used to inhibit corrosion, they are mainly polar substances that are adsorbed fastly on metal surfaces.

The mechanism is based on creating a protective monomolecular layer on the surface of metal that prevents acidic
and other active agents from acting on it. The corrosion inhibitors introduced into L.O. includes:

1. Sulfurized oils.
2. Sulfurized esters of some fatty acids.
3. Sulfides of alkyl phenols.
4. Phosphids (ester of phosphrous acids).

d. Anti - Oxidants:

Depending of the field of applications of oils anti-oxidants are divided into low and high temperature
ones.

Oils are oxidized either through the entire volume i.e. in a thick layer or in a thin layer when it is fed
through cylinder- piston friction unit. In the latter case the oil is under especially severe operating
conditions (elevated temperature, contact with air (O2) and contact with the metal).

Motor oils subjected to oxidation in a thin layer are improved by adding high temperature antioxidants
e.g. (salts of dithiophospheric acid esters).

e. Detergent & Dispersing Additives:

Lubricating oils for internal combustion engines function under conditions facilitating their oxidation and
thermal decomposition, which the long run results in the deposition of various ppts, carbon particles, and
formation of gummy film on the engine components. Adding detergent and dispersing agents into oils can
reduce the amount of deposits formed.

Detergents contain compounds whose molecules have long alkyl chains and polar groups. The alkyl chain
facilitates the creation of an affinity to the oil while the reactivity of the polar group enable the additive to
be adsorbed on the metallic surface of the engine which prevents the adhesion of the carbonaceous and
gummy materials.

8. Lubricating Greases

Greases are semi-solid products (i.e. products with no fluidity at room temperature). They have been in
use to reduce friction and wear in mechanisms and machines, and also to protect metals from corrosion.
They form a special class of lubricants prepared by incorporating a well dispersed solid thickener into
lubricating oils to limit then fluidity.

52
Greases are colloidal systems having a space structure formed by the thickener particles. The liquid phase
is kept in a semi solid state owing to attraction forces of solid particles. X-ray structural analysis shows
that most grease have a fibrous structure.

They are suitable for services under complicated operating conditions where lubricating oil are in efficient
e.g. (lubricating of open system that cannot retain LO, gear transmissions, roller, ball bearing and for
vacuum equipment.

The properties depend on the type of oil used, type of the thickener and concentration of the thickener and
the additives used.

Greases are divided into three main types:

1. Greases in, which solids dissolving in oils at temperatures close to them melting points and
forming true solutions with the oils.
These solids (thickeners) include solid hydrocarbons such as paraffin wax, ceresine, and
petrolatum.

2. Greases in which solids not interacting with oils but dispersing in them to form a colloid. Soaps are
used for this purpose.

This type includes 85-90 % of all the greases produced and used at the present. Several groups of
these greases are distinguished depending on the soap cation.

The first one includes greases prepared with alkali metal (Na, Li) soaps. These greases are stable
even at low (5 - 6 %) thickener concentrations. Depending on the thickener concentration and
nature of the soap's organic radical, these greases become fluid at temperatures from 100 to 200°C
and even higher. Lithium greases are frost-resistant.

The second group includes greases prepared with alkaline – earth metal (Ca, Ba) soap. They are
quite stable with a soap content of 8 - 10 %. The calcium grease "solid oil" is an example of such
greases. It is water proof and can be used in a moist medium.

Greases prepared with Al, Pb, and Zn soaps are used much less often. Soap greases are chiefly
employed as antifriction lubricants, but they also have protective properties.

3. Greases in, which thermally stable organic and inorganic finely grounded substances, are the
thickeners. These substances include urea, mica, and silica gel. These greases cost, much more than
soap and hydrocarbon ones, and are used when soap greases cannot be used, for example in
aggressive media.

53
 9. Asphalt
1. Asphalts are dark plastics petroleum products, liquid, semi-solid and solids depending on the
grade.

2. Asphalts having the highest viscosity among all petroleum refining products.

3. Asphalts are complicated colloidal system of asphaltenes and associated high Molecular wt.
resins in a medium of oil and low Molecular wt. Resins.

4. The asphaltenes depending on their ratio can form either rigid frame work or individual
micelles adsorbing and retaining the resins. The oils are the medium in which the resins dissolve
and asphaltenes swell.

The Ratios of the Components Affects Asphalt Properties:

1. An increase in asphaltenes makes an asphalt harder.

2. Resins improve the elasticity of an asphalt and its cementing properties.
3. Oils make an asphalt frost - resistant.

The Main Purposes of Paving Asphalt are:

1. Binding and gluing together of mineral materials (crushed stone, sand).

2. Giving the hydrophobic character to them.
3. Filling the spaces between particles. This is why the strength and service life of asphalt
pavements depends on the quality of asphalt.

Asphalt can be produced in one of the following ways:

1. By the deep vacuum distillation of fuel oil (Mazot). This asphalt is called (straight - run asphalt)
2. By the oxidation of residual petroleum products by air at a high temperature.

10. Waxes

A major part of the commercial waxes is produced in petroleum refinery during the processing of the diesel
and lube oil fractions of paraffinic petroleum.

Uses:

▪ Paper - match - inks - detergent - cosmetics - food industry – chemical synthesis.

▪ Waxes except those grades intended for synthesis and matches may have oil content > 5
%.

54
Waxes are separated from petroleum fractions by:
▪ Direct cooling
▪ Cooling and use of selective solvent

The unpurified wax resulting from the two ways need further treatment.
In case of distillate, it is named gatch, and in case of residue, it named petrolatum.

Gatch and petrolatum have some amount of oil, so, to produce commercial wax and ceresine, they must
be deoiled, deoiling is performed either by sweating or by using a suitable solvents.

(2.5) Vacuum Column [10][15]

Figure 2.21 Real Life Company Vacuum Column

Crude oil is first refined in an Atmospheric Distillation Column. Fractions of crude oil such as lighter gases
(C1-C4), gasoline, naphtha, kerosene, fuel oil, diesel etc. are separated in the atmospheric distillation
column. The after taking out these lighter hydrocarbon cuts, heavy residue remaining at the bottom of the
atmospheric distillation column needs to be refined. These heavy hydrocarbon residues are sent to a
Vacuum Distillation Column for further separation of hydrocarbons under reduced pressure.

Heavies from the atmospheric distillation column are heated to approximately 400˚C in a fired heater and
fed to the vacuum distillation column where they are fractionated into light gas oil, heavy gas oil and
vacuum reside. Some heavy hydrocarbons cannot be boiled at the operating temperature and pressure
conditions in the atmospheric distillation column.

55
Hence, they exit the bottom of the column in liquid state and are sent to the vacuum distillation column
where they can be boiled at a lower temperature when pressure is significantly reduced. Absolute
operating pressure in a Vacuum Tower can be reduced to 20 mm of Hg or less (atmospheric pressure is
760 mm Hg). In addition, superheated steam is injected with the feed and in the tower bottom to reduce
hydrocarbon partial pressure to 10 mm of mercury or less. Lower partial pressure of the hydrocarbons
makes it even more easier for them to be vaporized, thus consuming less heat energy for the process.

A typical process flow of such a vacuum distillation column is presented in the figure below. Steam ejectors
can be used to suck the lighter hydrocarbon vapors at low pressure from the top of the column. These
vapors are then cooled down to condense the steam which had been introduced in the column earlier. The
condensed oily water is removed and can be recycled to the column after boiling it. Hydrocarbon vapors
are taken out at this stage.

Two different cuts of hydrocarbons - 'light vacuum gas oil' and 'heavy vacuum gas oil' are separated in the
vacuum distillation column at different stages of the column, based on the difference between their boiling
point ranges. The liquid being drawn at low pressure needs to be pumped. Then it is heated and partially
recycled back to the column. Part of it is taken out as vacuum distillation products - 'light vacuum gas oil'
or 'heavy vacuum gas oil'. Light vacuum gas Oil is sent to a hydrotreater and then to a 'catalytic cracking'
unit to obtain smaller chain hydrocarbons. Heavy vacuum gas oil is also sent for cracking using hydrogen
in a 'hydrocracking unit' to produce smaller chain hydrocarbons.

Heavy hydrocarbons which cannot be boiled even under reduced pressure remain at the bottom of the
column and are pumped out as 'vacuum residue'. The vacuum distillation column bottom residue can only
be used for producing coke in a 'coker unit' or to produce bitumen.

Figure 2.22 Vacuum distillation unit and processing paths

56
Entrainment in Vacuum Columns:

The equilibrium on a bubble plate depends on the intimacy of contact between vapor and liquid. If this
contact or bubbling is too violent, liquid particles will be carried from one plate to the next by the vapor
and this will tend to destroy the separation. that has been obtained and this called entrainment.

We have to distinguish between two types of entrainment:

Entrainment by splashing:

This type of entrainment is caused by the high velocities of the vapor through the depth of liquid on the
tray.

High velocities of the vapor through the liquid are required for good mixing and good mass transfer
between the two phases but very high velocities are not required because they will cause entrainment by
splashing. This type of entrainment can be overcome by proper spacing of the trays (to give a chance for
the particles entrained due to splashing to lose their kinetic energy before reaching the upper plate).

Entrainment by carrying:

The vapor moving between plates assumes certain velocities depending on the volumetric flow rate of the
vapor and the cross-sectional area of the column. Every linear velocity of the vapor is capable of carrying
with it, liquid particles of a certain size and this size increases as the velocity increases. We put a limit on
the linear velocity to control this type of entrainment. The design put an upper limit on the linear velocity
of the vapor called the maximum allowable vapor velocity.

Entrainment is a more serious problem in vacuum column than those operating under atmospheric-
conditions as in introducing vacuum leads to higher vapor load (i.e) higher vapor velocity.

The problem of entrainment at the feed zone of the vacuum column can be solved by one of two ways or
both:
a. The feed is introduced tangentially.
b. Installing a pad of wire mesh (demister) below the lower plate in rectifying section.

57
 (2.6) Storage of Petroleum Products [16]

➢ Why it’s important?

Storage of liquid petroleum products, such as motor fuel and heating fuel, as well as other hazardous substances
present a threat to public health and the environment. Holes due to corrosion, improper installation and spills and
overfills when filling tanks are major causes of the problems faced when leakage occurs. A small gasoline leak of
one drop per second can result in the release of about 400 gallons of gasoline into the groundwater in one year.

At low levels of contamination, fuel contaminants in water cannot be detected by smell or taste, yet the seemingly
pure water may be contaminated to the point of affecting human health. Preventing tank spills and leaks is
especially important because of how rapidly gasoline, diesel and fuel oil can move through surface layers and into
groundwater and other toxic substances can move to the atmosphere.

➢ Types of Liquids

Selection of type of tank generally depends on ambient conditions and the product handled.

Flash Point

The minimum temperature of a liquid at which sufficient vapor is given off to form an ignitable mixture with the
air, near the surface of the liquid or within the vessel used.

Figure 2.23 Classification of Petroleum Liquids to be stored

58
 ❖ Storage Tanks
➢ Minimum Operating Inventory

Great emphasis is placed on the minimum operating inventory. Inventory below this level is not available for
consumer use because it is required to fill pipelines, tank bottoms, and refinery process equipment; facilitate
blending to meet product specifications; prepare for planned maintenance periods; handle unavoidable but
anticipated emergencies; and sustain uninterrupted operations. Runouts and shortages would begin to occur if
inventory were to fall below this level.

➢ Maximum Operating Inventory

Exceeding that level can cause problems such as slowdowns or interruptions in the system. The empty space in
tankage provides room for thermal expansion of the contents (protecting against accidental overfilling). receipt of
inventory. and unavoidable but anticipated events such as emergencies and schedule changes.

Figure 2.24 Storage Tanks Parts

59
Based on position, shape, structure and capacity, there are two categories of petroleum product storage tanks:

1) Underground tanks: is any tank which is so installed that at least 50 per cent of its mass is below the
adjacent ground level.
2) Aboveground tanks: is a tank which is located at or above grade, including both horizontal, vertical tanks
and spherical tanks. They’re commonly divided to:

a) Fixed Roof Tanks – Cone & Dome Roofs

b) Floating Roof Tanks – External & Internal

➢ Underground Tanks

a) Achieve environmental benefits. Ex, VOC emissions from underground tanks are very low or non-existent.
The main reasons are: the temperature of the underground storage tank is low and stable, the product is under
pressure and the breathing gases from the underground storage tank are not led to atmosphere but to other
cavers. b) The land above underground storage tanks is free for other purposes. c) Improve safety.
* But may cause water supply contamination in case of leakage.

Figure 2.25 Underground Storage Tanks

➢ Aboveground (Fixed Roof Tanks – Cone & Dome Roofs)

It refers to the storage tank for storing liquid with high flash points (eg. fuel oil, water, diesel, kerosene, bitumen)

Figure 2.26 Domed Coned Aboveground Storage Tanks

60
The fixed-roof tank is the least expensive to construct and is generally considered the minimum acceptable
equipment for storing liquids.

Breathing losses; during storage of the liquid there will be vapor emissions from tank breathing caused by the
difference in night and day temperatures and by changes in atmospheric pressure. To a certain extent, pressure
controllers and insulation can prevent breathing losses.

Figure 2.27 Breathing losses in fixed roofs tanks

➢ Aboveground Tanks (Floating Roof Tanks – External & Internal)

The floating roof tanks are developed to store volatile liquids to minimize the loss of valuable vapors, as well as, to
minimize the hazard of dangerous vapor formation underneath a fixed roof.

Internal floating roof tank can prevent the wind, sand, rain, snow and dust from invading, guarantee the quality of
stored liquid absolutely. What’s more, the internal floating roof floats upon the liquid making the liquid has no
vapor space, reducing evaporation loss 85%-96%, reducing the risk of air pollution, fire and explosion, it can easily
ensure the quality of stored liquid, especially is suitable for the storage of high-grade gasoline, jet fuel and toxic
petrochemical products.

External floating roof tanks are used to store crudes, light products and intermediate stocks having a vapor
pressure of more than 14kPa but less than 86 kPa at normal storage temperature.

Internal floating roof tanks are used for liquids with low flash-points (eg. gasoline, ethanol).

Figure 2.28 External & Internal Floating Roof Tanks

61
➢ Storage Tanks Equipment

There are several pieces of equipment associated with storage tanks that improve or augment the operation of
the tank system. Some of this equipment are:

o Tank dike
o Spray Nozzles
o Sumps
o Risers
o Siphons
o Spreaders
o Agitators
o Thief Hatch
o Pressure Relief Valves

o Tank dike - Used to hold the contents of a tank in case of a leak or a fire.

Figure 2.29 Tank dike

o Spray Nozzles - Used in critical areas around the tank as fire-fighting technique.

Figure 2.30 Tank Spray Nozzles

62
o Sumps - Used to allow a place for solids to accumulate and to allow a place to pump liquids.

Figure 2.31 Tank Sumps

o Risers - Used to make liquid enter a tank at a high level.

Figure 2.32 Tank Risers

o Siphons - Used to remove liquid from the bottom of a tank

Figure 2.33 Tank Siphons

63
o Spreaders - Used to make liquid enter a tank in a widely distributed spray rather than in a single stream

Figure 2.34 Tank Spreaders

o Agitators - Used to move liquids within the tank and agitate solids & liquids.

Figure 2.35 Tank Agitators

o Thief Hatch - Allows access to the inside of a tank and when closed acts as a seal and over-pressure
protection device.

Figure 2.36 Tank Thief Hatch

64
 - Tank Thief

Liquid in a tank is sampled to determine the volume, amount of water still contained in the oil, and the gravity of
the oil. A thief is a sealed sample container with a valve which may be opened with a rope. An empty thief is
lowered into a tank and its valve opened to trap a sample of the liquid. Samples which represent liquid at several
levels in the tank are usually taken.

Figure 2.37 Tank Thief

o Pressure Relief Valves - Used to keep the pressure from becoming excessive.

Figure 2.38 Tank Pressure Relief Valve

65
 Chapter (3)
Naphtha Processing

Figure 3.1 Refinery Processing Process

(3.1) Cracking

In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic
molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light
hydrocarbons, by the breaking of carbon-carbon bonds in the precursors. The rate of cracking and the end products
are strongly dependent on the temperature and presence of catalysts. Cracking is the breakdown of a large alkane
into smaller, more useful alkenes. Simply put, hydrocarbon cracking is the process of breaking a long-chain of
hydrocarbons into short ones. This process requires high temperatures and high pressure. [17]

66
Importance [18]

Petrol (gasoline) contains a mixture of hydrocarbons, with 5 to 10 carbon atoms. The mixture of C 5-C10 hydrocarbons
obtained directly from the distillation of crude oil contains a high proportion of straight-chain alkanes. However, if
this mixture is used as petrol, it does serious damage to a car's engine. Petrol containing a high proportion of straight
chain alkanes tends to ignite in the cylinder of the car engine as the piston increases the pressure and before the
cylinder reaches the optimum position. Ideally, the mixture of petrol vapor and air is ignited with a spark at a
predetermined position of the piston in the cylinder. This problem of premature ignition is referred to as pre-ignition
and also as engine knock. The term knock is used as pre-ignition can be heard. Severe knock can cause serious engine
damage.

However, branched-chain alkanes, cycloalkanes and aromatic hydrocarbons are much more resistant to knock, and
straight-chain alkanes are converted into them in a series of processes in the refinery which are described in this
unit.

The resistance of petrol to knock is measured in terms of an octane rating (octane number). The higher the
number, the less likely is a fuel to pre-ignite.

The octane rating is on a scale where heptane is given an arbitrary score of 0 and 2,2,4-trimethylpentane (iso-
octane) one of 100. Thus, a petrol with the same knocking characteristics as a mixture of 95% 2,2,4-
trimethylpentane and 5% heptane has an octane rating of 95. A rating of 95 does not mean that the petrol contains
just iso-octane and heptane in these proportions, but that it has the same tendency to knock as this mixture.

The octane rating of petrol usually available for cars range from 95 upwards and contain a mixture of straight-chain,
branched, cyclic and aromatic hydrocarbons, produced by the processes described below.

These processes are also used to convert straight-chain hydrocarbons to hydrocarbons which are much more useful
to make chemicals which are then used to make a huge range of compounds from polymers to pharmaceuticals.

History[19]

Among several variants of thermal cracking methods (variously known as the "Shukhov cracking process", "Burton
cracking process", "Burton-Humphreys cracking process", and "Dubbs cracking process") Vladimir Shukhov, a
Russian engineer, invented and patented the first in 1891. One installation was used to a limited extent in Russia, but
development was not followed up. In the first decade of the 20th century the American engineers William Merriam
Burton and Robert E. Humphreys independently developed and patented a similar process as U.S. patent 1,049,667
on June 8, 1908. Among its advantages was the fact that both the condenser and the boiler were continuously kept
under pressure.

Just a few years after the Russian Revolution, Russia was desperate to develop industry and earn foreign exchange,
so their oil industry eventually did obtain much of their technology from foreign companies, largely American.[4] At
about that time, fluid catalytic cracking was being explored and developed and soon replaced most of the purely
thermal cracking processes in the fossil fuel processing industry. The replacement was not complete; many types of
cracking, including pure thermal cracking, still are in use, depending on the nature of the feedstock and the products
required to satisfy market demands. Thermal cracking remains important, for example in producing naphtha, gas
oil, and coke, and more sophisticated forms of thermal cracking have been developed for various purposes. These
include visbreaking, steam cracking, and coking.

67
Cracking is conducted nowadays commonly, by two processes

• Steam cracking which produces high yields of alkenes

• Catalytic cracking in which a catalyst is employed, and which produces high yields of branched and cyclic
alkanes.

The processing processes of most of the Crude Oil Products are conducted using these two processes as shown in the
figure below.

Figure 3.2 Crude Oil Products Processing Processes

(3.2) Steam Cracking [20][21]

Steam cracking is a petrochemical process in which saturated hydrocarbons are broken down into smaller, often
unsaturated, hydrocarbons. It is the principal industrial method for producing the lighter alkenes (or commonly
olefins), including ethene (or ethylene) and propene (or propylene). Steam cracker units are facilities in which a
feedstock such as naphtha, liquefied petroleum gas (LPG), ethane, propane or butane is thermally cracked through
the use of steam in a bank of pyrolysis furnaces to produce lighter hydrocarbons. The products obtained depend on
the composition of the feed, the hydrocarbon-to-steam ratio, and on the cracking temperature and furnace residence
time.

In steam cracking, a gaseous or liquid hydrocarbon feed like naphtha, LPG or ethane is diluted with steam and briefly
heated in a furnace without the presence of oxygen. Typically, the reaction temperature is very high, at around
850 °C, but the reaction is only allowed to take place very briefly. In modern cracking furnaces, the residence time is
reduced to milliseconds to improve yield, resulting in gas velocities up to the speed of sound.

68
Figure 3.3 Feedstock Comparison for Ethylene Production

Figure 3.4 Steam Cracking Process Products Uses

69
Process Description

Figure 3.5 Steam Cracking Process Flowsheet

A simplified flowsheet of this process is shown in Figure 3.5, detailing the main units of the process as well as the
main products. The most important elements of this process are represented by highlighted thicker lines,
representing the feed and main products (olefins), as well as the steam cracking furnace, which is the reactor and
“heart” of the chemical plant. The operations shown in blue are only present on plants running with liquid
feedstocks (such as naphtha).

The cracking furnace is the most important unit of this process. The hydrocarbon feedstock enters the furnace in
the convection section, where it is pre-heated by heat exchange against flue gases. It is then mixed with steam
(dilution steam), and the resulting mixture is further heated to temperatures of 500−680°C, which favor the
cracking reactions.

This mixture of feed and steam, in the gaseous state, enters the radiant section of the furnace, where radiant coils
act as tubular reactors, submitting the hydrocarbons to cracking reactions for periods of 0.1−0.5𝑠. This section of
the furnace operates at temperatures between 600−860°C, which are maintained through heat transfer with a
firebox, where fuel burners reach temperatures between 1000−1200°C. Due to the endothermicity of the cracking
reactions occurring, high heat fluxes are required. For the cracking of naphtha, and depending on the operating
conditions (which heavily influence the severity of cracking), the product stream is made up of (in 𝑤𝑡.%)
25−35%of ethylene, 14−18%of propylene, 4−6%of butadiene as well as ~14%of methane and 5−10%of aromatics,
namely BTX.

After exiting the furnace, the resulting stream, in the gaseous phase, and with a high content on light olefins is
subjected to a series of treatments to remove condensates, water and other undesired components before the
fractionation step. The cracked gas then leaves the radiant coil at 800−860°C (coil outlet temperature), and is
cooled during a period of 0.02−0.1𝑠to 550−650°Cto prevent further cracking of valuable reaction products as well
the formation of coke, which tends to occur at higher temperatures.

70
This cooling process occurs in the transfer-line exchangers (TLE), by indirect quenching. An oil quench, which is
only used only for liquid feedstocks, due to higher temperatures at the exit of the radiant coil, is used to reduce the
temperature down to around 230°C.

Figure 3.6 Heating System in Cracking Furnace

Next, a primary fractionator (gasoline fractionator) is used in order to separate the pyrolysis fuel oil (heavier
hydrocarbons) from the main stream. Part of the pyrolysis fuel oil is cooled and recycled back to perform cracked
gas quenching. To be further processed, the hydrocarbon product stream is then cooled to near ambient
temperature by means of water quench tower, in which it contacts with a large descending water stream. To
compress the cracked gas, a series of 4 to 6 compression stages with inter-stage coolers is used, allowing the
cracked gas to reach pressures up to 35bars, while maintaining temperatures below 100°C. The condensates, as
well as water and other heavier components are removed during this cooling process, alongside with 𝐻2𝑆and 𝐶𝑂2,
which are removed by contacting with an alkaline solution (acid gas removal).

The resulting gas needs to be dried in order to remove water (up to<1𝑝𝑝𝑚), in order to proceed for the
fractionation equipment. The gas drying is achieved with molecular sieves beds. Finally, the cracked and now
purified gas is chilled and separated into its product streams (ethylene, propylene, crude 𝐶4 and pyrolysis gasoline
and gas oil), by means of a fractionation train composed by the following distillation columns: demethaniser,
deethaniser, depropaniser, debutaniser, ethylene fractionator and propylene fractionator.

71
Figure 3.7 shows a view of a real life steam cracking unit illustrating Some of the columns discussed above:
1 - A debutaniser which separates the C4 hydrocarbons from the C1 - C3 hydrocarbons
2 - A depropaniser which separates out the C3 hydrocarbons
3 - A deethaniser which separates out the C2 hydrocarbons
4 - A demethaniser which separates out the methane
5 - A C3 splitter which separates propene from propane
6 - A C2 splitter which separates ethene from ethane

Figure 3.7 Real Life Steam Cracking Unit

A steam cracker is one of the most technically complex and energy intensive plants in the chemical industry. It has
equipment operating from 100 K to 1400 K and near vacuum to 100 atm. In fact, Stream Cracking is the most
energy consuming process in the chemical industry and globally uses approximately 8% of the sector’s total
primary energy use. Therefore, alternatives have been introduced to try saving more energy with better yield of
products such as catalytic cracking.

(3.3) Catalytic Cracking

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. [22]

72
Catalytic cracking is similar to steam/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 materials
called extrudites. [22]

There are three basic functions in the catalytic cracking process:

• Reaction – Feedstock reacts with catalyst and cracks into different hydrocarbons;
• Regeneration – Catalyst is reactivated by burning off coke; and
• Fractionation – Cracked hydrocarbon stream is separated into various products.

Catalytic cracking technologies can lead to energy saving up to 20%. [22]

Figure 3.8 Energy Saving in Catalytic Cracking

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. [22]

73
A catalyst allows lower reaction temperatures to be used. For example, in fluidized catalytic cracking, the feedstock
is gas oil which is vaporized and passed through a zeolite, produced as a fine powder, heated to about 700-800 K in
the reactor. It is so fine that it behaves like a fluid and continuously flows out of the furnace with the cracking
products. The temperature, residence time and the catalyst determine the product proportions. [22]

After cracking, the catalyst is separated from the products, regenerated by burning off deposited carbon in air (900
K), and subsequently recycled. [22]

Figure 3.9 Catalytic Cracking Process

Catalytic Reforming [23]

Catalytic cracking and catalytic reforming are two processes used in the conversion of crude oil into useful
products. Catalytic cracking is the breakdown of large hydrocarbon compounds into small hydrocarbon molecules
with the use of moderate temperatures and pressures in the presence of catalysts. Catalytic reforming is the
conversion of low octane naphtha into high-octane reformate products. Both these processes use a catalyst for the
progression of the reaction. Therefore, both these reactions are very useful in increasing the octane number of the
fuel that is obtained from the refinery.

The main difference between catalytic cracking and catalytic reforming is that catalytic cracking gives cracked
products whereas catalytic reforming gives reformate products.

74
 Figure 3.10 Catalytic Cracking Vs Catalytic Reforming

Figure 3.11 shows a view of three fixed bed reactors which operate in series at an oil refinery. The reforming
reaction which produces aromatic hydrocarbons and hydrogen takes place in reactor 1, followed by
isomerization reactions in reactor 2 and finally in reactor 3 cracking reactions.

It also provides the chemical industry with very important compounds such as benzene, methylbenzene, the
dimethylbenzenes, ethylbenzene and cyclohexane which are key materials for the polymer and other industries.

The alkanes, usually the naphtha fraction, are mixed with hydrogen and passed over a catalyst at a 700 K and a
pressure of a 30 atm. The catalyst is generally platinum, or rhenium dispersed on alumina. Because platinum is
involved, the reforming is sometimes called platforming. The hydrogen ensures that the resulting alkenes and
cycloalkenes subsequently react with hydrogen to form saturated compounds.

75
 Figure 3.11 Real Life Catalytic Reforming Reactors

Hydrocracking [24]

One of the most far-reaching developments of the refining industry in the 1950s was the use of hydrogen, made
possible in part by the availability of hydrogen as a by-product of catalytic reforming. Unlike a hydrotreater,
hydrocracking uses hydrogen to break C-C bonds (hydrotreatment is conducted prior to hydrocracking to protect
the catalysts in a hydrocracking process). In the year 2010, 265 × 106 tons of petroleum was processed with this
technology. The main feedstock is vacuum gas oil, a heavy fraction of petroleum.

The products of this process are saturated hydrocarbons; depending on the reaction conditions (temperature,
pressure, catalyst activity) these products range from ethane, LPG to heavier hydrocarbons consisting mostly of
isoparaffins. Hydrocracking is normally facilitated by a bifunctional catalyst that is capable of rearranging and
breaking hydrocarbon chains as well as adding hydrogen to aromatics and olefins to produce naphthenes and
alkanes.

The major products from hydrocracking are jet fuel and diesel, but low sulphur naphtha fractions and LPG are also
produced. All these products have a very low content of sulfur and other contaminants. It is very common in
Europe and Asia because those regions have high demand for diesel and kerosene. In the US, fluid catalytic cracking
is more common because the demand for gasoline is higher.

76
The hydrocracking process 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, 400-800 °C), in the
presence of hydrogen and special catalysts.

The primary functions of hydrogen are, thus:

1. preventing the formation of polycyclic aromatic compounds if feedstock has a high paraffinic content,
2. reducing tar formation,
3. reducing impurities,
4. preventing buildup of coke on the catalyst,
5. converting sulfur and nitrogen compounds present in the feedstock to hydrogen sulfide and ammonia, and
6. achieving high cetane number fuel

Figure 3.12 Different Cracking Processes

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 (3.4) Methaforming

Methaforming is a modern catalytic process that makes a motor gasoline or gasoline blendstock by joint processing
of two components: [25]

- Naphtha: straight-run gasoline, gas condensate and other similar types of naphtha feedstocks (main
feed), and
- Ethanol, methanol, other alcohols or ethers, light olefins and their mixtures (co- feed).
The typical products of Methaforming are: [25]

- Gasoline or gasoline blendstock (Methaformate) with standard-compliant sulfur and aromatics content.
The yield of Methaformate is 75-92% of the naphtha feed* with 85-95 RON driven by operator
economics. The process conditions can be tuned to produce a concentrate of aromatics (benzene-
toluene-xylene, BTX) instead of gasoline blendstock.
- Liquefied petroleum gas (LPG) and pure butane, which may be separated from the LPG.
- Hydrogen rich gas (HRG) or simply fuel gas.

Figure 3.13 Methaforming Unit

78
The key features of the Methaforming process that determine its applicability and economics are: [25]

Flexibility with regard to the qualities of the feedstocks opens up highly profitable opportunities to make valuable
products from low value feeds, in some cases amounting to a “waste to energy” operation. See Feedstocks for more
details.

Superior capital and operating efficiency, especially at 5 000 bpd (200k tpa) or less. The smallest profitable
Methaformer operates at about 50 bpd (2k tpa), the largest currently under design is 12k bpd (480k tpa). See
Process Description.

Reduced carbon footprint and ability to use ethanol as co-feed for gasoline production, giving the operators in
certain geographies additional benefits from carbon credits (see Process Description).

Ability to produce standard-compliant RON 90-92 gasoline in a single unit, including sulfur and benzene reduction,
makes it possible to run a Methaformer as a standalone unit or as a capacity extension in an existing refinery.

When to Choose Methaforming: [25]

Figure 3.14 Methaforming Playing Roles

79
Types of Naphtha: [26]
The feed requirements are presented here in a condensed form, for the most frequently encountered feeds
(condensate, virgin naphtha).

Methaforming has been successfully used to process the following hydrocarbon feeds:

• straight-run gasolines (virgin naphthas), including full range, light, and heavy naphthas,

• gas condensates,

• natural gasoline,

• pyrolysis gasoline,

• raffinates from aromatics extraction units,

• light FCC naphthas (with 20-25% wt. of olefins),

• benzene-rich naphthas (up to 10% vol. of benzene in the feed),

• narrow fractions of C6-C7 hydrocarbons (boiling range 60-85оC),

• light naphthas and solvents (up to 30% vol. of C5 components), including those of synthetic origin (e.g. the
products of Fischer-Tropsch process, known as GTL naphtha).

❖ Light Naphtha

The light naphtha analysis provides balances for light paraffinic / lean naphtha that is used as a feed for steam
crackers and boils typically between 50⁰F (C5) and 160⁰F. Light naphtha balances include natural gasoline, the
lightest naphtha that is produced in natural gas processing plants. Light naphtha balances also include heavy
naphtha that has low N+A content and is therefore a better feed for steam cracking than for heavy naphtha
reforming. The majority of light naphtha is produced in refinery.

Light Naphtha Supply Sources: Light Naphtha Demand Sectors:

‒ Natural gasoline ‒ Crude blending
‒ Condensate splitting ‒ Steam cracking
‒ Crude distillation ‒ Paraffinic solvents
‒ Hydrocracking ‒ Direct blending of motor gasoline
‒ Coking ‒ Isomerization
‒ Hydrotreating ‒ Reforming to mogas and avgas
‒ Blended heavy naphtha ‒ Reforming to aromatics
‒ Raffinate ‒ Other (e.g. burning for heat generation,
‒ Gas- and Coal-to-Liquid gasifcation
to methane/syngas, losses, etc.)

Table 3.1 - Light Naphtha Supply & Demand

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 ❖ Heavy Naphtha

The heavy naphtha analysis provides balances for heavy naphthenic / rich naphtha that is good feed for heavy
naphtha reformers, and typically boils between 160⁰F and 370⁰F (C11). Heavy naphtha balances exclude heavy
naphtha that has low N+A, content below approximately 35%. However, the heavy naphtha balances include an
excess of good or slightly lower-quality heavy naphtha that is blended into full range paraffinic naphtha (which is
part of the light naphtha balances), whose trade is more liquid. As with light naphtha, a majority of heavy naphtha
is produced in refineries. Total production of heavy naphtha is about twice as large in volume as the production of
light naphtha.

Heavy Naphtha Supply Sources: Heavy Naphtha Demand Sectors:

‒ Condensate splitting ‒ Reforming to mogas and avgas

‒ Crude distillation ‒ Reforming to aromatics

‒ Hydrocracking ‒ Direct blending of motor gasoline

‒ Coking ‒ Blending of full range naphtha

‒ Hydrotreating ‒ Other (burning of heat generation, gasification to

methane/syngas, change in kerosene demand, losses,
etc.)
Table 3.2 - Heavy Naphtha Supply & Demand

Figure 3.15 Light Naphtha Processing Processes

81
Table 3.3 shows a Sample Material Balance of a Methaformer with Full Range Naphtha as a Feed.

Table 3.3

Table 3.4 shows a Typical Properties of Naphthas That Were Successfully Processed by Methaforming.

Table 3.4

Process Chemistry [25]

Naphthas from different sources vary greatly in their hydrocarbon composition and therefore in the ease of
conversion in isomerization and reforming, as well as, in Methaforming.

Methaforming will convert most of the normal paraffins, naphthenes and olefins to isoparaffins, and aromatics.

There are numerous chemical reactions that occur during the Methaforming process. Some of these reactions are
highlighted here.

82
Upon contact with the catalyst, alcohol yields a corresponding alkyl radical in a highly exothermic reaction of
alcohol dehydration. The heat of this reaction supports the subsequent endothermic dehydrogenation of
naphthenes (see figure below); for simplicity, shown with methanol cofeed).

The alkyl radical from alcohol dehydration can alkylate aromatic groups, e.g. converting most of benzene to
toluene, xylene and C9 aromatics (see Table 3.5), or react with itself to make longer chain radicals, further
converted to higher olefins and aromatics.

Olefins in the feedstock follow a conversion pathway similar to the alcohol. Newly formed aromatics can be further
alkylated; paraffins and naphthenes can be further converted to isoparaffins and aromatics.

The content of fused-ring aromatics (e.g.naphthalene) in the product remains below 0.5%.

The occurrence of the endo- and exothermic reactions in the same vessel translates into a significant economic and
environmental advantage of Methaforming over the traditional methods of naphtha processing due to the reduced
reheat duty. For example, with the FRN+ethanol feed combination, the need for fuel gas in Methaforming is 0.58
gCO2/MJ, or about 1/5 of the corresponding number for the traditional reforming and isomerization suite (3.2
gCO2/MJ).
The water formed in the alcohol dehydration becomes steam that reduces coke formation on the catalyst, ensuring
a longer catalyst cycle. Every step in the pathways is an equilibrium reaction and hence the products of the
conversion process will depend on process parameters.

Table 3.5 – Example of the Aromatic Shift

Figure 3.16 Dehydration and Dehydrogenation Reactions

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Process Description [25]

Figure 3.17 Methaforming Illustrative Flow Diagram

The design provides for the joint processing of feedstock supplied by pump P-1 (naphtha) and by pump P-2
(alcohol). Heating and vaporization of naphtha and alcohol are performed sequentially in the recuperative heat
exchanger HE-1 and furnace F-1.

After heating to 360-430°C (680-806°F), the gaseous feed mixture is fed into reactor R-1 or R-2 which operate
alternately (~800 hr on feed and ~50 hours of regeneration). The catalytic process occurs in the reactor converting
alcohol and naphtha into Methaformate (gasoline blendstock).

The reaction products at a temperature of 360-430°C (680-806°F) go to the tube side of the alcohol heat exchanger
HE-2 and then are cooled further in heat exchanger HE-1, followed by air cooler AC-1. The reaction products cooled
to 35oC (95°F) are then separated in a three phase separator S-1. Gas (HRG) from S-1 is fed to the off gas
compressor GC-1, then sent offsite. The liquid phase of the product stream is stratified and decanted in S-1. The
aqueous layer is sent to water treating and hydrocarbons go to pump P-3. From there, the hydrocarbon product is
preheated in heat exchanger HE-4 and directed to stabilizer ST.

84
The stabilized Methaformate is withdrawn from the bottom of stabilizer ST. The Methaformate, after cooling in
HE-4 and air cooler AC-3 to 45°C (113°F) is routed off-site via product tank T.

The overheads of stabilizer ST are cooled in air cooler AC-2 and fed into the reflux drum S-3, which is a three-phase
separator. Uncondensed vapors from the S-3 are routed to the fuel system, and the water is discharged to
wastewater treating. The liquid hydrocarbon product is a propane-butane fraction, which goes to pump P-4 and is
returned to stabilizer ST as reflux with the balance off-site as LPG.

Catalyst [25]
The Methaforming process uses a zeolite catalyst designed for producing high-octane hydrocarbon fractions
(gasolines, their components, aromatic hydrocarbon concentrates), from low-octane hydrocarbon fractions, with a
co-feed of oxygen-containing compounds (alcohols, ethers), and/or olefins.

The catalyst is in pellet form consisting of a high-silica zeolite of the pentasil group and a binder containing silica
and/or alumina. The zeolite is promoted using salts of zinc and rare earth elements.

Regeneration of the Catalyst

The regeneration of the catalyst is carried out with nitrogen-air mixture. The nitrogen-air mixture is compressed
by compressor GC-2 and heated to 350-550°C (662-1,022°F) in heat exchanger HE-3 and furnace VH-2, and then
fed to the reactor R-1 or 2. Exhaust regeneration gas containing nitrogen, carbon dioxide and water is cooled in
exchanger HE-3 and air cooler AC-4, wherein a portion of the water condenses and is removed in separator S-2
with the gases discharged into the atmosphere or scrubbed.

The expected cycle time is from 33 days (800 hours) to 17 days (400 hours) minimum, depending on the feed
qualities and operating conditions. The amount of coke on the surface of the catalyst at the beginning of the
working cycle is 0.3-0.5%wt., and at the end of the cycle, up to 10%.

Regeneration is typically carried out within 2 days, depending on the circulation rate and the amount of coke on the
catalyst. The temperature during catalyst regeneration grows from 280 to 510 °C as the oxygen concentration in
the circulating nitrogen/air mixture is increased from 1.5% to 18%.

Table 3.6 – Properties of the Catalyst

85
Reactor [27]
The reaction of converting the naphtha together with alcohol and/or olefins to produce high octane gasoline is
carried out in a fixed bed, gas phase reactor. Overall enthalpy change of the reaction mixture during the reaction is
small i.e. inlet and outlet temperature are comparable. This is because the dehydration of alcohol is highly
exothermic, while the dehydrogenation of naphthenes is highly endothermic. In general, throughout the catalyst
bed, it is desirable for the temperature to remain within ±15°C (27oF) of the design value. A multi-bed reactor with
divided input of alcohol to the beds is used to maintain a satisfactory temperature profile.

Figure 3.18 Economical Benefits Compared to Alternatives

More Industrial Advantages [25]

• Share of co-feed (alcohols, ethers, olefins) can range from 15 to 50% of the naphtha feed;
• RON of Methaformate: 85-95, can be managed by changing the reactor inlet temperature and/or the ratio of co-
feed to naphtha;
• Long cycle length (up to 33 days) and operational life of the catalyst (3-5 years);
• Inexpensive non-precious metal catalyst;
• Similarity to hydrotreatment process, with similar equipment costs, and a possibility for a low-cost revamp of an
existing hydrotreater or reformer into a methaformer;
• When feed requirements are observed, the products do not contain components that may lead to gumming;
• Produces hydrogen-rich gas (HRG) for use in other refinery units.

• Serving incremental demand for gasoline at 100-5000 bpd (40-200k tpa). When a refiner sees an opportunity to
sell up to 5k bpd (200k tpa) additional gasoline after all debottlenecking opportunities have been exhausted, they
should consider using Methaforming. Reforming and isomerization have much higher capital cost per ton or barrell
of feed or product and typically require higher operating capacities to justify the investment. Adding a Methaformer
in such situation is a capital-efficient solution with a much quicker payback period.

86
 Figure 3.19 Reduced Reactions in Methaforming

Methaforming produces high-octane gasoline from low-octane hydrocarbons and methanol at 1/3 the cost with
comparable yields

• One Simple Step Conversion of Hydrocarbons with Methanol into Gasoline.

• High yield of high-octane gasoline blendstock
• Lower Capital and operating costs due to the less equipment and less sever conditions used.
• Substantially Lower CAPEX and OPEX
• Lower Temperature and pressure than semi-regen Catalytic Reforming
• No Hydrogen Addition, no need for Recycle
• Very Low Product Benzene and n-Paraffins
• Non-Noble Metal Catalyst
• Tolerates Feed Sulfur
• Lower Octane Sensitivity [RON minus MON] than Catalytic Reformate
• Higher Yield of Gasoline Blend Stream (Methaformate) than semi-regen Catalytic Reforming
• Reduce CO2 emissions by ~300kg per ton of feed.

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Utility Requirements [27]

Figure 3.20 Methaforming Unit Utilities

Approximate requirements for such utilities in the production mode per unit of naphtha feed are shown below in
Table 3.7

Table 3.7 – Methaforming Unit Utilities Requirements

88
 Chapter (4)
Petroleum Refinery &
Naphtha Methaforming Simulation

(4.1) Introduction

Aspen HYSYS (or simply HYSYS) is a chemical process simulator used to mathematically model chemical processes,
from unit operations to full chemical plants and refineries. HYSYS is able to perform many of the core calculations
of chemical engineering, including those concerned with mass balance, energy balance, vapor-liquid equilibrium,
heat transfer, mass transfer, chemical kinetics, fractionation, and pressure drop. HYSYS is used extensively in
industry and academia for steady-state and dynamic simulation, process design, performance modelling, and
optimization.

Aspen HYSYS is an application that provides models for the analysis of the feasibilities of processes. It is often
applied in the study and investigation of several operating parameters on various processes. It is an effective tool,
offering a high degree of efficiency in accomplishing process design. The flexibility accompanying the logical and
consistent approach to how HYSYS delivers its capabilities makes it an extremely efficient multipurpose simulation
process tool.

The preferred fluid package for the process under consideration is Peng-Robinson equation of state (EOS) since it
can handle the hypothetical components (pseudo-components). Pseudo-components are coded variables used to
simplify design construction and model fitting. The crude oil feed properties are provided as a crude assay which is
essentially the chemical evaluation of crude oil feedstock by petroleum testing laboratories.

Using HYSYS V10, this chapter will cover a full simulation for the Petroleum Refinery and Naphtha Methaforming
including Crude Oil Preheat Train, Preflashing unit, Heating unit, Atmospheric Crude Tower, Vacuum Crude
Tower, Naphtha Methaforming Units.

89
Overall Plant Process Design Using HYSYS
Figure 4.1 Overall Plant Design
90
Figure 4.2 Overall Plant Design Sectioned

91
 (4.2) Crude Oil Data Generation

Create new simulation file

When running under Windows 10 you can start the program from Start, the all programs list, Aspen
HYSYS, Aspen HYSYS V10. When the program opens choose the New button.

Define the Components & the Property Models

Specify components, fluid property packages, & crude oil assays

Figure 4.3 Defining Components List

The first step is to add a set of pure chemical species to represent the light components of the crude oils. With
Component Lists highlighted click on the Add button. From the list of pure components pick water, methane,
ethane, propane, i-butane, n-butane, i-pentane, & n- pentane. Note that you can pick a single component at a time
or highlight components & add at the same time. You can also reorder the components in the list & drag to a new
position.

92
 Figure 4.4 Components List Options

The next step is to pick a fluid property package. From the Fluid Packages screen click the Add button. Choose the
Peng-Robinson option and make sure it is associated with Component List – 1.

Figure 4.5 Fluid Property Package

93
We now want to add assay data for the crude oil: Light Crude was used and the data to be added, from the Exxon Mobil
Refining & Supply Company, is shown in the following figure.

Figure 4.6 Crude Oil Assay Data

94
The following steps show how to enter the data for Light Crude. Similar steps should be used for the other crude
oils. The steps will be shown using the Oil Manager2.

Click on the Oil Manager button in the Home tab. You will have the options to install individual crude oil assays &
then create a blend of the assays

Figure 4.7 Oil Manager

Click on the Input Assay button & then the Add button. In the Assay Definition section we want to use Bulk
Properties, specify a TBP Assay Data Type, input compositions for the Light Ends, and input an independent
Density Curve. Ensure the Assay Basis is Mass. When all of these are specified the Input Data should look like
below.

Figure 4.8 Oil Manager Input Assay

95
Let’s input the TBP curve on a wt% basis for Light Crude. Click on the Edit Assay… button. Since we will be
entering 12 data points enter 11 for the Num of Points to Add & click the Add Data Points button (since 1 is already
showing). Now the table of Cumulative wt% Yield values (scaled 0 to 100) vs. temperatures (in °F) can be entered.
Click OK

Figure 4.9 Light Crude Distillation Input Data

Now we’ll add in the composition of the light

ends. Make the Light Ends option active & the
form will change to allow you to enter the
compositions (based on the component list
previously specified). Make sure you change
the Light Ends Basis to Mass%.

Figure 4.10 Light Crude Light Ends Input Data

96
 Now we’ll add in the density data. Make the Density
option active & the form will change to show you the
density vs. yield data entered. Click on the Edit Assay…
button. Since we will be entering 12 data points enter 11
for the Num of Points to Add & click the Add Data Points
button (since 1 is already showing). Now the table of
Cumulative wt% Yield values at the middle of the cut
(scaled 0 to 100) vs. standard liquid density values (in
lb/ft3) can be entered. Click OK. Note that even though
the standard liquid density might be in the crude oil assay
in other forms (such as specific gravity of API gravity)
HYSYS will request the information in a specific form & it
cannot be changed on this form.

Figure 4.11 Density Input Data

Let’s finish adding in the data needed to characterize the assay and allow HYSYS to create pseudo components.
Make the Bulk Props option active & the form will change to allow you to enter the data. The only information we
have to add is the standard liquid density for the whole crude. Enter this value in the Standard Density field. Note
that other units can be used on this form. Further note that whatever units are used for the data entry HYSYS will
convert the value to the units the form is expecting (in this case API gravity).

Figure 4.12 Light Crude Input Data

97
Even though we can now characterize the pseudo components for the flash calculations we still need to add the
sulfur distribution so that this can be tracked. First, we’ll have to define a User Property that represents the sulfur
content. Click on User Properties either from the tree structure in the left-hand column or the appropriate button
under the Home tab. When the User Properties form comes up press the Add… button.

Figure 4.13 User Properties

On the UserProp-1 form choose the Mass Fraction option & leave the F1 through F5 mixing parameters to
the default 1 & 0 values. (These will give an untranslated mass fraction mixing of the pure & pseudo
component values.) Set the values for the pure components as zeroes.

Figure 4.14 Basic User Properties Definitions

98
Let’s make the label for this property more meaningful. Return to the User Properties tab and
single click the UserProp-1 label. Now type in “Sulfur Vals”.

Figure 4.15 User Properties Sulfur Input

Now we can add the sulfur distribution for the assay.

Click on Assay-1 in the tree structure in the left-hand
column & choose the User Curves tab.
Highlight Sulfur Vals in the Available Properties
column & press Add--->. Under the User Curve Data
area retain the Independent setting for the Table
Type, enter the whole crude value for the Bulk Value,
and set the lower and upper limits to 0 and 100 (scroll
down the list to find these properties). Press the
Edit… button at the bottom of the form to enter the
assay values. Press OK.

Figure 4.16 Sulfur Distribution

One more thing to clean up for the assay, changing its name. Click on Input Assay in the tree structure of the left-
hand column. In the Input Assay form single click Assay- 1 & type Light Crude.

Figure 4.17 User Curves

99
Specify crude oil blend, & install into flowsheet

One more cleanup step, changing the name of the blend. Select Output Blend in the tree structure of the left-hand
column. In the tabbed form select Blend-1 and change to Light Oil.

Figure 4.18 Output Blend

The next step is to install the

blend into the flowsheet. From
this tabbed form select Oil
Manager and then select Install
Oil from the next form. Now we
get a form that we can install one
or more of the oils. We’re only
interested in installing the blend,
Light Oil. In the Stream Name
column enter Crude Oil
for Light Oil. Click Install.

Figure 4.19 Installing Blends

100
As a final step let’s make sur everything is calculated & the pseudo components are installed into the component
list. Select Oil Manager in the tree structure in the left-hand column. At the bottom of the form click Calculate
All. Now when you look at the Component List you should see a series of pseudo components after the pure
components chosen earlier.

Figure 4.20 Components List-1

Set up & Solve the Flowsheet

Units Used in Simulation

Before actually setting up the simulation we should determine what set of units are being used. The
preference for this example is to use U.S. Customary units (temperature in °F, liquid flow in bbl/day,
mass flow in lb/hr, etc.). There is a default unit set, Refining, that is almost everything that we will
want.

Under the Home tab there is a section for Units that show the
current set being used & a button to change options within a unit
set. For this problem the default is a set called NewUser1 (for new
files the starting set is dependent on what was previously used on
the particular computer being used). To ensure the actual set
being used let’s create a new one which we will call Refining-US.
Click on the Unit Sets button to bring up the form to examine the
available unit sets & change (if desired).

Figure 4.21 Unit Sets

101
 In the lower section let’s start with the refining unit set. Select refining & press Copy. A new unit set will
be created (here called NewUser2). Double click on this name & enter Refining- US.

Figure 4.22 Units of Measure

In the upper section we can set the units used for various properties in the simulation. We can see that
most units used are very reasonable. For example, temperature is in °F, standard volumetric flow is in
bbl/day, & pressure is in psia.

Figure 4.23 Display Units

102
The pressure units would normally be OK, but we’d like to see gauge pressure in this problem instead (especially
since all of the operating conditions will be given in this way). We can change the units by clicking on the pressure’s
dropdown list & choosing psig instead. Click OK when done to close this form.

Figure 4.24 Display Units Pressure Alteration

(4.3) Preheating, Preflashing & Heating Units

Figure 4.25 Overall Units Design

103
Crude Oil Feed & Preheat

Figure 4.26 Feed Preheating Unit Design

When you activate the Simulation you’ll see a single stream called Crude Oil. We want to process this stream
through two heat exchangers (to model the preheat before & after the Desalter) and a Mixer to set an expected
amount of water in the Crude Oil coming from the Desalter. One way to start the setup is to define the unit &
stream attachments before worrying about defining stream compositions & conditions. This can be done by
dragging the appropriate units from the Model Palette to the flowsheet (2 Heaters & one Mixer) and then
using the Design Connection window to create & attach the streams. For example, after double-clicking on the
Heater representing Preheat-1 the Design Connection window should look like the following. Note the
following:
• The Crude Oil stream was associated with the Inlet by pulling down the list & choosing
this existing stream. It exists because it was created in the Properties definition step when
you clicked the Install Oil button.
• The steam names Q-Preheat-1 & Warm Crude 1 can be typed into the Energy & Outlet stream
areas. Since these streams do not yet exist they will be created & shown on the PFD.
• The name of the Heater can be changed by double-clicking on the Name field & replacing
with what you want (here Preheat-1).

Figure 4.27 Preheater1 Connections

104
The following are the conditions to be set on the operations.
• Crude Oil Feed: 100°F, 300 psig, 100,000 bpd
• Preheat-1 outlet: 260°F, 294 psig
• Desalter outlet: 260°F, 294 psig, 500 bpd of water
• Preheat-2 outlet: 450°F, 260 psig

The conditions on the streams can either be set directly on the stream through its forms, indirectly
using the unit forms, or a combination of the two. (There are actually other options using Adjust
operations & spreadsheets, but these will be discussed later.)

Double-click on the Crude Oil stream to open up the entry forms for this stream. Note that the flow rate
comes from Oil Manager, but we’re going to overwrite this. Note that once you enter the pressure &
temperature the necessary conditions to define the phase condition for Crude Oil are complete & the
flash calculations are performed; this is designated by the stream taking on a new color in the flowsheet
& the message OK is shown at the bottom the stream’s form.

Figure 4.28 Crude Oil Conditions

Double-click on the unit for Preheater-1 & select the Conditions option under the Worksheet tab. Let’s
define the pressure & temperature in this window. Note these are sufficient conditions to flash the outlet
stream & determine the required heat.

Operating conditions (such as pressure & temperature) & compositions can be set either from the
stream forms or the unit forms; there is greater flexibility in set setting compositions of a stream from
the stream forms.

105
 Figure 4.29 Preheater1 Conditions

Desalter Water: Here we’ll set the entrained water by opening up the input form for Desalter Water. On
the Worksheet tab select Composition. Click on the Edit… button, enter 1 for the fraction of H2O, click
the Normalize button, and then OK. Next, we will set the pressure of the entrained water (same as the
outlet from the Desalter) & the flowrate. Note that we will not set the temperature at this time.

Figure 4.30 Desalter Water Conditions

106
Figure 4.31 Desalter Water Conditions Molar Flow

Figure 4.32 Desalter Water Compositions

107
The Mixer: Now let’s set the conditions for the outlet of the Desalter. Double click on the Mixer and click
on the Worksheet tab. Note that the pressure of the outlet stream has been determined (set as the lowest
pressure of all streams being mixed) & the standard liquid flowrate has been determined (since this is just
additive of the two streams into the Mixer). Now, let’s specify the temperature of the outlet of the Desalter;
note that the temperature of the water stream has been back-calculated to enforce the adiabatic nature of
the Mixer operation.

Figure 4.33 Mixer Connections

Before specifying outlet

temperature:

Figure 4.34

Mixer Conditions-1

After specifying outlet

temperature:

Figure 4.35

Mixer Conditions-2

108
 Now we can change the name from Mix-100 to mixer1

Figure 4.36 Mixer Renaming

Preflash

Preflash separate crude oil to two parts: liquid and gas

For increased capacity of distillation tower and Crude is transferred to Naphtha Stabilizer and Crude Heaters
Liquid stream is transferred from crude oil to furnace
Gas stream to separator to transfer fuel gas and stabilized naphtha
Naphtha Stabilizer is better and more gasoline
Condensed to recover LPG which is treated in caustic and amine treating unit.
Stabilized naphtha is further separated into light, medium and heavy naphtha.

Figure 4.37 Preflashing Unit Design

109
Create a new Separator on the flowsheet & call it Preflash. Enter the following connections & set the
following outlet conditions to match the approximate atmospheric separator, from design click on
connection and parameter.

Figure 4.38 Preflash Connections

Figure 4.39 Preflash Design Parameters

110
Click on Worksheet, select temperature and pressure
Preflash vapor (Gas stream) entry in separator to transfer fuel gas and stabilized naphtha

Figure 4.40 Separator Unit Design

Create a new Separator on the flowsheet & call it separator Enter the following connections.

Figure 4.41 Separator Connections

111
 Figure 4.42 Separator Conditions

Heating the Crude Oil:

Figure 4.43 Heating Unit Design

112
Create a new Heater on the flowsheet & call it Furnace. Change the icon to look like a heater instead of a shell &
tube heat exchanger. Enter the following connections & set the following outlet conditions to match the
approximate atmospheric column.

Figure 4.44 Furnace Connections

Figure 4.45 Furnace Parameters

113
 Figure 4.46 Furnace Conditions

This portion of the PFD should look like the figure.

Figure 4.47 Furnace Design

Figure 4.48 The Full Unit Output Conditions

114
(4.4) Distillation Atmospheric Tower Unit

Figure 4.49 Atmospheric Unit Overall Design

115
Figure 4.50 Atmospheric Tower Environment

116
The next step is to set up the Atmospheric Distillation Column. Table 4.1 contains the conditions &
configuration for this column.

The fired heater on the feed is separate from the column environment & will be created first. Create a new
Heater on the flowsheet & call it Atm Heater. Change the icon to look like a heater instead of a shell & tube
heat exchanger. Enter the following connections & set the following outlet conditions to match the
approximate atmospheric column conditions in Table 4.1.
Type Operating Parameter
Trays & Efficiencies 50 trays. Numbering from top:
Trays 1 to 6: 80%
Trays 7 to 10: 50%
Trays 11 to 16: 70%
Trays 17 to 30: 50%
Trays 31 to 39: 30%
Tray 40: 100%
Trays 41 to 50: 30%
Condenser Type Total Condenser; 130°F (approximate)
Distillate product 410°F D86 T95; 30,200 bpd (approximate)
Reboiler Type None, Direct Fired Heater
Pressures Condenser: 4 psig
Top Tray: 12 psig
Bottom Tray: 22 psig
Temperatures Top Tray #1 250°F (estimate)
Bottom Tray #50 650°F (estimate)
Feed Locations Crude oil to Tray #40
Stripping Steam at bottom (Tray #50) – 20,000 lb/hr @ 500°F, 150 psig
Feed Heater Outlet @ 25 psig & 635°F
Desire is 2,500 bpd overflash (liquid rate from tray above feed, Tray #39)
Side Strippers Kerosene Stripper
10 trays @ 30% efficiency
Kerosene draw from Tray #10, vapor returned to Tray #6
Stripping steam @ bottom (Tray #10) – 2500 lb/hr @ 500°F & 150 psig
Kerosene product 525°F D86 T95; 8800 bpd product (approximate)
Diesel Stripper
10 trays @ 30% efficiency
Diesel draw from Tray #20, vapor returned to Tray #16
Stripping steam @ bottom (Tray #10) – 2500 lb/hr @ 500°F & 150 psig
Diesel product 645°F D86 T95; 10,240 bpd product (approximate)
AGO Stripper
10 trays @ 30% efficiency
AGO draw from Tray #30, vapor returned to Tray #26
Stripping steam @ bottom (Tray #10) – 2500 lb/hr @ 500°F & 150 psig
AGO product 750°F D86 T95; 3835 bpd product (approximate)
Pumparounds Kerosene Pumparound
Draw from Tray #10, returned to Tray #7
25,000 bpd flow, 200°F return temperature

Diesel Pumparound
Draw from Tray #20, returned to Tray #17
15,000 bpd flow, 250°F return temperature
AGO Pumparound
Draw from Tray #30, returned to Tray #27
10,000 bpd flow, 350°F return temperature

Table 4.1 - Atmospheric Column Conditions

117
When you double click on the column for the first time a wizard starts and will guide you through
entering information. If you don’t fill it all in, don’t worry – you can always specify the information from
the forms & column sub-flowsheet.

The first step in the

wizard is to set up the
basic information for
the main feeds &
products (but not the
side products which
will be processed
through side
strippers). Fill in the
information as shown
below. Make sure you
check the box for
Water Draw. When
done press Next>.

Figure 4.51 Distillation Column Inputs

The next step is to set up

the basic pressure profile
in the column. Fill in values
& press Next>.

Figure 4.52 Refluxed Absorber Pressure Inputs

118
 Press Next>. On the third
screen we will set an
estimate for the condenser
temperature. Though the
other temperatures are not
required it’s usually good
practice to enter values. For
an atmospheric crude
tower reasonable starting
points are 250°F & 650°F
for the top & bottom stages,
respectively.

Figure 4.53 Refluxed Absorber Temperature Inputs

Press Next>. On the fourth

screen we’ll set an estimate
for the distillate rate.

Figure 4.54 Refluxed Absorber Distillate Rate Inputs

Press the Side Ops> button to start setting up the side strippers & pumparounds. We’ll skip this first side
operation screen since none of the side strippers are reboiled (they use stripping steam instead). Press
Next>.

119
 Now we can start adding
the basic information for
the three side strippers.
To start entering the
configuration information
for each side stripper
press the Add Side
Stripper button; when
done press the Install
button. When done with
the three side strippers
press the Next> button.

Figure 4.55 Side Operations Inputs

We do not have any side rectifiers. Press the Next> button.

Now we can start adding

the basic information for
the three pumparounds.
To start entering the
configuration information
for each pumparound
press the Add Pump-
Around button; when
done press the Install
button. When done with
the three pumparounds
press the Next> button.

Figure 4.56 Pumparounds Inputs

We do not have any vapor bypasses. Press the Next> button.

120
 Now we can enter the
side product flows
through the side
strippers. Enter the
estimates for the
flowrates out the bottom
of the strippers & then
press Next>.

Figure 4.57 Side Products Inputs

Now we can set the specs

on the pumparounds.
Enter the flowrate values
& the values associated
with the heat exchanger
duties. Note that all of the
duty/temperature specs
are Return T type. When
done press Next>.

Figure 4.58 Pump-Around Specs

Now we can set the pressures in the side strippers. Use the default values with no changes. Press Next>.

Now we can set the pressure drops across the pumparounds. Use the default values of zero. Press Done.

121
Distillation columns are different from the rest of the HYSYS operations in that they do not automatically
run the first time they are created; rather, you must press the Run button when everything has been set
up properly. However, we still have a couple more changes to make so let’s not do this yet.

First, let’s specify the stage efficiencies to model the stages as real trays. Under the Parameters tab select
Efficiencies. Make sure that Overall & User Specified items are highlighted. Now let’s start applying the efficiencies
in Table 4.1. Note that stages associated with the side strippers are listed in this table as if part of the main column
(in a way they are, but that’s a subject for a different discussion).

Figure 4.59 Atmospheric Tower Efficiencies

122
Figure 4.60 Atmospheric Tower Efficiencies Cont’d

123
The next requirement is to specify the steam streams. This can be done using the Worksheet tab. Select
Conditions and specify the temperature, pressure, & mass flowrate values. Select Compositions; now the
compositions can be set as 100% H2O (entering a value of 1 will bring up the Input Composition form;
press the Normalize button & then OK). Note that once these values are entered for the steam streams
those flash calculations can be completed; the associated calculations for the product streams cannot be
done until the tower calculations are completed.

Figure 4.61 Atmospheric Tower Conditions

Figure 4.62 Atmospheric Tower Conditions Cont’d

124
 Figure 4.63 Atmospheric Tower Compositions

Even though we don’t have all of the operating specs added we can do an initial run of the simulation by
pressing Run. You should get a converged solution within 10 iterations.

How can the distillation column equations be solved without putting the composition specs? This is because the
“estimated” flowrates entered during the setup are used as the actual specifications. We can see this by checking
the Spec Summary setting under the Design tab. Notice that all of these flowrate specs have checks in the Active
column; this means that these values are the specifications to which the solution is driven.

Figure 4.64 Atmospheric Tower Specs Summary

125
Let’s now add the composition specs but not make them active. Select Specs under the Design tab. In the Column
Specifications area we can add, remove, or change any of the specs that will show up in the Summary. Let’s first
add the ASTM D86 95 vol% temperature spec for the Naphtha stream. Click Add… In the list that comes up choose
Column Cut Point (do not choose End Point Based Column Cut Pint Spec near the bottom of the list) & click Add
Spec(s)… Call the spec Naphtha D86 T95, associate the spec with the liquid phase off of the Condenser, set the %
as 95, and set the Spec Value as 410°F.

Figure 4.65 Column Specification Types

Once we close the input form we can see information about the specification details. The value is supposed to be
410°F but because the spec is not active the value is 419.4°F. Close, but not close enough. In the actual operation of
the tower we would adjust the distillate draw rate to make this spec. In HYSYS we make the Distillate Rate spec
inactive & make the Naphtha D86 T95 spec active. The easiest way to do this is from the Specs Summary form.

Figure 4.66 Atmospheric Tower Design Specs

126
We can create similar design specs for the
Kerosene, Diesel, & AGO D86 T95 values. Each
time we make the T95 spec active we will make the
corresponding production rate inactive.
Note that when we make these specifications the
stream associated with the spec will be the liquid
from the bottom of the appropriate side stripper.
Finally, when you compare the actual production
rates to the initial estimates you may find that each
change in a T95 spec may change other production
rates, not just the one associated with that spec.
For example, adding all of these T95 specs will
change the naphtha
rate to 29,260 bpd.

Figure 4.67 Specs Parameters

Figure 4.68 Atmospheric Tower Monitor

127
 Figure 4.69 Atmospheric Tower Connections

Figure 4.70 Atmospheric Tower Output Compositions

128
 Atmospheric Tower Products

Figure 4.71 Light Gas Conditions

Figure 4.72 Naphtha Conditions

129
Figure 4.73 Kerosene Conditions

Figure 4.74 Diesel Conditions

130
 Figure 4.75 AGO Conditions

Figure 4.76 Atm Residue Conditions

131
(4.5) Vacuum Tower Unit

Figure 4.77 Vacuum Tower Unit Design

Figure 4.78 Vacuum Tower Environment

132
Type Operating Parameter
“Trays” & 14 trays. Numbering from
Efficiencies top: Tray 1: 100%
Trays 2 to 11: 50%
Tray 12: 100%
Trays 13 to 14: 30%
Condenser Type No condenser, LVGO pumparound liquid return to top stage
Reboiler Type None, Direct Fired Heater
Pressures Top Tray: 50 mmHg
Bottom Tray: 62 mmHg
Temperatures Top 180°F (controlled by top LVGO pumparound)
Feed Locations Crude oil to Tray #12
Stripping Steam at bottom (Tray #14) – 20,000 lb/hr @ 500°F, 150 psig
Feed Heater 20,000 lb/hr steam injected into heater coils with the Atmospheric Resid
feedstock (500°F & 150 psig)
Outlet @ 180 mmHg & 760°F (max); would like 3,000 bpd excess wash liquid
(liquid rate
from tray above feed, #11)
Pumparounds LVGO Pumparound
Draw from Tray #4, returned to Tray #1
22,300 bpd flow, outlet temperature adjusted to control top temperature of tower;
approximately 85°F, 42 MMBtu/hr cooling
HVGO Pumparound
Draw from Tray #8, returned to Tray #5
50,000 bpd flow, 150°F cooling
Products LVGO from Tray #4; 915°F D1160 T95; 5,000 bpd
(approximate) HVGO from Tray #8, 1050°F D1160 T95; 21,000
bpd (approximate) Slop Wax from Tray #11, 1,000 bp
Vacuum resid from bottom
Table 4.2 - Vacuum Column Conditions

Figure 4.79 Mixer Connections

133
 Figure 4.80 Steam Conditions

The fired Vacuum Heater is separate from the column environment & will be created next. Create a new
Heater on the flowsheet & call it Vac Heater. Change the icon to look like a heater instead of a shell &
tube heat exchanger. Enter the following connections & set the following outlet conditions to match the
vacuum column conditions. Note that even though the pressure is specified as 180 mmHg(0C) the value
is immediately converted to the units used in the flowsheet, here psig.

Figure 4.81 Furnace Vacuum Connections

134
 Figure 4.82 Furnace Vacuum Conditions

On the next form we’ll initialize the pressure profile. Again, even though the pressures are input in units of
mmHg(0C) they get converted to psig. Click Next>.

On the next form we’ll initialize

the pressure profile. Again, even
though the pressures are input
in units of mmHg(0C) they get
converted to psig. Click Next>.

Figure 4.83 Absorber Column Input

135
 The next form will allow us to
add temperature estimates &
flow information for the top
pumparound. Enter the data for
the LVGO Pumparound.
We will skip adding
temperature estimates on this
form & show how they can be
added later. Click Side Ops>.

Figure 4.84 Pumparound Inputs

There are no side strippers or rectifiers so skip the next 3 forms for Reboiled Side Stripper
Connections, Steam Stripped Side Stripper Connections, & Side Rectifier Connections.

There is already one

pumparound defined (since
we specified a pumparound
return to provide the top
stage reflux). Let’s changed the
Name from the default to
LVGO Pumparound. Then click
Add Pump-Around and define
the HVGO Pumparound. Click
Install to add to the list. Click
Next> when done.

Figure 4.85 Side Operations Input

136
We will skip the next form for Vapor Bypass Connections.

The next form allows us to add

the HVGO Pumparound specs.
Note that the specs for the
LVGO Pumparound were
previously entered & are
shown here. Click Next> when
done.

Figure 4.86 Pumparound Specs

On the last form we will

accept zero pressure drops
through the pumparounds.
Click Done…

Figure 4.87 Pumparound Pressure Specs

137
 Before we try
running the column,
we need to enter the
efficiencies for the
stages. Select
Efficiencies under the
Parameters tab &
enter the values.

Figure 4.88 Vacuum Column Efficiencies

We skipped adding temperature estimates before, but we can add them now. Go to the Profiles item under the
Parameters tab. It’s typical to have a top temperature of about 150°F (this will actually be changed to be one of
nd
our specifications) & a bottom temperature of 700°F. You may also want to specify the 2 stage temperature of
325°F (since there is a significant cooling between the top & next stage).

Figure 4.89 Vacuum Column Profiles

138
Before we can run the column, we have to specify something about the side draws (LVGO, HVGO
Let’s specify the estimated flowrates and use these as specifications. Click on the Specs Summary item under the
Design tab; note there are items in this list for LVGO Rate, HVGO
Rate, & Slop Wax Rate. You could try to specify the values
here, but unfortunately the default units are molar rates, not volumetric. So, we’ll have to go back to the Specs
option & individually select the item for rate, press the View… button, & make the appropriate changes. When
done you can go back to the Specs Summary item to see that all values have been added.

Figure 4.90 Vacuum Column Specs Summary

Figure 4.91 LVGO Rate

139
Now let’s change the performance of the
LVGO Pumparound to adjust the return
temperature in that pumparound to meet
the temperature spec at the top of the
column. Select the Specs item under the
Design tab & click Add… Select Column
Temperature in the list of Column
Specification Types & click Add Spec(s)…
add a spec for the top temperature. To
make it active go to the Spec Summary
item, uncheck the LVGO
Pumparound_TRet(Pa) & check
the Top Temperature spec.

Figure 4.92 Column Specification Types

The final step is to

define the steam to the
bottom of the column.
Under the Worksheet tab
go to the Compositions
item. Enter a 1 for the
H2O value for Vac
Column Steam. This
brings up the screen to
add detail to the
composition; click
Normalize & OK. Select
the Conditions item &
specify the Temperature,
Pressure, & Mass
Flow.

Figure 4.93 Vacuum Column Compositions

140
 Figure 4.94 Vacuum Column Conditions

You may not even need to press Run. Once you enter the remaining steam information the Vacuum
Column should automatically run & converge fairly quickly.

The Vacuum Column has converged but to the flowrates that should be estimates, not the composition
specs (as defined by the T95 values). We can add the D1160 specs for the LVGO & HVGO in a similar
manner to the Atmospheric Column specs except that these streams are direct liquid draws from the
main column & do not go through side strippers. To set the LVGO spec first Add a Column Cut Point
from the Specs item on the Design tab. However, for right now we do not want to make them active;
click on the Summary tab & uncheck the Active box. You can also go to the Specs Summary item &
make sure that these new D1160 specs are not checked in the Active column.

141
 Figure 4.95 Column LVGO & HVGO specs

It is also useful to add specs for the

liquids flowing from the LVGO to
the HVGO section (from tray #4)
and the overflash back to feed tray
(from tray #11). These can be added
as a Column Liquid Flow spec. Make
sure you specify the values as Std
Ideal Vol for the Flow Basis &
ensure that the Active box is
unchecked on the
Summary tab’s form.

Figure 4.96 Column Liquid Flow Spec

142
Figure 4.97 Vacuum Column Output Compositions

143
 Vacuum Tower Products

Figure 4.98 Vacuum Gases Conditions

Figure 4.99 LVGO Conditions

144
 Figure 4.100 HHGO Conditions

Figure 4.101 Vacuum Reaid Conditions

145
 (4.6) Naphtha Methaforming Units

Figure 4.102 Naphtha Methaforming Unit Design

Mixing of Naphtha

First step Mixing of naphtha from atmospheric tower with naphtha stabilizer from preflash by mixer

Figure 4.103 Naphtha Mixing Unit Design

Create a new mixer on the flowsheet & call it mixer of naphtha -and select first stream naphtha stabilizer from
preflash and second stream naphtha from atmospheric tower

146
Figure 4.104 Mixer Connections

Figure 4.105 Mixer Conditions

147
 Figure 4.106 Mixing Conditions

Place a Pump on the

flowsheet & define the
following connections.
Retain the default adiabatic
efficiency (75%). Set the
outlet pressure as 165 psig
in the Worksheet tab.

Figure 4.107 Pump Connections

Figure 4.108 Pump Parameters

148
 Figure 4.109 Pump Conditions

Increase the temperature from 136F to 380F by heater

Place a Heater on the flowsheet

& define the following
connections. Set the pressure
drop in the Parameters section
(Delta P). Since the outlet
pressure is calculated from the
pressure drop it does not have
to be set on the Worksheet tab.
However, we still need to set the
outlet temperature & this can be
done on the Worksheet
tab.

Figure 4.110 Heater Connections

149
Figure 4.111 Heater Conditions

Figure 4.112 Heater Parameter

150
Heating and vaporization of naphtha from 380 to 806 F, Converted heating naphtha to vaporization to reaction
with vaporization methanol by furnace.

Figure 4.113 Furnace Design

Figure 4.114 Furnace Connections

Figure 4.115 Furnace Conditions

151
The process can accept methanol and gas would need to be cleaned up as is typically ethanol solutions with up to
50% wt. of water done before it enters the fuel gas system.

Figure 4.116 Methanol Reaction Design

Create a new composite

on the flowsheet & define the following connections

Figure 4.117

Model Palette Options

Figure 4.118 Methanol Material Stream Conditions

152
 Figure 4.119 Methanol Material Stream Compositions

Increase the pressure from 10 to 115 Pisg by pump

Figure 4.120 Pump Connections

153
 Figure 4.121 Pump Conditions

Increase the temperature from 90 F to 420 F by heater

Figure 4.122 Methanol Heater Connections

154
 Figure 4.123 Methanol Heater Conditions

Vaporization of methanol by furnace, from 420 to 800 F

Figure 4.124 Methanol Vaporization Design

Figure 4.125 Methanol Furnace Connections

155
 Figure 4.126 Methanol Furnace Conditions

Mixing reaction between vaporized naphtha and vaporized methanol by mixing

Create a new mixer on the flowsheet & call it methaforming reactor and select first stream naphtha from furnace
and second stream methanol from methanol furnace.

Figure 4.127 Methaforming Reactor Connections

156
 Figure 4.128 Methaforming Reactor Conditions

Cooling methformation from 805 F to 250 F

Create a new cooler on the flowsheet & define the following connections

Figure 4.129 Stabilized Feed Conditions

157
 Figure 4.130 Stabilized Feed Compositions

Type Operating Parameter

Feed Prep Increase pressure to 250 psig; use default adiabatic efficiency for pump (75%)
Preheat to 250°F; assume negligible pressure drop through exchanger
Trays & Efficiencies 45 trays. Number from top. All trays 80% efficiency
Condenser Type Total condenser
1.5 reflux ratio
Reboiler Type Kettle reboiler
Pressures Condenser: 150 psig
Top Tray: 150 psig
Bottom Tray: 160 psig
Reboiler: 160 psig
Temperature No other estimates needed
Feed Locations Unstabilized Naphtha to Tray #22
Products Overhead LPGs, 5,500 bpd
Stabilized naphtha from bottom
Table 4.3 - Methaformate Stabilizer Column Conditions

158
Now we can define the Debutanizer. Just like with the Atmospheric Distillation Column HYSYS will start the
process with a multi-step wizard to walk you through the basic configuration. From the Columns tab in the model
Palette chose the Distillation Column sub-flowsheet (the one with both a condenser & a reboiler).

The next step is to pick a type

of reboiler. The first entitled
Once-through depicts a kettle
reboiler & is the one we want
(liquid from the bottom tray is
the feed to the reboiler,
produced vapors are returned
to the bottom tray and the
liquid exits as the bottoms
product). The other two
configurations are for
thermosiphon reboilers; though
used commercially they will not
be chosen for this example.
Click Next>
when done.

Figure 4.131 Reboiler Configuration

The next form is for entering

the basic pressure profile.
Enter the values from Table.
Click Next> when done.

Figure 4.132 Reboiler Inputs

159
For this tower we will skip entering temperature estimates. Click Next>.

On the next form enter the

reflux ratio & distillate rate.
Click Done… when finished.

Figure 4.133 Reboiler Reflux Ratio

The final step before trying to

run is to specify the stage
efficiencies to model the stages
as real trays. Under the
Parameters tab select
Efficiencies. Make sure that
Overall & User Specified items
are highlighted. Apply the
same efficiency to all stages
representing trays, leaving the
efficiencies for the Condenser
& Reboiler at 1.0.

Figure 4.134 Debutanizer Efficiencies

160
Figure 4.135 Condenser Connections

Figure 4.136 Condenser Conditions

161
Figure 4.137 Reboiler Connections

Figure 4.138 Reboiler Conditions

162
Figure 4.139 Methaformate Stabilizer Monitor

Figure 4.140 Methaformate Stabilizer Profiles

163
 Figure 4.141 Methaformate Stabilizer Spec Summary

Now we can click on the Run button. The convergence should be very rapid.

Figure 4.142 Methaformate Stabilizer Conditions

164
 Figure 4.143 Methaformate Stabilizer Properties

Products of Methaforming of Naphtha

1. Gasoline 95 Octane Number 70%

Figure 4.144 Gasoline Conditions

165
2. LPG 22 %

Figure 4.145 LPG Conditions

3. Water 8%

Figure 4.146 Water Conditions

166
Figure 4.147 Methaforming Units Outputs Compositions

Naphtha HYSYS Data Analysis

Figure 4.148 Column Properties Vs Tray Position

167
Figure 4.149 Component Ratio Vs Tray Position

Figure 4.150 Flow Vs Tray Position

168
Figure 4.151 Composition Vs Tray Position

Figure 4.152 Pressure Vs Tray Position

169
Figure 4.153 Temperature Vs Tray Position

170
 Chapter (5)
Sensitivity Analysis

(5.1) Introduction [28]

What is Sensitivity Analysis?

The technique used to determine how independent variable values will impact a particular dependent variable
under a given set of assumptions is defined as sensitive analysis. Its usage will depend on one or more input
variables within the specific boundaries, such as the effect that changes in interest rates will have on a bond’s price.

It is also known as the what – if analysis. Sensitivity analysis can be used for any activity or system. All from
planning a family vacation with the variables in mind to the decisions at corporate levels can be done through
sensitivity analysis.

It helps in analyzing how sensitive the output is, by the changes in one input while keeping the other inputs
constant.

Sensitivity analysis works on the simple principle: Change the model and observe the behavior.

The parameters that one needs to note while doing the above are:

A) Experimental design: It includes combination of parameters that are to be varied. This includes a check on
which and how many parameters need to vary at a given point in time, assigning values (maximum and minimum
levels) before the experiment, study the correlations: positive or negative and accordingly assign values for the
combination.

B) What to vary: The different parameters that can be chosen to vary in the model could be:
a) the number of activities
b) the objective in relation to the risk assumed and the profits expected
c) technical parameters
d) number of constraints and its limits

C) What to observe:
a) the value of the objective as per the strategy
b) value of the decision variables
c) value of the objective function between two strategies adopted

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Measurement of sensitivity analysis

Below are mentioned the steps used to conduct sensitivity analysis:

1. Firstly, the base case output is defined; say the NPV at a particular base case input value (V1) for which the
sensitivity is to be measured. All the other inputs of the model are kept constant.
2. Then the value of the output at a new value of the input (V2) while keeping other inputs constant is
calculated.
3. Find the percentage change in the output and the percentage change in the input.
4. The sensitivity is calculated by dividing the percentage change in output by the percentage change in input.

This process of testing sensitivity for another input (say cash flows growth rate) while keeping the rest of inputs
constant is repeated till the sensitivity figure for each of the inputs is obtained. The conclusion would be that the
higher the sensitivity figure, the more sensitive the output is to any change in that input and vice versa.

Methods of Sensitivity Analysis

There are different methods to carry out the sensitivity analysis:

• Modeling and simulation techniques

• Scenario management tools through Microsoft excel

There are mainly two approaches to analyzing sensitivity:

• Local Sensitivity Analysis

• Global Sensitivity Analysis

Local sensitivity analysis is derivative based (numerical or analytical). The term local indicates that the
derivatives are taken at a single point. This method is apt for simple cost functions, but not feasible for complex
models, like models with discontinuities do not always have derivatives.

Mathematically, the sensitivity of the cost function with respect to certain parameters is equal to the partial
derivative of the cost function with respect to those parameters.

Local sensitivity analysis is a one-at-a-time (OAT) technique that analyzes the impact of one parameter on the cost
function at a time, keeping the other parameters fixed.

Global sensitivity analysis is the second approach to sensitivity analysis, often implemented using Monte Carlo
techniques. This approach uses a global set of samples to explore the design space.

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The various techniques widely applied include:

• Differential sensitivity analysis: It is also referred to the direct method. It involves solving simple partial
derivatives to temporal sensitivity analysis. Although this method is computationally efficient, solving
equations is intensive task to handle.
• One at a time sensitivity measures: It is the most fundamental method with partial differentiation, in
which varying parameters values are taken one at a time. It is also called as local analysis as it is an
indicator only for the addressed point estimates and not the entire distribution.
• Factorial Analysis: It involves the selection of given number of samples for a specific parameter and then
running the model for the combinations. The outcome is then used to carry out parameter sensitivity.

Through the sensitivity index one can calculate the output % difference when one input parameter varies from
minimum to maximum value.

• Correlation analysis helps in defining the relation between independent and dependent variables.
• Regression analysis is a comprehensive method used to get responses for complex models.
• Subjective sensitivity analysis: In this method the individual parameters are analyzed. This is a subjective
method, simple, qualitative and an easy method to rule out input parameters.

Using Sensitivity Analysis for decision making

One of the key applications of Sensitivity analysis is in the utilization of models by managers and decision-makers.
All the content needed for the decision model can be fully utilized only through the repeated application of
sensitivity analysis. It helps decision analysts to understand the uncertainties, pros and cons with the limitations
and scope of a decision model.
Most if not all decisions are made under uncertainty. It is the optimal solution in decision making for various
parameters that are approximations. One approach to come to conclusion is by replacing all the uncertain
parameters with expected values and then carry out sensitivity analysis. It would be a breather for a decision maker
if he / she has some indication as to how sensitive will the choices be with changes in one or more inputs.

Uses of Sensitivity Analysis

• Testing the robustness of the results of a model or system in the presence of uncertainty.
• Increased understanding of the relationships between input and output variables in a system or model.
• Uncertainty reduction, through the identification of model inputs that cause significant uncertainty in the
output and should therefore be the focus of attention in order to increase robustness (perhaps by further
research).

• Searching for errors in the model (by encountering unexpected relationships between inputs and outputs).
• Model simplification – fixing model inputs that have no effect on the output, or identifying and removing
redundant parts of the model structure.
• Enhancing communication from modelers to decision makers (e.g. by making recommendations more
credible, understandable, compelling or persuasive).
• Finding regions in the space of input factors for which the model output is either maximum or minimum or
meets some optimum criterion.

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 • In case of calibrating models with large number of parameters, a primary sensitivity test can ease the
calibration stage by focusing on the sensitive parameters. Not knowing the sensitivity of parameters can
result in time being uselessly spent on non-sensitive ones.
• To seek to identify important connections between observations, model inputs, and predictions or forecasts,
leading to the development of better models

(5.2) Application in the Proposed Plant [29]

Crude Oil Feed & Products in Distillation Tower

Crude Type API Sulfur, Light Naphtha Kerosene Diesel Gas Vacuum
Name & Location wt% Gas Oil Residue

Sable Island (Canada) Light 61.1 0.003 1.9 83.8 9.8 3.9 0.3 0.2
Gudrun Blen (Norway) light 50 0.086 3.3 51.7 15.4 12.8 13.3 3.4
Brent Blend (UK) Light 40 0.347 3 38 16.5 15.8 3.5 23.2
HOOPS Blend (USA) light 35.2 1.15 2.3 24.3 17.6 14.7 16.6 14.9
Volve (Norway) Medium 29.1 1.78 4.6 18 13.1 16.6 33.0 18.3
Cold Lake (Canada) Heavy 19.7 3.95 0.7 16.2 6.3 12.7 30.7 33.5

Table 5.1 – Europe & North America Crude Oils Products Comparison

Figure 5.1 Excel Data Generation

174
 Europe & North America Crudes Analysis

90

80

70

60

50

40

30

20

10

0
API=61.1 API=50 API=40 API=35.2 API=29.1 API=19.7

Light Gas Naphtha Kerosene Diesel Gas Oil Residue

Figure 5.2 Europe & North America Crudes Analysis Bar Chart

Europe & North America Crudes Analysis

120

100

80

60

40

20

0
API=61.1 API=50 API=40 API=35.2 API=29.1 API=19.7

Light Gas Naphtha Kerosene Diesel Gas Oil Residue

Figure 5.3 Europe & North America Crudes Analysis Bar Chart 2

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 Crude Type API Sulfur, Light Naphtha Kerosene Diesel Gas Vacuum
Name & Location wt% Gas Oil Residue

Marib Light (Yemen) Light 45.1 0.13% 3.2 42.7 14.8 13.9 8.6 6.7

Terengganu (Malaysia) Condensate 73.1 0.002 1.2 90.2 6 2.3 0.3 0.1
Azeri Light (Azerbaijan) Light 35.3 0.21% 1.3 18 16.0 20.4 31.3 12.9
Basrah Light (Iraq) Medium 29.9 2.93% 1.4 19.6 13.9 15.2 27.9 22.0
Basrah Heavy (Iraq) Heavy 24 3.83% 1.6 15.9 11.4 14.2 29.3 27.5
Upper Zakum (United Medium 33.9 1.74% 3.1 22.2 15.1 16.3 26.7 16.6
Arab Emirates)
Table 5.2 – Middle East & Asia Crude Oils Products Comparison

Figure 5.4 Excel Data Generation

176
 Middle East & Asia Crudes Analysis
100

90

80

70

60

50

40

30

20

10

0
API=45.1 API=73.1 API=35.3 API=29.9 API=24 API=33.9

Light Gas Naphtha Kerosene Diesel Gas Oil Vacuum Residue

Figure 5.5 Middle East & Asia Crudes Analysis Bar Chart

Middle East & Asia Crudes Analysis

120

100

80

60

40

20

0
API=45.1 API=73.1 API=35.3 API=29.9 API=24 API=33.9

Light Gas Naphtha Kerosene Diesel Gas Oil Vacuum Residue

Figure 5.6 Middle East & Asia Crudes Analysis Bar Chart 2

177
 Crude Type API Sulfur, Light Naphtha Kerosene Diesel Gas Vacuum
Name & Location wt% Gas oil Residue

Yoho Terminal (Nigeria) Light 40.5 0.06 1.6 31.7 19.8 21.3 22.9 2.6
Qua Iboe (Nigeria) Light 37.6 0.10 2.2 26.3 17.9 22.3 26.1 5.2
Zafiro Blend (Equitorial Medium 30.0 0.25 1.4 19.5 16.8 20.1 29.5 12.8
Guinea)
Doba Blend (Chad) Medium 25.8 0.09 0.3 5.7 7.5 14.0 37.8 34.7

Table 5.3 – Africa Crude Oils Products Comparison

Figure 5.7 Excel Data Generation

178
 Africa Crudes Analysis
100
90
80
70
60
50
40
30
20
10
0
API=40.5 API=37.6 API=30 API=25.8

Light Gas Naphtha Kerosene Diesel Gas oil Residue

Figure 5.8 Africa Crudes Analysis Bar Chart

Africa Crudes Analysis

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
API=40.5 API=37.6 API=30 API=25.8

Light Gas Naphtha Kerosene Diesel Gas oil Residue

Figure 5.9 Africa Crudes Analysis Bar Chart 2

179
Crude API $ (US Dollars per Barrel)
WTI [North America] 39.6 68.56
Brent Blend crude [UK] 40 67.47
Saudi Light Oil (Saudi Arabia) 34 71.88
Basra Light Oil (Iraq) 33.7 70.45
Light Iranian oil (Iran) 33.1 67.6
Nigeria's Bonny Light oil 35.4 68.65
Saudi Arabian heavy (Saudi Arabia) 28.7 58
Heavy Iranian oil (Iran) 30.2 60.57
Arabian Super Light (Saudi Arabia) 50.75 76
Hardisty Light (Canada) 20.9 46.91
Tapis (Malaysia) 43 76.01
Maya ( Mexico) 21.5° 58.34
Table 5.4 – Some Crude Oils API & Prices

Crude Oil Prices

$ (US Dollars per Barrel)

80
70
60
50
40
30
20
10
0

Figure 5.10 Crude Oils Prices Compared to API Bar Chart

180
 Comments

With reference to, Tables 1.1, 1.2, 1.3, 5.1, 5.2, 5.3, 5.4 & Figures 1.5, 3.18, 5.1 to 5.10, we can deduce the
following:

- An important classification that affects the crude oil quality and pricing is based on the API. Since it’s
stated that from API 10-26, the crude is considered heavy, and from API 26-35, the crude is considered
medium, and from API 35 and higher, the crude is considered Light. Therefore, it’s understood that the
crude we used, Brent Blend, API 40, is a Light Crude.

- We have discussed that the classifications of crude oils as light or heavy depend on its density and
specific gravity, since it’s calculated by the formula: API gravity = (141.5/SG) – 131.5 Where SG =
Specific gravity of oil. Therefore, from table 5.4, since increasing the API which makes the crude
lighter increasing its quality and its products quality, therefore the petrochemical and petroleum
markets demand is higher, so the price gets higher, this justifies, for example, the high price of Brent
Blend Crude, 67.47$ per barrel, compared to other crudes around the world.

- Also, the lighter crudes, including Brent Blend, has lower percentage of sulfur, 0.347%, which makes
it cleaner and this increases the quality of its products and therefore makes it more expensive that
other crudes.

- The 3 tables & figures (5.1, 5.2, 5.3) shows a list of comparisons of crude oils based on the
geographical location identifying the compositions of products produced from the atmospheric tower
distillation for each case. When compared with other crudes in the area or other areas stated, Brent
Blend Crude, gives a high percentage of Naphtha Production 38% which significantly affects the
Gasoline produced from the petroleum plants where increasing the Naphtha Production increases the
Gasoline Obtained.

- An important advantage of our plant unit design is the use of Methaforming for the processing of
naphtha, many advantages have been discussed in chapter 3 for such process including the economic
advantages. Numerically, the feed of crude oil was around 100,000 bpd of which 38% where
converted to Naphtha, 38,000 bpd which was used as a feed component for the Methaforming Process
which costs less than the usual catalytic process. When compared to figure 3.18, for a 38K bpd, it gives
a yield profit of 239.4 million dollars per year compared to 180.5 if using the catalytic reformer.

181
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