Al-Neelain University

Graduate College

HYSYS APPLICATION FOR THE PRODUCTION OFGASOLINE FROM NAPHTHA

A Thesis Submitted in Partial Fulfillment of the Requirementsfor the degree of M.Sc. in Chemical Engineering

By:

Eng: ELFadil ELhag Madani Fadl ELmula Awad

B.Sc (Hon. in Chemical Engineering) Al-Neelain University

Supervisor By:

Prof. Babiker Krama Abdalla Mohammed

May 2017

I

Al-Neelain University

Graduate College

HYSYS APPLICATION FOR THE PRODUCTION OFGASOLINE FROM NAPHTHA

A Thesis Submitted in Partial Fulfillment of the Requirementsfor the degree of M.Sc. in Chemical Engineering

By:

Eng: ELFadil ELhag Madani Fadl ELmula Awad

B.Sc (Hon. in Chemical Engineering) Al-Neelain University

Supervisor By:

Prof. Babiker Krama Abdalla Mohammed

May 2017

II

DedicationTo my dearest mother…………

To my father …………… ………

To all my family …………………

To all my teachers………………

To all my friends…………………

I dedicate this humble work

I

Acknowledgements

First of all I thank almighty ALLAH for giving me the courage

and the determination, as well as guidance in conducting this

research study, despite all difficulties. I would like to

acknowledge with thanks and gratitude my supervisor

Prof.Babiker Kramah Abdullah Mohammed for his help and

patience. I would like to thank Eng. Muhammad ELsir for

helping me in the project. At last I would like to thank everyone

who contributed in this research. Thanks are due to my family

and all my friends for their support, patience and

encouragement.

II

Abstract

Catalytic reforming is a major conversion process in petroleum refinery and

petrochemical industries. The reforming process is a catalytic process which converts

low octane naphtha as into higher octane reformate products for gasoline blending and

aromatic rich reformate for aromatic production. Basically, the process re-arranges or

re-s structures the hydrocarbon molecules in the naphtha feedstock’s as well as

breaking some of the molecules into smaller molecules.

The objectives of this project was applied HYSYS programs to production of gasoline

from naphtha by used all equipments units in this industry and design catalytic

reforming unit to produce large amount of high octane gasoline from low octane

naphtha by HYSYS.

The design started by choosing suitable properties of streams in put to unit and

component of feed in put different physical properties and chemical properties for

material streams. The results of production after the HYSYS application to production

of gasoline from naphtha by catalytic reforming unit applied as shown as in table:

Component Output production (kg/hr)Gasoline 171500

LPG 1714Off gasses 506.7

المستخلـص

III

تعتبرعملية اإلصالح الحفزي عملية تحويلة رئيسية في مصفاة البترول والصناعات البتروكيماوي<ة. عملي<ة اإلص<الح

الحفزي هي عملية تحفيزيه يتم فيها تحويل النفتا منخفضة الرقم االوكتانى< كما في منتجات إصالح ذات رقم أوكت<<انى

أعلى لمزج البنزين واالص<الحات< الغني<ة العطري<<ة إلنت<<اج العطري<<ة. في األس<<اس هي، عملي<ة إع<ادة ت<<رتيب أو إع<ادة

تركيب هياكل الجزيئات الهيدروكربونية في المواد الخام النافثا وكذلك كسر بعض الجزيئات في جزيئات أصغر.

واله<<دف من ه<<ذا المش<<روع< هوتط<<بيق< برن<<امج الهايس<<س النت<<اج الج<<ازولين من النافث<<ا باس<<تخدام مجموع<<ة االجه<<زه

المستخدمة فى كل وحدة و تصميم< وحدة إصالح الحفاز إلنتاج كمية كبيرة من البنزين ذو رقم أوكتان ع<<الي من النفت<<ا

ذو أوكتان منخفض باستخدام< برنامج الهايسس.

ب<<دأ التص<<ميم< باختي<<ار خص<<ائص مناس<<بة لتي<<ارات المكون<<ات الداخل<<ه والخارج<<ه م<<ع اختالف الخص<<ائص الفيزيائي<<ة

والكيميائيه لكل مكون من التيارات وكان ملخص نتائج المنتجات بعد تطبيق<<ات الهايس<<س النت<<اج الج<<ازولين من النافث<<ا

مبينه في الجدول ادناه:

المكون (kg/hr) االنتاجGasoline 171500

LPG 1714Off gasses 506.7

Table of Content

IV

Dedication I

Acknowledgment II

Abstract III

Arabic Abstract IV

Table of Content V

List of Tables V I

List of Figures VII

NomenclatureVIII

Chapter One: Introduction

1.1 General introduction 15

2.1 Objective of the Study: 15

1.3 Introduction. 16

1.4 The most important uses of petroleum 16

1.3 Petroleum Chemistry 18

1.4 Petroleum Composition 20

V

1.5 The Classification of Petroleum 21

1.6 Fuel from Crude 22

1.7 Refining processes 23

1.7.1 Separation Processes 23

1.7.2 Conversion Processes 24

1.7.3 Thermal Cracking Processes 24

1.7.2.2 Catalytic Processes 24

1.7.3 Treatment Processes 24

1.8 Major Refinery Products 25

1.9 Naphtha 26

1.9.1The major source of petroleum naphtha in a petroleum refinery 27

1.9.2 Uses 27

1.9.3 Manufacturing 281.10 Gasoline 29

1.10.1 Properties 29

VI

V

1.10.1.1 Research Octane Number 29

1.10.1.2 Reid Vapor Pressure 29

1.10.1.3 Distillation 30

1.10.1.4Volatility 30

1.10.1.5 Stability 31

1.11 gasoline blend component 32

1.11.1 FCCU Cat Naphtha 32

1.11.2 Catalytic Reformate 32

1.12 Production of Gasoline 33

1.12.1 UOP Butamer Isomerization Process 34

1.12.2 UOP Penex Process 34

1.14 Catalytic Reforming 35

Chapter two : Introduction about Process simulation and hysys programapplication

2.1 process simulation 36

VII

2.1.1 introduction 36

2.1.2 modeling 36

2.1.3 classification of models 37

2.1.4 elements of the models 37

2.1.5 structure of the simulation model 38

2.1.6 process synthesis/production problem 39

2.1.7 modeling objects in chemical engineering 39

2.1.8 software for process simulation39

2.1.9 software process simulation(flow sheeting programs) 40

2.1.10 chemical plant system 40

2.2 HYSYS application 42

2.2.1 introduction 42

2.2.1.1 history 42

2.2.2 software and hardware 43

VIII

2.2.3 a little about hysys 44

Chapter three: Materials and Method

3.1 catalytic reforming 48

3.1.1 reformer feed characterization 48

3.2 Detailed Processes Description49

3.3 Process Flow Diagram (PFD) 56

Chapter four: Process simulation and Results or Discussion

4.1 Feed properties59

4.2 Reactor configuration:59

4.3 Continuous catalytic reforming (CCR) process step runs59

4.4 step of all unit after CCR running:68

4.5 result82

Chapter Five :Conclusions and Recommendations

5.1 conclusions87

5.2 recommendations88

5.3 references89

IX

5.4 Appendix 93

5.4.1 Appendix A 93

5.42 Appendix B 94

List of Tables

Table (1.1): Gasoline Specifications 33

Table(3.1) RON) of the products of naphthenes dehydrogenation reaction 53

Table (3.2): RON of the Aromatics produced in the Second Reactor55

Table (4.1): feed properties 62

Table (4.2): reactor configuration 62

Table(4.2):the result of hyysy program 85

X

List of Figures

Fig (2.1): aspen hysys picture 46

Figure (3:1): PFD of the Reforming Section of CCR Unit57

Fig (4.1): select cat reforming60

Fig (4.2): Enter Simulation Environment60

Fig (4.3) CCR configuration61

Fig (4.4) type of reformer and number of reaction61

Fig (4.5): reactor dimensions and catalyst loadings.62

Fig (4.6): calibration factors.62

Fig (4.7): reformer sub model.63

Fig (4.8): reformer reactor section (the properties feed type)63

Fig (4.9): reformer reactor section (feed section)64

Fig (4.10) reformer reactor section (operation and feed tabs65

XI

Fig (4.11): reformer reactor section (reactors temperatures specification)65

Fig (4.12): reformer reactor section (catalyst circulates rate)66

Fig (4.13): reformer reactor section (heater temperatures)66

Fig (4.13): reformer reactor section (solver page)67

Fig (4.14): run and result67

Figure (4.15a): mixer design page68

Fig(4.15b):mixer worksheet data68

Fig (4.16a): heat exchanger worksheet data69

Fig (4.16b): heat exchanger design69

Fig (4.17a): the cooler worksheet data70

Fig (4.17b): the cooler design70

Fig (4.18a): separator worksheet71

Fig (4.18b) the separator designs71

Fig (4.19): tee worksheet72

XII

Fig (4.20): separator (V-101) worksheet72

Fig (4.21a): compressor (K-100) design73

Fig (4.21b): compressor (K-100) worksheet73

Fig (4.22): cooler E-103 worksheet74

Fig (4.23): separator V-102 worksheet74

Fig (4.24): compressor k-101 worksheet75

Fig (4.25): the mixer MIX-101 worksheet75

Fig (4.26): pump P-101 worksheet76

Fig (4.27): the mixer MX-102 worksheet76

Fig (4.28): the cooler E -102 worksheet77

Fig (4.29): separator V-103 worksheet77

Fig (4.30): heat exchanger E-105 worksheet78

Fig (4.31): the column design connections79

Fig (4.32): the column worksheet connection79

XIII

Fig (4.33): the column monitor80

Fig (4.34): the cooler E-106 worksheet data81

Fig(4.35):final gasoline stream81

Fig (A.1): flow sheet from Google to CCR unit production of gasoline from naphtha 87

Fig (A.2): refinery data component list or impurities 88

Fig (A.3): UOP CCR UNIT 89

Fig (B.1) Refinery of Khartoum overview unit CCR 90

Fig (B.2): reaction section refinery 91

Fig(B.4): stripper section 92

Fig (B.5): Separation unit 93

Fig (B.6) Recontacting system 94

XIV

Nomenclature

A Aromatic componentASTMD American stander test method for distillation

°C Celsius degreeC Carbons atoms

C 5+¿¿

ReformateCCR Continues catalytic reformingC2CL4 Chloriding agent

EP End pointsFBP Final boiling point

FCCU Fluidized continues catalytic unitHYSYS Hyprotech simulation system

H 2 Hydrogen

XV

HTN Hydrotreated naphthaIBP Initial boiling pointK Watson characterization factor

LCN Light catalytic naphthaLPG Liquid petroleum gasLSR Light straight runMpa Mega PascalMON Motor octane numberMSDS material safety data sheet

N NapthenesP Paraffins

RON Research octane numberRVP Reid vapor pressure

R Regress modelS Simple model

UOP Unit of productionVOL% Volume percentageVGO Vacuum gas oil

VM&P Varnish maker & painters

XVI

Chapter One

Introduction

XVII

XVIII

Chapter One

Introduction

1.1General Introduction:

When most people think of petroleum they think of gasoline and diesel fuel. They

may even conjure up images of jet fuel, but most will rarely consider the other

unexpected places that petroleum byproducts show up in modern life. Because

crude oil contains a vast number of different hydrocarbons, various refined

products have found their way into everything from plastics to pharmaceuticals.

The industry that uses petroleum to produce other chemicals is referred to as the

petrochemical industry. It is estimated that industrialized nations currently

consume petrochemical products at a rate of three and a half gallons of oil per day.

That means that, excluding fuel oil, modern life results in each citizen of an

industrial nation using over 1,200 gallons of oil per year. [14]

1.2 Objective of the Study:

The objectives of the project module used application hysys programmer to

production of gasoline from naphtha and design the catalytic reforming to produce

gasoline from naphtha or development the unit by hysys simulation to achieve hi

quality production from gasoline.

The Process modeling to build, develop and improve models for the calculation of

properties. And Process simulation to make a production process of a material into

a process flow diagram and study case.

1

Literature Review

1.3 Introduction

The first automotive combustion engines, so-called Otto engines, were developed

in the last quarter of the 19th century in Germany. The fuel was a relatively

volatile hydrocarbon obtained from coal gas. With a boiling point near 85 °C

(octanes boil about 40 °C higher), it was well suited for early carburetors

(evaporators). The development of a "spray nozzle" carburetor enabled the use of

less volatile fuels. Further improvements in engine efficiency were attempted at

higher compression ratios, but early attempts were blocked by knocking

(premature explosion of fuel). In the 1920s, antiknock compounds were introduced

by Thomas Midgley Jr. and Boyd, specifically tetra ethyl lead (TEL). This

innovation started a cycle of improvements in fuel efficiency that coincided with

the large-scale development of oil refining to provide more products in the boiling

range of gasoline. In the 1950s oil refineries started to focus on high octane fuels,

and then detergents were added to gasoline to clean the jets in carburetors. The

1970s witnessed greater attention to the environmental consequences of burning

gasoline. These considerations led to the phasing out of TEL and its replacement

by other antiknock compounds. Subsequently, low-sulfur gasoline was introduced,

in part to preserve the catalysts in modern exhaust systems.

"Gasoline" is the term that is used in North America to refer to the most popular

automobile fuel. The Oxford English Dictionary dates the first use to 1863, when it

was spelled "gasolene." It was never a trademark, although it may have been

derived from older trademarks such as "Cazeline" and "Gazeline".Variant spellings

of "gasoline" had been used to refer to raw petroleum since the 16th century. [1] [2]

2

1.4 The most important uses of petroleum

In the production of ammonia to be used as the nitrogen source in

agricultural fertilizers.

Methane from natural gas.

Agriculture also depends on the use of pesticides to ensure consistent,

healthy crop yields. Pesticides are almost all produced from oil. In essence,

from running farm machinery to fertilizing plants, agriculture is one of the

largest users of petroleum based products.

Plastic is a staple of modern life.

Tires are made of rubber.

Pharmaceuticals: Mineral oil and petrolatum are petroleum byproducts

used in many creams and topical pharmaceuticals. Tar, for psoriasis and

dandruff, is also produced from petroleum. Most pharmaceuticals are

complex organic molecules, which have their basis in smaller, simpler

organic molecules. Most of these precursors are petroleum byproducts.

Dyes, Detergents, and Other: Petroleum distillates such as benzene, toluene,

xylene, and others provide the raw material for products that include dyes,

synthetic detergents, and fabrics. Benzene and toluene are the starting materials

used to make polyurethanes, which are used in surfactants, oils, and even to

varnish wood. Even sulfuric acid has its origins in the sulfur that is removed from

petroleum. Petroleum refining has evolved continuously in response to changing

consumer demand for better and different products. The original requirement was

to produce kerosene as a cheaper and better source of light than whale oil. The

development of the internal combustion engine led to the production of gasoline

and diesel fuels. The evolution of the airplane created a need first for high-octane

3

aviation gasoline and then for jet fuel, a sophisticated form of the original product,

kerosene. Present day refineries produce a variety of products including many

required as feedstocks for the petrochemical industry. [3] [4]

1.5 Petroleum Chemistry

Petroleum Chemistry is made of a mixture of different hydrocarbons. The most

prolific hydrocarbons found in the chemistry of petroleum are alkanes, these are

also sometimes knows as branched or linear hydrocarbons.

A significant percentage of the remaining chemical compound is the made up of

aromatic hydrocarbons and cycloalkanes. Additionally petroleum chemistry

contains several more complex hydrocarbons such as asphaltenes. Each

geographical location and hence oil field will produce a raw petroleum with a

different combination of molecules depending upon the overall percentage of each

hydrocarbon it contains, this directly affects the coloration and viscosity of the

petroleum chemistry.

The primary form of hydrocarbons in the chemistry of petroleum is the alkanes,

which are also often named Paraffins. These are termed saturated hydrocarbons

and the exhibit either branched or straight molecule chains.

The Paraffins are very pure hydrocarbons and contain only hydrogen and carbon; it

is the alkanes which give petroleum chemistry its combustible nature. Depending

upon the type of alkanes present in the raw petroleum chemistry it will be suitable

for different applications. For fuel purposes only the alkanes from the following

groups will be used: Pentane and Octane will be refined into gasoline, hexadecane

and nonane will be refined into kerosene or diesel or used as a component in the

4

production of jet fuel, hexadecane will be refined into fuel oil or heating oil. When

it comes to the chemistry of petroleum which does not contain a significant

quantity of the kinds of Paraffins required to produce a combustible fuel then

things become simpler, as many The exception to this are the petroleum molecules

which have less than five carbon atoms, these are a form of natural petroleum gas

and will either be burned away or harvested and sold under pressure as LPG

(Liquid Petroleum Gas).The cycloalkanes, which are also often referred to as the

naphthenes are classed as a saturated form of hydrocarbon. By saturated we mean

the molecule contains either one or several carbon rings with atoms of hydrogen

attached to them. These hydrocarbons display almost identical properties to

paraffins but have a much higher point of combustion. [15]

Lastly, the aromatic hydrocarbons are another form of unsaturated hydrocarbon.

The specific difference between the other hydrocarbons in the petroleum molecule

is that the aromatic hydrocarbons will contain benzene rings, with atoms of

hydrogen attached to them. Aromatic hydrocarbons tend to produce far more

emissions when combusted, many will have a sweet, sickly smell to them, hence

the name aromatic hydrocarbons.

The quantity and percentages of the specific types of hydrocarbons in

raw petroleum chemistry can be determined by testing in a laboratory. The process

involves extracting the, molecules using some form of solvent and then separating

them using a gas chromatograph. Finally an instrument such as a mass

spectrometer will be used to examine the separate molecules in the chemical

compound of the sample. [5] [7]

5

1.6 Petroleum Composition:

Most people presume petroleum to be similar to gasoline or petrol, simply a less

pure form, which needs to be refined. In actuality the chemical composition of

petroleum in its raw state can vary extremely. This variation is the reason why

petroleum composition differs so much in color and viscosity between crude oil

fields and geographical areas.

Petroleum, or crude oil as it is now usually referred too when raw, contains several

chemical compounds, the most prolific being the hydrocarbons themselves which

give the petroleum composition its combustible nature. Although the composition

of petroleum will contain many trace elements the key compounds are carbon

(93% – 97%), hydrogen (10% - 14%), nitrogen (0.1% - 2%), oxygen (01.% - 1.5%)

and sulphur (0.5% - 6%) with a few trace metals making up a very small

percentage of the petroleum composition. The actual overall properties of each

different petroleum source are defined by the percentage of the four main

hydrocarbons found within petroleum as part of the petroleum composition. The

percentages for these hydrocarbons can vary greatly, giving the crude oil a quite

distinct compound personality depending upon geographic region. These

hydrocarbons are typically present in petroleum at the following percentages:

paraffins (15% - 60%), napthenes (30% - 60%), aromatics (3% to 30%), with

asphaltics making up the remainder. The composition of petroleum is defined as

laid out above, and it is this composition which gives the crude oil its properties.

Raw petroleum is usually dark brown or almost black although some fields deliver

a greenish or sometimes yellow petroleum. Depending upon the field and the way

the petroleum composition was formed the crude oil will also differ in viscosity. A

lighter, less dense raw petroleum composition with a compound that contains

6

higher percentages of hydrocarbons is much more profitable as a fuel source.

Whereas other, denser petroleum composition with a less flammable level of

hydrocarbons and sulphur are expensive to refine into a fuel and are therefore more

suitable for plastics manufacturing and other uses. Unfortunately the worlds

reserves of light petroleum (light crude oil) are severely depleted and refineries are

forced to refine and process more and more heavy crude oil and bitumen. [7]

1.7 The Classification of Petroleum:

In general,if the crude oil contains high levels of sulphur the petroleum

classification is termed ‘sour, if it has relatively low levels of sulphur the

petroleum classification is termed ‘sweet'. If the raw petroleum is of a high density

then the petroleum classification is termed ‘heavy' and if it is of a low density the

petroleum classification is termed 'light'. Density of oil is determined by the length

of the hydrocarbons it contains. If it contains a great deal of long-chain

hydrocarbons, the petroleum will be denser. If it contains a greater proportion of

short-chain hydrocarbons it will be less dense. Besides chain length, the ratio of

carbon to hydrogen also helps to determine the density of a particular hydrocarbon.

The greater the amount of hydrogen in relation to carbon, the lighter the

hydrocarbon will be. Less dense oil will float on top of denser oil and is generally

easier to pump.

The hydrocarbons in crude oil can generally be divided into four categories:

Paraffins: These can make up 15 to 60% of crude and have a carbon to

hydrogen ratio of 1:2, which means they contain twice the amount of

hydrogen as they do carbon. These are generally straight or branched chains,

but never cyclic (circular) compounds. Paraffins are the desired content in

7

crude and what are used to make fuels. The shorter the paraffins are, the

lighter the crude is.

Napthenes: These can make up 30 to 60% of crude and have a carbon to

hydrogen ratio of 1:2. These are cyclic compounds and can be thought of as

cycloparaffins. They are higher in density than equivalent paraffins and are

more viscous.

Aromatics: These can constitute anywhere from 3 to 30% of crude. They

are undesirable because burning those results in soot. They have a much less

hydrogen in comparison to carbon than is found in paraffins. They are also

more viscous.

Asphaltics: These average about 6% in most crude. They have a carbon to

hydrogen ratio of approximately 1:1, making them very dense. They are

generally undesirable in crude, but their 'stickiness' makes them excellent for

use in road construction. [7]

1.8 Fuel from Crude:

The primary uses of crude oil to this point have been in the production of fuel. A

single barrel of crude oil can produces the following components, which are listed

by percent of the barrel they constitute.

42% Gasoline

22% Diesel

9% Jet Fuel

5% Fuel Oil

4% Liquefied Petroleum Gases

18% Other products[5]

8

1.9 Refining processes:

Petroleum refining refers to the process of converting crude oil into useful

products. Crude oil is composed of hundreds of different hydrocarbon molecules,

which are separated through the process of refining. The process is divided into

three basic steps: separation, conversion, and treatment.

1.9.1 Separation Processes:

After desalting, crude oil introduced to an atmospheric distillation unit operating at

pressures slightly above atmospheric and at temperatures ranging from 340-370°C.

The atmospheric column normally contains 30 to 50 trays. To extract more

distillates from the atmospheric residue, the bottom from the atmospheric

distillation unit is sent to vacuum distillation operating at 50 mmHg. The

atmospheric residues are distilled under vacuum because the boiling temperature

decreases with a lowering of pressure. Inside the columns, the liquids and vapors

separate into components or fractions according to weight and boiling point. The

lightest fractions, including gasoline and liquid petroleum gas (LPG), vaporize and

rise to the top of the tower, where they condense back to liquids. Medium weight

liquid including kerosene and diesel oil distillates, stay in middle. Heavier liquids,

called gas oils, separate lower down, while the heaviest fractions with the highest

boiling settle at the bottom.

1.9.2 Conversion Processes:

Thermal Cracking Processes:

The thermal cracking process was developed, which subjected heavy fuels to both

pressure and intense heat, physically breaking the large molecules into smaller

9

ones to produce additional gasoline and distillate fuels. Visbreaking is another

form of thermal cracking to produce more desirable and valuable products.

Catalytic Processes:

Higher-Compression gasoline engines require higher-octane gasoline with better

ant knocking characteristics. Alkylation, another catalytic process developed in the

early 1940s, produced more high-octane aviation gasoline and petrochemical

feedstock’s for explosives and synthetic rubber. Subsequently, catalytic

isomerization was developed to covert hydrocarbons to produce increased

quantities of Alkylation feedstock’s. Improved catalysts and process methods such

as hydrocracking and reforming were developed throughout the 1960s to increase

gasoline yields and improve antiknock characteristic. These catalytic processes

also produced hydrocarbon molecules with a double bond and formed the basis of

the modern petrochemical industry.

1.9.3Treatment Processes:

Throughout the history of refining, various treatment methods have been used to

remove non hydrocarbons, impurities, and other constituents that adversely affect

the properties of finished products or reduce the efficiency of the conversion

processes. Treating can involve chemical reaction and/or physical separation.

Typical examples of treating are chemical sweetening, acid treating, clay

contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent

dewaxing. Sweetening compounds and acids desulfurize crude oil before

processing and treat products during and after processing.

10

1.10 Major Refinery Products:

Kerosene: Kerosene, also known as lamp oil, is a combustible hydrocarbon

liquid widely used as a fuel in industry and households. Kerosene is widely

used to power jet engines of aircraft (jet fuel) and some rocket engines, and

is also commonly used as a cooking and lighting fuel and for fire toys.

Liquefied petroleum (LPG):

LPG, which consists principally of propane and butane, is produced for use

as fuel and is an intermediate material in the manufacture of petrochemicals.

The important specifications for proper performance include vapor pressure

and control of contaminants.

Gasoline: The most important refinery product is motor gasoline, a blend of

hydrocarbons with boiling ranges from ambient temperatures to about 400℉.

Distillate Fuels: Distillate fuels and domestic heating oils have boiling

ranges of about 400-700 .The desirable qualities required for distillate fuels

include controlled flash and pour points, clean burning, no deposit formation

in storage tanks, and a proper diesel fuel cetane rating for good starting and

combustion.

Residual Fuels: Many marine vessels, power plants, commercial buildings

and industrial facilities use residual fuels or combinations of residual and

distillate fuels for heating and processing. The two most critical

specifications of residual fuels are viscosity and low sulfur content for

environmental control.

Coke and Asphalt: Coke is almost pure carbon with a variety of uses from

electrodes to charcoals briquettes. Asphalt, used for roads and roofing

materials, must be inert to most chemicals and weather conditions.

11

Solvents: A variety of products, whose boiling points and hydrocarbon

composition are closely controlled, are produced for use as solvents. These

include benzene, toluene, and xylene.

Petrochemicals: Many products derived from crude oil refining such as

ethylene, propylene, butylene, and isobutylene are primarily intended for use

as petrochemical feed stocks in the production of plastics, synthetic fibers,

synthetic rubbers, and other products.

Lubricants: Special refining processes produce lubricating oil base stocks.

Additives such as demulsifiers, antioxidants, and viscosity improvers are

blended into the base stocks to provide the characteristics required for motor

oils, industrial greases, lubricants, and cutting oils. [5] [6]

1.11 Naphtha:

Petroleum naphtha is an intermediate hydrocarbon liquid stream derived from the

refining of crude oil. It is most usually desulfurized and then catalytically

reformed, which re-arranges or re-structures the hydrocarbon molecules in the

naphtha as well as breaking some of the molecules into smaller molecules to

produce a high-octane component of gasoline (or petrol).Naphtha is a general term

as each refinery produces its own naphtha as with their own unique initial and final

boiling points and other physical and compositional characteristics.Naphthas may

also be produced from other material such as coal tar, shale deposits, tar sands and

the destructive distillation of wood. [16]

1.11.1The major source of petroleum naphtha in a petroleum refinery:

The first unit process in a petroleum refinery is the crude oil distillation unit. The

overhead liquid distillate from that unit is called virgin or straight-run naphtha and

that distillate is the largest source of naphtha in most petroleum refineries. The

naphtha is a mixture of many different hydrocarbon compounds. It has an initial

12

boiling point (IBP) of about 35 °C and a final boiling point (FBP) of about 200 °C,

and it contains paraffins, naphthenes (cyclic paraffins) and aromatic hydrocarbons

ranging from those containing 4 carbon atoms to those containing about 10 or 11

carbon atoms.

The virgin naphtha is often further distilled into two streams:

a virgin light naphtha with an IBP of about 30 °C and a FBP of about 145 °C

containing most (but not all) of the hydrocarbons with 6 or less carbon atoms

A virgin heavy naphtha containing most (but not all) of the hydrocarbons

with more than 6 carbon atoms. The heavy naphtha has an IBP of about

140 °C and a FBP of about 205 °C.

1.11.2 Uses:

Some petroleum refineries also produce small amounts of specialty naphtha as for

use as solvents, cleaning fluids, paint and varnish diluents, asphalt diluents, rubber

industry solvents, dry-cleaning, cigarette lighters, and portable camping stove and

lantern fuels. That specialty naphtha’s are subjected to various purification

processes.

Sometimes the specialty naphtha’s are called petroleum ether, petroleum spirits,

mineral spirits, paraffin, benzene, hexanes, ligroin, white oil or white gas, painters

naphtha, refined solvent naphtha and Varnish makers' & painters' naphtha (VM&P)

. The best way to determine the boiling range and other compositional

characteristics of any of the specialty naphtha is to read the Material Safety Data

Sheet (MSDS) for the specific naphtha of interest.

1.11.3 Manufacturing:

13

In general, naphtha may be prepared by any one of several methods, which include

fractionation of straight -run, cracked, and reforming distillates, or even

fractionation of crude petroleum; solvent extraction; hydrogenation of cracked

distillates; polymerization of unsaturated compounds (olefins); and alkylation

processes. The naphtha may be a combination of product streams from more than

one of these processes. The more common method of naphtha preparation is

distillation. Depending on the design of the distillation unit, either one or two

naphtha steams may be produced: a single naphtha with an end point of about 205

C (400 F) and similar to straight –run gasoline or this same fraction divided into

light naphtha and heavy naphtha. On a much larger scale, petroleum naphtha is

also used in the petrochemicals industry as feedstock to steam reformers and steam

crackers for the production of hydrogen (which may be and is converted into

ammonia for fertilizers), ethylene and other olefins. Natural gas is also used as

feedstock to steam reformers and steam crackers. [5] [6]

1.12 Gasoline:

Gasoline, also called gas (United States and Canada), or petrol (Britain) or benzene

(Europe) is a mixture of volatile, flammable liquid hydrocarbons derived from

petroleum and used as fuel for internal-combustion engines. It is also used as a

solvent for oils and fats. Gasoline became the preferred automobile fuel because of

its high energy of combustion and capacity to mix readily with air in a carburetor.

Gasoline is a mixture of hydrocarbons that usually boil below 180 C (355 F) or, at

most, below 200 C (390 F). The hydrocarbon constituents in this boiling range are

those that have 4 to 12 carbon atoms in their molecular structure and fall into three

general types: paraffins (including the cyclo paraffins and branched materials),

naphthenes, and aromatics. Gasoline is still in great demand as a major product

14

from petroleum. Several components are blended to produce gasoline of high

antiknock quality, ease of starting, low tendency to vapor lock, and low engine

deposits. The components used in blending motor gasoline include light straight-

run (LSR) gasoline or isomerate, catalytic reformate, catalytically cracked

gasoline, hydrocracked gasoline, polymer gasoline, alkylate and n-butane.

1.12.1Properties:

1.12.1.1 Research Octane Number:

The research octane number (RON) is defined as the percentage by volume of iso-

octane in a mixture of iso-octane and n-heptane that knocks with some intensity as

the fuel is being tested.

The octane number is a relative measure of knocking, or the

tendency to self-ignition of a fuel in a spark-ignited internal

combustion engine.

1.12.1.2 Reid Vapor Pressure:

A gasoline engine needs a fuel that is sufficiently volatile to allow easy formation

of the fuel vapor-air mixture required for combustion. The Reid Vapor Pressure

(RVP) is vapor pressure of gasoline at 100°F. RVP and boiling range determine the

ease of starting, the engine warm up, and the vapor lock temperature. The RVP of

various gasoline grades varies between 35 and 84 kPa. RVP specifications of

gasoline are being reduced to the minimum level possible to reduce hydrocarbon

emissions from the storage and handling of gasoline.

15

1.12.1.3 Distillation:

Gasoline’s tendency to vaporize is also characterized by determining a series of

temperatures at which various percentages of the fuel have evaporated as described

in ASTM D 86. The temperatures at which 10, 50, and 90 percent evaporation

occur define the volatility of gasoline. The 10 percent evaporated temperature is

directly affected by the seasonal blending of gasoline. This temperature must be

low enough to provide easy cold starting but also high enough to minimize vapor

lock and hot weather derivability problems. The 50 percent evaporated

temperature must be low enough to provide good warm up and cool weather

drivability without being too low to cause hot weather drivability and vapor lock

problems. The 90 percent and final boiling point (FBP) must be low enough to

minimize crankcase and combustion chamber deposits, spark plug fouling, and

dilution of engine oil. The higher boiling fractions of gasoline have a significant

effect on the emission levels of undesirable levels of hydrocarbons and aldehydes

from automobile exhaust.

1.12.1.4 Volatility:

His volatility of gasoline is determined by the Reid vapor pressure (RVP) test. The

reid vapour pressure (RVP) of a product is the vapour pressure determined in a

volume of air four times the liquid volume at 37.8 (100 ).

1.12.1.5 Stability:

Olefinic compounds can be oxidized and polymerized to form gums. Olefins

oxidation which leads to gum formation occurs in gasoline as a result of improper

storage. The presence of gum in gasoline can cause deposits in the engine; these

16

deposits increased greatly as the gum content in gasoline is increased from zero up

to 7 or 10 mg. Engine deposits affect fuel efficiency and emissions. [5] [6]

Table (1.1): Gasoline Specifications:

Characteristics Specifications

Definition Mixture of hydrocarbons of mineral or

synthetic origin and, possibly,

oxygenates

Aspect Clear and bright

Color Green (2 mg/l of blue + 2 mg/l of

yellow)

Density 725 kg/m³ ≤ density ≤ 780 kg/m³ at 15

Sulfur Content ≤ 0.10 weigh %

Copper Strip Corrosion 3 h at 50

Existent gum content after washing ≤ 5 mg/100 ml

Research Octane Number (RON) Motor

Octane Number (MON)

RON ≥ 95

MON ≥ 85

Lead Content ≤ 0.013 g/l

Benzene Content ≤ 5 vol %

Stability to Oxidation ≥ 360 min

Phosphorus Content No phosphorous compound should be

present

Water Tolerance No separated water

17

1.13 Gasoline blends components:

1.13.1 FCCU Cat Naphtha:

Feed to the FCCU unit is vacuum gas oil from the vacuum distillation of reduced

crude. The vacuum gas oil (VGO) may be desulfurized to reduce sulfur in FCCU

products. FCCU is the catalytic cracking of VGO to produce gases, light cat

naphtha (LCN), medium cat naphtha, light cycle oil, heavy cycle oils, and decant

oil. Approximately 43 vol % of VGO feed is converted to LCN, and another 16 vol

% is converted to heavy cat naphtha. LCN is an excellent blend stock for gasoline

blending with a RON of 93 and a MON of 81. Medium cat naphtha (MCN) also

has good RON and MON values but consists of higher boiling components with an

ASTM distillation range of 265 to 365°F compared with a distillation range of 105

to 250°F for LCN. [8] [5]

1.13.2 Catalytic Reformate:

Catalytic reforming is one of the key processes for increasing the octane number of

straight run naphtha. Feed to the unit is straight run heavy naphtha cut from 185 to

340°F. Feed is first hydrotreated to remove sulfur, nitrogen, and other catalyst

poisons. Reformate has a very high aromatic content with high RON and MON.

The octane number of reformate can be increased by increasing the severity of the

reforming reactions. Most reforming units for gasoline manufacture are designed

for (95 to 100) reformate octane. Vol % yield of C5+ reformate is typically 80 vol

%. Yield decreases with the increase in octane number. Because the reformer feed

18

is not limiting, reformer capacity can be chosen independently according to

gasoline requirements.

1.14 Production of Gasoline:

Catalytic reforming of heavy naphtha and isomerization of light naphtha constitute

a very important source of products having high octane numbers which are key

components in the production of gasoline. Environmental regulations limit on the

benzene content in gasoline. If benzene is present in the final gasoline it produces

carcinogenic material on combustion. Elimination of benzene forming

hydrocarbons, such as, hexane will prevent the formation of benzene, and this can

be achieved by increasing the initial point of heavy naphtha. These light paraffinic

hydrocarbons can be used in an isomerization unit to produce high octane number

isomers. The hydrotreated naphtha (HTN) is fractionated into heavy naphtha

which is used as a feed to the reforming unit and light naphtha which used as a

feed to the isomerization unit. There are two reasons for this fractionation: the first

is that light hydrocarbons tend to hydrocrack in the reformer. The second is that

hydrocarbons tend to form benzene in the reformer. Gasoline specifications

require a very low value of benzene due to its carcinogenic effect.

1.15 Isomerization:

Isomerization is the process in which light straight chain paraffins of low RON

(C6, C5 and C4) are transformed with proper catalyst into branched chains with the

same carbon number and high octane numbers. There are two types of

isomerization catalysts: the standard Pt/chlorinated alumina with high chlorine

19

content, which is considered quite active, and the Pt/zeolite catalyst. There are two

types of isomerization processes.

1.15.1 UOP Butamer Isomerization Process :

The butane feed is separated into isobutene and n-butane in a distillation column.

The n-butane stream is withdrawn from the bottom of the column. It is mixed with

a hydrogen-rich recycle gas and preheated by heat exchanger with reactor effluent.

The mixed feed is heated to the required reaction temperature in a fired heater and

then passed to the reactor containing a platinum catalyst. The n-butane is

isomerized to isobutane. The hydrogen-rich gas is separated from the reaction

product in the high-pressure separator and recycled back in the process. A small

quantity of make-up hydrogen gas is mixed with the recycle gas to maintain the

required percentage of hydrogen in it. The dissolved gas and breakdown products

are removed in a stabilization column. The bottom product from the stabilizer

containing n-butane and isobutane is fed to the distillation column for the

separation into isobutane and n-butane.

1.15.2 UOP Penex Process :

Penex process is a single pass isomerization using a high-activity chlorided

alumina catalyst. Recycle options are available by adding product iso/normal

paraffin separation consisting of molecular sieves (Molex process) or fractionation

(deisohexanizer).Feed is dried over molecular sieves, mixed with dried make-up

hydrogen; steam heated and passed over the fixed-bed catalyst. The reactor

20

effluent passes directly to the stabilizer after heat exchanger. The stabilizer

bottoms are sent to gasoline blending in a single phase operation or to separation

(molecular sieve or fractionation) in a recycle operation.

1.16 Catalytic Reforming:

Catalytic reforming is a chemical process used to transform the low octane

naphtha into more valuable high-octane gasoline components without changing the

boiling point range. This process involves rearranging or reconstructing of

hydrocarbons molecules in the low octane naphtha to convert them into aromatics

or iso-paraffins which have high octane numbers. The main process product is

called reformate and it contains hydrocarbons molecules with more complex

shapes having higher octane values than the hydrocarbons in the naphtha

feedstock. The process also produces very significant amounts of by-product

hydrogen-rich gas for use in hydrotreating or other processes involved in the

petroleum refinery. Other by- products are small amounts of methane, ethane,

propane, and butanes. [8] [9]

21

Chapter Two

Process simulation

22

Chapter two

2.1 Process simulation

2.1.1 Introduction:

2.1.1.1 Main principle:

Process simulation is used for the design, development, analysis, and optimization

of technical processes such as: chemical plants, chemical processes, environmental

systems, power stations, complex manufacturing operations, biological processes,

and similar technical functions. Process simulation is a model-based representation

of chemical, physical, biological, and other technical processes and unit

operations in software. Basic prerequisites are a thorough knowledge of chemical

and physical properties [17] of pure components and mixtures, of reactions, and of

mathematical models which, in combination, allow the calculation of a process in

computers. Process simulation software describes processes in flow

diagrams where unit operations are positioned and connected by product or educts

streams. The software has to solve the mass and energy balance to find a stable

operating point. The goal of a process simulation is to find optimal conditions for

an examined process. This is essentially an optimization problem which has to be

solved in an iterative process.Process simulation always uses models which

23

introduce approximations and assumptions but allow the description of a property

over a wide range of temperatures and pressures which might not be covered by

real data. Models also allow interpolation and extrapolation - within certain limits

and enable the search for conditions outside the range of known properties.

2.1.2 Modeling:

The development of models for a better representation of real processes is the core

of the further development of the simulation software. Model development is done

on the chemical engineering side but also in control engineering and for the

improvement of mathematical simulation techniques. Process simulation is

therefore one of the few fields where scientists from chemistry, physics, computer

science, mathematics, and several engineering fields work together. A lot of efforts

are made to develop new and improved models for the calculation of properties.

This includes for example the description of

Thermophysical properties like vapor pressures, viscosities, caloric data, etc.

of pure components and mixtures

Properties of different apparatuses like reactors, distillation columns, pumps,

etc.

chemical reactions and kinetics

environmental and safety-related data

Two main different types of models can be distinguished:

1. Rather simple equations and correlations where parameters are fitted to

experimental data.

2. Predictive methods where properties are estimated.

24

The equations and correlations are normally preferred because they describe the

property (almost) exactly. To obtain reliable parameters it is necessary to have

experimental data which are usually obtained from factual data banks or, if no data

are publicly available, from measurements.

Using predictive methods is much cheaper than experimental work and also than

data from data banks. Despite this big advantage predicted properties are normally

only used in early steps of the process development to find first approximate

solutions and to exclude wrong pathways because these estimation methods

normally introduce higher errors than correlations obtained from real data.

Process simulation also encouraged the further development of mathematical

models in the fields of numeri’s and the solving of complex problems [18][19]

2.1.3 Classification of the models:

Black box – white box

Black box – know nothing about process in apparatus, only dependences

between inputs and outputs are established. Practical realisation of Black

box is the neural network.

Deterministic – Stochastic

Deterministic – for one given set of inputs only one set of outputs

is calculated with probability equal 1.

Stochastic – random phenomenon effects on process course (e.g.

weather), output set is given as distribution of random variables.

2.1.4 Elements of the model:

1. Balance dependences

Based upon basic nature laws

25

of conservation of mass

of conservation of energy

of conservation of atoms number

Of conservation of electric charge, etc.

Balance equation (for mass):

(overall and for specific component without reaction)

Input – Output = Accumulation

or (for specific component if chemical reactions presents)

Input – Output +Source = Accumulation

2. Constitutive equations

Newton eq. – for viscous friction

Fourier eq. – for heat conduction

Fick eq. – for mass diffusion

3. Phase equilibrium equations – important for mass transfer

4. Physical properties equations – for calculation parameters as functions of

temperature, pressure and concentrations.

5. Geometrical dependences – involve influence of apparatus geometry on

transfer coefficients – convectional streams.

2.2.5 Structure of the simulation model:

Structure corresponds to type of model equations

Structure depends on:

Type of object work:

Continuous, steady running

Periodic, unsteady running

Distribution of parameters in space

26

md2 xdt2

=−ηdxdt

∂Q∂ t

=−λ∮S

∇⃗ Td { S⃗¿

∂φ∂ t

=−D∂2φ

∂ x2

Equal in every point of apparatus – aggregated parameters

(butch reactor with ideal mixing)

Parameters are space dependent– displaced parameters

2.2.6 Process synthesis/design problem:

The act of creation of a new process.

Given:

o inputs (some feeding streams can be added/changed latter)

o Outputs (some byproducts may be unknown)

To find:

o Flowsheet (topology)

o equipment parameters

o operations conditions

2.2.7 Modelling objects in chemical and process engineering:

1. Unit operation

2. Process build-up on a few unit operations

2.2.8 Software for process simulation:

Universal software:

Worksheets – Excel, Calc (Open Office)

Mathematical software – MathCAD, Matlab

Specialized software – process simulators. Equipped with:

Data base of apparatus models

27

Data base of components and mixtures properties

Solver engine

User friendly interface

2.2.9 Software process simulators (flow sheeting programs)

Started in early 70’

At the beginning dedicated to special processes

Progress toward universality

Some actual process simulators:

1. ASPEN Tech /HYSYS

2. ChemCAD

3. PRO/II

4. ProSim

5. Design II for Windows

2.2.10 Chemical plant system

Contemporary systems are complex, i.e. consist the apparatus set connected

with material and energy streams.

Most systems of many apparatus and streams.

Simulations can be used during:

28

Investigation works – new technology

Project step – new plants (technology exists),

Runtime problem identification/solving – existing systems (technology and

plant exists)

2.2 Hysys application

2.2.1 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.[20] HYSYS is used extensively in

industry and academia for steady-state and dynamic simulation, process design,

performance modelling, and optimization.

2.2.1.1History:

HYSYS was first conceived and created by the Canadian company Hyprotech,

founded by researchers from the University of Calgary. The HYSYS Version 1.1

Reference Volume was published in 1996.[21] In May 2002, AspenTech acquired

Hyprotech, including HYSYS. Following a 2004 ruling by the United States

Federal Trade Commission, AspenTech was forced to divest its Hyprotech

assets, including HYSYS source code, ultimately selling these to Honeywell.

Honeywell was also able to hire a number of HYSYS developers, ultimately

mobilizing these resources to produce UNISIM. The divestment agreement

29

specified that AspenTech would retain rights to market and develop most

Hyprotech products (including HYSYS) royalty-free.] As of late 2016, AspenTech

continues to produce HYSYS, and it is considered number one in the industry, the

default standard.[22]

2.2.2 Software and Hardware

The HYSYS program, like most other software, is continually being developed and

new versions are released frequently. This book covers HYSYS, Version 2004.1. It

should be emphasized, however, that this book covers the basics of HYSYS which

do not change that much from version to version. The book covers the use of

HYSYS on computers that use the Windows operating system. It is assumed that

the software is installed on the computer, and the user has basic knowledge of

operating the computer. [10]

HYSYS is a powerful engineering simulation tool, has been uniquely created with

respect to the program architecture, interface design, engineering capabilities, and

interactive operation. The integrated steady state and dynamic modeling

capabilities, where the same model can be evaluated from either perspective with

full sharing of process information, represent a significant advancement in the

engineering software industry. The various components that comprise HYSYS

provide an extremely powerful approach to steady state modeling. At a

fundamental level, the comprehensive selection of operations and property

methods allows you to model a wide range of processes with confidence. Perhaps

even more important is how the HYSYS approach to modeling maximizes your

return on simulation time through increased process understanding. To

comprehend why HYSYS is such a powerful engineering simulation tool, you need

look no further than its strong thermodynamic foundation. The inherent flexibility

30

contributed through its design, combined with the unparalleled accuracy and

robustness provided by its property package calculations leads to the presentation

of a more realistic model. HYSYS is widely used in universities and colleges in

introductory and advanced courses especially in chemical engineering. In industry

the software is used in research, development, modeling and design. HYSYS

serves as the engineering platform for modeling processes from Upstream, through

Gas Processing and Cryogenic facilities, to Refining and Chemicals processes.

There are several key aspects of HYSYS which have been designed specifically to

maximize the engineer efficiency in using simulation technology. Usability and

efficiency are two obvious attributes, which HYSYS has and continues to excel at.

The single model concept is key not only to the individual engineer €™s

efficiency, but to the efficiency of an organization. Books about HYSYS are

sometimes difficult to find. HYSYS has been used for research and development in

universities and colleges for many years. In the last few years, however, HYSYS is

being introduced to universities and colleges students as the first (and sometimes

the only) computer simulator they learn. For these students there is a need for a

book that teaches HYSYS assuming no prior experience in computer simulation.

2.2.3 a Little about HYSYS

The goal of programs like HYSYS and Aspen is, of course, to provide you with the

capability to design an entire process as completely and accurately as possible.

Most (though not all) of the differences between the two lie in their user interfaces.

Having gone through the design class with Aspen, I am of the personal opinion that

HYSYS has a much better and intuitive interface than Aspen. You have the option

of using either simulation package, but recommend using HYSYS unless you run

against something that only Aspen will do. I will try to warn you of all the

limitations of HYSYS that you might encounter in advance.

31

Unlike Aspen, HYSYS does not wait until you've entered everything before

beginning calculations. It always calculates as much as it can at all time and results

are always available, even during calculations. Any changes that you make to the

data are automatically propagated throughout the program to anywhere that entry

appears and all necessary recalculations are instantly carried out. It tends to be a lot

easier to catch errors this way as you build your simulation. However, there are

times when you will not want HYSYS calculating the entire flowsheet over again

every time you make a small change. Hence, the existence of the environments.

While you are in one environment, calculations in the other environments are

placed on hold. Every case (as HYSYS calls each individual simulation file) has

two or more environments. The one that contains all the items you expect to see,

the streams, unit operations such as reactors, separators, columns, mixers, etc., and

various utilities, is the simulation environment. At the top of that environmental

hierarchy (and the only one required) is the Case environment and the Main

flowsheet. (Aside: both the name "Case" and the tag "Main" are defaults and can

be changed in the "Main Properties" view under the Simulation menu). Though the

entire simulation may be placed in the Main flowsheet, columns and templates are

automatically brought in as Sub-flowsheet. Sub-flow sheets can be thought of as

modular programs. You can have as many as you like, nested as deep as you like

(though you tend to not need to put additional sub-flowsheet under a column

flowsheet).

The other environment, and the one you actually have to deal with first when you

start a case, is the basis environment. The basis environment is the place that you

define the thermodynamic package you wish to use (Peng-Robinson, Margules,

etc.), the components that will be used in your simulation and any reactions that

32

may occur. If dealing with a Petrochemical application, there is also an oil

environment that may be reached only from the basis environment.

There are two files that HYSYS reads whenever you start HYSYS. One of these is

the Preferences File; the other is the workbook format file. The preferences file

tells HYSYS many important things like which units you want to use, where to

look first for your stored files etc. You can have multiple preference files saved (or

you can just build up various unit sets, etc., in one file you alter upon need), but the

one that is loaded upon startup is the file named hysys.prf in the directory from

which HYSYS is started. If you launch HYSYS from your start menu, your user's

profile has been configured with Y:\Hysys as the start directory (note that if you

are not in a design class group, you won't have a Y drive, because the purpose of

they drive is to save group work). If you look at the contents of that directory you

will see, in addition to some other stuff, that I have placed a hysys.prf file in there

for you. That is the file that must be overwritten if you want to make changes to

your default preferences (though changes are automatically saved to the preference

file when you save your simulation, so overwriting should not often be

necessary). You may have noticed the other file I put there, hysys. Work that file is

responsible for the appearance of your workbook. The workbook shows you the

contents of every stream in your process and the connections of every unit (if you

really wanted to you could make your entire simulation using the Workbook and

never even look at the PFD). Without the hysys. Work file, unless the file has

undergone changes to its workbook which got saved with that particular case, the

default is for the workbook to only show two pages: Streams and Unit Ops. Now,

if you've done any reading of the manuals or working of the tutorials you were

probably expecting four pages: Material Streams, Compositions, Energy Streams,

and Unit Ops. The Workbook is much harder to work with without the extra info

33

these pages provide. The file I provided restores these other pages, but again it is

only automatically loaded if the Start Menu was used to launch HYSYS. [11]

Chapter Three

Materials and Method

34

Chapter Three

Material and Methods

3.1 Catalytic reforming:

Catalytic reforming is the process of transforming C7–C10 hydrocarbons with

low octane numbers to aromatics and iso-paraffins which have high octane

numbers. It is a highly endothermic process requiring large amounts of energy. The

modern catalytic reforming process was first introduced by UOP in 1940. Since

then, there have been many different types of reforming

1. Semi-regenerative.

2. Cyclic.

3. Moving-bed or continuous catalyst regeneration.

3.1.1 Reformer Feed Characterization:

- The main feed comes from:

- Hydrotreated heavy naphtha. Or from hydrotreated coker naphtha

- Feeds are characterized by the Watson characterization factor (K),

naphthenes (N) vol% and aromatics (A) vol% in which (N+2A) must be

defined.

35

- Initial boiling points (IBP) and end points (EP) for feeds.

- Feeds can be also characterized by the hydrocarbon family and their

number of carbon atoms.

-

36

3.2 Detailed Processes Description:

The naphtha feed stream is treated at very low pressure in three reactors over a

slow moving bimetallic catalyst bed in a hydrogen environment at relatively high

temperature and low pressure. Under these conditions of low pressure and high

temperature, the rate of coke lay down on the catalyst is relatively high. The

catalyst is withdrawn at a fixed rate from the reaction section to be regenerated in a

continuous catalyst regeneration unit and returned to the reaction section the

design, operation and control strategies of this unit are such as to maximize the

production of aromatics and to ensure consistent quality of the rich hydrogen gas

There are three primary products from this reforming section: reformate with high

aromatics content (C 5+¿¿ ),rich hydrogen gas and LPG stream or(C 1− C4) cut .

The feed is a mixture of straight run naphtha (20 wt. %) and hydro treated cooker

naphtha (80 wt. %). The feed consists of 71.5 vol% paraffins, 19 vol% naphthenes,

9.5 vol% aromatics and negligible amounts of sulfur, nitrogen and water. The feed

specific gravity is 0.725. The reforming catalyst is a high purity alumina based

catalyst, impregnated with platinum and promoters. It is highly sensitive to

impurities in the feedstock. A chloriding agent (C2Cl4) and water are injected for

optimum reforming catalyst performance. A sulfiding agent is injected

continuously in the feed to prevent metallic coking in the 2 4 reactors. The naphtha

feed is at 90 ℃ and 1.2 Mp. It mixed with the hydrogen recycle stream coming

from the compressor (C-101) at 0.450 Mpa, and then enters the feed heat.

Exchanger (E-101). The amount of the hydrogen stream is 185.7kg/hr of fresh

naphtha feed. The heat exchanger (E-101) designed for minimum pressure drop

and maximum heat recovery against reactor effluent. The combined naphtha feed

and hydrogen are preheated in the heat exchanger (E-101) against the third reactor

(R-103) effluent. They leave at 250 and 0.490 Mpa. Then they are further heated in

37

the first fired heater (H-101) to 510 which is the required temperature for the first

reactor (R-101).The pressure drops in the fired heater (H-101) from 0.475 to 0.44

Mpa. In the first reactor (R-101), naphthenes dehydrogenation and isomerization

reactions occur. Naphthenic compounds i.e. cyclo hexanes, methyl cyclo hexane,

dimethyl cyclo hexane up to naphthenes are dehydrogenated respectively into

benzene, toluene, xylenes (C 9 ) and (C 10 ) aromatics with the production of 3 moles

of hydrogen per mole of naphthene. The cyclohexane reaction writes as follows:

Cyclohexane Benzene

CH

CH

CH

CH HC

HC

CH 2

CH 2

CH 2

H C 2

H C 2

+ 3H 2

CH 2

Thermodynamically the reaction is highly endothermic and is favored by high

temperature and low pressure.

Table (3.1): (RON) of the products of naphthenes dehydrogenation reaction

Aromatic RON

Cyclohexane 83.00

Dimethyl cyclo hexane 74.40

Benzene 71.70

Toluene 114.8

m-xylene 120.0

m-xylene 117.5

The product the first reactor (R -101) leave at 393.5 and 0.420 Mpa .the first

reactor (R-101) product is reheated in the second fired heater (H-102) to 510℃

This is the required inlet temperature of the second reactor (R-102).The pressure

drops in the fired heater(H-102) from 0.42 to 0.395M pa. Dehydrogenation of

naphthenes continues in the second reactor (R-102). Naphthenes isomerization and

38

paraffin's isomerization, hydrocracking and dehydrocyclization also occur in the

second reactor (R-102). The pressure drops in the fired heater (H-102) from 0.42 to

0.395M pa. Dehydrogenation of naphthenes continues in the second reactor (R-

102). Naphthenes Isomerization and paraffin's isomerization, hydrocracking and

dehydrocyclization also occur in the second reactor (R-102).The isomerization of

an alkyl cyclo pentane into an alkyl cyclo hexane involves a ring rearrangement

and is desirable because of the subsequent dehydrogenation of the Alkyl

cyclohexane into an aromatic. Because of the difficulty of the ring rearrangement,

the risk of ring opening resulting in paraffin is high. The reaction is slightly

endothermic and it can be summarized as follows:

Alkylcyclohexane (Methylcyclohexane)

Alkylcyclopentane (Ethylcyclopentane)

Theoretically, at the selected operating temperature (510°C) the thermodynamics

limits the alkyl cyclohexane formation. But the subsequent dehydrogenation of the

alkyl cyclohexane into an aromatic shifts the reaction towards the desired

direction. This type of reaction is easier for higher carbon number. The octane

number increase is significant when considering the end product (aromatics) as

shown in table 2.3.

Table (3.2): RON of the Aromatics produced in the Second Reactor:

39

Aromatic RON

Ethylcyclopentane 67.2

Methyl cyclohexane 74.8

Toluene 120

Paraffin's isomerization reaction can be written as follows:

C H 7 16

+ H 2

C H 7 14

CH2 CH

2 CH

2

CH2

CH2

CH3

CH3

CH

CH3

CH3

CH2

CH2

CH2 CH

These reactions are fast, slightly exothermic and do not affect the number of

carbons. The paraffin's isomerization results in a slight increase of the octane

number. From a kinetic view point high temperature favors isomerization but

hydrogen partial pressure is indifferent. These reactions are promoted by the acidic

function of the catalyst Support. Paraffin’s dehydrocyclization is a several step

reaction which applies either to the normal paraffin's (linear) or iso-paraffins

(branched).It involves a dehydrogenation with a naphthene and the subsequent

dehydrogenation of the naphthene. At the selected operating Conditions, this

reaction rate is much lower than that of naphthene dehydrogenation (30/1).The

reaction can be summarized as follows:

40

Methylcyclohexane

CH2

CH2

CH CH2

CH3

CH3

CH

CH2

CH2

CH2

CH2

CHCH

3 H C

2

Toluene

H C2

CH2 CH

2

CH2 CH

2

CH CH3 CH

3

CH CH

CH CH

HCC

+ 3H2

Hydrocracking affects either paraffins (normal or iso) or naphthenes. It is parallel

reaction to paraffin dehydrocyclization. It can be schematized by a first step of

dehydrogenation which promoted by the metallic function of the catalyst, followed

by a breakage of the resulting olefin and the hydrogenation of the subsequent short

chain olefin. The second reaction is promoted by the acidic function of the catalyst.

Hydrocracking also affects the naphthenes; the overall reaction can be summarized

as follows:

41

+ H 2

C H 7 16

or

+ H 2

C H 6 14

CH - C H 3 5 9

CH - C H 3 6 11

Reaction (dehydrocyclization), hydrocracking becomes significant as the

temperature increases. It is also favored by high pressure The reactions in the

second reactor are less endothermic; the outlet temperature of the second reactor

(R-102) is 405 , and still requires reheating to 510 in the third fired (H-103) before

entering the third reactor (R-103). The reheating is required to enable the paraffin

dehydrocyclization to proceed. The pressure drops in the fired heater (H-103) from

0.375 to 0.35 Mpa.

A combination of paraffin dehydrocyclization and hydrocracking take place in the

third reactor (R-103). The effluent leaves the third reactor (R-103) at approximately

420°C and at pressure 0.33 Mpa.

In the three reactors the feed contacts the reforming catalyst which is divided

approximately in the ratio 20/30/50. In the continuous regeneration process the

catalyst circulates continuously: in the reactors; in the space between the scallops

and the central pipe from the top to the bottom, from one reactor bottom to the top

of the next one, from the last reactor (R-103) to the regeneration unit for

regeneration and from the regeneration unit to the first reactor (R-101).

The effluent from the reactor (R-103) exchange heat in the heat exchanger (E-101).

against reactor feed and leaves at temperature 231 °C and pressure 0.28 Mpa.

42

Further cooling occurs in the air cooler (A-101) to 42°C before entering the

separator drum (V-101). The operating conditions of the separator drum (V-101)

are 42 °C and 0.23 Mpa. The separator drum (V-101) separates liquid from vapor.

The vapor stream mainly constitutes of hydrogen. A portion of the separated gas is

compressed by the gas compressor (C-101) driven by a steam turbine to 0.450 Mpa

and mixed with the naphtha feed stream. The remaining part of the hydrogen rich

gas stream is routed to the compressor (C-102 A/B) through a knockout drum (V-

102). This drum is placed before the compressor inlet to prevent liquid drops from

entering and damaging the compressor. The compressor (C-102 A/B) provides two

stages compression. The H2 production gas compresses from 0.23 Mpa to 0.31 Mpa

in the first stage. The air cooler (A-102) cools the hydrogen rich gas to 40°C. The

knockout drum (V-103) which operates at 40℃ and 0.290 Mpa is required to

remove the condensed hydrocarbons. The condensed liquid from (V-103) is mixed

with the liquid leaving the separator drum (V-101) and pumped by a pump (P-101)

to 2.64 Mpa. The hydrogen rich gas from the separator drum (V-103) enters the

second stage of the compressor (C-102 A/B) and leaves at 3.32 Mpa. Then it is

recontacted with the stream leaving the pump (P-101) and cools in the air cooler

(A-102) to 35℃ . the purpose of this recontact is to increase the hydrogen purity.

After cooling in the air cooler (A-102) the stream enters the separator drum (V-

104). The operating conditions of the separator drum (V-104) are 35 and 3.3 Mpa.

These conditions of the separator drum (V-104) are designed for a high content of

hydrogen in the hydrogen rich gas product. The vapor stream from this separator is

the hydrogen rich gas product which is used in the naphtha hydrotreating section.

The liquid stream from the separator drum (V-104) is the hydrocarbon stream

which is sent to the LPG recovery and stabilization section.

43

The separated liquid from the separator drum (V-104) is heated in the stabilizer

feed/bottom exchanger (E-102) to 110℃ .. The stabilizer reduces the C4 in the

reformate to less than 1.0 wt %. The stabilizer top and bottom temperatures are

60.36℃ and 251.5℃ respectively. The stabilizer top and bottom pressures are

1.581 and 1.786 Mpa respectively. The stabilizer bottom is heated with a fired

reboiler.

The stabilizer overheads are condensed in air cooler (A-104). A portion of the

produced stream is sent to the top of the stabilizer (T-101) as reflux. The remaining

part is withdrawn as LPG product stream. Bottoms from the stabilizer enter the

stabilizer feed/bottom exchanger (E-102) and cooled to 192. Further cooling occurs

in the cooler (A-103) to 40℃. The produced reformate constitutes of more than 99

wt. %C 5+¿¿. Its RON is 99.6 and its specific gravity is 0.786. [12] [13]

3.3 Process Flow Diagram (PFD)

Process Flow Diagram (PFD) of the Reforming Section is shown in figure

Legend of the PFD of the Reforming Section

E-101 Heat Exchanger H-101 Fired Heater R-101 Reactor

H-102 Fired Heater R-102 Reactor H-103 Fired Heater

R-103 Reactor A-101 Air Cooler V-101 Separator Drum

C-101 Compressor V-102 Separator Drum C-102 A/B Compressor

A-102 Air Cooler V-103 Separator Drum P-101 Pump

A-103 Air Cooler V-104 Separator Drum P-102 Pump

E-102 Heat Exchanger T-101 Stabilizer P-103 Pump

H-104 Reboiler A-104 Air Cooler P-104 Pump

E-103 Cooler

44

Figure (3:1): PFD of the Reforming Section of CCR Unit [12]

45

Chapter Four

Results and Discussion

46

Chapter Four

Process simulation and Results or Discussion

4.1 Feed properties:

Table (4.1): feed properties

ASTM D.86 (Wt %) P N AIBP 78 C2 - -5% 90 C 3 - -10% 96 C4 - -30% 108 C 5 3.74 0.37 0.0050% 118 C 6 8.93 2.27 0.1470% 133 C7 13.32 4.81 0.9090% 152 C 8 17.32 7.00 2.0095% 160 C 9 15.98 5.59 2.25EBP 170 C 10+¿¿ 8.99 2.12 0.94S.G. Sum 68.28 22.16 6.23

4.2 Reactor configuration:

Table (4.2): reactor configuration

Reactor bed Length(m) Loading Inlet temp(℃) ∆T(℃)1 0.54 1.275e4 516.0 110.42 0.69 1.913e4 513.1 64.23 0.96 3.188e4 513.0 36.4

4.3 Continuous catalytic reforming (CCR) process step runs:

1. Importing reformer component list. To import these components, we click

‘Import’ and navigate to the directory location, “C:\Program Files\

AspenTech\Aspen HYSYS” and select the “CatReform.cml” as shown in

fig(4.1):

47

Fig (4.1): select cat reforming

2. Once we have import the component the fluid package defined by hysys, we

can return to the Simulation Basis Manager and click on ‘Enter Simulation

Environment’ to begin building the process model. Current fluid packages

(REFSRK).as shown as fig(4.2)

Fig (4.2): Enter Simulation Environment

3. We can bring the up the advanced palette by pressing F6 , We select the

Reformer icon from the Refining Reactors palette and click on the

48

Refomericon and place the icon the flowsheet, We choose ‘Configure a New

Reformer Unit’

Fig (4.3) CCR configuration

4. The reformer configuration requires choosing the type of reformer, number

of reactors as shown below( CCR with 3 Beds)

Fig (4.4) type of reformer and number of reaction

49

5. Enter the reactor dimensions and catalyst loadings.

Fig (4.5): reactor dimensions and catalyst loadings.

6. Choose calibration factors.

Fig (4.6): calibration factors.

50

7. Drill down to the Reformer sub model. Enter the Reformer sub-model by

clicking on “Reformer” Environment.

Fig (4.7): reformer sub model.

8. Double-clicking on the Reactor sub-model icon to bring up the Reactor sub-

model window.

Fig (4.8): reformer reactor section (the properties feed type)

51

9. Enter the measured bulk property information in the “Properties” section of

the Feed Data Tab as shown in below figure.

Fig (4.9): reformer reactor section (feed section)

10.Once we enter the bulk feed information, it is important to “Hold” the

solver. By design, Aspen HYSYS will attempt to recalculate the model the

instant we make a change. This can be inconvenient and may cause

convergence problems when we change many variables. To “Hold” the

solver, simply select the Red Stop sign in the top toolbar of the flowsheet

window.

52

11.enter other operation details by navigating to the “Operation” Tab and

“Feeds” section of the Reformer sub-model, inter Feed Flow , pressure

Temperature as :shown below

Fig (4.10) reformer reactor section (operation and feed tabs)

12.enter the “Reactor Control” section and define the operating temperature of

each bed

Fig (4.11): reformer reactor section (reactors temperatures specification)

53

13.Enter an estimate for the catalyst circulate rate since we are modeling a CCR

unit as shown below:

Fig (4.12): reformer reactor section (catalyst circulates rate)

14.Enter product heater temperature and pressure

Fig (4.13): reformer reactor section (heater temperatures)

54

15.Solver page:

Fig (4.13): reformer reactor section (solver page)

16.Run case study:

17.Result:

Fig (4.14): run and result

55

4.4 step of all units after CCR running:

After CCR running the feed naphtha mixed with hydrogen in mix-100 shown in thefigure (4.15a):

Figure (4.15a): mixer design page

The data of feed and hydrogen shown in in figure (4.15b) :

Fig(4.15b):mixer worksheet data

56

The stream from mixer entered the heat exchange with the effluent from CCR unit.

The heat exchange performs two sided energy and material balance calculations.

The heat exchanger is capable of solving temperature, pressure, heat flows,

material stream flows and overall unit coefficient*Area. The effluent from CCR

unit used to heat a cold stream (to h.x out from mixer) in the shell and tube

respectively. The figure (4.16a) as shown data input to heat exchange and figure

(4.16b) as shown the heat exchange simulation.

Fig (4.16a): heat exchanger worksheet data

57

Fig (4.16b): heat exchanger design

The stream (to cooler) out from heat exchange entre to cooler to cold product(decrease temperature) to help in separations liquid from vapor as shown in figure(4.17a) and the design cooler as shown as fig (4.17b).

Fig (4.17a): the cooler worksheet data.

Fig (4.17b): the cooler design.

58

The stream out from cooler enters the separator to separate liquid from vapor. Thedata input to separator as shown in fig (4.18a) and fig (4.18b) the separator design.

Fig (4.18a): separator worksheet

Fig (4.18b) the separator designs.

59

The vapor stream enters to the tee (TEE-100) to separate hydrogen stream andproduct (sep-3) as shown in fig (4.19)

Fig (4.19): tee worksheet.

The stream (to sep-3) enters to another separator (V-101) to separate the vapourstream (to comp) from liquid stream (to mix) the data input to separator as shownin fig ( )

Fig (4.20): separator (V-101) worksheet

60

The vapour stream (to comp) enter to the compressor (K-100) and the outputstream (to cooler-2) enter to cooler (E-103) the data worksheet as shown in fig(4.22) and the worksheet of compressor as shown as fig (4.21b) or the designcompressor as shown as fig (4.21a).

Fig (4.21a): compressor (K-100) design.

Fig (4.21b): compressor (K-100) worksheet.

61

Fig (4.22): cooler E-103 worksheet

The stream out from cooler (E-103) enter to separator (V-102) .the data worksheetas shown in fig (4.23).

Fig (4.23): separator V-102 worksheet

62

The outlet stream vapour (Exfeed) from separator (V-102) entre to compressor (K-101), the worksheet data as shown in fig (4.24).

Fig (4.24): compressor k-101 worksheet.

The outlet stream from compressor (K-101) enters to mixer (mix-101) with stream(to pump.1) out from separator (V-100), the worksheet data as shown in fig (4.25)

Fig (4.25): the mixer MIX-101 worksheet.

63

The outlet stream (to pump11) from mix (Mix-101) enters to pump (P-100)

The worksheet data as shown in fig (4.26)

Fig (4.26): pump P-101 worksheet.

The stream (pumpout) outlet rom pump (P-100) enters to mixer (mix-102) withstream (to mix) and stream (to mix), the worksheet data as shown in fig (4.27)

Fig (4.27): the mixer MX-102 worksheet.

64

The stream (out f mix) outlet from mixer (mix -102) enters to cooler (E-104) thedata worksheet as shown in fig (4.28)

Fig (4.28): the cooler E -102 worksheet.

The stream outlet from cooler (E-104) enters to last separator (V-103) to separatehydrogen from liquid stream, the worksheet data as shown in fig (4.29)

Fig (4.29): separator V-103 worksheet.

65

The stream (to heating) outlet from separator (V-103) enters to heat exchanger

(E-105) with stream outlets from bottom liquid column (T-100/col1 fluid pkg:

REFSRK/Aspen Properties (SRK)), the worksheet data as shown in fig (4.30)

Fig (4.30): heat exchanger E-105 worksheet

The outlet stream (to stabilizer) enters to column (T-100 col1 fluid package:REFSRK/Aspen Properties (SRK)) to separation the material.as shown I fig (4.31)and the data shown as fig (4.32).

66

Fig (4.31): the column design connections

Fig (4.32): the column worksheet connection.

67

When input the data click the done button, HYSYS will open the column proprietyview, access the monitor page on the design tab as shown as fig (4.33)

Fig (4.33): the column monitor

Before the converge the column the specification as shown above to enter the valuefor the ov hd prod rate specification .once value entered the column will startrunning and should converge. The stream (to cooling) out from heat exchangeenters to cooler to cold the .the final gasoline. The data as shown in fig (4.34)

68

Fig (4.34): the cooler E-106 worksheet data

Fig(4.35):final gasoline stream

69

4.5 Result:

The result from application hysys programe of catalytic reforming to production ofgasoline from naptha in the table(4.3) as shown as

Table(4.2):the result of hyysy program

Name Pressure [kPa]

Temperature [C]

Mass Flow[lb/hr]

Std Ideal Liq VolFlow [barrel/day]

Vapor /Phase

FractionNaphtha 1200 90 110230 10105 0Hydrogen 536 87 13786.2 13388.4 1

to H.XTO COOLER 280 323.139 383166 34416 1TO HEATER 475 230 124016 23493.4 1

to sep-2 230 42 383166 34416 0.005sep-3 230 42 330.595 63.941 1

to sep-3 230 42 120 23.2094 1Hydropro 230 42 210.595 40.7316 1to comp 230 42 120 23.2094 1to mix 230 42 0 0 0

to cooler -2 310 64.918 120 23.2094 1to pump11 230 41.9991 382896 34358.5 8.11832E-06pump out 264.47

442.012 382896 34358.5 0

to sep 033 3320 35 120 23.2094 0.876Ex feed 3320 35 59.3856 16.6973 1

to comp2 3320 35 60.6144 6.51207 0Tomixx 3326 35.0401 59.3856 16.6973 1

out f mixx 230 41.9987 382956 34375.2 0.0019to se[ -4 330 35 382956 34375.2 0.00083

hydrogen3 330 35 33.1113 8.4512 1to heating 330 35 382923 34366.8 0to cooling 1500 192.426 378028 33712.3 0

to stabilizer 3350 110 382923 34366.8 0off gases 1581 40.8123 1116.99 168.015 1

LPG 1581 40.8121 3777.85 486.482 5.68677E-07GASOLINE 1786 247.61 378028 33712.3 1.20379E-05

FINALGASOLINE

1750 26 378028 33712.3 0

H22 821.3 30.87 65139.4 25237.5 0.995292Effluent 1200 420 383166 34416 1

H 230 25.5597 65383.1 25286.7 1

70

Chapter Five

Conclusions andRecommendations

71

Chapter Five

Conclusions and Recommendations

5.1 Conclusions:

Catalytic reforming process converts the low octane naphtha into more

valuable high-octane gasoline components.

From the reaction analysis it can be concluded:

a) Dehydrogenation reactions are very fast, about one order of magnitude

faster than the other reactions.

b) Low pressure favors all desirable reactions and reduces cracking. To

compensate the detrimental effect of low pressure on coking, low pressure

reformer requires continuous catalyst regeneration.

c) An increase in temperature favors the kinetics of dehydrogenation,

isomerization, dehydrocyclization, but accelerates the degradation

reactions (cracking, coking) even more. Consequently an increase in

temperature leads to an increased octane associated with a decrease in

reformate yield.

d) The reaction rates of such important reactions as paraffins

dehydrocyclization increase noticeably with the number of carbon atoms.

Cyclization is faster for C8 paraffin than for C7 and for C7 than for C6.

Consequently the C7 - C10 fraction is the most suitable feed.

72

5.2 Recommendations:

Continuous catalytic reforming process represents a step change in reforming

technology compared to semi regenerative. Since its introduction, it gained wide

acceptance around the world and it is recommended to change semi regenerative

units to continuous.

The reforming catalyst is highly sensitive to impurities in the feedstock. Some are

considered reversible poisons, others irreversible. Thus, the naphtha feed is

recommended to pass through hydrotreating unit before entering the catalytic

reforming unit in order to remove sulphur, nitrogen and oxygen which can all

deactivate the reforming catalyst.

In order to ensure the optimum use of the catalyst, regeneration must be achieved

periodically to remove the temporary poisons from the contaminated catalyst.

Otherwise, these poisons may reduce the catalyst life.

73

References

1. M.A.Fahim,T.A.Al-Sahhaf, A.S. Elkilani. Fundamentals of Petroleum

Refining, 1st Edition, Elesvier B.V, UK (2010).

2. James H. Gary, Glenn E. Handwerk., Petroleum Refining Technology and

Economics, 4th Edition, Marcel Dekker, Inc, NY (2001).

3. Rakesh Rathi. Petroleum Refining Processes, SBS Publishers &

Distributors Pvt. Ltd, New Delhi (2007).

4. Dr. Ram Prasad., Petroleum Refining Technology, Afif Printers, Lal, Quan,

Delhi (2000).

5. Jean-Pierre Wauquier., Crude Oil Petroleum Products Process Flow Sheet,

Edition Technip, (1995).

6. George J. Antos, Abdullah M. Aitani. , Catalytic Naphtha Reforming,

Second Edition, Marcel Dekker Inc, NY. (2004).

7. James G. Speight, the Chemistry and Technology of Petroleum, 4th Edition,

Taylor & Francis Group, LLC (2007).

8. Jean-Pierre Wauquier, Crude Oil Petroleum Products Process Flow Sheet,

Edition Technip, (1995).

9. http://www.petroleum.co.uk/other-uses-of-petroleum

10. Abd Hamid, Mohd. Kamaruddin (2007) HYSYS: an introduction to

chemical engineering simulation for UTM Degree++ program. Manual.

University Technology Malaysia. (Unpublished)

11.http://www.owlnet.rice.edu/~ceng403/hysys/intro.html

12.Khartoum Refinery Company.

13.Khartoum university(2012), production of gasoline from naphtha by

catalytic reforming for degree B.Sc in chemical engineering

14.www.CHE.com

74

15.http://www.petroleum.co.uk/chemistry

16.https://en.wikipedia.org/wiki/Petroleum_naphtha)

17.Rhodes C.L., “The Process Simulation Revolution: Thermophysical

Property Needs and Concerns”, J.Chem.Eng.Data, 41, 947-950, 1996

18.Saeger R.B., Bishnoi P.R., “A Modified 'Inside-Out' Algorithm for

Simulation of Multistage Multicomponent Separation Processes Using the

UNIFAC Group-Contribution Method”, Can.J.Chem.Eng., 64, 759-767,

1986.

19. Mallya J.U., Zitney S.E., Choudhary S., Stadtherr M.A., “Parallel Frontal

Solver for Large-Scale Process Simulation and Optimization″, AIChE J.,

43(4), 1032-1040, 1997

20.Shukor, Hafiza; Ku Ismail, Ku Syahidah; Mohd Johar, Hafizah. "ERT 214

MATERIAL AND ENERGY BALANCE HYSYS SIMULATION

MANUAL" (PDF). Retrieved 4 December 2016.

21.Gani, R.;Jørgensen,S.B. (2001). European Symposium on Computer Aided

Process Engineering-11:11th European Symposium of the Working Party on

Computer AidedProcessEngineering.Elsevier.p.534.ISBN 9780080531298.

Retrieved 10 December 2016.

22."Optimize Hydrocarbon Processes with Aspen HYSYS®". Retrieved 10

December 2016.

75

5.4 Appendix A

5.4.1 Appendix A:

Fig (A.1): flow sheet from Google to CCR unit production of gasoline fromnaphtha

Fig (A.2): refinery data component list or impurities.

Fig (A.3): UOP CCR UNIT

5.4.2 Appendix B

Refinery flow sheet:

Fig (B.1) Refinery of Khartoum overview unit CCR

Fig (B.2): reaction section refinery

Fig(B.4): stripper section

Fig (B.5): Separation unit

Fig (B.6) Recontacting system