Contents

CHAPTER: 1 INTRODUCTION 1.1 TYPES OF NAPHTHA 1.1.1 PARAFFINIC NAPHTHA 1.1.2 HEAVY NAPHTHA 1.2 PRODUCTION IN REFINERIES 1.3 HYDRO-TREATING 1.3.1 PRINCIPAL IMPURITIES 1.3.2 SULFUR SPECIES IN NAPHTHA 1.4 DESULPHURIZATION PROCESSES 1.5 HYDRO-DESULFURIZATION 1.6 REACTIONS OF SULPHUR REMOVAL 1.6.1 CATALYSTS CHAPTER: 2 LITERATURE SURVEY 2.1 HISTORY 2.2 SULFUR REMOVAL TECHNIQUES 2.2.1 HYDRO-TREATING 2.2.2 DESULFURIZATION CHAPTER: 3 MARKET SURVEY CHAPTER: 4 CAPACITY SELECTION CHAPTER: 5 PLANT LOCATION AND SITE SELECTION 5.1.1 RAW MATERIALS 5.1.2 MARKETS 6 6 6 7 7 8 8 8 9 10 11 11 12 12 13 13 14 15 16 19 19 19

5.1.4 CLIMATE 5.1.5 TRANSPORTATION 5.1.6 WATER SUPPLY 5.1.7 WASTE DISPOSAL 5.1.9 TAXATION 5.1.10 5.1.11 5.1.12 SITE CHARACTERISTICS FLOODS AND FIRE PROTECTION COMMUNITY FACTORS

20 20 20 20 21 21 21 21 22 22 24 24 24 24 24 24 24 24 24 24 25 25 25 25 25 25 25 25 25 25

5.2 SELECTION CRITERIA 5.2.1 LIST OF ALL REFINERIES IN PAKISTAN CHAPTER: 6 PROCESSES SELECTION 6.1 PRIME G+ 6.1.1 BASIC CHEMISTRY 6.1.2 PROCESS CONFIGURATION 6.1.3 REACTION CONDITIONS 6.1.4 STRENGTHS 6.1.5 WEAKNESSES 6.1.6 COMMERCIAL UNITS 6.2 CD HYDRO 6.2.1 SUITED FOR BOIL RANGE 6.2.2 BASIC CHEMISTRY 6.2.3 PROCESS CONFIGURATION 6.2.4 REACTION CONDITION 6.2.5 STRENGTHS 6.2.6 WEAKNESSES 6.2.7 COMMERCIAL UNITS 6.3 CD HDS 6.3.1 SUITED FOR BOIL RANGE 6.3.2 BASIC CHEMISTRY 6.3.4 REACTION CONDITION

6.3.5 STRENGTHS 6.3.6 WEAKNESSES 6.3.7 COMMERCIAL UNITS 6.4 ISAL PROCESS 6.4.1 SUITED FOR BOIL RANGE 6.4.2 BASIC CHEMISTRY 6.4.3 PROCESS CONFIGURATION 6.4.4 REACTION CONDITION 6.4.5 STRENGTHS 6.4.6 WEAKNESSES 6.5 SCAN FINING PROCESS 6.5.1 SUITED FOR BOIL RANGE 6.5.2 BASIC CHEMISTRY 6.5.3 PROCESS CONFIGURATION 6.5.4 REACTION CONDITION 6.5.5 STRENGTHS 6.5.6 WEAKNESSES 6.5.7 COMMERCIAL UNITS 6.6 SELECTION OF COMMERCIAL HDS PROCESS CHAPTER: 7 PROCESS DESCRIPTION 7.1 NAPHTHA HYDRO-DESULPHURIZATION PROCESS 7.1.1 PRE-TREATMENT 7.1.3 MIXING OF HYDROGEN GAS WITH NAPHTHA 7.1.4 EFFLUENT HEAT EXCHANGER E-101 7.1.5 FIRED HEATER H-101 7.1.6 REACTOR V-101 7.1.8 SEPARATOR V-102 7.1.9 STRIPPER V-103 7.1.10 HEAT EXCHANGER E-105 7.1.12 AMINE UNIT

26 26 26 26 26 26 26 26 26 26 27 27 27 27 27 27 27 27 27 29 29 29 30 30 30 30 31 31 31 32

7.1.13 PUMP P-103 7.1.14 FIRED HEATER H-102 7.1.15 HEAT EXCHANGERS E-105 AND E-106 CHAPTER: 8 PHYSICAL AND CHEMICAL PROPERTIES 8.1 PHYSICAL DATA 8.2 REACTIVITY PROFILE 8.3 FLAMMABILITY CHAPTER: 9 USES OF NAPHTHA 9.1 CATALYTIC REFORMING 9.2 AROMATIC PRODUCTION 9.3 FERTILIZER/PETROCHEMICAL INDUSTRY 9.4 NAPHTHA STEAM CRACKER 9.5 POWER PLANT FUEL 9.6 OTHER APPLICATIONS CHAPTER: 10 SAFETY & ENVIRONMENT STUDY 10.1 INTRODUCTION 10.2 SOCIAL AND HEALTHCARE IMPACTS 10.2.1 ROUTES OF EXPOSURE 10.2.2 IMPACTS ON ANIMALS 10.2.3 IMPACTS ON HUMAN 10.2.4 SIGNS AND SYMPTOMS OF EXPOSURE 10.2.5 EMERGENCY MEDICAL PROCEDURES 10.3 EXPOSURE SOURCES AND CONTROL METHODS 10.4 CONTROL 10.4.1 PERSONAL HYGIENE PROCEDURES 10.4.2 STORAGE 10.4.3 SPILLS AND LEAKS

32 32 32 34 34 34 35 36 36 36 37 37 37 38 39 39 39 39 39 39 40 40 40 41 41 41 41

REFERENCES

43

INTRODUCTION

INTRODUCTION
Naphtha is a combination of hydrocarbons between C5 and C20. Originally the term naphtha designated as a colorless flammable liquid obtained from the ground in Persia. Later it is applied to a number of other natural liquid substances having similar properties. Naphtha term is usually limited to a class of colorless, volatile, flammable liquid hydrocarbon mixtures obtained as one of the more volatile fractions in the fractional distillation of petroleum (when it is known as petroleum naphtha), in the fractional distillation of coal tar (coal-tar naphtha), and in a similar distillation of wood as wood naphtha, it is having a wide application as a solvent for different organic

substances, such as fats and rubber, and in manufacturing of varnish. Common application is as lighter fluids and feedstock for different chemical processes. Because of its dissolving property it is vital as a cleaning fluid; it is also incorporated in certain laundry soaps. Coal-tar naphtha has greater solvent power than petroleum naphtha. Technically, gasoline and kerosene are considered as naphtha.

1.1

Types of Naphtha

There are two major types of Naphtha 1. Paraffinic naphtha 2. Heavy naphtha

1.1.1 Paraffinic naphtha

Generally speaking, less dense (lighter) naphtha have a higher paraffinic content. Therefore these are also referred as paraffinic naphtha. The important application of this naphtha is as a feedstock in the petrochemical production of olefins. Thats why they are sometimes referred as or light distillate feedstock (LDF). These naphtha types can also be called as straight run gasoline (SRG) or light virgin naphtha (LVN). When utilized as a feedstock in petrochemical steam crackers, naphtha is heated in the presence of water vapor and the absence of oxygen or air until the hydrocarbon molecules break apart. The initial or primary products of the cracking process are olefins (ethylene / Hydrodesulphurization of Naphtha

INTRODUCTION

ethene, propylene / propene and butadiene). When naphtha is used as a feedstock in catalytic reforming, the primary products are aromatics including benzene, xylene, and toluene. The olefins are widely used as feedstock for derivative units that produce plastics for example (polyethylene and polypropylene), synthetic fiber precursors (acrylonitrile), industrial chemicals (glycols for instance) while the aromatics are utilized for octane boosting in fuel blending as well as PET (polyethylene teraphthalate) feedstock, paint and coating solvents.

1.1.2 Heavy naphtha

The heavier or rather denser types are usually richer in naphthenic and aromatics and therefore also referred as naphthenic and aromatics (N & As). These can also be widely used in the petrochemical industry but more often are used as a feedstock for refinery catalytic reformers where they convert the lower octane naphtha to a higher octane product called reformate. Alternative names for these types are Straight Run Benzene (SRB) or Heavy Virgin Naphtha (HVN).

1.2

Production in Refineries

As we know that big sources of naphtha are refineries. Naphtha is actually obtained in petroleum refineries as one of the intermediate products from the distillation of crude oil. It is an intermediate liquid between the light gases in the crude oil and the heavier liquid kerosene. Naphtha is volatile, flammable and has specific gravity of about 0.7. The generic name 'naphtha' describes a range of different refinery intermediate products usually used in different applications. To complicate the matter further, similar naphtha types are often referred to by different names. The different naphtha is distinguished by: 1. Density 2. Paraffinic content 3. Olefinic content 4. Naphthenic content 5. Aromatic content

Hydrodesulphurization of Naphtha

INTRODUCTION

1.3

Hydro-treating

Hydro-treating processes specially aim at the removal of impurities such as sulfur and nitrogen from distillate fuels like naphtha, kerosene, and diesel by treating the feed with hydrogen at elevated temperature and pressure in the presence of a catalyst. Hydrotreating has been extended widely in recent years to atmospheric resides to reduce the sulfur and metal contents of resides for producing low-sulfur fuel oils. The operating conditions of treatment are a function of type of feed and the desulfurization levels desired in the treated product. The feed types considered are given here 1. Naphtha 2. Kerosene 3. Gas oils 4. Atmospheric resides or reduced crudes

1.3.1 Principal Impurities

The general principal impurities to be removed are; 1. Sulfur 2. Nitrogen 3. Oxygen 4. Olefins

1.3.2 Sulfur Species in Naphtha

Knowledge of the exact nature of the sulfur compounds in naphtha can help in determining the severity required in HDS. In addition, it can also reveal the nature of sulfur compounds that remain after treatment. This information provides better information of the function of catalysts and aid in selection of suitable catalysts on the basis of selectivity for the removal of the sulfur compounds. The amount and types of sulfur compounds present in the naphtha are determined by the source of the crude and its genesis. The sulfur compounds include elemental sulfur, hydrogen, sulfide, disulfide, sulfides, mercaptans and thiophenes. Characterization of sulfur compounds in naphtha

Hydrodesulphurization of Naphtha

INTRODUCTION

(particularly in hydro-treated naphtha) is very difficult because of very low concentrations.

1.4

Desulphurization Processes

A modern refinery is a highly integrated industrial plant, the main task of which is to efficiently produce high yields of valuable products from a crude oil feed of variable composition. Employing different physical and chemical processes such as distillation, extraction, reforming, hydrogenation, cracking and blending the refinery converts crude oil to higher value products. The main products are liquid petroleum gas, gasoline, jet and diesel fuels, wax, lubricants, bitumen and petrochemicals. Energy and hydrogen for internal and external use are also produced in a refinery. Currently, refineries meet changing societal needs concerning product specifications and quality by upgrading existing technologies and continuously developing advanced technologies. Changes in refining processes are made in response to external driving forces taking into account the inherent limitations of the refinery. Environmental restrictions regarding the quality of transportation fuels produced and the emissions from the refinery itself are currently the most important issues, as well as the most costly to meet. The primary goal of the recently proposed regulations (by the Directive of the European Parliament and the Environmental Protection Agency (EPA) Clean Air Act is to reduce the sulfur content of transportation fuels. The CO2 emitted by the refinery into the atmosphere is limited by the Kyoto protocol. According to various estimation models, $1015 billion in the European refinery industry and up to $16 billion in US and Canadian refineries will be invested in direct response to the new environmental cleanfuel legislation. Gasoline, diesel and non-transportation fuels account for 7580% of the total refinery products. Most of the desulfurization processes are therefore dealing with the streams forming of these end products. Sulfur present in the fuels leads to air pollution like SOx, generated by vehicle engines. In order to minimize the negative health and environmental effects of automotive exhaust emissions, the sulfur level in motor fuels is minimized. New sulfur limits of 30 to 50 ppm for gasoline and diesel marketed in the European Hydrodesulphurization of Naphtha

INTRODUCTION

10

community and the USA will be introduced starting from January 1, 2005. Germany has even passed legislation limiting the sulfur in diesel and gasoline to 10 ppm as of November, 2001. In fact, zero-emission and, as a consequence, zero levels of S are called for worldwide in coming 510 years. Such ultra-low-sulfur fuels requirements have consequences for the refinery.

1.5

Hydro-desulfurization

Hydro-desulfurization (HDS) is a catalytic chemical process widely used to remove sulfur from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur is to reduce the sulfur dioxide (SO2) emissions that comes from those fuels utilizing in automotive vehicles, aircraft, gas or oil burning power plants, railroad locomotives, ships, residential, industrial furnaces, and other forms of fuel combustion. Another important reason for removing sulfur from the naphtha streams within a petroleum refinery is that sulfur, even in very low concentrations, poisons the noble metal catalysts (platinum and rhenium) in the catalytic reforming units that are subsequently utilized to upgrade the octane rating of the naphtha streams. The industrial hydro-desulfurization processes include facilities for the capture and removal of the resulting hydrogen sulfide (H2S) gas. In petroleum refineries, the hydrogen sulfide gas is then subsequently converted into by-product elemental sulfur or sulfuric acid. In fact, the vast majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was by-product sulfur from refineries and other hydrocarbon processing plants. An HDS unit in the petroleum refining industry is also often referred to as a hydro-treater. Most of the petroleum refinery naphtha requires the removal of sulfur compounds down to very low levels (a few parts per million or less). That is usually accomplished in a catalytic chemical process called hydrodesulphurization which converts the sulfur compounds into hydrogen sulfidegas that is removed from the naphtha by distillation. The hydrogen sulfide gas is then captured in amine gas treating units and subsequently converted into byproduct elemental sulfur. Hydrodesulphurization of Naphtha

11

1.6

Reactions of Sulphur Removal

C-C-C-C-C-C-SH + H2 C-C-C-S-C-C-C +2H2 C-C-C-S-S-C-C-C +3H2 C-C-C = C-C + H2S C-C-C-C-C-C + H2S 2C-C-C + H2S 2C-C-C + 2H2S C-C-C-C-C-C-S

a. (Mercaptance) b. c. (Sulphide) (Disulphide)

d. (Thiophenic)

1.6.1 Catalysts
The catalyst consists of two parts, the catalyst support and the active elements. The support consists of solid substances with high porosity and able to withstand the high temperature, high pressure, and the environment effects encountered in HDS reactors. The support used by the HDS catalyst is alumina in the form of balls. The active elements are the metals deposited on the support in form of oxides. The principal types of catalyst used in the HDS service are 1. Cobalt (molybdenum on alumina support). This is the general catalyst for HDS service. The catalyst used in HDS is CoMo/Al2O3. 2. Nickel (molybdenum on alumina support). This is used especially for denitrification. 3. Cobalt (molybdenum and other metals on neutral support).

Hydrodesulphurization of Naphtha

LITERATURE SURVEY

12

LITERATURE SURVEY
2.1 History

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). In addition, naphtha may also be produced from coal tar, shale deposits, and tar sands. Most uses of petroleum refinery naphtha require the removal of sulfur compounds down to very low levels (a few parts per million or less).Although reactions involving catalytic hydrogenation of organic substances were known prior to 1897, the property of finely divided nickel to catalyze the fixation of hydrogen on hydrocarbon (ethylene, benzene) double bonds was discovered by the French chemist Paul Sabatier. Thus, he found that unsaturated hydrocarbons in the vapor phase could be converted into saturated hydrocarbons by using hydrogen and a catalytic metal. His work was the foundation of the modern catalytic hydrogenation process. Soon after Sabatier's work, a German chemist, Wilhelm Normann, found that catalytic hydrogenation could be used to convert unsaturated fatty acids or glycerides in the liquid phase into saturated ones. He was awarded a patent in Germany in 1902and in Britain in 1903, which was the beginning of what is now a worldwide industry. In the mid-1950s, the first noble metal catalytic reforming process (the Platformer process) was commercialized. In 1997, the commercial technology for controlling the sulfur content of full-range FCC naphtha was what is now called conventional hydrotreating. A number of technology providers offered conventional hydro-treating processes for full-range FCC naphtha and other naphtha streams. Collectively, these processes had accumulated considerable commercial experience. They were reliable and well-understood, and could accomplish the necessary degree of sulfur control. Conventional FCC naphtha hydro-treating processes are expensive because they are nonselective. In the course of removing sulfur, they also saturate essentially all of the olefins Hydrodesulphurization of Naphtha

LITERATURE SURVEY

13

present in FCC naphtha. Olefin saturation leads to high octane loss (> 10 numbers) and high hydrogen consumption, which account for the high cost of conventional hydrotreating. A number of new processes had reached Commercial status by the end of 1999 like Selective Hydro-treating, non-selectivehydro-treating, and sorption, Selective Hydrotreatingachieves desulfurization with little olefins saturation (and hence little loss of octane). Non-selective Hydro-treating + Octane Recovery achieves desulfurization with partial or total olefins saturation (with attendant octane loss), but recovers most of the lost octane by secondary reactions (e.g. isomerization). Sorption achieves desulfurization with little olefins saturation (and hence little loss of octane).The chemistry of naphtha hydrodesulfurization is well-established and relatively well- understood. In the decades that followed, various proprietary catalytic hydrodesulfurization processes have been commercialized. Currently, virtually all of the petroleum refineries worldwide have one or more HDS units.

2.2

Sulfur Removal Techniques

2.2.1 Hydro-treating
Hydro-treating is the one of more mature refining processes still practiced today. Refiners began using catalytic hydro-treating in the 1950 to remove undesirable material from refining products streams. This process effectively removes contaminants such as sulfur, nitrogen, olefins, metals and aromatics. The chemistry of hydro-treatment can be further divided into three categories 1. Hydro-dearomatization: This is used to remove aromatic impurities from the feedstock. 2. Hydro-nitrification: This is used to remove the nitrogen compounds from feedstock. 3. Hydro-desulfurization: This is used to remove impurities the sulfur compounds from the feedstock. The utility of most hydro-treating efforts is desulfurization. Sulfur hydrocarbons are present in crude oil with many varying forms. New product specification limit for the

Hydrodesulphurization of Naphtha

LITERATURE SURVEY

14

amount of sulfur present in finished products set by the environmental agencies is much stricter, thus greater efforts will be needed to remove more sulfur containing compounds throughout the fuel blending pool. Notably, more complex high boiling point sulfur compounds must be extracted from the blending pool to meet lower fuel specification depending upon the severity of the operation. Hydro-treating is done at elevated temperature and pressures. High temperature and pressure are needed to open the complex ring compounds and remove the sulfur molecules. Hydro-treating is a versatile cleanup step; however, its hydrogen consumption is very high. Most refineries are able to meet their hydrogen demand with hydrogen recovered from catalytic reforming. However as refiner intensify hydro-treatment efforts to meet tighter specification for products; hydrogen demand will increase much more. Consequently one option to balance hydrogen consumption is to construct outside hydrogen plants to meet present and future hydrogen needs.

2.2.2 Desulfurization
Desulfurization is a catalytic chemical process widely used to remove sulfur from natural gas and from refined petroleum products such as gasoline, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur is to reduce the sulfur dioxide (SO 2) emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion. Another important reason for removing sulfur from the naphtha streams within a petroleum refinery is that sulfur, even in extremely low concentrations, poisons the noble metal catalysts (platinum and rhenium) in the catalytic reforming units that are subsequently used to upgrade the octane rating of the naphtha streams. Two general methods of reducing the amount of sulfur have been developed, first involves the solvent extraction of the sulfur compounds and in second most of the sulfur compounds are decomposed by using of hydrocarbon of the original sulfur compounds.

Hydrodesulphurization of Naphtha

MARKET SURVEY

15

MARKET SURVEY
Naphtha, an intermediate product from refinery, is important for the manufacture of petrochemicals. Pakistan has the Naphtha production facility of around 0.7 to 0.8 million tons/ Annum. Nearly all Naphtha produced is exported, due to absence of Naphtha cracker unit in Pakistan. There are 5 major refineries around Pakistan producing Naphtha: PRL (Pakistan Refinery Limited), NRL (National Refinery Limited), ARL (Attock Refinery Limited) and BYCO (Formerly Bosicor), Pak Arab refinery (PARCO).The following table represents the exports of naphtha from January 2010 to February 2012 by Pakistan.

Months
February-2012 January-2012 December-2011 November-2011 October-2011 September-2011 August-2011 July-2011 June-2011 May-2011 April-2011 March-2011 February-2011 January-2011 December-2010 November-2010 October-2010 September-2010 August-2010 July-2010 June-2010 May-2010 April-2010 March-2010 February-2010 January-2010

Naphtha Units
51,880.00 72,463.00 49,547.00 45,505.00 75,733.00 50,912.00 81,247.00 78,719.00 78,110.00 40,790.00 78,150.00 88,741.00 30,903.00 81,944.00 63,965.00 78,570.00 59,859.00 65,190.00 94,606.00 32,545.00 77,998.00 50,835.00 53,135.00 41,092.00 81,140.00 30,442.00 MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT MT

Hydrodesulphurization of Naphtha

CAPACITY SELECTION

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CAPACITY SELECTION
Demand data for crude oil in Pakistan is given in the following graph from year 1980 to 2008.

Figure 3.1 To determine the capacity for our system, we need to forecast the capacity by extrapolation of the data given in the fig 3.1 given above. To have a safe approximation of the capacity we should extrapolate this demand data to year 2016, because plant erection time should also be considered at this stage. Following fig 3.2 shows the forecasted data for crude oil up to year 2016. Taking demand in year 2011 as a production in year 2016,

Hydrodesulphurization of Naphtha

CAPACITY SELECTION

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Production in year 2016 = 395 thousand barrels / day From Fig 3.2, demand in year 2016 is given as Demand in year 2016 = 475 thousand barrels / day So, Shortfall in year 2016 = 80 thousand barrels / day As, Volume percent of naphtha in crude oil = 21 % So, Capacity required in year 2016 to fulfill total naphtha demand = (Short fall in year 2016) (Volume Percent of naphtha in crude oil) Capacity required in year 2016 to fulfill total naphtha demand = 80 0.21 Capacity required in year 2016 = 16.8 thousand barrels / day

Now for a safe design we have to consider a value less than this calculated demand, because in the case of sudden decrease in the demand it can cause a huge loss of investment. Here we are considering half of this demand as our capacity for our design project i.e. Capacity Selected = 8.4 thousand barrels / day

Hydrodesulphurization of Naphtha

18

Fig 3.2Extrapolation of data for crude oil demand in Pakistan

Hydrodesulphurization of Naphtha

PLANT LOCATION AND SITE SELECTION

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PLANT LOCATION AND SITE SELECTION

The location of chemical plant has a crucial effect on the profitability and the scope for future expansion. Many factors must be considered in selecting a general plant site location. The procedure for choosing a specific plant location can be presented in a series of required steps. After the site is selected factors that go into getting facility built, including permitting and other necessary legal steps need to be considered. Following are the major factors should be considered while selecting a site for plant. 1. Raw Material Availability 2. Markets 3. Energy Availability 4. Climate 5. Transportation 6. Water Supply 7. Waste Disposal 8. Labor Supply 9. Taxation 10. Site Characteristics 11. Flood & Fire Protection 12. Community Factors

5.1.1 Raw Materials

The source of raw materials is the most influencing in selection of a plant site. It is particularly true when large volumes are consumer because storage and transportation changes can be reduced. Attention should be given to purchased price, distance from the source, purity and storage needs.

5.1.2 Markets
The location of markets or distribution centers affects the cost of product distribution and time as well. So proximity to major markets is important consideration. The markets are needed for the by-product as well as final product. Hydrodesulphurization of Naphtha

PLANT LOCATION AND SITE SELECTION

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5.1.3 Energy Availability

Power and steam are needed in large quantity in any plant so, fuel is an essential need. So, power and fuel can be combined as one single factor for selection of site. If plant needs large amount of coal or oil location near a mine is feasible.

5.1.4 Climate
If plant is located in a cold climate, cost may be increased by construction of protective shelters near process area. Contrary to this, special cooling towers shall be needed if prevailing temperatures are high. Excessive humidity and extreme weathers both have a serious effect on economic operation of the plant.

5.1.5 Transportation
Railroads and highways are common means of transportation in industries. The kind and quantity of materials determine the type to be used. Attention should be given to changes and condition of railroads too. The proximity to railroad center etc. should also be considered. Where possible, efforts should be made to have a site close to all three kinds of facilities, but certainly at least two are imperative.

5.1.6 Water Supply

The gasification plants consume large amounts of water for cooling of coming gases etc. the plant should be located where a dependable source of water is present. A large lake or river is preferable, although a deep well can do the job where needs are not too large. The level of existing water table can be obtained from local geological survey department. The temperature, salt contents, sand or silt, bacteriological contents and cost are important factors.

5.1.7 Waste Disposal

In recent years a number of legal restrictions has been placed upon the method of waste disposal of all 3 physical states. So, the selected site should have proper facilities for disposal of wastes. Attention should be given to potential needs for additional waste treatment facilities.

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5.1.8 Labor Supply

The type of labor available in the vicinity of the proposed site must be examined. Consideration should be given to prevailing pay-scales and number of working hours as well as variation in productivity of workers.

5.1.9 Taxation
State and local tax regulations on income state, unemployment insurance and similar items vary from one location to other. Infect zoning difficulties and obtaining the many required permits can be much important in term of cost and time delay than a number of other factors.

5.1.10 Site Characteristics

The land characteristics at a particular place should be examined carefully. The topography of land and soil should be considered as it has great effect on cost. Also even though no immediate expansion is planned, the plant should be constructed on a place where additional space is available.

5.1.11 Floods and Fire Protection

Many plants are located near rivers or oceans and have a great risk of flood or storms. The history of this kind of sites should be examined and the consequences of such incidents be examined. Protection against fire is also important factor to select a site. In case of major fire, assistance from surroundings should not be over looked.

5.1.12 Community Factors

The character and facilities of a community can affect the location of plant. If the least number of facilities for plant personnel does not exist, it is a burden for the plant to subsidize these facilities. Cultural facilities of community are important for growth. Schools, mosques, cinemas and gardens make a community progressive. The existence of low taxes can be good only when community is free of all debts.

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5.2

Selection Criteria

A number of different factors are described in the above section. We can consider any one or more than one factors as our basic criteria to select a location for our plant. Here we will consider the proximity to the raw material as basic factor for the location selection. For our project the raw material is basically the straight run naphtha from the crude distillation unit. So we need to locate our plant near some refinery which can provide the straight run naphtha from the crude distillation unit, otherwise we will require an installation of the crude distillation unit also the other streams from the crude distillation unit will be a problem to fix.

5.2.1 List of all Refineries in Pakistan

Pakistan has following nine different oil refineries located at different location along the country. The capacity data for these refineries is shown in table 5.1 1. Pak Arab refinery in Mehmood Kot in Muzaffar Garh District (PARCO), Punjab, Pakistan 2. Byco Oil Pakistan Limited in District Hub, Lasbela, Balochistan 3. Byco Petroleum Pakistan Limited (BPL) 4. Pakistan Refinery Limited (PRL) in coastal belt of Karachi, Pakistan 5. National Refinery Limited (NRL) in Keamari oils peers in Karachi 6. Attock Refinery Limited (ARL) 7. Enar Petroleum Refining Facility (EPRF) 8. Trans Aisa Refinery Limited (TRL) 9. Taba Refinery Limited (TRL)

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REFINERIES

CAPACITY Barrels / day m3 / day

16,000 16,000 4,800 2,400 8,300 7,300 480 15,300 12,100

Pak-Arab Refinery (PARCO) Byco Oil Pakistan Limited (BOPL) Byco Petroleum Pakistan Limited (BPL) Pakistan Refinery Limited (PRL) National Refinery Limited (NRL) Attock Refinery Limited (ARL) Enar Petroleum Refining Facility (EPRF) TransAisa Refinery Limited (TRL) Taba Refinery Limited (TRL)

100,000 100,000 30,000 15,000 52,000 46,000 3,000 96,000 76,000

Table 5.1 Pak-Arab Refinery (PARCO) has high capacity and safe location according the recent situation in Pakistan, any location near PARCO seems to be the best location for the project because the plant must be installed where availability of raw material is easy and guaranteed.

Hydrodesulphurization of Naphtha

PROCESSES SELECTION

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PROCESSES SELECTION
There are several processes for the hydrodesulphurization of naphtha. Some of these are as follows. 1. Prime G+ process 2. SCAN fining process 3. CD hydro/CDHDS process 4. ISAL process

6.1

Prime G+

6.1.1 Basic chemistry

Mild hydrogenation to convert mercaptans to high boiling sulfides, then selective hydrodesulphurization is done.

6.1.2 Process configuration

Full naphtha treated for mercaptan conversion followed by light naphtha splitter, medium and heavy naphtha then treated over a catalyst.

6.1.3 Reaction conditions

320 psig and 570 F 1st reactions

6.1.4 Strengths
Low pressure low capital cost low use of hydrogen high yield.

6.1.5 Weaknesses
Some octane loss.

6.1.6 Commercial units

This process is commercially available.

6.2

CD hydro

6.2.1 Suited for boil range

This process is suitable for light naphtha.

Hydrodesulphurization of Naphtha

PROCESSES SELECTION

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6.2.2 Basic Chemistry

Convert mercaptans to heavy boiling sulfides.

6.2.3 Process Configuration

Catalyst placed on the top trays inside the splitter of light naphtha and medium and heavy naphtha.

6.2.4 Reaction condition

75 psig and 214 F

6.2.5 Strengths
Complete mercaptans removal Ability to gain octane No waste streams

6.2.6 Weaknesses
Catalyst cost is high Larger columns are used It cannot remove larger disulfides

6.2.7 Commercial units

This process is commercially available.

6.3

CD HDS

6.3.1 Suited for boil range

Medium and heavy naphtha

6.3.2 Basic Chemistry

Selective hydrodesulphurization

6.3.3 Process Configuration

Catalyst placed on top and bottom trays inside medium and heavy naphtha splitter columns

6.3.4 Reaction condition

250 psig and 489 F 250 psig and 623 F

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6.3.5 Strengths
Reason able octane loss Low consumption of hydrogen High yield

6.3.6 Weaknesses
High catalyst cost

6.3.7 Commercial units

This process is in design phase.

6.4

ISAL Process

6.4.1 Suited for boil range

Medium and heavy naphtha

6.4.2 Basic Chemistry

Non selective HDS followed by isomerization for octane recovery.

6.4.3 Process Configuration

Single reactors with two catalyst flow scheme like conventional hydro treater.

6.4.4 Reaction condition

600 psig

6.4.5 Strengths
Ability to recover full octane

6.4.6 Weaknesses
High pressure High capital cost Yield loss at full octane recovery High hydrogen consumption

6.4.7 Commercial units

This process is commercially not available.

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6.5

Scan fining process

6.5.1 Suited for boil range

Medium and heavy naphtha.

6.5.2 Basic Chemistry

Selective hydrodesulphurization

6.5.3 Process Configuration

It uses a conventional hydrodesulphurization unit.

6.5.4 Reaction condition

370 psig and 608 F

6.5.5 Strengths
High yield Low octane loss. Low hydrogen consumption Low capital cost

6.5.6 Weaknesses
Some octane loss.

6.5.7 Commercial units

This process is commercially available.

6.6

Selection of commercial HDS process

The following points are considered in order to select the suitable process. The boil range of the feed suitable Basic chemistry Process configuration Reaction conditions Strengths and weaknesses Commercial units and references for each process Now from all the processes, a fair comparison can be made for the selection of the HDS process for naphtha. First, we can shorten the list of processes available by taking commercial units as criteria. As CD HDS and ISAL are the processes not available Hydrodesulphurization of Naphtha

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commercially, so these will be cut down from the list. Now feed boiling range can be made as criteria to further shorten the available processes list. In our process we are considering the heavy naphtha cut as our feed, now the only process in the short list which does not support the heavy feed is CD Hydro. Now the short list includes only Prime G+ andSCAN fining processes. Also the basic chemistry required for our process is the selective hydro-desulfurization reactions and the only process in the short list fulfilling this requirement is the SCAN fining process. SCAN fining is the abbreviation of Selective Catalytic Naphtha hydro fining. This process provide very big advantage of conventional HDS configuration, this means that with a very little modifications the conventional HDS plant can be upgraded to the SCAN fining and this is a very major advantage due to the lowered capital cost.

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PROCESS DESCRIPTION
The refinery HDS feed stocks (naphtha, kerosene, diesel oil and heavier oils) contain a wide range of organic sulphur compounds, including thiols, thiophenes, organic sulphides and disulphides, and many others. These organic sulfur compounds are products of the degradation of sulphur containing biological components, present during the natural formation of the fossil fuel, petroleum crude oil. When the HDS process is used to desulphurize refinery naphtha, it is necessary to remove the total sulphur down to the parts per million ranges or lower in order to prevent poisoning the noble metal catalysts in the subsequent catalytic reforming of the naphtha.

7.1

Naphtha Hydro-desulphurization Process

Naphtha Hydro-desulfurization is an essential step to produce cleaner gasoline from different feed stocks: straight run, condensate, cracked naphtha feed stocks (Coker, VB, cracked catalytic naphtha). The feed becomes suitable for subsequent treatments after the process of hydrodesulfurization. 1. Catalytic reforming to improve octane 2. Hydrogen production via steam reforming

7.1.1 Pre-treatment
First step is pre-treatment. In pre-treatment, feed is treated with hydrogen in the presence of a catalyst, under suitable operating conditions so that feed contaminants may be removed.

7.1.2 Charge Pump P-101

The purpose of pump is basically to deliver the feed at high pressures. The feed enters the pump at low pressure and exits at higher pressures. Naphtha as feed enters the HDS unit

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at 104F through charge pump P-101 and leaves the pump at 462 psig with same temperature.

7.1.3 Mixing of Hydrogen Gas with Naphtha

Hydrogen gas coming from hydrogen plant or CAT reforming unit after passing through hydrogen compressor C-101 mixes with Naphtha feed at 415 Psig.

7.1.4 Effluent Heat Exchanger E-101

Heat exchanger is used so that it reduces or increases the temperature of any stream by exchanging heat with other stream where temperature difference acts as a driving force. The hydrogen/Naphtha mixture enters effluent heat exchanger E-101 where its temperature rises to 450F and pressure is 393 Psig.

7.1.5 Fired Heater H-101

Fired heater is also a heat exchanger. Mixture is then further heated to 606 F in a feed heater H-101 with pressure of 371 Psig. Now this feed is ready for reaction.

7.1.6 Reactor V-101

A reactor is the unit process where the conversion takes place via a chemical reaction which may be supported by a catalyst or a group of catalysts. This heated feed/hydrogen mixture enters the reactor V-101 at the top where desulfurization takes place. The desulfurizer reactor contains Co-Mo catalyst placed on alumina. The effluents of the reactor are; 1. Desulfurized naphtha 2. Excess hydrogen 3. H2S

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7.1.7 Effluent Heat Exchanger E-101, Effluent Cooler E-102 and Effluent Trim Cooler E-103
The effluents leave the reactor at 608F and 327 Psig and enter the feed effluent heat exchanger E-101, effluent cooler E-102 and effluent trim cooler E-103 in succession, where they are partially condensed and cooled to 104F at 289 psig. These consecutive heat exchangers perform their duty to cool the product from the reactor to 104oF.After passing these three heat exchangers the feed is ready to separate in the flash separator.

7.1.8 Separator V-102

A separator is a unit operation where the separation between two phases takes place. The cooled and condensed effluents then flow to high pressure separator V-102. Here separation between the vapor and the liquid phases takes place. The vapors from this separator drum contain H2S, light hydrocarbons formed as a result of desulfurization reactions and excess hydrogen. These vapors are purged and sent out of units battery limits.

7.1.9 Stripper V-103

The liquid from V-102 is preheated through a heat exchange with the stripper bottom in heat exchanger E-105 before charging to the stripper column V-103, where the dissolved hydrogen and H2S contained in the HP separator liquid is removed as overhead product. The gross overhead product from V-103 is partially condensed through heat exchanger E104. The uncondensed vapor, containing most of the separated H2S, is sent to an amine unit for H2S recovery. The liquid is refluxed back to the column through pump P-103.

7.1.10 Heat exchanger E-105

The liquid obtained as bottom product from separator Drum V-102 is pre-heated in heat exchanger E-105 to 360F. This pre heated liquid is then charged to stripper re-boiler flash column.

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7.1.11 Heat Exchanger E-104

Dissolved hydrogen and H2S contained in HP separator liquid are removed as overhead products, and are partially condensed through heat exchanger E-104.

7.1.12 Amine Unit

The uncondensed vapor, containing most of the separated H2S, is sent to an amine unit for H2S recovery.

7.1.13 Pump P-103

The liquid is refluxed back to the column through pump P-103.

7.1.14 Fired Heater H-102

The column is reboiled with a fired heater H-102. The bottom recirculation is provided by P-102.

7.1.15 Heat exchangers E-105 and E-106

The stripper bottom product is cooled by heat exchange with incoming feed in E- 105 and next in E-106 to 100F before going out of units battery limits.

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PHYSICAL AND CHEMICAL PROPERTIES

Naphtha is colorless (kerosene odor) or red-brown (aromatic odor) liquid and is insoluble in water. It is incompatible with strong oxidizers. The following data show the properties in detail.

8.1

Physical data

1. Molecular weight: 100215 g/mol (approximately) 2. Density: 0.750.785 g/cm3 3. Boiling point (at 760 mm Hg): 150 to 220 degrees C (302 to 428 degrees F) (approximately) 4. Specific gravity (water = 1): 0.86 to 0.89 5. Vapor pressure at 20 degrees C (68 degrees F): Less than 5 mm Hg 6. Solubility: Insoluble in water; miscible in absolute alcohol, benzene, toluene, chloroform, carbon disulfide, carbon tetrachloride oils (except castor oil), and xylene.

8.2

Reactivity Profile

NAPHTHA is incompatible with strong oxidizing agents such as nitric acid. Charring may occur followed by ignition of unreacted material and nearby combustibles. In other settings, mostly unreactive. Not affected by aqueous solutions of acids, alkalis, most oxidizing agents, and most reducing agents. Burns when heated sufficiently or when ignited in the presence of air. May be ignited by strong oxidizing agents. Conditions contributing to instability are Heat, sparks, open flames, and other sources of ignition. Incompatibilities are Contact between coal tar naphtha and strong oxidizers such as chlorine and chlorine dioxide should be avoided.

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8.3

Flammability

1. Flash point: 37.8 to 42.8 degrees C (100 to 109 degrees F) (closed cup) 2. Auto ignition temperature: 277 degrees C (531 degrees F) 3. Extinguishant: For small fires use dry chemical, carbon dioxide, water spray, or regular foam. Use water spray, fog, or regular foam to fight large fires involving coal tar naphtha.

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USES OF NAPHTHA
9.1 Catalytic Reforming

Catalytic reforming is an important refinery process for the manufacture of the gasoline from naphtha. Straight run naphtha from crude oil distillation consists mainly of paraffins and naphthenes. It has a low octane number and cannot be used for gasoline blending. The reformate octane number can be increasing the process severity, that is increasing the reactor temperature or decreasing the space velocity. Dehydrogenation reactions convert naphthenes to aromatics with higher octane number. Dehydrocyclization reactions convert normal paraffins to naphthenes and isomerization of n-paraffins to branched hydrocarbons. Naphtha with high naphthenes contents are preferred fed for the catalytic reforming. The reforming process also produces hydrogen gas which can be used for the hydro-desulfurization. Naphtha feed for the reformer unit comes from the naphtha desulfurization unit where naphthas sulfur and nitrogen are both reduced to below 0.5 ppm.

9.2

Aromatic Production

Benzene, toluene and xylene are the important feedstocks for the petrochemical industry. Benzene ranks in the top 20 chemicals worldwide in terms of production volumes. Benzene is used in the manufacturer of plastics, resins, nylon, synthetic fibers, rubber, lubricants, detergents, drugs, pesticide and in many other industries. The catalytic reforming of naphtha is also used for the production of aromatics such as benzene, toluene and xylenes. The only difference from the cat reformer for motor gasoline is that reforming operation is carried out at a higher severity in continuous catalytic regeneration configuration. Aromatics from reformate are separated from non -aromatics by solvent extraction.

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9.3

Fertilizer/Petrochemical Industry

Naphtha is used as feedstock for the manufacture of the nitrogen fertilizer such as urea, ammonium nitrate, ammonium sulfate and so on. In region where natural or associated gas is not available, naphtha is the professional feedstock. Naphtha is also used for the manufacturing of the methyl alcohol with large industrial demand. Naphtha is gasified and next reacted at high temperature with steam over nickel catalyst that converts naphtha to carbon monoxide and hydrogen. Carbon monoxide reacts with more steam to produce more hydrogen and carbon dioxide. Hydrogen is reacted with nitrogen from air to form ammonia.

9.4

Naphtha Steam Cracker

Naphtha is one of basic raw material for the production of the ethylene and propylene. Ethylene is the largest volume produced chemical produced worldwide. Ethylene has no direct use but used exclusively as building block. Ethylene, propylene and C4 olefins are used for the production of the plastics, films textiles and pharmaceuticals and so on. The bulk of the worldwide commercial production of olefins is based on the thermal cracking of naphtha or heavier hydrocarbons with steam. The process is called pyrolysis, or steam cracking. Pyrolysis converts heavier hydrocarbon into the small fractions primarily ethylene and propylene by removing hydrogen.

9.5

Power Plant Fuel

Naphtha is increasingly being use as the fuel for the gas based power plants or liquefied natural gas. Naphtha as fuel cannot compete with natural gas due to higher price but because of the shortage of natural gas feedstock, power plant production in many regions of the worlds use the naphtha as fuel, to meet the requirement of the electric power. Naphtha with high aromatic content can be used. Net heat of combustion is 1130 KJ/Kg with much more than the naphtha on per unit volume basis. Use of naphtha in place of gas requires the high operating conditions. Also use of naphtha result in higher corrosion rate due to sulfur in the naphtha which in turn causes shorter run length.

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9.6

Other Applications

1. Industrial solvents and cleaning fluids 2. A commonly available general purpose solvent designated as "VM&P" naphtha, which stands for "varnish makers' and painters'" 3. An oil painting medium 4. An ingredient in shoe polish 5. An ingredient in some lighter fluids for wick type lighters such as Zippo lighters 6. An adulterant to petrol 7. A fuel for portable stoves and lanterns, camp fuel. 8. As a coating for elemental lithium metal, to prevent oxidation (mineral oil is also used for this purpose) 9. As the working fluid (and sometimes, fuel) in the (external combustion) naphtha engine. 10. As a cleaning solution for watch parts during servicing.

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SAFETY & ENVIRONMENT STUDY

10.1 Introduction
Environmental impact assessment is defined as a process of identifying, predicting, evaluating and mitigating the biophysical, social, and other relevant effects of development proposals prior to major decisions being taken and commitments made The impacts identified by the environment impact assessment may be positive or negative. Positive impacts will be an advantage for the environment whereas the negative impacts will be required to reduce to make the project practical.

10.2 Social and Healthcare Impacts

The social and health impacts of naphtha can be described as;

10.2.1 Routes of Exposure

Exposure to naphtha can occur through inhalation, ingestion, and eye or skin contact.

10.2.2 Impacts on Animals

Naphtha is an irritant and has caused damage to the liver, kidneys, and spleen in experimental animals. The lowest lethal concentration (LC) reported in rats is 1,600 ppm for 6 hours. This exposure also resulted in behavioral changes that included somnolence. Damage to the liver, kidneys, and spleen of experimental animals has been reported, but no further information was available on the exposures causing these effects.

10.2.3 Impacts on Human

There are no well documented reports of industrial injury resulting from the inhalation of naphtha; however naphtha is expected to be an irritant of the skin, eyes, and mucous membranes and a central nervous system depressant. A general discussion of the toxicity of naphtha indicated that exposures to high concentrations would result in central nervous system depression and that direct contact between the liquid and the skin could result in "chapping" and possibly photosensitivity if contact was repeated. Naphtha may cause

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skin irritation due to its defatting action. Skin burns may also result if the liquid is held in contact with the skin by contaminated clothing. Because of the benzene content of the naphtha, exposures could be expected to result in blood changes such as leukopenia, aplastic anemia, or leukemia. Cardiovascular system and respiratory system effects are also considered potential responses to exposures naphtha.

10.2.4 Signs and Symptoms of Exposure

No signs or symptoms of exposure to naphtha have been reported in humans and animals.

10.2.5 Emergency Medical Procedures

Remove an incapacitated worker from further exposure and implement appropriate emergency procedures (e.g., those mostly listed on the Material Safety Data Sheet required by OSHA's Hazard Communication Standard). All workers should be familiar with emergency procedures, the location and proper use of emergency equipment, and methods of protecting themselves during rescue operations.

10.3 Exposure Sources and Control Methods

The following operations may involve naphtha and lead to worker exposures to this substance 1. The manufacture and transportation of naphtha 2. Use as a solvent Methods that are effective in controlling worker exposures to coal tar naphtha, depending on the feasibility of implementation, are as follows Process enclosure Local exhaust ventilation General dilution ventilation Personal protective equipment

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10.4 Control
10.4.1 Personal Hygiene Procedures
If coal tar naphtha contacts the skin, workers should immediately wash the affected areas with large amounts of soap and water, and seek medical attention immediately. Clothing contaminated with naphtha should be removed immediately, and provisions should be made for the safe removal of the chemical from the clothing. Persons laundering the clothes should be informed of the hazardous properties of naphtha, particularly its potential for causing eye, skin, and mucous membrane irritation. A worker who handles naphtha should thoroughly wash hands, forearms, and face with soap and water before eating, using tobacco products, using toilet facilities, applying cosmetics, or taking medication. Workers should not eat, drink, use tobacco products, apply cosmetics, or take medication in areas where naphtha or a solution containing naphtha is handled, processed, or stored.

10.4.2 Storage
Naphtha should be stored in a cool, dry, well-ventilated area in tightly sealed containers that are labeled in accordance with OSHA's Hazard Communication Standard. Containers of naphtha should be protected from physical damage and ignition sources, and should be stored separately from strong oxidizers such as chlorine and chlorine dioxide.

10.4.3 Spills and Leaks

In the event of a spill or leak involving coal tar naphtha, persons not wearing protective equipment and clothing should be restricted from contaminated areas until cleanup has been completed. The following steps should be undertaken following a spill or leak. 1. Do not touch the spilled material; stop the leak if it is possible to do so without risk. 2. Notify safety personnel. 3. Remove all sources of heat and ignition. 4. Ventilate the area of the spill or leak. 5. Water spray may be used to reduce vapors, but the spray may not prevent ignition in closed spaces. Hydrodesulphurization of Naphtha

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6. For small spills, take up with sand or other noncombustible absorbent material and place into closed containers for later disposal. 7. For large liquid spills, build dikes far ahead of the spill to contain the coal tar naphtha for later reclamation or disposal.

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References
1. http://wiki.answers.com/Q/What_is_the_chemical_formula_of_naphtha 2. http://encyclopedia2.thefreedictionary.com/Naptha 3. http://en.wikipedia.org/wiki/Naphtha 4. http://www.globalspec.com/reference/25508/203279/chapter-two- distillatehydrotreating 5. http://peakholding.com.pk/Commodities.htm

6. Surinder Parkash, Ph.D., Petroleum Fuels Manufacturing Handbook, ELSVIER publishers, 2010. 7. http://en.wikipedia.org/wiki/Hydrodesulfurization#Catalysts 8. http://en.wikipedia.org/wiki/Petroleum_naphtha 9. http://www.che.lsu.edu/COURSES/4205/2000/Mattson/HDS.htm 10. Syed Ahmad Ali and Nadir A. Al-Baghli,Overview of FCC Gasoline Post-treating Technologies. 11. http://www.ocac.org.pk 12. http://www.indexmundi.com/energy.aspx?country=pk&product=oil&graph=cons 13. http://www.osha.gov/SLTC/healthguidelines/naphtha-coaltar/recognition.html 14. R. K. Sinnott, Chemical Engineering Design, Chemical Engineering, Volume 6, Fourth Edition, 2005. 15. http://en.wikipedia.org/wiki/List_of_oil_refineries 16. http://www.kiefersworld.com/refinery-distillation/naphtha-hydrodesulfurizationprocess.html Hydrodesulphurization of Naphtha