CHAPTER # 01

Introduction & History

INTRODUCTION & HISTORY

1.1. HISTORY Of CRUDE OIL:
Petroleum is a complex liquid mixture of organic compounds. It is generally defined as an oily flammable bituminous liquid that may vary from almost colorless to black, occurs in many places in the upper strata of the earth, is a complex mixture of hydrocarbons with small amounts of other substances, and is prepared for use as gasoline, naphtha, or other products by various refining process. The first recorded use of petroleum dates back over 5000 years ago when it was recognized that the heavier derivatives of petroleum (asphalts) could be used for caulking and as an adhesive for jewelry and construction purposes. There is also documented use of asphalt for medicinal purposes. Approximately 2000 years ago, Arabian scientists developed methods for distillation of petroleum which were introduced into Europe by way of Spain. Interest in petroleum was also documented in china since petroleum was encountered when drilling for salt and appears on documents of the third century A.D. The Baku region of northern Persia was also reported (by Marco polo in 1271 1273) to have a commercial petroleum industry. The interest in petroleum continued up to modern times with an increasing in naphtha when it was discovered that this material could be used as an illuminant and as a supplement to asphaltic incendiaries for use during warfare. The naphtha of that time was obtained from shallow wells or by the destructive distillation of asphalt. This can perhaps be equated to the modern day cooking operations where the overall objective of the process is to convert residue into liquid fuels. The modern oil industry began in 1859 with the discovery and subsequent commercialization of petroleum in Pennsylvania (Bell, 1945). After the completion of first well (by Edurn Drake), the surrounding areas were 1-1

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Introduction & History

immediately leased and extensive drilling took place, (crude oil output in the united states increased to approximately 10 million bbl in 1874.

In 1861 the first cargo oil, contained in wooden barrels, was sent across the Atlantic to London, and by the 1870s refineries, tank cars, and pipelines had become characteristic features of the industry. The end of the nineteenth century was characterized by the opening up of the oil fields in the Far East. At the outbreak of World War 1 in 1914, the two major producers were the United States and Russia but supplies of oil were also being obtained from Indonesia, Romania, and Mexico. During the 1920s and 1930s, attention was also focused on other area for oil production such as the United States, the Middle East, and Indonesia.

In the past 1945 era, Middle Eastern countries continued to rise in importance because of new discoveries of vast reserves. The United States, though continuing to be the biggest producer, was also the major consumer and thus was not a major exporter of oil. At present time, many countries are recognized have reserves of crude oil. At current rates of production, proven oil reserves are sufficient for only 30 years and more reserves need to be discovered to replace those being consumed. For example, oil production from the organization of Petroleum Exporting countries (OPEC) grew by more than 13 % during 1986 with Saudi Arabias production increasing by some 45 % during the year. In the non-OPEC countries, the decline in production was realized predominantly by the United States where output decreased by 3 %. In fact, according to these data, the U.S has less than 10 years of proven reserves at the current rate of output compared with more than 90 years of output in Saudi Arabia or an average of some 85 years of output at current 1-2

CHAPTER # 01

Introduction & History

production rates for the whole Middle Eastern countries. In addition, the United States is one of the largest importers of petroleum. In summary, the world oil consumption increased by 2.5 % in 1986 and reached 59.9 million bbl / day. This is the highest rate of growth since 1978.

History of Petroleum Refining and Oil Field in Pakistan:

First oil well Kundal near Mianwali was drilled in 1866. In 1915, the first oil field of Pakistan was discovered by Attock Oil Company, with the passage of time, other fields such as Dakni, Dhalian, Joyamir, Balkser, Dhernal, Dhowdak, Toot, Mianal, Badeen was discovered in Pakistan. Different oil companies are searching for oil and gas such as PPL (Pakistan Petroleum Ltd), OGDC (OIL & GAS Development Corporation), UNION TEXAS LASMO. The first oil refinery by the name of Attock oil refinery Ltd in Pakistan came on stream in 1922, with capacity of 25000 bbl / day but the present capacity is about 40000 bbl / day. Second oil Refinery (Pakistan Refinery Ltd) was started from 1962 whose present capacity is about 50000 bbl / day. Third Oil refinery (National Refinery Ltd) was established in 1963 whose capacity is about 65000 bbl / day. Pakistan is importing crude oil from Saudi Arabia, Iran, United Arab Emirates, etc. It is hoped that the dream of self sufficiency of Pakistan is production of oil will be fulfilled (inshallah).

ORIGIN OF PETROLEUM:
Petroleum is by far the most commonly used liquid fuel source. Since there is a wide variation in the properties of crude Petroleum, the proportions in which the different fractions occur vary with origin. Thus some crude oils have higher proportions of the lower boiling components where as others have higher proportions of residuum (asphaltic components).

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Introduction & History

Of the several theories advanced concerning the origin of petroleum, the theory of vegetal origin is the most widely accepted today, it holds that enormous quantities of gelatinous vegetation accumulated in clays and sands along seacoasts or lakes. Shifting currents then buried the organic material in layers of sediment which protected it from the normal processes of decay. Subsequent changes in the earth structure eventually subjected the entrapped vegetal matter to enormously high pressures and temperatures which brought about a type of semi destructive distillation. This along with other metamorphic processes resulted in the formation of petroleum. Geologic studies indicate that petroleum that probably was not formed in the pools where it is founds today. The deposits of crude petroleum were undoubtedly formed near seashores, but the action of the surrounding water gradually shifted the location of the oil pool. After a period of many centuries, the oil was forced through layers of porous rock strata until it finally became entrapped under a dome capped by hard rock. This made it impossible for the gas or oil to escape, and the water kept the pool of oil under pressure.

PRODUCTION OF CRUDE OIL:

In drilling for oil, the oil retaining cap rock above the deposit is penetrated, and the existing pressure forces the oil, gas, and some water to the surface. An attempt is made to locate the bottom of the well at the richest part of the oil bearing rock. This procedure makes it possible to keep out much of the water which would otherwise come up with the oil and gas. As the petroleum is removed from the underground deposit, the water moves in to take its place. Eventually the material under pressure decreases to the point where it will no longer force the oil and gas to the surface. When this occurs, gas or water may be pumped back into the well to increase the pressure and force the crude oil from the pool. 1-4

CHAPTER # 01

Introduction & History

Under the natural pressure of the well, this may run to 1000 psi or higher, great quantities of hydrocarbon vapors are absorbed in the liquid petroleum and much liquid is held in suspension in the gases. As the crude and gas are pumped from the well, they are passed through a separator or trap, where the liquid and the gases are separated. After a preliminary purification process in a field treating plant, the crude oil is pumped through pipelines to the refinery. This treating plant reduces the dirt and water in the crude oil to less than 3% so as to minimize pipe-line troubles.

Types of crude oil:

Petroleum oils or crude oils are brownish green to black liquids composed chiefly of carbon and hydrogen. They contain many thousands of individuals compounds ranging from light gases such as methane to heavy asphaltic materials to heavy asphaltic materials that are solid when separated from the oil. Crudes are commonly classified according to the residue from their distillation. This deposits on the relative contents of three hydrocarbons namely paraffins, napthenes, and aromatics.

1. Asphaltic Base:
Containing very little paraffin wax and a residual primarily as asphaltic (Predominantly condensed aromatics). Sulphur, oxygen and nitrogen contents are often relatively high. Light and intermediate fractions have high percentage of napthenes. These crude oils are particularly suitable for making high quality gasoline, machine oils and asphalt.

2. Paraffin Base:
Containing little or no asphaltic materials, are good sources of paraffin wax, quality motor lube oils and high grade kerosene. They usually have lower nonhydrocarbon content than do the asphalt base crudes. 1-5

CHAPTER # 01
3. Mixed Base:

Introduction & History

Containing considerable amounts of both wax and asphalt. Virtually all products can be obtained, although at lower yields than from the two classes.

COMPOSITION OF CRUDE OIL (PETROLEUM):

Crude oil has physical and chemical characteristics that vary widely from one production field to another and even within the same field. The roughest form of characterization is the classification of light and heavy crude. Because crude oil is composed essentially of hydrocarbon molecules plus organic compounds of Sulphur, oxygen and nitrogen as well as compounds containing metallic constituents, particularly vanadium, nickel, iron and copper. Crude oil specific gravity varies inversely with its H/C atomic ratio, and for various crude oils specific gravities will range from 0.7 to 1.0; they are often expressed in degrees API (American Petroleum Institute) which will vary between 70 and 5.

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CHAPTER # 01

Introduction & History

Figure:

Principal Petroleum Products, their boiling range

temperatures and their number of carbon atoms.

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CHAPTER # 01 OIL REFINERY:

Introduction & History

Raw or unprocessed crude oil is not generally useful. Although light, sweet (low viscosity, low sulfur) crude oil has been directly as a burner fuel for steam vessel propulsion, the lighter elements form explosive vapors in the fuel tanks and are therefore hazardous, especially in warships. Instead, the hundreds of different hydrocarbon molecules in crude oil are separated in a refinery into components which can be used as fuels, lubricants and as feedstock in petrochemical processes that manufacture such products as plastics, detergents, polyesters. Petroleum, fossil fuels are burned in internal combustion engines to provide power for ships, automobiles, aircraft engines, lawn movers, chainsaws and other machines. Different boiling points allow the hydrocarbons to be separated by distillation. Since the lighter liquid products are in great demand for use in internal combustion engines, a modern refinery will convert heavy hydrocarbons and lighter gaseous elements into these higher value products. Oil can be used in a variety of ways because it contains hydrocarbons of varying molecular masses, forms and lengths such as paraffins, aromatics, naphthenes (or cycloalkanes), alkenes, dienes, alkynes while the molecules in crude oil include different atoms such as sulfur and nitrogen, the hydrocarbons are the most common form of molecules, which are molecules of varying lengths and complexity made of hydrogen and carbon atoms, and a small number of oxygen atoms. The differences in the structure of these molecules account for their varying physical and chemical properties, and it is this variety that makes crude oil useful in a board range of applications. Once separated and purified of any contaminants and impurities, the fuel or lubricant can be sold without further processing. Smaller molecules such as isobutene and propylene or butylenes can be recombined to meet specific octane requirements by processes such as alkylations, or less commonly, dimerization. Octane grade of gasoline can also be improved by catalytic 1-8 solvents, elastomers, and fibers such as nylon and

CHAPTER # 01

Introduction & History

reforming, which involves removing hydrogen products such as aromatics. Intermediate products such as gasoils can be reprocessed to break heavy, long-chained oil into a lighter short-chained one, by various forms of cracking such as fluid cracking, thermal cracking, and hydrocracking. The final step in gasoline production is the blending of fuels with different octane ratings, vapor pressures, and other properties to meet product specifications. -Oil refineries are large scale plants, processing about a hundred thousand to several hundred thousand barrels of crude oil a day. Because of the high capacity, many of the units operate continuously, as opposed to processing in batches, at steady state or nearly steady state for

months to years. The high capacity also makes process optimization and advanced process control very desirable.

Major Products:
Major products are usually grouped into three categories: light distillates (LPG, gasoline, and naphtha), middle distillates (kerosene, diesel), heavy distillates and residuum (heavy fuel oil, lubricating oils, wax, and asphalt). This classification is based on the way I think snakes mate oil is distilled and separated into fractions (called distillates and residuum) as in above drawing. Liquid petroleum gas (LPG) Gasoline (also known as Petrol) Naphtha Kerosene and related jet aircraft fuels. Diesel fuel Fuel oils Lubricating oils Paraffin wax 1-9

CHAPTER # 01
Asphalt and tar Petroleum coke

Introduction & History

Common units:
Desalter unit washes out salt from the crude oil before it enters the Atmospheric distillation unit distills crude oil into fractions. Vacuum distillation unit further distills residual bottoms after Naphtha hydrotreater unit uses hydrogen to desulfrize naphtha from

atmospheric distillation unit.

atmospheric distillation. atmospheric distillation. Must hydro treat the naphtha before sending to a catalytic reformer unit. Catalytic reformer unit is used to convert the naphtha-boiling range molecules into higher octane reformate (reformer product). The reformate has higher content of aromatics and cyclic hydrocarbons. An important by product of a reformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreaters or the hydrocracker. Distillate hydrotreater unit desulfrizes distillates (such as diesel) after Fluid catalytic cracker (FCC) unit upgrades heavier fractions into Hydrocracker unit uses hydrogen to upgrade heavier fractions into Visbreaking unit upgrades heavy residual oils by thermally cracking Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to atmospheric distillation. lighter, more valuable products. lighter, more valuable products. them into lighter, more valuable reduced viscosity products. organic disulfides. Cooking units (delayed cooking, fluid Coker, and flexicoker) process

very heavy residual oils into gasoline and diesel fuel, leaving petroleum coke as a residual product. 1-10

CHAPTER # 01
Alkylation unit produces blending. Dimerization unit

Introduction & History

high-octane component for gasoline

converts olefins into higher-octane gasoline

blending components. For example, butanes can be dimerized into isooctane which may subsequently be hydrogenated to form isooctane. There are also other uses for Dimerization. Isomerization unit converts linear molecules to higher-octane branched molecules for blending into gasoline or feed to Alkylation units. Steam reforming unit produces hydrogen for the hydrotreaters and Liquefied gas storage units for propane and similar gaseous fuels at hydrocracker. pressure sufficient to maintain in liquid form. These are usually spherical vessels or bullets (horizontal vessels with rounded ends. Storage tank for crude oil and finished products, usually cylindrical, with some sort of vapor emission control and surrounded by an earthen berm to contain spills. Amine gas treater, Claus unit and tail gas treatment for converting hydrogen sulfide from hydrodesulphurization into elemental sulfur. Unity units such as cooling towers for circulating cooling water, boiler plants for steam generation, instrument air systems consisting of API separators, dissolved air flotation (DAF) unit and some type of further treatment (such as an activated sludge biotreater) to make such water suitable for reuse or for disposal. Solvent refining units use solvent such as cresol or furfural to

remove unwanted, mainly asphaltenic materials from lubricating oil stock (or diesel stock). Solvent dewaxing units remove the heavy waxy constituents petrolatum from vacuum distillation products.

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Introduction & History

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Introduction & History

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CHAPTER # 01 Crude Oil:

Introduction & History

The word CRUDE means Rock, so as evidence from name, the oil obtained from Rock is crude oil. A Mixture of various hydro carbons believed to be formed by Decay and Decomposition of Marine animals as well as Prehistoric forest under Earth crust at High Pressure and Temperature millions of years ago.

The crude oil contains hundreds of different hydrocarbons, present in different proportions and each has its own characteristics/properties. The crude oil also contains small quantities of water and salts depending on the source it extracted.

General Composition of Crude:

Types of Crude (w.r.t. Gravity):

Light Crude:

The Crude having gravity less than 0.86 or which contains more quantity of lighter fractions. Heavy Crude: The crude having gravity 0.86 or greater is called heavy crude or which contains heavier fractions.

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CHAPTER # 01 Types of Crude (w.r.t. Sulfur):

Sweet Crude: Sour Crude:

Introduction & History

The Crude having sulfur contents less than 0.5 ppm. The crude having sulfur contents 0.5 ppm or more.

Types of Crude (w.r.t. Components):

Paraffinic Crude:

Crude which contains paraffinic wax type residue. Asphaltic Crude:

Crude which contains more asphatic components in its residue. This crude is used for making Bitumen/Asphalt.

Types of Crude:
Salty Crude:

The crude having salts greater than 1 PTB is called salted crude.

Impurities in Crude:
Impurities refer to the Undesirable components in crude which

creates/can create problem in plant hardware when crude is processed. Removal of these impurities is necessary. Impurities includes salts of Ca & Mg, sand, slit, drilling mud, iron oxide & sulfide, leaves, trashes, water, sulfur, metals like Ni, Fe, As and Naphthenic acids.

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CHAPTER # 01

Introduction & History

NAPHTHA:
Naphtha is a general term used to describe special boiling point spirits having a boiling range of approximately 30 to 180
o

C. As it has all boiling ranges,

therefore, it is usually called as Full Boiling Range Naphtha (FBRN). Naphtha or FBRN is widely used in petrochemical industries as a feed stock. It is a highly volatile product, manufactured from crude oil by direct atmospheric distillation and by catalytic cracking of heavy residues.

COMPOSITION OF NAPHTHA:
Naphtha essentially consists of following hydrocarbon compounds, namely; 1. Paraffins 2. Olefins 3. Naphthenes 4. Aromatics

1. PARAFFINS (Alkanes):
Paraffins are further divided into three categories, these are;

n-paraffins Iso-paraffins Branched paraffins

n-paraffins:

The straight chain hydrocarbons are normally called as n-paraffin. All normal paraffin hydrocarbons from C1-C33 have been isolated from petroleum or crude oil.

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CHAPTER # 01
CH3-CH2-R

Introduction & History

Iso-paraffins:

The hydrocarbons having a methyl group on the number two (2) carbon atom of n-paraffin, such hydrocarbons are known to be Iso-paraffins. CH3 CH3-CH3-CH3-R *R is usually a methyl group (CH3).

Branched Paraffins.

These hydrocarbons have an alkyl group or groups usually methyl further down the carbon chain. CH3

CH3-CH2-CH-R

2. OLEFINS:
These are unsaturated hydrocarbon compounds and their presence in Naphtha would lead to: a) Possible gum formation in presence of air b) Increased coking in the pre-heater tubes of the hydro-desulphurization section

c) Increased hydrogen consumption in the hydro-desulphurization section Therefore, the olefin content in Naphtha is kept to the minimum and in manufacturing specifications. It is limited to maximum 1% on volume basis. The 1-17

CHAPTER # 01
ethylene, propylene and butadiene.

Introduction & History

three most important olefins used for the production of petrochemicals are

The removal of olefins from the naphtha feed is very essential as they exhibit highly exothermic reaction during their removal from the naphtha feed. It is to be carefully noticed

that in straight run naphthas the olefin contents are nil, where as cracked naphthas contains olefin contents. a) Linear Olefins: C-C-C-C = C-C b) Cyclic Olefins: C C C

C C

3. NAPHTHENES:

These are saturated cyclic hydrocarbons, many of which have methyl groups. These are also named as Cyclo-paraffins. The lower boiling petroleum fractions contain appreciable quantities of cyclo-pentanes and cyclo-hexanes. The presence of a high percentage of cyclo-pentanes and cyclo-hexanes in a gasoline is important because they are precursors of aromatic hydrocarbons. The dehydrogenation of cyclo-hexane and methyl-cyclo-hexane to benzene and toluene respectively, and the isomerization followed by the dehydrogenation of methyl-cyclo-pentane and di-methyl-cyclo-pentane to benzene and toluene are the major reactions in the catalytic reforming of straight run gasoline. C C C CH3 C C C CH R 1-18 C C C

CHAPTER # 01

Introduction & History

Alkyl-cyclo-pentanes R is usually methyl group (CH3)

Alkyl-cyclo-hexane

PROPERTIES:
To obtain the product known as naphtha, a complex soup of chemicals is broken into another range of chemicals, which are then graded and isolated mainly by their specific gravity and volatility. As a result, the product contains a range of distinct chemicals with a range of properties. They generally have a molecular weight range of 100-215, a specific gravity range of 0.75-0.85, and a boiling point range of 70-430 F. Their vapor pressure is usually less than 5 mm mercury.

Naphthas are insoluble in water. They are colorless (with a kerosene odor) or red-brown (with an aromatic odor). They are incompatible with strong oxidizers. Generally speaking, less dense naphthas ("light naphthas") have a

higher paraffin content. They are therefore also called paraffinic naphtha. The denser naphthas ("heavy naphthas") are usually richer in Naphthenes and aromatics, and they are therefore referred to as N&A's.

USES:
Paraffinic (or light) naphthas:
The main application for paraffinic ("light") naphthas is as feedstock in the petrochemical production of olefins. This is also the reason they are sometimes referred to as "light distillate feedstock" or LDF. (These naphtha types may also be called "straight run gasoline" (SRG) or "light virgin naphtha" (LVN).)

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CHAPTER # 01

Introduction & History

When used as feedstock in petrochemical steam crackers, the naphtha is heated in the presence of water vapor and the absence of oxygen or air until the hydrocarbon molecules fall apart. The primary products of the cracking process are olefins (ethylene / ethene, propylene / propene and butadiene) and aromatics (benzene and toluene). These are used as feedstock for derivative units that produce plastics (polyethylene and polypropylene, for example), synthetic fiber precursors (acrylonitrile), and industrial chemicals (glycols, for instance).

Heavy naphthas:
The "heavy" naphthas can also be used in the petrochemical industry, but they are more often used as 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).

ADDITIONAL APPLICATIONS:

Naphthas are also used in other applications, such as: In the production of gasoline. In industrial solvents and cleaning fluids An oil painting medium The sole ingredient in the home cleaning fluid Energize, which has been

discontinued. You can purchase this type of naphtha at any hardware store. An ingredient in shoe polish An ingredient in some lighter fluids for wick type lighters such as Zippo

lighters. An adulterant to petrol

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CHAPTER # 01
gas or Coleman fuel.

Introduction & History

A fuel for portable stoves and lanterns, sold in North America as white

Historically, as a probable ingredient in Greek fire (together with grease,

oil, sulfur, and naturally occurring saltpeter from the desert).

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