LARSEN & TOUBRO LIMITED

Prepared by : NJ Date : 18-Oct-04

Dept Equipment Project

: : :

Technology Center

Page 1 Doc. No. TECP - 003

Report on Petroleum Refinery Processes

REPORT ON PETROLEUM REFINERY PROCESSES

TECP - 003 DOC. No.

3-Aug-04 Date

Nitin Joseph Prepared By Approved By

LARSEN & TOUBRO LIMITED
Prepared by : NJ Date : 18-Oct-04

Dept Equipment Project

: : :

Technology Center

Page 2 Doc. No. TECP - 003

Report on Petroleum Refinery Processes

CONTENTS 1. INTRODUCTION 2. CRUDE OIL PROPERTIES 3. REFINING PROCESSES 4. CRUDE OIL PRETREATMENT 5. DISTILLATION 6. SOLVENT EXTRACTION AND DEWAXING 7. THERMAL CRACKING 8. CATALYTIC CRACKING 9. HYDROCRACKING 10. CATALYTIC REFORMING 11. CATALYTIC HYDROTREATING 12. ISOMERIZATION 13. POLYMERIZATION 14. ALKYLATION 15. SWEETENING AND TREATING 16. ASPHALT PRODUCTION 17. BLENDING 18. LUBRICANT, WAX AND GREASE MANUFACTURING 19. GLOSSARY

LARSEN & TOUBRO LIMITED
Prepared by : NJ Date : 18-Oct-04

Dept Equipment Project

: : :

Technology Center

Page 3 Doc. No. TECP - 003

Report on Petroleum Refinery Processes

INTRODUCTION Crude oil is a complicated mixture of hydrocarbons, with a varying composition depending on its source. The hydrocarbons in crude oil have different boiling points, according to the number of carbon atoms their molecules contain and how they are arranged. Crude oils are such a useful starting point for so many different substances because they contain hydrocarbons. Hydrocarbons are molecules that contain hydrogen and carbon and come in various lengths and structures, from straight chains to branching chains to rings.

Dept : Technology Center Equipment : Page

LARSEN & TOUBRO LIMITED 1

REPORT ON PETROLEU M REFINERY PROCESSES

Project : Prepared by : NJ Date : 18-Oct-04 Report on Petroleum Refinery Processes Doc. No. TECP - 003

TECP - 003 3Aug-04 Nitin Joseph DOC. No. Date Fig. 1 OUTPUTS FROM REFINERY Prepared By Approved By Petroleum refining begins with the distillation, or fractionation of crude oils into separate hydrocarbon groups. Dept : Technology The resultant products are directly related to the characteristics of crude processed. The safe and orderly Center processing of crude oil into flammable gases, liquids at high temperatures and pressures using vessels, Equipment : equipment, and piping subjected to stress and corrosion requires considerable knowledge, control and Page expertise. LARSEN & TOUBRO
LIMITED 2
Project : Prepared by : NJ Date : 18-Oct-04 Report on

LARSEN & TOUBRO LIMITED
Prepared by : NJ Date : 18-Oct-04

Dept Equipment Project

: : :

Technology Center

Page 4 Doc. No. TECP - 003

Report on Petroleum Refinery Processes

Classification Of Crude Oil: Crude oil may be classified as CRUDE OIL LIGHT CRUDE Generally Methane, Ethane, Propane Used as raw materials for fertilizers, plastics Adhesives, dyes explosives etc. HEAVY CRUDE (LIQUID) Fuels, fuel oil, fertilizers, Asphalt Tar, Solvents, Detergents etc.

Crude may be further classified as i. ii. iii. Sweet Crude: < 0.5% Sulphur Normal Crude: 2 – 3 Sulphur Sour Crude: > 3% Sulphur

Another type of classification is based on the chemical composition of the crude Paraffin-Base Crude Oils These contain higher molecular weight paraffins which are solid at room temperature, but little or no asphaltic (bituminous) matter. They can produce high-grade lubricating oils. Asphaltic-Base Crude Oils Contain large proportions of asphaltic matter, and little or no paraffin. Some are predominantly naphthenes so yield lubricating oil that is more sensitive to temperature changes than the paraffin-base crudes. Mixed-Base Crude Oils The "gray area" between the two types above. Both paraffins and naphthenes are present, as well as aromatic hydrocarbons. Most crudes fit this category.

TECP .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 5 Doc. calcium chloride) The properties of crude are as follows Specific Gravity : 0. vanadium. disulfides.84% Hydrogen . napthenic or aromatic based on the predominant proportion of similar Hydrocarbons. magnesium chloride. Hydrocarbons found in crude may be of the following types 1. Crude oils are generally classified as paraffinic. . phenols. the hydrocarbon chain carries the full compliment of hydrogen atoms. • • Consist of straight chain (normal). arsenic) Salts .1 to 3% (hydrogen sulfide.14% Sulphur .003 Report on Petroleum Refinery Processes CRUDE OIL PROPERTIES On an average crude oil is made up of the following components • • • • • • • Carbon . Paraffins (Alkanes) • • general formula: CnH2n+2 (n is a whole number.669 to 0. usually from 1 to 20) These compounds are saturated hydrocarbons with all carbon bonds satisfied. iron.less than 1% (nickel. sulfides. carboxylic acids) Metals . ketones. that is.less than 1% (basic compounds with amine groups) Oxygen . elemental sulfur) Nitrogen .less than 1% (sodium chloride. No.less than 1% (found in organic compounds such as carbon dioxide.99 API Gravity: = 10 – 50 Viscosity: 1 – 4 centipoises Chemical Properties Crude oils are complex mixtures containing many different Hydrocarbons compounds that vary in appearance and composition from one oil field to another.or branched-chain ( isomers) atoms The lighter straight chain molecules are found in gases and paraffin waxes. copper.

pentane. ethane. • ringed structures with one or more rings. They have at least one benzene ring. straight molecule that connects to the benzene ring) They are unsaturated ring type (cyclic) compounds which react because they have carbon atoms that are deficient in hydrogen. .Y (Y is a longer. butane. TECP .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 6 Doc. No.003 Report on Petroleum Refinery Processes • The branched chain (isomer) parrafins are usually found in heavier fractions of crude oil and have higher octane numbers than normal parrafins. isobutane. hexane 2.Aromatics • • general formula: C6H5 . propane. • examples: methane.

examples: benzene.Napthenes or Cycloalkanes • • general formula: CnH2n (n is a whole number usually from 1 to 20) ringed structures with closed rings (cyclic) CYCLOHEXANE ( C6 H12 ) METHYL CYCLOPENTANE ( C6 H12 ) • • • • found in all fractions of crude except the very lightest. methyl cyclopentane 4. with alternating double and single bonds between the carbons typically liquids and are found in heavier fractions of crude oil. TECP . usually from 1 to 20) ETHYLENE ( C2 H4 ) 1.BUTENE ( C4 H8 ) I SOBUTENE ( C4 H8 ) linear or branched chain molecules containing one carbon-carbon double-bond can be liquid or .Other hydrocarbons • Alkenes general formula: CnH2n (n is a whole number.003 Report on Petroleum Refinery Processes • • • rings contain six carbon atoms. rings contain only single bonds between the carbon atoms typically liquids at room temperature examples: cyclohexane. napthalene 3.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 7 Doc. No.

No. Nitrogen oxides can form in process furnaces. the corrosive sulfur compounds have an obnoxious odor. 3. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes.g. TECP . and calcium chloride in suspension or dissolved in entrained water (brine). iron. and fouling. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion. Oxygen Compounds. Sulfur Compounds. and nickel prior to processing as they can poison certain catalysts. 4. and vanadium are often found in crude oils in small quantities and are removed during the refining process. but as a rule the proportion. 5.) or as elemental sulfur.003 Report on Petroleum Refinery Processes gas examples: ethylene. Metals. ketones. 2. and/or nickel.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 8 Doc. Each crude oil has different amounts and types of sulfur compounds. and more often in heavier fractions of crude oil as non basic compounds that may also include trace metals such as copper. etc. and carboxylic acids occur in crude oils in varying amounts. vanadium. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. isobutene • Dienes and Alkynes general formula: CnH2n-2 (n is a whole number. usually from 1 to 20) linear or branched chain molecules containing two carbon-carbon double-bonds can be liquid or gas examples: acetylene.BUTADI ENE ( C4 H6 ) 1. and tubes. mercaptans.3. Trace Metals. Nitrogen is found in lighter fractions of crude oil as basic compounds. vanadium. 1. magnesium chloride. Other corrosive substances are elemental sulfur and mercaptans. butadienes ACETYLENE ( C2 H2 ) 1. Crude oils often contain inorganic salts such as sodium chloride. butene. Salts. ducts. as compounds (e. thiophenes. equipment corrosion. including nickel. sulfides. Oxygen compounds such as phenols. Sulfur may be present in crude oil as hydrogen sulfide (H2S). Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the . Moreover.BUTADI ENE ( C4 H6 ) Nonhydrocarbons. These salts must be removed or neutralized before processing to prevent catalyst poisoning. Nitrogen Compounds. It is also desirable to remove trace amounts of arsenic. stability.2. disulfides. and complexity of the compounds are greater in heavier crude-oil fractions.

No. Naphthenic Acids. . Carbon Dioxide. which causes fouling and corrosion. which may become corrosive at temperatures above 230° C when the acid value of the crude is above a certain level. Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude. Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH4Cl). 6.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 9 Doc. or from steam used in the distillation process.003 Report on Petroleum Refinery Processes subsequent formation of hydrochloric acid when crude is heated. TECP . 7. Some crude oils contain naphthenic (organic) acids.

Heavy 60 15 25 2.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 10 Doc.) N a pht .2 36 28 60 Saudi . No.003 Report on Petroleum Refinery Processes TYPI CAL APPROXI M ATE CH ARACTERI STI CS AN D PROPERTI ES AN D GASOLI N E POTEN TI AL OF V ARI OU S CRUD ES ( Re pr e se nt a t iv e a v e r a ge num be r s) Cr ude sour ce Pa r a ffin ( % v ol) Ar om a t ics ( % v ol) N a pht h e n e s ( % v ol) Sulfur ( % w t) API gr a vit y ( a ppr ox . yie ld ( % v ol) Oct a n e n o ( t ypica l) Niger ian .Light 63 19 18 2 34 22 40 Saudi . TECP .Light 37 9 54 0.1 28 23 .

Texas Sour 46 22 32 1.4 40 - USA .4 37 31 50 .Midcont . No.W.Brent 50 16 34 0. TECP .3 30 2 60 Venezuela .003 Report on Petroleum Refinery Processes 35 Venezuela . Sw eet 0.9 32 33 55 Nort h Sea .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 11 Doc.Heavy 35 12 53 2.Light 52 14 34 1.5 24 18 50 USA .

Chevron Texaco 8. ExxonMobil 4. Conoco Phillips 9. Lurgie Oil And Gas Chemie 16. TOTAL 6. Shell 5. TECP . John Brown 12. BP .AMOCO 7. Haldor Topsoe 15. Kvaerner 17. Kellog Brown & Root 14. Engineers India Limited 3. SASOL TECHNOLOGIES 10. ABB Lummus Global 13. UOP 2.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 12 Doc. Stone & Webster Engineering Company . AXENS 11.003 Report on Petroleum Refinery Processes PROCESS LICENSORS Some of the major process licensors are 1. No.

The tables that follow give brief description of the various process. No.003 Report on Petroleum Refinery Processes REFINING PROCESSES The figure in the following page shows in general the processes that are carried out on the crude oil to convert it to end products.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 13 Doc. TECP . Some of the important processes are explained in detail in the further chapters .

2 .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 14 Doc. No. TECP .003 Report on Petroleum Refinery Processes Fig.

coke Gasoline. distillate.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 15 Doc. residual Gas oil. distillate petrochemical feedstock Gas oil. distillate petrochemical feedstock Gas oil. lube stock. No. CO2 steam Atm tower Cracked heavy fuel/ naphtha. residual Conversion – Decomposition Processes Process Name Catalytic cracking Coking Hydrocracking *Hydrogen steam reforming *Steam cracking Visbreaking Action Alteration Polymerize Hydrogenate Decompose Decompose Decompose Method Catalytic Thermal Catalytic Thermal/catalytic Thermal Thermal Purpose Upgrade gasoline Convert vacuum residuals Convert to lighter HC’s Produce hydrogen Crack large molecules Reduce viscosity Feedstock(s) Product(s) Gas oil. cracked oil. CO. Gasoline. O2. gas oil. coke. gas. coke. TECP . tar tower residual Conversion – Unification Processes Process Name Alkylation Action Combining Method Catalytic Purpose Unite olefins Feedstock(s) Tower Product(s) Iso-octane . Lighter.003 Report on Petroleum Refinery Processes Fractionation Processes Process Name Atmospheric distillation Vacuum distillation Action Separation Separation Method Thermal Thermal Purpose Separate fractions Separate w/o cracking Feedstock(s) Desalted crude oil Atmospheric tower residual Product(s) Gas. distillate residual Atmospheric Distillate. higher-quality residual products Desulfurized Hydrogen.

TECP . pentane. petrochemical stocks Conversion – Alteration or Arrangement Processes Process Name Catalytic reforming Isomerization Action Alteration/ dehydration Rearrange Method Catalytic Catalytic Purpose Upgrade low-octane naphtha Convert straight chain to branch Feedstock(s) Coker/hydrocracker naphtha Butane. fatty acid. alkyl metal Cracked olefins (alkylate) Lubricating grease High-octane naphtha.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 16 Doc. hexane Product(s) High octane. Reformate/aromatic Isobutane/ pentane/ hexane Treatment Processes Process Name *Amine treating Desalting Drying & sweetening Action Treatment Dehydration Treatment Method Absorption Absorption Absorption / Purpose Remove acidic contaminants Remove contaminants Remove H2O Feedstock(s) Sour gas.003 Report on Petroleum Refinery Processes & isoparaffins Grease compounding Polymerizing Combining Polymerize Thermal Catalytic Combine soaps & oils Unite 2 or more olefins isobutane/cracker olefin Lube oil. hydrocarbons w/CO2 and H2S Crude oil liquid Product(s) Acid free gases & liquid hydrocarbons Desalted crude oil Sweet and dry . No.

distillate Untreated distillate/gasoline hydrocarbons High quality diesel & lube oil Desulfurized olefins Cracker feed. contaminants Remove impurities. saturate HC’s Improve viscosity index. No. convert mercaptan hydrocarbons. TECP . color Remove asphalt Remove wax from lube stocks Separate unsaturated oils Remove H2S. LPG. asphalt Dewaxed lube basestock High-octane gasoline High-quality distillate/gasoline Solvent deasphalting Solvent dewaxing Solvent extraction Sweetening . lube High quality lube oils Heavy lube oil. propane Vacuum tower lube oils Gas oil.003 Report on Petroleum Refinery Processes thermal *Furfural extraction Hydrodesulfurization Hydrotreating *Phenol extraction Solvent extraction Treatment Hydrogenation Solvent extraction Treatment Treatment Solvent extraction Treatment Absorption Catalytic Catalytic Absorption / thermal Absorption Cool/ filter Absorption /precipitation Catalytic & sulfur compounds Upgrade mid distillate & lubes Remove sulfur. reformate. distillate. alkylation feedstock Cycle oils & lube feed-stocks High-sulfur residual/ gas oil Residuals.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 17 Doc. cracked HC’s Lube oil base stocks Vacuum Tower residual.

Wastewater and contaminants are discharged . No. suspended solids. water and chemical surfactant (demulsifiers) are added to the crude. 3 CRUDE OIL DESALTING Fig. In chemical desalting. Surfactants are added only when the crude has a large amount of suspended solids. and fouling of equipment and to prevent poisoning the catalysts in processing units. TECP . heated so that salts and other impurities dissolve into the water or attach to the water. Both methods of desalting are continuous. plugging. The feedstock crude oil is heated to between 65° and 175°C to reduce viscosity and surface tension for easier mixing and separation of the water. Refineries are able to desalt crude to less than 5 lbs/1000bl. Electrical desalting is the application of high-voltage electrostatic charges to concentrate suspended water globules in the bottom of the settling tank. The two most typical methods of crude-oil desalting. 4 ELECTROSTATIC DESALTING A Third method makes the use of a packed column that facilitates the use of crude oil and brine through the agency of an absorbant. and water-soluble trace metals. chemical and electrostatic separation. As a first step in the refining process.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 18 Doc.003 Report on Petroleum Refinery Processes CRUDE OIL PRETREATMENT Crude oil often contains water. In both methods other chemicals may be added. these contaminants must be removed by desalting (dehydration). and then held in a tank where they settle out. Caustic or acid may be added to adjust the pH of the water wash. use hot water as the extraction agent. The temperature is limited by the vapor pressure of the crude-oil feedstock. CHEMICA L ADDITIVES OPTIONAL CRUDE HIGH VOLTAGE SETTLER PACKED COLUMN SETTLING TANK DESALTED CRUDE OIL BRINE DESALTED CRUDE OIL BRINE DESALTED CRUDE OIL BRINE HOT WATER Fig. to reduce corrosion. Ammonia is often used to reduce corrosion. inorganic salts.

CRUDE OIL FLASHING This is done frequently to reduce corrosion in the principal distillation column. In flashing. Feedstock Crude oil From Storage Process Treating Typical products . TECP . flashes into vapour that rises up the column &liquid residue that drops downward. The temperature varies from 320°C to 430°C according to the type of crude oil and pressure of the fractioning tower. It is a rough separation method to separate the crude at initial stage.to . No. which ultimately supplies all the heat required for operation of crude unit.unit • Desalted crude to Atmospheric distillation tower Waste water to Treatment • . desalted crude is heat exchanged against other heat sources that are available to recover maximum heat before the crude is charged to the heater.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 19 Doc. Crude enters the flash zone of the fractioning tower. The desalted crude is continuously drawn from the top of the settling tanks and sent to the crude distillation (fractionating) tower.003 Report on Petroleum Refinery Processes from the bottom of the settling tank to the wastewater treatment facility.

at pressures slightly above atmospheric and at temperatures ranging from 340° to 370° C (above these temperatures undesirable thermal cracking may occur). it can be separated by distillation into groups of hydrocarbons that boil between two specified boiling points. 6 TEMPERATURE DISTRIBUTION IN A DISTILLATION TOWER FRACTIONING TOWER (STRIPPER) PRIMARY FLASH COLUMN GAS SEPERATOR ATOSPHERIC DISTILLATION . No. Two types of distillation are performed: atmospheric and vacuum. light distillates. The main fractions or "cuts" obtained have specific boilingpoint ranges and can be classified in order of decreasing volatility into gases. gas oils. The feedstock then flows to a directfired crude charge heater where it is fed into the vertical distillation column just above the bottom.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 20 Doc.003 Report on Petroleum Refinery Processes DISTILLATION Introduction The first step in the refining process is the separation of crude oil into various fractions or straight-run cuts by distillation in atmospheric and vacuum towers. TECP . middle distillates. 5 CRUDE DISTILLATION ASPHALT Atmospheric Distillation The desalted crude feedstock is preheated using recovered process heat. All but the heaviest fractions flash into vapor GASES 105°C 150°C Crude Input 200°C 280°C 340°C LIGHT NAPTHA HEAVY NAPTHA KEROSENE LIGHT GAS OIL HEAVY GAS OIL RESIDUM Fig. and residuum. Because crude oil is a mixture of hydrocarbons with different boiling temperatures. GASES NAPTHA KEROSENE DIESEL OIL VACUUM DISTILLATION GAS OIL LIGHT LUBE OIL MEDIUM LUBE OIL HEAVY LUBE OIL CRUDE LIGHT OIL (PETROL) HEATER Fig.

The equipment is also similar. Steam is often used in towers to lower the vapor pressure and create a partial vacuum. Products ranging from uncondensed fixed gases at the top to heavy fuel oils at the bottom can be taken continuously from a fractionating tower.003 Report on Petroleum Refinery Processes As the hot vapour rises in the tower. and heavy residual for propane de-asphalting Other Distillation Towers Within refineries there are numerous other. A typical first-phase vacuum tower may produce gas oils. The process takes place in one or more vacuum distillation towers. Another larger column is used to separate ethyl benzene and xylene. The latter permit the vapors to bubble through the liquid on the tray. The purpose of stripping is to remove more volatile components and thus reduce the flash point of the side stream product. The internal designs of some vacuum towers are different from atmospheric towers in that random packing and demister pads are used instead of trays. The fractionating tower. where the higher temperature causes reevaporation. The principles of vacuum distillation resemble those of fractional distillation except that larger diameter columns are used to maintain comparable vapor velocities at the reduced pressures. heating oil. a de-propanizer is a small column designed to separate propane and lighter gases from butane and heavier components. smaller distillation towers called columns. Columns all work on the same principles as the towers described above. At each tray. and scrubbing operation is repeated many times until the desired degree of product purity is reached. kerosene. its temperature is reduced. vapors from below enter perforations under the bubble caps. a steel cylinder about 120 feet high. For example. Fig. contains horizontal steel trays for separating and collecting the liquids. condensing. The evaporation. An overflow pipe drains the condensed liquids from each tray back to the tray below.7 BUBBLE CAPS Vacuum Distillation In order to further distill the residuum or topped crude from the atmospheric tower at higher temperatures.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 21 Doc. reduced pressure is required to prevent thermal cracking. Fractioning Tower (Stripper) This process is carried out immediately after atmospheric distillation. At successively higher points on the tower. Heavy fuel oil or asphalt residue is taken from the bottom. gasoline. Then. causing some condensation at the temperature of that tray. lubricating-oil base stocks. side streams from certain trays are taken off to obtain the desired fractions. and uncondensed gases (which condense at lower temperatures) are drawn off. designed to separate specific and unique products. No. the various major products including lubricating oil. . Small "bubble" towers called strippers use steam to remove trace amounts of light products from heavier product streams. TECP .

TECP .003 Report on Petroleum Refinery Processes Distillation Atmospheric Feedstock Crude oil From Storage Process Treating Typical products .unit • Desalted crude to Atmospheric distillation tower Waste water to Treatment Gas oils To Catalytic cracker Lubricants To Hydrotreating or solvent Residual To Deasphalter.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 22 Doc. visbreaker. No.to . or coker • Vacuum Residuals Atmospheric tower Separation • • • .

The most widely used extraction solvents are phenol. aromatic hydrocarbons from lubricant and grease stocks. No. but all have the same general steps. which are: (1) mixing the feedstock with a solvent. Fig. and (3) recovering the solvent from the wax and de-waxed oil for recycling by distillation and steam stripping. and 2. 8 SCHEMATIC DIAGRAM OF SOLVENT EXTRACTION UNIT Solvent De-waxing Solvent de-waxing is used to remove wax from either distillate or residual basestock at any stage in the refining process. and the finished product requirements.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 23 Doc. the contaminants present. or fractionation. and improve finished products by removing unsaturated.003 Report on Petroleum Refinery Processes SOLVENT EXTRACTION AND DEWAXING Solvent Extraction The purpose of solvent extraction is to prevent corrosion. furfural. nitrobenzene. and impurities from the product stream by dissolving or precipitation. The solvent is then regenerated to be used again in the process. naphthenes. Other solvents less frequently used are liquid sulfur dioxide. The solvent extraction process separates aromatics. Electric precipitation may be used for separation of inorganic compounds. evaporation. The feedstock is first dried and then treated using a continuous countercurrent solvent treatment operation. There are several processes in use for solvent de-waxing. and residual trace amounts are subsequently removed from the raffinate by steam stripping or vacuum flashing. The selection of specific processes and chemical agents depends on the nature of the feedstock being treated. The solvent is separated from the product stream by heating. TECP . (2) precipitating the wax from the mixture by chilling. .2’ dichloroethyl ether. protect catalyst in subsequent processes. and cresylic acid.

Other solvents that are sometimes used include benzene. In addition.Lube waxing basestock Vacuum tower Treating • • • . petroleum naphtha.to .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 24 Doc. kerosene From Atmospheric tower Process Treating and blending Typical products . distillates. and sulfur dioxide. Process Solvent Extraction Feedstock Naphthas.003 Report on Petroleum Refinery Processes Fig.unit • • • High octane gasoline To Storage Refined fuels blending To Treating and Spent agents To Treatment and blending De-waxed Lubes To Hydrotreating Wax To Hydrotreating Spent agents To Treatment or recycle Solvent De. which dissolves little wax at low temperatures and acts as a wax precipitating agent. propane. No. and methyl ethyl ketone (MEK). 9 SCHEMATIC DIAGRAM OF SOLVENT DEWAXING UNIT Usually two solvents are used: toluene. which dissolves the oil and maintains fluidity at low temperatures. ethylene dichloride. TECP . methylene chloride. methyl isobutyl ketone. there is a catalytic process used as an alternate to solvent de-waxing.

ar thermal cracking process use temperature in the range of 455-540°C and pressures of 7-70 kg/cm2 A common thermal cracking process is the Dubbs process in which reduced crude is charged and it employs the concept of recycling in which the gas oil is combined with fresh feedstock for further cracking. When a 12 carbon atom typical of straight run gas oil is cracked. TECP ." a process that breaks or cracks the heavier. Further the paraffin has an octane number approaching zero. . fuel oil. Cracked oils are more resistant to cracking than straight run oil. higher boiling-point petroleum fractions into more valuable products such as gasoline. No. CH3(CH2)10CH3 STRAIGHT OIL CH3(CH2)4CH3 + CH2=CH(CH2)3 PARAFFIN OLEFIN The paraffin is almost the same as the straight run oil but the olefin is new. The streams from heaters are combined and sent to a soaking chamber where additional time is provided to complete the cracking actions. and gas oils. Heavy distillates are removed from the lower section and are pumped to separate heaters. but still can be cracked to produce more gasoline. subsequent refinery processes change the product mix by altering the molecular structure of the hydrocarbons. This is carried out till the oil is almost decomposed. one may be a six carbon paraffin hydrocarbon & the other a six carbon olefin hydrocarbon. it breaks into two parts. Fig. Majority of regu. In a typical application of thermal cracking the feedstock is preheated by direct exchange with the cracked products in fractioning columns. but the olefin has an octane approaching 100. Because the simple distillation of crude oil produces amounts and types of products that are not consistent with those required by the marketplace. One of the ways of accomplishing this change is through "cracking. This is done in a recycling operation in hich the cracked gas oil is combined with fresh feed for another trip to the cracking unit. Cracked Gasoline and middle distillate fractions are removed from the upper section of the column. thermal decomposition is caused at a significant rate.003 Report on Petroleum Refinery Processes THERMAL CRACKING Thermal cracking is the thermal decomposition of crude having high molecular weight & high boiling points.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 25 Doc. The remaining cracked products are sent to fractionating columns. 10 THERMAL CRACKING The process of thermal cracking can be explained as given below When petroleum fractions are heated to temperatures over 350°C. to form oils with lower molecular weights and boiling points. The cracked products are then thermally separated in a low pressure flash chamber where a heavy fuel oil is removed from the bottom.

It is then quenched with cool gas oil to control overcracking. The reaction time is also important.LARSEN & TOUBRO LIMITED Prepared by QUENCH LIGHT OIL HEATER Dept Equipment Project : : : Technology Center Page 26 Doc. Middle distillates may also be produced. The thermally cracked residue tar. 11 THERMAL CRACKING PROCESS Lower pressures (less than 7 kg/cm2) and temperature in excess of 500°C tend to produce lower molecular weight Hydrocarbons than those produced at higher pressures (28 – 70 kg/cm2) and temperature below 500°C. is vacuum-flashed in a stripper and the distillate recycled. Mild cracking conditions favour a high yield of gasoline components with low gas and coke production. which accumulates in the bottom of the fractionation tower. but gasoline quality is not that high whereas more severe conditions give increased gas and coke production but low quantity of gasoline (but of higher quality) However recycled oils become increasingly refractory upon repeated cracking and if they are not required as a fuel oil stock they may be subjected to a coking operation to increase gasoline yield or refined by means of a hydrogen process. Light feeds (gas oils) and recycled oils require longer reaction times than readily cracked heavier residues. Residual from the atmospheric distillation tower is heated (450°500° C) at atmospheric pressure and mildly cracked in a heater. Visbreaking Visbreaking. a mild form of thermal cracking. No. depending on product demand. Recycle of light oil (middle distillates or fuel oil) fraction also affects the product state of thermal cracker. Visbreaking is used to reduce the pour point of waxy residues and reduce the viscosity of residues used for blending with lighter fuel oils. significantly lowers the viscosity of heavy crude-oil residue without affecting the boiling point range. . TECP . and flashed in a distillation tower.003 : NJ Date : 18-Oct-04 Report on Petroleum Refinery Processes RESIDUM FLASH TOWER SEPERATOR REACTION CHAMBER FLASH TOWER FRACTIONER PETROL STRIPPER HEAVY OIL HEATER FURNACE OIL FUEL OIL CRUDE CHARGE FUEL OIL Fig.

" The two most common processes are delayed coking and continuous (contact or fluid) coking.. The most common feeds are ethane.003 Report on Petroleum Refinery Processes Fig. No. The feedstock range from ethane to vacuum gas oil. and at pressures slightly above atmospheric. Steam cracking is carried out at temperatures of 800-870 °C. with heavier feeds giving higher yields of by-products such as naphtha. and the crude feedstock. 12 SCHEMATIC SKETCH OF A VIS BREAKING UNIT Steam Cracking Process Steam cracking is a petrochemical process sometimes used in refineries to produce olefinic raw materials (e.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 27 Doc. Naphtha produced from steam cracking contains benzene. The process so completely reduces hydrogen that the residue is a form of carbon called "coke. needed to allow the cracking reactions to proceed to completion.In delayed coking the heated charge (typically residuum from atmospheric distillation towers) is transferred to large coke drums. and needle coke) depending upon the reaction mechanism.75-2. . Initially the heavy feedstock is fed to a furnace. Three typical types of coke are obtained (sponge coke. Coking Processes Coking is a severe method of thermal cracking used to upgrade heavy residuals into lighter products or distillates. The heavier hydrocarbons produced in the fractionator are recycled through the furnace. butane. The full drum is steamed to strip out uncracked hydrocarbons. and naphtha.2 kg/cm2. ethylene) from various feedstock for petrochemicals manufacture. After the coke reaches a predetermined level in one drum. The mixture is passed from the heater to one or more coker drums where the hot material is held approximately 24 hours (delayed) at pressures of 1. Coking produces straight-run gasoline (coker naphtha) and various middle-distillate fractions used as catalytic cracking feedstock.1 kg/cm2) and is designed and controlled to prevent premature coking in the heater tubes. until it cracks into lighter products. which is extracted prior to hydrotreating. which heats the residuum to high temperatures (430-500°C) at low pressures (1. temperature. and gas oils are separated out.g.75-5. TECP . Delayed Coking . time. naphtha. honeycomb coke. which provide the long residence time. Residual from steam cracking is sometimes blended into heavy fuels. Vapors from the drums are returned to a fractionator where gas. the flow is diverted to another drum to maintain continuous operation.

In continuous coking. recycled coke particles to feedstock in a radial mixer. Process Licensors Visbreaking: This is process licensed by UOP Steam Cracking: This process is licensed by AXENS Delayed Coking: This process is licensed by UOP. The coke is mechanically removed by an auger rising from the bottom of the drum.Continuous (contact or fluid) coking is a moving-bed process that operates at temperatures higher than delayed coking. at a pressure of 3. Gases and vapors are taken from the reactor.to . Continuous Coking .5 kg/cm2. AXENS Fluid Coking And Flexicoking: This process is licensed by ExxonMobil Feedstock Naphtha. The process is automatic in that there is a continuous flow of coke and feedstock. TECP . No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 28 Doc. The remaining coke is dropped into the preheater for recycling with feedstock. Coking occurs both in the reactor and in the surge drum. and fractionated. recycle Gas oil to Catalytic cracking CATALYTIC CRACKING . thermal cracking occurs by using heat transferred from hot. blending Process Decomposition Typical products .unit • • • • Gasoline or distillate To Hydrotreating Vapor To Hydrotreater Residue To Stripper or recycle Gases To Gas plant Clarified oil Tars Catalytic cracker Various units Decomposition Coke to Shipping. quenched to stop any further reaction. and de-coked by mechanical or hydraulic methods. Hydraulic decoking consists of fracturing the coke bed with high-pressure water ejected from a rotating cutter. 13 DELAYED COKING cooled by water injection. The reacted coke enters a surge drum and is lifted to a feeder and classifier where the larger coke particles are removed as product.003 Report on Petroleum Refinery Processes Fig. called a reactor. gasoline From Distillation column.

Regeneration . which is maintained in an aerated or fluidized state by the oil vapors. catalytic activities include dehydrogenation.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 29 Doc. Use of a catalyst in the cracking reaction increases the yield of improvedquality products under much less severe operating conditions than in thermal cracking. The catalytic cracking process is very flexible. and petrochemical feedstock. and isomerization.Cracked hydrocarbon stream is separated into various products. moving-bed catalytic cracking. . gasoline. LPG. in which the oil is cracked in the presence of a finely divided catalyst. Catalytic cracking is similar to thermal cracking except that catalysts facilitate the conversion of the heavier molecules into lighter products. The catalysts used in refinery cracking units are typically solid materials (zeolite.7-1. There are three basic functions in the catalytic racking process: • • • Reaction . There are three types of catalytic cracking processes are fluid catalytic cracking (FCC). Typical temperatures are from 450-510° C at much lower pressures of 0. Fluid Catalytic Cracking The most common process is FCC. and operating parameters can be adjusted to meet changing product demand. fuller' earth.Feedstock reacts with catalyst and cracks into different hydrocarbons. bauxite. This process rearranges the molecular structure of hydrocarbon compounds to convert heavy hydrocarbon feedstock into lighter fractions such as kerosene.Catalyst is reactivated by burning off coke. TECP . hydrogenation. aluminum hydrosilicate.003 Report on Petroleum Refinery Processes Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to increase the quality and quantity of lighter. In addition to cracking. treated bentonite clay. No. more desirable products and decrease the amount of residuals. and Fractionation .4 kg/cm2. and s silica-alumina) that come in the form of powders. beads. pellets or shaped materials called extrudites. and Thermofor catalytic cracking (TCC). heating oil.

the charge is cracked at 0. 14 SCHEMATIC SKETCH OF FCC UNIT The fluid cracker consists of a catalyst section and a fractionating section that operate together as an integrated processing unit. and finally to a regenerator. form the catalyst circulation unit. with the standpipe and riser. naphtha. The catalyst is in the form of pellets that are moved continuously to the top of the unit by conveyor or pneumatic lift tubes to a storage hopper. vaporized. .1 kg/cm2. The catalyst section contains the reactor and regenerator. Moving Bed Catalytic Cracking The moving-bed catalytic cracking process is similar to the FCC process. and wet gas. TECP . Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. where most of the coke deposits burn off at the bottom where preheated air and spent catalyst are mixed. As the mixture travels up the riser. and some of the heavy oil is recycled to the riser. The fluid catalyst is continuously circulated between the reactor and the regenerator using air.003 Report on Petroleum Refinery Processes Fig. The "reactor" no longer functions as a reactor. regenerated catalyst as it enters the riser leading to the reactor. and steam as the conveying media. and raised to reactor temperature (480-540° C) by the hot catalyst. In the more modern FCC units. The charge is combined with a recycle stream within the riser. oil.7-2.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 30 Doc. The regenerator and hopper are isolated from the reactor by steam seals. which. A typical FCC process involves mixing a preheated hydrocarbon charge with hot. The cracked product is separated into recycle gas. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process. This cracking continues until the oil vapors are separated from the catalyst in the reactor cyclones. clarified oil. oil vapors. distillate. The resultant product stream (cracked product) is then charged to a fractionating column where it is separated into fractions. it merely serves as a holding vessel for the cyclones. No. then flow downward by gravity through the reactor. all cracking takes place in the riser. Spent catalyst flows through the catalyst stripper to the regenerator.

TECP . Feedstock Deasphalted oils From Deashpalter Process Decomposition.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 31 Doc. coker visbreaker Decomposition. and recycled. No.to . alteration • • . blend.003 Report on Petroleum Refinery Processes Thermofor Catalytic Cracking In a typical thermofor catalytic cracking unit. SWEC have developed FCC processes. alteration Typical products . or recycle Petrochem feedstock To Petrochem or other Residue To Residual fuel blend Gasoline To Treater or blend Gases To Gas plant Gas oils Towers.unit • • • Middle distillates To Hydrotreat. The flue gas from regeneration is sent to a carbon-monoxide boiler for heat recovery. The vapors are separated from the catalyst and sent to a fractionating tower. cooled. EMRE. the preheated feedstock flows by gravity through the catalytic reactor bed. Process Licensors Almost all the process licensors have developed catalytic cracking process especially UOP. The spent catalyst is regenerated.

wherein heavier feedstock are cracked in the presence of hydrogen to produce more desirable products. and gas oil). No. After the hydrocarbon leaves the first stage. jet fuel. both of which are important in highquality jet fuel. Hydrocracking is used for feedstock that are difficult to process by either catalytic cracking or reforming. Hydrocracking Process In the first stage. Hydrogenation also serves to convert sulfur and nitrogen compounds present in the feedstock to hydrogen sulfide and ammonia. . The hydrocracking process largely depends on the nature of the feedstock and the relative rates of the two competing reactions. When the feedstock has a high paraffinic content. The hydrogen is recycled to the feedstock. Another important role of hydrogen in the hydrocracking process is to reduce tar formation and prevent buildup of coke on the catalyst. Depending on the products desired (gasoline components. where catalysts convert sulfur and nitrogen compounds to hydrogen sulfide and ammonia.003 Report on Petroleum Refinery Processes HYDROCRACKING Hydrocracking is a two-stage process combining catalytic cracking and hydrogenation. Hydrocracking produces relatively large amounts of isobutane for alkylation feedstock. it is cooled and liquefied and run through a hydrocarbon separator. in the presence of hydrogen and special catalysts. the fractionator is run to cut out some portion of the first stage reactor out-turn. the primary function of hydrogen is to prevent the formation of polycyclic aromatic compounds. The process employs high pressure. and hydrogen. Kerosene-range material can be taken as a separate side-draw product or included in the fractionator bottoms with the gas oil. a catalyst. The liquid is charged to a fractionator. since these feedstock are characterized usually by a high polycyclic aromatic content and/or high concentrations of the two principal catalyst poisons. preheated feedstock is mixed with recycled hydrogen and sent to the first-stage reactor. Limited hydrocracking also occurs. Heavy aromatic feedstock is converted into lighter products under a wide range of very high pressures (70-140 kg/cm2) and fairly high temperatures (400-800° C).LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 32 Doc. Hydrocracking also performs isomerization for pour-point control and smoke-point control. TECP . high temperature. sulfur and nitrogen compounds. hydrogenation and cracking.

003 Report on Petroleum Refinery Processes Fig. coker Reformer Decomposition. ExxonMobil Gas oils Hydrogen Vacuum tower.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 33 Doc. cracking. No. distillates To Blending Recycle. TECP . Process Licensor This process is licensed by Chevron. hydrogenation Decomposition. Since this material has already been subjected to some hydrogenation. the operations of the second stage are more severe (higher temperatures and pressures). and reforming in the first stage. the second stage product is separated from the hydrogen and charged to the fractionator. reformer gas To Gas plant • . Like the outturn of the first stage. 15 SCHEMATIC SKETCH OF A TWO STAGE HYDROCRACKING UNIT The fractionator bottoms are again mixed with a hydrogen stream and charged to the second stage. hydrogenation • Gasoline.

The effluent from the last reactor is cooled and sent to a separator to permit removal of the hydrogen-rich gas stream from the top of the separator for recycling. powerforming. Most processes use platinum as the active catalyst. The naphtha feedstock is then mixed with hydrogen.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 34 Doc. TECP .003 Report on Petroleum Refinery Processes CATALYTIC REFORMING Catalytic reforming is an important process used to convert low-octane naphthas into high-octane gasoline blending components called reformates. butanes and lighter go overhead and are sent to the saturated gas plant. the feedstock is prepared to specification. reformates can be produced with very high concentrations of toluene. Reforming represents the total effect of numerous reactions such as cracking. There are many different commercial catalytic reforming processes including platforming. and aromatic content) and catalysts used. 16 SCHEMATIC SKETCH OF CATALYTIC REFORMING (PLATFORMING) PROCESS In the platforming process. and isomerization taking place simultaneously. Hydrogen. by combination of hydrotreatment and distillation. benzene. Fig. dehydrogenation. and other aromatics useful in gasoline blending and petrochemical processing. is separated from the reformate for recycling and use in other processes. and passed through a series of alternating furnace and fixed-bed reactors containing a platinum catalyst. No. vaporized. More or less standard is a feed preparation section in which. naphthene. olefin. ultraforming. The liquid product from the bottom of the separator is sent to a fractionator called a stabilizer (butanizer). xylene. and Thermofor catalytic reforming. a significant by-product. Depending on the properties of the naphtha feedstock (as measured by the paraffin. Sometimes platinum is combined with a second catalyst (bimetallic catalyst) such as rhenium or another noble metal. . It makes a bottom product called reformate. polymerization. the first step is preparation of the naphtha feed to remove impurities from the naphtha and reduce catalyst degradation. A catalytic reformer comprises a reactor section and a product-recovery section.

No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 35 Doc. dehydrogenate Typical products .1 kg/cm2).unit • • High octane gasoline . hydrotreat. dehydrogenate Rearrange.5-14. and some facilities regenerate all of the reactors during turnarounds. TECP .to . Some catalytic reforming systems continuously regenerate the catalyst in other systems. Blending Aromatics To Petrochemical Hydrogen To Recycle. . Gas To Gas plant Naphthene-rich fractions Straight-run naphtha Hydrocracker.003 Report on Petroleum Refinery Processes Some catalytic reformers operate at low pressure (3. etc. One reactor at a time is taken off-stream for catalyst regeneration. and others operate at high pressures (up to 70 kg/cm2). Feedstock Desulfurized naphtha From Coker Process Rearrange. hydrodesulfur Atmospheric fractionator Rearrange. dehydrogenate • • .

The hydrogen-rich gas from the high-pressure separation is recycled to combine with the feedstock. the catalysts. Catalytic Hydrodesulfurization Process Hydrotreating for sulfur removal is called hydrodesulfurization. and to upgrade middle-distillate petroleum fractions into finished kerosene. diesel fuel. and heating fuel oils.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 36 Doc. TECP .003 Report on Petroleum Refinery Processes CATALYTIC HYDROTREATING Catalytic hydrotreating is a hydrogenation process used to remove about 90% of contaminants such as nitrogen. preheated in a fired heater (150-220° C) and then charged under pressure (up to 70 kg/cm2) through a fixed-bed catalytic reactor. 17 SCHEMATIC SKETCH OF HYDRO-DESULPHURIZATION PROCESS In the reactor. the feedstock is deaerated and mixed with hydrogen. oxygen. In . the sulfur and nitrogen compounds in the feedstock are converted into H2S and NH3. if not removed from the petroleum fractions as they travel through the refinery processing units. sulfur. hydrotreating is done prior to processes such as catalytic reforming so that the catalyst is not contaminated by untreated feedstock. These contaminants. No. The reaction products leave the reactor and after cooling to a low temperature enter a liquid/gas separator. and the quality of the finished product. In a typical catalytic hydrodesulfurization unit. Fig. hydrotreating converts olefins and aromatics to saturated compounds. and the low-pressure gas stream rich in H2S is sent to a gas treating unit where H2S is removed. Hydrotreating is also used prior to catalytic cracking to reduce sulfur and improve product yields. can have detrimental effects on the equipment. and metals from liquid petroleum fractions. The clean gas is then suitable as fuel for the refinery furnaces. The liquid stream is the product from hydrotreating and is normally sent to a stripping column for removal of H2S and other undesirable components. In addition. Typically.

catalytic & thermal cracker Process Treating. treater Gas To Gas plant . However. odor. No. hydrogenation Typical products .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 37 Doc.unit • • • • • Naphtha To Blending Hydrogen To Recycle Distillates To Blending H2S. Other Hydrotreating Processes Hydrotreating processes differ depending upon the feedstock available and catalysts used. a suitable route in view of its high octane number.to . and gum-forming tendencies of this material. Mild lube hydrotreating also may be used following solvent processing. color.003 Report on Petroleum Refinery Processes cases where steam is used for stripping. Process Licensor This process is licensed by ExxonMobil Hydrodesulfurization Process Feedstock Naphthas. which are cleaner-burning compounds. Lube-oil hydrotreating uses catalytic treatment of the oil with hydrogen to improve product quality. Hydrotreating also can be employed to improve the quality of pyrolysis gasoline (pygas). residuals From Atmospheric & vacuum tower. ammonia To Sulfure plant. Hydrotreatment of a kerosene fraction can convert aromatics into naphthenes. and acid nature of the oil. whereby conversion of diolefins into mono-olefins provides an acceptable product for motor gas blending. TECP . distillates sour gas oil. The quality of pygas. can be satisfactorily improved by hydrotreating. Hydro desulfurized products are blended or used as catalytic reforming feedstock. the outlet for pygas has been motor gasoline blending. The objectives in mild lube hydrotreating include saturation of olefins and improvements in color. a by-product from the manufacture of ethylene. only small portions can be blended untreated owing to the unacceptable odor. the product is sent to a vacuum drier for removal of water. Hydrotreating can be used to improve the burning characteristics of distillates such as kerosene. Traditionally. which is high in diolefin content.

and then heated to reactor temperature. 1. 18 SCHEMATIC SKETCH OF BUTANE ISOMERIZATION In a typical low-temperature process. Isomerization is similar to catalytic reforming in that the hydrocarbon molecules are rearranged.003 Report on Petroleum Refinery Processes ISOMERIZATION Isomerization converts n-butane. It is then passed over supported-metal catalyst in the first reactor where benzene and olefins are hydrogenated. Hydrogen is flashed off in a high-pressure separator and the hydrogen chloride removed in a stripper column. . and the conversion of normal pentanes and hexanes into higher branched isomers for gasoline blending. isomerization just converts normal paraffins to isoparaffins. Butane isomerization produces feedstock for alkylation. which are found in abundance in straight-run gasoline. No. Isomerization is important for the conversion of n-butane into isobutane. but unlike catalytic reforming. 2. The resultant butane mixture is sent to a fractionator (deisobutanizer) to separate n-butane from the isobutane product. Fig. The straight-chain paraffins are converted to their branched-chain counterparts whose component atoms are the same but are arranged in a different geometric structure.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 38 Doc. In a typical C5/C6 isomerization process. dried and desulphurized feedstock is mixed with a small amount of organic chloride and recycled hydrogen. Platinum or another metal catalyst is used for the higher-temperature processes. butane (C4) isomerization and pentane/hexane (C5/C6) isomerization. There are two distinct isomerization processes. the feed to the isomerization plant is n-butane or mixed butanes mixed with hydrogen (to inhibit olefin formation) and passed to the reactor at 110-170°C and 14-21 kg/cm2. to provide additional feedstock for alkylation units. TECP . Pentane/hexane isomerization increases the octane number of the light gasoline components npentane and n-hexane. n-pentane and n-hexane into their respective isoparaffins of substantially higher octane number. Aluminum chloride catalyst plus hydrogen chloride are universally used for the low-temperature processes.

and stabilized before going to storage.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 39 Doc. Process Licensor This process is licensed by UOP. TECP . The isomerate is washed (caustic and water).unit • n-Butane C4 Isomerization C5 n-Pentane Isomerization C6 n-Hexane Isomerization Isobutane To Alkylation Isopentane To Blending Isohexene To Blending Gas To Gas Plant • • • .003 Report on Petroleum Refinery Processes Fig. The reactor effluent is then cooled and subsequently separated in the product separator into two streams: a liquid product (isomerate) and a recycle hydrogen-gas stream. 19 SCHEMATIC SKETCH OF PENTANE AND HEXANE ISOMERIZATION The feed next goes to the isomerization reactor where the paraffins are catalytically isomerized to isoparaffins.to . No. Axxens Process Feedstock From Various processes Various processes Various processes Process Rearrangement Rearrangement Rearrangement Typical products . acid stripped.

where an exothermic polymeric reaction occurs. propylene. The reaction products leaving the reactor are sent to stabilization and/or fractionator systems to separate saturated and unreacted gases from the polymer gasoline product. Polymerization may be accomplished thermally or in the presence of a catalyst at lower temperatures. Polymerization combines two or more identical olefin molecules to form a single molecule with the same elements in the same proportions as the original molecules. The olefin feedstock is pretreated to remove sulfur and other undesirable compounds. No. 20 SCHEMATIC SKETCH OF POLYMERIZATION PROCESS Feedstock Olefins From Cracking processes Process Unification Typical products .003 Report on Petroleum Refinery Processes POLYMERIZATION Polymerization in the petroleum industry is the process of converting light olefin gases including ethylene. TECP .unit • • • High octane naphta To Gasoline blending Petrochem. and butylene into hydrocarbons of higher molecular weight and higher octane number that can be used as gasoline blending stocks.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 40 Doc. In the catalytic process the feedstock is either passed over a solid phosphoric acid catalyst or comes in contact with liquid phosphoric acid. gas To Storage .to . feedstock To Petrochemical Liquefied petro. Fig. This reaction requires cooling water and the injection of cold feedstock into the reactor to control temperatures between 150-230° C at pressures from 14 kg/cm2 to 84 kg/cm2.

TECP . branched-chain paraffinic hydrocarbons. The reactor is divided into zones. Fig. The product is called alkylate and is composed of a mixture of high-octane. The alkylate obtained from the deisobutanizer can then go directly to motor-fuel blending or be rerun to produce aviation-grade blending stock. with olefins fed through distributors to each zone. amylene. and the acid is returned to the reactor. Alkylate is a premium blending stock because it has exceptional antiknock properties and is clean burning. The hydrocarbon phase is hot-water washed with caustic for pH control before being successively depropanized. and fresh isobutane) enters the reactor and contacts the concentrated sulfuric acid catalyst (in concentrations of 85% to 95% for good operation and to minimize corrosion). 21 SCHEMATIC SKETCH OF SULPHURIC ACID ALKYLATION PROCESS . The reactor effluent is separated into hydrocarbon and acid phases in a settler. The octane number of the alkylate depends mainly upon the kind of olefins used and upon operating conditions.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 41 Doc. either sulfuric acid or hydrofluoric acid. and debutanized. deisobutanized. Sulfuric Acid Alkylation Process In cascade type sulfuric acid (H2SO4) alkylation units. The isobutane is recycled to the feed.003 Report on Petroleum Refinery Processes ALKYLATION Alkylation combines low-molecular-weight olefins (primarily a mixture of propylene and butylene) with isobutene in the presence of a catalyst. No. the feedstock (propylene. butylene. and the sulfuric acid and isobutanes flowing over baffles from zone to zone.

to . Isobutane is recycled to the reaction zone and alkylate is sent to product blending. and alkylate from the bottom of the main fractionator is sent to product blending. Half of the dried feedstock is charged to the first reactor. The main fractionator overhead. the bottom product of which is motor alkylate. and excess (recycle) isobutane. olefin and isobutane feedstock are dried and fed to a combination reactor/settler system.In the Phillips process. along with recycle and makeup isobutane. alkylate.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 42 Doc. The reactor effluent then goes to its settler. consisting of propane. normal butane. where the acid is recycled and the hydrocarbon charged to the second reactor. and sent to storage.unit High octane gasoline To Blending n-Butane & propane To Stripper or blender SWEETENING AND TREATING . TECP . 22 SCHEMATIC SKETCH OF HYDROFLURIC ACID ALKYLATION UOP Process . No. Overhead from the main fractionator goes to a depropanizer. consisting mainly of propane. Subsequent processing is similar to the Phillips process. Phillips Process . The other half of the feedstock also goes to the second reactor. the reactor effluent flows to a settler (separating vessel) where the acid separates from the hydrocarbons. The top layer of hydrocarbons (hydrocarbon phase). isobutane. Isobutane is withdrawn from the main fractionator and recycled to the reactor/settler. Feedstock Petroleum gas Olefins From Distillation or cracking Cat.003 Report on Petroleum Refinery Processes Hydrofluoric Acid Alkylation Process Phillips and UOP are the two common types of hydrofluoric acid alkylation processes in use. Propane with trace amount of HF goes to an HF stripper for HF removal and is then catalytically defluorinated.The UOP process uses two reactors with separate settlers. with the settler acid being recycled and the hydrocarbons charged to the main fractionator. is charged to the main fractionator. treated. or hydrocracking Process Unification Unification Typical products . Upon leaving the reaction zone. goes to a depropanizer. and HF. The acid layer at the bottom of the separating vessel is recycled. Fig.

Caustic treating with sodium (or potassium) hydroxide is used to improve odor and color by removing organic acids (naphthenic acids. H2S) by a caustic wash. nitrogen. phenols) and sulfur compounds (mercaptans. color. methyl alcohol and cresols). dissolved metals and inorganic salts. treats sulfur compounds (hydrogen sulfide. Sweetening. and end-product specifications. By combining caustic soda solution with various solubility promoters (e. amount and type of impurities in the fractions to be treated. Drying is accomplished by . Caustic liquid (sodium hydroxide). amine compounds (diethanolamine) or fixed-bed catalyst sweetening also may be used. Fig. and oxidation stability. odor. a major refinery treatment of gasoline. No. the extent to which the process removes the impurities. and adsorption agents. Treating materials include acids. and oxygen.g. or just before sending the finished product to storage. and resinous and asphaltic compounds. stability. heavier components are sent to gasoline blending. Sweetening also reduces concentrations of carbon dioxide. propane is recovered for LPG. and other properties of the oil.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 43 Doc. Treating can be accomplished at an intermediate stage in the refining process. solvents. and propylene is removed for use in petrochemicals. and stability. It is used to improve the odor. up to 99% of all mercaptans as well as oxygen and nitrogen compounds can be dissolved from petroleum fractions. carbon residue. TECP . Acid.003 Report on Petroleum Refinery Processes Treating is a means by which contaminants such as organic compounds containing sulfur. Clay/lime treatment of acid-refined oil removes traces of asphaltic materials and other compounds improving product color. thiophene and mercaptan) to improve color. Choices of a treating method depend on the nature of the petroleum fractions. and soluble salts dissolved in emulsified water are removed from petroleum fractions or streams. Caustic. oxidizing. Drying and Sweetening Feedstock from various refinery units are sent to gas treating plants where butanes and butenes are removed for use as alkylation feedstock. nitrogen. and oxygen compounds. Sulfuric acid treating results in partial or complete removal of unsaturated hydrocarbons. or Clay Treating Sulfuric acid is the most commonly used acid treating process.. 23 SCHEMATIC SKETCH OF MOLECULAR SIEVE DRYING AND SWEETENING Some mercaptans are removed by water-soluble chemicals. odor. alkalis. sulfur.

Knockout pots are used to remove water and hydrocarbons from feed gas streams. Hydrogen Sulfide Scrubbing Hydrogen sulfide scrubbing is a common treating process in which the hydrocarbon feedstock is first scrubbed to prevent catalyst poisoning. which uses both thermal and catalytic-conversion reactions. The gases are then exposed to a catalyst to recover additional sulfur. intermediates From Various Process Treatment Typical products .to . No. Sulfur vapor from burning and conversion is condensed and recovered.unit • • • • Butane & butene To Alkylation Propane. desulfurization methods vary from ambient temperature-activated charcoal absorption to high-temperature catalytic hydrogenation followed by zinc oxide treating. Depending on the feedstock and the nature of contaminants. Some processes simultaneously dry and sweeten by adsorption on molecular sieves. A typical process produces elemental sulfur by burning hydrogen sulfide under controlled conditions. distillates To Storage Gasoline To Blending Propylene To Petrochemical .003 Report on Petroleum Refinery Processes the use of water absorption or adsorption agents to remove water from the products. TECP . Sulfur Recovery Sulfur recovery converts hydrogen sulfide in sour gases and hydrocarbon streams to elemental sulfur. The most widely used recovery system is the Claus process. finished products. Feedstock Gases.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 44 Doc.

In vacuum distillation. are added during and/or after blending to provide specific properties not inherent in hydrocarbons. Asphalt for roofing materials is produced by air blowing. Additives including octane enhancers.003 Report on Petroleum Refinery Processes ASPHALT Asphalt is a portion of the residual fraction that remains after primary distillation operations. anti-oxidants.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 45 Doc. jet fuel. The dehydrogenization of the asphalt forms hydrogen sulfide. It is further processed to impart characteristics required by its final use. Steam. detergents. catalytic cracking feedstock. Residual is heated in a pipe still almost to its flash point and charged to a blowing tower where hot air is injected for a predetermined time. etc. which is recycled. No. carbon residues.unit • • • • Heavy lube oil To Treating or lube blending Asphalt To Storage of shipping Deasphalted oil To Hydrotreat & catalytic cracker Propane To Recycle BLENDING Blending is the physical mixture of a number of different liquid hydrocarbons to produce a finished product with certain desired characteristics. and paraffins from the feedstock. or batch blended in tanks and vessels. Products can be blended in-line through a manifold system. The products are then evaporated and steam stripped to recover the propane. distillates. Feedstock and liquid propane are pumped to an extraction tower at precisely controlled mixtures. and asphalt. is then passed through a scrubber to condense the hydrocarbons. and kerosene is accomplished by injecting proportionate amounts of each component into the main stream where turbulence promotes thorough mixing. metal deactivators. Separation occurs in a rotating disc contactor. reduced crude From Atmospheric tower & Vacuum tower Process Treatment Typical products . generally used to produce road-tar asphalt. A third process used to produce asphalt is solvent deasphalting. . metals. the residual is heated to about 400° C and charged to a column where vacuum is applied to prevent cracking. and the oxidation creates sulfur dioxide. TECP .to . heavy oil fractions are separated to produce heavy lubricating oil. Deasphalting also removes some sulfur and nitrogen compounds. which uses propane (or hexane) as a solvent. anti-knock agents. and pressures of 25-42 kg/cm2. In this extraction process. based on differences in solubility. used to blanket the top of the tower to entrain the various contaminants. gum and rust inhibitors. temperatures (18-48° C). In-line blending of gasoline. Feedstock Residual.

Process Treatment • Typical products .). WAX AND GREASE MANUFACTURING Lubricating oils and waxes are refined from the residual fractions of atmospheric and vacuum distillation. the raffinate is mixed with phenol in the treating section at temperatures below 200° C. Reduced crude from the vacuum unit is deasphalted and combined with straight-run lubricating oil feedstock. etc. etc.003 Report on Petroleum Refinery Processes LUBRICANT. Phenol is then separated from the treated oil and recycled. industrial lubricants. The solvent is recovered from the oil by flashing and steam stripping. carbon residue. TECP . color. chilled. hydrotreating solvent extraction. The primary objective of the various lubricating oil refinery processes is to remove asphalts.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 46 Doc. The wax is continuously removed by filters and cold solvent-washed to recover retained oil. filtered. lithium. and oxidation stability in extremely selective extraction processes using solvents (furfural. preheated. aluminum.unit Dewaxed raffinate To Lube blend or compound. The wax is then heated with hot solvent. No. In a typical phenol unit. Wax Manufacturing Process Raffinate from the extraction unit contains a considerable amount of wax that must be removed by solvent extraction and crystallization. and metal working oils. The crystallization temperature is attained by the evaporation of propane in the chiller and filter feed tanks.) in the soap and the additives used. and given a final wash to remove all oil. Lubricating Oil Process The dewaxed raffinate is blended with other distillate fractions and further treated for viscosity index. The raffinate is mixed with a solvent (propane) and pre-cooled in heat exchangers. sulfur. grease compounding Wax To Storage or shipping • . etc. Feedstock Lube feedstock and additives From Vacuum tower. Grease Compounding Grease is made by blending metallic soaps (salts of long-chained fatty acids) and additives into a lubricating oil medium at temperatures of 200-315°C. sodium. additive response.to . The treated lube-oil base stocks are then mixed and/or compounded with additives to meet the required physical and chemical characteristics of motor oils. solvent dewaxing. and paraffinic and isoparaffinic waxes from residual fractions.Grease may be either batch-produced or continuously compounded. and solvent-extracted (usually with phenol or furfural) to produce raffinate. The characteristics of the grease depend to a great extent on the metallic element (calcium. sulfonated aromatics. stability. phenol.

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