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Prepared by : NJ Date : 18-Oct-04
Dept Equipment Project
: : :
Page 1 Doc. No. TECP - 003
Report on Petroleum Refinery Processes
REPORT ON PETROLEUM REFINERY PROCESSES
TECP - 003 DOC. No.
Nitin Joseph Prepared By Approved By
LARSEN & TOUBRO LIMITED
Prepared by : NJ Date : 18-Oct-04
Dept Equipment Project
: : :
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
: : :
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
Project : Prepared by : NJ Date : 18-Oct-04 Report on
LARSEN & TOUBRO LIMITED
Prepared by : NJ Date : 18-Oct-04
Dept Equipment Project
: : :
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.
the hydrocarbon chain carries the full compliment of hydrogen atoms. copper. . TECP .less than 1% (basic compounds with amine groups) Oxygen . Paraffins (Alkanes) • • general formula: CnH2n+2 (n is a whole number. that is. elemental sulfur) Nitrogen . iron.1 to 3% (hydrogen sulfide. Hydrocarbons found in crude may be of the following types 1.or branched-chain ( isomers) atoms The lighter straight chain molecules are found in gases and paraffin waxes.003 Report on Petroleum Refinery Processes CRUDE OIL PROPERTIES On an average crude oil is made up of the following components • • • • • • • Carbon . arsenic) Salts . usually from 1 to 20) These compounds are saturated hydrocarbons with all carbon bonds satisfied. No. calcium chloride) The properties of crude are as follows Specific Gravity : 0. vanadium.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.less than 1% (sodium chloride. phenols. ketones. carboxylic acids) Metals . sulfides. napthenic or aromatic based on the predominant proportion of similar Hydrocarbons. disulfides.less than 1% (found in organic compounds such as carbon dioxide.less than 1% (nickel. magnesium chloride.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 5 Doc.14% Sulphur .669 to 0. • • Consist of straight chain (normal).84% Hydrogen . Crude oils are generally classified as paraffinic.
Aromatics • • general formula: C6H5 . ethane. 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. No.Y (Y is a longer. isobutane. butane. • examples: methane. • ringed structures with one or more rings. . TECP . pentane. They have at least one benzene ring.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 6 Doc. hexane 2. propane.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.
methyl cyclopentane 4.BUTENE ( C4 H8 ) I SOBUTENE ( C4 H8 ) linear or branched chain molecules containing one carbon-carbon double-bond can be liquid or . napthalene 3. usually from 1 to 20) ETHYLENE ( C2 H4 ) 1. examples: benzene. with alternating double and single bonds between the carbons typically liquids and are found in heavier fractions of crude oil. rings contain only single bonds between the carbon atoms typically liquids at room temperature examples: cyclohexane.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 7 Doc.003 Report on Petroleum Refinery Processes • • • rings contain six carbon atoms.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.Other hydrocarbons • Alkenes general formula: CnH2n (n is a whole number. TECP . No.
stability. ducts.BUTADI ENE ( C4 H6 ) 1. sulfides. butene. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units.BUTADI ENE ( C4 H6 ) Nonhydrocarbons. etc. and complexity of the compounds are greater in heavier crude-oil fractions. ketones. 1. Crude oils often contain inorganic salts such as sodium chloride. and carboxylic acids occur in crude oils in varying amounts. iron. 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. butadienes ACETYLENE ( C2 H2 ) 1. TECP . and nickel prior to processing as they can poison certain catalysts. magnesium chloride. and calcium chloride in suspension or dissolved in entrained water (brine). but as a rule the proportion. and fouling. It is also desirable to remove trace amounts of arsenic. disulfides.) or as elemental sulfur.g. as compounds (e. vanadium. Metals. vanadium.2.003 Report on Petroleum Refinery Processes gas examples: ethylene. the corrosive sulfur compounds have an obnoxious odor. Oxygen Compounds. 5. Moreover. Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the . equipment corrosion. and tubes. No.3. Oxygen compounds such as phenols. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion. 2. Nitrogen Compounds. These salts must be removed or neutralized before processing to prevent catalyst poisoning. Salts.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 8 Doc. and vanadium are often found in crude oils in small quantities and are removed during the refining process. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes. including nickel. Nitrogen is found in lighter fractions of crude oil as basic compounds. 3. mercaptans. isobutene • Dienes and Alkynes general formula: CnH2n-2 (n is a whole number. Nitrogen oxides can form in process furnaces. 4. usually from 1 to 20) linear or branched chain molecules containing two carbon-carbon double-bonds can be liquid or gas examples: acetylene. thiophenes. Sulfur may be present in crude oil as hydrogen sulfide (H2S). Sulfur Compounds. and/or nickel. Other corrosive substances are elemental sulfur and mercaptans. Trace Metals.
Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH4Cl).003 Report on Petroleum Refinery Processes subsequent formation of hydrochloric acid when crude is heated. 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. 7. . 6. No. Naphthenic Acids. TECP . Some crude oils contain naphthenic (organic) acids. or from steam used in the distillation process. Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 9 Doc.
LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 10 Doc.Heavy 60 15 25 2. TECP .) N a pht . No.2 36 28 60 Saudi .1 28 23 .Light 63 19 18 2 34 22 40 Saudi .Light 37 9 54 0.003 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 .
Brent 50 16 34 0. Texas Sour 46 22 32 1.3 30 2 60 Venezuela .4 40 - USA . TECP .4 37 31 50 .003 Report on Petroleum Refinery Processes 35 Venezuela .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 11 Doc.Heavy 35 12 53 2.W. No. Sw eet 0.9 32 33 55 Nort h Sea .Midcont .Light 52 14 34 1.5 24 18 50 USA .
TECP . Conoco Phillips 9. No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 12 Doc. Engineers India Limited 3. Kellog Brown & Root 14. Kvaerner 17. Shell 5. Lurgie Oil And Gas Chemie 16. BP . Haldor Topsoe 15.003 Report on Petroleum Refinery Processes PROCESS LICENSORS Some of the major process licensors are 1. TOTAL 6. John Brown 12. Chevron Texaco 8. AXENS 11. ExxonMobil 4. ABB Lummus Global 13. SASOL TECHNOLOGIES 10.AMOCO 7. Stone & Webster Engineering Company . UOP 2.
Some of the important processes are explained in detail in the further chapters .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. The tables that follow give brief description of the various process. No. TECP .
No.003 Report on Petroleum Refinery Processes Fig.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 14 Doc. TECP . 2 .
distillate residual Atmospheric Distillate. coke Gasoline. residual Gas oil. No. gas oil. coke. coke. CO.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 15 Doc. TECP . tar tower residual Conversion – Unification Processes Process Name Alkylation Action Combining Method Catalytic Purpose Unite olefins Feedstock(s) Tower Product(s) Iso-octane . cracked oil. distillate petrochemical feedstock Gas oil. O2. 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. gas. higher-quality residual products Desulfurized Hydrogen.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. Gasoline. lube stock. Lighter. distillate. CO2 steam Atm tower Cracked heavy fuel/ naphtha. distillate petrochemical feedstock Gas oil.
No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 16 Doc. fatty acid.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 . 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. pentane. hexane Product(s) High octane. TECP . alkyl metal Cracked olefins (alkylate) Lubricating grease High-octane naphtha. 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.
cracked HC’s Lube oil base stocks Vacuum Tower residual. convert mercaptan hydrocarbons. TECP . LPG. lube High quality lube oils Heavy lube oil. saturate HC’s Improve viscosity index.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.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 17 Doc. asphalt Dewaxed lube basestock High-octane gasoline High-quality distillate/gasoline Solvent deasphalting Solvent dewaxing Solvent extraction Sweetening . propane Vacuum tower lube oils Gas oil. alkylation feedstock Cycle oils & lube feed-stocks High-sulfur residual/ gas oil Residuals. contaminants Remove impurities. distillate Untreated distillate/gasoline hydrocarbons High quality diesel & lube oil Desulfurized olefins Cracker feed. color Remove asphalt Remove wax from lube stocks Separate unsaturated oils Remove H2S. reformate. No. distillate.
plugging. In both methods other chemicals may be added. In chemical desalting. Both methods of desalting are continuous. Surfactants are added only when the crude has a large amount of suspended solids. 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.003 Report on Petroleum Refinery Processes CRUDE OIL PRETREATMENT Crude oil often contains water. to reduce corrosion. and water-soluble trace metals. chemical and electrostatic separation. 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. 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.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 18 Doc. use hot water as the extraction agent. inorganic salts. Refineries are able to desalt crude to less than 5 lbs/1000bl. water and chemical surfactant (demulsifiers) are added to the crude. and then held in a tank where they settle out. Electrical desalting is the application of high-voltage electrostatic charges to concentrate suspended water globules in the bottom of the settling tank. 3 CRUDE OIL DESALTING Fig. As a first step in the refining process. The two most typical methods of crude-oil desalting. TECP . Ammonia is often used to reduce corrosion. The temperature is limited by the vapor pressure of the crude-oil feedstock. No. Wastewater and contaminants are discharged . and fouling of equipment and to prevent poisoning the catalysts in processing units. Caustic or acid may be added to adjust the pH of the water wash. suspended solids. heated so that salts and other impurities dissolve into the water or attach to the water. these contaminants must be removed by desalting (dehydration).
to . flashes into vapour that rises up the column &liquid residue that drops downward. The desalted crude is continuously drawn from the top of the settling tanks and sent to the crude distillation (fractionating) tower. TECP .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 19 Doc.003 Report on Petroleum Refinery Processes from the bottom of the settling tank to the wastewater treatment facility. 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. Crude enters the flash zone of the fractioning tower.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. No. which ultimately supplies all the heat required for operation of crude unit. Feedstock Crude oil From Storage Process Treating Typical products . In flashing. CRUDE OIL FLASHING This is done frequently to reduce corrosion in the principal distillation column.
Two types of distillation are performed: atmospheric and vacuum. No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 20 Doc. 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. GASES NAPTHA KEROSENE DIESEL OIL VACUUM DISTILLATION GAS OIL LIGHT LUBE OIL MEDIUM LUBE OIL HEAVY LUBE OIL CRUDE LIGHT OIL (PETROL) HEATER Fig. gas oils. and residuum. 5 CRUDE DISTILLATION ASPHALT Atmospheric Distillation The desalted crude feedstock is preheated using recovered process heat. 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 .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 . The feedstock then flows to a directfired crude charge heater where it is fed into the vertical distillation column just above the bottom. light distillates. middle distillates. Because crude oil is a mixture of hydrocarbons with different boiling temperatures. at pressures slightly above atmospheric and at temperatures ranging from 340° to 370° C (above these temperatures undesirable thermal cracking may occur). The main fractions or "cuts" obtained have specific boilingpoint ranges and can be classified in order of decreasing volatility into gases.
LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 21 Doc.003 Report on Petroleum Refinery Processes As the hot vapour rises in the tower. a de-propanizer is a small column designed to separate propane and lighter gases from butane and heavier components. Then. where the higher temperature causes reevaporation. Columns all work on the same principles as the towers described above. An overflow pipe drains the condensed liquids from each tray back to the tray below. Steam is often used in towers to lower the vapor pressure and create a partial vacuum. and uncondensed gases (which condense at lower temperatures) are drawn off. Fractioning Tower (Stripper) This process is carried out immediately after atmospheric distillation. 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. and heavy residual for propane de-asphalting Other Distillation Towers Within refineries there are numerous other. the various major products including lubricating oil. The internal designs of some vacuum towers are different from atmospheric towers in that random packing and demister pads are used instead of trays. causing some condensation at the temperature of that tray. and scrubbing operation is repeated many times until the desired degree of product purity is reached. The latter permit the vapors to bubble through the liquid on the tray. Heavy fuel oil or asphalt residue is taken from the bottom. At each tray. smaller distillation towers called columns. reduced pressure is required to prevent thermal cracking. The evaporation. Small "bubble" towers called strippers use steam to remove trace amounts of light products from heavier product streams. At successively higher points on the tower.7 BUBBLE CAPS Vacuum Distillation In order to further distill the residuum or topped crude from the atmospheric tower at higher temperatures. kerosene. side streams from certain trays are taken off to obtain the desired fractions. lubricating-oil base stocks. its temperature is reduced. Another larger column is used to separate ethyl benzene and xylene. Fig. heating oil. No. . For example. contains horizontal steel trays for separating and collecting the liquids. The fractionating tower. vapors from below enter perforations under the bubble caps. The equipment is also similar. Products ranging from uncondensed fixed gases at the top to heavy fuel oils at the bottom can be taken continuously from a fractionating tower. condensing. A typical first-phase vacuum tower may produce gas oils. The purpose of stripping is to remove more volatile components and thus reduce the flash point of the side stream product. gasoline. designed to separate specific and unique products. TECP . The process takes place in one or more vacuum distillation towers. a steel cylinder about 120 feet high.
visbreaker.003 Report on Petroleum Refinery Processes Distillation Atmospheric Feedstock Crude oil From Storage Process Treating Typical products .to . TECP . or coker • Vacuum Residuals Atmospheric tower Separation • • • .unit • Desalted crude to Atmospheric distillation tower Waste water to Treatment Gas oils To Catalytic cracker Lubricants To Hydrotreating or solvent Residual To Deasphalter. No.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 22 Doc.
aromatic hydrocarbons from lubricant and grease stocks. which are: (1) mixing the feedstock with a solvent. nitrobenzene. No. naphthenes. and impurities from the product stream by dissolving or precipitation.003 Report on Petroleum Refinery Processes SOLVENT EXTRACTION AND DEWAXING Solvent Extraction The purpose of solvent extraction is to prevent corrosion. or fractionation. protect catalyst in subsequent processes. and residual trace amounts are subsequently removed from the raffinate by steam stripping or vacuum flashing. The most widely used extraction solvents are phenol. (2) precipitating the wax from the mixture by chilling. Electric precipitation may be used for separation of inorganic compounds. The selection of specific processes and chemical agents depends on the nature of the feedstock being treated. the contaminants present. . The feedstock is first dried and then treated using a continuous countercurrent solvent treatment operation. and 2. The solvent is then regenerated to be used again in the process. and the finished product requirements. and cresylic acid. but all have the same general steps.2’ dichloroethyl ether.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 23 Doc. evaporation. furfural. and (3) recovering the solvent from the wax and de-waxed oil for recycling by distillation and steam stripping. and improve finished products by removing unsaturated. TECP . Other solvents less frequently used are liquid sulfur dioxide. 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. The solvent is separated from the product stream by heating. There are several processes in use for solvent de-waxing. The solvent extraction process separates aromatics. Fig.
In addition. which dissolves the oil and maintains fluidity at low temperatures.Lube waxing basestock Vacuum tower Treating • • • . which dissolves little wax at low temperatures and acts as a wax precipitating agent. TECP . methylene chloride.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. ethylene dichloride. and methyl ethyl ketone (MEK).003 Report on Petroleum Refinery Processes Fig.to . there is a catalytic process used as an alternate to solvent de-waxing. kerosene From Atmospheric tower Process Treating and blending Typical products .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 24 Doc. Other solvents that are sometimes used include benzene. propane. methyl isobutyl ketone. petroleum naphtha. No. Process Solvent Extraction Feedstock Naphthas. 9 SCHEMATIC DIAGRAM OF SOLVENT DEWAXING UNIT Usually two solvents are used: toluene. and sulfur dioxide. distillates.
Cracked oils are more resistant to cracking than straight run oil." a process that breaks or cracks the heavier. higher boiling-point petroleum fractions into more valuable products such as gasoline. Cracked Gasoline and middle distillate fractions are removed from the upper section of the column. TECP . but the olefin has an octane approaching 100.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 25 Doc. Fig. No. one may be a six carbon paraffin hydrocarbon & the other a six carbon olefin hydrocarbon. 10 THERMAL CRACKING The process of thermal cracking can be explained as given below When petroleum fractions are heated to temperatures over 350°C. The streams from heaters are combined and sent to a soaking chamber where additional time is provided to complete the cracking actions. 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. to form oils with lower molecular weights and boiling points. Heavy distillates are removed from the lower section and are pumped to separate heaters. Further the paraffin has an octane number approaching zero. The cracked products are then thermally separated in a low pressure flash chamber where a heavy fuel oil is removed from the bottom. thermal decomposition is caused at a significant rate. Majority of regu. The remaining cracked products are sent to fractionating columns. 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. In a typical application of thermal cracking the feedstock is preheated by direct exchange with the cracked products in fractioning columns.003 Report on Petroleum Refinery Processes THERMAL CRACKING Thermal cracking is the thermal decomposition of crude having high molecular weight & high boiling points. .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. but still can be cracked to produce more gasoline. This is carried out till the oil is almost decomposed. and gas oils. fuel oil. it breaks into two parts. 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. subsequent refinery processes change the product mix by altering the molecular structure of the hydrocarbons. When a 12 carbon atom typical of straight run gas oil is cracked.
LARSEN & TOUBRO LIMITED Prepared by QUENCH LIGHT OIL HEATER Dept Equipment Project : : : Technology Center Page 26 Doc. is vacuum-flashed in a stripper and the distillate recycled. Visbreaking Visbreaking. Light feeds (gas oils) and recycled oils require longer reaction times than readily cracked heavier residues. 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. Recycle of light oil (middle distillates or fuel oil) fraction also affects the product state of thermal cracker. and flashed in a distillation tower. a mild form of thermal cracking. Residual from the atmospheric distillation tower is heated (450°500° C) at atmospheric pressure and mildly cracked in a heater. depending on product demand. . 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. It is then quenched with cool gas oil to control overcracking. The thermally cracked residue tar. which accumulates in the bottom of the fractionation tower. Mild cracking conditions favour a high yield of gasoline components with low gas and coke production. TECP . 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. The reaction time is also important. Middle distillates may also be produced. No.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.
1 kg/cm2) and is designed and controlled to prevent premature coking in the heater tubes. Delayed Coking . The process so completely reduces hydrogen that the residue is a form of carbon called "coke. Vapors from the drums are returned to a fractionator where gas. 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. Steam cracking is carried out at temperatures of 800-870 °C..2 kg/cm2.75-2. which is extracted prior to hydrotreating.003 Report on Petroleum Refinery Processes Fig. which heats the residuum to high temperatures (430-500°C) at low pressures (1. temperature. The full drum is steamed to strip out uncracked hydrocarbons. honeycomb coke." The two most common processes are delayed coking and continuous (contact or fluid) coking. The heavier hydrocarbons produced in the fractionator are recycled through the furnace. After the coke reaches a predetermined level in one drum. Three typical types of coke are obtained (sponge coke. and needle coke) depending upon the reaction mechanism. with heavier feeds giving higher yields of by-products such as naphtha. The feedstock range from ethane to vacuum gas oil. Coking Processes Coking is a severe method of thermal cracking used to upgrade heavy residuals into lighter products or distillates. naphtha. and gas oils are separated out. needed to allow the cracking reactions to proceed to completion. 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. ethylene) from various feedstock for petrochemicals manufacture.g. butane.75-5. and at pressures slightly above atmospheric.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 27 Doc.In delayed coking the heated charge (typically residuum from atmospheric distillation towers) is transferred to large coke drums. and naphtha. . Residual from steam cracking is sometimes blended into heavy fuels. Initially the heavy feedstock is fed to a furnace. No. time. Naphtha produced from steam cracking contains benzene. which provide the long residence time. Coking produces straight-run gasoline (coker naphtha) and various middle-distillate fractions used as catalytic cracking feedstock. and the crude feedstock. TECP . the flow is diverted to another drum to maintain continuous operation. until it cracks into lighter products. The most common feeds are ethane.
The remaining coke is dropped into the preheater for recycling with feedstock.to . AXENS Fluid Coking And Flexicoking: This process is licensed by ExxonMobil Feedstock Naphtha. 13 DELAYED COKING cooled by water injection. recycle Gas oil to Catalytic cracking CATALYTIC CRACKING . at a pressure of 3.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 28 Doc. called a reactor. and fractionated. quenched to stop any further reaction. The reacted coke enters a surge drum and is lifted to a feeder and classifier where the larger coke particles are removed as product. Continuous Coking . The process is automatic in that there is a continuous flow of coke and feedstock. 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. In continuous coking.5 kg/cm2. Hydraulic decoking consists of fracturing the coke bed with high-pressure water ejected from a rotating cutter.Continuous (contact or fluid) coking is a moving-bed process that operates at temperatures higher than delayed coking. No. thermal cracking occurs by using heat transferred from hot. and de-coked by mechanical or hydraulic methods. recycled coke particles to feedstock in a radial mixer.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. TECP . blending Process Decomposition Typical products . Coking occurs both in the reactor and in the surge drum.003 Report on Petroleum Refinery Processes Fig. Gases and vapors are taken from the reactor. gasoline From Distillation column.
in which the oil is cracked in the presence of a finely divided catalyst. This process rearranges the molecular structure of hydrocarbon compounds to convert heavy hydrocarbon feedstock into lighter fractions such as kerosene. The catalytic cracking process is very flexible. catalytic activities include dehydrogenation.Feedstock reacts with catalyst and cracks into different hydrocarbons. bauxite. gasoline. Regeneration .4 kg/cm2. Typical temperatures are from 450-510° C at much lower pressures of 0. beads. more desirable products and decrease the amount of residuals. aluminum hydrosilicate. There are three basic functions in the catalytic racking process: • • • Reaction . treated bentonite clay. pellets or shaped materials called extrudites. Fluid Catalytic Cracking The most common process is FCC.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. TECP . . which is maintained in an aerated or fluidized state by the oil vapors. The catalysts used in refinery cracking units are typically solid materials (zeolite. and isomerization. and s silica-alumina) that come in the form of powders. and operating parameters can be adjusted to meet changing product demand.Catalyst is reactivated by burning off coke. hydrogenation. Catalytic cracking is similar to thermal cracking except that catalysts facilitate the conversion of the heavier molecules into lighter products. fuller' earth. No. heating oil. There are three types of catalytic cracking processes are fluid catalytic cracking (FCC).003 Report on Petroleum Refinery Processes Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to increase the quality and quantity of lighter. moving-bed catalytic cracking. and Fractionation . and Thermofor catalytic cracking (TCC).Cracked hydrocarbon stream is separated into various products.7-1. LPG. In addition to cracking. and petrochemical feedstock.
7-2. distillate.1 kg/cm2.003 Report on Petroleum Refinery Processes Fig. then flow downward by gravity through the reactor.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 30 Doc. and steam as the conveying media. the charge is cracked at 0. and raised to reactor temperature (480-540° C) by the hot catalyst. with the standpipe and riser. and some of the heavy oil is recycled to the riser. The cracked product is separated into recycle gas. A typical FCC process involves mixing a preheated hydrocarbon charge with hot. As the mixture travels up the riser. oil. form the catalyst circulation unit. Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. clarified oil. and wet gas. and finally to a regenerator. The fluid catalyst is continuously circulated between the reactor and the regenerator using air. Spent catalyst flows through the catalyst stripper to the regenerator. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process. 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. 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. it merely serves as a holding vessel for the cyclones. TECP . which. The "reactor" no longer functions as a reactor. In the more modern FCC units. vaporized. The regenerator and hopper are isolated from the reactor by steam seals. regenerated catalyst as it enters the riser leading to the reactor. The catalyst section contains the reactor and regenerator. Moving Bed Catalytic Cracking The moving-bed catalytic cracking process is similar to the FCC process. . This cracking continues until the oil vapors are separated from the catalyst in the reactor cyclones. oil vapors. The resultant product stream (cracked product) is then charged to a fractionating column where it is separated into fractions. The charge is combined with a recycle stream within the riser. all cracking takes place in the riser. where most of the coke deposits burn off at the bottom where preheated air and spent catalyst are mixed. naphtha. No.
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. SWEC have developed FCC processes. and recycled. The spent catalyst is regenerated. No. alteration • • .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 31 Doc. coker visbreaker Decomposition. EMRE. Feedstock Deasphalted oils From Deashpalter Process Decomposition.003 Report on Petroleum Refinery Processes Thermofor Catalytic Cracking In a typical thermofor catalytic cracking unit. 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. The flue gas from regeneration is sent to a carbon-monoxide boiler for heat recovery. blend. cooled. alteration Typical products .unit • • • Middle distillates To Hydrotreat. The vapors are separated from the catalyst and sent to a fractionating tower.to . TECP .
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. Hydrogenation also serves to convert sulfur and nitrogen compounds present in the feedstock to hydrogen sulfide and ammonia. Hydrocracking Process In the first stage. the primary function of hydrogen is to prevent the formation of polycyclic aromatic compounds. The process employs high pressure. Hydrocracking produces relatively large amounts of isobutane for alkylation feedstock. The hydrogen is recycled to the feedstock. Depending on the products desired (gasoline components. Kerosene-range material can be taken as a separate side-draw product or included in the fractionator bottoms with the gas oil. TECP .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 32 Doc. Limited hydrocracking also occurs. in the presence of hydrogen and special catalysts. hydrogenation and cracking. When the feedstock has a high paraffinic content.003 Report on Petroleum Refinery Processes HYDROCRACKING Hydrocracking is a two-stage process combining catalytic cracking and hydrogenation. a catalyst. wherein heavier feedstock are cracked in the presence of hydrogen to produce more desirable products. where catalysts convert sulfur and nitrogen compounds to hydrogen sulfide and ammonia. the fractionator is run to cut out some portion of the first stage reactor out-turn. The hydrocracking process largely depends on the nature of the feedstock and the relative rates of the two competing reactions. Another important role of hydrogen in the hydrocracking process is to reduce tar formation and prevent buildup of coke on the catalyst. high temperature. since these feedstock are characterized usually by a high polycyclic aromatic content and/or high concentrations of the two principal catalyst poisons. jet fuel. sulfur and nitrogen compounds. preheated feedstock is mixed with recycled hydrogen and sent to the first-stage reactor. The liquid is charged to a fractionator. No. After the hydrocarbon leaves the first stage. 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). and hydrogen. and gas oil). . it is cooled and liquefied and run through a hydrocarbon separator. Hydrocracking also performs isomerization for pour-point control and smoke-point control.
distillates To Blending Recycle. Process Licensor This process is licensed by Chevron. coker Reformer Decomposition. and reforming in the first stage. ExxonMobil Gas oils Hydrogen Vacuum tower. the operations of the second stage are more severe (higher temperatures and pressures). reformer gas To Gas plant • . hydrogenation Decomposition. the second stage product is separated from the hydrogen and charged to the fractionator. Since this material has already been subjected to some hydrogenation. Like the outturn of the first stage. No.003 Report on Petroleum Refinery Processes Fig. hydrogenation • Gasoline. cracking.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 33 Doc. TECP . 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.
the feedstock is prepared to specification. and aromatic content) and catalysts used. Fig. powerforming. and Thermofor catalytic reforming.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 34 Doc. TECP . No. a significant by-product. by combination of hydrotreatment and distillation. More or less standard is a feed preparation section in which. Hydrogen. ultraforming. 16 SCHEMATIC SKETCH OF CATALYTIC REFORMING (PLATFORMING) PROCESS In the platforming process. 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. Reforming represents the total effect of numerous reactions such as cracking. and passed through a series of alternating furnace and fixed-bed reactors containing a platinum catalyst. It makes a bottom product called reformate. The liquid product from the bottom of the separator is sent to a fractionator called a stabilizer (butanizer). . and other aromatics useful in gasoline blending and petrochemical processing. is separated from the reformate for recycling and use in other processes. dehydrogenation. The naphtha feedstock is then mixed with hydrogen. A catalytic reformer comprises a reactor section and a product-recovery section. Depending on the properties of the naphtha feedstock (as measured by the paraffin. butanes and lighter go overhead and are sent to the saturated gas plant. polymerization. vaporized. benzene. and isomerization taking place simultaneously. reformates can be produced with very high concentrations of toluene. Most processes use platinum as the active catalyst. Sometimes platinum is combined with a second catalyst (bimetallic catalyst) such as rhenium or another noble metal. the first step is preparation of the naphtha feed to remove impurities from the naphtha and reduce catalyst degradation. naphthene.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. xylene. olefin. There are many different commercial catalytic reforming processes including platforming.
1 kg/cm2). dehydrogenate Typical products . and others operate at high pressures (up to 70 kg/cm2).003 Report on Petroleum Refinery Processes Some catalytic reformers operate at low pressure (3. Gas To Gas plant Naphthene-rich fractions Straight-run naphtha Hydrocracker.5-14.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 35 Doc. and some facilities regenerate all of the reactors during turnarounds. dehydrogenate Rearrange. No. . Some catalytic reforming systems continuously regenerate the catalyst in other systems. hydrodesulfur Atmospheric fractionator Rearrange. One reactor at a time is taken off-stream for catalyst regeneration.to .unit • • High octane gasoline . hydrotreat. dehydrogenate • • . Blending Aromatics To Petrochemical Hydrogen To Recycle. etc. Feedstock Desulfurized naphtha From Coker Process Rearrange. TECP .
oxygen. Hydrotreating is also used prior to catalytic cracking to reduce sulfur and improve product yields.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 36 Doc. In . if not removed from the petroleum fractions as they travel through the refinery processing units. Typically. sulfur. the catalysts.003 Report on Petroleum Refinery Processes CATALYTIC HYDROTREATING Catalytic hydrotreating is a hydrogenation process used to remove about 90% of contaminants such as nitrogen. The clean gas is then suitable as fuel for the refinery furnaces. and heating fuel oils. 17 SCHEMATIC SKETCH OF HYDRO-DESULPHURIZATION PROCESS In the reactor. and to upgrade middle-distillate petroleum fractions into finished kerosene. These contaminants. The hydrogen-rich gas from the high-pressure separation is recycled to combine with the feedstock. No. The liquid stream is the product from hydrotreating and is normally sent to a stripping column for removal of H2S and other undesirable components. hydrotreating converts olefins and aromatics to saturated compounds. and metals from liquid petroleum fractions. In addition. the feedstock is deaerated and mixed with hydrogen. hydrotreating is done prior to processes such as catalytic reforming so that the catalyst is not contaminated by untreated feedstock. TECP . Catalytic Hydrodesulfurization Process Hydrotreating for sulfur removal is called hydrodesulfurization. preheated in a fired heater (150-220° C) and then charged under pressure (up to 70 kg/cm2) through a fixed-bed catalytic reactor. Fig. diesel fuel. 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. can have detrimental effects on the equipment. and the low-pressure gas stream rich in H2S is sent to a gas treating unit where H2S is removed. In a typical catalytic hydrodesulfurization unit. the sulfur and nitrogen compounds in the feedstock are converted into H2S and NH3.
003 Report on Petroleum Refinery Processes cases where steam is used for stripping. However. which is high in diolefin content. odor. and gum-forming tendencies of this material. No. can be satisfactorily improved by hydrotreating. Traditionally.unit • • • • • Naphtha To Blending Hydrogen To Recycle Distillates To Blending H2S. a by-product from the manufacture of ethylene.to . and acid nature of the oil. The objectives in mild lube hydrotreating include saturation of olefins and improvements in color.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 37 Doc. TECP . hydrogenation Typical products . the product is sent to a vacuum drier for removal of water. Hydro desulfurized products are blended or used as catalytic reforming feedstock. a suitable route in view of its high octane number. which are cleaner-burning compounds. the outlet for pygas has been motor gasoline blending. Hydrotreating can be used to improve the burning characteristics of distillates such as kerosene. residuals From Atmospheric & vacuum tower. catalytic & thermal cracker Process Treating. color. Process Licensor This process is licensed by ExxonMobil Hydrodesulfurization Process Feedstock Naphthas. only small portions can be blended untreated owing to the unacceptable odor. distillates sour gas oil. whereby conversion of diolefins into mono-olefins provides an acceptable product for motor gas blending. Mild lube hydrotreating also may be used following solvent processing. ammonia To Sulfure plant. The quality of pygas. Hydrotreating also can be employed to improve the quality of pyrolysis gasoline (pygas). treater Gas To Gas plant . Hydrotreatment of a kerosene fraction can convert aromatics into naphthenes. Other Hydrotreating Processes Hydrotreating processes differ depending upon the feedstock available and catalysts used. Lube-oil hydrotreating uses catalytic treatment of the oil with hydrogen to improve product quality.
No. In a typical C5/C6 isomerization process. TECP . There are two distinct isomerization processes. 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. Butane isomerization produces feedstock for alkylation. Isomerization is similar to catalytic reforming in that the hydrocarbon molecules are rearranged.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 38 Doc. 2. butane (C4) isomerization and pentane/hexane (C5/C6) isomerization. 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. Isomerization is important for the conversion of n-butane into isobutane. Hydrogen is flashed off in a high-pressure separator and the hydrogen chloride removed in a stripper column. 18 SCHEMATIC SKETCH OF BUTANE ISOMERIZATION In a typical low-temperature process. and the conversion of normal pentanes and hexanes into higher branched isomers for gasoline blending. . Pentane/hexane isomerization increases the octane number of the light gasoline components npentane and n-hexane. to provide additional feedstock for alkylation units. The resultant butane mixture is sent to a fractionator (deisobutanizer) to separate n-butane from the isobutane product. It is then passed over supported-metal catalyst in the first reactor where benzene and olefins are hydrogenated. Platinum or another metal catalyst is used for the higher-temperature processes. Fig. n-pentane and n-hexane into their respective isoparaffins of substantially higher octane number. 1. and then heated to reactor temperature. Aluminum chloride catalyst plus hydrogen chloride are universally used for the low-temperature processes. isomerization just converts normal paraffins to isoparaffins. but unlike catalytic reforming. which are found in abundance in straight-run gasoline. dried and desulphurized feedstock is mixed with a small amount of organic chloride and recycled hydrogen.003 Report on Petroleum Refinery Processes ISOMERIZATION Isomerization converts n-butane.
LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 39 Doc. 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.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 • • • . 19 SCHEMATIC SKETCH OF PENTANE AND HEXANE ISOMERIZATION The feed next goes to the isomerization reactor where the paraffins are catalytically isomerized to isoparaffins. TECP . No. acid stripped. Axxens Process Feedstock From Various processes Various processes Various processes Process Rearrangement Rearrangement Rearrangement Typical products . and stabilized before going to storage.to .003 Report on Petroleum Refinery Processes Fig. The isomerate is washed (caustic and water). Process Licensor This process is licensed by UOP.
feedstock To Petrochemical Liquefied petro. TECP . and butylene into hydrocarbons of higher molecular weight and higher octane number that can be used as gasoline blending stocks. Fig.unit • • • High octane naphta To Gasoline blending Petrochem.to . where an exothermic polymeric reaction occurs. 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. Polymerization may be accomplished thermally or in the presence of a catalyst at lower temperatures. 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.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 40 Doc. 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. No. In the catalytic process the feedstock is either passed over a solid phosphoric acid catalyst or comes in contact with liquid phosphoric acid. propylene. 20 SCHEMATIC SKETCH OF POLYMERIZATION PROCESS Feedstock Olefins From Cracking processes Process Unification Typical products . gas To Storage . The olefin feedstock is pretreated to remove sulfur and other undesirable compounds.003 Report on Petroleum Refinery Processes POLYMERIZATION Polymerization in the petroleum industry is the process of converting light olefin gases including ethylene.
either sulfuric acid or hydrofluoric acid. 21 SCHEMATIC SKETCH OF SULPHURIC ACID ALKYLATION PROCESS .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 41 Doc. and the sulfuric acid and isobutanes flowing over baffles from zone to zone. Fig. No. The reactor is divided into zones. the feedstock (propylene. branched-chain paraffinic hydrocarbons. and the acid is returned to the reactor. butylene. The octane number of the alkylate depends mainly upon the kind of olefins used and upon operating conditions. The hydrocarbon phase is hot-water washed with caustic for pH control before being successively depropanized. The alkylate obtained from the deisobutanizer can then go directly to motor-fuel blending or be rerun to produce aviation-grade blending stock. TECP . 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).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. amylene. The isobutane is recycled to the feed. Sulfuric Acid Alkylation Process In cascade type sulfuric acid (H2SO4) alkylation units. and debutanized. The reactor effluent is separated into hydrocarbon and acid phases in a settler. deisobutanized. with olefins fed through distributors to each zone. Alkylate is a premium blending stock because it has exceptional antiknock properties and is clean burning. The product is called alkylate and is composed of a mixture of high-octane.
The reactor effluent then goes to its settler. consisting of propane. normal butane.The UOP process uses two reactors with separate settlers. Upon leaving the reaction zone.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.unit High octane gasoline To Blending n-Butane & propane To Stripper or blender SWEETENING AND TREATING . Phillips Process . The top layer of hydrocarbons (hydrocarbon phase). and sent to storage. and excess (recycle) isobutane. with the settler acid being recycled and the hydrocarbons charged to the main fractionator. The main fractionator overhead. Subsequent processing is similar to the Phillips process. the reactor effluent flows to a settler (separating vessel) where the acid separates from the hydrocarbons. treated. 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. No. along with recycle and makeup isobutane. and HF. or hydrocracking Process Unification Unification Typical products . Propane with trace amount of HF goes to an HF stripper for HF removal and is then catalytically defluorinated. Isobutane is withdrawn from the main fractionator and recycled to the reactor/settler. olefin and isobutane feedstock are dried and fed to a combination reactor/settler system. Feedstock Petroleum gas Olefins From Distillation or cracking Cat. Overhead from the main fractionator goes to a depropanizer.to . alkylate.In the Phillips process. TECP . is charged to the main fractionator. 22 SCHEMATIC SKETCH OF HYDROFLURIC ACID ALKYLATION UOP Process . goes to a depropanizer. the bottom product of which is motor alkylate. where the acid is recycled and the hydrocarbon charged to the second reactor. isobutane. The other half of the feedstock also goes to the second reactor. Isobutane is recycled to the reaction zone and alkylate is sent to product blending. The acid layer at the bottom of the separating vessel is recycled. consisting mainly of propane. Fig.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 42 Doc.
Sweetening. and resinous and asphaltic compounds. Sweetening also reduces concentrations of carbon dioxide. dissolved metals and inorganic salts. It is used to improve the odor. By combining caustic soda solution with various solubility promoters (e. Caustic treating with sodium (or potassium) hydroxide is used to improve odor and color by removing organic acids (naphthenic acids. Fig. No. and soluble salts dissolved in emulsified water are removed from petroleum fractions or streams. 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.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 43 Doc. Choices of a treating method depend on the nature of the petroleum fractions. thiophene and mercaptan) to improve color. Sulfuric acid treating results in partial or complete removal of unsaturated hydrocarbons. Clay/lime treatment of acid-refined oil removes traces of asphaltic materials and other compounds improving product color.g. color. stability. heavier components are sent to gasoline blending. carbon residue. or just before sending the finished product to storage. 23 SCHEMATIC SKETCH OF MOLECULAR SIEVE DRYING AND SWEETENING Some mercaptans are removed by water-soluble chemicals.003 Report on Petroleum Refinery Processes Treating is a means by which contaminants such as organic compounds containing sulfur. sulfur. and oxygen. Treating materials include acids. solvents. and end-product specifications. TECP . the extent to which the process removes the impurities. odor. alkalis. methyl alcohol and cresols). odor. amount and type of impurities in the fractions to be treated.. Caustic liquid (sodium hydroxide). and oxidation stability. up to 99% of all mercaptans as well as oxygen and nitrogen compounds can be dissolved from petroleum fractions. propane is recovered for LPG. and adsorption agents. H2S) by a caustic wash. and stability. Caustic. oxidizing. nitrogen. nitrogen. treats sulfur compounds (hydrogen sulfide. Treating can be accomplished at an intermediate stage in the refining process. phenols) and sulfur compounds (mercaptans. and other properties of the oil. a major refinery treatment of gasoline. or Clay Treating Sulfuric acid is the most commonly used acid treating process. Drying is accomplished by . and oxygen compounds. and propylene is removed for use in petrochemicals. Acid. amine compounds (diethanolamine) or fixed-bed catalyst sweetening also may be used.
intermediates From Various Process Treatment Typical products . desulfurization methods vary from ambient temperature-activated charcoal absorption to high-temperature catalytic hydrogenation followed by zinc oxide treating. Sulfur Recovery Sulfur recovery converts hydrogen sulfide in sour gases and hydrocarbon streams to elemental sulfur.unit • • • • Butane & butene To Alkylation Propane. finished products. A typical process produces elemental sulfur by burning hydrogen sulfide under controlled conditions. Depending on the feedstock and the nature of contaminants.to . Sulfur vapor from burning and conversion is condensed and recovered. TECP . The gases are then exposed to a catalyst to recover additional sulfur. Hydrogen Sulfide Scrubbing Hydrogen sulfide scrubbing is a common treating process in which the hydrocarbon feedstock is first scrubbed to prevent catalyst poisoning. Some processes simultaneously dry and sweeten by adsorption on molecular sieves. distillates To Storage Gasoline To Blending Propylene To Petrochemical .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 44 Doc. Knockout pots are used to remove water and hydrocarbons from feed gas streams. which uses both thermal and catalytic-conversion reactions. The most widely used recovery system is the Claus process. No. Feedstock Gases.003 Report on Petroleum Refinery Processes the use of water absorption or adsorption agents to remove water from the products.
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. anti-oxidants. Deasphalting also removes some sulfur and nitrogen compounds. The products are then evaporated and steam stripped to recover the propane. TECP .LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 45 Doc. Separation occurs in a rotating disc contactor. Feedstock Residual. and the oxidation creates sulfur dioxide. and paraffins from the feedstock. generally used to produce road-tar asphalt. distillates. In-line blending of gasoline. temperatures (18-48° C). the residual is heated to about 400° C and charged to a column where vacuum is applied to prevent cracking. which uses propane (or hexane) as a solvent. Steam. gum and rust inhibitors. and pressures of 25-42 kg/cm2.to . catalytic cracking feedstock. metals. heavy oil fractions are separated to produce heavy lubricating oil. reduced crude From Atmospheric tower & Vacuum tower Process Treatment Typical products . detergents. carbon residues. In this extraction process. . anti-knock agents. are added during and/or after blending to provide specific properties not inherent in hydrocarbons. and asphalt. used to blanket the top of the tower to entrain the various contaminants. In vacuum distillation. Additives including octane enhancers. It is further processed to impart characteristics required by its final use. The dehydrogenization of the asphalt forms hydrogen sulfide.003 Report on Petroleum Refinery Processes ASPHALT Asphalt is a portion of the residual fraction that remains after primary distillation operations. which is recycled. jet fuel. metal deactivators. is then passed through a scrubber to condense the hydrocarbons. based on differences in solubility.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. etc. Feedstock and liquid propane are pumped to an extraction tower at precisely controlled mixtures. Asphalt for roofing materials is produced by air blowing. and kerosene is accomplished by injecting proportionate amounts of each component into the main stream where turbulence promotes thorough mixing. No. A third process used to produce asphalt is solvent deasphalting. Products can be blended in-line through a manifold system. or batch blended in tanks and vessels.
etc. 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. grease compounding Wax To Storage or shipping • . No. Wax Manufacturing Process Raffinate from the extraction unit contains a considerable amount of wax that must be removed by solvent extraction and crystallization. and given a final wash to remove all oil. the raffinate is mixed with phenol in the treating section at temperatures below 200° C. sulfur. sulfonated aromatics. Phenol is then separated from the treated oil and recycled. and solvent-extracted (usually with phenol or furfural) to produce raffinate.LARSEN & TOUBRO LIMITED Prepared by : NJ Date : 18-Oct-04 Dept Equipment Project : : : Technology Center Page 46 Doc. and metal working oils. Feedstock Lube feedstock and additives From Vacuum tower. additive response.003 Report on Petroleum Refinery Processes LUBRICANT. and paraffinic and isoparaffinic waxes from residual fractions.). Reduced crude from the vacuum unit is deasphalted and combined with straight-run lubricating oil feedstock. WAX AND GREASE MANUFACTURING Lubricating oils and waxes are refined from the residual fractions of atmospheric and vacuum distillation.to .) in the soap and the additives used. The solvent is recovered from the oil by flashing and steam stripping. preheated. Process Treatment • Typical products .unit Dewaxed raffinate To Lube blend or compound. aluminum. and oxidation stability in extremely selective extraction processes using solvents (furfural.Grease may be either batch-produced or continuously compounded. The raffinate is mixed with a solvent (propane) and pre-cooled in heat exchangers. chilled. etc. The characteristics of the grease depend to a great extent on the metallic element (calcium. color. lithium. 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. The wax is continuously removed by filters and cold solvent-washed to recover retained oil. The primary objective of the various lubricating oil refinery processes is to remove asphalts. phenol. solvent dewaxing. filtered. The wax is then heated with hot solvent. The crystallization temperature is attained by the evaporation of propane in the chiller and filter feed tanks. TECP . carbon residue. In a typical phenol unit. hydrotreating solvent extraction. stability. industrial lubricants. sodium. Lubricating Oil Process The dewaxed raffinate is blended with other distillate fractions and further treated for viscosity index. etc.