Refining

MB-107

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COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)

Course Code: MB-107 Course Name: Refining © UNIVERSITY OF PETROLEUM & ENERGY STUDIES

Contents

Unit 1 Unit 2 Unit 3 Unit 4 Unit 5 Unit 6 Unit 7 Unit 8 Unit 9 Unit 10 Unit 11

Growth & Development of Refining Industry in India ................................... 1 Crude Oil and its Characteristics ...................................................................... 7 Specifications of Petroleum Products & Related Tests ................................ 23 Integrated Refinery & Petrochemical Plants ................................................. 53 Future Refining Scenario .................................................................................. 85 Advances in Petroleum Refining ..................................................................... 89 Hydrocarbon Loss Minimization ...................................................................... 93 Energy Conservation ......................................................................................... 95 Gross Refining Margin ...................................................................................... 99 Oil Accounting .................................................................................................. 103 Excise & Custom – Petroleum Products ....................................................... 107

Various refining processes used in the refineries have been dealt in this module.Objective The objective of this course is to give an insight into various facets of petroleum refining for producing finished products of the desired specifications. Characteristics of crude and specifications of various petroleum products have been explained in detail. . Dealing with growth and development of petroleum refining industry in India. latest advancements in various technologies for improving profitability of the refineries in the face of increasingly stringent product specifications for meeting environmental stipulations have also been described.

Starting with the establishment of the first public sector refinery at Guwahati (Assam) in 1962. fertilizers etc. it has come a long way with the setting up of most modern. These refineries need to be run efficiently so as to make profits. Characteristics of crude oil and specifications of various petroleum products have been explained in detail. The module on refining covers various facets of petroleum refining. petrochemicals. The crude processing capacity of the country has increased from 6 MMTPA in 1962 to 113 MMTPA as of today.An Overview Refining of petroleum for producing fuel and related products for automobiles. . Oil companies in India have met the challenges of the petroleum market product demands with the desired stringent specifications from time to time. by making changes/ improvements in their processes while at the same time sustaining their profitability. domestic consumption and meeting the needs of the power sector. For setting up a 6 MMTPA capacity refinery complex with marketing facilities. Dealing with growth and development of petroleum refining industry in India. and hence need to be modernised and updated from time to time. Various refining processes used in the refineries have been dealt with in this module. and other industries. investments to the tune of Rs 5000 crores are required. India has 17 operating refineries processing both indigenous and imported crudes. The refineries are highly capital-intensive industries with a medium gestation period and produce crucial products for meeting the country's needs including that of defence. latest advancements in various technologies for improving profitability of the refineries in the face of increasingly stringent product specifications for meeting environmental stipulations have also been described. is very vital for the economic progress of the country. The refining industry in India has made tremendous progress since independence with its march in time with the country's economic growth and overall progress. state of the art and highly energy efficient refineries of the present day.

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there is a thrust on increasing their supply by enhancing refining capacity. the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Get an overview of the growth of the Indian Refining Industry after independence. Assam Oil Company was formed. y y With the growth of industry and improvement in the living standard of people. Know about special features of Indian Refining Industry. Setting up of three coastal refineries by Multi National Oil Companies (MNCs) 1947. Oil Production started at Digboi.1957 . demand for petroleum products is increasing rapidly.1 Unit 1 Growth and Development of Refining Industry in India Objectives After studying the unit. The Important Milestones 1866 1889 1893 1899 1901 Oil discovery at Nahorpung. First Refinery started at Margharita. Assam. First refinery in India started soon after oil production started in Digboi. Now we are having seventeen operating refineries with a total capacity of 113 MMTPA. Consequently. Get a good idea of various challenges facing the industry in the present time/in future and strategies for meeting the same. Assam. Thereafter addition of refineries and capacity augmentation continued unabated. Assam. Assam. Digboi Refinery was commissioned supplanting the earlier refinery at Margarita.

Assets of erstwhile Assam Oil Co. Panipat Refinery of IOC commissioned. were taken over and vested in IOC as Assam Oil Division (AOD). __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~.e. IRL was dissolved and merged with Indian Oil Co. 1956 - 1958 1958 - - 1959 - 1962 - 1963 - 1964 - 1974 1981 - 1998 - . was formed for manufacture of lube oils and greases. Ltd. technology and year of establishment and expanded capacity wherever applicable by the end of 10th 5 year plan i. 1954 Indian Oil exploration with the help of Russian Geologists.75 MMTPA) under IRL. Indian Oil Company formed for marketing of petroleum products.YO FP E TR OLEUM & EN ER GY 2 Activity 1 A Reader may like to draw a Geneological Chart of the current refineries operative in India. Discovery of Cambay oil field. 2006 – 07. UNIV ER SIT ST U DI ES k~ e k . The first refinery in the public sector commissioned at Guwahati (0. Oil India Ltd (OIL) was formed as a joint venture company between Government of India and Burmah Oil Co. Inc. Indian Refineries Ltd (IRL) was formed in the public sector to install refineries and pipelines in India. IOBL became part of IOCL. Formation of Oil and Natural Gas Commission for exploration and production of crude oil and gas. and Mobil Petroleum Co. Indian Oil Blending Ltd – A JV between Indian Oil Co. to form Indian Oil Corporation Ltd (IOCL). k ‘ k f D r o’ 2 at Mumbai (Esso & Burmah Shell) 1 at Vizag (Caltex) The MNCs were already marketing petroleum products in India by then. Please classify by company.

UNIV ER SIT ST U DI ES k~ e k . Future Outlook* (as per 2025 vision document) Total Refining Capacity MMTPA 2002 – 03 Barauni Expansion Haldia Expansion HPCL. Numaligarh refinery commissioned. commissioned. Mumbai Expansion CPCL. In the five decades since independence. 16 refineries have been added in the public/private/ joint sectors (including three in the private sector by MNCs.YO FP E TR OLEUM & EN ER GY fo u n ~. Nagapatinam RPL Expansion Essar Oil 2003 – 04 Koyali Expansion Panipat Expansion BPCL Expansion CPCL Expansion BRPL Expansion Paradip Essar Oil Expansion Nagarjuna Oil 2004 – 05 Kochi Refinery Expansion 2005 – 06 Essar Oil Expansion RPL Expansion Bhatinda 2006 – 07 BRPL Expansion Bina * The anticipated growth in petroleum products may not take place 135 __________________ __________________ 170 176 214 221 . which subsequently became PSU’s). k ‘ kf D r o’ UNIT 1 Growth and Development of Refining Industry in India 3 Activity 1 B What are various options for increasing the Refining Capacity in the country? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 1999 2000 - Reliance Petroleum Refinery at Jamnagar.

9.. 3. 11. 4. 15. Nagapatinam Mangalore Refineries & Petrochemicals Ltd. Jamnagar Numaligarh Refineries Ltd. 12.5) 6. 14.00 27. 2. kerosene) Prevalence of old as well as modern technologies u .50 6.30 (6. Mathura Hindustan Petroleum Corporation Limited. k ‘ k f D r o’ Refining Capacity in India as in the year 2002 Year of Commissioning 1901 1962 1964 1965 1974 1982 1975 1954 1955 1966 1969 1972 1994 1995 1998 1999 2000 1.75 (7.YO FP E TR OLEUM & EN ER GY 4 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ No. 6. Vizag Hindustan Petroleum Corporation Limited.50 5.50 (9. Mangalore Indian Oil Corporation Limited Panipat Reliance Petroleum Limited. 10.50 8.00 3. Haldia Indian Oil Corporation Limited. 7. Cochin Chennai Petroleum Corporation Limited.5) 2.50 7. Digboi Indian Oil Corporation Limited. Guwahati Indian Oil Corporation Limited. UNIV ER SIT ST U DI ES k~ e k .35 0. 13..00 3.00 112. Koyali Indian Oil Corporation Limited. Mumbai Bharat Petroleum Corporation Limited. Mumbai Cochin Refineries Limited. Bongaigaon Madras Refineries Limited (CBR). Refineries MMTPA Refining fo u n ~. Chennia Bongaigaon Refineries Limited.0) 13.65 1.00 (9. Indian Oil Corporation Limited. Barauni Indian Oil Corporation Limited. 8.5) 7. Numaligarh Total Capacity 0. 5.0) 6.45 Indian Refining Industry – Emerging Scenario u u u u u u Shifting product demand Stringent product specifications Stringent environmental regulations Feedstock quality deterioration Globalisation Deregulation of oil and gas sector Indian Refining Industry – Special Features u Larger requirement of middle distillates (diesel.5 (18) 3.90 7.50 (10. 17. 16.

YO FP E TR OLEUM & EN ER GY fo u n ~. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u Value addition to refinery streams Increased emphasis on Process Control/ Automation Evolutionary/innovative technological changes expected rather than revolutionary ones Refineries to be integrated . distillates) Meeting higher standards of product qualities More emphasis on environment Value addition to refineries Technologies to improve margins Zero emission refinery u u u u u Capacity Increase (To Meet Demand of Petroleum Products ) u u u Low cost revamps/ addition of units Run length improvement of units Infrastructure development for crude receipt/storage/ distribution Installation of matching secondary processing plants. Describe special features of Downstream Industry. u Future Technological Challenges u Meeting higher demand of petroleum products (viz. Strategies for Indian Refineries u u u Residue upgradation technologies for heavy crudes Technologies for producing lighter fuels Process technologies to improve quality with respect to: – – performance parameters eco-friendly products ii. u .compact and flexible with respect to crude/ product mix. k ‘ kf D r o’ UNIT 1 Growth and Development of Refining Industry in India 5 Activity 1 C i. u A few refineries with size far lower than world standards. Challenges faced and strategies to meet the same. UNIV ER SIT ST U DI ES k~ e k .

Toluene. Generation of power from heavy ends Distillation Range Improvement u New residue conversion technologies like FCC. RDS-RFCC Advanced controls and optimisation Advanced catalysts Continuous simulation of plants/ product mix through computer models Prudent selection of technologies and proper integration of secondary units/ plants. Lab. butene – 1. P – Xylene etc. butene – 2. Hexane. k ‘ k f D r o’ Value Addition u Production of value added products from refinery streams Propylene. UNIV ER SIT ST U DI ES k~ e k . Benzene. N – Paraffin. Hydrocracker. . u Review Questions 1. Please identify technological challenges that refineries will face in future.YO FP E TR OLEUM & EN ER GY 6 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u u u Refining fo u n ~.

Composition varies widely: – – – By geographical location Mix of individual wells Variance of wells with time Chemistry of Petroleum Crude oil contains almost all known hydrocarbons and nonhydrocarbons. __________________ y y y Crude Oil Characteristics and its Significance (General Information) Crude oils are formed by the action of geological processes on the remains of ancient marine life. different types of crudes and their characteristics. It is a complex mixture of hydrocarbons and over 16.000 compounds have been identified in one sample. . mud and salts which get associated during its production and transportation. the learner will be able to: y Activity 2 A How is the crude oil formed? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the chemistry of petroleum. Get an idea of various crudes used in Indian Refineries. it also contains impurities like water. Appreciate the difference between Indian crudes and typical middle east crudes.7 Unit 2 Crude Oil and Its Characteristics Objectives After studying the unit. Develop an insight into the significance of various characteristics of crudes and method of determination of the same. As it is drawn from the earth.

Nickel. Magnesium. Paraffins Cyclopentanes iii. Atmospheric distillation is adopted for separating the compounds present into various fractions upto 366ºC:i. Cycloheptanes Di-cyclo-paraffins Benzenes vii. The purely hydrocarbon content may be as high as 97% and as low as 50% for heavy crude oils. Dinuclear and polynuclear Aromatics are present in smaller amounts in compounds containing metallic constituents such as Vanadium. Copper. The non-hydrocarbon portion retains hydrocarbon characteristics as the molecules contain one or two atoms of elements other than carbon and hydrogen.YO FP E TR OLEUM & EN ER GY 8 Activity 2 B What are the type of hydrocarbons present in the crude? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Cyclohexanes iv. vi. Iron. ii. UNIV ER SIT ST U DI ES k~ e k . Napthenic and Aromatic categories. The carbon content is between 83 to 87% and hydrogen content between 11 to 14%. Aromatic cycloparaffins viii. v. k ‘ k f D r o’ Crude oil. Calcium. The ratio of carbon to hydrogen increases from the low to high molecular weight fraction due to increase in polynuclear aromatic and multi ring cycloparaffins in these higher boiling fractions. Zinc. Based on proportion of types of hydrocarbon. Based on boiling point. C5–90º C light naptha iii. the basic raw material of refining industry. Besides impurities such as Sulphur. the fractions are separated and given secondary treatment to utilise it as finished products. 140ºC–204ºC Mineral Turpentine Oil (MTO) . 90ºC–140ºC heavy naptha iv. Nitrogen and Oxygen compounds mostly present in high boiling point fractions are also present in crude oil. ii. is a mixture of eight different hydrocarbon families: i. Titanium etc. ethane. propane and butane. Overhead gases containing mainly methane. it can be divided into Paraffin.

UNIV ER SIT ST U DI ES k~ e k . ii. Various fractions obtained from atmospheric and vacuum distillation are given further treatment to meet required specifications for use.YO FP E TR OLEUM & EN ER GY fo u n ~. Crude Assay Data are utilised for the following: u u u u u u u u u u Crude oil selection Crude oil grading Crude valorization Crude swapping Crude imports Creation of new infrastructure at the existing refineries Grassroot refineries Production planning management Inventory problems Demand/supply gaps Types of Evaluations Preliminary Assay u Crude characteristics – Consistency of crude supply.e. This is done to assess the utility of the crude for processing for production of various products and their yields. . How do you classify crudes based on proportion of type of hydrocarbon present in them? v. What is Crude Assay? How are these Assays utilized? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Crude Assay Crude Assay is the determination of properties of various fractions of crude oil. 140ºC–240ºC Aviatin Turbine Fuel (ATF) 140ºC–270º Kerosene vii. vi. raw Lube Distillate and short residue. Reduced Crude Oil (RCO) is subjected to vacuum distillation for obtaining vacuum gas oils. 340ºC–366ºC Jute Batching Oil (JBO) 366ºC plus fraction i. 270ºC–340ºC Gas oil viii. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 9 Activity 2 C i.

TBP assay u Yield data and key u characteristics of straight run cuts in fuel range and long residue Detailed Evaluation u Design data for grass root refinery u TBP assay in atmospheric and vacuum range Selection and design of secondary conversion units.YO FP E TR OLEUM & EN ER GY 10 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~. u Product optimisation u u Information Required u u u Base and general properties of crude oil Presence of impurities Operating and design data – – – Fractionating or TBP distillation curves Equilibrium of flash vaporization curves API or specific gravity curves of each fraction distilled. k ‘ k f D r o’ Short Evaluation u Crude characteristics u Absorption of new crude in fuel refinery To study the change in quality of crude over a period of time Detailed characterisation of crude oil including all micro constituents. . FBP characterisation of several long and short residues. Yield and characteristics of sets of distillates in atmospheric and vacuum range with variation in IBP. UNIV ER SIT ST U DI ES k~ e k .

k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 11 Notes __________________ __________________ __________________ __________________ __________________ u Property curves of fractions vs% distilled – – – Mid% curves Yield% curves ISO% curves u Properties and yield of straight run fractions and residues Detailed composition of light distillates Hydrocarbon Type Distribution of Middle and Heavy Distillates __________________ __________________ __________________ __________________ __________________ u u Characteristics of Crude Oil Basic Properties Density & API Reid Vapour Pressure (RVP) Light End Analysis Pour Point Viscosity Wax Content Asphaltenes Carbon Residue Ash Content Distillation Characteristic (D86 or D285) Base of Crude Oil Impurities Water Content Salt Content BS & W Sulphur Content Nitrogen Content Inorganic and Total Acid Trace Metals Crude Oil Characteristics and their Significance Density Density is used for: u u u u Weight to volume or vice versa calculations Checking the consistency of crude supply Control of refinery operations Used in various correlations .YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k .

90 35.9000 0.1 52.6 78.8821 0.4 27.8448 0.7920 0.7930 0.8952 0.0 65.5 60.29 TYPE I I P I I P I I I I I P I I I I I N N N I I N I I N I TOTAL DISTILLATE UPTO 370ºC 79.9430 0.8986 0.85 41.8675 0.64 22.10 21. k ‘ k f D r o’ Also gives a rough indication of type of crude oil MASS (M) VOLUME (V) M/V Density = 141.0 54.55 28.6 60.39 17.9210 0.8495 0.8727 0.35 36.7 42.8484 0.8278 0.1 60.9242 0.50 31.8 28.80 39.55 35.5 API GRAVITY= SP.0 44.YO FP E TR OLEUM & EN ER GY 12 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Specific GRAVITY= M’/V (WATER) u Refining fo u n ~.6 22.85 31.2 60.8553 0. UNIV ER SIT ST U DI ES k~ e k .8527 0. Gujarat Geliki Nahorkatiya Kuwait IF IR.7 31.8414 0.8161 0.91 18.GR AT 60/60°F –131.6 47.10 30.5 43.7 51.9507 API 47.00 35.9340 0.4 60.87 25.5 Examples: Water Kerosene Motor Gasoline = 10 API = 45 API = 58 API Natural Gasoline = 75 API Crude oils are categorised based on gravity Light grades Medium grades Heavy grades CRUDE Narimanam Ankleshwar Jotana Bombay High Heera Kalol Rumaila Ratna Rostam Jhalora Basrah Sobashan N. Oman Elmorgan Jorajan Kharsang Lakwa Jhalora Kothana Rudrasagar Sanand N.Kadi Mix Badarpur Santhol : Above 33 degree API : 23-33 degree API : upto 22 degree API Density 0.7 61.9 .40 33.84 27.0 48.2 52.16 34.30 31.62 36.7 53.8688 0.9 47.8496 0.8549 0.20 35.3 24.8412 0.08 46.99 33.0 59.45 19.8698 0.50 25.22 26.8910 0.0 55.

6 Kg/cm2 0.5% of Sulphur Sour grades >0.YO FP E TR OLEUM & EN ER GY fo u n ~. TYPICAL HYDROCARBON ANALYSIS Components C1 C2 C3 ISO-C4 N-C4 ISO-CS N-C5 TOTAL % WT on Crude ND TRACES 0. u Sulfur is a measure of “sourness” and “sweetness” of crude Sweet grades<0. Kg/cm2 14.3 0.05 Light end analysis carried out by GLC actually gives the percentage of hydrocarbons upto C5 and is the basis of assessing the LPG potential of crude.1 Kg/cm2 6. Component Propane Butane Crude Oil RVP.3 0.1 0.5 1. __________________ __________________ __________________ Reid Vapour Pressure (RVP) and Light End Analysis RVP indicates relative Percentage of gaseous and lighter hydrocarbons in crude oil.3 . k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 13 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Sulphur Crude oils are also categorised based on sulphur.01-0.1 0.5% of Sulphur Sulphur is passed on to products as much as regulations or market accepts. UNIV ER SIT ST U DI ES k~ e k . It is removed in hydrotreater by reacting with H2 and recovered as elemental sulfur in SRU.

3 Pour Point u u Indicates relative amount of wax present in crude oil Is the temperature below which pumping and transportation problems may be encountered Along with viscosity.0 85.°C Viscosity Kinematic cst AT 37.9 +30 Refining fo u n ~.5 9.84 45.18. AT 32°C 24°C 18°C 16°C 7.P.9 30.0 5.32 BH Crude 10. C.7 16. UNIV ER SIT ST U DI ES k~ e k .0 17. These hydrocarbons u u u Affect the flow behaviour of crude Affect the product quality of gas oil.7 45.7 43. is used in pumping and design calculations: u Wax Content Normal paraffins above C16 are solid at somewhat ambient temperatures.0 330. k ‘ k f D r o’ Flow Characteristics of Crude Oils Basrah Crude 3. VGO and asphalt Lube manufacture is also dependent on wax content of the crude. Salt Content It is measure of contamination in crude that will cause overhead corrosion or foul up exchangers by settling and .0 12.YO FP E TR OLEUM & EN ER GY 14 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Characteristics WAX.0 222. 4.6 14.5 -24 6.0 4.30.0 2. 50°C Geological Characteristics Yield Value Dynes/ cm2 AT 32°C 24°C 18°C 16°C Plastic Viscosity. % WT Pour Point.0 10. 3.8 °C.

Ca: 10%. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 15 Activity 2 D i. Mg. .1 POSTULATED STRUCTURE OF STABLISED EMULSION __________________ __________________ __________________ __________________ __________________ __________________ Problems Encountered Due to Salts u u Irregular behaviour in distillation Equipment corrosion in the atmospheric distillation caused by HCL liberated due to hydrolysis of chlorides Increased Consumption of Amonia u Salt is a major cause of blocking and fouling of heat exchangers Residual product contamination 100 Total Chloride evolved as HCL % Ashci % u • • • • 75 50 25 • 0 0 100 200 • 300 400 PTB as Salt Content of Crude PTO AS NACL u Salts may vary widely in ratio of metal ions. Resins Particulates Brine Droplet Asphaltenes Na+ COONa+ COOWaxy Agglomerates ii. UNIV ER SIT ST U DI ES k~ e k . K.YO FP E TR OLEUM & EN ER GY fo u n ~. Mg: 15-20%. Method of determination of salt content. their bad effects and how are these impurities removed? iii. BS&W & Viscosity. though common averages are – Na: 70-75%. What are various impurities in crudes. __________________ __________________ Alkyl Benzene Carboxylates Naphthenates __________________ __________________ FIGURE 2. Ca. How do you separate various fractions present in crudes? sealing. It is removed in desalter by washing and settling mainly chlorides and sulphates of Na.

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Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u

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Mg is most prolific producer of HCL with Ca and Na in descending order Small quantities of HCL may substantially enhance corrosion of sulphur compounds

Methods for Determination of Salt Content
1. 2. IP 77/72 ASTM D3230 Extraction with water KCNS/Ag No 3 titration Conductivity measurement based on calibration with Na, Ca, Mg chlorides standard solutions in mixed alcohol.

Sediment and Water
— Sediment has no relationship with salt but both might increase with connate water Sediment Fine particles of sand clay, volcanic ash, drilling mud, rust, iron sulphide, metals and scale Plugging Abrasion and residual product contamination

Damaging Effects

Water causes irregular behaviour in distillation.

Sediment in crude oil is measured by the following methods: BS & W Sediment by extraction Water content ASTM D 96 ASTM D 4007 DEAN & STARK ASTM D 4006 – Sediment in crude is determined for custody transfer purposes Lower the sediments and water, higher the reliability of the unit. It is also a major pointer for corrosive materials in crude.

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UNIT 2

Crude Oil and its Characteristics

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Activity 2 E Significance of TAN & KUOP. __________________ __________________ __________________ __________________ __________________ __________________

Asphaltenes, Carbon Residue and Ash Content Asphaltenes
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Are polynuclear condensed aromatic hydrocarbons having high molecular weight These are insoluble in heptane and soluble in Benzene/ Toluene Asphaltenes and carbon residue indicate the extent to which heavy hydrocarbons are present in crude oil.

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Ash Content
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Metallic constituents concentrate in the ash of the crude oil

Carbon Residue
It’s a carbonacous residue formed after evaporation and pyrolysis of the sample. The residue is coke and determined by – – – Conradson residue method ASTM D 189 Ramsbottom carbon residue ASTM D 624 Micro-carbon residue method ASTM D 4630

Viscosity
It is a measure of resistance to flow and is an important parameter for effective desalting. It is also highly dependant on temperature. High viscosity crudes need high temperatures for effective desalting. There is a limit for temperature in desalters operation.

KUOP
It is a measure of parafinity vis-à-vis aromaticity of crude. High KUOP is desired for high conversion in FCC, aromatic molecules cannot be cracked in FCC. They will simply take a ride through the plant.

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Activity 2 F What are various crudes processed in Indian Refineries? Where are Indigenous crude found? What is the sulphur content of Indian crudes? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________

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TAN
TAN is actually Total Acid Number. It is a measure of Naphthenic Acid (NA) contents in crude. This leads to corrosion in various sections of the unit. Over 1,500 known NA species are present in crude. All napthenic acids are not corrosive. Latest research indicates that TAN is not a complete Corrosion Index. TAN with 2.5 may corrode at higher rate than TAN with say 6 ! Detailed metallurgical reviews and monitoring mechanisms must be put in place.

Selection of Crude Oil
Technology trends in petroleum refining are driven by the external forces of product demand, product specifications (including environmental consideration), feed stock quality and availability. Crude oil will gradually become heavier and higher in sulphur content. Refineries, of late, have been sincerely attempting to produce fuels to comply with stricter environmental regulations particularly gasoline and diesel and are in the process of reducing the sulphur levels in distillates and fuel oil. Attention is now also being paid to reduce lead and benzene levels in gasoline. Various gasoline and diesel specifications applicable worldwide are given in the later part of this chapter. Crude processed in India are: 1. Indigenous crude oil sources a. b. c. d. e. Bombay high and satellite fields North Gujarat and Ankaleshwar crude Assam crudes KG Basin-Rava crude Cauvery Basin crude

All the above crudes are low sulphur =<0.5% wt, low metal content, poor potential to yield LOBS and bitumen, and some are waxy in character.

. POUR POINT+27ºC WAX CONTENT 8.1 31.041 % Wt. KUOP 11. VISC. 40 VOLT CRUDE MIX ºAPI 46. UNIV ER SIT ST U DI ES k~ e k . 2.92% WI.58 POUR POINT +48 KIN. NAPH 40. .9 3 17.6 19. b.P.7 SMOKE POINT 14mm Arom. Gulf Region Nigeria Malaysia Australia The above crudes are specially selected for production of Bitumen/LOBS/ATF. E. 1:1 % VOL F. POUR POINT+21 WAX CONTENT 6. 73. Gases upto 20ºC Naphtha I.O.T.77% Wt. 67.8% Wt KUOP 12.8% Wt.T. 15% VOL.10 KIN VISC. k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 19 Activity 2 G What straight run fractions are obtained in Atmospheric Distillation? And in Vacuum Distillation? __________________ __________________ __________________ 2. GAS OIL 250–370ºC Vacuum GAS OIL 370–530ºC.4 4. SMOKE PT.8% VOL.8 AROM: 6.P.9 ASSAM CRUDE MIX ºAPI 29.–48ºC DIESEL INDEX 67 POUR +POINT +6ºC KUOP 12-70 KIN. F.2 23.8 5 34.30 NORTH GUJARAT CRUDE MIX ºAPI 26.24% Wr.6% V.7 27. 5.2 22. __________________ __________________ __________________ __________________ __________________ __________________ Comparison of Crudes Comparison of Indian crudes and typical Middle-east crude mix for yield and key properties of straight run cuts:1. d. __________________ 1 2 AROM.<–60ºC DIESEL INDEX 33 POUR POINT –9ºC KUOP II-61 KIN.O. POUR POINT + 68ºC 24.P. 0.5 SMOKE POINT 27mm AROM. 6. VISC. AT 100º C 8. 52% VOL COTANE NO.17%Wt.YO FP E TR OLEUM & EN ER GY fo u n ~.140ºc KEROSENE 140-250ºC 4. 23 mm AROM. C+.8 1-2 15. c. These crudes are having varying range of sulphur from low of high. POUR POINT +30ºC WAX CONTENT 10. 36% VOL.5 CCR 9.9% Wt. 16% Vol NAPH. beside fuel products.9 SULPHUR 0. Short Residue 530º.120 SI ºAPI 13.N.0 GANDHAR+ANKLESWAR (60. AT 100ºC 405 0St API 16.T. AT 100ºC 150(27 0SI CCR 14.85 SULPHUR 0.6% VOL OCTANE No.9ºC 7 0St ºAPI 3.-54ºC DIESEL INDEX 57 POUR POINT +3 KUOP 12.4 10-1 3.9 18.2 6 6.B. VISC.3 N. AT 96.P.0 AROW 5. 3.3 4 27. Imported crudes are sourced mostly from: a.83 SULPHUR 0.

PT–57ºC DIESEL INDEX 58 POUR POINT –12ºC KUOP 12. 16% Vol. PT. type of products. their significance and typical values/ units of measurement. 18. NAPH.T. OCTANE NO.1 SULPHUR 2. VISC. 26.35. a mixture of crudes is selected for a refinery to optimise the cost and meeting products quality specifications. VISC.37 KIN VISC.4 % Wt POUR POINT+ 60ºC NARIMANAM CRUDE ºAPI 47. AT 100ºC 903.085% Wt. k ‘ k f D r o’ 2. Review Questions 1. ) ºAPI 31.1 22. POUR POINT 0 WAX CONTENT 2. 69-6 SMOKE POINT 17mm AROM.08 SULPHUR 0. metallurgy of existing plant and equipment.83 0St API 16.P. POUR POIN T(–30ºC WAX CONTENT 1. AT 100ºC 5. Mostly.6% VOL.35 SULPHER 0.7 30.7 4.17% Wt.7 20.8% Wt. IRANIAN FOMAN (56: 36: 6 VOL.28% Wt. processing schemes of refineries. 25% VOL OCTANE NO.–56ºC DIESEL INDEX 58 POUR +POINT –9ºC KUOP 11-94 KIN.70 6.85% Wt.4 15.9% VOL. CCR 10.1 ARON 21.1 24. POUR POINT+ 30ºC WAX CONTENT 10. F.7 16..98 24.8 18. KUOP 11.36 0St 18. AT 98.9 2. Describe different characteristics of crudes dealt with in this unit.8 SMOKE POINT 26mm AROM.61. Draw a comparison of indigenous crudes with Typical Middle East Crude(s) vis-à-vis important specifications of Petroleum Products. 2.98 0St API 7. crudes are selected after evaluating detailed crude Assay Data.1% Wt. AT 100ºC 4.650St 10.43 CCR 19.98 Selection of Crude(s) for a Refinery Based on product demand.2% Wt.31 KIN VISC.3% VOL.2 1. F.5 28. POUR POINT +72ºC BOMBAY HIGH ºAPI 39.9 SMOKE POINT 27mm Arom. -49ºC DIESEL INDEX 56 POUR POINT +3ºC KUOP 12. F.51 CCR 19.YO FP E TR OLEUM & EN ER GY 20 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ ºAPI 9. .7 Refining fo u n ~. KUOP II. POUR POINT + 54ºC KIN.4 AROM 7.9ºC 5.0 21. UNIV ER SIT ST U DI ES k~ e k .9 30.5 Kuwait+Lt. 53.6 ARON 4% VOL.6% Wt. KUOP 11.3% VOL OCTANE No.

e. UNIV ER SIT ST U DI ES k~ e k . can you produce a. d. b. From which Indian crudes.YO FP E TR OLEUM & EN ER GY fo u n ~. ATF Bitumen Lubes Micro-crystalline wax Good Quality Calcined Petroleum Coke __________________ __________________ __________________ __________________ __________________ . k ‘ kf D r o’ UNIT 2 Crude Oil and its Characteristics 21 Notes __________________ __________________ __________________ __________________ __________________ 3. c.

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their significance and their determination/tests. the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the specifications of various petroleum products.23 Unit 3 Specifications of Petroleum Products and Related Tests Objectives After studying the unit. Bharat III/IV. These quantified characteristics are called “specifications”. y Appreciate crucial specification of HSD & MS from Environmental Pollution Standpoint & Strategies for meeting stringent norms for future Euro III/IV. Some important tests conducted on petroleum products and included in specifications: Flash Point Pour Point Distillation Copper Corrosion Silver Corrosion Sulphur Viscosity Potential Gum Existent Gum RON MON AKI Cetane Number Cetane Index Smoke Point Aniline Point Carbon Residue Vapour Pressure Color BMCI Bromine Number Benzene Content Density Sediment Water Weathering Test . These characteristics are quantified to make them absolute and also to remove any ambiguity in the interpretation. Specifications What are Specifications? Any material which is intended for use in a particular application should have certain characteristics so that it is suitable for use in that application.

Motor Gasoline which is used in spark ignition internal combustion engines. Unlike pure compounds. If the oil does not move.YO FP E TR OLEUM & EN ER GY 24 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. k ‘ k f D r o’ Significance of Tests Flash Point It is the minimum temperature at which the sample gives sufficient vapour which forms an explosive mixture with air giving a flash when a flame is applied to it under conditions of the test method. has the following specifications for distillation: Recovery upto 70o C Recovery upto 100o C Recovery upto 180o C 10 to 45% Min 40 to 70% Min 90% v Min . petroleum oils are mixtures of several hydrocarbons and so will have a boiling range instead of boiling point. Each country has it own legislation with respect to flash point depending upon the climatic conditions of the country. The temperature at which the oil becomes immobile (does not move) is termed as pour point when tested under the conditions of the test methods. Distillation The volatility of an oil is indicated by its distillation characteristics. wax separates out from them making the oil immobile. If the vapour so formed is sufficient to form an explosive mixture with air. Pour Point When heavy petroleum oils containing wax are allowed to settle (like in storage tanks). it forms vapour above it depending upon the ambient temperature. The oil should have suitable boiling range (volatility) so that it can be used in a particular application. UNIV ER SIT ST U DI ES k~ e k . For example. When a product like kerosene is stored either at home or at a commercial location. it cannot be pumped. there would be explosions when a small naked flame is exposed to it. Flash point is associated with safety during storage and application in some respects.

The specification for recovery at 180oC and final boiling point are set to prevent crank case oil dilution and unburnt hydrocarbon in tail gases (air pollution). If the product is corrosive. The specification for recovery at 100oC is set to give power to engine and take load. the burner in a kerosene stove. Silver Corrosion This test is done for Aviation Turbine Fuel (ATF)–Jet A1 Type Some aircrafts of civil aviation and defence use a silver lining in the fuel transfer lines. stove body itself. Hence this test is done for ATF.YO FP E TR OLEUM & EN ER GY fo u n ~. Western countries and USA do not use this test any more. the fuel should easily vaporise to a sufficient degree so that when a spark is applied it can ignite. high speed diesel and fuel oils. This quality is called “easy start”. The maximum limit of 45% is laid to prevent some other undesirable effects such as vapour lock. storage vessels etc. Global efforts are being made to minimise the sulphur content in motor gasoline. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 25 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Since the application is in a spark ignition engine. The specification for recovery at 70 o C is laid to meet this requirement. Copper corrosion test indicates whether the product is corrosive to copper containing alloys or not. Copper Corrosion The fuel product comes on contact with metal parts such as transfer pipe from storage tank. This is a requirement for Indian region only. the fuel should not be corrosive to silver. is a pollutant to the air and affects life. it will corrode these parts and reduces their life. storage tank itself. storage and transportation equipment like pumps. Sulphur Sulphur. besides being corrosive to the fuel systems. . In order to protect this lining. This test is applicable to all fuels.

These type of residues are excluded from the specification. The specification is 40 mg per litre max. It does not show the exact amount of gum that would form on storage but gives a directional indication. The most common are Kinematic Viscosity measured in centi-stokes and Saybolt Universal Viscosity measured in seconds. it gives flow properties which are needed for pump selection for transporting. The unit of measurement is mg per liter. Viscosity is measured in several ways. .YO FP E TR OLEUM & EN ER GY 26 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Some solid material is added to MS deliberately for some purposes. This is required to prevent wear and tear in the moving parts of a machine on account of metal to metal contact. Example: Dye to identify the MS from others. Existent Gum This test is applicable to motor gasoline. That is why this test is done on MS. the residue gets deposited in the carburetor and other parts after the gasoline is vaporised. UNIV ER SIT ST U DI ES k~ e k . One point should be noted. For fuel oils. Viscosity is an important property for lube oils because it gives the lubricating property to the oil. If motor gasoline contains any soluble solid residue. k ‘ k f D r o’ Viscosity Viscosity is the resistance to flow. Olefins are oxidised by atmospheric oxygen to a gummy material which sticks to the carburetor jet of the vehicle or inlet valve leading to valve sticking which in turn results in the malfunction of the engine. The unit of absolute or dynamic viscosity is Poise and that of kinematic viscosity is Stoke. Such deposit may clog the jet and prevent fuel flow due to which the engine stops. This type of gum is characterised by Potential Gum test. Potential Gum This test is applicable to motor gasoline which may contain unsaturated hydrocarbons (olefins).

Some of them have lower octane numbers than corresponding napthenes and some other higher octane number depending upon the branching of the iso paraffin. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 27 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Octane Number It is defined as the per cent volume of iso octane in a mixture of iso octane and normal heptane that gives the same knocking as that of the fuel when tested under defined conditions. When used singly. However. Toluene has a RON 107 when it is a single component system. For example. it behaves as if its octane number is > 120. Some schools of thought say that in multi-component systems. UNIV ER SIT ST U DI ES k~ e k . like naptha.3 Dimethyl Pentane 2 Methyl Hexene-1 Toluene 24. Next comes napthenes followed by iso paraffins. this is only a general rule and may differ in the case of iso paraffins. Similarly Octane numbers of olefins may also differ slightly as given below: l l l l l l l l l l l n-Hexane Cyclohexane 2. Iso octane is assigned a value of 100 and normal heptane 0 octane number.2 Dimethy 1 Butane 2-Methyl Pentane Hexene-2 Benzene N-Heptane Methyl Cyclohexane 2. the hydrocarbons behave in some way and when used in a mixture.8 83 91. olefins and aromatics for the same carbon number.YO FP E TR OLEUM & EN ER GY fo u n ~.8 73. octane number is additive on weight percent basis. Normal paraffins have the lowest octane number. But when it is mixed with other hydrocarbons. Some others believe that it is additive on mol. .4 90 >100 0 75 88 92 107 Octane numbers are not truly additive. they behave in another way.

k ‘ k f D r o’ per cent basis. This test has reverse characteristics of octane number. AKI = (RON + MON)/2 Anti Knock Index is regarded as more critical for engine performance than RON alone. Test Condition RON 600 RPM 13 o -125o F MON 900 RPM Variable 300 o F 100 o F Engine speed Spark advance Mixture Temp In Take Air Temp AKI (Anti Knock Index) It is defined as the average of RON and MON. although it is a primary fuel. Another consideration for using HMN is its easier availability. Here. olefins and aromatics in general . Research Octane Number and Motor Octane Number. In effect.YO FP E TR OLEUM & EN ER GY 28 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. These are determined under different conditions of the test. Cetane Number This test is applicable to diesel fuels which use ignition by compression. So. This is hepta Methyl Nonane (HMN). normal paraffins have highest cetane number followed by naphthenes. UNIV ER SIT ST U DI ES k~ e k . there are always some exceptions and some deviations. n-Cetane is assigned a value of 100 and alpha methyl naphthalene a value of 0. It turns red when exposed to air. Alpha methyl naphthalene has some storage stability problem. a secondary fuel for routine use is also stated in the test method. iso paraffins. Cetane number is defined as the per cent volume of n-cetane in a mixture of n-Cetane and alpha methyl naphthalene that would give the same knocking as that of the fuel under test.

If the kerosene gives smoke when it burns. __________________ __________________ __________________ Aniline Point Aniline point is the minimum temperature at which equal volumes of sample and aniline are miscible. Smoke Point Smoke point is defined as the maximum length of the flame which does not give smoke when tested under prescribed conditions using the prescribed apparatus. Naphthenic hydrocarbons have intermediate aniline points. So the higher the flame without smoke. Smoke point shows the hydrocarbon nature of the fuel. Paraffins contain highest hydrogen content for the same carbon number. But if the kerosene starts giving smoke. The specification of smoke point for kerosene in our country is 18 mm minimum. . Aniline point gives the hydrocarbon nature of the oil. Smoke point is related to hydrogen content of the fuel. Aromatic hydrocarbons have lower aniline points and paraffinic hydrocarbons have higher aniline points. So the smoke point of paraffins is highest. As the flame size increases the light given out would also be more. The main purpose of kerosene is for use in lantern.YO FP E TR OLEUM & EN ER GY fo u n ~. the better. Cetane index is not applicable to fuels containing cetane improves. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 29 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ but the order may vary depending upon the chain length of iso paraffins. the height of the flame has no meaning. UNIV ER SIT ST U DI ES k~ e k . The higher the hydrogen content. Paraffins have high smoke points followed by naphthenes and then by aromatics. the higher will be the smoke point. Cetane Index It is an alternative to cetane number. The test is applicable primarily to kerosene. it gives less light. It is nearly equal to cetane number but not an actually determined value required cetane engine.

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Aniline point in combination with density /specific gravity/ API gravity gives a quick idea of some important properties like Diesel Index, Aniline-Gravity Product which are important properties for diesel and ATF. Aniline gravity product is an alternative to calorific value.

Carbon Residue
Every oil, when it burns, forms a carbon deposit which is very difficult to burn. This carbon deposits on burner tips chocking the orifices due to which the flow of oil stops and burner tip needs to be cleaned. If this carbon deposit is more, the burner tips have to be cleaned more frequently. Carbon residue test gives an indication of the amount of carbon that would form when the oil is pyrolysed and burned. There are two methods to determine carbon residue: 1. 2. Ramsbottom Carbon Residue (RCR) Conradson Carbon Residue (CCR)

Vapor Pressure
This is an indirect method of estimating most extreme low temperatures under which initial vaporisation can be expected to take place. It can be considered as a semi quantitative measure of the amount of most volatile material present in the product. It can also be used as a means of predicting the maximum pressures which may be experienced at fuel tank temperatures.

Colour
Two types of tests are applicable to petroleum products 1) Saybolt colour and 2) ASTM Color. The former is applicable to white oils like kerosene, naphtha, MTO etc and the other is applicable to diesel, vacuum distillates etc. The colour gives an indication of the degree of refining or contamination with foreign bodies.

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31
Notes __________________ __________________ __________________

BMCI (Bureau of Mines Correlation Index)
BMCI is an indication of predominant nature of Hydrocarbons in a product. All normal paraffins have BMCI zero or less than zero. A high BMCI indicates predominantly Aromatic nature. A low BMCI indicates predominantly paraffinic nature. Intermediate BMCI indicates mixtures of both and also naphthenic nature. BMCI more than 100 indicates presence of condensed rings. BMCI of some hydrocarbons
Hydrocarbon N Paraffins Iso Paraffins Cyclohexane Benzene BMCI 0 or < 0 < 15 50 99

__________________ __________________ __________________ __________________ __________________ __________________ __________________

BMCI is a calculated value form density and 50% boiling point. It is defined as, BMCI – (48640 / K) + (473.7 * G) – 456.8 Where, K = 50% Boiling Point in G = Specific Gravity @ 20
o

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There are graphical correlations between BMCI and Viscosity and Density also which are nearly equal to the calculated value.

Bromine Number
Bromine number is defined as the grams of bromine that react with 100 grams of the sample. Bromine number gives the olefinity of the sample.

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Olefins react with bromine giving additional products. Each double bond absorbs two atoms of bromine. Example:
CH3CH2CH2CH2CHBRCH2Br

Benzene Content
This test is applicable to motor gasoline. Benzene is carcinogenic (causes cancer). Its limit in MS is recognised by all countries. The specification for benzene in India is 5%v for general supplies and 1% v max for supplies to NCR.

Density
Petroleum products are liquids. They are sold on a volume basis but the custody transfers are effected on weight basis. Density is required for mass balance calculation and is also useful for several correlations which indicate the hydrocarbon nature and other properties. Some of such correlations are, BMCI, Kuop, VGC.

Weathering Test
This test is applicable to LPG. It indicates the amount of non vaporisable matter in LPG.

Specifications of Petroleum Products
LPG (IS 4796)
Test Density Volatility (95% Ev Temp) C Vapor Pressure @ 38 C Copper Corrosion @ 38 C Sulphur Odor %w -o o o

Unit kg / M3 kg / cm2

Specification Report +2 Max 7 Max 1 Max 0.05 Max Identifiable

UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 33 Activity 3 A What are different Petroleum Products? __________________ __________________ Motor Gasoline (IS 2796 .1 max 0...YO FP E TR OLEUM & EN ER GY fo u n ~.013 35-60 750 max 950 max 5 max 1max for NCR 1 __________________ __________________ PC Naphtha Test Appearance Color Density @ 15 C Distillation IBP FBP Total Paraffins Normal Paraffins Iso/Nor Paraffin Ratio n C6 nC7 %w %w kg/M3 C C %w %w ASTM D 5443 ASTMD 5443 Unit Method Visual Visual P:16 P:18 Requirement Clear and Bright Colourless To Report 28 min 160 74 min 36 min 1.05 max To Report To Report Contd.2000) Test Color Density @ 15 C Distillation Recover @ 70 C % v Recovery @ 100 C % v Recovery @ 180 C % v Final Boiling Point C Research Octane Number Anti Knock Index Existent Gum (Solvent washed) Potential Gum Sulphur Lead as Pb Reid Vapor Pressure VLI Summer Winter Benzene %v Cu Corrosion @ 50 C for 3 Hrs Water Tolerance Summer Winter Oxygenates % v ASTM D 4815-89 NB: 1) MFA containing Phosphorus compounds should not be used 2) Potential Gum before doping MFA 10 0 15 max o o o o o o Unit -kg / M3 Method Visual P:16 P : 18 Requirement Orange 710 – 770 10 – 45 40 – 70 90 min 215 max __________________ __________________ __________________ __________________ __________________ __________________ P:27 P:26 & P:27 gm/M3 gm/M3 %w gm/1 KPa P:29 p:147 P:34 ASTM D 5059 P:39 --ASTMD 3606 P:15 88 min 84 min 40 max 50 max 0. .

ATF? How do these affect performance? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Aromatics Olefins Total Sulphur Mercaptan Sulphur Reid Vapor Pressure @ 38ºC Chlorides Lead Arsenic and Mercury ppm w ppb w ASTMD 4929 P:82 ICP %w %w ppm w ppm w Kpa P:23 P:34 B P:109 P:39 Refining 10 max 1 max 100 – 250 150 max To Report fo u n ~.0 max 0..25 max mm %w Aviation Turbine Fuel (IS 1571 .30 max 0. HSD. UNIV ER SIT ST U DI ES k~ e k .. 0.015 max 25 max 5. k ‘ k f D r o’ 5 max 100 max To Report Superior Kerosene (IS 1459 .1974) Test Acidity (Inorganic) Burning Quality Char value Bloom on chimney Color (Saybolt) Undyed Dyed Copper Corrosion @ 50 o C for 3 Hrs Density @ 15 o C Distillation Recovery @ 200 Final Boiling Point Flash Point Abel Smoke Point Total Sulphur o Unit mgKOH/gm Method P:2 Requirement Nil mg/kg Oil P:5 20 max not darker than grey Units P:14 +10 Blue P:15 kg/M3 P:16 Not worse than 1 To Report C %v o o P:18 20 min 300 max C C P:20 P:31 P:34 35 min 18 min 0.1992) Test Appearance Unit -Method Visual Requirement Bright. Petrochemical Naphtha.003 Acidity Total Aromatics Olefins Total sulphur Mercaptan sulphur mg KOH/gm %v %v %w %w P:113 P:23 P:23 P:34B P:109 Contd. .YO FP E TR OLEUM & EN ER GY 34 Activity 3 B What are the key specifications of Motor Spirit. LPG. Free from solid matter and visually undissolved water.

2 max 0.Density @ 15 degree C kg/M3 P.0 max 4800 25 min 3.775 to 0.01 0. ..3 (on 10 % residue) 48 min ASTMD 4737 46 min P:10 3 Winter Contd. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 35 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Distillation 10 % v Recovered at 50 % v Recorded at 90 % Recovered at Final Boiling Point Flash Point Density @ 15 C Freezing Point Kinematic Viscosity @ Minus 20 C Aniline Gravity Product Smoke point Naphthalenes Copper Corrosion % 100 degree C for 2 Hrs Silver Corrosion @ 50 degree C for 4 Hours Thermal Stability Pressure Differential Tube Rating Visual mm P:97 Visual 25 max 3 max No Peacock Or abnormal color deposits 7 max 85 min 50 to 450 --IP 227 1 max --P:15 1 max cST --mm %v P:25 P:3 ISO 3014 ISO 3014 8..840 Minus 47 max __________________ __________________ Existent Gum MSEP Electrical Conductivity Lubricity mm mg/100 ml --ps/M P:29 P:142 IP 274 ASTMD 5001 Report High Speed Diesel (IS 1460 – 2000) Test Acidity Inorganic Acidity Total Aah RCR Cetane Number OR Cetane Index Pour Point Copper Corrosion @ 100 degree C for 3 Hrs .0 max degree C degree C degree C degree C degree C kg/M3 degree C P:18 P:18 P:18 P:18 P:20B P:16 P:11 205 max Report Report 300 max 38 min 0.15 P:16 1 max 820-860 Unit mg KOH/Gm mg KOH / Gm %w %w ------- Method P:2 P:2 P:4 P:8 P:9 Requirement Nil 0.YO FP E TR OLEUM & EN ER GY fo u n ~..

005 max 0.0 0. k ‘ k f D r o’ 85 min 95 min 35 min 2..5 to 15.5 max 12 Summer 21 Winter Copper Corrosion @ 100 deg C for 3 Hrs Flash Point (PMCC) Kin Vis @ 40 deg C Sediments Density @ 15 deg C Total Sulphur Water content --deg C cST %w kg / M3 %w %v P:15 P:21 P:25 P:30 P:16 P:33 P:40 2 max 66 min 2.05 0.5 max Kin Viscosity @ 40 deg C Sediments Total Sulphur Water Content CFPP __________________ Lubricity HFRR Scardia Micron at 60o C.02 max 1.05 max 910 max 0.1 Max Report 1. UNIV ER SIT ST U DI ES k~ e k .05 max PSS --0.35 max 0.0 Max 8 max Unit %w Method P: 132 Requirement 10 max PSS 8 max Contd.7 0..YO FP E TR OLEUM & EN ER GY 36 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Total Sediments mg/100 ml UOP 413 Distillation Recovery at 350 degree C % v Recovery at 370 degree C % v Flash Point degree C cST %w %w %v deg C P:18 P:18 P:20 P:25 P:30 P:33 P:40 P:110 Refining fo u n ~.0 to 5.05 max 6 Winter 18 Summer 1.3 max 0 max 0 max Petroleum Coke (IS 8402 . .25 max 1b 66 min 2. 400 Proposed Light Diesel Oil (IS 1460 .2000) Test Acidity Inorganic Ash RCR on whole sample Pour Point Unit mg KOH/Gm %w %w deg C Method P:2 P:4 P:8 P:10 Requirement Nil 0.0 0.5 to 5.0 max 0.1994) Test Moisture as Received Moisture after Initial drying Ash on Dry basis Volatile Matter %w %w %w P: 132 P: 126 P: 134 2.8 max 0.45 max 11 max --1.25 0.

5 max 88 min 7.0 max __________________ __________________ __________________ ppm w ppm w ppm w ppm w UOP 389 Report 150 max 1600 max 400 max 150 max __________________ __________________ __________________ __________________ __________________ ASTMD 4097 50 MIN Kcal/ Kg --8000 min…………. UNIV ER SIT ST U DI ES k~ e k .These are described below: Paraffins (Cn H2n+2) – – – – – Thermally and chemically most stable compounds. Composition of motor gasoline profoundly affects its performance in the engine and equally controls its behaviour under storage and handling. Have poor octane number Increasing the chain length reduces the octane number Knock resistance increases with branching Adding methyl groups (CH3) to the side chain in the central position increases the knock resistance Olefins (Cn H2n) – – Oxidation and thermal stability is poor in general More knock resistance than their corresponding saturated compounds. __________________ Properties of Petroleum Products and their Significance Gasoline Effect of Chemical Composition on Gasoline Quality Octane number is the most important property of motor gasoline.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests kg/ M3 P: 133 Report 560 min 37 Notes __________________ Density (Dry) Fixed Carbon (On Dry Basis) Total Sulphur Trace metals Silicon as Si Iron as Fe Vanadium as V Nickel as Ni Hardgrove Grindability Index GCV %w %w Calculation 85 min P: 33 2. .

Aromatics (CnH2n-6CnH2n-12 etc) – Aromatics have excellent knock resistance qualities.8 11. Heat of Vap. Oxygen Cont. k ‘ k f D r o’ Cycloparaffins (CnH2n) – – – Poorer knock resistance than corresponding aromatics Lengthening of side chain decreases knock resistance Branching of side chain is beneficial.YO FP E TR OLEUM & EN ER GY 38 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.2 10.9) 43 Trace 65 6.0 82. Btu/Gal (J/lit) Net Heat comb. Properties of Gasoline and Oxygenated Compounds Property Chem. UNIV ER SIT ST U DI ES k~ e k .6 32 50 46 35 60 27 74 22 88 18 111 0 Methanol CH30H Ethanol C2H5OH Isopropyl Alcohol C3H70H Tertiary Butyl Alcohol C4H90H MTBE C4H9OCH3 Gasline C8H15 (Av. MJ/Kg SolubiSolubility in water.8) 21 ∞ 2600 (9. % mass B.5) 32 ∞ 1700 (6.7 30-20 14. Formulae Mol.1 55 11. there is an induction period before normal hot .3 9.2) 35 4.8 800 (2.ºC StoichioMeteric A/F Lat. g/100g water RON MON 101 82-87 3300 (11.3) 28 ∞ 2100 (7.P.3 82. Wt.) 107 108 112 113 116 87-93 Gasoline Properties Needed for Acceptable Performance Fuel Performance Required Handling and Storage Property Controlled for Automotive Gasoline Volatility Vapour (Water/Sediments/Gum) Copper Corrosion Combustion Engine Cleanliness Octane Number Volatility/Distillation Range Gravity Hydrocarbon Compostion Sulphur Existent Gum Oxidation Stability Pressure Contamination Combustion and Knock Before combustion.4 78.1) 35 ∞ 900 (3. air and fuel is heated up in combustion chamber.

aldehydes and peracids prevents knock due to their ability to dissociate and promote such type of intermediate reactions. – – – Loss of power due to reduction in volumetric efficiency Exhaust valve corrosion Spark plug fouling . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 39 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ flame occurs. Low Anti-knock Value: Paraffins Combustion Chamber Deposits Deposits are formed by – – – – Incomplete Combustion Partial Oxidation Cracking Condensation and Polymerisation of fuel and lubricants May contain nonvolatile reaction products of additives – Deposits can lead to: – Pre-ignition Peak pressure and temperature will increase due to apparent increase in compression ratio and poor heat transfer due to heat insulation effect. Formation of peroxides.YO FP E TR OLEUM & EN ER GY fo u n ~. oxidation of fuel takes place with the formation of intermediate products such as peroxides. Knocking Tendency High Anti-knock Value: Aromatics. isoparaffins with little branching. Naphthenes. aldehydes and peracids. During this induction period. Isoparaffins (highly branched) Intermediate Anti-knock Value: Mixed parffins e. UNIV ER SIT ST U DI ES k~ e k .g.

UNIV ER SIT ST U DI ES k~ e k . Ease of starting depends on: y y y y Fuel volatility Engine design Cranking speed Engine oil viscosity Warm Up and Acceleration It depends on: 1.YO FP E TR OLEUM & EN ER GY 40 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Fuel volatility and ambient temperature Provision for thermostatical controlled hot spots. Volatility influences: – – – – – – Ease of starting Rate of warm up and acceleration Tendency to vapour lock Carburettor icing Crankase dilation Fuel economy Ease of Starting For a cold engine start. Vapour Lock and Percolation Vapour lock is a function of : 1. Volatility characteristics of fuel Fuel requirement of engine at the moment Ability of fuel pump to handle the vapour . k ‘ k f D r o’ Volatility Volatility of gasoline is its tendency to pass from liquid to vapour phase. Warm up is mainly a cold weather problem. enough gasoline in the intake air must be evaporated. 2. 2. 3.

__________________ __________________ __________________ __________________ __________________ __________________ __________________ Reid vapour pressure (RVP) Controls the volatility due to lighter ends. temperature and barometric pressure.YO FP E TR OLEUM & EN ER GY fo u n ~. 5.2 6 8 . ASTM D-86 Distillation Significant temperatures are – – – – – – 2. UNIV ER SIT ST U DI ES k~ e k . FBP Non-volatile residue left in the flask.6 0 . Carburetor Icing It occurs due to following: – – Stoppage of the fuel flow due to clogging of the jetice Formation of ice on the walls of carburetor ventenary which causes the engine to stall due to over-rich fuel/ air mixture . underbonet Measurement of Volatility 1.1 5 . Vapour lock index (VLI) 10 RVP+ E 70 Gives better indication of vapor locking. Initial boiling point Temperature corresponding to 10% Vol.6 P ro p a n e B u ta n e M o to r G a s o lin e 1 4 . Temperature corresponding to 90% Vol. The temperature and pressure in the fuel system The temperature of ambient air. TYPICAL VALUES OF VAPOUR PRESSURES (RVP) K g /c m 2 PSI 200 80 10 KPa 1 3 8 2 . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 41 Notes __________________ __________________ __________________ 4. Temperature corresponding to 50% Vol.7 3.8 5 4 9 .

Sulphur and nitrogen compounds also take part in these reactions Gum formation is influenced by storage conditions. Remedial Measures – – Control of fuel volatility Providing heating of carburetor body or the intake air. and may lead to valve burning May cause malfunctioning of carburetor float or impair the functioning of throttle Deposits formed in the intake may restrict engine breathing and reduce the efficiency of hot spots resulting in increased warm up period It can lead to increased sludge and varnish deposits in the engine. temperature. and catalysts particularly traces of copper. Impact of Gum Formation y May cause intake valve sticking due to deposition of Gum. particularly during warm up period Providing greater throttle opening during starting By incorporation of anti-icing agents Anti-freeze type Surface active agents – – Oxidation Stability Gum formation takes place in storage due to oxidation/ polymerisation reaction undergone by the unsaturated hydrocarbons and it accelerates at higher temperatures. what is its impact and how is it overcome? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ l l Refining fo u n ~. y y y . k ‘ k f D r o’ – – High volatility of fuel Cold and humid climate are favorable for icing.YO FP E TR OLEUM & EN ER GY 42 Activity 3 C How is gum formed in motor spirit. access of air and light. UNIV ER SIT ST U DI ES k~ e k . Gum is a rubber like resinous material and is insoluble in later stage of formation.

YO FP E TR OLEUM & EN ER GY fo u n ~. A direct result of leakage of unburnt fuel can be corrosion of engine parts.005% Max 0. Sulphur. Stringent specifications are required to be followed due to environmental considerations. Automotive industry requirement for meeting Euro III/ IV emission standards for Motor Gasoline. If these H2S and COS are mainly corrosive and RSH is distinctively unpleasant. on oxidation.05% Max 2. RON 89 91 93 Benzene content Aromatics Olefins Lead Content Sulphur Content Oxygen Content MON 79 to continue for old cars 81 to be widely available 83 to continue for high CR cars 1% Max 40% Max 25% Max 0. forms oxides of sulphur which react with water to form sulphuric acid.70 Max __________________ __________________ __________________ __________________ __________________ __________________ Diesel Fuels BIS Grades of Diesel Fuels There are three grades of diesel: – – – High Speed Diesel (HSD) Light Diesel Oil (LDO) Marine Diesel (MD) . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 43 Notes __________________ __________________ __________________ __________________ Sulphur Compounds and Corrosiveness: Most of the sulphur compounds are removed in the manufacturing processes. UNIV ER SIT ST U DI ES k~ e k .

Volatility . Stability Exhaust Emission Standards Effect of Diesel Fuel Hydrocarbon Type Composition on its Quality Paraffins – – – Have the best combustion characteristics and highest cetane numbers With molecular weight of n-parrafins.Cloud/Pour pt.Corrosive constituents .Cetane Number .Contaminants Control characteristics . With branching cetane number is lowered. . cetane number increases Isoparaffins have lower cetane numbers than the paraffins of same carbon numbers.Flow .Gravity .Volatility .Flash Points . UNIV ER SIT ST U DI ES k~ e k .Ignition Delay . k ‘ k f D r o’ HSD Blending Components (Typical) B0ILING RANGE ºC 148-204 204-260 250-315 315-350 204-343 204-343 204-340 CETANE NUMBER 28-42 45-50 45-50 50-55 15-20 50-60 15-20 FUEL Performance Requirements Performance Handling & Storage Property . Sulphur Content.Metals . SR Gas Oil Heavy Gas Oil LT.Cloud & Pour Point Cleanliness Use During .Copper corrosion .Viscosity .Heat content . Cycle Oil Hydro Cracker Go Coker Kerosene Refining fo u n ~.Heavier constituents .Distillation Range .YO FP E TR OLEUM & EN ER GY 44 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Heavy SR Naphtha Kerosine LT. Olefins – Olefins have lower cetane numbers than paraffins of corresponding structures and follow similar rules of branching .CFPP Combustion . Bottom Ash Content.Water & sediments .Corrosive constituents Carbon Residue on 10%.

Aromatics – Impart lowest cetane number and most important factor controlling the cetane number of cracked gas oil Aromatics ring condensation and the side chain branching on rings that cause molecular configuration of lowest cetane numbers. large quantities of oil are gathered in the combustion chamber. As a result of abnormal ignition delay. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 45 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ – Presence of olefins gives rise to poor oxidation stability. – Ignition Quality This is the most important property that controls combustion process.YO FP E TR OLEUM & EN ER GY fo u n ~. Naphthenes – Naphthenes follow olefins in cetane quality but are a good deal higher than aromatics. Spontaneous burning and detonation of this surplus fuel in combustion chamber causes rough ignition which is termed as diesel knock or cetane knocking. 44 Additive dozes 1. It is measured as a cetane number which is a measure of ignition delay and is controlled by – – – – Fuel composition and characteristics Engine design Fuel and air inlet temperature Degree of atomisation.5% Isoproyle Nitrate n – Amyl Nitrate Increase in CN 17 23 . Cetane Improver Additives Base Diesel Cetane No.

YO FP E TR OLEUM & EN ER GY 46 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~.0 to 5. are generally preheated.0 cst. u u u Cloud Point u Congealing wax settles out and blocks fuel system line and filters. Heavy distillates. As a result combustion is impaired and power economy is decreased. k ‘ k f D r o’ Cyclohexyl Nitrate Octyl Nitrate 22 19 Flow Properties Viscosity u Viscosity of diesel fuel has an effect on handling of the fuel by pump and injector system. Lubricating oil properties of such fuels are usually poor HSD viscosity range is generally 2. u u Cold Filter Plugging Point (CFPP) u Cloud point being a static test does not truly represent actual running conditions. UNIV ER SIT ST U DI ES k~ e k . when used as diesel fuel. High viscosities can cause – – – Poor atomisation Large droplets High spray jet penetration u Low viscosity results in a spray which is too soft and thus does not penetrate sufficiently. Cloud point indicates the temperature at which waxes start precipitating. The temperature at which precipitation occurs depends on the composition and boiling range of the fuel. CFPP is defined as highest temperature expressed as a multiple of 1 o C at which the fuel when cooled u .

u Water and Sediments u These may come into the fuel through contamination during storage and handling. The test can also be used to detect contamination by heavy residues.YO FP E TR OLEUM & EN ER GY fo u n ~. Pour Point u Pour point gives a useful guide to the lowest temperature at which the fuel can be cooled with setting. UNIV ER SIT ST U DI ES k~ e k . Cleanliness in Use Carbon Residue u Gives some indication of coke forming / deposit forming tendencies in the engine. They can cause clogging of filters. ash. u u u u Ash Content u Indicates the presence of small quantities of metallic soap or volatile porphyrines. u u . Deposits are mainly carbonaceous matter. Unburned metallic constituents have abrasive action and cause wear by adversely affecting the nature of deposits. Type of deposits is also an important factor. Maintenance life and period of over-haul mainly depends on deposit control. Hard abrasive deposits can do more harm than soft fluffy deposits. Sediments cause wear and create deposits both in the injection system and engine itself. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 47 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ under prescribed conditions will not flow through a filter or requires more than 60 sec for 20 ml to pass through. resins etc.

k ‘ k f D r o’ Sediment and Gum Forming Reactions (Diesel Fuel Stability) 1. UNIV ER SIT ST U DI ES k~ e k . Corrosive Constituents Sulphur Content u Strict emission regulations require stringent sulphur specifications Due to high sulphur... Esterification reactions Aromatic Hydrocarbons + Hetrocylic Nitrogen + Benzothiols Multi-step Process Reaction Time …… ….. Low speed diesel engines can tolerate more sulphur. Gum Weeks to months These are more predominant in diesel fuel instability. combustion products corrode and also contribute to deposit formation. Oxidative Gum Reactions Alkenee + Oxygen Reaction time 2. …. because – – – They are large in size and are stationary They are high power output type They run under relatively constant speed and load conditions Their operating temperatures. cooling water and combustion zone temperatures tend to remain at u u – . Sediments Weeks to months …… Hours to weeks …. Acid – Base Reactions Organic acid + Basic Nitrogen …… Sediments Reaction Time 3.YO FP E TR OLEUM & EN ER GY 48 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.

Components of Residual Fuel Oils u u u u u u u Long residue Short residue Heavy cycle oil. Acid value u u Total and Inorganic Potentiometeric Acid/Base titration __________________ Residual Fuels Oils Changes in quality of fuel oils in Indian refineries are due to: u u u Frequent changes in crude quality and blend ratios Intake of more of heavy crudes Introduction of various secondary conversion processes for maximisation of middle distillates. Tests carried out u u Estimation of sulphur content Copper strip corrosion test. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 49 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ an equilibrium rather than to fluctuate between high and low. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY fo u n ~. clarified oil from FCC Hydrocracker bottoms Visbroken products TAR from thermal conversion process Slop Uses u u u u Steam boilers Industrial applications requiring heat Gas turbines Diesel engines .

sulphur compounds. AI2O3.reduce excess air . Fe2O3 NaAIO2 has high melting point (3272 oF). UNIV ER SIT ST U DI ES k~ e k . sludge Na. . V in fuel form low melting point sulphated ash Problems Plugging of fuel lines strainer and burner tips Causes Oxidation of the fuel to produce acid and sludge Refining fo u n ~. In combustion.magnesium additives . economiser. It causes metal spalling or breaking off of pieces of refractory due to its high thermal expansion.YO FP E TR OLEUM & EN ER GY 50 Activity 3 D Effect of metals in furnace oil? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Fuel system corrosion Acidic. u u u u Effect of Metals u Vanadium is a major metallic impurity in residual fuel oil. Na converts to V converts to Na2O + Na2SO4 V2O5 + V2O4 ® Na2 V2O5. water. Sodium is recognised as a potential corrosion problem. Causes corrosion in high temperature zone. Na2 V2O4 5V2O5 (Low melting ash deposits) u u u Other ash deposits are SiO2.combination of both High temperature fouling & corrosion Effect of Sulphur u u Raises dew point of fuel gases Increases formation of sulphur deposits in boiler passages. air–preheater and chimney Reduces efficiency by reducing permissible temperature Accelerates formation of gum and sediments during storage Corrosion of process and plant equipment Sulphur pick by product. k ‘ k f D r o’ Summary of Fireside Problems Related to Fuel Quality Solutions Addition of inhibitors and sludge dispersants Application of corrosion inhibitors .

MS. 3. What is the significance of following tests and to what petroleum product these are related: 2. LPG and PC Naphtha? (Refer Unit 4 & Bibliography). Flash point Distillation Smoke point Octane number Cetane number Viscosity Silver corrosion BMCI Weathering test Copper corrosion Vapour pressure __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ What specifications for Motor Spirit and HSD are related to environmental pollution? What are the limits for these specifications for Euro III / IV standards? What strategies are being adopted to improve these specifications to desired ones from the present values? What would be the impact on cost of production? (Refer Bibliography) What streams of Process Plants in a Refinery are utilised to produce HSD. k ‘ kf D r o’ UNIT 3 Specifications of Petroleum Products & Related Tests 51 Notes __________________ Review Questions 1. UNIV ER SIT ST U DI ES k~ e k . 4.YO FP E TR OLEUM & EN ER GY fo u n ~. .

.

4. Reforming. The raw streams from CDU are treated in Merox. 3. Economies of scale – Minimum 9-12 MMTPA refining capacity. Naphtha. MTO. to minimise processing cost and optimise product distribution. Then it is taken to Crude Distillation Unit (CDU) which operates at atmospheric pressure for fractionation into Gas. 2. provides faster delivery and at lower cost. Isomerisation and Fluid Catalytic Cracking plants to obtain components of . y y Now a days. Jute Batching Oil (JBO) and Reduced Crude Oil (RCO). Give insight into the feeds composition of various process plants for production of finished products. Diesel. Kerosene. RCO is fractionated in Vacuum Distillation Unit (VDU) to get VGO and raw lube cuts. Hydrotreatment. emphasis is laid on the following: 1. 4. A typical integrated refinery and petrochemical plant set up is shown in attached block flow diagram. ATF. Supply chain optimisation from crude to products. (Fig. the learner will be able to: y Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the functioning of various process plants in a refinery and their integration with one another.53 Unit 4 Integrated Refinery and Petrochemical Plants Objectives After studying the unit. Refining and petrochemical plants are integrated. Feedstock flexibility – To utilise low cost crudes. LPG.1) Crude is normally received by tankers or pipelines into crude tanks and allowed to settle for separation of water and sludge. Give an overview of various off-site facilities in a Refinery.

This also helps in environmental protection. Propylene. The short residue obtained from VDU fractionator bottom is partly treated in coker unit to get lighter value added products alongwith raw petroleum coke. Asphalt and vacuum residue can also be utilised for production of bitumen or as fuel for furnaces and boilers. propylene. Sulphur present in crude and various streams is converted to H 2S during processing. The Raw Petroleum Coke (RPC) is used for generation of power and calcined petroleum coke. olefins. In Sulphur plant. Vacuum residue can also be treated to extract out Deasphalted Oil (DAO) and the residue left is asphalt. Hydrogen plant is installed to produce hydrogen for meeting the requirement of various Hydrotreatment processes. DAO is treated in aromatic extraction unit. VGO is treated in FCCU to get LPG. various aromatics and naphthas are obtained which are used as raw materials for polypropylene and aromatic petrochemical plant. From FCCU. dewaxing unit and hydrofinishing unit to obtain bright stock which is used for Lube oils and grease manufacture.1 INTEGRATED REFINERY AND PETROCHEMICAL BLOCK DIAGRAM finished saleable products. Raw lube cuts are treated for removal of aromatics and wax and are hydrotreated to get lube oil base stock. k ‘ k f D r o’ Naphtha Kerosen Kerosene Gasolene Petro Diesel LPG Aro PP MPP Paraxylene Polypropelene Power FIGURE 4. it is converted to elemental sulphur which is sold as by-product. . Petrochemical feedstocks and components for motor spirit and diesel. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY 54 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Coker Sulfur CRUDE CRUDE TANKS CDU/ VDU FCC Propylene Refining fo u n ~.

2. FIGURE 4.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 55 Notes __________________ __________________ __________________ __________________ Crude Distillation Brief process descriptions have been provided (please refer block flow diagram of CDU. 3.3 CRUDE AND VACCUM DISTILLATION UNIT IN A REFINERY . VDU and SGU). C o l. LK/ATF HK Diesel JBO LVGO V a c. This part has three main sections. Fumace HVGO TO FCC Lube distillates Vacuum Residue to Belayed Coker/ Bitumen. 1.2 BLOCK FLOW DIAGRAM OF CDU/VDU/SGU FIGURE 4. Desalting Distillation-Atmospheric & Vacuum Saturated Gas Concentration Unit (SGU) Other streams from other limits S G C Lean Gas LPG to Marox Naptha to Hydrotreater __________________ __________________ __________________ __________________ __________________ __________________ Crude in Desalter Flash Drum Water in Brine Out Preheat 2 Preheat 3 Preheat 1 F u r n a c e Atm osp heri c Col. UNIV ER SIT ST U DI ES k~ e k .

can cause severe corrosion in crude units. The purpose of hot preheat train is to recover heat from pump arounds to reduce furnace duty. Hence. Then it is passed through a desalter after being mixed with de-emulsifier and water thru a mixer valve. Then it is taken to the flash drum. UNIV ER SIT ST U DI ES k~ e k . In the desalter. Na. The flashed crude is passed through hot preheat exchangers and further heated from 190°C to 250–260°C. in small proportions in crude. The fractions below 165°C are withdrawn as column overheads and sent to SGU. it is important to remove the salts from crude prior to distillation. Desalters remove salts.YO FP E TR OLEUM & EN ER GY 56 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. crude passes through high electric field. Here mainly gases. Furnace provides required heat for fractionation in atmospheric column and crude is heated upto 385°C. CI. particularly in the overhead section. etc. SO4. The salt dissolved in water settles at the bottom as brine and desalted crude with less than one parts per thousand barrel comes out from the top of the vessel. The desalters are designed for 99% salt removal and reach less than 1 ptb (part per thousand barrels) in desalted crude. Crude oil received from tank farm is heated from 30 to 140150ºC in cold preheat trains. Heavies boiling at more than . From the top we get lighter components which directly go to the crude column. Several refineries worldwide have faced emergency shutdowns or have had to release hydrocarbons due to corrosion and material failures. These salts. however. k ‘ k f D r o’ Desalting The crude oil is contaminated with various impurities– mainly salts of Ca. LPG and FRN are separated. Distillation – Atmospheric & Vacuum The desalted crude is then heated from 140º to 190º C at 25 Kg/a2 pressure by heating with a heavier hot stream. The heated crude is fractionated in atmospheric distillation column of CDU. This is done by recovering heat from outgoing products streams from the unit. Mg. This prepares crude for efficient desalting. sludge and mud from crude to avoid corrosion and fouling in exchangers columns and downstream equipment. Separation of water containing salt is enhanced by deemulsifier.

LK. the other distillation products are intermediates viz. Naptha (C 5 to 165ºC) for sending to fertilizer or petrochemicals plants as feedstock.5 to 3. LPG (C 3+C 4) for domestic and industrial use after removal of Mercaptanes in Merox Unit. Besides the straight run products such as LPG.01 to 0.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k . Saturated Gas Concentration (SGU) The overhead liquid and gases from CDU. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 57 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 386º C are reheated under vacuum condition (to avoid cracking) and fractionated in vacuum column of VDU. The Heavy Kero (HK) fraction is blended with diesel fraction. HK and Diesel. The Light Kero (LK) fraction is routed as SKO to RTF directly or via Kero Merox unit as ATF. The diesel fractions can be routed to DHT or RTF as required.5% 21 to 22% 23 to 26% Cut range deg C < C2s C3–C4s C5s to 16s 165 – 227 227 – 270 270 – 370 370 – 392 <392 Fuel Gas LPG FRN LK / ATF HK Diesel HAGO RCO (Atm. 3.0 to 1.5 to 3.03% 1. The LPG is sent to LPG Merox unit for treatment before sending to RTF. The typical streams obtained from crude oil by Atmospheric and Vacuum distillation are given in the following table: % of crude input 0.5% 11 to 14% 10 to 11% 6 to 7% 16 to 17% 2. Residue) LVGO HVGO VR . Naphtha. Gases (C 1+C 2 ) for burning into furnaces or as petrochemical feedstock after H2S is removed in Amine Treating Unit.0% 2. (1) Gas Oil (HAGO+LVGO+HVGO) which become feedstock for FCC after treatment in VGOHT and (2) VR which becomes feedstock for delayed coker. reformer and hydrotreaters of petro-chemical complex are passed through this plant to separate into following fractions: 1. The FRN is directly sent to the HNUU in the aromatics complex. 2.

Improve Diesel cetane no. Remove contaminants like organomettalic compounds. Produce low sulphur. Reduce aromatics and nitrogen in diesel. safety and environment (HSE) aspects. Operating parameters such as pressure. 5. 6. 7. Diesel Hydro-Treatment The purpose of diesel hydrotreating unit is to: u u u Remove sulphur and nitrogen Convert olefins/aromatics to saturated compounds. UNIV ER SIT ST U DI ES k~ e k . Health. oxygenates and The catalysts used in this plant are oxides of Ni and Mo/Co & Mo impregnated on alumina base. Crude mix and product yield pattern Corrosion impact on various equipment should be known. colour stable diesel. Health of equipment and run length of unit is vital. flows. Energy conservation knowledge and skills of operating crews. 2. temperature. Quality control of crude and products. light coker . 3. 4. u u u The feed to the unit consists of a mixture of SR diesel and heavy kerosene from the Crude Unit. Salient Features u 98% desulphurisation and 70% denitrification (VGO hydrotreater). k ‘ k f D r o’ Product specifications and significance of the same is given in Unit 3 Operating issues which need attention are: 1.YO FP E TR OLEUM & EN ER GY 58 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. 8.

Recycled gas is added as a quench between the beds to quench the top bed heat of reaction.YO FP E TR OLEUM & EN ER GY fo u n ~. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 59 Notes __________________ gas oil. consisting of one inert and three different types of catalysts. The combined feed heater heats the feed up to the reactor inlet temperature. heats up the fresh feed. The reactor effluent is cooled through a series of heat exchangers where it. the reactor effluent enters the separator. the stripper feed. The separator is a horizontal vessel with a water boot that separates the recycled gas from the stripper feed and the wash water from the stripper feed. MP and LP steam.4 HYDROTREATER BLOCK-FLOW DIAGRAM Brief Description of the diesel hydro-treater follows. The feed is pumped through cold and hot feed-reactor effluent exchangers and then with recycled gas streams through the combined feed heater. HCO from the Delayed Coking Unit and LCO from FCCU Diesel Hydrotreater Make up H2 Ovhd. the recycled gas and then provides heat for generation of HP. in turn. The reactor consists of one vessel with two beds of catalysts. UNIV ER SIT ST U DI ES k~ e k . From the product condenser. A wash water stream is then injected into the reactor effluent before final cooling in the air-product condenser. The recycle gas goes through a recycled gas water cooler and knockout drum to remove heavier hydrocarbon components before entering the . condensor Recycle gas Diesel Diesel VGO LN VGO Product separator Stripper Hydrotreater To waste water system LN __________________ __________________ Offgas to SGCU __________________ __________________ __________________ __________________ __________________ __________________ __________________ FIGURE 4.

VGO Hydro-treatment This is similar to diesel hydro-treater and is used for preparing feed for FCC. Both the net off gas and the unstabilised naphtha liquid that are produced are routed to the Saturated Gas Concentration Unit. reactor effluent. The stripper bottom is cooled through a series of exchangers. FIGURE 4. The stripper is used to remove H2S from the diesel product. The top of the vessel contains a water wash section to pick up any entrained amine. This scrubber is used to remove H2S from the recycled gas by bringing it in contact with a liquid stream of lean amine. The stripper feed is heated in a series of exchangers where it in turn cools the stripper bottoms. and also to separate unstabilised naphtha from the diesel product. and is then mixed with makeup gas hydrogen before entering the recycle gas compressor. UNIV ER SIT ST U DI ES k~ e k . before entering the stripper column.5 HYDRO-TREATER/ HYDRO-CRACKER IN A REFINERY .YO FP E TR OLEUM & EN ER GY 60 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. The recycled gas exits from the top of the recycle gas scrubber. then further cooled by air and water before entering the diesel product coalescer and the salt drier which removes water prior to routing to the diesel product blending system. k ‘ k f D r o’ recycled gas scrubber.

Process Description Feed (Refinery Fuel Gas. in the form of H2S. and removal of chloride by sodium aluminate. UNIV ER SIT ST U DI ES k~ e k . H2S is absorbed in Zno bed. (ii) saturated LPG. Refer hydrogen plant block flow diagram Recycle H2 Refinery fuel gas Natural gas LPG Main pumping section Naphtha (future) Refinery general fuel gas Waste gas Feed gas compr. The function of pre-treatment section is to remove sulphur in feed by hydrogenation. (iii) Natural gas. .6 HYDROGEN PLANT BLOCK FLOW DIAGRAM Hydrogen Feed Feed for hydrogen production plant — (i) Refinery fuel gas. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 61 Notes __________________ Hydrogen Production and Management Hydrogen Production Plant Hydrogen is produced commercially using following technologies: (i) Partial oxidisation __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ (ii) Coal gasification (iii) Electrolysis of water (iv) Steam hydrocarbon reforming (v) Platforming – as a by-product. the catalyst used is CoMo or NaMo. or Natural Gas or LPG or Hydrotreated Light Naphtha) is first mixed with recycle hydrogen and passed through pre-treatment section. (iv) Light Naphtha. HP BFW Steam Generator HP steam export Product H2 __________________ Feed purification Steam reformer Shift & gas cooling Gas purification FIGURE 4.YO FP E TR OLEUM & EN ER GY fo u n ~.

. This process is endothermic and heat is supplied by fuel firing. PSA Cycle One PSA cycle is built up of 2 basic phases: Adsorption and Regeneration Regeneration of PSA Bed The regeneration phase is a chain of sub-phases consisting of: l l l l High to low pressure transition: Expansion Provide purge and dump Purging at low pressure Low to high pressure transition back to adsorption pressure: Repressurization. Following reactions take place: Steam Reforming CH4 + H2O l 3H2 + CO CO + H2O l H2 + CO2 Water Gas Shift CO + H2O l H2 + CO2 Steam is added in excess to promote above reactions. Hydrogen gas produced is purified by pressure swing adsorption (PSA) method. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY 62 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. double stage pre-treatment is used. then single stage pre-treatment is adopted. k ‘ k f D r o’ If sulphur is <200 ppm. The De-sulphurised feed is pre-heated with steam and passed through Nickle Catalyst packed in Vertical narrow tubes mounted in the reformer furnance. For sulphur >200 ppm.

which is separated from caustic and product in caustic sulphur. In case of ATF/Kerosene and Gasoline treatment. first it is mixed with caustic. through high pressure compressors and the excess gas is led to refinery fuel gas system. ATF/Kerosene and Gasoline are removed by this process. Treated LPG is passed through reactor and mixed with caustic solution containing merox catalyst. HSD. Merox (Mercaptan Oxidation) Treatment Process Description Merox is the abbreviation of Mercaptan Oxidation. Caustic in recycled. Then it passes through extractor to remove mercaptan. In this process mercaptan is separated from hydrocarbon by washing with caustic solution. Organic sulphur from LPG. Hydrogen Sulfide (H2S) from LPG is removed by extraction with regenerated lean Amine in Amine Treating Unit (A TU). k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 63 Notes __________________ __________________ __________________ __________________ __________________ Hydrogen Management Hydrogen gas in the refinery comes from (i) Hydrogen production plant – as described above (ii) Catalytic reformers in the refinery in the integrated petro-chemical plant __________________ __________________ __________________ __________________ __________________ The hydrogen from both the sources is supplied to various consumers like hydro-treatment plants etc. Need of hydrogen is increasing day after day for treating the products like motor spirit. Sweetened product is stored in intermediate tanks before blending into finished product. Treated sweet LPG free of H2S and Mercaptan is sent to storage.YO FP E TR OLEUM & EN ER GY fo u n ~. fuel oils and feeds for FCC and other plants for bringing down sulphur. . air and catalyst and then passed to reactor to convert mercaptanes to Disulfides. UNIV ER SIT ST U DI ES k~ e k . Then. it is washed with water to remove caustic. The separated merceptan is oxidised into disulfide form which can be disposed of in slop stream.

u FIGURE 4. UNIV ER SIT ST U DI ES k~ e k . to the aqueous phase. . or the thiol portion of the mercaptane.YO FP E TR OLEUM & EN ER GY 64 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. k ‘ k f D r o’ Following reactions take place Mercaptan gets converted into disulfides 4RSH + O2 2RSSR + 2H2O Caustic Regeneration RSH + (oil phase) NaOH Aqueous phase NaSR+ H2O (Sodium Mercaptide soluble in Aqueous phase) Catalyst 4NaSR+02+2H2O (Aqueous Phase) 45ºC 2RSSR+4NaOH (oil Phase) The purpose of caustic in Merox process is: u To transfer the mercaptane.7 MEROX TREATMENT PROCESS BLOCK FLOW DIAGRAM This process is used for treating LPG. Sulphur Recovery Plant The objective of sulphur recovery plant is to convert H2S to elemental sulphur. To supply the alkaline environment needed for the reaction to proceed in the desired direction. Gasoline and ATF.

Acid gases from ARU Thermal reactor Claus reactor CBA reactor Air Condenser 1 Condenser 2 Condenser 3 To tail gas incinerato Sour gases from WWSU Liquid sulfur degassing pit Air To sulphur granulation unit FIGURE 4. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 65 Notes __________________ __________________ Sulphur recovery is required because of: l l Increasing demand for environmental friendly fuels.8 SULPHUR PLANT BLOCK FLOW DIAGRAM The sulphur condensed is routed to Liquid Sulphur Degassing Pit. __________________ __________________ __________________ __________________ __________________ __________________ l Salient features of sulphur plant are: l l l Minimum sulphur recovery level of 98.7% Ammonia destruction capability Turndown capability 25% __________________ __________________ Process Description Refer sulphur plant block flow diagram (Figure 4. The vapour from the claus reactor outlet is passed .8) Acid gasses from Amin Recovery Unit (ARU) and sour gasses from sour water stripper are heated in pre-treater and burnt in presence of regulated quantity of air from CLAUS Air Blower in CLAUS Reaction Funance. The product from claus reaction funance is passed thru 1st and 2nd pass condensers. Tightening of emission standards by government/ Regulatory bodies.. . UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY fo u n ~. The unreacted vapour is passed thru claus reactor. Increased used of high sulphur and heavier crudes in future.

The condensed sulphur is routed to liquid sulphur degassing pit and the remaining gases are taken to tail gas incinerator for burning and releasing thru high stack. The outlet vapour is passed thru 1st and 2nd pass of CBA condenser. The off-gases from sulphur degassing pit is recycled to CBA section for recovery of sulphur.YO FP E TR OLEUM & EN ER GY 66 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. The uncondensed vapour is passed through Cold Bed Adsorption (CBA) Reactors 1st and 2nd passes. Sulphur after Degassing is taken to granulation unit from where it goes for despatch to market. . the reaction is called Claus Reaction” 2H2S + SO2 3/nSn + 2H2O n=No. u 1/3rd of total H2S in feed gas is burned to SO2. The condensed sulphur is taken to Liquid Sulphur Degassing Pit. this SO2 reacts with remaining H2S to give elemental Sulphur in Claus Reactor H2S+3/20 2àSO2+H2O 2H2S + SO2à3/n Sn+2H2O Overall Reaction 3H2S + 3/2 O2à3/nSn + 3H2O Process Variables Air to Acid Gas Ratio u H2S/SO2 Ratio = 2:1 344ºC 650+ –50ºC Claus Reactor Outlet Temp Incinerator Temperature Amine Treating Unit (ATU) The purpose of this process unit is to remove H2S from fuel gases to meet environmental requirements. k ‘ k f D r o’ thru 1st and 2nd pass condensers. of atoms in Sulphur molecule. What is Claus Reaction? “When two molecules of Hydrogen Sulphide (H2S) react with one molecule of Sulphur Dioxide (SO 2) to give elemental sulphur in the presence of Alumina Catalyst. UNIV ER SIT ST U DI ES k~ e k .

The rich Amine is then pumped through heater where it is heated by the hot lean amine stream coming from bottom of Amine stripper.YO FP E TR OLEUM & EN ER GY fo u n ~. The lean Amine from bottom of the stripper exchanges heat with Rich Amine and then pumped to storage tank through cooler for recycling to Amine Absorber. Hydrogen sulfide H2S OR HSH is a weak acid and ionizes in water to form hydrogen ions and sulfide ions. UNIV ER SIT ST U DI ES k~ e k .9 SIMPLIFIED BLOCK DIAGRAM – ATU Process Chemistry The circulating amine is 35% MDEA solution. By counter current flow H2S is absorbed in Amine and sweet fuel gas (FG) free of H2S comes out from column top. In the stripper. Amine Acid Gas from top of the column is routed to sulphur recovery plant along with sour gases from other process units. Absorption Section Sweet FG __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Lean Amine FG Abs Stpr Regeneration Section Lean Amine Header Rich Amine Header Amine Storage Section FIGURE 4. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 67 Notes __________________ __________________ Process Description Refer figure 4.9 simplified block flow diagram The fuel gas containing H2S is introduced in Middle section of Amine Absorber Column where Lean Methyl Diethanol is introduced near top section. The rich Amine from bottom of the absorber column is taken to Flash Drum where any fuel gas carried over is separated out. HSH H+ + SH– .

The heavy hydrocarbon fractions in these vapours condense in lower section of the column and are withdrawn from bottom along with primary feed by secondary feed pump. Overall (CH 2OHCH 2) 2NCH 3+H 2S (CH2OHCH2)2NSCH3 Delayed Coking Coker Unit The purpose of coking unit is to produce valuable distillates and Petroleum coke (by-product) by upgrading heavy residual stocks from vacuum distillation and other process units generating heavy stock. k ‘ k f D r o’ Ethanol amines or weak bases ionize in water to form amine as hydroxyl ions (CH 2OHCH 2)2NCH 3+H 20 CH2OHCH2)2NHCH3+OH When H2S dissolves into the solution containing the amine ions. Slops from various other process units which do not find proper home can also be processed in coker to get valuable products. coker gasoline. coker gas oil. it will react to form a weakly bonded salt of the acid and the base. coker furnace oil. residual furnace oil and coke. The feed to this unit is subjected to severe thermal cracking thereby producing refinery fuel gas. UNIV ER SIT ST U DI ES k~ e k . coker kerosene. Process Description Refer block flow diagram of coker Feed is preheated by exchanging heat with hot streams. The hot cracked hydrocarbon vapours from coke chambers top via a separator enters the zone of abovementioned fractionator column. (CH2OHCH 2)2 NCH 3+SH (CH2OHCH2)2NSCH3 The sulfide ion is absorbed by the amine solution. This unit is also known as delayed coker. . it is heated to 250ºC in convection section of the furnace before it enters the bottom section of fractionator column. Thereafter.YO FP E TR OLEUM & EN ER GY 68 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~.

Heavy Kerosene (HK). products withdrawn are Light Kerosene (LK). From the fractionator. Facilities are also provided in the plant to produce LPG and release fuel gases to fuel gas system. After crushing and sizing.10 COKER BLOCK FLOW DIAGRAM The secondary feed is heated in the remaining part of the convection section and full radiation section of the furnace to around 500ºC and enters the coke chambers where final cracking takes place. UNIV ER SIT ST U DI ES k~ e k . gas oil and coking fuel oil (CFO). Fractionator vapour top is condensed in over head condenser to produce gas and coker gasoline and coker naphtha (light coker naphtha and heavy coker naphtha). The liquid product accumulated at separator bottom is pumped out as Residual Fuel Oil (RFO). is cooled by steam and water and thereafter removed by hydraulic de-coking method which cuts the hard coke with high pressure water jets. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants Heavy cycle gas oil HP flare Light cycle gas oil To HNUU To LNUU Unsat LPG Merox unit 69 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ LLP Flare Vacuum Residue tank Coker Unsat gas conc. The vapours from top of the coke chambers is quenched with cold vacuum distillates before it enters the separator. . it is transported to store yard or sent to coke calcination plant. The coke is removed by grab crane.YO FP E TR OLEUM & EN ER GY fo u n ~. The petroleum coke is accumulated in coke-chamber. The vapour is routed to bottom of fractionator as mentioned earlier. unit To LPG spheres FG distribution system To flare Coker consumption To light slop oil tank FO tank Rich amine Lean amine Amine treating Coke handling system To heavy slop oil tank __________________ To ETP FIGURE 4.

it is brought in to contact with the staged feeds supplied as finely atomised droplets. Gas oil (HCGO) etc. combine with one another to give even larger molecules than those in the original stock. LPG.YO FP E TR OLEUM & EN ER GY 70 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u u u Refining fo u n ~. In this column. UNIV ER SIT ST U DI ES k~ e k . middle distillates and decanted oil are obtained. which are reactive. k ‘ k f D r o’ Advantages of Delayed Coker u Minimum investment for given value addition Zero fuel oil generation Coke can be used as fuel for power plant. Fluidised Catalytic Cracking (FCC) Fluid Catalytic Cracking has developed into a major upgrading process in the oil refining industry for conversion of heavy fuel oil into more valuable products ranging from light olefins to LPG. Kero. forming cracked fuel oil and coke. naphtha and middle distillates. The attractiveness of FCC process is to its flexibility to process wide range of feedstocks from a variety of crudes and its favourable economics of operation. After pre-acceleration. Capability to process refinery slops and sludge. No catalyst cost. Gasoline. and the reactive once polymerise. Hot regenerated catalyst is mixed at the bottom of reactor with raw feed and steam. high throughput and minimise LCO and bottoms. Diesel (LCGO). Feed instantaneously vaporises and travels up the riser with the catalyst where conversion reaction takes place. The objective is to maximise Olefins. mainly LPG. . the vapour is disengaged from catalyst. The spent catalyst is steam stripped to remove hydrocarbon vapour and then sent to two stage regenerators for burning coke before it is recycled to reactor alongwith makeup catalyst to reactor. C7 – C9 aromatics. The vapour is sent to main fractionating column. The more stable molecules leave the system as cracked Naphta. At the top of reactor. Mechanism of Coking Cracking is a phenomenon by which large oil molecules are thermally decomposed into smaller lower-boiling molecules: at the same time some of these molecules.

. FCC __________________ __________________ __________________ __________________ FIGURE 4. Flue gases are sent to CO boiler and thereafter to a clean up system to remove particulates. Fuel Gas and heavies. UNIV ER SIT ST U DI ES k~ e k . LPG. H2. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 71 Notes __________________ __________________ __________________ __________________ __________________ __________________ Air is injected in catalyst regenerator for burning coke. Light Reformate.11 FCC UNIT BLOCK FLOW DIAGRAM Petrochemical Process Plants Aromatics Plant The aromatics complex is a fully integrated facility for the production of paraxylene and orthoxylene. Water generated in the system leaves with flue gas from Power Recovery Train.YO FP E TR OLEUM & EN ER GY fo u n ~. ZSM additive is added to catalyst to increase LPG yield. The Paraxylene plant consists of the following units. Residues are also used as feedstock in RFCC.12 Aromatics Complex Block Diagram Flow). sulfur. SOx and NOx. (Refer figure 4. comprising of platformer primarily to produce feed for main plants. Heavy Naphtha Unionfining Unit (HNUU) The function of this hydrotreating unit is to treat the feed naphtha and remove impurities like heavy metals. Aromatics complex processes special cut naptha to produce paraxylene and orthoxylene as the major products and some other by-products which include Benzene.

for the production of aromatics for downstream unit processing and separation. k ‘ k f D r o’ nitrogen and olefins. . which takes place in Cyclemax CCR. a sidecut stream with a 215°C endpoint for use as a gasoline blending component and a heavy aromatic bottom stream to be used as fuel oil. Xylene Fractionation Unit Xylene fractionation unit includes a xylene column and associated equipments to fractionate “Isomar” Deheptaniser bottoms and “Tatoray” Toluene column bottoms into an overhead product that is suitable as feedstock to the Parex process unit.YO FP E TR OLEUM & EN ER GY 72 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. stripper column bottoms. Dehydrogenation of naphthenes Hydrocracking of paraffins Isomerisation Dehydrocyclisation of paraffins The spent catalyst is regenerated continuously in situ. UNIV ER SIT ST U DI ES k~ e k . Orthoxylene Fractionation Unit This unit includes an orthoxylene column and associated equipments for the production of a high purity orthoxylene product and a heavy aromatic column and associated equipments for the production of a C9-C1O aromatic overhead stream to be used as feed to the “Tatoray unit”. 3. The column is designed to both recover Orthoxylene into the bottom product or to minimise the loss of Orthoxylene into the bottom products Xylene rich overhead vapor are used as heating medium in Raffinate & Extract . which are poison for Platformer catalyst. Major reactions taking place in platforming unit are as follows: 1. Column Reboilers & also to generate MP Steam. 2. 4. Platformer Unit The platformer unit processes hydrotreated naphtha from the Heavy Naptha Unifining unit.

The molecular sieve is basically Y type zeolite (alumina silica) which preferentially adsorbs PX. stripper. Two streams come out of the chambers known as raffinate stream and extract stream. Paraxylene is withdrawn from bottom and overhead product Toluene is recycled back to Tatoray unit.YO FP E TR OLEUM & EN ER GY fo u n ~. Toulene column bottoms and C8 isomerates from Isomar section are fed to the xylene fractionation column. Feed and desorbent goes to the Parex adsorbent chambers via rotary valve. The extract stream consist of PX. two parallel reactor trans. PX and Toluene are separated as overhead products in extract column (feed to finishing column) while the bottom product Desorbent is recycled to Parex absorbent chambers. . Toluene and Desorbent. Its side cut product which is mixed xylenes lean in paraxylene. PX and Toluene are separated in a finishing column. Objective of the units is to maximise xylene production by transalkylation of C7 and C9 aromatics. PX gets adsorbed on the molecular sieve and subsequently desorbed. UNIV ER SIT ST U DI ES k~ e k . is fed to isomer unit while the bottom product desorbent is recycled back to Parex adsorbent chambers. Isomer is a catalytic isomerisation process to efficiently convert a mixture of C8 aromatics to a near equilibrium mix that favours PX and OX production from metaxylene and ethyl benzene. The overhead product of the xylene columns are feed to the parex unit. benzene are toluene column. The Tatoray unit includes reformer splitter column. Raffinate stream is fed to the raffinate column. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 73 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Parex Process Unit The process is selective adsorption of Paraxylene (PX) on molecular sieve and subsequent desorption of PX by a suitable desorbent.

13 Propylene Block Flow Diagram) The plant consists of: 1. Purification Section: For propylene “to remove impurities like Sulphur. CO. Impurities like CO. O 2 ' purification section for hydrogen and nitrogen gas before supplying them to reaction area. k ‘ k f D r o’ Polypropylene It is designed to produce homo. The main raw materials are propylene and hydrogen.YO FP E TR OLEUM & EN ER GY 74 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. FIGURE 4. CO2 from H2 and O2 from N2 are removed. (Refer Figure 4. UNIV ER SIT ST U DI ES k~ e k . random and impact copolymer. CO 2 .12 AROMATCS COMPLEX BLOCK FLOW DIAGRAM .

YO FP E TR OLEUM & EN ER GY fo u n ~. The unreacted monomers are purged with light recycles and sent for recovery to vent recovery system. . PP requires the incorporation of a variety of additives to aid its processing and achieve the end use properties. Reaction Section: Here polymerisation reaction of purified propylene takes place in fluidised bed reactor in the presence of slurry catalyst (TiC14. 3. UNIV ER SIT ST U DI ES k~ e k .13 POLYPROPYLENE BLOCK FLOW DIAGRAM 2. purified hydrogen and selectivity control agent Peraethoxy Ethyl Benzoate or N-Proypl Trimethoxy Silane in the reactor. The polymer is fed into the melt pump to develop necessary pressure for extrusion through the die plate. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 75 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ FIGURE 4. The pellets are then dried. co-catalyst Triethyl Aluminium. classified and conveyed to the blending silos from where they are bagged. supported on MgCl2 in slurry form in mineral oil). The conveying gas which is a mix of hydrocarbon and nitrogen is separated from the resin in disengaging section of product receiver. Pelleting Section: Polypropylene (PP) resin is transferred from reactor to product receiver using dense phase conveying system. The Polymer strands are palletised in underwater pelletiser and the pellets are carried by pellet water system to agglomerate remover where chunks and clusters are removed.

7 3. All waste flammable gases are vented to the HP or LP flare header.0% 8.0% 8. Typical Refinery and Petrochemicals complex – Product Pattern Propylene LPG Gasoline Naphtha Reformate (Petrochemicals feed) HSD/SK/ATF Coke Sulphur Fuel and Loss 2.0 11.3 2.1 5.3 7.8 100.9 11.0% 7.1 16.1 63. k ‘ k f D r o’ 4.5% 9.2 -18.YO FP E TR OLEUM & EN ER GY 76 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Vent Recovery Section: This system is designed to recover monomer. UNIV ER SIT ST U DI ES k~ e k .5% Typical Refinery Product Pattern Input Crude Oil Products LPG Net Naphtha MS Others Light Distillates ATF SKO HSD LDO Others Middle Distillates LSHS for sale Others Heavy Ends Total Prods Gross F&L Total 2.0 35.6 6. polymer and nitrogen.0 .0% 1.5% 7.6 9.0 % of Crude 100.6 93.0% 8.0 1.5% 48. which are passed through knockout pot and burnt at flare stack burning tip.

Gas Oil (CGO) CFO RFO RPC GAS Loss Total 2.3 6.5 -24.6 7.9 0.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k .7 20.4 100.9 0. Gasoline Cok.5 4.5 100.3 9.5 12.7 12.5 22.5 14.5 6.0 17.3 2.0 __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Typical Yield Pattern of Delayed Coking Unit Input = RCO Output: LPG Cok.0 100% 53. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 77 Notes __________________ Typical Yield Pattern of FCC Feed: Low ‘S’ VGO CGO DWO VR Output Gas H2S LPG Gasoline TCO CLO Coke Loss Total 3.5 53. Kero-I (LK) Cok. Kero-II (HK) Cok.5 16.0 100% .4 8.

YO FP E TR OLEUM & EN ER GY 78 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Input: VGO H2 Total Output H2S GAS LPG LT. Before bringing the crude from oil fields.3 3.0 27. and increased customer expectations.0 Refining fo u n ~. Health and Environmental stipulations. water and sludge are removed by settling and processing through desalters. k ‘ k f D r o’ Typical Yield Pattern of Hydro-treater Offsite Facilities and its Management In a Refinery. Traditionally.0 2. Naphtha SKO/ATF HSD Bottoms Loss Total 1. stringent safety. gas. now more and more emphasis is given for improved profitability through: l l l l Improved operations Advanced process control system Good inventory management Optimisation of storage facilities & other offsites. Naphtha Hy.0 100.0 43. However.2 1. Crude oil receipt Normally crude oil is received in land locked refineries through crude pipelines from the production source. In . with Refinery margin shrinking. more attention used to be given to process units.5 4.0 11. UNIV ER SIT ST U DI ES k~ e k .2 102. Major offsite functions in a Refinery are: 1.8 10. 80% to 90% area is covered by offsite facilities.0 0.0 102.

water and associated salts are removed before bringing crude to refineries. Unless crude preparation is done properly. the unit performance will be affected adversely due to fouling of pipes. furnace tube corrosion. size of crude oil tanker varies from small to very large. crude oil storage is being increased from 15 days to 45 days of the refinery capacity.YO FP E TR OLEUM & EN ER GY fo u n ~. all other products are blends of various streams from different units. Flexibility is also provided for alternative routing of streams incase there is change in demand in product pattern. Facilities for water draining and reprocessing of offspec. This is removed by allowing the crude to settle in the tanks and draining from bottom to the effluent treatment system. The final removal of water associated with salts and sludge takes place in desalter in the crude distillation unit. number of products marketed. streams are provided. Quantity of crude received in the refinery is monitored by measuring dip of receiving tank and flow metre readings installed on crude pipeline. Due to strategic reasons. Except LPG and Naptha. Depending on the capacity of refinery. 2. Crude preparation for feeding to distillation units Though in the oil field. crude oil is received through tankers. Light and heavy . UNIV ER SIT ST U DI ES k~ e k . Receiving rundown streams from various units From crude distillation unit and other secondary units. major quantity of sludge. most of which are to be treated in secondary processing units and blended in required proportion to produce finished products which are then dispatched to the market. types of crude oil processed. crude tankage available. India imports almost 70% of its crude oil requirement. Depending on the capacity of the refinery. corrosion of various equipments and upsets in plant operation. draft available at receiving oil jetty. exchangers. we get various products streams. yet some quantities of sludge and water still are received in the refinery tanks. 3. complexity of the refinery. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 79 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ coastal refineries. This will also lead to increased fuel consumption and loss in the units. the tankages provided for receipt of rundown streams varies.

k ‘ k f D r o’ slop tanks are also provided to receive offspec. The same are reprocessed in the units in a regulated manner during normal run. Co-ordination with laboratory After blending of various streams and circulation in tank. then the certificate of quality is issued by the laboratory. Blending the rundown streams Various straight run streams and secondary processing units streams are mixed in suitable proportion for the production of finished marketable petroleum products. UNIV ER SIT ST U DI ES k~ e k . Pipelines Rail Road Coastal . It is proposed to provide 35 days storage capacity based on 75% utilisation factor. Petroleum products are evacuated from the refinery by following modes: 1. Streams during start up. Despatch of finished products: The certified products are stored in finished product tanks before dispatch. SKO and HSD is being augmented. emergencies and upsets in the plants. samples of products are sent to the laboratory for testing. product is despatched to market. the tankage for receiving rundown streams can be minimised. 4. After settling in tank for draining any water and testing the sample in the laboratory to ensure that it meets quality specifications. The mixture is circulated in the tank to make it of uniform quality. Storage facility at various locations particularly for MS. 5. 2. Thereafter. 6. Once the product meets the quality specification as per BIS or customers requirement. By on-line blending and utilising advanced process control. shutdown. Pump stations are provided for transfer of products.YO FP E TR OLEUM & EN ER GY 80 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. it is dispatched to market. 3. 4.

FO. which are used to supply product to nearby locations by road. LSHS etc. 2. etc. Rail: Tank wagons are the second bulk carrier specially constructed for this purpose and can take products to far off places. 2.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k . Minimum transit loss Planned product movement Flexibility in operation independent of other transportation systems. 3. 3. The wagons for transporting heavy products such as FO. For short distance and small quantity of coastal product movement. 4. barges are used. During floods and natural calamities. it is not affected. it is possible that the products reach their destination in a "refinery-good" condition. Coastal: Tankers of various capacities are used for dispatch of product from coastal refineries.70%). . are provided with steam coils for heating the product before unloading at the destination. Naptha etc. Pipelines: Out of the above dispatch modes of petroleum products. This is so even in respect of sensitive quality control products such as ATF. With advanced control system and proper operation. Road: The third mode of transportation is tank lorries or tank trucks. Pipeline systems have following in-built advantages over other means of transportation available for petroleum products: 1. Steam coils are provided to heat the product before unloading in case of tank trucks for Bitumen. The products movement of the refinery gets adversely affected due to failure/breakdown of transport system. It is the second cheapest mode of transport next to large capacity tankers. 4. LSHS. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 81 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 1. The large capacity tankers are the cheapest mode of transport. 5. maximum dispatch takes place through pipelines (60 .

this system is provided.YO FP E TR OLEUM & EN ER GY 82 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. flare headers are provided for collecting off gases from process units and offsite areas. b. make-up to fire water supply system and make up to drinking water treatment system. Fresh water supply system: This provides utility water supply. to an extent beyond which through-put of process units is cut thus affecting the production. c. Refinery water supply The following important water supply systems exist in the refinery. . 3. In critical areas. Three categories of flare systems are provided: a. Blow-down 2. Fire water supply system: Throughout the process units and offsites areas. However. the fire water supply pipeline network is laid in the form of ring. make up to the circulating water system. It is having chemical treatment system to avoid scaling and corrosion in related pipelines and equipment. Firewater tanks are provided in offsites area to have an immediate supply source for fighting any major fire. k ‘ k f D r o’ Flexibility to a small extent exists to switch over from one mode to other mode. Flare management To take care of emergency release of gaseous hydrocarbon. High pressure flare Low pressure flare H2S flare 8. 1. UNIV ER SIT ST U DI ES k~ e k . long distance throw nozzles are provided. refinery builds up stock in its tanks during such emergencies. After seperating the entrained liquid. Recirculating hot and cold water system: For cooling of hot products. Cooling Towers are also provided in the system where water is cooled by evaporation before recirculation. the gas is burnt at high point to avoid hazard and pollution. 7.

. compressors and other equipment. Nitrogen is 5. In fuel gas. driving steam turbines and power generation. Hydrogen. Make up water is taken from fresh water system. once through cooling water system is used and sea water is utilised for the cooling of products. For meeting any emergency. and maintaining inert atmosphere in the process unit equipment. UNIV ER SIT ST U DI ES k~ e k . varying range of fuels from LDO to Asphalts are used. k ‘ kf D r o’ UNIT 4 Integrated Refinery and Petrochemical Plants 83 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ in the form of leakage and manual draining is provided to avoid build up of salt concentration. Steam is used for heating. In some of the coastal refineries. 4. For fuel oil. blanketing tanks from atmospheric oxygen in the case of lubes and other products which form explosive mixture when coming in contact with air. captive power plant is provided in the refinery. atomisation of fuel oil before burning in furnace. Superheated and saturated steam at various pressures are also supplied for process units and offsites area from this system. ethane and purged gases from hydrogen units are used. stripping in columns. and boilers in captive power plant. The supply system is maintained at constant pressure. load shedding scheme exists. It is a very hazardous gas to handle as the flame can not be seen. It is utilised in hydro-treatment units. fire-fighting. Fuel oil and fuel gas system: For providing fuel supply to process units furnaces. Nitrogen is used for catalyst regeneration. Captive power plant: To provide uninterrupted power and steam supply for running the pumps.YO FP E TR OLEUM & EN ER GY fo u n ~. mostly methane. Nitrogen and air supply systems: Hydrogen is generated in Hydrogen plant or catalytic reformer unit. this system is provided. To ensure supply of steam and power to critical plants/equipment in emergencies. blending facilities and pumping system are provided for supply of fuel oil to furnaces and boilers. Storage tanks. Fresh water is used in DM plant before utilising in boilers for steam generation. 6. alternative source of power supply from outside is also lined up.

Yield pattern. Furnace Oil. 2. Air is used for utility purposes. 2. The function of each process plant (11 plants) Feed composition iii. Explain briefly in your own works. PC Naphtha and Fertilizer Naphtha. HSD. specially their impact whenever there is a failure. What are the important offsite facilities in a refinery? How do these facilities affect the proper functioning of the refinery? Explain each facility wise. . Review Questions for all Process Plants 1. decoking of furnace tubes and instrumentation etc. MS. catalyst regeneration.YO FP E TR OLEUM & EN ER GY 84 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. k ‘ k f D r o’ produced in generators installed in the refinery or is purchased from outside. ATF. iv. Critical parameters for optimal operation Which components of various process streams in different process plants (% wise) are utilized for the prouction of LPG. It is taken from atmosphere and compressed before using. ii. UNIV ER SIT ST U DI ES k~ e k . i. Review Questions for Offsites 1.

y Keeping in view environmental considerations. To improve profitability and meet statutory requirements. cost optimisation. Strategies for overcoming various challenges. __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. energy conservation and product quality requirement. it is envisaged that future refineries will have to face many challenges – they will be highly complex.85 Unit 5 Future Refining Scenario Activity 5 A Describe the scenario of availability of sweet & sour crudes in the next two decades. This will call for superior metallurgy in the plants and pre and post treatment of oil products leading to higher capital and operating costs. the learner will be able to: y __________________ __________________ __________________ __________________ __________________ Understand Future Refining Scenario in terms of availability of crudes. future refineries will have to be ready to process heavy and sour crudes. dwindling refinery margins etc. diversified and fully automated. following actions need to be taken: u u u u u u u Distillates yield improvement Production of high value products Energy optimisation Hydrocarbon loss minimisation Effective environmental management Product quality upgradation Product inventory reduction . therefore. stringent specifications of various petroleum products. Worldwide availability of sweet and light crude is decreasing. integrated.

power plants? How does it improve the Bottom Lines? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~. the Netherlands and Italy.YO FP E TR OLEUM & EN ER GY 86 Activity 5 B What do you understand from Integration of Refinery with petrochemicals/ fertilizers. k ‘ k f D r o’ Besides conventional process units. petrochemicals and fertilizers u Synergy in power with fertilizer co-production – Efficient utilisation of low value refinery residue for production of power. Co-production of value added fertilizer. No additional raw material handling and common fire fighting facilities. future refineries will also have: u Quality related units: – – – – Facilities for benzene management DHDS (Diesel Hydro-desulphurisation) Fuel oil HDS (Hydro-desulphurisation) Hydrotreatment. Overall economics considerably enhanced Already under way in the USA. UNIV ER SIT ST U DI ES k~ e k . Environment management related units: – – – – – – Tail gas treatment High efficiency SRUs (Sulphur Recovery Units) Bottom of the barrel upgradation related unit Computerised integrated refinery Energy efficient processes Diversified and integrated refinery with power plant. – – – – u Refinery of 21st century – – Operate with fewer & highly educated people Few operators grouped in a central blast proof control room like the cockpit of modern aeroplanes. Power plant supplies power and steam required in refinery. .

2. So as to conform to Emission norms.YO FP E TR OLEUM & EN ER GY fo u n ~. UNIV ER SIT ST U DI ES k~ e k . What do you understand from flexibility of Refinery operations in the competitive environment? . k ‘ kf D r o’ UNIT 5 Future Refining Scenario 87 Notes __________________ __________________ __________________ – – Possible employment of robots Computerised system supervising operations automatically On-line analysers and blending Computerised performance monitoring Automated dispatch and offsites operations Flexible work hours – – – – __________________ __________________ __________________ __________________ __________________ __________________ __________________ In the new refineries. HSD and FO. What modifications would be needed in refinery process plants for Changing over from sweet crude to sour crude Technological improvements/additions for meeting future more stringent specifications of HSD and MS. Plant/ equipment should require less space. To increase/improve profitability. Reduction of FO production and increase in distillate production to 85%+. u Review Questions 1. following technology gaps and to be covered: u u Reduction of ‘S’ (sulphur) from MS.

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Declining refining margins Improved engine design/automobiles need better quality fuel and lubricating oils. 2. 1. Reduced growth in fuel oil demand. Crude oil is becoming heavier and higher in sulphur and metal content. Improved and integrated refining u Production of better quality products . the learner will be able to: y Note __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand in a generic fashion advances in refining process technologies For making eco-friendly products For value addition to improve the bottomline For best practices in refining operations For energy optimization Various issues faced by the refining industry have led to many major developments in this area. 4. Advances in refining technology can be broadly divided into the following categories. 5. Stringent environmental regulation for cleaner products/processes and demand for quality products. 3. Rapid growth in light/middle distillates. The challenges are: 1. 6.89 Unit 6 Advances in Petroleum Refining Objectives After studying the unit.

Mobil distillate Dewaxing (MDDW) to upgrade heavy fuel oil to high quality distillate and gas yield of 93. in Refining Process Technologies? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~. Some of them are listed below: u u Distillation Fluid Catalytic Cracking (FCC). 2. Hydro cracking u u – u Super Oil Cracking (SOC) of heavy distillates to get 90% conversion to distillates. Hydro processing – Hydro treatment of various streams including residues. k ‘ k f D r o’ Residuation in residues/heavier ends Management of power and utilities. Improvements are taking place in many areas. u u u u u u .YO FP E TR OLEUM & EN ER GY 90 Activity 6 A What are known/proven improvements as on date. Delayed coking – Needle coke manufacturing. Value addition u u u u Petrochemicals production Better quality and increased lube oil production Power generation from heavier petroleum products Speciality chemicals production. Visbreaker–Soaker Technology. Resid Fluid Catalytic cracking (RFCC). Isomerisation Catalytic Reforming Alkylation Etherification Power generation by petroleum residue and coke by using Gasification Combined Cycle (GCC) technology.95%. UNIV ER SIT ST U DI ES k~ e k .

etc) are being developed and increasingly used for optimization. design and optimal control and technology development. trouble shooting. UNIV ER SIT ST U DI ES k~ e k . FCC. Typical application of information technology in a refinery Refinery planning Primary logistic management __________________ __________________ __________________ __________________ __________________ __________________ __________________ – – Guide logistic planning Refinery scheduling Primary logistic management Secondary logistic management u Significance of process modelling Trouble shooting Reactor design Pilot plant scale up Catalyst health monitoring Modelling and simulation Catalyst selection & optimisation Operator training Feedstock selection Process optimisation u u Refinery integration and value addition strategies Small and medium refineries . Hydrocracking.g. k ‘ kf D r o’ UNIT 6 Advances in Petroleum Refining 91 Notes __________________ __________________ __________________ In this process alongwith power. steam and H2 can be produced which are required in the refinery.. Decision Making and Business Profitability.YO FP E TR OLEUM & EN ER GY fo u n ~. Modelling simulation are being used for: – Information Gathering. u u More and more use of information technology. Accurate process models for different processes (e. Cat Reforming.

.YO FP E TR OLEUM & EN ER GY 92 Activity 6 B What are various routes for value addition in Petroleum Refining? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u u Refining fo u n ~. UNIV ER SIT ST U DI ES k~ e k . Explain the following processes and relate the same to the relevant products: 2. needle coke production Microcrystalline wax production Alpha-olefins production Larger refineries – – – Petrochemical integration and speciality products Integration of refining and power generation – IGCC Technology Lubes and fuel integration Other major strategies of integration – – – Integration with IT Process simulation and optimisation Advanced control and hierarchical control systems Review Questions 1. Isomerization Alkylation Etherification DHDS Catalytic reforming Catalytic cracking Thermal cracking (Refer Bibliography) Explain the known/proven processes of Hydrogen Generation from heavy residues/petroleum coke/ coal bed methane? How is IT utilised for improved/on-line performance monitoring of refineries? 3. k ‘ k f D r o’ – – – – Integration with speciality chemicals for value addition Anode grade coke.

ii. What should be ideal losses in any Process Control? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Understand the significance of losses in a refinery and their impact on profitability Understand sources/areas of losses and measures adopted by the refineries for their reduction. hydrocarbon losses take place on various accounts. Auditing of the systems and operations will lead to continuous improvement. B. y During the processing of crude petroleum products. Efforts are to be made to bring the loss to a level of less than 0. Measuring devices in storage tanks and custody transfers for proper accounting Automating road/rail dispatch facilities.93 Unit 7 Hydrocarbon Loss Minimisation Objectives After studying the unit. the learner will be able to: y Activity 7 A i. Conversion of fixed roof tanks to floating roof tanks for low flash products including diesel and use of proper type of roof seals. . handling and dispatches from refinery. Real losses i.3% of crude processed. Vapour recovery from flare and product loading facilities Handling of light hydrocarbon slop in process unit and offsite area in closed blow down system iii. ii. Following areas need to be monitored/looked into: A. Apparent losses i.

v. Close monitoring of BSW in crude processed to avoid plant upsets and increased losses. cost of crude being $ 25/barrel? . Routing of all sour gases to sulphur recovery unit ix. ii. Review Questions 1. Routing of off gases from vacuum column to furnaces. viii. What are international standards for Refinery Losses? What methods have been adopted in Indian refineries to bring down the losses to International standard? Refining fo u n ~. k ‘ k f D r o’ iv. if the losses are reduced by 0. Automatic tank gauging Use of proper mixers in crude tanks for minimising sludge formation and modern method of removal and recovery of only sludge/oil to reduce loss Minimising slop generation to reduce evaporation loss in slop handling system vi.YO FP E TR OLEUM & EN ER GY 94 Activity 7 B i. What is BS&W? How is it related with losses in Refining operations? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ vii. UNIV ER SIT ST U DI ES k~ e k . What will be the order of magnitude of savings in a six million tones per year capacity refinery.2%.

Energy efficient processes/equipment such as furnaces. Some of the areas given below need to be looked into: 1. Provision of air preheter in furnace. 2. 4. What strategies have been adopted to optimize energy consumption. For old refineries For grass-root refineries __________________ __________________ __________________ Objectives After studying the unit. the learner will be able to: y __________________ __________________ __________________ Appreciate the role of/ urgency for energy conservation and optimisation of energy consumption in refining industry. Direct hot feed from one unit to another unit without passing through intermediate tanks.95 Unit 8 Energy Conservation Activity 8 A i. Optimisation of heat exchangers train – use of pinch technology. 3. Get a generic idea of various strategies adopted for energy optimisation. Proper insulation of hot products and steam lines. pumps. 5. Integration of heat – exchange system of the units to utilize the heat from hot stream of another unit – crude distillation unit and vacuum distillation units are heat integrated. . __________________ __________________ __________________ __________________ y Conservation of oil and gas has assumed greater importance in view of the emphasis on demand side management of energy. Average fuel loss in the refineries in India during 2000–01 was 7-35% which is higher compared to global levels (of similar configuration). exchangers etc. Energy optimisation for a refinery begins early in the development and design stage with the establishment of a set of energy saving guidelines applicable to the project.

12. Benchmarking. Reflux ratio in distillation process Solvent feed ratio in extraction process 7. 15.YO FP E TR OLEUM & EN ER GY 96 Activity 8 B How do DDCS and advanced process controls help conserve energy? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. 16. gap analysis and setting targets. k ‘ k f D r o’ 6. Heat recovery from process streams for heating colder process streams/ boiler feed water. 8. Low level heat recovery. 10. Use of microprocessor based control system alongwith DDCS (Digital Distributed Control System) and advanced process control. 13. 11. ii. UNIV ER SIT ST U DI ES k~ e k . Optimisation of i. Review Questions 1. Power generation in new refinery will be through combined cycle operation integrated with gasification. Pressure reduction of steam through a control valve will be minimised. 14. Minimise leakage through glands/seals of pumps. Energy audit for continuous improvement of energy performance. Steam system – High pressure steam will be cascaded down to lower level by back pressure turbines either generating power or coupled with various key process compressors and pumps. Soot blowers for convection section of furnaces to improve heat recovery in furnaces. 17. Use of soaker technology for visbreaking. compressors and turbines. 9. Steam generation from hot streams. How does energy consumption at Indian refineries compare with best run refineries over-seas? Express this in energy consumption indices like EII (Energy Intensity Index) NRG Factor in MBTU's per NRGF for fuel + loss .

. Enumerate some important measures of this nature which the refineries/ chemical industries take. k ‘ kf D r o’ UNIT 8 Energy Conservation 97 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 2. UNIV ER SIT ST U DI ES k~ e k .YO FP E TR OLEUM & EN ER GY fo u n ~. Explain the role of house-keeping measures for bringing down energy consumption resulting in energy conservation.

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u . the learner will be able to: y __________________ __________________ __________________ Provide an appreciation for various elements affecting GRM which in essence is the profitability of a refinery. y Gross Refining Margin (GRM) is the differential between the product realisation and the cost of crude processed to obtain these products. GRM of a particular refinery will depend upon various internal and external factors. u u External Factors u u The international prices of various crudes and products The demand and supply balance of various products refined by the refinery The duty structure prevailing in the country relating to crude and products. Acquaint with the netback estimation method used for selection of crude for any refinery.99 Unit 9 Gross Refining Margin Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. Some of these factors are discussed below: Internal Factors u The crude mix (low sulphur and high sulphur) processed by the refinery The secondary processing facilities available with the refinery which affect the product yield of the refinery The fuel used and losses incurred in the production processes.

. Printing. Depreciation: Operating cost includes depreciation on plant and machinery. Catalysts are used in various reformers and other secondary processing facilities. overtime. Repair and maintenance cost: It is incurred in various mechanical. General administrative cost: This cost includes expenses such as traveling. Establishment cost: This is related to the manpower deployed and includes the salary and wages paid to staff. some of which are as under: u Power and fuel: Fuel is used either directly in the refining process or to generate power and utilities to be used in the refining process. various chemicals and catalysts are used. The purpose of chemicals is mainly to improve the quality of products so as to meet the desired specifications. Fuel may be purchased from outside suppliers (like natural gas). insurance and other related overhead expenditure. FO or HSD) may be used as fuel.YO FP E TR OLEUM & EN ER GY 100 Activity 9 A What are various factors which affect GRM? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ u Refining fo u n ~. This is virtually the net profit to the refinery. bonus etc. UNIV ER SIT ST U DI ES k~ e k . Chemicals and catalysts: During the refining process of petroleum products. power from electricity board or internal refined products (like LSHS. Net Margin = Gross margin – Operating cost. electrical and civil jobs carried out for the maintenance of plant and machinery. furniture. u u u u Net Margin The net margin is the difference between gross margin and operating cost. equipment and other fixed assets used in the refining process towards general wear and tear. k ‘ k f D r o’ Operating Cost of the Refinery The operating cost of the refinery includes various elements.

net back estimation is used to evaluate the suitable crude for the refinery. All these 7 crudes are sweet (low sulphur) crudes. the estimated realisation is calculated on the basis of expected yield from the particular refinery for a specific crude. Attachment 2 gives a sample netback calculation to select the best crude out any of seven crudes. gross margin should be increased and operating cost reduced by increased efficiency in refining operations. The crude which is having higher net back to the refinery is normally procured for it. wharfage. Attachment 1 shows a sample calculation for gross and net margin for a refinery. F. ATTACHMENT 1: GROSS MARGIN Realisation of transfer of products Cost of crude (inclusive of freight. For the purpose of procurement of crude for a particular refinery. . customs duty) Gross margin Th’put-MMT GROSS margin Rs/MT Margin – Rs/BBL Margin – US $/BBL Less: Operating cost Rs/MT Net margin Rs/MT 4050 3720 330 3.YO FP E TR OLEUM & EN ER GY fo u n ~.30 500 329 __________________ __________________ __________________ __________________ __________________ Net back estimation In the net back system.Dos gives the highest netback of Rs 1054/MT vs TAPIS with lowest netback of Rs 41/MT. UNIV ER SIT ST U DI ES k~ e k . k ‘ kf D r o’ UNIT 9 Gross Refining Margin 101 Activity 9 B Explain how netback estimation method is used for crude selection for a refinery? __________________ __________________ Rs/Crores __________________ __________________ __________________ For higher profitability. considered.98 829 112 US $ 2.

SHS RPC SULPHUR SL.0 11987 12593 6 6 ESCRAVOS 11987 2 5 13 11 51 TAPIS 12859 5 10 12 11 53 0 0 1 0 0 8 100 91. UNIV ER SIT ST U DI ES k~ e k . WAX F&L TOTAL DIST% CRUDE VALUE.0 11994 12570 0 6 100 82.RS/MT PROD VALUE. 11714 5 5 12 11 54 0 0 1 1 0 11 100 87. RS/MT NET BACK. RS/MT 421 1054 740 Refining fo u n ~.0 11994 12780 100 476 606 41 100 686 Review Questions 1.0 11361 12415 F.YO FP E TR OLEUM & EN ER GY 102 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ CRUDE PRICE LPG NAP MS SKO HSD OF L. LT.0 12859 12900 MIRI 11994 4 3 12 11 59 0 0 1 1 0 9 100 89.0 11987 12408 0 1 1 0 12 100 86. k ‘ k f D r o’ ATTACHMENT 2: SAMPLE WORKING OF NETBACK CALCULATIONS PROD PRICE RS/MT 14599 12260 14832 13617 14361 10100 10100 5535 256 13851 0 BRENT BL 11987 7 8 12 11 48 0 1 2 1 0 10 100 86. .DOS 11361 5 0 12 11 58 BON. RS/MT LESS IPN COST.0 11714 12454 LABUAN 11994 4 2 12 11 58 0 0 2 1 0 10 100 87. What are the most crucial factors and which are indeed controllable. affecting GRM? What are various options for reducing Refining Costs in competitive world? 2.

intermediates and finished petroleum products is done by operations personnel. While the physical handling of crude oil.103 Unit 10 Oil Accounting Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Objectives After studying the unit. although the discharge of duty obligation is allowed to be deferred to the time of removal from the refinery/onward removal to warehouse. 2. the learner will be able to: y __________________ __________________ __________________ Provide a general idea of accounting methods for crude and petroleum products and its significance. Accounting of Crude Oil Receipts and Duty Implications Thereon Crude oil received under bond from port locations and rewarehoused in a refinery needs to be accounted on FIFO basis and appropriate customs duty is required to be paid and accounted for the quantity taken in the process of refining. the Oil Accounting Section of the finance department of a refinery/warehouse is responsible for correct depiction of the quantitative and financial records pertaining to the crude oil and petroleum products. The following are its key functions. Accounting of Manufactured Petroleum products and Those Received for Blending. Quantitative accountal and correct payment of duties on finished petroleum products is the focal area of the oil accounting section. 1. The duty liability on petroleum products arises when the process of manufacture is completed. Hence. etc. tank accountal of receipts and removals is to be . This is known as ex-bonding of crude.

the liability likely to arise during a working day is to be deposited in advance through treasury challan at the bank and the deposit credit is to be utilised in accordance with the invoices issued for the clearances. This is done through the PLA (Personal Ledger Account). 5. . The DSA (Daily Stock Account) is to be maintained for opening balances. production. k ‘ k f D r o’ maintained by taking dip measurements and quality testing reports. 3. the invoice/application for duty-free removal is the cornerstone for correct excise assessment of removals. the excise duty liability is determined at the time of removal from the refinery warehouse. Intimations/declarations are to be submitted to the range office for any act or action that may be regarded as having an impact on revenue. The control over inputs and outputs during this refining process is achieved through the daily material balancing done through the quantitative measurement of tank and line-fill quantities of the crude. The production statistics are correlated to the standard product pattern and the actual distillate yield for any particular period of time. dispatch and closing balances of all certified finished products of the refinery warehouse. Material Balancing. intermediaries and finished products. Whether the goods removed are duty-paid or under bond. With the invoice being the document in support of cenvat credit claim that may accrue to a customer. 4. For duty-paid goods. UNIV ER SIT ST U DI ES k~ e k . Compliance of Excise Procedure and Maintenance of Records The excise department tests compliance of law and procedure primarily through the records maintained by the oil accounts section of the assessee.YO FP E TR OLEUM & EN ER GY 104 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. Despatch of Finished Petroleum Products Assessment to central excise duties is invoice-based. Production Statistics and Periodical returns and Statements As the crude oil is processed through a combination of distillation and blending. intermediary products arise during the course of manufacture of certified finished petroleum products.

Records. etc prepared by the oil accounting section are open to inspection by the range office. . if any. k ‘ kf D r o’ UNIT 10 Oil Accounting 105 Notes __________________ __________________ __________________ __________________ __________________ __________________ __________________ Statutory returns as per excise procedure are filed periodically by the oil accounts section with the range office. are normally issued through the oil accounts section. UNIV ER SIT ST U DI ES k~ e k . show cause notices. Method and system of accounting crude and petroleum products in a refinery? How is the excise/customs procedure followed by oil accounting section? __________________ __________________ __________________ 2. returns. Review Questions 1. documents. Letters.YO FP E TR OLEUM & EN ER GY fo u n ~.

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These products are either removed on payment of excise duty. indigenous and imported. The primary raw material for finished petroleum products is crude oil. the learner will be able to: y Activity 11 A What is the present level of custom and excise duties on crude and various petroleum products? What is the rationale for fixing the same? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Give an overview of excise and customs procedures/formalities as applicable. tank wagon (railways). etc) for sale therefrom. Products belonging to oil marketing companies are also dealt through intercompany transactions. etc who are licensed to deal with manufactured excisable goods without payment of duty. Indigenous crude oil attracts Nil rate of excise duty.107 Unit 11 Excise and Custom – Petroleum Products Objectives After studying the unit. tank lorries (oil tankers). y The removal of petroleum products manufactured in refineries is either to direct customers or through marketing network (warehouses/ depots/terminals. or under bond without payment of excise duty. Imported crude of different varieties as per . In the latter case. Indigenous crude oil is sourced from Gujarat and Assam oilfields and from offshore oilfields of India. FCI. the goods are removed under bond to special industrial undertakings like SEBs. or barges (through waterways). whereas imported crude oil attracts 10% customs duty. The products are removed through pipelines. Provide an appreciation for the manner in which custom and excise duties affect profitability. In certain cases. the duty obligation on the manufactured goods is discharged from the warehouse when it is finally cleared for sale.

additional duty of excise (Re. The excise assessee is required to take necessary actions to be within the legal and procedural requirement of excise and customs law. During discharge of excise duty obligations arising on the removal of finished petroleum products from the refineries on duty-paid basis. the refineries use the accumulated cenvat credit in lieu of cash payment.YO FP E TR OLEUM & EN ER GY 108 Activity 11 B When is it desirable to export/ import any product based on custom/excise duties prevailing? __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ Refining fo u n ~. on selective basis by notification. The additional duty of customs levied under the Customs Tariff Act and the excise duty levied under the Central Excise Tariff Act are allowed to be set-off as duty credit by the refineries (manufacturer) under the Cenvat Credit Scheme of central excise. . without physical supervision of the department. While crude oil only attracts the basic customs duty. In the event of excess refining capacity (with glut in the market). and recently introduced special additional duty of excise on MS. At the refinery/warehouse. Petroleum products are handled under the SelfAssessment Scheme of Self Removal Procedure (SRP) of central excise. the department is represented by the jurisdictional officerin-charge (superintendent) of the Excise Range Office who has been given power of unified customs and central excise control over imported crude oil and excisable finished products of the refinery. of special excise duty. Other than basic excise duty. 1 per litre on Motor Spirit commonly known as petrol and on high speed diesel oil commonly known as diesel). Review Questions 1. what level(s) of production should be maintained to meet domestic demand and export the product? What is the significance of bonded warehouse? How are crude and products removed and accountal done? 2. UNIV ER SIT ST U DI ES k~ e k . other items of import attract additional duty of customs (equivalent to the excise duty attracted for such items under the central excise tariff) and special additional duty of customs on selective basis as notified. there is a levy. k ‘ k f D r o’ processing requirement are brought through different ports of the country.

4. R&D Report No. 7. Bhaskar Rao. Eric Robinson and Dr. Nelson. 4. Nelson. 3. B. Crook Refinery Loss Controls . W.L.G. 11.Kennetha A. Khanna Publishers.N. Handbook of Petroleum Refining Process. Malaysia Hydrocarbon Processing New Challenges. 9.IOC. Truesdale and J.D. 10. 96018. John J. W. Khanna Publishers. G. 5. Kharagpur Advances in Petroleum Chemistry and Refining . Kobe.Course Manual Presented by Dr. . 8. IIT.K. John Miles on 20-21 May 1996 at Singapore. Meyers A layman's Introduction to Oil Refining .G. Dauglas AMOS Course contents on Refinery Loss Control by Dr. 6. Dr.YO FP E TR OLEUM & EN ER GY fo u n ~.G. G. 1996. John Miles at Singapore.Graw Hill. Sarkar. 6. Sarkar. Mc. k ‘ kf D r o’ UNIT 11 Excise and Custom – Petroleum Products 109 Notes __________________ Bibliography 1. UNIV ER SIT ST U DI ES k~ e k . 3. Dehradun. March. Dr. Robert A. 2. Dr. Delhi Petroleum Refining Engineering. Eric Robinson and Dr. Petroleum Monthly Publication. Moketta The Chemistry and Technology of Petroleum (Mercel Dekkar). 8. Indian Institute of Petroleum. Advanced Petroleum Refining. Advanced Petroleum Refining. 5. References 1. Speight J. McGraw Hill Modern Petroleum Refining Processes. 20-21st May. Crook "Managing Modern Offsite Operation" by Patrick B. Technologies Options for Refineries . Petroleum Refining Engineering. Reading materials of programme on Refining & Petrochemicals of various Petroleum Companies. 7. __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ __________________ 2.N. 1996 KBC Petrofine Users Manual A Layman's Introduction to Oil Refining . Delhi Reading Material of Programme on Petroleum Refining and Petrochemical Technology.D.L.