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Fundamentals of refining

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Fundamentals of refining

  1. 1. Refining MB-107 OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k~ e k ; k ‘ k f D r o’ COLLEGE OF MANAGEMENT AND ECONOMICS STUDIES (CMES)
  2. 2. Course Code: MB-107 Course Name: Refining © UNIVERSITY OF PETROLEUM & ENERGY STUDIES
  3. 3. Contents Unit 1 Growth & Development of Refining Industry in India ................................... 1 Unit 2 Crude Oil and its Characteristics ...................................................................... 7 Unit 3 Specifications of Petroleum Products & Related Tests ................................ 23 Unit 4 Integrated Refinery & Petrochemical Plants ................................................. 53 Unit 5 Future Refining Scenario .................................................................................. 85 Unit 6 Advances in Petroleum Refining ..................................................................... 89 Unit 7 Hydrocarbon Loss Minimization ...................................................................... 93 Unit 8 Energy Conservation ......................................................................................... 95 Unit 9 Gross Refining Margin ...................................................................................... 99 Unit 10 Oil Accounting .................................................................................................. 103 Unit 11 Excise & Custom – Petroleum Products ....................................................... 107
  4. 4. 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. Various refining processes used in the refineries have been dealt in this module. 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.
  5. 5. An Overview Refining of petroleum for producing fuel and related products for automobiles, domestic consumption and meeting the needs of the power sector, petrochemicals, fertilizers etc. and other industries, 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. Starting with the establishment of the first public sector refinery at Guwahati (Assam) in 1962, it has come a long way with the setting up of most modern, state of the art and highly energy efficient refineries of the present day. India has 17 operating refineries processing both indigenous and imported crudes. The crude processing capacity of the country has increased from 6 MMTPA in 1962 to 113 MMTPA as of today. 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. 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. For setting up a 6 MMTPA capacity refinery complex with marketing facilities, investments to the tune of Rs 5000 crores are required. These refineries need to be run efficiently so as to make profits, and hence need to be modernised and updated from time to time. The module on refining covers various facets of petroleum refining. Various refining processes used in the refineries have been dealt with in this module. Characteristics of crude oil 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.
  6. 6. 1 Unit 1 Notes __________________ __________________ Growth and Development of __________________ Refining Industry in India __________________ __________________ __________________ __________________ __________________ Objectives __________________ After studying the unit, the learner will be able to: __________________ y Get an overview of the growth of the Indian Refining Industry after independence. y Know about special features of Indian Refining Industry. y Get a good idea of various challenges facing the industry in the present time/in future and strategies for meeting the same. With the growth of industry and improvement in the living standard of people, demand for petroleum products is increasing rapidly. Consequently, there is a thrust on increasing their supply by enhancing refining capacity. First refinery in India started soon after oil production started in Digboi, Assam. Thereafter addition of refineries and capacity augmentation continued unabated. Now we are having seventeen operating refineries with a total capacity of 113 MMTPA. The Important Milestones 1866 - Oil discovery at Nahorpung, Assam. 1889 - Oil Production started at Digboi, Assam. 1893 - First Refinery started at Margharita, Assam. 1899 - Assam Oil Company was formed. 1901 - Digboi Refinery was commissioned supplanting the earlier refinery at Margarita. 1947- 1957 Setting up of three coastal refineries by Multi National Oil Companies (MNCs)
  7. 7. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 2 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Activity 1 A u 2 at Mumbai (Esso & Burmah Shell) Reader may like to draw a Geneological Chart of the current u 1 at Vizag (Caltex) refineries operative in India. Please classify by company, The MNCs were already marketing petroleum technology and year of products in India by then. establishment and expanded capacity wherever applicable by 1954 - Indian Oil exploration with the help of Russian the end of 10th 5 year plan i.e. 2006 – 07. Geologists. __________________ 1956 - Formation of Oil and Natural Gas Commission __________________ for exploration and production of crude oil and __________________ gas. __________________ 1958 - Discovery of Cambay oil field. __________________ __________________ 1958 - Indian Refineries Ltd (IRL) was formed in the __________________ public sector to install refineries and pipelines in India. __________________ __________________ - Oil India Ltd (OIL) was formed as a joint __________________ venture company between Government of India and Burmah Oil Co. 1959 - Indian Oil Company formed for marketing of petroleum products. 1962 - The first refinery in the public sector commissioned at Guwahati (0.75 MMTPA) under IRL. 1963 - Indian Oil Blending Ltd – A JV between Indian Oil Co. and Mobil Petroleum Co. Inc. was formed for manufacture of lube oils and greases. 1964 - IRL was dissolved and merged with Indian Oil Co. Ltd, to form Indian Oil Corporation Ltd (IOCL). 1974 - IOBL became part of IOCL. 1981 - Assets of erstwhile Assam Oil Co. were taken over and vested in IOC as Assam Oil Division (AOD). 1998 - Panipat Refinery of IOC commissioned.
  8. 8. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 1 Growth and Development of Refining Industry in India 3 1999 - Reliance Petroleum Refinery at Jamnagar, Activity 1 B commissioned. What are various options for increasing the Refining Capacity 2000 - Numaligarh refinery commissioned. in the country? __________________ 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, which subsequently __________________ became PSU’s). __________________ __________________ Future Outlook* (as per 2025 vision document) __________________ Total Refining Capacity __________________ MMTPA __________________ 2002 – 03 135 __________________ Barauni Expansion __________________ Haldia Expansion HPCL, Mumbai Expansion CPCL, Nagapatinam RPL Expansion Essar Oil 2003 – 04 170 Koyali Expansion Panipat Expansion BPCL Expansion CPCL Expansion BRPL Expansion Paradip Essar Oil Expansion Nagarjuna Oil 2004 – 05 176 Kochi Refinery Expansion 2005 – 06 214 Essar Oil Expansion RPL Expansion Bhatinda 2006 – 07 221 BRPL Expansion Bina * The anticipated growth in petroleum products may not take place
  9. 9. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 4 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes Refining Capacity in India as in the year 2002 __________________ No. Refineries MMTPA Year of __________________ Commissioning __________________ 1. Indian Oil Corporation Limited, Digboi 0.65 1901 __________________ 2. Indian Oil Corporation Limited, Guwahati 1.00 1962 __________________ 3. Indian Oil Corporation Limited, Barauni 3.30 (6.0) 1964 __________________ 4. Indian Oil Corporation Limited, Koyali 13.5 (18) 1965 __________________ 5. Indian Oil Corporation Limited, Haldia 3.75 (7.5) 1974 __________________ 6. Indian Oil Corporation Limited, Mathura 7.50 1982 __________________ 7. Hindustan Petroleum Corporation Limited, Vizag 7.50 1975 __________________ 8. Hindustan Petroleum Corporation Limited, Mumbai 5.50 1954 9. Bharat Petroleum Corporation Limited, Mumbai 8.90 1955 10. Cochin Refineries Limited, Cochin 7.50 (10.5) 1966 11. Chennai Petroleum Corporation Limited, Chennia 6.50 (9.5) 1969 12. Bongaigaon Refineries Limited, Bongaigaon 2.35 1972 13. Madras Refineries Limited (CBR), Nagapatinam 0.50 1994 14. Mangalore Refineries & Petrochemicals Ltd., Mangalore 6.00 (9.0) 1995 15. Indian Oil Corporation Limited Panipat 6.00 1998 16. Reliance Petroleum Limited, Jamnagar 27.00 1999 17. Numaligarh Refineries Ltd., Numaligarh 3.00 2000 Total Capacity 112.45 Indian Refining Industry – Emerging Scenario u Shifting product demand u Stringent product specifications u Stringent environmental regulations u Feedstock quality deterioration u Globalisation u Deregulation of oil and gas sector Indian Refining Industry – Special Features u Larger requirement of middle distillates (diesel, kerosene) u Prevalence of old as well as modern technologies
  10. 10. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 1 Growth and Development of Refining Industry in India 5 u A few refineries with size far lower than world Activity 1 C standards. i. Describe special features of Downstream Industry. Strategies for Indian Refineries ii. Challenges faced and strategies to meet the same. u Residue upgradation technologies for heavy crudes __________________ u Technologies for producing lighter fuels __________________ u Process technologies to improve quality with respect to: __________________ __________________ – performance parameters __________________ – eco-friendly products __________________ u Value addition to refinery streams __________________ u Increased emphasis on Process Control/ Automation __________________ __________________ u Evolutionary/innovative technological changes expected __________________ rather than revolutionary ones u Refineries to be integrated ,compact and flexible with respect to crude/ product mix. Future Technological Challenges u Meeting higher demand of petroleum products (viz. distillates) u Meeting higher standards of product qualities u More emphasis on environment u Value addition to refineries u Technologies to improve margins u Zero emission refinery Capacity Increase (To Meet Demand of Petroleum Products ) u Low cost revamps/ addition of units u Run length improvement of units u Infrastructure development for crude receipt/storage/ distribution u Installation of matching secondary processing plants.
  11. 11. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 6 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes Value Addition __________________ u Production of value added products from refinery __________________ streams __________________ u Propylene, butene – 1, butene – 2, N – Paraffin, Lab, __________________ Benzene, Toluene, Hexane, P – Xylene etc. __________________ __________________ u Generation of power from heavy ends __________________ Distillation Range Improvement __________________ __________________ u New residue conversion technologies like FCC, Hydrocracker, RDS-RFCC __________________ u Advanced controls and optimisation u Advanced catalysts u Continuous simulation of plants/ product mix through computer models u Prudent selection of technologies and proper integration of secondary units/ plants. Review Questions 1. Please identify technological challenges that refineries will face in future.
  12. 12. 7 Unit 2 Activity 2 A How is the crude oil formed? __________________ Crude Oil and Its __________________ Characteristics __________________ __________________ __________________ __________________ __________________ Objectives __________________ After studying the unit, the learner will be able to: __________________ y Understand the chemistry of petroleum, different types of crudes __________________ and their characteristics. y Develop an insight into the significance of various characteristics of crudes and method of determination of the same. y Get an idea of various crudes used in Indian Refineries. y Appreciate the difference between Indian crudes and typical middle east crudes. 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. It is a complex mixture of hydrocarbons and over 16,000 compounds have been identified in one sample. 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 non- hydrocarbons. As it is drawn from the earth, it also contains impurities like water, mud and salts which get associated during its production and transportation.
  13. 13. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 8 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Activity 2 B Crude oil, the basic raw material of refining industry, is a What are the type of hydrocarbons mixture of eight different hydrocarbon families: present in the crude? __________________ i. Paraffins __________________ ii. Cyclopentanes __________________ iii. Cyclohexanes __________________ __________________ iv. Cycloheptanes __________________ v. Di-cyclo-paraffins __________________ vi. Benzenes __________________ __________________ vii. Aromatic cycloparaffins __________________ viii. Dinuclear and polynuclear Aromatics are present in smaller amounts in compounds containing metallic constituents such as Vanadium, Nickel, Iron, Copper, Magnesium, Calcium, Zinc, Titanium etc. Besides impurities such as Sulphur, Nitrogen and Oxygen compounds mostly present in high boiling point fractions are also present in crude oil. Based on boiling point, the fractions are separated and given secondary treatment to utilise it as finished products. Based on proportion of types of hydrocarbon, it can be divided into Paraffin, Napthenic and Aromatic categories. The purely hydrocarbon content may be as high as 97% and as low as 50% for heavy crude oils. The non-hydrocarbon portion retains hydrocarbon characteristics as the molecules contain one or two atoms of elements other than carbon and hydrogen. The carbon content is between 83 to 87% and hydrogen content between 11 to 14%. 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. Atmospheric distillation is adopted for separating the compounds present into various fractions upto 366ºC:- i. Overhead gases containing mainly methane, ethane, propane and butane. ii. C5–90º C light naptha iii. 90ºC–140ºC heavy naptha iv. 140ºC–204ºC Mineral Turpentine Oil (MTO)
  14. 14. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 9 v. 140ºC–240ºC Aviatin Turbine Fuel (ATF) Activity 2 C i. How do you classify crudes vi. 140ºC–270º Kerosene based on proportion of type of hydrocarbon present in them? vii. 270ºC–340ºC Gas oil ii. What is Crude Assay? How are these Assays utilized? viii. 340ºC–366ºC Jute Batching Oil (JBO) __________________ 366ºC plus fraction i.e. Reduced Crude Oil (RCO) is subjected __________________ to vacuum distillation for obtaining vacuum gas oils, raw __________________ Lube Distillate and short residue. Various fractions obtained __________________ from atmospheric and vacuum distillation are given further __________________ treatment to meet required specifications for use. __________________ Crude Assay __________________ __________________ Crude Assay is the determination of properties of various __________________ fractions of crude oil. This is done to assess the utility __________________ of the crude for processing for production of various products and their yields. Crude Assay Data are utilised for the following: u Crude oil selection u Crude oil grading u Crude valorization u Crude swapping u Crude imports u Creation of new infrastructure at the existing refineries u Grassroot refineries u Production planning management u Inventory problems u Demand/supply gaps Types of Evaluations Preliminary Assay u Crude characteristics – Consistency of crude supply.
  15. 15. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 10 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes Short Evaluation __________________ u Crude characteristics u Absorption of new __________________ crude in fuel refinery __________________ __________________ u TBP assay u To study the change in __________________ quality of crude over a period of time __________________ __________________ u Yield data and key u Detailed characteri- __________________ characteristics of straight sation of crude oil __________________ run cuts in fuel range and including all micro long residue constituents. __________________ Detailed Evaluation u Design data for grass u TBP assay in root refinery atmospheric and vacuum range u Product optimisation u Selection and design of secondary conversion units. u Yield and characterist- ics of sets of distillates in atmospheric and vacuum range with variation in IBP, FBP characterisation of several long and short residues. Information Required u Base and general properties of crude oil u Presence of impurities u Operating and design data – Fractionating or TBP distillation curves – Equilibrium of flash vaporization curves – API or specific gravity curves of each fraction distilled.
  16. 16. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 11 u Property curves of fractions vs% distilled Notes __________________ – Mid% curves __________________ – Yield% curves __________________ __________________ – ISO% curves __________________ u Properties and yield of straight run fractions and __________________ residues __________________ u Detailed composition of light distillates __________________ __________________ u Hydrocarbon Type Distribution of Middle and Heavy __________________ Distillates Characteristics of Crude Oil Basic Properties Impurities Density & API Water Content Reid Vapour Pressure (RVP) Salt Content Light End Analysis BS & W Pour Point Sulphur Content Viscosity Nitrogen Content Wax Content Inorganic and Asphaltenes Total Acid Carbon Residue Trace Metals Ash Content Distillation Characteristic (D86 or D285) Base of Crude Oil Crude Oil Characteristics and their Significance Density Density is used for: u Weight to volume or vice versa calculations u Checking the consistency of crude supply u Control of refinery operations u Used in various correlations
  17. 17. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 12 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes u Also gives a rough indication of type of crude oil __________________ MASS (M) __________________ Density = VOLUME (V) __________________ __________________ M/V Specific GRAVITY= __________________ M’/V (WATER) __________________ __________________ 141.5 API GRAVITY= –131.5 __________________ SP.GR AT 60/60°F __________________ __________________ Examples: Water = 10 API Kerosene = 45 API Motor Gasoline = 58 API Natural Gasoline = 75 API Crude oils are categorised based on gravity Light grades : Above 33 degree API Medium grades : 23-33 degree API Heavy grades : upto 22 degree API CRUDE Density API TYPE TOTAL DISTILLATE UPTO 370ºC Narimanam 0.7920 47.08 I 79.6 Ankleshwar 0.7930 46.85 I 78.2 Jotana 0.8161 41.80 P 52.0 Bombay High 0.8278 39.35 I 65.4 Heera 0.8412 36.62 I 60.6 Kalol 0.8414 36.55 P 47.0 Rumaila 0.8448 35.90 I 55.7 Ratna 0.8484 35.20 I 51.0 Rostam 0.8495 35.00 I 59.7 Jhalora 0.8496 35.16 I 42.1 Basrah 0.8527 34.40 I 52.5 Sobashan 0.8549 33.99 P 43.0 N. Gujarat 0.8553 33.85 I 44.0 Geliki 0.8675 31.50 I 54.5 Nahorkatiya 0.8688 31.30 I 60.9 Kuwait IF IR. 0.8698 31.10 I 47.0 Oman Elmorgan 0.8727 30.55 I 48.1 Jorajan 0.8821 28.84 N 60.7 Kharsang 0.8910 27.22 N 61.7 Lakwa 0.8952 26.50 N 53.7 Jhalora 0.8986 25.87 I 31.8 Kothana 0.9000 25.64 I 28.2 Rudrasagar 0.9210 22.10 N 60.3 Sanand 0.9242 21.45 I 24.4 N- Kadi Mix 0.9340 19.91 I 27.6 Badarpur 0.9430 18.39 N 60.6 Santhol 0.9507 17.29 I 22.9
  18. 18. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 13 Sulphur Notes __________________ Crude oils are also categorised based on sulphur. __________________ u Sulfur is a measure of “sourness” and “sweetness” of __________________ crude __________________ - Sweet grades<0.5% of Sulphur __________________ __________________ - Sour grades >0.5% of Sulphur __________________ Sulphur is passed on to products as much as regulations or __________________ market accepts. It is removed in hydrotreater by reacting __________________ with H2 and recovered as elemental sulfur in SRU. __________________ Reid Vapour Pressure (RVP) and Light End Analysis RVP indicates relative Percentage of gaseous and lighter hydrocarbons in crude oil. Component RVP, Kg/cm2 Propane 14.1 Kg/cm2 Butane 6.6 Kg/cm2 Crude Oil 0.01-0.05 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. TYPICAL HYDROCARBON ANALYSIS Components % WT on Crude C1 ND C2 TRACES C3 0.1 ISO-C4 0.1 N-C4 0.3 ISO-CS 0.3 N-C5 0.5 TOTAL 1.3
  19. 19. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 14 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes Flow Characteristics of Crude Oils __________________ __________________ Characteristics BH Crude Basrah Crude __________________ WAX, % WT 10.9 3.5 __________________ Pour Point,°C +30 -24 __________________ Viscosity Kinematic cst __________________ AT 37.8 °C, 50°C 4.30, 3.32 6.18, 4.84 Geological Characteristics __________________ Yield Value Dynes/ cm2 AT __________________ 32°C 45.0 2.0 __________________ 24°C 85.0 5.0 __________________ 18°C 222.0 10.0 16°C 330.0 12.5 Plastic Viscosity, C.P. AT 32°C 7.9 9.6 24°C 30.7 14.7 18°C 43.7 16.0 16°C 45.0 17.3 Pour Point u Indicates relative amount of wax present in crude oil u Is the temperature below which pumping and transportation problems may be encountered u Along with viscosity, is used in pumping and design calculations: Wax Content Normal paraffins above C16 are solid at somewhat ambient temperatures. These hydrocarbons u Affect the flow behaviour of crude u Affect the product quality of gas oil, VGO and asphalt u 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
  20. 20. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 15 sealing. It is removed in desalter by washing and settling Activity 2 D mainly chlorides and sulphates of Na, K, Ca, Mg. i. How do you separate various fractions present in crudes? Resins Waxy Agglomerates ii. What are various impurities in Particulates crudes, their bad effects and how are these impurities Brine Droplet removed? iii. Method of determination of Asphaltenes Na+ Na+ salt content, BS&W & Viscosity. COO- COO- Alkyl Benzene __________________ __________________ Naphthenates Carboxylates __________________ __________________ FIGURE 2.1 POSTULATED STRUCTURE OF STABLISED EMULSION __________________ Problems Encountered Due to Salts __________________ __________________ u Irregular behaviour in distillation __________________ u 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 u Residual product contamination 100 • Total Chloride evolved as HCL % Ashci % 75 • • 50 • 25 • • 0 0 100 200 300 400 Salt Content of Crude PTO AS NACL PTB as u Salts may vary widely in ratio of metal ions, though common averages are – Na: 70-75%, Mg: 15-20%, Ca: 10%.
  21. 21. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 16 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes u Mg is most prolific producer of HCL with Ca and Na in __________________ descending order __________________ u Small quantities of HCL may substantially enhance __________________ corrosion of sulphur compounds __________________ __________________ Methods for Determination of Salt Content __________________ 1. IP 77/72 Extraction with water KCNS/Ag No 3 __________________ titration __________________ 2. ASTM D3230 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 – Damaging Effects Plugging Abrasion and residual product contamination – Water causes irregular behaviour in distillation. Sediment in crude oil is measured by the following methods: BS & W ASTM D 96 Sediment by extraction ASTM D 4007 Water content 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.
  22. 22. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 17 Asphaltenes, Carbon Residue and Ash Content Activity 2 E Significance of TAN & KUOP. Asphaltenes __________________ u Are polynuclear condensed aromatic hydrocarbons __________________ having high molecular weight __________________ __________________ u These are insoluble in heptane and soluble in Benzene/ __________________ Toluene __________________ u Asphaltenes and carbon residue indicate the extent to __________________ which heavy hydrocarbons are present in crude oil. __________________ Ash Content __________________ __________________ u 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.
  23. 23. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 18 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Activity 2 F TAN What are various crudes processed in Indian Refineries? TAN is actually Total Acid Number. Where are Indigenous crude It is a measure of Naphthenic Acid (NA) contents in crude. found? What is the sulphur content of Indian crudes? 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. Bombay high and satellite fields b. North Gujarat and Ankaleshwar crude c. Assam crudes d. KG Basin-Rava crude e. 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.
  24. 24. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 19 2. Imported crudes are sourced mostly from: Activity 2 G What straight run fractions are a. Gulf Region obtained in Atmospheric Distillation? And in Vacuum b. Nigeria Distillation? c. Malaysia __________________ __________________ d. Australia __________________ The above crudes are specially selected for production of __________________ Bitumen/LOBS/ATF, beside fuel products. __________________ These crudes are having varying range of sulphur from low __________________ of high. __________________ Comparison of Crudes __________________ __________________ Comparison of Indian crudes and typical Middle-east crude __________________ mix for yield and key properties of straight run cuts:- 1. Gases upto 20ºC 4. GAS OIL 250–370ºC 2. Naphtha I.B.P.- 140ºc 5. Vacuum GAS OIL 370–530ºC, 3. KEROSENE 140-250ºC 6. Short Residue 530º, C+. 1 1-2 AROW 5.8% VOL. 0.4 3.8 AROM. 16% Vol NAPH 40.6% NAPH. 52% VOL 4.4 AROM: 6.6% 2 V.O.N.O. 24.9 COTANE NO. 15.0 VOL 73.7 SMOKE PT. 23 10-1 OCTANE No. mm AROM. 1:1 % 67.5 VOL F.P.T.-54ºC SMOKE POINT SMOKE POINT 14mm 27mm 3 Arom. 36% 17.6 DIESEL INDEX 57 19.2 AROM. 15% VOL. 22.3 VOL. POUR POINT +3 F.P.T.–48ºC E.P.T.<–60ºC DIESEL INDEX DIESEL INDEX KUOP 12.10 67 POUR +POINT 23.9 33 KIN VISC. AT 31.2 POUR POINT 27.1 100º C +6ºC 4 –9ºC 8.120 SI KUOP 12-70 KIN. VISC. AT 18.8 KUOP II-61 ºAPI 13.58 100ºC KIN. VISC. AT POUR POINT 34.7 405 0St 5 96.9ºC +48 7 0St 27.2 API 16.5 KIN. VISC. AT 100ºC 150(27 0SI CCR 9.92% WI. POUR POINT + 6.3 CCR 14.77% Wt. 6 ºAPI 3.8 68ºC N.9 ASSAM CRUDE NORTH GUJARAT GANDHAR+ANKLE- MIX ºAPI 29.85 CRUDE MIX SWAR (60. 40 VOLT SULPHUR 0.24% ºAPI 26.83 CRUDE MIX Wr. POUR POINT SULPHUR 0.17%Wt. ºAPI 46.9 +30ºC WAX POUR POINT+21 SULPHUR 0.041 % Wt. CONTENT 10.8% WAX CONTENT POUR POINT+27ºC Wt. 6.8% Wt WAX CONTENT 8.9% KUOP 11.30 KUOP 12.0 Wt.
  25. 25. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES 20 Refining fo n ~; k ; k ‘ k f D r o’ k~ e Notes 1.9 2.7 2.1 __________________ ARON 21.3% ARON 4% VOL. AROM 7.3% VOL VOL. NAPH. 25% OCTANE 10.7 18.6 30.4 OCTANE No. 53.8 __________________ VOL OCTANE NO.61.9 NO. 69-6 SMOKE POINT __________________ 26mm SMOKE POINT AROM. 18.6% __________________ 17mm VOL. F.P.T.–56ºC AROM. 26.9% 20.9 SMOKE POINT 24.7 16.1 __________________ VOL. F. PT. -49ºC 27mm Arom. 16% DIESEL INDEX Vol,. F. PT–57ºC 58 DIESEL INDEX POUR +POINT __________________ –9ºC 56 DIESEL INDEX 18.1 POUR POINT 24.0 58 21.8 KUOP 11-94 __________________ +3ºC POUR POINT KIN. VISC. AT –12ºC 100ºC __________________ KUOP 12.37 KIN 5.98 0St 22.5 __________________ VISC. AT 98.9ºC KUOP 12.31 KIN 28.4 15.7 API 7.43 5.36 0St VISC. AT 100ºC CCR 19.85% Wt. __________________ 4.83 0St POUR POINT + ºAPI 9.51 54ºC CCR 19.2% Wt. API 16.35, CCR KIN. VISC. AT 30.5 6.2 4.7 100ºC POUR POINT 10.4 % Wt POUR +72ºC POINT+ 60ºC 903.650St BOMBAY HIGH ºAPI NARIMANAM Kuwait+Lt. IRANIAN 39.35 SULPHER CRUDE FOMAN (56: 36: 6 VOL. ) 0.17% Wt. POUR ºAPI 47.08 ºAPI 31.1 POINT+ 30ºC WAX SULPHUR 0.085% SULPHUR 2.28% Wt. CONTENT 10.6% Wt. POUR POINT 0 POUR POIN T(–30ºC Wt. KUOP 11.70 WAX CONTENT WAX CONTENT 1.1% 2.8% Wt. KUOP Wt. KUOP II.98 11.98 Selection of Crude(s) for a Refinery Based on product demand, type of products, processing schemes of refineries, metallurgy of existing plant and equipment, crudes are selected after evaluating detailed crude Assay Data. Mostly, a mixture of crudes is selected for a refinery to optimise the cost and meeting products quality specifications. Review Questions 1. Describe different characteristics of crudes dealt with in this unit, their significance and typical values/ units of measurement. 2. Draw a comparison of indigenous crudes with Typical Middle East Crude(s) vis-à-vis important specifications of Petroleum Products.
  26. 26. OLEUM & E TR EN FP ER YO GY u UNIV ER SIT ST U DI ES fo n ~; k ; k ‘ kf D r o’ k~ e UNIT 2 Crude Oil and its Characteristics 21 3. From which Indian crudes, can you produce Notes __________________ a. ATF __________________ b. Bitumen __________________ __________________ c. Lubes __________________ d. Micro-crystalline wax __________________ e. Good Quality Calcined Petroleum Coke __________________ __________________ __________________ __________________
  27. 27. 23 Unit 3 Notes __________________ __________________ Specifications of Petroleum __________________ Products and Related Tests __________________ __________________ __________________ __________________ __________________ Objectives __________________ After studying the unit, the learner will be able to: __________________ y Understand the specifications of various petroleum products, their significance and their determination/tests. y Appreciate crucial specification of HSD & MS from Environmental Pollution Standpoint & Strategies for meeting stringent norms for future Euro III/IV, Bharat III/IV. 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. These characteristics are quantified to make them absolute and also to remove any ambiguity in the interpretation. These quantified characteristics are called “specifications”. Some important tests conducted on petroleum products and included in specifications: Flash Point RON Color Pour Point MON BMCI Distillation AKI Bromine Number Copper Corrosion Cetane Number Benzene Content Silver Corrosion Cetane Index Density Sulphur Smoke Point Sediment Viscosity Aniline Point Water Potential Gum Carbon Residue Weathering Test Existent Gum Vapour Pressure

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