© Macmillan India Ltd., 2007 All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, without permission. Any person who does any unauthorised act in relation to this publication may be liable to criminal prosecution and civil claims for damages. First published, 2007 Reprinted, 2008 MACMILLAN INDIA LTD. Delhi Chennai Jaipur Mumbai Patna Bangalore Bhopal Chandigarh Coimbatore Cuttack Guwahati Hubli Hyderabad Lucknow Madurai Nagpur Pune Raipur Thiravananthapuram Visakhapatnam Companies and representatives throughout the world ISBN 1 ISBN 13: |403-93197-6 918-1403-93197-9 Published by Rajiv Beri for Macmillan India Lid 210 Ansari Roed, Daryaganj. New Delhi 110002 Laser typeset by ADD Computers A-4/B-49, Joshi Colony, Patparganj Exin., Delhi 110092 Printed at Sanat Printers 312, EPIP, Kundii, Haryana This book is meant for educational and learning purposes. The author(s) of the book has/have taken all reasonable care to ensure that the contents of the bock do not violate any existing conyright or other intellectual property rights of any person in any manner whatsoever. In the event the author(s) hashhave been unable to track any source and if any copyright has been inadvertently infringed, please notify the publisher in writing for comective actionCONTENTS Foreword Preface Acknowledgements 1_INTRODUCTION 1.1 Petrochemical Industry ... 1 1.2 Structure of Petrochemical Complexes ... 7 1.3___Feedstock for Petrochemicals 12 1.4 Profile of Petrochemicals and their End Products ... 24 ‘LS__Indian Petrochemical Industries ... 27, References ... 33 2_PROFILE OF INDIAN PETROLEUM AND PETROCHEMICAL INDUSTRY 21 Indian Petroleum Industry ... 34 21.1 Refining Capacity and Throughput ~ 37 2.1.2 Consumption of Petroleum Products — 39 2.2 The Indian Petrochemical Industry ... 41 2.3. Petrochemical Feedstock in India ... 48 23.1 Petroleum Fractions - 49 2.3.2__Natural Gas = $1 2.3.3 Tertiary Recycling ~ 53 2.34 — Pyrolysis Gasoline — 54 2.4 — Petrochemical Product Profile ... 54 24.1 Polymers ~ 54 2.4.2 Synthetic Fibre - 57 2.4.3 Synthetic Rubber - 59 2.4.4 Synthetic Detergent — 60 24.5 Petrochemical Base Intermediates - 61 References ... 64 3. PETROLEUM REFINING 3.1 The Physical and Chemical Properties of Hydrocarbons ... 69 2.2__Crude Oil Evaluation ... 72 3.3 Quality of Crude Oils Processed in India ... 75 i : P ical F 78 35 uality Assessment of Products ... 79 ils... 7! 3.7___Natural Gas Processing ... 80 3.8 Petroleum Refining Processes ... 80 3.9 Feedstock for Secondary Conversions ... 87 3.10 Sulphur Recovery Processes ... 89 Vil xi 1-33xiv Contents 3.11 The Petroleum Products ... 90 3.12 Major Products Demand, Quality Scenario and New Technologies ... 91 References 94 4, OLEFINS PRODUCTION BD 4.1 Steam Cracking for Production of Olefins ... 96 4.2 Gas Sweetening Unit ... 97 4.3 CC, Extraction Unit ... 100 44 Steam Cracking Process Technology ... 101 4.41 Hot Section = 101 4.4.2 Cracked Gas Compression and Dehydration ... 104 443 Cold Section = 104 4.44 Demethanizer - 108 445 Pressure Swing Adsorption - 105 4.4.6 Deethanizer — 105 447 4.48 449 4.410 4.411 4.4.12 4.413 4.4.14 4415 4.4.16 4.417 4.4.18 4.4.19 4.4.20 4.4.21 Acetylene Hydrogenation Unit — 106 Ethylene Separation ~ 106 Depropanizer ~ 106 C, Hydrogenation - 106 Debutanizer ~ 106 Pyrolysis Gasoline Fractionator - 107 Fuel Oil Stripper - 107 Ethylene Plant Refrigeration Section - 107 Cracking Severity - 108 Equivalent Residence Time - 109 Operating Variables in Steam Cracking — 109 Thermal Cracking Reactions - 112 Coke Formation, Decoking in Thermal Cracker - 114 Furnace Run Length ~ 117 Design of Thermal Cracking Furnace - 117 4.5 Emerging Technologies for Production of Olefins ... 120 4.51 452 4.5.3 454 4.5.5 4.5.6 4.5.7 Oxidative Coupling of Methane ~ 120 Ethylene from Methane and Naphtha by an Integrated Process - 122 Dehydrogenation of Paraffins - 122 Methanol to Olefin Technology - 123 Deep Catalytic Cracking Technology - 123 Olefin Conversion Technology ~ 123 Catalytic Pyrolysis Process -123 4.6 Alpha Olefins ... 123 References ... 126 5. PROCESSING OF OLEFINIC C, AND C, CUT FROM. STEAM CRACKING AND FLUID CATALYTIC CRACKING 130-148, S.A Fluid Catalytic Cracking ... 130 SAA 5.2 513 5.14 Growth of FCC Technology ~ 132 Chemistry of Cracking and Process Variables ~ 134 FCC Feed Pretreatment ~ 134 Description of the FCC Process - 134Contents xv 5.2__FCC Gases as Petrochemical Feedstock ... 137 5.3. Processing of C, Stream from Steam Cracker and FCC .., 139 5.4 Oxygenates from Refinery C, and C; Stream ... 139 1 Methyl Tertiary Butyl Ether (MTBE) - 142 2 New Technologies for Replacement of MTBE - 144 43 Tertiary Amyl Methyl Ether (TAME) ~ 144 5.44 — Mixed Ethers from C, Streams - 146 5.5 Upgrading of C, Cut for Recovery of C; Chemicals ... 146 References ... 147 AROMATIC PRODUCTION 149-185, 6.1 Petroleum Feedstock for Aromatic Hydrocarbons ... 152 6.2 Aromatic Hydrocarbon Production ... 153, 6.3 Catalytic Reforming ... 154 6.3.1 Reactions in Catalytic Reforming ~ 156 6.3.2 Reforming Catalyst — 158 6.3.3 Reforming Processes ~ 160 6.3.4 Process Variables in Catalytic Reforming - 164 64 Pyrolysis Gasoline as Aromatics Feedstock ... 166 6.5 Aromatics Separation from Reformate and Pyrolysis Gasoline ... 167 6.5.1 Aromatics Extraction = 157 6.5.2 Aromatics Separation ~ 169 6.6 _p-Xylene ... 169 6.7 _ Emerging Technologies for the Production of BTX ... 174 6.7.1 The BP-UOP Cyclar Process ~ 174 6.7.2 Dearomatizing of Naphtha - 176 6.8 Aromatic Conversion Processes ... 176 6.8.1 Disproportionation of Toluene ~ 178 6.8.2 Hydrodealkylation ~ 179 6.8.3 Isomerization - 181 References ... 184 METHANE AND SYNTHESIS GAS DERIVATIVES 186-231 7.1 Synthesis Gas and Ammonia ... 188 7.1.1 Synthesis Gas and Ammonia Manufacture from Steam Reforming - 188 7.1.2 Synthesis Gas and Ammonia Manufacture from - Aaidaaee aa Z2_Urea 192 7.3 _ Synthesis Gas ... 193 7.3.1 Process Technology ~ 194 7.3.2 Carbon Monoxide - 196 7.3.3 Fischer-Tropsch Syn Gas Technology - 198 7.4 Methanol ... 198 7.4.1 Process Technology - 200 7.5 Formaldehyde ... 205 7.5.1 Process Technology ~ 207 Z.6__Aceric Acid ... 209 7.6.1 Process Technology - 211 7.7 Hydrogen Cyanide ... 216xvi Contents 7.8 Hydrazine ... 217 7.9 Carbon Disulphide .. 7.10 Pentaerythritol ... 218 7.11 Hexamethylene Tetramine ... 219 7.12 Hexamethylene Diamine ... 220 7.13. Melamine ... 220 7.14 Chloromethanes ... 221 7.14.1 Process Technology — 222 7.15 Methyl Amines ... 222 7.15.1 Process Technology - 225 7.16 Dimethyl Formamide ... 226 7.16.1 Process Technology — 226 7.17 Dimethyl Acetamide ... 227 7.A7A Process Technology ~ 227 7.18 Acetylene ... 228 7181 Process Technology - 228 References ... 230 6._ETHYLENE AND ETHYLENE DERIVATIVES 22 8.1__Ethylene ... 232 8.2 Ethylene Oxide ... 235 8.2.1 Process Technology ~ 237 8.2.2 Process Hazards - 240 8.2.3. Ethylene Oxide Storage - 240 8.3. Monoethylene Glycol .... 240 8.3.1 Process Technology — 241 8.4 Vinyl Chloride ... 241 8.4.1 Process Technology — 243 8.5 Vinyl Acetate ... 245 8.5.1 Process Technology - 246 8.6 Acetaldehyde ... 247 8.6.1 Process Technology ~ 248 8.7 Ethanol ... 250 8.7.1 Process Technology — 251 8.8 Acetic Anhydride ... 253 8.8.1 Process Technology - 253 8.9 Ethyl Acetate ... 254 8.10 Ethyl Chloride ... 254 11 Ethanol Amines ... 255 218 8.11.1 Process Technology ~ 255 8.12 Perchloroethylene and Trichloroethylene ... 256 8.13 Ethylene Glycol Mono Ethyl Ether 8.14 Ethylene Glycol Mono Butyl Ether 8.15 Ethylene Carbonate ... 257 8.16 Vinyl Fluoride ... 257 8.17 Vinylidiene Fluoride 8.18 Ethylene Dibromide References ... 2589. PROPYLENE AND PROPYLENE DERIVATIVES 91 Sources of Propylene ... 263 9.1.1 Propylene Recovery from Fluid Catalytic Cracking - 266 Propane Dehydrogenation - 266 Metathesis — 267 914 AS 9.2 Propylene Oxide ... 270 92.1 Process Technology ~ 271 93 Propylene Glycol ... 274 93.1 Process Technology ~ 274 94 Propylene Glycol Mono Methyl Ether 9.5 Isopropyl Alcohol ... 275 95.1 Process Technology ~ 275 96 Acetone ... 277 96.1 Process Technology ~ 277 97 Acrylonitrile ... 278 98 — Cumene ... 279 98.1 Process Technology ~ 279 9.9 Methyl Methacrylate ... 280 9.9.1 Process Technology - 280 9.10 Butyraldehydes and Butanols ... 283 9.11 2-Ethyl Hexanol ... 285 9.12_Methyl Iso Butyl Ketone ... 287 9.12.1 Process Technology ~ 287 9.13 Diacetone Alcohol ... 288 9.14 Isophorone ... 288 9.15 Propylene Carbonate ... 289 9.16 Allyl Chloride ... 289 9.17 Epichlorohydrin ... 289 9.18 Acrylic Acid ... 290 9.18.1 Process Technology - 291 919 Acrylamide ... 292 References ... 292 10. C, AND C, COMPOUNDS 10.1 Butadiene ... 294 10.1.1 Process Technology - 297 10.2. 1-Butene ... 300 10.3 n-Butenes ... 301 10.4 Isobutylene ... 301 10.5 n-Butane ... 302 10.6 Octenes ... 302 10.7 1,4-Butanediol ... 302 10.7.1 Process Technology — 303 10.8 Chloroprene ... 305 10.8.1 Process Technology - 305, 10.9 Isoprene ... 305 10.9.1 Process Technology ~ 306 Debydrogenation of Paraffins - 268 9. Methanol to Propylene ~ 270 274 Contents xvii 260-293 294-310xviii Contents 10.10 Cyclopentadiene and Dicyclopentadiene ... 309 10.10.1 Process Technology — 310 10.11 Piperylene, Isoamylene and 1-Pentene ... 310 References ... 310 . AROMATICS-BTX DERIVATIVES 311-345 11.1 Ethyl Benzene and Styrene ... 311 1.1.1 Process Technology ~ 315 11,2 Phthalic Anhydride ... 318 11.2.1 Process Technology ~ 319 11.3. Linear Alkyl Benzene ... 320 11.3.1. Process Technology ~ 322 11.4.1 Process Technology ~ 327 11.5 Maleic Anhydride ... 327 11.5.1. Process Technology - 330 11.6 Nitrobenzene and Aniline ... 331 11.6.1 Process Technology for Nitrobenzene - 332 11.6.2 Process Technology for Aniline ~ 333 11.7. Bisphenol-A ... 334 11.7.1 Process Technology - 335 11.8 Alpha Methyl Styrene ... 336 11.9 Dodecyl Phenol ... 336 11.10 Fumaric Acid ... 336 11.11 Tsophthalic Acid 337 11.11.1 Process Technology - 337 11.12 Benzoic Acid ... 337 11.13 Benzyl Chloride, Benzal Chloride and Benzotrichloride ... 338 11.14 Benzaldehyde ... 339 11.15 Nitrotoluenes ... 340 11.16 Cyamene ... 341 11.17 Cresols ... 341 11.18 Nonylphenol ... 341 11.19 Diisopropyl Benzene ... 342 11.20 Hydroquinone ... 342 11.21 Anthraquinone ... 342 11.22. p-Diethyl Benzene ... 343 References .. 344 12, POLYMERS, ELASTOMERS, FOLYURETHANES. 12.1 Characteristics of Polymer ... 349 12.2 Classification of Polymers ... 353 12.3 Polymerization Reactions 12.4 Polymerization Reactors 12.5 Polyethylene ... 361 12.5.1 Process Technology for Polyethylene ~ 363 12.6 Polypropylene ... 371 2 Process Technology ~ 373s Contents xix 12.7 Polyvinyl Chloride ... 379 12.7.1 Process Technology for PVC - 381 12.8 Polystyrene ... 382 12.8.1 Process Technology ~ 382 12.9 Epoxy Resin ... 384 12.9.1. Process Technology ~ 384 12.10 Polycarbonates ... 385 12.11 Thermoplastic Polyesters ... 387 12.12 Formaldehyde Resins ... 387 12.12.1 Phenol-Formaldehyde - 388 12.12.2 Urea and Melamine-Formaldehyde — 388 12.13 Polyurethane ... 389 12.14 Synthetic Rubber ... 391 12.14.1 Classification of Rubber (Elastomer) - 391 12.15 Styrene-Butadiene Rubber ... 398 1215.1 Process Technology ~ 398 12.16 Polybutadiene ... 399 12.16.1 Process Technology - 400 12.17 Nitrile Rubber ... 400 12.17.1 Process Technology — 401 12.18 Polytetrafluoroethylene ... 402 12.19 Ethylene Vinyl Acetate ... 402 12.20 Polymethylmethacrylate ... 403 References ... 404 }. SYNTHETIC FIBRES 407-440 13.1 Cyclohexane ... 412 13.1.1 Process Technology - 412 13.2. Caprolactam ... 413 13.2.1 Manufacture of Caprolactam — 413 13.3 Adipic Acid ... 421 13.3.1 Process Technology ~ 421 By 4 Adiponitrile ... 424 Hexamethylene Diamene ... 425 ae Terephthalic Acid and Dimethyl Terephthalate ... 425 13.6.1 Dimethyl Terephthalate - 426 13.6.2 Terepbthalic Acid ~ 427 13.7 Acrylonitrile ... 431 13.7.1 Process Technology - 431 13.8 Polyester Fibre (Polyethylene Terephthalate) ... 433 13.9 Nylon 66 ... 435 13.10 Nylon 6 ... 436 13.11 Acrylic Fibre ... 437 13.11.1 Process Technology - 438 References ... 439xx Contents 14, ENVIRONMENTAL MANAGEMENT IN PETROCHEMICAL INDUSTRIES 441-468 14.1 Environmental Pollution Control: Acts, Regulations and Standards ... 443 14.2 Environmental Pollution in Petroleum and Petrochemical Industry ... 449 14.3 Environmental Impact Assessment ... 459 14.4 Waste Management and Environmental Pollution Control: Strategies ... 460 15.1.1 Classification of Corrosion ~ 471 15.12 Theory of Corrosion = 471 15.1.3 Forms of Corrosion = 471 15.14 Factors Affecting Corrosion ~ 473 15.2. Corrosion Monitoring ... 473 15.3. Corrosion in Petroleum and Petrochemical Industries ... 474 15.4 Corrosion in Pipelines ... 478 15.4.1 Internal Pipeline Corrosion ~ 478 15.4.2 External Pipeline Corrosion ~ 479 Pte feet ae 15.5_Cortosion Prevention and Control ... 479 15.5.1. Selecting Corrosion Resistant Material of Construction - 480 15.5.2__Corrosion Inbibitors = 484 15.5.3 Desiyn Consideration ~ 484 15.5.4 Isolation of the Material from the Corrosive Atmosphere ~ 486 15.5.5 Coating ~ 486 15.6 Corrosion Monitoring ... 488 References __ 488 Glossary of Terms Appendix A: Commonly Used Abbreviations in Petroleum and Petrochemical Industry Appendix B: Physical and Chemical Characteristics of Major Hydrocarbons Appendix C: SI Units and Conversion Tables Appendix D: Approximate International Cost of Petrochemicals Appendix E: Mojor Petroleum, Petrochemical, Fertilizer and Chemical Industries in India Appendix F: Major Research and Consultancy Organizations Appendix G: Major Manufacturing Associations Index S01 Su 51S S47 562Chapter 1 Introduction 1.1. PETROCHEMICAL INDUSTRY Petrochemical industry has been playing important role in the social, cultural and economic growth of a nation and in providing basic needs of mankind, namely food, shelter and clothing. Today petrochemicals are an indispensable part of our life and are also providing key feedstock to chemical industry for making thousands of different chemicals which people usually encounter as end or consumer products. Modern petrochemical industry has been able to meet requirement of a large number of products which are being used in some form or other in daily life and is closely linked with the socio-economic needs of people which includes packaging to agriculture, automobiles to telecommunication, construction to home appliances, healthcare to personal care, pesticides to fertilizer, textile to tyte cord, chemicals to dyes, pharmaceuticals and explosives. ‘The petrochemical industry is the largest segment within the US$ 1,600 billion global chemical industry, of which it has a share of around 40 per cent. The petrochemical industry is dominated by two kinds of players: oil and gas companies that have integrated to extract chemicals from their products and chemical companies producing a variety of chemicals, including commodity plastics. An increasing demand of the growing world population and limited resources like coal, chemical, cotton, jute, wood, natural rubber, molasses and alcohol based chemicals, etc., has resulted in the higher production of synthetic materials, derived from petroleum, as substitute of natural resources. Petrochemical industry is among the mother industry that forms the base of any developed and diversified industrial economy. Table 1.1 shows the petrochemical socio- economic linkage. The origin of petrochemical industry dates back to 1920 when isopropanol was manufactured on a large scale from propylene obtained from cracking process during manufacture of gasoline petrochemicals. The petrochemical industry grew to its current prominence largely in the twentieth century and the bulk of its market penetration and geographic spread from its beginnings in the US, Western Europe and Japan occurred in the second half of the twentieth century from 1950 onwards [Plotkin and Swanson, 1999]. Ethylene glycol was the first petrochemical in the true sense, synthesized by Union Carbide in 1923, Although beginning of petrochemical industries was in 1920, however, intensive development of petrochemical industry took place during, and after, World War Il (W W II) when there was a tremendous growth in the demand for polymers, explosives, chemical intermediates, etc. The original feedstocks for organic chemical industries are coal, coal tar, fats, oils and molasses. Chemical feedstock sources are given in Figure 1.1. However, W W II gave real impetous to utilization of petroleum and natural gas petroleum products and quantitatively 95 per cent of the organic chemicals are now based on petrochemicals derived from petroleum and natural gas feedstock. It is estimated that 7-10seounog yoojspaed jeoMeyD 44 aunBly smsohied aaa ! se, | =F tuatuna ens = t ensoera | furmeaes]| ovrunganuo | “SEPEIPOULEW! seqqry ae v “eonuatD nears t ws] t sone nt REE jouer [asquonkny I t t F j 1 annjurAioy "i | [wear] Gey seen Gere sonoma, | T oe Kur} (Caer f poi] [tla ||| ep recomea|| ¥ -F ovoikwa Z T vcnarverah|-——> p> 2 z C fi t euewert uoUILAY ouopena | [evotcou | Irate | —epao t “Ft ¥ F on suovina_ ft ¥ tt orkuorony anne Fo pue® ee LT anna T 19k ts s——} t youewns 2H+09 (@oramen) Cooma) (emenon Gas)Introduction 3 per cent of the carbon in hydrocarbon output of the world in terms of gas oil is utilized as feedstock in the petrochemical industry. Table 1.1 Petrochemical Socio-economic Linkage Group of Product Plastics and Polymers ‘Synthetic rubber ‘Synthetic fore ‘Synthetic detergents Industrial chemicals Fertilizers Areas Agricultural water management, packaging, automobiles, telecommun- ications, health and hygiene, education, transportation, building ‘Transportation industry, chemical, electrical, electronics, adhesives, sealants, coatings Textile, transportation, industrial fabrics, geo-textiles, non-woven fabrics Health and hygiene Drugs and pharmaceuticals, pesticides, explosives, surface coating, dyes and intermediates, lubricating oil additives, adhesive, oil field chemicals, antioxidants, chemicals, metal extraction, printing ink, paints, corrosion inhibitors, solvents, perfumes, food additives Agriculture, polymers Although the petrochemical industry is an American phenomenon created by oil and chemical companies in the US in the 1930s and early 1940s, the technical origins of this industry are found just as much in Europe as in US, The most important petrochemicals were first synthesized in Germany between 1900 and 1930, but from feedstock other than petroleum [Spitz, 1988]. Historical dates for the first commercial production of some important organic chemicals are given in Table 1.2 [Spitz, 1988]. One of the major issues responsible for directing worldwide Table 1.2 Historical Dates for the First Commercial Production of Some Important Organic Chemicals Chemical Producers Year Phenol F. Raschig (Germany), Hottmann — LaRoche (Switzerland) 1901 Carbon tetrachloride | Grieshaim — Elektron (Germany) 1903 Tnichloroethyiene Wacker (Germany) 1908 Etnylene Griesheim ~ Elektron (Germany) 1913 Ammonia BASF (Germany) 1913 Acetic acid Wacker (Germany) 1916 Ethylene oxi BASF (Germany) 1916 Acetaldehyde Hoechst (Germany) 1916 Acetone Hoechst (Germany) 1917 ‘Weitzman (UK) Stenderd cil of NJ (US) Vinyl acetate Shawinigan Chemicals (Canada) 1920 Methanol BASF (Germany) 1923 Butanol BASF (Germany) 1923 Vinyl chloride Wacker (Germany) 19304 Petrochemical Process Technology growth of petrochemical industry, has been the availability of feedstock. There has been tremendous growth in the petrochemical industry during the last four decades due to overall increase in the basic needs of the society. Petrochemical milestones are presented in Table 1.3. Although the need of aviation gasoline during W W Il was the driving force of refineries, synthetic rubber was another product which was responsible for the rapid growth of petrochemicals industry as it was needed for the tyre industry [Spitz, 1988]. The fast development of synthetic rubber industry resulted in an increased demand of styrene which requires ethylene and benzene. Another aromatic, to have gained importance, was toluene. This resulted in rise in the production of aromatics from catalytic reforming process, which was earlier supplied from coke oven plants. The development in the catalytic reforming catalyst and upgradation in regeneration technologies resulted in better yield, selectivity, activity, stability and regeneratibility with less coke formation. The petrochemical industry is highly technological and capital-intensive. Developments in petrochemical technology are taking place very fast. Tremendous efforts and huge resources are being continuously spent on increasing the size of the plant, the yield through continuous upgradation of catalyst, reducing energy consumption and cost reduction through novel process rate, new technologies or scale-up approaches. Due to various technological and engineering developments, the petrochemical industry has been able to reduce cost of production. Changes in technology and raw materials have shifted regularly and frequently towards lower costs and competitive production, less energy consumption through better conversion efficiency, a broader spectrum of product grades to meet specific needs, such as in case of detergents, reduction in pollution load. Some of the factors which have motivated the rapid expansion of petrochemical industry have been due to continuous upgradation of steam cracking furnaces, catalytic reforming process and effective Fluid Catalytic Cracking (FCC) gas recovery system. Fast development in separation process, especially liquid-liquid extraction, extractive distillation and adsorption due to development of new solvents and adsorbents, has facilitated enhanced recovery of olefins, paraffins, and aromatics in more pure form. Udex process, Sorbex processes ~ Parex, Olex, Molex - are some of the developments in the separation process which has made possible the recovery of high purity p-xylene from other xylene isomers, paraffins from kerosene stream for LAB, non-aromatics from aromatics during manufacture of BTX and olefins from C, and C; stream of crackers. There was tremendous increase in the demand of the plastics and synthetic fibres after W W II, which led to further rapid growth of the petrochemical industry. Although fertilizer industry is not part of petrochemical industry, however, on account of a rapid rise in demand of food grain, there has been continuous upgradation of ammonia technologies, which has improved availability of synthesis gases for production of methanol and CO products. Table 1.3 Petrochemicals Milestones 1828 Michael Faraday first produced ethyl alcohol from ethylene 1839 The modem plastics industry is born when Charles Goodyear discovers elastic material resistant to heat and cold 1855 French chemist Marcelin Berthelot makes isopropanol from propylene by route of ethylene to ethanol 1863 Berthelot forms acetylene by passing methane gas across an electric arc 1892 French researcher Moissan demonstrates that hydrolyzing calcium carbide can make acetylene Late-1800s People’s Gas Light and Coke Co. and partners form Union Garbide in ChicagoIntroduction § 1901 1904 1904 1906 1907 1908 1908 1911 1913 1913 1914 1915 1916 1917 1917 1917 1920 1921 1922 1924 1925 1925 1925 1925 1920s Heyden Chemical Works starts limited production of formaldehyde Fritz Haber develops ammonia synthesis process using expensive rare earth catalyst Carl G. Fischer and James A. Allison form Prest-O-Lite Co. to commercialize portable lighting with acetylene in the US. First commercial nitric acid plant is built in Bochum, Germany, 300 kg/day Leo Hendrik Baekeland synthesizes ‘Bakelite’, the world’s first synthetic plastic The American Institute of Chemical Engineers (AIChE) is founded Jacques Branderberger. a Swiss chemist, invents Cellophane BASF chemist Carl Bosch directs development of the first feasible process for synthesizing ammonia from hydrogen and nitrogen gases BASF Starts up the first plant for synthesizing ammonia (using the Haber-Bosch process) and begins production of nitrogenous fertilizers The Griesheim works of Hoechst A.G. sterts producing vinyl chloride monomer, the first true synthetic fiore, on a commercial scale The Condensite Co. builds the first synthetic phenol plant Dow builds the first major US styrene plant in Velasco George ©. Curme, Jr. and his coworkers at the Mellon Institute of Industrial Research in Pittsburgh develop a high frequency arc process that produced acetylene from a gas ail feedstock The United Carbide and Carbon Co. is founded by joining Prest-O-Lite, Linda Air Products Co., National Carbon Co, and Union Carbide. The companies were all studying how to make ethylene from natural gas or ethylene from ethane BASF Bayer and Hoechst join directors of three other companies and Griesheim-Elektron to form the precursor of |.G. Farbenindustrie Harold Hibbert of the Melion Institute obtains a US patent that describes the use of ethylene: alycol to lower the freezing point of water in automotive cooling systems ER & E produces the first commercial petrochemical from gaseous refinery byproducts: Isopropyl alcohol (rubbing alcohol) Union Carbide completes and puts in operation a hydrocarbon separations and cracking plant. Union Carbide can now separate light HDS and make limited quantities of ethylene from natural gas BASF develops the first large scale urea synthesis process based on ammonia and carbonic acid Matthias Pier and Bosch develop a commercial methanol process at BASF, using zinc~ copper catalyst rather than distillation of wood Union Carbide starts up the first US plant designed specifically to produce ethylene in South Charleston, W. Va. \.G. Farben cartel is established through the combination of German's largest chemical firms, including Badische Anilin and Soda Fabrik (BASF), Farbwerke Hoechst, and Farbenfabriken Bayer Standard Oil of New Jersey sets up technology exchange agreements with I.G. Farben Naugatuck Chemical Co. is the 1st firm to build a polystyrene plant Tennessee Eastman establishes a chemical operation in Kingsport, Tenn., to make materials for production of photographic film, including acetic anhydride and cellulose acetate (Contd...)6 Petrochemical Process Technology (Contd. from Table 1.3) 1927 1927 1927 1928 Late-1920s 1929 1929 1929 1929 1930s Early-1930s Early-1930s 1930s 1933 Mid-1930s Mid-1930s 1934 1935 1936 1937 1938 1939 1940 1942 1943 DuPont makes Cellophane moisture-proof Prestone successfully markets glycol antifreeze. Carbide gained a 14-year monopoly before DuPont and Dow became a producer before W W II Shell Group starts research on steam cracking butane to ethylene and higher olefins Godfrey L. Cabot Inc. and United Carbon Co. introduce the modern furnaca black process, using either gas or oil to produce carbon black Carbide discovers that ethylene dichioride is a prime dry cleaning fluid and also excellent solvent for tetra ethyl lead Shell starts up a 20 TPD ammonia plant based on coke-oven gases produced at Ymuiden, Holland. It is based on the Mont Cenis ammonia process Carbide starts producing acetone, which could be made cheaper synthetically than by the traditional fermentation route First production of vinyl chloride, produced by cracking ethylene dichloride occurs ‘Wulff and Mark develop the |.G. Farben technology for styrene monomer Shell Oil and California Standard together purchase UOP Baumann, initially a member of BASF's ammonia laboratory, develops a commercially successful electric arc process to double the yield of acetylene Wolfen works of |G. Farben brings a plant on stream to polymerize vinyl chloride, Pe-Ce fibre, and the first truly synthetic fibre material Imperial Chemical Industries, England, obtains basic patents on LOPE Imperial Chemical Industries, England, discovers polyethylene .G. Farben and Standard Oil Co. (Nu) develop 2 commercial process to produce acetylene via an electric arc process. Esso's Baton Rouge refinery produces 300 tonnes/annum of acetylene with this process Germany begins development work to crack petroleum distillates from Austrian and Romanian oil fields to ethylene Rohm and Haas begin production of methyl amines via high pressure catalytic dehydration of ammonia and methanol. It commences production of methy! methacrylate resins in mid 1930s, marketed as Plexiglass Wellace H. Carothers, DuPont, discovers Nylon Shell commercializes the world's first polymerization plant in its East Chicago, Ind. Refinery Exxon Research & Engineering chemists discover artificial rubber, butyl, which is used in most inner tubes in about 6,00,000 military vehicles during W W II DuPont chemist, Roy J. Plunkett, discovers Poly Tetra Fluoro Ethylene (PTFE), trade market Tefton The first polyethylene plant, based on ICI's Alkthene patent, is constructed and comes on stream in 1939 with a nominal capacity of 100 tonnes/annum Burnawerke Huels starts up a plant to produce Buna-S synthetic rubber for W W Il; German Buna production reaches 1,17,000 tonnes/annum by 1944 ‘Shell successfully adapts the UOP alkylation process to make cumene (isopropyl benzene) from coal tar benzene and propylene. By mid-1942, Shell is operating synthetic cumene plants at Wood River, Ill, and Norco, La A 30,000 tonnes butadiene plant is built at Baytown at a cost of $19 million and placed in ‘operation in 1943Introduction 7 After WWII 1947 1949 Early-1950s 1952 1952 1952 1953 1955 1956 1957 1959 1961 1964 1971 1977 1990 Celanese Co. constructs a multiproduct propane oxidation plant at Bishop, Tex., the first of its kind UOP commercializes a process to make alkyl benzene, one of the building blocks of commercial taundry detergents Union Carbide’s Linde division (now UOP) develops and patents the first commercially significant synthetic molecular sieve zeolites, MOLSIV adsorbents Karl Ziegler develops the technology for low-pressure, high density polyethylene \.G. Farben is abolished and its manufacturing plants are regrouped largely under three major firms: BASF, Hoechst and Bayer in an antitust settlement, the US government and ICI agree that ICI would license its PE technology in the US on a non-exclusive basis Celanese Co. discovers that liquid-phase oxidation of butane is more selective than vapour-phase oxidation. Celanese builds a plant at Pampa, Tex Naphthachimie, a JV of Pechiney and Kuhimann, Europe, starts up a plant using Scientific Design Co. Inc.’s new process to manufacture ethylene oxide and ethylene glycol Hoechst builds the first low-pressure polyethylene plant. By 1957, six plants using Ziegler technology to make polyolefins came on stream After developing breakthrough catalyst for the oxidation of p-xylene to terephthalic acid in very high yields, in 1956, Scientific Design Co. Inc. sells its rights to the oxidation technology to Amoco Chemicals Co. Amoco Chemicals develops and commercializes the technology in its plant in Joliet, Ili Polypropylene arrives on the scene Shell and UOP commercialize an even better aromatic extraction process than Udex, using Sulpholane as the solvent IFP commercializes its benzene hydrogenation to cyclohexane process at the El refinery, Laoq, France UOP commercializes the Sorbex process, which simulates the countercurrent flow of a liquid feed over a solid bed of adsorbent UOP introduces the Parex process for high efficiency recovery of high purity paraxyiene. The Parex process quickly replaces fractional crystallization Linear low-density polyethylene comes on the scene ‘The Clean Air Act Amendments of 1990 sets limits on certain emissions from all kinds of petroleum processing plants in the US Courtesy: Oil and Gas Journal, 13 December 1999. 1.2 STRUCTURE OF PETROCHEMICAL COMPLEXES The petrochemical complexes involve one or a combination of the following operations: « The manufacture of basic raw materials like syn gas, methane, ethylene, propylene, acetylene, butadiene, benzene, toluene, xylenes, ete. The basic building processes include partial oxidation, steam reforming, catalytic and thermal cracking, alkylation, dealkylation, hydrogenation, disproportionation, isomerization, etc. The commonly used unit operations ate distillation, extractive distillation, azeotropic distillation, crystallization, membrane separation, adsorption, absorption, solvent extraction, etc.8 Petrochemical Process Technology RAW MATERIALS: Natural Gas (atsociated/non-essodated gas NGL, NG condensate) Petroleum fractions (Refinery gases, Nephtha, Kerosene, Wax, Gas oi) I UNIT PROCESSES Cracking, Reforming, Deaikylation, Akkyiavon Disproportonation, Isomerization, Oligomerization, Partial oxidation, etc —. ‘BASIC CHEMICALS: Nethane, Acetyene, Ethy‘ene, Propytono, Butenes, Butadiene, Benzene, Toluene, cole, el. ‘Oxidation, Nitraton, Chiornaton, Hydrogen, Oxygen, | a en er : rm iydrogenaton, Dehydrogenation hone, Mixed acid ibn, Dale Plastics end Resins: ‘Synthetic Fibres: Synhete Reber Intermediates and UF. PF. MF, LOPE, Nylon 6, Nylon 86, SBR, BR, NBR, Misceleneots LLDPE, HOPE, PVC, Polyester, Chioroprene, Products. Drugs, Polypropyene, Acryic Fite, et. Isoprene, et. Dyes, Pesticides, Poystyene, ABS Detergents, Piastcizers, Plast, ec, Ferizers Figure 1.2 Structure of Petrochemicals Complex © Manufacture of intermediate chemicals derived from the above basic chemicals by various unit processes like oxidation, hydrogenation, chlorination, nitration, alkylation, dehydrogenation along with various unit operations like distillation, absorption, extraction, adsorption, etc. © Manufacture of target chemicals and polymers that may be used in the manufacture of target products and chemicals to meet the consumer needs. It includes plastics, synthetic fibres, synthetic rubber, detergents, explosives, dyes, intermediates and pesticides. The structure of petrochemical complexes and products derived from various petrochemicals are shown in Figure 1.2. Figure 1.3 illustrates overall view of a petrochemical complex starting from production of synthesis gas, olefins, aromatics, manufacture of intermediates and finished products like plastic, synthetic fibre, synthetic rubber, ete. Figure 1.4 shows basic building blocks and petroleum-petrochemical interface. Figures 1.5~1.7, show the product flow diagram of three large petrochemical complexes of Indian Petrochemical Co. Ltd at Vadodara, Nagothane and Gandhar comprising a combination of a large number of processes and products. Petroleum and petrochemical industries have close links and have always benefited from their symbiotic relationship and any variation in the cost of crude oil and petroleum products will have a direct impact on the overall economy of petrochemicals. Providing more petrochemical feedstock instead of fuel is drawing earnest attention. A typical example of integration of petroleum refinery and petrochemical Industries is Reliance industries with one petroleum and three petrochemical complexes, Bongaigaon Petroleum and Petrochemicals (Figures 1.8-1.10). Reliance JamnagarIntroduction 9 +[Frdeaer Methane [Steam |_[Syntresis|_.| Urea [—*Lreteming | >|" ‘onortite sf rethanat | —» Formaidehyee Natural ge = and natural vettyiene ‘gas bad Monosthylone glycol 7 Ethylene: Ethylene oxide Diethylene glyco! ‘Trethylene glycol Emylene dchionae 1. in cuaite] +f ove pone -+[_Potveronvene L_, Lo Acnjoriite ol Acrylic Neopia Steam | ol Prony jo uid I+ Cumene r+ Phenol T L»| Propylene oxide |») Isopropyi alcohol Pyrolysis G gavatire re{_ Synthetic rubber a Lt ey aiream and Foe +{_ Butadiene }te[ SBR, Pe, AB ind C5.eam nel _nrobyrane Isobutene ++} MTBE Titans and LF crsiream +f isoprene Bbatene Otetns nom paren [aor Caiavic | ,[ Aromatic], f Tee aI] IS LL oemen teforming |] separation Denzerie [benzene(LAB)] up Demet tat ]}+{ Gumene _}-+[Acetone |-+[Bis tena Toluene Lo} totone ote! ,rouene || Tene Phenol L [en ma [ol Syren Serzoicacé] Lal Styrene fo] Syripen Eihyions Pathak ed ee Synthote lene mvt |-+f Poxy DNTITPA, ie =a Isophthalc|_, [Unsaturated] mesons |} acid polyesters 1 Figure 1.3 Overall View of Petrochemical Complox10 Petrochemical Process Technology lend gas Petroleum refinery Petrochemical production exploration Natural ‘Steam of Synthesis |_| Methanal, Formaldehyde’ 928 reforming 985 Acatic acd, etc. +| Methane |—»| Chlorinated metnanes ‘Steam [> _Qlefins —> Polymers grocking | Pyrcyais gasol Bonzene reforming [~*| separaton [Sane FOC gasse «| Cataytic |_. tor cy and C5 recovery Vacuum a ae a Ccago ue Figure 1.4 Petroleum and Petrochemical Interface Refinery is one of the biggest integrated refinery and petrochemical plant in Asia. In the changing scenario, petroleum refining and petrochemical production integration will be of vital importance for maximizing the use of byproducts and improving overall economy of a petroleum refinery. IOC Panipat refinery and IOC Vadodara are the other two refineries, which have entered in the field of manufacture of petrochemicals, viz., terephthalic acid, polyester and linear alkyl benzene, respectively, IOC Panipat is also planning to go for naphtha cracker for production of olefins and polymer.Introduction 11 Naphtha 2yene ‘Methanol ws 1 | ae Pare Dinetha ij “Linen xylene terephthalate i is om rw ‘ONT plant + res | laseace = a = Se Lite] APU at Be we Ee as, HES 7 _scioe | hie Sn aa “Ik ns aaa + oletivene Eihylere m=) a= se] eee | ee ‘Diethylene acid | Ethylene slyco. BEthy hex on aser] [eae aa - es HEE + koyiene = ia fa Koylene CP ‘Aorgooe last fombate) [P| Peeve ‘Ammonia : ie ae ' | iene cen cee PP plant > Acryonitite Dosa) T i = 1» ‘Acrylonitile ” [Fiydrocyanie ‘rot ‘alll a Pay Pr come + Cisamer ‘epgaton ant Butadiene | fem} gi oes aa ora Ce from F Butadiene benzene. eH at. Soxow Sa) | .Fearaer ==) Ee sae ART 7 qesoline. on ll = ate a ies i a feedstock a janes alae v Indian Petrocherticals Corporation Limited Figure 1.5 Product Profile of IPCL Vadodara Courtesy: IPCL Vadodara.12 Petrochemical Process Technology . +1 Indothene PRODUCT FLOW DIAGRAM Nagothane Complex Low aensty povethylene plant —] Indotnene LL +| Ethylene ° one Indothene HO povetinlenepant t—*| 1-Butene Ethane!Propane — +| Ethylene glycol T ‘Butane pant || Ettyiene oxide }+| Dietrylene alyeo! (Ges cracker pant ! vnro L_Lrrenyee on Propane!Propylene| +} Koylene cP | — Csstream pokprccsene t+} Koyiene lent Figure 1.6 IPCL Nagothane Product Flow Diagram Courtesy: IPCL Vadodara. 1.3. FEEDSTOCK FOR PETROCHEMICALS One of the major issues, responsible for the worldwide growth of petrochemical industry, has been the availability of feedstock, which has led to replacement of the natural resources such as coal, molasses, fats, etc. Basic feedstock used in the petrochemicals industry for manufacture of olefins and aromatics are derived either from natural gas or petroleum fractions. These includes natural gas (associated or non-associated), condensate, naphtha, kerosene, catalytic cracking and reformer gases, waxes, pyrolysis gasoline. Summary of the feedstock, their source and process technology involved, is presented in Table 1.4 [Mall, 1994]. World proven reserves of oil (Figure 1.11), total oil production and consumption, world refinery throughput are shown in Tables 1,5-1.8 [BP, 2004]. World proven reserves of natural gas, natural gas production and consumption, is presented in Tables 1.9-1.11 and Figure 1.12 [BP, 2004].Chor aati plant Introduction 13 salt Ethylene Rich gas i af ewes mature ZC ‘Separaion plant Lean gas Proven Reserves of Oil: (Gas cracker plant aa fe ent SS pm Da —| Viny’ LL, ain — Te cove ee ae Ethytone salt ——C EOIEG plant “Ammoria Propylene C, mixture Tndothone OOo Figure 1.7 \PCL Gandhar Piant Product Flow Diagram Coutesy: IPCL Vadodara, Ethylene ‘ayco! ‘Aeryonitile ‘Acetoitile Fiydrocyanie ‘acid Generally include those quantities of oil that geological and engineering information indicates with reasonable certainty and can be recovered in the future from known reservoirs under existing economic and operating conditions. Reserves-to-Production (R/P) Ratio: If the reserves remaining at the end of the year are divided by the production in that year, the result is the length of time that those remaining reserves would last if production were to continue at that very level.14 Petrochemical Process Technology Jamnagar complex £ Pett Propyiene Ethyene ‘Bune i f z | vem EDC €0 : | f 1 | i PYC DEG ‘MEG TES HOPEMLDPE ||! Pxt") PTA® pert) Poyester chips Wool viscose sikyam Fabrics ! {1) Plant also operational at Jamnagar complex | | Abbro- Full Name ‘Abbre- Rae. anaes Cees unieas coor | veto a (8) Pant operational at Haz compen DEG | Bretiyene aiea et | Pohthyene wrepihait Dit | Benetyrtowpnialats | Pry | Polyester lament yn FDC | Etylenadvatorde” | PP | Polpropsene £0. | Etyene onde Por | Pobesor sta fore Hore | Heh denety poretnfene | Pm | Pues teroptnate sie UAB | Linear shybonzne” "| bv Point choise ttbee | Crear oer corny me | Paroxere Polyethylene cs | Mono-emyere gyeot | 166 | trenytene gyoot NGL | Nauratgas wu va | Vnytchetce monomer NP | Nema paren Figure 1.8 Product Flow Chart of Reliance Industries: A backward Integration Courtesy: Reliance Industries Ltd.uoedleDuog “gua -Aseynog Kreuyey uceBleSu0g jo Weyomo|s GE esnBiy au Je Ten wOTeUR 2900 Je — a aS Daten wpe [Lox a oc {.00#-0ZE) 10 Se8 AnvaHy (0,028) 10 ‘apn poonpay 357]. : ost (Do02E-022) NO SEO ws ai ii | 7 = [_ wermnmoon | FE waraeeam| § “SOeAxe SnewOKe AABOH a g ‘sdos 2 SNOT Speme qeuoe wey | 32 19H z cepa wessy | = eI FOF i wana] § ra (O.081-Sh1) Weuodwos-cey | = = J Gasr-OH aude TULF nt J a ‘souolkx sopeuiase pox aieuoebieGuog “Jug -Asauneg wesBeig Moj4 yoNPog (1d4) PI] SjeolWeYsosjeq pue AJeuysy UoebjeGu0g Of", “aunBy seuuojas 2pphoes epsuowostio Bn ‘ayesueu os; 1UER |(swo) onnés| naWwoUnD $ Ff 3 euceu 2 seyeaned fo 33 [aemoey 4 sauoey ae saye90 aay wn ax votopky dn oxen exis sts9ko asp enous z ‘rue aeeundam svonet a vgewia iW Lh ‘opnlg. 0 tin wieina TORS mn +] ed oa sre0zUeeKUON ua auayhe-esed xe1e3 LIntroduction 17 Table 1.4 Natural Gas and Petroleum Fractions as Petrochemicals Feedstock Petroleum Source Composition Intermediate Intermediate Fractions Processes Feedstock and Natural Gases Refinery cases Distilation, catalytic | Methane, ethane, | Liquefaction, LPG, ethylene cracking, catalytic] propane, butane, BP | cracking propylene, butane, roferming Up to 26°C butacione Naphtha Distllation, thermal | C,-C,, hydrocarbon, | Cracking, reforming |Ethylene, propylene, and catalytic BP 70-200°C alkylation, butane, cracking, visbreakin disproportiona-tion, | butadiene, benzene, isomerization toluene, xylene Kerosane Distillation and Cy-Cyg hydrocarbon, | Fractionation to Linear CC, secondary BP 175-275°C obtain Cjg-C,, range |alkanes conversion hycrocarbon processes Gas oll Distillation of crude | Cyg-Cog Cracking Ethylene, propylene, oil and cracking | hydrocarbons, butadiene, butylene BP 200-4008C Wax Dowaxing of Cy-Cyg hydrocarbon | Cracking Cg-Cyp alkanes lubricating oll Pyrolysis gasoline Ethylene cracker | Aromatic, alkenes, | Hydrogenation Aromatics dienes, alkanes, | | distillation, extraction, eycloalkane, etc, | crystallization, adsorption Natural gases and Gas fields and crude Hydrogen, methane, | Cracking, reforming, Ethylene, propylene, naturel gas condensate | oll stabilzation ‘ethane, propane, | separation LPG aromatics, etc. pentane, aromatics etc. Petroleum coke Crude oil Carbon Residue upgradation |Carbon electrode, process. Acetylene, gasification Asia Pacic 4% ise amanciin 5. and Cont. America 4% Saavahaticas Attica 9% Asia Pacite 6% Middle <— Afica act 4180 patea ey Middle |¢_ S-2nd Cent. East >| ‘America 9% 63% Europe and Eurasia 9% So Figure 1.11 Global Distribution of Proven Oil Figure 1.12 Global Distribution of Proven Natural Reserves Gas Reserves Source: BP 2004, Statistical Review Source: BP 2004, Statistical Review of World Energy, available online at of World Energy, available online at www.bp.comistatisticalreview 2004. www.bp.comistatisticalreview 2004.18 Petrochemical Process Technology Table 1.5 World Proven Reserves of Oil (in thousand million barrels) At End 1983 At End 1993 At End 2002 At End 2003 | Reserve/Production Ratio (end of 2003) 723 1,023.6 1,146.3 1,147.7 410 Table 1.6 Total World Production’ of Oil (in million tonnes) Year 1993 2000 2003 Million tonnes 3,187 3,604.4 3,697.0 Thousand barrels daily 66,006 74,669 76,777 “Includes crude oil, shale oil, oil sands and NGLs (natural gas liquids — the liquid content of natural gas where this is recovered separately). Excludes liquid fuels from other sources such as coal derivatives. Table 1.7 Total World Consumption* of Oil (in milion tonnes) Year 1993 2000 2003 Million tonnes 3,139.3 3,526.1 3,638.6 Thousand barrels daily 66,687 75,483 78,112 “Inland demand plus international aviation and marine bunkers and refinery fuel and loss. Table 1.8 Total World Refinery Throughputs (in thousand barrels daily) Year 1993 2000 2003 Refinery throughput 61,261 68,752 71,001 Source: BP 2004, Statistical Review of World Energy, available online at www.bp.comistatisticalreview2004. Table 1.9 Total World Proven Reserves of Natural Ges (trillion cubic metres) At End 1983 At End 1993 At End 2002 At End 2003 | Reserve/Production Ratio (end of 2003) 92.68 141.08 175.15 175.78 67.1 Source: BP 2004, Statistical Review of World Energy, available online at www.bp.com/statisticalreview2004. Table 1.10 Total World Production* of Natural Gas Year 1993 2000 2003 Billion cubic metres 2,080.0 2,433.0 2,618.5 *Million tonnes oil equivalent 1,872.0 2,189.7 2,356.6 “Excluding gas flared or recycled. Source: BP 2004, Statistical Review of World Energy, available online at www.bp.com/statisticalreview2004Introduction 19 Table 1.11 Total World Consumption of Natural Gas Year 1993 2000 2003 Billion cubic metres 2,076.6 2,437.2 2,891.0 Million tonnes oil equivalent } 1,869.0 2,193.5 2,331.9 Looking to the future increasing petrochemical feedstock and petrochemicals building blocks, the refinery of twenty-first century will look more like a petrochemical refinery than today’s refinery. The petrochemical business will form a part of overall refining business. It will maximize high value products, minimize commodity products and produce engineered molecules for specific applications [Katzer et al., 2000]. The global petrochemical industry provides added value to natural gas liquids, refined product such as naphtha, gas oil and other hydrocarbons such as methane, ethane, propane, etc. Separating them into C; fraction (for fertilizer unit], C, and C, fractions for petrochemicals and C, and C, fractions can achieve optimum use of natural gas for domestic LPG and petrochemicals. Natural gas may occur in gas fields, underground reservoirs as non-associated gas or associated gas along with crude oil. Natural gas liquid obtained by liquefying the natural gas is also attracting considerable interest because of the ease of transportation and better utilization. The condensate obtained during processing of gases is also an important source of LPG and NGL and is of interest for production of petrochemicals. Characteristics of natural gas and its utilization as feedstock for petrochemicals are given in Figures 1.13, 1.14 and 1.15. Worldwide naphtha and ethane are two main feedstock with naphtha being the dominant one. Naphtha will continue to dominate the ethylene feedstock slate since availability of gaseous feedstock is location specific, however-the natural gas resource must be available in adequate quantity. With increasing demand of petrochemical, naphtha will be unable to keep up with the demand, with a consequential rise in price. The obvious alternatives are ethanol and other gas liquids [Chaiyavech, 2003]. The outlook for feedstock is one of the most pressing issues facing petrochemical industry and in view of the excess capacity and globalization there is urgent need to minimize production costs to remain competitive in the market. Generally the heavier the feed produces the greater the amount of propylene, C,s and pyrolysis gasoline and conversely the lighter the feedstock is used to lower the yield of these products, in both cases relative to ethylene. Natural gas is an important feedstock for fertilizer and petrochemicals and is also an important source of methane, ethane, propane and other hydrocarbons. Although historically, condensate was not widely used for olefin manufacture, its availability is increasing rapidly and higher consumption is expected in future. It is going to be one of the promising feedstock for the production of olefins and aromatics in the case of naphthenic base. With an increasing demand of light petroleum products, gas oil use for production of olefin is expected to increase in future, Olefins and aromatics are two important petrochemical feedstock and high demand growth is forecast for aromatics. Worldwide ethylene and benzene demand has almost doubled during the last 15 years and steady growth is expected. Asia ethylene feed slate: actual feedstock uses given in Table 1.12 [Chaiyavech, 2003]. Although ethylene can be derived from more than one feedstock, however, naphtha will remain the dominant feedstock for 50-55 per cent of the ethylene produced. Feedstock share of ethylene is given in Figure 1.16 [Rappaport, 2003]. A higher demand for naphtha is expected to result in more gas oil cracking. Propylene is another important petrochemical and its demand is expected to increase to 90 MMT by the year 2015. Although most of the propylene is co-produced along with ethylene, higher propylene recovery from refineries will be required. Due to disparity betweea the growth in ethylene andaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Introduction 21 INC (2001) world petrochemical feedstock analysis, over 50 per cent of the world’s ethylene supply is produced from naphtha and this feedstock is expected to retain its dominant position over the next 20 years [CMAI, 2001]. The demand for ethylene is forecast to double, reaching 216 million tonnes by 2020, driven by strong demands for polyethylene and vinyls, while global demand for propylene is forecast at an annual growth rate of 5 per cent per year. Nearly 65 per cent of the world’s propylene is produced as a byproduct of ethylene from steam crackers. Table 1.12 Asia Ethylene Feed Slate: Actual Feedstock Use Million Tonnes 2000 2002 2005 2010 Ethane 24 31 36 5.1 Propane 06 1.0 12 18 Butane 0.3 03 04 0.5 Gas Oil (AGO/VGO) 11.0 14.7 "7 10.5 Field condensate* 24 16 14 14 Naphtha 60.9 64.7 747 42.3 *Direct condensate cracking, Nephtha from condensate splitters, counts as Naphtha. Courtesy: Hydrocarbon Asia, July/August 2003 (Chaiyavech, 2003). [— Welding [> Acetylene —>} L_» chemical ieedstock- acetoninie [—* Phosgene ———+ isocyanate [—* Hon + adiponitrile, acatone, cyenohyarin, sodium cyanice o{ Mathane EDTA Pathod [—* Chioromethanes [—* Cc ————+ Trichloro Fuore methane, dichioro fuore methane ‘—+ methanol ——— Formaldehyde, dimethyl formamiae Le sine [— FT liquids ——e Fuei [> Dimetny ether —> Fuel Le [— Acrylonitrile L+ Urea, Formaldehyde ‘+ caprolactam Se ee Vinyl acetate, Chioroethyler Figure 1.14 Natural Gas, Coal Bed Methane, Gas Hydrate as Petrochemical Feedstock22. Petrochemical Process Technology [—> Polymer (HDPE, LDPE, LLDPE) a [> Ethylene —} chemical intermediates - Ethylene oxide, re, L Ethylane glycol, Acetaldehyde, Ethyl aleohol, Fears Acetic anhydride 1 viny! chioride —» Polymer (Pvc) ‘Acrylonitrie, Cumene, Isopropanol Propylene ——* propyiene oxide, Acetone, MMA, |. resyne— en ata samt 1+ Pyrolysis gasoline. Fuel ee Senta Mt Figure 1.15 Natural Gas as Petrochemical Feedstock Condensate Condensate 5% 2% Gas cil (14%) Lee 11% age) Emane (6%) Nephtha 46% Naphtha 18% Figure 1.16 Feedstock Share of Ethylene 2001 Courtesy: Hydrocarbon Asia, July/August 2003 (Chalyavech, 2003). ‘As naphtha crackers are highly influenced by oil pricing, recent trend is towards more ethane based crackers, which require less capital investment. As ethane cracking becomes more prevalent, less propylene will be co-produced in the crackers, recovery of propylene will be of greater interest. With this interest in conversion of LPG to petrochemicals, newer processes to convert LPG into lighter olefins, benzene, toluene, xylenes will find increasing acceptance in the petrochemical industry. It is likely that the demand of LPG will rise faster than naphtha and natural gasas petrochemical feedstock. Because more natural gas is available, methanol conversion technology will attract more attention and is an economically viable option. Already some commercial projects on conversion of methanol to polyethylene and polypropylene are under commercialization. Several UOP/HYDRO MTO, LURGI Methanol to propylene technologiesIntroduction 23 are under implementation on a commercial scale. Reliance Group in India is also thinking of installing 2 MTO complex (Methanol: 1.8 million tonnes, polyethylene: 0.38 million tonnes, polypropylene: 0.30 million tonnes) based on MTO technology. Another concept to meet the requirement of petrochemicals gaining importance is the tertiary treatment of plastic waste for better recycling and utilization of polymer waste. Strong growth in demand for petrochemicals during recent years has resulted in considerable pressure on feedstock supplies and hence the prices. Even though natural gas liquid supplies are increasing, petrochemical demand is growing more rapidly so more heavy liquids, naphtha, gas oil, condensate are required. As per CMAI, over 50 per cent of the worlds ethylene supply is produced from naphtha and this feedstock is expected to retain its dominant position over the next 20 years. Steam crackers typically produce about 15 per cent (w/w) propylene and provide almost 70 per cent of the propylene and consumed by the petrochemical industry whereas the FCC units of petroleum refinery is the next largest propylene source and supplying about 30 per cent of the petrochemical requirement [Zinger, 2000]. The traditional focus of the FCC unit is shifting increasingly from that of a producer of transportation fuels to that of a supplier of key petrochemical feedstock. In the next few years the refiners operating FCC units will look increasingly to the petrochemical market to boost their revenues [Nee, 2003]. The worldwide demand growth rate for propylene will far exceed that of GDP over the next ten years, driven primarily by economic expansion in Asia. The global demand growth rate for propylene is forecast to remain above 5 per cent per annum in the next ten years. As the demand for propylene has increased rapidly there has been considerable interest in improving refining and petrochemical integration through specialized FCC processes which raise propylene yield as high as 20 per cent against 6 per cent from the conventional FCC processes [Niccum et al., 2001]. Deep catalytic cracking (DCC) iscommonly proven FCC process for selectively cracking a variety of hydrocarbons feedstock to high olefins. Integrating DCC into a refinery offers an attractive opportunity to produce large quantities of value added light olefins, which may be sold as petrochemical feedstock. ‘With tightening naphtha feedstock availability in future, it is expected that natural gas will play an important role in meeting feedstock requirement for the petrochemical sector. Natural gas reserves are being rapidly developed throughout the world. India is no exception to this. The year 2002 has been historic in the hydrocarbon sector in India and many milestones were crossed because of new oil and gas exploration policy and discovery of huge natural gas deposits. A new concept is likely to surface in hydrocarbon sector, i.e. natural gas refinery, which will be based on the Fischer-Tropsch technology, such as the Exxon AGC-21 process, and Methanol to Gasoline Technology such as the Mobil MTG process [Katzer et al., 2000; Kaufmann et al., 2000; Kam et al., 1984; Garg and Badoni, 2003]. The Fischer-Tropsch technology will play an increasing role in refining as the technology moves from the field of gas to liquids conversion, through a phase of integration with conventional refining technology of choice for the twenty-first century. Major feedstock used in Indian petrochemical industry are naphtha, natural gas and kerosene, India produces about 22 billion m? per annum of natural gas and 34 million tonnes per annum of crude oil. India’s refining capacity is around 115 million tonnes and the petroleum product consumption has moved up by compounded annual growth rate of 10 per cent every year for the next few ycars to achicve the projection of 148 million tonnes per annum by 2006-07. About 24 per cent of total naphtha produced is used in the petrochemical industry. Ethylene capacity based on naphtha in India is about 52 per cent, which is closer to the international standard of 51.5 per cent. Usage of natural gas (ethane, propane and ethane/propane) is 41 per cent as against the global figure of 36 per cent.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.26 Petrochemical Process Technology Regional shares of new petrochemical investment (2002-2012) Other Asia Market pole > North America y? Westem Europe, Figure 1.18 Regional Shares of New Petrochemical Investment Courtesy: Dr P. Bjacek SRI Consulting Top twenty product capacity expansion totals comparative New investment between 2002 and 2012 Midde East China Etnylene Ethylene Methancl PE PE PTA Xyfenes Propylene EG Pvc Propylene vem PP Ec p-xylene B EO Styrene sM PET, Mat PET, Mot Xylenes Benzene Methanol PTA Xylene 8 PP fim TBE Ps PET, ss Benzene Acetic acid FET, SS VAM Toluene Dc eo a0 PO 0 2000 = 4000» 6000» «8000 0 1000 2000 3000 4000 Figure 1.19 Top Twenty Products Investment Plan in Middle East and China Courtesy: Dr P. Bjacek SRI Consutting.Introduction 27 1.5 | INDIAN PETROCHEMICAL INDUSTRIES India is a country with a population of more than one billion people and a GDP of over one half trillion dollars with a GDP growth of 6.2 from 1995 through 2000. India profile is given in Table 1.14 [Pandia, 2003; Hazra, 2005]. India dominates in the Indian subcontinent, which includes Pakistan, Bangladesh, Sri Lanka, Afghanistan, Nepal and others, due to its size, with 78.6 per cent of the regional total GDP. Chemical industry in India is one of the oldest industries, which has shown impressive growth over the years and has been among the fastest growing sectors of the Indian economy. It is also one of the most diversified of all industrial sectors covering a large number of commercial processes [Annual Report (C&P), 2004-05]. The Indian chemical industry ranks 12th by volume in the world for production of chemicals. With current sales turnover of USS 30 billion and accounts for 3 per cent of the total India GDP, 20 per cent of the national revenue and 13-14 per cent of total exports [Annual Report (C&P), 2004-05}. The Indian chemical industry produces a wide spectrum of products, which include pharmaceuticals, dyes, man-made fibres, plastics, pesticides, fertilizers, cosmetics and toiletries, Table 1.14 India— A Profile Surface area 3.3 million km? Population 1.06 billion Coastline 6,000 km Porttraffic ‘Over 350MTPA Road length Over 3 million km Express way 14,000 km 10,000 km (under construction) Highways 34.000 km Railways 1,00,000 track/km Vehicle Population, Capacity and Production Increasing vehicle population Growth in vehicle population Passenger Car Production (2001-02) (Largest in Asia, 2nd in the world) From 9.24 million (Pre-1996) to 49.5 million (2000) More than fivefold in just a 4-year time span 0.86 million CAGR (1995-2002) ~ 8.2% PA. Two Wheeler Production (2001-02) 4.32 million CAGR (1996-2002) BAMPA, Overall Vehicle Production (2001-02) 5.37 million CAGR (1995-2002) 7.4%P.A, cpp USS 650 bilion Growth rate 7-8% Foreign Exchange reserves US$ 130 billion Contribution of GDP by Agriculture: 25% Industry: 24% Services: 51% Export US$ 80 billion Import US$ 130 billion Source: Pandia, 2003; Hazra, 2005.28 Petrochemical Process Technology paint, auxiliary chemicals and a range of organic and inorganic compounds, speciality chemicals and performance chemicals for application ranging from automobiles, construction, chemicals and food. Indian chemical industry has a future potential of 100 billion by 2010 with an annual growth rate of 15.5 per cent (Chemical Engineering World, 2003]. Sectorwise break up of chemical industry is given in Figure 1.20. Chemical import in India is about 4 billion USD (Figure 1.21). Indian chemical industry turnover in 2004-05 was US$ 30 billion and projected to be USS 60 billion in 2010-11[Hazra, 2005]. Per Capita Consumption of Petrochemicals India vis-i-vis China and World is given in Figure 1.22. yee end pains 5% tui i | Inorganics 8% Organics 16% Figure 1.20 Indian Chemical Industry Courtesy: Chemical News, May 2005. Synthetic resins and polymers (20%), Inorganic chemicals Petro Chemicals 59% Organic ‘chemicals ‘Synthetic rubber 4% Dyes 5% Synthotic fibres 2% Pharma 9% Figure 1.21 Chemical Import in India Courtesy: Chemical industry Digest, Annual, January 2004.Introduction 29 25 164 kgPoreon 04 ‘ lA. Elasiomer Surfactent Synihetic fre Plastic Perrochemicals Figure 1.22 Per Capita Consumption of Petrochemicals in India vis-8-vis China and World Courtesy: Chemical News, July 2005, Indian Chemical industries today, has assets worth about USS 28 billion, which constitute approximately 6.7 per cent of India’s gross domestic product. It is the 3rd largest in Asia and 12th largest in the world. The chemical industries have been making rapid strides during recent years because of the increasing availability of petrochemicals as feedstock from petrochemical industry, which has a major role in the future development of Indian chemical industry. Indian petrochemical industry can be divided into four major segments: Basic Petrochemicals: This serves as basic building blocks, e.g. Synthesis gas, olefins, aromatics. Polymers and Elastomers: Polyethylenes (HDPE, LDPE, LLDPE), PVC, polypropylene, polystyrene, styrene butadiene rubber, nitrile butadiene rubber, butyl rubber, ethylene propylene dimer, ABS plastics. Fibre Intermediates and Synthetic Fibre 1. Fibre Intermediates: p-xylene, mono-ethylene glycol, PTA/DMT, acrylonitrile, cyclohexane, Ethylene oxide and caprolactam 2. Synthetic Fibre (filament yarn and staple fibres): Nylon 6, Polyester, Acrylic fibre. Chemical Intermediates: Liner alkyl benzene, methanol, formaldehyde, maleic anhydride, phthalic anhydride, vinyl acetate monomer, phenols, ethylene oxide, acetic acid, acetaldehyde, acetic anhydride, chloromethanes, ethanol amines, etc. Today petrochemical products permeate the entire spectrum of daily use items and cover almost every sphere of life - clothing, housing, construction, furniture, automobiles, household items, toys, agriculture, horticulture, irrigation, packaging, medical appliances, etc. Petrochemical industry in India began with the setting up of the first Naphtha Cracker by Union Carbide in 1966, which was followed by naphtha cracker by NOCIL, Thane, and IPCL, Vadodara. Since then it has made a phenomenal growth and continues to be one of the fastest growing core sectors of the economy, In India, naphtha is a major feedstock for ethylene. Theaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.chapter Profile of Indian Petroleum and Petrochemical Industry Although Indian petroleum and petrochemical industries are not very old, they have revolutionized cour lives and are providing the basic needs of a rapidly growing, expanding and highly technical civilization as a source of energy for domestic, industrial, transport sectors and as feedstock for fertilizers, synthetic fibres, synthetic rubbers, polymers, intermediates, explosives, agrochemicals, dyes and paints, etc. The hydrocarbon sector is also playing an important role in meeting around 42 per cent of India’s primary energy requirements. Share of future energy supply for crude and gas requirements is presented in Table 2.1 [Soni, 2003]. Petroleum and petrochemical industries are closely interlinked and the latter is totally dependent on petroleum industry for feedstock. The rapid growth of petroleum industry has given real impetous to the growth of Indian chemical industry where the sales is US$ 30 billion due to availability of petroleum feedstock — for further downstream processing to commodity and value added products. With increasing demands of petroleum feedstock and petrochemicals some of the refineries have entered the field of integrated refinery and petrochemical complex in India. Table 2.1 Future Energy Supply, Crude and Gas Requirements Supply Source to Meet Demand Projected Demand Years Percentage of Total ‘Chia Gas Coal Oi Gas Hydel | Nuclear | MTPA Olefin 1997-98 55 35 T 2 1 69 110 2001-02 50 32 15 2 4 12 154 2008-07 50 32 15 2 1 173 231 2010-11 53 32 14 2 1 190 313 2024-25 50 30 15 2 3 364 391 2.1 INDIAN PETROLEUM INDUSTRY The search of oil in India began in 1866. Oil exploration began with Burmah Oil Company (BOC). Large reserves of oil were discovered by BOC in Naharkatiya in 1953 and 1956. Although indigenous production of crude oil went up from 0.25 million tonnes in 1948 to 0.39 million tonnes in 1956, real growth in crude oil exploration and production began only during 1957-67 with the setting up of Oil and Natural Gas Commission in August 1956 and Oil India, a joint venture of Government of India and Burmah Oil Company, in 1959 with the objectivesProfile of Indian Petroleum and Petrochemical Indusiry 35 of planning, promoting and implementing programmes for exploration and exploitation of petroleum resources throughout the country, Since then continuous efforts have been made to intensify the production of oil and gas in the country. Various onland and offshore exploratory drilling of crude oil was started in various parts of the country which include Jammu & Kashmir, Punjab, Assam, Rajasthan, Gujarat, Western coast, Bombay High and the Krishna~Godawari basins. The new revolutionary licensing policy will provide an impetus to crude oil exploration in the country. The growth of Indian Petroleum Industry is presented in Table 2.2 [Chopra, 2003]. Crude oil production during 2003-04 was 33.40 million tonnes while the gas production was 31.962 billion cubic metres. Number of measures is being taken to bridge the growing gap Table 2.2 Growth of Indian Refining Industry Year Growth 1886 Oildiscovery atNahorpung 1882 ‘Assam Railway and Trading Co. acquired rights for oll exploration 1889 Oilproduction started at Digboi 1833 Rights were grantedto Assam Oi syndicate tostar refining and first refinery started at Margherita, Assam 1899 Digboi Refinery commissioned supplanting above refinery with a capacity of 500 barrels 1921 Butmah OilCo. started cil exploration 1991 Crude cil production equals 2,50,006 tonnes 1947-57 Muttinational oll companies Burmah Shell, Esso Stanvac set-up two refineries at Mumbai and Caltex at Visakhapatnam, Exploration of ol in Upper Assam atNaharkatia and Moren by BOC 1954 Indian oil exploration with Russian geologists 1956 Formation of Oiland Natural Gas Commission and production of crude oll and gas. Discovery of Cambay Oilfield 1958 Public sector Indian Refineries Ltd (IRL) came into oil field (to create refining and pipeline infrastructure) 1959 ilIndia Ltd formed.as joint venture between Governmentof India and Burmah Oil Company 1962 First public sector refinery started at Guwahati by Indian Oil Refinery Ltd 1962 {Indian Oil Blencing Ltd (IOBL) was formed for manufacture of lube oll and greases (Joint venture between Indian Oil Company and Mobil PetroleumCo,} 1984 IRL and Indan Oil Company merged to form Indian OilCo. Ltd 1965 Engineers India Ltd started 1987-77 Discovery of oiland gas at Dabka, Santhal and Balol in Gujaret, Amguri, Charaii and Borholla in ‘Assamand Baramura in Tripura 1974 Borholla in Assam: Baramura in Tripura 1974 1OBL became part of OCL 197-87 Discovary of olin large quantities at Bombay High 1977-87 Discoveries of oll and gas in the Bombay offshore area (Panna field, Bassein field, Mumbai Ofishore, Hoera, Rattna, South and Mid Tapi. Oil and gas reserves discovered at Gandhar and Dahej (Cambay Basin) 1981 Cilandgas found in Krishna-Godavari-Cavery Basin 1995 ilwas found in Gachar (Assam) and Nagaland 1998 ‘Assam Oil Co. morgod with IOCL as Assam Oil division 1999 First joint sector refinery MRPL commissioned 2000 Panipat Refinery of indian Oil Co. commissioned, Reliance Petroleum Refinery commissioned at Jamnagar, Gujarat. Numaligarh Refinery in Assam commissioned 2008-08 Indian oil entered the patrocherrical seen with production of LAB and TPA/Polyester36 Petrochemical Process Technology between indigenous crude production which is about 33 million tonnes and likely demand which is expected to reach 244 million tonnes in 2011 and 370 million tonnes in 2020-21 [Chemical Engincoring World, December 2002]. Several measures have been taken to enhance hydrocarbon reserves and its production in the country. This includes: development of new fields, additional development of existing field, scaling up and implementation of enhanced oil recovery schemes; indenting on the services of international experts, improved maintenance of reservoir health, conduct of 3-D seismic surveys for precise reservoir delineation, application and optimization of artificial lift operations; stimulation of wells, optimization and redistribution of water injection and infill drilling, encouraging participation of private and joint venture companies in the exploration programme and activation of the NELP. In the first four rounds of New Exploration Licensing Policy (NELP}, 90 blocks covering 9.0 lakh sq. km were signed and the total area under exploration has grow up to 12,40,000 sq. km. Today as much as 74 per cent of area under exploration belongs to the NELP blocks. The exploration investment in three phases are about Rs 19,050 crore, which is expected to substantially increase in case of discoveries of hydrocarbon [Annual Report, 2004-05]. Exploration under NELP has shown positive results with discoveries made in Krishna~Godavari deep water and in Cambay onland, including significant gas discovery in the Krishna~Godavari (K-G) Basin. To give impetus to its exploration and production, the Government of India has formulated a CBM policy. Under the Coal Bed Methane (CBM) Policy, eight blocks have been allocated in the states of Jharkhand, Madhya Pradesh and West Bengal for exploration and production of coal bed methane, which is an environment friendly, non-conventional source of gas. A profile of Indian Petroleum Industry is shown in Table 2.3 [Annual Report, 2004-05]. Coal bed methane which is an environment friendly clean fuel is similar to conventional natural gas. Contracts with PSUs/ private sector for thirteen blocks have been signed on nomination basis. Today Reliance, Essar and Videocon are hunting for oil along with multinationals like Premier Oil, Caien Energy and Shell. With the participation of private sector, oil and gas exploration and drilling has changed completely. Reliance with its gas discovery in Block Dé in the K-G Basin with an initial availability of 14 tillion cubic feet (390 billion cubic metres) is the biggest success of private sector [Annual Report, 2004-05]. Oil and gas continue to play a predominant role in meeting energy requirements of the country and 45 per cent of the total energy needs would be met by the oil and gas sector, though with some amount of interchange between oil and gas. Gas production during 2003-04 was 33.37 million tonnes. The petroleum industry in India stands out as an example of the strides made by the country in its march towards economic self-reliance. At the time of Independence in 1947, international companies controlled the industry. Indigenous expertise was scarce, if not non-existent. Today 50 years later, the industry is almost entirely in the public domain with skill and technical know-how comparable to the highest international standards. To meet the growing demand of petroleum products, the refining capacity in the country has gradually increased over the years by setting-up of new refineries in the country as well as by expanding the capacity of the existing refineries. During the past five decades, there has been a significant increase in crude production; from 0.25 to 33.345 million tonnes and in refining capacity from 0.3 to 121.84 million tonnes per annum which is expected to 90 up to 170 million tonnes by the end of Tenth Plan with product demand of 156 million tonnes. A real breakthrough in the petroleum refining industry has been in the setting up of the Reliance refinery project at Jamnagar with one of the largest grassroots refinery in the world offering more than 27 million tonnes refining capacity.Profile of Indian Petroleum and Petrochemical Industry 37 Table 2.3. Profile of indian Petroleum Industry Parameters Unit 1990-91 1995-96 1998-99 1999-00 2000-01 2001-02 2003-04 Reserves 1. Crude oil Million 716 660 703 732 tonnes 2. Natural gas Billion 692 75 648 760 cubic metre Production 1. Crude oil "000 "93,021 36,167 32,722 31,949 32,426 32,082 33,373 2. Natural gas tonnes | 17,998 22,639 27,428 28,446 29,477 29,714 31,962 Production of Petroleum Products 4, Light distillates | 000 10,023 12,433 13,776 18,314 25,048 26,639 31,971 2. Middle disiilates | tonnes | 26,344 29.941 36,168 44,995 52,445 54.409 60,018 3. Heavy ends 12,195 12,707 14,600 16,102 18,121 19,056 21,474 4, Total 48,562 55,081 64,544 79,411 95,614 1,00,004 1,13,463 Consumption of Petroleum Products 4. Light distillates | ‘000 9,801 13,143 17,958 20,473 21,770 22,916 24,948 2. Middle distilates | tonnes | 33,106 45,460 51,686 54,259 52,854 50,661 50,549 3. Heavy ends 12,128 13,915 15,122 15,919 15,362 15,515 16,633 4. Total 55,035 72,518 84,766 90,651 89,986 89,092 92,130 Total Import of Petroleum Products ‘000 74,413 83,364 85,715 98,435 tonnes Total Export of Petroleum Products "000 746 8,365 10,065 14,620 tonnes Source: Annual Report, 2004-05 2.1.1 Refining Capacity and Throughput There are 18 refineries (16 in the public sectors, one in the joint sector and one in private sector) in the country with a capacity of 121.48 million tonnes. A new grassroot refinery and the expansion of existing refineries will enhance the refining capacity to about 129 million tonnes (excluding export oriented units by the end of Ninth Plan). The estimated demand of the products would be about 112 MTPA. As per the latest outlook, the refining capacity is expected to be about 129 million tonnes by the end of Ninth Plan and about 170 million tonnes by end of Tenth Plan with a product demand of 156 MTPA. Total Refining capacity in India is shown in Table 2.4. Proposed refineries in India are presented in Table 2.5.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.Profile of Indian Petroleum and Petrochemical Industry 51 Table 2.25 Kerosene Requirement by LAB Plant Year 1AB n-Paraffin Kerosene Kerosene Retumn Demand Require Input Stream (000 tonnes) 1999-00 300 270 1,352 4,081 2000-01 323 291 1,453 1,162 2001-02 347 312 1,682 1,249 2002-03 373, 336 1,678 1,343 2003-04 401 361 1,804 1,443 2004-05 431 388 1,939 1,551 Source: Masood, 2002. 2.3.2 Natural Gas Natural gas accounts for nearly half of the total hydrocarbons resources in India. Total natural gas proven reserve was about 927 billion cubic metres in 2003-04. Natural gas production during 2003-04 was 31.95 billion cubic metres. The growth in consumption of natural gas is expected to increase from the current level of 65 MSCMD to 231 MSCMD in 2006-07 and would reach 391 MSCMD by 2025 [Chemical Engineering World, 2002]. A number of gas discoveries have been made in many of the Indian sediments basin, which includes Cambay basin, Upper Assam basin, Bombay offshore basin, Tripura, Krishna~Godavari Basin and Cauvery Basin as well as Rajasthan. Oil and Natural Gas Co. (ONGC) and Oil India Ltd are the two major producers of gas in India. Realizing the importance of natural gas as petrochemical feedstock GAIL was set up in 1984 to transport, treat, process, fractionate, blend, purify, and create necessary infrastructure facilities for the utilization of natural gas or associated gas. Although natural gas has been utilized in Assam and Gujarat since the sixties, there was a measurable increase in production and utilization of natural gas in the late seventies with the development of Bombay High fields and again in the late eighties when the south basin field in western offshore began production. Before the discovery of Bombay High fields in 1974, gas hardly figured in the overall Indian primary feedstock. Prior to recent discoveries of natural gas India’s estimated reserve of natural gas was 639 billion cubic metres. Natural gas production (onshore and offshore) during 2003-04 was about 31,962 million cubic metres. Natural gas consumption has grown at 9 per cent per annum over the last 5 years. Reliance with its gas discovery in Block Dé in the Krishna—Godavari Basin is a huge success of the private sector, which is estimated to be at trillions of cubic metre Carin Energy, has also stuck significant quantities of gas. It is expected that with new gas finds in the next 15-20 years, India can become exporter of gas. Condensate production of about 0.88 million tonnes per annum is expected from free gas processing of 20 million Nm. An analysis of condensates indicates an aromatics content of about 18-19 per cent, Natural gas production scenario in India is presented in Table 2.26. Natural gas demand scenario is given in Table 2.27. Total natural gas demand for a gas cracker of 3,00,000-4,00,000 tonnes of ethylene capacity is around 7-11 millions standard cubic metres per day depending on the composition of C,/C3. Availability of natural gas to various petrochemical complexes will be greatly influenced by the effective utilization and supply of the52 Petrochemical Process Technology gas through existing pipelines, as even in the presently planned gas cracker adequate gas availability is not ensured, Oil and Natural Gas Co. (ONGC) and Oil India Ltd (OIL) are the main producers of gas. OIL is operating in Assam and Rajasthan whereas ONGC is operating in the western offshore fields and in other states. The gas produced in the western offshore fields is brought to Uran in Maharashtra and partly in Gujarat, The gas brought to Uran is used in and around Mumbai. The gas brought to Hazira is sour gas and after sweetening is fed to Hazire—Bijaipur- Jagdishpur pipeline which passes through Gujarat, Madhya Pradesh, Rajasthan, Uttar Pradesh, Delhi and Haryana. ‘The gas produced in Assam and Gujarat is utilized in the respective states. There have been demands from southern states for a Southern grid to carry gas from the western offshore gas fields and other sources to south India. The concept of a southern grid has been accepted in principle. The gas produced by ONGC and the JV consortiums is marketed by GAIL. The gas produced by OIL is marketed by Oil itself. Table 2.26 Natural Gas Production Scenario in India (million cubic metre) 1990-91 1995-96 2000-01 2001-02 2003-04 ‘Onshore 3,916 5,738 7,728 7,858 8,972 Offshore 14,082 16,901 21,752 21,856 22,990 Total 17,998 22,639 29.477 29.744 31,962 Source: Annual Report, 2004-05, Table 2.27 Natural Gas Demand Scenario (milion cubic metres per day) Year 2001-02 2006-07 2011-12 Demand 151 231 313 Supply 72 86 86 Deficit 79 145 227 Table 2.28 Sector-Wise Consumption of Natural Gas Sector MMSMD Percent Fertilizer 263 25 Power 405 39 Sponge Iron 61 6 Others 244 24 Internal Usage 65 6 Total 103.8 100 ‘Source: Reliance Review of Energy Markets, 2002-03, As crude oil production has to be maintained at the maximum possible level, production of associated gas may exceed the demand of the handling capacity. This results in flaring of gas. However, ONGC, GAIL and OIL have now set-up transportation and compression facilities in order to progressively reduce flaring of gas. As a result of the marketing efforts made by GAIL, the flaring which was 30 per cent in the Seventh Plan period has reduced to less than 7 per cent currently. Even this is mainly in the North-Eastern region. Natural gas is presently a source ofProfile of Indian Petroleum and Petrochemical Industry $3 half of the LPG produced in the country. LPG is now being extracted from gas at Duliajan in Assam, Bijaipur in Madhya Pradesh, Hazira and Vaghodia in Gujarat, Uran in Maharashtra, Patta in Uttar Pradesh and Nagapattnam in Tamil Nadu. Two new plants were set-up at Lakwa in Assam and Ussar in Maharashtra during 1998-99. One more plant has been set-up at Gandhar in Gujarat. Natural gas containing C,/C,, which is feedstock for petrochemical industry, is currently being produced at Uran for Maharashtra gas cracker complex at Nagothane. GAIL has set-up a 3 lakh TPA of ethylene gas based petrochemical complex at Auraiya in 1998-99. Major projects implemented for production/transportation and utilization of natural gas are: the Gas Flaring Reduction Project, the HBJ Upgradation: LPG Extraction Plants at Ussar and Lakwa Petrochemical Project at Auraiya, Uttar Pradesh. Major projects under implementation are: Mumbai Gas Distribution Project and Delhi City Distribution project, LNG projects Dahej and Kochi, Kandla- Loni LPG pipeline and Gas Processing complex at Gandhar. The natural gas (associated and non-associated gas) is available from four region: (a) North- East region; (b) Western region (on shore); (c) South Basin fields and (d) Offshore. The gases are not available at one place and a good network of collection is essential in order to recover the valuable C,/C; fraction and NGL that can be made available for petrochemical complexes. Availability of gas from the HBJ pipeline with existing capacity, seems to be diminishing for petrochemicals unless and until additional gas becomes available in future, With the existing capacity, GAIL is finding it difficult to meet the demand of the existing and proposed fertilizer and power complexes. Some of the emerging technologies for optimum utilization of natural gas are oxidative coupling of methane to ethylene, aromatization of C-C fractions in natural gas. 2.3.3. Tertiary Recycling Today plastic industry exceeds that of steel and aluminium combined. Consumption of plastic has increased considerably during recent years and the present production of polymers is around 3.3 million tonnes. This significant increase has led to a similar increase in plastics disposal volume, Plastic waste contributed to the solid waste stream about 7 per cent by weight and possibly twice that by volume. The current and anticipated total plastics demand, recyclable and available plastic scenario is presented in Table 2.29. Plastic waste processing techniques involve primary, secondary, tertiary and quaternary recycling. Chemical recycling of plastics may involve either pyrolysis or chemical decomposition of plastics which involves hydrolysis, hydrocracking and depolymerization. Pyrolysis of plastics is well known as an analytical procedure and is also a potential method of recycling polymers. During pyrolysis depolymerization of polymers takes place and polymers decompose into smaller molecules or monomers. Recycling of polymers back into petrochemicals is a promising concept that can help meet the future demand of petrochemical feedstock as well as for better recycling and utilization of polymer waste [Malhotra and Taneja, 1997]. Table 2.29 Demand, Recyclables and Total Available Plastics ('000 tonnes) Year Demand Wastes Total 1995-96 1,889 876 2,759 2001-02 4,374 1,966 6,340 2006-07 8,054 3,624 11,678aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.70 Petrochemical Process Technology (Cond... from Table 3.3) Hydrogen Distinguishing Major Remerks Family Characteristics Hydrocarbons lsoparaffins Branched carbon Isobutane, The number of possible isomers (isoalkenes) chain Isopentane, increases in geometric progre- Neopentane, ssion as the number of carbon lsooctane atoms increases Olefins One pair of carbon | Ethylene, Propylene | General formula C,H, (Alkenes) atoms Olefins are not present in crude oil but are formed during the processes. Undesirable in the finished product because of their high reactivity. Low molecular weight olefins have good antiknock properties Naphthenes 5 or 6 carbon atoms | Cyclopentane, The average crude oil contains in ring Cyclohexane about 50% by weight naphthenes. and their alkylated | Naphthenes are modestly good derivatives components of gasoline Aromatics 6-carbon atom in ring | Benzene, Toluene, Aromatics are not desirable in with three around Xylene, Ethyl kerosene and lubricating oil. linkage Benzene, Cumene, | Benzene is carcinogenic and Naphthalene hence undesirablo pertof gasoline. In general aromatic increases with increase in molecular weight NON-HYDROCARBONS Non-hydrocarbons Compounds Remarks ‘Sulphur compounds Nitrogen compounds Oxygen compounds Hydrogen sulphide, Mercaptans Quinoline, pyridine, pyrrole, indole, carbazole Undesirable due to foul odour. Heavier crude oil contains higher percentage of sulphur. Normally 0.5 -7% Presence of nitrogen compounds in gasoline and kerosene degrade the colour of product on exposure to sunlight. They may cause gum formation. Normally less than 0.2% These acids cause corrosion problem at various stages of processing and pollution problem. Normally traces to 2%.Petroleum Refining 71 Table 3.4 Structures of Hydrocarbons in Petroleum and Petrochemicals Typical Family Members Paraffins (alkanes) Isoparaffins (isoalkanes) Olofins (alkenes) Naphthenes Aromatics Acetylenes Straight chain C,Hoy 42 Branched Carbon chain CHa +2 n'= 4 of more, number of isomers increases in geom- etric proportion of branched carbon chain CoH en Structured ring compounds (Cycloparaffins) Cyclic compound containing benzene ring CHon 2 Mothane (CH,) Ethane (C,H,) CH,-CH, Propane (CaH,) CH,CH,CH, Butane (C,Hyo) CH,CHCH,CH, Pentane (CsH,2) CH,CH,CH,CH,CH, Hexane (CgH,4) CHgCH,CH,CH,CH,CH, Cts Cy Cts a Hs KO Ch; Hs cH, ‘CH, Neopentane isobutane (CyHyo)_—Isopentane (CeHy2) Ethylene (CH,) Propylene (CsH,) Butylene (C,H) H.c— CH Hee CHe ‘CHa Cyclopentane (CsHyo) Cle Hoc “ch, Hoo\ _CH2 cH, Cyclohexane (CeH;2) 1, 2-dimethyl cyclohexane (CaHi6) Propyne _CH-C==CH.72. Petrochemical Process Technology 3.2. CRUDE OIL EVALUATION Crude oil exhibits wide variation in composition and properties. Crude oil evaluation is one of the important activities carried out in refineries and research laboratories. Change in the crude quality has multifarious effects that include changes in the product quality, change in the processing scheme, throughput, material of construction, economics and effluent quality. Table 3.5 shows requirement of various parameters for evaluation of crude oil, petrochemical feedstock and product quality (Bhatnagar, 1996]. Table 3.5 Requirement of Various Parameters for Evaluation of Crude Oil, Petrochemical Feedstock and Product Quality Product Information Required LPG Specific gravity, API, sulphur, RVP, pour point, wax. viscosity. water. salt, acidity, alkalinity, TBP yield, LPG potential, trace metals Naphtha Copper strip test, total volatile sulphur, vapour pressure at 65°C, volatility, dryness, odour, composition, free water content, gross calorific value, Composition C.-C, hydrocarbon, unsaturated hydrocarbon Reformulated gasoline | Specific gravity, paraffins, naphthenes and aromatic content, RON, MON, sulphur, nitrogen, chloride, metals, nitrogen, RVP, aromatics/olefins, gross calorific value Kerosene RVP, sulphur, aromatics, benzene, olefins, oxygenates. specific gravity, RON, MON, oxidation stability, gums, antiknock index, lead content, vapour lock index, copper corrosion test, colour Aviation turbine fuel | Acidity, burnability quality, colour, copper strip corrosion test, distillation range flash point, smoke point, total sulphur and density Diesel Stability (thermal stability or TDR span), contaminants, conductivity, volatility, fluidity, combustion, copper strip anc silver strip test, freezing point Light diesel oll and high| Acidity, ash, colour, residue, pour point, flash point, kinematic viscosity, sediment, speed diesel oil total sulphur, water content, copper strip test Gas oils Specific gravity, paraffins, naphthenes and aromatic content, smoke point, freezing point, sulphur, aniline point, copper strip corrosion, doctor test, and thermal stability test Vacuum gas oils ‘Specific gravity, viscosity, cetane number/diesel index, nitrogen, carbon residue, oxidation stability, flash point, aromatics, polycyclic aromatics, acidity, sediment, RVP, moisture, RON/MON FCC feedstock Specific gravity, RVP, pour point, flash point, anine point, total sulphur, CCR% Catalytic reforming Specific gravity, distilation (IBP °C/FBP °C), benzene, toluene, xylene, total feed and reformate | sulphur Residues Specific gravity, sulphur, nitrogen, metals, asphaltenes, viscosity, aniline point Lube cuts Specific gravity, viscosity, nitrogen, metals, asphaltenes, viscosity, mid distilate vol. % curves, viscosity yield curves, CCR, cloud point, solvent treating ‘susceptibility Greases Penetration, softening point Detergent alkylate Specific gravity, bromine index, saybolt colour, doctor test, water, sulphonation, biodegradability, paraffins, n-alkyl benzene, average molecular weight Fuel cil Acidity, ash, carbon residue, copper strip corrosion test, sediment, flash point, smoke point, sulphur Bitumen Specific gravity, penetration, softening point, ductility, flash point, matter soluble in carbon disulphideaa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.74. Petrochemical Process Technology Parameters Copper strip corrosion test Water, salt and sediments Base of the crude oil TBP Assay Gum Colour Antiknock quality (octane number) Significanc This test serves as @ measure of poss- ible difficuties with copper, brass, bronze part of the fuel system These cause irregular behaviour in the distillation and cause blocking and fouling of heat exchanger and result in corrosion For characterization of the crude cil base- paraffiniciintermediate/Naphthenic and for measure of the aromaticily. Various parameters used are characterization factor, BMCI, VGC. It is done for generating distilation data and for study of variations of some key properties throughout the distillation range Itis indication of gum at the time of test and amount of deposition during service time Indication of the thoroughness of the refining process Octane number is the percentage of iso- octane in the reference fuel, which match the knocking tendency of the fuel under test Description Water content is determined by Dean and Stark method. Sediment and water is determined by centrifuging a mixture of crude oil and toluene. Salt content is determined by titrating the water extract with KCNS/AgNO,. Characterization factor ¥fgiG 1D. OF. at 15.6/15.6°C) Tg = Mean avg. boiling point in Rankine; paraffinic base, k 2 12.1; intermediate base, k = 11.5 — 12.1; naphthenic, k = 11.5; aromatics, k = 9.8 ~ 12.0 BMC (Bureau of Mines Correlation Index) BMCI = 48640/K + 473.7 g-456.8 K = avg. boiling point in K, g = Sp. gr. at 16.6/15.6°C 8MCI value: paraffinic < 15; intermediate =15 - 50; naphthenic > 50 viscosity gravity correlation (VGC) _ 10G —1.0782log(V - 38) 10 -log(V - 38) Gis specific gravity and V is Saybolt universal viscosity paraffinic base: 0.60 ~ 0.83, intermediate base: 0.83 — 0.88, naphthenic base: 0.88 - 0.95 Ke G vec Research octane number (RON) and Motor octane number (MON) are two methods used. Anti knock index (AKI) = (RON+ MON)/2.Petroleum Refining 75 Parameters Significance Description Cetane number Cetane number is the percentage of cetane, which must be mixed with heptamethylnonane to give the same ignition performance as fuel in question Stability test It is used for the evaluation of storage stability and resistance to oxidation Diesel index Itis indication of ignition qu. ofa diesel| Diesel inde, (Aniline point in °F x API) /4100 Diesel index = (Cetane number- 100.72 Weathering test for _| This test shows the volatility of the LPG LPG Frass breaking point | This Is the temperature below which the [bitumen tends to break rather than flow 3.3. QUALITY OF CRUDE OILS PROCESSED IN INDIA The total capacity of crude oil production in India is not adequate to meet the country’s demand of crude oil and petroleum products. In order to meet the total requirement, about 7 million tonnes of crude is being imported. The various sources of indigenous and imported crude oils are given below: Indigenous crude oil ‘Assam crude, North Gujarat and Ankleshwer crude, Bombay High, Satelite field, KG basin, Rava Crude, Cauvery Basin crude Imported crude oil ‘Arab mix, Lavan blond, Uppor Zker, Iran mix, Dubai, Kuwait, Suez mix, Zeit bay, Arab medium, Quaibce, Mir light, Bonny light Characteristics of various crude oils are given in Table 3.6-3.10. Yield of the various products also varies with the type of crude being processed. The change of crude oil quality has multifarious effects, which include change of product pattern, change in processing scheme, throughput, material of construction, economics and effluent quality [Mishra and Unnikrishnan, 1996]. Typical yield pattern of some of the crude oil is given in Table 3.11. Table 3.6 Characteristics of Various Crude Oil Sources of indigenous Crude Salient Features ‘Assam Crude Nahorkatia/Moran | 31°API, Sulphur0.3%, Pour point+30°C, High aromatics, Total cistilate yield 65% ONGC, Lakwa, Rudrasagar 27°API, Sulphur 0.3%, High aromatics, Distilate yield 57% Ankieshwar Crude 48° API, Sulphur 0.1%, Pour point +18°C, Distillate yield 80-82% (Light distillates, 24%, Middle distillate 47%), Wax cortent 9.9%, total sulphur 0.02% North Gujarat Cride 28° API, Suphur content 0.1%, Pour point +27°C, Distillate yiold low 33-28%, High organic acclity MumbaiHligh Crude 38° API, Sulphur 0.2%, Pour point +30°C, Distillate yield 65-70% (Light distillate 24%, Middle distillates 48%), High aromatics Narimanam Crude 46° API, Sulphur 0.1%, Pour poirt 3°C, Distilate yield 80% KG Basin Rawva Crude 36° API, Sulphur 0.1%, Pour point +30°C, Distillate yield 61% Source: Mishra and Unnikrishnan, 1996.76 Petrochemical Process Technology Table 3.7 Typical Properties of Various Types of Crude Oil Crude Properties Kuwait Upper Zakum Arab Mix Basrah Light API Gravity 344 33.1 30.8 33.7 Sp. Gravity, 60°F/60°F 0.868 0.8591 0.8712 0.8559 ‘Sulphur, wt.% 252 2 24 1.95 Nitrogen, wt.% 0.12 0.0973 0.137 0.095 15 -27 -15 15 Pour Point, °C 30 8.77 22 18 Vanadium, ppm 8 69 72 5 Nickel, ppm 53 4.42 5.44 418 Con. Carbon, wt.% 0.06 wn - 0.01 Ash Content, wt.% 3 ce 5 1 Salt, Ibs/1000 bbls 978 - 9.41 65 Kv@37.8CST Courtosy: IOC Panipat Refinery. Table 3.8 Typical Properties of Various Types of Crude Oil HS Crude Dubai Suez Mix | Lower ‘Arab Med | Mendji Blend ZAKUM Zulut API Gravity 34 31.9 406 314 30.1 Sp. Gravity, 60°F/60°F 0.8699 0.8654 0.8216 0.8696 0.875 Sulphur, w.% 2 1.52 1.05 2.48 1.11 Nitrogen, wt.% 0.17 0.22 0.0525 0.137 ca Pour Point, °C 2 3 15 -33 9 Vanadium, ppm 42 44 036 43 65 Nickel, ppm 14 25 03 13 55 Con. Carbon, wt% 4.62 3.6 1.96 5.05 47 Ash Content, wt.% = = oO ™ 0.05 Salt, lbs/1000 bbls - - 1 5 - 7.48 8.74 29 11.01 17.9 Courtesy: IOC Panipat Refinery. Table 3.9 Typical Properties of Various Types of Crude Oil Bombay] Quai- | Brent | Brega | ES | Zaire | Bonny | Escrands| Planca| Ekofisk| Seria High | Boe | Blend Sider ut Lt. API Gravity 39.2 35.8 | 38.6 |40.4 ]37.0 [31.7 |35.3 | 364 | 40.1 | 43.4 [36.2 ‘Sp. Gravity, 0.82 | 0.84 | 0.83) 0.82) 0.84] 0.87] 0.85) 0.84 | 0.82] 0.811] 0.84 60°F/60°F ‘Sulphur, wi% 0.15 | 0.12 | 0.29) 0.21] 0.45] 0.13] 0.11] 012 | 0.11) 0.14 | 0.07 Nitrogen, wt% | 0.015| 0.054] 0.09] 0.1 | 0.14) - | - 0.095] 0.08] — 0.02 Pour Point, °C 9 9 9 0 9 27 3 6 3 2 3 (Contd...)(Contd... from Table 3.7) Petroleum Refining 77 Bombay| Quai- | Brent | Brega| ES | Zaire | Bonny | Escrands|Planca| Ekofisk| Seria High | Boe | Biend Sider u Lt. Vanadium, ppm | 0.1 | 03 | 25) 27] 1.74) 15] 04] 04 | 01! 0.11] 03 Nickel, ppm. 14/33 | 08] 35 | 481178} 12] 43 | 01 | 1.65] 05 Conradson 4.2 | 092 | 1.68] 1.67/ 3 | 3.58] 1 43 | 09 | 124] 03 Carbon, wt.% Ash Content, 0.01 | 0 o |o |- |= | oo} - - - - wt.% Salt, Ibs! 15 92 | 28] - |- | - |12 2 - - 415 1000 bbis, Kv@37.8 CST 3.75 | 3.57 | 3.64] 3.58] 5.56) 5.56] 3.49] 3.51 | 3.09] 3.14 | 2.69 Courtesy: IOC Panipat Refinery. Table 3.10 Typical Characteristics of Assam Crude Parameters Analysis Characteristics Unit Range Density at 15°C gfec 0.8781-0.8839 Water content vol.% 43-72 Sediment wt% 0.0018-0.002 Salt content wt% 0,008-0.01 Typical Characteristics of the Crude Characteristics Unit Range Density at 15°C. gfcc 0.8824 API gravity 28.86 Water content vol.% 34 BS&W vol.% 4.0 Pour point = +18 Salt content w% 0.007 Ky at 40°C Cyt 64 Kv at 50°C 46 RCR w% 2.2 Sulphur wt% 0.22 ASTM distillation IBP °c "1 5% °C 103 10% °c 129 20% °c 185 30% °c 251 40% °c 288 Rec at 300°C vol.% 43.0 Courtesy: BRPL Assam.78 Petrochemical Process Technology Table 3.11 Typical Yield Pattern of Some of the rude Oil Product |80mbay | Quai- | Brent | Brega | ES | Zaire | Bonny | Escrands| Planca| Ekofisk | Seria High | Boe | Blend Sider ut ut LPG 29 | 26] 32| 28] 33] 20! 27) 25 | 26] 29] 24 MSU/L 10.0 | 10.0 | 100] 10.0] 10.0} 10.0 | 10.0] 10.0 | 10.0] 10.9} 100 Naphtha aa | 73] 117] 421] 1.7] 1.7) 89] 87 | 129] 219] 18 ATF 37 | 37] 37] 37] 37] 371 37) 37 | 37] 37] 37 SKO 83 | 83] 83] a3] a3] 83] 83) @3 | 83; 83] 83 HsD 51.3 | 544 | 467 | 469] 46.4] 46.4 | 54.0] 542 | 49.5| 37.8 | 535 FO 00 | 00] 00] oo] 00] 00} 09] oo | 00} o9|] oo HPS 36 | 46] 73] 71] 174] 187] 33/ 35 | 38] 64] 17 Bitumen 0.0 0.0} 00} 00} 00] 00 0.0! 00 0.0) 00} 00 ‘Sulphur 04 | 04] 04] 04] 05] 05] 04) 04 | 05) 03] 02 FaL a7 | a7| 87| a7| a7| a7] a7| a7 | 87) 87] 87 Total 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0/ 100.0 | 100.0 | 100.9 | 100.0 Courtesy: IOC Panipat Refinery. 3.4 EVALUATION OF PETROCHEMICAL FEEDSTOCK Feedstock quality has important impact on the product quality and cost of production in petrochemical plants during the manufacture of aromatics, olefins, surfactants and other products. Feed quality and the presence of impurities influence the reactions, catalysts, product quality, etc. Some of the impurities like sulphur compounds, nitrogen compounds, chlorides, metals, water content, etc., poison the catalysts during various catalytic reactions. Presence of various hydrocarbons like naphthenes, paraffins, aromatics, etc., influence the reformate yield, olefin and LAB production. Therefore, quality monitoring and improvement efforts for better quality of products, feedstock with minimum impurities to minimize the pretreatment cost is of significant importance. Various parameters and their importance in evaluation of petrochemical feedstock are given below: Feedstock Density, colour, ASTM distillation, moisture, RVP analysis Ethylene and propylene | Paraffin and aromatic content, higher paraffinic feedstock yields higher olefins. feedstock ‘Component analysis of the FCC for propylene content. Density, colour, ASTM distillation, moisture, RVP enalysis Naphtha as reformer Higher aromatics and non-volatile material, sulphur content. chloride content, feedstock heavy metal content, moisture content, density, colour, ASTM distillation, RVP. Higher aromatics result in carbon deposit Natural gas Component analysis, sulphur content LAB feedstock Normal paraffin having C,g~C,, carbon is used for LAB. Normal paraffin content. and carbon range is determined Benzene Benzene is feedstock for caprolactam, phenol, cyclohexane, nitrobenzene, etc. High purity benzene (around 99.9%) is desired so purity of benzene is desired. ‘Some of the parameters are feed index points, crystallizing point, and cistillation range Higher aromatic and sulphur content, non-volatile material, sulphur content are the some important parametersPetroleum Refining 79 Naphtha as reformer Aromatics content, volatile material, sulphur content, chloride content, heavy feedstock metal content, moisture content MTBE Suspended materials, sediments, contaminants, sulphur content, solvent washed gum content, copper strip corrosion test, methanol content, water content, vapour pressure UB Specific gravity, appearance, colour, Bromine number, Doctor test Polypropylene feedstock | Component analysis for knowing the propylene content Kerosene for LAB Specific gravity, bolling point, colour, flash point, smoke point, sulphur, percentage of various carbon numbers, saybolt colour, bromine index, total normal paraffins. Desired components of feedstock are Cyp-C,, paraffin 3.5 QUALITY ASSESSMENT OF PRODUCTS The assessment of the quality of product is of equal importance. Some of the important parameters are specific gravity, smoke point, pour point, viscosity, freezing point, stability test, corrosion tests, flammability tests, acidity and alkalinity, ash, sediment, wax, sulphur, inorganic constituents and contaminants, organic constituents, RON and MON tests, etc. Requirement of various parameters for evaluation of crude oil, petrochemical feedstock and product quality is given in Table 3.5. 3.6 PRETREATMENT OF CRUDE OILS Crude oil comes from the ground and is mixed with variety of substances like gases, water, dirt (minerals), etc. Impurities in the crude oil are either oleophobic or oleophilic. Oleophobic impurities include salt, mainly chloride and impurities of Na, K, Ca and Mg; sediments such as salt, sand, mud, iron oxide, iron sulphide, etc., and water is present as soluble emulsified and/or finely dispersed water. Another class of impurities in crude oil are oleophilic, which are soluble, e.g. sulphur compounds, organometallic compounds, Ni, V, Fe and As, etc., naphthenic acids and nitrogen compounds, Pretreatment of the crude oil removes the oleophobic impurities. Pretreatment of the crude oil is important if the crude oil is to be transported effectively and to be processed without causing fouling and corrosion in the subsequent operation starting from distillation, catalytic reforming and secondary conversion processes. Pretreatment takes place in two way © Field separation * Crude desalting Field separation is the first step to remove the gases, water and dirt that accompany crude oil coming from the ground and is located in the field near the site of the oil wells. The field separator is often no more than a large vessel, which gives a quicting zone to permit gravity separation of three phases: gases, crude oil and water (with entrained dirt). Crude desalting is a water washing operation performed at the refinery site to get additional crude oil clean up. The crude oil coming from field separator will continue to have some water/ brine and dirt entrained with it. Water washing removes much of the water-soluble minerals and entrained solids (impurities). There are two types of desalting ~ single and multistage desalting.80 Petrochemical Process Technology ‘Commercial crudes, salt contents of range 10-200 ppb, earlier 10-20 ppb, were considered satisfactorily low. However, many refiners now aim at 5 ppb or less (1-2 ppb) which is not possible through single stage desalting, hence two stage desalting is required. Single stage desalting with water recycle is usually justified if salt content in crude is less than 40 ppb. Two-stage desalting involves dehydration followed by desalting. Double stage desalting is better for residuum hydrotreating. Fuel oil quality is better. 3.7. NATURAL GAS PROCESSING Natural gas is one of the important feedstock for fertilizer and petrochemicals. Natural gas is a mixture of gaseous hydrocarbons with methane as a major constituent. Dry natural gas is a gas that does not contain readily condensate hydrocarbon. Wet natural gas is a gas, which contains more than 2 gallons condensate per 1,000 cubic feet of gas. Wet natural gas has lower methane content. Sour natural gas contains appreciable quantities of hydrogen sulphide. Natural gas liquids consist of constituents condensed from natural and associated gases and are hydrocarbons, ethane through pentanes. Typical characteristics of natural gas are given in Figure 1.13. There are two sources of natural gas associated gas found along with crude oil and unassociated gas which is in isolation of heavier fraction and found in gas field underground reservoirs broadly similar to oil reservoirs. The wet natural gas contains relatively higher ethane and is co-product of crude oil production. The processing and separation of associated gas involves stabilization of well fluid for separation of water, oil and gas. The oil goes for removal of water emulsion and salts before it is used in the refinery. The water after separation of oil is recycled. The gas along with condensate {goes to separator for separation of gas and condensate. The natural gas liquid is fractionated into their separate components. Typical condensate processing unit involves removal of H)S and CO), recovery of LPG and natural gas liquid. The condensate processing plant consists of separator for water removal, stripping column for removal of H,S and LPG recovery column. Further processing of natural gas depends upon the types of compound present in it. A dry gas low in sulphide content needs little pretreatment or no treatment except to adjust the moisture content while processing of the sour natural gas requires removal of hydrogen sulphide and carbon dioxide. The processing of sour natural gas involves sweetening for removal of HyS and CO, using monoethanol amine and diethanol amine as absorbing mediums. The steam stripping regenerates absorbent. Other solvents used for separation of H,$ gas are sulpholane, sulpholane- carbonate, mixture of sulpholane and alkanol amines (Sulfil process, Merox process). Molecular sieves are used for removal of moisture, HS, mercaptans (RSH) and carbonyl sulphide. Membrane process is another promising process for treatment of natural gas for removal of sour gases. 3.8 PETROLEUM REFINING PROCESSES Refining of crude oils or petroleum essentially consists of primary separation processes and secondary conversion processes. Petroleum refining process is che separation of the different hydrocarbons present in the crude oil into useful fractions and conversion of some of the hydrocarbons into products having higher quality performance. Atmospheric and vacuum distillation of crude oils is the main primary separation processes producing various straight run products, e.g, gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the light and middle distillates, i.e. gasoline, kerosene and diesel are more in demand than their directPetroleum Refining 81 availability from crude oils all over the world. There has been continuous development and upgradation of process technologies, catalyst, size and capacity of the plants, Typical flow diagram of a refinery is given in Figure 3.1. Process Description Desalting Distillation of crude of Atmospheric distillation Vacuum distillation Desalting process is used for removal of the salts, like chlorides of calcium, magnesium and sodium and other impurities, as these are corrosive in nature. Desalting process consists of three main stages heating, mixing and settling. Emulsifying the crude oil and then separating the salt dissolved in water carry out desalting. Two phases water/oil is separated either by using chemical to break down the emulsion or by passing high potential electric current. Typical flow diagram of Electric desalting process is given in Figure 3.2 ‘The process steps involves the crude oll distillation, crude receiving, filtration, crude preheating before desalting, desalting, crude oil preheating, raising temperature with fired heaters, atmospheric distillation and vacuums distillation unit and product routing. Product streams are gaseous hydrocarbons, fuel gases, LPG, light gasoline, naphtha, kerosene, aviation turbine fuel, diesel fuel and heavy fuel, bitumen, wax, lubricating oil. Typical block diagram for atmospheric and vacuum distillation of crude oll i in Figure 3.3 Distilation of the desalted crude oil is carried out at 340-350°C resulting into gases, LPG, gasoline, naphtha, kerosene, diesel and atmospheric residue (fuel oil). The desalted crude is preheated in a series of heat exchangers, and furnace to raise temperature to about 400°C and sent to distillation column where the crude oil is fractionated into different low boiling components. Distitation column Top Flash Temperature, °C 117-123 351-357 Pressure, kg/cm? = -2.2-2.5 2.5-2.9 Distillation of the residue from atmospheric distilation column is carried out to make it suitable for catalytic cracking or hydrocracking or manufacturing of lubricating oils and a residue which may be air blown or further distilled for bitumen. In order to avoid cracking of the atmospheric residue during further fractionation, which requires high temperature, distilation of heavy residue from atmospheric column is done under vacuum. This permits the fractionation at much lower temperatures. Vacuum residue is processed in bitumen plant, visbreaker used for blending fuel oil Distillation column Top Flash Temperature, °C 70-80 390-395 Pressure, mm of Hg 70-90 130-150 The stripper bottom is finished product. The separator gases are sent to amine wash for removal of HS (Contd...)82. Petrochemical Process Technology (Contd... from Table) Progess Catalytic reforming Fluid catalytic cracking (FOC) and Residue fl dised catalytic cracking (RFCC) Hydrocracking Description Catalytic reforming process is a major refining operation for converting low octane naphtha to high-octane motor gasoline blending stock and aromatic concentrates rich in benzene, toluene and xylenes (BTX). Reactions involved are dehydrogenation, isomerization, dehydrocyclization, and hydrocracking. Various types of catalytic reforming processes are Platforming (UOP), Powerforming (Esso), Ultraforming (Standard oil), Houdriforming (Houdry), Reforming (Chervron), Magnaforming (Engelhard, ARCO), Catalytic reforming (IFP, Engelhard, Kellogg, Ashi, Amoco); various products are reformate/aromatics, hydrogen rich gases, fuel gas. Temperature maintained in the reactor is 500-515°C and pressure is 26 kg/cm. Various parameters affecting the reforming process are — reaction temperature, space velocity, reaction pressure, H/HC ratio, feedstock characteristics, catalyst poisons, chloride, water, sulphur compounds in the feedstock (see Chapter 6 for more detail) Catalytic cracking of the vacuum gas oil produces valuable hydrocarbons including LPG, gasoline and diesel biending stocks. The various reactions involved are cleavage, isomerization, alkylation, dehydrogenation, and aromatization. Catalyst used is zeolite based. The FCC unit consists of catalytic section - reactor and regenerator, fractionation section and gas concentration unit (Temp.: 500-700°C). Products from FCC are fuel gas, LPG, gasoline, HSD component, LDO component, fuel cil. Cracking reactions: Alkyl Paraffin = Paraffin + olefin Alkyl naphthene = Naphthene + olefin Alkyl aromatic = aromatic + olefin RFCC is similar to FCC process where desulphurized residue is cracked over a hot stream of fluidized catalyst to produce gas, LPG, gasoline, cycle oil and clarified oil (see Chapter 5 for more detail) Primary feedstock for hydrocracking units are LPG, stabilized naphtha, heavy naphtha, aviation turbine fuel, superior kerosene, high speed diesal, fluid catalytic cracking feed. Hydrocracking technology also reduces the sulphur emission. The feedstock to hydrocracker are vacuum gas oil and other heavier hydrocarbon, The product produced from hydrocracker depends on type of catalyst. Catalyst life decreases with increase in feed rate and conversion and increases with increase in hydrogen partial pressure makeup gas puny, reactor pressure, recycle gas rate and recycle gas purity. A typical hydrocracking unit consists of makeup hydrogen section, reaction section, fractionation section, and light end recovery section. Catalyst used is dual function catalyst. Hydrocracking of hydrocarbons is an extremely versatile catalytic cracking process in which feedstock ranging from naphtha to vacuum residue can be processed in presence of hydrogen and catalyst to produce any desired product lighter than the feed. Process variables are temperature, reactor pressure, space velocity, nitrogen content and hydrogen sulphide content. Hydrocracking is increased with high temperature, high pressure and low space velocity. The process is carried out in two stages. Various hydrocracking technologies are given in Table 3.12Petroleum Refining 83 Process Kerosene hydrode- sulphurization Merox process Vapour recovery unit Diesel Oil Hydro Desulphurization Lube oil extraction unit Wax plant Alkylation unit Diesel hydrodesulph- urization plant Aromatics extraction unit Lubricating oil refining plants Description Hydrodesulphurization is done to reduce sulphur content of raw kerosene (ATF/JPS). The process consists of hydrotreatment of kerosene. The separation of reaction gases is done in two-stage separator. The stripper bottom is finished product. The separator gases are sent to amine wash for removal of HS This process is used for removal of mercaptans or for conversion of mercaptans into disulphide. The process is combination of mercaptan extraction and sweetening. Low molecular weight mercaptans are caustic soluble and are removed by washing with caustic. Tho caustic is regenerated by blowing air in the presence of merox catalyst. The methyl mercaptan is, converted to dimethy! disulphide. The reactions involved are: RSH + NaOH — RSNa + H,0 2NaSR + 1/20, + H,0 — 2NaOH + RSSR ‘The disulphide formed is separated from the caustic in the separator. Merox process unit mainly consist of naphtha merox unit and gasoline merox unit This unit consists of vapour recovery. The function of vapour recovery section is to separate gas, LPG and light gasoline. The merox unit is used for sweetening of LPG. The merox unit consists of an amine wash section and ‘sweetening unit This unit desulphurizes the diesel by catalytic hydrogenation. The reactor gases are separated in separator and the treated diesel is sent to stripper for removal of light ends. Typical desulphurization reactions convert thiophenes, thiols to straight chein, branched chain paraffins and hydrogen sulphide This unit involves the primary extraction of heavy distillates to make a range of lubricating oils This involves dewaxing of lube oil after extraction and then deoiling of the crude wax, clay treatment for removing colour and final purification of wax by dehydrogenation Alkylation is done to synthesize the very high-octane components for gasoline out of byproduct gases from process primary distillation of crude oils. In refinery, low molecular weight olefins are reacted with isoparaffins to make higher molecule isoparaffins of high octane number. Alkylation catalyst: concentrated sulphuric acid and hydrofluoric acid. Process variables are reaction temperature, acid strength, isobutane concentration and olefin space: velocity. The various products are LPG grade propane, normal butane, C+ alkylate, tar In this plant catalytic hydrodesulphurization of diesel is done to reduce sulp- hur content to less than 0.05%. With recent fuel regulations this process becomes extremely important This unit is used to separate naphtha into its aromatics useful as such in industry as solvents or for chemical manufacture o for high-octane gasoline and non-eromatics are valuable for special aviation fuels or as feedstock for petrochemicals ‘This process is used to remove resinous type impurities from lubricating oil ‘stocks and blend facilities to achieve the finished products by blending and the incorporation of additives (Contd...aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.88 Petrochemical Process Technology Process Technology Description Remarks Licensers IFP Process Process is based on a new dual catalyst] Product: Middle distillates, very low Kellog Brown and Root system (using hydrotreatment catalyst -| prototype hydrocracking — catalyst zeolite for| upgrading of vacuum gas oil alone or| blended with light cycle oil, deasphalted oi, visbreaker or coker gas oil) ‘The processes used are one-, tiwo- or three-| stage ebullated bed reactor system for| catalytic hydrocracking, desulphurization of] residue and heavy oil using H-oil process. ‘Typical Operating Condition: ‘Temperature 770-840°F, LHSV 0.1-0.9 h', Conversion 95% This process is based on MKA Fining, HDC process and converts a wide variety of| feedstock including vacuum gas oil, coker| gas oil and FCC cycle oils into high quality, low sulphur fuels ‘sulphur fuel oil, extra quality FCC feed or high viscosity index lube base stock. Eleven units have been licensed Product: Full range of distillates, upgraded residues, transportation fuel, FCC and low sulphur fuel oil Product: A wide range of high quality, low sulphur distilate feeds and blending stocks including LPG, high octane gasoline, reformer naphtha, jet fuels, kerosene, diesel oil Source: Refining Processes, 1998: Verma, 2000; Verma, 2002. Various residues upgradation technologies are given in Table 3.13 [Dickenson et al., 1997). Some of the future needs for upgradation of the residues are: Deep cut vacuum distillation for maximizing FCC/Hydrocracker feed Basic data, design, hardware Possibility of developing indigenous technology in shorter span/time Development of catalyst for FCC/hydrocracker having more metals and asphaltenes tolerance Development of hardware for FCC/hydrocracker Development/improvement of residue hydrotreatment (HDS, HDN, HDM, HDAs, HDR, HDCCO), residue cracking, residue hydrocracking, super critical extraction technologies with/ without conventional technologies, e.g. coking, visbreaking, solvent extraction . and aqueous catalytic pyrolysis Development of newer processes, e.g. catalytic hydro-visbreaking, flash hydropyrolysis, Development/improvement of technologies for gasification of residues, waste co-processing along with pitches (minimizing environmental impact and development of infrastructure) « Examples of China for deep catalytic cracking (DCC) technology, Japan (Nippon Oil) for Hydrocracking catalyst, etc.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.92 Petrochemical Process Technology Table 3.18 Changing Scenario In Diesel Specifications Period Specifications Prior to 1993 Sulphur: 1.0-0.2% (Sweden 0.001-0.05% from 1991) Cetane —: No limit (Sweden : 47-50 from 1991) 1993-2000 Aromatics ; No limits (Sweden: §-25% from 1991) Sulphur; 0.2-0.05% Cetane : 40-46 min. Beyond 2000 Aromatics : 35% max. (California 10% max) Sulphur: Further reduction to Sweden levels Cetane Further increase 40-46 min. Aromatics : Further reduction Volatility increase over present level ‘Source: Abs+Halabi et al., 1997. Table 3.19 Gasoline Specifications Characteristics Bharat Stage 1 | Euro il Equivalent | Euro IV Equivalent ‘Sulphur, mass%, total max. 0.05 159(mgrkg) s0(mg/kg) RVP, KPa, max. 35-60 60 60 Benzene, vol.%, max. 3 1 1 Aromatics, vol.%, max. - 42 35 Olefins, vol.%, max. - 21 2 Distillation @recov. up to 70°C, vol.% 10-45 10-45 10-45 @recov. up to 100°C, vol.% 40-70 40-70 40-70 @recov. up to 180°C, vol.% 90 75 min. (150°C) 75 min. (150°C) Final BP,, °C, max. 215 210 210 Residue, vol.%, max. 2 2 2 RON, 88 1 ot RON, - a 84 Table 3.20 Diesel Specification Characteristics Bharat Stage It Euro Equivalent Euro IV Equivaient Sulphur, mass%, total max. 0.08 360(mg/kg) 50(mg/kg) Cetane no, min. 48 51 54 45(Assam crude) | 48(Assam crude) | 48(Assam crude) Polycylic aromatics HC = WW at (PAH) wt.%, max. Distillation 85 min. @ 360°C and 360°C 360°C 95% vol. Recovery 95 min. @370°C at‘C, max.Petroleum Refining 93 Returns on refining assets have fallen to inadequate levels due to low growth for major refined products, poor upgrading margins, increased competition and there is need for refinery/ petrochemical integration, process technology developments. Factors influencing Petroleum Refining Industry are: * Crude oil prices and growing demand of petroleum products (developing Asia, Asia-Pacific) © Decline in domestic crude oil production (USA, India, etc.) © Gradually increasing heavier feedstock « Investment in billions of dollars for environmental protection © Low profit margins Major challenges which Indian refineries are likely to face are: # Increasing products demand from 88.2 MTPA (1997-98) to 155.3 MTPA (2006-07) * Demand for better products quality and new environmental regulations # Decreasing quality of feedstock # Increasing ‘$? (>1.5 per cent) in the feedstock # Decreasing API gravity (<0.8) (Heavier crudes) # Increasing level of micro-constituents © Value addition Key issues facing Indian Refineries are low margins and unacceptable profitability, requirements posed by changes in product specifications resulting from environmental consideration; focus on improving bottom-line of existing assets. Expected Trends in Refining in India are (Chopra, 2000}: © Higher conversion, better yield and improved efficiency to generate more value from each barrel of crude oil * Reforming of naphtha © Process to increase LPG production © Conversion process like hydro cracker to convert heavy ends into middle distillates Residue upgradation © Hydrodesulphurization * Improvements in lube oil production ‘© Hydrogenation process to improve stability © An alternative additive for octane improvement, which is as effective as TEL « Fuel additives to improve stability and undue deposit forming tendencies Environmentally sound © Energy efficient with lower energy intensity © Safe and easy to operate ‘© Operation with minimum inventory © Sustainable, valuable and profitable development ‘© Complete synergy between refineries and product consumers © Integration of petrochemical for value addition * Adoption of GTL technology Emerging Indian scenario of product quality are: © Increased production of motor gasoline * Demand for better quality products (fuels and lubricants) meeting new environmental regulations94 Petrochemical Process Technology * Lube base stocks (high viscosity index, high oxidation stability, low pour point, low volatility) @ Feel oil (low sulphur) © Hydroprocessing (HC-Fuel and Lube, MHC, HDT, etc.) * Reformulated product, e.g. reformulated gasoline and synthetic lubes © Additives # Redefinition of catalytic reforming technology *# Selective dehydrogenation * Hydroisomerization Hydrocatalytic isodewaxing (diesel/lubes) Alkylation ‘* Development of environment friendly solid acid catalysts © More hydroprocessing units to consume heavier feedstock for production of value product having better quality stability, low sulphur Extensive efforts towards technology adsorption, adaptation, development/improvement In order to mect the challenge of declining resources of crude oil, some of the area that has received considerable interest are tapping of coal bed methane and gas hydrates, gas to liquid technology. Coal bed methane is technologically proven to be economic energy source. As India has vast coal deposits, it can be of great potential of coal bed methane. In order to explore and produce non-conventional source of natural gas from coal bearing areas, Government of India had formulated a CBM policy providing attractive fiscal and contractual framework for exploration and production of coal bed methane. Eight blocks in the states of Jharkhand, Madhya Pradesh and West Bengal has been awarded for exploration and production of coal bed methane. Gas hydrate is another area that has vast potential as future viable source of energy. Looking to the availability of huge amount of natural gas and other methane bearing stream of refinery, Gas to liquid technology (GTL) originally developed by German scientist Franz Fischer, the Fischer Tropsch process is again getting great attention all over the world as future promising technology. This technology can convert natural gas or any methane dominated resource into middle distillate or any other fuel and non-fuel products [Garg and Badoni, 2003]. REFERENCES Absi-Halabi, M., A. Stamislaus, H. Qabazard, “Trends in Catalysis Research to Meet Future Refining Needs’, Hydrocarbon Processing, February 1997, p. 45. Banks, R.E., PJ. King, ‘Chemistry and Physics of Petroleum in Modern Petroleum Technology’, vol. I and Il, Sth edition, New York, John Wiley & Sons, 1986. Bhatnagar, A.K., ‘Analytical Development in Crude Oil and Product Characterization in Challenges in Crude Oil Evaluation, edited by J.M. Nagpal, Tata McGraw-Hill Publishing Company Ltd, New Delhi, 1996, p. 1. BP 2004, ‘Statistical Review of World Energy’, available online at www.bp.convstatisticalreview2004. Chopra, S.J., ‘Refinery for Future’, QUP short-term course on advances in Hydrocarbon Engineering, 23 June-4 July 2003, IIT Roorkee, India, Dickenson, R.L., FE. Biasea, BL. Schulman, HE. Johnson, ‘Refinery Options for Converting and Utilizing Heavy Fuel’, Hydrocarbon Processing, February 1997, p. 25. Gamson, B.W., RH. Elkins, ‘Sulphur from Hydrogen Sulphide’, Chemical Engineering Progress, April 1953, p. 203,Petroleum Refining 95 Garg, M.O., R.P. Badoni, ‘Gas to Liquid Technologies: Challenges and Opportunities’, Chemical Industry Digest, vol. 56, May/June 2003, p. 56. Goar, B.G., A. Goar, ‘Sulphur Recovery Process’, Energy Progress, vol. 6, no. 2, 1986, p. 71. Hobson, G.D., W. Pokl, Modern Petroleum Technology, vol. | and Il, Sth edition, John Wiley & Sons, New York, 1986. Katzer, J.R, P.R. Michael, A.V, Spare, ‘Petroleum Refining: Poised for Profound Changes’, Chemical Engineering Progress, July 2000, p. 41. La Gas, J.A., J. Borsboom, G. Heijkoop, ‘Clauss Process Gets Extra Boost’, Hydrocarbon Processing, April 1989, p. 40. Luinstra, E.A., PE. d’Haene, ‘Catalyst Added to Clauss Furnace Reduced Sulphur Losses’, Hydrocarbon Processing, July 1989, p. 53. MePherrson, LJ, M.E. Olive, ‘Alkylation, Isomerization, Polymerization, Hydrotreatment and Sulphur Production’, Modern Petroleum Technology, vol. I and Ul, Sth edition, John Wiley & Sons, New York, 1986, p. 179. Mishra, A.K., A. Unnikrishnan, ‘Overview of the Quality of Crude Oils Processed in India’, in Challenges in Crude Oil Evaluation, edited by J.M., Nagpal, Tata McGraw-Hill Publishing Company Ltd, New Delhi, 1996, p. 22. “Petroleum in the 21st Century’, Oil and Gas Journal, 13 December 1999, pp. 115-116. ‘Refining Processes 98’, Hydrocarbon Processing, November 1998, p. 82. Speight, J.G., The Chemistry and Technology of Petroleum, 3rd edition, Marcel Dekker Inc., 1999, p. 149. Verma, R.P, ‘Challenges and Related Strategies in Petroleum Refining Industry in the 21% Century’, AICTE Staff Induction training programme held at IIT Roorkee, India, 3-22 January, 2000. Verma, R.P, ‘Hydroprocessing: Indian Scenario’, Indian Chemical Engineer, Special issue 38, vol. 1, 2002, p. 38. ADDITIONAL READINGS Chopra, S.J, M.K. Joshi, ‘Transforming the Indian Refining Industry - An Overview’, indian Chemical Engineer, Special issue 4, vol. 1, 2002. Dave, R.R., M.L. Khurana, ‘Evaluation of Feedstock for Aromatics, Olefins and Surfactants’ in Challenges in Crude Oil Evaluation, edited by J.M., Nagpal, Tata McGraw Hill Publishing Company Ltd, New Delhi, 1996, p. 139. ‘Environmental Processes 98°, Hydrocarbon Processing, August 1998, pp. 87-88. Gary, J.H., G.E. Handwerk, Petroleum Refining, Marcel Dekker Inc., New York, 1975. Gruse, W.A., D.R. Stevens, Chemical Technology of Petroleum, Tata-McGraw Hill Book Co. Inc., 3rd edition, 1960, Gupta, A.K., ‘Clean Fuels and Petrochemical Synergies’, QIP short term course on advances in Hydrocarbon Engineering, 23 June-4 July 2003, IIT Roorkee, India. ‘IP Standard Methods for Analysis and Testing of Petroleum and Related Products and British Standards 2000 Rules’, vol. I, John Phipps Energy Institute, London, 2004. Kuchhal, Y.K., M.O. Garg, S. Singhal, ‘Fuel Quality Management in Indian Refining Industry’, Indian Chemical Engineer, Special issue 38, vol. 1, 2002, p. 38. “Standard Methods for Analysis and Testing of Petroleum and Related Products’, vol. I and Il, John Wiley & Sons, London, 1993.chapter“ Olefins Production Olefins are major building blocks for petrochemicals. Because of their reactivity and versatility ~ especially the light olefins like ethylene, propylene, butenes, butadiene, etc., there has been tremendous growth in the demand of olefins. Olefins are finding wide application in the manufacture of polymers, chemical intermediates and synthetic rubber. Ethylene itself forms a basic building block for a large number of petrochemicals and is quoted as king of chemicals. As on 1 January 2003, world ethylene capacity was 109.4 million tonnes per annum [Oil and Gas Journal, 2003]. Light olefin demand typically grows faster than GDP. Steam cracking is the major source of production of olefins. Fluid catalytic cracking is the other source for C4, Cs olefins. Some of the emerging technologies for the production of olefins are oxidative coupling of methane, catalytic dehydrogenation and deep catalytic cracking and methanol to olefin technology. 4.1 STEAM CRACKING FOR PRODUCTION OF OLEFINS The steam cracker remains the fundamental unit of the global petrochemical industry and is at the heart of any petrochemical complex and produces a large number of products and byproducts such as olefins, namely ethylene, propylene, butadiene, butane and butenes, isoprene, etc., as well as pyrolysis gasoline. These products serve as basic feedstock for many chemicals, intermediates which are used in the production of polymers, synthetic fibres, synthetic rubbers, pesticides, pharmaceuticals, dyes, explosives and other organic chemicals. World steam cracker by region is given in Table 4.1 [CMAI, 1999]. The various feedstock used in steam cracker are naphtha, natural gas liquid, gas oil, ethane, propane and ethane-propane mixture. Table 4.1 World Steam Crackers Region 1999 2000 2001 2002 2003 North America 63 64 68 66 68 South America 14 15 15 16 16 Europe (including FSU) 85 85 85 85 85 Africa 5 6 8 6 6 Middle East 12 14 4 18 18 Indian subcontinent 7 8 8 8 8 Northeast Asia 87 58 58 58 58 ‘Southeast Asia 13 13 13 15 16 World Total 256 263 265 272 273 Courtesy: CMA, 1999.Olefins Production 97 The choice of the feedstock for olefin production depends on the availability of raw materials and the range of downstream products. Naphtha has made up about 50-55 per cent of ethylene feedstock sources since 1992. The complexity of steam cracking and production of olefins depends on the feedstock, Olefin plants are complex and costly with both complexity and cost that increases with heaviness of feedstock. Heavier feedstock produces a wide variety of olefins requiring more complex separation and recovery process. Although earlier production of olefins was from lighter feedstock like ethane, propane and naphtha, heavier feedstocks are also gaining importance because production of ethylene from heavy liquids will increase as demands grow. Present uncertainity in petrochemical feedstock market requires that ethylene plants must be designed for a variety of products [Zdonik and Haywood, 1975]. The gas cracker plants have two additional units: gas sweetening for the removal of CO, and H,S; and a gas fractionation unit for separation of methane from C,/C; fraction. Although basic steam cracking technology remains same for naphtha, gas oil and natural gas, different configurations of steam cracking plants are available from various process licensors, details of which is given in Table 4.2 [Petrochemical Processes, 2003]. 4.2 GAS SWEETENING UNIT Steam cracker plants using natural gas as feedstock contain gas-sweetening unit. Sweetening can be defined as removal of acid gases like H,S and CO, present in the natural gas. A typical composition of natural gas is given below: Percentage composition: C, = 84.06, C, = 9.38, C; = 0.99, Cy = 0.04, CO, = 5.52, H,S = 4ppm, N, = 0.01. Natural gas contains CO, and H,S and this gas is fedto a C,-C, recovery unit for cryogenic separation. If CO, component of the gas is not removed, it will freeze (freezing point: -77°C) resulting in the choking of pipelines. Some of the process technologies available for separation of CO, are amine sweetening using MEA, DEA process and membrane process. However, amine- sweetening process is most commonly used and CO, is removed by absorption in two parallel high pressure absorbers. The gas is fed to two absorber columns at 52 kg/cm* and 30°C operating in parallel. The raw gas is taken into raw gas drum for separation of any moisture present in the gas before passing to the absorber. Each absorber is fitted with valve trays. Lean diethanol amine solution (40 per cent) is fed to column top at tray number 2 at 51.4 kg/cm? and 45°C. The gas is countercurrently contacted with the absorbent DEA so that CO, in the gas gets absorbed into the solution. CO, in the gas reacts with amine to form amine carbamate. CO, +2R,NH > R,NCOO-+ R,NHS CO, also reacts with water and hydroxyl ions to form carbonic acid and bicarbonate ions. CO,+H,O -» H,COy CO, + OH" HCO; The carbonic acid reacts with amine to form amine bicarbonate (HCO, R,NH,) and amine carbonate [CO,(R,NH;),]. The treated gas leaves from the column top at 45°C and contains less than 50 ppm of CO;. The treated gas from both the columns is combined and sent to the water wash column, Lean amine temperature is to be kept 10-15°C higher than the feed gas temperature so as to prevent heavier component in the feed gas from condensing.98 Petrochemical Process Technology Table 4.2 Steam Cracking Technologies Process Technology Description Remarks M.W. Kellogg ‘Technology ‘Stone and Webster Engineering Co. Linde A.G. ABB Lummus Global Brown and Root Engineering and Construction Technil KTJ, Techni! petrol Kellogg's cracking furnaces incorporate low reaction times in range of 0.1 second with high outlet temperature (870°C). This is based on Millisecond technology and is more selective to olefin forming reactions This process uses two main process technologies: USC (Ultra Selective Cracking) pyrolysis and quenches system and ARSCF (Advance Recovery System Cold Fractionation). Pyrolysis occurs under the temperature, time control specific to the feedstock and product requirement. ARS minimizes refrigeration using dephlegmation gas shield and distributed distillation This technology uses highly selective pyrocrack type furnaces optimized with respect to residence time, temperature and pressure profiles with highest olefin yield. Cracked gas recovery system includes front end deethanizer. isothermal C, front end hydrogenated reactor cold train, demethanizer and heat pump (low pressure ethylene fractionator) This technology uses tubular SRT (Short Residence Time) pyrolysis with extremely high olefin yield, long run length fumaces and mechanical integrity ‘This technology comprises kinetic tach- nology interaction, compaction pyrolysis. section and Brown & Root recovery sec- tion using low capital scheme using deethanizer or deproparizer as the first column The furnace is designed for maximum olefin yields with high flexibility polypropylene/ethylene ratios. Hydrogen is purified in PSA unit Single pass ethylene yields up to 54% for ethane, 35% for naphtha and 30% for gas oil. More than 70 ethylene plants are in operation. Total capacity is 12 MTPA. Feed: Ethane to vacuum gas oils Ethylene yields range from 57% (ethane) to 28% (heavy hydrogenated gas oils). Specific energy varies from 3,000-6,000 kcal/kg. More than hundred ethylene units are in production. Feed: Ethane to hydrocracked residues Ethylene yield is 25%, 35%, 45%, and 55% for gas oils, naphtha, LPG and ethane, respectively. Related specific energy consumption: 6,000; 5,000; 4,000; 3,000 kcal/ig of ethylene. More than 35 plantsarein operation with over 13 million tonnes of ethylene production Ethylene yield Is 64%, 45%, 44%, 34.4%, 28%, 25.9%, 22%, 34.7% for ethane, propane, butane, naphtha, atmospheric light, heavy, vacuum and hydrocracked, respectively, Approximately 40% of world’s ethylene plants use this technology. Olefin yields are optimized for spacific client economics. Feed: Ethane through gas oil Yields of ethylene are 81.6%, 46.7%, 40.9 %, 39%, 34.5%, 26.9% for ethane, propane, butane, naphtha (light, naphtha full range, respectively) and atmospheric gas oil, respectively. Specific energy varies between 3,100 kcal/kg C, for ethane to 5,500 kcal/kg C, for atmospheric gas oi! Courtesy: Hydrocarbon Processing, Petrochemical Processes, 2003,Olefins Production 99 After CO, absorption, the rich amine is collected atthe bottom of each absorber column. This solution at 52 kg/om? and a temperature of 72°C is routed to the amine recovery unit for separation of CO, where first itis sent to amine flash drum for separation of hydrocarbons. The rich amine solution is then sent to regenerator for stripping CO, after preheating to 110°C, which is passed through series of filters for removal of solid scales, dissolved hydrocarbons and solvent degradation products which can promote corrosion and foaming problems. After CO, absorption the treated gas is fed into the bottom of sweet gas wash water column where the gas is countercurrently contacted with circulating water to remove any DEA solution carried over with the treated gas. The treated gas after cooling is sent to the C,/C, recovery section for extraction of C,/C; component. Process flow diagram for gas sweetening is given in Figure 4.1. Typical composition of natural gas before and after separation is given in Table 4.3. ee fot). o ru a} | {di il | oe lire] LE i ie Lt Fier] we | — gee A = tank oo Knockout drum| Regenerated = |} ty M/ i wears i UN AN I (aaa | cotter Figure 4.1 Gas Sweetening by Amine Absorption Based on lower ope:rating costs, comparable capital cost and only slightly higher product loss (including fuel), mer branes have demonstrated a flexible, cost effective alternative to amine treating for some natural gas processing applications [Cook and Losin, 1995]. A typical two- stage membrane process f ‘or removal of CO, from natural gas is given in Figure 4.2 [Cook and Losin, 1995]. Separation of CO, by membrane is based on the principle that some gases pass more teadily and others are : retained by the membranes. Membrane processes have shown economic advantage over amines s-ystem over a wide range of feed gas compositions and flow rates. Membranes have been fo und competitive at the lower flow rates and for high carbon dioxide concentrations [Spillman, 1989].100 Petrochemical Process Technology Table 4.3 Composition of Natural Gas Before and After Separation Component Natural Gas Lean Gas Bottom Product Percentage (After Separation of | (Demethanizer Bottom) Heavier Fraction) N, 0.05, 0.05 - co, 457 13 ppm - c, 83.91 98.4 - c, 6.93 1.54 0.51 C3 3.09 0.01 79.14 Cy 1.18 - 18.02 Cy 0.023 - 228 Cot 0.04 a = Sp. gr. 0.6852 0.561 - Cal. value 8,873 8,203 - (kcal/kg) Proveater Ze stage Natural_,| Soparaton ct | [| membrane = entrained conaminants q Liquids J inter Ly and stage | 4 Separator 2rd stags Uquics Permeate containing CO,, HS, moisture, atc. Figure 4.2. Typical Two-Stage Membrane System Process for Processing of Natural Gas 4.3. C,/C, EXTRACTION UNIT ‘The sweetened gas from gas sweetening plant is fed to the feed gas knock out drum for separation of any entrapped liquid from the feed gas and then it is compressed and cooled to about 17°C. It is then sent to feed gas moisture separator and feed gas-drying section for removal of traces of moisture. The gases after passing through filter arc sont through series of exchangers for cooling to below -60°C and then sent to the cold section. In the cold section the gases are sent to demethanizer column for separation of methane from the C,/C3. The temperature in theOlefins Production 101 demethanizer maintained is about -101°C. Typical composition of C, and C; feed to gas cracker is shown in Table 4 Table 4.4 Typical Compositions of C, and C, Feed to Gas Cracker C, 6.04% c, 90.45% Cy 0.81% cy 0.62% Cs 0.03% Others Balance 4.4. STEAM CRACKING PROCESS TECHNOLOGY “The steam cracking section comprises a hot section and a cold section. The cracking of hydrocarbons and separation of cracked light gases from heavier fraction pyrolysis gasoline takes place in the hot section while the separation of light cracked gases ethylene, propylene, butadiene and other fractions takes place in cold section which operates below 0°C. Process flow diagram of steam cracking of naphtha/NGL is given in Figure 4.3. 4.4.1 Hot Section The cracker furnace may be divided into three sections: convection zones, radiation zones and quench section (transfer line exchanger). The hydrocarbon feedstock is preheated by quench water and steam before entering the convection zone of the furnace where it is further preheated and mixed with superheated steam, which is added as a diluent. The steam minimizes the side reaction responsible for the formation of coke during pyrolysis and improves the selectivity to produce desired olefins by lowering hydrocarbon partial pressure. Requirement of steam will depend upon the type of feedstock; the lighter hydrocarbon requires less steam as compared to heavier feedstock. Steam cracking relative cost according to feedstock is given in Table 4.5. Steam requirement in steam cracker is given in Table 4.6 (Wiseman, 1986]. Energy requirement pattern for olefin production is given in Table 4.7 [Gupta, 2000]. Table 4.5 Steam Cracking Relative Cost according to Feed Stock Feedstock Relative Investment Cost Ethane 1.00 Propane 115 Butane 1.20 Naphtha 1.45 Atmospheric gas oil 1.65 Vacuum gas oil 1.84qwejd 1079849 ENUGENFION 49} 1004S MOLY Ss@d014 f° BUN q Ble emton acon : a aa) ij == mm = 3 aa gone 3 g |} pue eusyédoud apensen + a a ag eh 1 han a youand youand jong = i euyosed: emo} OU) se6ueyoxe} aoe, sells] § aro || anor . | eon pee) equden: sain oe ‘spua KETOlefins Production 103 Table 4.6 Steam Requirement in Steam Cracking Feed kg Steam/kg of Hydrocarbon Ethane 02-04 Propane 0.3-0.5 Naphtha 04-08 Gas oil 08-4.0 Table 4.7. Energy Requirement for Olefin Production Feedstock Specific Energy Consumption kcal/ag of Ethylene kcal/kg of Olefin Ethane 310 3,050 Propane 4,100 3,050 Ethane/Propane 3,600 3,300 Naphtha 5,000 3,050 The hydrocarbon and steam preheated in convection zone in the upper part of the furnace enter the radiant section_of furnace at about 650°C and total pressure of 1.7 bar, where pyrolysis of feed takes place. The coil length in the radiant section varies from 60 m for a naphtha cracker to 85 m for an ethane cracking unit. The residence time varies for different feedstock is around 0,15-1,2 s and the Reynolds number is of the order of 3,00,000. The effluent leaves at about 830-870°C and total pressure of 1.7 bar. The burners are gas fired and are cither radiant or of the long flame type [Froment, 1981]. The flue gas temperature may be of the order of 1,200°C with the inner tube skin temperature of 1,008°C. The reaction is highly endothermic and heats flux ranges from 55-85 kJ/m?. The radiant coil outlet temperature is controlled to achieve desired ethylene and propylene yield [Froment, 1981]. Pyrolysis of any hydrocarbon feedstock is always accompanied by coke formation, which deposits on the walls of the tubular reactor. Under typical operating conditions, the coke formation in naphtha pyrolysis is about 0.01 wt. per cent of the feed [Towfighi et al., 2001]. The furnace effluent is rapidly quenched in USX double pipe exchangers and multi-tubular heat exchanger called TLX in which it is cooled to 350°C. The effluent is further quenched by direct contact with quench oil before entering the quench oil tower, where besides cooling the furnace effluent, the separation of gasoline and lighter products from the fuel oil also takes place. Quenching is essential in order to restrict the polymerization reactions. Ethylene cracking effluent must be quenched uniformly and rapidly for high product yield and to stop olefin secondary reactions which cause coke formation and shorten unit run length. Quenching is basically performed in two ways directly by oil or water or indirectly by a quench cooler or transfer line exchangers. The basic requirements for cracked product quench coolers are: rapid and uniform cooling, small pressure drop, maximum heat recovery, long continuous run length and low maintenance. The cracked gas overhead of the quench oil tower is further cooled in the quench water tower by direct contact with water and is finally sent to primary fractionation column. The gases are separated at the top and are sent to compression section for separation and purification of cracked products. Furnace variables and relationships104 Petrochemical Process Technology are given in Table 4.8. Part of the flue gas heat is typically recovered to produce superheated high pressure steam. Pyrolysis of any hydrocarbon feedstock is always accompanied by coke formation, which depends on the walls of the tubular reactor. Under typical operating conditions the coke formation in naphtha pyrolysis is about 0.01 wt. per cent of the feed [Towfighi et al., 2001]. The simulation or design of radiant coils require detailed kinetics based upon radical reaction scheme and a rigorous description of hydrodynamics and heat transfer. The modelling of temperature distribution in the firebox and the local heat flux towards the coils require detailed formulation of radiative heat transfer. Fuel oil stripper separates wash oil from heavier fuel oil component. Table 4.8 Furnace Variables and Relationships Fixed condition Tube diameter, coil length, convection configuration Operating variables ‘Stearn/hydrocarbon ratio, coil outlet pressure, hydrocarbon feed, heat release, X-air draft Operating restraints TMT radiation coil peak temperature, maximum fire box temperature, maximum pressure drop, maximurn/minimum mass verity Dependent variables Yield pattern, conversion, residence time, coil outlet temperature, fire box temperature, steam produced, furnace run length 4.4.2 Cracked Gas Compression and Dehydration The effluent from primary fractionation column is compressed in four or five stages on centrifugal ‘compressor containing intercoolers and then to a separator drum. The condensate from separator drum enters a stripper where the higher fractions are recovered. The gas before entering the final stage compression is desulphurized by passing through a caustic scrubber containing 10 per cent caustic where the separation of sulphur compounds and CO, takes place. The removal of CO, from gas is essential in order to meet the product quality in which ethylene should be less than 1 ppm. Removal of CO, also protects the downstream catalytic operation. The removal also avoids corrosion and formation of CO, ice in the cold section. Spent caustic is then sent to caustic deoiling drum, degassing drum and spent caustic oxidation unit for removal of hydrocarbon like benzene and polymers. The cracked gases are dried in dehydrators containing molecular sieves before entering the cold section. Plant designed to process higher sulphur content feedstock (e.g. >500 ppm) often contains a regenerative acid gas removal system upstream of caustic scrubber. 4.4.3 Cold Section The dried cracked gas after removal of sulphur compounds, CO, and moisture are sent to cold section where it is cooled to-165°C in cascade refrigeration system using propylene and ethylene. The cold section contains demethanizer, deethanizer, acetylene hydrogenation unit, ethylene separation, depropanizer, C, hydrogenation and debutanizer. Typical composition of cracked gases, product ethylene and propylene from a gas cracker plant is given in Table 4.9.Olefins Production 105 Table 4.9 Typical Composition and Properties of Cracked Gas, Ethylene and Propyiene Component Cracked Gas Ethylene Propylene cH, 20.42 0.9 ppm CoHg 13.46 100 ppm CH, 35.91 Balance CH, 0.38 0.2 ppm C3Hy 0.66 15 C3Hg 1.49 Balance CHio 0.02 CeHi9 Nil Methyl acetylene 0.02 Propadiene 0.03 1,3-Butadiene 03 50-100 ppm H, Balance co, 0.5 Mol. wt. 28.05 42.08 Partial pressure, ka/em? 17.84 19.26 Enthalpy, kcal/kg 25.36 1.41 Entropy, kcal/kg 4.211 1.153 Density, kg/m? 450.964 463.947 Reduced pressure, kg/cm? 0.342 0.411 Reduced temperature, °C 0.847 0.847 4.4.4 Demethanizer The cracked gases after cooling to ~165°C are sent to demethanizer which operates at pressure of about 7 atm in case of low pressure demethanizer or 355 atm in case of high pressure demethanizer. The purpose of demethanizer is to make sharp separation between methane and ethylene. Demethanizer operating performance is very much dependent on its feed condition, temperature, pressure and flow rates. Demethanizer operation is most sensitive to flow rates and temperature and least sensitive to pressure. The demethanizer section consists of three stage fractional condensor, a pre-stripper column, main demethanizer column, demethanizer rectifier and demethanizer overhead rectifier. 4.4.5 Pressure Swing Adsorption (PSA) Some of the steam cracker plants have pressure swing adsorption process to purify the crude hydrogen stream supplied from the demethanizer system. The unit produces high purity hydrogen stream. PSA units utilize multiple beds to provide continuous and constant hydrogen. 4.4.6 Deethanizer The demethanizer bottom portion consisting of ethylene and heavier fraction is sent to a deethanizer which is essentially a fractionator operating at a pressure of about 24 kg/cm? and temperature -10°C. The deethanizer separates the demethanizer bottom into C, overhead and C; is sent to depropanizer for separation of propane.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.aa You have either reached a page that is unavailable for viewing or reached your viewing limit for this book.