CONTENTS CHAPTER 1—Origia, Formation and Composi- tion of Petroleum 1d Origin and Formation of Petrolium 1.2 Reserves and Deposits of World 13 Indian Petroleum Industry 1.4 Composition of Petroleum ‘CHAPTER 2—Petrolein Processing Data 2.1 Evaluation of Petrolium - a 2.2 Thermal Properties of Petroleum Fractions + 2.3 Important Products Properties & Test Methods oo CHAPTER 3—Fractionation of Petroleum 3.1 Dehydration and Desalting of Crudes one 3.2 Heating of Crude—Pipe Still Heaters 3.3 Distillation of Petroleum 3.4 Blending of Gasoline CHAPTER 4—Treatment Techniques 4.1 Fraction—Impurities 4.2 Treatment of Gasoline 4.3 Treatment of Kerosene 4.4 Treatment of Lubes 4.5 Wax and Purification ave Page 1—53 12 19 54-172 34 19 95 173—233 173 178 197 219 234—309 234 252 262 272 295CHAPTER 5—Thermal and Catalytical 5.1 Cracking one 5.2 Catalytic Cracking ose 5.3 Catalytic Reforming 3.4 Naphtha Cracking 5.5 Coking 5.6 Hydrogen Processes © 5.7 Alkylation Processes 5.8 Tsomerisation Processes 5.9 Polymer Gasolines. - CHAPTER 6—Asphalt Technology we 61 Source of Asphalt s 6.2 Air Blowing of Bitumen 6.3 Upgradation of Heavy Crudes Subject Index ve Page 310—416 310 326 352 373 383 402 4iL 417—423 417 420 423 425 —428 CHAPTER 1 Origin, Formation and Composition of Petroleum 11 Origin and Formation of Petroleum : Today, most of the countries in the world are importers of energy. The fossil fuels, accumulated over aeons of geological activity are irreversibly consumed at a rate more-than million times faster than they were formed, This has left us in a pre- carious position especially for petroleum and its products. The hike in price of petroleum and its products, both in national-and international scenes is ftequent for two simple reasons; the mounting demands and fast depletion of reserves. The import- ance df petroleum in. present day civilization is ever increasing due to its unmatched contribution for our energy requirements, in lubrication and in petrochemical field. ‘Thus. its competence to serve mankind is unquestionable and unique too. Sixty percent of the energy needs of the world are met by petroleum. The advent of LC. and Jet engines have revolutionalised the tech- niques of motive power, a fact, without which the rumbling civi- lisation would have to contend with a snails-pace.: Such a pre- ium stock of limited resuiirces is fast depleting, perhaps due to indiscriminate and wanton consumption. The important question today is how long can the reserves meet the demand even with sky high prices? The high degree of conservation and restrictions in consumption may draw out the global re- serves to another century at the consumption rate of today, Then, what-? According to Mayer and. Hocott “There is no dearth of petroleum and natural gas resources remaining in the earth. As a matter of fact, there is no foreseen shortage of available sup-4 MODERN PETROLEUM REFINING PROCESSES hydrocarbon gases. Further, surprisingly no oil well was ever sighted with any fossil remains of such animals. This is how the long flourished hopes of this natural fat theory had to be -given up. . : There are other schools of thoughts concerning the origin and formation of petroleum; some of which are listed. below : Thomas-Graham €1843) was of the view that natural naphtha must be a product of action upon vegetable matter of - high temperature. Chaptal (1845) was of the opinion, that when plants became entirely decomposed into vegetable moulds these contained certain oils which escaped decomposition. J. W. Draper (1846) suggested the action of natural heat of earth on coal. Popoff (1875) showed that methane could be produced by decomposition of cellulose. Hoppe-Seyler in 1886 showed that bacteria could produce methane, as is ever evident in swampy areas. Treibs (1934) discovered some of the plant pigments and biological matter in crudes ; micro-scopic organic remains found jn crudes actually prompted API to launch a big project API 43 to investigate thoroughly.* A bright explanation by Mikhailovosky, N. Potering and N.C. Anderson seems to be near the goal. Accordingly, the source of petroleum was not a definite species of flora as initiat- ed by Engler, but the organic matter of sea oozes consisting of remains of plants and animal organisms. The initial decomtposi- tion of the vegetable and animal matter is a result of activity of micro-organisms ; later the organic matter underwent changes due to pressure and temperature of the crest of the earth. Emphas- izing the fact, Arkhagelskey, prophesied that petroleum took birth in argillaceous rocks enriched with organic matter and later ‘migrated and got stored in arenaceous rocks. The extension works @f P. Trusk and G, Petrov in U.S.A. characterised the composition and content of organic matter in rocks of different ages. Controversies always flare up, one school advocates— temperature—pressure distillation or by tectonic stress. Another school advocates as a biochemical process; yet another sees it purely as a chemical or radioactivity reaction—and so on. However, biochemical** theory has been received with some favour, as it is concerried with low temperature and pressure, and bacteria of versatility. Thus it may be concluded that the ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 5 formation is via a combination of physi iologi «aes sical and biological pro- cesses rather than individually. Petroleum formations) from ganic mass may expounded by two distinct : namely physical and biological, . E ses 1.1.4 PuystcaL METHODS It conjures all the parameters in an’ i reaction ideal depends upon the factors like : : : ma 1. Heat, 2. Pressure 3. Heat and pressure, 4. Catalysts 5. Radio activity. . 1.1.5 Brotocican Meruons : All the biologic methods a: i vents tach ace re governed by source and envi- 1. By preservation of hyd i ydrocarbons synthes: source sediment organisms, vathesised by the 2 Biologi . : A ce reduction (anerobic or aerobic) sources, (a) Fatty acids, | (b) Proteins and amino acids, (c) Carbohydrates, . 3. Biological and “Physical methods, such. as (a) By condensation of bacterially produced methane un . : tayo Pressure and temperature in presence of €b) By bacterial modification of sediments. Arr (ABC) completely relates to the transformation of auanc material into petroleum, C, E. Zobell in his report of is _ Droject mentioned that conversion is genuinely a micro-bio- toe a Process,” Bacteria, as described by Zobell can survive in act in alf critical conditions, from 0° to 85°C, under extreme Pressures “io 0,000 kg/cm? and also at well depths of 10,462 Laboratory tests confirmed that ‘Lipoclasti 1 stic’ anaerobes the pacity to split long chain hydrocarbons to shorter ain “ vidence in biogeneicity does not differentiate between vege:6 MODERN PETROLEUM REFINING PROCESSES table and animal source.’ Close association of crude oil with marine remains suggests ‘hat it is from fish molluscs, lamelli- branches, diatoms foraminiferae and other sea creatures, known from their fossilised remains to have been present in immense quantities in. ancient seas. Preponderanée of petroleum known today is derived from ancient biological matter, particularly from lipid rich lower marine plants such as plankton, Terrestrial plants supply terpens, which suggests the phenomenon of atmos- pheric volatilisation of vegetation, The nature of recent hydro- carbons found, does however support the biogenic origin; the main reason being the presence of odd carbon number. These matters are often referred as kerogen or mother substances for shale, According to Kenneth Kobe, petroleum results from a series of biochemical and chemical reactions which start with organic remains of dead micro organisms.* Bacteria are involved in first transformation of the constituents of decaying micro-organisms into hydrocarbons, Anerobic conditions keep porphyrins to remain in crude ; if oxygeiy had been there these would have been decomposed. Bacteria can also decomposé organic matter to COs, HLS, etc. Further, it is discovered that no bacteria can produce more than C,-compounds, thus C,: to Ci, compounds must have been formed from marine fife as is evident from certain Gambian crudes.® Most organisms are found to generate petroleum in their. meta-- bolic ‘processes too (Meyer and Hocott). Crude’ oils found in the younger sedimentary deposits do in fact contain appreciable amounts of oxygen and_ nitrogen. This shows organic material as the source. “McNab et al divid- ed crudes into three types depending upom the time of deposit? Tertiary crudes : 11X10°—74X10* years of age (Eocene oil) (asphaltic crudes) Mesozoicera oil : 75X10°—200X10* years of age Paleozoic crudes : 200% 10°—500X10* years of age (Parraffinic Crudes) Brooks and Frost concluded that the organic matter can be decomposed easily under the action of natural catalyst as well as bacteria1 The evidence of bacteria in sedimentary ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 7 rocks is positive and the organics are initially decomposed to acids and gases (CH,), till the activity of bacteria ceases due to frankensteinism. I, M, Gubkin demonstrated that the formation of petroleum and gas. from organics, scattered in argillaceous rocks .was a local process and started really with accumulation of organic matter in sea oozes, be it the tats or carbohydrates. Apart from this, sothe. scientists regard that the hydrogenation ‘of carbon oxides results in-CH,-chains, which may be congenially taking place under the catalytic activity of earth’s crest under favourable conditions of temperature and -pressure. But this is only a derived literature thrusted to explain and can never match with the quantum of oil. Thus every new thought merely results in more sterile addendum. The overall explanation hitherto may be summed up in two steps: firstly the action of bacteria in contributing the lighter fractions, secondly continuous catalytic action of earth at depths of 1-2 Km to yield heavier hydro- carbons. It is observed with the depth of mine and time of formation and storage, the API gravity of crude and paraffincity increase becausé of severity of reactions, which is in full agree-- ment with the above picture?" , _ These are all possible natural reactions occuring over the ages, and petroleum hydrocarbons might have been formed by many processes and each contributing its own share, may be small, In conclusion, regarding the biologic origin .of~ petroleum there need not be any doubt, because of the oil assaciation with sediments containing a relatively large amount of organic matter, the presence of optically active compounds and complex sub- stances ‘of obvious biologicat origin. Oil is alsa absent from formations having adequate traps and porous stra‘a, but with- out any organic material, The formation is at low temperature, usually less: than 200°C or even 100°C. The thermophilic bacteria (bacteria that can survive at high temperature) plays the major role in conversion of this organic mass into liquid hydrocarbons, 1.2 - Reserves and Deposits of World : There are very few parts.of the world which are self sufficient in energy. USSR and Eastern Europe are largely self8 MODERN PETROLEUM REFINING PROCESSES sufficient in energy and they never look for outside supplies of oil. Middle East, Africa, the major oil producers are exporters of huge energy, while Japan is a jeading importer of energy. U.S.A, is~also energy producing country, but its commitments have grown to such am_extent, that it is now a major importer of energy. Petroleum deposits maitily ‘occur in some elevated sections of porous sandy strata."* Sedimentary rocks accumulate in sea bed’ at a very slow ‘rate. These layers over millions of years stratify under pressure and temperature and are transformed into metamorphic rocks, sand stones, marbles, ,etc. These are the basic reservoirs of gas and oil. Whenever fissures and! disloca- tions in zones of earth occur, oil and gas reach surface and get burnt continuously by accidental fires” like lightning, ete. and sometimes oil drains to nearby streams too. A false understand- ing prevails that volcanic eruptions are followed by huge quanti- ties of hydrocarbons, It is seen coal is more uniformly distributed throughout the world rather than oil; oit is scattered randomly -and 80% of oil found to date occurs in what has been called oil-axis-pole.“” Gulf Carribbean, Mesopotamian and Persian Gulf are such areas confined to depressions on earth’s-erest: ' Initial migration. of oil takes place during compaction of dense shales.* Although the migration mechanism is not fully understood, evidently it is not effective, with the result, much oil is left in the formations. At present oil from such source is not economically recoverable. Bacteria in marine sediments may also contribute to the liberation of oil from oil bearing materials in various ways. According to Stone and Zobell obvious import is the bacterial ‘decomposition of organic complex in which oil is trapped. Secondly by dissolving carbonates or sulfates on which oil is absorbed by action of bacterial: acids. Thirdly bacterial gases reduce the viscosity of oll. . In Soviet Union, the South Caspein Bas'n, Ural-Volga Basin, and Western Siberian Basins are famous for hydrocarbon deposits which rank next only to Irano-Arabian Basin, the richest in the world, Once the richest basin, Aspheron-Peninsula has been ex- Phoited since last hundred years, An idea can be had through ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 9 ‘approximate records that oil extracted throughout the world till 1975 is about 43,000 MMT, a considerable amount of which was produced during 70’s only. Kuwait, a small country with 18% of world reserves hald its 4th position for a long time in the production of .oil after U.S.A, ULS.S.R. and Venezuela, but. now Iran and Saudi Arabia have, surpaséed Kuwait. Saudi Arabia is about 100 times bigger than Kuwait and is ranking next to Iran with 10MMbbls, per day. Kuwait is producing approximately 1.25MMbbls. per day. U.S. crudes are relatively less sulfur ones and make up about 7% of world reserves.* Venezuela and African crudes of relatively low sulfur content constitute about 10% world oil reserves. African countries like Libya, Algeria and Nigeria account to abott 300 million tones- per annum. A. characteristic feature of the oil wells near Middle East is high yields per well. Iraq and Iran are famous for such types of wells, which can produce: even 10,000-20,000 tons per day per well. Thus near and Middle East countries with highest proven reserves of 70% of world’s petroleum stock holds the controk in the, energy export. At ‘present the trade is: governed by OPEC*; fortythree percent of world’ crude produced in 1972 was shared among ‘the group members, which is-very much true today also, 1.2.1 Wortp RESERVES ~ Several estimates of world hydrocarbon reserves were made by. almost all leading institutions: and companies. As .furnished by Weeks the estimates of proven reserves are 1,900X10° bbls of oil against the estimates of Warman (British: Petroleum Com- pany) 1,200 to Z,000X10° bbls. There is no congruency of expression in these reserves; one can judge by the: following ultimate reserves as presented by Richard G. Sieidl**, how the estimates once cited regularly change with better methods of surveys and techniques. *OPEC : Organisation of Petroleum Exporting Countries A 13 Mem- * ber body consists of : _ . (4) Algeria, (2) Iran, (3) Iraq, (4) Saudi Arabia, (5) Gabon, (6) Kuwait, (7) Ecquador, (8) Libya, (9) Indonesia, (10) Nigeria, (11) Qatar, (12), United Arab Emirats, (13) Venezula,10 MODERN PETROLEUM REFINING PROCESSES 1965 Hendricks 2,480 X 10° bbls 1968 Shell Company 1,800 X 10° _,, * 1970 Moody 1,800.X 10° _,, 1971 U.S. National 2,670 X 10° ,, Petroleum Council 1972 Weeks (8th WPC, 3,650 X 10° _,, 2, P 99-106) 1975 Whiting (recover- 556.2 X 10° bhis and (Jan. Ist) - able) 80 X 10" cuM., gas. 1977. Harry Warmen’® 270 X 10° Tons of oil (Jan, 1st) (recoverable oil reserves) Gas equivalent to 55 X 10° ton of oil Total proven. reserves as per Whiting goes upto 2,2000X 10° bbis of oil and.250X 10% Cu.M. of gas; of which 30% will be a offshore product and rest onshore, Cumulative oil production of world till January 1974, was put around 270X10° bbl oil and 20X10" Cu.M. of gas... . Next to coal, natural gas reserves of 60 billion tons oil equivalent are highest in the, world ; with a proven to potential capacity of 30% for gas and 60% for oil, the.chance of finding more. amount of gas is always bright. John J. McKetta®*’ et ‘al have presented the following data on the available energy of today (1980): and estimates of feserves of energy sources : Available energy today : Fossil Fuels Oil 570 X 10° bbls Natural gas 2,500 Exajoules - Coal 637 X 10° Shale 30 gigatons Tar. sands 15.30 gigatons Nuclear. Source 3100 MW. ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM i Renewable Energy: Geothermal 132 MW Hydroelectric 5.7 Exajoules Solar negligible World oil estimates 240-260 gigatons Natural gas 10,500 Exajoules Of which undiscovered 8,150 Exajoules Coal 10,125 billion tons Of which known 637 billion tons reserves Nuclear : Uranium 3 Million tons Thorium 630 Thousand tons Additional undiscovered : 80-280 Million tons Uranium . Exajoule = 160 Million barrels Gigaton = Billion barrels . At present the production of oil in the world is about 2300 ‘MMta and gas over one trillion cubic meters, and is expected to reach a maximum production of 2700-2800 MMta of oil during. this decade and likely to witness a drop in production by the end of this century to a quantity 2000 MMta. A further drop is likely. by“2050 AD to! about 1500MMta. Long range predic: tions are unwarranted, due to the volatile political situations and "war clouds hanging on-every part of the world, Perhaps time may not be kind enough to permit man to utilise the last tonne of oil due to man’s cupidity and insecurity prevailing on every part of the globe. . Fears of impending oil, shortage have raised hopes of find- ing huge deposits of oil even under deep oceans, The activity now-a-days is more confined to such areas. According to Klemme there are 334 giant fields in 66 basins that contains 70-75% of oil. Indian subcontinent is placed. in Type 4 basin (India and Assam) and the costal bet in pulled apart basins. Estimated sedimentary rocks of the world, by D. Ion and Hehdricks is about 62X10" tons, which’ contain an organic e12 MODERN PETROLEUM REFINING PROCESSES matter of 3.510" tons, which in turn can yield a hydrocarbon content of 7.7X 10% tons.17 1.3 Indian Petroleum Industry The world’s petroleum industry dates back to first refinery of 5 bbl capacity at Pittusburg, started by Samuel Kier in 1855. Incidentally the first oil well was dug by Drake in August 1859 at Titusville. Indian oil industry was not lagging very much at its inception, as the first oil well was dug in 1866 and the first refinery started in 1893. Assam Oil Company’s refinery at Digboi was the only major refinery till 1954. People were under firm impression that there was no possibility of finding oil resources in India, International Oil Companies as a group had written off India, as a barren land where there was no possibility of oil being found, except in parts of Assam. The Government of India when it started the refineries on sea coasts it was based on the hope of getting oil from international market. Providence helped India to invite the Russian experts ; accordingly in 1955, a team of top geologists and oi! experts arrived. Discreet surveys made by the team showed promising areas, In a short time, the discovery of Cambay oil field (1958) followed by Ankaleswar, strengthened hopes and launched the collaboration between USSR and India, The birth of ONGC, discovery of new oil fields in eastern and western parts of country, had laid the major path for the country’s progress on the oil front. Since 1949 to 1960 Standard Vacuum Oil Company alone explored the West Bengal basin and -later jointly with Govern- ‘ment of India. Till a year back, the major crude producing concerns in India were Oil India Limited, Oil and Natural Gas Commission and Assam Oil Company. Now all private sector industries are taken over by the Government. Real foundation of oil Industry in India took place during the second Five Year plan (1956-61) when the Government of India launched, a planned programme of exploration, production refining and distribution of oil. Accordingly ONGC took birth in August 1956 with assigned duties of exploration and produc- tion of oil, on-shore as well as offshore. Next to come into oil field was Oil India Limited a joint venture of Government ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 13 of India and Burmah Oil Company (1956), whicti was given lease to explore and produce oil in North-Eastern parts of India, Indian Oil Corporation Ltd. floated in 1958 had come into éxistence with the objectives of procuring, processing of oi and distribution. It has been divided into two wings as Refinery Wing and Marketing Division. The Refinery Wing takes care of procurement, processing and installing of new refineries,. while the Marketing division takes all necessary steps to distribute the Products to every corner of the country and export certain products, . Compared to developed countries, like USA, where 30% of reserves were already consumed, the developing countries, parti- cularly India has a bright future. 1.3.1 OIL AND Gas SCENE : India’s sedimentary area is about 1.42 million sq kilometres, of which 0.42 million sq.km is offshore area, spread over 6000 km coastal line, and 0.4 million sq km area is available in the form of continental slope, while the remaining area is land based."* India’s offshore basins are divided into 8 regions as shown in Fig. 1.1. The hydrocarbon potentiality of the entire area is 15 billion tons. The biggest offshore activity started with the discovery of Bombay High in 1973. Prior to this, seismic surveys launched in 1963, successfully located’ the offshore structures at Adiabet, the mouth of Narmada; other successful areas like Rann of Kutch, Gulf of Mannar,.Cambay, Coastal Kerala, Coromondel Palk Bay soon followed. With the help of Sagar Samrat, self propelled jack up ring, the production at Bombay High started-in 1974. In just seven years, the production increased by 100 times to 400,000 BPD. This was possible be- cause the infrastructural facilities. like separation of gas-oil- water mixtures, transportation through submersible pipe line to Uran.and Trombay terminals were made available, In 1981, a gas processing platform BHN was commissioned. Soon South Central Bassein platforms were added to handle 25,000 BPD. An LPG plant and crude stabilisation were commissioned in 1981 in Uran. The LPG plant capacity of Uran is 0.49 M?TA. South Bassein biggest offshore gas strike finally became the center of gas activity due to the construction of biggest offshore platform.14 MODERN PETROLEUM REFINING. PROCESSES Here the listed activities like separation of gas from oil, pump- ing of crude and dehydration of gas take place. Ratna Platform, a satellite field venture outside Bombay High was commissioned in 1982. Other platforms at Panna and Heera would be avail- able soon. South Bassein free gas can be produced at a rate of 20 million cubic meters/day. This gas goes to Hazira gas com- plex, where sweetening and dehydration etc. take place and this is the biggest of its kind, capable to handle 20 million cubic meters/day in two phases each of 10 million cubic meters, LPG plant at Hazira is. capable of producing 1.52 lakh tons LPG & 1.02 lakh ton NGLS, when full production reaches 5 lakh tons of LPG would be available. 1.3.2 HBJ—Gas Grup (Fig. 1.1 (a)) Associated gas comes out along with the oil; when the oil production has to be stepped up, the amount of associated gas naturally increases, But with insufficient infrastructural facilities to consume the gas, most of the gas (even up to 70%) was boot- lessly flared. In the last decade itself more than 5,000 crores of rupees worth gas was flared. Government has, though launched various plans to conserve energy, renewable energy sources etc. failed in this direction. However, though delayed a gas line of 1740 km joining Hazira to Jagdishpur via. Bijaipur, wasfi nal- ised, And already a stretch of 700 km is completed. This giant line known as HB3 line will have a string of six fertiliser units and power plants of capacity 4000: MW and can supply gas to IPCL at Baroda, and with small additions the gas can reach Faridabad, Kanpur, Saleempur. Petro-chemicals Complex and many other gas consuming units, The capacity of the linethrough is 20 million cubic meters, can carry up to 33 million cubic me- ters per day. 3 million cubic meters per day. Compared to North scene, Krishna-Godavari basin, though activities are pursued lately, has come up with a blueprint of utilising gas. Presently 60,000 cu metres of gas per day through asmall pipe line of 72 km long joining Narsapur to Kovvur has come into operation.’ Smal! lines like this will be laid to link up power plants at Vijayawada and Fertilisers at Kakinada, when the gas production exceeds a million cubic metres/day. Presently the capacity of gas collecting modules is only 4.6 lakh ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM : ; ; RAJASTHAN UTTARPRADESH &@ THERMAL POWER ST. COMPRESSOR STATION MASTER CONTROL RECEIVING TERMINAL FERTILIZER PLANT RECEIVING TERMINAL A OESPATCH TERMI oO Ww a pe PIPE ROUTE AWADHYA PRADESH GUJARAT Fig. 1.1 (a) GAIL, HBJ gas pipe line. 1516 : MODERN PETROLEUM REFINING PROCESSES cubic metres based at Narsapur. 1.3.3, ACTIVITY IN SIXTH AND SEVENTH PLANS Of all the quinequennium plans Sixth Plan proved to be the fruitful one*’, The oil production trebled (from 10 M?TA to 30 M®TA), gas production increased many times (2385 million cubic metres, to 9774 million cubic metres). This was possible because of the relentless efforts of ONGC. Oil India Ltd. could provide only a marginal increase in crude production. Though a number of sizeable, small prospective areas were add- ed, a giant structure like Bombay High could not be discovered. LPG production also -increased to a million tons against 6.91 lakh tons in the beginning of the plan. The refining picture was also encouraging. Mathura refinery commenced production, and with expansion of the existing refineries, the capacity touched 45.M®TA from 26 M?TA. The discovery of Krishna-Godavari- Cauvery basin—highly prospective areas—is another milestone in Indian petroleum industry. Against this background the actual 7th Plan performance is distressing. Only ten wells were discovered, three onshore and 7 Offshore. Even the discovered K-G basin could not be vigor- ously exploited. In the terminal year of the plan, with great difficulty the crude production may touch 34 M*T. Bombay High is stagnating at 21.M’ TA. An addition of 1 to 1.5 M°T oil is possible from K-G, Cauvery basins. Oil India and ONGC in eastern region can give no more than 5.6 M*T while ONGC & OIL in western region may add 6-7 M?T, This picture clearly shows the possibility of importing 20 M*T of crude in the terminal year of the plan, along with 3 M°T of products, 1.3.4 CRUDE AND GAS RESERVES Geological reserves as estimated in 1988 amount to 4.5 billion tons oil and 1,2 trillion cubic metres gas. While gas pro- duction in 86-87 was 10 billion cubic metres, it shot up to 14.8 billion cubic metres in 87-88, and the spree of 20-30% increase in gas production in next three-four years will continue. The increase can be more if the consumption facilities can be in- creased from the present level of 10 billion cubic meters. Simi- larly'* the LPG production ‘at Uran and Hazira will reach full ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 17 capacity. The LPG plant at Bijaipur on HBJ line has not yet been commissioned. Presently the LPG sources are: Uran Plant 0.45 (Million tons) Hazira 0.50 » Bijaipur 0.40 (Not yet commissioned) Oil India Ltd., Duliajan —_—(0.40 (Million tons) MRL _ 012 ” Ankaleswar 0.40 » Koyali 0.14 ” Haldia Refinery 0.02 ” Cochin Refinery 0.12. ” Bharat Refinery 0.14 » Vizag Refinery. 0.08 » Barauni 0.04 * Guwahati. 0.01 » Mathura 0.20 (Million tons) HPCL, Bombay gt » AS 1.3.5, REFINING PICTURE AND ADDITIONS The refining capacity has been presently brought up to 50 M? TA and by the end of 8th Plan 70 M’TA may Ee available, However, secondary processing facilities like FCCS and Hydro- cracker were induced into refineries. Three units of 1 M* TA were added to Koyali, Mathura and Cochin refineries, while thg other three FCC capacities were increased (HP, Bombay, Vizae & MRL). With these additions secondary processing facilities went up by 7 M*TA. Hydrocracker is another new addition at Koyali refinery. Plans are ready to errect two refineries each of 6 M°TA at Karnal and Mangalore and one more small refinery in Assam and mini refineries at Cauvery basin are likely-to materialise. The capacities of the refineries is shown in Table 1.4(a). eee hydrocracker installed at Koyali would give 29,000 tons LPG, 6.91 lakh tons of HSD, 6.01 lakh tons of superior Kerosene ‘and ATF, followed by 11.3 lakh tons LSHS. Cochin refineries expansion to six million tons, has a provision to instal Hydro- cracker. Thus the FCC-HC-combinations would gain much16 MODERN PETROLEUM REFINING PROCESSES eubic metres based at Narsapur. 21.3.3, ACTIVITY IN SIXTH AND SEVENTH PLANS ; - Of all the quinequennium plans Sixth Plan proved to be the fruitful one®. The oil production trebled (from 10 M°TA to 30 M®TA), gas production increased many. times (2385 million cubic metres, to 9774-million cubic metres). This was possible because of the relentless efforts of ONGC. Oil India Ltd. could provide only a marginal increase in crude production. Though a number of sizeable, small prospective areas were add- ed, a giant structure like Bombay High could not be discovered. LPG production also-increased to a million tong against 6.91 lakh tons in the beginning of the plan, The refining picture was also encouraging. Mathura refinery commenced production; and with expansion of the existing refineries, the capacity touched 45.M°TA from 26 M*TA. The discovery of Krishna-Godavari- Cauvery basin—highly prospective: areas—is another milestone in Indian petroleum industry: Against this background the actual 7th Plan performance is distressing. Only ten wells were discovered, three onshore and 7 Offshore. Even the discovered K-G basin could not be vigor- ously exploited. In the terminal year of the plan, with great difficulty the crude production n may touch 34 M*T. Bombay High is stagnating at 21 M’ TA. An addition of 1 to 1.5 M®T oil is possible from K-G, Cauvery basins, Oil India‘and ONGC in eastern region can give no more than 5.6 M*T while ONGC & OIL in western region may add 6-7 M?T. This picture clearly shows the Possibility of importing 20 M'T of crude in the terminal year of the plan, along with 3 M*T of products, - 1.3.4 CRUDE AND GAS RESERVES Geological reserves as estimated in 1988 amount to 4.5 billion tons oil and 1.2 trillion cubic metres gas. While gas pro- duction in 86-87 was 10 billion cubic metres, it shot up to 14.8 billion cubic metres in 87-88, and the spree of 20-30% increase in gas production in next three-four years will continue. The increase can be more if the consumption. facilities can be in- creased from the present level of 10 billion cubic meters. Simi- larly" the LPG production ‘at Uran.and Hazira will reach full . ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 17 capacity. The LPG plant at Bijaipur on HBJ line has not yet been commissioned. Presently the LPG sources are: Uran Plant *0.45 (Million tons) Hazira : 0.50 ow Bijaipur 0.40 (Not yet commissioned) Oil India Ltd., Duliajan —_—-0.40 (Million tons) MRL _ 0.12 ” Ankaleswar 0.40 » Koyali 0.14 ” Haldia Refinery 0.02 - ” Cochin Refinery 0.12 . ” Bharat Refinery 0.14 - * Vizag Refinery. 0.08 » Barauni 0.04 ” Guwahati 0.01 ” Mathura 0.20 (Million tons) HPCL, Bombay ge 1.3.5, REFINING PICTURE AND ADDITIONS ‘The refining capacity has been presently brought up to 50 M* TA and by the end of 8th Plan 70 M'TA may Be Available. However, secondary processing facilities like FCCS and Hydro- cracker were induced into refineries. Three units of 1 M? TA were added to Koyali, Mathura and Cochin refineries, while: thg other three FCC capacities were increased (HP, Bombay, Vizae & MRL). With these additions secondary processing facilities went up by 7 M*TA. Hydrocracker is another new addition at Koyali refinery. Plans are ready to errect two refineries each of 6 M°TA at Karnal and Matigalore and one more small refinery in Assam and mini refineries at Cauvery basin are likely-to materialise. The capacities of the refineries is shown in Table 14a) aoe hydrocracker installed at Koyali would give 29,000 tons LPG, 6.91 lakh tons of HSD, 6.01 takh tons of superior Kerosene and ATF, followed by 11.3 lakh tons LSHS. Cochin refineries expansion to six million tons, has a provision to instal Hydro- cracker. Thus the FCC-HC-combinations would gain much18 MODERN PETROLEUM REFINING PROCESSES” importance in present day refining of Indian crudes. 1.3.6 Reserves (see Fig. 1-1 (b)) The reserves of India are going up day by day, due to the improved technological skills and massive investments. The 7th Plan additions itself constitute nearly 1000 M?T of hydrocarbon deposits. The following are some known reserves. KG offshore 13 M®T oil and 3 BCUM gas KG Basin 370 M®T oil KG basin wells are producing initially 600 bbls/day. The pro- duction can be increased to 2000 bbis/day per well by intro- ducing early production system (EPS) and the gas flow rates touch as high as 52,000 CUM per day. Amalapuram wells 1,300 bbls/day Mandapeta wells © 52,000 CuM/day Razole, Bhiminipally, Tatipaka, Pasarlapudi 3 M®CuM/day Cauvery Basin 370 M*T Vedanarayanapuram . wells yield 1500 bbls/day (Rich quality oil of 40% gasoline . 25% kerosene ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 19 Bikaneer 25 M*T Jaisalmeer 1 BCu M; 75 M? T 1.4 lakh Cu M/day Tapati Structure 14.2 M? CuM Bombay High(1 RS) 1000 M?T BHN 100 M?T 1,4 Composition of Petroleum Petroleum occurs in nature in all three possible states solid, liquid and gas. The liquid petroleum is usually coloured from dark brown to bluish black or black, exhibiting some times’ bloom or fluorescence. The semi-solid or solid petroleum is well known by the name pitch, usually black in colour. The famous pitch lake of Trinidad is an example of such vast deposits of petro- leum in solid state. Such kind of deposits ate assumed to form after the evaporation or migration of lighter fractions, The gase- ‘ous deposits of petroleum are known as natural gas deposits, where sometimes wild gasolines’ are also accompanied. Gas from condensate reservoirs contain a good portion of lighter - fractions of a boiling point upto 30°C. Associated -reserviors contain gas mainly in‘dissolved form in liquid petroleum. Although the composition of petroleum depends not, very. much on the origin of formation, but certainly change with the time of formation, storage and different stratas through which it migrated. It is a homogeneous mixture of various hydro- carbons of saturates and ring-structures. The average ultimate composition of petroleum is mainly given in terms of consti- tuents of hydrocarbons, namely carbon and hydrogen as follows : Carbon : 84-86% 11% Diesel) Bhuvanagiri'wells 150-200 bbls/day Gas’ 52,000 CuM/day Nagapattanam wells —:150-200 bbls/day Madanam coast wells 4,300 bbls/day Assam Free gas 34 BCu M Associate gas 27BCuM Assam/Arunachal 59 M°T Assam-Arkan Basin 3 Billion ton Hydro-Carbon (One lakh sq km) reserves Tripura gas fields 881 BCu M (Gas yields 1.3 lakh Cu M per day) Rukia 4.5 lakh Cu M per day) Rajasthan Hydrogen : 11-14% The other major elements of importance are sulfur, oxygen and nitrogen. These elements in hydrocarbons are usually treated as impurities because of their inherent properties like odour, colour corrosiveness etc. Generally these three elements com- bined, do not exceed 5% on an average. Exception to this state- ment can be traced im some Gulf crudes, Russian crudes and20 MODERN PETROLEUM REFINING PROCESSES ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 21 Mexican crudes. Ratwi (Neutral zone) contain as much as 5% of sulfur alone. Middle East and Gulf crudes contain upto 3%, compared to these, crudes from East possess very less ‘amount of sulfur, examples being Indonesian, Indian, Nigerian, and Libyan crudes.* The crudes of U.K., like Beryl, contain upto 0.5% sulfur, The bulk of petroleum is made up of hydrocarbons. of saturated compounds like paraffins, naphthenes and unsaturated cyclic compounds mainly aromatics, The highest carbon atom present in the ‘crude is Cro. Further, except first few hydrocarbons, ajl other hydrocarbons exhibit isomerism. The general properties of these homologous series are discussed below : 3 i te 33 14.1 PaRarrins me GyHeass isthe general formula of paraffins. First three - 2s compounds are gases while compounds upto Cy, are liquids and $e beyond that, they assume semisolid consistancy. Well ‘beyond ok Cyo assume shape of solid blocks, sometimes even crystalline By forms. . There are number of isomeric compounds for each com- 23 pound, profoundly differing in properties, For example, upto : G, no isomers are possible, C, exhibits only two isomers, as 3 shown here : : . & c i i é | 3 + C-C-C-C C-C-C i g »-butane i-butane ¢ REFINERY REFINERY aXD PETROCHEMICAL SEUTMENTARY AREA’ And C, exhibits three isomers. The number of isomers increases as the number of carbon atoms increase. C.sHy, exhibits 802 isomeric forms. MAMANAD! 12,010 444m VIL BENGAL VI ANDAMANS 35,860 04 kon sYwpos ZZ 14.1.1 General properties of porafins Paraffins are stable, not attacked by sulphuric acid or other oxidising agents. However, paraffins of higher order > Cy are Prone to oxidation. Even usual oxidising agents like potassium permanganate can cause good amount of oxidation, The apti- tude to contribute the substituted products with halogens has magnified the petrochemical industry, Higher paraffins are very22 MODERN PETROLEUM REFINING PROCESSES much insoluble in water ; though the.lower ones are soluble in ethers and alcohols. (Fig. 12) _ 7 “Paraffins upto’ 3 carbon atoms have inclination to form hydrates such as CH, 7H,O, CzH..7H.O and these hydrates offer clogging and corrosion difficulties. Hence drying is essential before usage. , . The specific gravity of the series increases with molecular weight, still paraffins have less specific gravity andl. boiling point than aromatics. Viscosity of paraffins is less but viscosity ,in- dex is high im contrast to aromatics. -The smoke point of the paraffins is very high, with: poor illuminating characteristics, The pour point of paraffins is usually high ; due to this paraffin rich crudes and products bring difficulties in transporation and storage. Isomers differ from m-paraffins by having slightly low boil- ing points, low pour points, high viscosity and viscosity index. Usually “é-paraffins, are more reactive than n-paraffins but burn like n-paraffins without much illumination and smoking, 340 240 120 (1), ALKANES (2) ALCOHOLS +03) ACIDS BOILING POINT, °C 8 6 8 2 16 20 CARBON ATOMS Fic, 12 Boiling points of first fety alkanes alcohol and acids High molecular compounds (> Cy). may be of saturated or unsaturated nature, decompose if exposed to a temperature of above 370°C. Vacuum distillation is essential for distilling such boiling stocks to prevent them from thermal degradation. ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 23 1.42 Unsarurartes (Olefins and Properties) Olefins are represented by the general formula C,Hz,. The first four are gases and upto Cys are liquids and beyond Cys are solids, The boiling points of olefins are generally lower by few degrees than the saturated compounds of the same carbon number. Chemically these differ very much from paraffins. They are easily attacked by sulfuric acid and some of them even polymerize, Treat- ‘ment with sulfuric acid and subsequent hydrolysis yields alcohols (ég. isopropyl alcohol) and with permagnate oxidation, glycols are formed. Unsaturated compounds like olefins, diolefins, in general, do not appear in crudes to measurable quantities, however they are detected in some crudes, These unsaturates are mainly formed during cracking operations. The absence of unsaturates to a large extent can be best judged by the probable catalytic activity of the earth’s crest in converting unsaturates to saturates and ring structures. (1.4.3 ACETYLENES AND PROPERTIES (ALKYNES) The general formula for this series is C,Hay-2 These are isomeric with diolefins. Acetylenes yield crystalline compounds with ammonical solution of copper salts and are-attacked by sul- furic acid, Acetylenes can be readily hydrogenated to give stabie compounds. 144 DroLerins - These are represented by the formula CyHen-2 Like other unsaturates, these are produced during cracking reactions, These can be distinguished from acetylenes as they do not form salts with ammoniacal solutions of copper salts. But with mercuric chloride these form precipitates and sulfuric acid polymerises these un- saturates. 14.5 NaPHTHENES These are saturated ring compounds bearing the general formula C,H2,. The prominency of ring structure starts with | five carbon atoms. Although Cs and C, ring structures,?* are in existegce, their stability is decreased because of excessive strain (Bayer’s Strain Theory). Naphthenés are isomeric with olefins but differ profoundly in properties, Naphthenes exihibit both thea4 MODERN PETROLEUM REFINING PROCESSES, properties of saturated paraffins and unsaturated aromatics, the result of which, all the properties like sp. gravity, viscosity, pour point, thermal characteristics lie in between the two mentioned homologues. Usually, all the ring structures are having branched chains, where the isomeric character predominantly occurs, followed by positional isomerism in rings (Fig. 1.3). 1.4.6 ARoMatics The first ‘and smallest of the aromatics is benzene; other simple aromatics to follow are toluege, xylene, cumene etc. Even though benzene is unstaturated, yet. it follows the principles of substitution with halogens rather than addition, This is mainly due to symmetric grouping of closed ring structure and. resonance, Aromatics are usually having .high boiling points, low pour points (freezing points), high octane numbers, high viscosity and low viscosity index and these burn characteristically with a red flame with much soot. As these behave like saturates, they resist oxidation: In petroleum fractions aromatics beyond 3-ring structure (Anthracenes) are probably non-existent. Aromatics usually extend their presence from a temperature of 80° C onwards and well dominate in lower middle cuts and heavy cuts. Actually the light aromatics (BTX) do not exceed even 5% of crudes of general nature. Bulk of the aromatics are with side chains and naphthenes and exist in heavier portion of crudes. 1.4.7 Inorcanics : Sulfur compounds: Sulfur is found in most of the crudes ‘in variable amounts. Generally sulfur compounds are present in more quantities in higher molecular weight stocks. . Usually the sulfur content does not exceed 5%, however rare exemptions are : Venezula (5.25%), California. (USA 5.21%), Qaiyarah (Iraq—7% ) etc. crudes. . Sulfur in crude occurs in different forms jike free sulfur, hydrogen sulfide, mercaptans and thiophenes etc. These are frequently occuring compounds in almost all fractions of the crude though to a. different degree. Heavier fractions contain sulfides, polysulfides, sulphonates and sulphates. Sulfur occupies prominent position in refining due to its ominous problems of corrosion and odour, Pollution problems ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 25 ALKANES (CaHay.2) aeeee : 1 n- HEXANE H-¢-C-C— -C-C-H H HH HHH ISOMERS of C, ’ 2,2 Dimethyl butane 2.3 Dimethyl butane: Fic. 13 Structures of some organic compounds% MODERN PETROLEUM REFINING PROCESSES OLEFIN (TERPENS) CaHong __AROMATICS tenet ere] cal | ISOMERISM IN AROMATICS ~ GHs | CHs CHy ; ICH 1,2, 0-Xylene 1.3 mexylene . p-xylene Ethyl Benzene Mesitylene Cy Hy Hs . -CHs CHy ; Coy" : Hy Trimethyt benzene 1,2 Ethyl Toluene cHs : 1,3 Ethyl Toluene 1,6 Ethyl Totuene . Cas Fra. 1.3 (Cont.) ‘ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 27 OLEFINS (Cn Han? Y- Butylene (iso -butylene) CYCLO -PARAFFINS( Cy Han) Cyclo-hexane Cyclo - butane Cyclo - pentane DI -OLEFINS ( Cy Hon-2) CH2=C =CHz Allene CH2=CH.CH=CH2 Divinyt ( butadiene) CH)=C(CH3).CH =CHy Isoprene ( 2 methyl» 1,4 divinyl } _-CHy= C=CH.CHa ACETYLENE (ChHan_a) Cac HC =C-CH3 Methyl acetylene or Propyne-1 or Allyne CHy-C =C-CH, C,Hs~C #C-CH, Crotonylene or Butyne -2 Ethyf methyt acetylene or Pentyne-2 Fic. 13 (Cont)zB ‘MODERN PETROLEUM REFINING PROCESSES Mercaptans Ethyt mercaptan ‘Sulphones Heptyl Sulphone Sulphides Dimethy! sulphide Di Sulphides Dimethyl disulphide Sulfoxides Dimethyi suttoxide Thiophenes Butyl thiacyclohexane Sulphates. (CyHan +1)S04 R204 iow) Thio benzols Sulphonates es RSs Carbony! Sulphide cos . Cyclohexyi sulphide Cyt Thio cyclo heptane Fie. 1.3 (Coni.) ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM NITROGEN COMPOUNDS = |e © Methy! Quinoline Fia. 1.3 (Cont.) 29MODERN PETROLEUM REFINING PROCESSES OXYGEN (Naphthenic Acids ) compounns on oH ‘OH Porehyrins Fic. 13 (Cont.) ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 31. and following cost of waste treatment is punitive for all refiners with high sulfur-stocks. However, refiners habitually remove more detremental sulfur compounds and leave the less harmful ones into the products, as seen in the case of sulfides converted to disulfides in gasolines. Some of the sulphonates are regarded as good emulsifiers and detergents, hence promptly extracted for use in cutting oils. Conspicuous effect of sulfur is reflected in increasing the density of crude. : A correlation presented by Obolentsev* shows the influence of sulfur on gravity : ep =0,0087 (S%)*+-0.0607 (S%)+-0.7857 at 20° Different crudes are presented in Table 1.1. It clearly shows the effect of sulfur on API gravity of crude and pour point of “crude. All sulfur crudes mysteriously exhibit low pour points. Further, sulfur containing residuums when cracked leaves cross linked structures, resembling the phenomenon of’ valcaniza- tion of rubber and offer perennial problems in desulfurisation, Its presence in different fractions complicates the refining and treat- ment ‘methods. Yet another problem is, it desists the effects of additives. ‘Sulfur in. gasoline imevitably depresses the effect of lead and demands more amount of additive. When. crude -con- tains more than 0.5% S, it is denoted as high sulfur crude. A terse distinction, at this juncture between sour crudes and sul- ” fur crudes is desirable. _ Free hydrogen sulfide is available in some - crudes, which naturally fosters corrosion. Such crudes are classified as sour crudes ;. other. sulfur bearing compounds are not taken into this account. .The crudes containing sulfur compounds other than hydrogen sulfide a and exceeding 0.5 % are denoted as high sulfur crudes. 148 Oxycen anp NiTROGEN Oxygen and nitrogen do not occur -in free state either in crudes or in fractions, Nitrogen presence in free form is welt known in natural gas only, Oxygen occurs as oxygenated com- pounds like phenols, cresols, naphthenic acids, sulphonates, sul- phates and sulfoxides, Nitrogen exists in the form of indoles, pyridines, quinolines32 MODERN PETROLEUM REFINING PROCESSES Taste 1.1 Exrect or Sutrur on Gravity aNp Pour Point.® ee Crude API Pour . Sulfur % Point °c ‘Cyrus (Iran) 190 233 3.48 Iranian Heavy 308 —206 16° Kuwait . 312 -178 . 250 North Slope (USA) 268 —206 1.04 Quatar Marine (Quatar) 370 — 39 1.50 Romashkinskaya (USSR) 326 —239 161 Bassein (India) 38.45 +30 01s Nahorkatiya 310 +30 0.16 Ankleshwar 470 +5 0.05 Bombay High > 380 +30 very low Arabian (Light) (S. Arabia) 33,4 344 1.80 Atabian (Heavy) (S. Arabia) 28.2 4 2.84 Arjuna (Indonesia) © 377 +267 012 Bu, Attifel (Libya) 26 +30 - 0.10 Basrah “Ciraq) 33.9 . -HIS.O 2.05. Brass (Nigeria), - 43.0 ~206 0.08 Darius (Iran) : 33.9 179 2.45 and: amines, usually well below 2%. Nitrogen compounds -exasperate problems in ‘processing and stability of products. Catalyst deactivation or poisoning, gum formation are some of the offshoots of nitrogen. Nitrogen is present in two forms, basic and “on-basic. Basic nitrogen is characterised by its titratability with perchloric acids, whereas nonbasic nitrogen is not titratable: hence: no possibility of extraction. Most of the Ritrogent’ Pigments impart color to crude and fractions. The interesting "compounds of nitrogen are porphyrins. These are obtained. from living organisms and preserved in petroleum. Tt stands to reason that aneorobic conditions’ were prevailing during . petroleum formstion ; otherwise oxidation would have ORIGIN, FORMATION AND COMPOSITION OF PETROLEUM 33. destroyed them. Chlorophyll** is also a complex of porphyrin, where central atom is magnesium instead of nickel or vanadium or iron. Iron porphyrins are also known as heme, the constituents of red cell in the blood. Porphyrin*® * pigments are. usually associated in complex form with nietals like, copper, iron, vanadium and nickel. The proper understanding of these’ pigments*® 5, may augment the knowledge of origin and formation of petroleum. The following is an example of nitrogen complex : Gravity API — 388 Sulfur wt. % — 02-00% Vanadium ppm. — 05-25 Nickel ppm. — 10-170 Vanadyl porphyrin ppm. 0.7—1130 Nickel porphyrin ppm. © 1.0—390 14.9 AspHALTs, RESINS AND BITUMENS Asphalts are high molecular weight complex molecules, black in color, soluble preferably in aromatic solvents and carbon disulphide. Resins are mostly compounds of highly condense¢ ring structures, containing oxygen, sulfur and nitrogen, some- times inorganics too. Though bitumen is a manufactured pro- duct, it is essentially made up of three components, asphalts, resins and mineral oil. These three components comprise 2 colloidal system ; asphalts are suspended in oi and resins contri- bute to the stability of the system, 1.4.10. Less INorcanics . The other elements present are nickel, vanadium, iron, silica, sodium, magnesium, and halogens etc, Even though the analysis is not desirable as these metals hardly exceed 0.01%, yet may be analysed for sensitive purposes. The ash formation is mainly due to these metals and inorganics. Sometimes organometallic compounds are available in colloidal form. Inorganics always jeave a marked influence on fractions, for example halides may give off halogens during hydrolysis or thermal decomposition, Corrosion, pollution, ash etc, are mainly contributed by inorganics and, the quality of crude and fractions are always debased by these small amounts,