1 PETROLEUM EXPLORATION, PRODUCTION AND REFINING {.1INTRODUCTION Energy is known to play a vital and important role in the industrial and economic development of any country. Petroleum provides a relatively cheap and convenient source of energy as compared to other fuels such as coal and electricity. India is the 4th largest consumer of petroleum products in the Asia-Pacific region and 15th largest consumer in the world However, in crude il production, India ranks 22nd inthe world. The consumption is rowing annually at 6-7 percent while production of crude oil is stagnating. This mismatch totwoon domestic production oferude il and consumption af petroleum products has increased the dependency on imports to 47 percent of erude oil and 15 percent of petroleum product requirements, which amount to 25 percent of India's exports. Petroleum ie the foundation ofthe industrial civilization. It has shaped civilization since the ancient times. Many interesting references connected with the early use of petroleum, especially oil and bitumen, exist in ancient history. The‘eternal fires of Baku’ were {he result ofthe ignition of ol and natural gas from a seepage. Te basket in which the baby Moses was hidden was made waterproof with bitumen, The Tower of Babel was constructed using bitumen as mortar. In the Far Bast oil was used for lighting. It was rubbed into the eoats of camels to eure them of mange. The North American Indians used petroleum as amedicine, The Mexican Indiana valued bitumen as chewing-gum. Christopher Colum- bus used bitumen to make his ship seaworthy. Marco Polo observed that mineral oil burned well fo give both light and heat Its said that when Alexander the Great visited Persia, the inhabitants sprinkled the street with cil and se it alight. ‘The occurrence of crude ail without gas is rare. On the contrary, large deposits of gas cccur withoutoil, such as at Sind (Pakistan), Po taly) and Siberia (Russia). Oil is usually associated with gas in varying proportions known as gas/il ratio depending upon its chemical nature and physical conditions of ‘its occurrence like trap (natural barriers that prevent further flow of oi, depth, and temperature. Presence of gas in oil makes oil mobile and easly recoverable, The downstream products of crude ol on distillation and processing are varied and numerous, Some of the well known ones are fuel gas, petrol, domestic gas~ (LPC), naphtha, kerosine, diesel, fuel ol, lubricants, waxes and petroleum coke. Without oi ships, trains, aeroplanes "and industries will ome to a halt |. PETROLEUM REFINING TECHNOLOGY Ne ee eee ee mine ens eens theo er and ner Fe Neti erage epee pers tecmlgnh eRe ded evs es Da ee eee ering igh er puyol rg ma pct snicaty Race wn de cima oepeien emetic Se pes ee, a a en > wpe rac yee Face tray SK ck pat ln ee pe Les ee ener ened mag otc ena tht an ann rae ee ef tong opener peepee Sep ig rmee pepe peepee rely peg ae oe ee ere Parla peronireey epetoper pore teee ee ee Re ae ere ae ee ere re See a ene el ce ine ee, Shae a hit fe anny oe aden a aan et anes cepa een a a eee eres eee ee ee ee fs ome epee ent ee ae ee een eee nee ee SE pial eg oll carlin operon er re af viniscol ne ca aor a 20 ee ee ccieciae i a ne te eee Te eet ea bennn tenes ler ee EE ET TE see oO femelle ee eo ee i er esenad nee Se ee ee ee ea ee ees era ee ome ernie oil. In a normal oil pool gas remains at the top, oil below it and water further below. These eee a LAND GAS EXPLORATION Oil exploration is a complex process. It begins with prognostication and involves ax entire gamut of activities. The hunt for the hydrocarbons is fcused at the favourable Sr promising areas based on geological considerations. sfological survey aims a cloton hdmapping of uch areas which aati the eritern of being sedimentary rocks preeraly f paving vvia wih the presence of anticline structures of Massie (60 a= of belongs to this era), Gainezic (40 percent of oil produced belongs to this era) and {2D perveat ef cll produced belongs to this era) period. ; i ikaied aliiPETROLEUM EXPLORATION, PRODUCTION AND REENNNG Owing to the presence of fault planes a place, The analysis of surface samples detection of oil and gas is known as prech, Magmietic surveys are then dene ground or from the air by ait-horne mn ‘magnotic attraction on the surface d nd Basures, 1 seepage of tothe surface may take ofall, water andl or gas i uch casos, for emieal prospecting. Magnetometor sorvey_is carsod out ether onthe agnetOMeteF Tes Hated the principle that the ismic method of oil and gas exploration involves genration of wives in the subsurface and picking up the reflected waver by sisiong peoshonte heck ‘up the reflected waves by teaiive geophones which are laid along a line on the suriaea. The time taken for the. retire sguifee the sal Azough the subsurface-rocks-and these can be interpreted to assay ie nataneoocks wal their angle of dip The field stdies are supported by an equally elaborate tting of samples in the laboratory. ‘Sophisticated "modern equipment like "Electen Mlicrorepe, Mens ‘Spectrograph, X-rays Chromatograph, Nuclear Magnetic Resonance (NMR), Spectroscopy, Infra-red, Ultra-violet and Differential Thermal Analysis (DTA) are indispensable aids. On the basis ofall these studies, the most suitable places where ol is ikely tobe ound te Selected for dri 1.4 DRILLING FOR OIL AND GAS ‘The drilling equipment (shown in Fig. 1.1) consists of a tall huge tower called ‘derrick’ anchored to the ground, engines, mud pumps, water tanks, draw-works and many other modules. ‘The travelling block is suspended from the crow block ia large pulley at the top of the derrick). The swivel, attached by a large hook to the travelling block, can rotate freely, land the kelly is fitted onto this. Rotary table at the centre of the derrick floor holds the kelly (which has a square or hexagonal cross-soction) and can be rotated at a desired speed by the engine. To begin drilling, the Kelly is hauled up the derrick its bottom is fitted with a drill bit and lowered through the rotary table until that bit is resting on the earth. With the starting of the engine, the rotary table rotates the kelly and the drill bit which is pressed hard against the earth by the weight of the drill string above, cute and penetrates the rock at the bottom, “Much of the success of drilling depends on the quality of mud which isa specially prepared slurry of water, various chemicals and adhesives like barytes, bentonites, xanthanito. It is pumped through the drill column to carry out several important: functions such as removing cuttings to the surface, cooling the bit (heat generated is due to friction), lubricating the to reduce the hook load, retaining the side wall of 1¢ the hole by lowering a variety of instruments ts the formation fluids from running into hit, providing buoyancy tothe drill string. the ell from caving in, allowing to examin and balancing the formation pressure that preven so heat ine crgea en earatnedace a TToavoid this, a casing pipe is introduced into the hole, The annvlar portion between the hole ‘and the casing pipe is cemented. Further drillingis carried out with smaller diameter Bes0 sta certain depth a smaller diameter casing isintroduced and cemented in the samemannPETROLEUM REFINING TECHNOLOGY ron bec Drill outings Bit () (o Fig. 1.1 (2) Ding equipment (erick (0) Perforatonsn casing pipes to test ormaton Mu Coring is done to get a factual sample of the drilled rock to know its composition, its Physical properties like the grain size, porosity, packing of grains, permeability, its angle of dip, the fluids such as water and gas or ail, if present, and the evidence of life atthe time the rock was deposited. Coring may be of different types, namely, conventional core, side ‘wall core, rubber-sleeve coro, diamond core and wire-line core. While drilling, the geologists eontinuously collet, wash and examine the rock cuttings _ thatcome up tothe surface with mud and ascertain the nature of the rock and its fossil content..TION, PRODUCTION AND REFINING JoLEUM, EXPLORATION, perties, J principle that diferent rocks have different physical and electrical Pro Based 0 0 Characteristics ofthe su-ourface rocks are studied ere ‘er ion, sample ofthe Huds inthe well ean alo bo Drought upto the surface bY Jn\Mjevices calle dnilstem toot (DST). -During ding one often” encounters ‘Feu complication. The dil may ot tuck upd of te wall may cam ca es Racayt cesta ie dat bined are ed andres hy computer od msn te A by _gelopsto, geophysics, chomints and reservotr engineers jointly, They dei reed snast likely areas that could be dug up for oll. At this tage, the well ix taken over to ee oe ewe he oe en Ee ta ubseauent exploitation estas Inorder et he omatin ie allowed to cane nts the wl hy perforating the casing pe at the desired places with the hepa perforating em. The mud is gradually Spl hy watr Thon the hydra pressure. is" progressively reduced against the ‘maton premur. When the formation pressure exceed the hyleuptieprereo tel, the frmaton id borne to enter into the well The well then under production and the fluid is allowed to flow under controlled conditions through a choke or a bean. at produces ol, the well scaled an oil well and if it produces gas escape iti called a gas wall The oll and gas escape through a pressure vessel called separator which separates oil, £95 {nd water at reduced pressure, Ifno oll or gas is encountered, the wells abandoned dry At the initial stage oil and gaa rise to the surface under their own formation pressure. With continued production, formation pressure decreases and the viscous oil and gas cease | tm bosetfowing. Asa result, artificial iting such as sucker rod pump, water or gas injection tr plymer injection s employed for maintenance of pressure, pera 1.5 PRODUCTION OF CRUDE OIL AND NATURAL GAS rude petroleum is found inthe void spaces of porous rock along with gas and water. It is trapped under pressure beneath impermeable rock formations When the trapped formation is pierced, uid flows out ofthe trap into the well bore, The fuid in the well-bore in ited out ether naturally by the release of gas that lowers the head or with a mechanical bump to maintain the influx into the wellbore, However, the withdrawl of the. faid rose the reservoir lowers tho pressure therein and in turn’ the influx Fate into the well bore decreases, This-rate eventually decreases toa value insufficient to pay for the cont of lining ail accounts to only 15-20 percent of original il ia place. In some oil reservoirs which have a continuous aquifer the reservoir oil is replaced almost volume to volume by water and pressure decline is very gradual, This incrence ac recovery efficiency to the range of 40-60 percent of original oil in place. ‘The enhanced oil recovery (EOR) is Practiced in two stages: (a) Secondary recovery (b) rity recovery, The most popular conventional type of secondary, sesssery opie, the cuitural water drive reservoir, Water is injected into a series of wells n onlor ae tee, © adjoining producing well, Water, because ofits higher density, relatwvele choses reaettY operations than reservoirs operating under dri i rat v ler driving forces, particularly gas cap drive the depleted scat & Problem since the moving ol and/or the displacing fluid may pase ide It docs mor a, £28 cap. Water, however, has two major probleme that impede its efficiency. a egiish all ofthe oil from the pore spaces as it moves through the reservoir rock. “70 Percent of the oilis lft behind in the form of emall droplate ele within the larger iPETROLEUM REFINING TECHNOLOGY pores Second limitation is that the advancing water front bypasses significant portions of ro reservoir due’ to dificult well plocementa and unexpected geological configurations ‘This lack of perfect sweep efficiency is responsible for leaving Sehind crue ll in areas nat ‘ached by water ood. ‘Anumborof methods/techniques are employed to rocover the remaining oil The different techniques may be broadly classified into three categories: (a) Misciblefimmiscible displacement process + Miscible hydrocarbon displacement (LPG enriched gas & lean gas) «Carbon dioxide injection + Inert gas injection (Nitrogen, air, ete.) (&) Thermal recovery processes ‘= Stoam stimulation * Steam flooding (ineluding hot water) ‘Tn-situ combustion (€) Chemical flooding processes + Surfactant/polymer injection + Polymer injection + Alkaline flooding Selection of @ suitable EOR method requires @ careful analysis of reservoir configuration and the oil properties. Trapping and release of fluids from porous media is complex phenomena, For a sperifie system, trapping behaviouris controlled by (i) the pore geometry of rock matrix, (ji) fluidrock properties, in particular, wettability and ‘i) Muid-fuid interactions including viscosity, rock density dilference, interfacial tension and partition coefficient. The general properties of pore system, its shape, size and distribution in the rock plays an important role in trapping of ul. Iti established that (2) ‘Trapping of fluids occurs in unique and reproducible pattems which are controlled by capillary forces, (2) Nearly complote networks of interconnected equal size pores exist throughout the pore size distribution, (9) individual pores have good accessibility with adjacent pores, thereby allowing alternate paths of flow around isolated immobile phases, (4) Fluids can be trapped at pore constrictions for all degrees of wetting, Non-wetting Phases are trapped in discontinuous masses whose lengths are largely determined by interfacial tension and potential gradient. For selection cf suitable EOR methods laboratory investigation under simulated conditions of reservoir are necessary. Mathema cal models (8 phase, 5 dimension) are used to analyze the reservoir geometry. The past Performance of the reservoir is matched to predict the performance of reservoir under different operating conditions. Based on these modelling stuéies, the most suitable BOR ‘method is selected for maximum produetion ofthe oi in place. 1m India, the increase in crude oil production is not significant during the last 45 = ad new Belle with substantial reserve is discovered. The percentage of Samaty Tecovery in the total oil production is gradually decreasing, Rate of production from Bombay High is reported to have already shown the dosing tea Sone othe alt al Sie Gujarat under prevailing price structure have already reached theit mit. On economic terms, both ONGC and OIL may prefer to plug the wel, pullperROLEUM, EXPLORATION, PRODUCTION ANO REFINING 7 the pipe and abandon the field. It is better to use Tt dae mae pee a eo rics evens on al Th ‘ion may not find wide for how much will be produced and when. Gas ivan enriched gas and {optcntcn in Indi 1 i re that natal as or aoe st, func a tay ot su the sal indo nen, Siu awh sant se gut bo nearest ee eT soe evade ior Cont carbon deride in mor, It ‘seoimated that about ah eae ‘is required to recover a barrel of crude oil. Although thermal methods predominate as most successful BOR processes, they may not be. anplicable on a Iurge scale in India, Depth of the Indian reservoir and API values of 8 45 restrict the injection of steam or hot water for additional recovery because of apparently unattractive cost benefit ratio, Ofcoursein Western sector it may be sucessful in some reservoirs. Insiy Ombustion is the most difficult method to predict properly. Moreover, st is economical and successful in heavy oil recovery only. It appears that the chemical flooding viz. polymer flooding or surfactant-polymer flooding may prove successful in India. For ‘alkaline flooding, acid number of the crude must be high which is not so with Indian crudes. Polymer flooding method may become more popular in India not only for its: easy handling but also for the economic returns. Surfactant/polymer flooding is required to be assessed properly, particularly the non-compatible nature ‘of surfactant to various monovalent and Peent metal ions and in Indian reservoirs these metals are plenty, ‘The production of crude oil in India is given in Table 1.1. From a meagre 0.5 million tonnes of al produced from nne of the oldest eilfelde in the wortd-Dighel in Assam, the ‘eaNghous crude production is expected to go up to 44.49 MMTPA (million metne tonnes ‘he turn ofthe century. Till 1947, India used to produce around 0.5 to 0 y ‘katia fields of Assam. After independence in MNT ite public sector companies were formed by Government of India, namely Oil & Natural Gas Commission (ONGC) and Oil India ‘Limited (OTL) to explore and produce oil and natural gas in India fronrboth-ohslre-ana Ofshore Fields. Up to 1960, India was practically depending on imparted crude oi Hef atrook olin Cambay in 195859 andin Ankaleshwar fields (Gujarat) in 1960, aS et has in other parts of Gujarat such as Nawagnm, Abmedabed, Meheans, oe eo rfapt barn, ee, Biggst il feld struck by ONGC was Bombay High offshore fields in Arabian sea in 1974. In 1976, ONGC found a large sour gas reservoir at South Bassein, south of Bombay High offshore fields. Also, gas/ot! was found in smaller aaa cova, Panna, Ratna and Neelam offshore feds in Arabian sea een going through fluctuating fortunes. From & it dipped to 26.95 million tonnes in 1992-99 and ‘produced in the country. This reveals how anmeeves and how much it is dependent on Bombay Eigh. nevuntry is currently about 74 million standard cable an ality forsale i about 61 million standard cubic metres poor the country is in on shore oil* PETROLEUM REFINING TECHNOLOGY ‘Table 1.1 Production of Crude Oil in India Year ‘Grade oil production, ‘Million tonnes 1960-61 0.45, | 1965.66 3.48 1970-71 681 1975.96 8.45 1980.81 10.50 1985.86 30.16 1989.90 24.09 1990.91 38.00 1991.92 30.35 1992.98 2695) 1993.04 27.02 1994-95 32.24 1995.96 35.19 1997-98 33.865, 1.6 PETROLEUM REFINING, OPERATION AND OPTIMIZATION Crude oi in its raw form has got very limited use. By adopting various refining processes in the refineries, crude oils are separated into a number of fractions which are suitable for various uses. Crude oils received from oil fields are stored in refinery storage tanks. From these takes crude cil is fed to the atmospheric distillation unit. All the crude oils are basically mixture of hydrocarbons which can be physically separated in groups of different boiling range by the conventional process of distillation. The fractionation of crude cil yields the following streams in the order of rising boiling range * Methane, Ethane and Propane mixture + Liquefied Petroleum Gas (LPG) + Naphthas/Gasoline fractions + Kerosine/Aviation Turbine Fuel (ATF) ‘+ High Speed Diesel Oil (HSD) and Light Diesel Oil (LDO) + Reduced erude oil (RCO) Depending upon the crude oils properties and impurities present in them, the above Products are further treated to meet the required specification. Reduced Crude Oil is further Aistilled under vacuum to recover some more lighter fractions. This process produces light ‘Yacuum gas oil (LVGO), heavy vacuum gas oil (HVGO) and vacuum residue (VR). In order to meet the viscosity specification of fuel oi, heavy residues such as HVGO, RCO and VR are processed in visbreaking unit to reduce their viscosity. To produce bitumen, the vaccum Liventrd ae rblgen ia Speen Unit. To maximize the production of middle distil- lates, heavy residues such as are processed in fluid catalytic cra 10) unit, Sdrocracking unit and coking unit, Straight run naphtha of los Oeeane Neng pr ‘ncatalytic reforming unit to enhance its Octane Number. Reformate rich in benzene/toluenePETROLEUM, EXPLOFATION, PRODUCTION AN Rerun js used as feedstock for Udex uni it Crtain erudes such as Assam erude de atuee Pome de mies benzene and toluene, Kersine fractions frm cer eanents To naam, Tue donot meet specication on stoke reat ne ernie employed Ko point ofthese fractions, Edeleanu process in usually 1.6.1 Selection of Processes for Optimizati Optimization is the process, ining the bent scheme and fixing the unit conan mining the hes possible way of seleting the processes ites ct. The selection af procoproceasingscherne i to be optimized considering all the objective functions, The Ging ann H Gkcision makingin the selection oi proce ee towing factors would inluence the mee Process scheme fora given refinery + Product slate + Product specification + Tavestment and operating costs + Meritsddemorits of alternative processes, ‘Type of crude. The type of erude tobe processed in a refinery will have a bearing on the process scheme. For example, crudes containing high sulphur require the installation of desulphurisation processes/sweetaning processes for streams, Kerosine from Aghsjari crude has a peculiar problem of colour detericration on storage which cannot be corrected by treating in an Morox unit and hence desulphurisation unit would be required. Some erudes are not suitable for making Tubricating oils, and some are not suitable for making bitumen. Tn some cases the products do not require any treatment like some of the indigenous crudes els Therefore, each and every stream from the crude distillation unit has to be evaluated for making a suntable seheme of treatments/sccondary processing fuslitios Product slate. The capacity of the refinery, the type (lube or nan-lube) and size of the secondary processing units is largely governed by the product slate which in turn is decided by the demand of petroleum products. The process scheme is selected so as to match with the product slate. In India, generally the maximization of middle distillates isthe main criteria. In USA, the production of light distillates particularly, motor spirit is maximized in FCC unit by Keeping high severity operations, Ifthe objective isto maximize FISD in a refinery processing high sulphur erudes, it would be advantageous to provide an FCC unit with a desulphurisation unit either for straight-run gas oil or cycle oils so as to upgrade the heavier ends to the maximum possible extent as limited by sulphur specifications. For extreme maximization of middle distillates, a hydrocracker can also be considered which upgrades the heavy ends to the middle distillates (ATF/kerosine/HSD) better than any other known process. Yield of kerosine/HSD from a hydrocracker is of the order of 80 to 85 percent as compared to about 50 percent from FCC unit. Product specifications. Generally the treatment processes are governed by the specifications of the products, Depending on the type of erude processed and the quality of streams, a judicious selection of treating processes has to be made from a simple caustic wash, Mercx sweetening units to a hydro-desulphurisation unit. The flash point of the middle Gitte are often relaxed, with view to taximine these products, Therefore, to take advantage of such relaxed specifications, it would be desirable to provide « naphtha split column in the process scheme, so that heavy naphtha can be injected into ‘Kerosine/diesel cuts. Investment and operating costs. This isa very important point to be kept in view while fixing the refinery capacity, selecting the processes and sizing the unit capacities. However, the selection of process technology at times may entirely be governed by the products demand rather than by investment cost imitations. Investment costs are function of refinery size and“ eTOLEUMREFNG TES its complexity. Beonomy o sae for the same comply, rele a the Investment per unio rovesngeapastyprogestely sews intone ee, lant sie may become economical and in sme oer cases it may not be eraapar example, some oil companies do not consider it economical to provide FCC Unit of lees {6 MUTA capac Sima, the test trends arto rode gsc Sito 10 MIMTPA pec Some fhe plants are cnsuning high amount of fuels ulies This npc as toe Ioytncdow wil elerng apse, erm uc carson cen conoumption in about 8 tier Can thet of Fld cla erekor Further reser any of napa i onzumod be mest ne Hyaropen raguonent ef yccerecee a tial enray consumption inl rary woul eet the arderot 10 to 1 poet ‘asa be ests Go oan onc ett trek ing tran sitnto, cation snd avait ola exprisn Some ofthe eculoges fr pera stdeckanay epee ayacsbe Menace eas aRpROTaTIONIC Rolie ‘sta Hon eiacecn scsi mpm ty nat br ey aiessoe eal eh ‘Sopaioansushee Connects veuter val ceecacanansebes Demise Hon ffl ol whih naw ning pectin’ clpowher ith be cerive of reducing vl Sbecamctratad tuanl co sng ut Ws spite a ea tar einai, ie polls hesarda any HydreracingCnugha wary ial proses er maiming wie Sataiocheen ayitninooonagy ast lanion west ponte peceattiers are Drocerso no adopod fr et Lndrrracinget eduer we cll autores nk, eeeereestnterente meineeedilichesenannen cerca Niteaghur crude ued crates trom indigenous eres tzaane oes ow cages ‘ie etal eutents would be ble uted to is ps of ecole Maritalemorits of alternative processes. There may be tore than one proces todo ti mre gpa cyan Yr enapin aso aca fue ta emanating ee napiban an ulisntalyecholchas tote modo on te marta ean ortho oronen epeting cas sod quliy of tas prot Teroreaien of emo tk Kerri, apart fom conventional Edleann process ane could peacy choos Safes oom or ld hydroenaten in ender fo improve tho amke oer Be Ge eee at tomatic fromthe lube distin ether furan or poco esestion oad ae PACIty increase, 1.6.2 Optimization in a Running Refinery Optimization ofthe operation ofa running refinery is subjectol to the influence of various factors, There are some factors which are beyond refinery’ entre. These include (@) Crude mixture (6) Type of processing units (©) Demand pattern (@) Movement e (e)_ Product epec ) Brtemal streams @) Industral relations. ‘Those factors which are within refinery’s control ae given below. (@) ‘Toinvestigats the possibilities of improving over processing capacitios not only fr rade oil but also for secondary processing gaits, (®) ‘Toadopt various effetive measures ofcontrlling the erceon/corrosion in processing ‘nits to improve ther servic actors ne sa Ca() Toplan shut downs ofvarious units at opt consumptions ‘optimum time toavoid the increased utilities rete nh pe tet pening ‘more than one product. The blending pattornaf sane se BSD leona tance brs =n tes ned in the heaters and maintaining a proper cea 7 Goatees 1 @ proper control on utilities and chemical composi are being vtilized to ed in the production of 1.6.9 Refining Capacity in Indi: ‘The total refining capacity in India as on 14.1997 stands at 61.55 MMTPA of which 58.55 MMITPA is accounted for by the public sector refineries (Table 1.2), MRPL aceounts for the balance. With the ongoing commissioning of 10C's Panipat refinery, the total refining capacity will reach to 67.55 MMTPA. Several expansion projects and grascroot refineries have been planned to enhance the refining capacity in the country. About 31 million tonnes of additional refining capacity is likely to be ereated in the country in 1999 with the commissioning of a large private sector refinery and completion of the expansion programmes at three public sector/joint sector refineries. The major contribution is expected to come from the refinery being set up at Jamnagar by Reliance. The company has sealed up the capacity ofthe refinery 1027 MMTPA from the earlier plan of 15 MMTPA refinery. Among the publi sector refineries, 10C’s Gujarat refinery hao undertaken a Ra. 740 crore programme to expand its capacity by 3 MMTPA. HPCL's Visakhapatnam refinery has undertaken a Rs, 998 crore programme to expand its capacity by 3 MMTPA. MEPL, the joint venture between HPCL and the Aditya Birla group is expanding its capacity by 6 MMTPA at an estimated cost of Rs. $480 crore, IOC Barauni refinery has an installed capacity of 3.3 MMTPA. The capacity is primarily limited G0 cyane sae 1,1, 9imetylyetohecar ‘Table 2.3 Number of Isomers for Different Hydrocarbons Number of isomers CeHo butane) CoH (pentane) 3 Cathie (octane) (CaHlz0 nonane) ‘CroHlon decane) i Gist (pentadecane) — Caster (cicorane) l (CaoHiea (tetracontane)“The heavier fractions of crude o cana iy NS, gan ad rice | fe Decalin il contai Arenes or Aromaties. These are called aromatics (short for aromatic hydrocarbons) in the petroleum industry. These are unsaturated cyclic compounds and hence very reactive chemically. The first compound in this series is the benzene (Cs Hs). The structure of the benzene can be represented either by means of so-called Kekule formula or a Robinson-Armit ‘picture’. The Kelle structure of benzene is depicted below. H . aa ~ 4 al pu Ly In addition, alkyl derivatives of benzene, e.g. toluene, ethyltenzene, and ortho-,meta-,and para-xylenes, are present in crude oils. These mononuclear aromatics have a general formula Callen -6 Jpn Foxition. eg omen, Ortho Postion —+ 6 2 + Ortho Position Meta Position —+ 5|__J8 + Meta Postion Ye— Para Position Toluene or math benzene conens (Phenyimerore) cH ot gi g yom (Jen, ei, scjene ye etercene) ——(h-datrybeaene) (hfit PETROLEUM REFINING TECHNOLOGY Grade cl also contains polynuclear aromatic hydrocarbons such as biphenyl, naphthal 2, {methyl naphthalene, anthracene, phenanthrene ete. lene, \ Zo Bbneny Naphilene ——Antvacene Prensrtwone ‘The most common mononuclear aromatics found in erude cils are toluene and m-xylene, ‘The possible constituents of crude oils include polynuclear species containing up to at least ‘eight condensed rings. Many polycyclic aromatic hydrocarbons present in petroleum are carcinogens, ‘Alkenes, These are open-chain unsaturated hydrocarbons containing a carbon-carbon, : double bond. These contain the same carbon-hydrogen proportions as the monocyclic cycloalkanes. The first alkene, C2Hs, is known as ethylene (or ethene), and the heavier ‘members follow with the alkane prefix, and either the ‘ylene’ or ‘ene’ suffix. From butene ‘onwards, several structural isomers are possible depending on the location of the double bond within the basic carbon chain. Thus, for example, two straight-chain butenes would be expected, as follows: HHHH HHH Lo iii =C-C-C-H H-¢-G=C¢-C-H ae Hl i 4 H HE a H butt-ene burz-ene ‘The number indicates the number of the first of the doubly bonded carbon atoms, : numbered from the end nearer the double bond. In addition, the typical side-chain isomer is, [ expected, that is, Hs oH \ I c=c ry HCH isobutene (2-methylpropene) ‘The two possible geometrical isomers of but-2-ene are the following: H-C-CHs3 — CHs-C-H ll 1 H-C~CHy H-C-CH cebuzene —tansbutz-ene ‘These isomers are classified by the Latin prefixes cis (on this side) and trans (across) ___ indicating the relative locations of the two end are ete ‘methyl groups, Consequently, there are fournude O1S-CHEMISRY AND COMPOSITION, HOW H-C-H i I H 9, S0.994 20 6._|Naphthenicintermediate > 0.860 333 [0.s76-0.934[ 20-80 7._|Naphthenic > 0.860 38 > 0.934 20 8._|Paraffinic-Naphthenie <0.825 240 > 0.934 20 '9,_|Naphthenic-Paraffinie > 0.860 33 <0.876 [230Table 2.5 IFP Methoa _qqune o1S-CHEMIBRY AND COMPOSMon for ci [molarity coms ra ree le 1 arti Tiers tian 060 7 [More than 07 os Po amen nano Las tian 090 | [i incrnsiatsamnanic pene ea | es a. [Naphtheniciermedisio [Between dehy Betveen 0990-0575 9 [Aromalioparaffinie More then 0.800 [Less than 0.980 = isa ltrmeitg — pene oe Heise Perret rae ‘Table 2.6 Average Characteristics of Heavy Naphtha and Residue as per Base of Crude Oil “Heavy naphiha 2 _[Paraffinie-intermediate | 55-70 | 15-30 | 10-20 | 10.20 | 42Max.| 10-20 3. |Paraffinic-asphaltic 55-65 | 20-30 | 10-20 | 100-600 | 33 Max. | 5 Max. erie 7 Paraffins 125-180 ‘Naphthenes 110-120 a ae the values of Kuop of petroleum fractions can be used to indicate the predeminance ofa particular type of hydrocarbons in the fraction, The main usefulness of the factor lies in the complementary correlations developed between Kuyop and other properties such as hydrogen content, viscosity-gravity constant, specific heat, etc. as well as Kuor of feedstocks ‘and yields of products by processes such as coking ete.2s PETROLEUM REFINING TECH 2.4.2 Correlation Index ‘The eorrelaton index (CD, developed by US Bureau of Mines, i given by the following empirical equation: XS 43640 48840 473.7 G - 456.8 aS (22) where Tp is the average boiling point, °, determined by the standard Bureau of Mines distillation method and G is the specific gravity at 15.56°C/15 56°C. Cl values of a petroleum fraction between 0 and 15 indicate that the components ofthe fraction are predominantly paraffinic in nature. CI values between 15 and 50 indicate 4 predominance either of naphthenes or of mixtures of paraffins, naphthenes and aromatics in, the petroleum fraction. CI values above 50 indicate a predominance of aromatics in the fraction. i : 2.4.3 Method of Structural Group Analy: ‘The method of structural group analysis describes the character of the fraction in terms of elements constituting a hypothetical average molecule having the chemical and physical properties of the sum of the individual components of the fraction, according to their concentration, This method classifies the crude oils into seven classes (Table 2.7). Table 2.7 Denomination and Classification of Crude Oil Classes Class Denomination oferude ole (Caos delimitation by structural index values] 1 [Parafinie lacy 2 72 = 1 [Parafinie-naphthenie Cr 250; Cr + HC 2 80 I [Paraffinie aromatic Ce > 50; &Cp + %Ca2 90 1V__[Paraffinic.naphthenoaromatie Cy 2 50 ; Cx> BCy> 10 V__[Paraffinie-aromatie-naphthonic |seCe2 50 ; &Cn> %Cn % Cy> 10 Vi_|Naphthenie-aromatie Ce 50 ; 950 > Cy Vit |Aromaticnaphthenic Ge < 60, 043 Ow ‘BIBLIOGRAPHY 1. GD, Hobson (ed.), Modern Petroleum Technology, Part 1 (Chapter 9), 5th edition, John Wiley & Sons, New York, (1984). 2. LF. Hatch and S. Matar, From Hydrocarbons to Petrochemicals, Gulf Publishing Company, (1981). j 3. LF. Hatch, A chemical view of refining, Hydrocarbon Processing, Vol. 48, No.2, 77-78 (1967). 4. B.B. Agrawal and LB.Gulati, Trace metals in petroleum and petroleum products; Part I- Occurrence, nature & significance, Petroleum and Hydrocarbons, Vol. 6, No. 4, 193-197 (1972). 5. B.B. Agrawal and LB. Gulati, Trace metals in petroleum and petroleum products ; Part Il - Individual constituents and their signifi Petrol id Hydrocar- bons, Vol.6, No.4, 198-202(1973, wee 6. P. Jones, The presence of trace elements in crude oils and allied substances, The Institute of Petroleum, 73-76 (April-June 1988).3 ___ TRANSPORTATION OF WAXY CRUDE OILS 3. INTRODUCTION Crude oils contain # mixture of light and heavy hydrocarbons. "Typically, a stabilized oil nay contain paraffinic, naphthenic and aromatic componente vs hen ox Ooo te won, polars and asphaltenes may also be present. The lighter components in the crade oil keep the heavier components in solution. This solubility depends very strongly on the temperature. If the temperature of the oil is decreased, the solubility of the heavy hydrocarbons may be sufficiently reduced to cause precipitation ofthese components inhe form of solid wax crystals The polars and asphaltenes may also co-precipitate with wax crystals. The phenomenon of wax separation from petroleum fluids at low temperatures has been a problem to users of Patou products fora long period, Ian our in lubricating il reid ole anderde oils. ‘The presence of wax crystals changes the flow behaviour ofthe crude oil from Newtonian to non-Newtonian. The wax erystalz usually lond to higher viscosity with increased energy consumption for pumping and a decreased capacity, In addition, if the oil is cooled during transportation, the wax crystals tend to deposit on the colder pipe wall. Wax deposits can lead to increased pipeline roughness, reduced effective diameter, more frequent pigging require- ment and potential blockage. If these deposits get too thick, they can reduce the capacity of the pipeline and cause problems during pigging. Wax deposition in process equipment may lead to more frequent shutdowns and operational problems. In extreme cases, wax crystals ‘may also cause oil to gel and lead to problems of restarting the pipeline. Great potential savings can be derived from accurate prediction of wax formation, The knowledge ofthe magnitude of wax deposition ean lead to reduction of insulation requirements, for production and transportation systems. Conversely, problems with wax ean be addressed in an early stage of a project so that sufficient thermal insulation is planned for instead of expensive chemical injection and loss in capacity or loss of availability. Process heat loads can be reduced by increasing efficiency of heat transfer. Capacity reduction in heat exchangers «an be overcome. This reduction results from blockage or vibration problems, The size of export ‘pumps and flow lines can be reduced by an accurate knowledge ofthe effect of wax formation on crude viscosity. The minimum pigging frequency can be estimated. In addition, problems related to start up and shutdown can be solved cost effectively. ‘The erystallization of wax in crude oils causes severe difficulties in pipelining and storage. crystallization of waxes at low temperature causes reduced liquidity of waxy erude oils which considerably hampers the transportation of crude oils through long distance pipelines. _ Several methods exist for handling waxy crudes for ease of transportation. For example, igging the pipeline is useful for removing thin layers of wax oaly. A highly waxy crude may: PEIROLEUM REFINING TECHOLORy 3.2 PIPELINE TRANSPORTATION bee : eae For the transportation of large quantities of crude oils, pipelines are the most economie Ie eects eampartaionby pipeline guaratecs the best protestion rng Environment. Further, thereis no handling of other traffic andno disturbance by noise or ay pollution A continuous supply t the refineries is normally assured arc this isnot endangered By weather conditions such as fog, fey fads, or traffic conditions along inland waterways, such, as high or low water level, ice, ete. ‘However, each pipeline system requires very high investment which should be used most ‘economically, The most economical and efficient operation of a pipeline could be reached by tmeintaining a continuous constant flow rate without any interruption. Also, in respect of« reliableand continuous supply totherefineris, asteady-state throughput, with some seasona] fuctuations due to market requirements, should be envisaged. Otherwise, additional storage volume has to be provided for large quantities of crude oil and this would be very expensive, Interruptions by shutdown of a pipeline are by no means desirable. However, a shutdown may occur due to the following operational reasons: (a) There is an inadequate stock of ol in the terminal. This could be caused by distribution in tanker schedules, for instance, due to weather conditions. (b) There are no delivery requirements by the refineries fed by pipeline. This could be caused by dioruption in operationo of one or more af the proccaring unito of the refineries, fr instance, due to equipment breakdown. (c) A pressure test for leakage control of the pipeline has to be performed, (d) Repair, maintenance work on the pipeline system including pumps is required. nia) T™? PiPeline might be shutdown automatically by exceeding the operational sty limits. ‘These shutdowns are not expected to last longer than 3-4 day. Under extreme conditions ‘one could think of extraordinary long shutdowns. The reasons might be government action, earthquake, strike, war, etc. However, under normal conditions, they are not expected. When transporting waxy crue il, these operational posts of view are of considerable importance. 3.3 WAXY CRUDE OILS ‘The erude oils pumped in pipelines up to the early sixties generally showed normal characteristics in respect of pumping conditions such as viscosity and low pour point. However opening up of remote ol fields in North Africa and India in the 1960's to exploit the low sulphur (but waxy) crudes in these locations, and the need to pump these oils through the ‘uch colder pipelines has led oil producers to study the pampability of waxy erudes atsPoRTATION OF WAXY CRUDE OLS a Wi tobe the waxy. Such a classifi ication was based on the wax content of the crude and its pour it, The characteristics of s ‘ome of these crudes are given in Tabled.1. In contrast, most of ‘the Middle Bast crude oils have a pour point below O °C and wax content less than Twt.% and therefore pose no problems in pipeline transportation even at low temperatures. ‘Waxy erude oils exhibit non-Newtonian behaviour at temperatures below sbout 10°C above the pour point. The wax can crystallize as the erude is cooled to form gel ora partial gel. Under static conditions a rigid gel i formed, but ifthe erude is cooled while in motion, the apparent viscosity will increase but the material remains fluid. Thorofore, the rheological properties are functions of temperature, shear rate, shear stross and past history. Problems in pumping these crudes will occur ifthe tomperatare drops and the fluid becomes non-New- tonian and if gel formation occurs after a shutdown, Te pipeline feelity must be designed to recover from these problems or prevent them, A realistic approach should be developed based upon an extensive evaluation of the rheological behaviour of the crude oil under representative temperature and shear conditions. The two rheological parameters of which knovledge indispensable for transporting waxy crude ol through pipeline are viscosity and yield stress. Before we go further into rheological behaviour of the crude oils, few relevant terms that will be frequently used are defined below. ‘Table 8.1 Characteristics of Waxy Crude Oils Crude oi, “API gravity Pour point, °C. Wax content, wt. [Sizes 38 12 2 cas. 36 « 18 [Naharkatia indian a1 20 101 [Moran (india) 49) 30 135, ahi (Brazil 0 a5 28 Iinas (Sumatra) 36 a5 32 [Bombay High Cndia) 38 30 125 J 83.1 Definitions of Rheological Parameters ‘Shear stress. Consider the steady flow of «fluid in ahorizontal pipe of circular cross-sec- {jan The fui flows with an average velocity af U ina pipe of inside diameter D,'The preseuse Aiference between two points 1 and 2, separated by adistance of Li (Py ~ P), ‘The decrease in pressure in the fluid reflects the applied force causing the fluid to flow and if the flow is steady (ie, no change inthe flow and hence velocity), this force most ho Counter-balanced by a shear force of equal magnitude atthe wall ofthe pipe. If ts is the shave ‘ttess at the pipe wall, then force acting on the fuid at the wall must be —xDL ss, The ‘ssseleration), the sum of these two forces is zero. Therefore, we can write = 1b w+ DP -Po)= (3.1)PETROLEUM REFINING TECHN fi rely shows that the shear stress st the pipe wall is just ‘he above equation merely shows gg, follows that available shear stent inca of expression of oy he length ofthe ie Between (6 pup statons andy particular pipeline (cP avalolo shear stress can be incr meus he Drensre diferene, Th svat section length of pipe, An example of caleslation gf Pressure, Py, andor silat shear sre given Bel [STATION : VIRAMGAN TO ABU ROAD Static head at Viramgan eae ‘Static head at Abu Road Pamp suction -150m Differential head ofeach ofthe pumps at rated flow -294.8:m ‘Two pumps will be operated in series, 400m Pressure drop at Abu Road Pressure drop inthe line 294.8 x 2 + 15)-(261.0-283)-40 =3319m, 855 gm/nl Pressure dep wsn19 288 142 Density of erude at pumping temperature 08 psi Inside diameter of line 3.44" = 1.9599 Line length 2177 km Shear otras 403 » 1.9639 TRITT «3.28 x 1000 = 0,000339 psi 0.000339 2 = PRR, dynes! =23.4 dynavem* If the available shear stress is equal to or more than the maximum force needed ‘overcome the shear stress at the inner surface of the pipe, then the flow will be initiated. Shear rate. Consider two parallel planes of area A, separated by the differential diRASPORTATION OF WAXY CRUDE OILS, a For laminar flow in pipes, fiction loss is given by Pi= Pa) say BF hich can be rearranged in the form Pi Pp Dist) tw. ” : i BUD “BUD ‘Torefore for laminar flow, BUD; Rate of shear = 8U/D (3.3) and for turbulent ow, Rate of shear = (BU/D) Cr aa where Cris correction factor which depends upon Reynolds number. Yield stress. It measures the ability of fluid to restart its flow after shutdown of the transportation system. The yield stress ofan ol, at a given temperature is defined as the shear stress required to initiate flow. Itean thus be directly compared with the shear stress available or allowable in a pipeline. The yield stress of waxy crudes is influenced by its temperature history, shear history, aging and composition. 3.82 Rheological Classification of Fluids ‘There exists arate of shear and shear stress at each pointin aflowing fluid. In determining the rheology of fluids, any one of tho following basic behaviour patterns (fluid types) may be found upon agitation of the fluid at constant temperature. Newtonian fluide. A Newtonian fluid io ono whooe viscosity at a given temperature is independent of the rate of shear. There is a linear relationship between the shear stress and the rate of shear for a Newtonian fluid. The viscosity of a Newtonian fluid at a given temperature is constant regardless of the velocity, previous agitation or shearing ofthe fluid. hada] Newtonian uid] (Now-Newonins ad [rayne issn [“iteatropie (Bheopectic] [Proud plant] [Dilatnt Fig. 3.1 Rheological clasiicaton of tus.aa PETROLEUM REFINING TECHNOLOGY fon-Newtonian fluids. A non-Newtonian uid one whose viscosity ata given tempera ce ride tthear Aad having avisconlty geste han 20 Pa. iiely {bomen Newlonian The viscosity of non-Newtonian fluids may increase or decrease withthe tate of shear, depending on the type of fluid, The classification of non-Newtonian fais is ced in Fig. 8.1 er riane independent non-Newtonian fluids, A non-Nevtonia fluid is said to be time. independent ifthe shear stress at any rate of shear is constant with time. The properties of such fluids depend onlyon the magnitude of theimpased shear stresses and not onthe duration tthe stresses. eae Ti the viscosity decreases with increase in the rate of shear, the fluid is known as a pseudoplasti Nuid, This beheviouris generally restricted toa certain range of shear rates, At 2 very low or high shear rate, aid may be Newtonian Tithe viscosity increases with increase in rate of shear, the fluid is known as dilatent fuia Bingham plastic Muids exhibit a definite yield stress below which no flow occurs (the behaviour is that ofa solid), A finite force must be applied to produce movement. The linear relationship between the rate of shear and shear stress for Bingham-plastc fuids does not passthrough the origin, “Time-dependent non-Newtonian fluids. A non-Newtonian fluid is said tobe time-de- pendent ifthe shear stress changes with the duration of shear. In other words, the viscosity ofsuch fluids at any time depends on the amount of previous agitation or shearing of the uid. [Aud whose viscosity decreases with time at a given shear rate is called thixotropi. Ifthe viscosity ofa flu increases with time at a given shear rate, the fluid is called rheopectic Viscoelastic fluids. These exhibit many characteristics of solids, Their resistance to deformation is proportional to the usual viscous effect, plus an clastic effect that isa function oftime, When the rate of strain of uch a uid is suddenly increased, there is a relaxation time during which the stress changes from its original to a new steady-state value. Equations developed for pseudoplastic fluids can be applied to the steady-state flow of viscoelastic fiuids. Figure 9.2shows the variation of viscosity with shear rate fordifferent types of fluid, Curve ‘number 1 is typical of the response of a Newtonian fluid. A Bingham-plastie fluid is charac terized by a flow curve 2 which is a straight line having an inlercept to on the shear stress axis. The stress tis called the yield stress which must be exceeded for low to commence. The flow behaviour is described by an equation au, 7O" Mar (35) With pscudoplastie behaviour, the fluid displays increasing viscosity with decreasing ‘shear rate. This means that there isa non-linear relationship between shear stress and shear rate. Curve number 3 represents pseudoplastic behaviour. Dilatent behaviour is depicted by curve number 4. ‘Most waxy crude oil gels exhibit thixotropic or occasionally cheopectic behaviour. When @ waxy crud alli alowed to coal below is pour point under stare condition nv ping te Paraffins wll crystallize causing the entire mass of crude to gel, To initiate flow apain, afiite pressure is required. For waxy crudes, yield stress is an inverse function of temperature and increases with decreasing temperature. With the erude ol thats elo its pour point the wax crystal structures in the oil start to breakdown as flow This bres lepends ‘on the time and rate of shear. — Penne on ‘Start up pressure depends to a large extent on whether the oil is cooled under static or dynamic condition. For instance, the additional restart pressure will be substantially highercae | pera | 5 1 & epee i | Ge e_| sinc ae > aco nines i 1 ‘ fe re eee Shear rato ig. 22 Typical non Newtorin ids. for a statically cooled pipeline (the fluid was above the pour point while flowing and allowed to cool during shutdown of the pipeline) than for one that has been dynamically cocled (the fluid was already below pour point when pipeline was shutdown), i. the cooling occurved duc to the flow of the crude in the pipeline. 3.4, FLOW PROPERTIES OF WAXY CRUDE OILS ‘The viscosity of erude oi s perhaps its most important physical property. For mosterudes, atsufficiently high temperature, the viscosity ata given temperatures constant and thecrade, although chemically very complex, is asimpleNewtonian fluid. As the temperatureis reduced, however, the flow properties of a crude oil can readily change from the simple Newtonian to very complex flow behaviour due to the erystallization of waxes and the colloidal association of asphaltenes, The waxes basically consist of n-alkanes (nC1r ~ nCss) which erystallize to form an interlocking structure of plates, needle or mal-formed crystals. These crystals can entrap the oil into a geldlike structure that is capable of forming thick deposits in pipes andPETROLEUM REFINNG TECHNOLOGY ' n imstances) which still exhibit a yie na ca 35 PUMPABILITY CHARACTERISTICS OF WAXY CRUDE OILS In any pipeline design for waxy crude cils, we have to ensure (a) Operating safety. protecton ofthe pipeline agninst blockage bythe setting othe oil into a strong gel. The design should ensure a restart after static cooling of the pipeline to the lowest temperature expected to be encountered, () Operating economy, ic. maintaining a reasonable flowing viscosity with resulting economic levels of power consumption ‘As already explained, the waxy crude oils show complex rheological relationships. The pumping and restarting conditions of the pipeline require physical properties of the il which Should represent the actual conditions in the pipelines "These praportios shan he ensy to determine and hate good reproducibility. In the past in many pipelines this was controlled by the pour point of the crude oil. Normally, the specification stated that the pour point should rot exceed the prevailing ground temperature. It has long bocn known that this is not a satisfactory test. The reasons for this are + ‘The repeatability and reproducibility ofthe pour pointtest are bad, A reproducibility of 10°C is not uncommon; * The pour point test only measures the temperature at which an oil will flow under ‘4 small but indeterminate shear stress. It gives no indication of the higher shear stresses which are available in a normal pipeline. In addition tothe properties ofthe crude ol itself, two other factors exert a major influence ‘on the pumpability in any particular pipeline. These are * Ambient temperature conditions in the locality of the pipeline; and. ‘+ Whether the pipeline is buried or above the ground, Where there is a choice of whether the pipeline should be buried or above ground, itis sometimes argued that there is an advantage in having it above the ground so that use may be made of the heat effect of the solar radiation to assist in de-gelling the pipeline, While this ‘argument is true, it must be borne in mind that for cold weathers, it will most usually be found that unless the pipeline is lagged, the night ambient temperature conditions will often be such as to cause a marked reduction in throughput, or in extreme cases even stop the pipeline completely. This situation could even also arise during the day if the sky is overcast. Further, pin Pipeline is lagged, the rate of cooling is reduced but so is the effect of heating by solar radiation,snASPORTATION OF WAXY CRUDE OILS a an example, the 8 inch pipelin« A ere the Dick a aeekne Pumping crude oil from the Naharkatia oilfields in -Asgam India) to the Digbol refinery was initially lad above the ground but it was found that during the winter, the low night temperature caused the erude to go, efton restricting the Fe a pone Caan Ret Q8y- As result, the pipeline war subsequently buried it was found Possible to operate it continuously with the available pressure drop at the minimum ground temperature of about 19°C. Subsequently, the crue oil pipelines to Gauhati and Barauni refineries in India were also buried 1-2 meters below the surface, 3.5.1 Temperature For the judgement of the physical conditions ofthe pipeline and the behaviour of the waxy rude ol, the oil temperature inthe pipeline has to be known during normal operation and after a shutdown to determine the part of dynamic cooling and the part of static cooling. For a pipeline already in oporation, the temperature distribution due t dynamic cooling could be measured at the different locations over aperiodoftire oe For new pipelines, the oil temperatures and the dcrase by woling can be calculated i the following data are available: ea ore ‘= Ambient temperature ‘Soil temperature and its seasonal variations + Type of soil, its thermal conductivity (which depends upon the moisture content among other parameters) + Depth of pipeline From the actual oil temperature at any point of the pipeline during shutdown, the oil will ‘ool down statically. The temperature decrease can also be calculated. However, the calcula tion is so complicated that computers are normally used, Tn absence of calculated temperature profiles, reasonable assumptions can be made. In this case, however, the worst combination of dynamiclstatic cooling and lowest temperature will have to be found experimentally by conducting yield tests at various assumed dynamio/static cooling rates. A model pipeline test rig is used for the purpose. 8.5.2 Yield Stress-Model Pipeline Test In a specifically designed mixer, crude oil is subjected to cooling (if required) and continuous shearing which simulates the movement of crude through the pipeline. Simulation of static cooling in the tank is done in the same mixer without using the stirrer. Passage through pumps is simulated by forcing the crude oil through a capillary nozzle, Thereafter, the crude is transferred from the mixer (by compressed air) to a 16 m long 6 mm diameter model pipeline in which static cooling that would occur after a pipeline is shutdown is simulated. The yield stress to restart the flow of oil after the static cooling is determined by applying air pressure and flow development is observed at the available shear stress in case the restart value of shear stress (i.e. the yield stress) is less than or equal to available shear stress. It is sometime argued that the model pipeline test results are very conservative because ‘he effect of wax deposition on the pipe wall 's ignored. In an actual field during static cooling after the pipeline is shutdown, wax deposition will start at the pipe wall and this wax layer will act as insulation thus retarding further cooling. It is possible that the inner core of the Dipeline (nearer axis) is still fuid when the restart is taken. Therefore, the restart and ‘subsequent viscosity breakdown will be faster.s Pe OLEUN MERHING TECHNOLOGY correlation of the model pipeline test resalts for actual pipsine design is normally based aor te eepthene correlation are devebped bY the designers by lt ane este simulating the Beld condition in ates loop. * eonoval equation forealeulating restart pressure requirement for a cooled line is pa tlc A (3.6) ed, ¥ isthe yield stress of gelled crude (this value must be where P isthe pressure requir ; deere ra i Peetator tots and is different for static and dymamie cooling) is the line length, C is the eireumference of inside pipe wall Il and A is the cross sectional area of pipe. 3.5.3 Flow at Restart “Atthe time of restart ofthe pipeline because of very high viscosity, the flow rato is expected tobe low. This, however, depends on available shear stress as compared to the yield stress. In ‘any cage, the minimum flow conditions of the pumps have to be investigated. If a pump is, Operated at a very low flow rate, additional wear due to unbalanced flow is expected. Further, ue to the poor efficiency, thecil will be heated and, after ashort while, the allowable maximum temperature will be exceeded. This limits the allowable time for the operation of the pumps with low flow. If the restart flow rates do not meet the pump requirements, special pumps with ap. jate characteristics (high head, low flow) have to be used for restart of the pipeline, 3.5. Effective Pipeline Viscosity For detormining pressure gradients in the pipeline, effective pumping viscosities have to be determined. Using these viscosities, the conventional formulae can be used for calculation of pressure drop. ‘The effective pipeline viseosity for calculating frietional pressure drop at various flow rates, and temperatures can be predicted by rotational viscometer tests. Due to wax crystallization at low tomperature, the conventional capillary tube viscometers eannot be used. Moreover, for non-Newtonian fluids viscosity is dependent on shear rate. For this service as also for other slurry services, rotational viscometers are used. The sample is taken in a double walled cup (a refrigerant flowing in between the two walls). The outer eslinder is rotated by a variable speed motor. The inner cylinder is suspended from a torsion wire consisting of a stainless steel tube, the deflection being measured by a balanced pointer. The rpm of the outer cylinder ‘multiplied by the instrument constant gives the shear rate. The deflection reading of the pointer multiplied by another instrument constant gives shear stress. The ratio of shear stress to shear rate gives the viscosity of the fluid. ‘When the oil is at such a temperature that flow is non-Newtonian, the Reynolds number is a function of viscosity which itself is a function of the effective rate of shear. Therefore, a3 intermediate calculation is required to arrive at the appropriate pipeline viscosity for calculat- ‘ing pressure drops. ‘Viscosity of the oil to be pipelined is determined at various temperature and rate of shear by rotational viscometers. These are used to plot viscosity versus temperature curves for various rate of shear. This plot can be used to determine the temperature below which the oil will behave as non-Newtonian fluid. Itis required to find the effective viscosities of the oil for Pumping at different flow rates at various temperatures, ‘The first step is to use the plot of viscosity versus temperature and plot curves of viscosity versus rate of shear for different temperatures.1RASPORTATION OF WAXY CRUDE o1Lg ‘The second step is to plot curve » throughput as follows: oof viscosity versus rate of shear fx ara given flow ra Of shear for different pipeline For a given flow rate, an equivalent shear rate atae value for vsconity the Reynolds numer neat dermn Stree Reynolds nsimbr. Using a eat 0 the pte te this for different values of viscosity, a cans estive rate of cd by Ba, 3.3. Assuming the flow isin turbulent repo, the 36 METHODS FOR PIPELINE TRaNsPoRTATION OF Wax CRUDE OLS ne ofthe following methods for piplinne : lining waxy crud oils may be cnsidere (@) Sele pumps tallow aparallavenis urrangement, hich outraneoreatslower igher pressures when required. The pjng could be maniold sr that parallel arrangement would be accom Panay agement would be accommodated by repositioning of valves to handle (®)_ Use of separate low flow, high head farting. , ad pumps for rest (c) Side traps at frequent intervals to allow short sections to be started separately. (@) Reverse pumping to create back and forth pumping sequence: ea [pumping sequence which prohibits static (€) Use of pour point depressaute/low inprovers Adding hydrocarbon diluent such as a less waxy erude or ight distillate. () Injection of water to form a layer between pipe wall and erade. (A). Mixing water with erude to form an emulsion (@ Displacement with water or light hydrocarbon liquidin case of shutdown of pipeline. (#) Separation at higher than normal pressure tallow as much gas and light hydrocar- bons as possible to remain in the crude, (&) Conditioning the crude before pipelining to change the wax crystal structure and reduce pour point and viscosity. (@) Further sub-division of pipeline into smaller sogment or reducing batch length of waxy crude to increase maximum shear stress available. (m) Combination of the above methods. (OMW) emulsion reduces the flow properties tonearly the viscosity ofthe continuous water phase. An O/W emulsion pipeline handling 40000 barrels of oil per day (265 m’ h™?) of 70 vol.% crude ail has been operating in Kalimantan bereits Indonesia since 1962. Blending with a less waxy crude oil or distillate on “4 Properties by altering the wax solubility relationship ca of — mre os = inn luc crude ‘capacity of the pipeline. vat separ’ seasenac fron ute ale inet as dilution. There is one interesting case of a shear: and eee es ne aed favourably alter the flow properties of waxy crude oils in Assam recent Pipelining the crude as an oil in water« repens reeicasid point depressants/flow improvers have been developed that, in small concentration, affet the crystal growth, and as a result improve the flow properties. Of the various methods developed, the use of pour point depressants/flow improvers ig found to be more attractive. The main attraction ofthis metho is its relative cheapness Variability of dosage with respect tothe temperature and desired viscosity requirements 3.6.1 Use of Pour Point Depressants/Flow Improvers ‘The injection of pour paint depressant/flow improver additives appears to hold the greatest Promise of achieving the desired overall objectives of operational safety and operating economy. Flow improvers should have the capacity to '* reduce the pour point, viscosity and yield stress under dynamic conditions; and + restart the pumping after a shutdown with the available shear atress. Chemically pour point depressants/Mow improvers are ashless polymeric additives which ‘when added into the crude oil at 300-600 ppm level reduce the pour point and viscosity ofthe | crude oil. Polymeric materials widely used as pour point depressante/flow improvers are a) alkyl acrylate polymers and copolymers, (b) olefin alkyl maleate copolymers, (c) vinyl ester polymers and copolymers, and (d) alkylated polystyrene. Normally, the average molecular ‘weight of the commercial available pour point depressants for crude oils is between 2000 to 20000. Various fw tmprovars developed at RRL, Jorhat nda axoSWAT-104, SWAT-106, FRU and FIRI-B. These are polymers/copolymers, easily soluble in crude oil around 40-45°C and non-corrosive. They are used in pipelining erudes of Bombay High and Assam (India), 3.6.2 Mechanism of Flow Improvement When a waxy crude ol is cooled below its cloud point, the wax erystals form and begin to "elomerate and wih frtor temperature reduction rsial agglomeration reacheb a pontat which a gel structureis formed below the pour point due to interlocking of the growing crystals and dependent on constituents like resins, asphaltenes, asphalts, paraffin and microcrystal line waxes, ete, their molecular weight, structure and quantity and also on the rate of cooling and degree of agitation during cooling. When the additives or low improvers are added, they alter the wax crystal size and shape in some manner and prevent the tendency to interlock. The flow improvers or pour point depressants act by retarding the growth of the wax crystals. in the XY crystallographic plane, thereby producing smaller crystals of higher volume/surface ratio, It appears that the flow improvers cocrystallize with the growing wax erystal, leading to the formation of a fault in the otherwise compact regular wax erystal and resulting in diminished gel strength, so that by coating on to a growing wax crystal the flow improvers reduce the tondency of wax erystals to interlock. 3.6.3 Point of Additive Injection Asa general rule, the additives should be injected into the crude above or around its loud point and also at a temperature of some 20°C above the pour paint ofthe additive, The additive Pour point could be depressed considerably by cutting (diluting) the basic component with Kerosine, or aromatic solvents. The preferred location of injection should be at a point wher + Noheating of the oil is required (utilize the heat of formation) + Subsequent external application of heat can be avoided or minimised, * ‘The maximum benefit can be derived in the system downstream,qusronrATON OF WAXY CRUDE OI a “tof the above considerations point to ood 364 Pour Point Reduction by Additives vrarpoint meésurements.on erude lls a _Zourrent mefieroeniaon re lls have hem wd todte! Ln tomperstorchanding a aa bets a hey donot necessary pre the fa pore Cee car ante liminary screening of various additives fr thelr Additive injection into the crude stream at well ‘Was decided to process this crude too at these refineries. Efforts were made to find a suitable solution to the problem of pipeline transportation of this high pour point (30°C) Bombay High crude oil to these refineries during winter. It was re Toda pieine tess tht the line wil not be able to take setae cons neon Jow winter temperature of around 16°C. A number of flow improver additives ware tested for their effectiveness on Bombay High crude. From preliminary tests, Shell-swim-5T and Esso Paradyne-80 were reported to be the rast effective additives in lowering pour point, Further tests by rotational viscometers indicated that, for similar level of dosage, both effective viscosity and yield stress were reported to be lower in case of Shell-swim-ST as compared to Esso Paraiyne0, It was therefore concluded that shell-swim-ST is superior to Esso Paradyne-60, Subsequently, Shell-swim-ST was used for transportation of the Bombay High erude to Uran terminal through the submarine pipeline from the production platform. Extensive studies were subsequently done at IP, Dehradun and Gujarat Refinery to determine the optimum doping conditions for _Shell-swim-57 ia Bombay Tigh exude. From these studies the optimum doping levels were ‘reported to be 250-300ppm of the Shell-swim-ST The effect of doping temperature on the pour point was reported to be negligible. 3.6.5 Effect of Flow Improvers on Yield Stress and Viscosity Significant reduction in yield stress and effective viscosities can be achieved by doping waxy crude oils with flow improvers. The following results were reported for the effect of Shell-swim-ST (flow improver) on Bombay High crude oil, Doping tevel Yield stress @ 16°C Viscosity @ 16°C ppm dyneslem® oP Nil 330.0 450) 250 625, 45.0) 300, 625, 424) ‘a, 45.8 410 ‘These results show significant reduction in yield stress with 250 ppm doping. Fonts provement with higher doping levels i, however, marginal. Infact in some cases the trend reported to be reversed with higher doping levels, as shown below by the following mode! tests conducted by ONGC.i PETROLEUM REFINING TECHNO [ Dose Por eine Depew | Yield sirens at 16°C, dgrenom® | Vasonty at 16°C a low dep i ie a Tn 0a wl pin ae oe = wm eae 7 oD meron, ve a menue! Fence, optimum doping levels by extensive laboratory studies must be determined before starting additive injection. 3.66 Incorporation of Low Pour Point Crudes in Waxy Crudes ‘As mentioned earlier, tha ean be ono ofthe probable solutions to pipeline transp problems uf waxy crudes provided the low pour point crude is easily availabe for blending and fo problems are expected fo he encountered in processing the crude blend as far as product Specifications are concerned. Once again the example of Salaya-Koyali-Mathura pipeline becited here The Gujarat and Mathura refineris fed by this pipeline (Gujarat-party) are | process partly Bombay High crude and partly low pour point Middle East crude. A sms percentage of tho Middle Bast crude mixed with Bombay High crude will not result in Serious procossing problems, Tho reported results of laboratory studies on blends of East crude with Bombay High crude indicate thatthe incorporation of Basrah crude in d jambay High crude shows no further redetion in paur point. This could be due to re percentage of n-parains when Basrah crude is mixed, the effect of pour point dep being more predominant en n-paraffins as compared to iso-paraffins, However, a signfien reduction in the yield stress ofthe blend is reported, as shown Delow Crude blend | Yield value at 16°C, dynealem? 100% Bombay High 330.0 100% Bombay High with 250 ppm of pour point depressant 625 [90% Bombay High + 10% Basrah with 250 ppm pour point 50 \depressant q The doping tomperature is quite important as far as yield stresses far as yield strosses are concerned. blends of Basrah with Bombay High crude doped at 50°C is reported to give better results compared to temperature of 30°C. This is shown by the following experimental reported. (Crude blend |-—_—iiteld stress at 16°C, dynestem? 50°C Doping 30°C) Doping. 90% Bombay High + 10% wit it depregerng” * 10% Basrah with 250 ppm pour 50 25.0 [90% Bombay High + 10% Basrah wit y Hig ih with 300 ppm pour. 5.0 oe sos Bombay Higi> 10% Basra lpimedepressant ssh wit ith 400 ppm pour 30 Set4nasv0RTATION OF WAXY CRUDE OILS 3.6.7 Crude Oil Conditioning ‘This process is developed by Oil I sein which the crude oil is firth amie cooling and working through the jetermined rate. The result is the condi foil remains fuid at muct ower temperature and possesses satisfactory physical eee cud’ OH remains fluid at much In the actual process the crude oil is heated to a temperature of 100°C in tube heater Before entering into the tube heater, the crude oil pannes through heat exchenges eed ‘achanges heat with the outgoing oil from the heater, bringing down its temperttare to °C by dynamic cooling, The crude oi at 65°C in stored ina 4 pump to static cooling vessels, commonly called conditioning veanela, These vessels. ure actly shell and tube heat exchangers whch cnet ay ren fel Ae ccoling water is passed through tubes. The conditioning vessels follow a batch time cycle of 208 minutes to achieve cooling of crude oil from 65°C to 18.5°C (this includes filling time of ‘erude cil and its emptying out time also). The cooling ofthe crude il in the conditioning vessels is effected by circulating waters, namely intermediate and refrigerated waters. {ntermediate ‘water is maintained in a closed circuit through a pump and heat exchanger in which cooling ‘medium is the cooling water. The refrigerated water is also maintained in a closed circuit through a pump and absorption refrigeration machine The circuit water while lowing past ‘evaporator chamber of absorption refrigeration machine through tube bundles gets chilled ‘As the temperature of crude oil is brought down to the desired level of 18 ~ 20°C, the crude «il from conditioning vessels is emptied out automatically into conditioned oil storage tanks. ‘The conditioned oil from these tanks flows to pipeline pumps through a booster pump and this ‘completes the process of conditioning. BIBLIOGRAPHY 1 K.W, Won, Thermodynamics for solid solution - liquid - vapor equilibria : Wax phase formation from heavy hydrocarbon mixtures, Fluid Phase Equilibria, Vol. 30, pp. 265-279 (1986). : 2 JH Hansen, A. Predensiund, KS Pedersen and HP. Ronningsen, A ther- modynamic model for predicting wax formation in crude oils, AIChE J, Vol. 34, No. 12, pp. 1937-1942 (1988), 8 8. Ganguly, Rheological parassetersand elution to ypical tranipirtaton probleme of waxy crude oil, URJA, Vol. 26, No. 2, pp. 39-94 (1989). sieellanes 4 P. Datta, H. Dubey and K-L-Patel, Pipeline transportation of waxy the cil fields, Chemical Engineering World, Vol XXV. p69 45 (199 a 5. R. Prasad, Waxy crude oils, In PIPING DESIGN HANDBOOK, J.J. Mcketta, Marcel Dekker, (1992). © S Naik, CK. Pathak, and V_P. Sharma, Rffects of pour point depressants oe Waa Indian crude oil, IE(1) J., Vol. 69, Part CH2, pp. 60-63, (14 QUALITY CONTROL OF PETROLEUM PRODUCTS 4. INTRODUCTION Quality control of petroleum products is a necessity ifthe products are to give satisfactory performance to the customers. Keeping in view the usefulness of each product for specific purpose, standard organisations have drafted methods of tests and specifications. Bureaw of Indian Standard (BIS), New Delhi is one such organisation in India which standardises procedures and issues specifications. Institute of Petroleum (IP), U.K. and American Society for Testing & Materials (ASTM), U.S.A. are the other two important organisations whose methods and specifications are widely followed. Apart from BIS specifications, Contral Board Of Revenue, New Delhi has certain other specifications for the purpose of excise levy. Some of “theimportant limits set by them areforcarbon residue, flame height, flash point, and viscosity, CLASSIFICATION OF LABORATORY TESTS ‘Most of the laboratory tests can be broadly classified into seven groups based on the {following characteristics: ‘* Volatility = Combustion * Viscosity and consistency * Melting point + Oxidation * Corrosion and protection cellancous tests Volatility is the major determinant of the tendency of a hydrocarbon to produce potentially ally important to an engine's start and warm-up. Volatility losive vapours. It is also cr assessed by the following tests: (a) Distillation (®) Vapour pressure (6) lash point and fire point ‘The combustion properties of petroleum products are evaluated by the following tests (a) Antiknock quality-Octane number, Performance number (6) Ignition quality.Cetane number, Aniline point, Diesel index, Calculated cetane index (c) Calorifie value (@) Burning quality-Smoke point, Char valuePETROLEUM REFINING TECHN Sar ree aro Ce aneme ree el ee Se ten Engler) Redwood, Saybalt, \uation of storage stability and resistance include: ster or lesser extent, requently de to the presence sulphur compounds, organic acids (mainly naphthenic acids) and traces of brine. Therefore aaa ee ane eck designed to evaluate the coroiv potentialities the ptr products which are obtained by processing of crude oils. The following methods are available, (@) Total sulphur (©) Acidity and alkalinity (©) Copper-strip corrosion test (@ SiNerstrp corrosion tet for Aviation Turbine Fuels ‘The miscellaneous tests include: (a) Ash (8) Carbon residue (c) Colour (@) Density and specific gravity (6) Gas chromatography of petroleum gases and liquids (P Refractive index of hydrocarbon liquids () Lead in gasoline (h) Water separometer index (modified) (WSIM) (® Ductility ‘The definition, method and significance of tests mentioned above are given below. 44 DISTILLATION The laboratory distillation test comprises a simple process in which 100 ml sample vaperised in a sutaby designed Nask fitted with a themomeiar, nod condensed ice-cooled tube and collected in a measuring cylinder. Whereas an j ‘would exhibit single boiling point, commercial fuel blends bil over a range of tempe Corresponding readings of vapour temperature and condensate recovered. are made prescribed intervals and the results are plotted in the form of distillation carve, The Boiling point (IBP) is taken as the temperature observed at the fall of the first drop condensate, and the final boiling point (FBP) as the maximum temperature reached‘qususrY CONTROL OF PETROLEUM PRODUCIS atomization), and are indicati ig sewn ahead, carters cof the vaporization behaviour fuels n storage apo oes fd vepour oe), and in pston-engne manifolds (uniformity of istsbutontoeyinders). The txtent of tho distillation range for any given fuel we representative uf the availablity ofthat fuel from the parent crude oi. Fora fuel with «high demand tho aim a the supplier il be tp extend the distillation range as far ax practicable Howovey, duo to the interrelations hip between properties andthe associated problems, minimum and maximum limits respectively, tiny noed to be act forthe inital and fal boing point, ‘he significance ofthis test varies fem producto produc. Incas ere oi, he ASTM distillation data give some idea ofthe factions that could be allecte below SO0°C. If tis a true baling point (TB.P.) distillation, the TBP curve reveals alot of characteristics that are uel forthe design ofthe refinery. The 10v0l.% of daillaticn ot moto spin indication Uf the ease with which the engine can be siarte, Top high a FBP will cause rankcave dilation 4.4 VAPOUR PRESSURE Vapour pressure of a liquid fuel may be defined as the pressure exerted by the vapour ‘above the free surface of the liquid at the given temperature, For volatile, nonviscous petroleum products, itis determined by Reld method. This is the pressure exerted by vaywut ‘when it is in equilibrium with the liquid under the conditions of test, For liquefied petroleum, 5, the provedure is different and the determination should be done at 65°C. ‘The conditions ‘under which vapour pressures are determined give results which are not true because of the air which is invariably present in apparatus. The true vapour pressure is higher than the Reid ‘Vapour pressure by about 5 to 9 percent but this relationship varies widely. ‘The standard Reid apparatus consists of a fuel chamber connected to an air chamber of four times volume, and fitted with a pressure gauge. ‘This test is important with respect to safety in transport, vapour lock in the gasoline ‘engines, types of storage tanks employed and the starting characteristics of motor fuels. High ‘Vapour pressure entails loss of the product in storage and transportation. In case of motor spirit, it may cause vapour lock in the gasoline engines (5.051 POINT ANO FIRE PONT fash point and fire point can be taken as indirect measure of volatility of the product ‘The flash point is the lowest temperature at which application of test flame causes the vapour ve the ol to ignifa The fire point is the lowest temperature at which the ol! ignites and continues to burn for 6 second. ‘The determination of asi point of petroleum products consists ofheating a given volume of liquid at a standard rate of temperature rise until vapour is produced to such.a.degroe ae togive a flammable mixture with air ian enclosed space (i.e. closed flash point temperature) OF with air in an open cup (ie. the higher open flash point temperature), ignition resultinga PETROLEUM REFINNG TECHNOK from the application of a small flamé. At fire point, not only will the vapour-air mixture flagh, [Zabel apparatus is used for determining the closed cup flash point of petroleum producy we. ae eer se yoroery thet pune moter ame 4.6 OCTANE NUMBER le 4 ‘This isan important test for measuring the antienock quality of the gasoline (petrol of ‘motor spirit) The knocking ofthe motor fueleis compared wsing blends of reference fuels. The tandard reference fuelsused fer octane numbers below 100areiso-oetane and normal heptane hich are assigned values of 100 and 0, respectively, on the ae:ane number scale. The octane ‘numberof the fuelis defined asthe volume pereentage ofso-octanc(2, 2, 4-trimethy/ pentane) inablend with n-heptane which sequal tothe tet fuel in knock intensity under standat and closely controlled conditions of test in a single-cylinder, variable compression ra tngines, known as CFR engines. ‘Thus, a fuel of 87 octane number has a CFR en performance matching What ubtainable wilh a blend of 8? volunve percent isooctane and ‘olumepereentn-heptane, Theratingcan be done by either Research method or Motor method ‘The differences in the two methods are as follows: esearch method Motor method pm 600 900 Shark advance 13° btae > Variable Mixture heating No Yee ‘Octane number requirements of gasoline engines depend on their compression ratio. Ifthe lente fhe minimum requirements in respect of octane number it ensures trouble fee ‘operation. Apart from being a nuisance, the knocking in an engine may result i ‘energy and at times may eause severe damage to the engine. Sere = 4.7 PERFORMANCE NUMBER 3 use o estimate knocking characteristics of aviation bet a ing characteristics of aviation gasolines of octane number higher than 100. The standard reference fuels for knock ratings above 100 octane number Sf he performance num of an mgr nance number scale is based on engine power output, The performance number represents approximately the maximum knock-free power output. The eeau counOL OF PEROLEUMPRODUETS i eaace number shows the percentage increas in lcrft engine power for adton o octane number 100 eirmanse number 100)“ Pen eruiere nn ete a aneenae (nn gt of wiation gasoline above 100 octane number ean be dn by TPiaviaton method ean mixture ating); (GhSupersharge method (rich mixture rating); and (Bxtended moter method (tion method, the ratings done at 1200 rpm by comparing the combustion chamber teatro te fuel with those of the blends ef known performance number. This lean cee voting ves us an idea ofthe availability of knack limited power in spark inition ‘ogajerall engines when the sirrat ie under erising onions vn supercharge method, the rating i dan at 180 rpm by comparing the knock Limited gover afte fuel with thse for blends of ip actane and iooctane pus TEL. This is done at fetsant compression ratio by measuring indicated mean eflective pressure at enough points train te mature response carves forthe eamle an te reference fuels. When the knock Mated power for he sample bracketed between thoae fr two adjacent reference ful, the ering eran. Themen hea ak Tied power when the plane is under take-off conditions, Imertaded motor method the ratings done ina CFR engine normally aed fr rating of rotor gaslines by motor method (rpm=800) The knocking intensity of he fuel is bracketed Fetrecn reference fel propared frm io-otane and TEL and the performance number it tne by interpolation, “AACETANE NUMBER - ( Cotane number is related to the ignition delay ofa fuel in a diesel engine, i.e. how rapidly ombustion begins after injection of the fuel into the combustion chamber. ee {Cis Hs«, also called cetane) has a low ignition delay time and is the arbitrarily chosen high-quglity reference compound for the cetane scale. It has been assigned a cetane number st 100 The low quality reference compound is 2, 2, 446, 8, Sheptamethyl {Cis whieh has along ignition delay time and has ben assigned acetane aumsbatoPS) Mae dandard forthe clare scale show tat long-chain, saturated, unbranched hydrocarbons have high cetane numbers, while structural features such as branching or unsaturation lead Blower cane numbers) ‘Cotane number of diesel fuels is determined in a single cylinder CFR engine by comparing gion delay characteristics ofthe deel fuel ith that of reference blend of knows ssimber. Cetane mamber ofa desl fel s defined asthe whole number nearest to the Value determined by calculation from the percentage by volume of normal cetane in a blend ith heptamethyl nonane which matches the ignition quality of the test fuel when compared. ‘this method. The matching blend percentages to the first decimal are inserted in the ingequaticn to obtain the clane number cnunler= n-etane 015 optamethyl none) 4 The shorter the i ide ignition delay period, higher is the cetane numberof the fuel [Géstsne numb isthe index of gation quality of a fuel High etane number fuels will Hate easy starting of compression ignition engines, particularly in cold weathers, and ‘warm up. These also result in increased engine efficiency and power output) reduced any ber.UM REFINING TECHNOL .ceoftest engine, the diesel in che ignition quality ofthe fue noise. In thi exhaust smoke and odour and combust he ate aaa ete satane nex wil give an approximate i004 aoa olan be roughly assessed by the formel “Aetane Number ~ 0.72 x Diesel Index + 10 (aay SPAMINE PO eaten antl ro seule pep tenting pint of lis he be Se dl cnt art oon with ining wee ees ote same and mpi misty ura ole. ied a nr Tuo gay praine nese ih ey (ei nin pin indies ot ge of aromatic he oie ignition quality is poor. vex ; 17S NO alata a the ition quay of iw] ue, This is determined y Ce ee yn te nine pent othe sample. Alou 118 he Caan er rm perk nay afr widely fom the ectane number. Higher the Fee eee The mn quality af the dine! fe Tes normally wed a8 9 pide eee ne ee alan the abeence oe engine rhe direct measurement Sane nanber inde clelated flo __-Aniline point , °F x API (a) Diesel index = int al jesel index = Aniline gravity constant (6) Diesel index ah a Cetane number - 10 0.72 (48) Diesel index < A:TY.CALCULATED CETANE INDEX q Calculated Cetane Index (CCI) is based on specific gravity and the 10 percent, 50 percent and 90 percent distillation temperatures ofthe fuels and it gives numbers that correlate with ‘thé tngine-testing method, The relationship is given by the following four-variable equation; CCI = 45.2 + 0.0892 Tiow + (0.13140,901B) Teon + (0.0523 - 0.428) Ts0n + 0.00049 (Tio)? ~ (Teon)"] + 1078 + 608? (48) Tion= Tio -215,,°C Tio = 10 percent distillation temperature, °C ‘TsoN = Tey - 260, °C 0 percent distillation temperature, °C ‘Toon = Tso - 310°C Too = 90 precent distillation temperature, % Bae=850-085)_ 1 ne G= specific gravity at 15°Chis CCl is usoful for estimating cet ‘This CCL wef fx eatimating cotane numbers whan a tet engine i not avalabe Or aiect magurement "conveniently employed for estimating cetane number when the quat ple available is too small fr an engine rating 412 CALORIFIC VALUE Tnsisthequantiy feat release pa nt quantity ofa nhen itis are competes woth ox oducts of combustion returned to ambient temperature. This quantity {rhea line he het of endensation tent heat) 2 he orien faeniea tye Gllorifie value" o “higher calorific value" eee ‘Most heating applications cannot recover the heat of the water : over the heat ofthe water vapour, it simply escapes wat the vapour ot ofthe cine. The Pte het euntet Is thee mre east Indieated by subiracting this latent heat from the gross calorific value, andthe resultant vale rPealed the net calorific value, lower ealoefie valve. ne ve ana 'A weighed quantity of the sample is burned in a bomb calorimeter under controlled conditions. The ealorific value is calewlated from the weight «{ the sample and the rise in {emporature. can also be calculated fram the formulae ~Calorific value= 12400-2100? | 44.) in which calorie value ff ealfgm and is density at 15°C in fem Calorific value is a measure of the energy available in a fuel. Thus a knowledge of the calorific value of the fuel, and the efficiency of the heating equipment, is essential to compare the merits and running costs of different fuels and energy costs Its @ critical property of fuel, intended for use in weight-limited vehicles. 4.19 SMOKE POINT ‘Smoke point in the masini Mains ight i. iat which dos ful wil teen smcking when determined in a smoke point apparatus under specified conditions. ~ Smoke point apparatus comprises four main parts-lamp body, candle socket, candle and stand, The lamp body with chimney is fitted on the inside with apolished black engraved scale ‘which is marked in white. A galley is aecured in the lower par of the body. The candle socket ‘assembly is designed to give a smooth rise and fll over the total distance of travel. To ensure interchangeability the eandle is finished to close tolerances. The assembly is mounted on a stand. The sample is burned in a standard lamp with a specified wick for five minutes. The height of the lame is read when it leaves no smoky tail. “This is an important test for evaluation of illuminating oils (kerosines) for their ability to bum without producing smoke-and-the assessment of the burning quality of aviation fuels. Higher the smoke point better is its domestic use. It also serves as a guide to assess the. dromatic content of kerosines : 4.14 CHAR VALUE ‘The amount and nature of the deposits (char) produced on a wick during combustion depend on the hydrocarbon composition of the fuel arid-also on the design of the appliances in which it is used: Char occurs@s a result of the breakdown and decomposition of the kerosine under the local conditions existing at the wick surface, and these conditions will alsodetermine what proportion of the decomposed products remains on the wick.a PETROLEUM REFINING TECHNOL: ee f the resistance to gravity fi inematic viscosity is defined as the measure of the resistance to gravity flow of the pressure head being proportional to the density. The time of flow of a fix is directly proportional to its kinematic viscosity. The unit of Kinematic viscosity is cmt gp ‘Stoke. The unt most usually used in measurement of the kinematic viscosity of petroleum fuels is the centistoke (cSt) which is 2 Ba amis iste ae viscosit ‘own as absolute viscosity, is the ratio of applied shear a ate ora ea thea mcnaure of the resistance of @fuid to flow, The unit of dynane viscosity is gm/em.s or Poise. Dynamic viscosity may be obtained from kinematic viscosity by, multiplying it by the density of the fluid at the temperature at which measurement was made, ‘Kinematic viscosity may be measured as an absolute property of the fuel, or alternately as a conventional property that is dependent on the instrument and the method used. Both ‘approaches depend on the efflux time of a given volume of sample flowing under its own head through a restriction. This follows because the force acting the laminar (low speed) flow of a fluid through a restriction is approximately proportional to the dynamic viscosity, whereas the force promoting the flow is that due to gravity, and is proportional to the density of the fluid. Hence the time taken for the gravity flow of a given volume of sample through restriction is approximately proportional to the kinematic viscosity. ‘The conventional methods, which are generally simpler butless accurate, are represented by the Redwood instrument in the UK, Saybolt in the USA and Engler in continental Europe They each comprise a sample cup fitted with a standard-sized orifice in the base and surrounded by a water jacket containing a heating device. When the temperature reaches the { lovel, the orifice is unsealed and the time of flow is determined for the given volume af ple, The result is reported as Redwood or Saybolt universal second or as Engler degree, given by the efflux time ratio for the sample and for water. When the efflux time exceeds a specified maximum-for example 2000 s-due to high viscosity, use is made of a Redwood No. ora Saybolt Furol (fuel and road oils) instrument, incorporating a larger diameter orifice. ‘The absolute determination of kinematic viscosity generally employs a glass U-tube viscometer with a capillary tube built into one leg. The length-diameter ratio is such that end ‘effects are negligible and the precision is therefore higher. The instrument is suspended vertically in a thermostatically controlled water bath, and the time is measured for a given volume of sample to flow through the capillary. This measured time period is inserted into an equation to give a direct measure of the kinematic viscosity in centistokes. v=At-Bit A= instrument calibration constant; 5 instrument type constant, depending on the capillary diameter an a fhuig, i teases (48) where t= efflux time, s (Engler degree for Engler viscometer) Table 4.1 gives the values of A and B for Redw: iscosity is an important characteristic of a fu are adjusted according to the ood, Saybolt and Engler viscometers. 1 and it is used for the pump design. Pum viscosity and if itis out of the and fo fuel in the eylindgs, — on‘quauirY CONTROL OF PETROLEUM PRODUCTS + ‘Table 4.1 Instrument Cons wnt Values ‘Range of tine in second Bngler degre, a B s4stz100 00260 118 > 100 ‘000247 05 3265490 002458 10 390 oma 00 110 ‘07226 1.98 ‘> 100 ‘200220 1.35 Bstsa0 724 1.88 | 40 0.0216 os | leealer 195. B#} Bice ad viscosity at 100°C est 10°C, eSt | 200 | 6620 | ae | 17a | 510 | a1090 | 44500 | 13.410 210 | 7143 | 04s | 1900 | 520 | 32150 | 46460 | 14510 220 | 1684 | 9752_| 2068 | 50 | 93.210 | 48.440 | 15.230 | 250 | aza3 | 10485 | 2242 | 540 | 34270 | 50420 | 16.160 240 | esa | 11264 | 2423 | 5.50 | 35.390 | 52480 | 17.100 250 | 9417 | 12028 | 2611 | 5.60 | 35.390 | 18040 | 18040 aocs1 | 12858 [2807 | 5.70 | 97.450 | 56.430 | 1880 10.661 | 13672 | 3.008 | 580 | 98.510 | 58.430 | 19920 uisis | 1452 | 3217 | 590 | 39570 | 60.430 | 20.860 uses | 15.417 [3433 | 600 | 40650 | 62430 | 22740 az6n_| 16328 [3657 | 610 | 41.690 | 64.430 | 22.740 a3s77_| 17.263 [3886 | 620 | 42.750 | 66.490 | 23680 a4ior_| 18224 [4123 | 630 | 43810 | 68.490 | 24.020 330 | res | 19210 | 4367 | 640 | 44.880 | 70.430 | 25.550 3a40_| 15603 | 20222 | 4619 | 650 | 45.970 | 72460 | 26.490 350 | 16382 | 21258 | 4876 | 660 | 47080 | 74.550 | 27.470 360_| itaig | 22920 | 5141 | 670 | 48.220 | 76740 | 28500 370 | 1994 | 23407 | 5413 | 680 | 49.390 | 79.040 | 29.650 380_{ 18828 | 24520 | 5.692 | 690 | 50.590 | 81.440 | 30.850 390 | 19680 | 25657 | 5.977 700 | 51.820 | 83.920 | _ 32.100 400 | 20.550 |” 26.890 | 6.270 710 | 62.980 | 86.460 | 33.480 4.10 21.400 | 28.060 | 6.660 7.20 54.150 | 89.040 | 34.890 420 _| 22280 | 29.360_| 7.080 730 | 85.273 | 91.660 | 36.387 _| 4 a oe a “a0 7.550 7.40 56.473 | 94.095 | 97.622 a 60 ae 8.080 7.50 57.669 | 96.528 | 38.859 _| 8.680, 7.60. 58.873 98.958 | 40.085 460 _| 25.000 |" 35.350 | 9.350 7.70 | 60.069 Senta 1 sniane | 4190sPETROLEUM REFINING TECHN [asia [e317 we5 [001 [eer [aer t [Eto [Cantos [crest [amas | rag [0 | eos. wos [ mss [onto [amis [740 | 806 | e255 [Ee [ormer [cesone [sows | 745 | 19m.0 [anes [as 17793 | 5886.8 | 4107.5 | 720 | 17005 | soss0_| «1005 725 yai95 | Gosee | 4225.1 1 1 Jog (800) ~ log ( a] Tea 10+ FI [50 wd : 1¢ bitumen in °C. The penetrati aianrenuige have positive values of PI and those more affected by temperature change negatiyg turechange values. ‘FREEZING POINT Freezing point is the temperature at which erystals of hydrocarbons formed on coding tisappear when temperature of fuel is allowed to rise. "This method covers a procedure for the detection of separated solids in aviation reciprocat, ing engine and turbine engine fuels at any temperature likely to be encountered during fight oon the ground. oe CLOUD POINT AND POUR POINT Cloud point of petroleum products is the temperature at which a cloud or haze of cexystals appears at the bottom of the test jar when the oil is cooled under prescribed condi It is generally determined for products that are transparent in a 40-mm thick layer and: cloud points below 49°C. ‘The cold filter plugging point test is used to determine the extent to which diesel fuel «gas oil will flow, even though the temperature is below that at which wax crystals norms appear, ie. cloud point. Cloud point gives a rough idea ofthe temperature above which the oil can besafely! ‘without any fear of congealing or filter clogging. ‘our point is the lowest temperature expressed in multiple of 3°C at which the oil i ot 4 erved to flow when cooled and examined under preseribed conditions —Pour point is a well-established test to estimate the temperature at which a sample: becomes sufficiently solid to prevent its movement by pumping. The pour point tem} depends to a large extent on the thermal history of the sample. Also, the pour point i the waxy nature of the oils. DROP POINT OF GREASE ‘The standard drop point tests indicate that the temperature at which the thickener is soluble in the base oil that the grease becomes substantially fluid. Clay and dye ‘greases have no measurable drop points. ' ‘The drop point can be used to assess whether a greas rulation has Properly made or to obtain an indication of the typeof thichense which has been‘QUALITY CONTROL OF PETROLEUM PRODUCTS a aso of an unknown formulation. tt can Pee ee ektes pee Wot be used to measure the upper operating {21 MELTING AND SETTING POWNT oF wax "Aemting cescecatid hardin “ termine the sting pint of wate. Molten wax ‘The point at which the temperature remains within a range of 01°C for one minute is take asthe setting point. This method in not suitable for mlcresyetaline oe termediate woken or blends of paraffin waxes with these or any additives pee Taaelaebar ofa yoo lun Wax or petroleum is determine by applying a do of molten wax to a thermometer bulb, and noting the temperatare at which i songeais when thethermometerisretatedundr stared The msde "he drop melting pont of wax o pettus determined by record dito a Sevens br psoas anaes stvbicader fhe snnplfale onthe ba athensmaer etter anda hese re considered to be suitable for checking the constant quality of wax output in 4.22 SOFTENING POINT OF BITUMEN Bituminous materials do not change from the solid state to the liquid state at any definite temperature, but gradually become softer and less viscous as the temperature rises. For this, reason, the determination of the softening point must be made by a fixed arbitrary, and closely defined method. ‘The ooftening point io defined ao the temperature at which a substance attains a particular degree of softness under specified conditions of test. A steel ball of specified weight is placed upon a dise of sample contained within a metal ring of specified dimensions. The assembly is, heated at a constant rato and the temperature at which the sample becomes soft enough to allow the ball, enveloped in a bitumen, to fall to the specified distance is taken as the softening point. ‘The ring and ball test for softening point measures the temperature in °C at which a standard dise of bitumen confined in a metal ring softens to such an extent, when heated at a rate of 5*C/minute, that it deforms under the loading imposed by a small steel ball which falls a distance of 2.54 cm. ‘The determination of the softening point of bitumen is regarded by some as an indication of viscosity, although from the point of view of the application of bitumen its use is limited to that of its title. The softening point is used in the designation of hard bitumens and oxidized bitumens, 4.23 INDUCTION PERIOD OF GASOLINE Induction period of gasoline is the time clapsed between the placing of the bomb in the bath and break point at 100°C. Break point is the point in the pressure-time curve that is preceded by a pressure drop of exactly 2 psi within 16 minute and succeeded by a drop of not less than 2 psi in the next 15 minute. Fifty mililitre of the sample is enclosed in a bomb with oxygen at 100 psi and heated in a ‘ater bath at 100°C. The pressure is then recorded either on a chartor read every 15 minutes;| seceERSRaeuauntencs he induction period, bett re ge stability of the fuel. An induction period of a minute under laboratory conditions ensures storage ste leat thie curmelation may vary with different gasolines under different conditi teat result is reported as inductigg 3 2 : orser Fuets : ‘24 THERMAL STABILITY OF “Tower CIPTOT) ie sed to mons the high tempera send vl somal oan ts te tet elt contions whi can be relied sbi of gs rhe came: Te ue i pumped «fed vehi thos ceaing In a5 i eae stanen te iter where fol dred Ae atethrh a ee prat reies 600 io tt oe fr 82.5 Dura rls may em ar Cp aan of depo onan aluminiom heater tbe, and ranean fale ested unt wnstream ef the ster tobe eee saingliced na reeroirand the whl ystom pressing og ye eee eee gle phase easton nthe ated section. The fel pay aoa ghz 015 micron iter, to remove tac particulate mate, ad iy oe a ee here pete upwards nan anlar pace over an aluminium tend aera alse tal ier through aheat exchanger, col ity and beck h ae reero The eed and sed fel the roerva are sparaied by faut Lo ee ety aviual be ting ory placing the abe Tube Depo Rae Peis the tubes rotted ate constant spec and ite surface Scanned by to ight su eis fle toveen toa photscl Fhe photocell gives sul ow stot Asa, Uiftrenal pressure across the 1? nfron iter e measure The et rerle ae Indleatv of ful perfrmance during gas tarbine operation and be ped wanes telovelof depois that on form when gue contact ahested 4.25 GUM CONTENT ‘The gum compounds which can be present or produced in the fuel are classified into types for test evaluation. Existent gum may be already formed in the fuel and can be dep from solution as the fuel evaporates. Potential gum may be formed under extended st conditions during which unstable hydrocarbons are thereby polymerized and oxidized to gums. : pair is the amount of nonvolatile heptane insoluble residue left when the samy is evaporated in a jet of hot air at 160°C. For jet fuels, the evaporation is carried out in aj of superheated steam at 282°C. a nd Potential gum is the amount of ‘ount of gum formed after the sample is aged in an 0} stability bath and evaporated under specified conditions nD * 884 e(quauiry CONTROL OF PETROLEUM pRooUCTS a 426 TOTAL SULPHUR “This is determined by lamp method or wiekbold or wickbold procedure for vilatile petroleum products ang ty am mee er ber progut Slphur inthe samples ‘ciidized by combustion {td ip estimated volumetrically after absorption in HO» or by gravimetric methods after F eeiverting into barium sulphate Pee eee | "Sulphur compounds pose a cual problem: they not onl tal lem: they not only cause environmental pollution Nom tei combustion products but thee products ae also naturally corosive an ease were physical problems to engine parts. A knowledge of the sulphur content of petroleum Products is therefore of importance to both refines and use ma 4.27 ACIDITY AND ALKALINITY ‘New and used petroleum products may contain acidic constituents ‘ contain acide constituents present as additives or ts degradation products, such as oxidation products formed during service. Total acidity i a measure of the combined organic end inorganic aciitg,Y ‘The acdsin the sample are extracted in neutral alcohol and then titrated against standard alesholic potassuin hydroxide under hot conditions ‘Total acidity is an indication of the corrosive properties ofthe produ. Inorganic acidity isameasure of themineral acid present. Organic acidity is obtainedby deducting the inorganic acidity from the total acidity. m . )PPER-STRIP CORROSION TEST Petroleum products contain sulphur compounds, most of which are removed during ining. Of the sulphur compounds remaining in the petroleum product, however, some can have a corroding effect on various metals. This corrosivity is not necessarily directly related to the total sulphur content. The effect can vary according to other chemicals and types of yur compounds present. ‘A.cleaned and smoothly polished copper strip is immersed in the ss sined at the specified temperature for the specified length of time. This: ‘sample, washed-with”aromatic“and sulphur free petroleum spirit and examined for ce of etching, pitting oF discolouration, Its the jon standard colour code. The classification code indicates that the numbers 1, 2, 3 and ignate slight tarnish, moderate tarnish, dark tarnish and corrosion, respectively. Sub- ipts a-e describe a standard colour reproduction in the standard chart. For example, the ifiation code 1a indicates slight tarnish with a light orange colour. This test serves as a measure of possible difficulties with copper, brass, or bronze parts of fuel systems. om ae SILVER-STRIP CORROSION TEST FOR AVIATION TURBINE FUELS ‘A polished silver strip is completely immersed in Aviation Turbine Fuel at 45 + 1°C for a iod of 16 hour. At the end of this period, the silver strip is removed from the sample, washed ‘evaluated for corrosion against the set of standard. Since some parts of the fuel pumps in aircraft are made of silver, the corrosive tendency ‘the fuel for silver assumes special significance, The cumulative effect of corrosion on such ital component in the aireraft is hazardous.PETROLEUM REFINING TECHN 43008H rancous solids, auc sah can result from oil, water-soluble metallie compounds, oF ext lids, such ay dirt and rust. ne carbonaccous residue left is heated 4g ‘A Keown amount of sample is ignited and 800°C in a muffle furnace, coled aad weighed as ash aarsige ofthe amount ofa product's ash forming mate on wheat tnt ovodyt i suitable for use in a given appticaticn .g material ean provide informaticn # 431 CARBON RESIDUE é gnod as the amount of carbon residue left after evaporation ang, Fearon reese es on of relative coke forming tendency, ther Conrado residue pete produ ' 31.1 Conradson Method ; Sees unnpeis lced ina crasble and sutjected to destructive di Fn ene ee eerie and coking rescuons during Fixed period of seve ee es ed heating prt, the crusibecotsining the carbonscenu a eta and weighed. The rngue remaining is calculated ate rel ofthe eign sanpleanl reported a cnvadson carbon reside 4.31.2 Ramsbottom Method 7 ‘The sample after being weighed into a epocial glass bulb having a eapillary opening ie placed in a metal furnace maintained at 550°C for 20 + 1 minute, The sample is thus quickly heated to the point, at which all volatile shatter is evaporated vat of the bulb with or without decomposition while the heavier residue remaining in the bulb undergoes cracking and coking reactions. After a specified 20 minute heating period, the bulb isremoved from the bath, coled in a desiccator and again weighed. The residue remaining is calculated as the percentage the original sample and reported as ramsbottom carbon residue, Carbon residue gives a measure of the carbon depositing tendencies of a fuel oil when heated in a bulb under prescribed conditions. While not dirsetly correlating with engine deposits, this property is considered as an approximation. For example, carbon residue value of diesel fuel correlates with the amount of carbonaceous deposits the fuel will form in the combustion chamber of the engine. The expected carbon deposits in the combustion chamber is greater for higher value of the carbon residue. Carbon residue is al i calculation of vessels ‘arbon residue is also used in design 432. 0LOUR Colour isan indication of the degree of refining of the products. Various test methods used. for temeasuromentof elroy calur of petroleum product aloe ‘nd produc pplication range ae gven in abe 3. Me main ems equip 4.33 DENSITY AND SPECIFIC GRAVITY Density ofa fluid is its mass: a fame __| _Mainequipment | ‘Colour scale | ‘Application —_| sree [Biman per YM Colour |Colorimeter ii 4 ws Heavy petroleum | et, lubreating ols (Colour comparator Perma aise Lovibond tintometer [Colour standards of ik. [All petroleum products | ferent rating for red, vel lexcept black ols and | sree eee eee ___low hice ana neutral tine bitumen [gasoline colour glass [Dyed aviation gasoline Specific gravity is the ratio ofthe density ofa fluid tothat of water at the same temperature. ‘The temperature usually specified is 15 56°C. In the USA, specifi: gravity of an oil is often expressed as degrees API. API gravity is an arbitrary figure relatad to the specific gravity of petroleum products in accordance with the formula: M5 Speci ee Degrees API = ——____M.5__ Gravity at 15.56°C/15. 56°C (aay ‘The specific gravity i an indication of the type of hydrocarbon present, being highest for ‘aromatics and lowest for paraffins. The API gravity reverses this relationship. ‘The most accurate method of determining the specifie gravity fan oil is to weigh a known volume in a specific-gravity bottle at 15.56°C. A correction may be applied by measuring the specific gravity at come conventional temperature near 16°C end adding or eubtracting 0.00068 per °C above or below 15°C. ‘Another method for determining the specific gravity of the sil is ty means of a set of hiydrometers. A hydrometer is placed in the ol sample at 15.56°C and allowed to come to rest. ‘The specific gravity is shown on the scale at the point coincident vith the surface of the oi. ‘Accurate determinations of the density, specific gravity and API gravity of petroleum products are necessary for the conversion ‘of measured volumes to volumes at standard temperature of 15.56°C, When the volume of ol is known, its mass can be calculated. These factors govern the quality of crude petroleum. These properties, however, are uncertain indications of fuel quality, unless correlated with other properties, 4 correlation offuel density with particulate emissions indicates increasing particulate emissions with increasing density 4.34 GAS CHROMATOGRAPHY OF PETROLEUM GASES AND LIQUIDS "A measured volume of the gas sample is introduced into a chromatographic column and transported through the calumn, the sample is split into various components, either by ‘adsorption or partition, depending on the column packing. The composition of the sample is determined from the chromatograms by measuring the area underthe peaks. An identification of the components is done by noting the clution time, 435 REFRACTIVE INDEX OF HYDROCARBON LIQUIDS Refractive index is defined as the ratio of the velocity of light (of specified wavelength) in sir toits velocity in the substance under examination. It may alsobe defined as the sine of thePETROLEUM REFINING TECH 7 (Refractive intercept =n-8)] in the hydrocarbon fractions. (413) 10°C and p is the density at 20°C, em/em’ culated by knowing the refractive index 'e refractive intercept method. There id refractive index of hydrocarbon ‘dication of the content of aromatics 4.36 LEAD IN GASOLINE "The lead alky] is converted to lea with concentrated hydrochloric acid material present is removed by oxi gravimetrically as lead chromate. The method tal lead content of gasoline and other volatile distillates blen id or tetramethyl lead, etc.) F ‘Tetracthyl lead is added in gasoline to improve the octane number but it is highly fence, its concentration in gasoline is restricted and its handling is done with J chloride and extracted from the gasoline by refluxing ‘The avid extract is evaporated to dryness. Any organic idation with nitrie acid and the lead is determined ‘overs the gravimetric determination of the \ded with lead alkyls (tetraethy] ous. He ost precaution. "4.97 WATER GEPAROMETER INDEX (MODIFIED) (WSIM) ‘This is earried out with a water separometer. It measures the water separation charac- teristics of fuels expressed in terms of WSIM. ‘An emulsion of water and fuel is prepared and passed through a cell containing a standardized ‘fibreglass’ coalescer. The effluent from the cell is examined for entrained wat by light transmission. A numerical scale (0-100) rates the case with which the fuel releas ‘emulsified water. WSIM is a measure of fuel cleanliness relative to its freedom from surfactant materials. Ahigher WSIM rating indicates that the {uel is cleaner relative to surfactant materials. 4.38 DUCTILITY Bituminous surfaces exposed to varying temperature conditions under re : Hire conditions undergo a great deal ‘Expansion and contraction, Therefore an important characteristic of the binder ists ductility i —— luctility has an effect on the cracking of bituminous surfaces caused by traffic Prleeatte a pulty of bitumen is exprossed as the distance in centimeter to which a standard miavette fan be elongated before the thread formed breaks under the specified conditions. ‘smooth constant speed and contin peat pe ‘tinuous operation. The temperature is controlled Bitumen having hij 'tumen having high ductility may be more temperature susceptible.5 -PETROLEUM PRODUCTS 5.1 LIQUEFIED PETROLEUM GASES Liquefied petroleum gas, known as LPG or LP gas, is the term applied to a mixture of certain light hydrocarbons derived from petroleam which are gaseous at normal ambient temperature and atmospheric pressure but condensed ta the liquid state at ambient tempera- ture by application of moderate pressure. Although they are normally used as gases, they are stored and transported as liquids under pressure. They are sold as propane or butane or under the trade names such as Indane, Bharat gas, HP gas in India. 5.1.1 Composition of LPG Liquefied petroleum gases are usually mixtures of saturated and unsaturated hydrocar- bons in the Ca and Cs range. LPG consists of one or more of the following hydrocarbons: ‘+ Propane (Css) «+ Propylene (CoH) + n-butane (Calti0) psorbutane (Caltio) + Butylene (CaHls) ‘Traces to small quantities of one or more ofthe following hydrocarbons may also be present + Bthane (CaHe) + Ethylene (CoHO + Pentane (CsHi2) + Pentene (CsHti0) LPG separated from heavier hydrocarbons by a straight distillation process contains only the saturated hydrocarbons whereas LPG obtained from conversion processes euch as ther- rnaVeatalytic cracking, reforming and hydrocracking contains unsaturated hydrocarbons as well Bureau of Indian Standards (BIS) have categorised LPG as under: (A) Commercial butane — a hydrocarbon product composed predominantly of butanes, butylenes or their mixtures. (B) Commercial butane-propane mixture — a hydrocarbon product composed predominantly of a mixture of butanes and/or butylenes with propane and/or propylene, (©) Commercial propane —a hydrocarbon product composed predominantly of propane, propylene or their mixture. ‘The requirements of LPG are given in Table 5.1. LPG produced at Indian refineries conforms to grade B.1.2 Properties of LPG : xi ies and a high degree of pur LPGs are characterised by their bi eval ie Vapour sreascne one at the most imporeant characteristics of LPG. It determines the pressure that Orbe cxsrted by the gas at ambient temperature and therefore fects the requirements aarti the designed working pressures of storage vesse's. The main difference between vnmendial propane and commercial butane is in the vapour pressure (see Table 5.1). Typicg| els, Small quantities of LP causes condensation and e ible to see an escape of LPG. LPG, whether in liquid or vapour phase, is only slightly toxic. In the vapour phase, LPG is slightly anaesthetic if itis inhaled in high concentration, ‘Table 5.1 Requirements for Liquefied Petroleum Gases (IS:4576-1978) Requirements for [est meth ‘propane butane | butane 1. |Vapour pressure at 65°, gle? | 10 Na 7 | 2 [Volatility evaporation vempera 2 2 38 lave for 96 vol a 760 man Hi, °C, Max 8. [fetal volatile sulphur, w 5. [Hydrogen sulphide | _Atwent ‘Absent 6. [Dryness ‘Nofree | No free , oie a 5.1.8 Production of LPG There are two main sources of LPG. 8 of LPG. These are (a) Extraction of LPG from natural ga ete scar ga at well head; andaE ET Extraction of LPG from natural gas, There are several processes by which LPC pe extracted from natural gas, These are (a) Compression and cooling () Adsorption (e) Absorption (a) Cryogenic processes Cryogenic processes can be further divided in the different systems like 1. Refrigeration by direct expansion based on Joule-Thomson effect 2. Caseaded refrigeration using Cs as refrigerant; and 3. Turbo expander Refining of crude oils. Bulk of LPG supplies come from refineries. LPG is manufactured at the refineries by separation of the above mentioned gases from the main refinery gases produced from distillation, thermal/atalytic cracking, reforming and hydrocracking proces: tes. LPG recovery from various refinery processes in general is given below Yields of straight-run LPG from various Indian crudes processed are as follows: Ss Yield of straight-run LPG, wt.% [— Akestwer 8s North Gujarat] OS Bombay High 10 Naherkatia Lo ‘The LPG yield from the imported erudes processed in India is around 1.1.5 wt %. The yields of eracked LPG from conversion procosses are given in Table 5.2 ‘Table 5.2. Yields of cracked LPG from conversion processes Process Feed Main product | Yield oferackea | “LPG wes INaphtha Aromatic, gasoline Blendstock 510 (Catalvtioreterming [Catalyiceracking |Vacuum gas oll [Cycle ol for blending in diese oils | 2 |Residoam (Coke ‘Vacuum gas oil [Component of middle distilletes Refinery operations start with the fractional distillation of the crude oil. The overhead product from the crude distillation column which is unstabilised gasoline boiling up to 140°Cis condensed in the overhead condenser and fed to the stabiliser, where LPG is obtained 5 top product,—_—_-_-——s—efefeffefsfste PETROLEUM REFINING TECHNOLOGY absorbents to increase Tight ends ress eis fed toa debutaniser column, where cracked lighter ends in a stripper. The stripped gas! 108 ace irom debutaniser column it ane cher LP ihr op a eryes rece ie mere i oA Ai cua Toe Cre eigen ter ht araeaeein inher: "HS removal follwed by Merox treatment. The Merox process is one of oxidation of the Bsc Mar et enn ee ae ance ea baeimmrepererer ine tment renner Seer erp Im fluid catalytic cracking (FCC) unit, NAOH is regenerated. The inslble disulphide ie removed theraby reducing the ta sulphur. Odourisation. Since LG is used as domestic fuel the chances of fire in confined locations becomelargeinthe caso accidental leakage Being aasthisshnuld bemmnst cau eretble by smell alone Since constituents of LPG do not have any characteristic odour, it is comme” j practice to deliberately mix highly odoriferous additives in LPG to impart a distinct odour. | Most commonly used substances are low molecular weigh i ‘molecular weight organic thiols (mercaptans) which and serve as effective odour markers in diluted ype are thy] and propyl mereaptans, LPG is ist aptan (about 50 ppm) is usually added. the manufacture of various chemicals und ten eral combust als and olefing (by rine fe veel aan Pyrolysis). LPG supplied for domestie sountries and propane being in greater yond cutee: butanes predominating in warmer SS acs arn entre her ma Soldering, brazing, welding, anneal the caustic to a regenerator where sodium mereaptanine is converted to disulphide oil and” tion engine and a feedstock fr |peTROLEUMPRODUCTS a {ng and hardening, steel cutting ete. Asa fuel for internal combustion engines, itis extremel food, but it has yet to become popular. si eee senareTias Naphtha sa generic name given totight hydrocarbons bing in he gaoline range. eis a ight Bate obtained fom reining of ere lt The bling rangv af varios pes ot pavithas produced include: Cs~85#C, Cs 110°C, Gp~MB°C, Cp 160°, Cs 175 and G_-200°C In these initial Boling point (BP) is constant, Osher boiling ranges can be 60-85%, 85 ~ 110°C and 110 ~ 140°C Nophthas are usually classified as ight, intermediate tndhouvynaphthas, Ith nha faction bls below 100° tr clanifed alight naphtha Heavy naphtha boils above 150°C. For intermediate naphthe ths bailing range es between 100 and 150*Gype 52.1 Methods of Manufacture of Naphthas Naphtha is produced by atmosphere distillation of crude ol This is called straight-run rlaphtha. Several conversion processes such as visbreaking, fluid catalytig cracking, hydrocracking, coking also produce naphthas. These ar called cracked naphitas ‘Theimportant characteristics ofnaphthafractionsfrom diferent crudes aro givenin Table 53. The proper quality of naphtha for the petrochemical and the fertilizer industry ean be achieved by dearomatising the naphtha with or without reforming operations prior to extrac- tion of aromatics. High aromatic naphthe is na only a nuisance to these industries, but also funsumes extra energy inthe cracking operations without giving aay useful products Alo, it produces more coke and increases the downtime in bath the petrochemical and fertilizer Frdustries. On the other hand, the extracted aromatie traction can be used in the manufactare of synthetic fibres. 5:2 Composition of Naphthas Naphtha is a complex mixture of hydrocarbons. Its composition depends on the crude oil, processed and the conversion process employed, For the composition of naphthas, two types of analyses are usually carried out. These are: “Bidrcabon type analy 3 Individual component wise analysis x a ‘Thehydrocarbon type analysis determines the percentage f paraffins, olefins, naphthenes ‘and aromatios. Different types of compounds found in naphtha fractions for various uses are given in Table 5.4. The approximate carbon number range ofthe products is also given in the Same table. In Table 5.5, a summary of quality of the naphtha fractions from various indigenous and certain imported and worldwide available crudes with respect to the paraf- firnaphthene/aromatic contonts of their naphtha fractions are given. The value indicated is for the full range naphtha (Ce ~ 140°C). The hydrocarbon type composition of naphthas from Indian crudes is given in Table 5.6 for boiling ranges of 60 ~ 85°C, 110~ 120°C, 120 190% and 130 ~ 140°C. we a tor Senor» 52.3 Uses of Naphthas : ‘The major end-uses of naphthas are listed in Table 6.7. The use of naphthas in fertilizer and petrochemical industries and as gasoline is discussed belov.Table 6. Important Characteristics of Naphthas from Different Crudes ea Light Arabian Kuwait urban Davies No. | teristics 945" API) (315° APD G93" APH) (34° APD) Cs 178%} Cs 200re|cs — 175%¢] 0s -a00'c| cs 178°c]cx ao0rel Gs ~anstclo, 200 1 [Gravity om | arab [07 [on | 07a | ome | ons 1 oar ss/18%C * Meraderwes) *248 | 2480 | a980 [asa | aso | Gea) as | aan] a ae crude, we.) [* Sulphur, | 0.096 |” o101 0.03 | 0.08 | 0044 ) 007 | 0018 | 002 | 008 | ois wt 4 [Total mer- | 0.0412 | 0.0356 | 0.00019 | 00006 | oa1s | oom | os | ons |] captans, we 5. |oatretio | se4 [56a | 5a [697 | a7 | a8 | ei | ea] ans | amp 6. [PONA®, % rep] ss2 | sso | ne | coo — | oro | oso | ro | 50 w{ 20 | 306 | 20 | 20 — | 10 | wo | uo | 1s 4{ ss | 164 | 195 | wo | 70 | 90 | 150 | 10 | eo | 100 *Paralfin, Olefin, Naphthene, Aromatic 3 i 3Table 5.4 Types of Hydrocarbon in Nuphthas et eee Ts Ts | s |» [wo [Boiling point, °C __ [36 [69 [96 | a26 [asx | it fnypes of ompounds und coe [Normal paraffins eee ce ched paraffins ee pe pe ee [Sevaratedcyeic Tepe be Pe P [aromatics Mono Cee br bee [aromatics Di : : . [Aromatic naphthenes a = olaesl aromatic nonhydrocarbons PP plete | [aromatic oefina = . Po | PC | PC [olefins cyclic po bro [ro Lec [re | re Approximate carbon number range aes eferet7 {sie [2] Ligrine ey Precipitation naphtha VM & P naphtha anne} Free eee [Mineral spirits I —| (Gasoline ee Kerosene . — —} ex fle 7 [Petrochemical feedstocks *p-Present, “PC-Present in cracked naphtha only ‘Table 5.5 Hydrocarbon Type Composition of Naphthas Crude ‘Composition of napitha (Cs 180°C) Paraffin Nophthene ~ Aromatic [Assam (Mix), vol % 32-40 5243 16:17 North Gujarat, vol % 525 2 55 [Ankalesborar, vol 708 28 a8 Bombay High, vol 537 28 as | Iranian Light, wt % 515 aL na | Iranian Heavy, wt % 53.4 381 35 | [Basra vol 685 188. 127 Kirkud blend, vol % on 22 105 Heavy Maya, vol 606 21 2s [North Sea, wt. 59 38 8 | [Russia export blend, wt. % 385 82 as |Table 5.6 Hydrocarbon Typ. oe Composition of Naphthas trom Some Indian Crud. TBP Gut Rs ile it | Mette [lobes Redrsgar | Aaahwar Tomar) Pr a “2 x = £ N P A N ¥ * 9 63 28 1s | 41 | 4a 20-80 sas Posto eae 130-140 28 |. 22 22 52. 15 33 | 27 | 40 AcAromatics, N-Naphthenes, P-Paraffins Table 5.7 Major End-Uses of Naphthas Type of naphtha End-uses Light naphthas _|(a) Gas making gasoline (®) Special gasoline Intermediate naphthas (a) Aviation gasoline (6) Motor gasoline [) Marine gasoline (@) Commercial Solvents-Rubber, lacquer and pesticide diluents [ic) Benzene - High-ootane gasoline component, solvent, petrochemical manufacture (Toluene - Solvent, high-octane gasoline component, chemical intermediate, explosive ig) Xylenes - High-octane gasoline component, lacquer and enamels, chemical intermediate (h) Olefins and diolefins (Ammonia production vent for di (a) VM&P{Varnish manufacture and paints) naphtha, [() Thinner for paints, varnishes, lacquers Stoddard Solvent.JLEUM PRODUCTS i “Naphtha finds an extensive use as fertilizer feedstock where itis steam refo ive thesis gas, the starting material for Se eee ea fertilizers Crudes which yield fll range naphtha of high aromatic content of more than 10-12 percent aromatics are available and can ave fe armaticontn erent a lable and can be used by _leetrochemical industry, naphtha (C5 ~ 140°C) is used as feedstock for steam erackers, ducing hydrogen, methane, ethylene, propylene, the butenes, butadiene and to a lesser mt benzene and isoprene. Theso are the raw material for large number of petrochemicals Petrochemical industry needs crude with as little aromatics percentage as possible with 6 percent as a ‘benchmark’ naphtha ss per tho supplies available in the past from the nkaleshwar crude and from the imported Middle East crudes. The condensates (from LPG. gxtraction in natural gas plants) and the reformer raffinates ean supply only a fraction (about 25 percent) of the total naphtha requirement of the petrochemical industry, SBlalyticreforming of straight-ran naphtha yields a Cs ~ Cyreformate rch in the aromatic hydrocarbons, benzene, toluene, cthylhenzone and the xylenes, The raffinate remaining after 2 e aromatic hydrocarbons is sometimes used to augment straight-ran naphtha as steam-eracker feedstock. Naphtha-tange products from hydrocracking of heavier oil frac- are also very occasionally used as steam-eracker feedstocks, =|» /'” The steam-cracker feedstock is vaporized and steam is added in a ratio of about 0.3.0.5 of steam per tonne of naphtha, The mixture is heated rapidly to the cracking tempera: through tubular coils inside an cil- or gas-fired furnace, The temperature of operation ies from 750°C for medium/low severity to 900°C for high severity. To obtain the best yield ‘ethylene an important factor is a very short residence time, ¢ g 0.2% x This rednicos the amount of coke produced. Longer residence time, eg. 0.6, at low/medium severity increases Id of aromatics. “he use of naphtha as gasoline requires its high antiknck value or octane number. Depending on the crude source, the octane number of séraight-run naphtha varies in the range 0-70. Bombay High crude with its hich aromatic content is more suitable for gasoline eduction because on distillation, these crudes give high octane gasoline blending fractions, octane number of cracked naphtha from fluid catalytic cracking is about 92-94, The esent requirement of gasoline of 87 octane number for Indian vehicles is met by processing flarge amount of naphtha in catalytic reformer to boost its octane number. Catalyticreforming ‘straight-run naphtha yields a reformate of high octane number in the range of 93-94 3 MOTOR SPIRIT Motor spirit, commonly known as petrol or gasoline, is one of the most widely used troleum products. In countries like USA, the consumption of gasoline is very high and ts for about 40-45 percent of the total petroleum preduets consumed, but in India itis than 8 percent. 7 Tce ; Gasoline is employed in spark-ignition engines. The primary quality factors for gasoline optimal performance concern combustion, vat anleaines(afbth the engines d their emissions). Combustion in spark-ignition engines sheuld be smooth, starting atthe ing plug and spreading evenly through the combustion chamber. Volatility control of alines for spark-ignition engines provides for good start up and engine driveability regard= ‘of the geographical area of operation7” PETROLEUM REFINING TECHNOLOgy, 5.8.1 Spark-Ignition Engine Gasoline is pumped from the ta is the metering of liquid fuel and condition, A secondary function ist of the air-fuel mixture, The amount of ‘operated by the accelerated pedal. The air-fuel nk and delivered to the carburetor whose primary function Mir in the required ratio for any given engine operating atomization af the Fuel to achieve adequate homogeneity i minture is controlied by a butterfly valve or throttg mitre passes nt the inet manifld wher, creel ah the uid ofcome form of heating, vaporization ofthe feel is completed. The chargy, ett fect the skark plug. The pressure developed by the combustion process must be sma sniiy Sewanee ee thobot gases ave exhausted from the eyinders via the valves through the exhaust and silencer System Gnd ave Bnally emitted into the atmosphere. The main variables in the engine design axe'tne compression ratio, the shape of the combustion chamber, the cooling system and the timing ofthe spark. 6.3.2 Composition of Gasolines Cae en ne prepared by mixing various components product by refining presses suk ‘as atmospheric distillation, polymerization, isomerization, alkylation, catalytic reforming, atalytic cracking, hydrocracking, visbreaking.Itis usual to incorporate very small quantities certain additives in order to inhibit knocking, pre-ignition, gum formation, and icing ofthe a i ee : “Apart from its physical characteristies and the effect of additives such as gum inhibitors « anticknock compounds, the quality ofa gasoline depends on ts hydrocarbon composition Tts hydrocarbon composition must be of a type that does not readily cause detonation or knocking in the engine, Since gasoline consists of @ very large number of different hydrocar- bons, its composition is usually expressed in terms of hydrocarbon types (paraffins, olefin, ‘naphthonas and arematies) rather than in terms of individual hydrocarbons. This simplified Iethod of describing gasoline composition enables important inferences to be made as to the general behaviour ofthe gasoline. " Gasoline is a light distillate and consists ofthe fractions within the boiling range of 0 ta 180°C. It consists of hydrocarbons ranging from Cs to about Cio . The main types are: (a) normal or straight-chain paraffins, (6) iso or branched-chain paraffins, (c) eyeloparaftin, (4) aromatics and (e) olefins. Of these the normal paraffins are the major components in straight rrun naphthas. Generally speaking the actane number of normal paraffins beyond Ce is very poor. Iso-paraffins have highoetane numbers followed by cycloparaffins. Aromatics and olefins too have high octane numbers. High proportions of olefins are not tolerated in gasolines for reasons of storage stability and gum forming tendency. Catalytic reforming is employed to Improve cetane numberof straight-run naphtha, This process inereases the proportion of isoparaffins and aromatics. Gasoline is to be stored, handled and transported in successively smaller quantities until iteventually enters the automobile tank, Subsequent mevement and contact with sr is ible Fo cause deterioration af the gasoline andthe refining plan mustinclude steps to ensure goad stability ic. minimum gum formation during storage over'a reasonable period of time. 5.3.8 Properties of Gasolines 4 The assurance of proper gasoline quality is maintained by limiting and controlling mr characteris, Indian specifications of gasolines are given in Table 8, The fue aarp fess Eesclines that control gasoline quality arelisted in Table 9. Combustion quay Tastes thote properties which directly affect the ability of gasoline to ignite properly. Com primary performance indicator, The handling and storage 4peTROLEUMPRODUCTS nn Ae thereat, SOntamination during refinement and product shipment isvemen characteristic of cleanlineas Ss i ‘Retamination and Uhe degree ofinhesesnets dUring use is related to composition, trace ince problem versus ueelated avse rape gui ne Enuine perfor. 5 ‘Table 6.8 Requirements for Motor Gasolines (1S : 2796-1971) jg] Comet Iaieamiaemay — | tained No seslncs having oan narber | TY 4 |_| fa oo [i [ean View et 7 [2 [copperstrip oronion for hat 5% Not worse tua No. 1 Patt [a [Density at 15°, gmt Not imited but tobe report | P16 [a [Distilaton Pas |(a) Initial boiling point, *C Not limited but tobe reported [Recovery up to 70°C, vol Min 10 10 (c) Recovery up t0 125°C, vol Min. 0 0 a) Recovery p to 10°C, vol, Min. 0 30 [e) Final boiling point, °C, Max as 18 (Reside, vol, Max. 2 2 5 Octane number (Research method), Min ar 38 Pat 6. [Oxidation stability, minute, Min, aco uo Pa 7L_[Resdue on evaporation, mg/I00 ml, Max 4 40 P29 6 [Sulphur total, wt, Max. 025) 20 P34 3. [Load content (as Pb) e/, Max oe 090 [Prato P38 10. |Reid vapour pressure at 38°C, keffcm* g, 0.70 0.70 Psa9 tx. [Bxcise specification - Flash point below 24.4°C ‘Table 5.9 Fuel Properties Needed for Acceptable Performance Fuel performance required Property contra for gasoline (Combustion [Octane number Distitlation range = Gravity Hydrocarbon compotion Handling and storage [Volatility [Vapour pressure [Contamination (water/sediment) [Copper corrosion 0 [Cleanliness during ase ——_—(Sulphur [Bxistent gam = [StabitiyPETROLEUM REFINNG TECHNOLOg, combustion characterstoe Combustion nthe spark ition engine depends ma on at cs idelcnion, te ame nite ane sarin eto a fo ation spect unl ll he gale hasbeen barney AE thug pred every ara hee renng fhefame ruts inaminereate prey inensnin terpeatre rut pepe mistre where the fame havea imahe gn gs zone whichis tnt rand preavurein hw ond gat zone cnuses tho grain aa eae arent ternan prefame prose are he highly tempers, ae espe one acerai critical tvesbold concentration the ea sequteperonte a pete aria of te ame frontemanating rom the nace aera es ncnking fn ho other hand, he fame ot reaches hee a es gut apa the eral treahad pornid concentration, th eae Sri pln ir tre wil be without knock Figure 5.1 is diagram of the typical distillation curve for gasoline and its significance tp “spark ignition engine performance. The front-end (0 to 20 pereent evaporated) identifies cold starting and/or hot fuel handling characteristics of a full-boiling gasoline whereas the mig range (20 to 80 percent evaporated) is indicative of driveability and warm-up operation Long trip economy Carburetor icing Hot staling ‘Temperature, degC Warmup Fig 51 Typical dsitation curve for gasoin ‘The phenomenon of preignition is deposit cont penne is encountered in gasoline engines. its in the m chamber are supposed to be responsible for hot pots which are serpent 'm tail ends of fue! and lube oil accumulating itper 0LEUM PRODUCTS. Table 5.10 Fuel Effects on Sparicgniti ark Ignition Engine [Performance problem | — aa [Bxcesive engine wear igh anger oan ab ful: relatd causes Dirt icon) contaminat Inadequate cctane nomber Heavy ends contamination Preformed gum impurities [Poor combustion [Poor cold starting Improper volatility control ais |Wator contasination [Hot fuel problems [improper volatility control oa Heavy ends contamination igh sulphur content arburetor! indvetion system fouling Perfornied gum impurities [Soluble metal contaminante [Filter plugging |Water contamination (Dirt (silicon) contamination [Spark plug fouling, High aromatic content Volatility characteristics. The volatility of gasoline affects the performance of the engine in a number of ways, which are ease of starting, rate of warm-up, vapour lock, Carburetor icing and crankease dilution (the dilution of Une engine lubricating oi with the hhigher boiling constituents of the gasoline). The fuel must be sufficiently volatile to give easy starting, rapid warm-up, and adequate vaporization for proper distribution between the Glinders, Conversely, it must not be s0 volatile that vapour losses from the fuel tank are zcessive or that vapour is formed in the fuel line eausing vapour lock which may impede the flow of fuel to the carburetor. To some extent these conflicting requirements can be met by sing a more volatile gasoline in winter than in summer, but some degree of compromise is obviously necessary. Oxidation stability of gasoline. progressive oxidation deterioration. The res veskiues If present in the gasoline, the gummy residues can eause multiple ole. 40 residues. present inthe ne ne err, anf of data term nd i the epost formation in tre ony fuel specifications are critical about limits fresiduos on ovapers sombustion chamber. Many {wolePtont in Uno fuel existent gum), Special acerated ist ton ‘hiss measure of Eo Pe endeny af um fara om toage tenia mures are use fo det! dgradaton ofthe fl incontact with stmospberc 4° ‘and is due to auto-oxidation. Once initiated, ‘auto-oxidation of hydrocarbons is @ progressive tdi due fo autrasdation. Ones urosiaton arohpcnyronds, Terese: chain reaction The primary eda acting aschaincrerstenmbine won sear fas forming po nets tne tl Oh pl forming more hydroperoxide), Sac G,ekod gaslines are umang hem se particulary Pr ra alin wer at Taos Most petroleum products ae ss ora sptible to deterioration in composition and the presence of small amounts of nitroBens On prolonged storage gnsolines undergo a slow bat rit of this is formation of non-volatile gummy sulphur, organie acids and oxyEen. PEIRCE ele. tion of a drtaning in alos, fornston of gan aa aa tiarisce hat contrel the perma Ee cnoaed agers (a) Initiation c=c ——> cc lefin free radical (6) Propagation Te : do sc.c-0-0 freradizal_peroieftee cadet polymerses C-C-0-0-C-C" ra Poni (©) Termination Co + oct — ecco ‘tee radical “tre radial saturatad hydrecarbon cc + cco §=—_cco0cc Olefin free peroxide snon-polymeric radical {ree radical peroxide ©-C-0-0", + AH—¢-¢-0-0- +At eroxidefree inhibitor hydroperoxide —_—_low energy radical radical 5.3.4 Types of Additives Used in Gasolines “hs FeAuirements of specifications of gasolines are quite stringent. These requirements “cannot be met by refinery operations alone. The use of additives in gasolines has become imperative for the following reasons: |\{P Toenhance the properties of gasolines to meet the specification requirements; an {@) > introduce new properties which are notin the gasolines obtained by refining of crude oils 3 e Gaslineadtves aa dhe path these functions in an economical way. Various types of ives used in gaolines, their functions and eompositions arelistedin'Teule ‘saris an awe a ior \d cor ipositions are listed in Table 5.11. The type? (a) Anti-knock compounds (©) Metal deactivators (e) Detergents (@) Anti-icing compounds (PD Combustion improvers& 2} 7 duties used in spark ignition engines, Although several pes of compacta ee et cence ‘octane number, only lead alkyls gained commercial status. Some of the anti-knock ‘Table 5.11 Additives for Gasolines [Additive Function ITo improve octane quality lwithseavengers euch as etlens \ditromide aed ethylooe | [Methyleyelopentadieny] man- lganese trcarbony | icing additives ‘To minimise engine stalling and |Freezing point depressants such. ee power lar asec frmation asserts cco oe imearburetorsand fel lines |isprepanel) and glycols aexlene lyeat and | laipropytene glyco) Paani Ho minis gum formation and |[Ptengleno diamine and alt] Inpove dorage salty" |phaol compound Walder To preva etal of oxidation J. Nini peste deasaveng*" [praanctianine talons sich as copper Comberton chember deposit To minimise misfire due to load Organophasphovoan — Imodiers fouling of spark plugs and to |Not now widely used reduce ignition and preignition Anti-oxidants. Existent gum and oxidation stability requirements are present in most Sesaine specifications. The oxidative degradation of gasoline is believed to proceed vin a free ‘ragal chin reaction which involves peroxide radicals. Anti-oxidanta, auc as alkyl phevole inhibit this chain reaction by reacting with peroxide radical. Phenylene 've anti-oxidant than the alkyl phenol. This is particularly evident in Gaming Tatsning cefni blending components and despite its higher pric, phorglone acre gocrtin metals such as copper ean catalyze the oxidation seactont cod veel cetator inhibitors are used to prevent this action, The most common of thece are the ‘ate amize and propylene diamine derivatives of disalicyldene fuel cons, ‘cing compounds, Ice formation in carburetors can ‘upset air/fuel ratio and increase ‘umption. Under conditions ‘of high humidity and relatively low ‘ambient temperature, Teasing angeat2® inlet air can freeze within the carburetor fee reeclin wt rough engine Retked effect on toe wing Particularly during engine warm-up. Gasoline volatility has Additives, ce ‘on the tendeney for carburetor icing to oceur. Control of icing by the use of ition, "ever, presents a more Practical and economic alternative than varying gasolinewo PETROLEUM REFHING TEewotogy fei he aoa 0 a a toe en elas nk antl ape mers a ns 19.3.9 New Gasoline Blending Components In recent times, pollution from automobile exhausts has increased to alarming level. Starting from April 1, 1995, new cars sold in four metropolitan cities of India, ic. Delhi, Mumbai, Calcutta, Chennai are fitted with a catalytic converter on their exhaust pipes Catalytic converter is an anti-pollution device fitted to the exhaust system of vehicles. It helps prevent emission of noxious gases into the atmosphere. Itis tubular in shape and comprise ® honeycomb metallic or coramic dise coated with noble metals like platinum and palladium, Noble metals play the role of catalyst in a reaction which renders exhaust components like "carbon monoxide and hydrocarbons harmless by converting them into carbon dicxide and | ‘water. These metals arc spread over a large surface to provide intimate contact between | exhaust gases and catalysts, Catalytic ennverters are required to simultaneously remove | tangetted pollutants, resist catalyst poisoning by contaminants and last long There are > | | | | types of catalytic convertors. Two-way systems using platinum and palladium, which remove "only earbon monoxide and hydrocarbons leaving nitrogen cxides unchanged, The latter is ‘oxidized through air pump. Three-way catalytic systems employ platinum, palladium thodium to remove all three pollutants simultaneously. Lead in the gasoline is injurious t ‘the honeycomb disc of the converter and poisons the noble metals in the device and reduces its potency. ‘The requirement of producing unleaded gasoline will result in oetane shortages at many manufacturing sites. The use of oxygenates in gasolines is made for raising the gasoline Pool volume and its octane level, especially in the critical front-end range. The excellent burnin® Properties of oxygenated compounds result in increased operating efficiency of the engines, thus compensating for the lower calorific values of the oxygenates. Simultaneously, loweYr perno.eun PRODUCTS " a Er ican ainanatl Seni mecionllp eae re and other ay efficient than other liquid ‘Table 5.12 Properties of Oxygenated Motor Gasoline Components Characteristics Methyt alcohol] By aicohot | ere | TAME Norma boing point "C 646 785 564 v3 | [Density 254°C, yl 079 a9 on 07 Iaeclar weight 3206 4607 38.15 702.18 (Omen content, wi 500 347 182 157 | eat of combustion, Mig wn | 2694 gaz | 3939 [ea of vaporization, keg 1104 839 391 326 Pea pine, °C os 18 =20 = anton pont °C a6 28 460 =a Water slubibity wt 20°C, wt = = 13 | Water azeotope at 1 atin Temperature, °C None 782 522 z8_| water in azeatrope, wi. 7 44 32 20 (odane number (a) Research 122 121 15 108 Lio Metor 98 oT 97 [Riis imi i gasoline, vol B= 3 5 15 15 “Methanol with eampulsory cosolvent 60/40% agricultural products. “Gasohol” blends, ‘South America as well asin several U.S. tor tolerance than methanol and ponent. However, without hoa is mantctrdy frets ol Saas ea oe tt igh anti-knock value, make it more acceptable as a blending coms f0vernment subsidies its tly unattractive in most countries. MIBE. This is produced by a simple additive reaction of isobutylene with methanol. It meen a A te ewes ih sen le as om “* isobutylene content in the C, fractions from steam cra TCC (uid catalytic cragBB) of-gases ar Table from these sou iS very limited ker variegifOm 40 to 45 percentby weight whereas in FCC aff gases it byproduct. Isobutylene ean be product PETROLEUM REFINING TECHNOK, varies from 16 to 20 percent, Therefore, the prefer, fed by dehydrolysis of TEA. Isobutylene can aley ve an hire an cre ced rom Geld butane inh absence af oben sr we Fee ne tne ce omcrzed to nobutane which in turn i dshydrogenta}, produce isobutylene. ra ae ol el eed ea is normally practiced can be produced by catalytic reforming, ‘countries requiring 91 RON and above, since up to 91 RON gasoing ‘with relatively less yield loss. MTBE to the extent o 111 vol. is being blended in American and European gasolines. ‘TAME. This is a higher analog to MTBE, produced by additive reaction of tertiary amylenes and methanol in the presenc er boiling point and somewhat lowe eof acidic reaction promoters. TAME has a slightly octane value than MTBE. TAME is fully compatible ith gasoline hydrocarbon blends. However, its significance as anti-knock component has, up now, been limited. TAME is manufactured at some refineries as a means for chemically viding methanol to cracker light gasoline fractions. 5.3.6 Alternative Gasoline Fuels ‘The most potential alternative gasol line fuels for spark ignition engines, both from Indian context and world energy scenario, are liquefied petroleum gas(LPG), compressed natural gas (CNG), synfuels and alcohols. LPG. The use of LPG as fuel for spark-ignition engines has already been established. The advantages of LPG over liquid fuels include the following: (a) LPG mixes more readily with air. (6) Ttean be used at somewhat leaner air/fuel ratios, (c)_ Tt gives lower emissions of pollutants (carbon monoxide and unburnt hydrocarbons) (d) Itreduces combustion chamber deposits (©) It has excellent anti-knock performance, provided unsaturates are not present in excessive proportions (P Itis resistant to preignition (@) It gives excellent cold-start and. ‘The use of LPG as a fuel fo ‘warm-up performance. spark-ignition engines has a number of disadvantages aeons spark-ignition engines has a number of disadvantages. Thest (a) LPG must be stored and trans pressure, ‘ported in tanks capable of withstanding quite high (©) LPG tank is quite bulky. (©) ‘The performance of LPG in terms of emissions, power and economy is dependent 08 its composition. The C3/C rat ‘0 and the level of unsaturates strongly influenc®pernoLEUM PRODUCTS sriometry. Some of th “ stoiehiom 1 unsaturates have a stable to causing high-speed Keren N° T@!8tVEly poor motor octane number and are ONG. Compressed Natural Gas (CN es, Natural gas has a very | act low energy density, hence i : ence thas to be either eon igh pressures of about 200 bars or cole to Liga aia ae th eile fo ge adequate operating range Three, ic aed an CX. NG consists mainly of methane. The adv, iy ose tra The advantages of CNG as a fuel for spariignition (@)_ CNG in ihe gus with high ignition temperate and ange Nine ihe ih one with high ature and is no more dangerous Sa eet i temperature and pressure, CNG rapidly disperses into (&) The ostane number of CNG is about 190. anti-knoek agents, such as TEL. » ONE netlt ne edt (6) Minimum pollutant emission occurs. There i a Minimum pllstant emis os sigrfcant reduction of CO and (@) Combustion is more regular te) CNGhasa better col-starting characteristics, Unlikepetro, gas des not first have to be vaporized and does nl condense en cal engine compontats. Engines have alonglife,CNG does natcarbonizeparkplugsor wash out brenting 0 @) The use of CNG allows longer intervals between oil changes. In contrast to petro, gas is almost insoluble in engine oil. Consequently, lubricating cil retains its properties longer. One of :t8 main disadvantages is that CNG tanks take up space raduicing trunk space as for comparable energy storage, 5 times higher volume is required. Besides, CNG tanks add weight because heavy cylinders are required for storage of aatual gas at high pressures. CNG deen vehieles alsohave ashorter operating range compared to petrol vehicles. Also, refuelling station costs of CNG are very high. ‘Synfuels. Synthetic fuels (synfuels) can be produced from soa, cil shale and tar sands. A company, Saso, in South Africa is preducing synfuel from coal. The first step isthe complete fuafication ofcoal with steam and oxygen. Ater purification ofthe gas, a synthesis gas results that consists mainly of hydrogen, carbon monoxide and some methane, The next major step {sthoapathesisof hydrocarbons from the hydrogen and carbon monoxide over an iron catalyst This is the Fischer-Tropsch synthesis, I gives awide range of hydrocarbons of different chain, lengths and simultaneously a number of oxygenates such as alcohols and Ketones. After scrnration and recovery ofthese synthesis preduets from the reactor tail yas, the hydrocarbons fre further refined by conventional refinery processes such as isomerizatibn, alkylation, platforming, polymerization, ete. The result is series of products. ‘Alcohols, Alcohols such as methanol and ethanol have been proposed as an alternative fase for spark: ignition engines, Mothanol and ethanol differ markedly from gasoline in several charactoraties that are important to their distribution and use as a fuel for spark-ignition engines. Table 512 compares some ofthe mst sanfican characteristics ‘Compared tetypicalwasoline, methanol requires 44% as much airfor combustion, produces oq amare fyi Pesiires 37 times as much heat for vaporization The eorerpending Compara fa atRnol are: 61% a8 much air, 66% as much exergy, and 2.6 times the best 9 Vaporizetion. The ratios of heat of vaporization to heat of combustion show that for a givenPETROLEUM REFNG TECin — nano 0times a8 m2 pore the energy output, methanol requires 7.6 and ct 5 muh heat Lo Ver he gl ‘Resta cto ah sels hove a age bing yattin ne lover ele ga Fae eee sene eee n ambient temperatures but is too lean to jimite below gig 10 15°0. These characteristics together wit nt the high hots of vaporization lad to digg SE A a ige alcohol Doth aleahola are exe in starting an ening in eld im canbe abnarbed through the ski. It sil nto way soluble Methanol sigh atilife du tcomplete mixibility of methancl with wg 5.4 KEROSINE Kerosines are distillate fraction of crude ol in the boiling range of 150 ~ 250°C. Kero tt as toboin tne form of vapour and mixed withthe on gannatbe burt the ga mw combuntble mixture. All petroleum cil inl in te aun the comme uent when expoed tothe atmosphere, ahd there wil ar sere ret nonce Gasoline evaporates rapidly a ordinary ambient temperaty rerreesr se tporates morerlowly To schieve satisfactory combustion of erosne ediy ae eae ieneconary to ncrease the evaporation rate considerably. The meanyg aa rey on one factor: increasing the surface area ofthe oil tobe burned ag ser smperature The two types of burner design which achieve this all nto ety vaporizer or atomizer : Vaporizers rely on the inherent volatility of kerosine being sufficient if supplementary at ig mrable Once ignited the heat derives from the flame elf. The wick in a wick yy Sr provides the motive power to keep is surface continuowly supplied with ud, thee dy on. vorysallow ayer keresine being continuously heated by fame radiating prove the vaporization : “Atomising burners bresk wp the for into a very fine apray which increases the ss area enormously and enables th heat from te lame to erent the reqired vaporization lwo nabs the oxygen in he arto mix rapidly with the droplets and vapour toachieve combustion, 5.4.1 Manufacture of Kerosines Straight-run kerosine cut obtained from Assam crude as such is unsuitable for mar purposes because of its aromatics content. The main disadvantage of high aromatics can is that kerosine burns with a smoky flame. In order, therefore, :o produce a superior quali of kerosine which will burn with a stipulated flame height without smoke, the straight: kerosine is treated with liquid sulphur dioxide toreduce the aromatics content. Liquid sulphur dioxide process is also known as Edeleanu process. At the boiling point of sulphur dioxide ~ 10°, aromatic and unsaturated hydrocarbons are completely miscible with liquid sul dioxide but the paraffins and naphthenes are not. Sulphur dioxide also extracts cyclic sulp compounds and nitrogen compounds, a behaviour that makes the process useful in certain high sulphur kerosinés, Another process to treat kerosines from either sweet or sour crudes is hydrof Hydrofining of kerosinesis especially attractive in refineries where sweet crude isnot no available. It affects improvements in sulphur content, odour, colour and burning qualities! ‘measured by wick char). By hydrotreatment of a kerosine fraction, aromatics can be com into naphthenes, thereby producing an improvement in burning characteristics.JoLEUM PRODUCTS Pernouet 8s 4 ecaposil sf Rares Manoa yen of hidrcarons present inks ar:() prin) naphthen ican non hdration cps snanng nr, on yee a c hydrocarbons presnt varie fom 10 to ia For he same carbon funber,parafin have the least tendency towards smoke formation and aromatics the great Naphthenes are intermediate between the ether, Hence food quality Hoos Int conta a suffletently high proportion of parafinchydrcarbono weave aromas, 5.4.3 Properties of Kerosines Indian specifications for kerosines are given in Table 5.19. The smok. ven in Table 5.13. The smoke point of kerosine is important burning characteristic. The tendency of kerosine to smoke is mainly dependent the types of hydrocarbons present. The greater pereentaye of elemental carbon in aromatics pared with parafing means that high aromatic fuels willmko mare realy and Rene matics may have to be removed during the manufacture of Kerosines. The tendency of rosines to smoke decreases in the order: ee foe ‘Aromatics > Naphthenes > lsoparaffins > Paraffins ‘The tendency of paraffins tosmok th lecular weigh smoke inereases with increasein molecular weight. Branching olefin linkage in paraffins inereases the tendency to smoke. The tendency of naphthenes smoke decreases with increasing molecular weight and increases on addition of double bond ith inerease in molecular weight, the tendency of aromatics to smoke decreases. ‘Table 5.13 Requirements for Kerosines (18:1459-1974) Characteristics Requirement | Text method IS:1448 [aciaity, inorganic Nal P2 [Burning quality PS. (a) Char value ofl consumed, meg, Max 2 [e) Bloom on glass chimney ‘Not darker than grey [Colour (Saybol), Min. 10 pu | [Copper strip corrosion for 3h at 60°C [Not worse thas No.1 Pas [Distillation Pas (a) Recovery below 200°O, olf, Min 20 | (®) Final boiling point, °C, Max. 300 | [Flash point (AbeD, °C, Min. 35 Pa | [smoke point, um, Min 18 Pai | [otal sulphur, wt, Max. 0.250 P34 *21 (for defense), 20 (for railways) 40.20 for defense). 5.4.4 Uses of Kerosines Kerosine is used az domestic fuel. Iis used for cooking and lighting. Whether itis used -lighting in lamps or in cooking stoves, it has to be first turned into vapour. is is dor wicks or by pressure. The common wick stoves and lamps are ofthe first kind, Pressure ‘and petromax use high pressure to vaporize kerosine.fon hover night et eaten eng ome sree sy laevis le ag Si rece ht tt uupannfolauneT see eer ane Sa gn arses eto ern ah ge Poe mate ae stale ra material forthe manufacture of roma a acc pninateichacenetribepretctmeteeia, | devas rbot febrero samen Sanyo nt ikea coen cn tty Sal aflne eee poe we aus atacsanens Kerosine is also used to manut uased to control pests, weeds and fund! 5.5 AVIATION TURBINE FUELS ‘potential fuel for the gas turbine engines used in aircraft requires high thermal stability, high heat content, low vapour pressure, good combustion characteristics, good viscosity: ‘temperature relationship, high density, high specific heat, uniformity and good handling characteristics. The combustion properties of aviation turbine fuel (ATF) are gonorally ‘controlled using several of the following five tests: smoke point, luminometer number, omatics content, aniline point and gravity ‘The heat of combustion is normally calculated from the aniline point and gravity. Only basic types of ATFs, the kerosine type and the wide-cut gasoline type, are in general used ride The kerosine type of ATF is a much modified development of the iluminaing originally used in gas turbine engines, whilst the wide-cut gasoline type of ATF ist dorbeiing rang fuel including some gasoline fraction, In adation, number o speciale fuel grades are required for limited military use, as in supersonic aircraft wok rar orice that control ATF quality are listed in Table 5.14. Combustion quality a slant eet alec the ability of a fue to ignite properly. With oe Seuaeianne, assures delivery of fuel to the turbine nozzle with — “deposits to form in fea) ation characteristics. In turbine engines, the fuel should sits to form in fuel nozzles, fuel control ‘lade which will degreas ae systems, turbine blades, coatings‘High heat content per unit volume is required in high speed aircraft while ntent red in high speed aircraft while weight is more important in low speed aireraft. Naphthenes have high heet content per unit volume and paraffins per unit weight. Low vapour pressure is needed ta minimize evaporation losses. A foel with a dense molecular structure permits more energy to be packed in a given tank space. Fuels capacity as a coolant depends on specific heat and heat of vaporization. Fuels sould possess high smoke points, high luminometer number to minimize the temperature rise in Combustion tone fom fame radiatun: Normal parafine are the best from minonty and smoke point of view. Specific heat as related to density is the highest for paraffin, lowest for ‘aromatics and intermediate for naphthenes, a oman ‘Table 5.14 Fuel Properties Needed for Acceptable Performance Fuel performance required Property controlled (Combustion [Luminosity [Hydrocarbon composition [Thermal stability [Heat of combustion Handling and storage Flash point Viscosity [Contamination (wateveurfactant) [Particulates Microbiol eth [trace metals [Dieuation [Sulphur [Bxistent gum [Stability ‘The larger demand of ATFs cannot be met economically by straight-run ATF alone. Extensive hydrocracking and hydrotreating yield a product ofthe desired type. Hydrocracking has proven tobe a flexible process which can produce additional ATP. [somax process produces ATF from residual stocks that were previously used as heavy fuel. Arofing is the process to convert aromatics into naphthenes using a highly active sulphur resistant catalyst, giving the [ATF having high energy content per unit volume, and improved smoke point and luminometer number. This process is suitable for petroleum distillates between 60 ~949°C containing 5.30% aromatics. Previously SO2 extraction was used to remove aromatics but it reduces the yield of ATF and it is responsible for silver-strip corrosion. Merox process is used to remove ‘mereaptans, ‘Some fuels having high thermal stability do not retain thermal stability in storage; part ‘of this degradation is caused by trace materials that can catalyze oxidation, Hence to improve stability, metal deactivator, anti-oxidant and dispersant are to be added. 5.5.1 Composition of ATFs Aviation turbine fuels are distillate fractions of crude oil in the boiling range of 270°C, and consist predominantly of hydrocarbons. The minor constituents of ATFsrrr ereeeerree reece eee eee eee PETROLEUM REFINING TECHNOL ogy snofparticulate matter and consist of suiphur, nitrogen and oxygen compounds and traces of parti Wate, ‘Seontaminants. wands in ATFs and their ratio varies wiy ‘Paraffine and naphthenes are the major compound: —_ a ee a crode snare On aight basis theta of ombuotion ide highest fr paras over stomata adntermediatefornaphhencs. However, when ered on a volume basis, the order is reverse an wl ‘Aromaties are present in ATRs principally as monocyelic hydrocarbons with sm a gues tin otro and ec ing compounds Teds have a more uminows flame han parti, teats mains daron dopo, Thay cg many dastaners resent in lg lines to swell. For these reasons an upper limit to the ates in ot i specifications which is 20 vol.%. The presence of the polynuclear aromatics results in highiy Seen ais ete et tumutics ave good Tubrieity agents for control valves and fuel pumps in the fuel handling systems > The hydrotreating of ATPo tends to reduce aromatics, The most critical portion ofthe fue system to lubriity is the high pressure fuel pump whichis entirely fuel lubricated. This tends to increase the wear on the pump and so reduces its life. A smell quantity (10-12 ppm) of an approved corrosion inhibitor added to the fuel will protect the original systems. The most reasonable approach is to design fel systems, high pressure pumps in particular which can run on lowiubreity fuels. Olefins are limited to 6 vol.% on account of their instability, chemical reactivity and ease with which they form gums. They have good burning qualities and are intermediate between paraffins and naphthenes as regards heat of combustion "The non-hysroearhans present in ATTRe are enmpmnda containing sulphur, nitrogen and jxygen. ‘The amount of sulphur and nitrogen present is controlled by the crude source iposition and the processing scheme. The total sulphur content is limited to 0.2 wt‘%. fercaptan is controlled specifically for its corrosiveness to copper and cadmium and forts fisagrccable odour. The specifications limit the amount of mercaptan to less than 0.001 % Mercaptan and/or other complex corrosive compounds are limized by a copper-strip corrosion test, As a further protection against sulphide corrosion on silver parts, present in some fa pumps, a slver-strip corrosion test has been introduced. Nitrogen compounds occur mainly is the heavy end of the fuel and are detected in gums and sediments. The amount of nitrogen is controlled by thermal stability tests. Oxygen is controlled by acidity test, Gums contain a large amount of sulphur. They are, in fact, high-molecular weight, ‘non-volatile organic complexes of carbon, hydrogen, sulphur, oxygen and sometimes nitrogen. Gum formation can take place in fuels when stored ‘for a long time or under thermal stresses at high temperatures in modern high-speed aircraft. This latter effect can adversely affect ‘engine performance by blocking burner jets or fouling up heat exchangers. 5.5.2 Properties of ATFs The proper ATF quality is maintained by limiting and controlling specification chara i= Indian specifications of ATF are listed in Table 5.15. ’hysical properties. Physical properties such as density, tion temperature are of considerable importance with regard to. ‘These properties also affect storage and handling facilities. Density is an important parameter in the design of fuel tanks in aircraft. Fuels of © lerable density range can readily satisfy the essential quality requirements of ATF + 1618 usually necessary to limit the density of a particular type of fuel, e.g. kerosin® viscosity, volatility, autoign jengine and fuel system desistPETROLEUM PRODUCTS ‘Table 5.15 Requirements for Aviation Turbine Fusls-Kerosine Type K-60 Grade QS : 1871-1976) eect st Characteristics Fara x Requirement Test method Is sss | essence (Clear bright and free from id matter and unis \ |solved water at ambient \ emperature 2. laromaties, vol, Max a (oe 3. lOlefins, vol.%, Max. a |" P:230rP:48 | 4. [Net calorific valve, cal, Min 1025 t P:6 | 5. [Product of API gravity and aniline pol 5250 os | 6. [Copper content, ue/ce, Max 150 I = | 7. |Copper-strip corrosion for 2h at 00°C | _Notworse thanNot | Pris 8. |silver-strip corrosion at 451°C for 16 h Notexceeding 0) | IP: 227 | 9. [Distitletion | Pale | (a Initia boing point, °C ‘Not limited but to be | | reported (6) Recovery up to 200°C, vol%, Min. 20 { | Ce) Final boiling point,"C, Max. 288 { | (a) Residue, vol, Max. 18. | 4 \(e) Loss, vol.‘e, Max. 15 1 10. [Electrical conductivity, pS/M { Min. 50 { aia 300 | 11, [Existent gum, mg/100 mi, Max. a [eis sass ; 12. |Oxidation stability (16 h ageing) 2:2. Gibes [) Total gum content, mg/100 mi, Max 4 + |(®) Precipitate, mg/100 ml, Max. ‘To be reported separately | 18. |r int, (Abel), as :: PETROLEUM REFINING TECHNOLgg, * so ma 70 Pai (Peeing pin“, Mon |i: pton n 16. [Specs gravy ot 1561580 = on e 30 = a a Pos afer 18. Dacor test Max Tex re | 18 [otal sulphur, wt O20 1 20. fhernal stabi SFTOT =m Fer presure ifoonia Re 3 7) Sia wine Tons han 3 No Pease” | DERD ue oneal Perea : ‘or ‘abnormal’ colour ‘ment No.3 | ‘pals | (c) TDR, SPUN rating (Note 10), Max. 17. No. Peacock’ or i “abnormal colour deposits 21, [Total acidity, mg KOW/g, Max. 0.012 | 22, [Kinematic viscosity, eSt, Max: om P35 | (a)at —17.8°C 6 (bat ~ 34.40 5 i 24, | Water reaction P42 (Method A) [tq Interface rating, Max. 10), (o) Separation ‘Sharp separation, no emul sion or precipitate within ‘or upon either layer, 25, |Water separometer index modified 85 D25507KASTMIP) |(WSIND, Min 26, [Anti-oxidants, mg/i100 ml, Min. 86 Max. 240 “TFanti-ctatic additive ls presont in tho fel, Uhe water separometer index, modified shall be 70 mia ‘The volatility of ATFs controlled to minimize the loss of fuel from unpressurised aircra tanks due to boiling-off at high altitudes. For this reason the low volatility of kerosine tyPe ATP is desirable. Distillation specification requires at least 20 vol.% recovery up to 200°C. The 20 percent point controls front-end volatility, and ensures that the fuel will readily vaporiz® for cold starting and limit evaporation losses at high altitudes, ‘Auto-ignition of ATF can happen with a slight leak of fuel from the engine shortly aft" shutdown, or from a fuel line fracture during operation. The temperature for auto-igritio® increases with increase in vapour pressure. As the atmospheric pressures reduced the vapou" pressure of the fuel increases, and so the auto-ignition temperature increases. ial properties. Jet engines require the use of fuels which have low freezing point jaintain their flow properties..A high degree of thermal stability of fuels is required ‘®pernoveumPRooucrs 1 oid the formation of doposits and lacquers inthe heat exchangers and in the fuel tanks. The djant heat emitted in the combustion chamber of the engine and its effect on the life of the ot parts ofthe engine is aso important. This is controlled by the lurnimamet ardally by smoke point Aircraft ly at high altitudes with very low outside air temperature. This necessitates good pw temperature properties of the fuels. The specification of freezing point limit for ATF ix ased on the ability ofthe fuel to be pumped, and to flow effectively through the fuel handling em. At low temperatures the formation of wax erytals and wc crystals may clog and block ters preventing fuel flow. It is a safe practice to use a fuel that has a freezing point below s expected operating temperature. ATFs havo a freezing point specification of — 30°C aximum for keresine type and ~ 60°C maximum for a wide-cut gasoline type. The freezing int parameter affects the yield of ATF trom a particular cruce oil Because xt eontrals the boiling point which decroases with decrease in freezing pint of ATF. Fuels are now used as a coolant for engine oil, hydraulic and electronic equipments. On jh speed military aircraft and on supersonie transports the fui 8 also used as a heat sink or the air-conditioning systems and in the control of cabin air temperature. ‘The heat bsorption at cupersonic speeds results in considerable kinetic heating also. Hence, the fuel hould not oxidise and form gums, varnishes and deposits which will affect the efficiency of heat exchangers and also be lable to clog fuel filters, uel meters oF fuel injection nozzles into ‘the combustion chambers ‘The thermal stability of an ATF is controlled by the Jet Fuel Thermal Oxidation Tester IFTOT). The use of an anti-oxidant and « metal deactivator improves thermal stability ‘Combustion ina jet engine converts the chemical energy ofthe fuel into useful work. ‘The ality of combustion depends on the carbor/nydrogen ratio ofthe fue fixed by erude source nd type of processing) and the flame speed. The flame specd is also a fonction of fuel pmposition, as well as temperature and oxygen concentration. For ideal burning conditions lowest possible C/H ratio is required. The aromatic compounis present in the fuel are the most difficult toburn and ean result in the production af carbon, which forms smoke and henee Joes not release all ofits available energy. They also emit a high radiant heat from a kuminous 1. For this reason ATP specifications contain a maximum limit on aromatics content, A ification of smoke point is a direct control on combustion. Bre emissivity ofthe ame ie measured to sntsl the radiant hat in he prima zane of the combustion chamber. The apparatus for this test isa Tuminometer and the fuel under test ated oe fir arbitrary scale known as the luminometer numberof the fuel. Ahigh number jenotes a fuel of good tombastior quality-In Indian specifications a smoke point of 20 mm (minimum) and a total aromatics mit of 20 percent by volume give adequate contro ‘the wide-cut gasoline type of ATF, the best correlation with combustion deposits is Fe ee gare iaand Tuva knownea tho eveke vlad ISVI). It is defined as SSVI = smoke point + 0.42 (percent of fuel boiling below 208.4°C) Fuel-related problems. The fuol-related problems associated with gas turbine engine sation are listed in Table 5.16. AS is shown, the control of combustion characteristics nimizes carbon deposition in burner liners and on stationary turbine hardware, and also minimizes increase in burner liner temperatures caused by incandescent carbon particle diation. Luminous flames radiate more heat to these meta, parts than do nonluminous ames, resulting in higher metal tomperatures and reduction in component life. Relative to tamination, pas turbines operate best on clean fuel because of their sensitivity to particu debris, water, and metallic fel contaminants, Since these continuous combustion engine number andnel PETROLEUM REFINING TECHN, irs poet mn ini sod ot ihrer tn om Tn pect oon a rice metal (ie, sodium, calm, potas faminants that affect engine performance are tr = cl contamination, water suspended dirt/debris, fuel contaminati pe Miebrist vanadium, lead and copper), residual {hele surfactanta, microorganisms and refinery treating solution carry-over. 5.5.3 ATF Additive Varios ATP additives and their functions are listed in Table 5.17. These are described below. ‘Oxidation inhibitors (anti-oxidants) are used in ATFs to prevent gum formation ang 4, retard peroxide formation. The presence of peroxides in the Fuel will attack nitrile rubber} ‘used in the fuel system of aireraft engines ‘As a result of refinery processing copper may be present in ATFs. Copper is undesirabje in the fuel as it eatalyses oxidation reactions resulting in gum formation. A metal deactivator added in the fuel to remove any dissolved copper by chelating 6.16 Fuel Effects on Turbine Performance [Performance problem [ Probablefuei-reiated causes | Fear ombaation Hewlaninonstersumber oh llavenctepent High aromatics conn carbon residue values Heavier fel eontamination Races tines open igh uel iewity Low hydrogen content High sulphur?ietereatom content igh aromatics content Soluble meta contaminanta [Nowe plosring/wear High prticulatratamination Soluble metal contaminants [Heavy end impurities Marginal thermal stati High sulphur content Caplemesaaaoeipleccieeoem [Highsuiphortetere-wtom content | eavy ends contamination : [Thermally-reactive hydro [Low fuel viscosi flow fuelviscosity Marginal lubricit Water contaminationpETROLEU Ss 2 ‘Table 5.17 ATE Additives “Additive 7 are — Is revoke matin ad rt paid rman rain Sccliccdinton enero cnaton sec sting adatives [Nova the fesrng odie wai who alow — [Seidisipatradiives [To nereae the snd of the fl ands ees the pass o | [an electrostatic discharge causing explosion during high speed refuel | ling through 2 micronic Fiter |Used essentially for distribution pipeline protection, Exhibit beneficial [properties with respect to fuel lubricity Softee Ui acer ara wats sa colo es a odorata fs iahbt microbial and fungal ports sees tckeeess | At low temperatures clogging of Sites can occur in et reat, The effeciveadiives Beis parpoe aioe fo tr ctenth Shcms ouch oueatinteseeg tobe oak (i) Surftants,Alehels uch au eanel sheopeneeclang eel noe Ces such as dihyd alas ike heplene glyel nd geopsonseioel ac elesune at bts Bim Surictonts ae altatve aOR oo oe ‘Aviation turbine fuels can develop considerable electri charges in refinery storage tanks, Ess rl ealing anion snd ing socueuiea flnng patntoen: Onealy cease eek form due to static discharge and fuel ignition can occur if the spark energy exceeds 0.2 mJ. tier cnrivy of ATH isin the range af ODA plsomben the uo of sateSnepear Tadiive an rc this to 1000 picofl slowing rapid depation of charges on satemination of fel spoeble whan wate wars the dustin rata either by condensation or accidentally. Fuel soluble corrosion inhibitors have been used in ATF. Their Fe catatonia mary pecieations, Most popular types ae amine sls of high ‘molecular weight carboxylic, sulphonic or phosphoric acids. Some commercial types are alkyl aminophosphate, ethylene diamine dinonyl naphthalene, dimerized linoleic acid. ‘Anti-smoke additives can be used to reduce the amount of smoke emitted from jet engines on take-off. Fuel soluble biocides are used to inhibit microbial and fungoidal growth in aircraft fuel ‘systems. These are used periodically once every three to four months as a shock treatment. Another effective but costly approach is to add a biostat to tke fuel on a continual basis, [Oxidation inhibitors tion any dissolved copper to prevent catalysis of (Corrosion inhibitors 5.54 Storage and Handling Problems Particulate matter and free water are undesirable contaminants in ATFs. During transportation the fuel is liable to pick up dit, finely-divided rust and/or free water. Filter “separators are used in the distribution system to ensure the delivery of clean fuel nto sire ‘These remove solid particulate matter by filtration and separate out free water by a cpaless0 Action, These are designed to reduce free water to acceptable levels ( 30 ppm) and to rt the dirt level to less than 1 mg/l fuel. The most generally accepted system of me Particulate contamination is supplied by the Millpore Filter Corporation.PETROLEUM REFINING TECHNOL ogy, siya conductivity of about picosiemen/meter (pS!) kop, ion Kersine has a ionamin ioe ductivity of a fae ina tank may ed dice (CU), The opetnifak or meee Blecironice Ine. For compar’ waters cindy of 10" CU, Thus ATE haa ery ly ends ty demineralised water Os fects the rate at which the charged fens are romoved from the ue sn abate valu the fel bavalue time = 12/raductiity (CU) 8 ie gp indication of whether static change are likely to behazardousor nok. Charges con accumula, ia ot Mblc extent only if te relaxation time and the ha-value time are hi ean at eletrieal charges in handling of ATFs has long boon recov pl sf hasrd Auer ofr overng ping tein eli tog Haare aay sling) and setting times have been generally adopted by the major gt to ee ene acdce rane handling ofthese predust. As an adiional satay senator a static disipator additive may be added to ATFs. The additive permitted for use PNDERD 2496 specification is called ASA-S and its addition rate to the fuel is 1 ppm ttnaximnom, Phe amount of additive required depends upon the crude source from which the fut wan produced, since the additive response is affected by the variation in the chemia composition of the fuel. eis usual to dilute a stati dissipator additive with fuel before making tn addition te bulk fuel This is dane to ensure adequate dispersion of the additive inthe fel Satie dssipator additives (at the concentration used) have no effect on the thermal stability oroxdative stability ofthe fuel or its combustion quality. The presence of surfactant in the additive may reduce the water separometer index (modified) (WSIM) by about $ prints ‘Atypical avia as conductivity unit ( 56 DIESEL FUELS High speed diesel oil (HSD) and light diesel oil (LDO) are produced in our country. HSD iswidely used in diesel engines for automotive purposes, as in buses, lorries, diesel locomotives, Stationary and marine diesel engines as installed in ships or used for electricity generation consume LDO. Compared to the rest of world, India’s demand for diesel fuels is roughly six times that of the gasoline. Since straight-run diesel fraction Zor a given crude oil is fixed, ‘varying amounts of selected eracked distillates from conversion processes such as fluid satalyticcracking, hydrocracking, coking are used to increase the volume available for meeting the growing demand of diesel fuels. ihe primary quality factors of concern for compression-ignition engines are combustion, volatility and cleanliness (of both the engines and their luring use is related to composition, ‘erent stability of the particular fuel Sood ignition quality to ensure easy starting and be critically controlled to minimize environmental ‘trace contamination, and the degree of ini Diesel fuels for automotive use need smooth running. Sulphur content must pollution, corrosion, wear and tear. aepernoveum PRODUCTS « ‘Table 5.18 Fuel Properties Needed for Acceptable Performance Proparay controlled for desl fasta sail “Fuel performance required | _ “Property controled for disel fuels {Combustion iatlata range PEPE CEErereET? [Gravity (Copper corrosion [Cloud and pour point [Cleanliness during use (Carbon residue lash |Sulphor ‘Stability 5.6.1 Compression-Ignition (Diesel) Engine ‘The eompression-ignition (diesel) engine isa reciprocating internal combustion engine. In diesel engine the air intake to the engino cylinder is unthrottled and not premixed with fuel. Fig, 52. Typical escitoscope traces torcampression to"ae — i PETROLEUM REFINNG TECHNOL ogy sehioved spontancously without the aid of a sparking plug. Air induced intg Jenition is achieved spor Tenoure Is comprossed to a volume ralio somewhere near {og pliner tnd n tn angie spec and pplicben andthe ful expected tobe used. cee empression fuel is injected into the cylinder. set ahe diesel engine is a function ofthe compression rato, fq Cambios pee air and resulting ignition delay tine: | injestn timing, rapid homogeneous mixing of ful and a sulting sae injection ti oP ocuns jedivided inta separate stages. In thefirststage, airis eompresseg - east yressure many times and the temperatur to the required volume, This increases the Pi eto HegeC or more. As fue is injected intothis heated and turbulent airfor the second stage, mixing darn one and some presombustion oxidation of the fuel occurs. Combustion begins, Finally aa acs burning of the incoming fuel from the injector proceeds as the third stage. The seonar ignition tales place after injection starts, the smoother and quieter will the engine ‘operate. The quality ofthe fuel is a major factor influencing this delay Relative to combustion Fig 52 is a diagram of a time-pressure plot for combustion occurring in a compression ignition engine, The time interval between injection and the onset of the pressure rise is the ignition delay period. Distillate fuels having a high cetane number will show a short ignition delay period while those fuels with poor cetane numbers will give Tong ignition delay periods. Hydrocarbon composition directly affects the fual's physical combustion characteristics. The proper consistent combustion is influenced by physical fuel, characteristics, such as viscosity, API gravity, initial boiling point, 50% distillation tempers- ture and final boiling point. A rapid pressure rise results from the accurnulation of fuel inthe combustion chamber during the ignition delay period and the large number of ignition points occurring throughout the fuel/air mixture. With a long ignition delay time, the rapid pressure rise causes uncontrolled ineficient engine smoking. Itis this rapt pressure mise thatcan case Undesirable audible knocks, high stresses and severe engine vibration. To avoid these un- wanted, minute explosions causing knock, the pressure rise mus be kept even and consistent. ‘Thus, it is desirable to minimize ignition delay (measured by high cetane number). The fuel injection time can be reduced mechanically by selecting a proper nozzle spray pattern, injection pressure and a combustion chamber designed to create better fueV/air turbulence. A period of controlled burning results from even combustion with continual temperature rises throughout the fuel’s distillation range. For a given diesel engine, a fuel of higher cetane number causes 4 shorter ignition delay period. Consequently, higher cetane fuels generally cause lower preanare ee ries and lower peak pressures, Both tend to lessen combustion noise and allow improved combustion control, resulting in inereased engine efficiency and power output. In addition to these advantages, higher cetane fuels tend to result in easier starting, particularly in cold weather and faster engine warm-up. Reduced exhaust smoke and odour are als0 associated with higher cetane number fuels 5.6.2 Composition of Diesel Fuels Its a general property of hydrocarbons that the auto-ignition temperature is higher for a. va hydrocarbons. Therefore, the less volatile middle distillate fractions of rude oiling in the range of 150 - 400°C are suitable as diesel fuels, The hydrocarbe resent in able as diesel fuels, The hydrocarbons Pr the diesol fuels include paraifins, naphthenes, olefins, and aromatics. Carbon number of these fuels ranges from 12 to 18. Diesel fuels can contain both saturatea and straight or unbranched chain unsaturated hydrocarbons, but the latter are not present in large enough amounts € make fuel oxidation a problem. The aromatics that are present generally are oxidation resistantpernoLEUM PRODUCTS a of 168 Propertios of Diese Fuels Me apotent arses oteed fone ee fl are iste in Tale 5.19, tention aay pert in igh at aa into speed engines vied in large stationary and manne eaten Tac moe cael tected measure ofthe ignition quality of desl furl cotane urban. Cotene inde which Drowdee a measure of ignition quality very coe to etane none cosine seed, Zicalsted based on 10%, 60%, 20% cisilotontenvortereennd erates Dini hc nitrate or anine tana guy paresis onl) ae + than Cetane index When ition gules improver are added fuels, the ignition quality eannot be indicated either by etane Indes or deel tales, ues of ignition quality can lead to extended nition delay and esl the phasomenoe af ‘Bese knock’ This lend a decrease in ectency maby exhaust, eankeece ot fotos md Fertonacoruedopeitain paton rng ra, Tn general the cetane number scems tobe asscated wih the thermal stabi sssccated withthe thermal stability ofthe fuel hydrocarbons. Thu, higher malcular weight normel alkanes have high ceane numbers Generally, igh performance dicsel ols are require o have x eeane namber higher rar Innis, high speed diesel engines are suplied with dec! al tavingacatane guaber nore than 42 Welty isthe major determinant ofthe tendency of hydrcearbon to produce potentially eplosve vapours. Ie also is erically important t9 am engine tart nd Warr up. The fesence of high-boling point compenonts in fula can sigicenly affert the dope of el engines, Iti lees relevant formation of solid combustion deposits. Proper operation of an engine depends on the proper viscosity of the liquid fuel. The ‘viscosity of the liquid fuel is important to its flow through pipelines, injector nozzles, and orifices, and for atomization of the fuel in the evlinder. Diesel fuels should not creates any operational problems duringits use. For example, diesel fuels should not cause deposits to occur in fuel injector systems or critical piston ring areas, ‘The carbon residue value of diesel fuel correlates with the amount of carbonaceous deposits, which are formed in the combustion chamber of the engine. The higher carbon deposits in the combustion chamber are expected with the diesel fuels of higher carbon residues. ‘Table 5.19 Desirable Fuel Properties of Diesel Fuels Fuel characteristics Comments 1, [Cetane number|ia) A measure of ignition quality of diesel fuels |b) Diesel fuels having high cetane number show a short ignition delay c) High performance diesel fuels have cetane number higher than 45 (d) Higher molecular weight normal alkanes have high cetane numbers (e) Influences both gaseous and particulate emissions |() Has an influence on cold starting and on subsequent white smoke and noise lemissions \g) Cetane index whichis very close to cetane number is calculated based 08 (Tos, 50%, 90% distillation temperatures and specific gravity i (i) Fuels with high autoignition temperatures are more likely to cause diesel) knock pea fio ———PETROLEUM REFINING TECHN) oy, Tee eee [ay Affecta fuel performance and safety Ye tart and warm Up [important tan engine's tart. oor arnjgh baling components affects the degree of formation of nig Jeombustion depasits Id) Needed in tho estimation of cetane index. = (Specific gravity (a) Requi red for the conversion of measured volumes to volumes at standard ltemperature of 15°C |) Used in the calculation of eetane index (a) A measure of energy available in a fuel (A critical property of fuel intended for use in weight-limited vehicles (a) Indicates the presence of highly volatile and flammable materiale |) Measures the tendency of oil to form a flammable mixture with air Ic) Used to assess the overall flammability hazard of a material (a) Proper viscosity of Fuel required for proper operation of an engine (b) Important for flow of ol through pipelines, injector nozzles and orifices () Effective atomization of fuel in the eylinder requires limited range of vis- ‘cosity of the fuel to avoid excessive pumping pressures [Contamination |(a) Causes corrosion of equipments (©) Causes problems in processing (c) Required to accurately measure net volumes of actual fuel in sales, taxa tion, exchanges and custody transfer (ce) A uicasuse to assess relative degree of corrosivity (b) Indicates the presence of sulphur compounds elder plug: Gator for Inge storage tanks and pipelines af refineries and terminals (a) A measure of the performance of fuels under cold temperature conditions, |) Used as quality control sepeification or low temperature handling in- 10. (Carbon residue |(a) Correlates with the amount of earbonaceous deposits in the combustion chamber (6) Greater carbon depsits expected for higher values of carbon residue i, [a Indieates the potential o emission of particulate matter Je) Contain primarily earbon particles |) Soot carbonaceous particulates formed frm gas-phase processes) parties absorb and carry eareinogenie materials into environment as emission aé A fesse an i effect on human health. Excessive soot particles might clog the e- 2, c) Result from ol wateracluble metalic compounda or extrancou so jsuch as dirt and rust. a im (Can be used to decide products suitability for a given application 18. [Sulphur (a) Controlled to minimize corrosion, wear and tear \©) Causes environmental pollution from their combustion products Kc) Corrosive in nature and causes physical problems to engine parts__—_—) Particulate matter contains primarily carbon particles. Carbonaceous particulates that form from gas-phat Byrolysis of liquid ise processes are generally referred to as soct, and those that develop fro hydrocarbon fuels are generally referred to as coke. Because soot partic”‘pernOLEUM PRODUCTS. - see can absorb and carry carcinogen left on human health Sulphur content must be critically controlled to minimize corrosion, wear and tear Soiphur compounds pose a dual problem: they not only cause environmental pollution from eal problems to engine parts. Sulphur pollution and corrosioa were problems long before the NOx were known to affect the atmosphere. The general availability of low-sulphur fuels, however, diminished the concern with respect tothe sulphur ‘The performance problems versus fuel-related causes for compression-igntion (diesel) engines tre summarized in Table 620. The more eitial problems are thse relied to combustioh, injector nozzle/pump fouling and filter plugging. Indian specifications for diesel fuels aro listed in Tables 5.21-5.22, plugging, pecificat ‘Table 5.20 Fuel Effects on Compression-Ignition Engine Performance ie materials into the envirarment as emission, they ean Performance problem Probable fus-relcted cause Porcombustin, smoking [Loy rtane number; Water antanien; Improper daud pit Bicess cylinder wear Fuel aitution ; High culphur content Dir (ilicon) contamination Injector nozaleplugging wear [Soluble metal contaminants; Heavy end impurities; Preformed [gum impurities Injector pamp fouling sticking. [High sulphucthetero-atom conten Heavy ends contamination [Gasoline contamination Low uel viscosity IPiter plvgsing |Weter contamination ; Fuel impurities ; Improper cloud point IThermally-reactive hydrocarbons [Excess engine doposita leavy ends contamination; Low cetane number; High suk lphurihetaro-atom contant Table 5.21 Requirement for Diesel Fuels US: 1460-1974) Siva] ‘Characteristics ‘Requirement | Method of test 181448. 1. [Aciity, inorganic Ni Pid 2. |neidity, total, mg KOH/g, Max. 0.50 Pa 3.__[Ash, wt.%, Max 0.01 Ps 4. [Carbon residue (Ramsbottom), wt, Max. (020 Ps 5. [Cotane number, Min 420 P 6. [Pour pint, °C, Max. e P 7.__[Copper-strip corrosion for 3h at 100°C Not worse than No.1 | __P: 15 8. _[Distitlation-Reeovery at 366°C, vol, Min 20 Pils 9. [Flash point (Abel, °C, Min. a Piss, 10. [Kinematic viscosity at 38°C, St 20-75 P26, 11, |[Sediment, wi, Max. 0.08 P30 412, [Total sulphur, wt.%, Max. 05 [P83 or P:95 +18. [Water content, vol. %, Max 9.08 P40 14. [Total sediments, mg/100 ml, Max. 10. a ‘Scbject to seasonel changes, pour point varies from 0 to 18°C (for Naval applications)- PETROLEUM REFINING TECHN, 100 Table 5.22 Requirements for LDO Fuels (1S: 1460-1974) ‘Sto. Characteristics Requirement Mate fias~) ua | Nil 1. [Acidity inorganic a : 2 [Ash, wes, Max. [ a — 7 3. |earbon residue, we, Man | 158 1 + [Pour pint Max. 12 for winter Pao | rar point, °C, Max. 16 for summer = lempeneiparmmin Bron | Rat woe tan Noe | PE 6._ [Flash point, Pensky-Martens (closed), °C, Min. 66 Peat 7._ [Kinematic viscosity at 38°C, cSt 2.0-15.7 P25 Selman wt Max ov ra) ial sash, 8 ax is PiasorP apa aa oe i us P| *Winter-November to Febroary, both months inclusive { 5.64 Additives fr Diesel Fuels I. Diesel fuel additives are used to enhance fuel quality and are often cost-effective. Cetane improvers. These are used to increase cetane number of diesel fuels. Straight chain paraffins ignite readily under compression, but branched-chain paraffins and aromatics | react more slowly. Since diesel fuel’s ignition delay characteristic, and subsequent complete | versus incomplete fuel burning, directly influence overall engjne performance. Cetane number | of a diesel fuel reflects the ease with which it undergoes’ pression ignition and is an indicator of performance related properties which include cold starting, smoke emissions during warm-up, noise, power, exhaust emissions, fuel consumption and engine durability.» Cetane improvers are compounds which readily decompose to give free radicals and thus enhance the rate of chain initiation for hydrocarbon oxidaticn in diesel combustion. They Promote fast oxidation of fuels and thus improve their ignition characteristics. Cetant improvers are mainly alky! nitrates. Dependingon the base fuel’s cetane number and additive | ‘treat rate, it is possible to obtain very cost-effective improvements between three and sit cetane numbers with the iso-octyl nitrate. One cetane number increase requires about 100 | pounds per thousand barrels (ptb) cetane improver. Cetane ‘improvers Provide refineries with a simple and effective means of achieving ‘operational flexibility on a day to day basis. They are typically used to: * Upgrade HSD quality to meet specification requirements in conversion refiner | where economic benefits from the use of cracked components in HSD produetio= | * Give the flexibility thenic crude. Detergents. These are used as cleaners to remove carbon: gummy deposits {rom fuel injectors and to prevent farther formations Fuel gums cause moving pars 8 system to stick, especially close-tolerance components like injector needles and plus Tequired to process significant quantities of low cetane nspty ipermoceuMPRODUCTS 10 3. Lacquer and carbon deposited piston and mn injector needles restrict fel Now, distort the fuel Fray and often totaly block one or more holes in'a multe injector, Sfodern detergent sfarerecompored mainly fates amines nd amides, Odor -ycimidazonen re sil awed. However, some ofthese older-style detergents under the high tmperatures (71°C) and tigh pressures (1100 KPa) experienced in todays engines, react with deme nc form & blac, Silterplugging residue, These residues can block fel filters and wear close-talerance injection system parts in less than 1600 miles (or 50 hours) of operation, The detergent must silded to the base diesel fuel at a minimum dose sf song son ede ve el fa 0 to 0 pth to effect optimum engine Stabilizers. Theseretard the natural degradation of diese fuels during long-term store Because diese fels are organic in nature, they will dograde from the Utne of munatucnace unt the ume of we, The harmful effects of uel oxidation include e-arbon partials fallout and sedimentation sludge buildup in the fuel delivery system and fuel storage tanks, Bieflowing stabilizer additives are needed. no aaa iae ‘+ De-emulsifer to improve anti-haze and minimize fuewater suspension «Sludge retardant to limit deposit buildup. + Dispersant to break up fuel droplets, reduce surface tension and provide buifer barrier to prevent further deposits. + Rusteorrosion inhibitor to prevent pitting and erosion of metallie surfaces. + Metal deactivator to inhibit deterioration by trace metas, + Antioxidant to retard formation of gums and deposits Dispersant restricts the size of fuel particles and reduce the fuel’s surface tension. By lowering the fuel's surface tension, dispersant modifier additives such as polyamides, polyisobutane and succinimides cause the fuel droplets to break up and atomize more easily. Bectuse they are surfactants, they also are adsorbed onto metalic surfaces and provide buffer barrier to prevent future deposits and keep the surfaces ofthe combustion chambers ‘nd injotion nezsloecloan. Dieporcante provide adoquate performance when added te diesel, fuels at doses of only 20 to 25 pt. ‘Anti-corrosion and rustinhibitor additives are used to protect pipelines through which Aiceel fuels are transported. These form oily coating over metal surfaces as protection against corrosive attack. Usually the protection of fuel system from corrosion and rust requires only 305 ptb. Metal deactivators inhibit eatalytic decomposition and deterioration of diesel fuels by copper and other metals. Typical dosage levels of metal deactivators are 2 to 3 ptb. ‘Anti-oxidants retard the formation of fuél gums, sludges, sedimentation deposits and ‘xidation byproducts, One notable effect of fuel degradation during long-term storage of hydrotreated or hydrocracked low-sulphur diesels is peroxides formation. The anti-oridant sdditveis tobe added ta the diesel Fuel as soon after the manufacture as possible, The peroxide inhibitors are cost-effective at a treat rate of 3 to 6 pt Cold weather additives. Paraffins exist in all diesels and vary in amount depending on the crude oil refined. In cold temperatures, paraffins crystallize into wax, Without flow ‘odifer additives, this wax generally creates large, flat platelets ccystals that tend to clump together and clog fuel filters by adhering to the screen grids, The resulting engine starvation ‘an cause poor starting and engine shutdown. z Pour point depressants, flow improvers and cloud point reducers are three basic types of ‘old-ow modifiers. Wax (paraffin) content and the type of fuel will affect each of these Parameters as well as an additive's response when treated, Wax content in a finished fuel is "ainly a function of boiling range of the diese! fuel and the composition of the crude oil. Fuelsi _ rrcmnensum smaumemnueueaaeaaaeaes PETROLEUM REFINING TECHNOL ag, » omewhat smoller, nore consistently shared with wide bing range unl rm Sort tmonit, The narrow boiling rang died gat crystals that are more responsive 0 Ar tals that do not respond well to traditional cold, tend to form larger, nore dense 62% Cy chemicals that lower the pour point temperatur, ties Pour pine deoreents oe om eigen af wax rsa and modi, ‘Today’s pour point depressants work by changing® es aaitives reduce the erystal format he wancnystal's shape and size as they form. Th in, rate effectively ’ n also lower the + improve cold flterability, but they ca pour Flow improvors primarily improve ole atl formation bs forming nuclei and arresting of the fuel. These chemi Batelets, a formation of small, multi-axial needle ers aot: Instead ofthe lage £6" Pipe bolo the cloud point, sal Wax erytale begin, develop. A the fel omar’ molecules atach to erystal surfaces and block Fo ee ualler erystals. By virtue of their small size and multi-axial neciy Fo nsat these wax erystals pass more easily through fuel filters. Flow improver, srrangem at eaeured by cold-flter plugging point (CPP). The best performing CFP» ‘uultive requires dose rates between 65 and 125 pt. d “Antiwax settling additives (AWSA) are flow improvers that disperse wax crystaly uniformly. Normally, small, compact wax crystals tend to settle in tank bottoms, especially in nupltated storage tanks. These compounds create more porous (less dense) wax erystals with repelling charges that tend to prevent wax agglomerations into the larger/heavier wax crystal matrix. These additives work more efficiently in lower wax-content fuels and total wax content trill affect performance of all AWSA, Most distillate fuels can be effectively treated with [AWSAs at doses between 40 to 60 pt Cloud paint reducers lower the temperature at which fuel paraffins present in the diel fuels begin to haze or cloud. Generally, a reduction of approximately 2 to 3°C in the cloud point ‘can be achieved by the use of olefin-ester copolymer. Typical levels of cloud point depressant additives are 50 to 170 ptb. De-emulsifier and de-icer agents break any fue/water mixtures and prevent water frm freezing in cold temperatures. De-emulsifier additives can be of different chemical makeups. ‘The only effective de-icer additives are chemicals of glycol-ether type. These additives cheni- cally combine with water droplets (and dissolved water accumulations), break the surface connection with the fuel and lower the freezing point temperature in direct relation to the amount of de-emulsifier and de-icer present. These additives should be used in combination at dose rates of 10 to 20 ptb. Lubricity additives. Rotary or distributor-type injection pumy used rity ; 36 injection pumps are used inthe mo area diesel fuel injection equipment that rely on the fuel for lubrication. This contrasts vith imine pumps, mast commonly found in medium- and heavy-duty applications, me fame components are lubricated by engine ol. fuels lubricity can be loosely defined asi ty to reduce friction between moving metal parts and prevent wear. A more Tigi t definition is as follows: For two liquids ofthe st” 004-68) 40H, viscosity, if liquid A gives lower friction, wear © ° oer than liquid B, A is said to have he igher) lubricity. Generally, the new low-su! HCO-C(CHty (CH=CHGHs) CH, diesel fuels contain less aromatics (diaromati! polyaromatic) beesuse of the severe hydrotreai ‘Recessary to lower the total sulphur content.’ HaC-0-C4CHy)CH=CHCH, CH=CHICH,)CH, low-aromatic fuels negatively impact the fuels Fi. 83 Stucts of ypcaltigeerde mouse, D&tUFal lubrication tendency and increase the ° tltRt De le Oe Table 6.23 Fuel Properties of Vegetable Oils E SSS == SSS ‘scorty [Number | heating | oan ease 1 <9 Caneel (aera (aaa and | residue np ment = mm’ wine |e |e | co | wi [wis | wa | wa |e, Cantor aot [= [ara |. | ont | 260 | ener | te | 22 [cor] or (Corn so [are [sos | ai | aoe | 277 | os | me | | | or [tu [cottonseed | aa.5 | aus | ss | 17 | 150 | om | ove | oo | 4 | 0 | 0 | wo (Crambe 536 | «46 | 405 | 100 | a2 | 2m | som | 2 | 29 | os | ov | in Linseed 272 |e | a9s | 17 | 150 | 20 | sme | t [ a [cor] | | Peanut 39.6 418 39.8 12.8 an 9026 Tr 24 005 O1 is | [Rapeseed 310 | are | s07 | 29 246 [ous [te [30 [om | or ] ta Saflower | 13 | 418 | 205 | 188 250 | s1 [te [25 | 006 | 01 | te HOSuMower [2 | 491 | 305 | 122 2559001 [me] 24 | «om | 02 | ta Sesame 255 [402 | sos | 39 oe0 [9199 |r| 2 | 01 | cor] Soyabean | sz6 | a0 | 996 | 9 psu 9196 | ty | a7] cor [or [8 Sunfower} 339 | 71 | s96 | 72 moe |r] as Peo | or | ie ea ee = [aor fone Babess $6 fg tf ao fone PT aie peta ‘r= traces cot(PETROLELIS REFOENG TECHNOL OSS sty enhancement, Forlw-sulphor dices, rity is improved jy | for supplemental bri onan nal beet properties. Most fective abr agg tives require 308 pb 5.65 Alternative Diese! Fuels are under way in many cOUD inn ae ne ronment endl. Te rises mainly from the tandPos iin ton aupples ofeanventsonal ydroea tong apncally acceptable, economical mp rae lable From the wow point of these reas sete alternatives for diesel fuels Vegetable oils and their derivatives ‘coal eee Yoqetable oils and their derivat singin ren ae rain odin earch ran aerate dick | resent gone a tee ror den fn, Teale tie erienmental scala | + Petrocrops + Agricultural wastes ves. The basic constituent of vegetable sili feride molecule. Vegetable oils comprise of 90. sie ibe el een etn percent triglycerides and small amounts of mone- and diglycerides. These Fat acid generally 1-5 porcent), phospholipids, phosphatides,cazotenes,toopherds so hur compounds and traces of water. Triglycerides are esters of three fatty, sed and ooe Jivcerol Fatty acids vary in their earbon chain length and in number of double bonds. The itty acids which are commonly found in vegetable oils are stearcc, palmitic, oleic, Linoleic and linolenic. ‘The properties of vegetable oils are listed in Table 5.23. The kinematic viscosity of vegetable oils varies in the range of 20-40 eSt at 38°C. High viscosity of these oils is due to large molecular mass and chemical structure. Vegetable oils have high molecular weights in the range of 600-900, which are three or more times higher than diesel fuels. The flash point of vegetable oils are very high (above 200°C). The volumetric heating values of these ols are in the range of 39-40 Mu/kg which are low compared to diesel fuels (about 45 Mfg). The cetane numbers are in the range of $2-40. The iodine value ranges from 0 to 200 depending ‘upon unsaturation. The cloud and pour points of vegetable oils are higher than that of diese fuels. thas been found that the use of vegetable ols as diesel fuelsin conventional diesel engines leads to a number of problems which are related to the type and grade of oil and local climatic conditions, The high viscosity of vegetable ois interferes with the injection process and leads to poor fuel atomization. The inefficient mixing of oil with air contributes to incomplete combustion. The high flash point attributes to its lower volatility characteristics. This leads ta more deposit formation, carbonization of injector tips, ring sticking and lubricating oil dilution and degradation, The combination of high viscosity and low volatility of vegetable ails causes poor cold engine start up, misfire and ignition delay. Oxidative and thermal polymeriz tion of vegetable oils cause a deposition on the injector, forming a film that will continue to trap fuel and interfere with combustion. The injection, atomization, and combustion charac teristics of vegetable cils in diesel engines are significantly different from those of hydrocs™ bon-based diesel fuels. In long-term operation, vegetable oils normally develop gumming Instr eng sa Ting sticking. Another problem is incompatibility with conventional ae . Therefore, the engine must be more or less modified a tions of use fee eee wdified according to the condition: ‘The use of vegetable oils as diesel fuels in conventional diesel en, sires modification e mnventional diesel engines requires m« in their properties through physico-chemical processes. Considerable efforts have been to develop vegetable oil derivatives that would approximate the properties and performanc® | jper oLEUM PRODUCTS 105 atthe hydrocarbon-based diesel fuels. The probe ths frolsare mostly associated snk ea Broblems with substituting pure vegetable oils for Iday ood to reduce Che vices et DEA vitcolien. Tho roots of rareeciotection Spolysis, ‘he displacement ofasent) of Yesetable ola: Trancesterifcation alee cakes fon reaction of triglyceride using moth, from un esterby anath 'anol is represented by H : H Ee | eo R HCOH ROOCH : Cataiyat A H-C-OOR +3083 08 wc on + ROOCH | 1 + ae H.C-OH R00CHs \ a (Methanod (Triglyceride) (Glycerol) (Patty acid methyl esters) The fatty acid methyl esters are referred to as biodiesel The properties of biodiesel are a St ey etre sina Th pope ht biodiesel becomes a strong candidate to replace the diesel fuels if the need arises. The conversion of triglycerides into methyl esters'through transesterifcation process reduces the molecular weight to one-third that ofthe triglyceride, reduces the viseosty by a factor of about ight and increases the volatility marginally. Biodiesel has viscosity lose to diesel fuels. These ‘esters contain 10 to Ll percent oxygen by weight, which may encourage more combustion than hydrocarbon-based diesel fuels in an engine. Since the volatility ineroasos marginally, the starting problem persists in cold conditions. Methyl esters have lower volumetric heating values (about 12 percent) than diesel fuels buthas high cetane number and flash point. These esters have cloud point and pour point that are 15 ~ 25°C higher than those of diesel fuels. ‘The main advantages of using biodiesel are its renewability, better quality exhaust gas ‘emissions, and biodegradability. The organic carbon present in the biodiesel is photosynthetic in origin, and it does not contribute to a rise in the level of earbon dioxide in the atmosphere ‘and consequently to the greenhouse effect. Different technologies are currently available and used in the industrial production of biodiesel, which is sold under different trademarks. For example, there are the Italian processes Novamont and Ballestra, the French IFP, the German Henkel and ATT. Triglycerides can readily be transesterified batch wise at atmospheric pressure and at slightly elevated temperature of approximately 60- 70°C with an excess of methanol and in the presence of alkaline catalyst. The mixture atthe end of the reaction is allowed to settle. The lower glycerine layer is drawn off while the upper methyl ester layer is washed to remove: entrained glycerine and is then processed further. The excess methanol is recovered in the fondenser, sent to a rectifying column for purification and recycled. The Henkel pres 8 at 9000 kPa and 240°C and uses unrefined oil as feedstock, Unrefined ol, moti ‘excess and catalyst are metered and heated to 240°C before feeding into the rears ‘bulk of the excess methanol is flashed off as it leaves the reactor and is He lumn for purification. The recovered methanol is recycled into the systemg ‘Table 5.24 Fuel Properties of Biodiesel wiifenee”"[Rinematic] Qetane T Lower Cloud | Pour | Plash | Density | Water | Carton | Aah | Sadpnar] Copper smtener “I viscorty | Number | heating | eint | point | pee land weil residue ele oss value ment corsion mm/s MIL "C ° iy eft | vol.% | wee | wt% | wis, Peanut [49 [54 | ose | «5 | — | me | am] — | —}— > 7— Soyabean | 45 | 45 [ons [sor | 7 | ame | a5 | gas att al Ma [ete] Paint Pat —| Tee er Gavest| Ramer] Fane | Tose] ait | Pant | Tee Uses elven | sty induct) Pn eon “he ing ‘s| pains [esis seins eeePETROLEUM REFINING TECHNOL, vy manufacture isoparsdfinic solvents. In this preg | tow-boiling iso-paraffins, eg. isobutane reacts, with low-boiling aa ens isobutene | so etnies wh Tereacuona given Choker 8Arangag | iling above istllation, These alvents are manufactured from the fraction boiling rc on. These ay | practically odouriess due to their high inoparaftn eee ea oe at pes ae ‘Th Fnivents have a somewhat ow solvent power. These solve choice in photxpy vents have a somewhat iw urans paints ee. since these uses require 8 no-odour produ ing, hausehold products = iedstock source and other conditions in a refiner, tment, Depending om the fer ms sreclrestment, Depending soften raqired to prodvee marketable solventa et ce ee ec pi see es se reo | ain tac ice i a sri ae Fo a net omer ay | wren ent my ene Wh ap Oe ee surat eet Kan tmalensictchwoaneras | es Clay treatment is usually required for hydrotreated products to produce products of acceptable odour. Clay/activated carbon treatments can improve acid wash colour and remove cae ae ae a peas Sn enc 1 ei ct mts ln i ye eter deren wir eoeiegtasre Aare Se eae ec ne aaa reece ee eee ae eee = [Alkylation process is employed to 5.84 Properties of Hydrocarbon Solvents | ‘solvent is expected to perform several functions. These include (a) The preferential removal of one substance from another, (b) To cause a slid o viscous material to become fluid enough for use; (To permit its removal by evaporation; and (d) It must bo inert to the material it dissolves. ‘The quality of petroleum hydrocarbon solvents is judged by the characteristics of solvent power, rate of evaporation and odour, Afpeoensn chee ‘and chemical stability of the hydrocarbon solvents are of utmost importance. All solvents should be clear and free {rom suspended matter Most of thehydrocarbon solvents except afew high beiling are water whi Odour ofa solvent is becoming increasingly important. Odour in hydrocarbons is due impurities such x sulphur or osidied degradation products, Odour is important nent 85. such af photocpying degreasing, low-odour paints and household products. Aromat yarns usually mparssarp unpleasant our Naphthenes have wer ad ue ina ayes et 1 drying rate in surface coating end-uses is of utmost such application ‘he evaporation rato volatility ofa hydrocarbon salvent athe eer roee ean herceteipernoLEUM PRODUCTS, icder to minimize dust collectio oa Ang time should be short. Ths recat allow saesing the evaporation ratae sesame Svaparation rate of 1 =, ivent power oF solvency, i a measure product "The available testa Tor nasal of the Pimber, aniline point and dilution +, Retutt ay gives an indication of olven Sezente inthe oder ‘aromatics > Naphthenes > n-Paraf srafins > Isoparaing ‘Aniline point provides a useful means of dare solvents since aniline is a poor solvent fox = dromatica The aniline point eats veca aly hana = itly fast Tate of evaporation At theses 'gh to allow the devel, fe god fe butyl acetate hee tility of solvent to ato, Tho composition a Bower. For most pales ent to dale nen i dst ae unre ‘lydtcarhon sven he and resis, sent nn the solvent power of hydroeare aliphatic hydrccarons but an exocloaen he ly selected to measure he solvent power aliphatic Ne pina wich ea cul solution of Kaur resin daslvedstsburam ae a tpdrocarbon nolvent power. Thi test con Beene higher KB number implica higher solvent pewer since marca anced ates en ee than a poor one, Standards ae aluen (KB number = 105) an Gade eee ea vol toluene (KB number ~ 40). Commer sens hate KB vsloc ne es Sea 105. : own criteria of the 5.8.5 Uses of Hydrocarbon Solvents The end-uses of hydrocarbon solvents are listed in Tahls 5.9. The surface coating industries (paints, lacquers and printing inks) are by far the largest users of petroloum hydrocarbon solvents. The word ‘paint’ is usually applied vors broadly to cover pigmented materials. Non-pigmented paints arc often termed varnishes. Examples of paints are ol paint, chlorinated rubber paint, bituminous paint, stoving paint. The wl paint, based on a combine tion of vegetable oil and synthetic resin, isusedin house decoration The requirement othigher chemical or water resistance is met by chlorinated rubber paints, Bituminous paints are based cutback bituminy, The resin bnderin these systems sellin thohyércaron sven In stoving paints, a proportion of an oxygenated organic solvent, usually n-butyl aleabol, is to present. The type of resin and the desired viscosity deat the chemical typeof solvet tobe used. Most paints dry by solvent loss by polymerization. The volatility ‘oating ofthe paint. Rapid drying and high viscost Slow drying and low viscosities may cause sagging, Air drying paints are based on drying oils sue Synthetic resins, mainly alkyd resins. White spirit containing 15°) cy used inthe ol pair frmolations,Thisdissolvesa widerangenfres Fe oa, ith an acceptable visosty, The solubility of the resin nthe hydrocarn sf ing lazlyen tho resin ratio, Low aromatic hydrocarbon solvents wore tant, isconsiderably higher than the resin content. Ifthe a cs mes inthe stving ith aromatic hydrocarbon solvents are required. Asleneisvrey a tie hyeroerbon ifng of the paint film eannot occur with stving axwellasby chemical change them frming materials a the solvent power alc the appearance of he Sal fice may contribute towards unevennes ithe pat runs down veri surface Dra ngeed embined ith natural 6 eon eos coins, ivngsautions paints in which arom~ PETROLEUM RETIING ECOL, vents are mainly used. For household and similar paints, white SpTits With a very gy ed to give low odour or odourless paint ‘Table 6.29 End-uses of hydrocarbon solvents. End-wses Hydrocarbon solvent — eee ee ———sgrensing cl extraction, paint, printing inks, rubber i (anna, lacauers rc rte [Lube oil dewaxing, paints, lcquers, printing inks, rubber sola Low aromatics | Tigh aromatics Pisco [abs a dewaxing, skool dehydration shoal dewosng rubber solutions, pains =a Tate sa sotopng ioctl, rubber slitons pg | Seas eewS rte | Benzene ‘Toluene Xolenes [aoa 0-10) iss aay ceteeeaiig ey Wig rae Seca liek a ceetnetet exten Seaski | Premises = ' Kerosine solvents (160 — 300°C a, F Low aromatics [Dogreasing, catalyst carrier in polyolefin production, inse. scdes, pats, lacquers, printing inks greasing, insecticides, paints, laeque reclaiming igh aromatics printing inks, rabber Lacquers dry purely by solvent evaporation and hence no chemical change takes plat during drying. Nitrocellulose lacquers, a pigmented laequer are ased in repairs to motor ear. Unpigmented, ic. clear lacquers are used in furniture finishing. The solvents for cellule, vinyland eerylic lacquers are ketones, esters and ether aleohols in conjuction with hydrocarten solvents, In lacquer formulation the hydrocarbon solvent is used as a diluent and is diluting ower refers to the proportion of diluent that ean be added successfully. A correct balent® betsreen the different components in the solvent system during evaporation rust be mi- tained. Duc to short drying time, quite volatile solvents are chasen. SBPs of suitable buns ranges with high aromatic content may be used. Inaddition to mostofthe factors mentioned n extraction processesis to extract selectively #00! : product or raw material, e.g vegetable oil, pharmactt cals leaning and degresin, ee. Vegetable il provide a valeabe correct ll Try atsriale for sonp and paint manufacture. These cls are artroten fen cede usb Crdreenonsalvents, Vegetable ils of commercial importance incade serehoan cunflt™ ape seed and rice bran. The solvent for vegetable olextraci®™ Particular ingredient from a mixed produ yrL ed a Lie feo eS SERS 2. — SBeaese guvent losses during i sed extraction are urealin ag oreo tabeaee ee te ccuring in the sods, The preferred alvent fur the exer heen Hin, feed rade hexane (SBP 65/70), Vegetable oil indusiey een ‘eolgrede hens consuming around 90% of the total hexane production in India nt? ETade hexane, Other important extraction processes include pera sae and pyrethrum extrac- als dissolve in theydrocarbon selvent, Tastee low boiling SBP, rent, These processes use isshexane oF ee Fate i Prd ro aing aS gs. Th erly tnd aha polishes, ot. turpentine has bon repleced by white ees son ee tsseaNow many emulsion-based formulations Gores een Bi cening peri are svalabl. The ment ra hos ok Gina the wax. The oiling range is alo important in rms of raat ee seal Baling interval The concentration of a slvent Ins lei rane ene Sending nt can be a igh 70 pent in arts ne sn plo watorbated emulsions. Oxypenatedslventefgyclelierigncsereed oe iomulatons lycol etter ype aresed isonet ‘The hydrocarbon solvents are used in the producto of adhesivesand inthe manufacture crires. Adhesives play an important role n scveral manuctrng proses Cake ed fetwear, automobiles, the building industry, furniture and ether eaeanee dartlee te poctaging and labeling indostry Aahesves based on rubber are a relatively loco water resistant edhesiven The rubber ahuarbssalvent to give a sticky solution which may bo used as an adhesive The choot Scvet is mainly dependent on the typo of adhesive required, whether fast drying oso trying For adhesives based on natural rubber, aliphate SBES are suite For the manufacture of tre, a medium. to high bling SBP maybe used, The natural rubber bales are coated witha fine white powder fo prevent the ba from siking to cach ter ale coating solution ia propared using white pita 5 or 48 percent aromatic Inthe chemical industry, hydrocarbon salvents are widely ved x reason media during ttepeymerzation ofolfing, uth asethylene, popplene to form plastics and clastomers. The function of the hydrocarbon solvents differs from one process to another. A catalyst for the ‘anufactare of polyolefins usually introduced ato he easor ass suspension o arr thehydrocarbon solvent, At the same tine, the hydrocarbon solvent acta a solvent for he ‘onome. The hydrocarbon solvent helps to reduce the viscosity a he reaionproduts Tt lo helps in controlling the reactor temperature by taking up some of the heat of reaction. To erent atalyat poisoning, the hydrocarbon slven should be fe frm polar impurities, Paricvlar water, sulphur compounds and other volatile compounds of oxygen, mroge, Mine te Tis desirable that the olefins should be absent and aromatichydrecaron content elon: Ifthe plymerin formed asa suspension 4 balig SBP, fr example petane ‘thorane ie prefered. the polymer ie formed ination, Che eavent may be aromatic ee Soherane or high tiling SBP or white spirit Thessivent inthe manufactareoflow-densiy talethlene is used as carrier forthe peroxide catalyst used to initiate polymer reaction *tbelsin the removal ofhea from the reactor. Ava peroridecaalyt carrier, Mehl eter ‘tera cls are generally usod. In some instances, lnoparlfins, highly rl “Kerosine solvents are preferred. th combined polishing ieiont solvent power toSy ual i reaiing umes of hydrocarbon solvents are consumed in metal degreasing, electra, 5 are ‘loaning, hcusehold product, photocopyae Large vol component cleaning, ear Phospate et Piay and tal pores oe [erent li i eas pcre a eee Tas ig aa md es Potyetveste Pevallaeoe eyes ero at oncioners ; ) ‘SL No. Che eet ta TL [celour ASTM, Max. a L7.0 L70 72. [Pash pint, ensky Martens (lose), °C, Min, 100 1B 3. [Density at 15°C, gmt, Min 0.895 ons | 4. [Kinematic viscosity at 37.8°C, ¢St, Max. 15 16 5.__ |Pour point, °C, Max. 30. 30 &.__[Emulsifcation test Shall pass the test 7. [lodine value "Tobe reported 3. [pietation (a) Initial boiling point, °C. a 2 [ey Final boiling point, ST = (e) Residue, vol 2 a @_[UV absorbance test (a) Pyrene content, ppm, Max. % ee (6) Absorbance per em optical pat length, in the range loc UV wavelength, Max. 280-209 milimicron ry 3 300-219 millimieron rt = 220-369 millimieron 08. = 360-400 millimicron om a 5.9.8 White Oils, White oils are made by sulphuric acid treatment of petroleum distillates. Petroleum sulphonic acids are the main byproducts from the manufecture of white oils. Today petroleum sulphonates seem to be major product as they find extensive application in the formulation various products consumed in huge quantity in the world. Among them are (i) heavy du’ motor oils, (ii) cutting oils, (ii) rust preventives, (jv) textile cls, (v) leather ois, (ui) spray" and (vii) crude oil emulsion breakers (demulsifiers). Large quantities of sulphonates it form of calcium and barium salts are being utilized in the manufacture of motor oi detergents usually with oxidation and corrosion inhibitors, i Raw materials. White oil may be produced from any of the three types of crud®, 16 paraffinic, intermediate and naphthenic. For example, the naphthenic crude is Us ‘selected to produce white oil of high specific gravity and viscosity. ‘The paraffinic erud®: yields ‘A white oil af lower viscosity and specific gravity. White oll from paraffinic crude has extelesen ¢ resstnneo tnd lubricating qualities well ag ait for crtain waxes. Thin Latter Panta before ae treatment in order tether pros ae having opel charac Bir orto increas the yield an retuce the amount soa rey. Typen ond yeatment depend on the erude source, viscosity, presence of objectionable constit alte materials. I is usually essential to deasphaltize by means of propane and then BPe prt ofthe aromatic contents by slvent extraction with elven such a furl and Bhenol. I is desirable to dewax the distillates containing high percentage of wax, especially rrroduce medicinal grades of white cls, ‘Manufacturing processes. Various steps involved in the manufacture of white oil and Jphonates are: (a) Acid treatment; (6) Neutralization and sulphonate extraction; (©) Solvent removal and steaming to remove light ends; (@) Treatment with clay to remove colour constituents, {e)Solvent rocovery and sulphonate p nd (p Sludge disposal and acid recovery ‘The simplest method for producing white oil is by the batch process. In this process the be ol faction, contained in a cone bottomed tank, i treated with oleum in a series of dumps ing air for agitation. Between acid dumps, settling period of 24to 48 hours is used to permit pparation of the sludge which is drawn aff and disposed to the sewer or recovered in special facilities for further treatment to avoid pollution of rivers, ete. The sludge ean be roasted to duce byprodiict coke and sulphur dioxide which is reconverted to oloum. Such a plantexists ith Bi/s Madras Petro-Chomicals, Madras. The process of sludge treatment is economical "v when sufficient quantity of sludge is produced and the plantsfor white cil and transformer i run at their full capacity “The addition of too much oleum in the oil a a time chars the oil. Therefore, most efficient ction of oloum can be realized by successive contacts with oil which results in better reaction ime and temperature. Total acid treatment can spread into four or five such contacts which called “Shots” in white oil industry. After each contact or shot, the sludge is allov.ed to le and separated. This sludge contains unreacted acid, most af the water soluble sulphonic cids, called “green acids”, other reaction products and impurities, The remaining oil contains ilsoluble sulphonic acids called mahogany acids. When sufficient acid has been used to remove most of the unsaturated and aromatic ‘ents, the ol is transferred to a neutralizer and the sulphonic acids present in the oil neutralized with aqueous caustic or sodium carbonate solution. An emulsion is formed and fen with equimolar mixture of isopropyl alcohol and water. On settling, the lower layer of ueous solvent containing nearly all the mahogany soap and inorganic salts is drawn off and ocessed for solvent recovery and sulphonate purification. After the final water or alcohol |. the oil is heated and blown with air or superheated steam to remove residual moisture alcohol Finished oil is produced from the neutral oil by contacting with or percolating through an stve clay or bauxite. Sulphonates are purified by concentrating the crude solution of the soap ‘minimum water content and extracting the soap from the salts with concentrated isopropy] The alcohol is distilled from the soap after blending in a suitable oil to produce a duct having the proper concentration which may vary from 30 to 69 percent. ification;MR Maas es i. No. HPCL Bombay | SUN Cheracterien | Spinde|EVISpnde]tnurmatone [Tnrmediae | Tray to neutral HVI | neutral LVT | Neutrat HVE | 1. [Rinemati visa, Se eel l@atareo ver ise | axe a CT IC) At 97.8°C_ 3.24 3.5 7.67 BAT 13.23 2 | 2. [Viscosity index soo | a0 a0 eso | —ea0 a 3. |Specific gravity at 0.8647 09149 0.8823 0.9282 0.8097 os990 | as5.50 4. [Pour point, °6 soa a0 3a 30 < 5. |Conradion carbon residue, | 001 | oat con coe | 005 were © |Otumconsumption,wisen | 410 | 6am a0 aa [ao we ase stock zs [| 7 [eld of white of wi c0_| 360 wa za0__| 3 12.0 16.0 9.0 186 3 8 Yield ofsviphonates, wee | 100 | 78 i ware! | 120 ome |g 9, [Bauivslontweightofaul. | 480.0 a0 m0 i busca ry PO Ve ‘Very poor ‘Very poor z Tica & | Verypow | Vervpaor | Voor 3 10, _|Sludge separ ‘Sot sticky éee emer tT eee The total amount of both water ath water and oll soluble sulphonic acide formed for any particular mult Teperted to be independent of the temperature at which acid Porcentage of oil soluble sulphonic "18. direct function ofthe temperatureat which the acid treatment ids which are recoverable ducted. At lower te te direction of sludge layer but asthe temperaars sede aaa a gany acid in the all phase ie favored tothe eaten hat ecole a tions where only trace o mahogany ac reman'etneoange ekineore ater ature to 70°C or 8%C, the aludge release some cll wichicoorealt hele lots 3e mahogany acid contained in the sludge, ot higher 7 obtained at higher temperature. The ext iahogany sulphonate yields obtained by aracteristies of the ba: 80 that in general somewhat higher yields of jent to which advantage can be taken ofthe oil high treating temperatures may be limited by stock being treated. The quality of white oils made at higher eratures is somewhat poorer than corresponding products made at lower temperatures eum is reported to be the most effective in terme ofthe total acid required to produce a oil from a given distillate and yield of sulphonates per unit volume of acid used. fable 5.45 gives the properties of various naphthenic oils and their white oil yields, jonate yields with their average molecular weight, consumption of oleum. The yield of oil is very poor in the case of heavier oils. Indian specifications for industrial white oils iven Table 5.46. Indian, British and USA pharmacopia specifications are given in Table ises of white oils. The medicinal grades of white oils are widely used for the treatment constipation. Due to the inert character of the white oil and its resistance to tion, the major volume of white oil is consumed in techni applications and in the industries. A considerable volume of medicinal grade oil is sold in emulsion form, ly of the oll in water type, the emulsitying agont being agar-agar, gelatine, acacia ¢ lighter white oils are used as a vehicle in ointments such as a base for nasal sprays. ‘mixed with effective concentrations of germicides, white il finds extensive use as ababy ied after the bath to prevent chafing and rash. In the cosmetic industry white oils have become indispensable ingredient in the prepara: if cold creams, cleansing cream, vanishing cream, When added in small amounts to tooth fé and shaving cream, the lighter white oila are useful in preventing caking and drying of preparations. ite oil is also consumed in the manufacture of petroleum jelly. A good petroleum jelly 1a of roughly 20 porcent microcrystalline waxes and paraffin waxes and 80 percent white ‘Table 5.4¢ Requirements for industrial white cils (IS : 1083-1978) Characteristies Requirement for | Tar sin [tas oenat vy a 970, St foo [uses | oe | neon a = rapa an TsePETROLEUM REFINING: a [fete “a Pcie 2 oes eT Teen a SS ‘Table 6.47 Specifications of Britain, India and US.A. pharmacopia for liquid paraffin ‘Specific gravity at 204°C | Kinematic vis- | Colour] Readily | Solid | PbO | Wap eae Heotae| ar” | rae | |e eee bonizable| fon test oe a Tay | ak Has) ae tin’ | en) iain] 087-089] aasos7} eto | suo | v0 | Paw | Pose | Pam [oz [Hadia |" 065-080 | 086.0875 [6x0 | 300 | +30 | Tass | Pass | Pass usa] 086-0905 | 0928-088 | 331 | 97.0 | +30 | Fass | Pass | Pass [oso @15515.5°C |e 15,5/15.5°C) oD 5.9.9 Steam Turbine Oils Steam turbine oil for use in steam turbine system has several functions. Its primary fanction isto reduce friction and wear between opposed working surfaces. In addition to this, ithas to serve as a coolant and as a corrosion preventive. In most installations, itis also wed as the hydraulic medium in governors, over speed trips and emergency gears. The main qualities of the oil required to perform these functions are high oxidation stability, goo! demalsbiity, Tust prevention, anti-foam properties, appropriate viscosity and good air release characteristics During operation of a steam turbine the lube oil is subjected to relatively severe oxiitne conditions. These are due primarily tothe influence of heat, the presence of water, entrain! air and the catalytic action of substance in contact with the oil particularly copper and ferr0¥8 ‘metals. All turbine oils eventually oxidize under these conditions. Ifthe oil is allowed to remit in Service for a long period, it darkens, develops an acrid odour, forms deposits of lacquer Hudge and may cause corrosion. In order to overcome these undesirable effects, a turbit® Tao ly be formulated from a well refined base ol but it must also contain an oxida ave ang delet nibitor and a foam inhibitor. In addition, none of these inhibitors s ‘ny deleterious effects on the properties of the finished product.pernoLeumPnooucrs if Table 5.48 shows that when the solve {determined as per ASTM D-943) at the na light inerease in the severi jnereases manifold ont to feed ratio is increased, the oxidation life ume anti-oxidant level is increased manifold. With "Ny of extraction and slight rise in VI, the oxidation stability Table 5.48 Effect of Solvent to Feed Ratio on Oxidation Life of Steam Turbine Oil ss Charen Geist iS . 2a ir [i oare, ecterion pameaoh wea —| aa“ [ a} as ae 2. Hinerate wae ity at 37.8°C, SUS. 151.5 1515, 1512 | 151.2 2 sine Se ee 4 feline nur ta[ ms 43] 6s [ann point, "6 i2_[ 100 | 407 | 409 ¢_[eameeulin uae oa [as [106 | — 85 [Onto 80 acl ec ORE 5 [aes Bae [ao [eo | Most efficient anti-oxidant is 2,6-ditertiary para eresol (DBPC). In some formulation a mixture of DBPC and phenyl naphthylamine is used as it gives synergistic effect. ‘There are number of oxidation tests specified for the evaluation of oxidation stability of turbine oils, These are indicated in Table 5.49, siving the test condition, duration of test and post oxidation examination. ASTM D-943 is an internationally secepted test and findsits place in almostall the international specifications as well as reputed engine builders. In U.K.,1P-280 and IP-828 are slowly replacing the ASTM D-943. In fact IP-280 is a short duration, Le. 164 hours against 2000/3000 hours for ASTM D-943. The oil passing in one of these two tests is deemed to have met the ISO specifications. Any oil with ASTM D-943 life more than 3000 hours automatically meets IP-280 requirements also. But reverse is not true. BIS specifications are indicated in Table 5.50. Generally, turbine oils are supposed to serve in the turbine for 15 to 20 years. The quality of the oil during use is periodically checked to ‘assess deterioration in the quality of the oil. The cost ofthe turbine is many times more than the oil itself Any deterioration of the oil beyond a certain limits is not tolerable and the oil has to be rejected for further use. Table 5.51 gives the significance of the various tests, their acceptable values, ill-affects when these values are crossed and condemning limits of the oi. In India, light and heavy turbine oil base stocks are produced by M/s MRL, Madras and ‘Ms HPCL, Bombay. The characteristics of these base stocks from MRL and HPCL are given in Table 5.52. Indian Oil Corporation (Research and Development), Faridabad has developed ‘Turbine oils from MRL Turbine oil base stocks which are marketed under the brand name of Servoprime 11, 14, 17 and 21. These have been approved by BHEL (India), AEG (West Germany) and Stal-Laval (Sweden).aa Table 5.49 Oxidation test and conditions for turbine oils Name ot te ‘Test duration Tempera] Catalyst Airioxygen| Flow Examination ea ratespressure (Oxidation characteristics of /1000 hor till acidity of | 950.2] Steland | Oxygen | 3+051h |Acdity,Somespecifica’| inhibited steam turbine ols |2 mg KOH ol copper | one reqae sage, (ASTM D-949/1P-157) reached iron, and copper em ents [Oxidation stability ofin- _ [164h 120205] Copperand | Oxygen | 1+01 Uh |Volatile acids, soluble hibited mineral turbine oils iron naph- acidity, sludge and |(IP-280) thenates, otal oxidation products (Oxidation stability ofsteam [Till drop of 25 psi | 150=0.1| Copper | Oxygen | 90 psi oxygen [Time in minutes for turbine oils by rotating pressure |the drop of 25 psi pres bench (ASTM D-2272/1P- sure of oxygen. 229) "Assessment of the oxidation [Time in hours for ab | 150205 ‘Oxveen, 3 stability of mineral turbine. |sorption of 300 ml_ 3 oils during use (IP- 328) _Joxygen per 100 gil é = g5.50 Requirement fos xia heavy | 2.69 | 695 35 o_| [ash pint, a [Copper-strip corrosion at 100°C far 9 hrs than 1 Aes | Am [ an | ASB |Emul 40-40-0 40-40-0 0-400 | 40-100 | 7 Total acidity, mg KOH/y (after oxidation) [Foam stabiity T fee Nil lon args.s'e Nil Nal [c) At 24°C ofter testing at 93.5°0 Tor 7 Ir release value minutes to 0.2% air leontent at 50°C, Max. 59.10 Metal Working Oils In the majority of operations involving the cutting or forming of metals itis necessary to ‘employ a liquid as lubricant and as medium for removing the heat generated by friction and ty metalic deformation. The main types of metal-working oils are cutting ols, drawing oils and rolling oils Cutting Oils. Cutting oils are made mostly from mineral oil and emulsifiers. However, the neat cutting oils are made from fatty oils with extreme prossure additive since high Dressures and temperatures are encountered in the applications. In machine tool operations fovling action is necessary for the enhancement of tool life, Metal cutting operations are iikized in various machine tool operations like lathe milling or driling. The cutting too! is tale up othard materials such as high speed tool steel carbides, carbon steel, ete. The life of the too ean be significantly enhanced by using a coolant during the eperation. Besides cooling actin, lubrication and friction reduction are also important. Catting oils are the lubricants and coolants used in various cutting operations including turning drilling, thread-cutting, milling grinding, planning, ete. There aretwo principal types lfcutting oils-scluble (emulsifiable) cutting oils and straight cutting oils. "The soluble (emulsifiable) cutting oil, usually employed for light cutting operations i an fmlsion ato toreiecenity lube oil in water, the proportion varying from about 1:100 (or Trinding) (> 1:10 The oil contains an emulsifier, for instance the sodium salts of petrle0™ Ppho coke eat hur components rendering them spontaneously emulsifiable in water some cls additives preventing the formation of ruston ferrous metals are also incorPOr ated.[Symtom daring ser L ‘Oxidation |3000-4000 h for acidity 2 mg 'KOHig for some internation- al companies, 1S-1000-1500 h Acidity, sledge, lac ‘quer, arid edour, Mfects, condemning limits, ete, Ui effets [Acidity leads to corm ion of metal parts land impairs waver shedding propefacs \Condemningliniis| & ‘Acidity 1.1.5, darkening of o Siege nat permis tal ondaton picts | Thon kote send eee 1.08, Max shu 7 lade ead to cogsng of pipes a tor eieraies sina ostracism cae rng ‘Use lfe test 25 hfor ab. | tP.an = BS | een : = [Deposition afaladge on eving ua a | gr of 900 leven fr Repeal ici 00 [Rotating bomb oxidation |D-2072] - Retating bent oxidation: [D-2a7 Both lodge and lacquer ncroasevscay [Belew 6 anata drop of exygen Viscosity [As recommended by equip- | D-445 | Tnereasein vis |Indication of ation ofcom |S in vis Indication of excessive oxidation ofeon- [Sunes ate 5 ment manufacturer ost |tamination, may increase bearing loss and_[inceasealthcugh eet cotng cosy ierense ritecante | [tara | “Kir release [Air release up to 02 vol® air [IP-19| Excess ina foam. [Dificulty in operating of ol pumps and valueffoam:/at 50°C, Max., 18-5617 ngeerion’” [hydraulic ootrelsysems The perp will ‘ng (minutes not develop pressure because of compres: iklity of i sir more ei mow ens five to centitagal pump, Oxidation oe ii tnerave Aa ends wear of forbine lity remains te Is tacreased. Theol! shoud release the ar fs early as pool, Foaming also ead 0 over sping and considerable los of oi yar Water ot emat- Water may reach aditives stable emul. [02 605 Mex. va wr age area Ramanan, sees | setatatpeerance_|starvd ofa rusting of iron part separate TP.19) | ‘D.665 | Rusting of ron sur- [Magnetic iron oxide loads to abrasion and, Re inhbition a | Rust {Rust test with distilled and preventives|syathetic wea water pass faces and appew lrance of back. [aries of moa fadure of control gears, egy and wther working parts aL onMuzU WnaTOWIEand have achieved wopularity tcaune the work in hand ls mare easily vinible: Ty 1._|Kinematic viscosity ut s74°C, est | st-ag cet 033 | 51.95 “3 Viscosity Index I ana '3._ [Pour point, °C 9 g 6 i) [Colour ASTM a 15 | 10 2. Straight cutting oils are used for more severe ofan emulsion is insufficient. Fatty ol : he lubricating action re better in this respect than petroleum fractions bu tend to become rancid; for operations of medium severity mixtures of mineral and fatty oils are produced. The most severe cutting processes, however, require @ lubricant possessing extreme pressure (EP) properties. Oils containing various EP additives, including sulphurised fatty oils and chlorinated compounds, are used for these operations. ‘The product chosen depends on the metal being worked and on the prevailing mechanical conditions, Thus, in working copper and its alleys the oil may not contain fre sulphur, as this would blacken th surface ‘Table 5.53 Requirements of Soluble Cutting Oil (IS: 1116-1978) [ame] Ghanaeral = lak wa Iwaver, wit, Max, frothing test Copper-strip earrasion ut 100°C for 3 hours 2. |Water, wit 3. [Emulsion 4 5 | c Love temperature stability test When metal is drawn through dies for the manufacture of wires, rods, tub apes, a lubricant an Drawingoi and similar artieles, or when metal sheet is pressed into various Coolant is necessary in order to obtain a satisfactory finish and to prevent excessive wear of the dies and shapes. A wide range of substances including dry soap or soap solution, straight or emulsified mineral oils and numerous complex oil formulations are used in this eld Rolling oils. Metal sheets (e.g. aluminium foil, and steel, copper or brass plate) are manufactured by passing the metal through a number of rolls. Various Sbindle oils and white oils, either straight or emulsified and with or witl *mployed according to cireumstances, Tubricants, including out fatty ils are3.9.11 Miscellaneous OU. viscosity are used for lubricating the high-speed gp, Te industry, oils ofl0™ ! ig thei a Inthe textile industry one ot ion of textile machinery requires special precauty preventing contaminating have been developed. When contamination with oleae) thrown off rom movin ning emulsifiers are used, s0 that the oil may an cera avoided, lubricants contai sii od i may ean scouring (re uch ca weol and yon, The alton cf th Cty neo as before, to renter the ol readily removable For eylinder lubrication in refrigeration machinery, oils of low pour point are obvggy cuseni ifthe refgerant at completely mince with ol (am the can fa | rine ocde and Pen 22) ratvely tin ols are empayed, The produ is ual refined, so as to prevent reactions with the refrigerant, For refrigerating machines employ, fefrigerants miscible with oi (such as Freon 12 and metayl chloride), the lubricant hace Soe asvan ante tad wh ta reign * Special ols having very low vapour pressures are produced for lubricating mechan highacauim pumps Hyérecrton it ae pow employ to some extent a the vapor aedhiin vorwun dffesion paar Feta, | mle | 5.10 PETROLEUM WAXES Available references show that petroleum waxes were first recovered in quantity in te U.K. in about 1856-1897 by distilling Rangoon erude, imported in drums. These waxes wer utilized for replacing bees wax and spermaeeti in the manufacture of candles. Availability these cheap waxes immediately brought down the prices of candles in those days which were ill then made with costly bees wax and spermaceti, As a result, it was possible even forthe est to hight a candle, which was tll that time confined only ¢o the rich and the churches om this beginning, the trade started to grow and today petroleum waxes have many lustrial applications, Now these waxes constitute a range of valuable products from crude 5.10.1 Types of Petroleum Waxes ‘These are hydrocarbons type waxes and consist of normal and iso-paraffins and alkylted naphthenes in the range of Cyg~C7o. The commercial petroleum waxes can be broaly classified as paraffin wax, microcrystalline wax and petrolatum, Paraffin waxes constitute ie ‘major bulk of such waxes. The other two types, produced in comparatively smaller quantities also command a good market because of their certain specific end uses, The paraffin W135 are produced from waxy distillate of paraffin-base or mixed-base erudes of high pour pit ‘The microcrystalline waxes, on the other hand, are manufactured from the distillation revit? of the above crudes, waxy sludge deposited in their storage tanks or from sucker rod wax The latter material is a deposit generally scraped out of the casings of crude producing Wels Petrolatum, the third category of these waxes, are popularly known as Vaseline. These eatit microcrystalline waxes and oil, and can be produced only from certain suitable heavy disillat® or residue. The feasibility of manufacturing these waxes from a certain crude, theref® depends not only on the presence of wax in the crude but also on the nature, quantity anit distribution of the wax content in the crude itself, Incidentally, most of crudes curren!) produced in India are suitable for manufacturing paraffin and microcrystalline waxes.perro. UM PRODUCTS re i. ightly branched paraffins and has er Ts each of these typen, there oy adi three differenttypesof parc wa : namber of mal ofS. ting int grades spreading over pacain wax of Type 1 isan extra : Pa goight. This is mainly used for candi baraffin wax, fe man arat containing amaximum of0.5 percent oil (per than foodstuff packaging), tarpaul coating of paper for general packaging water proofing for- srades produced in : this type are 195/140°F, 140/145°F and 145/150% nen entation FDA pe tai in a oo tues. The requirements for the three types of paraffin waxes are given in Table 4.54, In addition, the requirements for paraffin wax for explosives and pyrotechnic industry IS explosive compositions and as a water proofing agent for paper shells, : Microcrystalline waxes. These contain a considerable quantity of branched-chain waxes in India are graded as follows: Grade I is a refined microcrystalline wax of flexible type with a melting point of 165°P. ee ee trade II is also a flexible type of microcrystalline wax. This éiffers from Grade I in that it is an extra refined wax. Its oil content is 4 percent. It is used in applications similar to Grade ‘Table 5.54 Requirement for Paraffin Wax (IS : 4654-1974) SiNo Characteristics Requirement for Type Type2_|__Type3 1.__[Metting point, °C (cooling curve) 45 to 75—— : 2 lash, wt%, Max. 0.03 0.03; 0.03 3 [acidity T | 310 —|(a) Organic, mg KOH/g, Max. 0.10 0.10 ; al _{(6) Inorganic, mg KOH/g, Max. 0.02 a . pear _| 4. |Saponification value, Max. 10 o fe 8 oss | 08[Colour (a) Lovibonds in 18" cll, Max. (AST, Max. cdl discolouration est [Ultra voilet (UV) absorbance per cen eee ieee nse, ooo aalinicens | 08 as) 290-29 mimics 2 lan) 500369 milo 0.083) 36-10 slimes 02a") 3 [Odour, Mos. 1 as ‘Table 5.58 Requirements for Paraffin Wax for Explosive and Pyrotechnic Industry (IS: 7401-1974) [acne Characteristics [ Regaiomentfar Sofigrade Hardgraie TL [Meng pat oling curve) *0 5156 wat 2. [acidity mg KOI, Ma. a0 010 3. [Loss on drying at 90°C, wt.‘%, Max. 0D 05 1 4. [Soponifiation val, Mx m7 1] 5. [Penetration by vient needle) mim, Max 3 ico [a Tash we, Max ea 08 | Grade II is a hard, higher melting type of wax. Its melting point is 190°F and oil contest is about 15 percent. Itis used in applications where low oil content is the major consideratin Main applications are polishes, carben paper, printing inks, paper coating and elcid) insulation. ‘The requirements for microcrystalline waxes are listed in Table 5.56. 5.10.2 Properties of Petroleum Waxes Paraffin waxes are snow-white solid crystalline material having melting points betwe= 45 to 75°C. These tasteless, odourless, chemically stable and translucent solid substances ‘a mixture of saturated paraffinic hydrocarbons having anything from 18 to 35 carbon atts per molecule. These waxes contain mainly normal paraffins with or without small propar™™ of so-and/or cycloparatffins. Microcrystalline waxes as the name implies are amorphous in appearance and may MY any colour from dark brown through amber to white depending upon the degree ofr ‘The average molecular weight ofthese waxesis normally inthe range of 600-700.They 1% “besides straight chain paraffins, iso-paraffins, monocyclopentyl-, monocyclob, clohexyl paraffins, aromatics and polycyclo-paraffins. These waxes have melting Peum PRODUCTS. 7 150 ‘Table 5.56 Requirem, ‘ents for Microcrystalline Wax (Characterit om Gg et Ieteing point, °C, Min eee 74 eae penetration a 2576, 1008, ae, | Be 5 Kisame af oO Sis [18821798 | asszazes | jeseazes | (Cotour: Saas ane S090 cr (a) Saybalt, Min a ~ (WAST, Min, Seay —| Fish pois, Ez ze 258 IrDs [ fepass [Topas | To pase nirocrystalline waxes and oil. All microcrystal paraatun. Ther formation semstodepandmuinly spn theseeetacecntr ea ofthe wax constituents rather than the nature of the oily constituent. - 5.10.) Manufacture of Petroleum Waxes, Initially cold settling, chilling and pressing methods wore practiced for producing petroleum waxes, But these methods had certain limitations in rospoct of filtration, proper development of wax crystals ete. and were not suitable for processing a wide range of waxy stocks The first major breakthrough in the wax production technology came up in 1927 when the frst commercial ketone deoiling plant was installed by Indiana Refining Co.,USA. Tn coming years, alternate processes, such as propane dewaxing/deciling, emulsion coiling, spray desing, electrie precipitation and magnetic separation were developed. However, the ketone devaxing/deoiling continues to be the most widely used process today. The ketone solvents tenerally used are methyl ethyl ketone (MEK) and methyl iso-butyl ketone (MIBK). In India, the production of petroleum wax started with the commissioning of the wax sveating plant of Assam Oil Company at Digboi Refinery. The wax sweating is a process of fectional melting solution and drainage. The molten wax is solidified in the coils of sweating stove and then heated at a slow and a controlled rate. The oil sweats, drips and finally esves| ‘vax cake of very low oil content which is then melted and treated with acid and clay for inproving its colour. This process cannot be employed for deciling ofall varieties of feedstocks Particularly slack waxes containing large percentage of iso-pazaffins which must be handled thesolvent deoiling process only. The production of paraffin wax at MRL, Madras and IOC, ‘aun is based on MIBK solvent deoiling process. 3.10.4 Uses of Petroleum Waxes f per outlet for ve ing candles is still eontinuing as a major outlet ag¢ old use of paraffin wax for making majo roduc. Inthe meantime, more and mare new uses have come into being uring the yeee PeMOLEUU REFN Tog ad wualities of Wax. One SUCH use of grades and a! ia paper® and cartons, 12% ferent, melting point, # ture of waxed PAPO! 8. Tt oo i.e, manufactire “peld in the coating technology siiicance ma asic as OPE eo base paper st My patibility with some of plastics re combine a cal wea tee Ay Dropertien Of Pevaper impervious to air, water and V2 pers and cartons areideally garth of wax males Pp enoicall stable th ae able tym iui tan“ ee discarded after use. La 's are also used as a wrapping mat by of Prod ce teay Tes wane apes areal wd ike bread soup tablet anor Wax allng with film forming materials Such 25 stan, protein or polymethyl alcobo ey aper board, including reduction in the tendency ye Improvements to the paper amt Fonhanced resistance to water vapour, ink and improyj re er id and plieblity and enon 2 renting miscues. temic aia ci — ax is used to improgné even, genset psig ib ent 0 alla pg enh petroleum wanes are used are very wide and include shoe polishes, wa seat eniturc create oor and linoleum polishes, cleansing and polishing Mads, oe. oe as esting: n the coating of fresh fruits and vegetables to preserve thea ton yn wp and thr rng ant fm the rong oat Thieme orarasings stone vex navolteaen Dryer es have app ng ie te isc wh ne cues ih atacand clo i progoted wat o reduce as permeability é inthe clerical induty waxes aroured noble making as aningrodiont of theinmlg nmterial i adndature wilh tbe oubetances and ana coating ofthe srvering S ertalgGe Oteable These are also used as dieectes medium in electrical papor condensers Parafin wasee are now being used aloo ea a raw material for the manufigared chlorinated hydrocarbons, detergents of alkane carboxylate ard primary or secondary alkj! ‘Sulphate types. Parafin wax of approximate carbon number range Gre Goo wa soe Ge=-Cplinsar 0 clfon vin stem cracking. Microcrystalline waxes are used to dope paraffin wax used in paper conversion and Polishes etc. Solution of paraffin waxes doped with these ‘waxes forms a smooth creamy paste instead of a rough salid mass on cooling due to diminished crystal size of the former. The! waxes ar alto used ns a aubstitute for expensive vopetable woven sesaioed tx nese sealing wax and in the eletieal indus Petrolatum or petroleum jellies are almost universally referred to as vaseline. In ft vaseline isa registered trade mark of an American company for, ‘such materials they predue® and hence should not be used to describe these materials as a class, Theee ave valued 286% and the highly refined whit lies find uae in pharmaceutical nde seven aaa 5.10. Quality Requirements-Industry-wise/Bind-Use Wise Mateh industry. The Indian standard for paraffin waxes apestes Type 9 ao eitalell ‘match industry. This is a semi-refined Wax with a maximum oil content of 3.5 wt%aru MPmeDUETS jum ASTM colour of 2.0. Digbet re, asics of 128 — 132°R for th finery produces rage this pur Doratin wax print, PerPet andi tirade mh eet ing Gandle manufacture. As per Ing Which fs mainly consumed by sie for making candles, The gy ian specif cation, estab ‘ ‘Pecification ve 2, refinec scale rat Se eens 2. rai a ol\pextiles. This covers the use of wax for sisi ot 20 Yellow ir 18" ee MUD Toned fr tis purpone a se byt Bre gc up (035 we is alo used, tas le mills, Nerms Maser Varieties of cloth, merch earn AK match Wax with an ell, pepe ad io admisture with paratic oe iD ewaring: Tas papetndert se b cavpsloar ant lasts aioe pernioe ee, compasley with some of the plastics hare were properties of paraffin vinx and plastics are combined cette Taig echlogy the case of food packaging, where the wax coating comes qn ed © base Paper. In ssn prain wa Type whch therequirements of food packaging, should be exclusively used 10G Biotor nat tndidentifiesitas PL grade (Paper industry grade) Wanusedanigredoctne ihe ee ity chewing eum) aust also conform toType L, Fe sateen ‘platens depending onthe qualiy ofthe falshed rotees Chlorinated paraitin wax. Chlorinated praia wet main usd in exe ype ot passing chloride (PVC) plaster av a oconday platicuee. Th aay pasones dees Phat, i aed up t'40 with ofthe PVG and abut B15 pore comb repacal Sy ‘Monated paraffin wax. some ues, ke compounding fr VCchon, upto pace ‘hinted paraffin we can be used Whlea certain minimum amount of chlorinated parafin wax (amt erenterered ary fom technical consideration, larger quantitn are ofan sed Nenu of he pie "totals favour ofchornatd paratn wax As rears he ity fax reed uftturing chlorinated parafin wax fr uve a secondary passa, epored Ua high oil content is nat desirable since it affects the heat stability of the product. Heat stebility Stzoaftre importa requirement of secondary pasties anditi measured by keeping techlrinated wax sample in an vena 180°C fer ehour and measuring the colour hangs satisfactory product should not show any colour change. Paraffin wax of Type2 is generally Shdfrye manatee hited aa aplosives The ordnane factories aswell as manufaturersfexlsivesand donate mad eatin ‘wax. The ordnance factories use paraffin wax partly to prepare protecti ‘ompositions for small arms. the Chemical products. Wax based emulsions are one o! jes, In the food hs nine are mavalyempoyod ty the ed etl FP ae ad industry, these emulsions are used for prolonging storege Ife of PermStA Ti ea ee ema aDs Tans either parain wa of ype 2 male TA "nulsions made for use as a resin substitute by the paper industry "=< containing a maximum oil content of 0.5 percent (TyPe 2). igre Wax with anol content up to 35 wt refined wax spevially produced to meet sajor procuets in this fieldPETROLEUM REFIING EEA, find usage in wood presery edidex emulsions, chemical products based on wax find wai OSs Fossey edt, rst preventive nain consumers of wax. Mainly pay, " Rubber industry. The tyre factories are ‘the ma pi ny ar rax of Type 2 is consumed by this industry. Wax is ification. However, the total qu: a tin other rubber goods, lke batten? Finwax of Type 2i8 used, that aren, hoves, bets, ands toys, ete. For this application, paraf ‘yp tha some uses match wax also Petrolatum. The three categories ive, Wey, Packaging industry, parsifin way I grades and mineral jelly, paraffin wax of Urclusively paraffin wax of Type 1. For commercial gra rleatord: ner ice Pe eared eh ea at ge arg maar oe rd tus ae men nel a or on ie Fe > ee satpro een tm Selene ee dopa me ect eicepelan a ee a ae Ben pa coe erate cae eee ed ee age as neocon 5.11 BITUMENS Bitumens comprise a range of products, derived from crude oils. These are essential) mixtures of hydrocarbon ae type molecules and exhibit thermoplastic behaviour. Bitumen hi been defined as follows: “Bitumen is a viscous liquid or a solid consisting essentially & possesses waterproofing, also found as a natural diprnousunt PRODUCTS ted with mineral matter.” tn th 163 sori or cometimes as in the USA bitume sara or sometimes asphalt coment, Non as described here is referred to as 5.11.1 Asphalts Asphalt 6a combination of bitumen and mineral notin senor refered toa spate MT a Papin. Inthe USA ipitemens were known in early eivilication, cks such as limestones and rock aephalts, These can be mined or quarried and contain up to 1d tt teen an one vane apne aig a se a Pe ee eee eatin ereepreen ST ya ee a ee en pr 5.112 Petroleum Bitumens ‘Thore are a number of different lasses of bitumens derived from erude ol refining. These include penetration bitumens, viscosity-graded asphalts, oxidized bitumens, ai-blown titumens, hard bitumens and cutback bitumens. Tho grades of product in each class are geno sly defined on the basis of a combination of two ofthe three characteristies- penetration ‘alue at 25°C, s2ftening point (ring and ball) and visosity. Penetration bitumens. These bitumens are defined by the upper and lower limits of penetration values. Commoa grades of penetration bitumens in use vary from 15 to 450 penetration, Specific ranges of softening point are required for particular penetration grade bitumen, This ensures the penetration index in the range from 1.0 to +10 Viscosity-graded asphalts. In the USA bitumens corresponding to those described shove are described as asphalt cements and are speeified on the basis of viscosity at 60°C which ranges from 200 to 4800 poise. ‘Oxidized bitumens, These bitumens are defined by their mean value of the ranges allowable for softening point and penetration values. For example, a commen grade such os 8505 has the mean value of 85 quoted for the permissible softening point range of . to °C given frst and then the mean value of the penetration range of 20 to 30, Common grade tttmens in this clase ere £85/25, 85/40, 100/40, 105/35, 105/15, 115/16. Oxidized bite tre somewhat rubbery in nature and exhibit a low temperature dependence an‘ Pa Penetration index from +2.0 to +8.0- sinblows bitemens. Bitumens proce using ei owing poset are known a3 aif mn bitumens. These are similar to oxidized bitumens. i vritumens, These aro imi a brittle in nature, They have pentration ris oo 2015 anne geaoraly designated by te prefix H (HVB in Germany) anlt Vy PETROLEUH REFINING TECH, Oy ange, eg, 1090, Bach grade also has « defined penetration range diving yy Paiute a ponetration index of 0 £0 +2.0 reefing en oe dang te ue Tt a mm a Oo ed eae with 8 to 14 pereent of kerosine. Bitumen emulsions. These are produced by mixing a bitumen with a sui a SoA erosine orga oil) to reeset as ese aon samt Eh Pe ha range 0 70m led ax emda The umes ne cera rap eae Natanars aes cputalifeabitumeng nese cee at maid bfunee ah cement th RA in meinen 5.11.3 Quality Specifications of Bitumens ‘National specifications in different countries are based on standard tests. These are mainly empirical in nature. The Indian standard for bitumens for road purposes and industrist applications are given in Tables 5.57-5.58. Specifications in general use mainly concentrate ‘on attempting to describe the physical and rheological propertics of bitumens. They include flash point and volatility tests, such as loss on heating. Chemical component tests, such at wax contents and asphaltenes, are applied in a few national specifications. 5.11.4 Physical and Chemical Characteristics of Bitumens Penetration grades of bitumens possess high ductlities, whereas oxidized bitumens have Iow duclites. The specific heat ofbitumens varies from 1.7 to 2.6 kiNke. 0 for temperataret in the range 0 to 200°C and the thermal canduetivity is 0.18 Wiim.K) for normal working temperature (9 250%) Low thermal eonductivity of bitumens ints the rate at which ise can be heated for use without causing local overheating. Such overheating may resilt i2 stn ence not soge under prc cnn itumens are complex mixtures containing a large num! ferent chemic pounds flat hgh nolcuar wight On an average, bancascotan 8 a ee! combined carbon, 12-15 percent hydrogen and 2-3 percent sulphur with oxygen in smal mounts, Employing chromatographic techniques bitumens are usually separated intB chemical omponentgroupe-asphatenes, resins, cyclic and saturates, Initaly asphalt tion of asphaltenes oe, Parafin (n-heptane). The remaining material, after preciit® is known as maltenes which is separated by chramatography over siict seValumina column, giving the saturates ax Sed the esas aoa rng the saturate as an-heptan uae, tho ysis as aouene wwoiat thea: pene peti aph dispe 50.6¢ satu hydr The comy 1 asph stab tole med Pept ool vise vita ts the’ the a The SSi rn o1 20 P ‘Table 5. 57 Requirements of Paving Bit ° is a 8: 1579-1961) ‘Dutilty at 27°C, cm, Min Hao on beting ee a [) Ponotraton of side en Sa tier wit in earbon aLBG WERT i hide we essed as per Asphaltenos are generally considered asi weight. The asphaltene content a tn vals, higher soRening pose aed eer peters for the asphaltenes and the proportion of resins to Stl or el pe character n the ten: Gyles onset es ee eee then aramatic compounds in ius ad apse the er eens Seer emer he peal nphatnes ay nk en ee Saiet orth ttl bitumen The averagenolamlar weit creer 005500 Me sunt faction comprises presominanty fhe sit and races phe Srearons resntin bitumen, together with ginspthensissfcone a armas Tesverage secular weight ange apposintaly saa fo that te yea the czar incline both wna oa: any treaes Bitumen canbe regarded s+ calla ytem costing of aphid slower mlaclar weight ly medi (males Th mil arena to be ‘ssphaltenes together with an absorbed sheath of high molecular weight aromatic resins as @ ‘thle sttng layer Away frm the entre he ml theres rua ansiton bs mat ei sols layer extend tarsi th les ata person Soin, The stblzed mile wil ot prectte unl lent aed retain he ting pera th dapeain mera esng he pales sioner Toren behavzu ofthe mens i omens esata Sum ection a atin The dete high they are pote il enudraly fess the rvs cane eee ee i ersae wth temperatures thegelcharacecferaia sot th sym, Sheets deeensrth eR erin tumens may be lost when they are heated to high temperatures. Further increas of naar eae sl charetr and they bene tran salios The none tourates, eis andwesins depend on tet molclar weight r re viscosity ofthe continuous phase imparts molecular weight the higher is the viscosity. The viscosity ccumpbare ceo ‘Ritherent viscosity to the bitumen which is increased by the presen et ets sosity to the bitumen ity ofthe maltenes to solvate he aphaltnes Tt “turatos contents ean lead to marked agglomeration of the asphsliones esins are dispersing agents ot ins to asphalteres governs to a dogreeoo TABLE 5.58 Requirements of Industrial Bitumens (IS : 702-1961) ‘SiNo | Charactaristica Requirement for grades Tan | 65s [750 [wins [asa | eos | 0s | aaens | wasio | Tee | Speci gravity at 27°C, Min, [1-105] 1-105 [11.05 1-106 | 11.05 [201-1.06| 101-105) 101-1.06|1.02-1.07|L02-107| 2, [Flash point, Pensky-Marten | 200 |~200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 | 200 (closed), °C, ‘Min. [Sofening point, °C 65.80] 65-70 | 70.80 | 90.0 | 6090 | as-t00 | sp-116 | 110420 | woe | as0am0 | [Penetration at 25°C, 100 g, 5 | 10-20| 20-80 | 25-95 [2080 [35-45] 1020 | 1525 | 820 | 72 | 210 | ‘V100 em Ductility at 27°C,em,Min. | 25 | 10 | 3 | 3 | 3 a 2 2 1 5. |Loss on heating, wt.%, Max. | 03 | 03 | 03 | os [03 | 03 | oa | 03 | 03 | 03 7. [Matter soluble in carbon dis | 99 | 99 | 99 | 99 | 99 | 99 v9 | 99 9 | 99 ulphide, w%, aeainesives lead to a large number of applications in road seer te ety tactasstrong - “The major applications are found in pavin, onstruction and maintenanee. Bitumen a 16 for roads and airfields. hydraulic uses such as Toofing, flooring and the corrosion protection is being used in the many different forms of road cations is governed y national standards for rad used in India is normally of 81/100 grade penetraten bitumen. In industrial usage mainly oxidized and penetration grades of Hones ne nen Snall quantities of hard grades, cutback bitumens or modified bitummns ee sles omplane Road applications. Various techniques are employed in using bitumens for the conateas tion and maintenance of roads, Roads constructed using bitumens as a binder are slereed to asflexiblepavements, Structural layers and wearing courses are asphalt izes coopacted to sigh density. Considerable thickness of asphalt, or only thin layer of mines, or bitunen, canbe sed to form surfacings for al lasses of roads Asphalt mixes are manufactured by heating and drying mixtures of graded crushed stone sndsand the mineral aggregate) and mixing thisina pug-millordrummixer with acontrolled quantity of penetration bitumen (typically 4 to 8 wt), A filler a else eded, This cau be limestone dust, portland cement, or stone fines. These operations are conducted in speial asphalt mixing plants. At the construction site the asphalt mix is fed through a mechanical laying machine, which spreads and compacts the asphalt mix to a defined thickness at a fixed width Final compaction to achieve maximum strength is conducted by rubber and/or steel tyred rollers. Special techniques can be adopted to mix aggregate or sands with eutback bitumens or emulsions. These may be conducted with only minor heating or at ambient temperature and aretherefore referred to as asphalt cold mixes. Such mixes may need farther processing such as eration (to remove volatiles over an extended period) before they can be used in building structural layers in ads in the same way as hot mixes i Surface dressing and surface treatments can be used to seal minor roads orto maintain road surfaces, which have suffered abrasion and loss of skid resistarce. Bitumens, cutbacks tremulsions are sprayed onto the surface being treated to give a uniform film of bitumen to hich chippings are applied. Light rolling is then conducted. Industrial uses, There are many industrial uses of bitumens, Important examples of Caan ed itumens (og humens wih tons SBS TENDER)ee = 1 oL00, employ a glass or plyestor et in placeaf oxidized bitumens. Many roofing felts today employ a glass orp reused nosaturantis required. Roofing felts madein tis ray, beeauseof the characte ; of the bitummens used, can be rolled for storage and provide flexible characterises i go i “avn temperate enitins experienced in roxfsrctres ai ; Tmpregnated fltsare also used for damp-proof courses in masonry. Mastic apy 7 which ae mixtures of fney-divided limestone or other fine ageregate with a high eas} (2-17 we) ofa hard penetration bitumen (15 to 30 penetration) are used in ooring st : roofing § ‘The clectrial properties of bitumens anable them to be used in wrappings and joining : : ‘ compounds fr heavy duty eables, Bitumens also find wide use in sound insulation pret tig in ar bedios and Moor mats and infor mountings for factory machinery. ‘To protect pipelines for oil, water, ete. coatings of bitumen enamel are applied ater g primer onto the cleaned metal surface. The enamel isan oxidized bitumen (eg. 116/15) wit, up to 80 percent of an inert filler, such as slate dust. The primer is a cutback of the oxide ‘ bitumen with a volatile solvent (white spirit Considerable quantitios of bitumen are used as binders to briquette coal fines. Bitumay used hot, or cold (grounded) or as an emulsion. Bitumen is alsoused as a pelletizing binder inthe recovery of mill scale and "red mud” stel wastes.'The most suitable bitumens are hand f and of low penetration index, eg. 85/2 or 90/1, (softening point/penetration at 25°C), Other i srades such as 15 penetration or HB0/90 may also be satisfactory i 1 5.12 PETROLEUM COKE ° Petroleum cokeis considered a valuable solid byproduct of crude oil refining. Itis produced 8 in refinery coking units using residual oils i.e. heavy fractions of the ervce oil ns feedstocks Basically, coking operations consist of heating the heavy oil feedstock to high temperatures, p thereby cracking the oil and driving off lighter products. ‘The residue remaining after the Femovaloflighterproductsunder controled temperature and pressure conditions pete F cake, c Qualities required for a petroleum coke are low sulphur, ash and metals contents, aswell P as certain properties such as low porosity, good conductivity and low coefficient of thermal is expansion. Good quality petroleum coke for electrode manufacture can be manufactured fom % high aromatic, high molecular weight petroleum stocks v fe 5.12.1 Types of Petroleum Cokes There are three different types of coking processes-delayed coking, fluid coking aé Aexicoking. These coking processes areal offestiveinconvertingrsidualetestoghereake. | products and concentrating the contaminants (sulphur, metals, ete) in the coke. TH st Petroleum coke produced from each of the three processes is distintly different, : Petslum cae rom themareconimon dlajedcikingiedsernees or needle coke, depending on its physical st i ara cokers i interopaed with repay ondeJoceuM PRODUCTS on Needle ci reduced om seca ag wae elles ‘selected aromatic feedstock . acks. Its unique structure tends Spelohar and metals than delayed coxa’ tM coke with reer Bernese Niacin vgn rast coe. ee fied ge ehsion of the fluid coknn’t 2 zeent) of the coke is gasified to low heat ra Pg Process in th {oke is called flexicoke, The flexicoke has role ent £%* fF refine oe The haratristie ofthe eken tent nase a anspor create material simia Eeinconsistncy Pattoleum eke fron se teas anda mach hander to sgelomerate ike shot 5.12.2 Properties of Petroleum Coke ‘The physical properties of petroleum Ibperent volatile matter and hence canponents may be soluble in hydra (890 kg/im?. Cerhon s the majorchemical constituent of petrateum coke, Dependingon pelea coke can contain about 86-99 vis ean aadonr nek ee Srarogen, sulphur, nitrogen and oxygen. The substantial portion of hiss siphon Coke nan ‘oniin upto 15 wt % sulphur. Low sulphur content of coe iodearablesr mekiweclercoe Ckewith high sulphur content of approximately 5 wt emay lead tovepourfrmation ce pufing) ding electrode manufacture and can result in anode fractures, Siphurin the ee ‘safinctionofsalphur in feed, coke make and sourcefthe rade cl In general a ow- sulphur rei containing, say 0.26 wt.% sulphur, produce cake with twice the sulphur content. Under normal conditions to meet a 1.5 wt.% sulphur in the coke, the sulphur content of the fd shoul be leas than about 0.9 wf. Larger amount of sulphur exists in sponge cakes han in eed cokes. Petroleum coke also contains trace amounts of metals such ‘nagesium, manganese, sodium and calcium, Under normal conditions, petroleum eake is stable and non-reactive and does not polymerize. Combustion of petroleum cokes produces ‘tides of sulphur and carbon. Incomplete combustion generates carbon monoxide also. Indian speifieations of petal cokes ar stdin Table 60, The most iortnt Drpurten of coke tobe used graphite electrode in steal production rae tothe electrodes tility to carry a current and to withstand the thermal eal mace heverapucter a funace, "Typical soke properties that relte to the properties of the electrode incuds ‘tient of thera Copenson (CTE), 2) bulk denis, (9) mechani strength of 5 Tang, partileaioe dierbution and (3) electrical resistivity of coke parties Ske Perties such as sulphur, ash and metal contents st ve juctian, some ‘ane properties are specific for the anode-grade coke ws “eal differences exist. icon, iron, vanadium, tents are also important ised in aluminium pr- ee age and Transportation of Petroleum Cokes fa to move the green coke. Dust from the piles is nommstt ported by tusk, alle, barge Green petroleum coke is nor! loaders or grab cranes can be u h controlled with water sprays. The coke can be tr prevent its contamination ‘The quality requirements for the production of both steel and aluminium differ significantly, ‘proximately 0.4-0.5 kg of calcined petroleum coke is used per kgof alumina produced. Caleined needle coke is used to manufacture graphite products as well as prebacked graphite electrodes Hee soe tig ci ee a cen ci acest ingest tm Instr ete eaisclnation of rence ture of electrodes the suitability of calcined petroleum coke is due to its improved binding guinea me In the energy (fuel) applications, the raw/green cokes are used. Many applications of petroleum coke require screening and grinding prior to combustion. Low Ht can rede eattae puter ing ieatally ire coke his een for steam coal in: “rs sana ue aly ca ck hat ben usted fr ten cl ntpernoLeumPRooucTs Table 5.59 Characterist Ties of cote espe ota | Sponge ake | | ‘Needle coke (Aromatic feed - thermal tara, ies of Petroleum Cokes [Lower ontaminants level |Neeule-tke appearans “Hardgrove Grindability Index Characteristics 80 percent passes 200 mi Table 5.60 Requirements of Petroleum Coke (IS : 8506-1977) Aecant oil) ‘Low volatile sl High carbon content Fluid coke Low volatiles ighor contaminants levels Low HGH (< 40) Flexieoke mt Requirement for Raw petroleum | Caleined petroleum coke cake [Moisture content (as received) wt.%, Max. 10 = (Moisture content (after initial drying for raw a oa [petroleum coke only), wt.%, Max. [Ash we.%, Max. 0.45, 05 WVolatile matter, wt.%, Max. 120 _ 04 Density (a) Bulk at 27°C, kel (6) Real * at 27°C, kgf, Min. [Fixed carbon, wt.%, Min [Total sulphur, wt %, Max. [Trace metals ‘industry a hi raph this may be settled between the purchaser and the supplier (a) Silicon, wt.%, Max. S oo [) tron, wt, Max. = oat (c) Vanadium’, wt.%, Max. = = or real density and low vanadium content product is required: the limitsm PETROLEUM REE HING Tee, 04) ‘Table 5.61 Typical End-Uses of Petroleum Coke ication Carbon source State Calcined ee ede [Ftectrodes for electrometallrgea faa Synthetic graphite [Aluminium anodes [TiO pigments (Carbon raiver Silicon earkide ‘Type of coke Needle coke Sponge Calcined ‘Sponge [Foundaries Coke ovens Sponge Sponge Shot Fluid Flexicoke Green lump [Space heatin Industrial boilers Utilities [Corgeneration Lime (Coment Green Green Green Green