Ti DRYDEN’S Outlines of Chemical Technology- M. GOPALA RAO «« MARSHALL SITTIG EAST-WEST PRESSDRYDEN’S OUTLINES OF CHEMICAL TECHNOLOGY —FOR THE 21st CENTURY ‘THIRD EDITION EDITED AND REVISED BY Head (1988-73) Engineering Kanpur, Ind Professor (1971-74) and. iat of Chasmical Dapartme indian Inssinte of Techaaies ‘Nonw resident in Charlonesville, Virginia AFFILIATED EAST-WEST PRESS PVT LTD New DefkiTABLE OF CONTENTS Prefice to the Second and Third Editions » Prefice to the First Edition Notes for Teachers 20.5.5 A Possible Course Outline . . Plant Inopection Trips Orientation»... « A, Introduotion pees eee 1B, Chetstoal Industries Facts and Figures C. Unit Operation and Unit Process Concepts +. + 1D, Gensral Principles Applied in Studying an Industry . « « Snorganie Chemical Industries... « Sulfue and Sulfuric Acid . . FRc and Indastrial Gases fs a Cryogenics in Chemical Technolo ( - -- He Ges Fertilizer Sodusmry =. Zens rans, Nitrogen Induatrica . « Phosphorus Industics Flecttochemical Industries. Chilor-Alkali Industry Chemicals from the Sea Cement and Lime Water and Airmm. M. Noclear Materials 20.2 see eee N. Explosives and Propellant... Natural Product Industries. <5 Ao Bible end Essential Os 6s ©. Paints and Varnishes (including Pigments) - 1D. Carbohydestes snd Fermentation Industries - . - Food Industry cee ee G. Coal and Cosl Chemicals - HH. Petroleum .- +5 ++ ‘TABLE OF CONTENTS ‘Soaps and Detergents; Glycerin... F, Polp snd Paper Industry «+ ++ > Synthetic Organic Cheaieal Industries <= -0e 0 cee 08 [A Petrochemicals—TThe Key Growth Area - cee M08 ‘a. Chemicals from ©, Compoanils Methane and Synthesis Gms) «= + +++ - ANS C. Chenseals from €; Compounds Gnylene and Acttyings) «vee 8 Dy Chemicals frum Cy Compose Propylene) «=e ns M6 Chemiale from C, Compounds (Busnes and Btents) «ees ee veers s MOH F, Chemicals frown Aromuticg o-oo eeeeecereeese ones een es G. Pestioider eee . cee SMT Hi. Pharomncentical Industry «++ oe 351 1 Blowchsology 5-000 20ceeeeneceeress 585 Polymerization Industries « veneers ners sn m4 ‘A. Polymerization Fundamentals -TABLE OF CONTENTS BL Polymerization Technology V Metallacgcal hndasiies AL Iron nd Steet 2 Aluminum Copper Pollution Control & Toxic Chemlcals A. Ale Pollution B, Water Pollution... -Exauaples of Pollution Control Practices ‘The Food Indusiry a: a Sample Industry Dealing with Pollution Control Problents 6... 2. +... eee ee Governmental Authorities for Environmental Clearance. im India 22. ee eee eae e ee Specieuen Application Porm for Obtaining N.O. Pollution AMIE eee eee ee yee eee tees ene Application of the Computer (o the Chemical Industry. . A. Computer su Engineering Tools B. Chomioal Enginecring/Technology . .. . History of Computers ‘The Place of Sofrwase Computers and Enginoering Education Computers aad Chemical Engincering . . . Ready-Made Programe/SoRware PackagesTABLE OF CONTENTS Computers and Process Design . Software and System Vendors Spreadsheets. [. Recent Advances in Computers und Comaunications—Interaet . Computers and Chemical Engineering—A Journal Object-Oriented Programming ond Chemical Engineering .. .. P, Chemical Engineering aad Computer Hardware... 0... « IX, Pertinent References... ese. eee - X. Leading Chemical Producers and Related Companies in IndiaI ORIENTATION 14, INTRODUCTION ongat the top of all manufseruring ion. A great aumber of theis products ia India. These chornicat industries also suppiy vital materials for preparation of drugs and growth of sgrisaltral food products ‘The nature of the chemical industcy is diffecont from Chemical caginccrs ate trai techoology and grastuate degrees of the industrial is Fepdamentals of chenttry, thermodynamics, Kinet, coginceing, and some always valid, even though the operations may appear complex at times, reg ees of outline nets vl e used to show Bow these fundamen have been poled. ‘These will be divided ino five categories for ease of sys 1. Inorganic chemical industries 2. Naural product iagustcios 3. Synthetic organic chemical industeiea 4. Polymerization industrica S. Metallucgical industries wD added szateria! on 6. Poliution control and toxic chemicals 7. Applications of te computer 10 the chomical industry Adtisonal study is recommended in temas of plant ingpection tripe and a computstion [nboratory in which detated material, energy, and equilibrium esloaating oe submitted with Dawe sheets for several industrial processesORIENTATION ‘As an aid to the description of some ofthe various positions walch a chemiea! enginese may assume, and as an aid :0 the seader of this book in helping him to fit the positon to his awn personality and capabilites, Table IA-1 is presented: Table 1A-1 ‘Qualifications Required for Varlous Jobs (Qualifications ‘Social tntetigence Numerical Ability Mechanical tierest Helping Ovhers Working with Date Jobe Teaching x Pere research Commercial esearch ‘Applied research Piet piont Design Production ‘Market research Market devetonrnese Sales “Technica service Atalyial Pacem Lae Povscanet Purchasing Accounting we fx « Colusrn beads eriginaly suggested by Artur Alki. psyshologie\ and epecialist im aptitade testing, (By ermssion af Chem & fg. News) Taker trom th attic "Happiness as x Gal" by Casl Pacifico, Chem a Big. News, 37 (4): 113 (dae, 26, 1959), Check your talent agains: the needs of the job and see waa: the future“micy hold for you,(CHEMICAL INDUSTRIES—FACTS AND FIGURES: IB, CHEMICAL INDUSTRIES—EACTS AND FIGURES 1, ‘The Production Picture for India ‘Tue Chemical Industry*s ahare in the nation's: gross industeial output is estimated 10 have risen from 2 mere eight percent in 1970-71 to about forty percent in 1995. The country bas become self-eufficient In almost all msfor heavy chesticala whlch form building blocks for several downstream products like drugs, dyestuffs, pesticides, plastica, paint, ete, See Tuble 13-1. Table IB-1 Annual Production/Use of Chemicals, Fertilizers and Pesticides (in Thousands of 'Tons) Te 1990.94 1991-92 1992.93 — dos (@) Chemicals : 1. Inorganic Chemicals 3,217.9 3,191.5 3,257.8 2, Organic Chemicale 567.6 on 716.0 3. Dyestuffs 210 20 287 4. Pesticides 9 Res 76.9 (b) Fenttizers 22,9212 23,308.00 22,712.8 7 7 rectory iy ‘The Indian cheemical Industry con catapult itself lato one of the leaders in some selected sectors notably all types of fertilizers, synthetic bers and specialty chemicals. Research and development in Tndia in this field Ws expected © make an impact on the globel scenario and India 5s likely to enter the world market significantly to design, commission and operate plants and provide services for them. Actually, the time of prepariiion of the third edition of this book—in 1995-96~ie a most ‘exciting tate to review the prospects of the Indian chemical industry. ‘Whereas for many years after independence in 1947, India had been 1 clotely costrolied economy with very fimited encouragement for foreiga iavestasent, a masked change occurred in about 1992 with the advent of a new government. Indian economy has undergone 6 transformution within a short span of three yoars. As @ result of the policy of coonomic reforms, lantched by the government, fadia has shed the goal of walning self-sufficiency in « closed coonomy and adopted the model of « free market, aiming al lobalization, The cesvhs ace acady vsibic. ‘Today, the granaries are full. The recessionary Dave of the economy is over and the industry is well 06 the road to revival.. Exports are booming and foreign exchange eserves surging. A large number of forvign investors have taken advantage, of the situation to come to India, ‘These include invltisational giants, tike Enron Corporation of the United States, General Motors, Motorola, Dsimler Benz of Germany, Toshiba of Tepan and xoF sana por au sexe Jo ave sued sy, 2 3 tuulul 30 aopeee| aade rqasefry w EON 3 EN, 3 g # 5 8CHEMICAL INDUSTRIES-FACTS AND FIGURES 5 Dacweco Corporation of Souxh Kore, fo meation only few. Hundreds of others are queting op eth investment proposals, seeking governmeat approval. sereiMaraational economy bes alwo underzoue major changer--some of them very significant © Indi ne major change hab boot the emergouce of the Gulf Stat a2 sepplier: not oaly of peroeom rave meters, bat of petrochemical prodacs, Ha the raw material ate here ore ie Pemats of au Oraanc-Iadn pipeline and postileSqucfled natural gas (LNG) ebipmens from (Qatar 10 - “Ane on the inteastionsl scene, the fall of the Soviet Ualon end the se-voification of Germany fave hect major effects on the worldwide chemical indostry. 2, The Raw Materiais Picture for India Te te well endivwed with e large variety of minerals, Coal and iron aft the country's ‘ring oieeal aso, while mica and manganese Gepost sre of world impor Except for caja however, he countty ix deficient in ore deposits of oer umjor non-ferrous miners any B the major source of tuner ‘Weal in Ida, but mineral depos exist in almost all sections of the country. vrecolewsn isthe rar raw aiateial lacking in adequste quantity fn Inde, ‘The towel demand for peosleun products by the trea yea of the Seventh Plan is reject at SS milion ton and expected to focrense to 90 milion tons by the turn ofthe cenrury, The westera oMhor + a to contribu betwen 27 and 30 milion tous of a annealy by the end of the Bigs Freee esent production evel is 20,milion tons, According to ONGC sources, the incrawed production would be contributed by feds other than the Boorbay High sets coal reenrves are eatimated st ovec 40 billion wns, but this i hard to qualify. Coking soul sre are probably about 23,000 lion tons. Iron ore reserves are estimated a about 20 aatontcie or §% of woul world reserves; Ind racks third in world deposits of manganese; nit sire toe weld producer of rica, supplying 80% of world output, New and saphisione’ ae ne snare surveying may yield olker mineral deposits now urknows. Consideciag the Zot fae conany's nig operations prevent peu ote extraction of seri $8 miners Frere coo maluen, lt produces three fuel minerals, ebovt a dozen memltic minerals and the rae eit minerals are of noc-micalic types. India is ane of the Targeat producers of iron on aes ot manganese ove, mica, baries, cc. in the worl’. Tt (x a matocof stiefation that seet is welfnfficioat in mnt a6 thirty odd miuccals which would otherwise have o be imported. ral snineras form the prinonry raw metedals for such diversified industeies ot irom and ‘reel, fer alloys, power, aluminum, cement, ee‘ORIENTATION Fig. IB-1. Map of India, ase om a map in Hinaraltndirier of ate & the Pai, Legend for Map of Tndia Commodity Symbol Commodity Symbol Commodity Aluminum) AL Kyanite Ky Phospmates Barite Ba Lead Po Sait Bauxite Bk Manganese = Ma. Tale Cement Plants Cem ice M Thorkam Coat € Natural gas NG Titanium Copper o Nitrogea (ammonia (utile Fenilizes Ez plants) Nu or ilmenite) Gola Aa Petroleum, Zinc lio & Steel Fe crude Pet Zirconium “US. Bureau of Mines (1992) ‘Symbol P Salt Te T™ T Zn Ze Fue B a report by te is shown below Fuels ep vsages, loin suffisient in a investors as a1 ‘il be necens Coat rem producer. Qa {o rise 1 keep the baaxite ve cof sagan do auality and ct contsin over Copper Limit also a deficit significant ex] higher Za cor Table IE Bauxite BaryiHom Chromite ron Ore Manganese Rare Earths Tiariue Zirconium This top crude cil, ma snpoossary) to the cranspors ‘consumption.CHEMICAL INDUSTRIES~FACTS AND FIGURES Figure IB-1 shows the map of India with the appreximate Iocations of mineral resources from, a report by the U.S, Bureau of Mines on worldwide mineral resources. The legcad to symbols is shown below the map. ‘Fels represent 90% by value cf all minerals produced. Yet despite one of the lowest energy usages, India is import depondent for 45% of its olf requirement. Et is only marginally solf sufficient in natural gas ond coal, The oil refining industry kas been throwa open to foreign investors as @ step towards privatization of te state contrutied moncpaly. Nationwide exploration will be necessary to reduce the dependence on the offshore Bombay High field ‘Coal reraaine tha principal fuel, Reserves are vast mud the Coumlry is the world’s fifth lexgest producer. Quality is generally poor and coking cosk depasits limited, howexer. Output will need te rise bo keop the energy balance; more if sing rapidly, the bauxite reserves are almost 5% of world total. Tron ore produetion Is below capacity because of stagnant domestic demand and redoced export orders, but the reserve base is large and of high uality and could compete in the Fer Eait with Australia and Brazil. Known copper reserves contain over 6 mt metal. They support an industry af 45,000 (py, all produced by Hindustan Copper Limited, whilst derand is 140,000 tpy.. The forecast for 2,025 is 350,000 tpy. Lead is also a deficit metal with « high growth profile, Domestic ceserver (2 rat esetal) could support significant expansion. Zine supply is closer ta balance and expanding ore rapidly because of the higher Zn content of the Pb-Zn ores. ‘Table [B-2 euramarizes the picture om the mineral reserves of Indi. Table 1-2 Mineral Reserves of India Reserves % World Total Bauxice 1,080 4a Beryllium 1 64,000 170 Chromite (a4 43 ron Ore a 3,300 5 Manganese 7 24 23 27 mi 43.0 15.0 no 73 Zirconium nt aL 43 tons _ gat = millions of tons ‘Source: "World Tadac of Resources and Popdation * (7034) ‘he Energy Picture for India ‘This wple includes the exploration and exploitation of the primary energy resources (coal crude cil, natural gas, uranium, water, biomsss, ete), the trunsportetion of these resources (if necessary) t0 the locations of conversion, the conversion of the resources into energy products, the traniporiation of the energy products to the coarumption points and finally the pattern of consumption.8 ORIENTATION Since indepeadence electricity generation capacity has multiplied by over fifty times from a meager 1,362 MW in 1947 to about 70,000 MW in 1994, ‘Though the average annual grovih rate tins been’ maintained at 10.3 pervent, there ix always a shortfall in meeting the target. The shortage in sapacity is as auch ex 10,000 MW. [Nearly 70 percent of the total installed capacity is thermal-based. In order to meet the contiauous growth, the unit sizes ave grown in stages from 30 MW, 60 MW, 110/120 MW, 200/210/250 MW to SOO MW. While this isthe scenario in power sector, in the induetelal side, : India har embarked upon macsive expansions in steel, sponge iron, fertilizer and refineries which all call for steam genecation for process as well as co-gencration. Ineustries have resorted to wse- of vaste heat from different processes for steams generation. ‘Ona national baste, he quantity availability of power has limited expansion in the chemical industry sad the quality of available power (power tripping and reduced voltages) has cased svore economic problems; in some cases this bas led to the necessity for in-house power generation which increases cost severely. The followiog zbulation from the Planning Commission gives a panoramic view of the ‘oncrgy future in Iodia. Table 1B-3 Projected Energy Consumption in the Indium Eoonomy 1 1999-2000 and 200405 Jepuropadu Anuitra Prodt -____198a-85__1999:2000 __2004-05 Kakinade OB Items Gross Gross Grose . Andina Prade Energy Share Energy Share Energy Share iO) eS) ‘Visoknapata Power Projee 1. Conmmerciad Energ Andhra Prad (8) Cosl and Ligeite ne 31 2M 3372 48 {) Noolear Energy < Mangalore 1 (ranium) 2 1 18rd 73 Power Proj {) Hydroelectric 4 2 10 2 1372 Karnataka {) Hydrocarbons 458 01ST 2087 29 Total Commercial TB Valley Th ‘Enorgy 1245 544,057 78 5,783 a2 Orissa TL, Non-Commercial Enérgy: , {@) Fuelwood 5 3007324 05 11 Dablot Com {b) Dungoake and Age. Gas-based Pr Waste 3216 a9 77 Maharastra ‘Total NoneCocaunercial Energy 10% 4 1211 2B 133218 Zet0 Unit Pe IL. GRAND TOTAL: 2323 100 $268 100 7,085 100 Tamil Nad ‘Saurce: “Eh ‘Youroe: —"Enaray Madeltig Far Tada, "Planilag Coramaton (1907) The inj understood b,Bombay Suburban Electric Supply (BSES) and CESC. wi ye LE is 4 tuition of power projects involving foreign participation which were Tated By the Cemral Govecament us of 1994. Theee nil hopetly hooker period, 1995-2000, ‘Table 13-4 ‘Seven Foreign Projects Cleared by the Central Government eee Project and State Promoters Capacity Cost aay (Rs crore) Jegurapadu QBPP VK Industries as a7 Andhra Pradesh Kelcinuda GPP Spectrum Power 208 748 Andhra Pradesh Generation Lid Visekhapainamn Thermal ‘Ashok Leyland, 3,000 Power Projest National Power Andhra Pradesh ple, UK Mangalore Thermal Cogontzix, Ine Power Project Karnataka IB Valley Therwat Project ABS Corp. Orissa Dahtol Combined Cycle Enron Power Gas-based Power Project Maharashera Zero Unit Power Project ST Power Syetome Tamit Nada Sources “Energy Sctnarla & Energy Magazine’ ie jineertance of nacear eacrgy in meeting the county's long term energy needs was "ederstoodby the planers, ight fom the begining. Recogoizing thi ouclertatnology cet10 ORIENTATION be subject to a progressively restrictive technology contral regiae and also tbat the Jong terta strategies for exploitation of the country’s vast thorium resources are bound to be somewhat lifforent from those of most other countries engaged in auclear power development, tremeadous emphasis was pieced om achieving self-reliance in techaology development. This policy hat sislded rich dividends and today one ean proudly use the realization of indigeoous capability in all aspects of the mucloar fuel cycle. ‘The followirg projects are providing avclear power according wo “Katharl’s Industrial Directory of Tria” (1934): 1) Turapur asornle Power Station (TAPS): ‘The station comprising two BWR (Boiling Water Resctor) units, each rated at 160 MW, has completed twenty-two yearr of successful commercial operation. Since the date of its commencement of commercial operation, the cumlative electricity generated from this station is featly 40,000 MUs (million British thervaal waits). It provides elcctccity 10 Maharashtia ad Gujprat, 2) Rajasthan Atomic Power Station (RAPS), ‘This station as two sits, each rated at 220MW. It genernted 1,087 MU last year, “This ow MU ts cue to RAPS 1 unit operating at restricted power level af 100 MW. It provides electricity to Rajasthan, 3) Madras Atomic Power Station (MAPS): With oa PHIWR (Presturized Heavy Water Renotar) unite, each raed a 235 MW, thle ition geacrated 2.16, MUs tast Year 10 spite of both the waite caaning ai 75% of full power levels. “tt provides electricity to Madras, © Narorn Atomie Power Station (NAPS): 1c han two PEW units, each of 285 MW and generates 538 MU oaly, stuce the unit 2 stented foncGoning only tom Janaary, 1992 and wperaiad only at 20 pence Ri pose Provide vlectrichty «9 UP and Dethi- ‘At present there are four major projects under construction to give total capacity of 2,320 MW. “The projects ae at Kadrapar Atoric Power Projects (KAP) 1 und 2. Kaige 1 and 2, RAPP 3 snd 4, TAPS 3 and 4 Nuclear source Hs clean, compact and conceatmaled. Nuclear is sconoenical. A unit of estoty from the nuciar power sions at Terspur aad Kalpekkam cont 40 t 8 pole pee KWH compared with 60 to 90 paise per KWH from thermal siations inthe respecive regione Jn spite of mishaps like Caeraoby] in the Ukraine and Three Mite Island in the U.S.A. which Aa Nery ete occurrence, the nucle power induety has an excellent track record of catey aad A Brexent seems fo be the visble solution for the deteioraing conventional sources in the ong for, For a discussion of the effects of energy costs on the cconomies of one eneegyintensive chemical (chlorine), tho reader is rl Chiga, U,9.A., and Saudi Arabia, year, Q) Coat (@) Raw Maar Stoel Pia (8) Pig Irné (4) Iron ore GS) Coment (6) Foodgrait (7) Ferttizes 8} Mineral ©CHEMICAL INDUSTRIES--FACTS AND FIGURES The Transportation Picture for India Transport is sa integral part of the economic picture ia the production of chemicals. Th relative volumes aad densitios of various caw materials and products and the relative freight rates by rail, sea, otc., go fat Yo determine the desirable location of any chemical manufacturing enterpiite end the profitability of fis operation, 4.4, Rail Transport ‘The Indien railway systern is the Dargest in Asia und the fourth largest im the world. The railway system comprises 33,600 km of broad-gauge 1.676-m track, 24,000 ka of meter gauge (1.00-m) track, and 4,250 km of narrow-gauge, 0. 762-m and 0.610-m rack. The total track length of all gauges is approximately 61,850 ken, of which 12,617 is double track and 6,500 km is electcified. The mixed-gange trackage introduces complexities, cuch as Loss of ‘ime in tranasbipaext and mukiple stockage of spare parts. The rail system has considerable ‘old equipment that Is unreliable and expensive to maimiain. At year end 1992, detailed plans ‘were revealed to upgrade the railroads through the nap of beavier rails of higher tensile stroagth, welded rails, and presteeaeed concrete sleepers to improve truck structure. Modern electronic devices were expected tn improve rellability of signals and telecommunications, a addiion, Tocomotives ‘were 10 bo upgraded to higher horsepower und greeter fuel ‘efficiency, coaches would be built of lighter weight and greater speed potential, and freigit ‘cars would be constructed of betier payload-to-weight ratio. During 1993-94, railways ‘exrtied 362.1 nailtion tons of revenua-carning traffic, a growth of 3.6% over the previous year, ‘Table TR-S summarizes statistics on goods traffic on Jodiam railways. Table IB-5 Goods Traffic on Tndlan Rallways (In Net M. Tous) (Estimated) () Coal 128.01 131.10 139.00 145.3 (2) Raw Material for 26.18 28.00 28.50 31.00 Steel Plant @) Pig Iron & Finished 10.68 10.20 nas 9 Steel ) ron ore 13.64 15.00 15.00 (S) Comest 2.91 27:50 28.50 nw (©) Foodgesin 24.00 23.50 25.00 (7) Pertilizer 16.10 17,20 3875 @) Miveral Oi 22.80 214.50 25.00 25100 Sources 7871 actors OF Taadaatrbes To XxORIENTATION 4.2. Road Transport India’s sod network: includea 515,000 ka of bard-rutface two-lane roads and approximately 1.12. Mm of gravel, loose-aurtace, of prepared earth routoa baving atleast onc Jane and, ia many siretebes, two lanes, Tals accondary system is not weil drained in all places, but generally ean secontimodate passing of vehicles beaded in opposite disections. Ax ia many Asian countries, eee 10 some remote areas ig by cart tracks, current or sbasdonod. ‘Road transport at present accounts for 50% of tal freight movement ad 80% of passenger leaffic. Ax indurtcial development and automobile: production grow. this will obviously be a priority item for growth as well. 4.3, Water Transport India bas an extensive cosstline of some 5,700 ku end a large domestic shipping induatcy with total tonnage ot 6 million as af the end of December, 1591. Among eleven ajor Poris, Bombay is the biggest port io Iadia handling more then 25% of the tolal trade hrough Indian ports. ‘There are 139 minor ports and aiove then 13 million tone of cargo is handled by all the existing ports, Ducing the Eighth Plan 1997-97, capacity of the major ‘ports ie proposed 10 be increased from 169,23 MT to 237.09 MI. The comimodiby-wi ‘breakup of the capacity is given below. ron Ore Fenilizecs (Raw and Fi ‘The country bas about 16,200 km of inland waierways, with 3,630 km navigable by large vettels. Principal seaports are Bombay, Caleuta, Cochin, Kandla, Madsas, New Mangaloce, and Port Blair in the Andaman Istancs. A newer port at Visakhspatoam is growing rapidly aad likely ‘sill beoome India's most active port in the next 5 to 10 years. Cochin Port has endured labor probletis and ruftered losses of traffic to other ports, Madras Port has recendly carned a reputation as the cleanest and most effciest port in Ind 4.4, Pipelinge Pipelines, relatively new wo Indie, consist of 3,497 kam for petroleum rude, 1,703 km for refined products, and 902 km for natural gas, in all totalling 6,102 km. Pipelines are vndergoing further development and expansion as new routos acd terminals ace being [proposed with increasing urgency. 4.5. Air Transport Tncia has s total of 345 airports, 292 of which are presently usable. Of these, 203 paved runways, 2 of them with ronways more than 3,659 m long, 59 of thea: with runways 2,440 to 3,659 miles, and 87 of thom with runways 1,220 to 2,439 m in length. Air service ulilizes about 98 large waospert aircraft. 5, ‘The Automobile Industry ag a Major Consumer of Chemicals Tn the developed countries, such ag the U.S., the automobile indvetry misy be thought of as « big “cnginc” which deives a number of supplier industries such as: ©” Steel for bodies and framesCHEMICAL INDUSTRIES—FACTS AND FIGURES Glass for windows Rubber for tree Petroleum aa 2 fuel Plactice for parts and fittings Lead for bettmries Copper for witing aud radiators ine for die oast handles Polymers for insulation snd flulshes ‘Platinum for pollution control devicea ‘Aluminum for engine and body parts and wheels Ceramics for insulation and brake linings As an cxemplo of this effect, “Cheatical Weekly Annual” for August 15, 1995 hes reported on the porsible implications of automotive Industry growth for the print indostry. First, they have surveyed possible projections ia production of verlous typos of veblcles as follows: FUTURE PROJECTIONS in Lakhe) Caregory Annas Growth 1994.95 rate & Mediun/Heavy Com. vehicles 1,03 om Light Commercial vehicles ry Las 13% Can 2.65 1s 19% Scooters 10.33 1794 9.5% Motorcycles 6.52 13.26 13% Mopeds 5.23 78 1% {in 2000-01 out of 7.5 Takh cars, Luxury cars will amount to 2.5 lakhs or shout 33%. These have inge implications for tho paint industry. Fiest of all, an economy oar coasumnca about 10-19 12 liters of paint as opposed to shout only 1.8 Iers for a scooter. Further, a hurury car will sume a larger quartity of paint than the economy car. Last but not the least, the car fishes ace the highest quality paints and hence i will upgmde the quality of paiots in general and automotive paiats in particular. hie could do @ lot of good to the pala industry. ‘Theve are. a qumber of foreign participations inthe automobile industry in the. process of aovelopment. These include: car Foreign Company Tnelan Company Cialo Daewoo, 8. Kores pom Ford Ford, USA Mahiadea & Mahindra Macuti Esteoos Suzuki, Japan Maruti Udyog Mercedes Mercedes-Benz, Germany TELCO. Opet Astra General Motors, USA General Motors (Indie)14 ORIENTATION Peugot 309 Peugot, Prince Premier Auto Rover Mostego Rover, UK, Sipani Automobiles Une Fit, Tialy Premier Auto ‘Ike bo appreciated thet the ahove ars resowned iaterastional companies and they have the highest standards for car finishing paints and go ihe standards of automotive paints made in Indie ‘ill bave fo stein international standards, ‘This will algo have a spill over effect aud the quality of otber paints will alsa Improve, So the growth and boom in the automotive industry is going to be 0 boon for the paint industry in more waye than ane! IC. UNIT OPERATION AND UNIT PROCESS CONCEPTS ‘A formula for suocotaful chemical industties production van be expressod as the equation: ‘Commercial Produstion = (Chemical Changes + Physlosl Changes). For solving this equation, chemical engineering applies fundamental knowledge of unit ‘proceseee and unit operations in a coordinated pattern for succcssful commescialization of chemical ‘Processes and products, The unit operation approsch is already familiar 1 chemica! engineering students. By a sombication of science aad cngincering principles, serice of walt operations for banding problems of physical changes bas been developed by the chemical engineering profession. ‘These 1nit operations can be applied to widely divergent manufacturing procedures wich no change in concept, merely a change in conditions. In like avanaer, the wait process convent cam be used in eyetematizing chemical reactions which are found in many typea of chemical industries, A chemical engiseer, thinkiag in tereas of unit processes, can apply previous chemical reaction ‘performance Knowledge to @ new type of chemical produced from one or more unit process steps. For example, aiteatone ace almost always exothermic and all of the physicsl-shemicel principles of equilibrium and reaction sates are similar. The selection of construction materials and cquipment for vait processes cau also be catzgorized. Liquid phase nitttions require a well- ‘agitated reactor design with provision for heat removal. Materials of construction sxe cAst iron. ‘Tables 1C-1 & IC-2 fist and briefly illustrate most of the unit processes and ani: operations seopectively oncountered in the chemical indutries. ‘The application of these unit building blocks ‘ill be amply dentonstrated throughout the boot. From the previous dincussion onc might think that it is a relavely easy job to commercialize. ‘a chamical process, However, the permutations and combinations of the bost of physical end Cchestical variables required to successfully produce chevtioa! products mean that each process studied will have important differences as well as sirilarities 10 other chemical processes. It 35 often the novelty of the approach which is the key to a bettcr process. We must be keenly aware of these differeoces as well aa unitizing approacbes. \UNIT OPERATION AND UNIT PROCESS CONCEPTS Table IC-1 Outtine of Unit Pracesses Ose ene Unit Process Typical Indueiry Ustag Process ire Process 1 Alkylation Petroleum Organic cheraicals Addition of alkyl radical (—CH,) with side chain final product c eat c=c—c—c +c_c—c cc ce ‘rouylene [castes c coc leer 22Atimethyipetine 2 Amination by Ammonolysia Dyestuffs Organic chemicals (CUCH CHy*C] + ANH — NHy-CHy- CH NH, Synthetic fibers cihlenedichlonde tyiece diamine HO; C(CH),CO;H + 2NHy + NOCH) CN sipc id salioniile 3. Amination by Reduction Dyestuffs Organic chemicals (CHyCH+NO,-CH, + 3H, + CHy-CH-NHy-CHy “nrgara ‘mopropylantar 4 Ammonoxidation asic Syntes CHyCHeCH + NB +1502 CHtCRCN 41,0 weigine anman” ae ese HOO, + ha -# 90 + C03 6 Caenylaion Organic cheats CH,OH+ 00 + CH,COOH Celi” ey eee 7 carwagaon Cac chem Cone + co, 225 peoone 8 Combustion Process heating CH + 20s 9 CO, + 24,0ORIENTATION 16 Typical Fadustry Unit Process Synthetic perfumes. @ Condensation Ccal.cHO + CH,CHIO “80H: caH.CH:CHCHO + HO enealcyde ecole ‘aunamsenye ° ° cf 1 ‘ 7 yor 7 LD N67 NY No 5 patie atte anoinene 40 Cracking or Pyrolysis COCO OCC HERES V1 Cyanidation or Cyanation HC:CH + HON 3 CHr:CH’CN BES +H ee ct. Neots cnc 32 Cyclization Z C—C=C—C—C—0 > CO 43. Dehydration CH,CH,OH 3 H.C:CH: + HO carplalcchol——thylene CxO, > 620 +0 colons hydride cakiem oxide 14 Dehydrogenation (CH, CH CH: CHa > CHy:CH CH:CHla + Hts ‘eomene i -busdiene 45 Diazetization and Coupling (a) R-NH; + HCL + HNO; + R—N{CI + 2H2O : () RENJ—CT eH NCH 3 RN=N—K NCH 16 Disproportonation CH: CHCMs + H;C:CH, + CH,CH,CH=CH, Preylenetiyleae butylene 47 Double Decomposition (metathesis) Ca(OH), + H;S04 > Ca804 + 24,0 Using Process Organic chemicals Dyestutts Petroleum, Desruction distillation of coal Organic chemicals Petroleam, Organic chemsicals Inorganic chemicals Synthetic rubber Dyestatts ‘Organic chemicals Inorganic ehemicels ' I i 18 9 a as Hycralys: Hydroxyl RCH Isomeriz: coc Nivration cHUNIT OPERATION AND UNIT PROCESS CONCEPTS Unit Process Typical Fader Using Process 18 Esterification Olle and fats Ale + Acid Soups . ROH + R‘COOH + R’COOR + H,0 Organic chemicals ROH + H,S0, — RHSO, + H,0 19 Halogenation Organic chemicals Cl= CH, + Ch, + CICH, CHC ethylene ctnyene dichloride Hs a O™ seas benzyl chloride ‘Organic chemicals H,C:CH; + 1,0 + CH,CH,OH Inorganic chemicals CaO + H,0 ~» CalOH)s ‘Hydroformytation Olefin ~> aldehyde with additional C RCH==CH, + CO + Hh + R(CH)— CHO Hydrogenation Organic chemicals Fots + wexes R=B’ +H) > RH—HR’ Coni hydrogenation Petroleum Organic chemicals | ' Hydrolysis CoHsCl + HO CgHjOH + HCI hlsrobenzene Phenct Hydrozylation gh Detergent manufacture oN RCHLOH + CH,—CH, ~ RCH AOCH, CH),0H cahylene oxide Isomerization © | eat ccc coe. ccc Petroleum Pett Explosives Dyestuffs Organic chemicals CHs-CH;CH,*NO, CH," CH, + HNO, CHy-CHNO, Crt, HNC CH +O, EZ Hr Gano, € CHyNO, aeropating‘ORIENTATION Unit Process ‘Typical industry Using Process 27 Oligomerization ‘Organic chemicals on sacHoncH, + | | hte i ) NA 1.3S.eyloasdonnene 28 Oxidation RCH,OH + 0 RCHO + RCOOH CH CH;-CH, CH, + 0, > 2CH;COOH + By-products 2CH, + 3/20, > HCECH + 31,0 29 Polymesization Organic chemicals Petroleum * Plastics Blastomers Syathetic fibers (8) Addition polymerization HC=CH; + H,C=CH, + —CH,—CH, Cl; —CH,— cthslene dime Scie + CHD, polyethylene ma HC@CHK + H,C=CHX—> H,C_CHX—GH=CHK Polyviay monomer FS CoH), w vosyving] polymer nonomer X = chloride, acetate (©) Condensation polymerization splitting off of small molecules such as H,O, NH, CH,O, NaC] a MAO Ry—F-—OH) 9 HOR a6—, OH 8 6 so- tH (9) HOCH, -CH40H « HOoe_-{< coos sine iy soo as > Alleyd resins + HLO 38 Reduction Polymer catalyst BTICy + Al > 3TICI, + AICI,‘UNIT OPERATION AND UNIT PROCESS CONCEPIS Unit Process Typical Industry Using Process S.C is Process 31 Sulfonation Dyestuffs DY ans0.4 oO “0 Surface active agents 32, Thionation ‘Organic chemicals Hc —cH HACCHCH:CH, + 28 4 || fl buaiene sutee HQ OCH A s +HS thiophene CH,OH + HS > CH,SH + 4,0 SSS Table 1C-2 Quiline of Unit Operations Unit Operation Schematic Representation 1 Distillation (a) Batch (Used for intermittent operation and handling small volumes of foed end productORIENTATION Unit Operation Schematic Representation Comments (®) Continuous fractionator Used for high volume | > continuous separation of | complex mixtures such as petoleurn fractions Connect these with appropriage dumps, reboilers, cxindensers and autoeuatie eonteale 2 Drying of Sottas (a) Spray drier ible for large eapacity ‘eration on liquid feed ty give Powdered, spherical, tree- flowing product; used in production of pigment 4 Baume stergeals. synthetic resins, and Imise. inorganic salis @u (0) Rotary drier ‘Suitable for drying tree flowing grenaar Solids which do not dust or stick; high-temp, versions arc kilns for cateining cemen, lime, ete, & S (© ‘Tunnel drier Applicable to drying pastes or powders in trays; alsa used to dry pottery, lumber, Teather, 4c, in sheet or shaped formsUNIT OPERATION AND UNIT PROCESS CONCEPTS Unit Operation 3 Bvaporation (@) Open pan ) Multiple effect A an Schematic Represeniation Commenis Used for smali batches; often of viscous mat'ls; such designs are easy (0 clean Used to achieve max. hear economy in evap’n of paper mill black liquor, sagar eyrups and sol'ns of inorganic chemicals 4) Extrectioa (a) Liguid-liguie (b) Solid-liquid (leeching) Used to contact solvent and Feed 1a give raffinaze and extract; widely adapted to removal of maphthenes. from Tube oil fractions using solvents such as furfural Involves removal of a. solute from a solid by means of a liquid solvent; often used in ore treatment to recover metal valuesUnit Operation § Fluid Handling fa) Centrifugal pump () Reciprocating pump or compressor fe) Jet ejector Fluid-solid Contacting 4a) Fixed bed (b) Fluid bed ORIENTATION ‘Schematic Representation aa ‘Mast widely used for liquids of all types; simple in ‘construction and maintenance Generatly used for higher pressure delivery; may be used for metericg or proportioning Used for low pressure operation of production of vacuum: steam often used as motive fluid Most widely used type of catalytic reactor; used with precious metal catelysts to minimize attrition losses: catalyst usually in form of pellets Used to contac: finely divided solids with reactant gases. e.g., erackiog catalyst with 0:1 ‘vapors and then with ait; 2leo ‘used in roasting of sulfide ores to give oxides and SO, 7 Fluid-soh (a) ContUNIT OPERATION AND UNIT PROCESS CONCEPTS Unit Operation fe) Moving bed Fluid-solid Separation (2) Centeifugation (©) Seuting tank (0) Wet scrubber Schematic Representation eg f Comments Combines virtues of fixed bee Teactor with ability to regenerate catalyst’ by movement to separate regeneration zome Used to separate very finely Givided solids from liquid or liquids from liquid emulsions Simple device used to remove large particles from gas stream by simple settling in iow- velocity zone Effective means of removing suspended particles from gas stream by contact with liquid shower‘ORIENTATION Unit Operation Schematic Representation Commence @ Crysiallizer Hot, nearly-saturated solutions are stirred and cooled to effect. | I" nucleation and crystal growth; 1 l ‘widely aed with inorganic salts (6) Fier (rotary) Vacuum applied 1 inerior of druen pulls fituate out of cake; axed (0 separate minerals from sures, pulp bers from water, ete, 9 Fiter press Sienplest typeof pressure filter; widely used; plates end fabric filter media may be made of a vatioty of edcrosion-tesistare materials (2) Cyclone separator Used to separate solid puricles OF liquid droplets from gases we permit product recovery or Yo cut down product lors and air pollution (@) Hiectrosttc procipiatoe ‘Used to remove fine dusts or mists suspended in gases; features high collection efficiency at wide vaciety of operating conditions (Bag fiter ‘Batteries of mobular fabric bags ‘bee mounted so solids may be removed continuously by flaw reversal and mechanical shaking ) Ter © Pr @UUNIT OPERATION AND UNIT PROCESS CONCEPTS Unit Operation Schematic Representation Comments ©) Thickoner-classifier Used to separate slurry into died” sludges and cleat liquid: used widely in mineral industries and in sowage effluent carifcedion (a) Gas holders ‘Used for low pressure storages of gases at constant pressure using liquid seal (usually water) 8 Fluid Storage Widely used for storage of liquids of al types, ueually at (©) Pressurized spheres Used for pressurized storage of Tiquefied yases or high vapor pressure liquids to permit safe storage with no vapor lasses (@) Underground - Used for large volume storage caverns of liquids or of liquefied gases25 ORIENTATION Unit Operation ‘Schematic Representation Comments : 9 Gascliquid Contacting @) Absorption ma ! Pg i (8) Stepping {Sotytony —¢Setrent) | i i I ae Lay 10 Heat Exchange (a) Fired heater i tb) Reboiter : Used for taking up w soiuble ges in a solvent liquid and ‘Producing a solution clus a icen exit Bus: ee. used in Ha8, removal trom hydrocarbons Used for removing a soluble ‘898 thom solution hy counter. Surrent contact with an inert as; used! to ecover solute ges ang regenerate solvent fer subsequent absorption step Used 10 heat perroieam fractions 10 distiliation or ‘cracking tomperaures in dircct- Fired tubes, Uses ratetai circulation: circulate frectionating tower bottom in heme exchange with steam, ee. ta provide uuecessary heat for fract onstion (ai Shell exchur () Jacke : © Dire (querUNIT OPERATION AND UNTT PROCESS CONCEPTS Unit Operesion Schematic Representation Commente (©) Condenser Usually water-cooled tubular struction to provide refhix and overhead product from fractionating cohunn (@) Shell and tube exchanger (@) Jacketed ketle Commen construction for reaction kettles; water or brine may be used for cooling; hot water, oil of Dowtherm for heating (quenching) soolant fluid (exg., wacer) with Process gases to give quick Ni quench, ¢.g., in hydrocarbon Dizect mixing Features intimate contact of Wey Pyrolysis to acetyleneORIENTATION " Unit Operation Membrane Sepacation (a) Dialysis (b) Gaseous diffusion Mixing (a Agitation (b) Solids blending Size Reduction and Bnlargement (@) Crashing Schematic Representation Used to separate mat’ls in sol'n having widely different mole, + €.8-, caustic from sugar or cellulose Uses microporous (2.9. Ni) tarrrs in mukistage operadons |__ to teparate ight (en UF — from heavy (eg, UR) components May beused for liquid-liquidor soligeliguid mixing in singls-or multiple compartments: widely used in process industies The device shown divides and recombines a granular mass over and over again to effect Uniformity Used typically in 4: 1 size reduction of hard materials from =5 {0 -20 mesh or =1 19 A mosk Wet or cry grinding may be carted out in presence of balis, pebbles or rods; feed may be 410-100 mesh and reduction ratio 10-15 t0 1UNIT OPERATION AND UNIT PROCESS CONCEPTS Unit Operation (6) Pelletizing "4 Solids Handling (2) Poeamatic conveying (b) Bucket elevators (4) Bek conveyor Schematic Representation Commenss Used to make tablets fron Powders of medicinals, catalysts, ote, Used originally for grain; now used widely for coment, catalysts, coke and powdered chemicals Used for elevating materials; can be used for moving powdered or granular rat's to and from storage ot between feaction vossels as in moving bed catalytic processes Versatile; can be used to mix and heat or cool: can be ‘operated! under pressute; useful for powders or sticky materials Can be used to handle targe volumes aver jong distances sconomicelly; used near horizontal; belting may be fabric or cubbercy ORIENTATION Unit Operation Schematic Representation Comments 15 Solidssolid Separation Wiro, plastic or fabric screens ‘are used t0 separate solids of varying shes (@) Screening | (&) Btuttiation May be used to remove fines from a solid by passage of 2 £585 (0 floidize and transport the fines (6) Froth foeation Finely ground (~50 mesh) ores acc suspended in water in Presence of flotation reagents (ea, RCOONa) and blown with ais; desired product collects in froth (@) digging One of the oldest processes ‘used for separation of heavy ‘minerals frow lighter gengues As well aa for separating coal from heavier contamioants a Unit Op fe) Magne reparat ID. 6 ‘Wethin an; congincecing wh tnd theie speci ‘out in 6 discus 1. Marke 2, Metho @c @P os 3. Chem @ > oe “Tae com to problems w cheaieal engi 1, Chem 2. Thee 3. Reset 4, Proce‘GENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY Univ Operation Schematic Representation Comments te) Magnetic Used to remove tramp iron separation from feed (0 subsequent {grinding and pulverizing steps: also used to concentrate ‘magnetic iron ores 1D. GENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY ‘Within any shemical industry there is mn inconceivable number of principles of science and caginscring which are continually being tied. We cannot possibly look at all of these principles ‘nd thei specific applications, even for one industry, Only the essential features can be pointed cout in a discussion of these topics 1, Market and Salat—Justification of the Industry 2. Methods of Production {a} Chemical reactions (©) Process flow dlagrame—flow sheets (©) Material requirements 3. Chemical Engiveeriag Problems @ Maoutacrering ) Economica ‘The complexitics which exist in studying the interetationships of these items can be reduced tt problems which have been sclved on the bosis of science and eaginccring pitciples learned in to In both types of reactions illosteatod, the maximum equilibrium yield te obtained ‘under isothermal conditions which is practically impossible to atta infinite volume reector systems, Au intermediate condition between the isothermal and adiebstic casos fznebieved, Reactioa Kinetioe as « fuaction of fenspecatare in also an important design consideration and very often stage-wise operation with heat exchange is practiced. ‘This js illusteued below for a threc-siage process with exothermic eoaction, The corollary exists for an cadetherraic reaction,QENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY Conenaro Dinanant Reactions 1 and 2 are operated at bigher average oy fo attain higher reaction. mates per unit volume. ‘Mechanism—tolecuinr, chain Catalysis—ostalytic, non-catalytic Enorgy Transfer—ediabatic, isotherms) oF ‘intermediate (non-adiabatl jaothermal) ‘Chemical Equations ‘Simple reaction equation AR ALBORORIENTATION ‘© Paralle! reaction equations [AR lass [A+BoR Athos lavpot [AOR * Complex series A+tBOR AtRGS AtSaT = Reversible reaction aA ot rR Ms aN =e 2X 4 22 Effect of Variables ‘Temperawre Pressure Reactant concentration Flow patterns and transport propertiesGENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY @ Reaction Rate Equations For the reaction aA + bB > R Moleculatity = a + 4 Order of resetion = m +, Slumple order resetion : molecularity = order of reaction For the reaction aA +B sh R435, For the reactions For the reaction(2) Specific reaction rate constant, & Units depend on order of reaction © Effect of temperature on reaction appears only in & Am Je-ERT (ay E = scivation energy, R ~ waivereal constant, 1” = sbichute ‘temperature, f J ™ proportionality constant [ihe expoaential effect of tempersture on reaction rate ia very important in process ‘considerations. @) Examples of process design using temspersture effect of reaction kinetice * Producing 2 high yield from an endothemnic reaction, Chemical rettion: 20H, C,H, + 31%; att = + How Diagram See aiso Wulf Process, Fig. 11B-9) Combustion Products Regenerative ceactor eystem Reactor 1 is on ““Heas-up"* Reactor 2 is on Make”(1) Specific reaction rate consent, & © Units depend on onder of reaction © Effect of temperature on reaction appears only in & Bs Je-ERT : 1) E = setivating energy, R ~ unlvarval constant, T = sheolute ‘temperature, J = proportionality constant (The exponeatial effect of teaperasue on teaction rale ix very important in process ‘comaiderstions. @) Examples of process design using tempemsture effect of reaction kinetics Producing a high yield from an endothermic reuction t Chemical reaction: 2CH, = Ch, + 3Hy al = + Flow Diagram See also Wulff Process, Fig. 1B-9) Combustion Products Regensrative reactor system Reactor # is on “Heat-up” Reactor 2 8 on Make!"GENBRAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY Conversion Dingram Fractional Conversion —.——-Ternperature te te “The product gates leave the resetor at, andl with an equilibrium conversion of y, 1 the cooling process were gradual, ax from %; 10 %, the composition of tke gases would be that predicted by the equilibrium eurve aad the conversion would decrease. By using water quench, the gas temperature is dropped so rapidly froxa 410 f that the nue of the reverse reaction, 5 ie CE Ch, fs essentially zero by the &"” effeci, with coaversion at ‘+ Producing high yield from a reversible seriea chomicsl reaction Chemical reaction: AsBec Fupw Discran Reaction Tintes9, Product with highest vied of B [Calmax)]Reaction Time, 6 ‘Thermodyzumic calculations ahow a very low yield of B. Howevee, by studying the reaction kinetics, it was determined thatthe reaction path pictured in the above conversion diagram was such that un economic Yield of B could bs obtained by queoching the reaction after time 6. Classification of Chemie] Reactors (0). Singplc batch bomozencous rectort [No addition or removal dusing reaction time intecval @) Seml-batch reactore ‘Addition andor removal of one ar move constnasnts @) Contiruont homogensous reactors @) Continuous heterogeneous reactors Exemple— Rid bed catalytic reactor (© Design Criteria for Reactor Systems (1) Eoouomie Considecations are Guiding Factor + Use continuous system for large sale, high pracuction ate * Use baich system for small quantities, intormitcat demand, very long holding times 2) Equipment Selection © Contiaueus process © Single pipe for homogeneous system with low reaction time * Packed or baffled towers for homogensous system with high hold-up time * Sted tak for bigh degree of agiuation, low holding time and mo detioental effects of backmixing © Batch process + Closed stirred tank Tank with outside reicoutetion @) Deviga Equations Process and ‘The design principles we be important area ¢ The desiga mechanical desi ‘mechanical des auuiliacies, ios between those ta design problensGENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY + Homogencour systems Batch reactora-~use integrated rate equations of the type listed in Section (d) Flow reactore Bifteo > en 2 = fraction convexsion desired; Vq = reactor vollame; ¥ = feed mate, volumeltime; § = holding tame The backmixing effects should he considered, particularly for Inrge diameter equipment. ‘© Heterogeneous systems ‘Used mostly for eatlytic eyeteme Bafa W/F > keg of catalyst to kg-moles of feedrime Tae rate equations for cualyticaysioma are largely empirical ‘+ Space velocity specifications Reactor designs frequently re baced on space velocity (SV). For homogencous rectors, SV isthe reciprocal of equation (F.1) sv =} 5 & reciprocal time units 3) ‘Space velocities for hetarogeneous reactor design are more arbitrary, but all are based in Principle on the recipcocal af equation (f.2) VHSV = volume hourly space velocity as volume (specify inlet or exit) at STP hex void volume of easier WHSV = weight hourly space velocity xg of food ‘TeX Weight of catalyst im RE 4. Process and Mechanical Design ‘The design phase of commercialization requires the synthesis of combination of all of the Principles we have discussed in Sections IC & ID 1-3, ‘This is probably the broadest and most important ates of endeavor for the chemical engineer, ‘The design of chemical plants is often divided into two parts: (1) process design, and (2) ‘mechanical design, Provesa design is conccmed with unit operations and processes, whereas mechanical design deals with consteuction details of equipment, foundations, buildings, process auxiliaries, installation, operation and msimenance details. There is considerable overlapping between these two divisions with chemical engineers taking the major role in solving the process design problems.a ORIBNTATION CChemigal Renctions Oxidation: $ + Ox + SOs; Oxidation: $07 + 402 S03, Hydration: $0, + 0 > H,S0, (aq), AH = -31.6 Keal Fig. ID-1. Biock disgram for manufacture of sulfuric acid and oleum by contact process. Storage] [Storage (a) Process Design ‘Only tock ding Research and developroen: work on chemical procese t usually completed to the point {Mh proceas design ‘where suiient inforioation is availble to prepare nserice of flow diagrams or flaw sheets which ‘sre aot usualy incorporate unit operations and unit processes to achieve the desired production, ‘underlined. Types of Flow Sh @) Proce "A. Blosk Dingrams. These aro simple rectangular box diggrams which give & Asta stad ‘graphic layout of the various steps in a process. An example is given it ‘usually be coal ‘Figure ID-1. o Brepeet: B. Simplified Engineering Flow Shoot. Visualization ofthe process in trms of + Rect Possible physical equipment to cary out the operations of the chemical = Separt process is one of the essential steps in formulating @ process design. A © Purify typical example of this type of flow sheet is shown in Figure A-4, Such “These inv flow sheets exist in alt degrees of complexity, giving stream quantities, chemical ru specifications, sat: snd energy belances, instrumentation devails, and 3) Desig process ruxiiaies requirexents, + Cob ©. Other Design Flow Sheets. A complete plant design requires 2 vast sumber Pre of intricate and detailed flow shects for such things us piping Iayout, electrical © Choo layout, instrumentation details, plant layout, ete. a | Spert Gases oot Molten Sulfur «Se ‘i mL 1s fettur 5 3 + Ds ener] 2 . Sean 2 8 an Tea ge }{Pesetorfcocie|—-} & 3 xcharger| ‘ooler "1S $. Economica 20 J ry Air [Cooler Cooler “ ” cy Fixed 98% ACK . ee voxwreRe ey eeGENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY 4“ Only block diageemas and simplified engineering flow shoets will be used to onderstend the oces design peicipes of chemical tchaology. Heat exchaagers for opdatum heat recovery fe aot amily shown. An arrow pointe out the start of the procest and the products ace vderlned. @ Process steps ‘As an clementary approach to met chemical proceases, the following troed stops can usually be consider 1 Prepare the reactants + React them * Separate the products > Purity the products These lavolve unk operatious and uit processes with the later most Importnt in any shemical reactor design probleass. 8) Design reps Collect all laboratory snd process development information + Prepare flow sects Z * Choose conventional desiga procedures for equipment designated on flow shects as unit operations ctlentod Design the reactors; this i¢ one of the major problems of the plant design job; ‘optimum design is critical: Select control instrumedtation for proceas mocitoring und enalyals Select tnd size matecals handling oquipment~pusipe, poing, conveyors, etc. ‘Design all peovess suzilistios ‘Make plant layouts Remi all designs for cos estimating Fiability Analysis of a Projected Cuemical Process Venture Capital Invescment Fixed capital for plant facilities Site Buildings Uitilidies plants Process equipment Storage facilities Auniliary utilities and emergency focilities ‘Working capital Raw materials inventory In-process inveatory Product inventory Maintenance and repair inveatory Accounts receivable credit carry-over ‘Minigaum cash reserveORIENTATION (2) Total Produce Cosss (@) Mamufvoturing costs © Rew material © Shipping containers © Operating costa Operating labor * Operating supervision * Operating supplies + Ublitieg (1) Blesecity @ Sioa © Water @) Fuel * Control laboratory * Miscellaneous ©) General expensce Preight and delivery + Administrative expense Sulea expense Research expense (8) Economic Analysis (@)_ Selling price Market analysis ‘ Prise-volumse relationship; present and aaticipated Application of products » Competition Tecome taxes Net and new earnings @)_ Proftsbilty Return om investnvent ‘Cost and profit charts Other methods of economic analysis + Payout time Interest rate of return on disconnted cash flow method ‘+ Project preseat worth The capital and total product costs ore estimated from proosis and m ‘sheets and specifications, once a market and sales analysis has beea coodaotedbeat exchanger a of a shellnd-tube exch schnager for & given the heat exchanger, Plmping coats, A heat exchanger ax o ‘Pumping Costs Heat Exchanger Fixed Charges Optimum Fluid Velocity Peles to choice of alennstes for g Complete plan aad economic de eet! 86 Squipment sed prone Seite, The use of computes 3ids metoriaily in colving tach decision-making probleme, ns BADiples of economic bicone ‘ROW up repeiedly in our study of the chemical Process industries, ‘chewslcal products there Parner Mernative routes available lepending on the cost) Acetaldehyde () Ceci + 10+ oe ©) LG + 04 oo © GHOH+ 0,4 () HC=CH +0: + (51 Caro Acetone ae (@) CavAcds + heat =» (Obsolete) ©) Fermentstion > ws 6) Isopropyl alootot - Hy @' (@)_ Isopropyl aleotol + 0; > ©) Propylene + 0,3 @ (£)Camene hydroperoxide + Acctone + Phenol Aceyloniite @ (a) ClimCH + HCN > 0 c o © @ oy Se @ ws @ © ® Butadiene . {@) Ethyl alcohol "22, ak {b) Acotaidehyde — 1,3-buranediol 22, (0) CHimeCH + CHO 125 1 4butanediot EO, @) CH -H; > ©) GiB - 2H, + CO City +O, GHe 9 CiHy + CoH >GENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY WW) Cott, 29 veotnytdiosane + © Cie + Cathy > Coprotactam ©) Cyelotexane 5 Cyctoneranone NOH, oe 5 ©) Cyctotexane OC, Cyctohexsnone Oxime -» ()Cyelobexane FMOM, oy cisperamone Oxine 9 (0) Cyctohexane PE, csprotactone —» ¥ eid (©) Toten. 2s cat, COOK Bs cya, coc HOSC:ONO (© Phenol #25 Cyclosexenel + Oxime > Glycerin See Figure ID-2 for a graphic representation of altemative routes to glycerol from, Propylene alone, There ace aiso: (@) Fermentation —3 ©) Hydrogenolysis of dextrose + (©) Fat splitting fn soap anfg. -» Ioprene (@)Asopentane - H; (b) Tsopentane + 0, + © Propylene + Dimer Hs, Asobutyiene S29, Dincehyidionane >» Chime CH + Acetone He, =H:0,3dlO1HD, 719 auarkdo. wy 2 tuarkdory EeGENERAL PRINCIPLES APPLIED IN STUDYING AN INDUSTRY 8) Phenal (8) Coal tar distillation ©) CH + 8,50, MOH, Celle + cr, MOH, ai, 1,80, Comene 4 F284 4 aoetone) Towne "5 Benanc acid 24 Catle+ BE, ati gcr 225 6 ect rsoyetedy Call, 7s Catt 25 canon SyII INORGANIC CHEMICAL INDUSTRIES Processes for the industrial prodction of inorganic chemicals arc historically the oldest of the commetcial chemical field. typicsl example was decarbouation of limestone (C4CO,) to produce quioklime (CaO) in the Egyptian, Greck and Roman civilizations. As knowledge of chemistry was Ioreased, procesoes became more complicated than just a simple preparetion from natusally- ‘occurring minerals. Today several of the tnorganic processes are equally us conmplex so many of ‘he processes found in the natural product or organic chemical iadutrics. ‘As a general slle, inorganic processes we sinipler and more casily developed than those clusified as organic processes. Tnorganic procester are usually oné or two simple reaction steps ‘with uo side reactions, irveversible for maximum yiells, end with no danger of thermal eoompositiog, A nuajor peoblec of the inorganic industry ie to obtain eooromic raw materials auffickenlly pure to give good yields of refined inorganic chemical products, Whesees the unit peooesses exnployed ace relatively simple, c.g.. neutralization or calcination, the development af suitable unit operation sequences to produce high purity inorgasic cheaicels with economical yighp is the major task of the chemical engineer in the inorganic chemtice! industries, aly a representative few of inorganic chemicals will be discumed in this book. Details of ‘processes forthe production of tker inorgsnic chemicals can be found in the chemical technology Beerature, Factocs which ere responsible for such high costs in the Indian chemica’ industries as a whole ase made up of « combination of the following factors: + Low capacity plants.ofen aot operating at fil capacity Higher fined capital investment since many of the plants arc fo mechanicat equipment is expensive + Scacity of raw materials, sometimes involving imports ‘+ Technological problems, particularly maintenance and repair © High cost of electric power, utilities and traneportaton ‘Those factors make it cifficul 10 compete in the world macket st the present time, A gradual eduction in cost ig expected as the industries grow and gain more experience. JIA, SULFUR AND SULFURIC ACID Sulfur Sulfuc is the basic raw material for manufacture of sulfuric scid, which is considered the barometer of India's industrial progeess. In more sdvanced couutrics this rule is ao longer valid ‘8 the overall jadustey grows rapidly with sulfuric asid virtually stable. Curteat production is at ‘the same level as that of the USA in about 19C0 and the per capita consuenption of acid in India is only 4% of that in the USA. Thete figures give indication of the temense development possiilices for Enis. z owes QE ERS. ey bee te 5 z &SULFUR AND SULFURIC ACID 1, Pertinent Properties of Sutfur it ims the chemical fmula 8 and an atomic wei ‘and a1 monoclinic solvents aad molten, ground powder and 2. Consumption Pattern 21 10908 of elfor-consiniag caw materials are converted 1 these commercial oxidized forms: Sulfte dioxide (soy) Sulfur wioxide 0) Sulfurio acid (80) Oieum (80, +50) 2.2. End usos for clemental sulfur are 3 3510 90% for sufute setd manufacture + Rest for production of: 80,, 80,, C5,, and PS, ‘uber vulcanization agents; gunpowder, sulfur dyes; Portes, sulfar concrete; Mautner oH MPPORIAly: 75 to paper aad pul, 3% to CS, manufacture, 73. The applications spectrum for sulfele seid i in U.S.A Phosphate feruizers 7” Taorgatic chemicals end pigmens Copper teasing ¢ Syothetie rubbers and plastics ‘+ ledastrial orpanie chenicas © Pup and paper + Other * Petroleum refining 3. Raw Materiats Sources Sulfite far, py ides of iron), hydrogen od eas fm the baraing of fuel oad smcling Fein, Elemental sulfur, pysites und sulfide, Muric acid in India. Sulfusic acid produces by hulfur exeept for Hindustan Capper Lid., ‘aad Cominco Binal, Alwaye whch are Respectively. Onc plant based on ison4 INORGANIC CHEMICAL INDUSTRIES The only deposits of suifur are found i the Pugs valley of Kesha, but doe to difialt eran Bee inca, nee deporte have not acquired dus economic iazportance, ‘Taree alternative souscns Sulfurie acid, however, lage scale, a5 a by-product in tke Suiiteen ant in the imeliew of 2ite, copper, ani other poa-ferus wietlr. | Fyries and Fhonpbete Chemicals Ld. opestes with » capacity of 400 tous of pyre ores per day. Bases of crore, two raf acid plania have been eet up in Sindki, In order ty naect thle imaremepir Rly, the FPCL bas embarked oa « new scheme ie produce 90 tone of pycis Ber © Blemental sulfur: from asit domes (USA, Sicily) {Hydrogen sulfide conversion from natural gap and industial gutce Cadian refinoriog ‘and many U.S. refinerios) ‘¢ Iron pyritca from Amjhore in Bihar State 3:2, Bkemeotal Suifur Mining (Frasch Provost) ‘Reference flow sheet: Figure MA-L Water (160°C) 6 tons {b) Dome operating capacity: 500-8000 tons/day of sulfur 3.2.5. Process description Welle drilled into free sulfur-bearing alt domes. ‘Thesc are fouad in the USA slong the Gulf Coast Treated hot wer ia pumped inte deport melt suifar, water moves Nomad aad ovtvard 10 blesder wells on cuter periphery of area where itis arated end “Tockerged. Molten alfuc sinks to bottom of casing and js jet posaped with comprested ihr tp mump-separation units ond shipment or storage. Fiteation is soroetimes used to remove carbonaceous and mineral matter. 3.2.6. Major engloeering problema (@) Heat transfer in aceting and shipping operations ()) Finding sultble sources of treated water © Corrosion . Oxidation-reduction of HS 3.3.1, Reference flow sheet: Figure 1TA-2 33.2. Chemical reactions (@ IHS + 30; +280, + 24,0; aH® = —247.89 Kal Ai, () SHS + 280, + Se) + 4,0; aH!" = —42.24 Keal‘ssxpond qosaiy fq Pra Ky See ayo oom yy 3.3 BIEN Due [rey “Tuas 4 oxtoxs oad, Aypecey STEA UORPOUT PHOS, 8 3 g 2 z 5 2BRIA BaSDS VOR AURIS OF uNINS | ' L 3 &sorubbing with ethanc 3.34, Quantitative requirements (ORS 1 etre ton of sulfur and 10088 yess HS 1.2tons; Air 1,700 Noe 'apacites: 20-600 tons/day 435. Process description BS sed sic burned in reaction 3.3.2(4). ‘The Brouct $0, oxltasa HS by Pinal waits 2°) S¥0-sage camigtic convater wee ‘ntercoaling and condensing” Sit Mato sn is sorubbe with molten sulfen 3.3.6, Major engizcering pecblens {a) Two-stage reactor design for cxothermle 80, oxidation of 1,8. 70.20% recta tit ft stage st 300-400°C range Polen By 250-500°C operstion ia secnedt ‘TMctoe to obiain favorable equilibrium, cnt acbaees for moken sulfur banding (©) Comosion (@) Floal olees-up of stack gases eat uifar from Pyrite (Finnieh Proceas) Reference flow sheet: Figure WAS ‘Chemical reastisns © Thermal dissosietion 1a FeSs YSW8) + FSCO); all = 415.98 Koa ‘300% ‘) General combustion resction Son 8+ O50, 18, 60, Hc0,, HO (©) Saifr recovery tom gasss—Hot age 2008 + 08, + 808 4 50 vcore ‘h, ¢ {) Sulfur rocovety trom gases Cold Alo, 280, ~ 41,0 +5, wre (© Roasting of Fe8 (pyertotite for 50, recovery Tata, PFS + SO. Rey + 28045 a = —295.09 Ko 1o0ore Quantitative requiroments @) Basis: 1 tom of elemental sults 24 5 Datity, 92% toial $ recovery) Pyritea ore (Amjhore) 4.4 tons Limestone 0.65 ton Foal off 9.76 toa Water 25 tons lectrisity 1.800 KWHSULFUR AND SULFURIC ACID Co-products: $0, from FeS roasting = 1.2 toms Fe, frou FeS roasting = 2.8 tons Electricity = 3,200 KWH total or 1,400 KWH nce ) Plant capacities: 250 tons/day as eletetal sulfur 3.4.4. Process description ‘Pyrices ore is dried ia a rotary Klin with fue geses and grou to —200 mesh, tis sisporsed with hot combustion gasea from oil burners atthe top of x vertical circular shaft furaace (5.5m diamieter x 10m height). Heat of dissociation and fusion is treasferred to the FeS, us It maves downward in fhe rurpeation. At tho bottom of the ventical shaft the ‘20ac3 change 90° axxl move horizontally. The liquid droplets of FeS are cought in the ‘molten horizontal bstch and aay silica gangue is trapped and fluxed with lime, flostin ‘8 1p of the molten FeS matte, ‘The liquid FeS is tapped periodically and granulate in water to produce ~4 mm grains for further coasting openstions, Hot gases at 1,300°C move chrouga & high-pressure heat recovery holler section (70 ‘ums. stain), cooling to 300°C. Dust is next separated by electrostatic previptation, Tee first sep in combined $ recovery is dooe in # high temperature catalviio reactor [see reaction 3.4.2ic)] where etrbon compounds with § are eliminated. The reaction gases, sfill containing $0, vod HS, are cooled to 150°C by passiog through @ low [rossure heat recovery boiler (4.5 atms, gape). This is followed by “cold stage” eatalytio feaction (see 3.4.2(4)] where slamioum oxide catalyzes the H,S+8O, reaction to produce S, vapor. After catalysis, sulfur gas is condensed on moiten sulfur droplets ina spray condenser. ‘The heat of fasion is recovered via low-pressure steam beiles (0.7 atm. gage). ‘The exit seascs are next wasted with water in another tower to further recover enteained and uncondonsed sulfor, ‘Tae sulfur usually contains arvenle which attacks the vanadium or platinum catalyst in the S0,-+80, contact process for H,S0,. It can be removed by contacting molten sulfur with mulk of lime in a continvous autoclave, Sulfur a: SO, for sulfuric acid can be obtained by coasting the granulated FeS from the smelting furnace. Fluidized roasting st 1,000°C produces 80; ges which ia cooled ‘in waste heat boiler, cleaned by cyclones snd electrostatic precipitation. ‘The hot cinders of iron oxide, suitable for blast furnace sinter ence, axe cooled oa coaveyors and shipped to steel plants, 3.4.8, Major engineering problems (2) Pyvites ore beneficiation The proccas was developed for pyrites ores of Finfand which have 1.5% Si0,, Indian ore at Amyjtore has §-7% SiO. and requires cither Notation intial or extra limestone to flux out the siisa, The later is preferred since there is a 30% loss of ore in ‘rencficiation. () Grinding ‘The particle Fize range of —260 mesh wes an cconomic balance betweer heat transfer rz from combustion gases plus residence time, a8 dicistad by rate of tall of particles, sower height, and grinding costs, (@) Substitution of coal for Fuel oil Low-grade fuel oll (s otly avaiable at the Amhore site at bigh coate, Smeking withINORGANIC CHEMICAL INDUSTRIES ag mala PIR w savings OF 20% inthe sont oF sulfur produced. Use of coat Pei COesideed tor pot plat evetopmneet tert ‘The question of wsing pulverized the smeker bumers or warking with scvondary combustion gases afr act ved. in the smelting fienace of fel without exesss sic is desirable to avaid ubhalacce of the UR only minor changes inthe orygenifucl nan, The control, 41, Hlementel Sulfue Deposits and Supply 2 BSA flraishes about 60% of world eulfoy Table WAsi S85 World Sulfur Production (in 10° Country Sources USA CIS Conada Poland PR Ching Japan Sutfur-all forms 1.4 St 09 1s Frosch z . - : Native (ined 1 S03 : —Prrites 02 03 12