1977 Petrochemical Handbook Issue World-wide demand for petrochemical derivatives appears set for an aver- age growth rate of 6-89 through the remainder of this decade. However, sirong demand for specific feedstocks will all for some changes and rising costs are certain to affect selling prices. Already some prices for basic intermediates hhave risen slightly but not sufficient for a fair return on investment. This will come as operating rates return to higher levels and geographical dislocations of supply/demand begin to equalize. We estimate 1978 world-wide capital investment for new petrochemical facilities will reach almost §12 billion. Basic intermediate petrochemicals con- tinue to be dominated by feedstock owners and more joint ventures are ap- pearing. 1977 Handbook Issue. Our industry advisors play a significant role in helping select those processes which appear in the Handbook. Again, we have included a second index of processes which were contributed but were omitted for lack of space. Processes have been arranged alphabetically by product for easy access by the reader. Our advisors: A conference with industry experts to establish the scope of the handbook is vital to its continuing success. ‘These advisors shown, left to right, in the photo with Petrochemicals Editor Tom Ponder were: M. G. A. Chadwick, ICI Americas; N. E. Ockerbloom, Sun Trading & Marine Trans. port Co, Ponder; Merritt G. Matbach, Shell Chemical Go.; M. C. Hyde, Chemicai Insight; Georges Porokhov, Rhone-Poulene. ‘The participation of these men at the conference does not constitute en- dorsement of HyorocarnoN Processinc over any other publication. However, their attendence does show the interest they have with sound technical content planned for the benefit of the Hydrocarbon Processing Industry. ‘November 1977 ‘Hynnooamnon’ Paccnssmvo Process index Acetaldehyde ‘Acetaldehyde Acetic acid ‘Acetic acid ‘Acetone Shit Acetylene removal « Acrylic acid & esters Acrylonitrile (Sohio process) Acrylonitrile Adiponitrile Adiponitrile Aniline «22+... 131 Benzene “(Detal) 132 Benzene... Benzoie acid Detergent alkylate Dimethylformamide . Dimethylterephthalate - Dimethylterephthalate - Dimethylterephthalnte |” Ethane. Bthylbenzene . Ethylbenzene Ethylene Ethylene Ethylene. Ethylene. Ethylene diamine... Ethylene oxide & glycol Bthylene oxide & glycol Ethylene glycol ethers Ethylene oxide & glycols Ethylene-propylene rubber 2Ethylhexonel . Ethylmereaptan ..... Formaldehyde 0.2.0... Formic add Higher secalcohols Higher oxo aleohols sobutylenePROCESS INDEX Maleie anhydride 180 Maleic anhydride . 181 Methanol 182 ‘Methanol 188 Methyl isobutyl ketone 184 Methyltert-butyl ether . 185 Neo acids y 196 Nitric acid. SBS ath Nitric acid. 188 Nylon 6 189 Oxo process. se190 2-Paraffins ei Pentacrythritol ....+e+s+eeeeee e192 Phenol ....ssss++++ so e193 Phthalic anbydride os... ees 10 Phthalic anbydride 195 Phthalic anhydride 196 Polyacctal resins 2197 Polyacetal resins 198 cirPolybutadione Polybutenes Polybut Polyester Polyester: Polyethylene (LD) Polyethylene (LD) Polyethylene (LD)... Polyethylene (LD)... Polyethylene (HD) Polyethylene (HD) Polyethylene (HD) ....... Polyethylene (LD) . Polyethylene (HD) Roly prerriens Polypropylene. Polypropylene - Polystyrene Polystyrene Polyvinylchloride Polyvinylehloride Contributors index [Air Products and Chemicals Tnc......182 Aldehyd GmbH 7 ARCO/Polymers, Ine. woe 205 ARCO Technology Ine..... 148, 145,286 Asahi Chemical Industry Co., Inc....-126 ATO Chimie 206,216, 218 ‘The Badger Co, Ine. «-----+1+--1%4 151, 174, 226, 238, BASF AG 135,172, 179, 10 Bayer AG... 120, 234 BP Chemicals Ltd. .. 119, 193, BP Trading Ltd. 222 Bunawerke Hils GmbH - C&T Gindler, Inc. CE Lummus 154,227 CChemische Werke Hills AG. .....185, 229 Compagnie Francaise de Raffinage.....173 Cosden Technology, Inc. 200, 217 Daicel Ltd, oo... ..eseseseese+ 16%, 221 Davy Powergas GanbH 187 Deutsche Texaco AG 121, 184 Dynamit Nobel AG 7 Engineering Products and Processes Union Carbide Corp. Espindesa Euteco SpA. Exxon Chemical Co. 162 130 191 188 197 186 116 Grande Paroiste . 128 Gulf Oil Chemicals Co, ..+2+.+++++-207 Hercules, Ine. «2.2.25 193 Hoechst AG ......140, 202, 208, 213, 219 ‘Hydrocarbon Research Inc. 150 Imperial Chemical Industries Ltd..182, 223 Institut Francais Du Petrole..144, 170, 224 Tnventa AG severe 189, 208, Kyowa Hakko Kogyo Co, Lid TB ‘The Leonard Process Co. Tne, 142,157, 166 Linde AG 2158 Lonza AG -13t Lurgi Gorp. esses 180, 183, Maruzen OH Go, ..2+2+esseseee01 0.237 Josef Meissner GmbH = 165, 182, ‘Ministry of Chemical Industry USSR. 127 ‘Mitsui Petrochemical Industries Led. ‘Mitsubishi Gas Chemical Coy Tne. . itnead et) ‘Mitsubishi Petrochemical Co., Ltd..-.225 Montedison SpA. +15, 214 Montefibre SpA 169 Naphtachimie ....+.+ 209 Nippon Sholubai Kagaku Kogyo Co, Lad. 123, 158, 171 148, 214 November Polyvinylchloride Propylene oxide Proteins Proteins Proteine Proteins Styrene .. Styrene Styrene... TTerephthalic acid ‘Terephthalic acid Vinyl acetate « Xylene. pXylene Xylene isomerization «2.2.6.2 +++ -298 Xylene Bomerization .. eet’) p-Xylene separation ........cse+ +240 Phillips Petroleum Co. .....199, 210, 215 J. F. Pritchard and Co. 2-281 allman Kellogg «129, 189, 155 Rhone-Poulene SA. +162, 195, 220 Rubrehemie AG 163 Salagitter Industricbau GmbH an Shell Development Co. .....159, 160, 175 Sid Richardson Carbon & Gasoline Co. 138 ‘Snamprogetti 161, 201, 204, 252 Sia Viscosa .. 134, 137, 168, Societe Chimiques Des Charbonnages. .228 Societe National EW-Aquitaine ......164 Stamicarbon BV . 196, 233 Stone & Webster Engineering Corp. ‘Techaip Tennessee Eastman Co, . ‘Toray Industries Inc. - Ube Industries, Ltd. UCB SA... Union Carbide Corp. UOP Process Division, UOP Tine. . 125, 138, 152, 177, 229, 239, 240, US. Industrial Chemicals Co. Veba-Chemie AG ‘Von Heyden . Wintershall AG 1977 Hyprocarson ProcessineAcetaldehyde—a2=1o omen Application: A process for acetaldehyde production by irect oxidation of ethylene, There arc two variations of the process, one using oxygen and the other using air, The choice depends on local conditions such as oxygen cost, utility prices and ethylene purity. Description: The process employs a catalyst solution of copper chloride containing small quantities of palladium chloride. The reactions may be summarized as follows: PdCl. C,H, + 2GuCl; + H,O > CH,CHO + 2HCI + 2GuCl 2CuCl+ 2HCI+ 40; > 2GuCl, + HO In the reaction, palladium chloride is reduced to elemental palladium and HC! and is re-oxidized by cupric chloride. During catalyst regeneration, the cuprous chloride is re- oxidized, ‘The reaction and regeneration steps canbe conducted separately or together. One-stage oxidation with oxygen: Ethylene and oxygen are fed into a vertical reactor which is filled with catalyst solution. ‘The reaction takes place under a slight pressure and at the boiling temperature of the aqueous solution. The reaction is exothermic by 58 kcal per mole acetaldehyde produced. This heat is removed by water evaporation, and the concentration of the catalyst solution js kept constant by means of a corresponding water sup- ply. Acetaldehyde produced is condensed and scrubbed with water from unreacted gas, which is recycled. Hyonocannow Procsssinc November 1977 Grade acetaldehyde thus obtained is separated fro byproducts and water by a two-stage distllatin. Raw materials and utilities (per 1,000 kg acetalde- hhyde) + Oneastage Ethylene (Min. 99.8% vol.), kg......... 670 Oxygen NaS ccs cein vedi ceceonso# 2758 Catalyst (PdChs), @ es... 09 CuCl. +270, g vos. 150 HCI (100%) as 30% sol., kg . + Cooling water (25°C), m® ... se 200 Process water, Mm? ..seccccsececse 6 Deionized water, m* 7g 8 Steam, kg 1,200 Blectric power, kWh’... 250 Personnel, 1 supervisor, 1 foreman, 3-4 operators per shift Yield, 9596. * Oxygen plant utilities not included Commercial installations: Plants with a total capacity of 2,240,000 tons/yr. are onstream (end of 1977), further 100,000 tons/yr. are under construction. References: Further information is available from ‘Hoechst-Uhde Corp., 560 Sylvan Ave., Englewood Cliffs, N.J., 07632, and Uhde GmbH, Deggingstrasse 10-12, 4600, Dortmund 1, Federal Republic of Germany. ANOUL on GUEVARA YA 7Acetaldehyde—ver-crm ac 118 Application: Process for production of pure acetaldehyde by dehydrogenation of ethanol. Description: Crude ethanol is concentrated together with the not converted ethanol in the ethanol recovery column. ‘The ethanol vapors are mixed with air in a definite ratio, which can be performed in an air saturator. Due to burning of most of the produced hydrogen with air the reaction on the silver catalyst is exothermic, this heat is recovered by making steam, The reaction gases are scrubbed with ethanol to dissolve the acetaldehyde and with water to avid soluble materials inthe offs, which Contains mainly nitrogen and hydrogen and is burnt. In the finishing column the produced acetaldehyde is sepa- rated from the not converted ethanol and water. An advantage of the process is besides the steam generation in the reactor the possibility to operate the finishing column without any steam consumption, when the ethanol recovery column is operated under pressure and its vapors are condensed in the reboilers of the finishing column. Utilities (per ton of acetaldehyde) : Steam 7 bar, ton... Power, kWh Gooling water, mi? Yield, “Yo. ‘The produced steam captive use for air compression. Commercial installation: Two large-scale plants for the production of acetaldehyde are in production, the total nnual capacity is 130,000 tons. November 1977 Hyprocannon ProcessivoAcetic acid —s cumcas uw. Application: A process for production of acetic acid by liquid phase oxidation with air of a light hydrocarbon distillate, Formic acid, propionic acid and optionally ace- tone are recovered as co-produets, Description: The feedstock consists of a light naphtha ‘comprising hydrocarbons in the Cy-C, range; oxidation gives a variety of products, but it has been found that intermediate oxidation products such as ketones and esters ‘can be recycled to extinction. The final useful products include organic acids, optionally acetone and a liquid residue which can be burnt to raise steam. Depending upon the selected process option, the feedstock and mode of operation, a total of 0.35-0.75 tons of co-produets (for- rie acid, propionic acid and acetone) per ton of acetic acid may be recovered as specification materials. ‘The oxidation, which is strongly exothermic, takes place in a stainless steel reactor operated at a temperature of 170°-200° C and a pressure of about 50 Kg./em?. The off-gas leaving the reactor is cooled in successive stages, and the condensates obtained are returned to the reactor, The liquid reaction product which comprises a complex mixture of organic acids, water and partially oxidized intermediates, is removed from the reactor and processed in a series of distillation columns, Hyprocarnon Processinc November 1977 Product isolation essentially comprises topping to re- move intermediate products, tailing to remove high boilers, dehydration and acids separation. Acetone is op- tionally extracted from the intermediates recycle stream in a small additional unit, All products are obtained in high purity and are st able for all commercial uses including, where appropriate, food and agricultural products A notable feature of the process is the application of many energy conservation techniques, Thus the heat of reaction is used to generate useful steam and the expan sion of high pressure off-gas is used to provide both elec- trical power, via turbine generators and process cooling, Commercial installations: BP Chemicals Ltd. operates three plants having a total acetic acid capacity of 180,000 tons/year at Hull, England. Process is operated under license by Rhone Poulenc Industries (France), Daicel Ltd. (Japan) and in the U.S.S.R. with acetic acid eapaci- ‘ies of 28,000, 15,000 and 35,000 tons/years, respectively. Licensor: Inquiries should be directed to: BP Chemicals Ltd., Licensing Division, Devonshire House, London WIX 6 AY. Reference: The Industrial Chemist, November 1962. UAL Y 19Acetic acid —sv: ac Application: A process for producing acetic acid from n-butene fraction, Description: n-butenes are converted to sec-butyl acetate recycled acetic acid in a reactor cascade in the liquid phase at 100-120° Cand 15-25 atm. ‘The catalyst used is ‘an acid fon exchange resin and is suspended in the re- action mixture. The catalyst is separated from the reactor effluent in a centrifuge and recycled to the reactors. The crude product is fed to the Cystripper to separate non- converted Ci, hydrocarbons. ‘The mixture of sec-butyl acetate and acetic acid with- drawn from the bottom is fed to the oxidizing reactor where the butyl acctate is oxidized with air at approxi- mately 200° C and 60 atm without catalyst. The vent gas obtained in the reactor separator is washed with acetic acid in the scrubber and subsequently afterburned in a catalytic oxidizer to convert carbon monoxide. This ges is expanded in a turbine to utilize the energy. Steam gen- erated in the reactor is partly used for distillation and after superheating with the exhaust gas leaving the cata- Iytic oxidizer, partly utilized in a condensing reheat tur- bine. The air compressor is driven with both turbines. Grude acetic acid is fed to the azeotropic column, where overhead non-converted butyl acetate, volatile by- products and water are withdrawn. The butyl acetate Upper layer accrued is recycled to the oxidizing reactor without any intermediate purification. The water sepa- rated as the lower layer is freed from dissolved organic components in the water stripper and purged from the 120 system. The water required for the azeotrope formation is recycled from the stripper bottom. The bottoms of the azeotropic column are freed from a small amount of high- boiling components in a flasher and fed to the formic acid column. The high boiling components are purged from the system. Overhead formic acid obtained is burned in the catalytic oxidizer. ‘The bottoms of the formic acid column are purified to refined acetic acid by redistillation Bottom product of the refining column is recycled to the flasher. The recycled acetic acid for the first reaction step is withdrawn as the lower side stream of the formic acid column, Rather than buming, the formic acid formed can be recovered in an additional distillation unit. This will re- quire modifications of the catalytic oxidizer and the steam utilization system, Yields: 800 kg n-butenes are converted per 1,000 kg acetic acid produced or in the case of formic acid re- covery, approximately 790 kg a-butenes and 100 kg formic acid per 1,000 kg acetic acid produced. Commercial plants: None. Basic design worked out in cooperation with Lurgi Mineraldltechnik GmbH. References: Hydrocarbon Processing, 49 (1970) 11, 117- 120; The Proceeding of the Seventh World Petroleum Congress, 59-65, and Hydrocarbon Processing, 58 (1974), 11, 103-113, Hydrocarbon Processing (1975), 11, 101. November 1977 Hyprocarnow ProczssinoAcetone—owrscie rexaco ac a A process for the manufacture of acetone purity 99.8%) from isopropanol (IPA). ption: Catalytic dehydrogenation of IPA is carried cout in the vapor phase at 250-270° C. GH,-CHOH-CH,—CH,-CO-CH, + Hz — 55.6 Beu The product mistue is partly condensed and pated to a vapor liquid separator. Acetone remaining in the vapor Phase is removed from the hydrogen in’ a subsequent cooling unit. The hydrogen has 2 purity of 99 vol. 9 and can be used directly for hydrogenation processes. ‘The crude acetone is distilled. 1.1 ton IPA per ton of Conversion per pass: 0%. Economics: A 25,000 metric ton/yr. plant required bat- tery limits investment of $2.6 MM and uses one operator. ton of acetone Utilities: Utility requirements per me of min. 99.8% purity are: Gooling water, gal. .........+.. 17,000 Steamy 99 peg bs, 4,500 Electricity, kwh «0.0.00. 100 Fuel, MBiu 20 15. Catalyst initial filing $20,000 approx.) Catalyst life III More than 4 years Commercial installations: In operation: onc 40,000 ton/yr. plant in Germany and one ‘4000 ton/yr. plant in Argentina. One Peruvian plant of 4,000 ton/yr. is under construction. Licensor: Deutsche Texaco AG through Texaco Develop- Para Meret an deren (Main). ‘November 1977 121Acetylene removal—srone ano wessrer encivesrinc cop. 122 Application: An absorption process for the removal and recovery of acetylene from an ethylene rich process stream. Product: High Purity Acetylene (99496) is produced. Description: An ethylene rich process stream containing acetylene is contacted with a solution of dimethyforma- mide (DMF) where most of the acetylene and some other gases are co-absorbed. The rich DMF solution is flashed at reduced pressure to liberate the majority of the co- absorbed gas. The remaining gas is preferentially removed jn an ethylene stripper. All flashed gas is recovered by reoyele. ‘The acetylene rich DMF is interchanged with hot lean DMF before entering the acetylene recovery column. The acetylene product is stripped from the DMF solution in the acetylene absorber and delivered to battery limits Investment: The investment for acetylene recovery is about comparable to the investment of the Acetylene Hydrogenation system normally employed. Experience: Stone & Webster has designed three oper- ating plants. November 1977 ‘Hyprocarnon PRocessINGAcrylic acid & esters —nrron sioxusa kacaKu Kosro co., 110. Application: A process for the manufacture of acrylic fed and estes ftom technical grade propylene, air and Description: Acrylic acid is produced directly from propylene in high yield by the vapor phase catalytic air oxidation process, In the improved process that has been in commercial operation lately, a part of the reaction gs leaving the absorber of acrylic acid is recycled to the oxidation reactor. This recycle system offers several important advantages compared to the conventional one- ass process. ‘The reaction can be conducted at much lower con- centration of steam in the reaction gas and no feed of fresh steam to the reactor is required. Consequently, the steam consumption is much reduced. A substantial reduc- tion in the consumption of propylene feed results owing to a more efficient utilization of propylene. The lower steam concentration in the product gas reduces the cool- ing duty in the absorber of acrylic acid and gives rise to higher concentrated aqueous solution of acrylic acid which helps to economize the following processing of solvent extraction and refining of acrylic acid. The waste ‘water effluent from the process is reduced correspondingly, and this is a particularly favorable feature when the waste water is treated by an incineration system. "Various acrylic esters are manufactured using acrylic acid thus obtained, For methyl and ethyl acrylates, the esterification reaction is conducted continuously ina liquid phase in the presence of an ion-exchange resin catalyst. From the reactor effluent unreacted alcohol is extracted and recycled. For butyl and 2ethylhexyl Hyprocanaon Paocessivc November 1977 acrylates, the reaction is conducted in. semi-continuous manner with only a slight excess of alcohol to acrylic acid. These reactions are almost quantitative, The high purity esters are obtained continuously by subsequent dis- tillations. Economics: 1. B/L. capital investment (1977, Japanese base) Acrylic acid (50,000 tons/year), 3600 MMYen, Methyl acrylate (20,000 tons/year) 700 MMYen 2, Raw materials and utilities consumption: Acrylic acid, 1 kg Propylene, 100%, kg ..-..-... 0.68 Catalyst and ax. chemicals, Yen 12.1 5 Steam, kg ..... 12 Electric power, kwh og Water, kg. is 35 Methyl acrylate, 1 kg Acrylic acid, ke 0.89 Methanol, kg ......-.. 0.38 Catalyst and aux. chemicals, Yen’. - 4 Steam, kg 42 Electric power, kwh 0.04 Water, kg aa as 1B Commercial installations: 40,000 tons/year at Nippon Shokubai's Himeji plant, Japan. The process has been licensed to Produits Chimiques Ugine Kuhlmann (France), Rohm and Haas Co. (United States), Societe Norsolor (France )and Petroleos Mexicanos (Mexico). Reference: Hyirocarbon Processing, November 1975, Vol. 54, No. 11, p. 106, AL VICTOR @ 128Acrylonitrile (Sohio process) —re savcre co., ne. Application: A process for the manufacture of acryloni- trile from propylene, anhydrous fertilizer grade ammonia and air. 9949 purity HGN and acetonitrile may be recovered as salable byproducts if desired. Description: The above feeds are introduced into a fd bed catalytic reactor operating at 5-30 psig and 750°- 950° F. ‘The reactor efluent is scrubbed in a countercur- rent absorber, and the organic materials are recovered from the absorber water by distillation. Hydrogen cyanide, water, light ends and high boiling impurities are removed from the crude acrylonitrile by fractionation to produce specification acrylonitrile product. A feature of the process isthe high conversion obtained on a once-through basis in the fluid bed reactor. Trouble- some separation and recycling of unreacted raw materials is unnecessary. Catalysts: The fiuid-bed catalyst currently employed (Catalyst 41) represents the third level of improvement since the process was first commercialized. It produces relatively more acrylonitrile and less byproduct acetoni- tile, 124 Operating conditions: The reactor operating conditions are defined above. Most of the fractionation is accom- plished at atmospheric pressure. Yields: Yields in excess of 0.85 pounds of acrylonitrile per pound of propylene feed are achieved. Over 0.10 pounds of byproduct HON can be recovered per pound of acrylonitrile. Commercial installations: More chan 45. plants throughout the world with an aggregate capacity exceed- ing 5 billion pounds per year of acrylonitrile. Plant capacities range from about 20 million pounds to about 350 million pounds per year of acrylonitrile, ‘The Badger Co., Inc., offers engineering, design and construction services for plants using: this process. References: HP/PR, Vol. 42, No. 11, Novernber 1963, p. 139; Chemical Engineering Progress, October 1960, p. 65; HP/PR, Vol, 41, No. 11, November 1962, p. 187; PR, Vol. 38, No. 7, July 1959, p. 264. November 1977 Hyprocarsow ProcrssineAcrylonitrile — monreoison s Application: A process for the manufacture of highs purity acrylonitile by propylene ammoxidation according to the following seaction: CH, CH — CH, + NH, + 3/20. > CH: CH-CN+3H.0 High-purity HGN is recovered as a byproduct. High- purity acetonitrile can also be recovered if desired. Typical propylene purity is over 90% but may be as low as 609% as long as the balance is mostly saturates. Process description: The combined feed is charged into a fluidized bed reactor where the reaction takes place in the presence of a very active catalyst. The reactor ceffiuent is passed through an absorber where acrylonitrile, HEN and acetonitrile are absorbed and the off-gas is recovered for its fuel value. ‘The purification process proceeds through the separa- tion of carbonyl compounds, the recovery of high-purity HIGN and the removal of acetonitrile. Acrylonitrile is finally dried, purified and recovered as a high-purity product. Hyprocarson Processinc November 1977 ./UOP PROCESS DIVISION, UOP INC. Operating conditions: Moderate pressures are used throughout, High pressure steam is generated in the re- action section and is used to drive the air blower and to satisfy the reboiler heat requirements in the separation and purification section. Fractionation heat requirements are minimized by using an efficient heat recovery system. Yields: On the average, the production of 1.00 unit of recovered high-purity acrylonitrile requires the consump- of tion of less than 1.18 units of propylene and 0.48 us ammonia, The unconverted ammonia may be recovered so that the net ammonia consumption reduces to 0.45 units. Specific production of high-purity HCN and acetonitrile is 0.06 and 0.03 units, respectively. Commercial operation: ‘Two commercial plants are currently in operation; one with recovery of high-purity acetonitrile. Several other units have been designed. Reference: 2nd International Petrochemical Conference, National Petroleum Refiners Association, San Francisco, March 27-29, 1977. 125Adiponitrile—asam cremcar moustay co., ur. Application: A process for the manufacture of high pusity,adiponirile (min. 98.896) by dire electro. yydrodimerization of acrylonitrile. Description: The Asahi process produces adiponitrile (ADN) by electro-hydrodimerization of acrylonitrile (AN) and consists of electrolysis, recovery and purification, AN js fed to the catholyte tank, where it is emulsified with supporting salt. The resultant emulsion is sent to the clectrolyzer and is constantly recirculated through the electrolyzer and the catholyte tank. A portion of AN dissolved in the catholyte is converted into ADN by an electro-hydrodimerization reaction on the cathode surface. This process utilizes cation exchange membranes which ‘migrate cations selectively, to prevent oxidation of the reaction mixture in the anode compartment. Cation exchange + ‘membrane - H,O-2- HL, 3 2) 40.+2H He ty Anolyte Catholyte HY ions to be consumed in the dimerization reaction migrate through the cation exchange membrane. ‘The supporting salt is of a simple formula such as tetraethyle amninonium, sulfate and has @ low affinity 0 onganic materials, Therefore the supporting salt can easily be separated from the oily layer * ‘A portion of the catholyte is sent to the AN stripper, 126 where unconverted AN and byproducts, such as pro- pionitrile (PN), are removed with a small quantity of water from the top. The top stream is separated into two layers in the decanter. Oily effluent is sent to the PN stripper, where AN is recovered from the top and then recycled to the catholyte tank. PN is removed from the bottom. Aqueous eflluent is sent to water stripper where dissolved AN is secovered together with the byproducts from the top. Water is removed from the bottom. The bottom stream of the AN stripper is separated. into two layers in the coalescer. The aqueous efiluent is recycled to the catholyte tank through the catholyte puri- fication unit. After removing dissolved water in the flush chamber, the oily eflluent is tent to the heavy cut column, where high boiling components such as trimer of AN are removed from the bottom, ‘The top stream of the heavy cut column is sent to the Ist light cut column, where low boiling components are removed from the top and ADN is obtained from the lower part of the column. ADN js recovered from the bottom stream of the heavy cut column and the top stream of the Ist light cut column for recycling to the proces Raw materials and utilities consumption: (per 1,000 kg of adiponitrile)—acrylonitrile, 1,100 kg; sulfurie acid (98%), 80 kgs electricity, 4,000 kwh; steam 3 tons; service life of the cation exchange membrane: { year plus, Commercial installation: Asahi Chemical has been operating its own plant with a capacity of 20,000 metric, tons/year since 1971 Reference: Cliemical Economy & Engineering Review, October 1975, page 20. November 1977 Hyprocaruon ProcessinoAdiponitrile—vee «.—mnistey oF crzmient wousray use Application: A process for reductive dimerization of acrylonitrile with continuous production of adiponitrile by direct electrolysis. Description: Reductive dimerization of acrylonitrile by the UCB/MCT Process is operated by direct electrolysis of an unstable aqueous emulsion of acrylonitrile into a one compartment electrolyzer without diaphragm. Process comprises mainly three steps: electrolysis, cisilation, rec- tification. Electrolysis: Acrylonitrile and water are fed to the elec- tuolyzer through which an emulsion of aqueous electrolyte solution with an organic phase is circulated. The extemal circulation loop comprises a cooler and a separator where the oxygen produced in the electrolyzer is taken of. The aqueous electrolyte solution, which contains a con- ductive salt, a protective anode agent and a surface ac- tive agent preferably quaternary ammonium salt, is con- tinuously recirculated. ‘A limited amount of organic phase in respect with adiponitrile production is leaving the separator as over- fiow and enters the distillation section. Distillation: In the first distillation column the greatest part of acrylonitrile and soluble water are separated and recycled. Tn the second column, remaining acrylonitrile and propionitrile are distilled under vacuum, where they fare separated in the third column under ‘atmospheric pressure with recycling of acrylonitrile. The fourth column gives technical adiponitrile as top product. Bot- tom product is evaporated under higher vacuum to sep- arate heavy oligomeric products. Hyprocanson Processino ©‘ November 1977 Purification: Technical adiponitrile is purified with vacuum distillation in two columns where light fractions such as succinonitrile, methylglutaronitrile and hydroxy- propionitrile are drawn olf and where higher boiling oducts are recycled. Adiponitrile obtained is ready for hydrogenation, Economics: The following economics are related to 1 ‘metric ton of end product ADN: 1, Raw materials and utilities rile 14170 to 1,190 kg 2830 kwh for electrolysis 950 kwh (other consumption in cluded refrigeration unit) Steam 4 tons Process water 250 kg Cooling water 17 m (from 28 to 38° G) 2. Byproducts Propionitrile 53 to 60 kg Heavy products = 125 kg Commercial plant: Process has been developed and in- dustzially proven in a semi-commercial plant operated in UGB's factory at Ostend, Belgium Licensors: UCB S.A—Licensing Department, Invest- ment and Industrial Property Direction, 4 chausiée de Charleroi, B-1060 Brussels, Belgium and V/O Licensin- torg, Kahovka $1, Moscow M-#61, USSR. References: U.S. patents: 3,616,321 /3,575,839/3,661,- 739, Belgian patent 684,136. Chimie et Industrie, Génie Ghimique, Vel. 104, No. 1, Jan. 1971. 127Ammonia— cranoe raroisse Application: A. process for converting synthesis gas (H: and Nz) into anhydrous liquid ammonia (99.8% concen- tration). Description: The process may be used with all synthesis gas prepared from various raw materials—natural gas, naphtha, refinery gas, heavy fuels, coal, etc. The process may be operated between 2,000 and 5,000 psig depending ‘upon the syngas compressor and gas preparation. The syn- gas should be from a nitrogen scrubbing unit without inerts or with inerts from methanation. Steam production at 500 to 2,000 psig is possible to recover as much reaction heat as possible. Converter: The converter is a vertical cylinder contain- ing 3 or 4 catalyst beds. The inlet gas is divided into two streams, the first cools the wall by circulation between the shell and the catalyst basket and is heated by the outlet gas in a countercurrent internal exchanger and starts the reaction in the upper bed. ‘The second is used as cooling quench between the beds. At the lower bed cit, the outlet gas passes through the internal exchanger. Depending upon the metallurgy, the wall may be exter~ nally steam-traced to avoid cooling during shutdown and startup. The converter is designed with a removable cap to allow easy internals dismantling, 128 Loop: The make-up gas enters the loop before the final chiller. At the loop recycle compressor discharge, the un- reacted gas leaving the cold gas-gas exchanger enters the hot gas-gas exchanger where it is countercurrently pre- hheated by the reacted gas leaving the economizer before entering the converter at about 190°C (150-230°C) ‘At the converter exit at about 370°C (360-410° G) the reacted gas passes successively through: economizer (boiler) , hot gas-gas exchanger, water or air cooled cooler, cold gasgas exchanger (where produced ammonia begins condensing), medium and low-pressure vaporizing an ‘monia chillers (where the produced ammonia is con- densed) and the separator. Anhydrous liquid ammonia produced is continuously extracted from the separator and degassed before delivery. If necessary, a permanent gas purge for control of loop inerts is installed immediately before the make-up gas inlet, After passing through a low-pressure vaporizing ammonia chiller, where the main part of the ammonia content is condensed and sent to production—the purge gas is generally burnt, In the same manner, the degassed ‘gas passes through another low-pressure vaporizing am- monia chiller before being added to the purge gas. Commercial installations: Grande Paroisse has am- monia experience dating back to 1919 and has continually updated the process in its own and its customers factories. November 1977 Hyprocarson ProcrssinoAmmonia—ruuman xenoes Application: A high-pressure steam hydrocarbon reform- ing. process for ammonia production from natural gas, refinery gas, coke oven gas or light hydrocarbons and air; also liquid hydrocarbons. Description: The catalytic steam hydrocarbon reforming process produces raw synthesis gas by steam reforming lunder pressure, followed by carbon monoxide shift, puri fication of raw synthesis gas, and ammonia synthesis, Features of the process include the efficient integrated generation of steam, the high level of process heat re~ covery, and the use of turbine driven centrifugal com- pressor. Tn the process, hydrocarbons are decomposed by steam according to the basic equation: CH, +H.0 ——> CO + 3Hs ‘The primary reformer converts about 70% of hydro~ carbon feed into raw synthesis gas, in the presence of steam using 2 nickel catalyst. Tin the secondary reformer, air is introduced to supply the nitrogen. The heat of combustion of the partially reformed gas supplies the energy to reform the remainder of the gas after reacting with the oxygen in the air. Secondary reformer effluent is cooled in waste heat boilers and delivered to the CO shift converter contain- ing two charges of catalyst: (1) conventional high tem- pefature catalyst in the fist shife stage, and (2) low temperature shift catalyst in the second stage. Shift reactor effluent, after heat recovery, is cooled and routed to the gas purification section. COs is te- Hypnocannon Processinc November 1977 moved from the synthesis gas in a regenerative hot car- bonate, MEA (monoethanolamine) or other standard COs removal systems Alter CO, removal, residual CO and Ct by methanation, The resulting pure synth¢ pressed, and mixed with a recycle stream which is intro- Guced to the last stage of the compressor. The gas is cooled with ammonia refrigeration, and anhydrous am- i the recycle stream is separated out. posed through 3, fed/efivent exe hesis converter, The effluent vapors inst feed and recycled anhydrous liquid am- changer to the sy from the converter are cooled to the synthesis loop, from whiel rmonia is condensed and separated Operating conditions: The exit pressure from the Pri- mary Reformer is normally 400-500 psig. Exit tempera- tures from the Primary and Secondary Reformers are approximately 1,500°F to 1,800° F, while shift reaction temperatures are about 800° F in the first shift stage, and 500° F in the second stage. Selection ammonia synthesis pressure depends on plant capacity and compressor selection. High capacity units Involving the use of centrifugal compressors have synthesis pressures in the range 2,000-4,500 psig, Commercial installations: More than 120 large-scale, single-train ammonia plants of Kellogg design are on- stream or contracted for throughout the world. By 1977, Kellogg-designed ammonia plants are expected to be pro: ducing at least half the world’s ammonia capacity. " On aU 129Ammonium nitrate—cerenour we. Application: A process for manufacturing fertilizer grade ammonium nitrate from anhydrous ammonia or urea off-gas and 55 to 60% nitric acid, Description: Ammonium nitrate is formed by the re- action of nitric acid with ammonia as follows: NH, + NHO, = NH,NO, Final concentration to above 99% is achieved in a fall- ing film evaporator. The concentrated melt may then be pumped to a SPHERODIZER granulation drum, as shown in the upper portion of the flow sheet, or to a prill tower as shown in the lower portion. In the SPHERODIZER granulation process, the molten ammonium nitrate is sprayed onto the rolling bed of solid particles in the drum, forming granules. These are cooled and screened. The product is cooled further, coated ‘ conditioned, and sent to storage or bagging. Oversized granules are crushed and recycled to the granulator, along with fines. These serve as nuclei for forming more product sized granules, Exit air from the evaporator, granulator and cooler is scrubbed in a wet scrubber. Advantages over prilling include: the product size may be varied as desired by changing the size of the opening 130 in the screens used; atmospheric pollution is eliminated, and the granular product has a greater hardness. It can be air-conveyed without serious breakage. In the prilling process, the melt is sprayed from the top, of a tall tower into a rising stream of air which solidifies grains, These are cooled and the droplets to form soli screened, A C&I/Girdler ad nucleating agent to produce unstressed crystals and sta- bilize the prills against temperature cycling through erys- tal transition phases. This reduces prill breakage during cooling and handling, thus markedly reducing the amount of product recycle. ‘The use of the additive, NUCLO- ADD, greatly reduces the surface coating agent required ‘The final product is essentially dust free. ve mixed with the melt acts as a Yield: The over-all yield of ammonia and nitric acid to ammonium nitrate is more than 99.5% on a nitrogen basis. Commercial installations: Production capacity of am- monium nitrate in plants engineered and/or built by (C&l/Girdler throughout the world is over 10,000 tons per day, with solids finishing in 36 prill tower installations and five SPHERODIZER granulation plants, November 1977 Hypnocarnon ProcessineAniline — tonza/resr cemicat corp. Applicatioy distillation. Economics: (ton/ton of aniline) ‘Mononitrobenzene Hydrogen... Steam (credit) Commercial installations: The new First Chemical Corporation 100,000,000 Ibs./year plant located in Pasea- goula, Missisippi (USA) started operations in June 1977. ‘The new process is a further development of the proven LONZA process operated by LONZA and several licen- sees over many years. The plant built under LONZA license by First Chemical Corporation about 10 years ago has led to an improved technology and a new long lasting catalyst which are both included in the new FCC: plant Inquiries: United States, Canada, Mexico, Bahamas, Bermudas and the Caribbean Islands Corp,, Jackson, Miss.; rest of the world: LONZA LTD., Basle (Switzerland) Hyprocanson Paocessio November 1977 Process for aniline production by catalytic hydrogenation of mononitrobenzene in the gas phase. Vaporized mononitrobenzene is hydro- genated over a fixed bed catalyst. The resulting aniline is separated and unreacted MNB and hydrogen are recir- culated to the reactors where they are mixed with feed MNB and make-up hydrogen. The aniline is purified by First Mississippi 131Benzene (Detol)—ar rrooucrs avo cremicats, ine. Application: To produce high purity benzene and heavier aromatics from toluene and/or xylenes and/or Gy and heavier aromatics. The main product is high purity benzene which meets all normal quality tests and has a freeze point of about 5.5°C. With C,+ aromatic feed- stocks, toluene and xylenes can also be taken as product. Description: Feed (toluene and/or xylenes and/or Co+ aromatics), together with a hydrogen containing gaseous stream, is heated at a specified pressure to the required reaction temperature and passed over a dealkylation cata- lyst. Reactor effluent is cooled by heat exchange. Benzene ‘and unconverted toluene and/or xylene and heavier aro- matics are condensed, then flow to a high pressure flash drum where the major portion of materials which boil below benzene are separated as gases. ‘The condensed liquid consisting of benzene, toluene and/or xylene and heavier aromatics is pumped to a stabilizer, Dissolved hydrogen, hydrogen sulfide and light hydrocarbons not removed in’the flash drum are stripped out. When benzene product must meet acid wash color specifications, the stabilizer bottoms are passed through a fixed bed clay treater, The clay treated aromatic liquid is then distilled in a benzene-fractionator to produce the desired specification benzene. ‘Unconiverted toluene and/or xylenes and heavier aro- matics are recycled through the catalyst with the fresh "Depending on the a purty of val Jepending on the quantity and purity of available make-up hydrogen, it may be desirable co, include, hydrogen concentration step to treat a portion of the vapors fram the igh presale fa drurm, by tnown tn the flow diagram. This maintains the desired hydrogen par- 132 tial pressure in the system while conserving hydrogen ‘A cryogenic hydeogen purification unit can be used. ids: Benzene yield in reactor effluent is 99.0 mel % of fresh toluene or heavier aromatic charge. typical mats- DETOL Mak Fresh Hy Ri Benzene Component, We. % Feed Gas Product i = 199 = = 50, fe = 8 = Go NA a2 8 2 Benzene a =i 99.97 Toluene wg 01 Gk GOB et. oe “Total 100.0 100.0 400.0 100.00 Lb,/b. raw charge 7000 0.199 “O44 0.758 Economics: Investment: Varies for feedstock, but on the basis of a 100-million-gpy plant with the material balance shown above, §/bpsd) .. 1,200 Typical utility requirements, per bbl. feed Electricity, kwh 58 Fuel, MM Btu O31" Cooling water, gal. 450 Steam, Ibs. . 144 * No exedit taken for vent gas streams Commercial installations: Nine plants with capacities ranging from about 12 million to 100 million gallons per year have been licensed. Licensor: Houdry Division of Air Products and Chem- icals, Inc. November 1977 Hyprocarzow ProcesstnoBenzene & xylenes (TATORAY) — 12ers NS woe mc. Application: A process for the transalkylation of methyl benzenes, typically toluene, and Cy aromatics, if desired, to produce benzene and xylenes, Predominant reactions ‘ CH, CH; I COO - Toluene Benaine X}fenes CH, CH, CHy Oey ence en ‘Toluene Trimethylbenzenes Xylenes Charge: Extracted tcluene and, if desired, Cy aromatics of low saturates content. Products: High quality benzene (typically 5.45° C mine imum solidification point) and xylenes (typically less than 1,000 ppm saturates). The xylenes product will have a low ethylbenzene content, Description: The flow scheme for the transalkylation of toluene and Cy’s is shown, The catalyst system permits high conversion per pass, has “stable activity, is totally rogenerable and is expected to have an ultimate life of at Teast 36 months, Process features are: (1) Product mole ratio of xylenes to benzene is adjustable by varying feedstock composition from toluene alone to blends of toluene and C, aromatics; (2) Operating conditions are much milder than in con: Hyprocarnon Processiva © November 1977 ventional hydrodealkylation processes; investment and utilities requirements are moderate; (3) Consumption of hydrogen is very low, and (#) ‘The products are essen- tially free of non-aromatics. Operating conditions: Moderate. Conventional equip- ment and materials of construction are used throughout the plant. Yields: With toluene feed, over-all selectivity of about 97% of theoretical is easily attained. The following repre sents a typical yield structure for a Tatoray operation with mixed Cy's in the feed stream, Feed We. Units ‘Toluene 48.9 Cr's SLL Products Benzene 20.9 Etiylbenzene 22 o-Xylene 141 ‘m-Xylene 346 Xylene 153 the balance being light end saturates and Cho"s Commercial installation: The fist, commeril_ plant for Toray, Japan, with designed annual capacity of 70,0 mt of fresh toluene feed, has been operating since 1968. A number of other units are in the design or construction, stage. Reference: S. Otani, S. Matsuoka and M. Sato, Japan Chemical Quarterly, 4, No. 6, 16, (1968). 133Benzoic acid—sa viscosa Application: A process to manufacture benzoic acid from nitration-grade toluene and air in presence of a cobalt- based catalyst. Chemical reaction: The reaction, performed by homoge- ‘neous catalysis in liquid phase is the following: Ouch + 0.5) co0 + HO Description: Toluene is oxidized by air over a soluble cobalt salt in a well-stired liquid phase reactor operating at about 9 kg/em*g and 165°C. "The exothermic heat of reaction is recovered by cit culating reactor liquid through a waste heat boiler which produces low pressure steam, Liquid effluent from the reactor goes to an atmospheric tower which recovers unreacted toluene and any mate- rial lighter than benzoic acid as overhead for recycle back to the reactors. A vapor sidestream is taken from the tower and rectified in a small column which produces pure benzoic acid as overhead product. Bottoms from this column are returned to the main tower, which is reboiled with hot oil. 134 Bottoms are extracted to recover cobalt catalyst, which is returned to the reaction section. ‘Vent gas from the reactors is cooled by exchange, cool- ing water and ammonia refrigeration to recover most of the toluene in the vent gas condensate, before expanding in a gas turbine to recover energy on the air compressor shaft. An activated carbon bed adsorber then recovers cstentially all remaining toluene. ‘The feedstock requirement is 0.03 ton of toluene and 0.02 kg of cobalt acetate (21% Co) per ton of benzoic acid. Commercial installations: Torviscosa (SNIA) Italy 22,000 metric ton/yr. Mantredonia (Societi Chimica Dauna) Italy: 100,000 metric ton/yr—Circik (Tech- mashimport) USSR: 100,000 metric ton/yr. (under con- struction). Bibliography: Italian pat. 657,641; 803,424; I. Donati, G. Sioli, M. Taverna, Chimica e Industria, 50, 997 (1968). November 1977 Hyprocarson Processincn-Butyraldehyde/ 2-Butanol—sss+ axnencsseuscuart Application: A process for the production of n-butyr- aldehyde and n-butanol from propylene, carbon monoxide and hydrogen by the oxo reaction, Description: ‘The reaction proceeds according to the following equations H.C- CH > CH,~ Cl CH, — CH, —CH.—CHO+H, = (CH, — CH, — CH; ~ CH, OH. In the oxo stage propylene is reacted at 140-170°C and 270-300 atm in liquid phase with carbon monoxide and hydrogen in the presence of dissolved cobalt catalyst ‘The cobalt catalyst is separated from the crude oxo prod- uct and recycled to the reactor without any substantial loss. The off-gas is used for steam raising. The propylene conversion is 96-99%. The isomeric butyraldehydes are removed from the crude oxo mixture in two series-connected columns. a-butyraldehyde can be used in the BASF 2-EH process The remainder containing butanols, esters and heavy ends is separated in a third column into a residue-free butanol fraction and a residue which is used as fuel n-Butyraldehyde is converted with hydrogen over a fixed bed catalyst at 130-160°C and 30-50 atm. ‘The crude n-butanol is combined with the butanol-containing Hyprocarnon Processivc © November 1977 fraction of the third aldehyde column, The crude n-butanol is purified by rectification in two columns, In the first stage column the low boiling impurities, iso- butanol and water are separated as overhead. The first runnings are used as fuel. The higher boiling impurities are removed in the second column by continuous dis- charge of the bottoms product and recycling to the butyraldehyde distillation. The pure n-butanol is taken overhead. The process involves no waste water or air pollution problems. Yield: For exclusive production of n-butyraldehyde, the yield is 100 kg of n-butyraldehyde and 11 kg of n-butanol as byproduct per 102 kg of propylene. Without use of n-butyraldchyde for 2-ethylhexanol or other purposes, the yield of n-butanol is 100 kg per 92 kg of propylene Commercial plants n-products only): 360,000 tons/ year at BASF Ludwigshafen, 336,000 tons/year at three Buropean plants, 292,000 tons/year at three plants over- seas and two plants with total 130,000 tons/year under construction. Reference: Chemic-Ingonicur-Technik, 17, 974-980 (1969). Further information is available from BASF, 6700 Ludwigshafen, West Germany. 135Caprolactam (low sulfate process-DSM)—x™"""—" Application: A process for the production of high-purity caprolactam starting from cyclohexanone, ammonia, hydrogen. Chemical reactions: NH, —+ NO + NO; dS = HP NEON Description: The hydroxylamine is produced in a gas liguid contactor starting from nitrate ions and hydrogen 4s in the presence of a noble metal catalyst. The basic reaction is the reduction of nitrate ions ac- cording to NO™+2H'+ 3H, > NH,OH* + 2H.0 in the presence of a buffering aci ‘The formed hydroxylamine reacts with pure cyclohexa- ‘none in the presence of an organic solvent, at a relatively low pH. The conversion of the cyclohexanone in this step is about 989. The remaining cyclohexanone is converted in a subsequent step, at a higher pH, so a conversion of 100% is obtained. The cyclohexanone oxime is separated from the solvent by distillation and pumped to the rearrangement unit, where through mixing with oleum the rearrangement of the cyclohexanone oxime configuration into the capro- Jactam configuration takes place. The rearrangement mixture is subsequently neutra- lized with aqueous ammonia and, after settling the erude caprolactam solution is decanted from the ammonium 136 HSO, 6 ° : ees | 1 | NH.OH (NEL) 0. sulfate solution, which latter can be processed to ferti- lizer grade crystals. Consumption per 1,000 kg of caprolactam: Cyclohexanone 905. tg Ammonia, 805 eg HO, 100% 1360 kg Hydrogen gas 96 ky Siem 6600 ie Power 224 kwh (Hydrogen compression not included) Cooling water 1100 m* BEW. 2500 ke Catalyst $ 10 Chemicals $3 Credit Ammonium sulfate 1600 kg Commercial installations: There are now four plants in operation and 3 others, with a total capacity of 150,000 metric tons/year, are under construction or in the com- missioning stage. ‘November 1977» Hvmmooannon PancaisaecCaprolactam—s" viscosa Application: A proces to manufacture caprolactam fom nitration-grade toluene, hydrogen, ammonia, Fiber-grade faked or molign caprolactam is produced without am- ‘onium sulfate byproduct. ‘Toluene and air are fed to the reactor in idation Or oetis0.5 C)-coon+ 0 is carried out at 165°C and 9 atm, The reaction product is a 30% solution of benzoic acid in toluene plus small quantity of reaction intermediates and byproducts, Frac- tionation gives unconverted toluene and reaction inter- mediates for recycle, pure benzoic and a bottom fraction of heavy byproducts. Benzoic is hydrogenated under pres- sure in presence of palladium catalyst in a series of con- tinuous stired tank reactors at 170°C and 15 atm, ()-c00H + a1 > (coon H The conversion is complete in a single pass. Cyclohexane- carboxylic acid is blended with oles and fed to the ‘multistage reactor where it is eonverted to caprolactam by reaction with nitrosylsulfurie ac This acid is produced in a conventional ammonia oxidation pnt, where the mitogen oxides are abrorbed in oleum. N.0, + H.S0, + SO; > 2NOHSO, ‘The basic process reaction is the following: Hyprocarnon Processivo November 1977 % (CH.). ()=000H + NoHso, + +00, +180, (ie i" H ‘The reaction temperature is controlled by evaporation of cyclohexane. The reactor effluent is diluted with water. Inconverted cyclohexanecarboxylic acid is recyled to the process. ‘The caprolactam solution is diluted with water to a concentration of about 50% sulfuric acid. This solution contacted with an alkyphenol solvent in a counter cur- ent extraction column. Sulfuric acid is taken from the bottom of this column and sent to the sulfur recovery section ‘The overhead extract is treated with water and caustic to remove traces of acid. It is fed to a series of fraction- ation towers to separate the caprolactam from the alkyl phenol solvent. Fiber grade’ caprolactam is obtained by usage of 1.1 ton toluene, 0.2 ton ammonia, 800 Nm* hydrogen per ton of caprolactam. This proces is completely ammonium sulfate free. Bibliography: Ttalian Pat. 603,606-604,795-608,873-666, 827-655,845-653 848-659,858-661,532. I. ‘Donati, C. Sioli, M. Taverna, Chimica e Industria, 50, 997 (1968). Ken K. Ushiba, “Caprolactam,” Stanford Research Institute, PEP Rep. No. 78, Suppl. B (1976). Ttalian Pat. 956,940- 956,941, R. Mattone, G. Sioli, L. Giufiné, Hydrocarbon Processing, 54, 83 (1975). 137Carbon black (Oil Furnace Black)—2°.1starsox catson Application: A proces: for the manufacture of carbon blacks from aromatic oils, Products include the general ASTM Classification Series of N100, N200, N300, N50O, 1N600 and N700 carbon blacks Description: On a continuous basis, a gas or liquid fuel is burned with excess air to completion and a preheated feedstock oil is atomized into the hot products of com- bbustion for thermal decomposition. The combustion and cracking reactions take place within specially designed refractory lined reactors. Process air is furnished by cen- trifugal blowers and is preheated by exchange with the hot reactor effluent. Internal reactor temperatures vary from 2,400 to 3,100° F depending on the carbon black grade being produced. ‘Upon leaving the reactor, but within the refractory~ lined section, the hot carbon-laden gases are shock cooled to 1,000° F by direct water sprays prior to entzy into the process air and oil exchangers. The cooled reactor efluent pases through a cyclonic agglomerator and then to a bag filter in which specially Gonted and treated glass fabric bags remove esentaly 100% of the suspended solids. The gascous effluent con~ tains approximately 50% water vapor and 35% nitrogen. The remaining 159% is made up of CO, CO, and Hs with small amounts of methane and acetylene. Carbon black is pneumatically conveyed from the col lection system to a small diameter collecting cyclone and then fed through a high speed pulverize to break up and disperse the very small quantities of hard agglomerates that may be present. ‘The pulverized black is then conveyed to the pelletizing 138 system where it is mixed with water and agitated in pin mixers to form small round pellets. The pellets, containing 35 to 50% water depending on black quality, are fed to an indirect fired rotary dryer for moistute removal. The finished product is stored in bulk tanks The product is shipped in covered hopper cars or automatically packed in S0-pound valve-type paper or polyethyene bags for shipment by rail or truck. ‘There has been very little dificulty, thus far, for oil furnace black plants in meeting all of the air pollution requirements that have been currently imposed regardless of geographic location, Aso, water” pollution poses no problem since there is no waste water discharge from the process Operating conditions: Feedstock oil quality, reactor design, flow rates and the close control of all operating conditions are extremely critical in determining and maine taining uniform high quality black consistent with the ASTM grading system, Yields: The yield of carbon black normally varies from 40 to 60% of the carbon content of the oil feed depend- ing on the aromatic content of the charge stock and the grade of black desired as the finished product. Commercial installation: Sid Richardson Carbon Co. plants are located at Big Spring, Texas, and Addis, La. Research and Development installation’ Sid Richardson Carbon Co.'s development pilot plant is located at Odessa, ‘Texas, and the Research Center is located at Fort Worth, ‘Texas November 1977 Hyprocannow ProcsssincChlorine recovery (Kel-Chlor process)—ruuman keuose Applications: Converts byproduct HCI to recyclable chlorine in processes for making chlorinated hydrocarbons and isocyanates and for metallurgical processing. Anhy- Grous HCl gas or aqueous solutions down to 20%6 concen- tration may be used. Description: The process oxidizes HC! to chlorine and water using nitrogen oxides as catalyst and circulating sulfuric acid as a catalyst carrier and water absorber. Overall conversion of HCI to liquid chlorine product is 99+%. In the process flow (shown for anhydrous HC! feed) the oxygen feed stream removes nitrogen oxides from the sulfuric acid before the acid leaves the stripper column, The oxygen and HCI partially react in the stripper in the presence of hot sulfuric acid which con- tains the catalyst. Oxidation reactions continue in the oxidizer, where reaction heat is removed by a circulating heat exchange medium from which steam is later gen- crated. Oxidation is completed in the absorber where nitrogen oxides and water of reaction are absorbed by the circulating sulfuric acid. Water is removed from the circulating sulfurie acid leaving the stripper by an adiabatic Rash under vacuum, Any traces of NO.Cl in the gas stream leaving the absorber are catalytically con- verted to NOG! in the silica gel contactor, the NOCI is absorbed! in sulfuric acid then stripped from it in the con ‘Hyprocanson Processinc November 1977 acid stripper and recycled. ‘The dry chlorine gas is lique- fied and stripped of dissolved oxygen and HCl. The liquid ehlorine product is comparable in quality to clec- trolytic chlorine ‘Typical quantities for production of one ton of liquid chlorine from anhydrous HCI feed HCI (1009), tons 1.030 Osygen (99.5%), tons 0.227 NaOH (5096 oe “) Ibs. iF H,SO, (9896), 15... e602 36 H,SO, (80%) pel ‘as purge, Ibs... ovens Power, kwh ..... 52 Cooling water, 20° F rise, gal. 12,900 Boiler feedwater, gal...... 24 Process water, gal....-..++++ 1 Commercial installations: One unit in operation since May 1974, capacity 600 tons/day expandable to 900- 1,000 tons/day. Reference: Hydrocarbon Processing, Vol. 53, No. 9, November 1974, pp. 151-156. jon of Pullman, Inc. censor: Pullman Kellogg, Di 139Chlorolysis—sors ac Application: Treatment of chlorinated hydrocarbon wastes with chlorine yielding carbon tetrachloride and hydrogen chloride, ‘Typical feedstocks are the residues from the production of COI, (based on methane), vinyl chloride, perchloroethylene, propylene oxide, ally! ‘chlor ide, chlorinated benzenes and toluencs. In principle, any hydrocarbon and its chlorinated derivatives can be uti lized. Description: The organic feedstock and chlorine react in the tubular reactor at approximately 200 bar and 600° G. In a cooling zone the produet is quenched with cold carbon tetrachloride. The separation of the mixture containing HCl, Cle COCI, (out of oxygen containing compounds in the feed- stocks), CCL, hexachloroethane and hexachlorobenzene is done by distillation. In a first column HCl, Cle, COCI: and CCl, are separated as head product; the high ‘boiling compounds are recycled from the bottom of this column to the reactor. Tn the following column hydrogen chloride, chlorine and phosgene go overhead and are separated in the next column, Chlorine is recycled to the reactor whereas hydro- gen chloride can be used for other organic synthesis, eg., in an oxychlorination unit, The bottom of this column contains Cl, and more or less phosgene which can be utilized in phosgene and oxychlorination processes. ‘The crude carbon tetrachloride from the bottom is 140 now purified in an atmospheric distillation column. The pure CCl is taken as a side stream from this column; Xt is free of trip-resp. perchloreethylene and therefore especially suitable for the production of fluorocarbons, ‘The bottom product of this column is used as quench liquid for the cooling zone of the reactor. The head product is treated in a caustic scrubber. The carbon tetrachloride is separated, dried and recycled to the feed of the pure CCl, column. Raw materials and utilities (per 1,000 kg carbon tetrachloride) Blectricity, kWh... 135 Steam (12 bar), lg 200000. 2s Steam (4.5 bar), kg satee ee 3 320 Gooling water (At= 10°), me.) 85 Fuel, keal ... ? 200,000 Consumption figure of chlorine depends on the feed stock available. Yield of carban tetrachloride from chlori- nated hydrocarbons: 9996, Commercial installations: Two plants with a total capacity of 58,000 tons/yr. are onstream (end of 1977) Another one of 36,000 tons/year CCl, is in the construc- tion stage. Roferonces: Further information is available from Hoechst-Uhde Corp,, 560 Syivan Ave., Englewood Clif, NJ, 07632, and Unde GmbH, Deggingstrasse 10-12, 4600 Dortmund 1, Federal Republic of Germany. November 1977 HyprocARBON ProcessiNGChloroparaffins —wwrssiu sc Application: A continuous process for production of chlorinated paraffins from chlorine and liquid normal paraffins. Description: Chlorinated paraffins with chlorine contents up to 70% are made by a new continuous route of thermal liquid phase chlorination. The process is avail: able for n-paraffin fractions within the whole Ci-Cin range. It operates with chlorine conversion rates of nearly 100%. Chlorination takes place in three bubble column re actors at a slight overpressure between 60 and 120°C. Gas entering at the bottom of the columns is reacted with down-flowing hydrocarbon feed. Fresh chlorine gas enters reactor 3 where it reacts with prechlorinated paraffins. The off-gas of reactor 3 then enters the bottom of reactor 2 and reacts in reactor 2 with low chlorinated paraffins from reactor 1. The off-gas of reactor 2 is reacted with fresh hydrocarbon feed, en- tering the top of reactor 1. The off-gas of reactor 1 which contains besides hydrogen chloride only very small quantities of chlorine, is used directly or is converted into 2 30% technical hydrochloric acid by the adiabatic HICI- Absorber. Hyprocarnon Processivo November 1977 In special cases the off-gas of reactor 3 passes through another HCl-Absorber for removing the excess of hydro- gen chloride and converting it into a 30% technical hy- drochloric acid before the gas enters reactor 2. Material: Borosilicate glass is used throughout the pro- cess plant for avoiding corrosion damages. Commercial installations: At present single-stream plants with production capacities of a maximum of 5,000 tons/yr. of chloroparaffin are operated, For larger ca- pacities several production streams are provided. So far two commercial plants for the process have been erected by Jenaer Glaswerk Schott u. Gen., Mainz. A license for another plant has been granted. The Winters- hrall plant at the Salabergen refinery has been operating since 1966, the plant of a licensee since 1975. References: Further information is available from Pro prietary Rights Service Corp., 180 East End Ave., New York, N.Y. 10028, and Wintershall AG, P. O. Box 104020, D-3500 Kassel, Federal Republic of Germany. uiCombination amines—re wonaro process co., inc. Application: A continuous process for the manufacture ‘of ethyl, isopropyl or cyclohexylamines in the same pro- cess plant from anhydrous ammonia and ethanol, isopro. ppanol or cyclohexanol, Products include: anhydrous mono, i and triethylamine, or mono and diisopropylamine, ot ‘mono and dicyclohexylamine. Description: Anyhydrous ammonia, ethyl, isopropyl or cyclohexyl alcohol, and recycle liquid along with recycle and fresh hydrogen gas are fed continuously at controlled rates to a vaporizer which converts the liquids to gas which then flows through a heat exchanger and super- heater to bring the gas stream up to reaction temperature bofore it enters the catalytic converter where a hydrogena~ tion catalyst promotes the reaction forming the amines. The reaction is exothermic and part of this heat of reac tion is recovered by passing the hot reaction gases through the heat exchanger to heat up the fonward gas flow. The product gas stream then flows through a condenser, and then into a gas separator where the excess hydrogen sep- arates and is largely recycled along with the fresh makeup hydrogen to the converter. From the gas separator, the liquefied mixture of am- ‘monia, amines and water feeds continuously to four col- uumas in series. The first column separates out the excess ammonia and returns it to the reaction system. The sec- ond column separates out the mono product which may be taken off to storage, or returned to recycle if itis not desired a5 a product. The third column takes off di prod~ 142 uct to storage or recycle while the bottoms pass into a decanter to separate the excess water before the stream passes into the fourth column which takes off excess water over head and returns it to the decanter while pure tri product is taken off the bottom to storage or returned to recycle if not wanted as product. This simplified four col- umn distillation system has been made possible by a new catalyst which converts all alcohol fed to the converter to amines, so that the need for an azeotrope breaking and alcohol recovery column, as used in existing plants, is climinated, This simplification reduces capital costs’ by 30% and reduces operating costs by 259% due to lower consumptions and better raw material yields ‘The foregoing description is based on ethylamines and the isopropyl and cyclohexylamines are procesied in a similar manner. The entire operation is continuous and instrumented s0 that one operator per shift controls the plant. Al process equipment and piping is fabricated of car bon steel which lasts indefinitely as the amines are excel- lent corrosion inhibitors. Yields: Over-all yield of both ammonia and the alcohol used is above 95% as compared to the 75 yield ob- tained on existing plant. Comme: jallations: Virginia Chemicals, West Norfolk, Va.; Union Carbide Corp., Taft, La.;'Indus- trialimport, Bucharest, Rumania; Montedison, Ttaly. November 1977 Hyprocarsow ProcrssinaCyclohexane —*c0 rcinorocy me. Applicati by catalytic hydrogenation of benzene. For production of high purity eyclohexane Description: Fresh benzene is catalytically hydrogenated in the vapor phase over a special noble metal catalyst to produce essentially complete conversion per past and theoretical cyclohexane yield. Fresh benzene is combined with makeup and reeycle hydrogen and preheated before entering the reactor, This specially designed reactor as- sures complete benzene conversion by providing plug flow. ‘The reactor design also eliminates the need to recycle cyclohexane for heat control by the use of steam genera- tion to remove the exothermic heat of reaction. ‘The reactor effiuent exchanges heat with the feed then {is cooled before entering the liquid-gas separator. Most of the hydrogen gas is recycled and some is vented. The separator liquid is sent to a stabilizer where lights are taken overhead, and the bottom stream is the pure cyelo- hexane product. Yields: Benzene conversion is above 99.9%, and the yield to cyclohexane is quantitive. The hydrogenation catalyst and reaction conditions are selected to inhibit isomerization of cyclohexane to form methylcyclopentane. Hyprocanton Proczssiva November 1977 Basis: Cyclohexane Purity99.94 mole % Gyclohexane Yield—107.6 wt% of Benzene Cyclohexane Recovered—106 wt% of Benzene Service Factor—350 days/year Hydrogen Consumption (90%) —3/1 mole hy- drogen per mole Benzene Operating requirement: (For 45,000 metric ton/yr. cyclohexane product) Util Power, kW. 120 Steam, kg/hr 1300 Steam (Generated), kg/hr . = (700) Cooling Water (17° CAT), m*/hr 45 Catalyst and chemicals: (Catalyst Life) 3 years mi Operating labor: One man per shift Investment: IBL, Erected Gulf Goast, 1977 1.0 MM§ Catalyst cost 0.056 MMS Commercial installations: Two plants—one in the United States, one in South America. Licensor: ARCO Technology Inc., Subsidiary of Atlantic Richfield Co. 443Cyclohexane—mstmur FRANCAIS DU PETROLE Application: Liquid-phase catalytic hydrogenation of benzene to produce high-purity cyclohexane from benzene and a hydrogen-rich gas Description: Hydrogenation is almost completely achieved in the liquid-phase reactor where the catalyst is kept in suspension by an external pump-around. Heat in excess is removed in an exchanger where low pressure steam is produced. A small catalytic pot acts as finishing reactor when the conversion of the main reactor drops below the required level either accidentally or when the catalyst has to be changed, After condensation, the reactor eflluent is flashed in HP separator. A stabilizer removes hydrogen and other light dissolved gases, Depending on hydrogen-rich gas composition and price, flashed gas from the separator may be recycled to the main reactor in order to obtain a better use of the hydrogen feed. Practically stoichiometric yields of cyclohexane from benzene are obtained, Product: The purity of the cyclohexane product depends on the putity of the benzene feed; nevertheless, it is of the highest purity that can be obtained. When processing 2 5.45° C crystallizing point benzene, a cyclohexane crys- M44 tallizing at 6.2° C (> 99.89% purity) is currently obtained without formation of impurities. Economics: The following data apply to a 100,000 metric tons/ys. eyelohexane unit: Investment (erected cost in battery limits, engineering fee excluded, French basis 1976) 7.1 x 10° FF Catalysts: Main reactor consumption 380,000 FF /yr. Finishing reactor consumption ... 20,000 FF/yr. Catalyst ultimate life varies with the benzene sulfur content ‘Utilities (when using an hydrogen with 959% purity) Electricity : 135 kWh/hr. Cooling water (At = 10°C) 10 m4/he. MP steam consumption 1.0 t/be. LP steam production . 13.0 t/br. Chilling medium 11,000 kal Commercial installations: 12 units are now in opera- tion and 8 units are under construction or engineering, including the world’s largest in Tran (220,000 t/yr.) Licensor: Institut Francais du Petrole. November 1977 Hyproaannon ProcessineDetergent alkylate —#20 tecnoiosy ie. Operating requirements: (per metric ton of linear from paraffins by chlorination and alkylation. Description: Paraffin is charged together with pure chlorine to the chlorination section. About 20% of the paraffin is chlorinated in a specially designed pipe reactor Which assures a high selectivity to monochloro paraffins Anhydrous hydrogen chloride gas is separated from the parafin-chloroparaffin mixture which then goes to the alkylation section, Benzene and aluminum chloride catalyst slurry are added to the alkylation reactors. The recycle catalyst activity is carefully controlled by addition of fresh aluminum or aluminum chloride so as to yield a high purity alkyl benzene product, Anhydrous hydrogen chloride gas is evolved in the alkylation, joining the gas from chlorination. The combined HCI streams go to a unit for regeneration of pure chlorine. The catalyst slurry is separated from the total raw alkylate and the total raw alkylate is neutralized. The raw alkylate containing benzene, paraffin, deter gent alkylate and heavy alkylate is separated by fractiona- tion in a manner to recycle dry benzene and paraffin back to the reactors. The detergent alkylate is then acid and clay treated to produce a high quality detergent alkylate for making biodegrable detergents, Operating requirements: (per metric ton of linear alkyl benzene) Hyprocarson Processinc November 1977 Raw materials: n-Paraffin, kg 800 Benzene, kg... eee. es eee B80 Chlorine vapor, kg 400 Byproduets: Heavy alkylate, kg HCI gas, kg... Chemicals: Al powder, ky 10 Flake caustic, kg ..... 36 Liquid caustic (50%), ke... ..60 C88 Ba og ola ete on ie SO, (98%), kg. 50 Uiilites Steam, kg Cooling Water, m? ..... Electric Power, kWh ........120 Fuel Oil (65% EA), kg. Operating labor: 3 men per shift. Commercial installations: Four plants for a total capacity of 100,00 metric tons/yr of linear alkyl benzene—2 plants in the United States, 1 plant in Germany and 1 plant in Japan. Licensor: ARCO Technology Inc., Subsidiary of Atlantic, Richfield Co. M5Dimethylformamide—ve s.. Application: A process for continuous production of dimethylformamide by direct synthesis from carbon monoxide and dimethylamine. Formamide and mono- methylformamide may be produced in the same way from tarbon monoxide and respectively from either ammonia or monomethylamine. Description: Direct synthesis of dimethylformamide from carbon monoxide and dimethylamine is carried out with high productivity and at moderate pressure (20 bars) ina gasliquid reactor of the “Loop Reactor” type en- abling increased. yields and reaction time. Process com- Drises three sections: reaction, evaporation, distillation Reaction: Carbon monoxide, dimethylamine and a small amount of methanol are fed continuously under pressure to the “Loop Reactor". External liquid circulation on the “Loop Reactor” enables efficent external cooling and also, owing to a special device installed inside the reactor, perfect aspiration and dispersion of the gas into the liquid. ‘The catalyst, preferably sodium methylate in metha- nolic solution, is continuously added to maintain im- proved reaction rate ‘Due to possible pressure of inert gases, a blow-off takes place to maintain partial pressure of carbon monoxide. Reaction solution is continuously drawn of to the evaporation section. Evaporation: In this section, dimethylformamide and methanol and also a small quantity of unreacted di- ‘methylamine are evaporated at atmospheric pressure, 46 Used catalyst, which is precipitated and concentrated in evaporator, is separated preferably by centrifuging, Distillation: The vapors coming from the evaporator are rectified and, at the top of the distillation column, methanol is obtained and recycled to the reactor. Pure dimethylformamide is separated in vapor phase im the middle of the column and the higher boiling resi- due is separated in an additional distillation column. Economics: The following economics are related to 1 zmetri¢ ton of pure DMF: Dimethylamine (100%) 630 kg Garbon monoxide (99.29%) * 420 keg Methanol at Catalyse 5 LP Steam 12t Cooling water (40°C to 50°C) 75m Bleeweity 52 kWh * Carbon monoxide at 50% may also be used but reaction pressure is higher and conversion of carbon monoxide is decreasing. Commercial plants: Process has been experimented and proven in pile plant with collaboration of BUSS. S.A Briterland: No commercial unit in operation. Liconsor: UCB §.A., Licensing Department, Investment and Industrial Property Direction, 4 Chausste de Charleroi, B-1060 Brussels, Belgium. References: Patent applic. GB 10,027/76; Hydrocarbon Processing, June 1976. November 1977 Hyprocarnon ProcessrwaDimethylterephthalate—orwamr wos axrenceseuiscuarr Application: A process for manufacture of fiber grade dimethylterephthaiate (DMT) from p-xylene and meth- Description: A mixture of p-xylene and p-anethyl toluate is owidized with air in the presence of heavy metal cata- lysis to produce p-toluic acid and monomethyl terephtha- late, These acids are then converted to p-methyl toluate and DMT. No reaction solvent is necessary during oxida- tion, Reactions are: Oxidation: CH, ~ C,H, — CH, + 1%4 0. + CH, ~ GH, - COOH + 1.0 CH,OOG ~ CyH, — CH, +14 Os ~ CH,OOC ~ G:H, — COOH + #0 Esterificatio (CH; ~ G:H, — COOH + CHL,OH > CH,— C,H, — COOCH, + H.0 (CH,OOG ~ G;H, ~ COOH + CH.OH > CH,OOC ~ C,H, — COOCH, + H,0 Pxylene and p-methyl toluate are subjected to continuous oxidation at 140-170° C and 4-8 bar with air and in the presence of a catalyst. The oxidate is esterified at 250-280° C and 20-25 bar. ‘The overhead methanol from the estrifer is recycled after distillation, The crude ester from the esterifier bottoms is distilled in a column where the overhead p-methyl toluate ‘Hyprocanson Processinc November 1977 is recycled to the oxidizer and the bottom product is sep- arated in a second column into erude DMT and rescue, Further purification is by crystallization from methanol, DMT is separated from methanol in centrifuges and finally distilled to fiber grade DMT (melting point of approximately 141°C) being taken overheads DMT. in molten form can be fed directly into. polycondensation or transported in tankears to the fiber plant, Raw material consumption: In kg per kg of product —p-xylene, 0.63; methanol, 0.38. Investment: A 150,000 metric ton/yr. plant (West Ger- man conditions July 1, 1977) including compressor sta- tion, active carbon absorption unit for off-gas, hot oil heating system and catalyst preparation are: (1) equi ment, fob. German. port, including engineering, DI 103 M, (2) civil work, DM 10 M, (3) construction DM 17M for a total of DM 130 Utilities: In units per kg of product—steam (14 atms.) 1.2 kg; fuel, 1,000 keal; electric power, 0.5 kWh. Commercial installations: Dynamit Nobel operates plants based on the Witten-DM'T-Process at Witten, Lule- orf and Steyerberg with a total capacity of 500,000 ton/yr. and participates ina 60,000 ton/yr, DMT plant of Pronor-Produtos Organicos SIA, Brazil. DMT repre- sents 70% of the total capacity of terephthalates with 23M tons by Dynamit Nobel and their licensees. In- Quiries may be divected to Dynamit Nobel AG, Troisdorf, Federal Republic of Germany. 147Dimethyl! terephthalate—wsu rrmoctemca: mousrnts, i. Application: A recently improved process for the manu- facture of high quality dimethyl terephthalate from erude terephthalic acid and methanl. Description: Terephthalic acid and methanol are put into a slurry form, pressurized, preheated, and then fed to the ingeniously designed esterification reactor wherein the ‘esterification is carried out at a high conversion rate. The reaction mixture containing the esterification product which is crude dimethyl terephthalate (DMT) is depres- surized and heated. Excess methanol and water formed in reaction step are flashed, vaporized and separated from the crude DMT, ‘The crude DMT is pretreated for removal of high boiling impurities before being fed to a special treatment reactor. Since among the impurities contained in the crude DMT are such substances that are aot easily removable merely by distillation, a special treat- ‘ment is carried out to purify the crude DMT. Namely, these impurities are converted into such substances that ‘can be zeadily removed by distillation. Final purification ‘of the crude DMT js performed by two-step vacuum Aistilation in which ow boiling and high boling impurt ties are removed. These impurities are fully concentrated and disposed of as heavy ends and light ends. ‘Vapor consisting of methanol and water leaving xterif- cation reactors is fed to the continuous distillation tower, ‘wherein the methanol solvent is dehydrated so that it can be reused for esterification. Yields: The yield of DMT from crude terephthalic acid is well over 98 percent. Commercial installations: Two plants (30,000 tons/yr. and 120,000 tons/yr. are in operation. November 1977 Hyprocarzon ProcessinoDimethyl terephthalate— Application: A process for the manufacture of poly- merization grade dimethyl terephthalate (DMT) from terephthalic acid and methanol Description: DMT jis produced by reacting technical grade terephthalic acid and methanol at moderate pres- sures and temperatures, No catalyst is required for the reaction and the product is purified by a unique distilla- tion process. The design of the reactor and distillation system results in attractive economies and small pollution potential. Single train plants having a capacity of 40,000 to 250,000 metric tons per year are practical. Raw material consumption: ‘Technical grade terephthalic acid. .0.87 kg/kg product Methanol. 34 kg /kg product Hypnocanson Paocessivc November 1977 EASTMAN KODAK CO., ‘TENNESSEE EASTMAN CO. DIVISION Investment: Battery limits capital investment for a 100,000-metric-ton-per-year plant built in the United States in 1977 is approximately $14 million, Utilities: Approximate heat required per kg of product— 11,000 Bru. Approximate power required per kg of product—0.09 kwh. Commercial installation: The process is in use by East- ‘man jin its plants in Kingsport, Tenn, and Columbia, South Carolina, where it produces hundreds of millions of pounds of DMT per year which is used in the manu- facture of polyester polymer for fiber, film and plastics. ‘The process has been licensed in the United States and to Intercontinental Quimica S.A. (Interquisa) of Madrid, Spain. Inquiries may be directed to Foster Wheeler Co Livingston, NJ., or Tennessee Eastman Co., Kingsport, Tenn. M9Ethane (M-B-E process)—#rrocarsow researc inc. Application: Liquid fuels such as naphtha and kerosine are thermally hydrocracked into three products: methane, benzene and ethane Description: Liquid feedstock is combined with hydrogen- ch gas and fed to the thermal hydrocracking. reactor. This reactor is an open chamber designed for plug flow with provision for quench to carefully control the highly exothermic reactions in the reactor. Cy+ saturated mate- rials are hydrocracked to methane and ethane. Any aro- ‘matic compounds are hydrodealkylated and high purity benzene is the ultimate product which ean be recovered from the liquid effluent in a conventional manner. [Net off-gas from the hydrocracking reactor goes to a ighly efficient cryogenic recovery unit. Here the methane is recovered at a sufficiently high purity for use as syn- thetic natural gas (SNG). An ethane rich stream is also recovered and can be fed to a pyrolysis unit for the production of ethylene. The necessary hydrogen for the ‘M-B-E reactions can be produced by the steam reforming of a portion of ethane or methane produced by the system. licensors: ‘The thermal hydrocracking technology is available for licensing from Hydrocarbon Research Ine., subsidiary of Dynalectron Corp. and ARCO Technology, Inc, subsidiary of Atlantic Richfield Co. 150 Typical operations Feedstock Naphtha _Kerosine oe oa 165 Feed rate, bpsd 11,330 6,000, Hydrogen, MMscfd 95% purity @ 350 psig 492 35 Products Benzene, bpsd 495548 SNG, MMsefd 35 psig, 90° F, HEV 1,000 Btu/scf 90% methane .... 2 252 Ethane prodact, tbs. hr. 91 wi.dp ethane 56,172 26,354 Utilities Power, KW. 5,000 3,600 Cooling water, gpm se. 2,000 2,500 Fuel, MMBtu/hr. LHV 32 - 600 psig steam exported, Ib. /hr. 60,000 22,000 Estimated investment US. Gulf Goast Battery Limits, $US. 16MM 16MM References: Oil & Gas Journal, May 30, 1977, and Hydrocarbon Processing, July 1977. November 1977 Hyprogansox ProcesstnoEthylbenzene (Mobil-Badger)— re savcer co., inc. Application: A process for the alkylation of benzene with ethylene to produce ethylbenzene suitable for the manufacture of styrene monomer. Economic operation with feedstocks containing as little as 109% ethylene is possible. Description: The Mobil/Badger ethylbenzene process consists of two major sections—reaction and distillation In the reaction section, fresh and recycle benzene are preheated, vaporized and then combined with an alkylaro- matics recycle stream and fresh ethylene and fed to a reactor containing a proprietary fixed-bed heterogencous catalyst developed by Mobil where alkylation of benzene with ethylene occurs in the vapor phase at high temper- ature and moderate pressure, Two reactors are included in the reaction system; one is onstream while the other is being regenerated. Reactor effluent vapor is passed to a presfractionator to recover unreacted benzene. Condensed pre-fractionator distillate is recycled to the reactor. Un= condensed light components which are vented from the system can be used as a fuel gas ‘The distillation section consists of three columns, the benzene recovery column, the ethylbenzene recovery column and the diethylbenzene recover column. In the benzene recovery column, benzene is recovered and re- cycled back to the reaction section, Ethylbenzene is then Hyprocarson Processivo November 1977 separated from higher boiling components in the ethyl- benzene recovery column. ‘The ethylbenzene product re- covered overhead from this column is suitable for the production of styrene monomer. The bottoms from the ethylbenzene recovery column are further distilled in the diethylbenzene recovery column, Diethylbenzene and other alkylaromatics are recovered and recycled to the reaction section. ‘The small amount of residue removed from the diethylbenzene recovery column can be used as fuel The small quantities of vent gas and residue produced can provide on the order of 25% of the onsite fuel requirements for the plant. Additionally, the process Gesign permits a high level of energy efficiency—on the order of 959% of the net process heat input and heat of reaction can be recovered as useful low and medium pressure steam, Furthermore, no polluting process waste streams are produced. The catalyst is non-corrosive, non- hazardous, environmentally inert and requires no special handling. General: ‘The process has heen selected for use in several world-scale ethylbenzene units having design capacities ranging from about 335,000 to about 465,000 metric tons per year. Licenses for the use of the process are offered by The Badger Go., Inc. 151Ethylbenzene (Alkar)—vor PROCESS DIVISION Applicatioy A process for producing ethylbenzene or other alkyl-aromatics by alkylating aromatics with 100% yield of the mono-alkyl-aromatics, ie, ethylbenzene, or substantially quantitative yields of dialkyl and polyallyl- aromatics are achieved. Newer units have employed high purity ethylene, but off-gas from catalytic eracking units, ‘coke oven gases and town gases have also been employed, Alkylaromatics of high purity and exceptionally low olefin content are made because the unique catalyst is selectively active for alkylation reactions. Polymerization of the olefin is virtually absent. Process description: The purified olefin-containing gas and feed benzene are combined with recycle benzene and, similarly, recycle polyaromatics are combined with recycle benzene, The combined feeds are raised to reaction tem- perature and enter the respective reactors, where they arc reacted over a specially prepared catalyst. Conversion of the olefins in the feed) gas to alkylbenzenes is essentially complete. Polyalkylbenzenes and benzene are transalkyl- ated to yield monoalkylated products ‘The reactor effluent is flashed to remove inert gases where applicable, The liquid from the lash dram is charged to the benzene column where unreacted benzene js fractionated from the product and returned to the reactor. Alkylbenzenes are distilled to yield the mono- alkylated product and the polyalkylbenzenes normally are recycled for transalkylation, Operating conditions: Operating conditions are mod- erate and no corrosion problems are encountered. Carbon steel is used throughout the plant. Investment costs are minimized. No sludge or byproducts are involved and catalyst lives of several years are generally experienced. Yields: Ethylene in the feed gas in concentrations as low as a few percent are converted almost completely on a ‘one-pass basis. Yields of virtually 100% monoallylated products are obtained. Commercial operations: Fourteen units have been placed in operation and several others are in design or construction stages. References: Oil & Gas j., Vol. 56, No. 13 (March 31, 1958) ; Petroleum Week, March 28, 1958, p. 38. November 1977 Hyorocarmow ProcessinoEthylene from liquids—s+» Application: A process for the production of polymer grade ethylene (99,95 mol. %) and propylene (99.9 mol %) from hydrocarbon liquids. Description: The simplified flow sheet shows @ typical process configuration tailored for liquid feedstocks, e. g.. fight and heavy naphthas, rafinate, kerosine, heavy gas cil Hydrocarbon feedstock, diluted with steam, is preheated and cracked in tubular furnaces, Linde-Selas furnace de- sign is optional adapted to specific requirements, i., high capacity, high severity and high selectivity, Furnaces avail- able are of the TSGC, SSC or LSUG ‘ype Hot pyrolysis gases are rapidly quenched in transfer line exthangers producing ‘high preseure steam and. by direct contact with quench oil, Further cooling is carried ‘out in the prefractionation section: In the primary frac- tnator the net production of heavy olf fs withdrawn from the bottom and the side of the tower, while waste heat from circulating quench oil is utilized to produce process steam. The overhead gases flow to a water quench tower where almost all process steam and heavy gasoline are condensed. Low level heat from circulating quench water can be recovered for other process steps. ‘The cooled raw gas is compressed to about 33 bars in ‘a multistage centrifugal compressor with interstage acid gas removal. Condensed gasoline components are sep- arated from water and stabilized. ‘The high pressure gas is dried by adsorption, cooled by exchange with propylene refrigerant and cold zecycle Hyprocarnow Processino November 1977 streams before entering the deethanize, The net overhead gas (Ceminus) ‘selectively hydrogenated for acejlene Removal and is then cooled by ethylene refrigerant and Cold recyle streams, with the condensate being separated at diferent temperature levels Final gas cooling is chewed by eaporaton of expanded eld condone, the remaining ga representing the hydrogen procuct “The Cerich low temperature condensates are sent to the demethanizer where methane product is recovered oveshead and the bottom ie fed to the C, spitien, to obtain high-purity ethylene overhesd, Ethane from botiom Se recycled to pyrolysis, ‘The deethantzer stom, containing all Cy and heavier components are further proceed by various separation Stops to recover gasoline, butadienerich Gy and a chem tal or polymer grade propylene product Refrigeration requirements are supplied by a propylene and ethylene compressor circuit in cascade arrangement, both compressors being of multistage centrifugal type. Yields: Following typical ethylene yields ean be obiained from various feedstocks when ethane is recycled: Light FR Atm. Vacuum Naphtha Naphtha Gas Oil Gas Oil wt Jo 404 33. 28 22.7 Commercial installations: The first plant in the world for the production of ethylene was built by Linde in 1921, Since then Linde AG has designed and constructed almost 100 ethylene plants in 16 countries, since 1965 ‘otal ethylene capacity of 6.5 million metsic tons/yr. 153Ethylene—c: tums Application: A process for the production of polymer- grade ethylene (99.9 vol. %). Major byproducts are pro- pylene (chemical or polymer-grade), a butadiene-rich C, stream and C,-C, aromatics-rich pyrolysis gasoline. he flow diagram shown is suitable for all feedstocks, ethane through gas ol, except as noted below: Pyrolysis setion: The hydrocarbon feedstock i pre- heated and cracked in the presence of steam in tubular SRT. (Short Residence Time). pyrolysis furnaces. The resultant product exit the furnace at 1 400-1,600° F and tre rapidly quenched in the transfer’ line exchangers ‘which (generate high-pressure steam, ‘The pyrolysis/ {uench system can fiandle the full range of naphtha and gas oll feedstocks, ‘The furnace efluent, after quenching, flows to the gasoline fractionator where the heavy oll Traction is Temoved from the gasoline and lighter fraction. No gaso- line fractionator is required when cracking only ethane and propane, ‘Compression, acid gas treating and fractionation: The raw gas from the quench tower # compressed in a rmultic Hage centrifugal compressor to between 300 and 550, Pag, Partray through the compression system, carbon Gioxide and hydrogen sulfide are removed. Hydrocarbons condensed in the fst charge compression stages are re fumed to the quench tower while those condensed in the latter stages are stripped and sent to the C:HSH +H.0 G.H,OH + G:H.SH — C.H, $-C.H, + H.0 With an excess of hydrogen sulfide, ethanol is com- pletely converted into water which is condensed and removed, and a mixture of approximately 90% of ethyl- mereaptan and 109% of diethylsulfide. Unreacted hydrogen sulfide, ethylmercaptan, diethyl sulfide and residual water are fed to a heptanol absorber, 164 where most of hydrogen sulfide and residual impurities are eliminated. After cooling, heptanol is recirculated back to the absorber and the recovered organic phase is sent to the distillation section in which ethylmercaptan and diethyl- sulfide are recovered. Operating conditions: Units which can be designed for the use of pure hydrogen sulfide or in mixture with car- bon dioxide are mainly with earbon steel constructed, except some parts of equipment and piping in contact with high concentrated hydrogen sulfide. Uses: Main use of ethylmercaptan is pesticides synthesis. Diethylulfde is a gas odorant Commercial installation: A 3,000 tons/year plant is operated in Lacq (France) since 1970. Licensor: Societe Nationale Elf-Aquitaine. November 1977 Hyprocarnow Procsssinsee Formaldehyde—-0= mss onan Application: A process for the continuous manufacture of aqueous formaldehyee solution from methanol Description: Formaldehyde formation proceeds accord- ing to these equations: CH,OH > CH.O+He ~20 keal CHOH + ¥ 0; > CHO + HO +38 keal ‘Two processes are used to, produce formaldehyde: silver or metallic oxide catalyst. (he silver process proceeds in exothermic reaction by dehydration and oxidation accord- ing to the above two equations, however, additional steam is required. The metallic oxide process’ proceeds in exo- thermic. reaction by oxidation according to the second equation, where, due to the higher heat effect, excess steam is produced, Silver catalyst: Air is mixed with methanol at 50°C to produce a 40% mixture. This air/methanol mixture pastes a silver granulate at 500° G, converting the mix- ture to gaseous formaldehyde, The hot formaldehyde gases are cooled under steam production and sent. to an absorp tion and washing colunin, where, with cooling and addi- tional wash water, the formaldehyde is condensed to an aqueous solution. For high yield and low byproducts, the reaction is controlled so that only about 60% of the methanol is converted into formaldehyde. The excess methanol is separated by distillation and recycled. Tower bottoms are methanol-free 37-50% formaldehyde solution. ‘An alternative method is to add steam to the methanol/ air mixture, then the silver catalyst can be operated at Hyprocarnon Processins November 1977 700° C and a formaldehyde solution with 2-49 methanol is obtained direct without distillation. Metallic oxide: A 7% mixture of methanol in air is prepared and sent to the reactor filled with feromolyb- denum oxide and is converted into gaseous formaldehyde at 300° C. The heat released during reaction is recovered as steam and may be exported. The formaldehyde gases are sent, as in the silver process, to an absorption and ‘washing'column, where, with cooling and additional wash water, the formaldehyde is condensed to a methanol-free 47-50% solution. No distillation is required, but the con- sumption of electrical energy and catalyst are higher and equipment expenditure is larger. Raw materials and utilities requirements: (Per met rie ton of 379% formaldehydk Silver/ Metallic Silver “Steam oxide ‘Methanol, 100%, kg ee 220 Steam, 5 atm gage, 50015000, Cooling water, 20" 35 5 40 Process water, ke 450-250 +50 Blecticity, koh 3 15 120 Catalyst, BM 1 15 3 Manpovier, per shift af t i Commercial installations: More than 10 formaldehyde plants have been erected throughout the world. The usual capacities were 10,000 to 40,000 tons/yr. Reference: Formaldehyde, Walker, J. Frederic, Reinhold Publishing Corp., Chapman & Hall Lid., London. 165Formic acid—me tronaro process co., inc. 166 Applications A simple continuous proces for the mani- facture of high purity formic acid from impure CO gas and HO. Description: In this process, a dilute or even impure or pure carbon monoxide gas is reacted with methanol to produce methylformate. This methylformate is hydrolyzed and the products of this hydrolysis are separated to pro- duce a pure formic acid and methanol, The methanol is recycled to the first stage of the process Gat, CH, OH + CO—} HCOO CH, Hc00 on, +1,.0-*S HcooH + cH.OH Yield on CO gas depends on the quality of the gas but yields are high Methanol usage is guaranteed at 4 Ibs. per 100 Ibs. of product. Utility consumptions: Steam 750 Ibs./100 bs. product Cooling water 4,000 gal./100 Ibs. product Electricity 10 kwh/100 bs./product Commercial installations: ‘This newly developed process will be commercialized by The Leonard Process Co., Inc., during 1977. November 1977 Hyprocarnow Processincal A process for the manufacture of glycerine acid from peracetic acid, allyl alcohol and acid in ethyl acetate containing a stabilizer, allyl alcohol and water is continuously fed into a reaction- distillation column, whose top operates under reduced pressure (100-150 mm Hg) to maintain the temperature (40-70° C) in a reaction zone, The exothermic heat of reaction is removed by ethyl acetate-water azeotropic dis- tillaton. Ethyl acetate dehydrated at an ethyl acetate recovery column is recycled into a reactor for manufae- turing peracetic acid. An efiluent discharged from the bottom of the reaction-distillation column is fed into a hydrating reactor to completely hydrolyze unreacted gly- idol. Then, allyl aleohol which still remains unreacted is removed at a light-end column, Acetic acid contained in a mixture which is discharged from the bottom of the light-end column is extracted by solvent at an extraction column, then dehydrated and finally refined. The solvent contained in a raffinate is removed at a solvent recovery column. The remaining mixture discharged from the solvent recovery column is Hyprocarson Procussinc November 1977 dehydrated by a multiple-effect evaporator and is further treated at rectification columns to produce glycerine. Dilycerine and acctins contained in the heavy-ends di charged from the rectification columns are recovered by other equipment and marketed for sae. Charactoristies: Because the reaction-dstllation column is specially designed, (1) the mixture in the column mildly reacts; (2) glycidol hardly polymerizes; (3) hydro- ‘gen peroxide scarcely produces; (4) ethyl acetate seldom hydrolizes, and (5) the exothermic heat of reaction effec- tively works to remove ethyl acetate from the reaction system, Further, the reaction-distillation column concur- rently functions as extractive-distillation column; as a result, no allyl alcohol is contained in the ethyl acetate recovered. References: Japanese Patent 603,400; U.S. Patent 3,609,198; British Patent 1,321,142; German Patent 1,903,441; French Patent 1,600,558; Canadian Patent £878,549, K. Yamagishi and O. Kageyama, “Make Glycer ine via Peraeetie Acid," Hydrocarbon Procesing, Novem- ber 1975, pp. 139-144. 167Hexahydrobenzoic acid—s™ viscosa 168 Application: Manufacture cyclohexane carboxylic acid, a useful chemical for producing caprolactam, cyclohexyla- ‘mine, eyelopentamethylene ketene, eyclohexylurea, dieyelo- hexylketone. Chemical reaction: ‘The aromatic ring of the benzoic acid is hydrogenated in liguid phase, in presence of a noble metal catalyst cat COOH > CooH+ aH VG, Description: Benzoic acid is hydrogenated to cyclohexane carboxylic acid over a catalyst supported on powdered active carbon, Reaction takes place in a series of agitated vessels operating at about 15 kg/em® g and 170°C. Each reactor contains an internal coll and an associated steam generation system for removal of exothermic heat of reaction by generation of low pressure steam. Chemical reaction goes essentially to completion. The liguid effluent is fed to the centrifugal extractor where the powdered catalyst is separated and returned to the reaction train, Pure cyclohexane carboxylic acid is then recovered by evaporation and recondensation to avoid any catalyst loss with the produce. ‘Specific feedstock requirements: 0.96 tons benzoic acid; 0.62 standard cu, m hydrogen 1 ton product. Commercial installation: Torviscosa (SNIA)_Tealy: 22,000 mtpy. Manfredonia (Societk Chimica Dauna) Italy: 100,000 mtpy. Cireik (Techmashimport) USSR: 100,000 mtpy (under construction). Bibliography: Tialian pat. 659,845; 666,827; 779,220; I, Donati, G. Sioli, M. Taverna, Chimica ¢ Industria, 50, 997, 1968; G. Sioli, Chem. Age of India, 21, 265, 1970. November 1977 Hyprocarnon ProcrssinaHexamethylenediamine—nonrrere sea Application: A process for the production of fiber grade hexamethylenediamine by hydrogenation of adiponitrile. Description: The continuous process is based on the following reaction: NE: CHa) oC (CH:), on ‘The reaction is carried out at a pressure lower than 50 g/em! and 2 temperature lover than 100°C, No solvents are require ‘Adiponittile, hydrogen and the catalyst are continu- ously fed to the reactor. ¢ reaction liquid mixture consist ethylenediamine and catalyst is mix« stream. The reactor outflows are: (1) excess hydrogen, that is mainly recycled to the reactor after water washing (2) 2 purge of catalyst, that is washed to recover hexametinyl- enediamine and is partly recycled to the reactor; and (8) clarified hexamethylenediamine to which the waters coming from the washing of hydrogen and catalyst are added ‘The raw hexamethylenediamine thus produced, contain- ing about 10% water is dehydrated and sent to the puri cation plant consisting of the following steps: (1) hexa- ethylenediamine evaporation to separate the largest part of high boiling products; (2) rectification to eliminate the low boiling products that are sent to a hexamethylenedia- ine recovery column; (3) rectification for the sepa tion of residual high boilings to obtain pure hexamethyl- Catalyst as cN (Cl) «ony 44H: mainly of hexa- by the hydrogen Hyprocarnon Processinc November 1977 enediamine as a top product; and (4) separation of heavy residues from the high boiling mixtures and recovery by istillation of residual hexamethylenediamine which is recycled. This continuous process offers easy construction of equipment, low investment costs, low labor requirement and high efficiency. Yields: The main requirements for production of 1,000 ig pure hexamethylenediamine are as follows: Raw material ‘Adiponitrile, KE oe... cseveeeeceseees 957 Hydrogen (at 98% purity), Nm* 900 Catalyst and chemicals, $US. ......... 10 Utilities Electric power, kWh ......+ cose 120 Cooling water, m? 2. 200 Steam (16 kg/cm), kg « s+ 4,000 Commercial installations: Two 90,000 ton/yr. plants are operated by Monsanto Co. in United States. A third 90,000 ton/yx. capacity plant is under construction in the United Kingdom by Polyammide Intermediates Ltd., a Monsanto-Montefibre joint-venture talian Patent No. 831,913, U.S.A. Patent No. 3,621,305, U.K. Patent No. 1,284,348. The process is also patented in other foreign countries. 169C.-Cs olefins (Dimersol process)—msr reancas ou remot Application: Selective codimerization or dimerization of propylene and/or butylene cuts from steam crackers, FOC units, etc. When dimerization of Cy olefinic cuts (C.+G.) oF codimerization of C, euts with C, cuts the Products are Gy olefins, C; olefins, C.-C, olefins for petro- chemical use (oxo synthesis, solvents, ete.). When dimeri- zation of C, olefinic cuts, product is high on blend for Sasoline pool. Description: The Dimersol process is characterized by a liquid phase reaction occurring at low pressure and am- bient temperature in the presence of 2 soluble catalyst system, The catalysts are continuously injected into the reactor and are destructed at the reactor outlet by am- monia and water addition. A good temperature control and product homogeneity is achieved by industrially proven pump around system. Commercial installation: One gasoline Dimersol unit is under construction. Licensor: Institut Francais du Petrole, 170 Yields and economies: For gasoline Dimersol: Steam FCC ercking propylene propylene Feedstock propylene (mal. %) mn 925 Propylene rich gas (t/yt.) 50,000 50,000, Product gasoline (t/yr.) 32,000 42,300, Gasoling characteriaties: Analysis: Thovhexenes (wt. $6) Nonenes (ort. 9) Heaviers (wt. %) Specific gravity RON clear Research blending value Clear 106 Loaded uz Investment (erected cost in battery limits, engineering excluded, French basis 1976) MM FF 3234 Usiiies: Blectricity (KWh/hr.) 34 Procets water (tons/h) 195265 Steam (ton/hr.) 125112 Cooling water (14° C rise) (tons/br.) a) Ammonia (FB/h:) 2 2 Catalyst (FP/ar.) 355 935 November 1977 Hyprocarnow ProcrssineNIPPON SHOKUB Al Higher sec-alcohols, ethoxylates —Kacacu ‘cocre Co., uo. Application: A process for the production of higher sec-alcohols and their cthoxylates from normal paraffins and ethylene oxide. Description: Higher sec-aleohols and their ethoxylates are produced by the liquid phase air oxidation of neparaffins and by the subsequent ethoxylation, ‘The reac~ tions proceed as follows: ‘Air/HBOs/ cH,~cH,~cH, =", Cite GH~ Cit on CAHLO/ Acid eat, cH, fee eee ee ‘CHs OH O(CH,CH;O) c34,0/ Base ca cH cu~ a SS CH~ HCH O(CH,CH;O} 5H O(CH,CH,O).H As a raw material, a mixture of n-paraffins having carbon numbers from 12 to 14 is used for versatility of surfactant performances. The oxidation is carried out at 150-190° G and nearly atmospheric pressure using a boric acid catalyst and a new ammoniac base co-catalyst. Prior to charging into the oxidation reactor, boric acid is dehy- rated in liquid n-paraffins to avoid clogging or agglomer- ization phenomena in oxidation zone. Conversion of n-paraffins is kept helow 209% to obtain high yield of sec-alcohols. Unreacted n-paraffing are re- ‘Hynrocanson Processine November 1977 covered from the reaction mixture by a simple flash dis- tillation at a reduced pressure. The sec-alcohols, in the form of borate ester, mainly boroxine, are withdrawn from the bottom of the flash distillation, from which boric acid is recovered by hydrolysis, and then the crude alco- hols are purified by caustic treatment and distillation Recovered boric acid is recycled to oxidation section after enystallization and dehydration. "The ethoxylation of sec-alcohols up to 3 mol ethoxy- lates is carried out using an acid catalyst. The product, 3 mol ethoxylate, is separated from the reaction mixture by stripping unreacted alcohols, most of which is recycled {0 the ethoxylation and a part of which is recycled back to the boration reactor to keep the product in good uniform quality. ‘The process from n-paraffins oxidation to 3 mol ethoxy- lation 1s fully integrated and continuous, and does not require hydrogenation step. Further ethoxylation is carried out just as primary aleokol or alkylphenol Raw material and utility consumption (per metric ton of 3 mol ethoxylate of Crs-Crz sec-aleohols) r-Paralfin, be ce e Ethylene oxi, hi 410 Chemicals, yen 10,000 Steam, ton a a 3 Blectrle power, Ey she 400 Cooling water, a oo 500 Process water, = 3 Commercial installation: 1000 tons/year (a5 3 mol Sthoxplats) at Nippon ‘Shokubais Kawasaki plant ‘Japan. : Reference: Hydrocarbon Procesing (in print) (1977). mHigher oxo alcohols—sas* axnencesauscaer Application: A process for the production of higher alcohols from linear or branched olefins or olefin mixtures, carbon monoxide and hydrogen by the oxo reaction. Description: For instance, in the case of non-I-ene, the reaction proceeds as follows: R-CH=CH,+CO+H. > — CHO + R~ GH (CHO) - CH, CH, — CH.OH + R ~ CH ~ CHOH ~ CH, In the oxo stage higher olefins are reacted at 150- 190° G and 200-300 bar in the liquid phase with carbon monoxide and hydrogen in the presence of a dissolved cobalt catalyst. ‘The cobalt catalyst is recycled without isolation o any substantial loss, The crude oxo mixture is converted with 172 hydrogen at 160-280°C and 250-300 bar over a fixed bed catalyst. Grude alcohols are purified by rectification. In the first column, hydrocarbons are separated overhead. In the subsequent column the alcohols are removed from the side stream. ‘The overhead products of the second and third column are recycled to the hydrogenation step. The high-boiling impurities are removed in the third column by continuous tharge of the bottom products ‘The off-gas, the hydrocarbons and the high-boiling products can be used for steam raising. The process in- volves neither waste water nor air pollution problems. Yield: ‘or 100 kg of decanol, 104 kg of propylene trimer are required. Commorcial plants: 40,000 tons/year at BASF Aktien- sesellschaft, Ludwigshafen, November 1977 Hypaocaraow ProcrssineIsobutylene—ror:-compacnte reancarse oe narninace Application: To recover polymerization grade isobutylene (IB) from Cy distillates from catalytic or steam cracking units, Description: Feed is contacted with 50% sulfuric acid in the reactor where IB is preferentially absorbed to form a sulfuric extract. The acid-hydrocarbon mixture flows to one or more settlers with counter-current acid to hydro- carbon flow. The hydrocarbon phase from the final settler is caustic and water washed to remove traces of acid and sent to storage. The IB-rich acid phase from the initial settler is flashed to remove the bulk of dissolved and ‘entrained hydrocarbon impurities as a small off-gas bleed stream, The flashed rich-acid stream goes to the regener ator where high temperature and low pressure regenerates IB vapors. The regenerated acid is recycled back to the reactor-settler. The regenerated IB vapors are compressed and fractionated in a single column 1 99.0-99.9% IB overhead. Small quantities of polymer gasoline is pro duced as bottoms of this tower. Operating conditions: ‘The reactor and settlers operate at less than 50°C with slight refrigeration in the final stage to ensure good IB cleanup. Sufficient pressure— 120-180 psig—ensures that the C, hydrocarbon remains liquid in this section. Yields: Normally, about 90% of the IB can be recovered 1s product and about 5% as byproduct high octane polymer gasoline. ‘Hyprocansow Processinc November 1977 + Investment and operating requirements for a TB unit are based on Cy fraction Economi 70,000 metric: ton/y from steam cracker! Investment (Ist quarter 1977 Western Europe excluding offsites, engineering and licensing fees), French Frances 30 10° Stream factor, J ..... i 90 Operators per shift 2 = 2 Utilities, per ton IB 150 psig steam, ky 7 1,900 40 psig steam, kg ‘600 Gooling water (AT = 18°F), m?... M5 Process water, m? 06 Electric power, kwh 02.0.5 200 Chemicals per ton of IB ‘Sulfuric acid (100%), kg «+--+. 02+ 20 Caustic (100%), kg a 16 Commercial installations: British Hydrocarbon Chem- icals, Ltd,, Grangemouth, Scotland, 99,000 metric tons/ye.; Polysar Belgium N.V., Anbwerp, Belgium, 60,000 metric tons/yr.; and SIR Consorzio Ind., Porto Tores, Italy, 45,000 metric tons/yr. under construction. References: Hydrocarbon Processing, May 1962, p. 119- 128; Chemical Engr. Progress, March 1965, p. 17; Con- gres Association Francaise des Techniciens du Petrole (1965). Licensor: Total-Compagnie Francaise de Raffinage. 173,THE BADGER Isophthalonitrile (Mitsubishi Gas Chemical/Badger) —T "42° 174 Application: A process for the manufacture of isophtha lonitrile from high-purity metaxylene, anhydrous ferti lizer grade ammonia and air. Benzonitrle may be recov- ered as a saleable byproduct if desired. Product: Tsophthalonitrile is a raw material in the manu facture of agricultural chemicals and aromatic diamines which in turn are used to produce high quality coatings, films and fibers. Description: Metaxylene, ammonia and air are intro- dluced into a fuid-bed catalytic reactor whe lene is primarily converted to aromatic ai dioxide and a small amount of hydrogen eyanide and car- bon monoxide are formed. The reactor effluent also con- tains small quantities of benzonitrile and metatoluniteile which may be recovered for sale, or utilized interally within the recovery portion of the process. The reactor effluent is scrubbed in a countercurrent quench system where the nitriles are recovered from the reaction gases, The offgas i cooled to minimize solvent losses and incinerated. The tecovered crude isophthalonitrile is purified by fractional distillation. Heavy byproduets are disposed of in the offges incinerator. ‘The isophthalonitrile. product is flaked and packaged for shipment. ‘The process includes facilities for containment, collec- tion and treatment of all liquid and gaseous waster, There are no net waste streams leaving the process. Commercial installations: The original commercial in- stallation has been operating in Japan since January 1970. The first commercial U.S, installation came on- stream in January 1973 November 1977 ‘Hyprocarsow ProcessineIsoprene—si DEVELOPMENT CO, Application: A process to produce high purity isoprene (1) by recovery of tertiary amylenes from a C, feed, (2) dehydrogenation of the amylenes to isoprene, and (3) recovery of isoprene from the reactor product. The unit for recovery of the tertiary amylenes may be at a site separate from the reaction and isoprene recovery units. Description: A Cs [eed from catalytic cracking may contain 20-30% wt. tertiary amylenes (2-methyl-butene-1 and 2-methyl-butene-2). The tertiary amylenes (TA) are recovered from the C. feed by reaction with aqueous acid, reversal of the reaction at a higher temperature and recovery of the TA from the acid with a higher boiling solvent. The recovery of the TA depends on the design of mixing and settling equipment, control of the temperatures for reaction and reversion, and control of the dispersion of the acid-hydrocarbon’ mixture in the process with additives, The amylenes unit is built of carbon steel. ‘The diagram does not show the equipment for caustic washing and water washing the hydrocarbon streams. To produce isoprene (IP) the TA are combined with recycled amylenes from the isoprene recovery unit and dehydrogenated after dilution with steam over a Shell catalyst, With this catalyst the run cycle is usually 24 hours with a one-hour regeneration. The dehydrogenation unit includes a compressor, absorber-stripper and columns for removal of a dry gat and C.-C, fraction for fuel. ‘The isoprene recovery unit is located near the dehydro- Hyprocarson Paocsssinc November 1977 genation unit. A sequence of extractive distillation with aqueous acetonitrile (ACN) solvent and straight frac- tionation is used to produce high purity isoprene and to recover unreacted amylenes for recycle to the reactor. ‘The change in volatilities between the C, components in a solvent environment and without solvent is used to make the over-all separations. The diagram does not show the solvent purification and hydrocarbon washing equip- ment. Yield: The tertiary amylenes recovery unit produces product stream containing 98% wt. tertiary amylenes at 75% recovery from the C, feed. The residual C,’s and a Cys fraction produced in the unit are used for gasoline blending, ‘The high purity isoprene contains 99,0-99.59% wt. iso ptene, 1-3 ppm wt. cyclopentadiene and 10-30 ppm wt. ‘alpha acetylenes, ‘The over-all conversion and recovery of tertiary amylenes to isoprene is 70%. ‘The major loss of tertiary amylenes occurs in the reactor. Commercial installation: Units using the Shell Iso- prene process are operated by Shell Nederland Chemie ‘at Pemis, Netherlands, and by B. F. Goodrich Chemicals at Port Neches, Texas. Licensor: Shell Development Co., One Shell Plaza, P.O. Box 2463, Houston, Texas 77001. 175Isopropano|—vess-creme ac Application: Process for production of isopropanol through direct hydration of propylene and demineralized water. Propylene concentrations between 60 and 100% can be used as feedstock. Isopropanol of 87.59% and 100% by weight either pure or impure suitable for motor fuel as anhydrous can be produced. Description: Liquid propylene and water are mixed with recycle gas from the rotating gas compressor and heated in exchangers by gases from the reactor, and then heated in the superheater with steam to 170-190°C and passed over the catalyst under a pressure of about 25-45 bar, Here the propylene and water are converted after the following equation CH, ~ CH= CH, + H,O > CH, CHOH CH, +123 keal ‘The gas charged with isopropanol leaving the reactor is cooled in heat exchangers, then fed to the scrubber, where the remaining isopropanol is removed. The uncon- verted propylene is returned to the reactor through the recycle compressor. Depending on the concentration of the feed propylene a part of this recycle gas is fed to the make up column in order to purify the recycle gas from such gasous components, which do not react under the conditions, ic. mainly propane. ‘The pressure of the dilute isopropanol, which is cole 176 lected at the base of the scrubber, is reduced in the orage tank. The crude is then fed to the two hydro- selection columns, where impurities are separated by extractive distillation with water. Azeotrop is withdrawn from the rectifying column. The azzotrop can be dehy- drated in two further columns with a dehydrating agent such as benzene or diisopropyl ether, The excess water, which occurs in some distillation columns, is not only used for scrubbing, but the remainder is desalted and used as process water again. Utilities (dehyde included per ton of isopropanel) Power, kWh. 40 Cooling water, m? 160 Steam (25 bar) keal 2.5 x 10° Yield (based on converted propylene) 97% Another advantage of the process is that ethanol can be produced in the same unit with only lite additional investment and without changing the catalyst, which requires a special treatment in the unit only. Commercial installation: Four large-scale plants for the producton of isopropanol are in production and a fifth one under construction, the total annual capacity is 400,000 tons. November 1977 Hyorocarnow ProcessieLinear alkylbenzenes (Pacol-detergent alkylation) —piision Application: A continuous catalytic dehydrogenation process combined with an HF-catalyzed allylation process, wherein appropriate linear paraffins are dehydrogenated to linear olefins which, in turn, are alkylated with ben- zene to form linear alkylbenzenes, an intermediate product for the production of biodegradable detergents. Process description: The Pacol dehydrogenation section consists of a catalytic fixed bed reactor which dehydro- genates, typically, CieCis or Cu-Cu Tinear paraffin Feeds at near equilibrium conversion, to the corresponding linear olefins with selectivities of about 90 wt.% to mono- olefins. The vapor phase reaction is carried out in the presence of excess hydrogen and at low pressure and moderately high temperature The detergent alkylation section consists of two reactor- settler units operating in series. Here the olefin-paraffin ‘mixture from the Pacol dehydrogenation section is thor- oughly mixed with benzene and then with anhydrous hiycrogen fluoride acid catalyst, The reactors are designed to maintain the acid-hydrocarbon emulsion and provide the required contact time and temperature to complete the reaction of the olefins with benzene. ‘The upper hydrocarbon phase from the No. 2 settler then flows to the fractionation section for the separation and recycle of dissolved HF acid as well as unreacted benzene to the HF reactors, while unreacted linear paraffins are recycled to the Pacol dehydrogenation Hyprocarson Processinc November 1977 reactor. The lower acid phase from the No. 1 settler flows to the HF regenerator column where heavy alkylate, soluble in the acid, is removed as a bottoms stream, while anhydrous HF is distilled overhead and recycled to the No. 2 HF reactor. A final rerun column separates the overhead) linear alkylbenzene product from the heavy alkylate bottoms stream. Yields: Based on 100 weights of linear alkylbenzene product, approximately 82 weights of linear paraffins and 4M weights of benzene are charged to the process. Product quality: The linear alkylbenzene product has the following typical properties: Bromine number ee sees O01 Saybolt color . 30+ Doctor test... raat ait Bee Linear alkylbenzene, web I 9 Unsulfonatables, % . sane 1 Biodegradability of the linear alkylbenzene sulfonate (ASTM D 2667), % coy Commercial installations: Four Pacol-detergent alkylate process combination units are in operation and 13 more are presently being constructed. U7]L-Lysine—«rowa saxko xosro co, uo. 178 Application: A process for production of L-lysine mono- hydrochloride from carbohydrate materials and/or acetic acid by fermentation, Description: The fermentation process is started by inoculation of L-lysine producing bacteria (auxotrophic mutants of Corynebacterium gluamicum) into the culture medium containing adequate amounts of carbohydrate materials and/or acetic acid and other nutrients, During the fermentation, the temperature is kept around at 30° C, and also aeration, agitation and pH control with am- ‘monia are inevitably required. After the fermentation, L-lysine is recovered from the fermented broth by passing the broth through a column of strongly acidic cation exchange resin. ‘The Lelysine Sdsorbed on the resin ie eluted vith ite ammonia, and the resulting eluate is condensed under reduced pressure ‘The condensate is neutralized with. hydrochloric acid, and then T-lysine monohydrochloride is crystallized out ‘from the condensate, separated by centrifuge and dried. If necessary, the product is recrystallized. Product properties: L-lysine monohydrochloride thus produced is strictly in accordance with the quality specifi- cations established by the Japanese government for food and feed additives and for pharmaceuticals. Commercial installation: Plants with a total capacity ‘of 17,000 tons/yr. are onstream in Japan (in 1976). Reference: Further technical information can be re- ferred from a monograph entitled The Microbial. Prow duction of Amino Acids edited by K. Yamada, S. Kino- shita, T. Tsunoda and K. Arima, and published from Kodansha Ltd. (Tokyo) and John Wiley & Sons, N.Y. November 1977 ‘Hyrocarson ProcessincMaleic anhydride—ss > Application: A continuous process for recovery of pure maleic anhydride (MA) from phthalic anhydride (PA) waste gas scrubber water. Description: Concentration of waste water and dehydra- tion of maleic acid. The scrubber water from the off gases of the PA process contains in solution about 20% of maleic acid and approx. 5% of other acids e.g. phthalic acid, benzoic acid and citraconie acid. The acid concen- tration of the waste water is increased under slight vacuum to about 959 in a system of evaporators which guarantee short residence time. All vapors are condensed, collected and recycled to the PA scrubbing section. The obtained concentrated melt of acids is sent toa special dehydrator where the molten dicarboxylic acids are mainly dehydrated to the corresponding anhyd- rides and evaporated. The vapors are partially condensed. Crude MA is obtained from the first condenser, while the second condenser yields a melt of MA and maleic acid which is reeycled to the dehydrator. ‘The remaining water vapors are retained in an injec- tion condenser whose recycle water is fed back to the PA scrubber. Further MA is evaporated in an agitated vessel from the melt leaving the dehydrator, High boiling material is removed as residue, which is collected in an intermediate storage vessel. This residue can be burned. Hyprocarson Processinc November 1977 Purification, The crude MA obtained in the frst con- denser is continuously distiled in a single column under vacuum. The pure MA is withdrawn at the top of the column. The bottoms contain higher boiling acids and anhyd- rides which are removed and incinerated ‘The pure MA produced has the following specification: Purity ‘min, 99.59% Solidifcation point rain, 524° Color number of melt ‘max, 20 Hazen (APHA) ‘alk content max. 0.002% Solubility, (1 g/25 ml axylene) clear solution Feedstock and yield: When using the BASF catalyst for PA production itis possible to recover from the off- gases of the PA switch condenser system approx. 5 wt.% of pure MA based on the amount of PA. produced, by suitable serubbing and working up of the scrubbing solution. Commercial plants: Recovery units for MA. from PA scrubber water are installed at BASF AG, Ludwigshafen and at BASF Canada. A license for this process has been granted to a customer in the U.S. The total installed capacity for recovery of MA according to this process is at present 14,000 metric tons per year. Reference: Hydrocarbon Processing, Vol. 54, No. 8, 107. 179Maleic anhydride (Bayer Application: Production of maleic anhydride from G,- fractions by selective oxidation of butene-I and butene-2, and butadiene, if present. ‘oduct: Maleic anhydride content min, 99.7; solidi tion point min, 52.5°C; ash content max. 10 ppm; iron content max. 5 ppm; color of melt APHA max. 20, Description: Filtered and compressed air is loaded with an evaporated butene mixture so that an ait/hydrocarbon ratio below the lower explosion limit results. The air/ butene mixture enters the tubular fixed-bed reactor where reaction takes place at approximately 400-440° C in the presence of a special catalyst. AA salt melt circulating around the tubes removes the reaction heat and maintains constant temperatures, The reaction heat is utilized for the generation of high pressure steam. ‘The reactor efluent containing maleic anhydride vapors, unconverted n-butane and small amounts of byproducts passes through a series of gas coolers where itis cooled to about 120° C before entering a scrubber. Crude maleic anhydride is recovered as aqueouis maleic acid solution in a scrubber with a concentration of about 40 we% ‘The waste gas leaving the scrubber contains unconverted nbutane and must be incinerated, if required, before discharging it to atmosphere. 180 process)—wrer corr. ‘The maleic acid solution is fed continuously to a dehy- ration column. In the presence of o-xylene, the maleic acid solution is dehydrated to maleic anhydride which is stlled under vacuum either in a batch distillation or in fa continuous system jointly developed by VEBA and Lurgi. Yields: 60 Ibs. maleic anhydride from 100 Ibs. C,-fraction (75% butene-1, butene-2) Utilities consumption per 1,000 Ibs. pure MAA: Electricity: 720 kwh Cooling water: 15,000 U.S. gal. (gradient 10°C) When air blower is driven by steam turbine, electricity consumption is only 180 kwh and surplus steam 40 bar depending on the composition of the C, fraction between 500 and 4,000 Ibs. Economics: Lifetime of catalyst more than 3 years. Ca- pacity of single reactor up to 2 million Ibs. per year with fan onstream time of 8,200 hours/year. Commercial installations: Bayer AG has an I1-million Ib,/yr. plant operating for 5 years which was expanded to 22 million Ibs./year in 1973. fensing: The process is licensed by Bayer AG or Lurgi Mineraléltechnik GmbH. November 1977 Hypnocarson Processinc.Maleic anhydride—+= ««. Application: A process for continuous production of maleic anhydride from benzene and air. Description: Maleic anhydride is produced in gaseous phase by catalytic oxidation of benzene (nitration grade) by air on an original UCB catalyst. The process comprises twa steps: Oxidation: ‘The filtered air is first compressed and then preheated by thermal exchange with the converted gases. The vaporized benzene is mixed with the air and the aix/benzene mixture, the ratio of which is automat- ically controlled, is passed on the catalyst. The reactor is of the tubular type with fixed bed of catalyst inside the tubes. The reaction temperature is maintained constant by means of a circulation of heat transfer salts which generates high pressure steam, The converted gases are stepwise cooled, fist in a waste heat recovery boiler where medium pressure steam is produced, then by preheating the reaction air. ‘The main part ofthe male anydide (50s to 6096) is continuously condensed by cooling the gases below the dew point of the anhydride bue above the dew point of water. This condenser, of a special design, needs never be put out of service for washing. The maleic anhydride remaining in the gases is absorbed in water to form a crude maleic acid solution Purification: The purification step, including dehydra- tion of the maleic acid and distillation of the erude anhy- dride, is performed continuously and thermally without use of any organic solvents as an entrainer, Hyprocarsow Paocessinc November 1977 The crude maleic acid solution is first evaporated under vacuum and afterwards thermally transformed to anhy- dride in a dehydration reactor specially developed in view ‘of reducing to the lowest possible level the isomerization of maleic acid to fumaric acid (less than 0.1% of the total output of the plant) ‘The already very pure maleic anhydride recovered after the dehydration unit is then continuously distilled under vacuum. The purification step can be operated at any ratio of anhydride to acid feed for flexible production Economics: High yields of both oxidation and purifica- tion: overall weight yield lies between 88 and 89¢%, Cata- lyst life: 2 years and over. Onstream factor: over 95%. Labor reduced to one operator per shif ‘Typical values of the end product—Solidifcation point: 52.5 to 52.7°C, Insoluble in xylene: none. Molten color: 5 to 10 APHA. Due to high selectivity of catalyst and utilization of a thermal dehydration technique, air and water pollution abatement facilities are minimal, ‘Commercial installations: The process is in commercial operation in UCB’s factories in Belgium and has been licensed 3 times with 2 in operation. Licensor: UCB S.A., Licensing Department, Investment and Industrial Property Direction, 4 chaussée de Charleroi, 1060 Brussels, Belgium. References: U.S. Patents 3,642,829; 3,993,671 ; 4,009,186. 181Methanol (ICI low pressure process)—inousmes‘i Application: A proces: for the manufacture of chemical or fuel grade methanol from gaseous, liquid or solid hydrocarbon feedstocks. Description: (Steam Reforming Application) The hydrocarbon feedstock is desulfurized by catalytic or absorptive processes mixed with process steam and passed forward to 2 tubular reformer. The reformed gas leaves the tubes at 800 to 850°C before passing to the heat recovery section. After cooling to ambient temperature it is compressed by a turbine driven centrifugal compressor to a pressure between 50 and 100 atm. The synthesis gas is added to the synthesis loop which comprises the follow- ing items: circulator; converter; heat exchanger; heat recovery exchanger; cooler, and separator. The crude product is distilled in’ two or three columns. Main features of the process arc: a highly stable copper based methanol synthesis catalyst, simple converter design and heat recovery and an optimized distillation system. The synthesis caialyst operates in the pressure range 50 to 100 atm at 200 to 300°C and has a life of up to four years, The converter is a pressure vessel con- taining a single bed of catalyst. The reaction is quenched at several levels by cold gas injected through specially designed spargers. Catalyst can be loaded through the top of the converter and discharged at the base in a matter of hours. Reaction heat is recovered from the con- verter efluent to preheat the high pressure boiler feed- water. The over-all heat recovery system involving the reformer and synthesis loop, together with the energy system is optimized to obtain maximum use of heat at all levels of temperature, thereby obtaining maximum econ- 182 ‘omy in the consumption of feedstocks. The distillation section is optimized for capital cost and energy consump- tion. A two oF three column system can be designed. to meet US. Federal Grade AA specification with a fading time greater than 60 minutes. (Partial Oxidation Application) Heavy fuel oil or coal are partially oxidized by oxygen and steam. The produet gas containing largely hydrogen and CO, together with some CO, and trace impurities is treated to remove sulfur compounds and adjusted to the optimum ratio of hyerogen to carbon oxides. Partial oxidation processes can operate at intermediate pressures such that no further compression is required belore the synthesis gas passes forward to the synthesis loop. Economics: Typical requirements per metric ton of methanol are: ‘Natural Gas Heavy (Noco, Fuel Gil Naphtha available) Feed and fuel K cals x 108 7800 17 78 Electric power kwH = 8835 35 Feed water m* 0.75 “115 115 Cooling water m* aE 70 Catalysts US. 1d 09 Commercial experience: Twenty plants are now in operation (two owned by ICI) and four are currently being designed or constructed. Plant sizes range from 50 ‘to 1,800 tonnes per day. November 1977 Hyprocarnow ProcessiNoMethanol (Lurgi low pressure process)—wre: cor. Application: A process for methanol manufacture from {gaseous and liquid hydrocarbons ranging from methane to asphalt. Description: (Steam reforming route)—Hydrocarbons— methane to naphtha—are desulfurized, mixed with steam and reformed at 830-850° G to synthesis gas containing hydrogen and carbon oxides. If feedstocks with low molecular weight are used, it may be economic to add CO: to avoid loop hydrogen build-up. High pressure steam is generated by the waste heat of the flue gas and the synthesis gas. Together with the steam raised in the synthesis reactor, it is used to power gas compression, at intermediate pressure for reforming and at low pressure for methanol distillation The synthesis gas is compressed to 50-80 atm, together with the reeyele gas in a centrifugal compressor, pre- heated, and charged to the reactor. In the shell and tube reactor, the tubes are filled with catalyst and the shell side filed, with boiling water. Re- action temperature (between 250-260°C) is controlled by the boiling water steam pressure. Good reaction heat transfer to the boiling water gives 1-14 kg of steam per kg of methanol and protects the catalyst even at abnormal operating conditions. The re- actor gases after the reactor feed/effluent exchanger are cooled and methanol is condensed and removed in a separator while the gas is recycled to the compressor. A small portion of gas is purged and used as hydrogenation gas for desulfurization or as fuel. ‘The crude methanol is refined and product methanol Hyprocarson Psocrssinc November 1977 meets U.S. Federal Standard Grade AA with a fading time greater than 60 minutes (Partial oxidation route) Heavy residues are partially oxidized by oxygen and steam at 1,400-1,450°C. and 55-60 atm, pressure, Product gas consists of equal parts of Hz and CO with traces of COs, CEL, HS and free carbon, Tt is water scrubbed to remove carbon and cooled. Carbon is recovered from the water and recycled:to the reactor. Alter desulfurization, part of the gas is sent to shift conversion to adjust to H/CO ratio. After CO; removal by Rectisol scrubbing, the gas streams are united and sent to synthesis, As the pressure after COs removal is 50-55 atm, no synthesis gas compressor is required, and the syn- thesis gas is fed directly to the recirculator. Economies: Typical requirements per metric ton of methanol are: Natural gas, Heavy residue Naphtha CO, available Feed, geal 8.35 3.93 57 Fuel, geal = 163 205, Elecisle poser, EWh 130) 0 ° Feedwater, tons ont oo 0.62 Gooline water, m* 5 40 35 (Chemicals ag catalysts, $US, os 1a. 1.02 Commercial installations: Five plants (130-1,360 tons/ day) are in operation and three others (450-2000 tons/ day) are under construction. References: Hydrocarbon Processing, September 1970; CRER, September 1971. 183Methyl isobutyl ketome—serscre rexaco ac Application: A process for the manufacture of methyl isobutyl ketone (min. purity 99.0%) from acetone and hydrogen. Doseription: Liquid acetone is charged via a pre-heater to.a fixed bed reactor where it is contacted with hydrogen. Condensation, dehydration and hydrogenation takes place simultaneously in the presence of an acidic catalyst loaded with palladium at 30 bar and 190-140° C. on, 2 CH.-CO-CH, -> CHs-CO-CH,-COHC cna CHS (CH,CO.CH = GQ" *+ GH,-CO.CH,CH{ CH, CH. ‘Hy 5 ‘The crude product containing about 35% MIBK is passed toa distillation unit. 18¢ Raw material consumption and conversion: 1.40 tons of acetone are used per ton of MIBK and conversion per pass is 40%. Utilities: Utility requirements per metric ton of MIBK of min, 99.09% purity are: Cooling water, gal. 79,000 Steam, 35 psig, Ibs 22,000 Steam, 300 prig, Ibs. 3,000 Electricity, kwh oe -. 360 Catalyst, SUS. 40 approx. Catalyst life, year 1 Commercial installations: One 8,000 ton/yr. plant is operating in Germany and one 4,000 ton/yr. plant is in operation in Argentina. Licensor: Deutsche Texaco AG through Texaco Develop- ‘ment Corp. or Edeleanu Gesellschaft mbH, Frankfurt (Main). November 1977 Hyprocarsow ProcrssiaMethyl-tert-butyl ether (MTB)—ctmscue were wus ac Application: Production of MTB by selective reaction cof methanol with isobutene contained in C,-hydrocarbon fractions and separation in either gasoline blending or chemical grade (> 99.89% purity) qualities. Description: The C,-hydrocarbons containing isobutene are passed with methanol over a long-live fixed-bed catalyst under mild conditions, isobutene being converted selectively according to the following equation: CH, = C(CH,). + CH, OH GH, - O- C(CHL), ‘The C,-cut of a steam cracker after butadiene extrac- tion containing up to 50% of isobutene is 2 particularly suitable feedstock. This BB fraction leads to a product containing approximately 60 wt.% of MTB mixed with unconverted C,-hydrocarbons and some methanol, which may be used directly as a gasoline blending mixture (Case 1) To obtain pure MTB, the reactor output passes through a debutanizer, The Ci-hydrocarbons are sep- arated leaving MTB as bottom product. ‘At maxitnum 959 isobutene conversion this MTB will have a purity of 2 98 wt.9% and is already well suited as high octane gasoline blending component (Case 2). A higher isobutene conversion of 98% and a higher purity MTB up to > 99.8 wi.%o can be attained with the Hyprocarson Paocessinc November 1977 use of a second column, in which excessive methanol is separated to be recyeled to the reaction, Raw materials, byproducts and utilities: (per ton of MTB with a typical purity of 99.495 at an isobutene conversion of 98%—Case 3) BB fraction, (1) 509% isobutene (1), kg Methanol, kg 392 Byproduct: spent Gy-fraction, kg 686 Steam, tons oO Cooling water, m= 6 Electricity, kwh 8 By means of additional equipment the small amount of ethanol in the spent Cr-fraction can be separated and recovered. The methanol consumption is then reduced to the theoretical amount. Commercial installations: One 60,000 tons/yr. plant is in operation and another 120,000 tons/yr. plant is under construction. Reference: Further information is available from Chemische Werke Hills AG, 4370 Marl, Federal Republic of Germany. 185Neo acids— on cxemicar co. Application: A continuous process for the production of high purty tertiary carboxylic acids from branched olefins by carbonylation and hydrolysis. Description: The synthesis of neo acids involves the addition of carbon monoxide to a branched olefin in the presenice of an acidic catalyst to produce a CO-catalyst- blefin complex, This is followed by hydrolysis of the com- plex to the corresponding tertiary monocarboxylic acid. ‘The complexing reaction mechanism is believed to involve the formation of carbonium ion by olefin-hyclrogen ion interactions. The CO then reacts with the carbonium jon to form an acyl carbonium ion. Equations 1-3 illus- trate the general synthesis of neo acid. RB R mate ——> Bb a) he KR Olefin Catalyst Carbonium Jon R iia ‘ n-00 —| eG 2) & fey Cab Ton = : é -co | +o Sess, R 186 h BG COOH (3) R Neo Acid Catalyst In this reaction an acid with a carbon number one higher than the olefin feed is produced. The carboxyl group will, in general, add to the carbon with the fewest hydrogen atoms, yielding the characteristic, highly stable neo structure, Operation: Neg acids are produced in a two-step pro- cess, In the first step, olefin, CO and the appropriate molar ratio of acidic catalyst are fed into a high pressure complexing reactor, where the stable reaction intermedi- ate is formed. Reactor offgas and acid complex are de- pressured in the degassing drum. The complex is subse- quently contacted with the required molar ratio of water, completing the hydrolysis reaction, In this latter step, the crude acid products are formed and the catalyst regener- ated for recycle to the reactor. The crude acid is then purified by fractionation to remove trace amounts of light, and heavy impurities. Commercial installation: Neo acids in a variety of molecular weights, particularly neo-pentanofe and_neo- decanoic acids, are produced at Exxon Chemicals Baton Rouge La, Plant, ‘The unit is currently starting up the first of a series of planned expansions which will triple its capacity. November 1977 Hyprocarnow PaoczssineNitric acid (SABAR Process)—»v rowercass omen Application: A process for producing nitric acid (80- 99% HNO,) from ammonia and air. Does not require ‘oxygen, refrigeration energy, dehydrating agents (sulfuric acid or magnesium nitrate). Nitric oxides in the tail gas can be reduced by absorption to below 200 ppm. Weak ‘acid at any rate and concentration can be produced simultaneously, Description: Gascous ammonia is mixed with air and converted to nitric oxides in the reactor on platinum- thodium catalysts. Ammonia conversion is at atmospheric pressure so that the reaction water—most of which must be passed out of the process—can be condensed with minimum absorption of nitric oxides. The atmospheric pressure conversion gives low platinum loss and a high yield, The reaction heat is used to produce steam and to preheat the tail gas prior to expansion. The reaction gases are finally cooled in the gat cooler condenser where the main portion of the reaction water is separated as 296 nitric acid condensate. After addition of secondary air which contains recycled nitrogen dioxide the nitrous gas is Compressed to between 6-13 bar abs. ‘The compressed gas enters the chemical absorption column where superazcotropic acid is formed. Nitrogen Hyprocanson Processinc November 1977, dioxide remaining in the gas is physically absorbed in nitrie acid which takes place in the physical absorption column. The nitric acid loaded with nitrogen dioxide flows to the desorption column where the nitrogen di- oxide is stripped by secondary air which is recycled to the main gas stream ahead of the compressor. Tail gas from the physical absorption is freed from nitric acid vapors, preheated and expanded in the tail gas turbine, The superazeotropic acid is stripped by secondary air to remove nitrogen dioxide and is sent to rectification where it is separated into high concentrated and azco- topic acid. The latter is recycled to the absorption section, Economics: Investment costs are substantially lower than those for “HOKO™ plants (requiring oxygen and refriger- ation units), and operating costs are lower unless oxygen and refrigeration are available at very low costs Commercial installations: The first 120 metric tons/ day SABAR process plant has been successfully operated over a period exceeding three years, during which time aan extensive test program for optimizing plant operation and further design has been performed. 187Nitric acid—#sricesa/exptosivos rio ninto, s.a. Application: Process for production of strong nitric acid (99% HINO.) by ammonia combustion, enrichment of reaction gases jn NOs, absorption of nitrogen oxides by nitric acid’ (68% HINO,) and distillation of the superazeotropic acid produced by absorption, Description: Ammonia is oxidized by air to NO at atmospheric pressure. Temperature of the reaction gases is lowered to the devwpoint in several heat exchangers and water is eliminated as a very weak acid solution (acidu- lated water). NO is oxidized to NO; by means of weak nitrie acid (55-60% HINO,) according to reaction NO+2HNO, +3 NO; +H.O ‘As three moles of NO; are made per mol of NO, the ‘gases became very rich in NOs and are then compressed fo 12 atm. Part of the NOs is absorbed in_azeotropic nitric acid to make a solution of 75-80% HNO, which is distilled to give strong acid (99% HINOs) and azeotropic acid which is returned to the superazeotropic absorption tower. The remainder gases, still rich in NOs, are absorbed ‘with part of the acidulated water to make 35-60% HNO, solution which is used to oxidize the NO to NO; ‘The tail gases after the second absorption contain less than 200 ppm of nitrogen oxides and are heated in several heat exchangers before being expanded to recover its energy. Process provides option to produce strong and weak nitrie acid in any proportion and it is to be said that this 188 versatility i e of two valves achieved by only adjusting the position the plant, Main advantage of the process is its low st. Basically, this ig because it does not sry oxygen plants nor brine installations. Over-all ammonia efficiency is very high because com- bustion is performed at low pressure and absorption is performed at high pressure in perforated trays, in such a way that tail gases meet the most stringent pollution regulations, Investment *, § million (ISBL) 102 Operating requirements per metsie ton of HNO; ‘Ammonia 20K ge Circulating cooling water (AT= 10° ©) 290 mt Electricity 5360 kwh Steam import 590 Kes Catalyst GOmgrs “For a 140 metric ton/‘day plant in Spa ‘The plants are fully automated and only 2 operators are required. Commercial installations: Process was patented in 1976; first plant is under construction for Fabricaciones Militares in Argentina. inquiries should be addressed to Espafiola de Investigacién y Desarrollo, 8.A. ESPINDESA, Rodriguez San Pedro 2, Madrid-15, Spain. Patents have been granted in the United States and several other countries. November 1977 Hyprocarson ProcessineNylon 6—nvewra ac Application: Process for the production of nylon 6 (polycaproamide 6—PAG) starting from caprolactam (LG) monomer, Description: Caprolactam (LC) is polymerized in the presence of water at elevated temperature by the Inventa \VK-tube method (VK = vereinfacht kontinuierlich). Pre- polymerization steps are added to accelerate the hydroly- sis of LC by elevated water content and to reduce the total reaction time—especially desirable in laxge capacity lines. Additives, eg. dulling agents, chain terminators, catalysis and some polymer modifying agents, can be added to the LG solution. A modern static mixer system helps to achieve plug flow in the VK-tubes. ‘The raw polymer at reaction equilibrium is extruded into strands and eut into granules. The 10% non-reacted ‘monomers and oligomers are removed in a continuously operating extraction column by hot water in counterflow to the chips, The extracted polymer is de-watered and ried continuously in the drying column with pure, hot, dry nitrogen recirculated in counterflow to the chips. The product is cooled to room temperature and blown to the storage silos. The relative viscosity of polymer from this process can range from 2.8 to 7.0, when post condensa- tion conditions are applied in the drying stage. Hyprocarsow Processinc November 1977 This process can also be used to produce copelyamides of these pure components—PA6, PA66, PAS, PA10 and PAI. Batch and continuous processes are available to fit all requirements regarding polymer grades, production flexi- bility and optimum plant size. The high degree of instru- mentation allows fully automatic plant operation with minimum manpower. Large scale capacity lines of 30-45 tons/day cut production costs to 2 minimum, Various methods are available for the recovery of LG from extract- ables and polymer waste and contribute to minimize the raw material costs Polyamide 6 together with its copolymers opens a wide range of applications from fibers and films to injection moulding, extrusion, sintering and hot melt adhesives. Commercial installations: More than 20 plants are in operation or under construction in Argentina, Belgium, Brazil, Colombia, Great Britain, India, Tualy, Japan, South Korea, Philippines, Rumania and Switzerland, Total licensed capacity is more than 140,000 tons/yr Licensor: Inventa AG. 189Oxo process—vmon carsive corr Application: A low pressure, rhodium catalyzed, pro- pylene hydroformylation process to produce n- and izo- butyraldehyde, Description: The over-all chemistry of propylene hydro- represented by the following equations: HHH Ld peeeGaHo | HHH GH, +H:+CO-| — m-butyraldehyde ‘so-butyraldehyde Synthesis gas (CO and Hy) are combined with propylene (CoH) feed in a feedstock pre-treatment section before being sent to the reaction/product separation section. Here, the reactants are combined with the organo-metallic 190 catalyst complex of rhodium. The three principal products formed are n-butyraldehyde, iso-butyraldehyde and pro- pane, Process parameters affecting their formation include the rhodium ligand solvent, temperature, the CO:Hs ratio and the propylene. Optimum process conditions are those which maximize n-butyraldehyde formation. ‘The rhodium catalyst is totally recovered and concen- twated for reuse. The reactor product is fractionated to recover propylene and propane for recycle as overhead. Bottoms go to fractionation columns for recovery of iso- and n-butyraldehyde, Operating conditions: The process operates from 100- 350 psig and about 100°C. The n- and iso- ratio is con- trolled over a wide range and is normally operated at 8:1 to 16:1, The process features case of startup and opera- tion, consistently high n-iso ratio, high selectivity of pro- pylene to nebutyraldehyde and no loss of rhodium. In addition, no synthesis gas compressor or high pres- sure pumps are required. Alo, there is no C, alcohols produced Commercial installations: Union Carbide operates large facility using this process at its Ponce, Puerto Rico, facili Reference: Hydrocarbon Processing, September 1976, p. 247-249, November 1977 Hyprocasnow Pxoczssion-Paraffins (Isosiv process-kerosine/gas oil range)— ENGINEERING PRODUCTS AND PROCESSES UNION CARBIDE CORI Application: A process for the separation of high purity normal paraffins in the Cio to Css range from branched- chain and cyclic hydrocarbons in Kerosine/gas oil feed- stock. Description: The kerosine gas/oil range Isosiv process employs the highly selective adsorption action of molee- uler sieves in a multiple-bed system. A purge is used to desorb normals The feed stream is pumped through a heat exchanger in which it is heated by the coproduet isomer stream, and then through a feed heater. As each adsorption bed reaches 2 predetermined loading of adsorbed normals, the feed stream is switched to the next bed in the system. The purge stream is then switched into the loaded bed to desorb the n-paraffins product. Both product streams finally pass through distillation columns which recover and recycle the purge material to the desorption section of the process. ‘The elevated temperatures required for vapor-phase adsorption cause some coke formation in the beds. To remove this accumulation, an integral burn-of system is provided for full continuous reactivation of the molecular sieves without plant shutdown. ‘Hyprocarnon Proczssinc November 1977 Economics: Typical costs for a medium-size Isotiv installation to produce 250 MM lbs./yr. of contained 180 molecular weight 1-paraffins are as follows: Tnvestment (including molecular sieves wentory), U.S. Gulf Coast, 1976, no off-sites $12,000,000 Operating costs (95% stream efficiency) $/D Fixed charges, 36,000 Royalty (5 years) $1,000 Labor—2 men/shift, plus supervision @ 25% $500 Utilities Fuel, at $2.00/MM Btu 35.500 Power, at $0,025 kawh $400 Water, at $0.05/M gal. $ 2 Steam, at $3.50/M Ibs. $ 70 Chemicals $ 600 Commercial installations: Four units on kerosine feed, fone on gas oil feed, and seven on combined Kerosine/gas oil feedstocks giving a total installed capacity of 2 MMM. Ibs, of n-paraffins per year. Others under design and con- struction. 191Pentaerythritol—sose masswer cman Applications Process for continuous preparation of pen- tacrythritol from acetaldehyde and formaldehyde inthe presence of sodium or calcium hydroxide Description: Pentacrythritol preparation occurs in a two- step process as follows: Aldol condensation cH,oH OH SOHO GHLCHO “SS HO-CHeG-CH0 CHO Cannizzaro reaction N cHOH CH.OH | CH.O —, HO.CH,-C-CH.OH + HCOOH OH: HOH In this process, both reactions are carried out in separate reactors’ which substantially reduce undesired byproducts formation. The starting materials—acetalde- hyde and formaldehyde— and NaOH solution or milk of lime are dosed into circulating reactors for the aldol condensation, After a defined reaction time, the solution passes a moderation zone in which the formation of pen- taerythritol is completed by the Cannizzaro reaction. ‘The 192 reaction is stopped with formic acid and the excess form- aldehyde steam stripped under pressure and recycled. ¢ formaldehyde-freesclation is evaporated as required for crystallization in a multi-step continuous unit and the crude pentaerythritol crystallized in multistep continuous crystallizing equipment and then continuously separated Yields: The yield of pentaerythritol referred to acetalde- hyde is about 80%. Raw materials and utility requirement: (per metric ton of pentaerythritol) Acetaldehvde (100%), kg «++ 420 Formaldehyde (100%), fag 2020001 1.100 Caustic soda (100), ke» ‘320 Galeium hydroxide (1003), ig’. 400 + In circulation lose to. be testored, kg 200 + Fomle aid (100%) ‘Without splitting, kg ...2.2.2+s.00005 120 Wat aotitingy 0200000 18 Methanol, ke = 30 Steam (10 bar), tone 20022001 15 Steam (20 bar)’ for splitting, tome is Power, kWh 450 Goolitg water” (35° G), 470 Gold water (5° C), mi « o ip ane of the Line procois ‘In care of recycling eatlyat Commercial installations: Plants are in operation in different countries. Usual capacities range between 1,000 ‘and 10,000 tons/ References: Tie Penveerythritols, Belo, B,, R. H. Barth and J. E, Snow, Reinhold Publishing Corp, Chapman & Hall, Lid, London. British patents: 998654, 1025649 and 1085108. November 1977 Hyprooarsow ProcrssinoPhenol —=> ctemicats ur. ano Hercutes inc. Application: A process for the production of phenol and acetone by the oxidation of cumene. Description: Cumene is oxidized with air to produce cumene hydroperoxide which is concentrated and cleaved to phenol and acetone by acid catalysis. After catalyst removal the cleavage mixture is fractionated to purify phenol and acetone products. High purity phenol and acetone is feature of the process design coupled with fhigh product yields (1.34 tonnes of cumene feed will produce 1 tonne of phenol and over 0.6 tonnes of acetone) ‘Design emphasis on reducing energy consumption has resulted in a process capable of utilizing several forms of heating fluids with an over-all energy consumption of less than 50% of earlier generation plants Careful attention is paid to safety aspects using simple but well proven operating techniques and long developed process design parameters. Operating time efficiency can be designed for 350 days/ year. Hyprocazson Paocessivc November 1977 No noxious byproducts are produced and special pre- cautions in plant siting and layout are not necessary. ‘The quantity and total BOD of aqueous effluent is small and organic residues from the process are a useful fuel, The phenol from cumene process was developed simul taneously by BP Chemicals Ltd. and Hercules Inc. over 25 years ago. Commercial installations: Total capacity of licensees’ plants built or now under construction amounts to some 4 billion pounds per annum. Recent licensees include Fenoquimia in Mexico (plant successfully commissi in 1975), Shell Oil Go, (USA) and Yacimientos Petroli- feros Fiscales (Argentina). Several licensees are under- taking expansion and modemization programs. Licensor: Inquiries should be directed to BP Chemicals Ltd,, Licensing Division, Denvonshire House, Piccadilly, London W1X GAY or to Hercules Inc., New Enterprise Department, Wilmington, Del. 19899. 193Phthalic anhydride—sas: a Application: A process for production of phthalic anhydride (PA) from o-xylene and air. o-Xylene is oxidized with air on a supported catalyst in a fixed bed reactor, Filtered ai compressed and passed through 2 preheater. ‘The o-xylene is pre- heated and vaporized by injection into the hot-air stream. The onylene/air mixture passes through the catalyst: filed mult-tube-reactor. The exothermic oxidation to PA fakes place at a relatively low temperature on_a. highly selective catalyst. The reaction heat is uted for steam generation. Only'a part of the produced steam is used in the plant; the excess can be exported. ‘The gases leaving the reactor are prtcooled in gas coolers and then passed to a separation system where PA desublimes in switch condensers which are cooled or heated with an automatically controlled time eycle. During loading the switch condensers are cooled by a heat-transter oil. Affer loading the crude PA is recovered by melting it fzom the fin tubes by circulating hot oil through the con- densers and collecting the molten crude product in a tank. The off-gases from the switch condensers still contain small amounts of byproducts and some traces of PA. For this reason they must be cleaned either ina water scrubber or by catalytic or thermal incineration. "The scrubbing water contains mainly maleie acid, which can economically be recovered by another process developed by BASF. Tn combining both processes there is no waste water to discharge. ‘The crude PA is pumped from the intermediate storage tank into a continuous thermal pretreatment section t0 convert the small amounts of phthalic acid into the 198 anhydride. From there crude PA is fed into the continuous two stage distillation, Catalyst: A newly developed catalyst allows the increase of the o-sylene loading to 60 g/m® air S.T.P. compared to formerly 40 g/m* for the standard catalyst, Thus the maximum capacity of a single reactor can be boosted up to 45,000 mt/yr. of PA. Moreover this catalyst has an extremely low pressure Grop, Substantial saving in energy can be accomplished by using a steam turbine for the blower. The steam required for the turbine can be raised in the reactor. The new catalyst has been successfully operated on industrial scale since over 2 years. Yield and product quality: The feedstock is commer- cial o-xylene of at least 95% purity. The new catalyst for high o-xylene concentration gives yields of 109 kg pure PA for each 10D kg of o-xylene (caleulated as 100% o-xylene content). As byproduct approx. 5 kg of maleic anhydride can be recovered for each 100 kg of PA. Product quality: PA’ 99.99% min Phthalic acid 0.01% max Moaleie anhydride 0.03% max. Benzoie acid 0.02% mae Ge 5 Hazen (APHA) Heat etal 1020 Hazen (APHA) Soli 131°C Licenses: From 1969 to 1976 20 licenses have been granted for the BASF PA process throughout the world for planis with a total capacity of more than 700,000 metric ton/yr. About 40% of the PA produced in the Western world from o-xylene is obtained by BASF process. November 1977 Hyprocaraon ProcessiePhthalic anhydride—sone.roune s.a Application: A process to produce phthalic anhydride from o-xylene and air. Description: o-Xylene is mixed with air and oxidized in 2 catalyst filed tubular reactor. After cooling in two heat exchangers, the gases are sent to a set of switch condensers to condense phthalic anhydride in the solid form. After melting, phthalic anhydride is submitted to a heat and chemical treatment and then purified in a continuous ‘two steps refining section. ‘The original catalyst and technology developed by Rhéne-Poutienc enables in the safest conditions, the oxida- tion of unusually concentrated o-xylene in the air feed. For a given phthalic anhydride capacity, the necessary air-quantity is much smaller than for conventional pro- cesses, as well as pressure drop. Of ‘course the oxidation and condensation vessels are smaller than usual processes, and consequently investment cost ‘The heat of reaction is used to generate high pressure steam which is used to drive the air blower through © back pressure steam turbine, which delivers medium pres- sure steam, a fair quantity of which is exported outside the plant, The main energy consumer of the process which is alr compression docs not require electricity. Only 150 kWh/ton of phthalic are required where 1,000 kWh/ton are necessary with the conventional routes. 3.5 ton of 160 psi steam are exported for one ton of phthalic anhydride. No pollution: After condensation, the process gases still contain organics (anhydrides, aldehydes, hydrocarbons) Hyprocarnon Processic November 1977 and carbon monoxide. Apart of the onganics (acids anhydrides and water soluble materials) can be removed by water scrubbing. For large plants, maleic anhydride or fumarie acl canbe recovere! fom this ac soltion y using Rhéne-Poulenc technology. For small plants suc! recovery is not economical. Even after scrubbing, the gases remain dangerously polluting. Rhéne-Poulenc has developed a catalytic system for the complete low tem- perature oxidation of the waste gases. No fuel is required, the reaction being thermically self sufficient. All the light products coming from the refining section faze burnt in the above mentioned device. Heavy impuri- tics are delivered either as solid pellets or molten material and burnt. Yields: 225 kg of pure o-xylene yield 1,000 kg of pure phthalic anhydride Product quality: Purity is better than 99.9% and solidi- fication point higher than 131°C. Commercial installations: Rhéne-Poulene operates 3 plants in France, and have licensed + plants in the Philip- pines, Spain, South Korea and Turkey. The Chauny, France (40,000 tons/yr.) and the Reposa, Spain (30,000 tons/yr.) are the largest single line plants known, Total installed or licensed capacity is 150,00 tons/yr. References: Hydrocarbon Processing, February 1974; Chem. Engr., March 1974; Information Chimie, October and December 1973. 195Phthalic anhydride—vow neve Application: Production of phthalic anhydride from o-xylene or naphthalene by choice of catalyst or a special catalyst for both feedstocks. Product: Phthalic anhydride (PA) content 99.9%; maleic anhydride max. 0.059%; benzoic acid max, 0.059%; Colo 5-10 Hazen (APHA); Heat Test: 10-20 Hazen; Solidi cation Point: 131°C. Description: Filtered and compressed oxidation air of 7-10 psig is heated to 140-160° C and loaded with evapo- rated naphthalene or o-xylene, ‘The mixture of naphthalene or o-xylene enters a re~ actor with vertical tubes holding the ballshape or granular catalyst, A salt melt circulating around the tubes removes the heat of reaction and maintains constant temperature conditions, The reaction heat is utilized for the generation of high pressure steam. The reactor effirent containing PA vapors is precooled in a waste heat boiler generating steam. By further cooling PA is then sublimated in specially designed finned tube switch condensers with optimal efficiency and safety. The crude PA deposited on the condensing surfaces is period- ically melted and discharged into a tank. The effluent gas is discharged to atmosphere after water scrubbing or incineration. The crude PA is pretreated thermally under atmospheric or reduced pressure, from where itis supplied to either a batchwise or a continuous vacuum distillation 196 system. Low and high boiling impurities are removed and the pure PA is obtained as a distillate which can be stored either in the molten state or flaked and bagged. Yields: Depending upon feedstock quality, 105-109 Ibs. PA per 100 Ibs, o-xylene; 94-98 lbs. PA’ per 100 Ibs. naphthalene. ‘A newly developed catalyst is recommended for both feedstocks or mixtures which yields 92-95 lbs. PA per 100 ls, naphthalene or 101-103 Ibs. PA per 100 Ibs. of e-xylene. Three commercial plants are using the new catalyst Economies: Commercially proven catalyst life is more than 3 years. Maintenance charges are about 29 of plant equipment investment, Single reactor capacity: up to 80 million Ibs,/yr. Onstream factor: 98-8996, Commercial installations: Up to the present time, 65 commercial plants with an installed capacity of more than 1,000,000-metric-tons-per year using the von Heyden process have been erected or are under construction. Forty-one of these operate on o-xylene basis. The licensor of the von Heyden process is PSA- LIZENZVERWERTUNGSGESELLSCHAFT (a joint venture of Chemische Fabrik von Heyden GmbH and Wacker Chemie GmbH, Munich) and world licensees are Davey Powergas GmbH, Colonge and Lurgi Min- eraloltechnik GmbH, Frankfurt/Main. November 1977 Hyprocarnon ProcrssinePolyacetal resins—enco sa. Appl anh ion: A process for continuous production of lrous formaldehyde, its polymeriaztion and stabiliza- tion to heavy-duty products. Description: Paraformaldehyde is obtained from for- ‘malin and dried. It is pyrolized to gaseous formaldehyde, purified from active produets on the polymerization cata- lyst, obtaining polymerization grade monomer. Polymerization of formaldehyde takes place in a reactor in concentrated slurry phase with the production of poly- coxymethylene diol with controlled structure. This is pos- sible with the use of modifiers ‘The raw polymer is then thermally stabilized following 2 etherification reaction by using a simplified technology, In this way several grades of polymer are available, with unusual thermal and alkali resistance and with typical ‘mechanical properties of tie acetal homopolymers. In final stages of the process antioxidants, stabilizers and pigments are introduced in order to get commercial grades for specific and general purposes. Inert diluent is purified and byproducts removed in an ancillary unit of the plant: Commercial installation: A 10,000 metric ton/yr. plant is planned for 1977 with startup in 1979 at S. Eufemia Calabria, Italy. ‘Hyprocarnon Processine November 1977 Raw material and utiliti product) Aqueous formaldehyde, Ib 85. Catalysts and chemicals, US. ¢ Bleetrie paves, kwh : (per pound of end- Steam, B Inert gas, Nit Cooling water, int CCompresied si, Nat oar Product properties: tn UNIT. Injection Extrsion “Tensile strength Kefet 700 700 Elongation at break ‘% 3 50 Taod impact strength notch Kgcm/em 7 10 Flexural strength Keven 0501080 Fleroral module Keven’ 901000 30,000 Hardness (Reckrell) ® 120 120 Heat dsortion ine Keven! *c 120 20 Heat dtortion ts Kye “c 0 170 Melting point (crt) ‘c 178 Specine weight Grfem® wee no change in properties hemical resistance o iter montis ("Room temp.) = (Water and died lla solution) References: The process steps are covered by 50 domes- tic patents and 250 foreign patents concerning all phases of the process including production of paraformaldehyde. 197Polyacetal resing—uver woustas, uo. Application: A slurry process in hydrocarbon diluent for the continuous manufacturing of polyoxymethylene- copolymer from formaldehyde and a cyclic ether with catalysts, Description: Formaldehyde is produced by the dehydra- tion and decomposition of hemiformal, derived from formalin and an alcohol. This gaseous formaldehyde is highly purified and absorbed in a hydrocarbon diluent. This formaldehyde solution is fed into the polymerization reactor with o cyclic ether and catalysts, to obtain a copolymer in slurry state. Molecular weight and comonomer content of the co- polymer are easily controlled by the respective selection of reaction conditions. ‘The copolymer is stabilized by the unique technique to obtain a excellent heat-resistant finished product. The solvent is purified and recycle. Raw materials and utilities: (per metric ton of end produet) Aqueous formaldehyde (379), tons 3.0 Catalysts and chemicals, yen . 51,000 Electric power, kWh 1,900 Steam, metric tons . 178 Gooling water, m* 1,000 198 Product properties Tensile strength, kg/cm? 590 Elongation at break, % ...0esceecccceee 36) Tensile modulus, kg/cm? ~ 21,300 Flexural strength, kg/cm? comp tame «BAO Flexural modulus, kg/em* 22,900 aod impact strength, kgvem/em (notched). 6.8 Heat distortion temperature, °C. 15 Hardiness (Rockwell), R-scale .. 19 ‘The finished copolymer shows high mechanical strength, superior thermal stability and excellent behavior in injec- tion molding. Commercial installation: A 10,000 metric ton/yr. plant is planned at Ube, Japan. References: The process steps are covered by 25 domes- tic patents and 42 foreign patents including production of a comonomer and purification of formaldehyde. November 1977 Hyprocarnon Procsssinecis-Polybutadiene—emues erect co. Application: A solution polymerization process for the continuous production of a high cis content polybutadiene rubber from butadiene. Description: The cispolybutadiene rubber process con- sists of four basic steps. They are (1) butadiene and solvent purification, (2) reaction and concentration, (8) blending and solvent removal and (4) drying and packaging. Butadiene low in acetylenes and other polar catalyst poisons is dried by fractionation and mixed with a solvent that has also been dried by fractionation. ‘This fresh stream is mixed with a recycle stream of butadiene and solvent from the concentrator step, and catalyst is added at a controlled rate to the total stream before it enters the reactors, The catalyst is varied as necessary to obtain high conversion of butadiene and to control Mooney viscosity of the polymer. The solvent-to- monomer ratio in the reactor train is chosen to give a low enough solution viscosity so conventional reactors can be used. A number of reactors are used in a train to give desired residence time. A suitable shortstop and antioxi- ‘dant are added to the polymer solution as it leaves the reactors. Any unreacted butadiene and part of the solvent are removed in the concentrator before the polymer solution is blended. ‘Hyprocarson Procrssinc ‘Novembér 1977 Polymer solution blending can be used to control the polymer Mooney viscosity at the desired level before removal of solvent in stream strippers. The water in the stripper overhead product is decanted and recycled to the strippers. The crumb-water slurry from the strippers is pumped to the drying area, ‘Water is removed {rom the crumb with a shaker screen followed by extrusion drying. The dry rubber is moved by a spiral conveyor to weigh scales and into a baler. Bales are passed through a metal detector and are film wrapped and placed in suitable packages. Operating conditions: The cis-polybistadiene process can be used to produce a polymer with any desired vis- cosity in the range of 90-70 ML+f, although the polymer ordinarily is produced in the 42-48 MI-# range. Reactor cooling is necessary for highest product quality Yields: The over-all conversion of butadiene to cit polybutadiene is ordinarily over 98%. Commercial installations: Seven plants with an approx- imate total annual capacity of 325,000 tons/yr. including plants located in France, Germany, Italy and Japan. 199Polybutenes—cosoe recmotosy, Application: Process for manufacturing liquid polybutene (polyisobutylene) from mixed C, hydrocarbon streams containing isobutylene. Products range in molecular weight from 300 to 2,700 and in viscosity from 40 to 30,000 Ssu at 210° F. Description: The feed stream to the process usually con- sists of a mixture of C, olefins and paraffins resulting from cracking or dehydrogenation operations. Streams from refinery catalytic crackers and from naphtha crackers are commonly used. Any C, and C components which may be in the feed are removed by distillation to minor con- centrations. ‘The feed must be reasonably low in contaminants, par- ticularly sulfur compounds and water. For this reason, the feedstock is usually treated for the removal of mercaptans, water washed and dried by distillation. Following preliminary treatment, the feed is pumped to the reactor, where liquid-phase polymerization occurs. Aluminum chloride catalyst is added continuously as a polymer slurry. The heat of reaction is removed by me- chanical refrigeration, In the reaction which takes place, isobutylene is preferentially converted to polymer, and lesser amounts of normal butenes are polymerized as well. ‘The reactor temperature and catalyst concentration are the primary means of controlling product properties. Removal of catalyst is achieved by an alk: followed by a water wash. wash 200 Inc. ‘The mixture emerging from the final wash consists of Cy hydrocarbons, specification polybutenes and light polymers. Separation is achieved in three steps. Firs, the butanes and unreacted butenes are removed by distillation under pressure. The overhead stream is essentially free of polymer and is suitable for further processing such as alkylation, polymerization and LPG production. When feeds containing high concentrations of isobutylene are used, part of the debutanizer overhead is recycled to the reactor. Second, the debutanizer bottoms stream is flashed at atmospheric pressure for the removal of low-boiling light polymers and traces of butane, Finally, the remaining light polymer is separated in a vacuum stripper in order to mest flash and viscosity specifications on the finished product. Following filtration, the vacuum stripper bottoms is sent to storage to await shipment in drums, tank trucks or tank cars, Polybutene has a number of important industrial appl cations, These products are used in the manufacture of caulking and sealing compounds, lube oil additives, electrical insulating oils, adhesives and countless other specialty applications. Commercial installations: The Cosden polybutene pro- cess is utilized in six commercial installations throughout the world, November 1977 Hyprocarnow ProczssincPolybutadiene — svamrrocem Application: A process for producing an extremely high cix-polybutadiene, showing improved processability and dynamic mechanical properties, using & highly efcient temary catalyst system based on depleted uranium com- pounds and operating in aliphatic solvent. Description: Fresh monomer is dried, separated from the polymerization inhibitor and fed to’ the polymerization fine along with the recycle solvent and the catalyst. The polymerization occurs above 40° C and can be performed at 95% monomer conversion, After the polymerization line the rubber solution is washed with 2 water solution of a complexing agent to Temove the catalyst residues, antioxidant added and homogenized in a blender, The rubber solution is then sent to the stripping section where a crumb slurry of solvent-free rubber is obtained. The overhead stream con- sists mainly of solvent and unreacted monomer, The solvent, distilled and dried, is recycled to the polymeriza~ tion line, while the unreacied monomer is sent back to its production line, Rubber crumbs, separated from water on a vibrating screen and dried, are then sent to baling and wrapping. ‘The uranium residues and the complexing agent in the water coming from the waohing and sipping sections Se recovered. The complexing agent is recycled while the cake of catalyst residues, conisining uranium oxides, is collected and sent to supplier for retreatment or disposal. ‘The uranium content in the rubber and in the waste water is extremely low and is controlled to comply with the most-demanding up-to-date requirements. ‘Hiyprocannon Proczssinc November 197 Raw materials and utility consumption (per metric ton of end-product): Butadiene (100%), bs Cataiyet and cherneals, Bette power, bh Cooling water, mt Process water, i Z eo en Product main properties: j,é cir content up to 999%; Mooney viscosity good control in a wide range of grades, total ash (% wt) < 0.1, Uranium content in the rubber (opm) < 30, and vals (fo we) < 05, Wwing to the extremely high cis-tacticity and to the favorable molecular weight distribution this rubber shows ‘an improved processability in respect to the existing poly- utadienes; the millability, the calenderability, the tacki- nes and the green strength are substantially improved land allow this polybutadiene to be processed without any unnecessary blending with other elastomers. Mechanical nd dynamic properties are significantly better than the Conventional cis-polybutadienes. Other characteristics, of this polybutadiene, such as abrasion resistance, friction coefficient, ageing resistance etc., are comparable to the best commercial polybutadienes. References: Ital. P. 946.105 (1971) ; Belg. P. 791.709; Bat, P. 1.406.461, 1.406.463, 1406464; Canad. P. 987-441; Ital, P. 971.308 (1972) ; Belg. P. 807.904, Brit P, 1.426635; Rubber chem. & Technol, 47, 1175 (1974) ; ‘Makramol. Chem, 175, 2021 (1974); ibid, 175, 2029 (1974); Angew, Makromol. Chem., 50, 87 (1976) ; ibid. 50, 101 (1976) ‘The process has been developed by the SNAMPRO- GETTI for ANIC, owner of the process. 201Polyester—torcisr ac Application: A process to manufacture polyethylene terephthalate (PET) from dimethyl terephthalate (DMT) or terephthalic acid (TPA) and ethylene glycol (EG). Description: The polycondensation is done by batch or continuous process depending on the users’ requirements such as capacity, types in the production program, ete. When starting from TPA the first step of forming the polymer is the esterification with EG to diglycol tereph- thalate (DGT), DMT is transesterified wth EG to DGT accordingly, The methanol set free in this step, can be sold or re-used in a DMT-plant. Under controlled temperature and vacuum the DGT condenses to polyester in agitated reactors. The polyester ‘melt is cooled and granulated to chips. (For spin fiber production the melt can be fed directly to the spinning machine, too.) 202 Raw materials and utilities (per 1,000 kg polyester chips-batch process) Dimethyl terephthalate, ky... ese. 1,050 Ethylene glycol, kg... 400 Methanol recovery, kg 330 Steam, kg $00 Cooling water, m? 2.2... 150 Blectricity, kwh ee. ceceeeececeeees 260 BBnel OP bead sll Sa tals bys el eva rge th Inert gas, Nm* sil «a ad sem Compresed air, Nm* ....... = 0 Commercial installations: Plants with a total capacity of approximately 450,000 tons/yr. are onstream (end of 1977). References: Further information is available from Hoechst-Uhde Corp., 560 Sylvan Avenue, Englewood Cliffs, N.J. 07652, and Uhde GmbH, Deggingstrasse 10-12, 4600 Dortmund 1, Federal Republic of Germany. November 1977 Hyprocarson ProcessinoPolyesters—mvaa ac Application: Processes for the production of polyethylene terephthalate (PET), starting from ethylene glycol (EG) and terephthalic acid (TPA) or dimethylterephthalate (DMT). Description: The conversion of monomers into polymer is a two-step batch process where the intermediate prod- uct is a low molecular precondensate. EG and TPA (DMT) together with additives are fed into the trans- esterification reactor under atmospheric pressure, pro- ‘gramed temperature raise and stirring, Water (methanol) is separated from EG on the top of the column under reflux, The reaction is completed with a certain excess of EG and the precondensate is transferred through a filter to the polycondensation reactor. Catalyst and other addi- tives are introduced and polycondensation reaction is carried out under stirring, raising temperature and vacuum, EG is separated through a highly efficient con- denser system, When the desired viscosity is reached, the polymer mass is extruded rapidly into strands and cut into chips under protecting cooling water. The wet chips are stored and dried in a fluidized bed type drier. A similar process is available where multiple polycon- densation reactors receive the precondensate ftom 2 con ‘Hyprocarson Processinc November 1977 tinuously operating transesterifieation step. Continuous transesterfication and continuous polycondensation allow the production of chips and/or direct melt spinning of fibers and filaments without intermediate solid phase. The single batch process standard capacity is 15 tons/ ontinuous or fully continuous lines day while the semi. are available in a large range up to 80 tons/day. Raw material costs are kept the lowest by suitable recycling steps for EG and fiber waste, The high degree of instrumentation and automatization ensures a precise plant operating with minimum labor cost. Polyethylene terephthalate is a suitable feedstock for a wide range of products, such as textile yarns, staple fiber, trecord and fabric, film and plastic materials, Commercial installations: More than 40 plants are in operation or under construction in Bulgaria, Republic of China, Great Britain, India, Ireland, Japan, Luxem- bourg, Nigeria, Pakistan, South Africa, Switzerland, Thi land, Turkey and Venezuela, Total licensed capacity is ‘more than 280,000 tons/yr. Licensor: Inventa AG 203,Polyethylene (LD) —«« Application: A process for the production of low density polyethylene by high pressure polymerization in a tubular reactor. Description: Ethylene feed is compressed to 200-300 kkg/em* by a multiservice compressor together with ethyl- ene from the low pressure recycle, containing chain transfer agent. After mixing with oxygen and with ethyl- ene coming from the intermediate pressure recycle, the gas is compressed to a final operating pressure of 3000- 2600 kg/em? by a hypercomprestor. ‘The high pressure compressed gas is fed into the jacketed tubular type re- actor together with peroxide when this kind of initiator is used, too, ‘The reaction heat is recovered as low pressure steam delivered at battery limits ‘The polymer-ethylene mixture is then expanded through a special let-down valve in order to separate the polymer from unreacted ethylene. The latter is cooled, purified from low molecular weight polymers (waxes) and recycled to hypercompressor suction, The polyethylene is further expanded to a lower pressure to release the ethylene stil dissolved. The gas released is cooled, purified from waxes, partly purged to prevent the build-up of contaminants, and recycled to the raultiserviee compressor station. ‘The degassed polymer is pelletized in a conventional pelletizing extruder where antioxidant and slip agents are added by proportioning pumps. The polymer pellets are then dried and collected in an analysis silo where the product is analyzed. After the analysis, the polymer is blended in a gravity blender and pneumatically conveyed to the storage and bagging section 204 Yields: Conversion up to 26% per pass is obtained, Products: A large range of grades with melt flow index ranging from 0.15 to 20 and density from 0.918 to 0.926 is produced with this process and marketed. High film grade quality is achieved without any. polymer” repro- cessing. Grades modified with vinyl-acetate can also be produced. Black compound technology is available. Economies: The following consumption data refer to mete fon of blended pelletized polyethylene. Ethylene (99.9% vol.), tons os 8 Electric power, kWh + 950-1000 Steam (25 kg/em*), tons 06 Cooling water (AT= 10°C), mt 130 Process Water, 1016 oes seeeseeeeseee 02 Catalyst and chemicals, $US. 0.2.0.0... 28% Recovery of steam (4 kg/em*), tons..... 08 * Depending on the grade produced Commercial installation: ANIC has 3 lines with a total capacity of 135,000 MTA (of which 80,000 MTA in a single fine). Other three lines for a total capacity of 110,000 MTA have been licensed in Algeria and Romania, Reference: Further information is available from Snam- ep. 4169/2010 Milano. November 1977 Hyprocarson ProcessinPolyethylene (LD)—asco/roumess, we Application: A process for the production of low density polyethylene and copolymers using free radical initiators at high pressures (1,800-3,000 atm) in a tubular reactor. Description: Fresh ethylene feed, with a purity in excess of 99.89%, is mixed with purified low pressure recycle. Initiator and chain transfer agents are added to the mixture, which is then compressed to 300 atm. This feed js then mixed with high pressure recycle and compressed to polymerization pressure in a hypercompressor and is continuously fed to a tubular reactor, wherein a portion of the ethylene is polymerized. Conversion is in the range ‘of 23-2696, depending on product type. Upon leaving the reactor, the ethylene-polyethylene mixture is expanded and enters a primary high pressure separator and, subsc- quently, a secondary low pressure separator. The ethylene from the two separators is cooled and dewaxed indi- vidually and recycled back to the appropriate compressor. ‘The polymer leaves the secondary separator and feeds an extruder where it is pelletized, cooled and conveyed to storage silos. ‘Hyprocarson Processinc November 1977 Raw materials and utility consumption: (Per metric ton of pelletized polyethylene) — Ethylene (tons) 1.020-1.080* Utilities: Steam, tons 0.600-1.000 (35 atm) * (0.600-1.000 ( 7 atm) generated* Cooling water, m* 150-180* Electricity, Kwh — 1,195-1,397* * Depending on the product type Commercial installations: ARCO Polymers is operating fa plant in Port Arthur, Texas, with a capacity of 400 MM lbs./yr. and has licenses in Italy and Argentina, Reference: ARCO Polymers, Inc., 1500 Market St., Philadelphia, Pa. 19101. 205Polyethylene (LD) — «te came Application: A process for the production of low density polyethylene grades covering all the applications of this product, by high pressure polymerization of ethylene in a tubular reactor using gaseous oxygen as an initiator. Description: Fresh ethylene, mixed with ethylene from ‘the low pressure recycle where initiator and chain transfer ‘agent are added, is first compressed to about 300 bars in a ‘multistage compressor. The feed combined with the me- dium pressure recycle is further compressed in a secondary compressor up to the actual reaction pressure (i.e, above 1,800 bars), before entering the jacketed tubular reactor consisting chiefly in three zones: preheating, reaction, and cooling, The discharged ethylene-polymer mixture is expanded through a special let-down valve and undergoes separation in two steps. After leaving the primary separator the medium pres- sure stream (mainly unreacted ethylene at 300 bars) is cooled and freed from waxes before being recycled to the secondary compressor. A second, so called low pressure separation ensures the recycle to the booster comprestor of the remaining tuncon- verted ethylene and the feeding of the production extruder with degassed polymer. 206 Yields: Conversion rates higher than 22 percent are achieved for the whole range of grades. Economics: Requirements per ton of pelletized poly- ‘ethylene are: Ethylene, tons : ee tons x: 1030) Chemicals, FFF (including compressor oils) ..8 to 10 Additives, FF¥ (average) «2... .c.c.2.2,+.5t0 12 (depending upon formulation) Utilities Steam, tons ..... eae an OS. Cooling water, m* s 150 Electricity, kwh 1,060 * French francs, 1977 conditions. Commercial installations: A process capacity of 890,000 tons/yr. including: 9 lines with an aggregate capacity of 360,000 tons/yr. operating at ATO Chimie's facilities in France (among which a single line of 75,000 tons/yr. started late 1973) and 10 lines under license totaling 470,000 tons/yr., in 6 countries: Spain (160,000 tons/yr. with a single line of 85,000 tons/yr. on stream in 1977) ; North Korea; India; Bulgaria; Poland and Yugo- slavia Licensor: ATO Chimie, November 1977 Hyprocarson ProcrssinePolyethylene (LD)— ou on cismens co. Application: A process for high pressure polymerization of ethylene using organic peroxides as reaction initiator. Description: Ethylene feed mixed with purified recycle is compressed to about 9,000 psi. It is then mixed with chain transfer agent and intermediate pressure recycle, and compressed in a secondary compressor to about 15,000 to 25,000 psi. It then enters a stirred autoclave reactor where initiator is added. Product leaves the reactor through a pressure control valve, and enters the primary separator. Here it is split into a gas and molten polymer. The gas phase, which is mostly unreacted ethylene, is cooled, passes through filters to remove waxes and is recycled ¢o the secondary compressor. ‘The molten polymer goes to the secondary separator where pressure is reduced to near atmospheric. The gas from this separator is purified and returned to the primary compressor. The molten polymer feeds into a pelletizing extruder, pellets are cooled and dried. Hyrocarnow Processine November 1977 Yields: Conversion per pass is 10-20%, depending on type of product. Economics: One ton of pelletized polyethylene requires the following: Utilities High pressure steam (400 psig) = -250 Ibs. Low pressure steam (50 psig) 1,000 tbs. Cooling water # 60,000 gals. ‘Make-up water . 800 gals. +--0.5 MM Btu a «1,500 kwh * Depending on the type product made. Fuel for oil heater Power Raw materials Ethylene 2,020 Ibs. Initiator - Up to 4 Ibs* Antioxidant Up to 3 Ibs.* ‘Hydrocarbon solvent --10 gals. Commercial installation: Gulf has two plants with « total capacity of over 400,000 tons/year. There is one plant under license producing 100,000 tons/year. 207Polyethylene (HD) —sorcis: ac Application: A process to manufacture high density polyethylene moulding powder or pellets at low pressure from ethylene, Description: Ethylene in addition with optionally small amounts of comonomers is continuously fed with catalyst and hydrocarbon diluent into largecsize polymerization reactors. The reaction takes place in a slurry and the polymer is obtained as powder. The polymerization nor- mally runs at pressures below 10 bar and temperatures between 80° and 90°C. The catalyst used in the reaction has a very high activity. Therefore, in large scale use the catalyst is added in such small quantities that there is no need for removal of catalyst, Due to almost complete conversion of ethylene, this process does not require any ethylene recycle or monomer recovery system. Most of the hydrocarbon diluent is removed from the polymer. Drying is performed in a closed circuit nitrogen drier like a fluidized bed drier. ‘The free-flowing HDPE powder with bulk densities between normally 400-440 kg/m? is pneumatically con- veyed and stored in powder bins where additional han- 208 dling like homogenizing can be performed. The HDPE powder can be used as such for further processing or it can be pelletized to natural colored or specifically modified ‘grades according to a variety of formulas available Raw materials and u powder) Ethylene and comonomers, kg Hydrogen, kg Hydrocarbon diluent, kg Catalyst (basis July 1977), DM (Staman Regie actis aed cnn Cooling water, m* i Electricity, kwh Nitrogen, Nm? ities (per 1,000 kg HDPE Commercial installations: Plants with a total capacity of 750,000 tons/year are onstream (mid-1977) ; further 35,000 tons/year are under construction, References: Further information is available from Hoechst-Uhde Corp., 560 Sylvan Ave., Englewood Clifis, NJ. 07682, and Unde GmbH, Deggingstrasse 10-12, 4600 Dortmund - 1, Federal Republic of Germany. November 1977 Hyprocarnon ProcessinePolyethylene (HD)—wa?racume Application: A process for high and medium density polyethylene manufacture from ethylene in the gas phase with high efficiency Ziegler type catalysts. Description: Ethylene is polymerized by reacting with catalyst particles in a fiuid bed reactor at 60 to 100°C under @ pressure between 15 and 30 bar. The reaction heat is removed by circulating the gas through 2 heat exchanger then compressing it for recycling to the reac- tor. The polymer is growing on the catalyst particles in- jected in the bed and is discharged in a gas separator ‘vessel where residual monomer (less than 3% by weight) is removed and recycled. For commercial grades of poly- ethylene, hydrogen is introduced in the circulating gas to control molecular weight. ‘Supported titanium and magnesium containing catalysts are used in this process. Very high yields are obtained and catalyst removal is not needed. The polymer is a free- flowing powder which can be fed directly to processing machines. A very broad range of polymer is achieved due to the outstanding versatility of the Ziegler type catalytic formulations used for obtaining narrow or lange molecular ‘weight distributions. High or medium densities are ob- Hyprocarnon Processivc November 1977 tained through homo or copolymerization, and high or ow melt indexes through control of molecular weight (by adjusting hydrogen content during the reaction) . Products: Polyethylenes having densities from 0.935 to 0.965 are obtained with conventional high density poly- ethylene broad molecular weight distributions or with very narrow molecular weight distributions. Economies: (per metric ton of polyethylene powder) Bihylene, kg 4,005-1,205 Comonomer, kg at dee cen BO Catalyst materials, French Francs 40-50 Electricity, kwh ger eaeniees 270 Steam, tons ...s.2c0+ ra 03 Inert gas (nitrogen), Nm* a 50 Cooling water, m* (make up) ...++-+ 37 Commercial installation: One plant is in operation at Lavera, France, Reactors of 80,000 tons/yr. capacity are best suited for application of this process. 209Polyethylene—rmurs rxrossun co. 210 Application: A relatively low-pressure process for the continuous production of polyethylene from ethylene of 99%" purity. Description: A solid catalyst is introduced into a reactor containing high purity ethylene and diluent, The product is withdrawn from the reactor and separated from a diluent, No catalyst removal is required because of the high productivity of the catalyst. The polymer in the form of a powder is fed to the extrusion equipment with selected additives to be sold in the form of pellets. ‘Temperatures and pressures in the system are moderate and the diluent is recovered and recycled to the reactor. Ethylene conversion is upwards of 979% The process, by virtue of its simplicity and reliability, makes for easy operation and high service factor. ‘The product covers the full range of density require- ments from 0.925 to 0.96 gm/ec and fills all market applications. Commercial installations: Soltex, Deer Park, Texas; Allied Chemical Corp., Baton Rouge, La.; National Petro Chemicals Corp, Deer Park, Texas; Phillips Petroleum Co,, Pasadena, Texas; Union Carbide Corp., Seadrift, Texas; Chemplex Co., Clinton, Towa, and Gulf Oil Corp., ‘Orange, Texas. Licensees also in England, Belgium, Brazil, France, Germany, Italy, Spain, Japan, Yugoslavia, Nor- way and Iraq. November 197 Hyprocaruon ProcessinePolyethylene (LD)—sazors Application: A process of high-pressure polymerization of ethylene initiated by oxygen and/or peroxides. Products: Granulated polyethylene, density and melt fow index in the 0.916-0.930 g/cm? range and 0.2-20 g/10 ‘min, range. Description: Ethylene feed, mixed with low-pressure recycle gas, initiator and modificator, is compressed to about 250-300 bars and added to the high-pressure recycle gas. This mixture is brought to its actual reaction pressure (about 2,500 bars) by a hypercompressor and fed into the jacketed tubular reactor, in which preheating, reaction and cooling of the gas occur. ‘The exothermic polymerization reaction is controlled by max. temperature and polymerization pressure After passing the so-called reactor valve, the polymer is separated from unconverted reaction gas in the primary separator, After passing the so-called product valve, the polyethylene melt is separated from remaining gas in the secondary separator. On its way back through the recycle system, the non- reacted ethylene is cooled and separated from oil and waxes. A small amount of low pressure recycle gas is purged from the process to a certain level of inerts. ‘The polyethylene from the secondary separator is gran- ulated in an extruder, in which it is also possible to homogenize the melt and incorporate additives. The cooled and dried polyethylene pellets are filled into a Hyprocanson Processivc November 1977 INDUSTRIEBAU_ GMBH hopper for the purpose of simultaneous analysis and further degassing, Yields: By this process, conversions of more than 25% per reactor thruput can be achieved Consumption: For 1,000 kg polyethylene granulate: (Average values for types in common international usage) Ethylene (99.9 vol. $4), tons 1.03 Electric energy, mvh 10 Steam, Geal - 06 Cooling water, m* 240 Commercial installations: At Nvopolotsk, USSR, a ‘one-line plant with a capacity of 50,000 tons/yr. USSR: Plants with a production line capacity of 75,000 t/p.a. and 120,000 t/p.a. are being planned. VEB-Leuna, GDR, a plant with a capacity of 25,000 t/p.a. VEB-Leuna, GDR, a plant with a line capacity of 60,000 t/pa. is being installed The POLYMIR-process licensed by V/O Licensintorg, Moscow, was developed by Produktionsvereinigung “Plastpolymer,”" Leningrad/USSR, and by VEB-Leuna- Werke “Walter Ulbricht” Leuna/GDR. One license for the construction of plant, operating by this process, was siven to Salagitter Industriebau Gesellschaft mbH, F-R.G. auPolyethylene (HD)—wmow carsive cone. Application: A gas phase process for the manufacture of high density polyethylene (HDPE) from ethylene. Description: A full commercial range of high density polyethylenes is made in a fluidized bed using supported, chromium-containing catalysts, The product is in dry, free-flowing granular form having ‘particle diameters averaging /4 millimeter and is substantially free of fines. Bulk density averages near 500 kg/cubic meter, Melt index and molecular weight distribution are controlled by catalyst selection and by choice of operating conditions. Polymer density is controlled by comonomer incorporation, High catalyst efficiencies eliminate the need for catalyst removal All unessentials are eliminated from this provess which results in extremely low levels of environmental pollution, eliminates potential fire and explosion hazards and makes the process easy to operate and maintain, A reactor with single-line capacity of 90,000 tons/year is in service and a 105,000 tons/year reactor is now being engineered, Gaseous ethylene, comonomer (as required) and dry catalyst are fed to a reaction system consisting of a fluid- bed reactor, cycle compressor and cycle cooler. The renc- tion occurs at below 300 psig (21 kg/cm*) and 85 to 105°C, depending upon the product desired. Circulating gat fuidizes the bed of growing polymer, provides mono- mer for the polymerization reaction and acts as the me- dium for heat removal. Heat of reaction is removed by cooling the circulating gas in a conventional heat ex- 212 changer. A standard, single-stage centrifugal compressor circulates the gas Granular product flows intermittently into the product discharge tanks. ‘The material entering the product dis- charge tanks is 95% polymer and 59% monomer by weight. Raw materials and utilities consumption: (per metric ton of granular polymer) Ethylene, kg* 1.020-1,000 Comonomer, kg, 10 Catalyst materials, § U.S. 4.0-6.5%* Steam, Negligible Electricity, kwh 260 Cooling water Negligible** Nitrogen, NM? 50 Assumes recovery of recompressed monomer and ex- cludes solids handling losses downstream of polymeri- zation. #*Catalyst material costs depend on the specific catalyst species. ##*A water-cooled reaction cycle cooler could be used in lieu of the ait-cooled heat exchanger shown. Products: Polymer density is easily controlled from 0.94 to 0,966 g/em?, Molecular weight distribution from nar- row to extremely wide. Commercial installation: There are 6 commercial plants and licenses have been granted for 3 more. November 1977 Hyprooarsow ProcxssinoPolypropylene —Hocts ac Application: A process to manufacture polypropylene homo or copolymers from propylene. Description: Propylene and, if required, ethylene as comonomer are fed into large-size polymerization reac- tors containing catalyst and alkyl aluminum activator sus- pended in a hydrocarbon diluent, Pressures up to 10 bar and temperatures between 55° and 65° G are being ap- plied. The polymer slurry is subsequently treated with alcohol for catalyst decomposition and extraction. Me- chanical removal of the major portion of the hydrocarbon diluent is followed by stream treatment to remove and recover the remaining hydrocarbon diluent. The product is then mechanically dewatered and dried with hot air. The polymer powder obtained can be homogenized and formulated in pneumatically operated powder bins and be used as moulding powder for some applications, On the other hand, it can be processed to natural, colored or specifically modified pellets according to a variety of formulas available. ‘The hydrocarbon diluent separated during the process is purified in and low-boilers are removed. olvent distillation, low-molecular polymers Hyprocarson Processic November 1977 Raw material and utilities (per 1,000 kg polypropylene powder) Propylene, kg 1,040 ‘Hydrogen, kg a. o1 Catalyst and chemicals, DM. .......2.0264 7 (basis April 1975) Hydrocarbon diluent, kg ..... sahtien e180 Alcohol, Bg ....eeseeeeee 10 Steam (20 bar), kg 1,300* Steam (3 bar), kg 1400" Cooling water, m* pereeyre 200 Electricity, kwh ..... : ee 200 Demineralized water, m? 1 Nitrogen, Nm* 40 *Incl. alcohol recovery. Commercial installations: Plants with a total capacity of 400,000 tons/year are onstream (mid-1977) ; further 40,000 tons/year are under construction. References: Further information is available from Hoechst-Uhde Corp., 560 Sylvan Ave., Englewood Cliffs, NJ. 07632, and Unde GmbH, Deggingstrasse 10-12, 4600 Dortmund - 1, Federal Republic of Germany. 213Polypropylene—nontwtson spac) NUTS Application: A continuous process to manufacture poly- propylene homopolymers and copolymers without catalyst removal using High Yield-High Stereospecificity Catalyst (HY-HS Catalyst). Description: Propylene, ethylene as comonomer and the catalyst system are fed into polymerization reactors con- taining a hydrocarbon solvent. Typical polymerization conditions are temperatures in the range of 50 to 80°C and pressures of 5 to 15 atmospheres. ‘The polymer slurry is transferred to a centrifuge to separate the solvent. The polymer is then dried, stabilized and extruded into pellets. Recovery of the hydrocarbon solvent separated during the process and removal of a small amount of atactic polymers formed in the reactors are carried out by simple dis lation, Catalyst performance: The HY-HS Catalyst employed leads in the polymerization stage to a yield of at least 300,000 g of polymer/g of Ti and to an isotactic index of 93-95. The polymer contains less than # ppm Ti. 214 Economies: Elimination of deashing and simplified sol- vent recovery make it possible to save approximately 20% fof plant investment cost needed for the conventional process plant. Furthermore, considerable savings in op erating costs can be obtained mainly on the following items: monomer consumptions, costs for eatalyst removal and effuent treatment, costs for solvent recovery and atactic removal section, labor costs, maintenance costs, ‘Total costs for production in new plants can be esti- mated at least 2 US. ¢/Ib. less than in case of conven- tional processes. Commercial installations: Mitsui Petrochemical Indus- ties, Ltd, and Montedison Sp.A., plants under con- struction by Novamont Corp, USA. and Montefina Belgium, ARCO Polymers, U.S.A,, under the HY-HS Catalyst License, Numerous negotiations for licenses are under way. November 1977 Hyprocarnon ProcessiNo:Polypropylene—murs eemo.um co. ‘Hyprocarsow Procrssinc Application: A process to produce polypropylene homo- polymer and copolymers continuously from propylene. sh and recycle monomer is introduced Descriptio into the reactor with the catalyst. Polymerization occurs at relatively low temperatures. The product, whether homopolymer or copolymer, is withdrawn as a slurry for separation from the hydrocarbon. Catalyst residues and soluble polymer are removed porated in the process. Soluble polymer in the product ‘an be varied to meet market requirements. The product in powder form is stabilized, pelleted, then dried and sent to storage. a unique system incor: ‘The process is ultimate in simplicity and, therefore, service factors are high. Propylene efficiency is high and ‘maintenance costs low. Impact grade copolymers of product, as well as the homopolymers, fill the known market applications. Commercial installations: ARCO Polymers, Inc. Deer Park, Texas; Phillips Petroleum Co., Pasadena, Texas, and Pertamina, Pladju, Sumatra, November 1977Polystyrene —*° om 216 Application: A continuous process for the radical (ther- mal) polymerization of styrene to produce, at low invest: ‘ment and production costs general purpote crystal as well as high impact polystyrene, Description: Styrene is polymerized continuously in stirred reactors provided with a special control of the reaction’s exothermicity. The resulting polymer is heated and devolstlized allowing thus the achievement of low residual amount of monomer. ‘The molten polystyrene can be supplied directly to inline processing such as: extrusion; pelletizing; colora~ tion; mixing; plasticizing and production of expanded sheets by direct gassing. "The products yielded by the process are characterized by: low polydispersity, good fluidity and processability, efficent rubber grafting (high impact grades). ‘They cover all applications of crystal and impact grades includ- ing: heat resistant polystyrene; biorientation; compound ing for extrusion, and injection moulding. Yields and economics: Requirements per ton of poly- styrene are: Styrene (plus polybutadiene and plasticizers, if any), tons es 101 Utilities: Electricity, kwh 150 Cooling water, m? 0000200000000 35 Heating (oil), tons 2.2.11. 0.03 Commercial installations: Different types of reactors matching any specific requirements and. sizes of units (from 5,000 to 30,000 tons/yr.) can be offered. Ucensor: ATO Chimie. November 1977 Hyprocarsow Processino| Application: A suspension polymerization process for the production of general purpose crystal homopolymers and rubber modified graft copolymers of polystyrene from styrene using catalysts and heat to secure the desired reaction rate, Description: Styrene monomer or a solution of polybuta- diene rubber in styrene monomer is suspended as small roplets in water. The polymerization reaction proceeds with the addition of catalysts and the application of heat and is controlled by chain transfer agents and by main- taining a constant temperature. Suspension is maintained by the addition of stabilizers and the agitation of the reactor, Alter the reaction is complete, the sluy of hard round beads in water is transferred to an agitated hold tank, Hold tank serves to free the reactor for further charging and as a feed tank for the centrifuge. Bead slurry in the hhold tanks is fed continuously to a centrifuge. A screw conveyor built into the centrifuge moves beads along the bow! wall and out of the water phase. Wet beads are Gischarged into a rotary dryer where final moisture is removed. Hot beads are conveyed to the storage bins to await blending and extrusion, Such items as lubricants, stabilizers, pigments and other Hypaooarson Procrssino November 197 Polystyrene—cosomn recanotocy, imc. additives may be added automatically to the bead blenders by presetting the feed sequencing mechanism. At the end of the mixing cycle, mix is automatically charged to the extruder feed hopper. Mines are melted and masticated by the extruder serew as heat and pressure increase. Product emerges as small strands that are pulled through a water trough and into multiknife pelletizing machines. The pellets are air-conveyed to test bins to await bag- ‘ging or alternatively; pellets may be conveyed from the test bins to bulk handling facilites for loading into trucks or rail cars, Process flexibility: An infinite number of basie crystal and impact polystyrene grades can be pradueed by chang- ing reaction conditions and by varying amounts and types of additives. A number of medium impact grades are pro- duced by blending impact grades with crystal prior to extrusion. The batch concept of the process permits small lots of specialty grades to be produced with no loss of intermediate product nor reduotion in eapacity. Commercial installations: The total capacity of plants utilizing the Cosden process is more than 600,000 metric tons/yr. 217Polyvinylchloride — + = 218 Application: A suspension process for radical polymeriza~ tion of vinyl chloride (VOM) covering the whole range of applications of PVC and achieving a very low amount of residual monomer in the resins thus rendering them especially suitable for food packaging. Description: The polymerization is performed in an aqueous medium acting both as a dispersing and heat transfer agent. Combinations of several initiators are used as well as automatic cleaning devices of the vessels avoid- ing human intervention, The advanced technology for degassing and stripping results in very high yields and low monomer content in the final resin (below 1 ppm). Spe- cial attention has been devoted to the engineering and realization of the plant s0 as to conform with the most stringent rules as rogards to the monomer level in the plant's atmosphere. Yields and economies: Requirements per ton of polymer are: MG, tons... 1.010 Chemicals, FF* - 65 (including stabilizers) Utilities: Steam, tons : a Cooling water, m* - 100 Process water, m? ean Blectricity, kwh: a see 120 = French Franes, 1977 conditions Commercial installations: ATO Chimie is operating a 100,000 tons/year plant. Licensor: ATO Chimie. November 1977 ‘Hypnocarson ProcessixePolyvinylchloride —rrest «< Application: A batch process for the manufacture of suspension PVG. Description: For a suspension polymerization vinyl chloride is finely distributed in the aqueous phase with the aid of protective colloids. In this state polymerization takes place at suitable temperatures and in the presence of high activity activators. Polymerization is carried out batchwise in stirred large size reactors. Reaction heat is removed by cooling water. The reaction mixture coming from the polymerization is an aqueous suspension of polymer. ‘This suspension is pumped into an intermediate tank and then into a degassing vessel in which the unreacted monomer is re« moved. ‘This vinyl chloride is purified, condensed and recycled. Polymer is separated from the suspension by centsf~ ugation. Drying of wet polymer is then performed in a drier by hot air. To achieve maximum uniformity in grain distribution’ the dried polymer is subsequently passed through a screen. Approx. 95% of the PVG powder has a particle size smaller than 200 ps. From the production plant PVC powder is fed pneu- matically to a silo from where it is taken for further processing like homogenization, bagging and loading. ‘The process includes extensive additional know-how for the reduction of vinyl chloride emission, VO level at work- ing place and minimum monomer content of final prod- uucis to meet the environmental regulations. There are available two different VOM degassing processes, Each of them offers specific advantages for different product grades. Hyprocarnon Proczssina November 1977 For the production of a high impact strength poly- vinyl chloride, suspension PVC is blended with chlor nated high density polyethylene in special deviees and filled into containers or bagged. If required FVC powder with high impact strength can be granulated in special extruders while adding iubricants and dyes. Raw material and utilities (per 1,000 kg suspension PVC powder including improved VC removal tech- nology) : Vinyl chloride, ke 1,020 Deionized water, m* aan, Chemical (basis April 1975), DM 25 Steam (22 bar), RE ..s--cesesesseeeeseese ese 1-50 Steam (5 bar), ig 1,300 Gooling water, mé . a -.70 Blectricity, kWh 290 Nitrogen, Nm ..... 30 Compressed air, Next 35 Commercial installations: Plants with a total capacity cof 130,000 tons/yr (suspension PVC) and 40,000 tons/yr (high impact PVG) are onstream (end of 197). Further 60,000 tons/yr. are under construction. yncest Further information is available from ‘Uhde Corp., 560 Sylvan Ave,, Englewood Cliffs NJ. 07632 and Uhde GmbHT, Deggingstrasse 10-12, 4600 Dortmund - 1, Federal Republic of Germany. 219