Daa aeta! eae ms ogee Rater tte Cee Formic acid — tue cconano process cO.—KEMIRA Application: A new continuous process for the manu. 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 hy- drolyzed and the products of this hydrolysis are sepa rated to produce a pure formic acid and methanol The methanol is recycled to the first stage of this pro- Cat. CH; OH +CO = HCOO CH: Cat HCOO CH; +H,O0 — HCOOH CH,;OH Yield on CO gas depends on the quality of the gas but yields are high Methanol usage is guaranteed at 4 Ib per 100 Ib of product Utility consumptions: Steam 1b/100 Ib product Cooling water 5,400 gal/100 Ib product Electricity 6 kWh/100 Ib product Commercial installation: Kemira Oy, Finland 20,000 metric tpyGoce Conny ETHYL ACETATE Googe ay Lace ect plication: A process for the manufacture of gly- ine and acetic acid from peracetic acid, allyl alcohol eription: A solution of 30% peracetic acid and 10. IeAcctic acid in ethyl acetate containing a stabilizer, alcohol and water is continuously fed into a reac Mdistillation column, whose top operates under re. muced pressure (100-150 mm Hg) to maintain the muperature (40—70°C) in a reaction zon MEIC heat of reaction is removed by ethyl acetate- BEF Azcotropic distillation. Ethyl acetate dehydrated Mam ethyl acetate recovery column is recycled into a pecor for manufacturing peracetic acid. An effluent Pehtiged from the bottom of gun is fed into a hydrating reactor to completely Pitelyze unreacted glycidol. Then, allyl alcohol Heli still remains unreacted is removed at a light-end mn, The exo- ne reaction-distillation Bacctc acid contained in a mixture which is dis- fe, from the bottom of the light-end column is ex faieq 2) solvent at an extraction column, then dehy- Bien finally refined. The solvent contained in a até is removed at a solvent recovery column. The ry aS mixture discharged from the solvent recov Bragg dehydrated by a multiple-effect evapora- Boas. s further treated as rectification columns to Mee glycerine. Di Bi |, lycerine and acetins contained leavy-ends discharged from the rectification Peete nt) erect ed pee) Sate Sond Eee Cn Peery COLUMNS columns are recovered by other equipment and marketed for sale. Characteristics: Because the reaction-cistillation col- umn is specially designed, (1) the mixture in the col- umn mildly reacts; (2) glycidol hardly polymerizers; (3) hydrogen peroxide scarcely produces; (4) ethyl acetate seldom hydrolizes, and (5) the exothermic heat of reac- tion effectively works to remove ethyl acetate from the Further, the reaction-distillation col- umn concurrently functions as extractive-distillation 4s a result, no allyl alcohol is contained in the ethyl acetate recovered reaction system column: 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 Gly- cerine via Peracetic Acid,” Hydrocarbon Processing, Nov 1975, pp. 139-144 Hydrocarbon Processing, November 1983 105KALINE oid cd Ea Er Peay ery Ree ead NIPPON SHOKUBAI Higher sec-alcohols, ethoxylates— kacakukocvo Application: A process for the production of higher sec-alcohols and their ethoxylates for detergent use from normal paraffins and ethylene oxide Description: Higher sec-alcohols and their ethoxylates are produced by the liquid phase air oxidation of n paraffins and by the subsequent ethoxylation, The reactions proceed as follows CHy~ CHe~ CH, AITHBOdco-cat ors, cH~ cH, oH Hem CHy~ cH, S#bOMACK Cat cy cH cH, oH O(CH.CH.O),H CH;~ CH,~ CH; aes mas CH;~CH~ CH; O(CH.CH.0).H O(CH.CH.0),H As a raw material, a mixture of n-paraffins having carbon numbers from 10 to 16 can be used. The oxid: tion is carried out at 150-190°C and nearly atmo- spheric pressure using a boric acid catalyst and an am- moniac base co-catalyst Conversion of n-paraffins is kept below 20% to ob- tain high yield of sec-alcohols. Unreacted n-paraffins are recovered from the reaction mixture by a simple flash distillation at a reduced pressure and then treated with hydrogen. The yield of alcohols re 108 Hydrocarbon Processing, November 1983 CO., LTD. 90% The sec-alcohols, in the form borate esters, are withdrawn from the bottom of i flash distillation, from which boric acid is recovered j hydrolysis, and then the crude alcohols are purified bj caustic treatment and distillation The ethoxylation of sec-alcohols up to 3 mol ethoxy late is carried out using an acid catalyst. The products mol ethoxylate, is separated from the reaction mixtile by stripping Further ethoxylatidl by 5 t using unreacted alcohols. 12 mol ethoxylates is carried 9 or The whole process from the n-paraffins oxidatiot through 3 mol ethoxylate, up to further ethoxylates fully int grated and continuous Raw material and utility consumption (per metric @! of products based on Cyy—C), sec-alcohols) For alcoho! For 3 mol ethoxyilt paraffin, kg 1,100 660 Ethylene oxide, kg = 440 Chemicals, yen 2,000 10,000 Steam, ton ia 15 Electric power, kwh 400 300 Cooling water, m 600 500 Process water, m 25 20 Commerical installation: 30,000 tons/yr (as 3 ™ ethoxylate) at Nippon Shokubai’s Kawasaki plant, pan Reference: Hydrocarbon Processing, Jan. No. 1, p. 145; and Nov, 1981, Vol. 60, No. 11, p. 1978, Vol. af 11)Gea Brae satan eee ag Piva! Pea atel Pes a tel r een bac ay] ed: Propylene 90-99% or lower purity oduct: Isopropanol of min. 99.9% purity. cess description: The direct hydration of propyl- Hie to isopropanol is carried out in a wickle process ith an ion exchange catalyst. Liquid propylene at ele Hated pressure is mixed with preheated water. The Mixture of water, and propylene in supercritical state Btharged to a fixed bed reactor and allowed to trickle @oynward concurrently over beds of ion exchange Bin. The hydration reaction occurs at temperatures BRM and 160°C and pressures in the range of SIE100 bar. Conversion of propyle Molding to the equation: @Hs—CH = CH, +H,O > CHy—CHOH-CHs; AH = —51.5 kJ/mole BLiguid aqueous alcohol and nonconverted gas phase Piopylene are drawn off from the bottom of the reac HOR designed as a high pressure vapor/liquid separator and water is ac- Ge aud reactor effluent is flashed into a low pres- qa seParator. The lean Cy HP Biss arc passed to a propylene column for reconcen- hand Tecycle of propylene to the reactor. The age alcohol fron: tie tov pressure separator is Be esed to a distillation column where di-isopropyl Tig Temoved overhead together with small Gag hts of IPA. This IPA is extracted with water and Ro Pack to the column. The bottoms are charged to a S©hd column, where isopropanol is taken overhead and LP-separator gas Piccola Bait) acl Cony x Sys) Water from the bot- as an aqueous azeotropic mixture and recy- tom of this column is treated by ion exchar cled to the reactor. Dehydration of the isopropanol/wa- ter mixture is carried out by azeotropic distillation using an entrainer. Heavy ends are separated in a side column. ‘Consumption: 0.75 mt of propylene per metric ton of IPA Gonversion: 93.4% wt. of propylene to isopropanol 5.0% wt. of propylene to di-isopropylether 1.6% wt. of unreacted propylene, incl. losses Conversion per pass: 75% Economics: A 30,000 metric tons per year plant re- quires battery limits investment of U.S. $8.5 million (German basis, mid 1983) Utilities: Utility req min. 99.9% purity ar Cooling water, m irements per metric ton of IPA of Process water, m? 07 Steam LP, metric t 18 Steam MP, metric t 03 Electricity, Wh 115 Chemicals + catalysts, $ approx. 3 Catalyst lite, months Commercial installations: One plant with a capacity cof 80,000 metric tons per year has been in operation in Germany since 1° nd one plant with a capacity of 30,000 metric tons per year in Taiwan was started up in 1983, Licensor: Deutsche velopment Corp. or Frankfurt am Main. Reference: Hydracarbon Processing, N 113-116. Erdél und Kohle, January 197. Texaco AG through Texaco De- Edeleanu Gesellschaft MBH pv. 197: pp: 19 pp Hydrocarbon Processing, November 1983107Dre tose fae omer cen pear) om 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 dehy- dration of maleic acid. The scrubber water from the off gases of the PA process contains in solution about 25% of maleic acid and approx. 5% of other acids e.g. phthalic acid, benzoic acid and citraconic acid. The acid concentration of the waste water is increased un: der slight vacuum to about 95% in a system of evapora tors which guarantee short residence time. All vapors are condensed, collected and recycled to the PA scrub- bing section. The obtained concentrated melt of acids is immedi- ately sent to a special dehydrator where the molten di carboxylic acids are mainly dehydrated to the corre sponding anhydrides 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 recycled to the de- hydrator an injection 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 interme- diate storage vessel. The remaining water vapors are retained in The crude MA obtained in the first hi Nia ia ee Pea’ res roa com oer Cd Oa Corea Eee ad under vacuum of the column The bottoms containing higher boiling acids and hydrides are removed and can be incinerated togethel with the residue from the dehydrator The pure MA produced has the following The pure MA is withdrawn at the (0p tion Purity min, 99.7% Solidification point min, §2.4°C { Color number of melt max, 20 Hazen (APHA) Ash content max. 0.002% ; Solubilty, (1 9/25 mil o-xylene) clear solution Feedstock and yield: When using the BASF catalyst for PA production it is possible to recover from the @ gases of the FA switch condenser system appro % of pure MA based on the amount of PA produced by suitable scrubbing and working up of the scrubbifil solution Commercial installations: Recovery units for ME from PA scrubber water are installed at BASF Ag Ludwigshafen and at BASF Canada. Three lice nel this process have been granted to customers in Ui U.S., Japan and in Europe. The ey for recovery of MA according to this process is alam ent 20,000 metric tons per year 4 Reference: Hydrocarbon Processing, Vol. 54, No. 8) 108orate ior yr Cree eed wolication: A process for the continuous production Pimaleic anhydride from butane and air Bescription: Maleic anhydride is produced in gaseous phase by catalytic oxidation of butane. Air and butane Gxidized to maleic anhydride over an ori Hstdeveloped by Sohio. High per pass conversion to maleic anhydride is obtained on a once through basis. @ the main part of the maleic anhydride in the reactor lent (up to 50%) is continuously condensed by inal cata hg the gases below the dew point of the anhydride ébove the dew point of water. This condenser, of a fal design, never needs to be put out of service Beitie purification step, including g dehydration of the able acid and distillation of the crude anhydride, is HOrmed continuously and thermally without use of Worganic solvents as an entrainer. The crude maleic Solution is first evaporated under vacuum, and elatds thermally transformed to anhydride in a de- Bilation reactor specially developed in view of reduc- BO the lowest possible level the isomerization of ma- AGd to fumaric acid already very pure maleic anhydride recovered te dehydration unit is then continuously dls Under vacuum. The purification step can be op- ME ny ratio of anhydride to acid feed for flex Boduction Sai) aleic anhydride = SOHIO/UCB S.A. Dane Meo ei ty Features:sIhe fluid bed reactor system has the follow ing advantages over the conventional fixed bed reactor system: safe operation with a lower air to butane ratio which reduces air compressor costs; ease of operation nd unloading, and maintenance; longer catalyst life; no molten salt or flammable heat transfer fluids; efficient energy utili- zation; lower capital cost; better onstream time. temperature control, catalyst loading Recovery and purification features are as follows: continuous operation; thermal dehydration without the use of solvents; optimum yield/recovery of maleic anhydride; high purity product; low steam and other utilities consumption. Yields: High yields are obtained in both oxidation and purification. The Sohio fluid bed catalyst gives molar yields well in excess of 50% on a once-through basis Fumaric acid may be recovered as a byproduct if de- sired Commercial installations: UCB has commercially op- ed the recovery and purification system with ma- leic anhydride produced from both benzene oxidation and as a byproduct of phthalic anhydride production The process has for butane feed fluid bed butane oxidation system in a plant facility Licensor: Sohio Chemical Co., Manager Licensing, Midland Building, Cleveland, Ohio 4411 U.S.A. UCB S.A., Licensing Department, 326 Avenue Louise, 1050 Brussels, Belgium. n licensed six times, one of which Sohio has successfully operated the ge-scale pilot Hydrocarbon Processing, November 1983 109Ga eeon ese Dns Application: A continuous process for the recovery of technical grade maleic anhydride from phthalic anhy- dride (PA) waste gas scrubber liquor and at the same time for gas pollution control in phthalic manufacture anhydride Description: Catalytic oxidation of o-xylene or naph thalene in PA manufacture leads to the production of maleic anhydride in the ratio of 5 to 6% of the pro- duced phthalic anhydride according to the type of cat- alyst which is utilized. This byproduct maleic anhy- dride is recovered in the PA process by water scrubbing of the gases leaving the switch condensers. After scrub: bing, the gases are free of organic impurities and may be released to the atmosphere while an aqueous solu- tion of maleic acid at 15 to 209 tion, which also contains some phthalic acid, benzoic is recovered. This solu- acid and citraconic acid, is concentrated in two stages to obtain a melt of the organic acids. The melt is then thermally dehydrated without use of any organic solvent as entrainer. The crude anhydride product is further purified by distill cal grade mi hydride tain the phthalic anhydride, the citraconic anhydride. the benzoic acid and a little of maleic anhydride are continuously removed in liquid form and disposed of in a conventional burner. The \ evolved during concentration, dehydration ion in view to obtain techni beeasil ay be easily 110 Hydrocarbon Processing, November 1983 Pree Maleic anhydride — ucesa oa a lation is condensed and recycled to the scrubber off PA plant Economics: 1) The process leads to technical gia anhydride, i.e., same grade as obtained by lytic oxidation of hydrocarbons, at a very low prod tion cost which results only from ilities consumphi_ the feedstock being at zero-cost. Consumption of i ties are the following per 1,000 Ib of end profil Steam 16,000 Ib—Electricity 140 kWh—Process Wil 1,200 gal—Cooling water 60,000 gal. 2) Typical chal teristics of end product: Solidification point 52.0] Molten color 10 APHA—Color stability 40 APB after heating one hour at 140°C Commercial installations: Two commercial plants in operation: 3,600 tpy in Belgium and 3,000 (Bh Russia. These two planis are the only ones in thew that effectively perform the recovery of commie grade maleic anhydride from phthalic anhydll scrubber liquor Licensor: UCB S.A., Licensin 1060 Brussels, Belgiu' Cologne, Germany. Department 326; Louise and Davy McKee References: L ing, 02-09-74; Hydrocarbon Processing, Nov mation Chimie, Jan. 16Sacer a | Panam tensa Methanol == HALDOR TOPSGE A/S Poplication: Low energy process for the manufacture BPlmethanol (any quality) from gaseous, liquid or solid Hdrocarbon feedstocks. Description: (Gaseous feedstocks and liquid feed HOAs with end boiling points below 240°C (464°F)) he main process steps are SVesulfurization of the feedstock by means of hot Mc Oxide at about 400°C (750°F). In case the feedstock EOitains refractory sulfur compounds, a hydrogena- IK Step is installed upstream of the zinc oxide vessel Reforming of the hydrocarbons at 16-20 kg/em*g 25-285 psig) by steam in a tubular furnace of the Pde wall fired type with radiant wall burners placed at Peral levels Bed for preheating of process fluids and combustion i as well as for superheating of high pressure steam. pe heat of the process gas is used for generation of Bilelipressure steam, boiler feed water preheating and PE Feboiling in the distillation section Ie synthesis gas produced in BE OF mainly tis, CO and COs with a conside SMplus of H. Faitthesis of methanol at 70-90 kg/em%g (1,000 NY psig) in three radial flow converters with indirect The hot flue gases from the furnace are e reformer is a mix- heat Only gas passing the converter system is con hange between the converters. The . used for boiler PAM Of the rte feed water preheating ‘d into methanol, the remainder is mixed with Pensa Ped sh synthesis gas and recirculated. The surplus of hy- drogen is removed in a purge stream, which also pre vents inerts such as nitrogen and methane from build- ing up in the synthesis loop depressurized in an expander, supplying part of the The purge gas is g power for compression of the synthesis gas. After expansion the purge gas is burnt as fuel in the reformer Heavy liquid and solid hydrocarbons application Heavy fuel oil or coal are converted into synthesis gas via gasification, partial CO-conversion using the Topsge sulfur tolerant shift process and H,S- and CO.- removal. The synthesis gas is sent to the methanol sythesis loop operating at 50-70 kg/cm2g (700-1,000 psig) and without considerable surplus of hydrogen. Consumption (Typical for operation with natural gas as feedstock. Figures are per metric ton of product): Product methanol Fuel grade Chemical grade Feed and fuel, kcal x 10! 73 73 Steam, kg 400 0 Demineralized water, k 790 90 Cooling water, m? 130 130 Electric power, kWh 15 5 Hydrocarbon Processing, November 1983111Pann ra Ca er Pens a eeateo aod Oma ES i | ener) Methanol (ICI low pressure process) — Application: A process for the manufacture of chemi- cal or fuel grade methanol from gaseous, liquid or solid hydrocarbon feedstocks. Description: (Steam Reforming Application) The hy drocarbon feedstock is desulfurized by catalytic or ab- sorptive processes, mixed with process steam and passed forward to a tubular reformer. The reformed gas leaves the tubes at 800-880°C before passing to the heat recovery section. After cooling to ambient tem: perature it is compressed by a turbine driven centrifu- gal compressor to a pressure between 50 and 100 atm The synthesis gas is added to the synthesis loop which comprises the following items; circulator heat exchanger, cooler and separator. The crude prod. uct is distilled in two or three columns. Main features of the process are: a highly stable cop- per based methanol synthesis catalyst, simple converter design and heat recovery and an optimized distillation system, The synthesis catalyst operates in the pressure converter range 50 to 100 atm at 200 to 300°C and has a life of up Heavy (No C2 to four years. The converter is a pressure vessel con- fuel oil Naphtha —_availablel taining a single bed of catalyst. Catalyst can be loaded Feed and fuel k cals 10° 7.8 a 4 aining a sing 2 atalyst ca aded Electric power ki 88 35 2 through the top of the converter and discharged at the Feed adores cx ; base in a matter of hours. The reaction is quenched at Cooling water m* 88 64 several levels by cool gas injected through specially de- Catalysts U.S. $ 18 18 signed spargers. The last quench may be replaced by an interchanger which heats the feed to the first bed. This design allows heat to be removed at a higher tem- perature from the loop in boiler feed water and water 112 Hydrocarbon Processing, November 1983 IMPERIAL CHEMICAL INDUSTRIES PLC for feedstock saturation. The overall heat recovery sf tem involving the reformer and synthesis loop, gether with the energy system is optimized to obiail maximum use of heat at all levels of temperatttt thereby obtaining maximum economy in the consti tion of feedstocks. The distillation section is optimize for capital cost and energy consumption. i (Partial Oxidation Application) Heavy fuel oil or ei are partially oxidized by oxygen and steam. The pri uct gas containing largely hydrogen and CO, togetlit with some CO and trace impurities is treated to rem0i sulphur compounds and adjusted to the optimum faa of hydrogen to carbon oxides. Partial oxidation pi cesses can operate at intermediate pressures such Ui no further compression is required before the syntli sis gas passes forward to the synthesis loop. Economics: Typical requirements per metric 00M methanol are ‘ Netural 8) arent Commercial experience: Twenty eight plants ate in operation (two owned by ICI) and twelve are rently being designed or constructed. Plant sié 500 metric tons per day from 50 tcal ree] aay ES co Mm Ee aucal pesca REFORMER Pa} eo cce) “iethanol Application: A process to produce methanol from gas 4nd liquid hydrocarbons (including heavy as: fenes) and from coal B conventionally desulfurized. About half the de- Mitized natural gas is mixed with steam and re- Hed at approx. 780°C and a pressure iain a gas containing hydrogen and carbon oxides ell as some 20% residual methane. This reformed HS mixed with the other half of the desulfurized nd the mixture i reformed BUVOXygen in an autothermal reactor at a tempera- Of approx. 950°C, yielding a methanol synthesis that contains umount of Hdtal methane and whose stoichiometric ratio & COs/CO + COs is approx. 2. The waste heat is re. pieted from the flue and ed gas to luce high-pressure steam which is then used in tur Sto drive the heavy machinery. Waste heat of ft temperature is used together with low-pressure él to heat the methanol distillation system thie syngas is compressed to 70-100 bar, preheated fed to the methanol reactor together with the recy- Bap Mn this tubular reactor, whose tubes are filled FAtalyst and cooled with boiling water on the out- Hs, CO and CO, are reacted at temperatures BENE between 240 and 270°C POd reaction heat transfer BSI=1.4 kg of steam/kg around 40 bar then furthe Tit to the boiling water methanol and, at the (Lurgi low pressure process) — rc Be Meo Soro rosa ur os ee accel Feeney) eet aeaoa fanccs urate Rae Mevet 3) same time, protects the catalyst against overheating even under abnormal operating conditions. On leaving the reactor, the reaction gas transfers its sensible heat to the reactor inlet gas, is then cooled and the metha nol is condensed. To avoid inert gas accumulation in the loop, a small gas rate is extracted and used to heat the steam reformer. The crude methanol is distilled to obtain a product methanol meeting the U.S. Federal Standard, Grade AA Specification The oxygen required for the secondary autothermal reforming stage is produced in an air separation unit that also supplies nitrogen (inert gas) and instrument air to the plant. A major advantage of this combined reforming route lies in its low natural gas consumption and in the compact desig (about one-fourth the size of of the steam reformer 1 conventional des Economies:* Typical consumption figures per metric ton of product methanol are Natural Heavy Gas Residue Coal Feed and fuel, GJ 29.7 383408 Electric power, kWh = = Raw water, t 34 25 $ 0 05 Commercial installations: Fourteen plants (150. 2,500 metric Uday) are in operation and 7 others are urrently under construction References: Hydrocarbon Processing, Nov. 1981 Hydrocarbon Processing, November 1983 113eats ee feontt ac Goan fowl rl saci a ae Methylamines — THE LEONARD PROCESS CO. 4 Yields: Ove Application: A continuous process for the manufacture of mono, di and trimethylamines, CHsNH(CHs)sNH and (CH,)sN from technical grade anhydrous ammonia and methanol Description: Ammonia, methanol and recycle liquid are fed continuously at controlled rates through a va- porizer, exchanger and superheater into an amination catalyst packed converter. Part of the exothermic reac- tion heat is used in the feed preheater The crude product is fed to a series of four distilla- tion columns. The first column separates excess am monia and part of the trimethylamine-ammonia aze twope which is recycled. Bottoms rMA column where water is added for extractive distillation and pure recycle, Bottoms are fed to the MMA column where > to the TMA goes overhead to product storage or pure monomethylamine goes overhead to storage or recycle. MMA column bottoms go to the DMA column where pure dimethylamine goes overhead to product storage or recycle with water drained from the bottom to waste. The reaction system is in perfect equilibrium and any amount of the tri, mono or dimethylamine can be taken off as product with any amount of unwanted product recycled which suppresses formation of an equivalent amount of that material. All products are 99.5% pure 114 Hydrocarbon Processing, November 1983 BLUNT PIO woomt me Wace Con an fee Croll yield of both ammonia and methanol above 95% j Raw materials used per 100 pounds of anhydrall product MMA DMA TMAg Methanol 106.4 146.6 1677 Ammonia, anhydrous 56.5 38.9 297 Utility consumptions per 100 pounds of anhydrol product Steam Water Electricity 750 pounds 3,500 gallons | 1 kWh Operator labor one operator per shift Capital cost: For a 20 million Ib/yr plant for 5 Dil MMA/2 TMA product ratio including two weeks fa material storage for methanol, and two weeks stomage for all 3 process plant, cost is $5 million based on current lab and material costs in the United States. hydrous products, complete battery limi Commercial Installations: Nineteen companies if different countries use the process, Estimated (il tonnage produced using the process in late 1983 % be 220,000 tons/yr. Plants recently completed for rea Fertilizer Co. (1980), Lee Chang Yung Chem (1982) and Zetra (Mexico) (1983)Acad Ed Methylamines — ucs sa. fication: A pollution-fre Pidliction of mono-, di-, and trimethylamine in what- Tatio starting from methanol and ammonia continuous process for fiption: Fresh ammonia, methanol and the recy Ssticam (amines +ammonia) are preheated, yapor fetid superheated in a stepwise heating system that He n optimum heat recovery from the further EPSOF the process without any disturbing effects. pili gas stream is then passed at controlled tempera Hie on an original high yield catalyst, especially devel ed by UCB and Harshaw BV, and the equilibrium ched at the reactor outlet; the equilibrium May be displaced by acting on the CHy/N ratio of feed in view to optimize the plant ope ation or pro- E distillation line, which is operated under pres. ai8 composed of five columns, each equipped with HP condenser and reboiler 1 excess of ammonia is obtained on top of the first # Beets bottoms of the second column represent the on Water and higher boiling byproducts; wi Wlimine is separated on top of the third column, udctive clistillation with water; extraction water is Hed as bottoms of the fourth column while the folumn separates DMA as bottoms and MMA on Mie Advantage of this scheme is that byproduct im- ISS; reaction pied in the etrime: water and unconverted methanol are nd do not have fur- tal effect on the proper operation of the second column Parc Cea es The bottoms of the second column represent the only very small quantity of liquid effluents which are to be disposed off by incineration amines refining columns. or biodegradation. A second significant characteristic of this five columns system is that the extraction water which is utilized in the third column to separate the tri- npurities bottom of the fourth column, may be continu the extractive distillation. A very performing gazeous effluent treatment system ren ders the process completely smell-proof On-line chromatographs are continuously control- ling the analyses of the intermediate and end products and methylamine and which is recovered free of at the ously recycled for a complete computerized process control system has also been commercialized If methylamines are noncorrosive products, certain byproducts are, however, highly corrosive and some well-defined parts of the equipment are to be made of stainless steel Economics: Ove all yield in both methanol and am- monia: 96.5% and over. Long life catalyst. End prod ucts qualities meet the strongest norms of purity. Low- est possible stream of liquid effluents. Commercial installation: The process has been com- mercially proven in UCB’s own methylamines plant in Belgium: Licensor: UCB S.A., Licensing Department, 326 Ave- nue Louise, 1050 Brussels, Belgium References: Belgian Patent 882,332, Hydrocarbon Pro July 1 Hydrocarbon Processing, November 1983115OXIDATION REACTORS cate aa cd Methyl methacrylate — Application: A process for the manufacture of methyl methacrylate (MMA) from isobutylene or tertiary bu- tanol, air, and methanol Description: Methacrylic acid (MAA) is produced di rectly from isobutylene or tertiary butanol in high yield by the vapor phase catalytic oxidation in two stages, which is carried out in the reactors of multi-tubular and fixed catalyst bed type. Product gas from the first stage reactor is directly introduced into the stage reactor without isolating methacrolein. MAA is scrubbed with water to obtain an aqueous so- lution of MAA and then unreacted methacrolein in the product gas is recovered and recycled to the second Effluent gas from the oxidation section is cata lytically incinerated and a part of the off gas is reused asa diluent for the reactor feed gas. MAA is extracted from the aqueous solution with an organic solvent MAA is continuously esterified in liquid phase in the presence of a catalyst. High purity MMA is obtained by extrac- tion and distillation. stage, After separation of a part of the solvent Economies: This process offers a more competitive route to MMA than the conventional acetone cyanohy- drin process. The catalysts are very stable and their lifetime is more than two years. B/L capital investment: 5,500 million yen for 40,000 tons/year MMA plant (as of October 1982, on Jar base) 116 Hydrocarbon Processing, November 1983 ee Mon sg area RATOR So caacauenl Eola} Ce ia eee Sa Cy om i errad NIPPON SHOKUBAI KAGAKU KOGYO CO., LTD. — SUMITOMO CHEMICAL CO., LTD. Raw materials and utilities consumption: y (per 1 kg of MMA) Isobutylene, 100% (kg) 0.8 Methanol (kg) 0.34 Catalyst and auxiliary chemicals (yen) 18 Steam (kg), (credit) 10 Electric power (kWh) 0.50 ; Cooling water (kg) 0.30 Commercial installation: A 15,000 tons/year Plant@ Nippon Shokubai’s Himeji site, Japan, which reflel substantially the above process, is onstream. A 40,00 tons/year plant of Nihon Methacryl Monomer if Niihama, Japan (50-50 joint venture of Sumitomo ail Nippon Shokubai), is under construction, incorpolal ing the process of above description, and is expected commence its commercial operation in Septembil 1984 ; 4 BR es ok aassay Soc ernst eA) eos ea C.-C; Mono-olefin | Application: Charge: Propane, isobutane, n-butane, isopentane @idior n-pentane. mono-olefins. For production of Cs-€ Products: Single or mixed mono-olefins for further Processing to fuels and petrochemicals Description: This adiabatic fixed bed catalytic process Dherates selectively on a single component or mixed R€dstock 10 produce single or mixed mono-olefins. Ta typical operation for isobutylene from isobu Pili, the feed is preheated to reaction temperature iNst reactor effluent and in a heater prior to contact After being cooled it catalyst in horizontal reactors BYgenerating steam and by exchange, effluent is com- PPieSed. C, + material in uncondensed gases is recov- Bed cryogenically. Liquid product is stabilized and Mecieither fractionated to recover the desired product fa is the case for isobutylene to MTBE, selectively PEcted to extract the product olefin Bore: operated valves are controlled by a cycle ep which programs the reaction, purging and re BMeration steps. Hydrocarbons are purged from the Osire: as ‘ tion g am reactor prior to regeneration, and combus ed after regeneration. he Catofin catalyst is in the form of cylindrical pel- AS con. sisting of active alumina impregnated with hromnic ! acta ases are pul oxide. Catalyst is regenerated in the luring off the coke formed during reaction with pitheated air ec [ones s (Catofin) — HOUDRY DIVISION OF AIR PRODUCTS AND CHEMICALS, INC. coe fee eal aaa Operating conditions: Are chosen to give essentially adiabatic operation. The heat required for the endo- thermic reaction during the onstream period is sup- plied during catalyst regeneration. The major process conditions normally will be within the following ranges: Temperature, °f 1,000-1,400 Pressure, in. HG absolute 10-20 Space velocity, v/h/v 1 Onstream period, min 7-15 Yields: When making butylenes or propylene, ulti mate yields of olefin from paraffin will be 75 to 90 weight percent of converted material. The optimum yield is determined by comparison of feed value vs. op- erating costs. Economics: (excludes product purification) Olefin Propylene lsobutylene Allen- Licensor: Air and Chemicals, Inc town, Pa. 18105 Reference: Oil & Gas Journal, Dec. 8, 1980, Products Hydrocarbon Processing, November 1983117Cauca y ty ra oS — or Cw Ce ad Nitric acid (SABAR process) Application: A process for producing nitric acid (80 99% HNOs) from ammonia and air, Does not require oxygen, refrigeration energ furic tail gas can be reduced by absorption to below 200 ppm. Weak acid at any rate and concentration can be produced simultaneously dehydrating agents (sul- acid or magnesium nitrate). Nitric oxides in the Description: Gaseous ammonia is mixed with air converted to nitric oxides in the reactor on platinum- rhodium catalysts. spheric pressure so that the reaction water—most of which must be passed out of the process—can be con densed with minimum absorption of nitric oxides. The Ammonia conversion is at atmo- atmospheric pressure conversion gives low platinum The reaction heat is used to produce steam and to preheat the tail gas prior to ex pansion, loss and a high yield. The reaction gases are finally cooled in the 4s cooler condenser where the main portion of the re- ction water is separated as 2% acid condensate After cled nitrogen dioxide the nitrous gas is compressed to addition of secondary air which contains recy- between 6-13 bar abs The compressed gas enters the chemical absorption column where superazeotropic acid is formed. Nitro- gen dioxide remaining in the gas is physically absorbed in nitric acid which takes place in the physical absorp- tion column ide flows to the desorption column where the nitrogen The nitric acid loaded with nitrogen diox- 118 Hydrocarbon Processing, November 1983 aay Cor ee oa Dae Sa corny UMN DAVY McKEE —— AKTIENGESELLSCHAFT dioxide is stripped by secondary air which is recyda to the main gas stream ahead of the compressor. Tl gas from th acid vapors, heated physcial absorption is freed from nif nd expanded in the tail gas til bine The superazeotropic acid is stripped by second and is sent to rectifid tion where it is separated into high concentrated di azeotropic acid. The latter is recycled to the absorp section air to remove nitrogen dioxide Economics: Investment costs are substantially 1084 than those for “HOKO” plants (requiring oxygen al refrigeration units), and operating costs are lower ti ‘n and refrigeration are available at very less oxyg costs. Consumption figures per metric ton of HNOs ate! Ammonia 281 kg Electricity 335 kWh Cooling water (A = 10°C) 180 m’ Catalyst 60 mg Steam plant is self-sufficient Commerical installations: A 120 metric tp SAIN plant is under successful operation since 1974 4M other plant is under construction for TechnoexPag CSSR.eos Pee aes CT eer) ra re oy A process for the continuous production Matric acid from ammonia and air ription: Gascous ammonia is combined with air id passed through platinum rhodium gauzes for con- ffision into nitrous oxide. Afier heat interchange the itolis oxide is compressed, again heat exchanged and €d through an absorber for conversion into nitric i The nitric acid produced is bleached with air and to storage. Off-gas from the bleaching ope: Beléd to the absorber Me process can be operated in two pressure modes: ed-pressure process: Here oxidation and absorp- BIS fixed at between 5 and 10 atmospheres. Ammo- Hand platinum consumption is higher but the invest- Mt is lower and utilities for the Bio pressure process (per metric ton of 100% nitric Operating pressure 8 atm.) are as follows Abhydrous ammonia 282 kg Be Catalyst 140 m seSteam excess 650 kg Pooling water 120 n Electric power 9 kWh ‘Pressure process: Superheated gaseous ammo- Pate air are mixed, then passed through platinum- Him gauzes, The oxidation pressure is fixed case ese) peor ern by case between 3.5 and 6.0 atm. The so-formed nitro- gen oxides are cooled, compressed and absorbed in a column equipped with perforated trays opera pressure fixed between 8 and 13 aun NOX content below 150 ppm are discharged to atmo- sphere after expansion in a gas turbine. Feedstock and utilitie acid: ing ata Tail gases with consumptions (per metric ton of 100% nitric 4-10 atm) are: © Anhydrous ammonia 280 kg © Catalyst 90 mg © Steam excess 900 kj © Cooling water 100 m* © Electric power 9 kWh Economics: Low nitric adapted to economic conditions and high operating re- acid cost due to the design liability due to the wide experience of Grande Paroisse. High antipollution performance with respect to NOX tail gas abatement resulting from the high absorption efficiency. Commercial installations: The first plant using Grande Paroisse process has been operating since 1957. Activities in nitric acid processing have since de. veloped to such an extent that for the last five years, 45% of recently built plants in the world use Grande Paroisse techniques. Hydrocarbon Processing, November 1983119Seine Sora Ear NDENSATION) a lea Nylon 6 — EMS-INVENTA AG Application: Continuous process for the production of Polyamide-6 chips suitable for injection moulding, ex- trusion, flat and blown film, fiber and continuous fila- ment yarn for textiles, carpets, fish net and tire cord manufacturing. Description: Caprolactam monomer is continuously polymerized in the presence of water, stabilizers and modifying additives by EMS-Inventa VK-tube method Prepolymerization is available for large units in order to reduce the volume of reactors resulting in a product of improved quality The raw polymer melt is extruded into strands and cut into granules. These chips contain approximately 10% of monomers and oligomers which are removed After dewatering of the extracted chips they are dried in a three-stage column system by hot and dry nitrogen. The instrumentation of this process line allows the fully automatic ope ing personnel The relative viscosity of the final chips can be varied according to requirements from 2.3 through 3.4 and by hot water in an extraction column ation with a minimum of supervis- up to 7.0 when solid state post condensation conditions are applied to the drying stage Capacities up to 40 tons per day of the above process have been realized: A variety of recovery process routes for the recycling of extractables (monomer and oligomers) from poly- 120 Hydrocarbon Processing, November 1983 ee eal merization and polymer waste from textile section help to cut down raw material costs. Chips from the above mentioned process are asi cessful feedstock for the application in all textile pit cesses, especially the new single stage H4S process [a the manufacture of flat textile filament yarn devel oped by EMS-Inventa AG Batch and continuous process steps are available dt fit all requirements regarding polymer grades, flexibil ity of output and plant size. Special efforts are given the plant design to achieve lowest material, energy alld personnel costs. Polyamide-6 together with its copolymers opens# wide field of application. Processes for the productial of Polyamide-6.6 and Polyamide 12 are also offered If EMS-Inventa AG. ; Commercial installations: More than 20 plants arel™ operation or under construction in Argentina, Bq gium, Brazil, Colombia, Great Britain, India, Ital¥p A pan, South Korea, Philippines, Rumania, Switzerlall Taiwan, U.S.A., Yugoslavia. Total licensed capaci more than 175,000 tons per year AeArNcs TREATMENT Offgas feo OXOREACTION No REMOVAL Application: The process is suitable for the production Blaldehydes and alcohols from olefins and syngas (car- Monoxide/hydrogen) scriptior i hydrogen in the presence of a catalyst forming an Bidehyde—together with a small amount of an alco- HOE -with one C atom more than the initial olefin. The Hilyst is removed from the oxo product and recycled Hille reactor Mcase the aldehyde is the desired product it is sep: ted from the oxo product in the aldehyde distilla~ hs The bottom product of this distillation is catalyti- Wy hydrogenated and distilled to isolate the alcohol. also possible, of course, to feed part of the isolated iehydle to the hydrogenation in order to ir Mount of alcohol.) Hass the alcohol is the only desired product no al Hae distillation is required. The oxo product is fed Bicttly to the hydrogenation. Sducts that can be manufactured by this process The olefin reacts with carbon monoxide rease the propionaldehyde n-butyraldehyde isobutyraldehyde isooctanol n-propanol n-butanol isobutanol isodecanol isononanol isotridecanol ene PrSiiire HYDROGENATION ALCOHOL DISTILLATION Yields: Examples for yields: Per 1,000 kg propylene (100 %) 1,260 kg n-C, aldehyde/alcohol 50 kg i-C, aldehyde/alcohol iisobutylene Per 1,000 kg 920 kg isononanol Commercial installations: The process is being used commercially in large-scale plants of Ruhrchemie and its licensees. References: Further information is available from Hoechst-Uhde Corp, 560 Sylvan Ave., Engelwood Cliffs, N.J. 07632 or Uhde GmbH, Friedrich-Uhde- Strasse 2, D-6232 Bad Soden, West Germany aeinen Application: An oxychlorination/oxyhydrochlorina tion process for the production of perchloroethylene and trichloroethylene without byproduct hydrogen chloride Description: The process can accept a wide range of low cost feedstocks, such as ethylene and/or chlorina- ted Cy hydrocarbons with chlorine and/or HCl and ox. ygen. The process can effectively use organic byprod ucts streams, e.g., light and heavy ends from vinyl chloride, chloromethanes, methylchloroform and ethe ylene dichloride plants. The ratio of products pro duced can be readily adjusted over a wide range. The overall reaction when ethylene dichloride and chlorine are used is as follows: 2CyHyCly + 1'2Cly + 1940. HCl; + CCl, + 342H,0 ® actual reaction is highly complex with substitu tive chlorination, crac king, bon burning all occurring Deacon reaction and car- simultaneously. The reac- tions are carried out in the presence of PPG's relative inexpensive oxychlorination catalyst In the flowsheet, ethylene dichloride, recycled chlorinated organics, chlorine and oxygen are fed to a fluid bed reactor. The reactor operates at moderate pressure and 600—900°F. The catalyst is contained in a vertical bundle of tubes. Reactor temperature is con- trolled and heat is removed by boiling liquid outside of the tubes within the reactor’s jacket. Reaction heat gen 122 Hydrocarbon Processing, November 1983 Perchloroethylene-trichloroethylene _ acest Peer ee oss! bed ted PPG INDUSTRIES, ING| erates a large portion of the ments. process steam requitt The reactor effluent, which contains chlorinated @h ‘ater, a small amount of HCl, c arbon dioxill and traces of other inert gases, is desuperheated ll condensed in a water cooled graphite exchan frigerated condenser is used to recover the final trite of organic from the inert gases before they afl and vented. The recovered crude prod (perchlor plus trichlor) is phase separated. The Del con reaction water contains some residual HCI whi can be neutralized or recovered The organic layer is dried by and fed to a distillation train w products into a crude tr stream ganic, scrubbed azeotropic distillatil hich splits the orgafil hlor and a crude perchlel The lights are separated overhead in ti trichlor still and recycled to the reactor with commen Gal trichlor from the still bottom. This product is ne alized, washed and dried prior to storage The crude perchlor loses high boilers in the bottoll stream. These heavies are flashed to remove tar all carbon and recycled to the reactor. The overhead fed to the perchlor still where intermediate boilers €01 centrate in the overheads and recycle to the react Bottoms (commercial perchlor) are neutralill washed and dried. Commercial installations: Worldwide perchlowilf chlor production capacity by PPG's single step proc is about 1 billion Ib/yrrr rs cond Eater etiption: Cumene is oxidized with air to produce Hifiene hydroperoxide which is concentrated and Byed to phenol and acetone in the presence of an eatalyst. The catalyst is removed, the cleavage mix- Beis fractionated and products are purified MIE process was pionee by BP Chemicals Ltd. Bi Hercules over 30 years ago. It is buttressed by ex- Bye development work over the years and the accu- Bilfied experience from the design and operation of Plants in many different locations. Bike process produces high quality phenol and ace: BSuitable for any application. The selectivity is bet- Man 95%; 1.34 tons of cumene will produce 1 ton Phenol and over 0.6 tons of acetone. Particular at- ih has been paid to energy consumption which is Han half that used in earlier plants with no loss of I. Process designs for individual ded by « team of specialists and are tailored to fit tility systems and client requirements. Be quantity and total BOD of aqueous effluent are Seal and the small quantity of organic residue Bathe process is a useful fuel ‘Rretcial installations: The total phenol capacity BElicensors' and licensees’ plants, built or now un- EMsiruction, is 2 million tons pa most of which is pPcrating. Recent licensees include: Shell Oil, U.S. eaten Dass Sar utaY virco a Ea peels RECOVERY (plant capacity 220,000 tons pa, plant commissioned in 1977), General Electric Co., U.S. (180,000 tons pa, plant commissioned in 1980), Neste Oy, Finland (50,000 tons pa, plant commissioned in 1981), and Ja pan Phenol Co., subsidiary of Mitsubishi Petrochemical Co., Japan (100,000 tons pa plant, commissioned in 1983). Several licensees are undertaking moderniza- programs. tic Licensors: Inquiries should be directed to BP Chemi cals Ltd., Licensing Division, Belgrave House, 76 Buckingham Palace Road, London SW1W OSU, Eng- land, or to Hercules Inc., Director of Licensing, 910 Market Street, Wilmington, Delaware 19899, U.S.A. Hydrocarbon Processina, November 1983 123Caio Cea ore Application: A process for production of phthalic an hydride (PA) from o-xylene and air Description: o-Xylene is oxidized with air on a sup- ported catalyst in a fixed bed reactor. Filtered air is compressed and passed through a preheater. The o- xylene is preheated and vaporized by injection into the hot-air stream. The o-xylene/air mixture through the catalyst-filled mult exothermic oxidation to PA takes place on a highly se- lective catalyst. The reaction heat is used for steam generation and high pressure steam can be exported By using a turbine instead of an electric motor for the air blower medium pressure st The gases leaving the reactor are precooled in a gas- passes ube-reactor. The am is exported cooler and then passed to a separation system where PA desublimes in switch condensers which are cooled or heated with an automatically controlled time cycle. During loading the switch condensers are cooled by a After loading the crude PA is recov- ered by melting it from the fin tubes by circulating hot oil through the condensers and collecting the molten crude product in a tank heat-transfer oil The off-gases from the switch condensers still con- tain small amounts of byproducts and traces of PA. For this reason they must be cleaned either in a water scrubber or by catalytic or thermal incineration. The scrubbing water contains mainly maleic acid, which can economically be recovered in the form of maleic anhy- 124 Hydrocarbon Processing, November 1983 Phthalic anhydride — BASF AKTIENGESELLSCHAFT Eee Rea re Se) dride by a BASF process. In combining both proces there is no waste water to discharge. The crude PA is pumped from the intermedi storage tank into a continuous thermal pretreatmé section to convert small amounts of phthalic acid il anhydride. From there crude PA is fed into the conti uous two stage distillation Catalyst: The energy saving 60 g PA process wol with a new developed catalyst, which allows o-xyld loading of 60 g/m! air S.T.P. The maximum capacit)j a single train PA reactor is 45,000 metric tons/yr. Yield and product quality: The feedstock is comm cial o-xylene of at least 95% purity. The 60 g catalff gives a yield of 109 kg pure PA per 100 kg o-xyle (calculated as 100% o-xylene content) Product quality: PA 99.9% min Phthalic ac 0.01% max. Maleic anhydride 0.02% max Benzoic acid 0.02% max Color of motten material Heat stability test Solidification point Licenses: As of March 5 Hazen (APHA) 10-20 Hazen (APHA) 131°C 1983 21 lic nises have Bt yr. Thus about 40% of the PA capacity in the world, based on o-xylene feedstock, are obtained BASF processes.Coed ea Seam ad oon Application: Production of phthalic anhydride from Xylene, napthalene or mixtures of both feedstocks by Tchoice of catalysts. ; benzoic acid max. 0.05%; \ 10 Hazen (APHA); Heat Test: 10-20 Hazen; lidification Point: 131°C iltered and compressed oxidation air of AD psig is heated to 140-160°C and loaded with evap Pitted naphthalene and/or o-xylene. The mixture of naphthalene and/or o-xylene enters Feactor with vertical tubes holding the ballshape or MME catalyst. A salt melt circulating around the tubes PiMoves the heat of reaction and maintains constant PMperature conditions. utilized lr the ge Bethe reactor effluent containing PA vapors is pre Spoled in. a waste heat boiler generating system. By fur HEF Cooling PA is then de-sublimated in specially de- ned finned tube switch condensers with optimal Hency and safety. The crude PA deposited on the Berdensing surfaces is periodically melte a The reaction heat is neration of high pressure steam. and dis- Etged into a tank. The effluent gas is discharged to aMOosphere ; ineration. The SLE PA is pretreated thermally under atmospheric eed pressure, from i, DYs¢ or a continuous vacuum Wand high boilir fter water scrubbing or in here it is supplied to either a listillation system. impurities are removed and the SRL PA is obtained as a distillate which can be stored Hein the molten state or flaked hthalic anhydride — von sevoen roo cote) Co Cars oc eet et Catalyst: There are special high performance catalysts for either o-xylene or naphthalene oxidation as well as a dual-type catalyst for both feedstocks and mixtures. All catalysts are optionally ball- or ring-shaped. They rams/im, are designed for hydrocarbon loading of 60 air S.T.P. Yields: Depending upon feedstock quality, 105-110 Ibs. PA per 100 Ibs. o-xylene; 93-98 Ibs. PA per 100 Ibs. naphthalene a total capacity of approx 100,000 metric tons per year are using the dual-type catalyst Plants with Economics: Commercially proven catalyst life is more than 3 years. Maintenance cha plant equipment investment. Sin s are about 2% of gle reactor capacity up to 100 million Ib/yr. Onstream factor: 98-99% Commercial installations: Up to the present time, 65 commercial plants with an installed capacity of more than 1,400,000 metric tons per year using the von Heyden process have been erected or are under con- struction. Forty-one of these operate on o-xylene basis The licensor of the von Heyden process is Psalizenz- verwertungsgesellschaft (a joint venture of Chemische abrik von Heyden GmbH and Wacker Chemie GmbH, Munich) and world licensees are Davy McKee AG, Cologne and Lurgi Kohle und Mineraldltechnik GmbH, Frankfur/Main References: Advances in Petrochemical Engineering 1. Chem. E. Symposium Series No. 50, Engineering, Jan. 29, 1979, pp. 62-63. 1976: Chemical Hydrocarbon Processing, November 1983 125Cau AUl Moe NURS SAR oT Urns occa ite TT ata Sony fice) Cn Ae eee Sn Vo Sed e ay eo meee) Plasticizers —— DAVY MCKEE—VON HEYDEN PROCESS j Application: Batch Process for the production of plas- ticizers by esterification of phthalic anhydride (PA) and a higher alcohol, or a mixture of alcohols, using an am- photeric catalyst Product: e.g., Di-octyl-phthalate Typical specification Purity (according to sa ponification number) min. 99.05 Color (APHA) 20 Acid number 0.03-0.04 Hydroxyl number 0.6 Description: Alcohol and liquid PA are fed into the es. terification reactor. Then the excess alcohol from the previous charge as well as catalyst are added and the reaction mixture is heated to the required esterifica tion temperature. Evaporated reaction water and alco. hol are condensed and separated, so that the alcohol can be recycled to the esterification reactor. After com pletion of the reaction, traces of unreacted monoester are neutralized with soda ash, followed by steam strip- ping of the excess alcohol. The overhead vapor mix ture is condensed, the alcoholic phase being separated from water and collected in the excess alcohol tank. The condensate is used to generate steam, which is then recycled for steam stripping, After drying the es. ter with nitrogen, filter aid is added and the ester is cooled and filtered. The pure product is then trans ferred to storage 126 Hydrocarbon Processing, November 1983 Raw materials and utility consumptions (per meu ton Di-octyl-phthaltate): Phthalic anhydride 382 kg 2. Ethyl. hexanol 680 hg Catalyst 1 kgs Cooling water (A = 10% 60 mu Electrical energy 20 KWH Economic features: © Low investment and production costs © Simple operation © Simple change-over to other plasticizers 7 © Through used closed loop steam system, the post ble pollution problems are minimized Commercial installations: | plant 10,000 ton/yearil Finland; 1 plant 20,000 ton/year in Yugoslavia; | plat 20,000 ton/year in Portugal (under construction),Ere Cot) er ar Coa) Ce pom Coens Perr Y -Polybutadiene — piurs reroucum co, pplication: A solution polymerization process for the Milintious production of a high cis content polybuta iti rubber from butadiene scription: The cis-polybutadiene rubber process isiss of four basic steps. They are (1) butadiene and Went purifications, (2) reaction and concentration, Jblending and solvent removal and (4) drying and ackaging. Biltadiene low in acetylenes and other polar catalyst hs is dried by fractionation and mixed with a sol- Mithat has also been dried by fractionation this fresh stream is mixed with a recycle stream of Hdiene and solvent from the concentrator step and Blyst is added at a controlled rate to the total stream get it enters the reactors. The catalyst is varied as “Ssary to obtain high conversion of butadiene and EShirol Mooney viscosity of the polymer. The sol- ef10-monomer ratio in the reactor train is chosen to {low enough solution viscosity so conventional re Ga cat be used. A number of reactors are used in a Ut give desired residence time. A suitable short- pPand antioxidant are added to the polymer solution ts the reactors. Any unreacted butadiene and Foaihe solvent are removed in the concentrator be {Polymer solution is blended Herel! Solution blending can be used to control the ML? Mooney viscosity at the desired level before al of solvent in stream strippers. The water in y ” the stripper overhead product is decanted and recy- cled to the strippers. The crumb-water slurry from the strippers is pumped to the drying area Water is removed from the crumb with a shaker screen followed by extrusion drying. The dry rubb moved by a spiral conveyor to weigh scales and into a baler. Bales are passed throug’ a metal detector and are film wrapped and placed in suitable packages Operating conditions: The cis-polybutadiene process can be used to produce a polymer with any desired vis. cosity in the range of 30-70 ML-4, although the poly- mer ordinarily is produced in the 48 ML-4 range Reactor cooling is necessary for highest product qual- ity Yields: The over-all conversion of butadiene to cis poly-butadiene is ordinarily over 98% Commercial installations: Seven proximate total annual capacity of 32 cluding plants located in France, Germany, Italy and Japan nts with an ap- 5,000 tons/yr in Hydrocarbon Processing, November 1983 127eager MO Ns aciac gee) cme) NS \ Polyesters — ewsinventa ac Application: Processes for the production of polyeth ylene terephthalate (PET) starting from ethylene gly- col (EG) and terephthalic acid (TPA) or dimethyl- terephthalate (DMT) Description: In a multistage continuous process the raw materials EG and TPA (DMT) are converted into a low molecular precondensate by esterification (transes- terification) and into high molecular, linear polymer by polycondensation reaction. Two routes aré for the esterification reaction available 1. Process being carried out under atmospheric 6 F pressure with corresponding ease of recycling and charging solid waste 2. A more common process being carried out under pressure and addition of TPA and EG as paste The reaction byproduct water (methanol) is sepa- rated from EG vapors in a reflux column. After add- ing catalyst, stabilizer and additives the prepolymer is forced through a superfine filter. Polycondensation re- action is performed under vacuum and elevated tem- perature. Special care went into the conception of the polymer finisher, which is equipped with a proprietary horizontal cage agitator without center-shaft, there- fore minimizing the build-up of solidifying polymer layers. EG vapors contaminated with oligomers are drawn off through a special condensing system and sent to a recovery unit Polymer melt can either be sent to a direct spinning 128 Hydrocarbon Processing, November 1983 errata) plant or transformed to chips. These continuous pi cesses are available with capacities ranging from 30M 120 Uday per line. The cooperation between EMS-INVENTA AG aif Karl Fischer Industrieanlagen GmbH makes availab an industrially well proven package of continud polyester process and production knéw-how. Batch process: Similar principles are applied to a ti stage batch process. The capacity of standard ball lines ranges up to 30 tons per day. Existing batch wansesterification plants can be verted to TPA feedstock by adding one continuous @ terification reactor. TPA onomical than DMT PET is used for the production of textile and tech cal grade fiber and filament yarn, bottles, film plastic materials. as feedstock is often more Commercial installations: and ml than 50 batch plants are in operation or under i 4 continuous struction in the following countries: Bulgaria, GI Britain, India, Indonesia, Ireland, Japan, Luxe bourg, Nigeria, Pakistan, South Africa, Switzerlall Taiwan, Thailand, Turkey and Venezuela. Actul censed capacity is more than 450,000 tons per ye Licensor: EMS-INVENTA AGPiensa Ohaccie) esa aes pplication: A process for the production of low den. By polyethylene by high pressure polymerization in a slibular reactor scription: Ethylene feed is compressed to 200-300 en? by a multiservice compressor together with eth Misie from the low pressure recycle, containing chain PEhsfer agent. After mixing with oxygen and with eth coming from the intermediate pressure recycle, ie Bas is compressed to a final operating pressure of gM00=2,600 kg/cm? by a hypercompressor. The h Stire compressed gas is fed into the jacketed tubu We reactor together with peroxide when this kind ihitator is used, too By the reaction heat is recovered as low pressure steam Bivered at battery limits. Ke polymer-ethylene mixture is then expanded igh a special let-down valve in order to separate E Polymer from unreacted ethylene. The latter is i €d, purified from low molecular weight polymers Pai)) and recycled to hypercompressor suction. The Sethylene is further expanded to a lower pressure palease the ethylene still dissolved Ie gas released is cooled, purified from waxes, HY purged to prevent the build-up of contaminants, Hecycled to the multiservice compressor suction leg. ¢84ssed polymer is pelletized in a conventional Stzing extruder where antioxidant and slip agents ky oded by proportioning pumps. The polymer pe @e then dried and collected in an analysis silo olyethylene (LD) — anc aot] Pe CMR ey where the product is analyzed. After the analysis, the polymer is blended in a gravity blender and pneumati- cally conveyed to the storage and bagging section Products: The Anic process allows to cover the com plete range of LDPE applications, by producing the relevant, most suitable grades. Each specific grade can be obtained by selecting the proper polymerization conditions and by a suitable proportioning of catalysts. High film grade quality is achieved without any poly- mer reprocessing. Grades modified with vinyl-acetate can also be produced. Black compound technology is available Economic: I metric to The following consumption data refer to of blended pelletized polyethylene thylene (99.9% vol), tons 1.01 Electric power, kWh 800-850 Steam (25 kg/cm?), to 0.15 Cooling water (AT = 10°C), m? 130 Process water, tons 0.65 Catalyst and chemicals, $U.S. 4-18" Recovery of steam (4 kg/cm’), tons 08 Commercial installations: ANIC has 4 lines with a to- tal capacity of 245,000 MTA (of which 90,000 MTA and 100,000 MTA in two single lines). Other four lines for a total capacity of 168,000 MTA have been licensed in Algeria and Romania Reference: Further information is available from Snamprogetti c.p. 12059/20120 Milano, Italy Hydrocarbon Processing, November 1963 129.CaurGad eto Cigsa) Cd Catalyst Cod Polyethylene (LD) — ARCO TECHNOLOGY, INC. Application: A process for the production of low den- sity polyethylene and copolymers using free radical ini tiators at high pressures (1,800-3,000 atm) in a tubular reactor Description: Fresh ethylene feed, with a purity in ex- cess of 99.8%, is mixed with purified low pressure re- cycle. Initiator agents are the mixture, which is then compressed to 300 atm This feed is then mixed with high pressure recycl compressed to polymerization pressure in a hypercom- and chain transfer added to and nuously fed to a tubular reactor, pressor and is cont wherein a portion of the ethylene is polymerized. Con- of 23-26%, depending on prod uct type. Upon leaving the reactor, the ethylene-poly- ethylene mixture is expanded and enters a primary high pressure separa version is in the ran a second: or and, subsequently The ethylene from the two separators is cooled and dewaxed individually and re- cycled back to the appropriate compressor. The poly mer leaves the secondary separator and feeds an extru der where it is pelletized, cooled and conveyed to ary low pressure separator storage silos. Raw materials and utility consumption: (Per metric ton of pelletized polyethylene) Ethylene (tons) 1,020-1.030 130 Hydrocarbon Processing, November 1983 Care) Dida ad SoU Pas Se ater) Part) eo Utilities: Steam, tons 0.600-1.000 (35 atm) 0.600—1.000 (7 atm) generattdy Cooling water, m* Electricity, kWh Depending on the product type Commercial installations: Arco has a plant in Port thur, Texas, with a capacity of 400 MM Ib/yr and li licenses in Italy and Argentina Licensor: Arco Technology, Inc., subsidiary of AUM] tic Richfield Co.FLUID BED REACTOR any forte Pe a eaucas lication: A process for high, medium and low den- Polyethylene manufacture from ethylene Siner in the gas phase with high efficiency Ziegler Catalysis and co- Bsctiption: Ethylene is (co)polymerized by reacting Mieatalyst particules in a fluid bed reactor at 60 to MGunder a pressure between 15 and 30 bar. The Bition heat is removed by circulating the gas through eat exchanger then compressing it for recycling to Eieactor. The polymer is growing on the catalyst Hictiles injected in the bed and is discharged in a PaTaior vessel where residual monomer is removed PErecycled, Hydrogen is introduced in the circulat- 635 to control molecular weight Tita nium and magnesium containing catalysts are M this process. High yields are obtained and cata- Ettioval is not needed. The polymer is a free- Bing powder which can be fed directly to processing les. A broad range of polymer is achieved due Bouistanding of the Ziegler type catalytic formula Used for obtaining narrow or large molecular distributions. High or low melt indexes are ob- through control of molecular weight, and high sum and low densities through homo or copoly- Be won. Light comonomers (Cs, C;) or higher can tse, = pects: Polyethy 5 lene having densities from 0.916 to ained with conventional high density LLDPE) —— BP CHIMIE GAS PRODUCT SEPARATOR Gas to recycle eae eae Be cae ee cue) or jolecular weight distributions. Melt in: from 0.05 to 100 or more are achieved polyethylene broad molecular weight distribution with narrow dexes MI. Economics: (Per metric ton of polyethylene powder) Olefins (ethylene + comonomers) kg 1,020 Cataiyst materials French francs 20 Power kWh 165 Steam (3 bais) t ot Inert gas (nitrogen) Nev 50 Cooling water (make up m 45 Commercial installations: One plant (40,000 tons/yr) has been in operation at Lavéra (South France) since 1975. Another one (100,000 t/yr) is scheduled for com. missioning the end of 1985. Hydrocarbon Processing, November 1983 131Pee re Application: A process for the production of ethylene butene-1 copolymer by a liquid pool technology using high-efficiency titanium supported catalysts. Hig yields of polymer provided by the new catalysts elir nate the need for removal of catalyst residues from re- actor product Description: Ethylene and butene-1 comonomer are continuously fed into a jacketed reacto are copolymerized in the presence of a light hydrocar- bon diluent (e.g., butane or propane), a chain-blocking agent (usually hydrogen), and a catalyst and cocatalyst The polymerization takes place at operating of between 200-400 psig, and temperatures ranging from 130 to 160°F The product is continuously withdrawn from the reac- where they with about 2 hours residence time. tor in the form of a slurry, which contains about 30- % resin particles. This slurry stream enters a sepa- rating unit where the pressure is reduced almost to atmospheric, causing the diluent and the remaining monomer and comonomer to flash off. The LLDPE is removed. After passing through a condenser, the recycle stream is separated and then dried and stabilized into liquid and gas components; the liquid (diluent) is pumped back into the reactor, while the gas (monomer and comonomer) is compressed before being returned to the reactor stream is necessary because the highly selective catalyst allows the polymerization to take place without form No purification step for the recycle 132 Hydrocarbon Processing, November 1983 Polyethylene (LLD) — EL PASO CHEMICAL Co. CONDENSER ed — DORs aN ey SEPARATC ing undesirable intermediate compounds, such as | molecular-weight polymer oils and waxes. Elimin of these materials prevents reactor fouling probled and improves heat transfer in the reactor. The prot operates with two types of high efficiency catalyst. type produces a conventional powder polymer, wil is extruded and pelletized, the second produces spherical-form polymer of 1.5 millimeter average ticle size that requires no pelletizing. Economics: Coupled with the “particle-form-cataly the process is expected to have the same low operatil and capital cost advantages of the gas phase proc For 100,000 metric ton/yr plant, consumption is: sté 0.2 ton/ton polymer; electricity 300 kWh/ton polyti ethylene + comonoi 1.03 ton/ton polymer; catalyst 0.05-0.07 kg/ton pal 4/shift. Battery limit investment: 3049 nillion U.S. dollars for spherical form polymer Commercial installations: One semi-commel plant with an annual capacity of 12,000 metric tome is operated by El Paso Chemical Co. at Odessa, T&™ Scaling up of the process is underway Licensor: El Paso Polyolefins Co.—Licensing Dept ment, P.O. Box 665, Paramus, N.J. 07652, References: Chiemical Engineering, May Catalyst Controls LLDPE’s Particle Geometry 13, 1982 ene by a New Economical Shirry Process. nitrogen 50 m'/ton polymer mer. LaborGaga Cote) polyethylene and ¢opolymers at high pressure in a Ebular reactor + Granulated polyethylene; density approxi Wy 0.91 melt flow index about 0.1- B10 min. Copolymers, especially with vinylacetate 30% concentrations, can be produced, too. 0.930 glem: etiption: Ethylene feed is mixed with the low pres Perecycle gas and precompressed, then mixed with Mitfor, high-pressure recycle gas, moderators and bly comonomers, and compressed to the final BSSstire. This reaction gas is continuously fed to the @éted tubular reactor Bie reaction mixture passes thre igh a special valve EWostage separation unit, consisting BF and low where Teaction gas is separated from the polymer melt Fecycled. According to the inerts present in the Basmall purge gas s of high pres- the uncon pressure separator eam can be taken from the land sent back to the ethylene purification unit E Polyethylene melt from the low pressure sepa melt granu: nd screened and Or is homogenized and granulated in fetta granulating head, dried BP the storage unit eOPMent: Single train capacities up to 180,000 tons/year could be offered at present. LDPE Gee ner scr es) Preemie) strong resins, special product types allowing 20% film downgauging due to improved mechanical properties. Conversion: The ethylene conversion rate is up to 36 percent per pass Economics: Consumption figures for 1000 kg of poly ethylene granulate: Pure ethylene (99.9%), kg" 020-1,030 Initiator and moderator, DM* appr. 4 Chemicals and lubricants, DM* appr 4 Electric power, kWh 785~1,080 Cooling water (At = 10°C), m 100-130 Steam (28 bar) consumption, ton" 2-02 Steam ( 3 bar) generation, ton* 035-05 Steam (10 bar) generation, ton* 2-0.35 Personnel requirement, men per shift 5 Commercial installations: Plants in United States, Germany, USSR, Japan, Spain, Pakistan, Netherlands, Canada, China and Thailand with a total capacity of more than 1,800,000 tons/yr are in production or un- Thailand) der construction (China References: Further information is available from Hoechst-Uhde Corp., 560 Sylvan Avenue, Englewood Cliffs, N.J. 07632 and Uhde GmbH, Friedrich-Uhde Strasse 15, D-4600 Dortmund 1, Federal Republic of Germany duipipee enti fie 19,ees) Coc ie po aie CNN uae cena eye Toe eo ; otor Polyethylene (HD) — sorcist ac Application: A process to manufacture high density polyethylene 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 large-size poly merization reactors. The reaction takes place in a slurry and the polymer is obtained as powder. The polymerization normally runs at pressures below 10 bar and temperatures between 80° and 90°C. The cata- lyst used in the reaction has a very high activity. There- fore in large scale use the catalyst is added in such small quantities that no removal of catalyst is necessary. Due to almost complete conversion of ethylene the process does not require any ethylene recycle or mono: mer recovery systems. Hydrocarbon diluent removal is done by centrifuging and final drying in a nitrogen op- erated fluidized bed drier. The main part of diluent is directly recycled into the process after centrifuging HDPE powder will be pelletized to natural, colore specifically modified grades according to a variety of ble formulas avai Raw materials and utilities (per 1,000 kg HDPE pel- lets) Ethylene and comonomers, kg Hydrogen, kg Hydrocarbon diluent, kg 134 Hydrocarbon Processing, November 1983 Catalyst, auxiliaries additives (basis 1980), DM Steam (5 bar), kg Cooling water (25°C Electricity, kWh Nitrogen, Nm’ At = 10°C), m' Commercial installations: Plants with a total capi over of 1,100,000 tons/yr are onstream (end of 198 further 120,000 tons/yr are under construction. References: Further information is available {id Hoechst-Uhde Corp., 560 Sylvan Avenue, Englewid Cliffs, N.J. 07632 and Uhde GmbH, Friedrich-Uli Strasse 15, 4600 Dortmund 1, Federal Republic of @ manyEpc CRM rzare Prey iN} ae cruey Sauna) Pplitation: Process for production of medium and Catalyst 1,300 Japanese Yen Bidensity polyethylene through polymerization of Steam 300 kg Plene under low pressure and in the presence of hy- Cooling water 100 M atbon solvent. N 40 NM Electric power 100 kWh scription: Ethylene (or mixture of ethylene and Benomer) is polymerized in the presence of solvent Commercial installations: Commercial plant of Mit- Pihe pressure lower than 10 kg/em Krature between 60 and 90°C lymer slurry discharged from reactor is sent to Biifuge after separation of unreacted ethylene alee and solvent are separated in centrifuge and Mier is further sent to drier. Recovered solvent is BS teactor directly. That means no de-ashing is nec- BY Owing to use of high mileage catalyst Molecular weight distribution can fully be gov by controlling polymerization conditions Hover, adjusting the comonomer quantity and BOBeR concentration, wide range of polyethylene, Be cdium density to high density and from high Bstade to ultra high molecular weight polymer, can Produced. g and the subishi Petrochemical Co., Ltd qumPtion of raw materials and utilities: (per &'on of powder polymer) Bene and comonomer 1,015 kg Oven, 10 kg Hydrocarbon Processing. November 1963 126136 Sd Pret Cae Brortd PELLET ves Polyethylene —— PHILLIPS PETROLEUM CO. 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 reac tor containing high purity ethylene and diluent. The produce 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 mod- crate and the diluent is recovered and recycled to the reactor. Ethylene conversion is upwards of 97% The process, by virtue of its simplicity and reliability make for easy operation and high service factor The product covers the full range of density require ments from 0.93 to 0.96 gm/cc and fills all market ap plications. Commercial installations: Soltex, Deer Park, Texas; Allied Chemical Corp., Baton Rouge, La; National Pe- tro Chemicals Corp., Deer Park, Texas; Phillips Petro leum Co., Pasadena, Texas; Union Carbide Corp., Sea drift, Texas; Chemplex Co., Clinton, Iowa, and Gulf Oil Corp., Orange, Texas. Licensees also in England, Belgium, Brazil, France, Germany, Italy, Spain, Japan, Yugoslavia, Norway, Iraq and Singapore Scheduled construction: CIL Canada Hydrocarbon Processing, November 1983MONOMER Caen c iret Sear | Mpplication: A process for the polymerization of pro: Hleic in a liquid pool of monomer by using high-cffi sfihicy Ziegler-Natta supported catalysts. High yields of Bieoregular polymer provided by the new catalysts Biiminate the need for removal of catalyst residue and Ktic material from reactor product Description: Purified liquid propylene monomer to: eller with Ziegler-Natta catalyst, aluminum alkyl ha- He cocatalyst and hydrogen (used for PSsbt control), is introduced to an agitated reactor al BEidy containing liquid propylene. The polymeriza POH Teaction takes place at 130-180°F and 400-600 BEE Propylene homopolymer forms as particles, and HS Product leaves the reactor in a slurry with un Eatted liquid propylene. The slurry enters a flash ves- Where the monomer is separated and recycled to be MKed with the feed Ethylene-propylene random copolymers are also diced in th Bywohomer in the polymerization vessel. Additionally molecular process by introducing ethylene as a ie e-propylene block copolymers are made by jy, lth the new high-efficiency catalyst, polymer yield new high-efficiency catalyst, polymer yields Bie order of 5,000-7,000 Ib/Ib of solid catalyst are hed. Also, the polymer produced with this catalyst pans 94-95% stereospecific (heptane-insoluble Btal; therefore, the removal of both catalyst resi aig the homopolymer, still containing active cata With ethylene in an lolypropylene — EL PASO CHEMICAL CO. mee cy ec eae a ees AND PELLETIZING dues and atactic polymer (deashing) is no longer neces sary After drying to eliminate residual monomer, the polymer powder is compounded with anti-oxidants and processing aids. The material is then extruded, pelletized and packaged. Economies: Very significant saving is achieved in pro: duction cost due to the elimination of the deashing step, increase in monomer yield, higher onstream fac increase in production rates and lower mainte nance costs. Steam usage is reduced by 85% and elec when compared with conventional liquid For a 91,000 metric ton/yr plant sumption is: steam, 0.5 kg/kg polymer; electricity, 470 550 kWh/ton polymer; cooling water, 70-100 m polymer. Labor: 4/shift. Battery limit investment cost $2 30 million U.S. Commercial installation pacity of 150,000 metric tons/yr in Odessa and Bayport, Texas. Two icenses have been also granted: one to Nigerian Oil Co. for a 35,000 metric tons/yr plant at Warri and the Azzawiya Oil Refining Co. for a 68,000 metric tons/yr unit at Ras Lanuf, Libya. Licensor: E] Paso Polyolefins Co.—Licensing Depart ment, P.O. Box 665, Paramus, N.J. 07652 U.S.A References: SPE Publication Feb. 23-24, 1981 April 20, 1981 tor tricity by 12% pool process con: Two plants, with a total ca ure operated by El Paso Products Co. other te Regional ‘Technical Conference Houston, Texas. Chemi cal Engineering, Hydrocarbon Processing, November 1983 137POLYMERIZATION CENTRIFUGING ar Ed Py [4 | MESES ernie MITSUI PETROCHEMICAL INDUSTRIES, LTD. Polypropylene — MONTEDISON S.p.A. Application: A continuous process to manufacture polypropylene homopolymers and copolymers without catalyst removal using High Yield-High stereospecific ity Catalyst (HY-HS Catalyst). The catalyst is a special, patented development of the companies. It may be used also with other polypropylene processes Description: Propylene, ethylene as comonomer and the catalyst system are fed into polymerization reactors containing a hydrocarbon solvent. Typical polymeriza tion conditions are temperatures in the range of 60 to 80°C and pressures of 5 to 15 atmospheres. The polymer slurry is transferred to a centrifuge to The polymer is then dried, stabi- lized and extruded into pellets Recovery of the hydrocarbon solvent separated dur- ing the process and removal of a small amount of atac- tic polymers formed in the reactors are carried out by simple distillation, separate the solvent Catalyst performance: The HY-HS Catalyst em- ployed leads in the polymerization stage to a yield of at least 1,000,000 g of polymer/g Ti and to an isotactic in- dex of 98-99. Economics: Elimination of deashing and simplified solvent recovery makes it possible to save approxi- mately 20 percent of plant investment cost needed for 138 Hydrocarbon Processing, November 1983 the conventional process plant. Furthermore, consi erable savings in operating costs can be obtain mainly on the following items: monomer consumpti0l costs for catalyst removal and effluent treatment, cos for solvent recovery and atactic removal section, lab costs, and maintenance costs Total costs for production in new plants can be ef mated at least 2 U.S. ¢/Ib less than in case of convell tional processes f Product specifications: All grades of homopolyie™ block and random copolymers may be produced. Commercial installations: Mitsui Petrochemical If dustries Ltd. and Montedison S.p.A.; many negli tions for licenses are underwayPME od ONAL see] iiction of propylene homopolymers and copoly- B by high yield-high stereo-specificity—spherical Bit catalyst jointly developed by Montedison and fist Petrochemical. Due to the performance of the ieatalyst, removal of the catalyst residue and of the ic polymer is not required; and the pelletization Mi also is not necessary Béscription: The polymerization is carried out in liq Monomer, in tubular loop reactors, and is followed sh and recycle of the unreacted monomer. The also includes an additives feeding section. The HFaditional steps, like catalyst separation, mono: BPecovery and purification, atactic polymer separa- MB Pelletization, etc., are unnecessary. The polymer Bow Teaction takes place at 60-80°C and 30-40 Biiylene-propylene random copolymers are also Hed by this process by introducing ethylene as Bhlomer into the polymerization reactors RE Production of block-copol copolymerization reactor operating in gas HoWnstream of liquid homopolymerization and ymers requires a BUS process lower grade, and therefore cheaper ene can be used propylene Mee mice of the usual polymerization grade pro- (99%) « an be used, provided the usual catalyst poi- eVe been re ‘moved. chemical grade an be used. Even refinery grade propyl Co Cs otk creer! rons aon} : ates Pct Yields: Catalyst performances: Polymer yields of 20,000 kg/ kg or higher of supported catalyst are obtained: the polymer produced with the new catalyst has an isotac- tic index of 96-99% and is free from fine size particles Economics: The high-yield process with polymerization in liquid monomer saves 40% of the investment cost in comparison with the con- ventional. The elimination of pelletization section saves a further 20% The investment costs for a plant based on SPHERI- POL about 40% of those re quired for conventional low yield, slurry processes Furthermore, considerable savings in operating costs are obtained (monomer, electric power, steam, la bor and maintenance costs). Raw materials and utilities (per 1,000 kg of PP) high stereospecificity low yield, slurry polymerization process, process are therefore nemicais & stabilizers 8 8 en 0 Product specifications: All grades of homopolymers, block and random copolymers with top level quality can be produced. Commercial installations: Italy, Brindisi, Montepoli- meri S.p.A. 70,000 vy capacity; Italy, Ferrara, Monte- polimeri S.p.A., 70,000 vy capacity. Licenses are of fered by Montedison and Mitsui Petrochemical Hydrocarbon Processing, November 1983 139are oat) ee ee Fae) foams [coon il 4 PURIF ed i eee) Polypropylene oma Crees Polypropylene — PHILLIPS PETROLEUM Co. Application: A process to produce polypropylene ho- mopolymer and ethylene copolymers continuously from propylene and ethylene Description: Fresh and recycle monomer and como- nomer when needed is introduced into the reactor with the catalyst. Polymerization occurs at relatively low temperatures. The product, whether homopoly- mer or copolymer, is withdrawn as a slurry for separa- tion from the hydrocarbon. Catalyst residues and solu- ble polymer are removed in a unique system incorporated in the process. Soluble polymer in the product can be varied to meet market requirements. The product in powder form is stabilized, pelleted, and sent to storage. The process is ultimate in simplicity and, therefore service factors are high, Propylene ef and maintenance costs low. The process is very adapta ble to most catalyst systems ers, as well as the homopolymers, fill the known market applications. iency is high Copoly Commercial installations: Arco Polymers, Inc., Deet Park, Texas; Phillips Petroleum Co., Pasadena, Texas and Pertamina, Pladju, Sumatra 140 Hydrocarbon Processing, November 1983reg REACTOR icagih ad Tas) Ea) PM Eee Application: As one of the oldest and most experi- fied producers of polystyrene, Arco Technology fis on its extensive technological and production Hise to tailor-make plants capable of producing eal purpose, impact or expandable polystyrene or HiyCombination thereof, using suspension technology Be extremely flexible facilities can follow the mar- EMitends, producing the wpes of polystyrene com- Biding the highest profitability scription: Styrene is polymerized in a water me- Bpcontaining the proper initiators and dispersion BUSiispension agents. Elastomers or blowing agents @dded to produce impact or expandable polysty- ® fespectively. The styrene is polymerized within iiich reactors unt Allon is reached Bi 50 ppm Pine polymer is moved to a wash kettle where acid is Sand the water is removed by centrifuging and 28: If required, pelletizing and/or sizing of the Bet is done after the polymer is dry the desired degree of polymer Total volatiles can be reduced to less Seas! Properties: An extremely wide range of poly Bae can be produced. Melt Flow, Condition G, can Hom less than 1.1 to over 13 gms/10 minutes. Izod ff, 2 20 be as high as 2.5 ft Ib/in. Vicats can be as p °° 19°F. By using various blending echniques, it lystyrene — arco technotocy, inc. Porm is possible to make many types from a small number of feedstocks. Commercial installations: In adit mercial U.S. plant, licenses have been granted in Ai gentina, Brazil, Finland, France, Japan, Mexico, Spain Sweden and Yugoslavia. n toa lai com- Licensor: Arco Technology, Inc., subsidiary of Adan- tic Richfield Co. Hydrocarbon Processing, November 1983141crea fone eos sing agent ee} Application: A batch process for the production of ex- pandable polystyrene beads Description: Styrene monomer and demineralized wa- ter are mixed in a jacketed batch reactor. Polymeriza- tion initiators and suspension agents are added and the polymerization started. Gassing agent is added during the polymerization and the reaction taken to comple tion on a programmed temperature cycle polymer is present as beads in aqueous suspension This suspension is transferred into a buffer vessel and then to a centrifuge. The separated beads are flash dried. The dried beads are screened to give the various size fractions required. Prior to packing the product is coated to improve its handling properties and perfor mance during subsequent processing. The beads can be made self-extinguishing by the addition of fire re tardant chemicals during the polymerization stage. The reacted Process features: © Controlled bead size and bead size distribution © Short production cycles with high phase ratios © High efficiency sieve screening © Highly effective external coating system © Simple effluent treatment © Polymerization and addition of gassing and fire re- tardant agents Il carried out in reactor 142 Hydrocarbon Processing, November 1983 Polystyrene —— SHELL/PETROCARBON FRACTIONATING eral eg Poteet ig © Designs include large reactor technology and fori small producer, single reactor mini-plants, Commercial installations: The Shell process has bed licensed in four different countries, Total produ capacity including that of Shell’s own installations is proximately 150,000 tpa. Licensor: Shell Research Ltd. Reference: Further information is available from trocarbon Developments Ltd., Sharston road, Milf chester N 4TB, England. Telephone: 061-99 Telex: 668782Ces plication: A suspension process for producing a i@range of PVC with high product quality using big Gor combined with excellent anti-fouling technique Minique cooling method, no need of refrigerated the batch Metization is done automatically by a sequential HOH ind uniform products; advanced technology lbnomer stripping and degassing provides VCM Mil the working area and VCM content in the Benet that comply with regulations. Bution control system, resulting in simplified op: Deionized water, suspending agents, cat- nd VOM are automatically charged into a reac~ hich is heated to operating temperature at pres BE 7 to 11 kg/em2g. After polymerization is Hd, unreacted VCM is stripped off, and the Se ttty is fed to a centrifuge and a continuous sin- The product PVC is peedand conveyed to the packing area. A VOM re- By Unit o) Unit operates throughout the plant, recoverir Hetcted VCM, which is recombined with the Economic: per ton of PVC) vom 1.01 tons Chemicals 9USS Steam 1.0 tons Electric power 200 kWh Cooling water 82°C) 110 m! (circulating quantity) Commercial installations. There are ten plants using this suspension polymerization technology. Hydrocarbon Processing, November 1983 143a Frosh food e Cee ues eas Propylene & butylenes (Oleflex) Application: A process for the continuous catalytic de hydrogenation of light paraffins, typically in the Cs to C; range, to their respective mono-olefins Description: The process is an extension of UOP's Pa- col process to the dehydrogenation of light paraffins The Pacol process is a continuous fixed-bed catalytic dehydrogenation process for the production of mono- olefins from paraffins in typically the Cy to Cio carbon range. The UOP Oleflex process is specifically de ned for the processing of light paraffins, This pro- cess combines the high activity and selectivity of a P: col-type catalyst with UOP’s highly successful continuous catalyst regeneration technology widely used in the catalytic reforming of hydrocarbons for the manufacture of high-octane gasolines (UOP’s Continu ous Platforming process) The UOP Oleflex process finds application in the manufacture of propylene from propane, isobutylene from isobutane, from n-butane and amy- lenes and isoamylene from pentane and isopentane. respectively. Other combinations based on mixed ( feeds, etc n-butenes, are equally possible. Typical overall process yields are 85% propylene on propane ane 91% i-butene on i-butane 81% n-butenes on n-bu When processing Cy’s, the UOP Oleflex process can be advantageously used in conjunction with UOP's Bu- 144 Hydrocarbon Processing, November 1983 Te) Bas) Light ends l ' ene Gaon UOP PROCESS DIVISIO! —— voP INC. ' tamer process for the isomerization of n-butane 10F butane, UOP’s C; Olex process for the recovery of high purity butylenes, UOP’s HF Alkylation process for ti production of high-octane motor fuel alkylate, Wil catalytic condensation for the production of gasolif distillate or petrochemical olefins, UOP Sorbutene fi extraction of I-butene, or with the Huels MTBE pit cess for the production of MTBE Commerical installations: Various UOP Oleflex will are in the study or design stages. Currently UOP his 5 Pacol units onstream with 6 or more in the designdl construction stages for plasticizer or detergent rani feedstocks. The basic technology for continuous Gl lyst regeneration has been demonstrated in the UM Continuous Platforming process with 42 units in ope ation an tion 1a further 42 units under design or consti References: Vora, B.V. and Imai, I n PM essing, Vol. 61 No. 4 Hydr April 1982, pp. 171eription: Perpropionic acid: aqueous hydro PEMXide is reacted with propionic acid in the presence Sulfuric acid to perpropionic acid (1). Perpropionic BGM iS recovered from the reaction mixture by extrac- Ho(2) with an inert organic solvent BSe of the extraction containing mainly HSO, and SHO. is concentrated in column (3) and recycled i). The organic extract is scrubbed with water (4) BM dried by azeotropic distillation (5), Fropylene oxide and recovery: The perpropionic lution is reacted with propylene (6). Propylene P recovered fro1 Potation in the The aqueous he reaction mixture by frac- ; ps: predistillation (7); ex ES propylene for recycle (8); propylene oxide (9); sol- lowing st ait for recycle (10); propionic acid also for recycle 0 Rags and Bayer AG. A pilot has t Years »perated for Pylene selectivity of the process is close to 100% Aino byproducts are being formed. The process is HOhmentally clean, avoiding problems with chlo BLACl, and chlorinated byproducts. The process Propylene oxide (Degussa/Bayer BAYER —— AKTIENGELLSCHAFT water is easily handled in a biological system The safety aspects related with the process have been thoroughly discussed and tested with German government authorities (BAM) whose approval for the concept developed has been given. Status of the process: capacity has been prepared. No commercial installa- tion Basic design for a 150,000 va Erdél and Kohle, Erdgas, Petrochemie 24, Compendium 78/79 Reference: pp. 507 Hydrocarbon Processing, November 1983145Cary STRIPPER ‘e Cd 4 i ett) Wie Propylene OXIAE — oarcer cemicat iwoustaies, 10. Application: A process for the manufacture of propyl- ene oxide and acetic acid by epoxidizing propylene with peracetic acid. Description: Propylene and a solution of 30% pera cetic acid and 10-15% acetic acid in ethyl acetate con taining stabilizer is continuously fed into a series of three specially designed reactors for epoxidation at 50-80°C under 9-12 atm 98% of the peracetic acid is reacted to give propylene oxide in 90-82% yield. Then, the reaction products are fed into a stripper and distilled at 1.3—5.0 kg/cm? From the top of the stripper, (1) a mixture of propyl- ene and propylene oxide mixture of ethyl acetate charged. The first mixture is liquefied by cooling and com- pression, and then fed into a propylene stripping col- umn operated at 12-15 atm., where propylene is re. 1 and recycled into the first reactor. Crude propylene oxide is discharged from the bottom of the propylene column into a light-end column and a pro- pylene oxide column as weil for refining The second mixture and a high boiler which is ob- tained from the bottom of the propylene oxide column are fed into recovery columns, where ethyl In about 2 to 3 hours, 97. and from its bottom, (2) a and acetic acid, are dis covere tate is recovered, and recycled into the peracetic ac actor Acetic acid is also recovered and used as it is or refined for many applications. 146 Hydrocarbon Processing, November 1983 itn Catt ame get) fot tT) Raed Caer Cary Pearcy Conn Gears | Characteristics: Because the reactors specially @ signed are used, the conversion of peracetic acid higher with byproducts produced in small quantilé than that now being made by other conventional 1@ tors. Further, the reactors, because they are of a bil bling type, are higher in heat transfer coefficell lower in capital cost and safer in operation q Reference: S. Patents 3,66: Patents 1,2 330, 1,2 2,008,308, 2,039,760; Canadian Patents 856,84 903,246. K. Yamagishi, et al, “Make Propylene Oxt Direct,” Hydrocarbon Processing. Nov. 1975, pp. MWe 104 5 654,094; Brith 3,619; French PatetlCa acres ed tenn Ss eueanal Pe Pa Sete bpplication: A continuous process for the manufac- lite ofa protein feeding stuff based on the fermenta- itt} of methanol by a selected micro-organism. Scription: Air, ammonia, methanol and other minor anic nutrients are sterilized and fed to a single ge pressure cycle fermenter which has no moving and was invented by ICI Agricultural Division at Ingham, England. The micro-organism, which is a fi Of the species methylophilus methylotrophus, is lined at a concentration of 30 g/l in the fermenter ML COntinuously withdrawing the circulating culture pietiaterial from the fermenter passes through floccu: $20 and separation stages to remove the bulk of the Twhich is then recycled to the fermenter. Novel en- ing developments permit continuous fermenta- Gey. be carried out in a sterile manner so that only the Bettied micro-organism is present in the fermenter Beet separation of the bulk of the water the product Sm is then processed by flash-drying to produce a lular product which is used, typically, in poultry SS Some of this material is ground to a fine powder Produce a product with the desired suspension Spputics for use in milk replacer diets for calves THLEEN is one of the most concentrated, energy- ighly digestible protein sources available for ani- ie CdS. It contains over 70% protein, is rich in the Hal amino acids, lysine and methionine—being oer Rea Eats Dea eo Ein Eee pase derived from living organisms it contains all the ele: ments necessary for healthy growth It gives significant animal performance improve- ments when used to replace soya or fishmeal in poul- try, pig and fish diets. It is also used in calf milk repla cers and young pig diets as a substitute for skimmed milk powder Hydrocarbon Processing, November 1983147(Nate 4 er ee Seon Styrene (Cosden/Badger) | Eiacent hy Panel aa oe a eek lary (ectsy 2a ont) conn) eee contr Seed De i i) aoa Ela eel ammo con a RESIDUE FINISHING Bast STORAGE via Mobil/Badger ethylbenzene — tie saocer co, inc. Application: Process for manufacturing styrene monomer by the alkylation of benzene with ethylene to ethylbenzene and subsequent dehydrogenation of the ethylbenzene to styrene. Description: Benzene is contacted with ethylene in the presence of a hetrogencous catalyst and recycle po- lyethylbenzene prefractionator to recover unreacted benzene for recy- cle to the reactor. Crude ethylbenzene from the bot The reactor effluent is directed to a tom of the prefractionator is subsequently charged to recycle benzene is first and the prod. uct ethylbenzene is separated from the heavy compo- nents, The heavy components are finally distilled to he reactor the distillation system. Here separated from the crude ethylbenzene separate polyethylbenzene for recycle t Ethylbenzene purity is consistent with the manufac ture of polymer grade styrene In the styrene section, fresh ethylbenzene is com bined with recycle ethylbenzene and charged to the de hydrogenation reaction section in admixture with su perheated steam. Reaction pressure and temperature are major control variables for maintaining a high con version per pass The styrene monomer recovery section consists of three columns. The small amount of benzene and to: luene produced by cracking in the dehydrogenation 148 Hydrocarbon Processing, November 1983 reaction is removed in the first column and revurné to the ethylbenzene system. Ethylbenzene for recycléh separated from the styrene monomer in the secoill column. This difficult separation is accomplished it single, high efficiency column. In the third column th styrene monomer is separated from small amounts tar and polymer formed during the operation. A nol sulfur inhibitor is added to minimize polymer form tion in the distillation train. Furthermore, no pollutif waste streams are produced Commercial installations: Styrene from ethylbet zene: The technology has been selected for use in 2 units having design capacities (single train) rangill from about 32,000 to about 455,000 metric tons pe year. The aggregate capacity of such units exceeds! million metric tons per year. Licenses for the use of technology are offered by The Badger Co., IncBaca) Pee) Roun ze Je Benzene | co foe cod Ca eae tats er MPplication: Manufacturing of high purity styrene lomier by alkylating benzene with ethylene to lice ethylbenzene which is dehydrogenated to sty- The Friedel Crafts reaction of benzene x in presence of aluminium chloride, is Bied Out in an homogeneous phase reaction system, BING a new “high temperature This al- @feduction of the reaction volume, a high conver recovery at a higher thermal level. lie is then sent to a neutralization system for re- technology HME traces of chlorides before feeding distillation High purity ethylbenzene is recovered and sent hydrogenation section. Unconverted b Batliyibenzenes are recycled to reaction Boll is burnt to furnace Baiibenzene is dehydrogenated by a catalytic reac- Me 888 phase in presence of superhe zene and residual ted steam @actction takes place under vacuum, in a multibed HON system with radial flow and low pressure EA fractionation train separates high purity sty puticonverted ethylbenzene which is recycled with Beccd, benzene recycled to alkylation section, tol 8 PYproduct, a small amount of tars which are BH the unit furnace Peg stlfur inhibitor is used to minimize polymer 0, and enables burning of tars without prob- The process condensates are treated in the unit, and recycled for steam generation. Process effluents: A small quantity of vent gas is dis- charged from alkylation section. This gas is treated for recovery of residual aromatics and Hel removal. A new patented technology can be proposed by CdF Chimie- Technip for the neutralization of alkylate. The only residue is a dry salt which can be upgraded as fertilizer component, without any aqueous efflue Raw materials and utilities: Faw materials (per metric ton of styrene] Ethylene Benzene (Toluene production Utilities (per metric ton MP steam, metric ton Fuel, 10°Kcal 'yrene): icals and catalyst U.S.Sit Commercial installations: Eight styrene plants lo- cated in various parts of the world, use the CdF Chi- mie-Technip technology. Capacities range from 15,000 to 300,000 metric tons per year. Other projects are at design sti Hydrocarbon Processing, November 1983 149CASCADE SULPHONATION SYSTEM Cruel ae SULPHONATION SYSTEM Raw material Sulphonation — BALLESTRA SpA. Application: Continuous process for the sulphonation and/or sulphation of natural and synthetic fatty alco- hols, linear or branched alkylbenzene alcohols, ethoxy- lated alcohols and generally all the raw materials for the detergent industry Description: The sulphonation and/or sulphation is carried out in exact proportion and correlation to the SOs gas according to stoichiometric ratio. By the sulphonation system in cascade, tt terial passes by transfer from one sulphonator to the next one, while the SO; that reaches them in parallel, subdivided into defined fractions per each sulphona tor, is dispersed by special turbines. By this way, a regu- lar advance of the degree of sulphonation is obtained from one sulphonator to the other. In the sulphona- tion of some raw materials (i.e., dodecylbenzene), the sulphonated product overflows into the ageing unit and into the subsequent final homogenizing unit, in which the reaction is completed by the exhaustion of the residual sulfur trioxide. The stabilization is then accomplished by adding a small water percentage With the film system by means of multitube film re actor, special products and shampoos base surfactants can be obtained. and in parallel film reactor is that it is able to maintain the exact pro portioning of the liquid compared to the gaseous reagent, thanks to a special and particularly simple de- vice that allows to obtain exact mole ratio of the reagents in each tube Both systems can operate separately The main advantage of the multitube 150 Hydrocarbon Processing, November 1983, Pang Vera Nelo) > deeper ty SCRUBBING (eee i i DOUBLE-STEP NEUTRALIZATION In this way, the higher degree of conve tained, as well as the best quality (unsulphor free SOs[H,SO,]) thanks also to the large heat & change surface available for the control of the react temperature. The sulfonic acid produced through these pit cesses is neutralized with one of the two systems f normal" and “high” active matter concentration (if to 70%), shown in figure, that can be applied to the til sulphonations alternatively. If alpha-olefins are pig cessed, a hydrolysis unit has to be added to the neut ization section. Economics: For the production of 3,000 kg/h of 1008 active matter, the estimated investment will be: US} $1,600,000 with the cascade sulphonation system i with the film sulphonation system (production of eous SO, included Commercial installation: The industrial plants i stalled all over the world are about 150 with the Gi cade sulphonation system and over 25 with the f sulphonation system. References: A. Davidsohn & B. M. Milwidsky “S¥f thetic Detergents,” published by Leonard Hill Bool ISE, AOCS Cong April 1980, “Natural Fatty Al@] hols, Their Comeback As Detergent Raw Materidl Review of Production and Processing Technology” Licensor: Ballestra S.p.Alication: A newly developed process for m Offiber grade terephtha thano nufac- ic acid from p-xylene and iption: The first sections of the process are the Reas the well-known DMT process of Dynamit No- oxidation of a mixture of p-xylene and p- i{toluate, esterification of the oxidate and sepa- Of the crude ester by distillation into a p-methyl fia tection and a fraction rich in terephthalic alde- ster, which are recycled in the oxidation, a resi- Fiction and crude DMT. The hydrolysis of the DMT is effected with water at 250 to 280°C, fol I) Separation of the resultant terephthalic acid, € By ent and working up of the aqueous reaction Git comprising methanol and byproducts ption: In kg per kg of product acetic acid, 0 ; make-up methanol, 0.05: ! For a 150,000 metric ton/yr plant (West BR Cehditions January 81) including compressor He ctve carbon absorption unit for off-gas, hot Bins system and catalyst regene BRU) equipme Ecting, DM 118 ation are 1 t, FOB. German port, includir x 10°, (2) civil work, DM 11 x 1¢ (3) construction DM 19x 10° for 148 x 108, a total of DM Utilities: In units per kg of product 4.2 MJ; electric power, 0.52 kWh The production of medium pure terephthalic acid (MTA) is possible with lower energy consumption and investment figures steam, 0; fuel, Hydrocarbon Processing, November 1983 151Pron eo Urea — snaverocer Application: A. process for the manufacture of urea from ammonia and carbon dioxide. Description: react at 150 kg/cm? to yield urea and ammonium carbamate The carbamate content of the reactor effluent is de- composed and separated in a single-stage high pres- recycle operating at reactor pressure. An ejector (feed ammonia is the driving medium) sup- plies the motive power to return the high pressure car bamate solution to the reactor in the synthesis loop avoiding the use of a pump and to obtain steady oper- ating conditions even with the carbamate condenser in- stalled at ground level. This layout is essential for larg plants. The solution outflowing the reactor is sent to carbamate decomposer (stripper) to obtain the dissoci- ation of carbamate. The stripping inedium is the NHs contained in the solution (self-stripping) The overhead vapors pass to the Ammonia and carbon dioxide sure carbamat igh pressure car- bamate condenser, in which the condensation permits the production of steam. Operating at 185°C and NH. Oz, mole ratio of 3.5:1 in the reactor and at 200°C in the stripper the CO, total conversion in the synthesis loop is nearly 90%. The urea solution leaving the strip: per is expanded and heated in two stages at succes sively low pressure where residual NHy and CO; are flashed off and then recovered and recycled as ammo: carbamate solution. nium Finishing. Any finishing can be coupled with the 152 Hydrocarbon Processing, November 1983 Co synthesis process: prilling, granulation both direct via crystallization. Different product quality (mail regarding biuret, hardness and sizes) are obtained. Pollution. The plant is free from pollution prol lems. All vents are washed in very high efficient equipment and are discharged to the atmosphere pf tically fre The process condensate is treated in order to recyd all NHy and COs to the plant. The urea content canb decreased to any value below 200 ppm down to a nel gible value in order to meet the most restrictive las > of ammonia Raw materials and utilities: The consumption of i materials and utilities referred to 1,000 kg of urea pi duced are (prilling case with electric motor for © compressor) Ammonia 570 kg Carbon dioxide 740 kg ‘Steam (23 kg/cm? sat) 850 kg Electric power 105 kWh Cooling water 70m Export steam 3 kg/om? sat 100 kg 3 Commercial installations: Twenty-five plants are aff in operation with capacity up to more than 2,000 F F F se cal ric tpd on a sing! struction, line. Fourteen plants are undeDoar Se lication: A continuous gas phase process for vinyl 84s F F ie starting from ethylene, acetic acid and oxygen tiption: Reaction: Vaporized acetic acid and eth leare mixed with oxygen and reacted in a fixed bed lat reactor. Supported noble metal catalysts are Which yield high average selectivities of 92% over PEwWhole service time. There is a choice of seve bf catalysts, depending on the size and location of Plant. The only major byproduct is CO». Steam is Blerated in the reactor by the exothermic heat of re- Mand used in the purification train Infication: Vinyl acetate is recovered from the re- Mi gas mixture by condensation and scrubbing Heacted ethylene is recycled to the reactor after re- fats CO, in a standard hot carbonate system. The EL. vinyl acetate is purified by distillation from ace- Sf which also is recycled, from water, light ends Ain acetaldehyde) and heavy ends. Safe operation Be Pect to fouling, corrosion and the explosion Hokthe reaction gas is ensured by extensive experi ronmental protection requirements can process has been developed together with Process economics have been continu- Ercial installations: Total capacity of this pro- @MOunts to more than 1,500,000 metric tons/yr Gna! capacities ranging between 15,000 and Metric tons/yr. The following companies are Carn Potency cr Vinyl acsate er Ce producing under Bayer's license: BP Chemicals, U.K.; Celanese, U.S.; CSR Chemicals, Australia; Du Pont Plastics, U.S.; Hoechst AG, Germany; Kuraray, Japan: Mitsubishi/Nippon Gohsei, Japan; Taqsa, Spain; Shin Etsu Chemicals, Japan; Showa Denko K.K., Japan State Authority, People’s Republic of China; Union Carbide Corp., U.S.; Wacker-Chemie, Germany; Poly- chem, India; Dairen Chemical Corp., Taiwan, ROC. References: Chemie Ing. Techn., Vol 40, 1968, pp. 781 3 Hydrocarbon Processing, Vol 47 No. 11, 1968, pp. 187—191;Chemistry and Industry, Vol 45, 1968, pp. 1559-1563; Chem Ind./Olef Symp., Bratislava, No. 2 1972; Hydrocarbon Processing, Nov. 1973, p. 189, Now 1977, p. 234 and Nov. 1979, p. 250; and Erdél and Kohle, Compendium 78/79, pp: 493-506. Hydrocarbon Processing, November 1983 153Olas ee} Poona Coto ee Coa rates Vinyl acetate separation Ped Mau Dey Coa hom i eT Te Oe) Eel saas senile] Vinyl acetate — us. oust cemicats co. Description: A vapor phase mixture of ethylene, acetic acid and oxygen is passed over a fixed catalyst bed in a multitube reactor. The noble metal catalyst is sup: ported on a special carrier inside the r tor tubes. Reactor effluent is cooled and passed successively through an absorber and water scrubber to separate the crude product and acetic acid from the vapor stream. The absorber and scrubber bottom streams are combined and fed to the primary tower in the purifica- tion system: The acid-free scrubber overhead, consisting of car- bon dioxide and water byproducts along with un- are compressed and fed to the carbon dioxide removal system. This compres- sion provides the driving force for the vapor traffic in the reaction section. reacted ethylene and oxygen. Carbon dioxide generated in the process is removed with a potassium carbonate absorption system. The ab- sorber overhead stream, primarily ethylene the acid tow turned to the reactor as feed is fed to rv where it is acid-humidified and re- The primary distillation system consists of the pri- mary tower and two auxiliary strippers with a common overhead condenser and receiver. In the primary tower, the vinyl acetate heavy impurities (lower boiling than acetic acid) and water are taken overhead. The bottom stream, con- dissolved gases, light and water and minor amounts of heavy impurities, is returned to the absorber, as absorbant 154 Hydrocarbon Processing, November 1983. and to the acid tower along with makeup acetic aad The overhead from the primary tower condens4 and separates into an organic and an aqueous layerl the decanter. Part of the vinyl acetate layer is return inder is fed tot drying tower for water removal. The aqueous layetl stripped to less than 10 ppm vinyl acetate Vinyl ac pumped to the lights tower where residual acetall® hyde and other light impurities are removed in tif 1. The bottom stream is sent to the prodilf tower in which heavy impurities are removed from i vinyl acetate product in the bottom fraction. The pt nsed and pumped to st to the column as reflux and the rem je from the bottom of the drying towers overt uct tower overhead is cond agi Yield: 91% vinyl acetate, 8% carbon dioxide, 1% oth better than 99% recovery of both ethylene and acti acid free and sad alyst system with two or more years life. Operalil conditions are carefully selected to avoid the use of The process is virtually corrosio otic alloys Commercial installations: The U.S.1. Chemicals @ plant at La Porte, Texas, has 600 million Ib/yr capadil In Japan, licensee Denki Ka 1 Ope ating a 110 million Ib/yr pl aku Kogyo has be nt since early 197: Reference: Hydrocarbon Processing, Nov. 1972, p- WlOtc Cece eel or Recs ee Pieter eeu ta re dichloride (EDC) as an intermediate and. Seoproduct fiption: In the oxychlorination (OHC!) section, Bijlene and recycle hydrogen chloride (HCl) from facking section are reacted with oxygen (or air) in iid bed reactor to form EDC. Heat removal is ef- @ by steam generation with the steam being uti- ii the EDC purification and VCM recovery sec ect chlorination step, ethylene and chlorine acted directly to produce EDC. Recent advances HS technology have resulted in considerable utili- BiVings over the conventional direct chlorination ler with racking section is EDC purifica- if re ecycle EDC from the Billed to furnace feed quality in the Pettion. Product specification EDC Ie from this section. uired, is cked to VEM and ‘acking section. In the HCI-VCM recovery “M, HCl and EDC are separated with the ing recycled to the OHCI section and EDC to fapttification. After separation, the VCM is fur Btreat ce, Mated to produce specification product Se sd acon enn eld eta alin Mero Veal oreo ree key Highly competitive raw material chlorine and ethyl- ene consumption figures are represented is also available from BFGood- rich for wastewater treatment and vent gas incinera Proven technolc tion. Commercial installations: Forty plants throughout the world with the following aggregate capacity EDG by OHCI—6,009,000 metric tpy EDC by direct chlorination—2,800,000 metric tpy VCM—6,435,000 metric tpy Plant capacities range from about 15,000 metric tpy VCM to about 480,000 metric tpy VOM. Licensor: The BFGoodrich Chemical Group, Cleve- land, Ohio, U.S.A. Hydrocarbon Processing, November 1983 155Set) Vinyl Chloride — mirsuitoastu cremicats, inc. Application: A process for vinyl chloride monomer (VCM) production from ethylene and chlorine Description: VCM is produced by thermal cracking of ethylene dichloride (EDC). In the direct chlorination section, ethylene and chlo- rine are fed into the reactor where the following reac- tion takes place ini the liquid phase of EDC at its boiling point CH +Ch > CHiCh The product EDC of this section is dry without chlo: rine and catalyst due to the boiling point technology There is no waste water produced in this section. In the oxychlorination section, excess ethylene and 1 the reaction loop. The fresh feed of ethylene, hydrogen chloride and ox- gen are mixed with the recycle gas, and then intro: duced into the reactor where the following reaction takes place on the fluidized catalyst of high quality C,H, +2HCI+ '20. C,H Cl +H »O The heat of reaction is removed by circulating hot water which is recovered as steam for EDC tion. The reaction mixture is cooled down, and both oxygen are totally recycled arow purifica EDC and water produced are condensed in the quencher. EDC is easily separated from the water by decantation, and sent to the dehydrator after caustic treatment. The total gas recycling technology results in maximum utilization of raw materials as well as no air pollution problem 358 Sedreneeiene Droeuetiitte Miter sae The dehydrated EDC is combined with the dry EE from direct chlorination section, and then sent tot EDC purification section where small quantity of lig and heavy impurities are separated out. In the EDC cracking section, the purified EDE cracked to VCM and hydrogen chloride under hil temperature and high pressure condition. CyH,Cly > CHyCl+ HCl The hot effluents from the EDC cracker in the EDC quencher In the VCM purification section, gaseous and lig streams are sent to the HCI column where hydrogt chloride is separated out and returned to the 0% chlorination section. Then, EDC is separated out in VCM column and recycled to the EDC purification & tion, VEM is finally dried by solid caustic Yields: Based on 100 kg of VEM product mately 47 kg of ethylene, 57 kg of chlorine and 14] of oxygen are consumed. Product quality: Vinyl chloride re quendli ppro Actual yearly record) min, 99,99 to, Hydrogen chloride trace Iron 0.02 wt ppm Acetylene 0.08 wt ppm Butadiene 2.92 wt ppm Methyl chloride Commercial installation: Plant with total capacitl§ 815,000 tons/year are onstream (end-1982), furtlt 19.42 wt ppm 610,000 tons/year are under constructionOXYCHLORINATION REAGTOR 6 RECOVERY aera esi atc iE | CRUDE EDC | Ora 7S ia eae ETHYLENE (cee ADDITION CHLORINATION Fra aro Worse ad The process as presented here is for a ed-integrated” vinyl chloride plant wherein vi- Hilchloride monomer (VCM) is the sole product and HIDE the hydrogen chloride (HCI) produced from the Btking of ethylene dichloride (EDC) is recycled to the hlorination unit and no externally produced hy {0 chloride is used as feed Under other cireum: KES, the process can be arranged to produce either Br both EDC and HCl as coproducts. The process B88 Well able to receive externally produced hydro: EN chloride balanced-integrated” arrang EDC is ced in both direct chlorination and oxychlorina Units asa feed. ment @thylene in the liquid phase by the addition reac 19 produce EDC CoHy+ Cl > CoH,Cl ation unit ethylene, oxygen and HCl ep acted in the vapor phase over a PPG-developed Sito produce EDC OH, + 2HC1+ 20, > CyH\Cl+ HO heat of reaction is recovered 1s high pressure ##Nd used in other portions of the process. rae QUENCH liny| Chloride — rec wnoustaes, inc. is 2019 rane CRACKING Te PURE cae wine fred cor se Due to the use of oxygen and the judicious choice of design and materials, the oxychlorination unit oper- ates at a high onstream factor, under moderate pres sure employing a simplified condensation system to provide high yields and essentially corrosion free oper- ation The crude EDC from the oxychlorination and direct chlorination units is combined with the EDC recycled from the cracking unit and purified by distillation Vinyl chloride monomer is prod cracking the purified EDC at high temperature, CoH, Cl) > CsH3Cl+ HCl The cracker effluent is quenched and the HCI sepa- rated and recycled to the oxychlorination unit. High purity polymer grade VCM is separated from the un- reacted EDC. The unreacted EDC ification unit ced by thermally is recycled to the The process has been designed and automated for h yield and high stream factor operation over a broad range of turndown. In addition to producing high purity polymerization grade VCM, the process enjoys essentially corrosion free operation, safe low manpower, hi low catalyst cost, infrequent decoking and low mainte- nance cost Commercial installations: Polymer grade VCM and EDC are produced by the PPG process in plants in the United States, Japan and Europe. The combined pacity of the plants now in operation and under con struction is more thar EDC and 3.6 billion pounds per year of VCM 5.7 billion pounds per year of Se alPp Xylene — ARCO TECHNOLOGY, INC. Application: A process for the recovery of the highest purity paraxylene commercially available by crystalliza- tion from mixed xylenes Description: In the two-stage crystallization process xylenes are cooled by exchange and then charged to the first stage crystallization, which consists of one crys- 40° to 0°C followed by a sec- ond crystallizer operated at —55° to — 70°C. Filtrate from the second stage joins the fresh xylenes going to The crystallizers are cooled by external refrigeration employing ethylene refrigerant within a few degrees of the eutectic temperature of the feedstock so that paraxylene recovery is very close to the theoretical maximum The first stage crystal slurry flows to a continuous tallizer operating at the first stage crystailization The final first stage crystallizer operates centrifuge where crystals of 85-90% paraxylene are removed from the filtrate First stage filtrate is exchanged a then leaves the unit for sale xy inst feed and feed for us xylenes or ¢ isomerization unit The first stage crystals are melted and then charged to a single second stage crystallizer, which operates at 20° to 0° depending on the feedstock and desired purity. The crystallizer is cooled externally with pro: pane refrigerant. The crystal crystallizer to a second stag which separates crystals from liquid The liquid filtrate, which is fairly high in paraxylene lurry flows from the continuous centrifuge et Ween j CAYSTALLIZER CENTRIFUGE content, is recycled to the first stage. The crystals al washed with toluene in the centrifuge and melted. T paraxylene stream is then fed to a paraxylene-tolueld wash and high purity paraxylene is taken as bot product The paraxylene crystallization process is usually 6 ployed in conjunction with a xylene isomerization pil Paraxylene is removed £10 the crystallization feedstock (a mixture of fresh Gs aI matics plus recycle) and the paraxylene-depleted @ aromatics from crystallization are charged to isomel cess such as Octafining. zation where Cg aromatics equilibrium is re-estil lished 4 Yields: Over 90% of theoretical yield Utilities: (per metric ton 99.5% purity paraxylene) § Steam (1.4 kg/m’) 410 kg Steam (17 kg/cm?) 340 kg Electricity 475 kWh Cooling water 79 M Commercial Installations: Eight installations with tal design capacity of 375,000 metric tons per yeum 99.5% plus purity paraxylene are operating. Inst ions are located in the U.S.A., China, Algeria, ATS tina and Russia Licensor: Arco Technology, Inc., subsidiary of At tic Richfield Co.Mplleation: A process to convert toluene or toluene BUCS aromatics to xylenes and benzene by dispropor- ion and transalkylation iption: ‘Toluene and ( 9 aromatics or only tol- Medre fed to a catalytic reactor where transalkylation HOF disproportionation take place to produce high BES of Cs aromatics and benzene. The catalyst used Process is an inexpensive non-noble metal that is ala high level of activity by continuous regener Hydrogen is not required so that the investment perating cost associated with a hydrogen recycle ation are not incurred. #Erring to the flow diagram, the fresh feed aro- Bplus recycle are heat exchanged with the reactor Rept and then raised to reaction temperature by a Heater. The vaporized feed enters the reactor ed with downward flowing cz In the Portion of the reactor, product vapor is sepa- ttom the catalyst, leaves the re Hen the reactor feed exchanger wed: The stabilized product is pumped to the qebation system to separate benzene Sand, if necessary, Cy aromatics. alyst, which has accumulated a small amount }Passes to the regenerator (kiln) where the coke HVed by bur ning with air. Steam is g esf8s from excess heat in the stack g lyst a d ctor, passes and is cooled and nerated in s. No spe- Cate SEPARATOR ECO Be ae Sey] ry i e ny 1 ees) ae ARCO TECHNOLOGY, INC. cial materials of construction are employed through- out the system. Yields: Over 95% of theoretical molar yields are ob. tained. Depending on the mixture of toluene and Ca aromatics charged to the process, Cs aromatics yields (predominantly xylenes) range from 55 to 84 weight percent of fresh feed while benzene ranges from 40 to 10 weight percent. Minor yields of gas, heavier aromat- ics, and coke (non-recoverable) make up the balance. Utilities: (Per metric ton of fresh feed) Fuel (heat absorbed) —_0.50-0.85 MM keal Power 20-35 kWh Steam (net) 100-200 kg Boiler feed water 0.4 MS Cooling water 3.57.0 MS Commercial installations: Five units are operating or are under construction in China, Taiwan, Mexico and U.S.A. with a total fresh feed capacity of 622,000 met- ric tpy. Licensor: Arco Technology, Inc., Subsidiary of Adan- tic Richfield Co. Hydrocarbon Processing, November 1983 159eos eae Application: Any non-equilibrium mixture of Cs aro matics is efficiently isomerized toward equilibrium The desired isomer (or isomers) is sepa reactor effluent and the remainder recycled ated from the Charge: The feedstock may be of any Cs aromatic mix- ture; e.g. gasoline from catalytic reformate or from pyrolysis The latter often contains as high as 40% ethylbenzene, which is no detriment to the operation Feedstocks may be pure solvent extracts or fractional heart-cuts containing as high as 25% saturates. Hydro: gen supply may be from catalytic reforming or any other suitable source. Chemical hydrogen consump- tion is minor Products: The purity of the product, usually para- or ortho- xylene, or both, depends primarily on the sepa- ration procedures involved. The Isomar process is readily adaptable to yielding pure para-xylene when coupled with a UOP Parex process unit or with conven- tional crystallization, and ortho-xylene of standard pu- rity when coupled with efficient fractionation. Even when saturates in the feedstock are high, o-xylene pu- rity of 99% plus may be met. Description: C. aromatic reactor feed, deficient in one or more components relative to equilibrium composi- tion, is processed over a fixed bed of catalyst in the presence of hydrogen. The liquid portion of the efflu- ent is fractionated to remove both light and heavy aro- 160 Hydrocarbon Processing, November 1983 Xylene isomerization (Isomar Cea eee me an ad UOP PROCESS DIVISION, = UOP INC. matic byproducts, as well as the cracked materials sulting from inclusion of saturates in the feel Para-xylene and/or ortho-xylene are separated from thy resulting fractionation heart-cut, thereby preparing recycle material to the Isomar reactor. Fuel gas Bj products are very low with UOP's newest Isomar cal lyst. Chloride addition is not required Operating conditions: ‘Temperature and pressttd are moderate, permitting the use of carbon steel ali other conventional equipment Yields: Commercialization of a new and Parex absorbent has demonstrated high efficiend in processing a feedstock high in ethylbenzene (Oi tent Isomar cata Wt units Feed composition Ethylbenzene p-Xylene m-Xylene o-Xylene Product yield o-Xylene p-Xylene 19.6 70.6 Commercial installations: Fifteen Isomar units li! been commissioned, and nine others are in design or construction stages.