Document bR2ZezKyN6vbYVoN2pMb23bg

MONSANTO COMPANY ORGANIC CHEMICALS DIVISION STANDARD MANUFACTURING PROCESS FOR AROCLORS - DEPARTMENT 246 Date: July 20, 1964 Author: D. E Harris DSW 200811 STLCOPCB4058875 ) . Dept. 246 - Process Description AROCLOR ' SECTION I . . , ' . 1. . ' ' SYNOPSIS OF PROCESS . . t Aroclor is a trade name used to designate chlorination products of .biphenyl, biphenyl high boilers, or mixtures of the two. Liquid- Aroclors are produced by chlorinating biphenyl to 21, 32, 42, 48, - 54, 60, and 62$ chlorine content. Chlorination above 63$ yields a solid product at normal temperatures. Liquid Aroclors are identified by four digit numbers: The last two digit numbers represent the -.chlorine content (percentage by weight), and the first two numbers represent the: Aroclor condition (crude or distilled). Crude Aroclors . . start with the prefix 11 whereas distilled Aroclors start with the . ' refix 12. For example, Aroclor 1242 is a distilled chlorinated iphenyl containing 42$ chlorine. `. . The first process step in the manufacture of Aroclors is a chlorina tion reaction. Biphenyl ( 0-0) and chlorine (CI2) gas in .the presence of a Ferric Chloride (FeC^) catalyst are reacted to form a chlorinated aromatic compound. Hydrogen chloride- (HC1) gas is liberated during this reaction and piped to the muriatic acid department. 'The exact chemistry of biphenyl chlorination Is . unknown. Many isomers are formed. A schematic representation'of biphenyl chlorination is as follows: . . '- . - .1 ri- varies. 3.05 --:-------> 6.-75 ' Cln >\ +n HC1-- . . 120-170C . /TTX ATX 36,200 n + n ..Cl2 FeCl3 V y--X^yBTU * BIPHENYL M.W. = 154 , ^ mt CHLORINE ` \ : V ' AROCLOR-,- HYDROGEN / - * M.w. = 71 .' M.W.= (254.1-, CHLORIDE . .` . v. ."395.6) ' M,W.=36'-.'5 ` .* . . `. .... * DSW 200812 STLCOPCB4058876 o Dept. 246 Process Description } 2. . AROCLOR , . SECTION I . .' SYNOPSIS OF PROCESS (Cont'd.) - The second process step Is the aeration and distillation of the crude ' ` Aroclor. Dry air is blown through the crude Aroclor for a period of two hours or more. Aeration removes most of the free hydrogen chloride. Distillation of crude Aroclof s'-is dons under vacuum auto- matically controlled with the controller pre-set between 30-50 mm Hg. ags. to obtain the best performance. Distillation of crude Aroclor . separates residue, lime, ferric chloride, and tars from the finished product. . The third ..pro cess step includes blending, filtration, and storage of ' Aroclors. Approximately 0.1 - 0.2$ by weight of Attapulgus earth is added to the distilled Aroclor. The mixture is agitated and filtered- to the finished product tank. The purpose of the Attapulgus earth Is to absorb moisture and chloride ion to improve the electrical ' properties of the Aroclor.. During, the filtration of distilled- Aroclor, 2 - 16 oz. samples of the finished product are taken to . the laboratory for control analyses. If the control analyses pass specifications, the batch is transferred to a storage tank. ' This process description will describe the production of Aroclors . 1242, 1248, 1254, 1260, 1254 xylene mix, and 1262. O - '' . DSW 200813 STLCOPCB4058877 . '* ) o Dept. 246 - Process Description AROCLOR . SECTION II ' ' ' FLOW SHEETS ' . This section contains the following flowsheets. 1. Complete process flow sheet. 2. Chlorination Reaction Step . 3. Aeration and Distillation 4. Blending, Filtration' and Storage. 3. O . , DSW 200814 STLCOPCB4058878 STLCOPCB4058879 i - si E oz> 5m r \ 3b _ liM# *M l&fni <z s2 o< i= --I < =* c* i-- LU OO I! < O DSW 200816 STLCOPCB4058880 3c U) STLCOPCB4058881 UNRESTRICTED INFORMATION Routine Tests Appearance and Color ' i Crystallizing Point GENERAL INFORMATION Distillation Range: First Drop to Dry Point .. Specification Light Yellow Cryst, Solid 68.7C, min. 2.5C, max. . Must include 255C within Range . . Method Number 10,252 10,298 . 10,299 This specification is the property of Monsanto Chemical Company and is for internal use only. . . IN SB (REV. 12/Bt) DSW 200818 STLCOPCB4058882 W. G. Krummrich Plant RAW MATERIAL SPECIFICATION ' PRODUCTION T. W. Dalton PROCUREMENT C. A. Pratte GENERAL DESCRIPTION MATERIAL CODE 33500 PLANT WGK "OT'TBfc MATERI ( Ferric Chloride Anhydride 5USING DEPT . 233 SUPPLIER McKesson 8* Robbins APPROVALS RESEARCH M. A. Terpstra QUALITY CONTROL (Chial Chcmlmt) W. J. Gresham CHEMICAL FORMULA mol wt. 162.21 SUPERSEDES SPECS OF . 11/15/62 Fe Cl3 SAMPLE FOR ANALYSIS 1 x 8 oz. W.M. Bottle CHARACTERISTIC LIMITS UNRESTRICTED INFORMATION ' ' . ISSUED BY ' J. P. Prader METHOD J.F.Q. Appearance ' ' . . Black powder or Granules .' ; i6-a Assay .` 97.0%, min. . ' . . 22-570 Sulfates " '. 0. 05%, max. . 120-570 Ferrous Salts .. ; Trace, max. , S-570-1 , .Solubility: . . 10:10 of Water ; . 112-B . . Complete to slightly , , . turbid, max. ' ' . - . 10:10 of Formula 30 Complete to slightly Alcoho> l . . turbid, max.. . 1 (R) Routine Anetyele, All other* Anatyxed by request only. DSW 200819 STLCOPCB4058883 r. n iwi^LabCiisLU v: RAW MATERIAL SPECIFICATION PRODUCTION P. E. Heisler PROCUREMENT C. A. Pratte GENERAL DESCRIPTION Ca (OH)2 SUPERSEDES SPECS OF . 6/20/63 ' CHARACTERISTIC MATERIAL CODE 38800 PLANT VICK MAT ERI } . Lime, Hydrated USING DEPTS. . 222, 246 DATE EFFECTIVE SUPPLIER 7/21/66 Mississippi Lime APPROVALS . RESEARCH M. E. Gibbs QUALITY CONTROL (Chief Chemist) W. J. Gresham Co. CHEMICAL FORMULA ' . SAMPLE FOR ANALYSIS 1 x 16 oz. W.M. Bottle LIMITS ISSUED BY * METHOD Appearance ' . . Fine white or slightly gray powder, free from lumps or gritty material' - Assay (Ca(OH)2) ", 92.00%, min. Carbonates as (CaC03) 3.00%, max. Magnesium 0.50%, max. Sulfates (as S03) . ' - 0.30%, max. .' - ,, .' 10, 188; 10,191. ' ' 10,193- ' 10,192: . 10,189 . Supplier's certificate of analysis to be sent, on day of shipment to: Chief Chemist, Monsanto Co., 'Mo ns ant o>.: 111. ` , ' (R) Routine AnaJyeie, Alt others Analyzed by request only WCK - 314 DSW 200820 STLCOPCB4058884 ,n ^9 - . W. G. Krummrich Plant RAW MATERIAL SPECIFICATION production P. E. Heisler PROCUREMENT C. A . Pratte * ' MATERIAL. CODE 19409 PLANT WGK MATE t Attapulgus Earth 200/UP USING OEPTS. 246 DATE EFFECTIVE 1-21-66 SUPPLIER Mineral &; Chemical Phillips Corp. APPROVALS RESEARCH . V/. D. Robinson ' QUALITY CONTROL (Chiel Chemist) W. J. Gresham general description ' CHEMICAL FORMULA supersedes SPECS OF .. 11/15/62 CHARACTERISTIC Clay - SAMPLE FOR ANALYSIS 2 x 16 oz. W.M. Bottles . LIMITS ISSUED B Y J. P. Prader METHOD UNRESTRICTED INFORMATION (R) Volatile Matter (at 950"C .) (R) Mesh Test: ' Through USS 325 _ / '' - 6-8% . / '. 90%, min. ' This material is not accepted without the supplier's analysis of the above properties. (R) Rout In WCK.SU All othsrs Analysed by cetpjast only. DS\N 2082A y STLCOPCB4058885  " r. r . I'.k \J>` m to li*, . RAW MATERIAL SPECIFICATION PRODUCTION ' J.M.C. , PROCUREMENT C.H.C. P.E.H., W.B.P., MATERIAL CODE MATERIAL 43099 PLANT Nit; fen Gas 8USING DEPT . -. ' WGK See Belov; DATE EFFECTIVE SUPPLIER FEB 181965 Air Rpri-nr.f.i on Sal p.q On,,____________ APPROVALS C.H.S. RESEARCH W.P.S R.W.B. . H.W.K. . M.A.T. . W.D.R. . T.A.fl OUALITY CONTROL (Chltl CbtnlaO W.J.G. C.H.R. J.S.M. GENERAL DESCRIPTION . CHEMICAL FORMULA ' Grade - 0. P. Special Nitrogen SUPERSEDES SPECS OF New CHARACTERISTIC sample for analysis . . - LIMITS ISSUED BY ' M. D. Dealv METHOD ' Assay (l) .' 99.9$, min. ' ; (2) Oxygen . Hydrogen DewPoint'' . ' ._ . 0 1' . $, max. - 0$ ', " . ' 76: - P. ; -. . . .. ^ .' -/ Typical Analysis Nitrogen . . . Argon :' Oxygen . Carbon Dioxide . . . Acetylene ' '. , i. . '' . , v . . 99.78$ . 0.12$ 0.1$ <.00005$ <.00005$ .. Nitrogen plus inert rare gases . Any analyses to' be obtained from supplier on request. B-215, 0-216, 244, 246, 247, E-25.4, A-255, 256, 267, 270. * DSW 200822 (TO Koutin* XncJytt*, XU othmrm Xnmlyimd by racu.al only. je_____________;___________ t ' r 1: STLCOPCB4058886 n . :' 1fic W. '' f t ^c LrT.*;- ;r?|fcipvL WA3* _ - ' ; RAW MATERIAL SPECIFICATION PRODUCTION J .E. Smith PROCUREMENT A. H. Smith MATERIAL CODE 64005 PLANT WGK DATE EFFECTIVE 6/21/66 MATE* | 5 Xylene USING DEPTS, ' A-255 SUPPLIER Chem Tech APPROVALS - ' RESEARCH C. Eaker (Nitro) QUALITY CONTROL (Chief Chemist) ' W. J. Gresham GENERAL DESCRIPTION ' CHEMICAL FORMULA C6H4{CH3)2 ' - mol. wt. 106, 16 SUPERSEDES SPECS OF 7/12/63 SAMPLE FOR ANALYSIS , 1 x 16 oz. CHARACTERISTIC . LIMITS . UNRESTRICTED INFORMATION' ISSUED BY J, P. Prader METHOD (R) Appearance (R) Sp. Gr. @15.5/15,5 "C. : (R) Distillation Range , .. Clear Colorless liquid 0. 860 - 0. 870 . ; T-2516 .. T-2518 o 1st Drop Dry Point ( 137C., min. . : 143C. , max. . .. 100% over in . 5C. , max. .. Acidity :. Sulfur compounds ' No free acid . Free of H2S and SQ2 Supplier's certificate of analysis to be sent on'day of shipment to: . . .' v Chief Chemist, Monsanto, Company,; Monsanto, 111. (R) Routine Anelyale, All others Analyzed by request only. DS\I\J 200823 STLCOPCB4058887 M ! ; .n P* ** P*' V A ORGANIC CHEMIC AL& DIVISION FINISHED PRODUCT SPECIFICATION PRODUCTION T. V/. Dalton SALES W. E. Ault GENERAL DESCRIPTION ' * PROOUCT CHLORINE, Liqu > OEPT. 232 plant PRODUCT CODE UC WGK 81059 Sales and Internal DATE EFFECTIVE JUN 2 9 1366 SALE* code 3060-000-06-03 APPROVALS I RESEARCH N. F. Mueller . quality CONTROL (Chiol Chemist) ' W. J. Gresham . CHEMICAL FORMULA 70 914 MOL WT. *' SUPERSEDES SPECS* OP 6/24/63 ' SAMPLE FOR ANALYSIS 1 x 40 ml. Beaker 3/4 full 0IS UEO DV CHARACTERISTIC LIMIT* UNRESTRICTED INFORMATION (R) Appearance Clear heavy liquid . (R) Color (R) Moisture . Amber to greenish yellow . 015%, max, '. . (R) O NVM ". . 01%, max. ' Iron as: - Fe. FeCl3.6H20 ^Report % Report % J. P. Prader METHOD 10,748 10,748 12,793 12,793 10,688 *When used in manufacture of AC1 products, the specification on Iron as Fe is 20 ppm max. (H.V.Moss) , .. \ For'use in Depts. 264, 258, 238, 243, 244 and 251. (R) Routine Analysis, All others Analyzed by request Only DSW 200824 STLCOPCB4058888 EORSAKTO CHEMICAL COMPANY ORGANIC CHEMICALS DIVISION Xrummrich and Anniston FINISHED PRODUCT --. SPECIFICATION U\ODUCT (WiJsaxe) Aroclor 1242 PRODUCT (GhtaicjJ Nmca*) ' !! PRODUCT CODE DEPT. OR J03 81101-82612 WGK-246-Ann.J7 USE Sales SALES CODE [1040-240-04/11/16-05/09 TYPE Non-Electrical Grade TYPE Issued W. G. Krummrich"pZa nt By B CKEU4CAL FORMULA Mixture mol tnr. SUPERSEDES SPECS OP 5-4-61 . SAMPLE FOR ANALYSIS . .: ___ :5 X 16 Og. W. M7 Pottles .. '___ ' - UNRESTRICTED INFORMATION ': Routine Tests' - . ' '. .. ' . `^ ' 'Specification . WGK ; Anniston Method No. ." Condition . ' ' ' ' , . - `Clear . .7." 10084 '- G-l. ' ` Color, APHA vv. " 100 max. " . .. 7' - .. . 10084 .. 046 7 Sp. Gr. (25/l5.5*C) . ' ;. 7 1.581 - 1.592 /. : 7 10114 052 ' ^Acidity (mg. KOK/g.) ; : : .' '.;Yy7\;-- 0.010, max. ' ;. - -7 10087 . 050 ' v; ' Moisture (h20) (ppm.) >.: 50,,max... 7 ; ' 10620 '' 047 ; General Tests . . ; 7. 7.'. ''/ . 7 Distillation Range . (ASTM D-20 Corrected) . 10$ Distilled by ^wt.-7' 90$ " " " . .10117 7 14-51-54. 525*0,.-min. V- /-' .7:"' .; 560C, max. 7' ' ' 7" Viscosity 100F. (SUS)."- 7.. ' Flash Point (*f) ' 7' ./J:.V:.v- 82-92 . 558' - 592 . ' 10086 10125 \ 049 " '= . -14-28-54 . Fire' Point ". 7; 7 ' '. .- .4..; None 7 . .10125 14-28-54 rn IN 84 (REV. 12/83) DSW 200825 STLCOPCB4058889 X KOKSANTO CHEMICAL COMPANY \ ORGANIC CHEMICALS DIVISION Krummrich and Anniston \ FINISHED PRODUCT J SPECIFICATION PRODUCT CODE DEPT. OR JOB j 81105 - 82615 WGK-246-Ann.27 Issued 7/15/64 usz W. G. Krummrich pisrnt Sales : SALES CODE . By/. _>i . 1040-280-04/ll/l6-05/09'' product t;sso) ; : type . Aroclor 1254 PRODUCT (Ctieaical Nasi) .. ' Non-Electrical Grade' . ' TYPE- ' ' CHEMICAL. FORMULA - ` '* . *' . . ` '' i . Mixture ' ' ; ' : . \ ' / >; \ : -- UOL WT. '' . ' . SUPERSEDESSFEC3 OF ' SAMPLE POR ANALYSIS ' : 5-^-6! -___________ ___ 5 x l6 oz. W. M. Bottles . .' . UNRESTRICTED INFORMATION Routine Tests . ' y- y. -. WGK Anniston . Specificatibh . : ' . . . Method No. Color, APHA . y . sp. Gr. 65/15.5*0 ,/'-///'. : ,.. . 100, max. .y -'10084 :. 046 . y ; ,1.495 -. 1.505 v '"y ,/;:ioii4;' 052 '' Acidity (mg. KOK/g.) y /,./... .,/ ,. 0.010, max. , . y - - : ' -y 10087 050.. , Moisture (h20) (ppm.) .:"y'y/ v 50, max.. \y Y; 10620 . 047 General Tests .: -:'; ' \ ' --. . Flash point.- ... \y--. '/' ;.' ' None .. .. ' '/- 10125. ' /.- 14-28-54 Viscosity 210*F, (SUS) -y/yy ; - 44-48. . ' 10086' ; 049':. '; y DSW 200826 STLCOPCB4058890 MONSANTO COMPANY ORGANIC CHEMICALS DIVISION ANNISTON, ALABAMA STANDARD MANUFACTURING PROCESS FOR BIPHENYL Date: November, 1965 Author: B. 0. Severson DSW 200827 STLCOPCB4058891 STANDARD MANUFACTURING PROCESS BIPHENYL SECTION I - SYNOPSIS OF PROCESS ' -\PART I - TUBULAR UNIT AREA '_ Biphenyl is manufactured in two general equipment areas: the.\ pyrolysis area known,as the tubular unit area, and the final * product distribution and draw-off area known as the still area. 4, . . The manufacture of Biphenyl starts in a ,pyrolysis process in which benzene, under conditions for controlled rearranging, is converted into a polypheny1 mixture. This polyphenyl mixture p which contains Biphenyl,' three Terphenyl Isomers, Tri-phenyleiie, Quatraphenyls, higher polyphenyls, tars, carbon, and hydrogen, is made by the continuous pyrolysis of benzene in a direct fired tubular furnace. The product split is controlled by varying conditions of benzene feed, converter pressure, furnace gradient temperature, converter exit temperature, promoter, and per cent of recycle polyphenyl added to the benzene feed stream. The process is operated at conditions to provide the production demand split between Biphenyl and the Terphenyls.under conditions that minimize quatraphenyl and coke lay-down, and' increases on stream time, tube preheater life, furnace efficiency, gas usage,, and external retention tank life. Each of the two furnaces and external piping is divided into two independent process streams. In effect, there are two tubular converters per furnace. To these furnace'converters a continuous stream of fresh and recycle benzene plus promoter is fed. The benzene feed first enters the vaporizer section in the top of the furnace. The vaporized benzene near 250C. leaves the furnace and passes through the shells of a series of external preheaters. These preheaters increase the productivity of the furnace and lower the gas consumption by' recovering heat from the polyphenyl- benzene product stream as it leaves the furnace through the tube side of these preheaters. The preheated benzene vapors,now raised to near 500C. where cracking is initiated, are returned to the converter section of the furnace. The preheaters and associated . external tankage is the most sensitive area for coke deposit and metal failure in the system. Operating techniques and conditions that reduce these problems are a part of the process. 1 The preheated vapors are returned to the top of the cracking or radiant section of the Selas furnace where, in.14 - 5,,-40' Incoloy 800 tubes, the temperature is raised by the 88 burner radiant gas- fired furnace to an exit bulk temperature of from 700 to 750C. DSW 200828 STLCOPCB4058892 Synopsis of Process Tubular Unit Area STANDARD MANUFACTURING PROC t BIPHENYL 2 Net conversion to polyphenyl is normally controlled between 5% and 20%. The profile temperature of the product stream is re gulated by the firing conditions of each of four rows of burners with the objective of controlling the conversion rate through the converter (radiant) section. ' *. . The benzene-polyphenyl stream emits from the furnace into a partially 'insulated unbaffled sojourn pot which provides ad ditional external cracking time for increased furnace pro ductivity. The product stream flows through a carbon grinding tank and then passes into the tube side of the Hastelloy X bundles in the external preheaters. The benzene-polyphenyl stream temperature is reduced to near 360C. as it raises the uncracked benzene in the shell side from 200C. to near 500C. ' The benzene-polyphenyl stream leaves the furnace area dnd enters the adjacent stripping area where the stream is separated into a benzene-free polyphenyl bottoms and .a recovered overhead benzene stream. The sequence of steps in,the stripping operation starts with the hot benzene-polyphenyl stream passing through the shell side of' a reboiler where it uses up most: of its remaining super heat to the column bottoms which are circulated on the tube side of the reboiler. The product stream continues from the re boiler to the 4th tray of the 12-plate column. The 12 Glitsch Ballast tray column utilizes the super heat delivered at the re boiler to strip unreacted benzene whith is' condensed by passing through the tube side of a recovered water cooled condenser. The condensed benzene, 80-95% of the feed to the column, is collected in a reflux tank. From here the recycle benzene'is returned by level control pumping to the furnace feed tank where it, .with make-up benzene, is recycled back to the pyrolysis furnace. A benzene reflux stream is used to control the column temperature so that the desired amount of polyphenyl is maintained in the benzene overhead cut. The benzene-free polyphenyT still bottoms, held near 270C., are pumped continuously to one or two 15,000 gallon crude polyphenyl storage tanks. These tanks also serve as feed tanks for the two still Biphenyl recovery system. , The benzene saturated by-product hydrogen, which is split off during the pyrolysis reaction, flows from the benzene reflux tank to the . hydrogen compressor area. Here the gas is compressed in a two-stage reciprocating compressor to 300 psig. The compressor system serves two purposes; the. primary being to recover benzene and return it to the feed tank, and the secondary to feed the by-product hydrogen into the natural gas stream which is firing the furnace. DSW 200829 STLCOPCB4058893 Synopsis of Process Tubular Unit Area STANDARD MANUFACTURING PROC k BIPHENYL 3. The cooling water required for the benzene condenser, hydrogen compressor area condensers, and the air compressor condensers, is supplied by a two section Fluor cooling tower. Here the water is chemically treated to maintain the required pH chlorine1'con centration and chromate concentration. The equipment in the benzene feed area, furnace area, stripping area, polyphenyl storage area, hydrogen compresser area,`and the water recovery system, are all controlled by one operator from a central control room. The control room area includes the motor control section, air compressor section with back-up CC>2 and the instrument panel board and the laboratory area. In summary, benzene under controlled temperature, pressure,; arid flow,is cracked into Biphenyl and Terphenyls in a direct fired tubular reactor. The polyphenyls formed are separated'from the excess benzene in a stripping column. From the column, benzene- free crude polyphenyl is delivered to the distillation area where Technical Biphenyl is recovered and crude Terphenyls are passed on to the Terphenyl distillation area. The equation for the reaction is 78.1 Benzene 154.2 Biphenyl 230.3 Terphenyls 228.3 Triphenylene 306.4 DSW 200830 STLCOPCB4058894 O SlPHEN\L PUOCt'bc-. F 0\W D\f\G:F</\N\ 1 ..I O o DSW 200831 STLCOPCB4058895 o Y=>\ F> YALVARL PROCt^ R\l POGr^U RECOVERY FLOW O \ A, G- FP A^ W\ (co^, ` HVoROQEN F R O xnA __ R,e; flu x. tahk (T?) O DSW 200832 STLCOPCB4058896 o O STANDARD MANUFACTURING PROCESS BIPHENYL | TUBULAR UNIT SECTION III. PROCESS IN DETAIL The process for producing a Biphenyl-Terphenyl mixture by pyrolysis of _/ benzene will be described in this section under the following headings: A. Process Control B. Critical Process C. Benzene Receiving and Feed Operation D. Furnace Operation E. Benzene Stripping Operation ' F. Hydrogen Compressor Operation G. Recovered Water System H. Control Room Operations A.- Process Control The various control loops of this system have the ultimate function'of controlling the output product stream at a predetermined Conversion. The net Conversion sets the ratio of Biphenyl to Terphenyl. The production rate of these two products is fixed by setting a net Conversion and a flow rate. . The benzene feed control system maintains a fixed level of make-up and recycle benzene in a feed tank. The benzene furnace feed from this tank is mixed with a meteredi. amount of acetone promoter and fed to the furnace at a set pressure and flow rate. , The furnace control loops consists of the exit product stream temperature cascaded with the natural gas feed to the radiant burners, and an independent back pressure control loop. The gas delivered to the burners is varied to hold the exit temperature constant and the back pressure holds a steady converter outlet.pressure. The benzene stripping column is refluxed controlled by the 10th plate temperature. The stripping column conditions determine the percentage polyphenyl in the benzene recycle stream which, in turn, effects the ratio of Biphenyl and Terphenyl in the product stream. The level controls for the column sump and for the benzene reflux receiver are used to deliver a uniform feed of recycled benzene to the furnace feed tank, and benzene free crude polyphenyl to the two product receivers. DSW 200833 STLCOPCB4058897 Process in Detail Tubular Unit Area )2 Shutdown protection is provided in the event of high or low benzol flows, high furnace stack temperature, high and low natural gas pressure and fiow. Two annunciator alarm systems warn of out of normal limit conditions* The hydrogen compressor system operation is controlled by a pressurecompressor unlosder loop on the./suction side of the compressors. Shut down loops are provided for low suction pressure and high receiver levels to protect the system. The recovered water system is controlled by a pressure-temperature loop that operates the'two discharge pumps and two tower fan systems at the cooling tower. Pressure controls on the instrument air system operate the two instrument air compressors and a back-up CO2 system. B.- Critical. Process Variables . . Any specific Conversion can be obtained by a great variety of different sets of conditions. The route makes no difference to.the composition of the product. However, the effects of this different route on process efficiency and production costs vary widely. The selection of the proper range of this critical variable is important to proper operation. - There are five critical process variables in the polyphenyl production system which determine the percent of benzene that is converted to polyphenyl. This percentage is referred: to as Conversion,and as this percent' ' Conversion increases, the ratio of Biphenyl to higher polyphenyls decrease. Thus, as Conversion is raised when the demand for Biphenyl increases, the production of Terphenyls and Quafcraphenyls increase at a faster rate than Biphenyl. .. Two of .the critical variables are; (1) benzene flow rate, which is referred to gallons per minute per pass, and (2) converter pressure as measured at the converter (radiant! section) outlet. These two variables determine residence time and gas concentration. The residence time, the average time for a unit of benzene to pass through the converter section of the furnace, . controls the conversion level. That is, while holding the other variables constant, Conversion will increase with increasing residence time. The normal range of benzene flow rates for current operations are from 35 to 50 gpm per pass. The normal pressure range for current operations is between 60 and 100 psig. The selection of these two variables is a compromise. Lowest unit gas costs can be obtained at the low benzene flows, however, low flame can cause excessive tube support temperatures and carbon laydown in the furnace and external piping. High benzene flows favor reduced Terphenyl production, best furnace life conditions at a higher gas and recovered water usage. The upper pressure is limited by the thickness and age of the tubing and cast return bends, and at the lower pressure, level is limited by the reduced productivity of the furnace. DSW 200834 STLCOPCB4058898 04 Monsanto Chemical Company ORGANIC CHF. ;'ALS DIVISION FINISHED PRODUCT SPECIFICATION product (Trade name) Biphenyl PRODUCT (Chemical name) Biphenyl ____ CHEMICAL FORMULA PRODUCT CODE ________ 826.01 METHOD IDENTITY SALES CODE 135-000-03-09 TYPE Technical TYPE Technical \ SUPERSEDES SPECS OF 7/8/65 \ c12H10 SPECIAL. JOB NO. SAMPLE FOR ANALYSIS lx 16 oz. can Issued 5/5/61 Anniston Plant By W. W. Klammer Revised to add ty. values 11-18-65 MOL WT. 154.20 USE Sales Characteristics Routine tests Appearance Crystallizing Point, C Color, Gardner Limits Typical-Values White to pale yellow crystals . 68.7 Min.. 6 Max. ' White crystals . 68.8 1.5 General Test (determined only on request) : ; Biphenyl, % . Napthalene, % 3 - Methylbiphenyl, % 4 - Methylbiphenyl, % 'i . Unknown, % Distillation Range, C 1st drop - Dry Point Must include 255C 99.9 0.001 0.05 0.02 <0.03 DSW 200835 This specification for internal use only STLCOPCB4058899 in IN lOO . MONSANTO CI-IE^'CAL COMPANY AGRICULTURAL CHEMICALS division { RAW MATERIAL Acetone FOR USE IN o ' RAW MATERIAL SPECIFICATION. OATt EFFECTIVE 12/18/64 ISSUE NO. 1 GRADE Anhydrous SUPPLIERS ) MATERIAL. NO. SUPERSEDES All other Monsanto, Chocolate Bayou. Tennessee Eastman, and Carbide & Carbon PRODUCTION (Plant Alznagcrf - PROCUREMENT (Procurement Mcnager) authorized (Quality Control birector) APPROVALS . -- R ese arwfAsstcDirector)- /s/ J. A. Stephens QUALITY control (Chief Chemist) fsl CffiR 12/18/64 GENERAL DESCRIPTION A clear water white liquid CHARACTERISTICS Appearance LI MITS Clear, water white METHOD NO, CB-393 . Water solubility -. No turbidity when diluted with water CB-393 Sp. Gr. @ 20/20 C. 0.791^0.794 CB-405 Dist. range @ 760 min. 1.0 C. to include 56.1 C. CB-406 Non volatile matter 0.002 gm/100 ml max. -407 Color 5 max. APHA CB-395 Acidity as acetic acid 0.002% max. CB-408 Alkalinity as NH^ 0.0005%, max. CB-409 Permanganate test . KMNO^ color retention for 30 minutes minimum CB-235 Moisture 0.5% max. CB-410 Foreign odor None CB-394 Note: Chocolate Bayou and other suppliers test each shipment on the above. Anniston normally makes no tests. DSW 200836 STLCOPCB4058900 Mo:.'sa::to C::e.v.:cal Co* ";akv ORGANIC CHEMICALS DlVlSiV^ ' ANNISTON, ALABAMA'PLANT' RAW MATERIAL _ SPECIFICATION MATERIAL .. ___________ ISOPROPANOL, CHEMICAL FORMULA - 99% | PRODUCT CODE 10950 METHOD IDENTITY j SUPPLIER I CARBIDE & CARBON ------ . --------------- Issued Sept. 11, 1957 STANDARDS DEPT. Anniston, Ala. Plant . By /s/W. B. Dunlap ' W. B. Dunlap MOL. WT. SUPERSEDES SPECS. OF SAMPLE FOR ANALYSIS 1 x 16 oz. Narrow mouth bottle UNCLASSIFIED SPECIFICATIONS General Tests Specifications Specific Gravity (20/20C) Distillation (760 ,m. m.) , Isopropanol (%) Acidity (%) (as Acid no.) Dilution Test Water (%) . . Non-Volatile (g/100 ml) Color (APHA) Odor . Suspended matter . Flash, point (F) , 0.7862 - 0.7876 Shall be entirely distilled within . 1C range'which shall include 82.3C 99.5 min. 0.002 max. as acetic acid '0.019 max. . Clear 0.5 max. . 0.002 max. . 10 max. Non-residual Substantially free 70 ' , Specification furnished by Supplier May 18, 1956 : ' : ' . .. DSW 200837 . STLCOPCB4058901 i,N 08 2w1o:;3a:jvo C:-:e-v.ical Cg;",a?jy . organic chemicals divis.% ANNISTON, ALABAMA PLANT . o RAW MATERIAL SPECIFICATION . MATERIAL PRODUCT CODE.. 14760 METHOD IDENTITY SUPPLIER ?ENZEN?, - NITRATION GRADE (ASTM D-835) CHEMICAL FORMULA ' , . SUPERSEDES SPECS* OF App. 1952 SAMPLE FOR ANALYSIS 2 x 16 oz. NN Bottles Issued Sept. 11, 1957 STANDARDS DEPT. ' . Anniston, Ala. Plant By /s/W. B. Dunlap W. 2. Dunlap Revised 11-18-65 To include typical values____________ MOL. WT. o Characteristics Appearance'' Acidity Acid wash test Color Crystallizing point Distilling range: 100% over in Range to include Specific gravity: 60/60?. - 25/25C. Copper corrosion . Sulphur compounds Total Sulfur., ppm Total Chlorine, 'ppm . Limits Typical Values Clear liquid with no Clear . .free water or sus- . pended matter ' ' . No free acid --- . . ' - . Barrett 2 max. --- ' . APKA 25 max. 5.30C.mih. wet 5 .. ' . ----- . . . basis ' _' . 5.39C. min. dry' ' 5.42 ,basis 1C. 80.1C. --- ' ---- ' ` ` - 0.8820 to 0.8860 ---- . ' 0.8740 to 0.8780 -- . Negative . . Tree of H2S and SO2 * ' - *' 1 . ' 200 Max!* . ( . 1 1 , . '1 , ' * . ' DSW 200838 * 1 ` ** * It STLCOPCB4058902 84 i'JiO'H ga nto Ckesaical Company ORGANIC CH .PALS DIVISION FINISHED PRODUCT SPECIFICATION PRODUCT (Trade name) Hydrogen PRODUCT (Chemical name) Hydrogen CHEMICAL. FORMULA product code -- METHOD IDENTITY Dent. f20 SALES CODE TYPE By-product TYPE By-product Mixture typical values SUPERSEDES OF 2-11-60 SPECIAL JOB NO. SAMPLE FOR ANALYSIS 100 cc Gas Burette Issued 11-18-65 Anniston Plant By 0. E, Dolin MOL WT. --- USE Internal - General Tests (made-only on request) Characteristics . ! Typical Value Hydrogen (H2), mole % 86.12 Methane (CH^), mole % 5.83 Ethane (CHg), mole % . 0.90 ' Ethylene (C2H4), mole % 0.55 Propane (CgHg), mole %. . 0.08 Propylene (C-jH^), mole. % Butanes .(C./jHn) , mole % . 0.17 0.02 Carbon dioxide (CC^/mole % 0.33 Hitrogen and carbon monoxide (N2&CO), mole % 2.16 Benzene- (C^Hg), mole % 3.84 DSW 200839 This specification is for internal use only STLCOPCB4058903 ) STANDARD MANUFACTURING PROCESS BIPHENYL . APPENDIX K - BACKGROUND OF PROCESS AND ANNUAL REMARKS Large scale commercial production of Biphenyl became feasible with the invention of the lead-pot process by Federal Phosphorus Company in 1927. These researchers recognized that the essential elements of successful conversion of benzol to Biphenyl were (1) preheat the vapors almost to reaction temperature, (2) quickly raise the vapor to reaction temperature, (3) remove and cool vapors immediately below reaction temperature. This was early accomplished by passing preheated benzol vapors through a bath of molten lead. Eventually 13 lead pot units were built at the Anniston. Plant in 5 different expansions, with only minor changes in design. A significant improvement was made in 1954, with installation of a larger converter pot in No. 'll Biphenyl unit, giving longer sojourn time with consequent greater capacity, lower temperature, less carbon and longer life. , A significant improvement in the basic process resulted from use of iso propanol promoter in 1948, giving the same conversion at lower temperature, thus increasing equipment life. Use of promoter was discontinued due to corrosion of auxiliary equipment, then permanently restored in 1954. In 1965, acetone replaced isopropanol, giving higher conversions at lower raw material cost. Research in 1927 had indicated that brief sojourn of benzol vapors in a heated tube would provide an alternate commercial process. Further research, particularly in 1950 and I960, established the basis for a tubular reactor. The first tubular unit was installed at Anniston in 1961, the second unit in 1964. The second unit featured 4 additional tubes in the converter section to provide longer sojourn. The carbon trap was relocated to catch carbon dislodged from exterior piping. Pre heaters were redesigned to increase vapor velocities on the shell side, and reduce carbon formation. These features successfully reduced mainten ance and increased conversion. The benzene stripping column integrated with each furnace so completely removes benzol that a head cut is no longer required on the Biphenyl stills. The original Biphenyl still was a direct-fired pot surmounted by a packed fractionating column. It was replaced in 1940 with a 20 tray bubble cap column and gas fired coil heater, and within the next two years this was duplicated to provide the present two stills. Originally operated as batch stills, both were revised in 1963 for semicor.tinuous operation with a boii- down every 24 hours, an improvement derived from complete removal of benzol in the stripping columns. ' Biphenyl was marketed originally as a solid in 250 pound drums. In early 1930's the present flaker was installed. At present, Biphenyl leaves the plant as solid in drums and tank cars, and as flaked in 100 pound bags. DSW 200840 STLCOPCB4058904 I o s3 Pi Cl >&o X ft P'1 t> Pi, 0: Is r1 I *0 f. c t A A 1 'A 1 tA <s l ;i hV 0 il 5, . j1 I' U 0 V, il V> l\ K i| u> <5 ! >1 1\ if ` PS 'S u0 PV.i tA 5| il \. s & * $N A 0 V c> .C < o C 0Q 0 5rr\ ; V. A V* XJ 5\ fh In "I x A SI X I faPi S< $ Pi s Ui * r 'A M >i Vt u SIXPI 'xIuC/ V il b 3f e ii 4e>s, 1A 1 S -O v O' k pi 1 $n N. DSW 200841 r6.\ \ STLCOPCB4058905