Document QJKKYqmqkdJExByJDdn15ZK38

MONSANTO COMPANY ORGANIC CREMIGES DIVISION W.G.K'*' ^tiANT STANI'' \ -\ V- \ Supersedes: Process I k 2,4-Dichlorc FOR ^ f -..U -. :*V S.V" .or Manufacture of Crude/V^.;^ '. , dated April, *1965; , \ ^ ' *s'.V- ..-"r V;\y. V,.V-1*!' '<: Prepared by . Paul A. Erzer Approved by H- * Malone.^pw^L>/*"^ . >;-v . ' ";!?;.-.r-./x|3ty-y .y --v i--. H . . f i . C s t v p t - ' . ^ This report contains confidential information .which is*'th^'-.^ property of; the Monsanto Company and which shall .-be.,disclosed;./"ViV only, to duly authorized persons. The r e c i p i e n t s held ,.;;- accountable for the filing and safe custody of 'the report .-u '/ which must be returned on demand. *'. - rV . /to U' Issued: fajnasbe*, 1968 , v'v - Copy 7 of_ / 3 L . v K03109q MONSANTO COMPANY ORGANIC CHEMICALS DIVISION W.G.KRUMMRICH PLANT STANDARD MANUFACTURING PROCESS FOR CRUDE 2,4 - DICRLOROPHENOL Supersedes : DEPARTMENT 236 ' `j i 1, . lift', -V.. - Prepared by This report contains confidential information .which is\the'1 r ' * property of :the Monsanto Company and which shali-be,. dis closed. only, to duly authorized persons. The recipient is held V accountable for the filing and safe custody of the report :;Y|. " . which must be returned on demand. :-'r.--' /io ia Issued: fuygsmUn, 1968 Copy y of_ j. K3lO 98 DISTRIBUTION SHEET 1 . Technical Information Center - JFQ \b- -v:'i 2. Technical Infonnation Center - JFQ, .*[./- ;v J ;.v .. **f'*-1*m* i*t**j;. * 3 . Central Reports - GO (Forward to permanent file in El Dorado/'Ark.) 4. Technical Production Manager - H. C. Carder - GO .ri' 3. Production Generl Superintendent - E. D. Malone"S*WGK\. . 6 . Production Supervisor - R, L. Fields * - WGK v:;. ^: 7. ' ' > WGK Technical Services Department Group Leader-- T.--E;'tGre`enman;'c:% .. - ,v-.: 8 . -WGK Process Research Section - CD. <C. Armstrong ? * -r1c -" '* 9. WGK Plant Library rlv, - 10. Extra V - 1-'?'^WA-^\4-y 11. Extra v' V - \ ->/ r ' Vs* --'-V : ! 12. Extra . t*: /y 'i M -' ;S}r. %& y-?-:' .',y: -;r,_ ?'? ... . :f ' ' ; . ' ,,* 7 . . v i;- y'm ;-r --V* ' * ' ' `' ' C . . ," -V,. -,.; --r s.;- K03L099 SECTION I SECTION II SECTION III * SECTIO N IV A PPEN D IX A A PPEN D IX B A P P E N D IX .' C* A PPEN D IX D A PPEN D IX E A PPEN D IX F . A PPEN D IX G A PPEN D IX H A PPEN D IX I A PPEN D IX J A PPEN D IX K A PPEN D IX L A PPEN D IX M A PPEN D IX N TABLE OF CONTENTS ; PAGE SYNOPSIS O F PRO CESS FLOW SHEETS - 3 ' /: . P R O C E S S IN D E T A IL A . CHARGING CHLORINATOR AND . SCRUBBER B . CHLORINATION C. PU M PIN G AND AERATION D . HC1- H A N D L IN G CO M M EN TS ON PR O C ESS A . RAW M A TERIA L YIELDS B . CA PACITY C. QUALITY . : EQ U IPM EN T LIST . v . > . .4 7- ! / 4 ,-7 - s v . O ;v:;r7 757./^^; 7-77, " ; ;y ^^7^; -v -* ^ t*. i ' **. - c-- '5-- `Wii7 - B i-7 , * *, . '-v ---.-7.- -7 m M O 13 7 7 . FINISHED GOODS AND RAW M ATERIA L ' ;-.1 4 r - '- - SPECIFICA TIO N S . ">777-~*./r-. s' ". * : Vi--'-,,*- 7 P H Y S IC A L C O N S T A N T S D A T A S H E E T S ' . * V"-Vl ' 1 5 - ^ 7 7 ; -7-7 *. . U TILITIES 7 :;7,77 -77,;7;7 = PERSONNEL PACKAGING AND SH IPPIN G ' M A TERIA L BALANCE 7 --. - - .;;. '-V`7 7 7 197 27 7 # > ; A T M O S P H E R E - S T R E A M D IS C H A R G3E .* '* v s '2 2 7 7 7 - 7 . 7 ' . " S >,^ 7 7 7 7 -7..V7-7y V** PROCESS CONTROL J.i!;, **.'. - - :- ;- i-*- -,..i. V. V. `, .... SA FETY AND TOXICITY DATA AND 24 ACCIDENT R EPO RTS -rfv' 7 v . - -V*r BACKGROUND OF PRO CESS AND ANNUAL REMARKS *l/ '"*\:i;* - TIM E CYCLES 26' ; Q UALITY CONSIDERATIONS - 27/ M ISCELLA N EO U S 28 K031IOO a m en d in g r e c o r d s h e e t 3 f. *.V * . . v". >-'` . Jt-.V f.-i'-v . ..-.-.I'--* .* .,! ,* . .... ; , i.' V - ." * . !> - : ... , ` ` ' K 03II0I e Dept. 236 - Process Description CRUDE 2,4 DICHLOROPHENOL <v \ SECTION I. - SYNOPSIS OP THE PROCESS - -' . Crude 2,4 Dichlorophenol is produced by the batchwise chlorination . of phenol and high parachlorophenol content fractions (minimum- ratio ' of phenol to ortho, of 4:1) from Dept.,237 using;snift gas chlorine, at a pressure of 2-4 psig. The chlorination is carried out between 70-90C. to a specific-gravity of 1.400-1.4o4.' The finished-product contains approximately 88# 2,4-Dlchlorophenol', 7-5#.2,6-Dichlorophenol, 2.5# 2,4,6-Trichlorophenol and 2# Monochlorophenol'The chlorinated product is transferred to a storage tank.to await loading into tank cars. - ' j -'1 The product is used exclusively for production of 2,4-Dichiorophen-. oxyacetic acid (2,4D.) in Department 262. : . . * 'r By-product HC1 gas is scrubbed with phenol, cooled..to ;-condense/out chlorophenol vapor, 'and scrubbed with sulfuric- acick The' HCl' -gas is then either transferred directly to Dept. 217 by pipeline or'absorbed in water and sewered. HC1 gas is used in Dept. .217 for the manufactur The standard yield on phenol has been established as 9 6 .99# of ' .theory. The standard usage of phenol is calculated as follows: Std, Lbs, of Phenol Used Cwt. 2,4-DCP Produced 57 *13 = 0.9o9 _ 59 *52 Lbs,/cwt. " ----- 1/n11 in? Dept, 236 - Process Description SECTION I - SYNOPSIS OF THE PROCESS >7 ' YIELDS i (contd.) The theoretical usage of chlorine is calculated-as Theo. Lbs, of Chlorine Used _ (2).(70.91) : . Cwt7 2,4-DCP Produced . " .163.01 . , 01 Lbs ;/cwt The standard yield on chlorine has been established-as. 95< so% : of theory. v 7/;Y The standard usage of chlorine is calculated as. follows': ; Std, Lbs, of Chlorine Used Cwt. 2,4^-DCP Produced 87.01 07958 9 1 OO Lbs./Cwt, i --*X ; - * * K031103 J. Dept. 236 - Process Description CRUDE 2 , V D C P SECTION III - PROCESS IN DETAIL A. CHARGING CHLORINATOR AND SCRUBBER The starting raw materials are U.S,P.Phenol -plus fractions, from'; ' . distilled, chlorophenols operation and "snift" gas chlorine.; Phenol is transferred at 65C. from the Phenol Department;by steel"pipe v:; .line into a-1 6 ,000 'gallon steel fractions (DCP) strage.' .tanki^; Fractions are transferred from Dept. 237 receivers into the-':V;''' - Fractions. (DCP) Storage Tank (Item 103 ) . The ratio-of ;phenol'- to,. . orthochlorophenol is maintained at a 4:1 minimum in this-tank.* , - This is necessary in order to insure production of' specification' grade Crude DCP. Chlorine is delivered from, the Chlorine1;Dept. directly by steel pipe line. .;;v* The batches are charged by transferring th Phenol-S'rubber J v / 1;; charge to the chlorinator. The phenol-chiorphenoi'fractions' r '.- blend from the Fractions Storage Tank is then charged';to 'the. Phenol Scrubber to a 40" outage. Additional-fractions frV-/ charged to the chlorinator to increase the quantity of material to 46" outage (#5 chlorinator) or 44-53" outage ("1,2,'3 r'4j'chlorinato dependent on gravity of Phenol Scrubber btch). B. -CHLORINATION Th U.S.P. Phenol is chlorinated batchwise`I-t\'a ra'toX5P0"2500 lbs./hr. in a monel system which consists of .a .1,300 glori'/}t;... chlorinator and an 1,150 gallon phenol scrubber. -; The ..chlorinator is equipped with an internal cooling c.oil and a chlorine,.^sparger In addition, #3 chlorinator is equipped with a'.steel'shell^arid. ;;;// tube.cooler. The contents of this chlorinator are continually circulated through this unit, where they are cooled with well water. -. --a \ The Phenol Scrubber Is a Jacketed vessel equipped with/a Turbo- '* Mixer agitator. This special agitator is used to increase .the contact of the chlorinator off-gas with the contents'.of they.. .. Phenol Scrubber. ' . v - / / ; ' / //!; ' '1 While charging the batch, well water Is applied to'.the..coils'in the chlorinator and scrubber. After the batch is .charged, chlorinflow Is started. The chlorine rate is automatically controlled to give a chlorination temperature of 80-90C. The phenol scrubbe: temperature Is controlled at 35-45C. by manual control of cooling water to the jacket. The chlorination Is continued until- the batch end-point gravity of 1.402 at 45/15*5C.(for virgin phenol raw material} to 1.404 at 45/15.5 C. (for fractions and phenol- as raw material) is reached. The specific gravity of the reaction mass is checked at two-hour intervals until the specific gravity reaches about 1.35* After this the gravity is checked more frequently. K031105 Dept. 236 - Process Description______ ..-',5.J , CRUDE 2, 4 DCF V" SEC TIO N III - P R O C E SS IN D E T A IL --- -- " * ~~ C. FINISHED BATCH TRA N SFER t j v ;.- \\ - '7 A t th e end of the c h lo rin atio n , the c h lo rin a to r b atch is tra n s fe rre d to th e 20, 000 gallon s te e l C ru d e D C P sto ra g e tan k (Item 105), /F ro m h e r e th e m a t e r i a l i s lo a d e d in to t a n k c a r s f o r t r a n s f e r to th e 2 , -4 -D ,>V';Vr, . % A cid D ept. (D ept. 262). ' D. HC1 HANDLING T hroughout th e ch lo rin atio n , the b y -p ro d u ct HCl fro m the chlo rination p ro c e ss is scrubbed w ith phenol in-the phenol sc ru b b e r by m eans of a d ra ft tube and ag itato r. H ere, unreacted chlorine fro m th e.ch lo rin ato r is rem oved by rea ctio n w ith the phenol. T e m p e ra tu re s of 35; -/45C . a re " m a in ta in ed d u rin g th is ex o th erm ic re a c tio n by co n tro llin g the w e ll'w a te r flow to th e ja c k e t. ' 7 7 - 1 v E n tra in e d ch lo ro p h en o ls in th e cooled H Cl o ff-g as leav in g the; s ru b b e r a re re c o v e re d in a B rin k M ist E lim in a to r and re tu rn e d to the P e n ta - c h lo r o p h e n o l p r o c e s s . T h e H C l o f f - g a s is th e n c o o le d in t h e 'M o n e l o f f - :,*;" g a s c o n d e n se r (Item 156) to a te m p e ra tu re of 20 - 30 C. T h e c h lo r o - p h e n o ls r e m a i n i n g in th e H C l g a s a r e r e m o v e d b y s c r u b b in g w i t h 's u l f u r i c /* a c id in a V e n tu ri c o n ta c to r. T he v irg in su lfu ric a c id h a s a 9 8 % 'assay ; : A 8 t h e s u l f u r i c a c id i s c o n ta c te d w ith s u l f u r i c a c i d , i t s assay ,an d ;-.;..; ./$'*// re a c tiv ity d e c re a se and its c o rro siv e n e ss in c re a s e s ./ The su lfu ric acid is t r a n s f e r r e d to th e s p e n t a c id s to ra g e ta n k w h en its a s s a y is re d u c e d ... 1 to 85% f r e e H^SO*. F r o m h e r e th e s p e n t a c i d i s . l o a d e d in to J t a n k 't r u c k s - f o r s h ip m e n t to th e to x ic d u m p . O ne 8, 000 g a llo n ta n k c a r .of 98% HjSO* ; is u se d e v e r y 3 - 1 /2 to 4 - 1 /2 w e e k s w hen s c ru b b in g H C l fro m the" P e n ta - ' c h lo r o p h e n o l, C r u d e D C P , a n d C r u d e P a r a c h l o r o p h e n o l (D ept*/-237 ) c h lo rin a tio n s . '\Vi-v , v ; : 7 T he clean ed H C l is piped to D ept. 217 fo r u se in th e p ro d u ctio n of c h lo ro - - s u lf o n ic a c id . E x c e s s H C l i s a b s o r b e d in w a t e r a t a 'd r o w n i n g j e t a n d ;; -r s e w e r e d . P r e s s u r e 'd r o p th r o u g h t h i s s y s t e m r e s u l t s in th e c h l o r i n a t o r and phenol scru b b er operating under 2 - 4 psig back p re ssu re . /T h e , : c h lo rin a to rs a r e equipped w ith a 20 p sig safety ru p tu re d isc , /T h e phenol s c r u b b e r s a r e e q u ip p ed w ith a 10 p s ig s a fe ty r u p tu r e d is c ,. / v *i'.W.'.rvM K031106 D ent. 236 -- P ro c e s s D e sc rip tio n CRUDE 2. 4-D C P SEC TIO N IV - C O M M EN TS ON P R O C E S S A, RAW M A TER IA L YIELD5 1 P h enol and C hlor ine Y ield a) C hlorina to r and S cru b b er E n train m en t The D e p a rtm e n t 237 c h lo r in a to r (#5) is e q u ip p ed w ith a n im p ro v e d 3 -rin g sp a rg e r. W hen th is re a c to r is used fo r C rude D C P m a n u fa c tu re , th e c h lo rin e flow to th e top rin g is sh u t off w hen b a tc h * g ra v ity re a c h e s 1. 300. This--is n e c e s s a ry in o rd e r to re d u c e th e c a rry -o v e r of en train m en t to and out of the phenol scru b b er.a n d the . re s u lta n t y ie ld lo s s . A t p r e s e n t th e D ep t. 236 C h lo rin a to r (#3) w hich is u sed p rim a rily fo r C rude D C P, is n o t equipped w ith the im p ro v e d s p a r g e r. T h is m a k e s it u n n e c e s s a ry .to u s e th e p ro c e d u re u sed on #5 C h lo rin ato r on the #3 u n it. . ... : T he follow ing d ata show s the d ifferen ce in lo s se s w hen the ,,chlorine' ( / ' flo w to th e to p r i n g i s s h u t o ff a t a b a tc h s p e c if ic g r a v i t y o i l . 300:- . -, .. ; - / . / T o tal L o ss of E quivalent Phenol f r o m ' #5 C h l o r i n a t o r 8c S c r u b b e r S hutting off c h lo rin e flow to top r in g a t 1. 300 b a tc h - s p e c if ic g r a v ity . V 73 lb s. /b a tc h " -* M ain tain in g c h lo rin e flow to a ll sp arg er rin g s for en tire batch. v . 772 lb s, /b a tc h r,; The tab le above is actu al data based on m a te ria l balanc lo sse s over 3-m onth p e rio d s, using o p e ra to r stick m e asu re m e n ts. " * - , - .**. b) V apor L o sse s fro m C h lo rin ato r and S c ru b b er r :V* In o rd e r to m in im ize v ap o r lo sse s fro m th ch lo rin a to r and scrubber* i t i s n e c e s s a r y to c o n t r o l t h e i r t e m p e r a t u r e s a t 90C . a n d 50 C . re sp e c tiv e ly o r le ss . If the te m p e ra tu re s in c re a se above th ese m axim a, vapor lo sse s ris e significantly. N orm al to tal m a te ria l balance lo sse s of equivalent phenol fro m the ch lo rin ato r and scru b b er range fro m 0 - 1 0 0 lbs. /b atch . 2. B y -P ro d u c t H ydrogen C h lo rid e G as Y ield K03H qj T he re c o v e ry of ch lo ro p h en o l HC1 gas is a fu nction of the ch lo ro su lfo n acid d e p a rtm e n t's ab ility to m atch th e ir dem and w ith th e chlorophenoL HC1 gas g e n eratio n ra te . M ajo r lo s s e s of th is g as a r e in c u rre d when it is n e c e s s a ry to drow n and sew er the g as. P lu g g ag e of one o r both HC1 tra n s m is s io n lin e s w ith ch lo ro p h en o ls cai r e s u lt in m a jo r lo s s e s of HC1 gas due to dro w n in g and se w e rin g . T he p r e s s u r e d ro p fo r a flow of 450 C FM th ro u g h one lin e sh o u ld b e in thf ^ TT ^ n rp sR iirp . d r cvds th r o u g h th e tw o t r a n s - Dept. 236 - Proccsa Description ^ *7;. CRUDE 2",4-PCP SECTION IV - COMMENTS ON PROCESS (contd.) . /' /. 2. By-Product Hydrogen Chloride Gas Yield ( ,./;) . ^ .Improper setting of the Dept. 236 contro. dve to the HC1 drovming Jet can cause significant losses- .f HC1, .This -, valve should be set to open when the IIC1 pressurein the v-. . transmission lines reaches 35 in H20. A lower setting will result.in increased HC1 losses. A higher setting may result in-flow of chlorophenol HC1 to Dept. 2l8 with the resultant chlorophenol contamination of their food grade muriatic acid : production. . - i:v I- Leakage of HC1 gas through"the Dept. 236 control:viv to. ; the HC1 drowning Jet can also result in high l o s s e s T h i s can be checked by shutting off water to the-Jet when-the. valve position indicator shows the valve is closed .^i-A blind flange on the catch tank (for the drowning Jet discharge) should be removed to determine whether HCl -is leaking through. V;' Chiorine assay also affects HC1 recovery; The 1ower'the chlorine assay (due to greater concentration.of air).tue lower the HC1. recovery. This is because the. HC1-transmission lines are flow limiting at high HC1 generation rtes Chlorine assay normally runs in the 80-90# range . V This --is based, on.' measurements made in 1967 Dept. 236* with a -continuous in-line chlorine analyzer. '' 3, Sulfuric Acid Yield The primary factor affecting sulfuric acid usage'Vis ^6penatiori of the HC1 off-gas condenser. With th condenser out of- . V- operation the usage is about 8.0 Ibs./cwt. Mol ten'-.Penta and Crude DCP. With the condenser in operation,', .the-usage is about 2.0 lbs./cwt. Molten Penta and -Crude DCP.V .These usages are based on a 20-25C. temperature of the gases leaving the condenser. *. B. CAPACITY Capacity of the Crude DCP chlorinators is a function of cooling capacity and chlorine flow rate. The capacity limiting variable for the #5 chlorinator under normal conditions is chlorine flow. Under present conditions, with a clean chlorinator cooler, the chlorination time should be about 4 hours. The* capacity limiting variable for the #3 chlorinator is also chlorine flow. Under present conditions, the chlorinatic time should be about 5*5 hrs. However batches have been run with a 4-hour chlorination time, when the chlorine flow was adequate. Dept. 236 - Process Description ' - - 8. CRUDE 2,4-PCP SECTION IV - COMMENTS ON PROCESS (contd.) B. 'CAPACITY (contd.) The capacity limiting variable for the #1, #2, or #4 chlorinator for Crude DCP is cooling capacity. C. QUALITY The primary quality consideration for Crude DCP is the 2,4 Diehl orophenol assay. ^ 1. Chlorine Sparger Design _ v V :\.' \ `\ The improved sparger installed in the Dept. 237 chlorinator (#5) made possible an increase of 1 - 1 ^ in-the Crude' DCP assay (from 8 7 .5^ to 88.5-89$). Work has been initiated to install a similar sparger in the #3* chlorinator in Dept. 236. * V-/ 7 ' * ' \ 2. Raw Material Composition The present`specification for Crude DCP calls for an'8 7 .0^ .. minimum assay. / *. X The chemistry of the Crude DCP chlorinations -is as follows: a) Parachlorophenol chlorinated to the'Crude DCP stage / .gives 100$ 2,4-Diehl orophenol. The mechanism for this reaction is as follows: OH + 2 c l2 2 HC1 + Cl' Cl Cl b) Orthochlorophenol chlorinator to the Crude DCP stage (l.400-1.404 S.G.) gives material having the following composition: K031109 Dept. 236 - Process Description CRUDE 2 j4-PCP SECTION IV - COMMENTS ON PROCESS (contd.) C, QUALITY (contd.) OH Cl + Clg OH HC1 + r V Cl 77# 2 ,4 -D C P (equation'not balanced) -10* __ 0 9. OH OH r^ V. ci ci -C l + ' ; .*. .v Cl -. ^ 1 9 # - *" . V 4 ' g v ; x 2 ,6-rDCP 2y4,6-TCP c) Phenol, chlorinated to the Crude DCP stage yields materials . having the following composition: . 88.5# 2,4-DCP 7.3# 3.5# f '-:0 .2# -, 0 .5# 2,6-DCP 2,4,6-TCP PCP . . OCP . Based on this work and actual experience, the^following operating guidelines have been set: a) Fractions from the Parachlorophenol refining operation csn be used as fraw material for Crude DCP If they are blended, with phenol to maintain a 4:1 phenol-orthochlorophenol weight ratio. b) T h e l a s t 50% o f ^the d r y f r a c t i o n c u t f r o m th e P a r a c h l o r o p h e n o l refining operation can be used as raw material for producing specification grade Crude DCP, without blending with phenol. This Is possible because of the high parachlorophenol content of these fractions. K031110 Dept. 236 - Procesa Description - 10. CRUDE 2,4-DCP SECTION IV - COMMENTS ON PROCESS (contd.) .C, QUALITY (contd.) c ) .Fractions from the Refined DCF refining operation'cannot'be used as raw.material for producing specification grade Crude DCF. V? v Water boritent of* Raw Material The present maximum control limit for water content.of,ravr . material used for Crude DCP is 0.1# HgO. An increase*in. water content to 0.15# will result In a rise of approximately.0.5# in = the -6-Dichlorophenol content of' the finished Crude DCP?';. An - increase in water content to 0";20# will result In about .a 1# '" rise in the.2,6-DCP content of the finished.product.This can be a good indicator of a cooling coil or cooler leak in the Crude DCP chlorlnatoy. - 4.. Degree of Chlorination Both over and under, chlorination can result in the/productidh'of low assay Crude DCP. At the present time the endpoint; control points for Crude DCP specific gravity are 1-.402 (for phenol raw .) material) and 1.404 (for fractions and phenol raw material) at 4 5 /1 5c. The graph In Figure 1.indicates the effect of the degree of chlorination on Crude DCP assay. v^:-Vr An experimental in-line Infra-Red (IR) analyzer has been5;installe on the #5 chlorinator for use in determining Mono chlorophenol and Crude DCP'endpoints (in place of the present specific'gravity .. method). Successful use of this unit will- result in a 0,5-1-0# ` increase in the average Crude DCP assay. . The IR analyzer will enable chlorination termination at the maximum, assay on-each bate i ' . t 5 . HC1 Off-Gas Quality HC1 off-gas quality is a function of the quantity.of chlorophenol remaining in the gas when it is transmitted to Dept. 217. This, '** In turn, is dependent on the efficiencies of the Phenol Scrubber, the Brinks Demister, the HC1 Off- Gas Condenser, and the. H^SOij. Scrubbing System. Since the total efficiency of these units approaches, but does not equal 100#, the HC1 contains a small .Quantity of chlorophenols, For this reason, chlorophenol HC1 gas cannot be used for making food grade muriatic acid in Dept. 218. Chlorophenol-HC1 gas Is used only In the production of Chlorosulfonic Acid in Dept. 217. K03IX11 J j A '.-~* 0 SXmL JJj?.h:LJ.i" 5o e. C "oay:-ijj-ina*' i . ' * 'rMi oi n ' nnnuwD nm 'MJ c: oix 51 "V*_Vf fvi* Dept. 2^6 - Process Description 12. CRUDE 2.4.-DP APPENDIX A - EQUIPMENT LIST . -, /.V ` Both Crude DCP and.Molten Pentachlorophenol are manufactured'in-the ' Dept. 236 equipment center. The number of Dept. 236 chlorinators used for Crude DCP manufacture varies depending on Crude DCP demand and refined chlorophenols production. The equipment list below is typical of the equipment used and shared by Crude DCP. NAME ITEM NO. EQUIPMENT NUMBER 'EQUIPMENT - U :. DESCRIPTION " * Chlorophenol Fractions (Crude DCP) Storage Tank Chlorophenol Fractions Tank Pump 103 21-3491 104 13' I.D.x 1 6 1 'High i6;000 Gai. uninsulated vertical, steel storage tank,. Tank equipped ` with heating coil. :,.;; . *:-, . v 4 .. . . #3 Chlorinator . #4 Chlorinator ll6 118 21-2015 21-3096 4'^9." I.D. x 1 0 ' Sigh 1300 Gal.' vertical insulated monel tank, equipped with.a monel cooling coll (area-1 3 3 . f t . ) #5 Chlorinator ' 122 21-3058 Same as'above but'without'coil Vessel*, located in Dept. 237J #3 Phenol Scrubber. 117 #4.Phenol Scrubber. 119 1 21-2016 21-3097 \ 6.'.I.D. x 5 * high vertical, 1200 Gal. Jacketed monel uninsulated tank, equipped . with a Turbo-Mixer .Agitator'`` system/. *. / - #5 Phenol Scrubber 123 #3 Chlorinator Cooler. 129 21-1914 38-2751 Same as above except located in Dept. 237 '' Steel shell and tube heat exchanger,. Water on tube side and process on shell side. Area 480 ft. 2 - #5 Chlorinator Cooler ^127 38-5714 # 3 -Cooler Circu lating Pump 128 18" O.D. x 15* long steel shell and tube heat exchanger, Water on 8-pass tube side. Process on 2-pass shell side. Area 700 ft. 2 3 " x l" cast iron centrifugal pump equipped with mechanical seal, 1800 RPM, 10 H.P.motor. K031113 4 Dept, 236 " Process Description CRUDE 2,4-PCP APPENDIX A - EQUIPMENT LIST (contd.) NAME ITEM NO. EQUIPMENT NUMBER #5 Cooler Circulating Pump 124 Crude DCP Transfer Pump 120 Crude DCP Storage 106 Tank Pump #5 Phenol Scrubber 125 Transfer Pump Crude DCP 107 Neutralizing tank. 21-2471 Crude DCP Storage 105 21-3519 Tank HC1 Brink Demister Chlorine Brink . Demister HC1 Off-Gas Condenser System Sulfuric Acid Scrubbing System Chlorophenol Air Scrubbing System ' - -v- . 13. - EQUIPMENT V` : DESCRIPTION' / 4 ,f x 3" ductile^ cast iron centrifugal pump equipped with outside mechanical seal', 1800 RFM,- 25 H.P.motor. Nominal capacity; ' ' f ` .. ' .< - `7 -?'i , \ " ,, l- . -V':>VV 6* I .D . x 7 ' highavertical, uninsulated 1500 gal.y steel tank. ' 1 3 ' I.D. x;i9V-6'riiilh,':, :' insula tjed, vertical ;..20,000 . gal. Bteel tahk;:vTank:equipp: with nickel eoiTv\ - See Molten =Penta SMP ' : 'A-l': .-itf-V . . .vis <,;Y .>,;';*, . ; - .* VV.' ;*" H:,r;' :: , , 7 ' :: ; y;';; .. . I;!*"' ' -' .11 ;^ . y '""* - .. i K031114 Dept, 236 - Process Description 14 CRUDE 2,4-DCP APPENDIX B - FINISHED GOODS AND RAW MATERIAL SPECIFICATIONS'// The following'raw materials are used in the process: , RAW MATERIAL Phenol Chlorine (Snlft Gas) Sulfuric Acid (98^) CODE NO. 810.40 810.59 815.03 The finished Product produced in the process i s : Crude 2,4-Dichlorophenol 810.83 Specifications for the materials follow on succeeding pages: ;* ' ; -Pi K031115 Monsanto OftOANIC CHEMICALS DIVISION FINISHED PRODUCT S P E C IF IC A T IO N PRODUCTION W. J . W ilson ALES. W. E . Ault c cwen al DESCRIPTION FROOuCT PLANT PH E N O L (USP) PHOOUCT CODE OCPT. 223 use WGK DATI EFFECTIVC 1- 2 1 - 6 6 ' APPROVALS NESCAHCH 81040 ALLS CODE SALES 7100-100-03-003 J . F . Quinn QUALITY CONTROL (C bU t ChemtaO .1 ..t . . W. J. G resham CHEMICAL FORMULA MOLITT. 9 4 .1 1 SUPERSEDES SPECS. OP 9/30/65 & 10/31/62 CHARACTERISTIC AMPLE FOR ANALYSIS 2 x 8 oz., GGS B o ttle LIMITS tSCUCD OY UNRESTRICTED INFORMATION (R) A p p earan ce C rystalline solid i, l ' :.: (R) C o lo r of M elt: Shipped in Nickel*; Stainless Steel or Lined C ontainers "r. APHA 10, m a x . * ' V jf.r P , P r a d e r METHOD ^ j, Ai 10 *!s l 5 ' ; ';:'' ' " -*v" 0 / 3 2 3 Shipped in Steel C o n tain ers AFHA 50, m ax. * (R} F o r e ig n O dor (R) Tufrbidity of M elt None . . - : ;* a r.7 34 ! :.'' v. S ta n d a rd No. 0, m a x . (None) > :10 /3 2 4 ^ (R) C ry sta lliz in g P o in t Non-Volatile Residue @ 100% m a x . 4 0 . 6 0 t' C . , m i n , 0.01%, m ax. ;-^;C'0;322 V; 1 0 , 3 2 5 '* Solution in: W ater (1:15) 10% N aOH (1:10) C lear and C olorless C lear and C olorless 10,326 D istilling R ange: ** F irst Drop 100% R ange 50% to D ry P o in t 180.0C., m in. 2, 0 C ., m ax. 0. 2 C, , m a x . .10,329 * At tim e of loading ** To be d eterm in ed on one c a r sam ple each day and a ll c a r and lot sam ples with a c ry stallizin g point low er than 40.65*C K 0 3 I1 1 6 RAW MATERIAL Dale Approved-PPZ.Af.i35S,. For Dept.Z2 s...ZJ.y-/" Monsanto OROANIC CHEMICALS DIVISION FINISHED PRODUCT S P E C IF IC A T IO N PRODUCTION T . W. D alton SALES OCNCRAL DESCRIPTION PRODUCT 1" "PLANT C h lo rin e (Snift G as) PRODUCT COOK USE 232 WGK 01059 SALES CODE In te rn a l 1 0 /1 8 /6 6 ' * ' V APPROVALS RKSEAHCH M. A. T erp stra QUALITYCONTROL (ChltsfChomliO W. J. G resham CHEMICAL FORMULA 11 M ixture MOL WT. up erseoc? s pe c s , op 1 2 /2 3 /6 3 CAMPLE FOR ANALYSIS 100 c ,c . G as B urette cKAnACTcniaric limiti UNRESTRICTED INFO RM A TIO N C h lo r in e (C l2) T ypical A nalyses 8o%,- B y V olum e O xygon (Oz) 3% " h C a r b o n D io x id e ( C 0 2) C arb o n M onoxide (CO) 1.5% " 0,1% If u. H y d ro g e n (H2) 1.0% " h ISSUED BV J. P , P rader method ' *. v * : j;rV ; ' . *__ , 'J; ` ** 'i',`v* y .V'.v'v'' In e rt G a ss e s (By d iffe re n c e ) 8.4% " M o is tu r e (H20 ) @ Std, C onditions .2 .4 X 10" 5 l b s ./ f t .s (A verage) *- _ ; v ' D irect pipeline tra n s fe rs to using D epts 233, 236, 237, 246 ... T his sp ecificatio n is fo r in te rn a l u se a t WGK P lan t only, . ' i > DateRmAAoWWproveMd.AJXUEMRl5JL9S.3 For Dept. K03U18 71 "" . M omC'Awto C h e m ic a l C o m pa n y INORGANIC CHEMICALS DIVISION FINISHED PRODUCT SPECIFICATION DATE EFFECTIVE 6/1/66 ISSUE NO. p r o d u c t io n (Plait Manager) E . !.. Boehm s al es (Salti Manager) A . . R*; .H a n d le m a n au t h o h iz eo (Qdity Control Director) J. S. M etcalf PRODUCT PLANT S u lfu ric A cid COUE NO, ----------------- -- WGK 8300-098' GRADE 98% . nUFCHSEOES 102 4 /1 5 /6 3 -- -- APPROVALS RESEARCH {Asr.t. U i i C C i s r ) E, E . M oore QUALITY CONTROL (Uf Utzdtt) W, J. G re sh a m ' ` G ? K ? ei h ' . O S f lC W IP T lO N An essentially clea r co lo rless vipcous liquid. ; -. *; , .. (R) ' CHAi:ACTi;;;rsYtcs A ppearance (R). C o l o r (R) T u r b i d i t y _ (R.) A s s a y , (AI) N itrate as H N 03 (Al) - i r o n a s F e LUOTO . W ater white to light .. y e l l o w l i q u i d . . 150 A F H A , M a x ] *' 250 A P H A , .'Max, -98.0 - 99.5% . 0, 001%, M ax, 0, 020%, M ax, " TYPCAL VALUES"* ' .'**- ' .. ". METHOD HO. . ...i o o .a p h a ' . ;/ TO, 215 60 A P H A ;- * 9.9,2%,- vi / 10, 2 1 7 ' : * ?* * 'l 2 i 6 '5 4 ` ":i 3 ' 1 0 . 2 1 9 : (RI ROUTINE ANALYSIS (Al) C f f E C m ? AT INTERVALS RAW MATERIAL Date Approved"? ) ! i. U l5^ For Dept. -XSjJ-ZZ ' ? *4 c y .6 T "-. K03U19 / I- u-juiiouiuu ORGANIC CHEMICALS DIVISION FINISHl-.D PRODUCT SP E C IF IC A T IO N PRODUCTION W. J . W ils o n ALE* central description 2,4-Dichlorophcno.lj Crude b-Urade LANT PRODUCT COOS U3C -- WGK "Jdra'te APPHOVAL* flCSLARCII 1ALL8i CIOOOOH3 In tern al Use DeDt.. 262---- R, Vi, B u c k n e l l QUALITV CONTROL (C h lst Cheutlrt) W./J. Gresham CHEMICAL FORMULA '' MOLWT. SUPERS COESSPECS. 0" 12-22-611 CHAflACTCH15TIC .1 11 ample for analysis 2 X l 6 o z . GGS B o t t l e s LIMIT* (R) A ppearan ce and C o lo r Amber L iq u id o r C r y s ta llin e Mass (R) 2,4-D C P Iso m er 87. o, m in .' (1 ) (R) -W ater 0. 10$ , m ax. (R) S p. G r. @1*5/15.5 c Anhydrous B a sis R eport (R) A c id ity (a s HCl) 0 .1 0 $ , max. 1 .. 1! 11 *-T* V / ^ 1 >mZ.- 1. BTI M B U C O M .- D, B e a ly METHOD ,~ 11308 . * -V ' . '- V' 12782 11310 11879 . ' `P T T T 'r -B cF is o m e r c o n t e n t w i l l a v e r a g e 8 8 $ m inim um . A pproxim ate iso m e ric co m p o sitio n o f th is p ro d u c t i s : / 2 , 4 - D ic h lo r o p h e 'n o l 87 . - 90$ 2 ,6 -D ich lo ro p h en o l 6 -8 $ * T richlorophenol 1*- 5$ M onochlorophenol *'0 - 1$ T his s p e c ific a tio n is fo r in te r n a l use, only. (R) Routine Analysis, All others Analysed by request Only K031120 Dept, 236 - Process Description CRUDE 2,'4-DCP APPENDIX C - PHYSICAL CONSTANTS .15, Dept, 236 - Process Description 16. CRUDE 2,4-PCP APPENDIX D - UTILITIES The following types and amounts of utilities are used In the process: TYPE Steam (80 psig) Electricity ' AMOUNT 1000 M#/mo. 40 CKWH/mo. Water (Purchased) 450 M Gal./mo. (Plant) 6000 M Gal./mo. * V -v USE V '8 - Stg. tank.coils/ tracers. Pump motors, instruments, lights. Equipment w a s h e s . ^ Chlorinator cooling coils, Phenol Scrubber cooling Jackets, HC1.drowning'jets, / floor* washes. ' K031122 Dept* 236 - Process Description 17. CRUDE 2,4-DCP APPENDIX E - PERSONNEL The- following personnel are required to maintain operations: CLASSIFICATION NUMBER OF MEN' JOB DESCRIPTION- Premium Operator Chief Operator l/shift As required Complete control of cfilorination to include charging raw material determining chlorination endpoin air blowing finished product, transferring product to finished product storage, procurement of necessary data and samples, and operation of sulfuric acid scrub j. Receive phenol from Dept. 223, empty and recharge sulfuric acic scrubber. "'A " Operator As'required Receive high para fractions fron Dept. 237 nB" Operator 237 Operator As required As required Transfer of finished product frc storage to tank cars'/- Transfer high para fractions to Dept. 236. .. K031123 Dept. 236 - Process Description 18. CRUDE 2,4_-DCP APPENDIX F - PACKAGING AND SHIPPING Crude 2,4-Dichlorophenol is packaged exclusively in tank cars for shipment to Dept. 262. The following cars are currently used for storage and shipment of the product: CAR NUMBER GATX 95388 NATX 18205 MONX 803 MONX 806 GATX 77006 MONX 824 NATX 18135 MONX 814 SHPX 22772 GATX 95286 SHPX 88727 NATX I8l4l SHPX 23866 GATX 76573 ' NOMINAL CAPACITY 10,000 8,000 G al . 8,000 8,000 8,000 8,000 it 11 11 8,000 8,000 8,000 11 10,000 10,000 8,000 8,000 8,000 it 11 11 11 11 MATERIAL OP CONSTRUCTS Sttteel 11 11 h 11 h M K031U4- Dept. 2 3 6 '- Process Description * CRUDE 2t4-DCP 19. APPENDIX G - MATERIAL BALANCE The material balance Is based on monthly inventory Information, since 6/66. Actual production observations were used when more formal information was not available. (6 K031U! Dept, 236 - Process Description CRUDE 2,4-DCP APPENDIX G - MATERIAL BALANCE (contd. RAW M A T E R IA L U S A G E S - L B S ./ C W T . Phenol C h lo rin e O rth o c h lo ro phenol P a ra c h lo ro phenol T o ta l How <ro to to * ON 1 If=- CO ON i *O-3 o33 . o 33 .? 33 LO cr\ H *ro o -4 VJl vo --Q - - on o -UvQoi__ o _Q__ M O o o ro H* M r0o0 VO -*3 VJl 4=__ cel _ PN_ 1-* H* LOON i UO)N hO-* bM o O J ^3 00 00 VJl VJl L O VJl v0o0 !--1 o > L;. --l ro 0 _Q__ VJ1 VJl __ -Pr 00 ^3 H -fr H -t=-4 -P= H 1 ro 0 o * ro LO O O O K 33 / Q 33 > > / s a s: / 33 ct / O 33 / ss t r / i-3 //CO 3333 -4 o v4or ? // SWSPi // SfeMCO vo o I-1 H Vr-0*` . b C h lo rin e ^ o Tn-- vo P h e n o l & ^ b F ra c tio n s o C ru d e DCP ^ HC1 O f f - -- ! Gas o "O R ecovered F ra c tio n s o -o H C l O f f - & Gas ' HCl O ff- ^ o o Ga3 LO I-* O ro -^4 ro M b o ro -4 H -Ol=r HCl O ff- Gas 3 S u l f u r i c rrA c id : ~ Spent A c id "P HCl O ff- P Gas P I c ro. o Dept.- 236 - Process Description APPENDIX G - MATERIAL BALANCE 21. . 'SUMMARY.OF MATERIAL BALANCE RESULTS RAW MATERIAL USAGES LBS./lOO LBS.PROD. MATERIAL BALANCE THEORY Material Bal. Usages lbs./lOO* lbs. Product 1. Phenol 57.730 59.000. 57.730 Process .-1.27 HgSO^ Spent Aci 59..O0" 2. Chlorine 87.000 91.00 . * 87.600 . Process 2.00 HgSb^ Spent Acj .1.4 91.000 To atmosphere *`/:0 . r * . i*V 1 , ;r- /:f. >* " ' ...' L-p' -S aa " * , . ' 'f v * ' v.>,:*' vt' " ' ;` *' K031127 Dept. 236 - Process Description 22. CRUDE 2 A DC? APPENDIX H - ATMOSPHERE -STREAM DISCHARGE Summarized below are materials discharged from the Crude 2,4 DCP process to the atmosphere or sowers. The quantities listed are based on the material balance shown in the previous section. Existing problem areas are listed even though actual quantities are unknown. Discharge'to Atmosphere ITEM tba/lOO lb. Pi ''.'duct 1 . Phenol storage tank Unknown vent (only phenolics) 2 ., HCI drowning jet Unknown 3. Vent on DCP Storage Unknown Total l b s , per Month based on Production Rate of 1 ,700,000 lbs./mo.' Unknown Unknown - Unknown HC1 and Phenolic Discharge to Sewer 1. . a . HC1 from drown ing Jet (under normal operations) a. HC1 19.1 b. Phenolics-trace 324,300 ------- b. HC1 from drown ing Jet (when 217 shut down) a. HCi 46.55 b. Phenolics 0.20 -792*,000 3,400 2. Drain line to sewer on Dept. 217 HCI line. Unknown Unknown Dept. 236 - Process Description 23. CRUDE 2,4 DCP APPENDIX I - PROCESS CONTROL SAMPLING POINT FREQUENCY REASON FOR SAMPLE 1. Chlorinator Every 2 hrs. Specific gravity & more is indication of toward end degree of chlor- of batch. ination. 2 : Tank Car Once from every full tank car. 1 -2 tank cars/day. To compare against' speci fications for Dept, 262. (2,4-D Mfg.) NORMAL RANGE 50 gravity points/hr. Finished product 1.4021.404 45/15.5c- METHOD _ # ___ Operator test (1131 Appearance & Color Amber, liq.or . 11-308 crystalline mass. Water 0.01-0.10# 1310 Acidity 2,4 DCP isomer 0.01-0.10#' 8 7 .O-90.O# I879 I2782 K 0 3 U 29 Proce** Area Or Step C 'HLCRIKATION }* foriable Or forameter . 1. Scrubber Iff-Gas temperature Description of Parameter As It irfects Safety, Quality, Yield late Or Other tffcct* yield. 1 ' s. Cooling Water Affect* rate, yields, quality. Bange For Best Frequency r Known Process Of Monitoring Performance By Supervision 35 - 50C , . Hourly by operator [Hot logged) - Measurement of Variable requency Method 1 Accuracy Jontinuous Temperatur Recorder 1C j Full water on coll if running v/o exchanger. Fll water on exchanger if using #3 chlorInator Hourly by operator (Hot loagcd) Continuous Valve pos ition with exchanger. Plow in dicator with coll. Unknown f. Entrain Affects quality, rate* ment Low entrain ment as definet by operator one foreman exper ience. Hourly by perator Continuous Site glass 11 2. Batch Data i. Batch Indicate* proper level to achieve Gravity quality 1.1*00-1.1*03 at T0C final batch gi V Ity b y operate fvery hour Operator intil ap gravity proach end analysis point and lien as iceded + 0.002 i. Aaaay Quality 07-90^ 2,1*OOP i'c-iclne Hon Routine Laboratory Analysis . ' Interaction With Other Variables How Control Variables Conn High temperature In Lower scrubber dicates entrainment temperature by hot ecrubVcr, under increasing cool charged scrubber, ing and reduce or bole in draft chlorine rate if tube. needed. Check that scrubber Is not undercharged. Chlorine added au tomatically to maintain tempera- Maintain flow The need t rate ln range at ally reduci maximum penalsoa- Indicates 1 ture. Water rate ble by entrain ment error determines chlorine ment. Do not use separator 1 rate and consequent' call when using ly process rate. external heat High flow rates can exchanger. chiarinato charge, or chlorine a cause excessive en trainment. High entraiment Control process can cause poor within ranges. quality on next Determine devia batch. Accompanied tion or problem b y high chlor. off If entrainment gas temperature, occurs. Reduce and scrubber temp. rate If necessary Results from plugget separator, or too fast gas addition. Low gravities mean Take adequate low 2,4 assay and hydrometer reod- an excess monochlori .lng near end of Eligh gravities mean hatch to be able a trlchlor excess, to control ln again with low 2,4 range. Stop chlor assay. ination while analyzing if near end point. lorrelatcs with Controlled by natch gravity direct -batch specific ly up to 1.402 and gravity. inversely after that 1 L.e. assay Increase is gravity increase! ind then decrease* lfter passing optl- Dun point. High vote r In feed, low phenol/ jrtho feed ratio, at i ilgh e n t r a i m e n t car :ause isomer shift 3 :hat low assays may iccur even if gravll y Ln control range. KC t Process Area Variable Or Or Step parameter Description of Parameter As It M f e c t s Safety, Quality, Yield Rate Or Other V.W MATERIALS 1. Blended fractions a. Phenol/ Ortho Ratio Affects isomer split causing low 2,k leaner product. Range For Beat Frequency r Known Process Of Monitoring Performance By Supervision _ Measurement of Variable "requency Method Accuracy At least 5 After blend at] parts Phenol once per day to 1 part Orthc Dally by iterator aLC anal ysis by Lab 0.1? b. Water c. Iron Causes 2-6 shift, builds up nickel salts, and causes corrosion* <0.08? * Darkens product and also 2-1*D ncld 18 pita max. In 262. Dully by chief operator.Poremi ,, by exception. (>0 .10 ?) D i-'y by operator lobatory Analysis Hon Boutina ton Routine 1a b o r a t o r y Analysis 0 .1 ? 1. Color lolor of feed propagates to final product 1 <5 0 0 APHA tor. Routine tou Routine Laboratory Analysis 10 Ap h a 2. Chlorine a. Header Indicates proper pressure at BD to 25-30 p-ig Hourly by ape Jontlnuovu Pressure Unknown Pressure maintain standard rates. ator on each Recorder batch sheet UATOH CHVYJIIC b, Demister Inlet Pressure Indicates some os header pressure. S5-36 pslg Monthly by foremai\ 1. Chlorlna- Indicates proper charge to malntalr 1*8-52" outage Each butch bjl tcr Charge rate, quality. operator - 2. Chlorlna- Time to drop scrubber to chlorinator Charge tor affect rate. Time 30 min. .2 5 min. Each butch by. operator bntl u '.Vj -_ [Pressure Oage Unknown Each bate) Stick by opera seasurcmenl tor 1 V2'1 Each Batch Time Interaction With Other Variables How Control Verlables Comments A high percentage Maintain at least 2-6 Isomer usua of ortho present a 5/l ratio. Max 6-7? of batch, will convert to the imise fractions higher, run QIC undesirable 2-6 usage. check of fecdst Lscner resulting In a 2-k lscner reduc Control of pher and fractions 1; tion. Extremely la essential tc high ratio can causi good blended fr a build-up of frac quality. tions Inventory due to under-use. /Ugh water content Rely on phenol causes an Increase department to con In 2-6 leaner. trol HpO, control fractions water content In 2 3 7 * High iron darkens Minimire recycle the color of all of washout batc)ec phenollce Dilute with water white plteno1 to lower color. Resulks in dark Control iron. Visual cl<eck m product. Usually chief operator caused by iron. dally basic. 1 dark, requeet to be 1 jn by 1 low pressure cuts Contact cltlorlnc chlorination rate dept, to determine since must lover cause of problem. cooling water flow Check demister In to maintain temper let pressure to ature . Low pressure tree pad is not eans low gas flow plugged. which can cause pool isomer distribution. Interacts with bead- Clean or replcrc r:r pressure directly demister pad wb'n iHigh pressure dif A P exceeds 3 pel ference . or once per ye.-. Overcharge causes cr - Charge to If vc' iaicU m trmlimcnt loss. proper level. li:ft scrub Undercharge cause sft-r drop, 1 rate loos. affect ?-k Is. subsequent ba Dong drops means Clteck tracers if Line blockage time of drop is too long. '1 K< Proce* Area Variable Or Or Step Parameter r wren c h a r g i n g * |. Scrubber JSpecific iravlty Ascription of Parameter As It Effects Safety/-Quality, Yield Rate Or Other Gravity determine* following batch quality and yield. Range For Best Frequency Known Process Of Monitoring Performance By Supervision 1.0 5 0 - 1.2 5 0 Each batch by at 70C operator Measurement of Variable frequency Method Accuracy Bach Satch Hydrometer 0 .0 0 1 test by operator i-. r 1 li. Scrubber Charge Indicate* proper level to prevent :Xce*sive entrn j.nment or Clg > :mi**lon. 1*0 " I" outage Each batch by operator Bach Batch > Stick Measure ment l/2 " 1N C. CHLORINATION 1 1 . Oa* Addition . Chlorinator Temp. Effects yields and product quality. 90 - 1D0C Hourly by operator Continuous Temp. Recorder Controller A 12 pt Recorder 1C 1C a. Scrubber temperature Affects ylcld3, air pollution. liO - 50WC Hourly by operator Continuoui Temp. Recorder * 1C c. Chlorlna- Affects quality. tar Off-Gaa Temperature 5 - loooc Hourly by o n t m u o u c Temp. operator Recorder (Not logged) Interaction 'Jltli Other Variable:- How Control Variables Can High gravities can Monitor gravities cause an lBomer for each charge. shift, reducing With low gravity 2-k l*oraer. Low observe entrain gravities can re ment and reduce sult In high en rate if needed. trainment on sub With high gravi sequent batch. ties, process the Do not ho] batch as 1 suit in pc when the t finally di chlorinetl batch but reduce rate to improve quality of follow ing scrubber. I f outage high, Add feedstock to 'off gas from chlorproper outage. inetor will not be scrubbed letting chlorine gas Into the HCl system und eventually to the a tew sphe re. low outage result In excessive phenol losses to the off gaa system. low temperature re Position controll :r sults In slow rates set point at pro since cooling be per temperature. comes limiting at Low batch/coil temp llfferences. High temperaturea result in excessive carry over to the scrubbei U g h temp give high Manual adjust aff gaa temperature cooling water ind resui'-o in yielc flow to Jacket to Loss to HOI mystem. maintain temper Indicative of poor ature . chlorinator opera tion or low Jacket :00ling water flow. Low temperature reduces scrubbing rfficlency, letting 31p Into MCI system. Low temperature ln- Check entrainment llcates low chlorine separator for flow and low chlor- pluggage. Lnator temp. High temperature indlcatt s :ntralnmen t . Dept, 236 - Process Description 24. CRUDE APPENDIX J - SAFETY AND TOXICITY DATA AND ACCIDENT REPORTS The following precautions should be heeded when in the dichlorophenc area. 1. Finished Products Handling:- (Reference: Sax Handbook of Dangeroi Chemicals) , CRUDE 2,4 DICHLOROFKENOL is corrosive to the skin. Small amounts spilled on the skin should be washed off immediately with the alcohol located in the-first aid stations located throughout the area. This alcohol wash should be followed by a thorough washir with soap and water. If a large amount Is spilled on the skin, the contaminated, area should be flushed immediately with a larg volume of water and then treated at the dispensary.. Safety showers are located throughout the area. A fresh change of clothes is provided daily for the operating work force. Wearing of safety glasses Is an essential part of Diehlorophenol operations'. 2. Raw Materials Handling: (Reference: Sax Handbook of Dangerous Chemicals) PHENOL is extremely corrosive to the skin and should be removed as previously stated. Sulfuric acid is also corrosive and should be removed immediately by flushing the contaminated area with a large volume of water. CHLORINE and HC1 gases are highl; irritating and dangerous. If the area must be entered when the: gases are present in large amounts , the protective gas masks located in the operating area should be worn. 3. FIRE Hazards The flash and fire points for Dept, 236 materials are: Flash Point Fire Point Phenol Crude 2,4 Dlchlorophenol 79C. 00C. 85C. 200C. While none of these materials are technically flammable, no burning or welding Is allowed on equipment until it has been washed clean and then gas tested. This is due to the possibility that any residual HC1 present may form Hydrogen by reacting with the metal of the vessel. K 0 3 1 136 -* Dept. 236 - Process Description 25. CRUDE DCF - APPENDIX K - Background of Process and Annual Remarks Crude DCP' is produced in chlorination equipment originally installed in Bldg. BD in 19^7, for.the production of Pentachlorophenol. Penta and Crude DCP requirements have steadily increased until a total of four chlorinators are now required. Most Crude DCP is produced in the #3 chlorinator which Is equipped with an external steel cooler.- Crude DCP Is also produced in #1, #2, and #4 chlorinators and the Dept. 237 chlorinator. Crude DCP is used exclusively by Dept. 262 for the production of 2,4-Dlchlorophenoxyacetic Acid (2,4~D). The Bldg. BD chlorinators are scheduled'to supply the Crude DCP. All other chlorination capacity is used for the production of Pentachlorophenol. Average monthly Crude DCI production In 1967 was 1,980,000#/mo. Requirements in 1968 are forecast at 2,l4o,000 lbs./mo. In order to satisfy increased demand for both . Crude DCP and Penta a capacity expansion project was initiated in late 1967. Tentative plans are to install another batch chlorinator to be used exclusively for Crude DCP .production. . APPENDIX K - Process Amendment Record Sheet Amendment No. Date Subject "A" to SMP Dated 4/65 7/ 26/65 Use of essentially all Dept. 237 fractions for Crude DCP Raw Material. Disposition Accepted 12/2/65 K0311.37 Dept, 236 - Process Description CRUDE DCP" Appendix L - Time Cycle A. Time Cycle Item #3 or #5 Chlorinator Time (Hrs.)______ Charge Chlorinator Charge Scrubber Chlorinate Pump to Storage Total 0.5 0.5o 3.78 0.5 5.28 * 26. # 1 j#2j#4 Chlorinator Time (Hrs,)______ 0.5 0.5 5.59 0.5 7.09 B. Capacity #3 or #5 chlorinator ,13j200 lbs. Crude"DCP/batch (720 hrs./mo.) (78# OST) `5*28 hrs./batch = 1,408,500 lbs./mo. Chlorine flow is the capacity-limiting factor. With adequate flow the OST would increase to 87^ and the capacity would increase correspondingly. Cooling capacity is the next capacity-limiting factor after chlorine flow. #1, #2, or #4 Chlorinator 13j200 lbs./batch (720 hrs,/mo.) (78# OST) 7.09 hrs./batch = 1,041,500 lbs./mo. Cooling capacity is- the capacity-limiting factor. After cooling capacity, chlorine flow is the next capacity-limiting factor. Nos. 3 and 5 chlorinators are equipped with external coolers. Nos. 1,2 and 4 chlorinators areequipped with lower capacity internal cooling coils. KO31138 Dept. 236 - Process Description 2.7. CRUDE DCP APPENDIX M - QUALITY CONSIDERATIONS CRUDE DCP ASSAY Maximum Crude DCP assay is desirable in order to maximize yields in the 2jk-D. operation. Recent calculations that each 1% increase in Crude DCP assay results in a $36jlOO/year yield savings in the 2j4-D. operation. HC1 and WATER CONTENT HC1 and water concentrations in the finished product must be minimized in order to minimize tank car and storage tank corrosion. Normally this is no problem and no special steps are necessary to. insure this. K03X139 Dept. 236 - Process Description CRUDE 2,4-D. APPENDIX N - MISCELLANEOUS Attached is the production Cost Standard for 1968. 28.