Document LKv1yv42vY8KZwoNyw1YJmYz

I. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOl STREET NEWARK, NEW JERSEY Serial No. Copy No. J V* ChaluPski> Plant Fil0S ^ -- j r et ur n t o JACKSON LABORATORY FILE ROOM NEWARK PLANT PIGMENT COLOR RESEARCH REPORT tT : ' Period Covered f t / v - S"d - 3 ? t -3 HJ 9797 FILE: DATE: H 0vt> &*<t & \J \ iv OO'iX/' VT.Jo 5 Cc if tox - 3a;a3?ieai Fils TM S3:53s;,rCl:l! Office (iSBoi) - LIM'J?:? File (22 - flQ BuilUm ?U3 o Clialapski ~ P3Um Files 'd . Bo Kiiuejc/io Jackson bebe Orshea:, * JPv 0 Gr&h@mf Me j>ovfc I3xfcr, fixiara ~ Sa&s** RETURN TO JACKSON LABORATORY FILE ROOM IS'LxKX PM1B C. >.: * F-F r<: v: Fi:;*..sX U3'00?t mmmmjdt: o# mo&mm f o r ms ior/aa? c?c n,&m IS - *: .' .IMS OF OFC FFHF $ 15K5 Fasv2m> Vy-.B CBiFGlii l~Xl~G~22$ mmys-iw bo x s * mains AipPOFFB l Si'-ri:! mu gxm&nmt 11/14/50 . i45:B ISfiti-iDj 13/18/50 DUP050068238 This is the sacorcl in sennae of axparts dealing with the seM-^orks sM plant doralcptitnt alna'llos c:C vanec s o s e fan'CFO a&&ttecSum si the Ika/gori rlrnin oc-'nici !>-<.{; 0/ iha ChonlasX Dlnisioa in the period 19n6 -- ii*f0, Iks xh-ni report (H,*f:-*rut 1) in this series Me rannl'M, of elrlive of ch:Xc.?pV;h.?.lXe scih .manufactures'! the prz; sot report So connonnsc! nith the invest!*- gations of the CPC cnraan uAiom neannion, An which phthaiic anhydride $ efelorphth&Xic aeM X>'*c:.' it), i'.nna,, congar chlorine ami catalyst an heated together in to fopr conger ohfhaloe:fanimP Ska seni works studies dieeuoaof in this rape^-t'nans'cenrled'out An tbs period .JiniejX946.jth.ru Fiafn i94$* vhilc olio plant work 'karMlesiod hare ms dope during the initial operation of'the Xanporb plant fro-':;! April September,, 194-8 o Tb a work dleon-nscd horn naa a ana F.Fs.Shrioii^ F* 3* Orah on ^ 0 AhlAlIrAa., IV-M writers, with the aseihkenen ef hr* ih,fho Service DIv Is Xc k i. daring ike davrlo rait n. i\ one ison0* J.H*8airdt OS ,. } arannon,, and the 3?' of Asa logins suing >V, plant steutrunipp asttu! dies* aT * .1 an i.i!a.' samprr; hl to that obie Aied is tbs labor-lr;r arl oa:ni->!:orsn . ;.nrB fee arnpnnsi la tas le- port ple.nl; exeAsreenb W the nrjo of the sr;.gp proccresss* f^na results of :. 3j. i-rorks and plant risvalegrrnfc etutli :S -O.i.1 ho CPC eors&amsafciao. no no tioo a aa anaaariosl ani too affects o. ` Tf.'Vi* on nm process are disc was ado ms2iJiSEiiiai 'lha H-aaufae turn cf copper phtbaioeAsnina pigments by the ^OF process involviaig basting together copper s'nXoridij rures soil phtiialie anhydride with a catalyst is cohered by a paiert assigned to X*C*I* <Hof*21 DuPont; is XIcnnsoo to c-terete under this peisnt* For a &ere do tailed''" discussion of the patent:, sec F.oferenos 3* smiiss` Since of Cpa prepex-'afio:.;. of eqopsr phlha3,oc:jaains la the B8Cfark hosisi^fiorha nap atartcc is Aninai^ lyiS5 'using as the haeie process the procedurs do'-elopei in ilia laboratory (isfo Af 6), Bib t o thud' used ih tho initial snai^uohka pi^par?- ii onn differed from that giush la Append Lc 1 orf.y ia that day ohion]hthalio acid m used in place of * the presacako and r'..?*.. rsaoiants -.e:.'C charged to keroseue ia the reactor at noon -te^psrnturiSt hoi'ore the start of heating* !he -si^ui'^^e'it nesO; jta the ^e^A-y.orJt 5 irtndisn mas purcMsad in. the used equip'iapt, narhet nnl ncs ill ,?aliu:I for the purpose? in addifcio.i to being in poor xnc' mice!, coalition* Thnae a^uipaent def icleaciaa worn % continttixsg sounca of oil 1 Xcialty 'throughout the setsl-uorfes studios and prerrsatsi the mtahlishaont of precise DUP050068239 ** -2 u'- operating ejolas or Aeitoite standards So t yields &M pigment qno.'V.tf* BomvTn ellh this o-niimvrnt it wss possible to estahlAsfc t>3 operability of tb3 proposed. ovaomj on a large scale* to clawoa** tor?.to the successful Pee of ototoruiltotoie /cil grayscale In the sw.cbea is '?rr ber'a /rurtotosto \*.-.v. tobto/ <, a?iA to prepare pc fee ' .el iii .moatit;/tiidfiaXopt for urcto onto eluSytol the milto" sequeat steps in tba process*, *&* plant eGuiumnt for the CFO eondenaction reaction differed fpois that used in the ssml-u-op&s in several respects* in addition to the matter of sis/a the agitator for the plant amt was .quite different from the esysi^ros&e egitator in. des .git and oparstioni the plant vessel was equipped uiih g ms.iom vapor :; Sue tor* (rhere-ss no sucli device rae used on ths se::/i-/or!*:s urlt? a arse aaltar was used in ths plant but" this device hto never cs-to operated sneceesfnXly in the eemtoworks* fuseyous difficulties worn crjccimtorcf dixring the first few eiteapift to oporatsp.n tie pi sat , too. 'f'c e/.-ytonuafetou pj'oeas.s ds':"st,0pad in the to/toUworks* A totoxl nw/ww:\;\;/ tf ito results of the. float appr-o;;;ir'intsXv' toetoatoe ir gluon ivitohla Ihe first attempt to carto out the .Taction in too plant yAetoto apparently safe.is factory quality pto ..r; hut ths entire /Xa:u;to calac? cm the reactor /rails bamm of eftcoss 1 r 1 / /se^ Xnaesa red T?si fey ha .reno^ed from ike vessel toy hand* JX'!ie s/coto pleat charge toiled to oru oh sati/f sotorily and 7iaided only a pur.oo-blur tar viiic.b hud to >0 scraped by hand froil the uentlaj a total. of si;* of the firet 31 race*** ehoryss CshargcB 102* 110* 112, 120, 12^^30) tohewod itx this toto ...? , In rtotoioa* the . reaction''vac euntor ally only nrto/tolly complete to totowra other inetanaee, to tototo the proa rat was obtained in ths form of pellais which cojiM not o b putoto' unto wsrs remoied tom ths reset ion vessel by draining the chmega into Tne' cliffienlilas at' this stags of tlie plant development work were aggravated toy tellurs of the reactor preduet pump to perform set isfactor ilys by the to'chii toy to oh Is in a item of molten v t b b iron the urea Bialtor;i and liy rap's/failure of ths heating unit for ths pig at tmntav bj :A uaribus auxiliaries. Frog$s in correcting these 5 iff lenities mm ratarclad toy three firae, oae of rbich oaussd fs.U.urs of the glass liatog of tbs rfahtor, socles itat Xr.g a wssto,s abntdoT'S. for rspato'., 'ihiio asothar' fir (due to lightsfsg} retosred th@ entire plant iaeparatols for e/vuere1 days* Shs'usual startup difficuHIes InrcXrtog loaktog Itouo, ytaap tailvvea* ate. * a.Bil the necessity for oo/t:feluuo,t:lj'm of oonstruchion work on ifee u&- completed parts c>f 'the hulldlogfoonpIicatcd ton sihaatiosu /l/jwt of t].:s plant nech.'--iiaal protoiem?; rer5 corrected m scon as naapewer could ton made aaaila tola to dp tin m-ommtj monk* Hoi'Tarcr.j other orotolehs 'uei'O not ;?o on.:lnklT solvod* fhs difficulties In, cupping the rsaetor slurry re<*a r-idueed toy nowmnting ths pmap miipeXlpy I'ros es closed typo to an 3ue. am e.xd toy Ijaereaeiag the agitator speed to the reactor iron 72 31PM to fu SE:h (charge 109) and Xm&T' (charge 111) to 120 &,?.!, Into this problAti w&s not com- tolstsly solved until problem of irnonnints reictioa -ms over-*- cams* ("ntowgtout aapari/ruca to:'liejatoi that a clto.nvl :imp-3i.Ier^.?ould probutol/ too satoiu factory ouos toe c:,/uticu vroU'.Em wae solved)^ DUP050068240 .0 Jnj UO.i'-SbSC A in::; stess for heating* coi ertebliek lag's revised' hastiag' cycle. Firing of .'ccro-nons n :-ovc ui this plcnt reactor ms successfully prevented by the glyals t. 'jaiisnh of moi ifylng tbs process so m to aTotcl the necessity for o-vring the verator .* v.ols'^hile ih kerosene In the vessel we a hoi* :racl by lnt*cv ,,o:n^ krart gs (C09 or nitrogen) into the vessel Infcre S:l>ehargtjg it on oonplsIlDii oftha reaction. Foaalng of the ruction. AbAtav end the for -: tioa of an adhesive -tar* .re.th.or then copper philvloevaMirs., nor the lire plant problems ^hlcli proven r-ost difficult erf rcc-viv*'! fn Ion;;:. * t, time for solution* Psit-har of thsso frollone h&h heoi: ,v;.w >t>*cd in either the lob one b or.? ex* ;x3ni-; rk@ frVdics* laber-'t'-r;. V /-etlga-*- tinm indicated tl:/f arefoef'c" c! the fnr? refher then plpocrt* iras a eda3`vrf-ics cV 1 vav iMs observe, lion'-vro en Jf.i'r.Tsd tv cell a la>crr .' f--~r n; *-.:v;!- .'orko cole fcy att 1 lions' 1 W0rkf i&ich also Indicated at foariEn of the chwgs nm mgnif led by so.eh 0.2.16 r. SJcru 1he alant prccenc nm coms;:- tiy modified bo as to reduce tba posnlhll1l,,;!,t,*-y o....f efT n*Hd.;*Ainm A letesratax'is for addition of mactant -* via the eper.. aaBfcoIa <- to t!.\e leeroeene 'was decreased * the length of ii/a the tssBbojs vas c.u:z> res kept t a k peZr&lsm enth:r.;ffeet see off sc to ths fcorose&e, agiti tiem of flip ksrosano in tho nrs-ecce of sir avo^sd ss`ismeh i pass ibis * Bhtl anicon-hns attlse ic the heros-sjse ijxm** cH&beXy upon opcn-lng the nenhohe to provico o fclee&ot of Inert omt tha licial6v llso* for a tire fniioring 6.*seo?err of the aerial onMatioa effectt only fresh bercsco'a nm used as a reeatioa aadim$ far & period thersefter^ o rontira control neothesis nm carried aui on eaci. batch of kerosasa before use, (A ,n*oc;* uvs for'cciid.lt!toning o;e''6:i^ed keroseta for rsuas{. lafclnlng treev ?h: ---Ith eancaatrateo si'h.fv-j'ic ecldj I'olloned by eentrlfuf ingj *:m da7olo5*od feut was nerer <4. pat Ijato pleat operation.} epos cpylioetioa ia the pleat of thass 5 e.aEres to prs?ent 'oxMetion^ m farther difficnltias wsra oeottBt^r(S kith failure'of the reaction no proceed normally aal foamltig bs reduced to within toler&ele Xhalt3* A great aargr wrl-etioM In the procea^ T'2rs tried Ib tlia plant Inrisli the psrioc? prior to diBCorery of tire effsssb of air osMatloa oa the i'eactlc-'-o kha results of* th.asa axper^^nts5 ierroXviag in many eases nariatloa ia ths traa:ntJ,ty and earner' of. sdiitioa'of catalyst* the order of addition of rsackaats* tim taaK pa:eetore and fflasmer of addition of aroos etc, * opart to stispieloB, la the sections on the cffacta of ynrfables phich follow, n attempt has hmn wale to ludlente tbs nsyaiinds of urcerrlci.' l.y isiroduoad iato tfe.s variablea froK- these eox'eeo*:* DUP050068241 , 4 - Kill fhs procaorra for the hty cuvl oration atop la the pra^ratlri of i-Z '*, -`a IPf is gives in Ippaniin Is the pro** cedure as .originally specified for the Pcvnwrfc plant is given in jlt while fchs Hswport plant prtcciirra ?c -'rd tried by crperieaoa gained during She ^etart-up* is gi^s; in p/nun'l; XXX* Sins effects of variation in the standard pyaceir.ra are di^awsed in a later part of this report* EmitBwemt il simplifies diagram of fba oonipnoat ns ad in the fetraiis semi-worlss studies of the 00 ads-.,: at ion reaction Is sivcx* in Figure I* A diagram of the Ammmt plart cruivvo it is gS'-mn is Figure XI* it is to he noted that, in addition to agitator design and constriction details $ ili-s plant aq'Uip o t Vc *` 1< fers iron flat ,,'nsec' In tho sosi-workS la that the plant unit :$ ip.iib $ notions vapor eductor to dre&si off the' fumes frost. ->"03 reactor, whcrcae such & unit was not incorporated in the sml*\{QY%.c dasiga* fhs plant halt is also pro** vi&eiTwith facilities for adding solten urns in bko reactor^ Boreas urea was added (in the solid state) by 'mae.ae of &. star v-alve in the case of the semi~orhs unit* (i ^ureo meltor" was installed in the seminaries hat wsa found to he i^ro^erly dsoigsisd and project to he inoperable)* ttm sswl-norks equipment used for the soRiinorls synthesis of CFG prior to start-up "of tVc Stenport plant 1e3prs.se.ated makeshift itsas obtained by purchase from the secondhand gsricat and re conditioned on the Hc^port plant* This unit comprised a 50 gallon, glass lined reactor, Snipped pith a Mhotac-u&i*o"r3taaX agitator ascl provided pith a ahor:s..i.-e.do$* stainless stool cover viih openings for k reflux condenser and other auxiliaries, and for introduction of raw si&torials'i agitation was provided by naans of a steel peddle type agitator <li:irs:a at-es<>60H?l* ksutivg was accomplished in the seal-- works by oirc.plafc.ing hot oil through the ..lacks!.; of the reactor frop -an elsctrically heated oil bath? cctlipg vps proriced by circulating cool oil through the jacket* The sssi^iaorks vessel vrm equipped with &. center bottom outlet co-.' rising a tsro-imh cant iron nipple to which was attacked a gate vale in a lias leading to e centri fugal pomp* : following -start-up of ths hsagort plant, a noa/lbO gallon glass lined reactor was installed in the somi-worls* fills unit much sacra closely simulated the Horport vlmvc ?sijml|xint than dM the original semi^70rfcs unit on yhich plant design tms based* igitatioa comparable to that provided in the Newport plant was furnished in the am reactor by moans of es agitator of design corrcsbonding to that of ill plant, ard, in contract to 1 original eouimint, the nan unit did sot provide sup:' opportriiity for contact DUP050068242 of the reaction aiediiaa with onpoaecL i&etalv 'Ursfortunetaly fclis mw semi**werto unit was Instsllac! too lets- during. the plant 3tert~uj> period to parsjit its suien?j-^a use* arJ. only * very fa\> reactions were carried out in it prior to cp^plciion of plant start-up.* Th& Hswport plant reactor comprised a standard !!ffatidlr{{ 1500 gallon glass lined reactor, equipped with a -Schuits-Koertlag noxious vapor condenser and other :>spessary auxiliaries, and heated by means of a Bowthsrs unit* (-Ss# figur XI)o DUP050068243 tm&j, * mb Mlfife %* SM xox 4/15/48 10a -4/20/f8 103 4/27A8 104 4/30/48 105 5/4/48 xo6107 xos. im. i.:.o 5/10/43 5A7A8 5/20/48 5/22/48 5/24/48 in 5/38/43 ixa 5/29/43 CrpmteIXtus ay1 scded nt X/5C (chargs temperature} ^Difficulty "J.th heating a it* IlnseesiTe fores 011 lowm CxC vi-ix-oanK c.t; reactor *;^lXs Crystalline ay a -.ddet 4 X100. he 0/C forstedU ferry product cdmd on reactor waXlre Crystalline urea added at l65GCt Charge e&mglsf firs bat class extinguished* 4fepsye'Eit1.y good CPC yield* Xhls yen the first charge trhieb could fee pumped frosa *e&dta? rZVLGh trouble with area' neltero Utxbmre .of moXtn. sad crystalline area added at 1350 ^aceBSarf to discharge blue (CPC) product to drums* Could not j h mj i inn reset-ion. t,ms,a0 lire 3 hsatod for 11 ho pm before adding; (.ajolteji) at x'35c, . bach dirfl-culby -?ith raaeter boating unit M with reactor discharge room* Product ' blue CCPCK Xo.Xtaa urea. i335C) used* lems-esss tired* wrecking battle* Charge 0K (bias CPC) and pimped sct.isfactori3.go first charge ja second Bettis* ryes at X33C Poor rsaeticSo Product in torsi cf fclus pellets discharged to drums trcm bottciu reactor btrfc let* Ores at Iv5cOe Charge 0*1C* aad pmp&& satis* facfcorJXyv Agitator peed increased to 90 BPS iron 72 OT. Proa added"to bet Cl65C) charge. Product Cdw and 'pusiped with no difficulty! Orca heated in nelter >> hours, FeIt s inoperable* tJrea added at 130>C (charge tenp.) Charge did not tmm blue* - la-actor cooled &' tar removed fey craplag* Agitator speed iaereefod /"ran 90.BM to 120 IPX* Procedm's reviseds cop.per okXorid add.-.-l at 145^3 (charge leny. ) Instead of X10C* followed.by catalyst* then race, at ly/hX* flood reaction* pMpoiS Ocl:o Procedure like 1.11 hut difficulty with plugged kzrt&zna lire* 'to CPC t-onoed. far r-anbrfX ' by scraping rone tor* * DUP050068244 T4a I page 2 BcAglLS2* Us M 113 6/1/43 . Remarks 'Procedure like 111'but `Volit** nolinsn urea addition ( 20/ at chor'.o hsuporrkirs of 1/0-0 a.scl 80/ I60l800) an? Catci - rk 1;* t\:o portions {14JO0 zm X60C), Satisfactory product* .Pn;,pa/lo slurry* 114 6/3/48 Procedure like 113* Ife-sS kerosene only* Satisfactory batch* X,l:5 6/3/48 Procedure like 113 except molten ursp. added at X$QGC m& 155*~l65C 0 icIrarye tm\p9)* XSsati fv&sh kerosene only* Sat Isfactory batch*. 116 6/4/48 Ps?csdr3 like 3X5* Satisfactory batch* IX? 6/60 Procedure like 115 except nude with "nsec?5 kerosene* Satisfactory talc/ but slightly ,/a.st:/* UB 6/7/48 .like XX? * , Satisfactory accept could net pmp* Drained from, paanf.opo 119 6/8/48 like 11?o folk except dif.2lealty tilth halting . y. ays ten and cojss trouble in pump lag* */ 200 6/9/48 First batch of crude gra-mi base (Cl-free CP0} Made like 11? except no elliorphtb&Xio acid used* Satisfactory* Pimp<1 oasiXy* 120 6/10/48 Like XX? Zo CPC formed* Car serened from reactor* 121 6/13/43 like 1X5 (.toe? as 11?) except only yirgia kerosene use?. Satisfactory,. 20D gals* slurry left i& reactor thru error-* 122 6/14/48 like 1X5 (srvio as 1.2.1). 6 at la fact cry * 123 6/15/43 like 11? (rsusad kercson"/* Satisfactory* 124 6/16/48 Dike ll?o faiisfaetcry* 125 6/16/48 like 11?* Zo CFG .forms/* Hseossary to oorapo tar from r2aater 12-6 6/22/4$ like 115 (Zlryla keroscue)* Piffieulty ith urea rcltar sr crystalliro ursa added r?ii!i harfe at X10'Ch /bird portion c? catalyst aMefl* Poor reaction*, Product as bins pallets,, lieesssary to drain product to druas* 12? 8/23/48 like 115* Satisfactory* 128 6/24/48 like 115 extant node kith "msec? keros so after steam distillation,, DUP050068245 Ssk 129 6/25/48 Like 1X5 except 50/50 b>ixtura sim,m distilled urn v It &j x kerosene* fhird portion'' of catalyst added* 6j;fcl&fgetcry product# ,130 6/27/48 14ka 129Wo GPCfor^d* far scraped from .'`'-.-.C'X'i'o 131 7/1/48 Lika 1X5 except mo nuts:? oa eductor ami kerosene boatad in reactor instead of in head tafcfc# 132 7/2/48 Oxidation effect dise-smrsd after 131* Control tests on kerosene started* Batch 232 eiade' like X3X except third portion of catalyst used* Ife reaction until third catalyst addition at 199*0* Seilsfsctcry area!not* J-ih 7/3/48 Lika 131 'sxespi trouble with nesting system,, Si:Ble:fac'*erf products 134 7/5/48 Lika 131* Satisfactor/# Building fired W lightning 7/6/4$* Shut down until '7/3/48* 135 7/10/43 14ke 131 Xrawbls with beating system; third porliox r-i cftslysh ailed-, Satisfactory results* ,136 7/13/48 13.1 rsEclcate sxcspt second portion of catalyst arm urea added st lio^i area as in 115# frcnfele with healing system, Product -satisfactory* 137 7/13/48 Like X"\6 except urea added at 13C*C# (charge tsap) o;d only css port ion of catalyet was 'used#' CaocaS after urea)* Satisfactory results*. 138-146 14? 7/29/48 L-Jr.s X3? -Satisfactory xssults in each case* oil reeewmts oxeept urea added at XX0G* iJrca. at i3'0(k Satisfactory batch* 148*15? 202 8/10/48 Like 147 Satisfactory results* Crude'grcc;\ hr, so (Oi-frod C?C>, First CPC hatch Bg.de -v/it!' emti--oxidant for kerosene and use of axxcniwai eurbu 'etc.# All reactants added at XX0G0 (charge ;-.amp*> exempt urea-, Satisfactory results* ' 8/11/46 Bike 202 ascent LB type CPC# Satisfactory results< 8/13/48 .203 8/14/48 Grubs green base CCI~tyse CPC)* Lika 202 except s&axls with previously used fc-ercsem {'First batch since 130 m&8$ with ^used" kerosene#) leeults satisfactory*- X62 Like 203 except. IS type CPC (use chlorphthalic acid) Molten urea added to all charges except where otherwise indicated* DUP050068246 MILinir, o' " ;U- . lie offsets o? various variables la the OPC condensation process are divensssfi la the sectionsnfeieh follow, it should ha noted Ike < many of the studies rare carried out with- use of equipment Kxid pi*cc::*`krca 'which a iffer appreciably tram that which iias suhecckienfly- :.-< gtv- as etarSard ami that the effect of oxygen on the reaction *'sa rot iiseoc r-ml until after completion of nearly oil the Seiii-xrorVs tOuiwcs sui moat, of the work .to*the plant* An attempt ba< bssm p c < 3 to armass the magnitude of the effect of these factors on tlis arprr'lrtuta 1 results and to indicate the significance of the results pretested here which were influcnecd in this wejv. Se?ai\?or!-:s runs wee a carried out with wee .of ttre different no .- - c3.$l typas of keros$?m an& with samples obtained hr fractio/ .stirs a comaerciel grade of kerosene* Poor yields, ?4$ and 5H of theory,, respectwere obtained trhen a kerosene freefelon with a boiling Tenge cf X95-225G {obtained by fractionating Mcaos kercaene) <ss seed in two reactions* fhe yield obtained to c control rn.i mo daring this period us lag Dco-lk-se was or Spy* Previous laboratory exper'i. onts had shews the fraeiiowetwd r atsrirl to glm yields comp t v Kk to those obtained with Peo-.feoo., `fhere is wo obvious explanation for the difference between labors toy/ ?:ml sert-worl's results* Tim semi** works cxporir.sntc -.an carried out wrd.er such conditions {All reocaents litwsd at rooa. temperature before the start of hatting) as was cubesquontly found to result in so serious air oxidation effects wed hr'cc cu.13ido.r33 significant* Kerosene losses with tbs fractionated meterlei CX9J"PS5GC) wars appreciably greater then with fee eo:' ?-sr:';ie:>ei typo k toll contains a* larger proportion of higher betting wateriaia (boiling range 190-5?^), no quantitative date ere ereilcblc regevc leg tine her.-2ss howevero (those experiments '-.Ift the low filing kerosene wera carried out with a view to the possible us a of such material to -simplify the problem of removal of kerosene from the reaction mixture by atam distillation.3 3ayol B's, an .insseticicle grads kerosene supplied by Standard Oil Ooe.pc-r of (Tsrssy, which is lower in price than *Peo-8aso** brand kcroeacs 'CAich was specif lad (originally) wa used in place of the lattet* material la 8 s.yntheses carried out la the emi-X'ork <S 40, 43, 42, 43* 44., 4*>, 92, 103). HsyiouS caking in the rx rher cccr.rrcd in the case of fear' of thebe synthasesU 5jBayol"B;s res found to be the e.nu&l of "Dco-Bsce*,insofar as yields cad quality of ;'.c glnwnnt obf^iasd with its use srs cojmsmsd, in the four eyntho;:wb ;'xi which serious caking ms avoided fh tendency to caking in the reactor 'mo much more pronounced with the Standard Oil product than with !5Ssc-Bnse,,9 apparently because of the greater losses of the former by volatilisation during the synthesis stow. It was concluded that 'ttBayol 8 ia a satisfactory .substitute fob a CocBcse" for the purpose in question if ears is taken to.jrvid excessive kerosene losses or if sufficient, kerosene it used vo compensate for the losses \It is believed that the DUP050068247 '<=> 10 results of these e:tae*imii :v$re nol effected Ijy oxidation of foaroson foubsocaont in cony Is tin). of Vais expe^Sj^mfo'l vo.rk9 the use of REayxl v!i his be un-s tt&zif&rM pleat practice..) Mo ^xp&rments copoemiag the us of different: e<xmoreial grad$ of kerosene ware carried oat in the Farrport riant oaring the pario4 bcmrsd by this report* Considerable rariaslows -yera mc it both s&sl*works and plant la the yu5.Bt.lt.f of boroso no ui?4 as the recntion nedltjm* I tiras obtainod that auBioflcas la this quantity had sayoffset oti aithfsf plf-eaat ssalitf or ;1M so long as sstff iciest fcsrosr' was pressnt to prouiio ocexsrt nixing of the reateats* For axrwois in tin first sya'ljsoIs rurrlrd sot In the I'ejporfc plant, ooly'-a total cf 6?(j grilons ef Jceroaano nos tisod far the synthesis pith the result that the entire oberfo caked in the roseter* despite tbs coking* the goslity cl the product m satis*factory uni the yield poo upjncuxlwately *-}Q$- of the theoretical, which compered f aversely uitli enbe&Citteni c c up fnoble y&thesos made v?lit 1200-1300 gal.leas, of Fareseaso file optlxuw yueutiiy of .kesosoi'ja for use as a reaction.. m$im is cetarminsi 'largely by the if:ysiocl charaoteristics of the eciUlpnerth used for the rcaotior.^irbicb greatly influence the Krcvibris of the losses of Irsroeenso ihls csFliaim (jnaatlty will u...K?orlsiefily wry with change in sf'f leiontty of the Boxicms aapop coiYinse>.*, the heat.log s^ese**, ste* 3 .A^5igailCs.tePpi,...S.a Illaidfei XisMSSliESsU Following dcnopgtratloa la the laboratory that greater yield# of 0?C wore obtained when nrs# ws added to the hot' reaction n.xxturs^ rather than to the okergo before start of hue, tipsy this oehoaia vm triad xa the eaBiworkcB to yield udye. .vugs which. ceul$ be consider*!. sxznXtleapt was evident in tan csml-'^onns as the result'of this hang#.* in yiet of the anbepant yield ir.ow ssa obtained lia the laboratory, with, the possibility' of .~m\B yield improvement in the 0s.1 I-- enhs ? s..rf also on car 0.3 of the nidoiat afpaBtaos as re. .ov-'* Ssc's^ssl loaning the ^hditioa of iinaa to the hsatsd Cl6>ftn} ohoryu was acxptsd'es -s'tri^srd sewi^works practise Itixmpts to faeilitats the adlitior of nr:n torn the use of iioltch materieljr'abhoT fhsi the nrystclliPo i:teocb;.ct., 'xar* axancosssfal In tbs ssi'i-incrks offing to eoliliflcElJon of the noltsa laaterlal ia the cold transfer llnss hetrson.'tile ac ltsx and th reactor ..i-DUP050068248 During the early stages ol* s amzztSs;^ crjs'i&HILm U2*cs was added to the hot ehsrga thru t.to n&kn hmhtoolc with m luaior difficulties $ sutsocru-snilhh. a star valla :t w tostsllsq, for urea addition in the ssto~Y..'rto 'unite A greet nary variations .in uathod of addition of uras us vs tried in tim plant, fbsrs is much m-^ertaiuty attached; to tfa re sults of thesa experiments; since they next carried out for fcfe moat' fart -without proper control of els* o^ddaticn effects,, It sms demonstrated* faowwr, that a pigisa'Bi yield of at least 85$ of the theoretical .could be obtained rlfcii addition of'area to the charge at temperature in tha range Iron ream temperature (about 75S S) up to iSoofo It .it hot possible to specify an optism temperature oh the basis af the results* tinder the conditions used in the 0.*mf molten urea *ma apparently fully as sftoetivo as live crystalline product. despite the fast abet sppratoabXo dnon>p;or itxcn of nvc.fi uoioobtaol.y occurs during lbs .rtoltlng In the pX?.nt i.mXtar. It is ycsriblo that cpj*e fully controlled ;tpertoon$e my <tls-ctoue. o. yield advantage to the use of the dry material! such, cm ntornrtogn - -If any - -.could bo axpsetscl to ba lass 'than 3f Ti& iin>s>rta.3.ca of goto agitation of the resettoil slurry during the b?> coMsmz t.Ion re-uotlsn nn-i demonstrated by laboratory studies of r,hi stay of the gracscsc topVy/oit yield and ostler pig-** msmi Quality m,s obtained cbm ootoxilonely.are altered so that better agitation v-ss obtained. (deference S) s Agitation nas found to be ro less topoit&ut under -ram to a orbs ccndifians than to the laboratory, In else vet a agitation to the $s&;lvorks reactor was found to lead to poor yield and severs eaxtog on. the reactor mils-, gad possibly also*" brought about a decrease In quality,, fhs effect of agitation changes were very .forcibly illustrated by a series f symtbssea to which agltuttos intensity was successtosly decreased owing to gradual wearin? a .ay of the steel agitator blades by corroslosTend srosicru fhe yields '($ of theory at dried crude stage) obiatoed over a period of IX IS aynihswasfduring which the, effective -area of the agitator Halo decreased to approximately one-half its lalttol relw, after which a rev agitstoi: was installed-* wore as show in fable 3-1, DUP050068249 JJ * SFFJ5C1;* 0? MX7AfXOl CEIKOIB OH PKiC-SKS ITEM) iM -eaiA^Torhs , >v. .x /* 40 47 48 51. :54 *5^' 57 field ilM&rmz) 81*31 78,2 83*0 57.5 . 63*3 $Ba? 51*5 SillJ-BE IS aas 3 ore Hone Savers Blight S-ovne Severe !!c t / Imitator after 5? fair Sadly corroded t! ts n v*badly corroded <1/2 gone)' 60 72*6 Hors Sood 61 34* a l:o eghing St 65 ' Hi * $ lo easing So u p corrosion *Jn addition to agitation changes, Pertain Minor variables -sutayed Into tbs 'batches in sm&tim* 'The effects of these latter ^ari&Meis is beliefs^ to bo srtsll oonparud to the agitation effects* In tttm.pt wc.$ mrs to ho IsKtiK^ tha sSifeet of 'very intense agitation on the HPG cov>n$ahI.oa reaction by carrying out the reaction in a vessel sonia-3d 'pith a oafenhsh high speed agitator of special design {"Co* 1'`iseolver'*) into ad c-* to provide very intense agitation,, Cl" ?o vorH ;m:$ Hone by ^iyente Depspbiiaat personnel in the labor;.* or I,* s of ths Scries Ho-'pore t Ion 5 CayusgasJfY*} the ggltatin x "icser Input In the aynt-issls cov.'aotsd with use of this agitator varied from 31 t-o 71 lU** :;ar 10CC gallons* It ms observed that the ^axicuz peraur (71 E.IV) was required daring the initial heat log period end that fsll.oyipg ^th reaction at VZJ&C the pomer gradually decreased to the lorar <31 H*?.} vain* It wee not possible to prepare a control with tfce usual rgiiative Intensity in this case as the physical equipment available iid not permit adjusts went to the nemal range of egltetlor.* Ho oualiby or yield advantage was evident for the experimental product as compared to the usual .saai-wor&s fejeterial* It Is the v-viter3 op.in.lon. tfcst add itiun&l study of the offact-of agitation variations on the confer saw; ion reaction is desirable* "Tm fact that no advantages rmvc evident t as the result of intense agitation is this partlcul^p experiment vis of doubtful significance"'in view of the since Sis covered narteed effect of atmospheric oxjyeea on the reaction? there was excellent opportunity for contact of the reaction sedluii with the teasphare la tills 0PP3Pl?nerrbo DUP050068250 So coieelasiya data ar ayaiXe'bla regarding Vm affect of agitation variations in the plant goulwisuw bib 'rotational speed of the agitator la the plant fraeto:f reu 1aerewe-sd tvmi the initial valuo of 72 'Hh to c.O fr k and rubseyua.whly to ISO HHu daring the period of plant 8t&r$~u? ` ?c So rot know with certainty nhat effects resuXtsd fr*3fei iiisso cgitrtiou litferetccsi theca changes were asdo daring a period of considerable difficulty with tba condensation reaction wheat the results yens sufceeqne&tly found to have been greatly influenced by the oxlcstioa effects of etao* sfeperic .oxygen* It is believed - without dyfluite proof - that the yield superiority of plant manufacture as compared to laboratory or se*al~'rrks performance.^ at the e orders allow stagsf is a eonseqmerc of better agitation in'the plant unite !b the swai-works;; pigment cuc'Uiy ana yield vers as good (within the experimental^ error} with wmrleci chlorphthalic acid prasscafca (35"^55S solids) as when it dried product wes used* <Compare 8t?h batches '2332-}- sdc with dried press-cake-, vs latches 323'9 pads ritli uiudricc presscaha>.) 1 p-nther large m.^ber of -syntheses were cone"looted under each of these conditions ^ os? led enlorphttelie acid -and wadriei chluylitbellw acid prc^eel-te of 33X`4<^g solids) and -while there tvaro oerslderuble vcrlr';it*jis in yield nw',sr each co.ndltion - apparently eo n eonsnmiswoe of ** coiitrollcd wcriahlec - a surrey of the fata .km lento no differences la either yield or quality 7?blc,b. reosowably can be ascribed to the use of bb ?ret pres scales rather then the fry mnicrial* The pre cision of the results is difficult to ent.lsa.ts with certainlyy it is the writsr^s opinion that any yield affect 1$ no greater than f$9 laboratory 3:cperiwcnts shosm! that better yield is obtained g whoa vat chlorphthglic acid 'prc.ssoeka is as oik* if the ayes is aided after the charge -hes been rested to an elevated tasr^sreturo -ret.ha* then at rope temperature. In all cwsa-a in oho csKil^workf revolving vat cblorphtBalic 1-011 prossoske* in r/kJ.ch yield data C`,,y obtaineds the urea was added e.t an, elevatei lawyer-step> which varied from 140C to iS5C A tow spni-vrorks syntheses vena carried out with addition of urea with the preaseuks efc woow ts-spare tar. Ho yield a at were obtained la such cases but It -vm aw^.aCX.lsfesd that pigsent of ths usual quality me* yrodatai* 111 the plant CPC syntheses wore carried out with utdrlss chlornhthalic acid pra-sr.c: ha. Oss attempt to obtain dried, material for use In b plant CrC cy demotion nvi-etlon risaltad in dscosaposlo tion of its chlorwhthalic mU. lescwuws of encode Xt c drier temperature CilOocK He further work wee done in the plant or. this i.e.tlsrw DUP050068251 6* temperature of the charge at til time of addition of chlorpbthalie acid prosper!.:: to the reactor was varied la the plant. from 1100C to X50C, a of. .La the sastov'. cafes frosa rocm tempera ture C20-=*30C) to ilStC *' X50C without effect which could be traced to this variable * It appeared to make no difference la the semi* works whether the other reactants were $Ma& at the time of addition of the ohlorphthalie acid or in some other order* 1# -previously noted, the precision of the results is not very groat and it Is possible that small, though significant, effects mj bar escaped our attention*- Reports fro lofe,!* CReferonee ? ,.. j) state that Tats of heating of the reacts.on slurry to reaction tormeratnre (195* 3^) has an' important influence on yialirj r&pto boating ito Sm?*T is reported to have requital in higher yields then was obtained with slower beating (> 4 htes*)* Ho yield dlffcTaneos which could m considered significant were observed os the result of differences la heating rote In the work ftt fo'aorto (A difference of at least 5$ to yield would hr required in order to leva been considered' significant In the 3v;ark -sexitoworks * to X. o.oo instance {.0*W*>26)S la the s'amt-woTfeSj because of fiiffloulty with the heating system, approximately 13 hours vms' rsqulra for how ting to 1950<3* in contrast to the usual tlac of 4? hours$ the field in the case of the siore slowly hented hatch t s o no less than that of the'mors rapidly hasted product., tTo offset on pig-wenl quality was observed at' the' result of variations in rata of beatiog under semi-works conditions* It 1$ possible, imaw* that nor* carefully controlled experiments might reveal differeases' which -iere undetected at the time because of poor control of our evslur.tlxj. nsthode, which were still under development at that tine* Similarly* the data do not permit of coy precise quantitative conclusions regarding the offset of variation to. rote of 'beetlag on yield or pigment quality in the plant* ^eXctively largo yield and , quality effects could have escaped detection in the plant because of inability to control satisfactorily the performance of the .sulfation and extraction steps which precede quality and yield fieterminationsf and also because of variations 'in., the degree of* oxidation of kerosene* ffee moat definite statement ?%ic.fc' am be hela on the basis of available inf drastics Is that no large yield tarieticna (in the writer*s opinion, greater than 10) resulted tTwi etorngS'S to the beating period oven ., sjbea this \m.$ increased frost the usual 3*4 hours to as such as ctol/2 hours* Quality affects? if any, resultant from differences in heating: rata were apparently vary small, sicca they were not detected by laboratory evaluation of the sulfatsd crude prodveto ^' DUP050068252 It is conjectured that the yield effect reported by X.C.X, wes associated with increased oxidation. of he teaone as the result of Xcmg heating la contact wit* air? tale oxidation effect ? .which ae unrecognised at tbs tins of tec I* tel* perk, has since''bean shown to hate a yarkad yield ixrCInane. It loos not sea unreason able., hofstgr, to predict that sir.; terlteg of tea charge daring certain temperature rangas would te-s an adverse effect on yield since urea is known bo decompose rapidly at temperatures below that at which the formation of blue pi'gmsut is first"detected? maintenance of such temperatures fox* long periods of fci:es might conceivably re sult in dacompo.sit.ioh of urea to products which would hot yield CPC-. 8* Six of the first 3C plant CPC eotesusation reactions carried oat la the Mewport unit yielded a. brownish tar instead of the desired copper phthal-ocysafcio slurry., Ike reaction mass in such instances solidified on. oven slight cooling below the reaction temperature of 195cte it was necessary to dig the reaction product from the synthesis vessel xarM'&Ily in such cases* .Ho such difficulty bad been encountered at any b.tes la the sesil-vorJsB or laboratory. Investigation rereeled that the difficulty was a consequence of oxidation of kercssswo either prior to or diwl.ug the condensation reaction** ttm difficulty was restricts to t.ba fewpayt plant apparently because only that unit was equipped, yith eta obnoxious vapor condenser which tended to draw r. currywt of air thru tbs kettle f thus promoting ad.dation. Send Utmss '/are particularly favorable for .oxidation during the early part of the start-up period because of the practice at this tte-s of Opening the reactor manhole to permit godition of urea to the hot charge (the urea me3,ter did not function satisfactorily at this time)* fith the manhole cover open* a strong current of sir ws.a pulled thru the kettle by the condenser* 0ndsr the co`ditions originally prevailing at the Newport plant, the oxidation effect was apparently cvxtela.titef 0 series of four or five good vmm * with coat inusd reuse of kerosene - was followed la some cases by a bad charge* viable 1}0 However,, in certain instances, an "unreactedeterjo mn obtained even when fresh kerosene was used, sufficient oxidation apparently occurring during the heat lug to prevent the reaction fro.o proceeding in norsag1 fashion* *$hia effect was discovered by wosrs of syntlosss carried but in open 2$Q ill beaterso A largo mteter of such synthases -were carried out at Iswport by the mmb&ra of the Cbeuieai Division start-up group, following which, the oxidation effect rr* confirmed In the Newark laboratory and semi-works* DUP050068253 Oxidation of kerosene apparently occurred at several points of the processi (1) During standing in ths unborgrcmv;4 storage teia&* tt is believed that the amount cf oxidation ralch' tools place at this point was mi serious* C2) Paring storage in the hasted kerosene lead tank* In this case there '-as opportunity for considerable oxidation since hot kerosene (llO^C) through which air mas bubbled ifrm liquid level indicator) mas in contact vith a copper heater (copper tends to promote oxidation}* (3) Tn the reactor* a this unit violently agitated hot kerosene v&s in contact with a rapidly moving current of air - induced by the noxious vapor condenser during certain stages of the reaction as originally carried cut.* It was at this point that most of the troublesome oxidation apparently occurred* (4) During sulfation ** tshich follows the coadensctibn step' ** hot Cll0**120C) kerosene mas violently agitated in the presence of air* fhe following physical, changes ..;r'a pu t * in a,a attempt to minimise kerosene oxidetioru O.) She liquid level indicator for"the hot kerosene lead tank ms activated ijy 'carbon dioxide rather, than by air* {2} The manhole of the yocetoy mas kept seeled %* much of the time as possiblc. (3) the agitator me not operated e:eeapt when necessary* (4; ih& water flow to the obnoxious vapor condenser was turned off entirely for a aumtar of runs| this was not a satisfactory arrangement he cause of the resulting fume heserd, so a method of operation was devised providing for operation of'the water .Jet only .after sealing the manhole cover* 4) fh temperature of addition of reactants thru the manhole was lowered* In addition to these physical changes.* a number of changes of a chemical nature ware introduced* .First*' a small quantity Co Jbs* per plant batch) of a petroleum $x&X-,oxijitar&*% Paranbn 441* ms added to the kerosene immediately f Hewing the .introduction of the solvent to the reactor* Second* A quantity (10 lbs* per plant batch) of solid ammonium carbonate -ma added to the k^roaem immediately follow* ing its addition to the .kettle and r like quantity was added to the salfator before transfer of the cha \;z to that unit 'W&s started* Tim addition of Paradox; vras decided upon following: k demons trat ion that under laboratory ootid it ions kerosene CDec-COese ) which had been fesated to 1950c over a half hour period could be used, successfully for a laboratory ^beaker5'1' synthesis if X# of- ?araaom had been added prior to heating* whereas such heating in. the absence of an anti-oxt&aat rsadared the kerosene of no value for this oso line use of amiaonihit carbonate was based on the supposition, that tbs gaseotia thermal decomposition products of this" ccspcuiid would provide as inert rtg<as blanket which would protect the kerosene by decreasing tlia oppor tunity for its contact with atmospheric 0 _; .;u ho tests were made to determine the effectiveness of this zn'tcnjnn carbonate treatment in slowins the oxidation of kerosene, is tha result of application of these steps , no .further serious difficult iso ware encountered because of oxidation of kerosene* even wife repeated reuse of the same kerosene* DUP050068254 During the course of these studies m citenoi wee made to establish, the maximum permissible detsswa of ox idetloii of kerosene for the -.application is Question aod to specify oxidation limits in terns of a peroxide number* it nrss seisblirhcd that satisfactory results could be obtained with use of Derosano with a cer oxide * number of 2.6 The mxhmm permissible peroxide number for keros sue to be used in this reaction was not definitely established* hcr'evey? it Is the writer*s opinion that the use of kereseae ivifch a' peroxide number greater than 3 io dangerous 9. fanias. No serious difficulty because of toenljig was encountered in either the laboratory or seml^vcjdcs syntheses.. Xn the plant* however* foaming of the charge presented operating hgarde* and caused cone Id arable yield Iocs in the case' of several .of the early batches'. In these instances too forxiag woolen became acuta upon addition of the initial portions cf t; ? wolt<wi urea to the hot charge (15C1?0CC.> with e second eta:,-; frequently occurring when the charge tempera ic.ro ranelsd tS$TM?$5G0 itmrapis to avoid this foaming behavior through, the addition of urea (cither molten or crystalline)** at a lower temperature ' ere unsuccessful* *vhiXe very careful control of the rat of addition .of i&olton urea was productive of some small benefit* During the course of this difficulty various sehasass wars tried involving the addition of urea at various temperatures and under various conditions? none of these schemes produced any Barked benefit* 11so* during this period, considerable attention was given to possible means for capture and disposal of the materiel lost from the kettle by foaming* lotion along this line was discontinued with discovery of the affect of oxidation of kerosene. The use In the synthesis step of severely oxidised .kerosene* as previously noted* led to the formation of a tar rather than CPC* with little foaming* while the Use of less extensively oxidised kerosene resulted' in formation of CFG with severe foaming. end unoxidised kerosene yielded CFC without serious foaming. Following action to control oxidation of kerosene| the foaming phobia-* was brought sender satisfactory con troJU (it is worthy of note that chills footing was brought within tolerable limits so that under aortal coeditIons the charge does not foam from the kettle* soma foaming does occur within the vessel. ite appreciable increase in batch also would be possible if foaming could be overcome completely.) 10. the Quantity of avmct&iua molyMata catalyst used In the first 39 siiworks syntheses (Sell 1A5 IB . 25) was the asount recommended on the basis cf prior laboratory work? this Quantity . (20$ lbs. a:ori?rx molybdate' per Newport batch, of CPC as outlined in ippsrsdix) m& subsoyuertly'rcccr.iej.<led for the viewport plant. DUP050068255 This oucntity was also used In a maaber of ubsoomsat batches CS,;5h"54t 55, 57. 58* 155, 163, x?9, 130-. 1.31, 2.43, ami 24?) out In most of the IB syntheses myyietS out in the serai~vrorlr.s after B-,fh-25 and prior to plant start-up* the quantity of catalyst ms incx'-eascfl by u fee ton x* l4?p ('this couva^pors to as increase iron 2*5 to 4*5 lbs * pop iewport plant batsb, }, Also, following plant start-up, several sari-ponks syntheses were imsd In which. two additions of catalyst wars used* each of which represented 5*0 lbs* pet* Ssynart slant batchy Is no case was there say effect -cm either flail or Quality milch conic; be reasonably attributed to the affect of changes'in catalyst quantity*' (fnfortuasfpely, si the tine most of this work was dose, large variations existed' from batch to hatch because of variations .in degrees of air oxidation, so that only largo offsets could be detected* In the -case of two hlorius-fysc CfC syuthsce, only one quantity of iiKsmoaim KcB.yMrty catalyst, corrapo'ming to 2, 5 lbs* per plant hatch CAppendix XI) was used in the saai-worlct* in the plant * large changes ^orc ole in the quantity of aimoaiwia wolyMate catalyst and in the ni of. addition of th catalyst,, In certain eaeas os such as sin tines the usual quantity of catalyst (o t 6 zz 2*5 15 lbs, catalyst -per hatch representing 1000 lbs* of phthslio anhydride) was used in the plant., The catalyst was also added si various' stages of the reaction and the total was added in several portions in a number of Xhstraces* Shis work w&$ carried out: during the period of plant difficulty and was based on. the supposition that the failures to obtain satisfactory reaction in the plant were duo to- Inhibition of catalyst activity or occlusion of the catalyst by solids h the reaction mixture, Th results of these variations are not eons id-eyed significant in view of the uih -controlled Influence of keros am oxidation on the results* Hub-* S-eqtmitly, satisfactorily controlled sjegaria-gats were errled out in which it was found that & reduction in catalyst quantity from 5 lbs* per batch ttwice the stand ere-, mount) to 2*5 lbs* produced no offset on yield or pigment quality* lie effect of decreasing the amount of catalyst to lest than tie specified saount of '2*5 -lbs4 per batch was net Investigated la the pleat daring the period covered by this report* A rmmbar of aswiwiorks experiments C6?f, 48-52, aM 5**"5&) "wrc carried out in which boric acid, with a,ni without sodium hydroxide, was de-si to the vzabion' mixture, In addition to, the usual amount of $3alu& molybdate (see scsilAxorks 'batches 48-58-s 59* esc! 61-64},, These experiments were cov.C acted. in syntheses or htorias-fyea GPQ .es well s with the LB type* 3?h primary object of the use of boric acid la tb.-a.ee eases v;es to retard corrosion of tbs steel agitator, with another object being to obtain & yield increase. The results ,P Which apparently indicate -a yield decrease from the use of boric acid v%uh the solybdat3|Srs -considered iacoBcluslvs beemioe of inability to control agitation satisfactorily DUP050068256 during this series of experiments i It m& necessary to replace the steel agitato* during the series of runs beoems-a of extreme corro.slongerpsiqr.i faers mc .b no decrease in rate of corrosion of the steel agitato* because of the use of baric acid* Ifee use of sodium hydroxide <2$ of phthslic anhydride) in the reaction mixture has been reported by X.C., X* (Eefereac 8} to result in improved yield of ehiorii^e-free pigment, sad certain laboratory yields obtained -at .lawsuit also indicated as much as a 5$ yield improvement from this source* (Other experiments indicated no yield improvement)-, the results of aesai-vorks study (see 8*W* 49, 50i 52* 5&t 59? Si? 82) of this factor were inconclusive for reasons discussed previously* 11* Anhydrous ..Conner Chloride One sw-si-nr-fix charge (3*?*275) ""es nade --ith use cf anhydrous copper chloride (CuOl^) instead of the dlhydrate (CuCX^ which is ordinarily us ad* 3?hars vxs no aponreat quality advantage from use of the anhydrous material* "fee data do not permit of a conclusion regarding yield effects as there rare appreciable yield losses in processing the material before yield determination. is, ays j b Jiite5S&w.. If o seal*corks syntheses {3sl3j 150), wo re carried out wibn -use of cliloupatballc nafoydrids manufactured by Niagara Alkali Company*{At the titan this work was dors, consideration was being given to the possibility of us lag chlcrphfbalie anhydride supplied by this Company in place, of chlorphtfealie acid of our own mai&tfactu*.)., fhe products htsimd were quits green compared to the -corresponding ones mad with chlorphtiisllc acid of the usual quality., in agreement with results obtained previously in the laboratory. Because of this tinctorial difference, no further consideration was given to the use of the t,Hiagarafl material. Mo * ield data xsre obtained in these semivworks experiments* 13* 3a. 119 l5 for ions consideration was given to the possible use of trichlorhengaa (TCB),rather than kerosene, $s tha medium for the CPC condensation reaction, ibis solvent (fCB), which is used by Orchem for this application, under laboratory condition gave a" product of better tinctorial't ''X41: than rres obtained with kerosene, particularly -when, the j> q.-1 nfc was separated from the reaction*slurry by f5.lt.ration folio sc by sailing with fresh !B,-, Semi-works synthssis S.W*-X19 was carried out with 2CB to determine the behavior of this solvent in the reaction under DUP050068257 r* SJQ * semi--works conditions* Wo unusual difficulty i?c& antscuntsrcd other than those cOBisccfuent on handling st toxic mat,'rial (tCB) la -equip ment not designed lor tlm/t purpose, The slurry ms sulfstsd and most of the solvent wse removal "by c-ntrliir-jlrg., fHa material centrifuged readily it* a saMi-.-.-orks performs basket centrifuge to yield a cake of ?0-75^ solids, The ccatnifu^ad CfC sulfate 3 then 'hydrolysed and the solvent ms steam distilled, from the alkaline medium with a steam consumption of iS lbs* per lb# of tCB, Both laboratory and semi-works grinds shewed the product to be superior i. intensity to any of the charges sm.de in ksrorsne* Four additional .semi-works synthases mm carried out bo provide further information regarding the process* In all cases, the*pliant obtained was superior In InternIty to Its kerosene counterpart, Ho*:everf there was groat variation in the character of the fi el syntbosis slurry and in behavior of the pigment oa sulfation* '.%i3te the Initial experiment indicated that the sulfation product did rot settle sufficiently well to permit separation of the solvent by decantation, It 'was possible'to separate a considerable proportion of the solvent in this way la subsequent runs unci it e:'^oared that process 'based on this typo of solvent separation alght bo do/sloped for plant use* .ifej or attention during this period was g -d ix ic at rebod upon solvent separation through use of a device such as a filter. It had been demonstrated In the laboratory that sane of the intensity superiority of the fOB materiel was Cue to tin solubility la this solvent of by-product 3rapyr.it log which arc not soluble in kerosene * and separation of the .solvent Ivor the pig-wivt in such a manner that these impurities were removed, with fcN ?.oivr.nt led to Improved intensity. It sms established that the pip.cut, as the sulfate, could be osparated from the solvent 1:-y sithar csvitrlfagat.ioa or* filtration,' Im attempt to carry out filtration of a semi-works batch to provide data for filter assign was wot; completely success ful sines' the sulfatstl slurry could rot be pumped from the reactor. However, the product was transferred to the filter by means of bucketsy where it filtered satisfactorily and cs washed with two 50 lb* portions of 2CB <40-50 lbs, of CPC), Iho product obtained on hydrolysis .and steam distillation of the hydrolysed sulfate ms Quite 8rubbery8 awd could not be pumped-, Hcrcrtkelcss., a portion of this material finished in the laboratory yielded a pigment of excellent tinctorial quality,. .it the time of this work, -e fine! choice of reaction medium for initial -plant operation became necessary la view "of the Immiasent start-up of the iewport plant and the urgency -of concentrating all our efforts on one process. On the basis of the information avail able at that time., .kerosene res chosen in preference -to fCB, the principal reasons for the choice being the economic advantage of the kerosene process because of the greater yield and. lower solvent cost, the -greater experience of the group with that process;S the rauch'greater toxicity of TCB u p coshered to kerosene, and the greater difficulty .sneouatersd In the eon 1~corks with solvent recovery with use of ICBo DUP050068258 ax fast relative merits of the ICS ??.:> kerosame procassasj as demonstrated by the United amcmut of \rurk dona elf Eswcpl^ mf h suwed up as follows s (l) ICB yields tbs more into roe plgpent. (2,) 1CB gives more fluid slurry so that less difficulty Is encountered with agitation :nrS reactor discharge ,, (33 Sbs kerosene process he" ir approclabl economic .advantage since the c<r. t of IBB is much greater than that of kero,sen - m either a volume or weight basis ** ami the lass (lbs*) of 103 in tbs ITewsrk trials wm at least ss great as with kerosene* AXso.g on the basis of Ifewark laboratory studies and information from Qvtihzm-p the higher yield Ci-Hh) .Is obtained in kerosene*, {Mo smZ'`VQ?k3 yield fats wore obtained at ffewark for A the W-B :<'oo?z!i bsceam of mo citrons difficulty of obtaining the ck.ia uadav the emu it ions of the experleasts ):A;| (4) f-CB is stuoh more tonic than .lotosone am special eon*sMeration mast bs given to this matter in equipment dee ign-. $ ; lbs Ximitcc rnoi>m of information available indicated that air oniestion offseta aro mab lass important with the FOB process than when I3r0.sens is used*, It ayozoco that it ray be necessary to re-emajlaft the KB process in the" event that pigment of opt Inn into no ity is required*. w--wISSCBBs 1* H-506,, Develofsaeat of Proco:.* for the Tkvwpori CPC Plant# X, Preparation of Chj.or->btfeilo Acia.., Inae<31950.* Sewark file 22304. 2* .S. Patents 2,197^^53 sad 2s21.4 s47?* Apisr to ICS* 3.0 X!M.6~24<> Final iaport,, Ceasrul Patent -Survey* Phthalocysnina figreats, Jiily, 1946, Ustmrk File 223*4. i0 IC!h-47-9 0:blorlnt*f3re3 CPCs Synth &a is ey PhtShalin lahyclriee A Urea. Xarosejns Method. February* 194?. Ksr#rfc File 223,4. 5* Esview of Id Phthalooyaaine Arts 4 digest; of ICI resorts in CuFout Ctmmaisy Files* Kercht 1946, Eewark File 223,4* DUP050068259 22 6<> **WQm&imX,, Fast Blue 5.B* Laljors'to'rjr Proem* Studies < February* 1948. file 223*4. 7* XCI Hapo?t H~3644,, G&ppsr Phthalocf&ntm* Preparation Uy the Sc i. *. n* Process * July, 2938/ 8. XCI Hapoyt l{-6392 :lFonastx*aXM Fast Bla Bt Preparation lay Solvent-Urea Proems in Prssetsce of Ganstie Soda GeeeaUer-,. 2949* DUP050068260 S-eai^Worfcs Procedure for Spithes is o.f 0P? To tbs saiM^anrks :J6 gallon glass- lined reactor. a4i? at room imapsrs.iur.'ig the following reactants la the order sBaa; 2X8 lbs* <34 gal* 3 of birosgmc (Hot X) Start agitator* then 40*5 Xna* (see Koto 2} phhtalxo anhydride* 0.22 lbs* <XC0 grama) of a^ojilv.>4 MclyMate (lots 3) 13-V lbs., at eovrpar tXX) chloride dlhy&rsta (Mot 4) ffmt to XXOcG {cire$?J&te hot oil thru reactor Jacket) To sgits ted starry at XiO^C > add lie5 lbs* p -s p lota 2) 4.~elZorphthaX.ie acid <100$ weight) press os .M?., Cloeo 'reactor and hsmt -charge to X65S arith -agitation end add orar 45 slant periodj via a a ter "xmlim* oast) awing haul and agitation during the .addition' 73*5 X'Pw opw hill Ira nrae- naat 'la chapp to 195*0 and hold at 195 + 5DC, tor four lours* than, cool tec;: reaction! sa&sa fee 150C (by cirewheting cold oil ibra th@ reactor Jacket) and pern it to the culfetor (steam still)* :u 5&eo-8asow, a deodorised insecticide spade kerosene, supplied, by I* Sonne born Sons, loo . , Has used in the esml^worlcs rang, a ecxcceenpt whore -otherwise indicated* 2-* The Quantities of phthalis anhydrie'e end chlorpbthallc. aid vr.;'i:- tweb as t a gi?e a noi . -atlo of phthalhs anhydride/ chlorchthalic /ell : 8'., '* The quantity of phthalio . (vtbyr.ride ad.c-c I v;as adjusted as necessary to compensate for the iisehloriaa tad phftnlie anhydride Cas phttiali acid) present in the crude cblorphtrsXie acid* The quantity of crude chlorphtl-elle acicl press cake added is sufficient t yield 11,5 lbs chlorphthalic acid* Ifationai knXlim or Monsanto pkibs lie anhydride was used la the sami*wrke studies* DUP050068261 m ^'1 3 Tha gasiatit^ of mmtmSxm sclyMato ordinarily usad in. the $erai~i?or&s *zm t^ice that specified for W& plant 3P T* Baker'* C.f mnoy&xm nolylx'c.te res usecU 4 Tbs qaa&tliy of copper clxloride Flryirete is ad,mated as necessary to ocnpaBtnta for rar lotions In rater content For example, during r-ost of the semt-rrorks runs this quantity -sas inersagto X&0 lfc-s because of excessive water content of the rafcsriaX* Harshaw*# tec-mleal grad copper color Ids dlhySrato ^es tised in tbs studies* DUP050068262 " 25 ** Original (Mawpori Plant Sfcartwup* April* 1940) Plant Procedure for Synthesis of CS*3* To rose tor at X0 - s.^y, add 540 gals * C3500O Of kerosene at 110Q (lot I) Start agitato? and add to the reactor oiw batch chlorphthalic acid .prasscaka (Kobe 2) Then s.<M to reactor 279 lbs- copper chloric! diliydrat (koto 3) ?9f Ibs- phthalic anhydride (Acts *" } 2.0 7 lbs -. ataiaoaioJK moljbdnis (Hot 55 Close reactor ssepliol and hairs agitated charge to X&5 during $0 Hlantss bp use of Dow them, fo agitated charge at 1.6 50 add oyer 45 minutes 1509 Xhs > urea (molten) at 13:1'135^5 (lot 6) Heat charge to 1$50 (with agitation) as rapidly as pea Ibis (33 time tad 2-2*5 brs* }. Hold charge at 195 & 3^C for 4 hours (aontiming agitation).* then pusp it to the sulfate?* Flush reactor with 3.00 gals. of hot CliO^C-) kerosa ns and pmp the. flush "to the -sulfator* ISSSS l. Jhe temper stare difference lbs tyeea the kettle gad the fcsrosen should hot be ..greater than 65Q. to avoid cracking of the glass kettle lining, Since the kettle will ordinarily be hot (from previous synthesis) hot kerosene is used* 2* The quantity of chlorplithalic' acid .preas-oake added was such as was calculated front seai^works experience to give a lalxtiirs of 1-..X7 ffiols of 4~chlo.rphth.alic acid with a total of 558 stole of ' phthalic anhydride and unehlorlasted phthalic aeld?wlien. mim with 797 lbs. of phthalic anhydride* The plant plans provided for the as (<m an ammlys& basis} of one plant batch of ehlorghthaXlc acid per synthesis charge, !ach chlorphthalic acid batch was estimated to contain <=> DUP050068263 26 325 lbs* (1*1? fflols) 4*hlorphtha!ic ac!5, 30 lbs* (0*20 mols) unchlorimated pfcthalic acid* The addition of 79? lbs* (5*33 mole) of pht'iallc anhydride to the ehlorphthalic acid batch \7&a calculated to yield the desired mixture of Id? mole of ehlorphtfealie acid v/ifch 5*58 <5*38 *s* *20) ols of imcblori&ated phthalio anhydride and phthalic acid* The mol % of chlorphthalic acid in the fixture ms calculated to be 100 % 1*17/6*75 * 17*3^ 3-. .Harehaw^s technical grade copper chloride ms used* The material was analysed for water content and in those Instances in which the analysis differed significantly from the theoretical <21*1$ water) the -quantity of copper salt was adjusted accordingly* 4.,, Commercial grade phthalio anhydride was used on an Bas isrt basis* See also fete 2* 5> Jet..* Baker's technical grads sr*nni snlyocate was used on ah rtas isM basis* the quantity spacl TJ *' fox4 the plant was only one half that used in most seni-uorks ~ jcoiaents* Experimental studies at Newark heel .shown such a reduction to hs -nmibls* 6* DuPont's urea was used* It was specified that heating tor a longer period amt at a higher temperature than the inlaws required to melt' the urea was to be avoided in order to minimise- thermal decomposition of the material* DUP050068264 27 c Sewport" Plant Process for Synthesis of 0-FC as of -Sapteiabsrs .If48* $o 'the glass lined 1500 gallon rsacios? add 7130 lbs* <1100 gallons cf deo3mB keromm at X10#C (lets I) Start agitate** and add via the kettle .manhole 10 lbs* ammonium, car hone to (llote 2} 3 lbs* 'Paranore 441 (fete, 25 Class manhole and heat kerosene to XI0C ` by .me&m of Doytherm* With agitator mm lag, add via the nacholra CXhe tshlopohthalis acid pressc.uke t s mined (^dredged") <* ydthva portion of the phtbuXle atfoydride) one batch of chXorpbtha.1 Xe acid press-cake (Hots* 3) 835 Vo~i ot phthalle anhydride (lots 3) Shoo add 285 lbs > copper chloride dihfdrats (note 4> and folios? Pith 5 'lbs, ammonium molybdate (Pets 5)' Heat charge Cmth agitation) to %$0G (lots 6) and add over 45 ninnies? continuing heating during addition 1500 lbs* molten urea at X35~138c0<> Heat charge to X95c< and hold, at X9$ for 4 baps* (Slurry Is agitated throughout the entire period)* At the end of the digestion period at 195*0 add to tha BnXf&uor 5 lbs* atsmoatua carbonate Pump to slurry to the sulfator. Plush the kettle tilth 1300 lbs* (200 gals3 of Deo^Basc tsar-os ne DUP050068265 28 - gojlg, <&ppnUx TT) X> The temperature difference batxmm ilia kettle .and .kerosene should foe no greater then 65*0$ a greater isapsrature differs once is likely to result :ln cracking of bbe glass lining of the kettle,. Since the kettle will ordinarily he hot fro the preceding synthesis, hot kerosene is usedo 2 The purpose of the ereoaium airboisata Is to provide m inert gas blanket (by thermal decomposition) and thereby decrease the &teat of oxidation of 'kerosene at this point# P&vanax 441 is aa anti-oxidant for pstyclenm and is also used to retard oxidation of the kerosene# 3, Gas 'batch of chlorphtbaXAe acid > prepared fro 536 pounds of phtfoalic anhydride ~ is .added for each synthesis charge# This quantity was found to give, with 835 lbs# of phthalic anhydride, approximately the desired, mixture of 1#2 r.oles of chlorohthali' acM with 5'6 mols of ntechioriouted phthalic anhydride# The chlorphthallc acid is used ^Tithomt analysis -fh quantities of phthalic anhydride used for chlorphthalic acid preparation and for the synthesis xmm changed from that originally specified (Appendix XI)? sines it was found that under plant condition more than the expected yield of cfolorphthalio acid was obtained :. 4',:. The quantity of copper (H) chloride dlhydr&ts was increased from the 2?$ lbs# originally specified to 285 lbs# to com** pensate for the excess water usually found in this ingredient* The original plant practice of analysing the copper chloride for water content wee discontinued and 285 lbs# of the is*4 d.ihydratewas used in ouch synthesis# is 5- <J< T* Baker* s technical grade gmsaonium molybdats/used on &n nvs ist! foes is > DUP050068266 TfSWSVsViS | |B8C*~^|tA jxem JHmrm / 4* CO MOONS SR ?-0' lO$ TttgftMfe WSM. TO TQtw ' ? sr OH. TO OBri*^$'"`-^? &C!.i> SMU m- on. ---04 I$f 8a ,/ aaormo ,'">oA5^vor f<34 1 ii 11 ill 11 If 3 it wmt-me m h &3) t o &TSU, ssMt*wo4^ r t o h $g4t* CAPftsm. OAOKSTSO . OIL HSATfie. svmi.s,%b &tfmtmm aw o iwm DUP050068267 b- j \H L V f S.J:; i i L,,i VC\ i L , W i ' iLj Y 1 SYNTHESiS CRUDE CPC Tmtw ... xvfcfcxw . *,y:\vY Ur40. /ro;- JsatWv #00~23 ** gb|er hfH&l nyfe frtun f ilizr f|res& T>*p Al&.rwib' Timi* Cflir-f iO&*?k 8`fwA sec o h o now L. ~~ -st-1 1 * * V*';: ..._ v--"- '- * i ** >i ;i ** * .* % *> *.* _ * Steelsis KetU& j3 ; ,*>,* v-- Rusts Bcttom "0aSdl&rte I4fe& KgsrQ&sin& frowi . j/* tfeftb*) twin 408'-2l llowst m fs'Oj-a Sotie^ 100* 2 0Gi*?tlnrm iSCrvicns .ftiO.Hs' in H*4j !*. fig&r. To io o * Osr $uf|i4w lOO`f.4 J " tme$ 5|s^!;S$S s5o |=ai eo.f'Y, for O^thsrm n'%&nf if#? **we f trt w.vK.'0>WAv*,X'j^s.trtwA* . pMmp 00*20 NOT#- Th C SQUIPNCfNT fS SHOWN A% Of TINS OF Pg&N? 5tAT*li# CHANOSS Wt(tl P*!# | gy&SC-QUff^YV/ t*<* O(m0NS$ STSTeTN-, PiPM!*, y&TA MNNffSW FAtsuTJffS. DUP050068268