Document 9XY3vmr2XXM4kpv8meRmO7EV

u ^ E. I. DU PONT DE NEMOURS & COMPANY 256 VANDERPOOl STREET NEWARK, NEW JERSEY Serial No. KN-54-34 Copy No, } 1 V) l NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Final Report "MONA.STRAL" GREEN GX, SEMI-WORKS STUDY Period Covered MftY, 1953 to DECEMBER, 1953 RLE: PATE: 223.42 1/20/55 ( i :(i |. | < X'i.X:- V : V - id - !d. fad sis S?i''5e'fc -i;;: > *'?-13 i - ?,ivtu < \ui&; {:, %- f j, Id, Cd;:d!aad: l^ayoa'i 5 - la Id dally/id- I, did. 5 - i?.o 1L> dxojdd' 7 jfl I El--:- Idit-I; o ~ M., .: . idadiad- I'ddid; 'i ,i; * -.1 ddid:. Cl vd . .-* Ild'ld in - SSxd/s 'll - BrE;: a ,i:l ^ KN-54-34 I WiadSd d>, d ': dxIlCill lllll 11.3 d IB? dd Eld id: 'ddTvB iddddla B; -..dd'idiSd a y-/- ijii; -;d.d, iid.i"'::-,:: didddd;, add . -r'd . . $ ..' '-..'a 3l.3.ddff*d I xidicfid ,a? ;A 10 :&i a : ' -jr.y-L/ . dl Ida ia ddad IXd-.^/S.V 3,3 illialla l/Bi/55 DUP050070015 .flv t V-if ?.. ' 'if X.,:: ''*&<<$ \-.X: ^XX . :- ,1 1 ;muv&^ vfO fe%fa fs#lil.sl^sl Sa XiilkE; '-A *?- i -*"-' <if! '. .1 $ fs4ts;sts% mss- ftm. tbtsfS \ / -~ mm% m& ti^etoriai 4*2* ffltsn f !&>, i *V / V 4 v' .i<- *i t -tv. to f fc3Ebt-p :4'^KEsafcisa : . *. c,>.\" &' : far wv t . l. ^''' d .- -f "1 - ''**.' & * * \ <\> . *- *- - <; r-u 1.>u *v _ > * H ; 5. - ..... !L c N * fj& isytxgss ssai p ?.M %x..% V, ,< `d- ' ^ . v'. SE , wm Mtai . ' ..v,E-\v^..f,3 Stl'W.Opse; la 0A ae . s'.,,i i'- && es ^s I;w 3^` !i wlfe'e pin,, & this mis i|,0` r-wf tit* 2ji ^t-Esy Pftts -(k-mm gty; ps-smE 3'j sessi'xsM tslta* ,v * _*,'. i : < .- :,, si-,- j. -V .!. lf./l`,jxaS,t4 !iis -Ww f. . u ^v s ei-'v :', -f f sm&sii' t^cs;'-! ...y 4iAt..V.E .2 r sf.tf* 1 i* i_ ' " * _ 1 " * -~JL ^ w J. vb & tjLaiOlaka vi5e? -s es ;&bs s I 'to fes is* ^rHlsig pm* data is t3 -ppM&teci: tfeo saj ; < r_ 'Ui'o ** '_-3iJ.cs o' ibo r`Lo;a '* ralrf (&am CSC gw**** .% the pis gsMJS A* SSKii..lE C Jig* 1) 1* ii^iL iSS? k Isl IQJP tls'lPr ?>$$& $. tbs Jfetspcrt Hast* m-s ;ased sr lbs f^gslPsprsEs steSy of i&a :k C?m-3u "15^ p-es^s.* fo safes fe&8t-S! gprsassio* iltc rot?*- c-adur Qsttm $% 4^sii*sd Aa {&#/g3.}e tbs ale^ isidit&Sii of ODOB to Vm rn^m&m sls-si?ys asd tbp .grfesflas isi.,i:f.d by flit* ptsisg d 'essh3sg* Ib.ll.' ,, $ v/. fi.trssirs, .urucos aximcitloa *& tti 'bail for oa* fetor vK-,i- ?otssA to Is w drcKsiss ^Xa Set? !wsat tltwia3. rrov^rfeiase. feistica JT tfe* QSK3B x e-L'S 'ics vf^oroos :agifeitim fmd ts? ^Lald ffc-ex .gsaiss* Ma- -- osstsg of tfe* GB 1?o**2M, dtb^b p3;sg.p,gD of */. ;av5- ^fass^ aoi llr fill past* ts* woc-rvtr.ctU. A jpressr mfctsa of 2s.}':; jdg**sd im mc88r7 for tbis S'- r*,,-i r;.i! ,ttfess. fesDf filt--::- 3tb- v*ralit^i myM. filtrata imtass a| -ysit te24sas;|- fc 1ft s %Swsr 42AfeA f 1 'fernsr feis^r .|!5sS DUP050070016 tia filter feed wee else beneficial in this respect* Bine wight ratios of OPGB/eelor above 0-o6/l gave enhanced quality, but; granules of sticky consistency, a modified process., wherein part of the O'DCB is added in the still, was preferred for ease of granule handling* Impurities must be removed fro the granules before steam distillation to avoid bXooiaingw in the final producto This we accomplished by vat or press washing* Press washing is the more .attractive, as less manipulation and mah mber is required* 11though elaborate washing is not essential, the washing should be carried to a wash filtrate pH of 5 or above -to ixmxm desired prc* duet quality* The first problem encountered in the distillation. Of granules was pellet formation,, laborawy rvae"y indicated that rapid steaming reduced the tendonjy torrid pc.'loo formation* However, plant experience showed the t'waa* High ratios of OBCB to pigment 4Xd5/ll and rapid, steaming - to prcaaote the formation' of pellets* The u# of ^Triton X-j x *" -vr of sodium stearate as a surface active agent in the stea% dint* .Marion eliminated pellet formation* Steam rates of S# -'s^vk*/# pigiment or less yielded pellet free products* The rat# f 013CB removal during steam distillate a of the granules was found to be k function of trmr cud gra.rv.1 sis only, and not rate of steam input* Analysl h rf 7BCB removal rate data indicated that; desorption of OBCB frnr th* jp*anul,*.fj occurs* A typical OB0B granule distillate curve shown in Figure 3 Additional ODCB treatment, obtained by refluxing 0*d5/l granules and also by further .granulation with -an additd anal 0*20 parts ODCB/parfc pigment prior to distillation yielded itor* intense and stronger products'* iasprovement in tinctorial properties of the product resulted from increased pH during distillation* phna* phate, trieodium phosphate, and sodium hydrossida were used* Best results were obtained when a pH of 11 or above was employed in the still charge* 3* Isolation of Final Product,; The shell of the 0008 granule persisted through the distillation* Therefore., handling and processing difficulties were encountered in pumping, filtering, and washing the distillation product* Thus, a hard settling -sandy' product resulted* Residual ODCB and acidity were noticeable in the product grains either after standing as a pulp or wet crushing or milling* DUP050070017 3 ' A slow mtt settling pulp can be made from distilled granules by colloid milling* Slower settling pulps were produced at closer mill settings, but product rubeut strength loss resulted when the color was milled at less than 0*0X0 inch mill clearance Sodium stearate {2$--on pigment) ms also found to dis perse the granule effectively during distillation, yielding a smooth .slow settling pulp which does not contain residual OBCB or acidity* 4* Hgme,^,.tetug!f!l Hard sandy granule shell remain after distillation* The dry, pulverised pigment exhibits a harsh texture, which renders the product unacceptable in ease of grinding on a roller mill, particularly with respect to rat of strength development, grit elimination, and in general mill behavior* High speed pulverisation of the dried product, wet pulverisation, colloid milling, colloid milling plus homogenisation# and acetone extraction of the pulp did not improve the texture* Alkaline extraction of colloid milled pulp gave some improvement* The us of sodium stearate as a detergent .and dispersing agent during granule distillation gave an improved textured product equal to GT-674-B, SD 121* With the advent of the new **70* pro cess Csss Fig* 2) developed in the laboratory, granule handling was eliminated and products of superior texture properties com pared with current green 0T-674-B, SB 121, resulted* Therefore, development work on the "Green Z5n type processes was discontinued* B. 1* crude Extraction? In the "70" process {Fig* 2) rotary drier Green Crude drowning was performed in the same manner as in the "25" process, except that the ODCB granulation was omitted at this point* Initially, crude Green GX was drowned in water (i#/gal) and extracted for 2 hours at 90=95 C, It was found that a 1 hour extraction without heating was sufficient to obtain good quality and disintegrate all the lumps of crude* , The extracted crude must be filtered and washed to remove impurities which cause "blooming", although only slight quality'differences were noted by varnish dryer runout* A press volume of 0*0244 cu ft./# pigment is required for this operation* Crude GX should be washed to a filtrate pH of 4*5 or above {equivalent to ca* 4000 ohms at NewportS DUP050070018 4* 2 Alkaline Extractionl The original laboratory process required that the extracted crude be boiled in caustic 0X6?#/# color) for one hour at a slurry concentration of 1# eeler/gallon* Semi-works study of this operation showed that identical results were obtained by ex tracting with 0*07# caustic/# color at room temperature for 15 minutes* Inferior quality resulted when lower .amounts of caustic were used* 3 SranulatiMSODCB granulation is performed in the steam distillation vessel under well agitated conditions using the alkaline extracted slurry* Early work' was performed using an ODCB addition rate of 0*55# ODCB/# pigment/hr* This rate was later increased to 5*0# ODCB/# pigment/hr* without adverse effect upon product quality* Varying granulation temperatures up to 90 C* did not affect product quality The addition of sodium stearate before granulation yielded a product of inferior quality* Finer ODCB granules result from the *?** process compared to the w25w process, pgroumably because the extracted crude is better dispersed in alkaline media Results of duplicate Semi-works mas showed the use of .75 lbs. ODCB/lbo color yielded slightly weaker products, whereas the use of 0*05# ODCB/# color or more gave products of strength equal to GT-674-B standard Masstone become lighter with increased 0BCB contact time* ODCB recovered from the steam distillation may be reused with no adverse effect on quality 4 DistillationI After the ODCB granulation step, stearic acid (336 on the weight of the color) and sodium nitrite (256 on the weight of the color) are added The ODCB steam distillation is then commenced using both jacket and live sparger steam* a Foaming In the initial Semi-works trials, sodium stearate, required for quality reasons, caused extreme foaming during dis tillation, and a very slow distillation rat resulted To obtain a practicable process, the following methods of fo$m suppression were investigatedt (1) variation of pH, sodium stearate concen tration, and addition of electrolytes; (2) substitution of nonfoaming detergents for sodium stearate; (3) addition of anti-foam agents; and |4) mechanical methods. DUP050070019 -5 lb found possifela .to fedao to faming toMoaey by lessening pH? tab inferior .qja&liiy rmsated* .Lower wants of soditWi etearat yielded jropweimly pasw pdgasnfc q^alit^ tdto no apparent decrease. la foasdng* to addition of m Hs&L* to fftoii*Bfc s^atobity to eltotost foam, yieMed a weak jwedwt* fe results of ike aoE-foascJsg d a&tl*-fo3 agent study are tatatotod in Tables 1 & 2* ^d^r&syl plxptee m found to be ff#stiv W twtfsrtog tie fom light and fragile tsd^oiseagrl phosphate hydro* lyses to filing eauetto, it should be repto^tosd mwmy ll/2 hours daring dieiiltotios* Other satiHP0aa agents w also fond to he offeetdv, hat .poor s&gwsb fu&lity resulted* tee promising lead result-. ires the study of aoa^foeasisag deborgeats* these w@ not puree!, as satisfactory stotedeal mane for font haadiing had. hem discovered* Maehaaioslly, the fom can he checked by a high wloeiiy, flat* tohtail water spray directed dowd m to toe surface of the still stony* foam is .roved by the' still agitation taster the spray, and is tons ssatefcaiH^ at a lew level in the still* 4 Sgsayei model #0.Q3XP spray w used to too S^~works wi & eerotsmi still liqaid level maintained ` by proper d^wkwat of jacket sterna* Sim a fins mist of still stony is ss&gstosd in toe vapor escaping frees to fas eerffes, a 6 into thick "ted&sk53 2 knitted wir demister Was mud to .rems this e&tratoroab* . Failure to raaovo entrgd^snt would rssbto .in poor yield of color. Lso, 0DC8 recovery wild be 1m aim the distillate is mlsifiei in to presume of sodirn stearate* & additions ptaggag of to condenser sight be mooabared* W Finished protest ftjoallty ms fmasii deteriorate progressively with decreasing pi belw 10*0* This degradation is .ftether aggravated by contact with carbon or stainless ebX used-in plant and Soai-^rks egsipmafe* ftereforos oanstto solution should be totrodmod into to still prior to toe addition of to oral* c) gates to rate of OBGB distillation ia toe "Qpaasa 25" proems appear! to be emtoolled by desorption !m grotaLss and not rate of siessa topsst. In the "^eea 70" process, the rat of OB removal ms found to be poportioaal to the stsasa throughput* It la postulated tost toe OP granule form! ia the "70" process is of sufficient fineness to &Hw rapid OB .desorption* A typical disillXation surr is show in Figaro 5- toe ffl rmtml to is limited by foa fosmtioa* instillation rates as high as 0*073 galloss of distiXlato/Bin*/sipam foot of still surface mm wed before essceesoloo fcasiag ss emoaatersd* St*, Sosaorsill 45s ^s* 2* T*E Otto H. fork .So*, 69 dSAapced Flas@p last Gr^ge, H* ,J DUP050070020 d) Sat fetefes Itos is t-M'ssto&tM Mss& s OS is a long-? &oii5!?l'0 in $W m of iistSXX&t* Ba to & way aosspXax mat f -w^pw plpisg Isi 4h pXmt^ *" poiast of thsg. SO e* 0&C8/500 eSo of 4irfe01fe is isdbcpsts-o Ifptm toiftollos f U $tm t& mlr is prwsals, fe# pt&p <$K?6&)* Barilj pAsafc msMitg 4UtodtlM p&ogfeai JSta&^siaB c&ttJ^r sf tMa &a$* It aw fowl thgt stew disiiiXod wios? tsss wil^f **|pfliead* isl t$w pro .if iwffisi.t pxmm mlws is ssaplsfwi H*< slr sd poor iwliisg awaits* 0*023 to 0*03$ 43/# eoXor -taw .fewpd to fc & saf.isfwtos^' p Xoadieg t o !w Hi tiasteiiCL _pwpti#s f t& fipiste4 prodmt mm' aofc offoeiad W ill , of &ehiag Hew***, t2xs fSMstai Qrm& &K s&o14 b feat iy m&li&i to a fiitwfc resisfcmoe of 2500 fe * irasra rmmr&L -f a portion of tl soltM. salt*. t$s *% 70* sXwyjr mm 4@@iraM settling ,, mm%% soft i @Xf settling 'rngmyed Kjltli I*=l24 o j p ^fitooen 2S* ,s&p* A ISMnoh Staiwr ihixSteea?m a3ja&fcwl mM tensed to b* opebXe of filtering ill pill! alwy? afe&ag ttss p&t$^ a* poapsibl palp of 25S solMs .eoa&oai* SI snjnls&ag & wl,lwiiaijBg wssid fes <0ininab(*l; t&e Shri^er ifeiotew? eksnM 1 esawiiIsred in onp sedition to rrojOmomBt of isolation. sqeipewa4. 6* Brooms Xi&M XieM# febaln$l ite. tbs Sgsi^wst .aw sli tl* Gfalorfnaiia iMss mm jpps*td Xs^w< .Sts Gmi totioa disitiXl&tioa Stem distilintioa 99,3$' 94,3^ 9S^ $&** aoaX^sls CoSi4f XOC^ CFG Orl0e `fen stoaa distiilatios & t^ssm tes w# of Swiwxte rmmmg- of- C^GS ai^gi $S* RTOTORaf!RSi X* lotefeo^k 1A&I So Eoports 'SB-54-? trt H"54*=# DUP050070021 X* Sotasy dryer - -as import Plsafe 2* 02i/hc^4iMLorMiasiss gr&$ .* $o*ay or .few 3 Sodim aitrite 1-5 {Sk FXsssfc) 4* G&wii ! aqpatL 4o 'JHi (Mmrnk SWb) 5o Sfca&si said => ;t#o*=f.t XS=5S tems 6 -|iK53gfeat. x Sesfcrwse Qw^aaS. DUP050070022 J. mm '*3& 1 ipood pLtsg Sa wfe$s& $ ?&* 2o Mi 20 mtsr 350 g@H* ,3 Idd wfciajr 4*ir &*& oga^l to 285# eoto* Wtoar $m shm& 4 Stis? 1 to* 5 PIXtw 3ja 22 Stmm <= 202 -Press* 6e tfesb COTfma - e b s 14QF. mte&pH s Is o eH b 4*0 oar s &o h r s j .loos t!a*a 3gy&ls^/g31osiB 7* Bsteap ps sad pises palp in 35 gallon fern *> ebtsia dsgr eootfvt* DUP050070023 jysiSBLix s.w* f e o o e s s ~ Bmm pismuTtoii a k d p b o bb c t is o ia t io k EQUIPMENT? X.o 29 Tank* complete with Q.G31F Spr&yco spray and 4** s 6 diameter fork demister* 2c Old wood press s 1.8% 0*125 ft3/fram le Add 6ra sate? in 29 Tank turn an agitator' 2o -Add Green CG mt? extracted pressealc Lot . lbs* ,s 35# dry*. 3 Make volume to 10 inches with water* 4 Add flake caustic I3S-7H) - stir 15 minute** 5* Add uniformly in 10 minutes --= JOfr BOB* 6 Record pH * 7* Add 320 grass sodium nitrite |[!?3K 8* Add 477 grams stearic acid CNeoFb 13*53I 9* .Add tricresyl phosphate * .10 cc* 10* Seal steam still* Turn on "water spray to 20-30 p.i and start distillation 11 Add 10 cc* tri-eresyl phosphate during distillation at 1 .hoar intervals 0 12* Stop distillation when no separate layer of BOB is found in 500 cc of distillate* 13 Record final pH ,, final volume in* #0BGB recovered lb* and # water condensed lb* 14* Filter slurry from 29 Tank in 10 frames old wood press * use 29 Tank pump Hecord pressure p.ai Time start . Time finish 15* Wash with 140*F water to less than 3' grains/gal* 16* Dump press record condition of cakes wt pe lb dry content % yield dry lb* DUP050070024 X.3Bt.._pM0g. of SacsreaslRg fe;na^igy_^_.?ffl^st ?#B< teoat Goapgirsi With Stearic Adi f^ocluet 8fcan&t* !<=$ Rosin *&11 Amfsi 2Hf Sfcearox CP Ahewcb ES &ndd K*0^ Star@x A<J B&d 11 H lignin Saifosi&t BrtJ 3 Brij 35 Stearic Acid + pkosptot Stearic Aeld * Ha Pyro phosphate fg 300 Mono Stearate Peg 2O0 Mono laur&t .Peg 300 Biolanrats Stearic Acid !feo~Fat X*-53 'Source** I239 |larkl Grocery stelf Amour WJL 2395 XHt 21&B kmmr Monsanto JHC I646 BX i??2 Atlas Atlas S <* u '* nx 2913 BI 2m BX 290? Amour ISgSKSli & weak 0; weak & weak t o weak ^sk t weak t ,, ak weak jj<, weak re weak 3U W8>&& vs weak vs weak s Maaatona dk* & * O 0e e ike dk 7 CO c=> -as, &' ea dfc. dk. ts Sfk sa ^Amount used ws J%> hy might* based sa color,, **QX numbers are Experl-sisatai Station file numbers . DUP050070025 :& iix'fes;. 2nsmmxM!x.Rmm tmmmm. s ;*;: ;1SJ;K >' $0 ,. iSsSCviii* fefevv? *> afeex-e^yi Efeo^fefe < Xvd-Vw?.y& jvEosxfefes-ss .-:. d.n Srllfemfe: 'eefe'ic? ?0 ! <>, ?' Pzlz tx&.XU.XX Vfe, fefeilfecae fe;fe!f Brfe.feD.: 0Zif ftX Xvfe 'dxkd-mm Cl'^v ^ * **< */,&. >' *.'; \iv fefe SI?? p? x??a Ffe Sfe 6? ,4I'6i UXiJ fet'efe.nfe ` A fe . Ifeetfefe. SfeULgtfe ?;r fife v S'^oife..,, fefefe ./ & ' ^ fe mew; Vi fi-f fe >-'3 v tfeife no;; :?,";> ciemXveii .fee fefene:-; life, fefeifefeft,- fe\" t 5Xb 55 feefeVe? Zvidxx:.: fefe feealJxe. Jife I* V V- j*. Z*Mm 13 Pin? Odl d.dexx .fee'. OiJ 'X^ai4 fet.fc6.i9 Brs&.koj? fossaec.;: Ho:*' Mr; frs&d Di.3, ice: feoc-tfe.efe Ho./ Cvfelij; J v 5' !f E(6.fe;tte V >6, fejv;gfeife:t 3 c Ife fifetgi>%zr. fife fife feeksfeioe fife fife Efefegfefefe:. fiiffeC* fife (fee? feofefe fife?? Ukvsixkt Ifefe.fi l&xzvk} id iiscMxdk} Bfelife Bxx-ax;; ecfefefe tkd.xx fifefeteo V fe V-V'-'-. -4'. Ifefe ,, &...fife. ifefi- 0 fifefe fife,, E ,fe v 1 if* S,,?, id - fii ;? fes. Ife fife fesfe :VJ *vJfe2? *> tfet IfefeUisfefe SteVce. xile ?enfeei;:i DUP050070026 ENCHNSERINQ DEPT. . I. W PONT P NEMOURS & 00. Qm.) DUP050070027 ni\M051.B ENGINEER!MG DEPT. E. L DU PONT DE NEMOURS 4 60, (INC.) DUP050070028 DUP050070029 Unc.rf M 28 $55 ton5Mu#: < DUP050070030