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Return to: CDP Dept. Jackson Laboratory R. & D. File Room TO: Return to: CDP Dept. Jackson Laboratory R. & D. File Room TO: Return to.- CDP Dept. Jackson Laboratory R. & D. File Room TO: Return to: CDP Dept. Jackson Laboratory R. & 0. File Room TO: Return to: CDP Dept. Jackson Laboratory R. & D. File Room TO: Return to; MU-1780 (Rev. 3/78) CDP Oept. Jackson Laboratory R. & D. File Room DUP050081 577 ", Yyf91, ' , ' I" tf/i/ra Po n t m h eh o u r s & c o mpan y Pigments Department SERIAL, HO Cop;/ . --. NEWPORT PLANT PIGMENT COLORS RESEARCH RPROFT SUBJECT; CQKTXIfQC'JS CK! SYNTYjSS.:.'! PSRI(> COVERED.* OCTOBER 1968 - *ESBn 1969 ttWEc * 9 - ..i. ) . < 9 RETURN TO JACKSON LABORATORY FILE ROOM DUP050081578 KN-69-12 COPY HO. IS' 1. Numerical File - 223.4 2. Research Office File, Newark - 223.4 3. Newark Library File - 223.4 4. M. Hunt/E. Gonick - Wilmington 5. W. S. Struve - Newark 6. F. F, Shrlch/Bo H. Perkins/Newark Library 7. P. J. Monahan - Newark (Vital Records) 8. E. L. Rodowsk&s/R M. Salami/J. D, Lojewski 9. F. L. Reig 10. R. H. Wetzel/J. W, Minnich/W. A. West 11. J. F. Maurer 12. Newport Colors Research File (M, C. Crossan) 13. Extra 14. Extra 15. Extra 16. Extra 17. Extra NEWPORT PLANT PIGMENT COLORS RESEARCH REPORT SUBJECT: CONTINUOUS CPC SYNTHESIS PERIOD COVERED: OCTOBER, 1968 - SEPTEMBER, 1969 SUBMITTED BY: F. L. REIG ,, ^ DATS SUBMITTED 9/11/69 APPROVED BY: J. F. MAUR: Continuous formation of a stable intermediate iaoindolenine can easily be formed in a pipe line "flow" reactor. Synthesis of CPC from the intermediate could be accomplished in a cascade or staged reactor. Benefits of CPC quality uniformity and simplicity of processing would be realized in such a synthesis system. r et u r H TO JACKSON I.A301A- FILE ROOM DUP050081 579 HH O TABLE OP CONTENTS Page I. INTRODUCTION 1 CONCLUSIONS 1 III. ACKNOT-JLEDGEMENI 2 IV. DISCUSSION 2 V. ATTACHMENTS 3 1,, Hastelloy C-27'6 Laboratory Reactor 2* Plow Reactor Concepts, 11/19/68 3 Pre-Start-up Survey - Continuous CPC Synthesis, 3/17/69 4 * Flow Reactor Laboratory Unit,, 3/25/69 5,, Postulated CPC Synthesis, 4/24/69 r DUP050081580 KN-69-12 Newport, Delaware INTRODUCTION The phthalie anhydride-urea process is used to make the major portion of copper phthalocyanine in this country. DuPont Pigments has used the process with a purified kerosene carrier since the conception of CPC manufacture at Newport in 1948. Some countries use phthalonitrile because of better yields and simplified processing but this raw material cannot be Justified economically in the United States because of the low cost of phthalie anhydride and urea. E. P. Klen3.ee suggested that a possible area of cost reduction might be realised in a semi-continuous process for making crude CPC over the batch process being used at Newport (Reference 1). Early semi-works acid flushings of the crude CPC synthesis mass indicated potential quality problems due to the margin of difference in impurity levels from batch CPC synthesis. In addition., since both flashing and HT drowning were visualized as `'flow" reactions, it seemed that additional benefits other than uniformity of quality might be realized by "flow" syn thesis route (Reference 2). Search of the literature indicates that intermediate isoindolenines in the route to CPC were highly stable compounds and could be produced in a "flow" reactor (Reference 3). Reference 1 - EFKlenke to JHCooper, "CPC Cost Reduction", 4/27/60 Reference 2 Reig "Flow Reactor Concepts", NB-3244-17ff, 3/25/69 ; Engineering Computation Sheets 1 and 2, 11/19/68 Reference 3 - ::Isoindolenines % Angewandte Chemie 68, pp 133-150, 1956 CONCLUSIONS The continuous formation of stable intermediate isoindolenines can easily be formed in a pipe line "flow" reactor. Benefits of uniformity of quality and simplicity of processing would be realized. The final formation of CPC would be difficult in a "flow" reactor but would present no problems in a cascade or staged stirred reactor system being fed by the Intermediate unit and being discharged by gravity flow or an open centrifugal pump* DUP050081581 H 2- 111 ACKHOWLEDQEMEHT Considerable guidance in the pursuit of this process concept in the laboratory was obtained from E0 F. Klenke and Ju W. Minnich, R, H. Wetsel offered several suggestions for equipment simplification. IV. DISCUSSION The initial work was carried out in the standard two liter CPC synthesis flask using normal plant concentrations for kerosene., phtbalic anhydride, urea, copper chloride, DBPC anti oxidant and ammonium molybdate catalyst". The amounts were: 63 a 95 & 11 .6 g PA Urea CuCls .22 g DBPC .325 8 450 ml AMM Deobase Kerosene If the ingredients are charged in the normal fashion and heated to the intermediate stage of reaction (120-135C.) considerable foaming due to the erratic evolution of COa was noted. It was observed if the ingredients x*ere highly dispersed, that is, high speed mixing in an Oster blender, the evolution of gas at the intermediate reaction stage was more uniform and rapid heat-up could be accomplished without foamover. P temperature profile is attached, When this mixture was fed to a 19 mm ID pyrex tube using a glass funnel as a feed reservoir and a flexible Teflon tubing between the funnel end reactor, a continuity of feed could not be established because of -plugging* If kerosene in the mix was reduced 30$, the feed required help from a blast rod slightly smaller than the stem of the reservoir funnel but the reactor gave a uniform discharge. The character of the di charge varied with the temperature maintained over the 36 inch length that was heated with Glascol heating tapes, operated in three separate 12 inch sections and controlled by an 0-120 V veri&c on each section. <0 CO At 104-A08oC., the intermediate product was a light bluish salt and some free kerosene. At 115-120, the salt was light green-grayish in appearance with free kerosene. The free r DUP050081582 -3 IV.. DISCUSSION (Continued) kerosene in both oases ms water white. If the temperature was elevated to 137`"1^0% a yellowish green product was ob tained and the kerosene imd a reddish tint. All three inter mediate products yielded CPC in good yield when heated as rapidly as possible (20 minutes) from room temperature to 313C. on a hot-plate in a beaker using a magnetic stirrer bar for agitation (Reference HB-3'2;44-39; 40) ,, If the cold well dispersed synthesis Ingredient mass was heated in a similar beaker# CPC was not formed but the product was a dark brown mass with considerable phth&limide, A 3 liter H&stelloy 0-276 reactor was converted into a 3~staged reactor unit with a continuous feed pump and -a method for discharging the reactor continuously (see Attachment #4). She initial run failed to yield useful rate data because of pluggage in the heat exchanger on the feed side shortly before start-up,, Attempts to bypass the heat exchanger were unsuccessful but analyses of material from the top and bottom stages of the reactor indicated all the feed (2400 grans) had converted to CPC. The heat exchanger was redesigned and several subsequent runs of two and 3-1/2 hours were successful-. (Ref; i8B-3243~10~X5). Using the 3.64il lbs../yr. Blue required for the October# 1968# CPC market potential would indicate a 300 lb ./hr. unit at 85$ utilisation# that is,? & 500 gallon reactor system (see Attachment #2). v. mrz&cmmms I* HasteXXoy C--276 Laboratory Reactor 2. Plow Reactor Concepts# 11/19/68 3. Pre~S.tart~up Survey - Continuous CPC Synthesis# 3/17/69 4. 'Flow Reactor Lab Unit,* 3/25/69 5. Postulated CPC Synthesis# 4/24/69 DUP050081583 DUP050081584 Cj C<L U/^VTrZ-J~-o y JL$<?> R? /9C.T0 tl. . C_ - >*v <& . ..... ' in i .ifcj>iii * arM Uf.r f*. ~ M . I'. . 2 -->| / A # *v` '"Tdfftx. \Zo<-oi*^Ni Cvn4 ' <2- Z$* *0 *,> . * *3 0 07 (Yh^ 3 *7 ^ fy>vt/ /W&H ... ^A( WU ^X-0 ^ rt '. . ' i !.,. f ; ./. 4 :'.V; 1 1: . i '1'V ; .'* ' i** ' i* 4. - J V.! ' ! . * : . V . //. MT -- 13,C. ASS.i$'' V'.' -r ;Vt* 't *-' J*;V. . : ' y J. *. ... \U i- > - v'y 'l'1. ' )'] ` f, < . ,. 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Continuous synthesis of CPC .by feeding a pre-mixed slurry at 4y C through a glass lined heat exchanger to a p-stago reactor which will too hold nfc 200*0' ujv;vl.<1 ii;; tumnurature. D, IVossurc or the unit ir, atnoc.pUo.ria except 'jl!- psi maximum across thy glass lined heat exchangc;i\ Temperature in KljvC inlot - 200*0 reactor and .150*0 product discharge. C, Sec sketch attached. liiagram.' 0. Initial syntheses {batch wise) have been completed in the 3 1 Haateiloy "C" reactor. ' XI.* 2o.uipr.cnt The equipment involved are: A.. Kactclloy "0" feed. pump with Teflon and carbon impeller. 3. Q1&&S lined heat exchanger, 1/4" nominal 02 feed pipe ancl 1/2" nominal 02 product Jacket. C. Three 1 Ilaatelloy "C11 staged reactor with 4 baffles and two turbine blades turned at 900 rpm by a compressed air turbine. * 3. Product pump - Sane as feed pump but connected to a variable speed drive to maintain constant level in the reactor. 122. Service Facilities Compressed o;ir for the reactor agitator, 1107 outlets for feed .and product pumps and the heavy duty heating Jacket on the reactor. DUP050081592 XV. Hazards A, Chemical iI . . Kerosene at 200*0 constitutes the major hazard,. B. Electrical , All electrical equipment has been grounded and have pull-out plugs lor lockout procedure. 6. Physical The glass heat exchanger (broken glass) and agitator speed (900 rpia) constitute the greatest physical hazards of the unit. V. Safeguards The ecminment is housed completely in the walk-in ventila tion hood. Adequate'exits, stairwells, etc., are provided for Lab 307. Fire extinguisher is located Immediately adjacent to the north door. VX. Protective Equipment ! A. Normal Operation 'Safety goggles and safety shoes. , B. Stand-by Equipment Safety shower located adjacent to hood. Fire extinguisher as noted in V. / i 1 {' l DUP050081593 DISTRIBUTIONtInclude) 1. Area Engr. Stuefer/V.H.Chambers. 2, Prod, or Res. Personnel J,W, Minnich/O. Grimm 3* Plant or Lab. Engineer P. L. Relg rr'T 4. S&p supv. ^ ,1, Uoody&Tl^RL'ddlsh FORM; #1094 News 2/8/06 DATE* 3AQ/69 Kl'iT'f-ACCK rrASffiE / TMJECT NO". : __ _ NEWPORT p l a n t EQUIPMENTS __Continuous CPC Synthesio *___________ -_____________ P.A. NO. ` None BLDG. NAME & NO, A-21 - Lab 307 3rd Floor The above bullding-and/er equipment haa been inspected and found acceptable with the following exceptionss ! Fabricate a plastic shield for operator protection in cape of " S-iass heat exchanger breakage. V S/l. C///P&/ : 2.' Locate operating switch for..f.e&d-.and product .pumps ..wfcalAa-Jthfi.-- ' walk.-In hood fJWM suggestion). 6/ 6 <f . -5." . ' : ' 6. ............................. . .7. 8 ... ... \ ..... : ___________ . .. . ,9.'. 10 .'ll. 12 TO BE USED ONLY WHERE MINOR OR NO CHANCES IN OPERATING PROCEDURES OR EQUIPMENT DESION ARE INVOLVED. 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