Document 6wbg0ZnkqwKe62V3M4kBp596m

8$9$E$B QP CPC By: R. C. B utton 12/69 E ,, I. DU PONT DE NEMOURS & COMPANY Pigments Department Newport Plant Serial Ho.: Copy No -: KN-69-20 A> SERIAL N O .: KM-S9-20 NEWPORT PLANT PICKENT COLOR RESEARCH REPORT DRY CHLORINATION STUDIES OF CPC Date; 12/69 RETURN TO JACKSON LABORATORY FILE ROOM DUP050081 767 KN-69-20 Numerical 2. Research Office Pile, Newark 223*41 3. Newark Library Pile, 223.^1 4. M, Hunt/E. Gonick, Pigments--Wilmington 5. W. S. Struve 6. F, F, Ehrich/E. F. Klenke/B. H. Perkine/Newark Library 7. P. J, Monahan, Newark (Vital Records) 8. R. H. Wetzel/J. P. Maurer/J, W. Minnioh/W. A. West, Newport 9. W. E. Miller, Newport 10, M. C, Cross an--Newport Pile 11, Extra 12, Extra 13* Extra 14, Extra SUBJECTS DRY CHLORINATION STUDIES OP CPC SUBMITTED BYS R, C. BUTTON APPROVED BYl J, P. MAURER DATE ISSUED; 12/69 DUP050081 768 DRY CHLORINATION STUDIES OF CPC I. SUMMARY The dry chlorination of CPC blue crude in the presence of A1C13 has been studied. A 1-liter agitated pot reactor was used with Cl2 gas fed through a dry mixture of CPC, AlClj, NaCl, and in some cases a diluent sand. Most of the runs were conducted at 300C. The amount of Aids was varied, but in all cases it was less than half than that of the eutectic melt process. Samples of the product were taken at various time intervals from as low as one hour up to IS hours. The samples were analysed first for percent purity of CPC by leaching with a mixed-solvents technique and second for organic chloride by Parr bomb fusion followed by Volhard titration. Dry rubouts were also made of the samples to give a qualitative check of the analyses. The quantitative analyses in the salt diluent runs are inconsistent and do not seem to correlate with the colors of the dry rubouts. Thus while the dry rubouts indicate a definite advantageous effect of the AlCls-NaCl, no conclusions can be drawn from the quantitative analysis. I believe the proposed process warrants further study, but only after the quantitative analysis and the dry rubouts can be Investigated and the differences explained or eliminated. II. INTRODUCTION The purpose of this research was to study a possible process for the chlorination of CPC, copper phthalocyanine (blue to green). The present Newport plant process is ,a reaction with sulfur dichloride under pressure. In a proposed expansion alternate chlorination processes are being considered, namely the eutectic melt process used, by Orchem and a dry chlorination process. It is this latter which was studied in the present research. Some work had been done with dry chlorination using fluidized beds of CPC and salt , (1. 2_, 3.)* Tempera tures were in the range 2Q0-40QC. and the process seemed promising up through the semiworks stage. At that point, however, development work was dropped and has been inactive for 20 years. DUP050081770 It was felt that the dry chlorination process should be examined using the AICI3 as a catalyst-complexing agent with possible better quality and lower temperatures than were possible in the previous work. The role of AICI3 in the present SCI2 process and.the eutectic melt process (both liquid phase reactions) has been established. The question is whether this same enhancing of chlorination will be accomplished in the proposed gas-solid chlorination at sub stantially lower concentrations of AlGlj (AlCl^CPC), Un less this process can be carried out at lower AICI3, then it probably will not be any better than the eutectic-melt pro cess. III. APPARATUS AND PROCEDURE The reactants were premilled-in two different manners-. In the early runs where large amounts of reactant were required, a ball mill with cyl pebs and roofing, nails was employed. In the later runs using only one-tenth the- reactants with sand diluent the Gharge was prepared by mortar and, pestle in a glove-bag. The chlorination was carried out in a 1-liter Pyrex resin flask with four tapered outlets in the cap. Tempera tures up to 375C. . were obtainable with a 335-watt heating mantle. A Tri-R Stir-R Model K-43 was used to drive an Inconel stirrer with helical blades, The speed was not measured but the setting was 3 on a range 0-10 for a rating 5O-IIOO rpm. This produced effective mixing in most cases except when sand was used as a diluent which settled to the bottom. This effect was advantageous as it kept the react ants up in th,e region of best agitation and higher chlorine concentration. Temperature was determined by thermocouples at two depths on the inner wall of the flask and was shown on a recorder. Chlorine was fed through copper tubing to a point above the stirrer blades but below the reactant level. The exit gases were to pass off through a NaOH solution bubbler, but instead vented around the stirring shaft seal. Most of the runs were isotnermal and controlled manually. The reactants were heated.and-agitated, and when the required temperature had been achieved, the chlorine gas was introduced and the timed run begun. Two or three times during a ran .the reaction was interrupted and cooled to take a sample. The flask was then reheated and the run restarted with introduction of chlorine. -2- DUP050081771 Three temperature levels were investigated but most of the runs were at 300C. Three levels of chlorine flow rate were used ranging from a stoichiometric rate equivalent to about 1 Cl atom per CPC molecule per hour up to about 1 Cl atom per CPC molecule per 4.4 minutes. Pour levels of AlCl3-NaCl eutectic in the reactants were used; namely CPCieutectic. ratios of 1:0, 1:0.5, 1:1, 1:2. Time did not permit a complete sequence of all variables at all levels, nor.was there an attempt to statistically design the sequence. Rather the areas were investigated on the basis of sequential decisions. The samples were analyzed first for percent purity of CPC by leaching with a mixed-solvents technique and second for organic chloride by Parr bomb fusion, fol lowed by Volhard titration. The reactants used in the experimental runs were: CPC Blue Crude (Lot #1378, 6/13/69, Newport) AICI3 (plant process chemical) NaCl (plant process chemical) A Differential Thermal Analysis technique was developed by J. E. Johnson to determine qualitatively the effect of temperature, reactant composition and gas flow rate on the rate and extent of reaction. By this means, it was hoped to screen the range of variables and thus concentrate the effort upon a narrow range, using the more involved agitated-pot reactor. The details of the DTA study are included in the appendix of this report, IV. RESULTS The yield as percentage chlorine in the CPC was shown to be a function of reaction time with parameters of chlorine flow rate, temperature and reactant composi tion. The following table shows the relationship. - 3- DUP050081772 RESULTS OP CHLORINATION RUN I n Runs 5 and 11, no A i d 3 was used b u t CPC :NaCl 1 :3 < *h N*J> K W- -V <1 * - o Ph HO a WIt H o o c m KOMno sinino-(M ont~--=r smnoo moN^r c-- vo c t \ m^r floocoocy<ooa>HSt-(MM)(o invo t- tn c m c m o o ^o !>o o o o o o c o o o 94o -a- ON ON H VO VO coco-sr^ Ov COOHCMOODs TOHOCVIOO c m -=r -=r sr isr imn h c m c o rH co cm na p>H. oo PncJ U rH P Sxo *(Xi. pOCUj3cQOJ 0) SW 'ri.U EH W COCO H O in H H OV OYf-OO CO ON VO VO CO CO CO VO On ON ON ON 0*00? 00^0*00 fc- m in ON rH CO rH VO CO rH VO O =r -a- in in in-=r vo t>- c- in invo in c m oo oo co co co coowoinocowooooooooooooooo ooooooo*oo ooo o 00*00.0 CMVOCMVOCMOO-=rOt^HCMCOHCOrH 0O-=T HCOHlAHtn x} trSo3t POr) -c<p1) Oohj raH bO tip St =r in in bO bO bO sf st st in in in 0000 O O >^=r _ -=t . St St PQ ^^ --) -- bQ bO too bD bO bO bO bO bO hO bO HP OOP Q O O O O O O O OOOO O O CM CM CM CM CM S<0 $3 CM CM CM CM CM CM kj pfolj fl> P3 oo H H PCCl PO P3 fl) Pb3O W3 HO S<BUCOk CM *O <D P 03 0 S3 OH ifHa B V 0 N0 rOH OOOO OOOO rH 1--I t--1 r--1 1111 till -- OOOO VO VO VO VO 0 0 rH 1 ,, On l --^ vo -- OH VO 0 ON CO ON ON VO -7 00------> VO -- VO H HH rH a p s O uO 4) 0 sx B 0) EH 00 0 in CM co. 00 + 0 t0 CM <0 in 0 CM 0 CM O o .O O CmO --CO ^CoO oCO ` c a P3 S5 cJnc3ooccjjooccjncdooci3onjnJP rH c m c o h t .=r nr tn in in VO VO VO >-- t~-CO OOCOPVOIOOHH rt rl HH -H DUP050081773 VI DISCUSSION OP RESULTS In the first three runs the effect of reaction temperature was Investigated at an arbitrarily selected reactant ratio and chlorine flow rate. At 200C. and lower the reaction was too slow to yield any useful information in this particular reactor. At a temperature of 375C. the reactants formed a hard cinder and jammed the agitator. For these reasons most of the runs were at 300C. In the first six runs the charge consisted of 200 g. of which 100 g. was CPC, except in Run 5 with 50 g. CPC. With this much CPC and the 60-10Occ/min, chlorine flow rate used In Runs 1-5, the maximum possible chlorination rate was approximately 1 to 2 Cl atom per CPC molecule per hour. Indeed this seems to be a maximum rate that some, but not all of the runs, approach. The analysis for percent chlorine for Run 5 is apparently in error since the.53*07% and 54.25% Cl in CPC is higher than 16 Cl atoms per molecule. Also, a blank on the unchlorinated reactants analyzed 37*6% rather than the expected 0%. This in combination with the impossibly high percent purity in Run 5 indi cates that some NaCl may not have been leached out by the mixed solvents and was assayed as CPC. Further evidence of the invalidity of the analysis of Run 5 is provided by a dry rubout of the products. While admittedly qualitative there is never theless a reasonable correlation between the color change from blue to green with a percent Cl of 0 to 47. However, in Run 5 the rubout colors look more like 10%, 20%, 30% (all +10%) rather than 43.3%, 53.07% and 54.25%. In Runs 7-11 the amount of CPC per charge was decreased to lOg and this equivalent increase in stoichio metric proportion of chorine should have reflected an equal or greater reaction rate. The analytical results, however, are generally low and inconsistent with the qualitative results of the dry rubout of the products. It appears as though the presence of the sand somehow adversely affects the quantitative analysis. -5- DUP050081774 VII. CONCLUSIONS It Is impossible to draw any conclusions regarding the effect of aluminum chloride from the analytical data. However, within the reliability of the dry rubout technique it certainly appears that dry chlori nation of CPC is markedly facilitated by the presence of AlCla-NaCl eutectic. Over the range of concentra tion studied the lower the ratio CPC:eutectic the greener the product. VIII. RECOMMENDATIONS 1, The process of dry chlorination of CPC in the presence of A1C13 should be investigated further, but only after a consistent analytical process for chlorine in CPC has been developed. -6- DUP050081775 Appendix DUP050081776 E. I. d u Po n t d e Ne mo u r s & Co mp a n y tMCOftWORATKO Wil min g t o n , De l a w a r e mm ENGINEERING DEPARTMENT August 7* 1969 R. LUTTON PIGMENTS DEPARTMENT NEWPORT PLANT ENGINEERING TEST CENTER THERMAL ANALYSIS OF CPC CHLORINATION Differential Thermal Analysis (DTA) has been used in this brief study to correlate several compositions and milling preparations with the type of exothermic chlorination indicated by DTA. No assays of the small samples (10-50 mg) were made, but green material resulted from all chlorination runs. We have concluded the following: .The method is not highly quantitative or reproducible due' to the following equipment limitations: 7;'V Lack of room in the sample tube for the standard ceramic thermocouple centering sleeve because of the chlorine feed tube. , Plugging of the chlorine feed tube. This was partially corrected by using a 1/4" tapered point instead of a blunt end. . The chlorination for all samples occurs across very broad temperature regions in the range 125-375C at a scanning rate of 20C/minute. Neither lower rates nor time-base studies were included. , Exothermic indications were observed on samples containing no sodium chloride or aluminum chloride (see Run 7, 1-2). . The ball-milled samples (T-l and T-5) appear to begin the exothermic reaction at a lower temperature than the hand- 7- ,7- ' milled samples. DUP050081777 2 August 7, 1969 R. button APPENDIX A-2 . Aluminum chloride sublimes beginning at about 40 C (see Run 12, T-7) . A small, low-temperature' (52C) endothermic indication of unknown type was observed on one DTA run at high resolution (Run 13, T-7). EXPERIMENTAL NOTES Chlorine was fed directly to the bottom of the glass capillary tube used for DTA. The metal thermal shield and glass bell jar were not used, and a 4" vent hose was mounted directly over the silver furnace block for rapid removal of the excess reactive chlorine. One result of the draft was large heat losses, so that the scanning may have decreased at the highest temperatures in spite of maximum driving voltage. * SUGGESTIONS FOR FURTHER WORK Improvements in the positioning and securing of the thermocouple and chlorine feed tube should result in greater reproducibility. Microanalysis of the products for pigment assay might be possible. One difficulty will be removal of the soluble chlorides with such smallsamples. . Isothermal time studies to show the duration of the reaction could be made. ENGINEERING SERVICE DIVISION ! Engineering Test Center J. E, Johnston JEJ:lsr Attachment DUP050081 778 APPENDIX A-3 3.1 SYSTEM DESCRIPTION The DTA system, is shown schematically in Figure 3C* S and in sample and reference respectively* The thermocouple com* mon sides are joined at B. The difference in temperature between sample and reference, AT, is indicated by the elec trical potential across the.points A-C. , Differential Temperature Signal -- -/ v r* 1 - * - . I I' l I High Gain, Low Noise I AT Preamplifier I I 1 l a -it ^ Range Control AT T (0.1 (o llTC/inl (10 to 200*C/it)) i i i --_r~-- i Recc rder i i ih< -1tx \ t * y C ij -'vV i-\i.'{*' Cell Assembly / Gas Purge ' (Plugged) <-- Coolant 'Vacuum Temperature Programmer- QController l7 Sample Temperature Signal '*.,r -V.v V *' * ' ' i. ' * ' FIGURE 3C Rate of Change (+30*CMt. to -SVCftnlnJ Starting Temperature (ContinuovtlyVkrfibli) ANALYZER SYSTEM . h ./' ... 1 v. .'i\ /-'V.I- 1. ; . 3-2 /'.v. '*.<1/.* , 'l; ;:y0^)`k^ * ''* . . . 1 ~ DUP050081779 APPENDIX A-4 o ,7: . /v :. -7. \7> SAMPLE LIST * . ' '' 7 `. *.; . , SAMPLE 77-7;: w e i g h t $> COMPOSITION. . ^pc 7 NaCl AlCli NOTES t -2 ; . 7 77.1007- . 0 77.; ; 0 . Un-milled, crude, "Lot ; ; : / 137a, 6/13/69". ;:v kerosene 1/2J& maximum ;> \ 'v7;.7 > : 25 75; A;' :7; 7.7;7. 0 77 Ball-milled, 7 hours 7^777: . ^ T-3 /* , . ; ' . ' ', T-4; y.f:' 7-7.9 7 7. 42.17 7 Ball-milled. Discarded , i '' due to CPC losses .7 ^ 7 ' found in mill ^,:--'7777 '7i 7.9 7, 742.1 Hand-milled 10 minutes, mortar and pestle v i'-'v.. '77 :fSSf 50: 7: ;7 7.9-77742.17:77T Ball-milled,- .7 hours 7^77:77'' .77C77 66.7; ;7 5.3 7 726 -7 , Hand-milled .m _ = T-7 ; '' ?** `10.57 ' 756.2; ' Hand-milled . JEJtlsr 6/6/69 ' i- ; .*/;. ' ; .* s 1 7ff\- V.'i ; vv.*' J~ 7 - '\" . * -7/ ^ ^ V> 7 ;V;7ip'./ f *'<'/ ' ` , '. \,y'S'*'.' DUP050081780 APPENDIX A-5 CPC CHLORINATION BY THERMAL ANALYSIS V i -': EQUIPMENT LIST Differential Thermal Analyzer .y \ Model 900 i; E. I. du Pont de Nemours & Co. Standard Cell . Instrument Products Division. Macro Tubes f. : Wilmington, Delaware 19898 (3 MM ID) ' . >:y : Chlorine Feed Tubes.050" OD x V y:,,;-" .043" id . - stainless steel . ` hypodermic V. tubing, : , No. 383175 Du Pont Experimental Station Stores Gas -Flowmeters; ; Brooks Sho-Rate Rotameter Tube R-2-15-AAA Sapphire float 0-77 cc/min air.., 0-43 5 cc/min chlorine . rx DUP050081781 M H tu a fx f OQVCT> blVtllOM DUP050081783 100 150 200 250 300 350 T. C (CORRECTED FORCHROMEL ALUMEL THERMOCOUPLES) DUP050081 784 DUP050081785 100 150 200 250 300 3S0 T. C (CORRECTED >OR CHROMEL ALUMEL THERMOCOUPLES) DUP050081786 SO 100 ISO 200 250 300 350 4 1 T, C (CORRECTED FOR CHROMEL ALUMFI T H F R M n m ilP I FS DUP050081787 100 111 150 1200 250 300 350 T .C (CORRECTED FOR CHROMEL ALUMEL THERMOCOUPLES) 4 DUP050081788 to o ISO 2 0 0 250 300 . 350 T, C (CORRECTED FOR CHROMEL ALUMEL THERMOCOUPLES} 400 ACKNOWLEDGEMENT The aid of Mrs. Margaret L. Greigg in the experimental program is gratefully acknowledged. LITERATURE CITED 1. Johnson, Paul R. "The Dry Chlorination of Copper Phthalocyanine in a Turbulent Bed Reactor," Progress Report JLR-59-l-#74, Jan. 13, 1947. Ser. #. 197332. Barnhart ,, G. , "Preparation of Polychloro CPC by Dry Chlorination," Progress Report JLR-59-1-G, No. 25, June 17, 1948, Ser. #19827. 3. Grimble, R.W., "Dry Chlorination of CPC in a 12" Diameter Fluid Bed Reactor," Progress-Report, JLR-59-1-G, No. 27, Nov. 4, 1949, Ser. #19999. DUP050081789