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rw E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOl STREET NEWARK, NEW JERSEY Serial No. KH-51-42 Copy No. 1. Numerical Re t u r n t o PliE ROOM ~i) l^ X ' NEWARK PLANT PIGMENT COLOR RESEARCH REPORT NEWPORT PHTHALOCYANINE PUNT ASSISTANCE Period Covered JANUARY, 1950 - JULY, 1951 \ NJ 9747 FILE: DATE: 223.4 11-2-51 Copy To? 1, Numerical Pile 2. Research Office (223*4) 3* Library File (223*4) 4* I H. Tully/A. Siegel 5. Jackson Laboratory, Orchem 6. P. D. Graham, Newport 7. V* Chalupski, S. J. H. Cooper ..9* Extra 10 e 11 12* n Serial No. KN-51-42 ' Copy No. 1. Numerical NEWPORT PLANT PIGMENT COLOR RESEARCH REPORT FINAL REPORT PHTHALQCYANINE PLANT ASSISTANCE JANUARY, 1950 - JULY, 1951 DATS SUBMITTED: 10-2-51 DATS 135 11-2-51 DUP050068775 TABLE OF CONTENTS Introduction Historical Summary and Conclusions "Monastral" Bins LB A* 4-Chlorphthalic Acid B. Synthesis C. Sulfation D. Solvent Hilling E. Extraction P. Quality Q. Yield H. Spray Drying "Monastral" Blue BO A. Production B. Quality "Monaetral* Green CPC A. Chlorination B. Reflux Condenser C. Dark Masstone D. Extraction of Crude Green S. Drying of Crude Green F. Solvent Hilling G. Extraction of Solvent Hilled Green H. Quality Process for Synthesis of "Monastral" Blue 13-Exhibit (1) Process for Sulfation of nHonastraltt Blue LB-Exhibit (2) 1 1 4 4 5 6 S B 9 10 10 11 U 11 12 12 14 14 15 17 IE 19 DUP050068776 TABLE OF CONTENTS (COKTD) Quality of "Monastral" Blue LB -Exhibit (3) Yield of "Monastral" Blue LB-Exhibit (4) Quality of "Kouaotral* Blue BO - Exhibit (5) Process for Chlorination of CPC - Exhibit (6) i Analyses of "Solids" from Reflux Condenser - Exhibit (?) Quality of "Monaatral" Breen - Exhibit (S) 20 21 22 25 27 22 DUP050068777 mmmsim This report is concerned with the work of the Chemical Division Plant Assistance Croup at the Newport "Monastral" Plant from January, 1950 to July, 1951 in standardisation and improvement of the processes for manufacture of the three phthalocyanine colors, "Monastral" Blue IB, Blue BG and Green, produced by the Pigments Department. This report represents a continuation of KN-51-39, Phthalocyanine Plant Assistance January, 1949 - January, 1950. vmmm The Newport CPC plant waa originally designed to produce two phthalocyanine pigments, "Monaatral" Fast Blue LB and "Monaatral" Green, at rates of 22,000# and 15,500#, respectively, per month in a five-day week. The basic synthetic processes were developed by Imperial Chemical Industries and the Organic Chemicals Department; but the currant Newport operations Include numerous modifications and more features resulting from work of the CPC Color Research Group at Newark. The manufacture of Blue LB at Newport la based on the reaction, in a specially refined kerosene, of phthalio anhydride, urea and copper chloride, catalysed with ammonium molybdate. A predetermined portion of the phthalio anhydride is replaced with 4-chlorphthalic acid to ?reduce a low chlorine CPC (3.$-4.5$), which is stable to crystal growth n aromatic paint thinnera* Concentrated sulfuric acid is added to the reaction slurry to sulfate the pigment and facilitate the separation of the kerosene. Following hydrolysis and a weak alkali extraction and drying, particle slse of the pigment is reduced by shot milling in aoetons to a standard strength level. The milled slurry la distilled to recover the solvent, and extracted with both weak add and alkali* The finished product is shipped to Newark as a 15# slurry for ths manu facture of toners, lakes and dispersed pastes* In the manufacture of polychlor CPC ("Monastral" Green)# the Blue synthesis is essentially the same as for Blue LB, except tnat4gchlor phthalio acid is net used in the initial condensation. The crude CPfcf is chlorinated with sulfur chloride to a chlorine content of 47 - 43.5# at elevated temperatures and pressures, following Which the crude Green is extracted, dried and shot milled in acetone* Provisions were not included in the original plant design for the production of "Monaatral" Blue BG, which la solvent milled chlorinefree CPC* It was first produced at Newport in March, 1949, using Blue IB equipment with no revisions* The omission of ohlorphthalie sold in the synthesis of Blue BG is the only major difference of operating technique between LB and BG* A. !,onaatra.l!,.^ljie,LB Attempts to use 4-chlorphthalic acid slurry, instead of presscake, were unsuccessful. The texture of BT-2&4-B end BT-304-D made from CPC synthesised with 4-CPA slurry was inferior to that made from DUP050068778 -2- 4-CPA presscake. Several trials of a revised 4 CPA process, developed by Jackson laboratory, were wade in 1950, the justification for the study was the elimination of chlorine fumes during the filtration operation, final evaluation showed that the revised (Remington) process gave satisfactory tinctorial properties although slightly weak; however, the fume condition in the operating area had been improved sufficiently by mechanical means to diminish interest in the Remington process. Slue LB was synthesised at an average rate of 53 syntheses per month. In only two esses was there any difficulty with oxidation of the kerosene in the CPC synthesis. This condition was improved con siderably, as compared to 1949. through the use of an anti-oxidant and a control test for oxidation of the kerosene on each batch. The oxidised kerosene was recovered by washing with concentrated sulfuric add to remove peroxides* A significant loss of production Was Incurred by excessive pumping cyclee of the synthesis slurries, which were more granular when synthesis temperatures exceeded the specifications (195 + 5*C). Although the automatic temperature controls wars inadequate, the diffi culty was eliminated by an extensive training program and more careful manual temperature control. The major process improvement in the manufacture of Blue IB was the adoption of the "Kerosene Flotation" (KP) Process in January, 1951# which completely eliminated the formation of pasty CPC that formerly occurred in the basket filtration procedure and reduced the sulfation cycle considerably to bring it In line with the synthesis cycle. The "Acid Flushing" (AF) Process, which was designed to give a kerosene-free presscake, was evaluated in the plant because no drying equipment was available after the dryer explosion, March 5* 1951. The "AF" trials were not encouraging, since the available plant equipment presented eevere limitations. Adaptation of the "AF" process to the plant would necessitate e siaeable capital investment, which cannot be justified. The seventh plant mill, which was installed in June, 1950, was responsible for a 25$ increase in Blue LB production. An increase in the acetone/CPC ratio for solvent milling from S.7/1 to 10/1 gave some indications of a slight strength improvement. The final alkaline extraction of Blue LB was eliminated from the process in September, 1950 after several extended plant trials had shown no quality deterioration. The quality of Newport's production of "Monastral" Blue IB was satisfactory with the exception of a 1-4$ average strength deficiency during the first six months of 1951* DUP050068779 -3- B- TEwfogtSfl"..Blue,.BO Three separate campaigns of Blue BO were made Between January, 1950 and July, 1951. "here were no quality deficiencies, except an average k% weakness in the first campaign in July, 1950. The third campaign in April, 1951, which represented the first use of If sulfated crude in 10 production, was from a quality standpoint the most success* ftt1 of any Blue BO produced at Newport to date. in During design and Installation of funs disposal facilities/the first half of 1950, the Green unit waa operated only experimentally. In August, 1950, regular production was resumed. A significant process improvement was made in April, 1951* when the catalyst, antimony oxide, wee replaced with anhydrous aluminum chloride. The violent exothermic reaction, which occurred between antimony oxide and sulfur chloride, was thus eliminated. In addition, the accumulation of solid material in the reflux condenser, was minimised. Interest In a green toner of jet masstone prompted plant trials involving the use of aluminum chloride in large excess. In the laboratory, it had been demonstrated that such a modification in the chlorination Increased the jetness of masstone; however, the plant tests failed to confirm the laboratory findings. In the extraction of crude Green; Triton X-101 (ex Rohm h Baas), a non-ionic surfactant, was used in place of Turkey Red Oil after January, 1950. A slight tinctorial improvement and a pronounced de creese in foaming resulted. An increase in drying temperature of crude Oreen from 100*0 to 125*0 was made in February, 1951 resulting in approximately a 20$ reduction in cycle with no deterioration of quality. In December, 1950, sodium chromate, whloh was used in the solvent milling operation, to prevent reduction of the Oreen CPC, was raplaesd with sodium nitrite. The latter has the advantage of not forming water insoluble reduction products not easily removed in sub sequent extractions. The average quality of Green CFG throughout the period covered by this report was on the defensive versus standard in intensity; however, the hue and strength were satisfactory, with the exception of a faw weak batches in 1950. A major portion of the efforts of the Plant Assistance Croup was directed toward elimination of dullness. Float of the process modifications discussed in this report were designed to improve the Intensity of Green GPG* DUP050068780 4 zwmmmijmM a. With the exception of two process variations, standard operating procedure was used throughout the period covered bp this report for manufacture of 4-chlorphthalic acid* Baaed on encouraging results in the Newark Semi-Works trials of 4-chlorphthallc slurry in place of preasceke, a series of plant syntheses was started* It was found that additional power was required for ths synthesis kettle agitator using slurry as compared to 4-CrA presscake. Zt was necessary to roplaos ths 10 H.P. agitator motor with a 15 H.P. motor. A second operating difficulty developed during dis charging of the kettle, the CPC synthesised from 4-CPA slurry was exceptionally granular,and the pigment slurry could not be pumped easily, this difficulty was believed to result from the presence of an increased quantity of sodium chloride, since the 4-CPA had not been filtered. Evaluation of the plant trial lots showed that Blue IM syn thesised from 4-CPA Blurry was inferior in texture when converted to BT-284-D and BT-304-D, and was weak as BL-2B8-D. Consequently, further study of 4-CPA slurry was abandoned. ths other process variation was a modification of ths chlori nation procedure developed in the Organic Chemicals Department by W. R. Remington. Interest in this process at Newport resulted from the need to eliminate s very undesirable fume situation in ths 4-CPA area. Incidental advantages of ths modification wars reduction in sodium chloride and chlorine consumptions and a significant increase in filter press capacity. The Remington process differs primarily from the standard hypochlorite chlorination process in that the disodium phbhalate solution is chlorinated at 50-60*C. with no exeess of sodium hydroxide. One plant trial of the Remington 4-chlorphthalic acid process was mads la October, 1950. No serious operating difficulties were:. encountered, with the exception of considerable trouble in pumping the chlorinated slurry to the filter press* However, it wee later established that incomplete solution of the phthallo anhydride wad responsible and the difficulty could have been avoided by more gradual addition of the phthalio to insure complete solution* the analysis of the first plant batch of Remington 4-CPA was as follows compered to a standard 4-CPA batch* * ! w Solids Total Chlorine Inorganic Chlorine Organic Chlorine 4-CPA (calc.) Had (ealo.) Free phthallc acid (calc.) DUP050068781 5- Laboratory grinds of Blue LB synthesised from the Remington 4-CPA were 3-5# weak, greed and intense versus controls* Ihen solvent allied in the plant* the LB/CPC using Remington 4-CPA was 102*100 and ws green versus standard BT-304-D. The chlorine content was 4.12JI* which is only slightly lower than average production. The product* when evaluated as ST-304-0 and BT-2S4-D in alkyd, was found to be nonreactive and equal in flocculation behavior and can stability to the BT-304-0 and BT-2B4-0 standards. Ink mill evaluation showed the prodnets to be equal to their standards in separation. Kegaan texture waa essentially equal in the case of BT-2B4-D, but inferior to standard at IT pass in BT-304-D, very slightly inferior at 3T and oqual at 5T. Two additional batehea of Remington 4-chlorphthalic acid were wade in March* 1951 and advent willed in the plant as three lots. The quality as compared to etandard BT-304-0 waa as follows* B 623 - 152 104*100 vs green ve intense 153 101*100 * 154 102*100 * The quality of Blue LB synthesised from Remington 4-CPA appears to be essentially equal to that of normal production* based on the three lots produced in the plant. Since the original justification for study of the Remington process, elimination of fumes,has besn satisfactorily corrected by mechanical meant (increased ventilation and air-blowing of the filter press)* it was decided to abandon any further plant study. & Blue CPC was synthesised at an average rate of 53 syntheses per month ranging from a low of 34 to a high of 6S for the period Covered by this report. The major reasons for low production in certain months were mechanical items* such as water in the kerosene through faulty decanter operation* failure of kerosene heating task coils, plugged urea lines* Dowtherm difficulties, repairs to glass lining and shutdowns to remove tools which wars accidentally dropped into the synthesis kettle. The Sewport Plant Process for the synthesis of "Hoaaetral" Blue LB as of June, 1951 is described in Exhibit (1). Several other causes of production delays* which pertain to the process rather than the equipment will be discussed in this report. Boring tho period, January, 1950 through June, 1951* evidence of kerosene oxidation was recerdsd twice. A sample of kerosene is analysed prior to each synthesis and* if there is any evidence of oxidation as determined by peroxide number* the kerosene is not used. DUP050068782 6 In both cases in which oxidation had apparently occurred, the kerosene was washed with concentrated sulfuric acid to remove peroxides prior to use. In neither case was the cause of oxidation determined; however, it way be significant that kerosene stocks were low, necessitating couplets discharge of storage tanks which contain relatively email quantities of an unidentified sludge and water* ft will he remembered that kerosene oxidation occurred quite frequently during the first two years of CPC operation at Hewport. Although the exact mechanism la not understood, it is well established that CFG formation is retarded by peroxide in the kerosene. The use of an anti-oxidant, Paranox 441 ex Ssso, which was started in 1949# has largely eliminated the difficulty, host of production was sustained in March, 1950 by a plant trial of IB syntheses using 4-chlorphthalic acid slurry in place of Kssseake (see Discussion under "Xonastral" Blue LB, Section "A"). A ee of approximately four houre per synthesis was incurred, since it wee necessary to vaporise large quantities of water from the 4-CPA slurry prior to addition of the other ingredients. In addition, signi ficant delays were encountered discharging the synthesis slurry from the resetion kettle. The pumping difficulties were attributable to the unusually granular character ' ^ of the pigment slurry, which was believed to be caused by larger than normal quantities of sodium Chloride remaining in the unfiltered 4-CPA slurry* Throughout the period covered by this report until April, 1951, a significant production loss was recorded practically every month beoauee of excessive pumping cycles resulting from the granular character of the CPC* It was found that batches synthesised at temperatures above specifications <195 5*C,), frequently led to discharge difficulties, while those within specifications caused no trouble* The automatic controls, which regulate the temperature, aim inadequate and require additional manual control by the operator* After a rather extensive operator training program and several minor modifications to the Dowtherm heating system, the temperature control problem was solved by April, 1951* C* Sulfation Sulfation of both "Moaastral* Blue LB and chlorine-free CPC was continued through 1950 with no significant process changes* The filtration "basket", screened with "Teflon", was used with moderate success; however, as the demands for additional production increased, it became apparent that a drastic process or equipment change was needed* During the latter part of 1950, the number of batches which could not be hydrolysed properly had been reduced to am average of about three per month; nevertheless, production losses due to manual removal of unhydrolysed presscake or "pelletised9 fPC were prohibitive. The best average cycle using the "basket" was approximately 14 hours. DUP050068783 In the fourth quarter of 1950, the Newark CPC Research Group developed the "Kerosene Flotation" process (KF) and. on January 4, 1951, the first plant trial was made at the Newport CPC plant. The "KF" process, which is described in Exhibit (2 J. differs from the "basket" filtration process in that the CPC synthesis slurry of kerosene is sulfated with 9$% sulfuric acid (1600# 96% sulfuric acid per LB synthesis of 1071# phthalic anhydride) and the kerosene ia then "floated" to the surface by addins water immediately without agitation. Follow* lng decantation of the kerosene, ice, sodium hydroxide solution (50) and additional water are added to effect hydrolysis of the CPC, The slurry is thsn adjusted to a pH of 9.0-10.0 with sodium hydroxide solution and extracted by the standard procedure. The first plant trial of the "KF" process was entirely satisfactory, with ths exception of some mechanical difficulty with the stews eductor used for kerosene decantation. After several minor revisions to the kerosene decanting equipment, the "KF" process was used the remainder of January, 1951 for the sulfation of 4$ batches, which represented the highest production rate yet achieved in the plant. In tha first week of February, 1951, there was some difficulty with the "KF" process resulting in formation of pallets, which could not be discharged from the sulfation tank. One process modification, addition Of 3000# of ice instead of 1500# prior to hydrolysis, corrected the difficulty with pellets. From February 6, 1951 through June, 1951, the plant experienced no difficulty with the process. The overall "KFr cycle was significantly less than the "basket" sulfation cycle and slightly Isss than ths synthesis cycle; and, for the first time in the Newport plant, production of crude CPO was not restricted by the sulfation operation. As a result of the CPC dryer explosion March 5, 1951, it was decided to evaluate another sulfation procedure modification, "Acid- Flushing" process (AF), since smaller scale evaluetlons at Newark indicated that relatively kerosene-free crudes could be obtained. Obviously, since no equipment was available for drying CPC, ths "AF" process appeared attractive, although complete quality evaluation was not available. Briefly, the "AF" process consists of dissolving the CPC synthesis slurry in 9$$ sulfuric acid (7 parts acid par part CPC) and drowning the solution In water. The plant trial of the "AF" process was unsatisfactory, because Severe equipment limitations and several operating difficulties pre vented a thorough evaluation. Based on the results <f the trial, it was Concluded that a major expenditure would be required for adaptation of the Newport plant to Acid Flushing. In the meantime, the facilities at Newark were modified to permit drying Newport crude CPC, and the need for complete kerosene removal prior to drying no longer existed. For this reason and subsequent evidence that add flushed CPC showed reactivity and flocculation in alkyd enamels in several instances, study of the "AF" process was abandoned. DUP050068784 -8- d. The particle sise reduction operation, shot milling in acetone, was continued throughout 1950 and the first four months in 1951 with no changes in procedure. The milling rate, 362# per 21 hours, is equal to 102.5% of the project design capacity. The seventh plant mill, which was installed June 29, 1950 increased Blue CPC production by 25% (five mills used for Blue and two for Qreen CPC) Ho difficulties were associated with the start-up of the seventh mill. in May, 1951, the acetone/CPC ratio was increased 15% from 8.7/1 to 10/1 as a result of milling studies at the Hswsrk Semi-Works, which indicated that the new ratio would improve the rate of milling. The study was continued for three weeks in the plant and, at first, there appeared to be a slight strength advantage (1-2%), although con siderably less-than that realised in the Semi-Works. The average of the entire three week study did not show any marked advantage) however, it is planned to repeat the evaluation. A second variable study, omission of dilutions, was also made in May, 1951 for a one week period, normally, 50% of the total acetone used for milling is charged initially, 20% after one hour and 30% after sin hours. Based on interpretation of power curves, it appeared that a higher average power and perhaps an improvement in milling would result if all the acetone were charged initially, Unfortunately, moat of the study was invalidated by an operating error, mining of Blue IB and Blue however, in the remainder, there appeared to be a 2-3% strength deficiency, instead of an improvement, even though the power required for milling was higher. * &&&c&ign The extraction procedure for Blue IB. subsequent to solvent milling, on January 1, 1950 consisted of a 2% sulfuric add extraction followed by a 3% ammonium hydroxide extraction. Ho changes wars made for the period covered by this report. In February, 1950, a study of amission of the alkaline extraction was initiated. This variable was evaluated simply by comparing quality of plant samples of non-alkalims extracted Blue LB with the final plant product A number of such evaluations khowsd no apparent quality deterioration associated with omission of alkaline extraction. The first plant evaluation of omission of the alkaline extraction was made in March, 1950. Ths evaluation of six lots of Blue LB in various formulations was as follows! 1. BP-173-B# BT-284-B and BT-304-D products were fully equal in ink mill behavior and Hegman texture to bheir controls* DUP050068785 -9- 2. BT-234-D and BL-262-D products vara fully equal to their controls in color and flocculation tested In alkyd. 3. BL-266-D products were very slightly on the defensive strengthwise versus standard by actual linoleum tests* As a result of the satisfactory evaluation of the above six lots* an additional 12,000# of Blue LB was made in Hay, 1951 without an alkaline extraction* The quality was entirely satisfactory in all Newark codes tested, with the exception of one lot of BT-2B4-D, which was inferior in texture to suitable controls* Additional production of Blue LB without an alkaline extraction was made in July, 1950 for a mors complete evaluation as BT**284-D. The average results of six lots of BT-2B4-D were as follows* fiubout evaluation - 1-555 weak va atd* Ink - 355 weak on the 5T passes vs. std. Vinyl - 555 weak vs. std. Alkyd - trace weak vs. std* In view of these results and the potential savings realisable from omission of the alkaline extraction, a two-month plant trial was started September 29, 1950 to provide data for a statistical evaluation. The reeults of the two^month trial of elimination of the alkaline extraction showed no significant quality degradation; hence, omission of the alkaline extraction was incorporated into the standard manu facturing procedure. F, Quality The quality of Newport Blue LB production is shown as Exhibit (3) averaged by months. The quality was satisfactory for the period covered by this report with the exception of 1*4$ average weakness compared to standard BT-304-D in the period, January, 1951 through June, 1951. From January, 1950 to February, 1951, 524 lots of Blue IB were produced without a tingle lot outside the strength specification, which is 555 of BT-304-D. In February, 1951. several lots, which wars 6f5 weaker than BT-304-D, were produced from the first plant crudes using the "Kerosene Flotation* sulfation procedure. Aleo, in February, 1951, several lots, which were 6-10% weak versus BT-304-D, were found to contain an appreciable quantity of beta phase CPC, probably indicating contamination with chlorine-free CPQ (Blue BO). In Hay. 1951, substandard production amounted to six lots, which wars 6-9$ weaker than BT-304-D. The exoeesive weakness was found to.be attributable, to ineffective press washing after the acid extraction, d j** corrected by more frequent inspection and replacsmsnt of plates DUP050068786 10 An extensive study of Sine 23 strength was initiated in June, 1951* There are indications that plant solvent silling in the present cycle of 21 hoars gives a product which averages 100:100 versus standard BT-304-D, when finished in the laboratory* Therefore, attention has bssn directed to improving the efficiency of the plant finishing to approximate that realisable in the laboratory. Two lots, which were finished on the aold side (pH *3.1 and 3.7) Instead of a minimum pH of 7*0, were 3% stronger by rubout than normal production, fending evalu ation of these lots as BT-304-D, additional study is planned. s. um The "Monastral" Blue LB yield for January. 1950 through June, 1951 ranged from 74.4* to Si.3* and averaged 77.5* as shown in Exhibit (4). All yields arm expressed as percentage of theoretical, calculated on a phthalic anhydride basis. Two process changes, which are believed to have improved yields, were made in 1950. As a result of data developed in the Newark Laboratory and Semi-Works, the quantity of oopper chloride dihydrate used in the synthesis of CPO was increased in May, 1950 from 9* to 103 of the theoretical requirement. The average yield increase for the subsequent thirteen months was 1.5* as compared to the previous four months. It is believed that the major portion of this increase is attributable to the increased quantity of copper chloride dihydrate. The second process change, regulation of the synthesis tempera ture within specifications, may be responsible for a portion of the Sold increase. According to information from the Organic Chemicals partmsnt, yield increases of 3-5* vers obtained by synthesising CPO btlow 195C as compared to 200-210*0. During the latter pert of 1950 and the first part of 1951# the number of syntheses at temperatures above 200*0 was gradually reduced until April, 1951, when excessive temperatures were eliminated (explained under "Monaatral" Blue 13, Section "B"). H. gmZ-S2lM In May, 1950, several experimental spray drying tests of crude Blue CPC were conducted at the Experimental Station in cooperation with the Engineering Service Division. Dsing an inlet temperature of 450*F and an outlet temperature of 200*F, the crude was dried success fully to a very fins powder of kerosene content ranging from 0.5% to 2.0*. Quality evaluation in the laboratory showed that the spray dried CPO isis at least equal to Suitable controls raids from pen-dried CPC. After the dryer explosion in March, 1951, interest was revived in spray drying both on a custom basis and as a replacement for the damaged plant dryers. Several spray drpng companies were contacted and drying was actually started at Spray Drying Service, Inc., Qarwood, N.J., but had to be discontinued since their equipment was inadequate for proper duet control. DUP050068787 Arrangements were made at the Experimental Station in April, 1951 to spray dry sufficient crude Blue IB for two plant mill charges (about 1000#). Again, due to inadequate dust recovery equipment, it was necessary to stop drying after only 270# was processed* Consequently the spray dried product was evaluated in the Newark Semi-Works, instead of the Newport Plant* The conclusions drawn from the evaluation were as follows: 1* Spray dried crude returns a slightly more intense product than tray-dried CPC. 2* Spray dried crude presents the possibility of an increase in mill loading. 3 Solvent milled spray dried crude at the standard loading shows no evidence of a mors rapid rate of strength de velopment than tray-dried crude 4. The apparent advantages of spray dried OPC do not con stitute sufficient justification for installation of a spray dryer as compared to P. & S. tray dryers* A. rS^ucy.on A total of 34,045# of Blue BO was produced in three campaigns in ths period covered by this report* The first Blue BO campaign in July 1950, 9**6#, was milled at a production rate 17m higher than previous campaigns as a result of a decrease in mill cycle from 36 to 30 hours* The next Blue BG campaign in October, 1950, which totalled 12,699#, was solvent milled in a 30 hour cycle: but the mill loading was increased 5% from 330# to 345# per charge. the third campaign, 11,45*#, was solvent milled in April, 1951 at the ahme production rate as the previous campaign* B Quality The quality of the July, 1950 Blue BG campaign averaged 104:100 and vs green compared to BT-297-D, 8W 373 and showed no indication of Blue LB contamination* Laboratory extraction of a number of plant mill samples resulted in an average quality of 99:100, vs green and s intense Two batches, H 657-75 and *0, which were 105:100 versus standard BT-297-D, Sw 373 as shown in Exhibit (5), were each improved to lOOilOO by additional laboratory washing, indicating that inadequate or ineffi cient plant washing was responsible for the plant weakness. Tbs Blue BG campaign in October, 1950 averaged 102:100, vs grape and wi intense versus BT-297-D, SW 373* This campaign showed the least contamination from Blue LB of any to date. The quantity of copper DUP050068788 n chloride dihydrate used lu the synthesis was increased to llOJt of theory as a result of laboratory studies, which indicated a significant yield increase* The actual plant yield for subject campaign improved k% on a phthalic anhydride basis* In April, 1951, the Slue BO campaign averaged 101:100, wa green and vs Intense versus standard BT-297-D, SW 373 and was considered the best BQ campaign produced at Newport from both quality and production standpoints. This campaign represents the first use of crude CPC sulfatsd by the "Kerosene Flotation" procedure for Blue BO. In-process sampling of a large number of batches showed that the final alkaline extraction of Blue BO does not improve quality* It is planned to eliminate the alkaline extraction following advent milling in subsequent Blue BQ production. A, agarjjBag^ioa The chlorination unit was operated on an experimental basis only from January, 1950 through July, 1950 while awaiting design and installation of adequate fume disposal facilities* Twenty chlorlnations were made in this period when the prevailing wind was away from the adjacent communities. After the fume scrubbing towers were installed in August, 1950, normal production of CPC Green was resumed* Between August, 1950 and July. 1951, an average of forty chlorinations per month was produced, ranging from a low Of twenty-one in August, 1950 to high of fifty-seven in May, 1951* Probably the most important process improvement that was developed in the period covered by this report was the substitution of anhydrous aluminum chloride for antimony oxide as the catalyst In the chlorination step* A rather violent exothermic reaction between anti mony oxide and sulfur chloride had been a constant source of difficulty, resulting in an accumulation of solid material in the reflux condenser and an occasional rupture of the autoclave safety disc* It was found by laboratory chlorinations that a polychloro CPC could be produced with aluminum chloride tinctorially equivalent to that with antimony oxide* After April, 1950, anhydrous aluminum chloride was used as the catalyst in the standard processor v There was no evidence of a reaction of sulfur chloride with aluminum chloride in the laboratory chlorinations; however, in the plant, occasionally a temperature rise occurred, which would at times reach 40-50*0. The literature reports complex compound formation of sulfur chloride with aluminum chloride* In the plant, it was possible to correlate dullness of the final product With a temperature rise in the autoclave, presumably resulting from a reaction between the sulfur chloride and aluminum chloride* The frequency of the temperature rises was reduced considerably by a modification of the method of addition of DUP050068789 - 13 - of ingredients* The aluminum chloride was "sandwiched" between the crude CPC Blue end the agitator rotated one complete turn prior to addition of sulfur chloride. In June* 1951 a second revision in the method of adding ingredients was responsible for complete elimination of such temperature rises. The entire quantity of sulfur chloride was charged to the autoclave,to which had been previously added crude CPC Blue and anhydrous copper chloride, the anhydrous aluminum chloride was then '"drowned" rapidly without agitation into the sulfur chloride with no detectable reaction* In March, 1950, two chlorinations were mad# with antimony tri chloride in place of antimony oxide as the catalyst. As a precaution against possible reaction violence, the batch slses were reduced to 25$ and 50$ of normal. The reflux condenser wae cleaned before the two chlorinations and inspected afterwards* Only one tube was found clogged, although a alsoablo quantity of solids was found at the vapor entrance to the condenser. By laboratory milling, both products wore strong, intense and equal in hue versus GT-674-D, lot 430. The use of anhydrous copper chloride in the chlorination was started in January, 1950 in the Newport Plant. It was demonstrated in the laboratory that the presence of copper chloride provided insurance against the possible bad effects of inorganic iron contamination, and appeared to offer a substantial tinctorial improvement over controls. Several plant experiments were made using 10 and 20$ anhydrous copper chloride on CPC Blue basis. Both quantities appeared to enhance quality significantly; however, there was no advantage in the larger quantity. The use of 10% anhydrous copper chloride On the pigment basis was adopted as standard practice. Three chlorinations were made in January, 1951 using crude Blue CPC, which had received an acid extraction in addition to tho usual alkaline extraction. Solvent milling of these, both in tho plant and laboratory, showed no tinctorial advantages for tho batches which received both extractions. Anhydrous aluminum chloride, transferred from Bdge Moor (ox Ohio Apox), was used successfully in August, 1950 in place of the more expensive and less readily available anhydrous aluminum chloride (pulverised) from the ffalllnckrodt Chemical Company. Tho use of the Ohio Apex product was continued as standard practice with substantial savings. In December, 1950, a slight leak around the main flange of the autoclave.body was observed. An Inspection of the joint revealed serious corrosion (about 70 pits) of the nickel-clad flange. The surface was refaeed with nickel and operated satisfactorily. In June, 1951# it was necessary to rewold several small pits during a scheduled shutdown. A series of chlorinations, produced in January, 1951, resulted in very dull products. The dullness was found to bo attributable to rechlorinatioh of CPC, which had been .recycled with the sulfur chloride DUP050068790 - 14 - a* ths result of the vapor outlet line being removed from the rotating dryer. Analyses of the sulfur chloride in the system showed a pigment content of 2-4#. After distillation of the contaminated sulfur chloride to effect removal of the pigment, Polychloro CPC of satisfactory quality was produced. A 10# batch site increase was tried experimentally in October 1950 for four chlorinations, Cl 239 to 242, inclusive. Tinctorial evaluation showed no detectable quality deterioration compared to suitable controls. An additional series of twenty chlorinations with the 10# increase confirmed the preliminary taste. On 11/9/50, tbs increased batch slse was adopted as standard practice. In December, 1950, six chlorinations with a second 10# increase in batch sis# ware mads successfully;) but the quality evaluation was completely invalidated by the introduction of other variables in subsequent operations. The Newport plant process for the chlorination of CPO as of Juno, 1951 is shown as Exhibit (6). B ftefl^.,CpadSPje|: The Andale condenser, which is used for refluxing sulfur chloride during the chlorination, contains sixty-one 5/3* nickel tubes. In ths sarly work when antimony oxide was used as the catalyst, flow was fre quently etopped in the condenser by the accumulation of solids. After replacement of antimony oxide with aluminum chloride, some blockage of the condenser occurred, but to a much lesser extent. The frequency of tube blockage and anelyeea of the *solids* removed from the Andale condenser are shown as Exhibit (7). When anhydrous aluminum chloride was substituted for antimony oxide (starting with chlorination #01-169), the amount of tube blockage was significantly less, the unusually ssvsre stoppage after chlorination #01 561 (57 tubes) is believed to be caused by pressure surges that occurred in this period rather than gradual accumulation* As shown in the table of "Analyses'', Exhibit (7), the nickel content increased significantly. This is probably caused by the presence of hydrochloric acid, which la a product of hydrolysis of sulfur chloride and also a by-product of the chlorination of CPO. The aluminum content ranged from 0*33# to 2.0#, in contrast to antimony which had been as high as 12.5#* It is interesting to note that the antimony content was 10.3, 1.99 and 1.13# respectively, on the three analyses after its usage wae stopped. It is believed that residual antimony in the sulfur chloride, which is recycled, is responsible. Inspection and cleaning of the reflux condenser requires about eight hours. It is planned to clean the condenser in the future after every 100 chlorinations. C. Maesfrone Ths majority of Newport production the first seven months of DUP050068791 15 - 1950 was solvent allied from Orchem*s eutectic crude Green. The outset one of solvent milled eutectio Green Is considerably darker than that produced by the sulfur chloride process* The need for a darker aasstone Green became apparent when the trade experienced difficulty In matching certain standards with the lighter aasstone Green supplied in the latter part of 1950. In the laboratory. It was demonstrated that a dark aasstone could be produced if aluminum chloride in excess of catalytic amounts were used in the chlorination* Tiro chlorinetIons, 01 503 and 504* were made in the plant 4/16/51 and 4/17/51* respectively, using 25% aluminum chloride on a CPC basia. For ease unexplained reason, the yields were unusually low on both chlorinatione as well as the control chlorinatione, Cl 505 and 506; however, sufficient crude was obtained for single mill charges. When evaluated at Hewark, the maeetone was slightly darker than that of the controls, but considerably lighter than that of the goal standard GT-674-D, lot 430. which is solvent milled 5 eutectic Green, fa view of the yield deficiencies, two chlorinatione with 25% aluminum chloride were scheduled 5/5/51. Curing addition of the sulfur chloride to the autoclave containing the CFO Blue and ashy* drous aluminum chloride, which had been partially dispersed by one rotation of the agitator, the pressure rose to 130 pal and the temperature to 112*0. The batch was very dull by both laboratory and plant processing, in conformity with past experience. In view of the apparent "violence" of this technique, the second scheduled chlorination was cancelled. On 5/15/51, two chlorinatione, 01 559 and 560, were made with 50% aluminum chloride on a CFO basis using ths modified procedure of charging the aluminum chloride to the sulfur chloride, which had bean used successfully with no reaction with the normal quantity of aluminum chloride (6%). There were no operating difficulties associated with these chlorinatione, with the exception of the liberation of an exces sive quantity of hydrogen chloride fumes that could not bs handled during the water extraction. The evaluation of 01 559 and 560, after solvent milling, as GT-674-D In lacquer, unfortunately, did not give a dark masstone compared to standard GT-674-D, lot 430, although it was slightly darker than the controls. The inability of the plant to match laboratory performance could not be explained and the dark masstone problem was referred to the laboratory for further study. The only significant modification in the extraction procedure in the period covered by this report was the substitution of Triton X-101 (alkyl phenol polyglycol ether ex Rohm and Baas)* a non-ionic surface active agent, for Turkey Red Oil. In concentrations of 0.5% on a CFG weight basis, Triton X-101 gave a more intense and yellow poly* chloro CPC than TRO in the laboratory. Xn January, 1950, Triton X-101 was evaluated in the extraction of Green crude and found to be essentially equal, if not slightly better, from a quality standpoint In addition, the foaming tendencies of the slurry were much lees pronounced than with TRO. Consequently, the use of Triton X-101 was adopted as standard practice * DUP050068792 - 16 - E. The drying temperature of crude Green was raiaed experimentally from 100* C to 125C for four batfhe a, Cl 407-410 inclusive, in February, 1951. Since there was no deleterious effect on quality, a drying temperature of 125*0 for 4$ hours Wae adopted as standard practice for the CPC plant dryer #4* After the dryer explosion in March, it became necessary to uee the Ti-Tint dryer at Newport for Green crude. It was found that an endpoint of 1.0% moisture could be obtained in 24 hours as compared to 4* hours in #4 dryer even though the 71-Tint dryer temperature was only 104*0. The more rapid drying was believed to be attributable to better air circulation. In June, 1951, the air circulation of #4 dryer wae improved to the point where crude Green containing 1% or less moisture could be obtained in 40-44 hours at 125*0. A maximum of 4o hours was required to maintain the desired production rate. F. 3olym.J,iiMM The standard milling conditions for Green at the beginning of 1950 were: ,400 # crude pigment 40 f trisodium phosphate 40 # sodium chromate 3o0 gals, acetone (minimum purity-90.5%) Mill 24 hours These conditions were used throughout the year until in December 1950, the sodium chromate Was replaced with an equivalent quantity of sodium nitrite. The replacement was made as a result of a laboratory study, which showed that sodium nitrite prevented reduction of the pigment as well as sodium chromate and, in addition, did not present the possibility of forming water insoluble compounds that could not be readily removed In subsequent extractions. During the first nine months of 1950, most of the crude Green vent milled at Newport was purchased from Orchem as shown in Exhibit a G. Extraction_of. goivent MliadJjgS The only process changes in the final alkaline and acid extractions Were emission of the sodium chromate in the acid extraction and elimi nation of heels. The omission of sodium chromate was tried experimentally as a result of an extensive laboratory and Semi-Works investigation at Newark and appeared to give a slight tinctorial improvement . In December 1950, the omission of sodium chromate in the acid extraction was adopted as standard practice. DUP050068793  17 - Also, in December, 1950, process "heels" were eliminated in the alkaline and acid extractions by a more accurate determination of the number of frames required for filtration and actual "washing" of the residual contents of a tank into the press* The change, which was prompted by the idea that extended extractions of a portion of each lot may be harmful to quality, appeared to result in a very slight improve ment in tinctorial properties, as judged from a statistical average of quality. H. Quality As shown in Exhibit (8), the tinctorial properties of Green varied considerably throughout the period covered by this report * the quality evaluation of the major portion of Green production during the first eight months of 1950, which was solvent milled eutectic Green purchased from Qrchem, is not included in the attached quality summary. The strength of Green production averaged 103:100 versus goal standard GT-674-D, lot 430 from January through December, 1950, but improved to 100:100 versus standard for January through June, 1951* This improvement appears to be attributable to the elimination of sodium chromate in the solvent milling and add extraction steps, as well aa Improvement in filtration and washing techniques of the two extractions. The hue of Green production for the period covered by this report averaged slightly on the blue side of QT-674-D, lot 430* Of a total of 210 lots, 164 were within the vs blue - ve yellow specifi cations, twenty-four were s blue, nineteen were blue and three were s yellow. The intensity of Green production varied widely from dull to intense versus standard GT-674-D, lot 430; however, the majority of production was on the dull side. Of the 210 lota, 112 ranged from a dull to s intense, ninety-four were dull and four were intense versus standard. In the early part of April* 1951* a new standard for Newport* GT-674-D, SW 2609, which was made at Newark from Newport synthesised Green, replaced the previous standard 0T-674-D, lot 430, which was made from aolvent milled eutectic Green. The major difference between the two standards was masstons, the maastone of 0T-674-D, SW 2609 being light vs GT-674-D, lot 430. The most serious tinctorial problem in 1950 was the inability of the plant to obtain consistantly CPC Green of satisfactory intensity. Most of the plant experiments and changes in standard operating pro cedures discussed in the other sections of this report under "Ibnastral" Green were designed toward improvement in Intensity. DUP050068794 18 - EXHIBIT (1) NEWPORT PLANT PROCESS FOR SYNTHESIS OF "MONASTRAL" BLUE LB _______ _____________Mjaurnb..a.................................. ..................... To the glass lined 1500 gallon reactor add; 7800 lbs. (1200 gala*} of "Deo Base" or Bayol D* Kerosene. Start agitator. 3 lbs* Paranox 441 (name recently changed to WS 1936 concentrate) (Note 1). Sample kerosene and determine peroxide number. If any measurable oxidation exists* do not use. (Note 2). Close manhole and heat to 110*C with Dowtherm. One batch chlorphthalie acid (Note 3). S35 lbs. phthalic anhydride. 300 lbs. copper chloride dihydrate (Note 4). 2.5 lbs. ammonium molybdate. (Note 5). Heat charge to 130*0. Then add: 1500 Iba. molten urea. Heat charge to 195*6 and hold for four hours at 195*5*0. Pump entire slurry to the Sulfator. NOTES 1. The purpose of the anti-oxidant ie to Inhibit oxidation of. the kerosene. 2. if a measurable peroxide number is found* the kerosene should be washed with concentrated sulfuric acid. ^ 3. One batch of chlorphthalic acid, which Is synthesised at Newport from 236 lbs. phthalic anhydride is the proper quantity to give the specified 4.0-5 *0Jt chlorine in Blue M/CPC. 4. This quantity was increased from 2S5 lbs. as a result of Seai-Worke study which showed a higher yield with an excess of copper chloride. \ ; | 5. Use U. T. Baker's Technical Grade on an "as ie" basis. .. - * Jt; DUP050068795 - 19 - EXHIBIT (2) NEWPORT PLANT PROCESS FOR SULFATION OF "MONASTRAL" BLUB LB BY THE "KEROSENE FIOTATIj QHIL (XFJ. PROCEDURE AS OF JUNE. 1951 After pumping one synthesis charge of Blue LB to the aulfator, add while agitating: 1560 lbs. $$% sulfuric acid in 1-1/2 hours. Stop agitator Start siphon and decant kerosene* Add 700 gals, water. Let settle one hour. Start siphon and decant all kerosene floated to surface* Add 5000 lbs. ice. Start agitator. Add 50% sodium hydroxide solution to pH of 7.0-S.0* Pump charge to extraction tank for alkaline extraction* DUP050068796 - 20 - EXHIBIT (3) But# January, 1950 February, 1950 March, 1950 April, 1950 May, 1950 m*> wo July, 1950 August, 1950 September, 1950 October, 1950 November, 1950 December, 1950 January, 1951 February, 1951 March, 1951 April, 1951 May, 1951 June, 1951 QUALITY OF "M0NA3TRAL" BLUE LB Packed Lots 8623-523 to 559 8623-560 to 596 8622-597 to 637 N623-638 tb 681 N623-682 to 728 86f3-?29 to 764 8623-765 to 799 11623-800 to 849 N623-850 to 889 8623-890 to 920 8623-921 to 966 8623-96? to 2 N623-3 to 45 8623-46 to 79 8623-80 to 97 8623-98 to 104 8623-105 to 147 8623-148 to 185 100:100 e green 101:100 s green 101:100 e green 100:100 ye green 99:100 ye green yye dull 99:100 tvs red ws dull 100:100 yye red vte dull 100:100 yye green yye dull 100:100 ye green ye dull 101:100 yye dull 101:100 ye green lOlflOO vrs green yye dull 102:100 a green ve intense 104:100 e green yye intense 104:100 e green ye intense 102:100 ye green e intense 103:100 ye green ye intehee 103:100 ye green ye;;'intenee DUP050068797 - 21 EXHIBIT (4) YIELD OF "MONASTRAL" BLUB IB Month January February March April May June July August September October November December January February March April May June Year 1950 1950 1950 1950 1950 1950 1950 1950 1950 1950 1950 1950 1951 1951 1951 1951 1951 1951 Yield* 77.0% 76.0% 75*0% 76.0% SO. 6% 76.5% 76.1% 76,0% 74.4%** 76.1% 77.6% 76.6% 76.2% 76.1% 61.3% 60.3%*** 77.2% 76.0% Expressed as % of theoretical based on phthalic anhydride cohsumptl * 1.2% low due to one synthesis, which was discarded, because a scraping knife fell into the glass lined kettle* ***1.2% low due to one synthesis, which was discarded, because a steel nut fell into the glass lined kettle* DUP050068798 Packed Lot N 657 -63 -64 -65 -66 -67 -61 -69 -70 -71 -72 -73 -74 -75 -76 -77 -76 -79 --do -61 -62 -63 ' -64 -65 -67 -66 -69 - 22 - EXHIBIT (5) QUALITY OF "MOHASTBAL" BLUB BO Quality ye BT-297-D. SV 373 July, 1950 if it tt it it i w it it it Cl it tt it it tt n n 99:100 ve red 105:100 e green 105:100 e green 105:100 e green 102:100 8 green 106:100 e green 106:100 s green 104:100 a green 104:100 s green 105:100 8 green 102:100 8 green 104:100 a green 105:100 we red we dull 106:100 8 red 104:100 VS dull 105:100 we red W8 dull 105:100 W8 red ve dull 105:100 ve dull 103:100 8 dull 103:100 we green we dull October, 1950 n tt a it 100:100 we green 100:100 we green 101:100 we green 102:100 we green 101:100 ve green 102:100 green a intense DUP050068799 H 657 -90 -91 -92 -93 -94 -95 -96 -97 -96 -99 -100 -101 -102 -103 -104 -105 -106 -107 -106 -109 -110 -111 -112 -113 -114 -115 --116 -117 October 1950 it w n ft if ti if April, 1951 it n if if * EXHIBIT (5) (CONT'D.) 102 MOO green intense 104M00 a green ws intense 105 MOO va green ws intense 105 MOO a green t y s intense 102 MOO a green a intense 106 MOO y v s green t v s intense 105 MOO s green 1041100 a green 103 MOO a green vs intense 101M00 a green ws intense 103 MOO a green wa intense 103 MOO vs green ws intense 103 MOO 78 green ws Intense 103i100 a green va intense 103 MOO vs green ws intense 104 MOO vs green ws intense 103 MOO vs red vs dull 102 MOO vs red vs dull 100:100 ws green 101 MOO ws green ws Intense 100:100 ws intense 100:100 ws intense 101:100 ws green ws intense 101:100 ws green ws intense . lOOllOO ws green wa intense 101 MOO vs green vs intense 101:100 s intense 102 MOO vs intense DUP050068800 H 657 -lid -119 -120 -121 -122 -123 -124 -125 -126 -127 -12* - 24 - April, 1951 tt n n n n,, tt n it n tt EXHIBIT (5) (CONT'D.) 101:100 t v s intense 100:100 s intense 103:100 s intense 102:100 s intense 100:100 vs intense 102:100 vs intense 101:100 vs intense 101:100 vs intense 102:100 s intense 100:100 ws intense 101:100 ws zed DUP050068801 - 25 - EXHIBIT (6) NEWPORT PLANT PROCESS FOR CHLORINATION OF CPC AS Of To the 400 gallon nickel-clad autoclave add; 244 lbs* chlorine-free crude Blue CPC (dried to kerosene content below 1#) 24 lbs* anhydrous copper chloride* 3400 lbs. sulfur dichloride (of minimum chlorine content of 67.5*) 15 lbs* anhydrous aluminum chloride. (Note 1) Close manhole and bolt securely. Start agitator. Set automatic pressure regulating valve at 265 pal. Check that cooling water is flowing through the reflux (Andale) condenser and brine through the tail condenser. Start hot water flowing from mixer through autoclave Jacket. An initial reaction will occur at approximately 70C. The rate of heating is most critical. The following rates should not be exceeded wider any conditions. (Note 2). After the reaction has occurred, heat with steam to 265 psi and 1758C. Hold 4 hours above 175*0 Cool to 125*0 and discharge sulfur chloride slurry to the rotating dryer for distillation. (Note 3). DUP050068802 - 26 - EXHIBIT (6) (CONT'D.) NOTES X. Ohio Apex Co. aluminum chloride (anhyd.) pellets are used. Aluminum chloride is added through the manhole and "drowned" in the sulfur chloride rapidly. 2. If specified heating rate is exceeded, hot water flow should he stopped immediately and cold Water started through the Autoclave jacket. >. Autoclave should he flushed with 500 lbs* sulfur chloride to remove pigment Which may interfere with operation of flush bottom discharge valve. DUP050068803 - 27 - EXHIBIT (?) ANALYSES OF"SOLIDS" REMOVED FROM REFLUX CONDENSER Bate 1-24*50 3-30-50 7-10-50 9-20-50 10-30-50 11-20-50 2-22-51 5-17-51 6-23-51 Number of Cblorlnatlong Cl 161-3 (3, Cl 164-0 (5 Cl 169-79 (3LI), Cl 100-219 40, 1 Cl 220-260 49 Cl 269-320 1 52: Cl 321-429 ao9) Cl 430-561 132!) Cl 562-610 (57) Number of Tabes Pluxxed 55 4 16 30 13 3 0 57 6 For Analyses, Tab^e Below A B C 0 1 Not Analyzed n f 0 A Antimony,# Nickel Iron Ammonia Sulfates Sulfur Extracted Solids Aluminum Chlorides 12.5 3.0 0.9 17.9 4.0 2,0 2.5 -- 52.0 B 12.5 1.5 0.0 16.9 1.3 49.6 ANALYSES 0 10.3 1.0 0.5 0.6 Trace 5.0 35.1 0.33 40.0 B 1.99 0.09 3.2O 0.64 20.3^ 10.96 5.70 1.53 29.9 JL 1.13 6.53 3.70 7.40 30.4 17.1 9.0 0.9 20.0 .JL None 0.5 1.2 6.2 26.5 0.1 4.1 2.0 25.5 Q None 6.0 4.0 0.0 13.0 0.7 6.2 1.2 22.0 DUP050068804 28 EXHIBIT (0) QUALITY OF POLTCHLORO CPC PRODUCED AT SEWFORT Packed Lot H-624 -225 -226 -244 -245 -246 -313 -314 -315 -316 -317 -310 -332 -333 -335 -336 -350 -351 -352 -353 -354 -355 -356 -357 Month - Tear Fob** 1950 n it March, 3.950 <t it August . 1950 it n it ft if ft n n ft September,1950 n ft it if n it nH If ft If ' m It n9 if If October, 1950 it H Quality re. Standard 0T-674-D. Lot 43 99:100 bine va intense 99:100 bins vs intense 102:100 bine e dull 96:100 bine dull 101:100 e bine ws intense 100:100 intense 104:100 intense 100:100 ws bine intense 103:100 vs yellow s dull 104:100 dull 102:100 dull 101:100 vs dull 104:100 vs dull 102:100 vs dull 100:100 s dull 107:100 vs bine vs dull 107:100 vs bine ws dull 106:100 dull 105:100 e blue s dull t 104:100 vs blue s dfiill . 105:100 s blue s dull 104:100 blue s dull 105:100 blue s dull DUP050068805 H-624 -35$ -359 -360 -361 -36a -363 -364 -363 -366 -367 -366 -369 -370 -371 -372 -373 -374 -375 -376 -377 -395 -396 -397 -39$ -399 -400 -401 -402 -403 - 29 - October, 1950 it Hi"' a tt 11 n n it 9 9 tt a November, 1950 it tt tt n n tt . 105:100 0 blue 0 dull 106:100 ve blue W8 dull 104:100 a blue TVS dull 106:100 ve blue 8 dull 106:100 ve blue 0 dull 106:100 ve blue 0 dull 109:100 0 blue 0 dull 103:100 8 blue dull 105:100 ve blue dull 107:100 ve blue dull 107:100 dull 104:100 e blue dull 104:100 0 blue dull 105:100 e blue 0 dull 111:100 blue ve dull 106:100 0 blue 0 dull I0a:100 blue we dull 105:100 ve blue ve dull 105 :100. ve blue ve dull 107:100 blue 106:100 dull 103:100 dull 103:100 e dull 103:100 dull 105:100 dull 103:100 dull 101:100 dull - 101:100 dull 101:100 dull DUP050068806 N-624 *404 *405 406 w. -406 -409 410 411 412 -413 -414 -415 -416 -417 -416 -419 --420 -421 -422 -423 -424 -425 -426 -427 -426 -429 -430 -431 - 30 * November, 1950 it tt tt n n n tt it it tt tt Becomber, 1950 tt a it it it tt December, 1950 m tt e e n it 101:100 dull 101:100 dull 104:100 dull 102:100 dull 104:100 dull 106:100 dull 104:100 dull 101:100 e dull 101:100 e dull 106:100 dull 103:100 dull 103:100 dull 102:100 dull 102:100 dull 106:100 dull 102:100 dull 101:100 dull 101:100 dull 1051100 dull 104:100 dull 101:100 dull 103:100 dull 102:100 dull 105:100 dull 104:100 dull 103:100 dull 104:100 dull 102:100 dull * DUP050068807 -432 -4i. -436 -437 --438 -439 -440 -443. -442 -443 *>*kUb -445 -446 -449 -450 -451 -452 -453 -454 -455 -456 -457 -456 -459 -460 -461 462 ~ 31 January* 1951 a a a a t n a a tt it it it t a a a a a a a a a a a a a a 104:100 dull 104:100 dull 104:100 dull 99:100 blue vs dull 99:100 blus dul| 100:100 blue a dull 100:100 blua va dull 102:100 a blue dull 101:100 a blue dull 102:100 a blue dull 110:100 intense 106:100 blue vs dull 104:100 dull 103:100 dull 106:100 blue * 102:100 dull 106:100 dull 106:100 dull 94:100 blue vs intense 103:100 dull 102:100 dull 102*100 dull 101:100 a blua dull 96:100 dull 96:100 dull 101:100 dull 96:100 vs blue dull 100:100 dull 101:100 vs blue dull DUP050068808 N-624 -463 -465 -466 -4^7 --468 -469 -470 -471 -472 -473 -474 -475 -476 -477 -476 -479 -460 -461 -482 -463 -464 -485 -469 -490 -491 -492 -493 -494 * 32 - January, 1951 February, 1951 a n a w. n it n . 11 it n n n it n 11 ti March, 1951 a n a a a a a a a 104:100 dull 103:100 dull 96:100 s blue dull loiiiob a blue a dull 102:100 ve blue dull 101:100 ya blue dull 101:100 ye blue a dull 100:100 ye blue a dull 100:100 a blue a dull 100:100 blue a dull 100:100 blue a dull 101:100 a blue a dull 100:100 ye blue a dull 100:100 ya blue a dull 100:100 ya blue a dull 100:100 ya blue dull 101:100 ya blue a dull 102:100 ya blue a dull 100:100 a blue 8 dull 101:100 ya blue dull 100:100 a blue 8 dull 101:100 blue a dull 100:100 blue va dull 103:100 a blue ya dull 102:100 ya blue ya dull 101:100 ya blue va dull 100:100 ya blue 101:100 a blue ya dull 100*100 ya blue a dull DUP050068809 H-624 -495 *496 -497 -496 -505 -506 -507 -506** -509 *510 -5U -512 *513 -514 -515 -516 -517 -516 -519 -520 -521 -522 -523 -524 -525 -526 -527 33 March, 1951 it n April, 1951 it tt n n n w tt it n tt it ii it April, 1951 n n May, 1951 tt n t 102l100 dull 101:100 dull 102S100 dull 101:100 vs blue dull 101:100 ve dull 102:100 e dull 103:100 dull 103:100 8 yellow 100:100 ve yellow 101:100 8 yellow 101:100 s yellow 101:100 ve yellow 100:100 ve yellow 100:100 we yellow ve dull 103:100 dull 101:100 dull 100:100 8 dull 100:100 dull 99:100 dull 96:100 dull 97:100 dull 97:100 dull 96:100 dull 97:100 8 dull 100:100 ws yellow ve dull 100:100 we intense 100:100 ws yellow DUP050068810 .624 >526 -529 -530 -531 -532 -533 -534 -535 -536 -537 -536 -539 -540 -541 -542 -543 -544 -545 -546 -547 -546 -549 -550 -551 -552 -553 -554 - 34 Hay, 1951 If It n It n n n tiit it n it R If n it it n June, 1951 n tt it it n 100:100 W8 intense 99:100 8 intense 99:100 8 intense we yellow 100:100 a yellow #:i0o va Intense 97:100 99:100 vs yellow we intense 99:100 vs intense vve yellow 96:100 vs intense 102:100 vs yellow vs dull 99:100 ws blue s dull 100:100 vs dull 103:100 dull 100:100 dull 100:100 dull 101?100 dull 103:100 dull 100:100 dull 100:100 dull 100:100 dull 93:100 blue dull 94:100 vs blue dull 96:100 vs blue^';%:duil: 103:100 dull 97:100 s blue s intense 95:100 dull 96:100 vs blue vs dull DUP050068811 N-624 -555 -556 -557 -553 -559 -560 -561 -562 -563 -564 -565 -566 -567 -563 -569 -570 -571 -572 - 35 June, 1951 n n it w tt # ti n tt w n n 96:100 w b blue vs dull 97:100 ws blue vvs dull 99*100 vs blue vs intense 97*100 ws blue vs dull 97*100 ws dull 100:100 s dull 99:100 vs blue vs dull 97*100 vs intense 94:100 ws intense 97*100 vs intense 97*100 we yellow 97*100 vs yellow vs dull 93*100 dull 93*100 dull 97*100 s dull 93*100 ws yellow ws dull 93:100 vs yellow vs Intense 99*100 vs yellow * Lots N-624-203 through 224* 227 through 243 247 through 312, 319 through 331, 337 through 349 and 373 through J|6 vers milled from Orchem eutectic crude green CPC, Started using new reference standard GT-674-D, SW 2609* DUP050068812