Document 4JYEYbVd2ngZX75EQObQOk6JG

ESTABLISHED iSOZ E. I. d u Po n t d e Ne mo u r s & Co mp a n y INCORPORATED Ne w p o r t , De l a w a r e 19804 PIGMENTS DEPARTMENT CC; W, S, Struve - Newark E, E. Jaffa - Newport C, W. Anderson * " February 14, 1977 TO: G, A. HAPKA - LEGAL - WILMINGTON FROM: R, J, GUSCHL - PIGMENTS - NEWPORT PATENT PROPOSAL CONTROLLED STJLFATI ON/HYDROLYSIS OF CPC-3B 1, Summary of the Invention A mixture of copper phthalocyanine containing an average of 0,70 chlorine atoms per molecule of phthalo cyanine is slurried or dissolved into concentrated sulfuric acid. The compound can be isolated as the tetrahydrosulfate and precipitated as CPC by the addition of water, By maintaining the temperature of the hydrosulfate before and during the addition of water, the size of the resulting crystallites of CPC can be controlled. When such a hy drolysis is performed below 5QC. , a product is generated which is equivalent in size and properties that that of a crude which has been milled for six hours in a bed of iron Spikes and cylinders. Such a pigment can be readily finished by milling in acetone to the desired particle size. It is the control of particle size by controlling the temperature of hydrolysis which, we feel is a new discovery. 2, State of the Art Several acid treatment methods are known in both pigment and dyestuffs technology for preparing finely divided products "Acid pasting" refers to a process in which the compound is slutried or dissolved in concentrated sulfuric acid and pre cipitated by pouring this solution into ice or water. In permutoid swelling, the pigment is treated with sufficiently strong sulfuric acid to bring about the change from beta to alpha crystalline forms. A narrow limit of acid strength con centration (.62.5-8Q. Q%) is used. ST drowning utilizes enough acid (.about 8 to 12 times the weight of pigment) to completely dissolve the pigment, The pigment is then recovered by mixing this solution with water with great turbulence to generate the desired properties. In these terms, the process described in BETTER THINGS BETTER LIVING . . . THROUGH CHEMISTRY * N35361 2 2, state of the Art (Continued) this proposal is a form of acid pasting in which water is added to the tetrahydrosulfate to recover this pigment. By controlling the temperature of this sulfate before water is added as well as the temperature of the water itself, we have demonstrated our ability to control the particle size of the product. Although no specific search of CPC finishing processes was undertaken, Moser's book (F. H. Moser and A. L. Thomas, "Phthalocyanine Compounds", ACS Monograph Series, 1963, New York, New York) is considered a definitive search of most CPC literature up to and including 1961 patents. Pages 153-157 are a good review of acid treatment methods to this date and are attached. More recently, a search of all patents relating to CPC finishing has been compiled and is maintained at Newport (contact C. W. Anderson), Of the literature covered in Moser, the following references are relative to our discovery (using Moser's reference numbers) 195 - Slurries of CPC-sulfate in 45-90% acid poured into water. ("Montecatini"Societa generals per 1'Industrie, mineraria ed agricola, British Patent 502,623 (Mar. 22, 1939); French Patent 826,232 (Mar. 25, 1938); Austria Patent 157,099 (Sept. 25, 1939); Italia Patent 354,407 (Nov. 22, 1937). 162 - Precipitation of CPC-sulfate from concentrated acid by adding water. The isolated sulfate is then hy drolyzed in boiling water, (Koike, E., and Yag, J., J.Chem. Soc. Japan, Ind. Chem. Sect,, 57, 552-5 (1954) 109 - Control of crystal size by causing precipitation of CPC from a 90% sulfuric acid solution by changing the temperature of the acid. (Gross, P.F. (to E. I. duPont deNemours & Co.), U.S. Patent 2,365,464 (Dec. 19, 1944) 220 - A detailed study of conditions for the acid pasting of CPC to obtain maximum dispersion of the pigment (O'Neal, G. M. (to the Sherwin-Williams Co,), U.S. Patent 2,367,519 (Jan, 16, 1945); British Patent 649,911 (Feb. 7, 1951). DUP050108925 MANUFACTURE 153 Acid Treatment Methods) One method used since the process was first patented is the proce dure used to prepare vat dyestuffs in a finely divided form. The com pound is slurried or dissolved in concentrated sulfuric acid and pre cipitated by pouring the solution into ice or water. This technique is known as "acid pasting." A number of factors affecting the process have been studied and have resulted in patented procedures. One early patent (195) relates to copper phthalocyanine slurries in sulfuric acid of 45 to 90~per cent'''concehfraUon. The slurry becomes thick_as the sulfate of copper phthalocyanine forms. After stirring two to four hours at roomjemperature the slurry is poured into cold water, maintained by adding ice, and. then diluted to give~a sulfuric acid con centration of 10' per cent'or'lessj' ft Ts "washed fy decantationuntil neutral, rosin or dispersers are added, followed by filtration, drying and grinding. Coprecipitation of a phthalocyanine with 5 per cent or less of a dif ferent phthalocyanine is said to improve the jetness of masstpne and brightness of print tone of the phthalocyanine present to the extent of 95 per cent markedly when tested in a printing ink formulation (59). Dilution of a solution of copper phthalocyanine in concentrated sulfuric acid with 50 per cent sulfuric acid at 50 until the copper phthalocyanine precipitates, and pouring this into four times its weight of cold water is said to give a cleaner, stronger, easier grinding product than can be obtained by pouring the original solution into cold water (114), In a similar study jropper phthalocyanine was dissolved in 92.4 per cent sul furic acid (162); the sulfate precipitated by adding water^(lj51), and the homogeneous sulfate suspension drowned in boiling water (163).; Borodkin found that precipitation of copper phthalocyanine sulfate ' with water I .- prior to drowning the sulfuric acid solution did not improve the purity of tint of the pigment (24). In the study of the acid pasting process Borodkin also found that the product of the phthalic anhydride-urea-solvent process contained a higher proportion of copper phthalocyanine than did a phthalic anhydrideurea-meit process. A small percentage of impurities was found to remain with copper phthalocyanine after acid pasting (19). These impurities were soluble in organic bases Such as pyridine, quinoline, aniline and dimethylaniiine. Copper phthalocyanine is insoluble in as much as fifteen times its weight of 85 per cent sulfuric acid at 20 on prolonged stirring but forms a mierosuspension of the sulfate (24). In 96 per cent sulfuric acid .it is soluble in twelve times its weight at 20. At 100 it is solu ble in seven times its weight of 85 per cent acid or five times its weight of 96 per cent acid. An unsatisfactory pigment is obtained with any con centration of sulfuric acid at temperatures above 100 v The addition of a DUP050108926 $>&?*$'****& H\ nI %'^gL`hl %$'&'; ^L> 154 PHTHALOCYANINE COMPO0NDS sulfonated castot oil to the drowning water does not give consistent results. From 5 to 10 per cent of a triethanolamine soap in the drowning water gives a pigment with improved dispersion properties. Acid-pasted pigments are improved in strength and dispersibility if they are precipitated in the presence of an emulsion of water immiscible alkali soluble material, preferably an organic film forming acid, liquid at the precipitation temperature, such as a fatty acid, and then washing Out the excess alkaline material. The pigment appears to retain a monomolecular layer of the soap (100). A purification method is described in which an acid stable phthalocyanine is slurried in sulfuric acid of 40-90 per cent concentration, sufficient to form the phthalocyanine sulfate, but not to dissolve it. The sulfate is filtered on glass cloth or porous stone. The sulfate is then placed in a large excess of water to recover the purified color or dissolved in 98-100 per cent acid before precipitation (67). The addition of certain substances to_a. pigment often enhaneesjts properties forjcertain uses. An example of this is the coprecipitatioh of 5 to 20 per cent of a higher fatty acid, such as lauric or stearic acid from a sulfuric acid solution by the acid pasting procedure (60). This results In a pigment more readily dispersible in rubber and similar plastics. Acids other than sulfuric acid have been suggested for the acid past ing, These include oleum (61), chlorosulfonic acid (59), phosphoric acid (145), p-toluenesulfonic acid (146), fused napthalpne-beta-sulfonic acid (144), and mixtures of organic sulfonic acids (146), A process for instantaneous dilution of the acid solution of copper phthalocyanine with turbulent flow in a special mixing nozzle forms the pigment in an extremely fine state of subdivision (66). This is said to reduce or prevent crystallization of the product When it is subjected to crystallizing solvents. Precipitation ,of copper phthalocyanine in the presence of a water immiscible organic liquid is said to enhance the softness and strength of the pigment (168,186). The sulfate olTcopper phthalocyanine may be made by stirring crude copper phthalocyanine with" a sufficient amount of fairly strong sulfuric acid in an inert organic liquid, especially nitrobenzene (186,173). The sulfate is hydrolyzed with an alcohol, filtered, Wasted with 'alcohol and dried. It is claimed that a good nonflocculating copper phthalocyanine pigment results. An acid pasting procedure that gives higher strength and at the same time improves pigment stability is suggested in a recent patent (176). Two hundred grams of hexylene glycol are dissolved in a thousand grams of sulfuric acid at 20-30. A slurry of 250 grams copper phthalocyanine in 125 grams of o-dichlorobenzene is added at 20-40. After stirring at DUP050108927 MANUFACTURE 155 40 for three hours the mixture is allowed to stand overnight. It is stirred and poured into fifteen liters of water at 60 with vigorous agita tion. The o-dichlorobenzene is removed by steam stripping, and the slurry is filtered and dried. The product is solvent stable and disperses readily in plastics and inks. Control of crystal size and form mav_.be. attained by causing precipitatipt},,Qf copper phthalocyanine from 90 per cent sulfuric acid by means of a change in temperature. Solution is attained at.70-1 lO^nd precipita tion by rapidly cooling the solution to -10 to +-30 (109^) A detailed study of conditions for the acid pasting of copper pfrtfialocvanine to obtain"maximum dispersion of the pigment has been described (220)) Solution in eight to eleven parts of 98 per cent sulfuric acid" per part of copper phthalocyanine is recommended along with dilution in ice water in the presence of surface active agents, Final dispersion is obtained by boiling the aqueous acid slurry. The production of very soft pigments of the phthalocyanine type may be attained by diluting a sulfuric acid solution of the pigment containing a sulfonated monocyclic aromatic hydrocarbon having more than one alkyl side chain (183). The sulfonated hydrocarbon should be present to the extent of at least 25 per cent by weight of the pigment. Xylene is a favored hydrocarbon. Similarly acid pasting in the presence of water soluble carboxylic acid, such as five to ten times the pigment weight of acetic, chloroacetie, or propionic acids gives a readily dispersible pigment (2). Pigment made according to the above process (183) may be reslurried as an alkaline presscake containing 10 per cent of pigment with a liquid hydrocarbon or chlorohydrocarbon until the pigment trans fers completely to the organic phase. The Organic liquid is then re moved by steam distillation and the product is filtered and dried to ob tain a nonfiocculating, strong, red-toned copper phthalocyanine (34), A mechanism for drowning a sulfuric acid solution of copper phthal ocyanine in water forces a very thin film of the solution 0.01 to 0.001 inches thick into water at a pressure up to 2500 psi (187). This is claimed to eliminate the formation of large particles which are said to form in drip or spray methods for introducing the sulfuric acid solution into water. Reduced amounts of sulfuric acid may be used in the acid pasting procedure by using a dough mixer to effect the mixing of the sulfuric acid and phthalocyanine pigment (30). An added advantage is claimed for the process as the pigment presscakes produced have high solids contents. The process also has an advantage in processing metal-free phthalocyanine because it gives less decomposition and, therefore, higher yields, A variation of the above process uses an acid stable, water-soluble, inorganic salt such as sodium sulfate in addition to the Sulfuric acid (38). Copper phthalocyanine may be mixed with a ife*' IS -id43v.i^:yv,--.-* 156 PHTHALOCYANINE COMPOUNDS Small amount (25 per cent of its weight) of 17 per cent oleum. It is then drowned in water at 98, cooled to 50, and an emulsion of xylene and Water is added. After stirring for half an hour the xylene is removed by steam distillation and a /3-type phthalocyanine is recovered fay filtration -(155). Another improvement in the process of acid milling a copper phthal ocyanine is the addition of from 2 to 30 per cent of the pigment weight of a dicarboxylic acid or anhydride, such as phthalic anhydride, to the system (158). The resulting pigment is said to be lower in grit, stronger in masstone, and undertone effect, and cleaner and brighter than the color obtained when the dicarboxylic acid anhydride is omitted. Another variation of the acid milling process uses a monocyclic aryl sulfonic acid in place of sulfuric acid (150). Improved texture and other advan tages are claimed, Metal phthalocyanines that have been made by the phthalonitrile proc ess in a saturated alicyclic hydrocarbon solvent in an autoclave ap parently tend to give a pigment which is noncrystallizing when proc essed by acid pasting and then subjected to a variety of treating agents including aliphatic isocyanates, alkyl amines and certain quaternary ammonium salts (74,77), octadecyi amine, Iauryl amine (75) or alkyl substituted ureas (76). A similar noncrystallizing effect can be obtained from the Same type of phthalocyanine by subjecting it to the process known as "permutoid Swelling." In this process the copper phthal ocyanine is slurried in sulfuric" acid of 62.5 to 80 per Cent concentration.-. This forms the acid salt and changes the crystalline form of the product to the y form. Products of the above procedure show remarkable resis tance to crystallization (73). The permutoid swelling process of phthalocyanine finishing was used in Germany (225), especially for the polychlorophthalocyanines. The /3-modification in which the pigment is generally obtained by synthesis from intermediates is changed to the tinctorially strong a-modification. The change to the ot-mpdification can be observed by preparing X-ray diffraction diagrams. By this means a preferred slurrying condition for each pigment is developed. In general die pigment is treated with sufficiently strong sulfuric acid to bring about the change from the /9- to the ex-crystalline form, but insufficient in concentration to dis solve it. This method has several advantages over the conventional acid pasting method: (a) the method is applicable to pigments which are not stable in sulfuric acid of sufficiently high strength to dissolve the pigment, but stable in acid of moderate concentration; (b) the method is applied to presscake by the careful addition of stronger acid followed by adjustment of acid concentration of the slurry; (c) the change from /3- to Ct-forra can be controlled by means of the concentration of acid, DUP050108929 ionic dvan- f fgSPC- SZmm, MANUFACTURE the time of contact, and the type of agitation; (d) usually the amount of sulfuric acid used is less than that required by the conventional acid pasting process; (e) the quality of die resulting pigment is improved in regard to shade and strength; (f) when the pigment is processed to a dry powder, the pigment produced by permutoid swelling is softer In texture than the acid pasted product. Disadvantages of the permutoid swelling process are that the sulfuric acid concentration must be controlled within narrow limits and that in some cases the concentration of sulfuric acid needed presents problems regarding materials of construction.. Specific conditions for permutoid swelling various types of phthal- ocyanines are given in the above reference, ^__. Several acid pasting procedures Were used in Germany-. (225), For dry colors, crude copper phthalocyanine-was-dissolvedJn..about-ia-timas-its weight of ^sulfuric acicLand,Jiluted with a relatively , small amount of water at 85, maintaining the drowning temperature at 135 Thi_sj;ives a product with a relatively soft texture. For paper_dyeing,.th.g_sulfuiic acid solution was sprayed into a mixture of ice and water. For general use as an aqueous dispersion the sulfuric acid solution was sprayed into water at 75-85. Another method for preparing a highly dispersed copper phthalocyanine requires drowning the 90-93 per cent sulfuric acid solution in an acid ified saturated ferrous sulfate solution. It is then further diluted, fil tered, and washed free of ferrous sulfate. The resulting presscake is readily redispersed (275). Conventional methods of acid pasting metal-free phthalocyanine are said to damage its brilliance. Conducting the operation in an inert atmosphere (free from oxygen) is said to give a superior product (189). Grinding Methods The second general method for finishing phthalocyanine pigments in volves a number of grinding procedures for particle size reduction by salt grinding or solvent grinding. These procedures have been developed principally in the past fifteen years, although the earliest references were in 1936 (132,210). These methods include (1) the so-called salt grinding methods:'grind ing a phthalocyanine color with a large amount of a soluble salt or other solid substance and (2) solvent grinding in suitable equipment with small media, such as small shot, sand, and small pebbles. Either method may be used to prepare the /3-type of phthalocyanine and for grinding phthalocyanbies which do not form a /3-type, as well as for grinding under condi tions which do not favor formation of the /3-type crystal (32), The salt-grinding method was briefly mentioned by Muhlbauer in 1936 II l 23 DUP050108930 -3 2. State of the Art (Continued) 225 - An HT drowning type of process in which the dry pigment is dissolved in about ten times its weight in sulfuric acid and diluted with a small amount of water at 35C. This dilute solution is then drowned into either ice and water (for papers) or water at 75-85C. (for general uses) (PB 85172 (Fiat Final Report No. 1313), (Feb, 1, 1948) 3. Advantages Over Existing Technology This discovery, if implemented in the Newport Plant, could result in elimination of the premilling step for BB crude for some codes. Additional milling capacity would be available and mill costs would be reduced. If we should instead con tinue to premill the material, sulfated and hydrolyzed at lower temperatures, it could be possible to develop a stronger, more intense product than currently available. Such a pre milled low temperature product would be equivalent to an "overmilled" product and approach ultimate strength. 4. experimental Examples Attached are three procedures for preparing and finishing pigment as in this proposal. Example 1 allows for sulfation and hydrolysis at any desired temperatures. In Table I, various examples were run within this procedure. Example 2 allows for laboratory milling operations of the crude to the finished code N-8510 for CPC-BB. Example 3 allows for conversion of N-8510 to BT-284, a DuPont product. Please note the use of the x-ray "Valley Parameter" in Table I. This value is an empirical number calculated from a full scan x-ray and reflects peak broadness. A value of 45-55 is typical for a normal (95C sulfation/hydrolysis plant pigment whereas a material which has been premilled 6 hrs. will have a valley parameter of 0-10. As reflected in Table I, our invention generates low valley parameters without premilling. In effect, the valley parameter reflects pigment crystallite size. DUP050108931 Example I Laboratory procedure for room temperature sulfation/hydrolysis of plant kerosene slurry (See Notebooks E12469-33 and E1Q663-91) Equipment: 5-liter PJ3F fitted with addition funel, condenser, overhead stirrer, heating mantle and thermometer. Procedure: 1. Reslurry BB synthesis slurry and remove a sample which will contain 193 g CPC-BB Record Batch # CPC-BB __ % Pure CPC in crude ......................... #g crude used ................ ' (Jg crude x % pure CPC should = 193 g) 2. Record the temperature of the slurry C. and turn agitator on (at this point, one can adjust temperature to any desired value), 3. Add dropwise over 90 minutes, 522 g concentrated R2SO4 4. After acid addition, stop agitation and allow flask contents to settle one hour 5. Decant off kerosene recovering any sulfate. Note con sistency of sulfate; grainy, pasty or balled 6. One hour after settling of step #4 has ended, proceed with hydrolysis. Try to measure temperature of sulfate before adding water. Adjust to desired temperature. 7. Hydrolysis:With no agitation, add dropwise but rapidly over 15 minutes 1375 ml of cold water (25C. or less). At the end of this addition, agitate for 30 minutes (Note agitator may be on during this addition but seems not to effect product.) 8. Add an additional 1800 ml of cold distilled water over 15 min. and stir an additional 15 minutes. 9. Add over 30 minute period, 505 g 50% NaOH solution 10. Check pH and adjust to 10 11. Heat solution to 90"C. and hold at 90C. for one hour 12. Cool, filter and wash until alkaline free to BrilliantYellow paper 13. Dry any part of presscake at 100C. 14. Obtain from Analytical Group: % CPC, % Cl in pure CPC, full scan x-ray and rubout product against N-8520 standard. DUP050108932 Example 2 Laboratory procedure for premilling and acetone milling CPC-BB to BBS (Based on information from E. W. Gillow Notebook E-8369-76) Premilling: To a one quart mill (steel container) charge 1500 g 1/8" steel shot 150 g #10D steel nails 100 g CPC . and mill 40 hours at max. noise level ( 300 PPM) on 2" dia. rollers Milling with Acetone: To a 2/3 gal. mill charge 4500 g 1/8" steel shot 120-150 g CPC 1000 ml acetone 2 drops Triton X-100 and mill 70 hours (58-72 acceptable) on 2" diameter rollers. at maximum noise level ( 260 PPM) Finishing: 1. Separate shot from pigment slurry 2. Transfer acetone slurry to proper size RBF. Wash out mill and shot with limited water. Add to acetone slurry.. 3. Begin steam sparge (do not use a heating mantle to heat acetone) and distill off acetone. Distillation will occur at 55-60C. and shoot up to 82C. when all recoverable acetone is off. Hold at 100C. for 20 minutes. 4. Dilute volume with distilled water to 4 liters. 5. Heat at 90C. for 1/2 hr. 6. Add 49.3 g sulfuric acid (27.4 ml cone.) 7. Adjust pH to ni 1.5 8. Heat at 95C. for 1/2 hr. 9. Filter and wash with warm (40-60C. ) water (2 1.) 10. Wash with a solution of 5 ml NH^OH (cone.) in 50 ml H2O 11. Wash again with 2 1. warm water 12. Wash with enough cold water to reach >2000 ohms 13. Reslurry with enough water to make easily stirrable 14. Adjust pH to 7 to 10.5 with more of the above mentioned NH4OH solution 15. .Filter and dry 16. Obtain from Analytical: full scan x-ray, % CPC, and % Cl on pure CPC and rubout product against N-8510 standard DUP050108933 Example 3 Laboratory procedure to make BT-284 from N-8510. (.CPC-BB). CSee Notebooks E12469-51 arid El066.3-105) Actual procedure given comes from E10663-105, 1. Reslurry 55 g. of E10663-72E into 460 ml water 2. Add slowly with agitation 4,40 g Baso^ (.3% extender) 3. Allow to stir one hour 4. Check pH. Adjust to range 8.0-10.0 5. If additional NaOH (50%) was added, stir an additional 30 min. 6. Filter and wash until alkaline free to B.Y, 7. Dry 24 hours at 100C, in vac. Oven 8. Grind powder 7 LSP 3/32* BP 1750 RPM (Max. temp. 210F.) 9. Rubout against BT-284 standard. This material is ready for paint evaluations. DU P050108934 4 5. Product Utility and Characterization The main use of this invention would be to produce existing products (such as CPC-BB, N-8510 (BBS) codes with a simplified process. We would use this invention to prepare small particle size pigment directly from hydrolysis. The main product de rived from N-8510 would be BT-284, a BB grade of CPC used as a dry pigment in paint applications. Several samples from the experimental section were converted to this end code to demonstrate acceptable properties. For example, in the laboratory we sulfated and hydrolyzed CPC-BB at 25C. to prepare a 3BU which is equivalent to size and phase to b b z (a premilled crude) (actual analysis 91.7% CPC, 4.04% Cl, 0% beta, VP=15). Half of this material was pre milled and acetone milled (E-10663-93B of Table I) and the other half was directly acetone milled (E-10663-93A). As a control, a sample of plant sulfated and hydrolyzed crude BBU (95C. ) was also treated (E-10663-95A premilled and acetone milled, 95B only acetone milled). Quality data versus N-8510 standard are given in Table II. TABLE II E-10663-93A 93B Masstone Value Dk4 Dkio Hue G5 Gs Chroma *5 1.10 Str. 97 94 Tint Hue GlO G11 Chroma Ho I15 95A 95B Dkio Dk2 g5 g7 ^0 15 97 g12 97 g20 112 d25 Five BT-284 samples were prepared from these four and standard N-8510. All used 8% BaS04 as an extender and samples were evaluated in 30j alkyd, Ford's t s a and acrylic lacquer 927 (Newark evaluations 76-232A, 233A and 231A re spectively) . A. E-10663-93A + 8% BaS04 B. E-10663-93B + 8% BaS04 C. E-10663-95A +8% BaS04 P. E-10663-95B+ 8% BaS04 E. Plant standard N-8510 +8% BaS04 DUP050108935 -5 5. Product Utility and Characterization (Continued) In Ford's ISA, all samples flocculated but C, D and E were more flocculated than A, b and 284 standard. In tint and metallics (10/90 and 50/50) A, B, C, D were stronger than E and standard although B and D were slightly green and dull, in 927 lacquer, the same orders were observed. In both Ford's ISA and 927 lacquer, whitening was barely discernible for all samples. In 30J alkyd, all six samples flocculated equally and again. A, B and C were stronger than standard in tints and metallics. Sample E was slightly stronger than standard and D was noticeably green and dull. Viscosities in 927 lacquer and Ford's TSA were all slightly greater than or equal to stan dard in the order A > BD> CE = standard . In 30-J alkyd , the order was E = standard yAB y CD. In summary, all four laboratory samples are good 284 with a preferred order of A?B = C> D. As for E (our proposed new standard BT-284), we may encounter minor flocculation difficulties in Ford's TSA and.927 lacquer. 6. Claims In this invention, we claim control of pigment particle size by controlling the temperature of sulfation and hydrolysis. Specifically, the temperature of hydrolysis controls particle size but in most cases, the temperature of sulfation carries over closely to the temperature of hydrolysis. The temperature of sulfation determines the completeness of sulfation. The invention is most useful when the temperature of hydrolysis is 50C. or less since the then produced pigment can be used to make BT-284 Without a premilling step. 7. Invention Record A report covering this material has been written and more completely describes the experiment. In this report (as well as part 4 of this proposal), appropriate references are made directly to the notebooks used. 8. Disclosure or Use Most of the work described in this proposal was per formed in our laboratory and all samples have been retained. Two plant tests were run to test extensions of these concepts DU P050108936 6 r8. Disclosure or Use (.Continued) In one plant test (August, 1976, XOP-451),, we pre pared N-8510. type BBS without premilling from crude pigment which had been plant sulfated and hydrolyzed (.957C,) , As expected, this material was weaker and duller than similar material which had also been premilled. There was no need to retain this material so it was blended with other production for sale. In February, 1977, XON-32 was run at 40C, (.sulfation] to generate a smaller particle size. Unfortunately, localized heating of the sulfate occurred during hydrolysis to generate a normal large size pigment. Apparently, the. large cake of sulfate readily absorbed the heat generated when water hit the acid. Unless this heat can be removed during hydrolysis (eg, a thin film of sulfate)., it will be difficult to follow this in vention in the plant in existing equipment, The effect is a real one if properly engineered. Since this material was not as expected, it was used in normal production. DUP050108937 E. X. DU PONT DE NEMOURS & COMPANY Pigments Department APPENDIX B w. S. Struve J. P. Galvin H, Matrick - Newark -n T- it G. M, Loughran - Newport A, F Lewis - II J, W, Ignace - I, A. Berkerceier - tt D, M. Strouss - It c. E, Woodruff - It W, G. Hoffman - It J. J. Adams ,, 11 E, E. Jaffe It C, W. Anderson II A. P. Smith >- fl P, H. Griswold - tt W. E. Miller - tl E, W, Gillow - ft (R. J. Guschl It D, J. Gilliland tt Library 11 File - tl Newport, Delav/are February 24, 1976 CPC III - NEWPORT XON NO. 17 TITLE: CPC-BB - Sulfation/Hydrolysis in Area III Development Tank OBJECTIVE: TO demonstrate sulfation/hydrolysis of CPC-BB in Area.Ill south development tank. To evaluate extent of sulfation, quality of product and feasibility of equipment use BACKGROUND:. This XON supercedes' XON No. 14, Additional work has shown a temperature of 90 insures complete sulfation in the laboratory,- On this basis the sulfation will be run at the highest temperature feasible; the slurry will be transferred at 90-95 C and the development tank preheated with steam. The temperature rise normal to sulfation should result in a run temperature greater than 90C. The scale-up of agitation from laboratory to plant is the area of greatest uncertainty and if sulfation temperature is at or above 90C any defficiencies in beta elimination can- then be definitely attributed to agitation and corrected accordingly. DUP050108938 2-. - STARTING DATE.: February/ 1976 APPENDIX B (CONTD.) NUMBER OF TESTS: ONE PRELIMINARY PRECAUTIONS; 1. Install KW meter on agitator drive of south, development tank. 2. Check development tank is empty. Flush with kerosene before use if necessary. 3. Turn steam sparge on in development tank 8 hrs. before test. Leave vent open and provide bottom drain to run off condensate. 4. Just before run turn steam off and simultaneously turn on CO2 purge at 50 cfm. CO2 purge is to remain on during subsequent sulfation and hydrolysis. 5. Charge of kerosene slurry should be in cooling tank. Initial temperature 90-95C. .6. Check that valving is set to transfer contents of cooling tank to south development tank. 7. Close off first floor to gas fork trucks. PROCEDURE; I. Transfer of kerosene slurry from cooling tank to south development tank. 1. Standard Operating procedure for charging. Charge volume will be3800 gal. from bottom of tank. II. Sulfation * (Be sure tank agitator is on before acid addition, 80 RPM) 1. From top, add 314.0 gal cone, sulfuric acid over a 3 hr period with agitation (80 RPM, 1.9 gpm). Power loading will be monitored during the entire sulfation period and agitation speed may be adjusted as required. Complete addition. Stir 15 min., stop agitation and test for complete sulfation. 2. To test for sulfation, remove test sample"of sulfate from bottom of tank-(use long rod and scrape sample from end fox testing by Research), 3. Check with Research before proceeding. IF NOT FULLY SULFATED, try the following in order until sulfation is complete: a. Turn tank agitator on for an additional hour. Stop agitation and test for sulfation as above. DU P050108939 II. Sulfation (Cont'd) -3- APPENDIX B (CONTD.) b. Turn tank agitator on and add an additional 157 gal. cone, sulfuric acid over a 1-1/2 hr. period. Stir 30 minutes.. Stop agitation and test for sulfation as above. c. Assume material will not sulfate completely. Proceed as if fully sulfated to salvage pigment. IF FULLY SULFATED 4. Allow tank contents to settle for one hour. Ill. Decantation* 1. After settling, begin decantation. Check for pigment in decantation stream. 2. Finish decantation. IV. Hydrolysis/Decantation* 1. From top. add 1900 gal. water. No agitation.! 2. Allow tank contents to settle for 1/2 hr. 3. Start kerosene decantation. Check for pigment in decantation stream. Shut off COj blanket. 4. Finish kerosene decantation. Add an additional 800 gal. water from tank bottom.. Approx, volume at this point, 3700 gal. Jog agitator 3-4 times. Steps V or vl, below are alternative routes. V. Transfer of Solution* 1. Check valving to acid tank trailer. 2. Start south development tank agitation. After 15 minutes, begin pumping tank contents to trailer. If slurry too thick to pump, water up to 1500 additional gal. may be added to loosen up, 3. When tank empty, close valving and transfer trailer to old plant. Two trailer loads will be required. v^- Filtration* 1. Filtration will only be carried out after an automatic fire damper has been installed in the ventilation duct for the filter. Temperature 70C, sparge with steam if required to reach and maintain 70C. Agitation 40 PPM. If slurry is too thick to pump, water up to 1500 gal may be added as required. DUP050108940 -4- APPENDIX B (CONTD.) V1 Filtration (Cont1d) 2, Use normal filtration - repulp - filtration procedure on the west pair of rotary filters. Flush the development tank with water as required to complete the transfer of hydrolyzed CPC to the filters. 3. Collect filter cake from discharge of north rotary filter in plastic-lined 55 gal. drums. VI. Dilution/Caustic Extraction The following procedure assumes dilution/extraction of the entire trailer slurry. This will not he possible due to volume of product. As the slurry** is divided, so scale down the following procedure: 1. Add 2500 gal. of cold water to 31 tank. 2. Start 31 tank agitator. 3. Add 428.0 gal. caustic to 31 tank. 4. Record volume and temp, in tank. 5. Pump trailer slurry to 31 tk. 6. Finish pumping to 31 tk. 7. Record final volume and temp, in 31 tk. 8. Agitator on. Add caustic to pH 10 or above using pH test paper. Record gals, used, 9. Heat 31 tk, to 90C. and hold at 90C. for one hour. 10. Press batch into necessary number crude presses (total charge 2700 crude) VII. Washing - Standard operating procedure. VIII. Drying - " " " '/ (*) Research to follow these steps in process. SAMPLES: Crude Slurry - 1 quart of each lot to south development tank. Crude Sulfate - Smear from bottom of tank at end of sulfation/hold. Crude Presscake - 1 qt. of each lot Packlot - 1 qt. of each lot Slurry to trailer - 1 qt. of each lot **In the case of filter cake in 55 gal. drums, see V1, repulp the and proceed with steps 1 thru 10. DUP050108941 -5- APPENDIX B (CONTD,). TESTING: Newport - Same as on any other CPC-BB. DISPOSITION: Newport Quality Control will arrange disposition into semi-finished BB production. SAFETY ASPECTS: Standard CPC-BB operating procedure. RESPONSIBILITY FOR CLOSING REPORT: K. M. Kolb - R&D APPROVALS: Quality Control DUP050108942 APPENDIX B (CONTD.) Mechanical Notes 1. Scrubber system is marginal but adequate if everything is closed tight on top, barometric legs are full of water and if CC>2 is turned off at critical times, A larger orifice in OVC line probably would help. 2. Agitation drive, not motor is marginal, to inadequate, it Slips from 78 or 80 down to 20-40 at the 80-90% point on each batch at about 50% power loading on electric motor. May simply require new belts or pully springs, or reconditioning, etc. Should be opened, checked, adjusted/ repaired etc. ad indicated. 3, Present batch drop/cooling tank/sandpiper transfer to S. Dev. tk. is cumbersom and a source of trouble. An automatic steam heating system on cooling tank plus cooling capabilities would be a great step forward. Beyond this however, we need a transfer pump which will work at higher temps., up to at least 175C, such as the pump used in CPC I. I think the cooling tank should remain in the circuit because of its value as a surge tank which should improve system flexibility (e.g. to clear the synthesis kettle if the S. Dev. tank were still in use at the end of a Synthesis). To get the most out of such a vessel automatic heating and cooling capacity are both required. 4, Decanting sight glass should be relocated so operator of decanter tube can see it, about 4-5 ft above floor, facing SE and with a permanent light. DU P050108943 2- - APPENDIX B (CONED.) Hechanical Notes (Cont1d) 5. A new sampling rod, like the present one but without a cup end is needed for VI 3. end like this n t A small shoulder on the by welding a bolt in would do but close the pipe so no liquid runs up into it. 6. Present decanter tube is probably too short. In each decantation of step VII we have run it all the way down and pumped only clear kerosene. Unless we are perfect on the first shot (highly unlikely) a longer tube would get more kero here. Also on decanter, the loose seal around the tube is at present caulked with "Mortite" to prevent leaks, effective but no good for the long haul, Some method (pietlock's choice) is needed to stop this gas leak on a more permanent basis. 7. Present thermowell is stainless steel and will eventaully fail in this service, also top weld at flange is highly Stressed in a chloride atmosphere and is prone to failure. Inspect while in service and replace with bottom hastelloy T/C ASAP. Present steam sparge is probably GK where it is for its purpose but should be replaced with hastelloy if not relocated, 8. Re-gasket. S. Dev. tank manhole with some elastomer which will stand service, present rubber is going and Teflon cuts and requires more than hand tight wing nuts tO seal well, 9. Split water flow to Dev. tank to reduce addition time and still not disturb sulfate. DUP050108944  APPROVALS; .. Go r,-. \ty/< o",c,W7Z r .g -3 r~*' APPENDIX C BB CRUDE SYNTHESIS - SULFATION SOP 110-A LOT NO. I t ( } ITS t h is CPR, 1 INSTRUCTIONS TV ! Pump /00 gals. Kerosene to the Dewater Tank. QUANTITY [ ,,STD..... RECC'D TUuGaiT 2. Filter one standard batch of 4-CPA into the Debater Tank. 3. Begin dewatering of the 4-CPA. 4, Charge the following dry chemicals to the synthesis solids bin in order listed: 1. Urea 4100# 2, Cuprous Chloride 445# 3. Molybdic Oxide 18# 4. D3PC 5# 1 3. PA 2100# 37^ Pump 1400 Gals.. initial kerosene to the synthesis' tank. 1400Gal Gal b. Heat the contents of the synthesis tank to ' 120" C. 120C c When 4-CPA dewatering is complete, feed the dewater tank product to the synthesis tank. 3. Fomo additional 300 sals, kerosene to the i synthesis tank. 9. Heat me contents of the synthesis tank to i 300Gal. Gal 120C. 120C 10, Hold at temperatiare for 15 minutes. 15 min. 11. Add the dry chemicals from the synthesis solids! C min. bin to the synthesis tank. 12. Heat contents of synthesis tank to 205C. 13. Hold contents of synthesis tank at 205C for ^-- 2 hrs. 14 ,, Pump 300 gals. Kerosene dilution to synthesis tank. 15. Drop batch from synthesis tank to the cooling 300Gal. Gal tank. 16. Pump 800 gals. Kerosene flush to synthesis tank SOOGal. Heat to 150C and hold 1/2 hour with agitation. |I/> Drop flush to cooling tank. 118. Check all top manholes and flanges closed on 1 South Development Tank, ; r-t Check bottom valve of Hold Tank closed and | charge 314 gals. Sultunc Acid to tank. 314Gal. Gal, J2U. Check draft oh South Development Xante. Minimum r drazt must be 3'1 H2O. jZi. Turn CQo purge to 3. Development Tank on full 111 | at least 1/2 before transferring batch from ! cooling tank. t1 s t! i DUP050108945 -2 SOP 110~A APPENDIX C (CONTD.) BB CRUDE SYNTHESIS SULFATION 0PE.il zv, ....... 23, 24, 25. 26, 27. 23, 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39, 40. tor n o . INSTEU-CTIOS3 J........ QUANTITY STD, R~C OPT) sen b'.iusn xanK i^raae _paxe-C-PDr .pw.T.tc.n...an... ......... ji REAL. ........ .. ............ 1: When ready to transfer ..b.?Jlclx..frem_,coollne:J .tank ! reduce CO, oursa on S. Development Tank to j 30 cfra......................................................... . 1 Ooen all valves in transfer line between trans-! er nSandpioer" d u o d and S. Development Tank. 1 Make sure all other valves in transfer line areif closed. 1 Adiust temperature in cooling tank to 100-105C 100* Must be pumped to S. Development Tank within ! 105C this temoerature range. 1 In BEAL position so to steo 11 of Flush Tank i Sequencer. 1 Manually ooen air to sandpiper and bottom valve! of cooling tank to set sreen advance lisht to so to steo 12, i Advance to step 12. open ~oead control full. ! When transfer complete, record temoerature in i S. Development tank. ! Turn off sandpiper pump, close valves in 'traps'-' far line, i .Start S. Development Tank agitator at full i speed. Should be 73 roa. I Set on automatic acid flow to S. Development Tank to deliver 1.9 gpm* Open Hold Tank bottom valve to begin acid feed. Periodically check area for KCX fumes during ! acid addition. After acid addition complete, continue agita- 1 tion for 15 minutes. ! Shut off S. Development Tank agitator. i Through 2!i nozzle insert dry sample dip rod. i Note: While sampling wear rubber gloves and i face shield. 1 Make a thin smear of sample on white paper. i If smear blue notify supervisor (see special j procedure for additional sulfation). j Allow il'l hour settling time .after agitation j 1/2 hr. Stopped. i hr, Start kerosene decantation, sandoioer pump at slow speed. S I I i . . ... i DU P050108946  -3- SOP 110-A APPENDIX C (CONT.) BB CRUDE SYNTHESIS - SULFATION LOT NO. 1' ATE Tim OPR. 1 INSTRUCTIONS i OUANTITY S TD, Ti|.ii-yRrr!TE/i-^C-"C>uE,li---D7^**' ^ H. . circle one (yes no). j,,, ..... ........ " ' 11 * i 42. Finish Kerosene decantation. 43. Add 1900 gal, of water to S. Development Tank at about 20 gpm. through the. line and meter 1 at the top of the tank. Add without agitation. 1900Gal Gal* 44. Let contents settle for 1 hour. 1 hour Hr. 45. Start Kerosene decantation. Check for pigment i in decantation stream (yes no) Circle one. . 46. Finish Kerosene decantation. 47. Add additional 800 gals, water to S, Develop- 800Gal. Gal meat Tank through bottom inlet' at fastest rate possible. 48. Jog S. Development Tank agitator 3-4 times. (3 or 4 revs, per jog) 49, Turn on agitator,increase to maximum speed (should be minimum /8 rpm). 30. Continue agitation for 30 minutes. 3 Chains, nans 51. Stop agitator, open manhole, hit bottom of tank with semolina rod. Should contact solid brick. if spft'pigment felt raagitate at-full speed. 1 for 30 minutes and retest. Dilute with~400 1 gallons additional water to slurry up'if needed! i52. When rod hits solid brick, batch is ready for | transfer. j ...... . . . . . . . . . . . . . . . . . . . . . . . . . ... .......... . .. . _ ..... . ............ j i j ADDITIONAL SULFATION SPECIAL PROCEDURE: 1. Add 157 gals. Sulfuric Acid to Hold Tank. 2. Start S. Development Tank agitator, increase .to maximum rpm. - 3. Start acid flow at 1.9 gom, 4. After acid addition comolete, continue agita- tion for 15 minutes. 5. Shut off S. Development Tank agitator. 6. Resample contents for smear test. | ! | | w* . DUP050108947 E. t. DU POOT DE NEMOURS & COMPANY * APPENDIX D W. s. Struve J. P. Galvin ' - Newark u - H, Matrick - G. M. Loughran - Newport A, F, Lewis - V. J, Lewis J, W. Ignace - - It I. A. Berkemeier - B, M. Strouss - C. E. Woodruff - W. G. Hoffman - J. J. Adams' - E. E. Jaffe C. W. Anderson - A. P. Smith P. H. Griswold - - W. E. Miller - E, W, C-illow R. J. Guschl D. J. Gilliland -r Library - File - If It 1! Tt 11 II M ir u t it !J It ir Newport, Delaware March 24, 1976 CPC III - NEWPORT XON NO. 21 TITLE: CPC-BB Agglomeration (Pelletization) OBJECTIVE: Prevention of CPC-BB separation from the kerosene/water emulsion and to determine the proper amount of Triton N-100 in the procedure. BACKGROUND: Following sulfation/hydrolysis of CPC-BB in Area III, the kerosene/water/cPC-BB emulsion is routinely stored in the South Development Tank, transferred via tractor to tanks 31 or 4?A of Area I, base extracted and pressed out in 33C and D. At times, a pigment/kerosene phase separates from the emulsion as either small pellets or' a slime making pressing impossible. We now feel that this is the result of over-agitation of the emulsion during hold period's or extraction pausing the emulsion to break (''buttering out the pigment"). The purpose of this XON is to prevent this separation and to list procedures to follow (in sequence) if a batch dees separate to save it. These procedures inco.roorate and build upon the knowledge of several shift, supervisors and their operators, DUP050108948 ' -%' n! APPENDIX D (CONTD.) 2- - PROCEDURE: Standard Area III BB Crude Synthesis-Sulfation Procedure (SOP 110-A) with the following changes: Up to Step 48, as is 48a - Add 2 gal.* Triton X-100 through manhole 49 - Turn on agitator, increase to maximum speed for 30 minutes. 50 t Stop .agitator, open manhole, probe bottom of tank with sampling rod. Should contact brick, if soft pigment cake is present, reagitate at fill speed for 30 minutes and retest. Dilute with 400 gal. additional water to slurry if needed. 51 - When rod contacts pigment-free brick, batch is ready for transfer. .... 52 - When batch transfer to Area I is delayed, reduce agitation speed to 20 rpm up to and through pumping to trailer. (*) This quantity may be adjusted by R&D based on operating performance at the 2 gal. level. If a batch separates in Area I before pressing, the following sequence of procedures is recommended: (1) Before too much of the aqueous caustic is lost to the pressing attempts, add 2 gal, Triton (and only 2 gal., more will not help) and recirculate the batch through the pump 2-3 hours. Retest for emulsion, (2) If still no emulsion, add 300 gal. kerosene and recirculate batch through pump 2-3 hours . Retest for emulsion. (3) If still no emulsion, drain -aqueous caustic layer until only pigment/kerosene is left in the tank. Add 40 inches kerosene to the tank and heat v/ith steam at 90-100C . Recirculate batch through pump 2-3 hrs. Test for creamy emulsion. When established, add enough water to fill tank to 85" and recirculate a final 1/2 hr. before pressing. (4) Remove aqueous layer and drum but kerosene slurry if pressing is still impossible. Do not sewer. DUP050108949 APPENDIX D (CONTD,) -3- HUMBER OF TEST BATCHES: To be determined SAMPLES: 1 gal. of each trailer batch (preferably taken at the end of first trailer load and beginning of second trailer load). 1 gal. of each batch which separates in Area I before treatment. As each attempt to reslurry is tried, keep one gallon for R&D until the emulsion is established. TESTING- Routine production testing. All above R&D samples go to R&D - Attention: R. J, Gusche DISPOSITION: Routine SAFETY: No new safety hazards are presented by the changes in process. CLOSING REPORT RESPONSIBILITY: R. J. Guschl APPROVALS: Production Quality Control R&D Environmental Control /tmi Safety DUP050108950 x-nc-*a rciv '.c- Qyy r*uW 6iTi.v.:isiw id-.:2 E. 1. d u Po n t d e Ne mo u r s & Co mp a n y INCORPORATED Ne w p o r t , De l a w a r e i9804 PIGMENTS DEPARTMENT APPENDIX D (CONTD.) CC: W. S. Struve - Newark A. P. Lewis - Newport 1. A. Berkemeier - " E. E. Jaffe -" C. W. Anderson - " N. J. Kane -" A. P. Smith- -" K. M. Kolb -" E. W. Gillow - " P. H. Griswold - " R. D. Nelson - " D. J. Gilliland - " W. E. Miller - " Newportj Delaware March 30, 1976 TO: VI. G. HOFFMAN - NEWPORT C. E. WOODRUFF - FROM: R. J. GUSCHL// - NEWPORT V TRANSFER, EXTRACTION AND PRESSING PROBLEMS OF CPC-.BB ABSTRACT To eliminate the problem of separation of CPC-BB batches before and during pressing, batches must move through sulfation, hydrolysis, transfer, extraction and pressing without delay. If delays are encountered, batch agitation must be minimized during holdovers. Laboratory experiments have established that just about any slurry of CPC-BB/kerosene/water (or caustic solution) after sulfation/ hydrolysis can be made "to separate" with sufficient agitation. By separation., 1 mean the agglomeration of pigment into pellets, slime or cakes which cannot be pressed .as the usual slurry. In controlled studies on .several plant lots, intense agitation (220 RPM) causes separation after 5-15 hours as compared to a control of mild agita tion (8o RPM) which did not separate even after 2A hours of agitation. High pigment content seems to lead to earlier separation. Excess kerosene does not seem to be a problem other than making good washing difficult/ The addition of-SI.30% (pigment basis) Triton X--100 sur factant to the solution before agitation prevents separation and- caking. Lesser amounts are less effective and encourage pellet formation over "slime1'. (1.5$ would be approximately A gal./synthesis batch.) In all eases where pellets, slime or cakes had been formed (plant or laboratory) high shear agitation by an electric blender re-established a good slurry. The presence of surfactant is beneficial only in main taining the slurry through subsequent agitation. BETTES THI.V3.3 FOS BETTES UViNG . . , TH `lOUO'ri CHZMlS rjtr DU P050108951 k*\ APPENDIX D (CONTD.) In summary, the agitation of each fca tch in both areas should be just enough to establish and maintain slurry, yet hot enough to cause separation. If separation should occur, high shear agitation is recommended to re-establish slurry. A study of the last ten batches processed in Area I has been consistent v/ith these findings; In all batches where separation had occurred and pressing had been difficult until the end, the batch had been agitated for more than one shift before pressing and was agitated for a total of 3 to 7 shifts before pressing was completed, i In the variety of approaches used to re-establish Slurry, recirculation through the centrifugal pump was common to all, s> The, long hold-up times before pressing were not always due to separation of the batch, but once the batch was delayed, the problem appeared or intensified. To eliminate these problems, we need only to coordinate our efforts vihen a batch is held up. We recommend the following; If a batch must stay in the south development tank for any extended period (one hour or more after the second water addition), turn off the agitator and restart 1/2 hour before transfer. For very long storage periods, some agitation every 6 hours is recommended to maintain slurry. The agitators in 47A and 31 tanks should be rewired for control free of the 24B and 24c pumps. If a batch cannot be pressed immediately after ex traction, stop agitation. If necessary due to separation, begin and maintain recirculation through . the centrifugal pump until ores sing..' Start the agitator only to prevent settling or when pressing begins. If pressing is interrupted for long periods/ stop agitation again. DUP050108952 APPENDIX D (CONTD.) *3- 0 Since we cannot divide synthesis batches evenly with our current procedure, short fills of the presses are inevitable and the preferred pro cedure is to wait for the next batch to fill the press. If this must continue, flush the press lines with water between batches. I feel the recent appearance of spare pumps at both ends qf the transfer operation will eliminate much of the trailer settling leading to this problem. & If a batch separates, follow an orderly procedure iri attempting to save it. We recommend the following sequence of procedures, all of which were developed over the years by Production personnel. We have merely formalized and verified them. By attempting to save the separated batch in the order below, we should be able to minimize time and effort. (1) Before too much of the aqueous caustic is lost to the pressing attempts, add 2 gal, Triton (and only 2 gal., more will not help) and recirculate the batch through the pump 2-3 hours. Retest for pressable slurry. (2)* If still no slurry, add 300 gal. kerosene and recirculate batch through pump 2-3 hours. Retest for pressable slurry. (3)* If still no slurry, drain aqueous caustic layer until only pigment/kerosene is left in the tank. Add 40 inches kerosene to the tank and heat with steam at S30-100C. Re circulate batch through punp 2-3 hours. Test for creamy slurry. When established, add enough water to fill tank to 8.5'1 and- re circulate a final 1/2 hr. before pressing. (4) Remove aqueous layer and drum out kerosene slurry if pressing is still impossible. Do not sewer. . (*) Please note the addition of excess kerosene in procedures #2 and #3 will make washing more difficult and lead to high water soluble salts. Accordingly, these approaches should not be tried unless #1 has been fully exhausted. . DU P050108953 CD F - - 4 - APPENDIX D (CONTD.) In many cases in the past month, one approach (such as #1) has been started in one shift and discontinued by the next before there has been time for sufficient recirculation. The next shift then tries their favorite method of dealing with this problem. In some cases, the problem just sits until a less pessimistic group comes on since not all groups shared this information. provide sufficient manpower or direction of existing manpower to see that a press begins washing as soon as it is filled and that after washing, it is dumped as soon as possible. Since B3 has always presented more problems than other grades, the tendency is to give preference to LC and green. Of course, we are interested in your comments and are will to provide further assistance if the above suggestions do not solv the problem. /tmj DUP050108954 APPENDIX E I. DU PONT PE NEMOURS & COMPANY CC: W. S. Struve G. M. Loughran Pigments Department A. F. Lewis V. J. Lewis J, W. Ignace I. A. Berkemeier D. M. Strouss C. E. Woodruff (5) w. G. Hoffman J. j. Adams E. E. Jaffe C. W. Anderson N. J. Kane A. P. Smith J. Guschl D, J. Gilliland R. D. Nelson VI. L, Monson Library File Newark Newport ri II II ir 11 n n n *i Hi ri V Newport, Delaware June 30> 1976 CPC I - NEWPORT XOP-451 TITLE: CPC-BB-BBS Without Premilling OBJECTIVE; To evaluate the quality of BBS (N-85IO) prepared in the plant without premilling before acetone milling BACKGROUND; Laboratory studies have shown that premilling BBU before standard acetone milling slightly enhances BBS quality (strength and intensity). We feel however, that current N-85IO from plant II (9pC. sulfation/hydrolysis) is already vs green and vs intense versus the current N-85IO standard, thus this enhancement of properties associated with premilling may not be necessary to meet the current standard. Since premilling capacity in Plant I will be production limiting in the future, it is necessary to demonstrate this variation of the process in the plant. STARTING DATE; July, 1976 NUMBER OF TESTS; v ` One packlot of N-85IO prepared without premilling (3 acetone millings) One packlot of N-85IO prepared with premilling as a control. (3 premillings, 3 acetone millings) For both experiments, R&D will carefully pick the BBU crude, Of the three lots selected for each milling, one will be representative of standard BBU, one of upper size limit and one of lower size limit (as reflected by valley parameter of x-ray). DUP050108955 APPENDIX E (CONTD.) -2 PRELIMINARY PRECAUTIONS: Be sure to use only the drums of BBU approved by R&D for this experiment. Standard acetone milling precautions. PROCEDURE: Standard acetone milling and finishing procedures. The only difference is that we are eliminating the premilling of BBU crude before acetone milling. SAMPLES: 1 gal. of the material charged to each acetone mill 1 gal. of acetone slurry after acetone milling (each) 5 gal. of the final packlot slurry for both the experimental batch and the control TESTING: Newport - Quality Control Newark - R&D will direct samples to G. Aldridge for evaluations in end-codes. DISPOSITION: Newport Quality Control will arrange for disposition into suitable production category. SAFETY ASPECTS: Standard safety associated with acetone milling RESPONSIBILITY FOR CLOSING REPORT: R. J. Guschl - R&D APPROVALS: /tmj Environmental ContrcQ. and Safety DUP050108956 E. I. DU PONT DE NEMOURS & COMPANY Pigments Department APPENDIX F CC: W. S. Struve - Newark R, Gedd - ' G. M. Loughran - Newport A. F. Lewis -" I. A. Berkemeier- " S. W. Severance ~ " D. M. Strouss - " V. J. Lewis -" J. W. Ignace - " J. J. Adams -" W. G. Hoffman - " C. E. Woodruff - " M. Barszcz -" G. Miller -" E,. E. Jaffa -" C. W. Anderson - " N. J. Kane -" P. H. Griswold - " E. W. Gillow ~ " R. D. Nelson - n D. J. Gilliland - " Newport, Delaware September 30> 1976 CPC II - NEWPORT XON-32 TITLE: Low Temperature Sulfation/Hydrolysis of BBU CPC-BBS Without Premilling OBJECTIVE: 1. Determine the quality of 3B products prepared from BB crude which has been sulfated/hydrolyzed at ^0C . and 68 C. 2. Develop a BBS process which does not need six tours of premilling. 3. Determine optimum combination of premilling/milling times for current BBS grades. BACKGROUND: In the Laboratory, we have established that BBS quality can be enhanced by either premilling the BBU before acetone milling or sulfating and hydrolyzing at temperatures .below 95C . (current plant operating temperature). We have found that lower temperature sulfation requires some extra acid to guarantee complete sulfation. When we lowered the temperature of sulfation/hydrolysis from 130C. to 95C., we observed a reduction in crude crystallite size to slightly below the pigmentary range. In the laboratory, we have demonstrated that crystallite size in the range of premilled product (BBZ) is produced when the temperature is below 50C. \ DUP050108957 APPENDIX F (CONTD.) -2- BACKGROUND: (Continued) Based on this finding, it may be possible to so enhance BBS strength by lowering the temperature to 40C. and eliminate the premilling step entirely. This would be advantageous in the near future when premilling capacity in Plant I becomes production limiting. A secondary benefit of this test will be to re-establish . the optimum sulfation/hydrolysis temperature and milling times for the current BBU quality levels. Since an earlier XQP (451) established that current BBS made without premilling is blendable, all materials generated by this experiment are expected to be used as product. STARTING DATS: September, 1976 NO. OP TESTS: The number and order of tests have been statistically selected to minimize variables and sampling. The following order of experiments must, therefore, be followed. Since samples will identify quality parameters, there is no need for packlot integrity. Run # Temperature to Drop to Sulfation Tk. Premill Period (Hrs.) Samples Taken from Acetone Milling (hrs . 1 1 68 C. 2 68 C. 3 40 4 40 5 95 6 95 7 68 8 40 9 95 10 o3 11 68 12 68 3 17.5, 25 3 17.5, 25 0 10, 25 oS' 10, 25 0 10, 25 6 10, 25 3 17.5, 25 3 17-5, 25 3 17.5, 25 0 17.5, 25 6 17.5, 25 3 10, 25 The remaining portions of any lot may be combined and used following standard premilling and milling procedures. PRELIMINARY PRECAUTIONS: 1, No substandard or reclaimed pigment is to be added to any batch covered by this XON. It is extremely important that each mill be charged exactly as described by Quality Control. 85B8SgES5SSSSS^Si DUP050108958 APPE-N--D---I-X----F- (CONTD.) PRELIMINARY PRECAUTIONS: 2. 'This XON should not be attempted until the spray nozzle for sulfuric acid is replaced in the South Development Tank. 3. Make necessary provisions to cool contents of the cooling tank to at least 40 C, before dropping to the South Development Tank.when called for. 4. The use of additional acid to achieve complete sul fation at all temperatures may make it harder to re establish slurry after hydrolysis (Step 40-50). Be sure Step #51 is followed and the slurry is uniform before transfer. 5. The use of additional acid (25$ more) will require additional base to reach the desired pH range for extraction. Increase the initial caustic charge by 150 gallons base (50$ HaOH solution). PROCEDURE: 1. Standard BB synthesis for all batches (Steps 1-24). 2. For all test synthesis batches, the following changes in SOP-110A are necessary: o Step 19 - .... and charge 393 gals. sulfuric acid to tank. "L o Step 25 - Adjust temperature in cooling tank to specified temperature. Must be pumped to South Development Tank at or near specified temperature. o Step 52 - When rods hits solid brick, batch is ready to transfer. If after transfer, pigment is still adhering to tank bottom, flush to North Development Tank with extra water, 4. For all preniiliings and acetone millings, standard milling and finishing procedures will be followed. The only changes will be In milling times, samples taken and in some cases, we will eliminate premlliing entirely. DUP050108959 APPENDIX F (CONTD.) -4- SAMPLES: 1,, For each of the 12 synthesis batches followed o 1/2 gal. BBU presscake 0 1/2 gal. dried BBU from tray drier 2. For each of the 12 premillings followed, one gallon of the premilled product at the end of the specified run. 3. For each of the 12 acetone millings followed* a one gallon sample of the mill contents taken at the specified periods. 4. For each of the final N-8510 packlots which are composed mostly of these batches, one quart of packlot slurry should be taken. TESTING: Newport - Quality Control for normal batch card samples. R&D for all R&D samples requested. Newark - R&D will direct samples to G. Aldridge for evaluations in end codes. DISPOSITON: Newport Quality Control will arrange for disposition into suitable production category. SAFETY ASPECTS: No' unusual hazards are anticipated during Plant I or II operations. RESPONSIBILITY FOR CLOSING REPORT: K, M. Kolb/R. j. Guschl - R&D APPROVALS: 'Manufacturing Gcu,! k RK&D SUo ervisor Manufacturing Area Supervisor' \Ji /traj DUP050108960 REFERENCES 1. W. L. Monson and L. R. Valencourt, KN-76-6A, "Economic evaluation of Proposed Processes for CPC-BB" 2. I. A. Berkemeier, P. H. Griswold and M. Barszcz, Newport Accident Investigation Report No. 1158, No injury Report No. 273, October 25, 1975 Fire 3. For example, the active solvent effect as described in R. J, Guschl, KN-77-2, "An improved Process for Finishing CPC-BB, The Active Solvent Effect" 4. R. D. Nelson, XON-22; Closing Report issued 9/17/76 5. W. L. Monson - Work in progress 6. Pigments Customer Complaint NO. IY-71-021C 7. K. M. Kolb - Mechanical notes to Manufacturing, back part of Appendix B to this report 8. To simulate actual plant kerosene losses, do not use chimney. Appropriate heels and caking will result. DUP050108961 Date Issued; September 13, 19.77 DISTRIBUTION; 1, E, Gonick - Wilmington 2, W, S, Struve - Newark 3, H, B. Clark ^ Wilmington 4, J, G, Ishikawa - Wilmington 5, E, J, Mead - Experimental Station 6, J, E, Romano - Newport 7, G, A, Hapka - Legal r- Wilmington 8, C, F, Rolle - Wilmington 9, E. E. Jaffe/Circulate and pile - Newport IQ., B, H, Perkins/A, P, Smith/Newark Library - Newark 11, C, W, Anderson - Newport 12, N. J, Kane/Newport Library - Newport 13, P, H, Griswold - Newport 14, W, A, West - Newport 15, W, E, Miller - Newport 16, K, M, Kolb - Newport 17, W. R. Bushey <- Experimental Station 18, H, Matrick/S, L. Sweet/J. Jackson -r Newark 19, R, Z, portney/V, A, Romito r- Newport 2Q, S, W, Severance - Newport 21, I, A, Berkemeier/W. G. Hoffman - Newport 22, R, D, Nelson - Newark 23, R. J. Guschl - Chestnut Run 24, Central Report Index - Chestnut Run 25, H i _ w 26, Newark Research File - Newark 27, Numerical Pile - Newark 28, Extra 29., * 3Q, DUP050108962