Document pBEkq5dJZ5mVyDxYranxoeXQX

V;, ^ - :l ` HCt-U v*? S 1 * ' ' i[*'m \' , . , j ' Return to: Ji.%* XlIjJXCH TO: ** i;J / Return jFILERCOtl-, ' i* ',TG: - ;`v:\ ' ! - ** ''"'O'.''-!' :v; .;... ^ni:^:^;t7^roa^:; L ^^ ^ N37215 <Z JLR-33-3T, No. 3. Serial Number .18728 flHMNMK Dr. H. W. Elley Dr, E, K. Bolton Dr.' Wm.' Kirk Mr. A. J. Wuertz for I.C.I. J. L. Piles Dr. S. S. Rossander (2) (1) (1) (3) / (1) 0 t<t ;$*"v X sL (oT: u< & Company Jackson Laboratory November 15, 1943. <% ' . ~i..V ' ' g 9%A'f: 1 / <Q 4":;. 1:4:5S-Tetra-Chloro-Anthraqulnone S e ria l Number l8 f2 Q JUR-35-37, Wo. 3. H. R. Lee, Group Leader Progress Report E. E. Beard Wm.` Dettwyler Written by: E, E. Beard S. S. Rossander. Division Head DUP050040749 1:4:5*8-Tetra-Chloro-Anthraquinone (Project No. 2077) __________________ E, E, Beard Wm. Dettwyler JLR-33-37, No. 3. Serial Number 18728. Object of the Investigation: 1 - To demonstrate in the Ponsol pilot set the one-step process of ring-closing ortho-benzoyl-benzoic acid (O.B.B.) followed by v chlorination to tetra-chloro-anthraquinone. 2 - To study the purification of crude 1:4:5:8-tetra-chloroanthraqulnone. ' 3 - To prepare 1:4:5:8-tetra-chloro-anthraquinone suitable ,for Ponsol Khaki 2G from mixed dichloro-anthraquinone as obtained from anthraquinone-l-sodiura sulfonate filtrates. Period Covered by Report: February 22, 1943 to July 23, 1945. Historical Background: The subject intermediate is employed in the manufacture of Ponsol Khaki 2G and, at present, is produced over two routes, known ,,as the solvent process and the acid process. The former consists of a solvent chlorination of 1:8 (or 5) dichloro-4:5- (or 8) dinitroanthraqulnone at high temperature (U.S.P. 1,969,044 to the 1,0,I.) and according to the latter method, either 1:5 or 1:8-dichloro-anthre quinone is chlorinated in oleum as solvent in the presence of iodine as catalyst. According to a more recent "acid process", O.B.B. is employed as starting material. The following tabulation, with references, covers the entire development program over the acid process routes. 1 - JLR-33-37, No. 1, Serial Number 17029 - On the use of the dichloro-anthraqulnones as starting material. 2 - AN-1321, Patent Search - The above method is neither patentable nor dominated. 3 - JLR-33-37, Ho. 2, Serial Number 17535 - On the use of O.B.B. as starting material. DUP050040750 4 - AN-1579 - Patent Search - The process, starting with O.B.B.,, and the products are not dominated. 5 - DuPont patent application. Serial Number 438,150, filed 4-8-42, on the subject process. 6 - Tentative Dye Works process via dichloro-anthraqulnone route * 11-6-40. 7 - Tentative Dye Works process via O.B.B. route - 5-28-41 17535-A - Employs 65# oleum, filtration from 93# acid. 8 - Tentative Dye Works process via O.B.B. route - 6-30-41 17535-B - Employs 25# oleum, found to be operable. , 9 - Tentative Dye Works process via O.B.B, route - 2-18-43 17535-0 - Employs 65# oleum, filtration from 98# acid and provision for recovery of the acid soluble as "F" fraction. This process was revised to provide for a hot acid filtration (85C. was used, but 120-130 is preferred) from 93# sulfuric acid. Recommendation was also made for enameled equipment throughout the set in order to satisfactorily accomodate the corrosive acid mixture which is heavily saturated with hydrochloric acid and chloro-sulfonic acid. The current process. Serial Number 17535-F of May 20, 1943, ..provides for drowning the entire chlorination mass in water and isolation of the crude mixture of chloro-anthraquinones. The tentative Dye Works process for the manufacture of 1:4:5:8tetra-chloro-anthraquinone pure via ortho-benzoyl-benzoic acid. Serial Number 17535-E of April 12, 1943 describes the purification of crude tetra-chloro-anthraquinone by means of filtration from hot concentrated sulfuric acid. Note 6 of said process reads as follows: "The filtration temperature of 85C. specified in this process, is only a compromise to meet existing equipment conditions. A filtra tion temperature of 1300, is preferred and would assure a rapid filtration. The nutsch must be built up with a silicate mortar in order to withstand the higher temperature", It was found that in the course of Ponsol pilot set experimental charges, that the compromise filtration temperature of 85C. was un satisfactory, the filtration being too slow as the result of cooling on the nutsch. The solvent purification described in the ctorrent process is adaptable to any quality of crude tetra-chloro-anthraquinone and assures greater ease of plant operation. The material obtained according to this process possesses very high purity. a2*` DUP050040751 The current process was developed In Jackson Laboratory during April-May 1943 and recorded in JLNB-3941, pages 156-168, Conclusions; a - Ring-closure of O.B.B. in the Ponsol Pilot Set followed by chlorination and drowning in water may be operated satisfactorily but acid filtration at 85C. of the acid-drowned chlorination mass was found to be unsatisfactory, b - Purification of the water-drowned acid crude l;h:5:8-- tetra-chloro-anthraquinone by means of solvent may be readily carried out as described in the tentative Dye Works process, Serial Number 17535*? of May 20, 194-3. c - The mixed chloro-anthraquinones obtained from the 1-anthraquinone-3ulfornate filtrate liquors are suitable for vise in the manu facture of 1:4:5:8-tetra-chloro-anthraquinone. Recommendations: 1 - That the solvent purification process, Serial No. 17535-? of May 20, 194-3 be employed for purification of the 1131 pounds of crude 1:4:5:8-tetra-chloro-anthraquinone which was produced In the Ponsol pilot set during February and March 1943, Charges 4, 5> and 6. 2 - That subsequent chlorinations of the ring-closed O.B.B, be drowned in water, filtered, and dried and the crude material puri fied as described above under (l). 3 - After investigating several charges of the Dye Works "solvent" tetra-chloro-anthraquinone (the best grade available at present) we conclude that this material contains an average of about 92$ pure lj4:5:8-tetra-chloro-anthraquinone. We recommend, therefore, the adoption of the recent tentative Dye Works process. Serial Number 17535**? for the purification of all the tetra-chloro-anthraquinone currently produced via the acid .chlorination route. The following benefits will be realized thereby: / a - Savings in 1-amino-anthraquinone consumption in the conden sation step to pentanthrimide. b - Increased yield of Ponsol Khaki 2G type paste from 26.8 to 31 parts per part of the purified tetra-chloro-anthraquinone. c - Decreased dichromate consumption in the Khaki 2Q oxidation step, DUP050040752 d - improved quality of Ponsol Khaki 2Q paste, particularly with reference to shade, strength and,specking in the pads, e - Possible elimination of the alkali-boiling step which follows the acid-dlchromate oxidation* or replacement of this operation by a simple alkali-washing of the oxidized cake on the filter press. (This cannot be recommended without further experi mentation.) Patent Situation: According to AH-1579 the processes and products are not dominated. DuPont patent application. Serial Number 458,150, which includes the subject matter of this report, was filed April 8, 1942. Plans for Future Work: Some further work is involved in establishing the recommended processes in the plant. Experimental Results t 1 - Pilot Set Production Starting with O.B.B. JhNB-3Q4l. pages l40-l43 Processes employed - Serial Number 17535-C, D, and E. Charges No. 4 - Produced 305 Lbs, tetra-chloro-anthraquinone 5 - Produced 371 Lb3. tetra-chloro-anthraquinone 6 - Produced 455 Lbs. tetra-chloro-anthraquinone Total 1131 Lbs. 1-2/3 Moles or 377 pounds O.B.B. was vised per charge. Process yield - 321 Lbs. tetra-chloro-anthraquinone = 55.6$ * 0.85 parts, Charge 4 was filtered from concentrated sulfuric acid and washed with concentrated sulfuric acid. The isolated material from this charge contains 38.7$ chlorine. Charge 5 was isolated in 3 parts as follows: DUP050040753 Part. 1 - filtration from acid, acid washed poorly - 110 Lbs. Part 2 - hot filtration from acid, larger volume of acid, acid washed poorly - 87 Lbs. Part.5 - drowned in water " iZ8 Lbs. Charge 5 - Total 571 Lbs. Charge 6 was drowned in water, filtered on press, washed acidfree and dried. 2 - Purification Studies JLNB-3Q41. pages 143-146. 160-168 A series of experiments on the fractionation of fractions ob tained by the acid and solvent separations of crude l:4:5:8-tetra,,chloro-anthraquinone was carried out prior to writing the solvent purification process. Serial Number 17535-F of May 20, 1943. The starting materials employed include, a - Water drowned tetra-chloro-anthraquinone prepared in the plant directly from O.B.B., Charge 5, Part 3* b - Charge 5, Part 1. We investigated both the insoluble and soluble fractions obtained on filtration of this material from sulfuric acid. c - Tetra-chloro-anthraquinone crude made from the dichloroanthraquinone mixture obtained from the 1-anthraquinone-sulfonate filtrate liquors. d - Dye Works "acid processed" tetra-chloro-anthraquinone (Charges 39 and 40) made from specially selected 1; 5 -dichloro-anthraquinone. e - Dye Works "solvent" processed tetra-chloro-anthraquinone. f - Highly purified l:4:5:8-tetra-ehloro-anthraquinone. The yield data, on filtration of the above starting materials from 5 parts of O.D.C.B. at 80C. is as follows: a - 57-60$ b - 70-80$ c - 44-50$ d - 57-60$ e - 89-93$ DUP050040754 A brief1of summary and conclusions from the separation and sola- . Mlity studies is taken from <ILNB-394l, pages 165-168. 1 - The crude tetra-chlor0-anthraquinone, Charge 5, Part 3 (chlorinated to 32.3$ chlorine) contains at least 9$ of anthraquinone This impurity is readily removed in concentrated sulfuric acid, "but is insoluble, to this extent in 5 parts (based on the crude) of O.D.C.B. at 80C. 2 - O.D.C.B. readily dissolves the low chlorinated and pentachlorinated material in the crude 1:4:5:8-tetra-chloro-anthraquinone. , 3 - A combination of the "acid" and "solvent" purifications, therefore, is best suited for the preparation of the purest possible 1:4:5:8-tetra-chloro-anthraquinone. 4 - Very pure 1:4:5:8-tetra-chioro-anthraquinone is nearly 100$ insoluble in five parts of O.D.C.B. at 80C. and also in 10 parts of 96-98$ sulfuric acid at 25-30C. 5 - Relatively high percentages of di~, tri~, or penta-chloroanthraquinones, as solvent soluble impurities, in the crude material, exert, in solvent, an increased solvent action on the pure 1:4:5*8tetra-chloro-anthraquinone. Ref: S-14 and 15, JLNB-3941, pages 164 and 167 Ref: JLMB-3941, pages 156-7 wherein the alcohol - insoluble crudes and the water drowned crudes are purified over O.D.C.B. Higher yields are obtained (in the O.D.C.B. insoluble fraction) when the alcohol soluble 1:8-dichloro-anthraquinone, for example, has been removed prior to purification from the ortho- dichloro-benzene solvent. 3-A - Khaki 20 Prepared Prom The l:4:5:8-Tetra-Chloro-Anthraqulnone 'Which Is Obtained By Acid chlorination of the Mixed Chloro-Anthraquinones Obtained from the 1-Anthra quinone -Sulfona te Filtrate Liquors JLDB-3941, pages 147-159 The following types of starting material (mixed chloro-anthraquinones) were employed: 1 - From aqueous chlorination of 1-anthraquinone-sulfonate filtrates which were prepared in laboratory sulfonations. 2 - From aqueous chlorinated filtrate liquors ("as is") which were Obtained from the Dye Works 1-anthraquinone sulfonate operation. ' DUP050040755 3 - Prom the aqueous chlorination of anthraquinone sulfonates that were isolated from Dye Works 1-anthraquinone-2-sulfonate filtrate liquors by 15$ salting on the acid side. The data obtained in the preparation and purification of crude tetra-chloro-anthraquinone from these materials, are summarized in JLNB-3941, pages 156-157 (cf. key on page 148). A graph prepared from the chlorination data of Exp. Wo. 10 is shown on page 8. DUP050040756 The starting material employed in Exp. Ho. 10 was the crude dichloro-anthraquinone obtained in the laboratory from 1-sulfoanthraquinone filtrate material which, in turn, was prepared in laboratory sulfnations. The analysis of the crude dichloro-anthraquinone mixture was 22.16# chlorine, sulfur nil, and melting range l46-l87C. The chlorination was carried out at 40C,. in the presence of iodine in 3.5 parts of oleum which contained 1.75 moles of SO per mole of the starting material (calculated as dichloroanthraquinone ). The chlorination was carried beyond' the usual end point in order to obtain the point shown on the graph, at 42.4# chlorine content. Samples of 10 to 20 grams each were withdrawn from the chlorination mass from time to time as the chlorination progressed. These were filtered, washed acid-free with water, then washed with alcohol until clear and finally slurried with alcohol and filtered. The alcohol insoluble portion was dried, refluxed a few minutes in 5 parts of ortho-dichloro-benzene and filtered therefrom at 80*0. The material so obtained was the pure A:4:5:8-tetra-chloro-anthraquinone and the percentage amount found in the crude tetra-chloro*.anthraquinone is plotted on the ordinate of the accompanying graph. The yield of the crude product in the chlorination step is quantitative since it is Isolated by drowningx in water. Experiments were carried out in which crude dichloro-anthra quinone from other sources was employed as the starting material i.e. (a) laboratory chlorinated 1-sulfo-anthraquinone plant filtrate, and (b) laboratory chlorinated sulfo-anthraquinones which were obtained after 15-20# salting of the 1-sulfo-anthraquinone plant filtrate liquors. The yields of the highly purified 1:4:5:8/1etra-chloro-anthraquinone (chlorine near 4l#, M.P. near 550C. ) \ obtained in these experiments were 44.8# and 42.6# respectively. The following data are included to provide a more complete account of the experiment (a) of the preceding paragraph. The chloro-anthraquinone mixture obtained in the laboratory by direct chlorination of by-product 1-anthraquinone-sulfonate Dye Works filtrate, contains 22# chlorine (1.67 atoms) and possesses a melting range of 144-1670. Said mixture, after chlorination in oleum for 17 hours, yields a crude product which contains 57.09# chlorine and possesses a melting range of 270-310C. The yield of crude is 1.25 parts which is the theoretical for tetra-chloro from 41chlo t o -anthraqulnone. ft. ,1.14 DUP050040757 xe.uriMvi.--4 V-. No, sse-'t 4MQSm^unt, *tHh iin<H heavy. ' *& 4 . . DUP050040758 It has since "been found advantageous to remove the anthraquinone-2-sodium sulfonate by 5# salting of the plant liquor (See Sec <3-B below). By further salting a mixed disulfonate is obtained which on chlorination gives a dichloro compound analyzing approximately 24.0# chlorine, This product on acid chlorination and solvent purification will give a 65# yield of solvent purified tetra-chloro-anthraquinone. One part of the pure tetra-chloro-anthraquinone yields 5.17 parts of pentanthrimide which Is equivalent, after fusion, dichromating and dyetesting, to 51.5 parts of Ponsol Khaki 20 type paste. The Dye Works figure is 26.8 parts, cf. JLR-55-57, No. 1, Serial Number 17,029, page 8 of November 6, 1940. The dyeings are green and bright vs. standard and the pads (without the alkaliboil treatment) are only slightly red. The paste, after oxidation in this experiment, was washed on the filter with a small amount of dilute caustic. , 5-B - 1:4:5:8-Tetra-Ghloro-Anthraquinone Prepared From Mixed Diehloro-Anthraqulnone Obtained From Plant Anthraqulnone 1-Sulfonate Filtrate After Removal of Anthraqulnone2-Sulfonate The mixed alpha-disulfonates were obtained from the Naphthalene Area where a trial separation on a plant scale was carried out based on the process as outlined in JLR-55-7, No, 2, Serial Number 18559, The mixed dichloro-anthraqulnones were made in the laboratory and contained on the average about 24# Dig. The chlorinations to the tetra-chloro-anthraquinone were at first carried out in 3.5 parts 13# oleum but were made later in 2.5 parts 17# oleum which gave a higher yield of purified tetra-chloro-anthraquinone. All crude ,.'tetra-chloro~anthraqulnones were crystallized from five parts of diehloro-benzene. . The results are tabulated below. DUP050040759 Table 1 ii ii ii ii it ii ii .jsrsr.sssssaas^s: SSSS^SSSBSSXSSSSSSta::ss b asmsssss asmtx.rs:s.s='8Sttjssss ss:s:38SRMSJlBViWl.mmmmmmmmmm Parts Oleum % Moles Oleum s o1 3 ................ % Crude TetraChloroAnthraauinone % Pure TetraChloroAnthra- auinone M.P. C. - % .'.0 L12T Reference JLKB-4130 ..Page. 5.5 2.5 2.5 2.0 Monohydrate 0,43 HC1S0 2.0 3 2.5 2.5 13 IT 26 22 IT 11.4 1.5 1.5 2.0 1.5 1*5 1.0 93 49.5 346 39.24 100 65.6 3*H5 39.43 100 60. T 348 40.56 93 100 97.5 99. 45.1 65.0 59.1 55.2 338 39.02 346 39.88 348 39.99 346 39.16 60 60 68 68 73 76 77 A chlorination carried out with three times the amount of Iodine gave no higher yield of tetra-chioro-anthraquinone. When only two parts of oleum are used for the chlorination the mass 1 becomes too thick to agitate and the chlorination is inhibited. The conclusions from the above results clearly indicate that mixed dichloro-anthraquinones free of beta-chloro-anthraqulnorte give a higher yield of purified 1:4:5:8-1e tra-chioro-anthraquInone and by cutting the amount of oleum used for the chlorination from 3.5 to 2.5 parts the yield can be boosted to 65$ of theory based on the 'dichloro-anthraquinone charged. A recommendation to this effect has been made to the plant. Submitted for typing ^December 3# 1943 Typed December>28, 1943 emh DUP050040760