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United States Patent (19) Mar. 28, 1995 US00540 1876A United States Patent (19) 11 Patent Number: 5,401,876 Correia et al. 45 Date of Patent: Mar. 28, 1995 (54 SYNTHESIS OF CHLOROACETIC ACIDS 6031 of 1910 United Kingdom ................ 562/603 1404503 6/1988 U.S.S.R. .............................. 562/603 75 Inventors: Yves Correia, Chateau Arnoux; Daniel Pellegrin, Grenoble, both of OTHER PUBLICATIONS France CA 78(20):128110p Opp et al “Removal of Chlorine, 73 Assignee: Elf Atochem S.A., Puteaux, France Phosgene, and Hydrogen Chloride from waste Gasses', 21 Appl. No.: 95,224 DE2121403, 1972, Abs. only. Primary Examiner-Raymond J. Henley, III 22 Filed: Jul. 23, 1993 Assistant Examiner-Keith MacMillan (30) Foreign Application Priority Data Attorney, Agent, or Firm-Burns, Doane, Swecker & Jul. 23, 1992 FR) France ................................ 92 09095 Mathis 5ll Int. Cl............................................... C07B 39/00 57 ABSTRACT 52 U.S. C. .................................................... 562/603 Chloroacetic acids and essentially pure hydrochloric 58) Field of Search ......................................... 562/603 acid are prepared by chlorinating acetic acid in the 56) References Cited presence of a catalytically effective amount of acetic anhydride, acetyl chloride, or admixture thereof, U.S. PATENT DOCUMENTS whereby byproducing a gaseous stream of crude hydro 2,826,610 3/1958 Morris et al. ....................... 562/603 chloric acid, contacting such gaseous stream with ac 4,003,723 1/1977 Schäfer et al. ...................... 562/603 tive charcoal to remove the chlorine values therefrom, 4,383,121 3/1983 Sugamiga et al. .................. 562/603 separating (i) pure hydrochloric acid and (ii) remaining FOREIGN PATENT DOCUMENTS products from the gaseous stream thus purified, and 552754 2/1958 Canada ................................ 562/603 recycling such remaining products (ii) to the medium of 749 128 10/1970 France .... ... 562/603 chlorination. 0127329 10/1981 Japan ................................... 562/603 1097.69 10/1964 Netherlands ........................ 562/603 16 Claims, 1 Drawing Sheet U.S. Patent Mar. 28, 1995 5,401,876 5,401,876 1. 2 of sulfuric acid and of acetic acid and then drying the SYNTHESS OF CHLOROACETIC ACDS washed product with concentrated sulfuric acid. Said JP-63/50,303 (Kokai), published Mar. 3, 1988, BACKGROUND OF THE INVENTION describes washing the crude gaseous hydrochloric acid 1. Field of the Invention stream, containing acetyl chloride below a specified The present invention relates to an improved process amount, with sulfuric acid. The acetyl chloride con for the preparation of chloroacetic acids, and, more tained in the crude hydrochloric acid stream is con especially, to an improved process for the chlorination verted into acetyl sulfate. of acetic acid wherein the byproduct crude gaseous Nonetheless, such processes require sulfuric acid and hydrochloric acid, containing chlorine and acetyl chlo 10 complicated mechanical apparatus. ride values, is purified and pure HCl recovered, while SUMMARY OF THE INVENTION other products are recycled to the medium of chlorina tion. Accordingly, a major object of the present invention 2. Description of the Prior Art is the provision of an improved, far simpler total synthe 15 sis of chloroacetic acids which does not require the Hydrochloric acid is produced, for example as a by addition of an extraneous compound such as sulfuric product during the synthesis of chloroacetic acids, by acid. reacting chlorine with acetic acid in the presence of Indeed, it has now unexpectedly been determined acetic anhydride or of acetyl chloride. Such synthesis is that it suffices to remove the chlorine contained in such described in Ullman's Encyclopaedia of Industrial Chem 20 crude hydrochloric acid, thus permitting same to be istry, 5th Edition, Vol. A6, pages 537-541. compressed without risk of corrosion. To this end, it is Acetic anhydride, acetylchloride, or mixture thereof, sufficient to contact the crude gaseous hydrochloric can be employed as a catalyst in this reaction. The reac acid stream with active charcoal. tion mechanisms are as follows: It has also now been determined that chlorine reacts 25 with acetyl chloride in the vapor phase on active char coal, and in a very short period of time, to form chloro (CH3CO2O + Cl2-G) acetyl chloride. O Briefly, the present invention features an improved R l process for the synthesis of chloroacetic acids by chlori CICH2C-O-CCH3 + HCl 30 nation of acetic acid in the presence of acetic anhydride O O or of acetyl chloride, thereby producing a gaseous stream of crude hydrochloric acid as a byproduct, and CICH6-o-c-CH3+ CH3COOH-Ge. which comprises: (a) contacting such gas stream with active charcoal CICH2COOH + (CH3CO)2O 35 until the chlorine values contained therein have been removed, CH3COCl.--Cl2-CICH2COCl.--HCl (b) separating, in the stream obtained in step (a), by CICH2COCl.--CH3COOH-CICH2COOH--CH- - means of at least one compression (pressurization) 3COC and one cooling sequence, (i) pure hydrochloric acid and (ii) other products, Afraction of the acetic anhydride is also converted to (c) recycling said other products (ii) into the reactor acetyl chloride: or reaction zone for the synthesis of the chloroace tic acids. 45 BRIEF DESCRIPTION OF THE DRAWING Thus produced are (i) a liquid phase containing acetic The FIGURE of Drawing is a schematic/diagram acid, monochloroacetic acid, acetyl chloride, chloroac matic illustration of suitable apparatus for carrying out etyl chloride, optionally acetic anhydride and the chlo the process of the present invention. ride thereof, and a minor amount of dichloroacetic acid and (ii) a gas phase essentially comprising hydrochloric 50 DETAILED DESCRIPTION OF PREFERRED acid and a few percent of chlorine, acetyl chloride, EMBODIMENT8 OF THE INVENTION chloroacetyl chloride, acetic acid and monochloroace More particularly according to the present invention, tic acid. This hydrochloric acid must be purified before the synthesis of chloroacetic acids can be carried out by being used, for example, as a reagent in an oxychlorina chlorination of acetic acid in the presence of acetic tion reaction. It is also preferable to recover the above 55 anhydride or of acetyl chloride as catalyst therefor. indicated compounds contained in the gaseous hydro Whether acetic anhydride or acetyl chloride is used, chloric acid stream to permit recycling same to the acetylchloride is always formed. Whether the synthesis synthesis of chloroacetic acids. is in the gas or liquid phase, the hydrochloric acid by Techniques for the purification of such crude gaseous product is always obtained in the gaseous form. This hydrochloric acid stream are known to this art. acid contains a few percent of chlorine (Cl2), of acetyl FR-2,311,749 and JP-63/50,303 (Kokai) relate that chloride, of chloroacetyl chloride, of acetic acid and of purification by condensation requires low temperatures monochloroacetic acid. taking account of the boiling point of acetylchloride. It Although it is possible to use any type of active char is necessary to employ both pressure and a low tempera coal and in any form, it is advantageous that it be consti ture, but the impure gaseous hydrochloric acid thus 65 tuted as a fixed bed and in the form of granules in order provided is very corrosive to compressors. to minimize the pressure drop of the gas stream to be FR-2,311,749 describes washing such crude gaseous purified. The charcoal is preferably employed in the hydrochloric acid stream with a concentrated solution form of granules of a size ranging from 2 to 3 mm. The 5,401,876 3 4. specific surface of the charcoal advantageously ranges umn and the column bottoms, including acetyl chloride from 300 to 1,200 m2/g. and hydrochioric acid, are mixed with the stream 17 to To attain a significant reaction rate, the reaction is be recycled to the reactor 1. The stream 19 is acetic carried out at a temperature ranging from 50 to 200 C. anhydride, introduced to compensate for process losses. and preferably from 100 to 150° C. 5 In order to further illustrate the present invention and Depending on the amount of chlorine and the tem the advantages thereof, the following specific example perature, a residence time of the gaseous hydrochloric is given, it being understood that same is intended only acid to be purified advantageously ranges from 0.1 to 20 as illustrative and in nowise limitative. seconds. The pressure is not critical; the hydrochloric acid to 10 EXAMPLE be purified is characteristically present at a pressure of The reaction was carried out in the apparatus shown from 0.5 to 5 bars absolute and at a temperature of from in the FIGURE of Drawing. 50 to 100° C. To obtain complete disappearance or A reactor for the chlorination of acetic acid operated stripping of the chlorine, it is apparent that the molar continuously and homogeneously. The pressure was 5 amount of acetyl chloride must be greater than that of 15 bars absolute and the temperature 130 C. the chlorine. It was observed that if the acetyl chloride The gas emerging from the reactor 1 had the compo to chlorine molar ratio is greater than 5, it is possible to sition by volume given below (stream 14): completely remove the chlorine, if its content ranges from 0.2% to 0.8% in the stream to be purified, for a Acetic acid 2.3% residence time of 2 to 3 seconds and at a temperature of 20 Monochloroacetic acid 1.4% 120 to 150 C. Acetyl chloride 4.1% Step (b) is per se known to this art. The stream ob Monochloroacetyl chloride .3% tained at the end of step (a) is cooled at a temperature of HC 90.4% from -25 C. to -350 C. Thus obtained are a liquid Cl2 0.5% phase consisting essentially of chloroacetyl chloride, of 25 acetic acid, of monochloroacetic acid and of a minor It was transferred through an 800 m2/g active char amount of acetyl chloride, and a gas phase of hydro coal bed maintained at 130 C., at a residence time of 2 chloric acid and of acetyl chloride.
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