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United States Patent 0 F” CC, Patented July 13, 1971

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United States Patent 0 F” CC, Patented July 13, 1971 3,592,593 United States Patent 0 F” CC, Patented July 13, 1971 1 2 Progress was made by the introduction of a process 3,592,593 PURIFICATION OF THIONYL CHLORIDE according to which sulfur is added to the re?ux stream Benno Bohm, Leverkusen, Germany, assignor t0 Farben at the head of a column in which thionyl chloride is evap fabriken Bayer Aktiengesellschaft, Leverkusen, Ger orated under a fractional distillation. The sulfur in the many re?ux stream reacts with the sulfur dichloride thereby No Drawing. Filed Dec. 6, 1967, Ser. No. 688,358 reducing the amount of the dichloride in the distillate. Claims priority, application 9Ggrmany, Dec. 10, 1966, The reaction according to Equation 2 however proceeds 50 slowly. Therefore the sulfur dichloride is only uncom Int. Cl. c0’1b 17/45 pletely removed from the vapors. The last parts of the US. Cl. 23—-203 6 Claims 10 sulfur dichloride are to be removed by repeated distilla tion under reflux. This however is hazardous as thionyl chloride forms itself sulfur dichloride under the condi~ ABSTRACT OF THE DISCLOSURE tions of prolonged re?ux-temperatures: Pure thionyl chloride can be obtained from a crude product containing besides sulfur dioxide and\ chlorine mainly sulfur chlorides contaminates by evaporating the It has now been found in accordance with the present in thionyl chloride at a temperature below the boiling point vention an improved process for the puri?cation of thionyl of sulfur monochloride (disulfur dichloride) and contact chloride by fractionally distilling oif thionyl chloride from ing the gaseous thionyl chloride with sulfur containing an sulfur chlorides impurities at a temperature lower than effective amount of iron or iron-compounds to convert the boiling point of sulfur monochloride whereby the gas any sulfur dichloride contaminating the gaseous thionyl eous thionyl chloride being distilled is contacted with sul chloride to liquid sulfur monochloride. fur to convert to liquid sulfur monochloride the sulfur dichloride contained in said gaseous thionyl chloride, conducting the liquid sulfur monochloride to the still of The present invention is concerned with a process for 25 the column and taking off puri?ed thionyl chloride at the the puri?cation of thionyl chloride. More particularly the head of the column the improvement which comprises present invention relates to a process for the removal of contacting said gaseous thionyl chloride with sulfur con sulfur chlorides from thionyl chloride. taining an elfective amount of an active iron product. On a technical scale thionyl chloride usually is obtained Suitable active products which can be used in accord by a process wherein sulfur dioxide or sulfur trioxide is 30 ance with the present invention are the sul?des such as reacted with chlorine and sulfur chlorides. Other known FeS, Fe2S3 and the like, the oxides such as F6203, Fe3O4, processes for the production of thionyl chloride are the FeO, ?nely divided iron powder, the inorganic iron salts direct synthesis from the elements sulfur, oxygen and such as the chlorides, sulfates, phosphates, nitrates and chlorine and the reaction of sulfuryl chloride with sulfur the like. Preferably the active iron products are used in ?nely chlorides. 35 The end-product of all these known processes is a crude divided form in an amount of between 0.01 to 10‘, pref thionyl chloride containing besides sulfur chlorides, sulfur erably of about 0.02 to 1 gram calculated as elementary dioxide and chlorine as impurities dissolved in the thionyl iron per 100 grams of sulfur. For obtaining a highly chloride. Sulfur dioxide and chlorine can be easily re active material the ?nely divided active iron products moved by distillation. The recontamination of the thionyl are suspended as homogeneously as possible in molten chloride with sulfur dioxide is usually avoided by hot sulfur which is then molded or merely chilled and dis condensation of the distillate in a so called ascending integrated into pieces. The size and form of sulfur pieces cooler, i.e. in counter?ow to the steam, and by chilling is not important. It must be possible to apply the sulfur the distillate to ambient temperature (IS-30° C.) sepa lumps into the head of the column on a suitable carrier rately from the steam. 45 such as a perforated plate or the like. The bed of Sulfur dichloride has a boiling point of about twenty solid sulfur is then contacted with the thionyl chloride degrees below the boiling point of thionyl chloride (79° vapors, whereby a solution of sulfur in thionyl chloride C.) whereas sulfur monochloride boils at about 138° C. is formed ?owing in counter-current direction to the thi Therefore, one should expect both sulfur chlorides to be onyl chloride vapors. separable from the thionyl chloride by fractional distil 50 The iron containing sulfur reacts very rapidly with the lation. At least a part of the sulfur dichloride‘ is removed sulfur dichloride present, thereby avoiding sulfur di with the low boiling fraction of the distillate however chloride contamination of the thionyl chloride which is during distillation some sulfur dichloride undergoes the taken off at the head of the column. reaction A sufficiently pure thionyl chloride thus can be pro 2SCl2z2S2C1+ C12 ( l ) 55 duced by a single step distillation, wherein the crude whereby sulfur monochloride is formed. The sulfur mono product containing the thionyl chloride and the impuri chloride on the other hand disproportionates according to ties mainly S02, chlorine and sulfur chlorides is evapo the reaction rated in a distillation column thereby contacting the szcipsclmts (2) vapors with the iron containing sulfur bed provided in 60 the top of the column. From the thionyl chloride vapor As the chlorine escapes at the head of the column equi the volatile sulfur dichloride is thus removed and a librium conditions are not established and a pure thionyl substantially pure‘ product is obtained. According to an chloride cannot be obtained as long as sulfur chlorides are other embodiment of the present invention the process present. A pure product therefore results only after re can be performed also in two steps to yield a still purer moving the major part of the sulfur dichloride and de 65 product and to improve the efficiency. stroying the removing sulfur chlorides under re?ux to In this two-step-process the vapor of the crude thionyl sulfur and chlorine. chloride is at ?rst fed into a column having a bed of In order to overcome this drawback it has been pro sulfur pieces as known per se, thereafter the fractional posed to add sulfur to heated liquid thionyl chloride. By distillation is repeated in a second smaller column con this method however only a poor yield of pure thionyl 70 taining a bed of the iron-modi?ed sulfur pieces. chloride can be obtained in the form of a distillate for By this preferred embodiment of the known process reason of the foregoing discussion. the larger part of the volatile sulfur dichlorides as well 3,592,593 3 4 as of the sulfur monochloride is removed already in the which was prepared by melting together 0.4 g. of FeCla ?rst step. To remove the smaller amounts of the sulfur and 400 g. of sulfur. dichloride remaining in the distillation product of the 37.9 kg./h. of a crude thionyl chloride product con ?rst column only a small amount of the iron-modi?ed taining 80.0% of SOCIZ, 14.5% of SClg, 4.3% of SZCIZ sulfur is necessary. This has the advantage that only and 1.1% of S02 were continually introduced into the small amounts of the iron compounds are brought into distillation vessel. In the continuous operation the mix the distillation residue containing mainly sulfur mono ture in the vessel, which boiled at 92° C., contained chloride, sulfur and thionyl chloride. The residues of 41.5% of SOCl2, 56.3% of SZCIZ and 2% of sulfur both steps can be used as starting material for the produc dissolved in the mixture; 15.8 kg./h. of the mixture ?ew tion of thionyl chloride. The process can be performed in off via the over?ow trap. 1.49 kg./h. of sulfur were the known types of fractional distilling columns, the consumed in the ?rst column and periodically replenished, invention lies in the process and not in a particular while 0.35 kg./h. of the iron-containing sulfur prepara apparatus. tion was consumed in the second column and replenished. The invention is further illustrated by the following At the same time, 23.4 kg. of the puri?ed product which examples without being restricted thereto. 15 was free from sulfur chlorides and which contained more than 99% of water-white SOClz were obtained from the EXAMPLE 1 condenser._ The process described below was carried out in a dis I claim: tillation equipment which consisted substantially of a 1. A process for recovering thionyl chloride from its ?ask of 1 litre capacity, which was equipped with an 20 admixture ‘with impurities including sulfur monochloride over?ow trap, a column of 5 cm. width and 67 cm. and sulfur dichloride, said process comprising the steps length and a re?ux condenser. The column was charged of fractionally distilling said mixture at a temperature at the lower 55 cm. of its length with Raschig rings of below the boiling point of sulfur monochloride and at 7 mm. diameter, at the upper 12 cm. with lumps of a which a gaseous mixture of thionyl chloride and sulfur sulfur preparation which was prepared by stirring 0.2 g. dichloride vaporizes, contacting said vapor mixture with of pyrite cinders into a melt of 300 g./hr.
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