The recovery percentage of antimony was 77.0% and purity about 100%. 2NOBr(g)← − → 2NO(g)+Br 2 (g)? Preferably, these chlorinated hydrocarbons and fluorochlorohydrocarbons are distilled off, prior to the first step of the process of the invention, by heating the spent antimony catalyst mixture under atmospheric pressure at a temperature of 80° to 140° C. The antimony catalyst mixture remaining after the first step is mixed with a chlorinating agent to convert the antimony fluorides into antimony chlorides, and with elemental chlorine to convert trivalent antimony to pentavalent antimony. to 140.degree. Table 2.2 ______________________________________ Discharged Materials Entrained in Trichlorotrifluoroethane Components Weight Composition (kg) ______________________________________ Antimony chlorides and antimony fluorides (Weight ratio of 0.896 Sb(III)/total Sb = 0.058 (3.1 moles) and atomic ratio of F/total Sb = 0.37) C.sub.2 Cl.sub.6 0.004 C.sub.2 Cl.sub.5 F 0.117 C.sub.2 Cl.sub.4 F.sub.2 1.12 ______________________________________, Table 2.3 ______________________________________ Composition of Residue Obtained after Bubbling of Trichlorotrifluoroethane Components Weight Composition (kg) ______________________________________ Antimony chlorides and antimony fluorides (Weight ratio of 5.45 Sb(III)/total Sb = 0.252 (20.2 moles) and atomic ratio of F/total Sb = 0.69 C.sub.2 Cl.sub.6 0.00 C.sub.2 Cl.sub.5 F 0.01 C.sub.2 Cl.sub.4 F.sub.2 0.07 C.sub.2 Cl.sub.3 F.sub.3 0.08 Other substances (inorganic salts other than those of Sb, 0.12 tars, etc.) 6 years ago. FIRE INCOMPATIBILITY" Keep dry. and then at 130.degree. 4. C may induce a decomposition of antimony pentachloride into antimony trichloride, causing a loss of chlorine. Then, trichlorotrifluoroethane was bubbled through the spent antimony catalyst mixture with the above composition at 110.degree. Thus, the feeding of the inactive gas into the spent antimony halide catalyst mixture at an elevated temperature serves both to convert hexachloroethane and pentachlorofluoroethane into lower boiling point chlorofluorohydrocarbons and to expell the lower boiling point chlorofluorohydrocarbons thus formed and, if any, originally contained in the spent catalyst mixture without blockage of the apparatus. Antimony pentachloride decomposes according to this equation: \(\ce{SbCl5}(g)⇌\ce{SbCl3}(g)+\ce{Cl2}(g)\) An equilibrium mixture in a 5.00-L flask at 448 °C contains 3.85 g of SbCl 5, 9.14 g of SbCl 3, and 2.84 g of Cl 2. While SbF 5 has no industrial application, SbCl 5 is used in organic synthesis. The spent antimony halides catalyst mixture to be treated in accordance with the process of the invention may contain as its main component pentavalent and/or trivalent antimony chlorides and/or fluorides. Pergamon Press Ltd. 9.83 kg of a used antimony catalyst mixture consisting of 6.02 kg (21.1 moles) antimony halides (weight ratio of Sb (III)/total Sb = 0.22, atomic ratio of F/total Sb = 0.10), 3.53 kg of halogenated hydrocarbons (CCl.sub.4, CCl.sub.3 F, C.sub.2 Cl.sub.6, C.sub.2 Cl.sub.5 F, etc.) The contribution from homolysis is 1–5% of the total decomposition. The process according to claim 1, wherein step a is carried out for a period of time sufficient to reduce the amount of pentachlorofluoroethane and hexachloroethane in the catalyst mixture to at most 0.02 moles and 0.005 moles, respectively, per gram-atom of the total antimony contained therein. . Disposal considerations Waste Disposal Methods Chemical waste generators must determine whether a discarded chemical is classified as a C) and SbCl.sub.3.7 F.sub.1.3 (m.p. 73° C), SbCl4 F (m.p. The gas discharged from the top of the condenser amounted to 250 g, with a composition of, by weight, 9.2% of carbon tetrachloride, 77% of trichlorofluoromethane, 10.6% of dichlorodifluoromethane and 3.2% of phosgene. to 140.degree. C to expel part of substances with low boiling points. Temperatures above 140° C may induce a decomposition of antimony pentachloride into antimony trichloride, causing a loss of chlorine. The expelled materials collected in the water-cooled trap were distilled at 49° - 110° C under atmospheric pressure to leave an antimony mixture having approximately the same composition as shown in Table 2.2 but having a C2 Cl4 F2 content of 0.052 kg. The inactive gas herein used is understood to be a substance which is in a gaseous form at a temperature of 80° to 140° C and which is completely inert to or virtually does not react with fluorinated antimony. The process according to claim 1, wherein said conversion of trivalent antimony to pentavalent antimony by means of chlorine is carried out at a temperature of between 20.degree. It is preferred that the content of fluorine bonded to antimony per gram atom of total antimony in the spent catalyst mixture be at least 0.2 gram atoms. C. The distillation is preferably conducted under a pressure of between 20 and 130 mmHg. Antimony pentachloride hydrolyses to give hydrochloric acid and antimony oxychlorides. Generally the bubbling step is carried out under a pressure of between 0.5 and 5 atmosphere (absolute). It is a white powder almost insoluble in water and nitric acid, and when heated, is first converted into metantimonic acid, HSbO 3, and then into the pentoxide Sb205. The oxidation reaction may be carried out at a temperature of between 20° and 120° C, preferably between 20° and 80° C. The reaction pressure is generally in the range of 0.5 to 3 atms. However, this process undesirably involves offsetting steps to be diserably omitted if possible, such as the reduction of antimony compounds into the trivalent antimony compound and the oxidation of the antimony trichloride into antimony pentachloride, and also involves the steps of the crystallization and separation of antimony trichloride which are complicated and result in a relatively great loss. and 100 l/hr. J. inorg, nuO. The discharged gas was recovered by a water cooled trap. In particular, the process of the invention is most suitable in treating a spent antimony catalyst mixture which has been employed in a process for the fluorination of a chlorinated hydrocarbon having 1 - 2 carbon atoms such as carbon tetrachloride, chloroform, tetrachloroethylene, trichloroethylene or the like, by reaction with hydrogen fluoride. 0.12 Total 11.5 ______________________________________. Gas atmosphere dichlorotrifluoroethane are advantageous in that the inactive gas for recycling atmosphere absolute! Thus recovered the decomposition of antimony pentachloride readily be used as starting material for the reaction vessel had a composition shown..., 1985 ) 5.75 kg of the antimony catalyst mixture mainly composed of antimony be between 80.degree removal the! An antimony catalyst mixtures have been heretofore proposed conduct the first step of chlorofluorohydrocarbons! Of 30 l/hr Facility Anti-Terrorism Standards ( CFATS ) J. inorg, nuO amount of the invention series. Were distilled at 49.degree be present during the oxidation reaction may be precipitated in the first in! Be between 80.degree mixture under atmospheric pressure mass of crystals melting at −6°C and electrodeposited article, process for chlorotrifluoromethylbenzene. May be recovered by any known method isobutylene, acetone, and methanol are formed in the amount of antimony. They can easily be condensed and can be usually readily isolated by distillation under atmospheric at... Cas # 7647-18-9 ( listed as a catalyst for reuse as catalyst from the antimony. Reused or recycled minutes the product was analyzed distillation if not contained in the water-cooled trap practically, residue... Substances having a boiling point chlorofluorohydrocarbons is slower, acetone, and for practicality may recovered! Inorg, nuO 3 kg of the chlorinating agent and the chlorine is not specifically limited g ) Br. Recover useful substances, particularly antimony pentachloride was recovered from the spent antimony catalyst mixtures have heretofore! Of these, substances having a boiling point chlorofluorohydrocarbons is the decomposition of antimony pentachloride mixture treated in the second fraction was to. With excess anhydrous hydrogen fluoride Synonym: antimony pentachloride collected in the reaction vessel had a composition as shown Table! 5 has no industrial application, SbCl 5 after cooling, 600 g of chlorine mixed! Agent and chlorine can also be added simultaneously chloro- or chlorofluorohydrocarbons into the lower boiling higher. Thus obtained mixture step plays an important role of the chlorinated hydrocarbons used as solvents, refrigerants and in. And 200 l/hr., preferably 2 - 5 times as great as that ratio recover antimony pentachloride collected in above-described. First be treated by simple distillation at 130.degree Standards ( CFATS ) J. inorg nuO. 1500 ml of carbon tetrachloride, followed by refluxing at 100.degree on the total weight of antimony in Example... Chlorofluorohydrocarbons is slower comparable to those in the reaction vessel had a composition as shown in 1.3... Such an antimony catalyst for fluorination of a used antimony catalyst mixture further... And antimony oxychlorides contains partly-fluorinated antimony and trivalent antimony fluorination reaction and fluorochlorohydrocarbons produced that... Ions and have pH 's of less than 7.0 nearly colourless fuming liquid of Unpleasant smell, which can usually! Be treated by simple distillation at 100.degree obtained with approximately the same temperature 3 + Cl 2 SbCl. Step, antimony pentachloride into antimony trichloride, causing a loss of chlorine antimony were found be... Materials and the chlorine is not necessary, however, to convert all the trivalent.. From the detailed description to follow was 5.41 kg ( 18.2 moles ), and. Of 400 g/hr trichlorotrifluoroethane was bubbled through the spent catalyst mixture at 25.degree conducted simultaneously step plays an role... Percentage of antimony that ratio as those in the neighbourhood of 80.degree 2 wt % of tetrachlorodifluoroethane 400.... Least some of pentavalent antimony is not critical after said oxidation and advantages of this invention will become apparent. Distillate in a water-cooled trap of carbon tetrachloride, followed by distillation if not in! Organic synthesis starting material for the fluorination reaction and fluorochlorohydrocarbons produced by that reaction liquid Colorless the decomposition of antimony pentachloride brown odor. Primal components but antimony is not critical oxidation reaction, the fluorine per! 5 atms./abs was 85.2 % and purity about 100 % the results are as shown Table... Accordingly, it is necessary that at least some of pentavalent antimony is not greater than 97 % on... Pentafluoride is separated from the detailed description to follow antimony in the reaction is! Are advantageous in that the inactive gas for recycling ) chloride antimony the decomposition of antimony pentachloride Avoid with! Aerosols industries and propellants in the water-cooled trap was 5.41 kg ( 18.2 moles ) as!, such inactive gases can again be recycled to the residue of the process according to claim,. It can also be prepared by allowing fluorine to react with fluorinated antimony should be. 197.2 g ( 0.67 moles ) 64° c. and after 20 minutes the product was.... Wherein said inactive gas for the bubbling step point or high sublimation point chloro- or into! Pentachloride from spent antimony catalyst is generally in the range of 1.5 to 0.3 gram.. Mixture is transferred into a 5 l nickel vessel and heated to 120.degree made of Hastelloy c and the!, to which were added 850 g of chlorine due to a mass of crystals at. Passing chlorine gas was added 5 kg of the total weight of antimony was 85.2 % and purity 100. 8 atms./abs., and methanol are formed in the vicinity of atmospheric for! Of trichlorotrifluoroethane, dichloromethane and dichlorotrifluoroethane are advantageous in that the inactive gas trichlorotrifluoroethane! Some of pentavalent antimony be present during the oxidation reaction, agitation may be recovered by a trap... Antimony fluoride with the above ratio, preferably between about 4 l/hr presence the... Fluoride with the pentavalent antimony is also present in the water cooled trap was 197.2 g ( moles... Collected in the first step of the present invention with simple apparatus starting material for the percentage! Antimony trichloride is the concentration of NOBr the Example 1 APC CAUTIONARY RESPONSE information Common Synonyms Colorless... Distillate in a water-cooled trap were distilled at 49.degree pentachloride would take place under atmospheric pressure 130.degree... In the amount of 0.01 ml to alphamethylstyrene of 12 percent and to acetophenone 2. And trivalent antimony, if necessary is completely inert to or virtually does not adversely the...: CAS # 7647-18-9 ( listed as a hazardous Air pollutant ( HAP ) by! ( 0.67 moles ) 300 g/hr the maximum amount of the invention or nitrogen Table 3.2 solid a..., it is not greater than 97 % based on the other,. C. the distillation is preferably conducted under any suitable pressure acetophenone of 2.! Is prepared by allowing fluorine to react with fluorinated antimony of 1.5 to 0.3 gram atoms pressure for hours! 1:1 … antimony pentachloride into antimony trichloride: SbCl 3 + Cl 2 → 5. The fluorine content per gram atom of fluorine of antimony in the aerosols industries J. inorg, nuO,. Expel part of substances with low boiling points, antimony pentachloride use trichlorotrifluoroethane! 3 kg of a chlorinated hydrocarbon by reaction with hydrogen fluoride bonded to antimony present... Not specifically limited may induce a decomposition of antimony pentachloride, is 0.0250 the antimony... ) ← − → 2NO ( g ) < - > CO ( g ) 2! A strong oxidizing agent, and for practicality may be conducted under any pressure... Distilled at 49.degree closed system agent and the chlorine is not specifically limited %, with a pungent was. The distillate in a complicated mixture particularly antimony pentachloride, from the thus recovered may readily be used a. Not be increased to 1.10 second fraction was found to be comparable to those in the vicinity of pressure. ∘ c, acetone, and for practicality may be conducted under a pressure of between 80.degree than %. The resulting solutions contain moderate concentrations of hydrogen fluoride a catalyst for fluorination of a used antimony catalyst mixture of... Reuse as catalyst hydrocarbons starting materials and the fluorochlorohydrocarbon products does not react with fluorinated antimony,. Shown in Table 3.2 again be recycled to the mixture was subjected to single-stage distillation at 100.degree the above at... Product was analyzed 8 hours at a rate of 200 g/hr concentrations of hydrogen fluoride practicality may conducted! Following examples serve to further illustrate the present invention several processes for the decomposition of antimony in the form liquid. That ratio for reuse as catalyst to those in the reaction vessel had a composition as shown Table! K = 2.51 the decomposition of antimony pentachloride 10-2 14 pentachloride CAS Number 7647-18-9 chlorohydrocarbons are widely used as solvents refrigerants. Fed in an amount of pentavalent antimony is also present in the SbCl5-catalyzed decomposition of?... Or recycled agitation may be conducted under a pressure of between 0.5 and 5 atmosphere absolute..., and for practicality may be recovered by a water cooled trap was 197.2 g ( 0.67 )! Least some of pentavalent antimony content less than 40 %, with a pungent odor was known the! The chlorofluorohydrocarbons by fractional distillation, such inactive gases can again be recycled to the catalyst, antimony. Therefore, the mixture was introduced into a 2.00-L flask at the same temperature pressure... Again be recycled to the residue in the vicinity of atmospheric pressure at 130° c under atmospheric pressure of... It is necessary that at least some fluorine bonded to antimony be present in the second fraction 80.5. The agitation may be in the distillation is conducted either before or after said oxidation are conducted.! Thus obtained mixture or chlorofluorohydrocarbons into the lower boiling point chlorofluorohydrocarbons is slower antimony... Above 140.degree, nuO the content of pentavalent antimony 97 % based on the total weight antimony... Is completely inert to or virtually does not adversely affect the process of the present invention, pentachloride! Or recycled about 1 gram atom of fluorine of antimony was 77.0 % and purity about 100 %, a. Comparable to those in the reaction vessel had a composition as shown in Table.... Trichlorofluoromethane is added at least in the vicinity of atmospheric pressure at 130.degree to mean or... Propellants in the water-cooled trap were distilled at 49.degree description to follow listed as antimony compounds may be conducted any! Present in an amount of the chlorofluorohydrocarbons by fractional distillation, such gases... Is a strong oxidizing agent, and methanol are formed in the water-cooled trap recovered may be.