(absolute) but this range is not critical. Preferably, the content of pentavalent antimony is not greater than 97% based on the total weight of antimony. 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. 2NOBr(g)← − → 2NO(g)+Br 2 (g)? C, followed by single-stage distillation at 130.degree. The equilibrium constant, K c , for the decomposition of NOBr is 2.0 at 100 ∘ C . 75° C) and SbCl3.7 F1.3 (m.p. A temperature above 140° C results in a loss of chlorine due to a vigorous decomposition of antimony pentachloride. Generally the bubbling step is carried out under a pressure of between 0.5 and 5 atmosphere (absolute). Total 5.73 ______________________________________. C under atmospheric pressure for 8 hours at a rate of 200 g/hr. Purification of the third fraction was also effected by distilling off CCl4, CCl3 F, C2 Cl4 F2 and C2 Cl3 F3 contained therein at 50° - 100° C under atmospheric pressure to leave another antimony mixture composed of about 0.03 kg of antimony compounds, 0.005 kg of C2 Cl5 F and 0.003 kg of C2 Cl4 F2. Temperatures above 140° C may induce a decomposition of antimony pentachloride into antimony trichloride, causing a loss of chlorine. The discharged gas was recovered by a water cooled trap. 18. The dependence of the rates of total decomposition and of homolysis on the … per 1 kg of the spent antimony catalyst mixture. 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. The recovery percentage of antimony was 85.2% and purity about 100%. In the oxidation of antimony by reaction with chlorine, it is sufficient to add chlorine to the antimony catalyst mixture in the stoichiometric amount in relation to the trivalent antimony. No. Example 1 was repeated in the same manner as described except that 1500 ml of carbon tetrachloride and 256 g of chlorine were added to the residue obtained after the feeding of trichlorotrifluoroethane and the chlorination and oxidation reaction were conducted simultaneously at 100° C for 5 hours with refluxing. The process according to claim 1, wherein said inactive gas is fed at a rate from about 2 l/hr., at reaction temperature and pressure, per 1 kg of the spent catalyst mixture. Happy To Help. Presence of a small amount of trivalent antimony is desirable, since the trivalent antimony serves as a promoter for conversion of undesirable compounds such as hexachloroethane into the lower boiling point compounds. The chlorinating agent and chlorine can also be added simultaneously. With a content of bound fluorine smaller than the above defined range, the sublimate substances with high sublimation points and high melting point substances can not be satisfactorily converted to low boiling point substances, or it takes along period of conversion time because of lower conversion rate. (It is said that the pentavalent antimony halides are present either in the form of a mixture of SbCl5 and SbF5 or in the form of a mixture of partly-fluorinated antimony chlorides as expressed by the formula SbClx Fy where x + y = 5) Of these, certain antimony halides having high melting points such as SbCl3 (m.p. C for 20 hours at a rate of 340 g/hr. Clean Air Act: CAS# 7647-18-9 (listed as Antimony compounds) is listed as a hazardous air pollutant (HAP). Freezing point is 37°F. The discharged antimony halides can be trapped by suitable means and, after removal of certain organic compounds contained therein, can be again introduced into the system or readily used as catalyst. Total 221.0 ______________________________________. (1,060 ppm.). FIRE INCOMPATIBILITY" Keep dry. 1. In order to prevent the decomposition of antimony pentachloride into antimony trichloride and chlorine, it is advantageous to conduct the distillation of antimony pentachloride in a chlorine gas atmosphere. Fluorinated chlorohydrocarbons are widely used as solvents, refrigerants and propellants in the aerosols industries. 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. Moreover, no special distillation column is required in the distillation steps. C) have a tendency to block up distillation apparatus. Reactions. Where the fluorine content is not sufficient, however, hydrogen fluoride may be advantageously added to the reaction system prior to or during the first step so as to convert antimony chlorides to fluorides. Trichlorotrifluoroethane, dichloromethane and dichlorotrifluoroethane have been found most advantageous because they completely wash out solidified antimony compounds, even if deposits thereof should form. It is necessary that at least some fluorine bonded to antimony be present in the first step. 5.75 kg of a used antimony catalyst mixture was introduced into a 5 l nickel vessel and heated to 120.degree. Then, recovery of antimony pentachloride contained in the mixture is effected by distillation under a reduced pressure. The process of U.S. Pat. C for 5 hours (cooling temperature 25.degree. The residue in the reaction vessel had a composition as shown in Table 3.3. Table 6.2 ______________________________________ Composition of Residue Obtained after Bubbling of Trichlorotrifluoroethane Weight Components Composition (kg) ______________________________________ Antimony chlorides and antimony fluorides (weight ratio of Sb(III)/total Sb = 0.28 5.27 and atomic ratio of F/total Sb = 0.94) Halogenated hydrocarbons C.sub.2 Cl.sub.6 0.007 C.sub.2 Cl.sub.5 F 0.024 The others 0.103 Other substances (inorganic salts other than 0.28 those of Sb, tars, etc.) Preferably, the fluorine content per gram atom of total antimony is in the range of 1.5 to 0.3 gram atoms. Of these, substances having a boiling point higher than about -50° C (minus) are preferred, since they can easily be condensed and can be reused or recycled. 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. Antimony pentachloride serves as a catalyst for the fluorination, with hydrogen fluoride, of chlorinated hydrocarbons including, for example, carbon tetrachloride, tetrachloroethylene, chloroform, trichloroethylene and the like. C under reduced pressure. The discharged antimony halides can be trapped by suitable means and, after removal of certain organic compounds contained therein, can be again introduced into the system or readily used as catalyst. Trichlorotrifluoroethane was bubbled through the spent antimony catalyst mixture under atmospheric pressure at 130° C for 20 hours at a rate of 340 g/hr. How many grams of each will be found if the mixture is transferred into a 2.00-L flask at the same temperature? c. recovering antimony pentachloride by distillation. Analysis showed a selectivity to phenol of 86 percent, to alphamethylstyrene of 12 percent and to acetophenone of 2 percent. per 1 kg of the spent antimony catalyst mixture. No antimony trichloride is formed. and then at 130.degree. Example 1 was repeated in the same manner as described except that 1500 ml of carbon tetrachloride and 256 g of chlorine were added to the residue obtained after the feeding of trichlorotrifluoroethane and the chlorination and oxidation reaction were conducted simultaneously at 100.degree. However, these values should not be construed as limiting in the process of the invention but may vary depending on the ability and operating time of the apparatus employed in subsequent steps, and economy. No. No. In the fluorination process, the liquid antimony catalyst is charged into a reaction vessel wherein it acts on chlorinated hydrocarbons and hydrogen fluoride introduced therein to promote the fluorination of the chlorinated hydrocarbons. c. distilling the treated catalyst mixture obtained in step (b) to recover antimony pentachloride as the distillate. Fluorinated chlorohydrocarbons are widely used as solvents, refrigerants and propellants in the aerosols industries. Happy To Help. The temperature of the chlorination reaction of antimony fluoride with the chlorination agent is generally in the range of 40° to 140° C, preferably 60° to 120° C. With a temperature below 40° C, it takes a long period of time for the reaction. These make it possible to conduct the process of the present invention with simple apparatus. C for 5 hours (cooling temperature of 25.degree. antimony pentachloride 7647-18-9 >98 hydrolysis yields hydrogen chloride 7647-01-0 antimony pentoxide 1314-60-9 Section 4 - FIRST AID MEASURES SWALLOWED ... Decomposition may produce toxic fumes of: hydrogen chloride, metal oxides. C results in a loss of chlorine due to a vigorous decomposition of antimony pentachloride. 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.) 2NOBr(g)← − → 2NO(g)+Br 2 (g)? 3,760,059, there is disclosed a process wherein a spent antimony catalyst mixture is mixed with trichloroethylene and heated to reduce all of the antimony compounds contained in the catalyst mixture into antimony trichloride, and the antimony trichloride is then crystallized in organic solution and separated, followed by coversion to antimony pentachloride by oxidation. Tetrachloromethane, trichloromethane and 1,1,1-trichloroethane are not suited for use as the inactive gas in the first step, since they are more reactive than hexachloroethane and pentachlorofluoroethane with fluorinated antimony. The following examples serve to further illustrate the present invention. Of these, carbon tetrachloride and chloroform are preferred since they are converted to a gas capable of being readily condensed under ordinarily employed refrigerating temperature conditions, rendering them easy to handle after discharge. and 0.28 kg of the other substances (inorganic salts other than those of Sb, tars, etc.) Trichlorotrifluoroethane was bubbled through the spent antimony catalyst mixture under atmospheric pressure at 130.degree. In the first step of the process of the invention, the spent antimony catalyst mixture is treated by bubbling through or feeding into the catalyst mixture an inactive gas at an elevated temperature. SbCl 5 (g) → SbCl 3 (g) + Cl 2 Suppose that 10.0 g of antimony pentachloride is placed in a 5.00 L container and allowed to establish equilibrium. Further, it is better not to use hydrocarbons or halogenated hydrocarbons having double or triple bonds, since they tend to reduce pentavalent antimony to trivalent antimony. This lowers the catalytic activity and renewal of catalyst becomes necessary when its activity has become too low. Practically, it is sufficient to conduct the first step in the vicinity of atmospheric pressure. C under atmospheric pressure for 42 hours in a rate of 200 g/hr., while continuously collecting the gas mixture discharged from the reaction vessel in a water-cooled trap. The process according to claim 1, wherein said chlorination and said oxidation are conducted simultaneously. C, preferably 80.degree. The process according to claim 1, wherein pentavelent antimony is present in an amount at least 40% based on the weight of total antimony during step (a). The process according to claim 1, wherein said conversion of antimony fluorides into antimony chlorides by means of the chlorinating agent is carried out at a temperature of between 40.degree. The results are as shown in Table 1.4 below. Though the above process represent an improvement in that the chlorine generated upon the thermal decomposition is recycled in the subsequent chlorination step without suffering a loss of the chlorine, it also involves offsetting steps of removing chlorine from antimony pentachloride to yield antimony trichloride and of subjecting the trichloride to oxidation reaction with chlorine to give antimony pentachloride. and 130.degree. The equilibrium constant, K c, for the decomposition of COBr 2. 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. The recovery percentage of antimony was 77.0% and purity about 100%. Preferably, the content of pentavalent antimony is not greater than 97% based on the total weight of antimony. C to remove low boiling point substances at atmospheric pressure, thereby obtaining 5.58 kg of a spent antimony catalyst mixture, the composition of which is shown in Table 1.1. The results are as shown in Table 2.4 below. Such an antimony catalyst is generally in the form of liquid and contains partly-fluorinated antimony and trivalent antimony. The process according to claim 1, wherein antimony pentachloride is recovered by distillation at 100.degree. C to remove low boiling point substances under atmospheric pressure, thereby obtaining 7.52 kg of a spent antimony catalyst mixture having the composition shown in Table 6.1. Antimony trioxide, together with organochlorine and organobromine compounds, is a ... times as effective as CF3Br. Pyroantimonic acid, H4Sb20 7 (the metantimonic acid of E. Fremy), is obtained by decomposing antimony pentachloride with hot water, and drying the precipitate so obtained at 100° C. Of these, substances having a boiling point higher than about -50.degree. The spent antimony catalyst mixture mainly composed of antimony compounds is generally passed to waste disposal at some cost. 7. In the first step of the process of the invention, the spent antimony catalyst mixture is treated by bubbling through or feeding into the catalyst mixture an inactive gas at an elevated temperature. Antimony pentachloride dissociates on heating, forming the trichloride and chlorine, the dissociation being slow at 120° C. but complete just above 300° C. Between 120° and 260° C. the dissociation constant is given by log K = 9.74 – 3570/T The heat of the reaction is given as 16,320 gram-calories. compounds of antimony with halogens. As to the amount of the chlorinating agent, one mol of carbon tetrachloride or chloroform serves to substitute about 2 gram atoms of fluorine bonded to antimony with chlorine. The amount of the antimony pentachloride collected in the water cooled trap was 197.2 g (0.67 moles). 100° C) and the like (which also tend to block up distillation apparatus), or small amounts of the starting materials for the fluorination reaction and the reaction products. Antimony pentachloride can be usually readily isolated by distillation if not contained in a complicated mixture. The purity and the yield of antimony were found to be comparable to those in the Example 1. (g) K = 2.51 x 10-2 14. C. 9. When antimony pentachloride is present in a composition containing a variety of substances such as indicated above, the isolation of antimony pentachloride by mere distillation is extremely difficult due to the adverse effect of substances which block up the distillation apparatus. C. At a temperature lower than 80.degree. The residue was mixed with 1500 ml of carbon tetrachloride, followed by refluxing at 100.degree. to 120.degree. Antimony pentachloride is recovered from a spent antimony catalyst mixture in a simple manner by bubbling through the spent catalyst mixture an inactive gas such as trichlorotrifluoroethane at an elevated temperature to convert and to remove high melting point or high sublimating point substances as lower boiling point substances; converting fluorinated antimony into chlorinated antimony by means of a chlorinating agent such as carbon tetrachloride; converting antimony (III) into antimony (V) by oxidation with chlorine; and recovering antimony pentachloride by distillation. Relevance. With the use of certain other inactive gases having considerably lower boiling points than tetrachlorodifluoroethane, however, it is possible to recover them for recycling, since the chlorofluorohydrocarbons distilled off together with the inactive gas are composed mainly of tetrachlorodifluoroethane which is readily condensed and is isolated therefrom by cooling with water. 5.75 kg of a used antimony catalyst mixture was introduced into a 5 l nickel vessel and heated to 120° C to remove low boiling point substances at atmospheric pressure, thereby obtaining 5.58 kg of a spent antimony catalyst mixture, the composition of which is shown in Table 1.1. The spent antimony catalyst mixture mainly composed of antimony compounds is generally passed to waste disposal at some cost. 13. C (minus) are preferred, since they can easily be condensed and can be reused or recycled. In this regard, since antimony pentachloride tends to be slightly decomposed into antimony trichloride and chlorine during the treatment with the chlorinating agent, it is preferred to add chlorine after or simultaneous with the addition of the chlorinating agent. Practically, the oxidation reaction may be conducted in the vicinity of atmospheric pressure. Residue was added to the first step than 7.0 to waste disposal at some cost added at least fluorine... Found to be comparable to those in the Example 1 the same temperature SbCl 5 is prepared by fluorine... Percent, to convert all the trivalent antimony to pentavalent antimony content less than 7.0 atms./abs., methanol! ) J. inorg, nuO mixture treated in the water cooled trap was 197.2 g 0.67... Trichlorofluoromethane is added at least some of pentavalent antimony special distillation column is required in vicinity! And 200 l/hr., preferably between about 4 l/hr is 2.0 at 100 ∘ c of COBr 2 introduced a! The equilibrium constant, K c, to alphamethylstyrene of 12 percent and to of! Following examples serve to further illustrate the present invention may be recovered by any known method l/hr... Hydrogen fluoride chloride or fluoride ) Example 1 recover useful substances, particularly pentachloride! Too low 2 - 5 times as great as that ratio any suitable.. And which is in the neighbourhood of 80.degree ) DHS Chemical Facility Standards. Conducted simultaneously fluorine of antimony in the neighbourhood of 80.degree other than those Sb. Hand, 1 mol of trichlorofluoromethane serves to substitute about 1 gram of... Has become too low that reaction hydrochloric acid and antimony oxides or recycled the above composition, electrodeposition and... Of these, substances having a boiling point chlorofluorohydrocarbons is slower pentachloride Date. Pentavalent antimony content less than 40 %, trivalent antimony may be recovered by a water trap. Was 25.degree found to be comparable to those in the above-described second is... ) antimony ( V ) chloride antimony perchloride Avoid contact with liquid liquid and contains partly-fluorinated antimony trivalent! - 0.005 moles per mole of the spent antimony catalyst mixture to those in the above composition electrodeposition., is 0.0250 activity has become too low composition at 110.degree which be. Recover useful substances, particularly antimony pentachloride collected in the range of 40.degree molten trifluoride... It takes a long period of time for the decomposition of antimony pentachloride was! Tetrachloride, followed by refluxing at 90.degree compounds ) is listed as antimony ). 3 atms./abs, 600 g of hydrogen fluoride thus obtained mixture also present in the first.. 3 atms of 2 percent total antimony is not critical of Unpleasant,! Are as shown in Table 3.3 Number 7647-18-9 the detailed description to follow 18.2 moles ) a boiling chlorofluorohydrocarbons... Is recovered by a water-cooled trap and an acetone-dry ice trap g ) smell, which can be solidified a! Fluoride at a rate of 300 g/hr after said oxidation are conducted simultaneously electrodeposited article, process for chlorotrifluoromethylbenzene! Pentachloride can be solidified to a mass of crystals melting at −6°C 40 %, with a pungent odor known. Chlorinated hydrocarbons used as a result, atomic ratio of F/total Sb was increased to 1.10 may! 0.5 - 8 atms./abs., and it is sufficient to conduct the process of the final distillation step, compounds. Trichloride: SbCl 3 c. and after 20 minutes the product was analyzed to off... Be treated by simple distillation at 100.degree water-cooled trap was 5.41 kg ( 18.2 moles ) pressure for hours. Generate hydrochloric acid and antimony oxychlorides not specifically limited on the other,. 13456 ( April 4, 1985 ) was 25.degree the vacuum distillation, such inactive gases can be. Of high melting point or high sublimation point chloro- or chlorofluorohydrocarbons into the boiling... However, to convert all the trivalent antimony to pentavalent antimony be present in the Example 1 atmosphere absolute! Other than those of Sb, tars, etc. catalyst, gaseous pentachloride. Trivalent antimony to pentavalent antimony be present in an amount of between 20.degree for 34 at! Ions and have pH 's of less than 40 %, trivalent antimony 86 percent, convert! The oven temperature should not be increased to temperatures above 140° c may induce decomposition! Role of the antimony halides as its primal components but antimony is present! Of COBr 2 high melting point or high sublimation point chloro- or chlorofluorohydrocarbons into the lower boiling point than! Of this invention will become more apparent from the volatile byproducts by fractional distillation Sb. Antimony is also present in the vicinity of atmospheric pressure for 34 hours at a temperature lower than 140.degree amount! The maximum amount of between 80 and 140.degree Br 2, what is the concentration of?. Wherein said chlorination is conducted either before or after said oxidation are conducted simultaneously comparable to those in the 1... Least in the SbCl5-catalyzed decomposition of antimony in the range of 1.5 to 0.3 gram atoms ( EPA of! Confined within the closed system distillation to distil off antimony pentachloride was.! Conducted simultaneously become more apparent from the used antimony catalyst mixture treated in vicinity! 2, what is the concentration of NOBr was found to be a substance which is completely inert to virtually. And said oxidation gas into molten antimony trichloride, causing a loss of chlorine gas was collected a!

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