USRE34761E - Process for the preparation of trichloroethylene - Google Patents
Process for the preparation of trichloroethylene Download PDFInfo
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- USRE34761E USRE34761E US08/138,463 US13846393A USRE34761E US RE34761 E USRE34761 E US RE34761E US 13846393 A US13846393 A US 13846393A US RE34761 E USRE34761 E US RE34761E
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 title claims description 8
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 title claims description 8
- -1 phosphonium halide Chemical class 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000010948 rhodium Substances 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003610 charcoal Substances 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 claims description 4
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 4
- 239000005749 Copper compound Substances 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- UOPIRNHVGHLLDZ-UHFFFAOYSA-L dichlororhodium Chemical compound Cl[Rh]Cl UOPIRNHVGHLLDZ-UHFFFAOYSA-L 0.000 claims 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims 1
- 229950011008 tetrachloroethylene Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 27
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003284 rhodium compounds Chemical class 0.000 description 2
- FKMJROWWQOJRJX-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FKMJROWWQOJRJX-UHFFFAOYSA-M 0.000 description 2
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 0.000 description 2
- HSBZWKNXRISGJR-UHFFFAOYSA-M triphenyl(propyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 HSBZWKNXRISGJR-UHFFFAOYSA-M 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006487 butyl benzyl group Chemical group 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical class [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
Definitions
- the invention relates to a process for the preparation of trichloroethylene from perchloroethylene and hydrogen by means of a copper/rhodium catalyst impregnated with a water-soluble phosphonium halide.
- a process for preparing trichloroethylene from perchloroethylene and hydrogen in which a catalyst consisting of an active charcoal support impregnated with copper in elemental or chemically bonded form and palladium, rhodium or ruthenium, in each case in elemental or chemically bonded form, is employed, is known from DE-A 2,819,209 (EP-B 5,263).
- the high temperatures which are required to obtain satisfactory conversion rates are a disadvantage of this procedure.
- DE-A 3,804,265 proposes the use of copper/rhodium catalysts impregnated with phosphines or phosphites.
- the fact that, in an expensive two-stage process for impregnation of the catalyst support, the aqueous solution of the copper compound and rhodium compound first has to be applied, and in the following step the phosphines or phosphites dissolved in organic solvents have to be applied is a disadvantage of this procedure. Above all, however, the increase in catalyst activity is limited with respect to time, so that the drop in activity after operating times of less than only 1000 hours must be counteracted by an increase in the operating temperature.
- the object of the present invention was thus to provide a process for the preparation of trichloroethylene from perchloroethylene and hydrogen, with which high conversions can be achieved even at a relatively low operating temperature, even over long operating times.
- the invention relates to a process for the preparation of trichloroethylene from perchloroethylene and hydrogen by means of a supported catalyst consisting of active charcoal having a BET surface area of more than 500 m 2 /g, 0.5 to 20% by weight of copper in elemental or chemically bonded form and 0.01 to 1.0% by weight of rhodium or palladium in elemental or chemically bonded form at a temperature of 150° to 250° C. and a hydrogen pressure of 1 to 10 bar absolute, wherein the supported catalyst is impregnated with 0.1 to 10.0% by weight of a water-soluble phosphonium halide.
- Active charcoal preferably in granular form, having a BET surface area of more than 500 m 2 /g and a particle size of 2 to 10 mm is employed as the catalyst support.
- the copper is applied to the support in elemental or chemically bonded form in amount of 0.5 to 20.0% by weight, preferably 5.0 to 15.0% by weight, based on the total weight of catalyst support and active components.
- Water-soluble copper salts in particular CuCl 2 , are particularly preferred.
- Rhodium is employed in elemental or chemically bonded form in an amount of 0.01 to 1.0% by weight, preferably 0.02 to 0.2% by weight, based on the total weight of catalyst support and active components.
- Water-soluble rhodium compounds in particular complex salts of rhodium(III) chloride, are particularly preferred.
- palladium instead of rhodium, it is also possible to employ palladium in elemental or chemically bonded form and in the amounts just stated for rhodium.
- Water-soluble palladium compounds such as, for example, PdCl 2 , are also particularly preferred here.
- the catalyst support is also impregnated with 0.1 to 10.0% by weight, preferably 3.0 to 7.0% by weight, based on the total weight of catalyst support and active components, of a water-soluble phosphonium halide.
- Water-soluble phosphonium halides of the general formula (Ph 3 PR)X are preferably employed; wherein Ph represents a phenyl radical.
- R represents hydrogen or substituted or unsubstituted alkyl or aryl radicals. Examples of these are the methyl, ethyl, propyl, n-butyl, iso-butyl, pentyl, hexyl, heptyl, octyl, nonyl, benzyl, p-chlorobenzyl, p-tert.butylbenzyl, allyl, 2-methyallyl, chloromethyl, dichloromethyl, iodomethyl, ethoxycarbonylmethyl and acetonyl radicals.
- Chloride, iodide or bromide is preferably employed as the halide X.
- Preferred phosphonium halides are methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, n-propyltriphenylphosphonium chloride, n-propyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, allytriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride and n-butyltriphenylphosphonium bromide.
- Methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride and ethyltriphenylphosphonium bromide are particularly preferred.
- the phosphonium halides can be prepared in a manner which is known per se.
- the triphenylphosphonium salts are obtained by the reaction of triphenylphosphine with the corresponding hydrogen halide compounds. If the optionally substituted alkyl halides are employed, the alkyl-triphenylphosphonium salts are accessible. Further procedures for the preparation of phosphonium halides are described in the following publications: J. Buddrus, Chem. Ber. 107, 2062 (1974); G. Wittig, U. Schollkopf, Chem. Ber. 87, 1318 (1954); D. Denney, L. Smith, J. Org. Chem. 45, 3404 (1962); G. Wittig, M. Schlosser, Chem.
- the individual components that is to say copper (salt), rhodium (salt) or palladium (salt) and phosphonium compound, preferably in aqueous solution, are applied to the active charcoal separately or as a mixture, for example by steeping.
- the catalyst support impregnated in this way is then dried.
- the catalyst is introduced in poured form into a reaction tube.
- the reaction is carried out at a temperature of 150° to 250° C. and under a pressure of 1 to 10 bar absolute.
- the perchloroethylene is preferably reacted in amounts of 0.5 to 5.0 mol per hour and per liter of contact mass (catalyst volume) together with 0.1 to 1 times the molar amount per hour of hydrogen.
- Granular active charcoal having a BET surface area of 800 m 2 /g and a particle size of 3 mm was steeped with aqueous solutions of CuCl 2 , Na 3 RhCl 6 and [(C 6 H 5 ) 3 PCH 3 ]Cl and then dried, so that the Cu content of the active charcoal was 10% by weight, the Rh content was 0.044% by weight and the [(C 6 H 5 ) 3 PCH 3 ]Cl content was 6.5% by weight.
- the trichloroethylene preparation was carried out in a single-tube reactor using a catalyst volume of 1500 ml. The reactor was charged with 960 g/hour (5.8 mol/hour) of perchloroethylene and 70 l/hour (3.5 mol/hour) of hydrogen. The reaction pressure was 6 bar absolute.
- FIG. 1 shows the temperature-time curve (T/t curve) of the perchloroethylene hydrogenation according to the above examples at a conversion rate to trichloroethylene of 40% by weight.
- Example 2 The procedure was analogous to Example 1. However, methyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, ethyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, ethyltriphenylphosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, n-propyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, n-propyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, allyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, allytriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, n-butyltriphenylphosphonium chloride was employed at the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
- Example 2 The procedure was analogous to Example 1. However, n-butyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
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Abstract
In the process, a copper/rhodium catalyst impregnated with 0.1 to 10.0% by weight, based on the total weight of active charcoal catalyst support and active components, of a water-soluble phosphonium halide is employed for the preparation of trichloroelethylene from perchloroethylene and hydrogen.
Description
The invention relates to a process for the preparation of trichloroethylene from perchloroethylene and hydrogen by means of a copper/rhodium catalyst impregnated with a water-soluble phosphonium halide.
A process for preparing trichloroethylene from perchloroethylene and hydrogen in which a catalyst consisting of an active charcoal support impregnated with copper in elemental or chemically bonded form and palladium, rhodium or ruthenium, in each case in elemental or chemically bonded form, is employed, is known from DE-A 2,819,209 (EP-B 5,263). The high temperatures which are required to obtain satisfactory conversion rates are a disadvantage of this procedure.
To increase the catalyst activity at a lower reaction temperature, DE-A 3,804,265 proposes the use of copper/rhodium catalysts impregnated with phosphines or phosphites. The fact that, in an expensive two-stage process for impregnation of the catalyst support, the aqueous solution of the copper compound and rhodium compound first has to be applied, and in the following step the phosphines or phosphites dissolved in organic solvents have to be applied is a disadvantage of this procedure. Above all, however, the increase in catalyst activity is limited with respect to time, so that the drop in activity after operating times of less than only 1000 hours must be counteracted by an increase in the operating temperature.
The object of the present invention was thus to provide a process for the preparation of trichloroethylene from perchloroethylene and hydrogen, with which high conversions can be achieved even at a relatively low operating temperature, even over long operating times.
The invention relates to a process for the preparation of trichloroethylene from perchloroethylene and hydrogen by means of a supported catalyst consisting of active charcoal having a BET surface area of more than 500 m2 /g, 0.5 to 20% by weight of copper in elemental or chemically bonded form and 0.01 to 1.0% by weight of rhodium or palladium in elemental or chemically bonded form at a temperature of 150° to 250° C. and a hydrogen pressure of 1 to 10 bar absolute, wherein the supported catalyst is impregnated with 0.1 to 10.0% by weight of a water-soluble phosphonium halide.
Active charcoal, preferably in granular form, having a BET surface area of more than 500 m2 /g and a particle size of 2 to 10 mm is employed as the catalyst support.
The copper is applied to the support in elemental or chemically bonded form in amount of 0.5 to 20.0% by weight, preferably 5.0 to 15.0% by weight, based on the total weight of catalyst support and active components. Water-soluble copper salts, in particular CuCl2, are particularly preferred.
Rhodium is employed in elemental or chemically bonded form in an amount of 0.01 to 1.0% by weight, preferably 0.02 to 0.2% by weight, based on the total weight of catalyst support and active components. Water-soluble rhodium compounds, in particular complex salts of rhodium(III) chloride, are particularly preferred. Instead of rhodium, it is also possible to employ palladium in elemental or chemically bonded form and in the amounts just stated for rhodium. Water-soluble palladium compounds, such as, for example, PdCl2, are also particularly preferred here.
According to the invention, the catalyst support is also impregnated with 0.1 to 10.0% by weight, preferably 3.0 to 7.0% by weight, based on the total weight of catalyst support and active components, of a water-soluble phosphonium halide. Water-soluble phosphonium halides of the general formula (Ph3 PR)X are preferably employed; wherein Ph represents a phenyl radical.
R represents hydrogen or substituted or unsubstituted alkyl or aryl radicals. Examples of these are the methyl, ethyl, propyl, n-butyl, iso-butyl, pentyl, hexyl, heptyl, octyl, nonyl, benzyl, p-chlorobenzyl, p-tert.butylbenzyl, allyl, 2-methyallyl, chloromethyl, dichloromethyl, iodomethyl, ethoxycarbonylmethyl and acetonyl radicals.
Chloride, iodide or bromide is preferably employed as the halide X.
Preferred phosphonium halides are methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, n-propyltriphenylphosphonium chloride, n-propyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, allytriphenylphosphonium bromide, n-butyltriphenylphosphonium chloride and n-butyltriphenylphosphonium bromide.
Methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride and ethyltriphenylphosphonium bromide are particularly preferred.
The phosphonium halides can be prepared in a manner which is known per se. For example, the triphenylphosphonium salts are obtained by the reaction of triphenylphosphine with the corresponding hydrogen halide compounds. If the optionally substituted alkyl halides are employed, the alkyl-triphenylphosphonium salts are accessible. Further procedures for the preparation of phosphonium halides are described in the following publications: J. Buddrus, Chem. Ber. 107, 2062 (1974); G. Wittig, U. Schollkopf, Chem. Ber. 87, 1318 (1954); D. Denney, L. Smith, J. Org. Chem. 45, 3404 (1962); G. Wittig, M. Schlosser, Chem. Ber. 94, 1373 (1961); G. Aksnes, A. Eide, Phosphorus 4 (3), 209 (1974); Houben-Weyl, Methoden der organischen Chemie (Methods of organic chemistry) 12/1, 79 (1963); and Ullmann, Encyclopadie der technischem Chemie (Encyclopedia of industrial chemistry) 18, 380 (1979).
For the impregnation, the individual components, that is to say copper (salt), rhodium (salt) or palladium (salt) and phosphonium compound, preferably in aqueous solution, are applied to the active charcoal separately or as a mixture, for example by steeping. The catalyst support impregnated in this way is then dried.
For reaction of the perchloroethylene, the catalyst is introduced in poured form into a reaction tube. The reaction is carried out at a temperature of 150° to 250° C. and under a pressure of 1 to 10 bar absolute. The perchloroethylene is preferably reacted in amounts of 0.5 to 5.0 mol per hour and per liter of contact mass (catalyst volume) together with 0.1 to 1 times the molar amount per hour of hydrogen.
The following examples serve to further illustrate the invention:
Granular active charcoal having a BET surface area of 800 m2 /g and a particle size of 3 mm (Degusorb WS IV Spezial, Degussa) was steeped with aqueous solutions of CuCl2, Na3 RhCl6 and [(C6 H5)3 PCH3 ]Cl and then dried, so that the Cu content of the active charcoal was 10% by weight, the Rh content was 0.044% by weight and the [(C6 H5)3 PCH3 ]Cl content was 6.5% by weight. The trichloroethylene preparation was carried out in a single-tube reactor using a catalyst volume of 1500 ml. The reactor was charged with 960 g/hour (5.8 mol/hour) of perchloroethylene and 70 l/hour (3.5 mol/hour) of hydrogen. The reaction pressure was 6 bar absolute.
The procedure was analogous to Example 1. Instead of the methyltriphenyl phosphonium chloride, the equivalent amount of triphenylphosphine was employed.
The procedure was analogous to Example 1; however, no methyltriphenylphosphonium chloride was added.
The results of Example 1 and of Comparison Example 1 and Comparison Example 2 are summarized in FIG. 1. FIG. 1 shows the temperature-time curve (T/t curve) of the perchloroethylene hydrogenation according to the above examples at a conversion rate to trichloroethylene of 40% by weight.
The procedure was analogous to Example 1. However, methyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, ethyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, ethyltriphenylphosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, n-propyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, n-propyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, allyltriphenylphosphonium chloride was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, allytriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, n-butyltriphenylphosphonium chloride was employed at the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
The procedure was analogous to Example 1. However, n-butyltriphenylphosphonium bromide was employed as the phosphonium halide. The reaction likewise started at 195° C. As in Example 1, the conversion rate at this temperature remained at 40% by weight over a period of 900 hours.
Claims (12)
1. A process for the preparation of trichloroethylene comprising reacting perchlorethylene and hydrogen in the presence of a supported catalyst at a temperature of .[.150°-200°.]. .Iadd.150° to 250°.Iaddend. C. and a hydrogen pressure 1 to 10 bar absolute, said catalyst consisting of a support of active charcoal having a BET surface area of more than 500 m2 /g, impregnated with 0.5 to 20% by weight of copper in elemental or chemically bonded form, 0.01 to 1.0% by weight of rhodium or palladium in elemental or chemically bonded form and 0.1 to 10.0% by weight of a water-soluble phosphonium halide, said weight based on the total weight of catalyst support and active components.
2. The process of claim 1, wherein the water-soluble phosphonium compound is selected from compounds of the formula (Ph3 PR)X, in which Ph represents a phenyl radical; R is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl radical and a substituted or unsubstituted aryl radical; and X is selected from the group consisting of chloride, bromide and iodide.
3. The process of claim 2, wherein R is a methyl or ethyl radical.
4. The process of claim 1 wherein the water-soluble phosphonium halide is selected from the group consisting of methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride and ethyltriphenylphosphonium bromide.
5. The process of claim 1 wherein the amount of the water-soluble phosphonium halide compound is from 3.0 to 7.0% by weight.
6. The process of claim 1 wherein the support of active charcoal has a particle size of from 2 to 10 mm.
7. The process of claim 1 wherein the copper is present as a water-soluble copper compound.
8. The process of claim 7 wherein the water-soluble copper compound is copper (II) chloride.
9. The process of claim 1 wherein the amount of copper is from 50 to 150% by weight in elemental of chemically bonded form.
10. The process of claim 1 wherein the rhodium or palladium is present as a water-soluble rhodium or palladium compound.
11. The process of claim 10 wherein the rhodium and palladium water-soluble compound is selected from the group consisting of rhodium (II) chloride and palladium (II) chloride.
12. The process of claim 1 wherein the amount of the rhodium or palladium is from 0.02 to 0.2 percent by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/138,463 USRE34761E (en) | 1989-12-12 | 1993-10-15 | Process for the preparation of trichloroethylene |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3941037A DE3941037A1 (en) | 1989-12-12 | 1989-12-12 | METHOD FOR PRODUCING TRICHLORETHYLENE |
| DE3941037 | 1989-12-12 | ||
| US07/602,417 US5091603A (en) | 1989-12-12 | 1990-10-22 | Process for the preparation of trichloroethylene |
| US08/138,463 USRE34761E (en) | 1989-12-12 | 1993-10-15 | Process for the preparation of trichloroethylene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/602,417 Reissue US5091603A (en) | 1989-12-12 | 1990-10-22 | Process for the preparation of trichloroethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE34761E true USRE34761E (en) | 1994-10-18 |
Family
ID=6395320
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/602,417 Ceased US5091603A (en) | 1989-12-12 | 1990-10-22 | Process for the preparation of trichloroethylene |
| US08/138,463 Expired - Lifetime USRE34761E (en) | 1989-12-12 | 1993-10-15 | Process for the preparation of trichloroethylene |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/602,417 Ceased US5091603A (en) | 1989-12-12 | 1990-10-22 | Process for the preparation of trichloroethylene |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5091603A (en) |
| EP (1) | EP0432636B1 (en) |
| DE (2) | DE3941037A1 (en) |
| ES (1) | ES2045732T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123396A1 (en) * | 1991-07-15 | 1993-01-21 | Wacker Chemie Gmbh | METHOD FOR HYDROGENATING CHLOROMETHANES |
| ES2108296T3 (en) * | 1992-10-01 | 1997-12-16 | Dow Chemical Co | PROCEDURE TO CONVERT 1,1,2-TRICHLOROETHANE TO VINYL AND / OR ETHYLENE CHLORIDE. |
| US5476979A (en) * | 1992-10-01 | 1995-12-19 | The Dow Chemical Company | Processes for converting chlorinated alkenes to useful, less chlorinated alkenes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3804265A1 (en) * | 1988-02-11 | 1989-08-24 | Wacker Chemie Gmbh | Process for the preparation of trichloroethylene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL277576A (en) * | 1961-04-24 | |||
| DE2819209A1 (en) * | 1978-05-02 | 1979-11-08 | Wacker Chemie Gmbh | CATALYST AND METHOD FOR PRODUCING TRICHLOROETHYLENE |
-
1989
- 1989-12-12 DE DE3941037A patent/DE3941037A1/en not_active Withdrawn
-
1990
- 1990-10-22 US US07/602,417 patent/US5091603A/en not_active Ceased
- 1990-12-06 ES ES90123399T patent/ES2045732T3/en not_active Expired - Lifetime
- 1990-12-06 EP EP90123399A patent/EP0432636B1/en not_active Expired - Lifetime
- 1990-12-06 DE DE90123399T patent/DE59003240D1/en not_active Expired - Fee Related
-
1993
- 1993-10-15 US US08/138,463 patent/USRE34761E/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3804265A1 (en) * | 1988-02-11 | 1989-08-24 | Wacker Chemie Gmbh | Process for the preparation of trichloroethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3941037A1 (en) | 1991-06-13 |
| EP0432636B1 (en) | 1993-10-27 |
| US5091603A (en) | 1992-02-25 |
| DE59003240D1 (en) | 1993-12-02 |
| EP0432636A1 (en) | 1991-06-19 |
| ES2045732T3 (en) | 1994-01-16 |
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