WO1996017683A1 - Catalyseur d'hydrogenation et procede associe - Google Patents
Catalyseur d'hydrogenation et procede associe Download PDFInfo
- Publication number
- WO1996017683A1 WO1996017683A1 PCT/GB1995/002837 GB9502837W WO9617683A1 WO 1996017683 A1 WO1996017683 A1 WO 1996017683A1 GB 9502837 W GB9502837 W GB 9502837W WO 9617683 A1 WO9617683 A1 WO 9617683A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- hydrogenation
- carbon
- platinum
- palladium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 42
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004338 Dichlorodifluoromethane Substances 0.000 abstract description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 7
- 238000007327 hydrogenolysis reaction Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 5
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 4
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004340 Chloropentafluoroethane Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 also known as HFA 32 Chemical compound 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001260 acyclic compounds Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MEXUFEQDCXZEON-UHFFFAOYSA-N bromochlorodifluoromethane Chemical compound FC(F)(Cl)Br MEXUFEQDCXZEON-UHFFFAOYSA-N 0.000 description 1
- GRCDJFHYVYUNHM-UHFFFAOYSA-N bromodifluoromethane Chemical compound FC(F)Br GRCDJFHYVYUNHM-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000005828 hydrofluoroalkanes Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- This invention relates to a catalyst, in particular a hydrogenolysis (the replacement of halogen by hydrogen in saturated molecules) and/or hydrogenation (addition of hydrogen across ethylenic double-bonds) catalyst, (hereafter referred to collectively as "hydrogenation”) and to hydrogenation processes employing the catalyst, in particular the hydrogenation of halofluorocarbons and hydrohalofluorocarbons to produce hydrofluoroalkanes, for example the hydrogenation of dichlorodifluoromethane and chlorodifluoromethane to produce difluoromethane, the hydrogenation of chloropentafluoroethane to produce pentafluoroethane and the hydrogenation of dichlorotetrafluoroethane and chlorotetrafluoroethane to produce tetrafluoroethane and especially 1, 1 , 1 ,2-tetrafluoroethane.
- a catalyst in particular a hydrogenolysis (the replacement of halogen by
- chlorofluorocarbons which are used on a large scale around the world, may be damaging the earth's protective ozone layer and there is now in place international agreement to ensure that their manufacture and use is restricted and eventually completely phased out.
- Chlorofluorocarbons are used, for example, as refrigerants, as foam blowing agents, as cleaning solvents and as propellants for aerosol sprays in which the variety of applications is virtually unlimited. Consequently, much effort is being devoted to finding suitable replacements for chlorofluorocarbons which will perform satisfactorily in the many applications in which chlorofluorocarbons are used but which will not have the aforementioned damaging effect on the ozone layer.
- Hydrofluorocarbons which do not contain chlorine but which contain hydrogen.
- Hydrofluorocarbons such as difluoromethane, also known as HFA 32, pentafluoroethane, also known as HFA 125 and 1, 1, 1 ,2-tetrafluoroethane, also known as HFA 134a, are of interest as replacements, in particular as replacements in refrigeration, air-conditioning and other applications.
- the present invention is based on the discovery that the activity and particularly the selectivity of palladium catalysts is improved by incorporating a controlled amount of platinum in the catalysts.
- a hydrogenation catalyst which comprises palladium and platinum in a ratio by weight of 2: 1 to 500: 1 carried on a support.
- the palladium and platinum components may be used alone or in combination with other metals, for example other Group VIII metals such as nickel, Group I B metals such as Ag and Au or even other metals.
- the metals are carried on a suitable support, for example alumina, fluorinated alumina, silica, silicon carbide or carbon but in particular alumina or carbon.
- a suitable support for example alumina, fluorinated alumina, silica, silicon carbide or carbon but in particular alumina or carbon.
- a carbon carrier where the carbon has a high surface area, eg greater than 200 m 2 /g.
- Activated carbon supports with low inorganic impurity levels are particularly suitable.
- the loading of the metal on the support material may be dependent at least to some extent on the particular metal catalyst/support combination being used and the difficulty of the hydrogenation reaction.
- the % w/w of combined palladium and platinum to support is typically from about 0.1% w/w to about 40% w/w, and preferably from about 0.5% w/w to about 20% w/w, more preferably from about 2.0% w/w to about 20% w/w and especially from about 5% w/w to about 15% w/w.
- the proportions of palladium and platinum present may vary within a wide range, although we prefer a catalyst in which there is at least twice as much palladium as platinum. We particularly prefer to employ palladium and platinum in the ratio by weight from about 2: 1 to about 500: 1 , and more preferably from about 3 : 1 to about 100: 1.
- a preferred catalyst comprises from about 0.5% to 20%, in particular from about 5 to 15% w/w palladium and from about 0.05% to about 5%, in particular from about 0.1% to about 4% by weight platinum, especially when supported on an active carbon. Overall the amount of platinum is usually in the range from about 0.01 % w/w to about 10% w/w of the catalyst.
- a typical method involves impregnating the support with an aqueous solution of a soluble salt of the metal, for example a halide, and thereafter drying the catalyst.
- the improved catalyst of the invention is particularly useful in the hydrogenation or hydrogenolysis of a halofluorocarbon or hydrohalofluorocarbon with hydrogen at elevated temperature and according to a second aspect of the invention there is provided a process for the production of a hydrofluorocarbon which comprises contacting a halofluorocarbon or hydrohalofluorocarbon with hydrogen at elevated temperature in the presence of the improved hydrogenation catalyst according to the invention
- halofluorocarbons and hydrohalofluorocarbons used as starting materials comprise at least one atom of chlorine or bromine and generally will be chlorofluorocarbons or hydrochlorofluorocarbons.
- the chlorofluorocarbon or hydrochlorofluorocarbon will typically comprise 1 , 2 or 3 carbon atoms although it may comprise more than 3, say up to 6, carbon atoms.
- the (hydro)halofluorocarbon may be unsaturated or saturated, cyclic or acyclic and straight chain or branched chain, although the (hydro)halofluorocarbon will usually be a straight chain saturated acyclic compound, that is a linear (hydro)halofluoroalkane.
- Particularly useful hydrogenation reactions in which a hydrogenation catalyst according to the invention may be employed include (a) the hydrogenation of a haloethane, in particular a chloroethane, having 4 fluorine atoms, for example 1 J -dichlorotetrafluoroethane, 1 ,2-dichlorotetrafluoroethane and chlorotetrafluoroethane to chlorotetrafluoroethane and/or tetrafluoroethane, in particular 1, 1 , 1 ,2-tetrafluoroethane and (b) the hydrogenation of a compound of formula CF 2 XY where X and Y are independently Cl, Br or H (but not both H) to difluoromethane.
- a haloethane in particular a chloroethane, having 4 fluorine atoms
- 1 J -dichlorotetrafluoroethane 1 ,2-dichlorotetra
- An important feature of successful hydrogenation catalysts is a high hydrogenolysis activity for carbon - chlorine and/or carbon - bromine bonds but a low hydrogenolysis rate for carbon-fluorine bonds, thus avoiding the loss of product by removal of fluorine atoms.
- the catalyst of the invention is particularly advantageously employed in the production of difluoromethane where it has a marked effect on improving the selectivity with which difuoromethane is produced by reducing the level of over reaction.
- a process for the production of difluoromethane which comprises reacting a compound of formula XYCF 2 wherein X and Y are each H, Cl or Br but at least one of X and Y is an atom other than hydrogen, with hydrogen at elevated temperature in the presence of a hydrogenation catalyst according to the invention.
- the process may be conveniently effected by feeding a stream comprising the compound of formula XYCF 2 and hydrogen, as a combined or as separate streams through a vessel containing the hydrogenation catalyst.
- the starting compounds of formula XYCF 2 are dichlorodifluoromethane, dibromodifluoromethane, chlorobromodifluoromethane, chlorodifluoromethane and bromodifluoromethane. Mixtures of the above compounds may be employed. Usually the compound of formula XYCF 2 will be a chlorinated difluoromethane and chlorodifluoromethane is the preferred starting compound.
- the proportion of hydrogen to starting compound of formula XYCF 2 may be varied considerably. Usually at least the stoichiometric amount of hydrogen is employed to replace the chlorine and/or bromine atom(s), and considerably greater than stoichiometric amounts, for example 4 or more moles of hydrogen per mole of starting compound may be employed. Where X and Y are each chlorine or bromine, it is preferred to employ at least two moles of hydrogen (the stoichiometric amount) per mole of starting compound. Where the starting compound of formula XYCF 2 is chlorodifluoromethane it is preferred to employ between 1 and 2 moles of hydrogen per mole of chlorodifluoromethane.
- Atmospheric or superatmospheric pressures for example up to about 60 barg may be employed.
- operation of the process of the invention at superatmospheric pressure substantially increases the selectivity of the process towards the production of difluoromethane.
- the process is preferably operated at a pressure in the range from about 2 bar to about 60 bar and more preferably from about 2 bar to about 30 bar, especially 5 bar to 30 bar.
- the reaction is suitably carried out in the vapour phase at a temperature which is at least about 150°C and not greater than about 500 C C, usually from about 225°C to about 400°C, and preferably from about 240°C to about 360°C.
- the most preferred temperature is dependent upon the pressure at which the process is operated; at atmospheric pressure, we prefer to operate the process at a temperature in the range from about 220°C to about 320°C whereas at a pressure of about 7.5 barg, we prefer to employ temperatures in the range from about 260°C to about 380°C.
- Contact times are usually in the range 1 to 60 seconds, especially 5 to 30 seconds when the reaction is carried out in the vapour phase.
- any unreacted hydrogen and other starting material, together with any organic by-products, may be recycled.
- a sample of carbon support (supplied by Norrit) with an approximate surface area area of 800 sq.m/g was crushed and sieved to generate particles in the size range 1.0- 1.2 mm. 50 cm 3 - 60 cm 3 of the crushed carbon was then washed in distilled water and the water drained through a no.4 sinter funnel. The washed carbon was then transferred to a Buchner flask . The target weight of palladium chloride or mixed metal chlorides were then dissolved in the minimum volume of warmed concentrated hydrochloric acid and the solution was added to the carbon particles in the Buchner flask.
- a further 200 cm 3 of distilled water was then added to the flask and the slurry was evaporated to dryness on a rotary evaporator using an oil bath temperature of 120°C.
- the catalyst was finished by heating the granules in a vacuum oven at 150°C for approximately 16 hours.
- the above catalyst preparation was repeated at a larger scale.
- the same method was employed with 300 cm 3 of carbon support and the particle diameter was increased to 3 mm.
- Catalyst "A” comprised a 10%w/w Pd metal on carbon catalyst and catalyst “B” comprised a 10% Pd plus 1.8%Pt catalyst on the same Norrit carbon support.
- the catalysts were each prepared by dissolving the metal halides in the minimum volume of hydrochloric acid and impregnating the 1-1.2mm granules of the carbon with the resultant solution. The slurry was agitated and evaporated to dryness. The catalyst was then degassed under a flow of nitrogen at 120°C for 16 hours to produce the finished catalyst.
- catalyst "A” 50 cm 3 of catalyst "A" was then charged to a l ⁇ n Inconel reactor and heated to 300°C in a 300 ml/min feed of nitrogen for a 2 hour period prior to testing.
- the test feed mixture was a 2.J molar feed ratio of hydrogen:CFC 115, which was fed at a flow rate of 180 ml/min to the conditioned catalyst.
- the catalyst was stabilised under these feed conditions for approximately two hours and then cooled under reaction conditions to approximately 200°C. Conversion of CFC 115 and selectivity to HFC 125 were measured and are shown in Table 4. At measured temperatures of 199°C, 213°C and 236°C, the 1 15 conversion was found to increase from approximately 66% to 84% and finally 97%, see examples Al, A2 and A3.
- the initial reaction selectivity was found to be 99.77 but fell to 99.59 with increasing feed conversion.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8517405A JPH10510206A (ja) | 1994-12-09 | 1995-12-06 | 水素化触媒及び水素化法 |
EP95938548A EP0796146A1 (fr) | 1994-12-09 | 1995-12-06 | Catalyseur d'hydrogenation et procede associe |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9424904.2A GB9424904D0 (en) | 1994-12-09 | 1994-12-09 | Hydrogenation Catalyst and Process |
GBGB9425058.6A GB9425058D0 (en) | 1994-12-13 | 1994-12-13 | Hyrogenation catalyst and process |
GB9425058.6 | 1994-12-13 | ||
GB9424904.2 | 1994-12-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996017683A1 true WO1996017683A1 (fr) | 1996-06-13 |
Family
ID=26306140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1995/002837 WO1996017683A1 (fr) | 1994-12-09 | 1995-12-06 | Catalyseur d'hydrogenation et procede associe |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0796146A1 (fr) |
JP (1) | JPH10510206A (fr) |
CA (1) | CA2206337A1 (fr) |
WO (1) | WO1996017683A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999024163A1 (fr) * | 1997-11-06 | 1999-05-20 | Gesellschaft Zur Beseitigung Von Umweltschäden Mbh | Catalyseur a support et procede permettant de produire des hydrofluorocarbures |
WO1999024162A1 (fr) * | 1997-11-06 | 1999-05-20 | Gesellschaft Zur Beseitigung Von Umweltschäden Mbh | Catalyseur et procede d'appauvrissement hydrogenant de cfc et d'halons contenus dans des phases gazeuses |
US7026521B1 (en) | 2005-03-28 | 2006-04-11 | Honeywell International Inc. | Methane and methyl chloride as selective reducing agent in the transformation of hydrochlorofluorocarbons or chlorofluorocarbons to hydrofluorocarbons |
CN111116307A (zh) * | 2019-12-25 | 2020-05-08 | 中船重工(邯郸)派瑞特种气体有限公司 | 一种高纯三氟甲烷的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049576A (en) * | 1974-10-04 | 1977-09-20 | Ashland Oil, Inc. | Platinum-palladium catalyst for selective hydrogenation of aromatics and olefins in hydrocarbon fractions |
GB2108953A (en) * | 1981-10-29 | 1983-05-25 | Shell Int Research | Process for the preparation of a chloropropyl compound |
EP0347830A2 (fr) * | 1988-06-21 | 1989-12-27 | Asahi Glass Company Ltd. | Procédé pour la fabrication d'éthane-1,1,1,2-tétrafluoro |
EP0419412A2 (fr) * | 1989-09-20 | 1991-03-27 | Ciba-Geigy Ag | Procédé pour la préparation de benzotriazoles |
JPH0429944A (ja) * | 1990-05-25 | 1992-01-31 | Asahi Glass Co Ltd | 含水素クロロフルオロカーボン類の製法 |
EP0519573A1 (fr) * | 1991-06-21 | 1992-12-23 | Shell Internationale Researchmaatschappij B.V. | Catalyseur d'hydrogénation et procédé |
-
1995
- 1995-12-06 JP JP8517405A patent/JPH10510206A/ja not_active Ceased
- 1995-12-06 WO PCT/GB1995/002837 patent/WO1996017683A1/fr not_active Application Discontinuation
- 1995-12-06 CA CA 2206337 patent/CA2206337A1/fr not_active Abandoned
- 1995-12-06 EP EP95938548A patent/EP0796146A1/fr not_active Ceased
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4049576A (en) * | 1974-10-04 | 1977-09-20 | Ashland Oil, Inc. | Platinum-palladium catalyst for selective hydrogenation of aromatics and olefins in hydrocarbon fractions |
GB2108953A (en) * | 1981-10-29 | 1983-05-25 | Shell Int Research | Process for the preparation of a chloropropyl compound |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999024163A1 (fr) * | 1997-11-06 | 1999-05-20 | Gesellschaft Zur Beseitigung Von Umweltschäden Mbh | Catalyseur a support et procede permettant de produire des hydrofluorocarbures |
WO1999024162A1 (fr) * | 1997-11-06 | 1999-05-20 | Gesellschaft Zur Beseitigung Von Umweltschäden Mbh | Catalyseur et procede d'appauvrissement hydrogenant de cfc et d'halons contenus dans des phases gazeuses |
US7026521B1 (en) | 2005-03-28 | 2006-04-11 | Honeywell International Inc. | Methane and methyl chloride as selective reducing agent in the transformation of hydrochlorofluorocarbons or chlorofluorocarbons to hydrofluorocarbons |
CN111116307A (zh) * | 2019-12-25 | 2020-05-08 | 中船重工(邯郸)派瑞特种气体有限公司 | 一种高纯三氟甲烷的制备方法 |
CN111116307B (zh) * | 2019-12-25 | 2022-08-19 | 中船(邯郸)派瑞特种气体股份有限公司 | 一种高纯三氟甲烷的制备方法 |
Also Published As
Publication number | Publication date |
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CA2206337A1 (fr) | 1996-06-13 |
JPH10510206A (ja) | 1998-10-06 |
EP0796146A1 (fr) | 1997-09-24 |
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