US20130131402A1 - Process for the synthesis of trifluoroethylene - Google Patents
Process for the synthesis of trifluoroethylene Download PDFInfo
- Publication number
- US20130131402A1 US20130131402A1 US13/704,001 US201113704001A US2013131402A1 US 20130131402 A1 US20130131402 A1 US 20130131402A1 US 201113704001 A US201113704001 A US 201113704001A US 2013131402 A1 US2013131402 A1 US 2013131402A1
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- US
- United States
- Prior art keywords
- activated carbon
- catalyst
- chlorotrifluoroethylene
- palladium
- trifluoroethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/42—Platinum
-
- B01J35/40—
-
- B01J35/617—
-
- B01J35/618—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Definitions
- the present invention relates to a catalytic process for the synthesis of trifluoroethylene.
- the invention relates to a process for the synthesis of trifluoroethylene by reaction of chlorotrifluoroethylene with hydrogen in the presence of a heterogeneous catalyst.
- U.S. Pat. No. 3,564,064 16.02.1971 discloses the catalytic gas-phase reaction of chlorotrifluoroethylene with hydrogen to produce trifluoroethylene in the presence of a catalyst comprising palladium or platinum supported on activated carbon. This process may proceed with high conversion of chlorotrifluoroethylene but with a parallel reduction in the yield of trifluoroethylene.
- a first object of the present invention is a process for preparing trifluoroethylene comprising contacting chlorotrifluoroethylene with hydrogen in the presence of a catalyst consisting of palladium or platinum supported on activated carbon, in which the activated carbon is extruded activated carbon.
- a second object is a catalyst for the hydrodechlorination of chlorotrifluoroethylene, said catalyst consisting of palladium or platinum supported on activated carbon, characterized in that the activated carbon is extruded activated carbon.
- activated carbon is generally used to collectively refer to processed carbonaceous materials characterized by a porous structure and a large internal surface area, generally comprised between 500 and 1500 m 2 /g.
- Activated carbon is obtained on a commercial scale from carbon containing raw materials, e.g. wood, peat, coconut shells, by chemical or gas activation.
- Activated carbon is commercially available in different forms, namely granular, powdered or extruded form.
- Extruded activated carbon is typically obtained from finely powdered raw materials by mixing with a suitable binder followed by extrusion, to form pellets or strands which are then cut into pieces. The pellets are then chemically activated or carbonized and finally gas activated. Typical extruded activated carbons have a pellet diameter in the range of 0.8 to 130 mm.
- Suitable extruded activated carbons for the process of the invention are available commercially for instance from Norit Nederland B.V., Degussa AG, Calgon Carbon Corporation.
- the process of the invention is preferably carried out in the gas-phase.
- a gaseous stream of hydrogen and chlorotrifluoroethylene is fed to the reaction zone and brought into contact with the catalyst held at a suitable temperature.
- the produced trifluoroethylene is recovered from the effluent gas.
- the reaction products and any unreacted starting material may be recovered and isolated by conventional methods.
- the main by-product of the process has been identified to be CH 2 FCHF 2 .
- the molar ratio between the hydrogen and the chlorotrifluoroethylene fed to the reaction zone is typically comprised between 0.75:1 and 1.25:1, preferably between 0.9:1 and 1.1:1.
- An inert gas may be optionally mixed with hydrogen and chlorotrifluoroethylene.
- Suitable inert gases are for instance nitrogen, helium, argon.
- the inert gas is nitrogen.
- the inert gas may serve as a diluent to reduce the concentration of the reactants and/or the products below the point where they form flammable mixtures.
- the concentration of chlorotrifluoroethylene in the gaseous stream fed to the reaction zone is conveniently comprised between 5 and 55% by volume, preferably between 10 and 50% by volume.
- the reaction pressure is not critical to the process. Generally the process is carried out at pressure of from 0.01 MPa to 0.5 MPa, preferably at a pressure of from about 0.05 MPa to 0.2 MPa.
- the reaction may be conducted at any suitable temperature, generally at a temperature in the range of from 100° C. to 350° C., preferably in the range of from 150° C. to 300° C., and more preferably in the range of from 200° C. to 250° C.
- the reaction contact time for the reactants may be any suitable contact time, usually a time of from 0.1 second to 100 seconds, preferably from 0.1 second to 60 seconds, and more preferably from 0.5 second to 30 seconds.
- any suitable space velocity of the reactants may be employed.
- the space velocity can be in the range from 0.2 to 50 gCTFE*h ⁇ 1 *g cat ⁇ 1 , preferably from 1 to 40 gCTFE*h ⁇ 1 *g cat ⁇ 1 and more preferably from 2 to 30 gCTFE*h ⁇ 1 *g cat ⁇ 1 .
- the process may be conducted in any suitable reaction vessel.
- the reaction vessel should be constructed of materials which are inert towards the reactants as well as the products, such as for example, Hastelloy, Inconel, Monel, stainless steel vessels.
- the process is carried out in a tubular stainless steel reactor, provided with suitable means to maintain the required temperature inside the reactor.
- the catalyst used in the process consists of platinum or palladium supported on extruded activated carbon.
- the catalyst consists of palladium supported on extruded activated carbon.
- the amount of metal supported on the extruded activated carbon is typically comprised between 0.05 and 5% by weight, preferably between 0.1 and 4% by weight, more preferably between 0.2 and 3% by weight, and even more preferably between 0.3 and 2.5% by weight.
- the catalyst may be prepared by conventional methods, such as the incipient wetness impregnation method. In such a method an aqueous solution of a suitable metal precursor is added to the support, dried, followed by reduction of the metal.
- a suitable metal precursor mention can be made of PdCl 2 , Pd(NO 3 ) 2 , H 2 PtCl 4 .
- NORIT® RX3 EXTRA (Norit Nederland B.V.) extruded activated carbon having BET area of 1400 m 2 /g
- NORIT® GCN 1240 (Norit Nederland B.V.) granular activated carbon having BET area of 1300 m 2 /g
- the activated carbon as received from the supplier was crushed and sieved in order to obtain granules with a diameter of 0.5-1 mm.
- the granules were dried under vacuum at 200° C. and then impregnated with incipient wetness method with an aqueous hydrochloridric solution of PdCl 2 to obtain different concentrations of palladium on the support.
- Catalyst activation Each catalyst was dried under a nitrogen flow at 300° C. for 6 h and then reduced in a H 2 /N 2 stream (5% by volume H 2 ) from room temperature to 350° C. with thermal ramp of 5° C./min. After 30 minutes at 350° C. hydrogen concentration was raised to 10% by volume and kept for 30 minutes, followed by a treatment with a hydrogen concentration of 50% by volume for 4 h. At the end of the treatment the catalyst was cooled at room temperature and characterized to determine the effective concentration of palladium.
- Catalyst C Following the general catalyst preparation procedure described above one catalyst was prepared using the granular activated carbon NORIT® GCN 1240 as the support and having a palladium concentration of 1.17% by weight (Catalyst C).
Abstract
A catalytic process for the synthesis of trifluoroethylene from chlorotrifluoroethylene which comprises contacting chlorotrifluoroethylene with hydrogen in the presence of a catalyst consisting of palladium or platinum supported on extruded activated carbon.
Description
- This application claims priority to European application No. 10168130.2 filed on Jul. 1, 2010, the whole content of this application being incorporated herein by reference for all purposes.
- The present invention relates to a catalytic process for the synthesis of trifluoroethylene. In particular the invention relates to a process for the synthesis of trifluoroethylene by reaction of chlorotrifluoroethylene with hydrogen in the presence of a heterogeneous catalyst.
- The hydrodechlorination of chlorotrifluoroethylene to yield trifluoroethylene has been previously described.
- Mention can be made of U.S. Pat. No. 2,802,887 (ALLIED CHEMICAL) 13.08.1957 which discloses the gas-phase reaction of chlorotrifluoroethylene with hydrogen to produce trifluoroethylene in the presence of a catalyst comprising palladium supported on activated carbon. The reaction however proceeds with both low conversion of chlorotrifluoroethylene and low yield in trifluoroethylene.
- U.S. Pat. No. 3,564,064 16.02.1971 discloses the catalytic gas-phase reaction of chlorotrifluoroethylene with hydrogen to produce trifluoroethylene in the presence of a catalyst comprising palladium or platinum supported on activated carbon. This process may proceed with high conversion of chlorotrifluoroethylene but with a parallel reduction in the yield of trifluoroethylene.
- In consideration of the high cost of chlorotrifluoroethylene it would be desirable to have available a process capable of maximizing the conversion of chlorotrifluoroethylene without compromising the overall yield in trifluoroethylene thereby increasing the profitability of the process.
- It has now been found that when using a supported platinum or palladium catalyst wherein the support for the noble metal is a specific form of activated carbon the reaction of chlorotrifluoroethylene with hydrogen proceeds with a high conversion of chlorotrifluoroethylene and without concurrently decreasing the selectivity towards the formation of trifluoroethylene. The advantages in productivity can be obtained even at low concentrations of the noble metal on the support and by working with a high dilution of chlorotrifluoroethylene by operating the process in the presence of an inert gas.
- A first object of the present invention is a process for preparing trifluoroethylene comprising contacting chlorotrifluoroethylene with hydrogen in the presence of a catalyst consisting of palladium or platinum supported on activated carbon, in which the activated carbon is extruded activated carbon.
- A second object is a catalyst for the hydrodechlorination of chlorotrifluoroethylene, said catalyst consisting of palladium or platinum supported on activated carbon, characterized in that the activated carbon is extruded activated carbon.
- The term “activated carbon” is generally used to collectively refer to processed carbonaceous materials characterized by a porous structure and a large internal surface area, generally comprised between 500 and 1500 m2/g. Activated carbon is obtained on a commercial scale from carbon containing raw materials, e.g. wood, peat, coconut shells, by chemical or gas activation. Activated carbon is commercially available in different forms, namely granular, powdered or extruded form.
- Extruded activated carbon is typically obtained from finely powdered raw materials by mixing with a suitable binder followed by extrusion, to form pellets or strands which are then cut into pieces. The pellets are then chemically activated or carbonized and finally gas activated. Typical extruded activated carbons have a pellet diameter in the range of 0.8 to 130 mm.
- Suitable extruded activated carbons for the process of the invention are available commercially for instance from Norit Nederland B.V., Degussa AG, Calgon Carbon Corporation.
- The process of the invention is preferably carried out in the gas-phase. In an embodiment of the inventive process a gaseous stream of hydrogen and chlorotrifluoroethylene is fed to the reaction zone and brought into contact with the catalyst held at a suitable temperature. The produced trifluoroethylene is recovered from the effluent gas. The reaction products and any unreacted starting material may be recovered and isolated by conventional methods. The main by-product of the process has been identified to be CH2FCHF2.
- The molar ratio between the hydrogen and the chlorotrifluoroethylene fed to the reaction zone is typically comprised between 0.75:1 and 1.25:1, preferably between 0.9:1 and 1.1:1.
- An inert gas may be optionally mixed with hydrogen and chlorotrifluoroethylene. Suitable inert gases are for instance nitrogen, helium, argon. Preferably the inert gas is nitrogen. The use of an inert gas in the process allows to better control the temperature of the exothermic reaction preventing local overheating of the catalyst bed and of the reactor, thus increasing productivity.
- Additionally, the inert gas may serve as a diluent to reduce the concentration of the reactants and/or the products below the point where they form flammable mixtures.
- The concentration of chlorotrifluoroethylene in the gaseous stream fed to the reaction zone is conveniently comprised between 5 and 55% by volume, preferably between 10 and 50% by volume.
- The reaction pressure is not critical to the process. Generally the process is carried out at pressure of from 0.01 MPa to 0.5 MPa, preferably at a pressure of from about 0.05 MPa to 0.2 MPa.
- The reaction may be conducted at any suitable temperature, generally at a temperature in the range of from 100° C. to 350° C., preferably in the range of from 150° C. to 300° C., and more preferably in the range of from 200° C. to 250° C.
- The reaction contact time for the reactants may be any suitable contact time, usually a time of from 0.1 second to 100 seconds, preferably from 0.1 second to 60 seconds, and more preferably from 0.5 second to 30 seconds.
- Any suitable space velocity of the reactants may be employed. For instance, in the case of chlorotrifluoroethylene the space velocity can be in the range from 0.2 to 50 gCTFE*h−1*gcat −1, preferably from 1 to 40 gCTFE*h−1*gcat −1 and more preferably from 2 to 30 gCTFE*h−1*gcat −1.
- The process may be conducted in any suitable reaction vessel. The reaction vessel should be constructed of materials which are inert towards the reactants as well as the products, such as for example, Hastelloy, Inconel, Monel, stainless steel vessels. Preferably the process is carried out in a tubular stainless steel reactor, provided with suitable means to maintain the required temperature inside the reactor.
- The catalyst used in the process consists of platinum or palladium supported on extruded activated carbon. Preferably the catalyst consists of palladium supported on extruded activated carbon.
- The amount of metal supported on the extruded activated carbon is typically comprised between 0.05 and 5% by weight, preferably between 0.1 and 4% by weight, more preferably between 0.2 and 3% by weight, and even more preferably between 0.3 and 2.5% by weight.
- The catalyst may be prepared by conventional methods, such as the incipient wetness impregnation method. In such a method an aqueous solution of a suitable metal precursor is added to the support, dried, followed by reduction of the metal. Among suitable precursors mention can be made of PdCl2, Pd(NO3)2, H2PtCl4.
- Should the disclosure of any of the patents, patent applications, and publications that are incorporated herein by reference conflict with the present description to the extent that it might render a term unclear, the present description shall take precedence.
- The invention is illustrated by the following illustrative, but non-limiting examples.
- NORIT® RX3 EXTRA (Norit Nederland B.V.) extruded activated carbon having BET area of 1400 m2/g
- NORIT® GCN 1240 (Norit Nederland B.V.) granular activated carbon having BET area of 1300 m2/g
- The activated carbon as received from the supplier was crushed and sieved in order to obtain granules with a diameter of 0.5-1 mm. The granules were dried under vacuum at 200° C. and then impregnated with incipient wetness method with an aqueous hydrochloridric solution of PdCl2 to obtain different concentrations of palladium on the support.
- Catalyst activation: Each catalyst was dried under a nitrogen flow at 300° C. for 6 h and then reduced in a H2/N2 stream (5% by volume H2) from room temperature to 350° C. with thermal ramp of 5° C./min. After 30 minutes at 350° C. hydrogen concentration was raised to 10% by volume and kept for 30 minutes, followed by a treatment with a hydrogen concentration of 50% by volume for 4 h. At the end of the treatment the catalyst was cooled at room temperature and characterized to determine the effective concentration of palladium.
- A sample of catalyst was loaded in a stainless steel AISI 316 down-flow tubular reactor (length=52 cm, internal diameter=10 mm). Quartz granules were positioned above and below the catalyst bed to assure the pre-heating of the gas mixture and to support the catalyst bed. Before each run the catalyst was dried at 350° C. for 4 h and reactivated following the activation procedure described above. The temperature was lowered to the reaction temperature, the reactants and the inert gas, when present, were fed to the catalyst bed. The effluent stream was analysed to determine the composition of the product mix (yield and selectivity).
- Following the general catalyst preparation procedure described above two catalyst were prepared using the extruded activated carbon NORIT® 3X EXTRA as the support and having different concentrations of palladium, as shown in Table 1.
-
TABLE 1 Catalyst Pd (% wt) A 1.14 B 0.51 - 2.0 g of each catalyst was loaded into the reactor and tested according to the general procedure described above. The molar ratio H2/chlorotrifluoroethylene was 1:1 and the temperature was set at 200° C. The reaction was carried out in the presence of nitrogen, the final concentration of chlorotrifluoroethylene in the gaseous stream for each run is reported in Table 2. The effluent gas from the reactor was analysed to determine the conversion of chlorotrifluoroethylene (CTFE) and the selectivity in trifluoroethylene (TrFE). The results reported in Table 2 below, show that the process proceeds with very high CTFE conversion rates and with high selectivity in TrFE. Furthermore, reducing the concentration of CTFE from 33 to 11% by volume does not affect the conversion and the selectivity of the process (Run 1 and 2).
-
TABLE 2 Space velocity Resi- (g/h dence Conver- Selec- CTFE *CTFE* time sion tivity Run Catalyst (vol %) gcat-1) (sec) CTFE (%) TrFE (%) 1 A 33 2.6 4.2 93 71 2 A 11 2.6 1.5 93 75 3 B 33 2.6 4.2 98 70 - Following the general catalyst preparation procedure described above one catalyst was prepared using the granular activated carbon NORIT® GCN 1240 as the support and having a palladium concentration of 1.17% by weight (Catalyst C).
- 0.5 g of catalyst A and C were loaded into the reactor and tested according to the general procedure described above. The molar ratio H2/chlorotrifluoroethylene was 1:1 and the temperature was set at 200-230° C. The reaction was carried out in the presence of nitrogen, the final concentration of chlorotrifluoroethylene in the gaseous stream for each run is reported in Table 3. The effluent gas from the reactor was analysed to determine the conversion of chlorotrifluoroethylene (CTFE) and the selectivity in trifluoroethylene (TrFE).
-
TABLE 3 Space velocity (g/h Residence CTFE *CTFE* time Conversion Selectivity Run Catalyst (vol %) gcat-1) (sec) CTFE (%) TrFE (%) 4 A 30 3.6 1.5 93 79 5 A 33 13.9 0.4 91 82 6 A 34 29.5 0.2 83 80 7 C 29 3.6 1.5 82 73 8 C 32 13.5 0.4 80 73 9 C 33 29.9 0.2 71 72 - The reported in Table 3 above (runs 4-6 vs. runs 7-9), show that using extruded activated carbon as the catalyst support, rather than a granular activated carbon, provides a higher conversion of CTFE, all the other process parameters being the same.
Claims (9)
1. A process for preparing trifluoroethylene comprising contacting chlorotrifluoroethylene with hydrogen in the presence of a catalyst consisting of palladium or platinum supported on activated carbon, wherein the activated carbon is extruded activated carbon.
2. The process according to claim 1 wherein the catalyst consists of said palladium supported on said extruded activated carbon.
3. The process according to claim 1 , said process is carried out in the gas-phase by contacting a gaseous stream of said chlorotrifluoroethylene and said hydrogen, with the catalyst.
4. The process according to claim 3 wherein the concentration of said chlorotrifluoroethylene in the gaseous stream is comprised between 5 and 55% by volume.
5. A catalyst consisting of palladium or platinum, supported on activated carbon, wherein that the activated carbon is extruded activated carbon.
6. The catalyst according to claim 5 wherein the amount of said palladium or said platinum supported on the extruded activated carbon is comprised between 0.05 and 5% by weight.
7. The catalyst according to claim 5 consisting of the palladium supported on activated carbon.
8. The catalyst according to claim 6 consisting of the palladium supported on activated carbon.
9. The process according to claim 3 wherein the gaseous stream of said chlorotrifluoroethylene and said hydrogen comprises an inert gas.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10168130 | 2010-07-01 | ||
EP10168130.2 | 2010-07-01 | ||
PCT/EP2011/060400 WO2012000853A1 (en) | 2010-07-01 | 2011-06-22 | Process for the synthesis of trifluoroethylene |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2011/060400 A-371-Of-International WO2012000853A1 (en) | 2010-07-01 | 2011-06-22 | Process for the synthesis of trifluoroethylene |
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US14/310,230 Division US9403742B2 (en) | 2010-07-01 | 2014-06-20 | Process for the synthesis of trifluoroethylene |
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US20130131402A1 true US20130131402A1 (en) | 2013-05-23 |
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US13/704,001 Abandoned US20130131402A1 (en) | 2010-07-01 | 2011-06-22 | Process for the synthesis of trifluoroethylene |
US14/310,230 Active US9403742B2 (en) | 2010-07-01 | 2014-06-20 | Process for the synthesis of trifluoroethylene |
US15/195,576 Abandoned US20160303543A1 (en) | 2010-07-01 | 2016-06-28 | Process for the synthesis of trifluoroethylene |
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US14/310,230 Active US9403742B2 (en) | 2010-07-01 | 2014-06-20 | Process for the synthesis of trifluoroethylene |
US15/195,576 Abandoned US20160303543A1 (en) | 2010-07-01 | 2016-06-28 | Process for the synthesis of trifluoroethylene |
Country Status (6)
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US (3) | US20130131402A1 (en) |
EP (1) | EP2588434B1 (en) |
JP (1) | JP5964823B2 (en) |
CN (1) | CN102971278B (en) |
RU (1) | RU2570812C2 (en) |
WO (1) | WO2012000853A1 (en) |
Cited By (4)
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US20170144949A1 (en) * | 2014-08-25 | 2017-05-25 | Asahi Glass Company, Limited | Method for producing hydrofluoroolefin |
US9862660B2 (en) | 2014-02-20 | 2018-01-09 | Asahi Glass Company, Limited | Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene |
US9988327B2 (en) * | 2014-08-25 | 2018-06-05 | Asahi Glass Company, Limited | Process for producing hydrofluoroolefin |
US10189758B2 (en) * | 2014-12-05 | 2019-01-29 | AGC Inc. | Method for producing hydrofluoroolefin |
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RU2570812C2 (en) * | 2010-07-01 | 2015-12-10 | Солвей Спешиалти Полимерс Итали С.П.А. | Method and catalyst for trifluoroethylene synthesis |
US9266800B2 (en) | 2012-02-02 | 2016-02-23 | Solvay Specialty Polymers Italy S.P.A. | Stable compositions of trifluoroethylene |
FR2987358B1 (en) * | 2012-02-28 | 2016-10-21 | Arkema France | PROCESS FOR THE SYNTHESIS OF TRIFLUOROETHYLENE FROM CHLOROTRIFLUOROETHYLENE |
WO2014178352A1 (en) * | 2013-04-30 | 2014-11-06 | 旭硝子株式会社 | Composition containing trifluoroethylene |
CN105164228B (en) * | 2013-04-30 | 2019-06-11 | Agc株式会社 | Working medium for heat cycle |
JP2021014410A (en) * | 2019-07-10 | 2021-02-12 | ダイキン工業株式会社 | Production method of vinyl compound |
CN110590495A (en) * | 2019-08-21 | 2019-12-20 | 福建省杭氟电子材料有限公司 | Preparation method of hexafluorobutadiene |
JP7348535B2 (en) * | 2021-07-15 | 2023-09-21 | ダイキン工業株式会社 | Alkene production method |
FR3135266A1 (en) * | 2022-05-03 | 2023-11-10 | Arkema France | Trifluoroethylene production process |
CN114797846A (en) * | 2022-05-24 | 2022-07-29 | 四川轻化工大学 | Catalyst for hydrodechlorination and preparation method thereof |
CN115722272B (en) * | 2022-12-07 | 2024-03-26 | 四川轻化工大学 | Preparation method and application of high-stability core-shell structure hydrodechlorination catalyst |
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US9862660B2 (en) | 2014-02-20 | 2018-01-09 | Asahi Glass Company, Limited | Method for purifying fluid that includes trifluoroethylene, and method for producing trifluoroethylene |
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Also Published As
Publication number | Publication date |
---|---|
US20160303543A1 (en) | 2016-10-20 |
JP2013534529A (en) | 2013-09-05 |
CN102971278A (en) | 2013-03-13 |
CN102971278B (en) | 2014-12-17 |
RU2013104169A (en) | 2014-08-10 |
JP5964823B2 (en) | 2016-08-03 |
US9403742B2 (en) | 2016-08-02 |
US20140303411A1 (en) | 2014-10-09 |
RU2570812C2 (en) | 2015-12-10 |
EP2588434A1 (en) | 2013-05-08 |
WO2012000853A1 (en) | 2012-01-05 |
EP2588434B1 (en) | 2016-11-02 |
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