CN112547070A - Catalyst for preparing chlorotrifluoroethylene and preparation method thereof - Google Patents
Catalyst for preparing chlorotrifluoroethylene and preparation method thereof Download PDFInfo
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- CN112547070A CN112547070A CN202011450384.9A CN202011450384A CN112547070A CN 112547070 A CN112547070 A CN 112547070A CN 202011450384 A CN202011450384 A CN 202011450384A CN 112547070 A CN112547070 A CN 112547070A
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- nickel alloy
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- porous copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 48
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 7
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
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Abstract
The invention relates to a catalyst for preparing chlorotrifluoroethylene and a preparation method thereof. The catalyst carrier is sintered porous copper-nickel alloy, the active component is Pd, the loading capacity of the Pd active component is 0.1-5 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness is 0.5-25 mm. The catalyst prepared by the invention can be used for hydrodechlorination reaction, is particularly suitable for industrial large-scale production of chlorotrifluoroethylene by catalytic hydrodechlorination of trichlorotrifluoroethane, and has the advantages of long service life, high reliability and the like.
Description
Technical Field
The invention belongs to the field of fluorine chemical industry, and particularly relates to a catalyst for preparing chlorotrifluoroethylene and a preparation method thereof.
Background
The catalytic hydrogenation and dechlorination of the trifluorotrichloroethane is the most potential production process for preparing the chlorotrifluoroethylene, and has the advantages of environmental protection, continuous production and the like.
The existing catalyst for preparing trifluorochloroethylene mainly comprises a non-noble metal type and a noble metal type, and a catalyst carrier mainly comprises active carbon and Al2O3And SiO2。
CN111013604A discloses a catalyst for catalytic hydrodechlorination, which is characterized by comprising an alloy catalyst, an auxiliary agent and a carrier, wherein the alloy catalyst takes element Ru as a main body, and any one or more of designated alloy elements Re, Ti, Cr, Ni, Al, Co, Cu, Nb, Ta, Ru, Pt or Ag is selected to form an alloy with Ru; the auxiliary agent is alkali metal or rare earth metal, and the carrier is an activated carbon carrier.
CN105944734B discloses a catalyst for preparing chlorotrifluoroethylene by catalytic hydrogenation and dechlorination of trifluorotrichloroethane, which comprises a first catalyst, a second catalyst, an auxiliary agent and a carrier, wherein the first catalyst is one of cobalt or rhodium, the dosage of the first catalyst is 0.1-15% of the total mass of the catalyst, the second catalyst is one of chromium or manganese, the dosage of the second catalyst is 0.5-22% of the total mass of the catalyst, the auxiliary agent is alkali metal potassium or rare earth metal rhenium, the dosage of the auxiliary agent is 0.1-5% of the total mass of the catalyst, and the carrier is SiO2And (3) a carrier.
EP0459463A discloses the influence of the properties of the support on the preparation of chlorotrifluoroethylene by catalytic hydrogenation, the conversion of chlorotrifluoroethane being below 50% when using alumina as support, which compares Pd-Hg/Al2O3Activity with Pd-Hg/C, frontThe amount of the catalyst was 1.3g, the Pd loading was 0.5%, the conversion was 54.7%, the amount of the catalyst of the latter was 0.6g, the Pd loading was 2%, and the conversion was 63.9%.
US5089454 discloses that when activated carbon, alumina, titania and other material are used as carrier, one or more of alkali metal and alkali earth metal salt is used as assistant, and VIII metal is used as active component of catalyst, the reaction temperature is 200-300 deg.c, and the conversion rate of chlorotrifluoroethylene is over 40%.
CN1460549 discloses a catalyst for preparing chlorotrifluoroethylene and trifluoroethylene by catalytic hydrogenation and dechlorination of 1, 1, 2-trifluoro-2, 2, 1-trichloroethane, which is characterized in that noble metal palladium and metal copper are used as main active components, alkali metal lithium and rare earth metal or metal lanthanum are added as modifying additives, and coconut shell activated carbon is used as a carrier; the dosage of the noble metal palladium is 0.5 to 0.4 percent of the total weight of the catalyst; the dosage of the adopted metal copper is 1 to 12 percent of the total weight of the catalyst; the dosage of the adopted metal lithium is 0.2 to 2 percent of the total weight of the catalyst; the dosage of the rare earth metal or the metal lanthanum is 0.5 to 4 percent of the total weight of the catalyst. The conversion rate of raw materials can reach 100 percent, and the highest CTFE selectivity can reach 84.7 percent.
Existing activated carbon, Al2O3And SiO2Although the carriers are used on a large scale, the carriers still have the problems of poor strength, low stability and the like, and further improvement is needed.
Disclosure of Invention
The invention aims to provide a catalyst for preparing chlorotrifluoroethylene, which has long service life and a preparation method thereof.
The technical scheme of the invention is as follows:
a catalyst for preparing chlorotrifluoroethylene, wherein a catalyst carrier is sintered porous copper-nickel alloy, an active component is Pd, the loading amount of the Pd active component is 0.1-5 wt%, preferably 0.1-2 wt%, and more preferably 0.5-1 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, preferably 60-200nm, and more preferably 80-150nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness of the sintered porous copper-nickel alloy is 0.5-25mm, preferably 1-20mm, and more preferably 2-10 mm.
The sintered porous copper-nickel alloy has a relatively uniform pore structure, and the pore volume of 50-300nm accounts for more than 80% of the total pore volume, preferably more than 85%.
The sintered porous copper-nickel alloy is a hollow cylinder, a hollow cube or a hollow cuboid.
The average particle diameter of the active component Pd is 5-30nm, preferably 6-10 nm.
Preferably, the hollow part of the sintered porous copper-nickel alloy is a through hole which penetrates through the hollow part up and down, and the diameter of the through hole is 0.1-10mm, preferably 2-8mm, and further preferably 4-6 mm.
Preferably, the sintered porous copper-nickel alloy is a hollow cylinder, and the height of the hollow cylinder is 5-50 mm.
Preferably, the sintered porous copper-nickel alloy is a hollow cube or a hollow cuboid, and the height of the sintered porous copper-nickel alloy is 5-50 mm.
The preparation method of the sintered porous copper-nickel alloy comprises the following steps: and sintering the nickel oxide powder and the copper oxide powder by a powder metallurgy method to prepare the sintered porous copper-nickel alloy.
Specifically, the average particle diameter of the nickel oxide powder is preferably 5 to 50nm, more preferably 10 to 30nm, and the average particle diameter of the copper oxide powder is preferably 5 to 50nm, more preferably 10 to 30 nm.
In one embodiment, a powder obtained by uniformly mixing nickel oxide and copper oxide is added to an aqueous solution of a dispersant and a binder to prepare a slurry, the slurry is granulated and molded, and the molded body is subjected to temperature programming and baking.
Preferably, the dispersant is low molecular weight sodium polyacrylate and the binder is polyvinyl alcohol. The dispersant of the invention has very excellent technical effect on inhibiting the agglomeration of nickel oxide powder and copper oxide powder.
Preferably, the dispersant is sodium polyacrylate with weight average molecular weight of 3000-4000 and the binder is polyvinyl alcohol with weight average molecular weight of 85000-95000.
Preferably, when the dispersant and the binder aqueous solution are prepared, the dispersant aqueous solution is prepared, then the binder is added, and the mixture is heated and uniformly mixed.
Preferably, when preparing the dispersant and the aqueous solution of the binder, firstly, the dispersant and the deionized water are mixed, stirred for 5-30min, the binder is added, heated to 60-80 ℃, stirred for 10-60min, and then cooled to room temperature.
Preferably, the mass ratio of the dispersing agent to the deionized water is 1: (10-100).
Preferably, the mass ratio of the binder to the deionized water is 1: (10-100).
Preferably, the nickel oxide and copper oxide uniformly mixed powder is added under stirring.
Preferably, the mass ratio of the nickel oxide to the copper oxide powder is (1-10): (1-10).
Preferably, the total proportion of nickel oxide powder and copper oxide powder in the resulting slurry is 60 to 80 wt%.
The slurry of the present invention can be granulated and formed by a granulation and forming method commonly used in the art.
Preferably, the temperature programming is carried out on the formed body, and during the roasting, the formed body is firstly programmed to the temperature of 300-500 ℃ in the nitrogen atmosphere, and then is switched to the 5% argon/hydrogen mixture atmosphere, and the temperature programming is carried out to the temperature of 800-1000 ℃ for roasting.
Preferably, the temperature of the formed body is programmed, and during the baking, the formed body is firstly heated to 300-500 ℃ at the speed of 5-20 ℃/min in the nitrogen atmosphere, the temperature is kept for 1-5 hours, then the formed body is switched to 5% argon/hydrogen mixture atmosphere, the temperature is heated to 800-1000 ℃ at the speed of 10-50 ℃/min, and the formed body is naturally cooled after the temperature is kept for 1-5 hours.
The sintered porous copper-nickel alloy prepared by the method is processed into required hollow cylinder, hollow cube, hollow cuboid and other regular shapes for standby.
The preparation method of the catalyst comprises the following steps:
(1) pretreating the sintered porous copper-nickel alloy;
(2) dipping active components on the pretreated sintered porous copper-nickel alloy;
(3) temperature programming and constant-temperature roasting.
The pretreatment in the step (1) comprises alkali washing, alcohol treatment, acid washing and/or liquid phase reduction.
Preferably, the above pretreatment steps are performed sequentially.
Preferably, the sintered porous copper-nickel alloy is sequentially subjected to four pretreatment steps of alkali washing, alcohol treatment, acid washing and liquid phase reduction, and deionized water is used for washing to be neutral after each step is finished.
Preferably, the alkaline washing is a treatment with a strong base containing an amino group. The strong base can be ammonia water, organic amine, etc. Preferably, the alkaline washing is immersion in 15-28 wt% ammonia solution for 5-30 min.
Preferably, the alcohol treatment is treatment with methanol, ethanol, isopropanol, or the like. Preferably, the alcohol treatment is immersion in ethanol for 5-30 min.
Preferably, the acid wash is a treatment with a strong acid that is non-oxidizing. The strong acid may be hydrochloric acid or the like. Preferably, the acid wash is a dip in a 10-30 wt% hydrochloric acid solution for 5-30 min.
Preferably, the liquid phase reduction is treatment with hydrazine hydrate, formaldehyde, or the like. Preferably, the liquid phase reduction is carried out by dipping in 35-40 wt% formaldehyde aqueous solution for 5-30 min.
The pretreatment step of the invention can fully remove impurities on the surface of the sintered porous copper-nickel alloy and improve the bonding strength between the sintered porous copper-nickel alloy and the metal active component.
And (3) when active components are impregnated in the step (2), immersing the pretreated sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 10-80 ℃, preferably 40-60 ℃, enabling the impregnating solution to circularly flow on the inner side and the outer side of a cavity of the sintered porous copper-nickel alloy by using a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 5-120min, preferably 30-60min, and washing the impregnated porous copper-nickel alloy to be neutral by using deionized water.
The impregnating solution comprises PdCl2、NaH2PO2·H2O, hydrochloric acid (38 wt%), NH3·H2O, ethylenediamine and water.
The pH of the impregnation solution is 7.5 to 11, preferably 9 to 10.
In the dipping solution of the invention, PdCl2Added according to the loading amount. NaH2PO2·H2O is 2-15g/L, hydrochloric acid (38 wt%) is 1-10mL/L, NH3·H2O is 10-200mL/L, and ethylenediamine is 5-50 mL/L.
In the present invention, ethylenediamine may be replaced with ammonium chloride, ammonium sulfate, etc.
In the step (3), the temperature is raised at a rate of 5-30 ℃/min, the constant-temperature roasting is carried out at 250-500 ℃ for 2-5 hours, and the atmosphere is hydrogen atmosphere. Preferably, the firing temperature may be 300-. And naturally cooling after roasting. The particle diameter of the active metal component Pd can be controlled within a desired average particle diameter range by performing the reduction roasting treatment at an appropriate temperature range and temperature rising rate.
Conventional Al is adopted in the prior art2O3And SiO2The supported catalyst prepared by the carriers has poor strength and is easy to pulverize, so that the acting force between the active component and the carriers is reduced, and the active component is easy to fall off and run off. The catalyst prepared by the method has high strength, the sintered porous copper-nickel alloy carrier has certain activity on hydrodechlorination reaction, the acting force between the active metal component and the sintered porous copper-nickel alloy carrier is strong, the active metal component is not easy to run off, and the catalyst has high stability.
The catalyst prepared by the invention can be used for hydrodechlorination reaction, is particularly suitable for industrial large-scale production of chlorotrifluoroethylene by catalytic hydrodechlorination of trichlorotrifluoroethane, and has the advantages of long service life, high reliability and the like.
Drawings
FIG. 1 is a schematic structural diagram of a hollow cylinder sintered porous Cu-Ni alloy in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: preparation of sintered porous copper-nickel alloy
Mixing sodium polyacrylate with weight average molecular weight of 3500 and deionized water (the mass of sodium polyacrylate: the mass of water is 1: 50), stirring for 10min, adding polyvinyl alcohol with weight average molecular weight of 90000 (the mass of polyvinyl alcohol: the mass of water is 1: 20), heating to 80 ℃, stirring for 30min, cooling to room temperature, adding powder (the mass of nickel oxide: the mass of copper oxide: 1) obtained by uniformly mixing nickel oxide powder with average particle size of 10nm and copper oxide powder with average particle size of 10nm under stirring, and making into slurry, wherein the total proportion of nickel oxide powder and copper oxide powder is 70 wt%.
And granulating and forming the slurry, heating the formed body to 400 ℃ at the speed of 10 ℃/min in a nitrogen atmosphere, keeping for 2 hours, then switching to a 5% argon/hydrogen mixture atmosphere, heating to 1000 ℃ at the speed of 20 ℃/min, keeping for 3 hours, and then naturally cooling.
The pore diameter of the sintered porous copper-nickel alloy was measured by a nitrogen adsorption method, and the pore volume of 50 to 300nm was 85% of the total pore volume, and the average pore diameter was 122 nm.
The sintered porous cupronickel alloy was processed into a hollow cylindrical structure as shown in fig. 1. The diameter of a through hole which is vertically communicated with the hollow part is 5mm, the wall thickness is 5mm, and the height is 10mm for standby.
Example 2: preparation of the catalyst
The hollow cylindrical sintered porous copper-nickel alloy prepared in example 1 was subjected to pretreatment including alkali washing, alcohol treatment, acid washing, and liquid phase reduction in this order, and then the pretreated sintered porous copper-nickel alloy was impregnated with an active component. The above steps are all washed to be neutral by deionized water.
The alkali washing is to dip in 20 wt% ammonia water solution for 10min, the alcohol treatment is to dip in ethanol for 10min, the acid washing is to dip in 20 wt% hydrochloric acid solution for 10min, and the liquid phase reduction is to dip in 35 wt% formaldehyde water solution for 10 min.
When active components are impregnated, immersing the pretreated hollow cylindrical sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 60 ℃, and enabling the impregnating solution to circularly flow on the inner side and the outer side of a hollow cylindrical sintered porous copper-nickel alloy cavity by adopting a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 60 min. And washing the mixture to be neutral by deionized water.
The components of the impregnating solution comprise PdCl2、NaH2PO2·H2O, hydrochloric acid (38 wt%), NH3·H2O, ethylenediamine and water, PdCl2Added according to the loading of 1 wt%, NaH2PO2·H2O is 5g/L, hydrochloric acid (38 wt%) is 2mL/L, NH3·H2O is 100mL/L, and ethylenediamine is 10 mL/L. The pH of the impregnation solution was 9.
Heating the hollow cylindrical sintered porous copper-nickel alloy impregnated with the active component to 350 ℃ at the speed of 10 ℃/min in a hydrogen atmosphere, keeping the temperature for 3 hours, and then naturally cooling.
The prepared catalyst is subjected to TEM characterization, and the average particle size of the active component Pd is 6.1 nm.
Example 3: preparation of the catalyst
The hollow cylindrical sintered porous copper-nickel alloy prepared in example 1 was subjected to pretreatment including alkali washing, acid washing, and liquid phase reduction in this order, and then the pretreated sintered porous copper-nickel alloy was impregnated with an active component. The above steps are all washed to be neutral by deionized water.
The alkali washing is to dip in 20 wt% ammonia water solution for 30min, the acid washing is to dip in 20 wt% hydrochloric acid solution for 20min, and the liquid phase is reduced to 35 wt% formaldehyde water solution for 20 min.
When active components are impregnated, immersing the pretreated hollow cylindrical sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 80 ℃, and enabling the impregnating solution to circularly flow on the inner side and the outer side of a hollow cylindrical sintered porous copper-nickel alloy cavity by adopting a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 30 min. And washing the mixture to be neutral by deionized water.
The components of the impregnating solution comprise PdCl2、NaH2PO2·H2O, hydrochloric acid (38 wt%), NH3·H2O, ethylenediamine and water, PdCl2Added according to the loading of 0.5 weight percent, NaH2PO2·H2O is 10g/L and hydrochloric acid (38 wt%) is 1mL/L，NH3·H2O is 200mL/L, and ethylenediamine is 30 mL/L. The pH of the impregnation solution was 10.
Heating the hollow cylindrical sintered porous copper-nickel alloy impregnated with the active component to 400 ℃ at the speed of 20 ℃/min in a hydrogen atmosphere, keeping the temperature for 4 hours, and then naturally cooling.
The prepared catalyst is subjected to TEM characterization, and the average particle size of the active component Pd is 6.8 nm.
Comparative example 1
In contrast to example 2, the catalyst support was SiO2The specific surface area is 380m2Per g, pore volume 0.8cm3/g。
Example 4: enhanced dechlorination test
The catalysts of examples 2 and 3 and comparative example 1 were loaded into a fixed bed reactor with an inner diameter of 10cm, and a mixed gas of hydrogen and trifluorotrichloroethane was introduced at 250 ℃ at a molar ratio of 1:1 and a space velocity of 300h-1The hydrogenation product was analyzed by Agilent 7890A gas chromatography.
The results show that with the catalyst of example 2, the conversion is 100% and the chlorotrifluoroethylene selectivity is 97.56%. After 200 hours, the conversion was still 100%.
With the catalyst of example 3, the conversion was 100% and the chlorotrifluoroethylene selectivity was 97.27%. After 200 hours, the conversion was still 100%.
With the catalyst of comparative example 1, the conversion was 98.58% and the chlorotrifluoroethylene selectivity was 95.12%. After 200 hours, the conversion was 91.87%.
Claims (10)
1. A catalyst for preparing chlorotrifluoroethylene, characterized in that: the catalyst carrier is sintered porous copper-nickel alloy, the active component is Pd, the loading capacity of the Pd active component is 0.1-5 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness is 0.5-25 mm.
2. The catalyst of claim 1, wherein: the sintered porous copper-nickel alloy is a hollow cylinder, a hollow cube or a hollow cuboid.
3. The catalyst of claim 1, wherein: the average particle diameter of the active component Pd is 5-30 nm.
4. The catalyst of claim 1, wherein: the hollow part of the sintered porous copper-nickel alloy is a through hole which penetrates through the hollow part up and down, and the diameter of the through hole is 0.1-10 mm.
5. A process for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
(1) pretreating the sintered porous copper-nickel alloy;
(2) dipping active components on the pretreated sintered porous copper-nickel alloy;
(3) temperature programming and constant-temperature roasting.
6. The method for preparing a catalyst according to claim 5, characterized in that: the pretreatment in the step (1) comprises alkali washing, alcohol treatment, acid washing and/or liquid phase reduction.
7. The method for preparing a catalyst according to claim 5, characterized in that: and (3) when active components are impregnated in the step (2), immersing the pretreated sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 10-80 ℃, enabling the impregnating solution to circularly flow on the inner side and the outer side of the sintered porous copper-nickel alloy cavity by adopting a liquid pump for 5-120min, and washing with deionized water to be neutral.
8. The method for preparing a catalyst according to claim 5, characterized in that: in the step (3), the temperature is raised at a rate of 5-30 ℃/min, the constant-temperature roasting is carried out at 250-500 ℃ for 2-5 hours, and the atmosphere is hydrogen atmosphere.
9. The method for preparing a catalyst according to claim 7, characterized in that: the impregnating solution comprises PdCl2、NaH2PO2·H2O, hydrochloric acid (38 wt%), NH3·H2O, ethylenediamine and water.
10. The method for preparing a catalyst according to claim 7 or 9, characterized in that: the pH of the impregnation liquid is 7.5-11.
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| CN103270009A (en) * | 2010-11-02 | 2013-08-28 | 纳幕尔杜邦公司 | Use of copper-ickel catalyst for dehalogenation of chlorofluorocompounds |
| CN109824473A (en) * | 2019-03-04 | 2019-05-31 | 浙江工业大学 | A kind of method that Pd-M alloy loaded catalyst prepares a fluoromethane |
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| CN103270009A (en) * | 2010-11-02 | 2013-08-28 | 纳幕尔杜邦公司 | Use of copper-ickel catalyst for dehalogenation of chlorofluorocompounds |
| CN109824473A (en) * | 2019-03-04 | 2019-05-31 | 浙江工业大学 | A kind of method that Pd-M alloy loaded catalyst prepares a fluoromethane |
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| CN114870858A (en) * | 2022-03-04 | 2022-08-09 | 中化蓝天集团有限公司 | Anti-carbon deposition catalyst, preparation method and application thereof |
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