CN115974936A - Preparation method and application of high-valence nickel catalyst for acetylene hydrochlorination - Google Patents
Preparation method and application of high-valence nickel catalyst for acetylene hydrochlorination Download PDFInfo
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- CN115974936A CN115974936A CN202211544815.7A CN202211544815A CN115974936A CN 115974936 A CN115974936 A CN 115974936A CN 202211544815 A CN202211544815 A CN 202211544815A CN 115974936 A CN115974936 A CN 115974936A
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- tetrafluoroborate
- acetylene
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- ionic liquid
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 91
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- -1 tetrafluoroborate Chemical compound 0.000 claims description 70
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 51
- 239000002270 dispersing agent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000002608 ionic liquid Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- VOHVZDULLRGWAA-UHFFFAOYSA-N CC1=C(C(=CC=C1)C)NC(=O)C1=CC=CC(=N1)C(=O)N Chemical compound CC1=C(C(=CC=C1)C)NC(=O)C1=CC=CC(=N1)C(=O)N VOHVZDULLRGWAA-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000110 cooling liquid Substances 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GDEWWRSTAFJRRQ-UHFFFAOYSA-N [4-(2-methylpropyl)phenyl] propanoate Chemical compound CCC(=O)OC1=CC=C(CC(C)C)C=C1 GDEWWRSTAFJRRQ-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 3
- HUJKNQNWWPEXLW-UHFFFAOYSA-N 2-methylpropylbenzene;propanoic acid Chemical compound CCC(O)=O.CC(C)CC1=CC=CC=C1 HUJKNQNWWPEXLW-UHFFFAOYSA-N 0.000 claims description 2
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- ZCFREEKATLZMOJ-UHFFFAOYSA-N 2,2,2-triphenylethylphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(CP)C1=CC=CC=C1 ZCFREEKATLZMOJ-UHFFFAOYSA-N 0.000 claims 1
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims 1
- 150000001462 antimony Chemical class 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 68
- 239000002184 metal Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 60
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 33
- 239000002243 precursor Substances 0.000 description 21
- 238000002791 soaking Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a high-valence nickel catalyst for hydrochlorination of acetylene. According to the invention, the low-valence nickel metal is oxidized into the high-valence nickel metal by a low-temperature stable complex oxidation method, so that the d electron number on the surface of the metal is increased, and the catalytic performance of the metal is improved; and the nickel catalyst is particularly suitable for acetylene hydrochlorination reaction by controlling reaction conditions, and shows high conversion rate, high selectivity and high stability in the acetylene hydrochlorination reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a nickel catalyst for acetylene hydrochlorination.
Background
Vinyl Chloride (VCM) is a monomer for the industrial production of polyvinyl chloride, and the large-scale production of vinyl chloride is widely known as acetylene (C) 2 H 2 ) Catalytic hydrochlorination of (1). Nearly 40% of the worldwide vinyl chloride production is produced by the calcium carbide process using mercuric chloride (HgCl) loaded on activated carbon 2 ) As a catalyst. However, these processes are not green, since mercury is a volatile toxic substance that is harmful to human health and the environment. In addition, mercury chloride is inevitably lost from the catalyst, which limits the life of the catalyst. The rapid depletion of mercury deposits and the protection of the environment and the health of people are urgently needed to be openedA novel mercury-free acetylene hydrochlorination catalyst is disclosed.
Ionic Liquid (also called room temperature Ionic Liquid), room temperature molten salt or organic Ionic Liquid, is a salt which is composed of organic cation and inorganic anion and is in Liquid state below 100 ℃. Most ionic liquids are in a liquid state at or near room temperature and have a degree of stability in water. Due to the diversity of organic cations and inorganic anions, new ionic liquid materials with special functions can be designed and synthesized by changing the proportion and combination, and are called as future solvents.
In the reported metal-based acetylene hydrochlorination catalysts, the metals are present in ionic form as active components and catalyze the reaction. The problems of the preparation of the ionic metal precursor and the prevention of the reduction of the active component are to be solved. Here, we have shown that the catalyst prepared by supporting the Ionic Liquid (IL) has higher activity and more stable conversion rate in the reaction than the catalyst without the ionic liquid. More importantly, we have found that the high-valence ionic nickel active center also shows unexpectedly excellent catalytic performance in a special ionic liquid system, and the mercury-free catalyst which is cheap, easy to obtain, efficient and stable provides an opportunity for a green route of large-scale vinyl chloride production.
Disclosure of Invention
Aiming at a series of problems existing in the acetylene hydrochlorination reaction, the invention provides a preparation method and application of a mercury-free, green and environment-friendly nickel catalyst for acetylene hydrochlorination, which is low in cost and good in catalytic performance.
In order to achieve the purpose, the invention adopts the technical scheme that;
in a first aspect, the present invention provides a method for preparing a nickel catalyst for hydrochlorination of acetylene, comprising:
(1) [ Ni ] represented by the formula (I) II (NCCH 3 )(L)]Dissolving with toluene, adding tetraethyl ammonium chloride, stirring the obtained solution at the speed of 100-300 r/min for 5-15 minutes at room temperature, carrying out ultrasonic treatment at the frequency of 15000 Hz-25000 Hz for 3-5 minutes, and then using ethyl acetateDemixing the solution by ether to form bright red crystals, and recovering to obtain a product 1;
said [ Ni ] II (NCCH 3 )(L)]In the formula, L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide;
(2) Dissolving the product 1 obtained in the step (1) in acetone, and cooling to-80 to-40 ℃ to obtain acetone cooling liquid; adding oxidant solution into acetone cooling liquid, stirring for 5-20 minutes at the speed of 100-300 r/min, and stirring at 1m W/cm 2 Performing microwave radiation for 1 to 3 hours at the low power density, centrifuging and drying to obtain a product 2; the oxidant solution is acetonitrile solution or hypochlorous acid aqueous solution of tris (4-bromophenyl) aminoacyl hexachloroantimonate;
(3) Mixing the product 2 obtained in the step (2) with a dispersing agent, adding an ionic liquid, fully mixing, adding a carbon carrier for impregnation treatment, and drying after full impregnation to obtain a nickel catalyst for acetylene hydrochlorination; the dispersing agent is selected from at least one of alcohols, nitriles, ethers, ketones, alkanes and benzene solvents; the mass ratio of nickel, ionic liquid and carbon carrier in the product 2 is 4-10;
the ionic liquid is selected from at least one or more of ionic liquids shown in the following structural formulas (1) to (4);
in the structural formula (1),
R 1 、R 2 、R 3 、R 4 each independently is C n H 2n+1 Or phenyl, n is an integer and n is greater than or equal to 1 and less than or equal to 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenylpropionate;
in the structural formula (2),
R 1 、R 2 、R 3 、R 4 each independently is C n H 2n+1 N is an integer and n is not less than 1 and not more than 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenylpropionate;
in the structural formula (3), the compound (A),
R 1 is H, CH 3 Or C 2 H 5 ；
R 2 Is C n H 2n+1 N is an integer and n is not less than 1 and not more than 6;
R 3 is C k H 2k+1 K is an integer and is not less than 1 and not more than 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenyl propionate;
in the structural formula (4),
R 1 、R 2 each independently is C n H 2n+1 N is an integer and n is not less than 1 and not more than 16;
R 3 is C n H 2n+1 Or O, n is an integer and n is more than or equal to 1 and less than or equal to 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, hexafluorophosphate, bistrifluoromethanesulfonate iminate or p-isobutylbenzene propionate. .
The nickel catalyst prepared by the invention contains novel activity shown as the following formulaCenter [ Ni ] III (Cl)(L)]：
Preferably, in the step (1), [ Ni ] is II (NCCH 3 )(L)]The mass ratio of the ammonium chloride to the tetraethyl ammonium chloride is 1:0.5-10, more preferably 1:0.5-1.0.
Preferably, in the step (2), the feeding ratio of the product 1 to the oxidant is 10g:0.01 to 0.2mol, more preferably 10g:0.01-0.05mol.
Preferably, in the step (2), the oxidizing agent solution is a hypochlorous acid aqueous solution.
Preferably, in step (2), the centrifugation conditions are: the centrifugal speed is 30-50 r/min, and the centrifugal time is 20-40 minutes.
Preferably, in the step (2), the drying conditions are as follows: vacuum drying at 20-30 deg.c for 20-40 min.
In step (2) of the present invention, the dispersant is at least one selected from alcohols, nitriles, ethers, ketones, alkanes and benzenes. The alcohol can be one or the combination of more than two of monohydric alcohol, dihydric alcohol and polyhydric alcohol; preferred alcohols are methanol, ethanol, n-propanol, isopropanol, propylene glycol, ethylene glycol, 1,4-butanediol, and the like, but are not limited to these alcohols. The nitrile may be a nitrile or an isonitrile; preferred nitriles are acetonitrile, propionitrile, malononitrile, acrylonitrile, etc., but are not limited to these nitriles. The ethers are preferably diphenyl ether, anisole, tetrahydrofuran, ethyl vinyl ether, etc., but are not limited to these ethers. The ketones are preferably acetylacetone, N-methylpyrrolidone, and the like, but are not limited to these ketones. The alkane is preferably hexadecane. The benzene dispersant is preferably 1-ethoxy-4-toluene, hydroxymethylphenol, o-diphenol, toluene, xylene, phenol, or the like, but is not limited thereto.
Preferably, the dispersant is selected from at least one of the following: methanol, ethanol, n-propanol, isopropanol, propylene glycol, ethylene glycol, 1,4-butanediol, acetonitrile, propionitrile, malononitrile, acrylonitrile; most preferably, the dispersant is acetonitrile.
Preferably, the ionic liquid represented by the formula (1) is selected from one of the following:
tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium tetrachloroferrite, trihexylhexadecylphosphonium trifluoromethanesulfonate, tributylmethylphosphonium p-toluenesulfonate, triphenylethylphosphonium bistrifluoromethanesulfonate.
Preferably, the ionic liquid represented by the formula (2) is selected from one of the following:
N-methoxyethyl-N-methyl-N, N-diethylammonium tetrafluoroborate, trihexylmethylammonium bis (trifluoromethanesulfonic acid) imide salt, tetraethylammonium p-toluenesulfonate salt.
Preferably, the ionic liquid represented by the formula (3) is selected from one of the following:
1-ethyl-2,3-dimethylimidazole hexafluorophosphate, 1-ethyl-2,3-dimethylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-propyl-3-butylimidazole tetrafluoroborate, 1-methyl-3-hexadecylimidazole bistrifluoromethanesulfonate, trimethylimidazole tetrafluoroborate, 1-methyl-3-octylimidazole hexafluorophosphate.
Preferably, the ionic liquid represented by the formula (4) is selected from one of the following:
N-butyl-N-methylpyrrolidine bistrifluoromethanesulfonimide salt, N-butyl-N-methylpyrrolidine hexafluorophosphate salt.
It is particularly preferred in the present invention that the ionic liquid is selected from one of the following:
a mixture of tetrabutylphosphonium tetrafluoroborate and trihexylmethylammonium bis (trifluoromethanesulfonic acid) imide salt, most preferably in a mass ratio of 1:3;
1-hexyl-3-methylimidazolium hexafluorophosphate and 1-propyl-1-methylpiperidine bis (trifluoromethanesulfonimide) salt, most preferably in a mass ratio of 1:5;
1-ethyl-2,3-dimethylimidazolium tetrafluoroborate and N-butyl-N-methylpyrrolidine bistrifluoromethylsulfonyl imide salt, most preferably in a mass ratio of 1:2;
a mixture of triphenylethylphosphine bistrifluoromethanesulfonimide salt and 1-propyl-3-butylimidazolium tetrafluoroborate, most preferably in a mass ratio of 1:1.
in step (3) of the present invention, the amount of the dispersant is determined according to the mass of the carrier used, and the principle is to make the impregnation solution sufficiently absorb the dispersant. The time of the impregnation treatment depends on the absorption of the impregnation solution, and the impregnation time is generally not less than 4 hours, for example, 4 to 6 hours. The drying process is carried out at 100 to 150 ℃ as the drying process is preferably carried out so as to ensure that the final catalyst is free of moisture.
Preferably, the carbon carrier is coconut shell activated carbon, and the specific surface area is 800-1500 m 2 The mesh number is 200-400.
In a second aspect, the invention provides the use of the nickel catalyst in the hydrochlorination of acetylene.
Compared with the prior art, the invention has the following innovation points and technical advantages:
(1) The invention provides a nickel catalyst for acetylene hydrochlorination, which oxidizes low-valence nickel metal into high-valence nickel metal by a low-temperature stable complex oxidation method, and increases the d electron number on the surface of the metal to improve the catalytic performance of the metal; and the nickel catalyst is particularly suitable for acetylene hydrochlorination reaction by controlling reaction conditions, and shows high conversion rate, high selectivity and high stability in the acetylene hydrochlorination reaction.
(2) The nickel catalyst for the hydrochlorination of acetylene has the advantages of excellent conductivity, mechanical strength and catalytic activity, good stability and environmental protection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the technical solutions will be further clearly and completely described by examples. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Activity used in examplesThe charcoal is coconut shell activated charcoal of activated charcoal Limited in Zhengzhou, and has a specific surface area of 1249m 2 (g), 325 mesh number. [ Ni ] II (NCCH 3 )(L)](L stands for N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide) was purchased from school procurement platforms.
Example 1
1) Will 30g [ 2 ], [ Ni ] II (NCCH 3 )(L)](L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide) was dissolved in 250mL of methanol, 15g of tetraethylammonium chloride was added, and the resulting solution was stirred at a rate of 200r/min at room temperature for 10 minutes, treated with an ultrasonic frequency of 20000Hz for 5 minutes, and allowed to stand at room temperature in a vacuum oven of-0.1 MPa for 1 hour. The solution was layered with 500mL of ether to form bright red crystals, which were filtered and recovered to give product 1, 20g in mass.
10g of product 1 were dissolved in 20mL of acetone and the resulting solution was cooled in a conical flask to the desired temperature (T = -80 ℃ C., for stabilization of the complex). Taking 10mL of 1moL/L hypochlorous acid standard aqueous solution, adding the solution into acetone cooling liquid of the product 1, stirring the solution for 10 minutes at the speed of 200r/min under the condition of low temperature and constant temperature of 80 ℃ below zero, processing the solution for 2 hours under the condition of microwave radiation with low power density (1 m W/cm < 2 >), centrifuging the solution for 30 minutes under the condition of 50r/min, standing the solution for 30 minutes under the normal temperature condition of a vacuum oven with pressure of 0.1MPa below zero to obtain a target product 2, wherein the nickel content of the prepared precursor is about 1g.
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of tetrabutyl phosphine tetrafluoroborate and trihexyl methylammonium bis (trifluoromethanesulfonate) imide salt in a mass ratio of 1:3, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture for 8 hours at 120 ℃ to obtain a catalyst 1;
3) Application of the catalyst 1 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1 strip (= 1.1)The process is carried out under the condition of one piece. At the initial stage of the reaction, the conversion rate of acetylene is 98.79 percent, and the selectivity of chloroethylene is 99.98 percent; after 1000 hours of reaction time, the acetylene conversion was 97.05% and the vinyl chloride selectivity was 99.95%.
Comparative example 1 catalyst preparation by selecting ethanol as dispersant
1) The same as example 1;
2) Preparation of the catalyst: adding ethanol serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, and adding 2g of tetrabutyl phosphine tetrafluoroborate and trihexyl methylammonium bis (trifluoromethanesulfonate) imide salt in a mass ratio of 1:3, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 2;
3) Application of catalyst 2 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial stage of the reaction, the conversion rate of acetylene is 94.34 percent, and the selectivity of vinyl chloride is 95.65 percent; after 1000 hours of reaction time, the acetylene conversion was 82.21% and the vinyl chloride selectivity was 95.13%.
Comparative example 2 treatment of precursor with different oxidants
1) Prepared from 30g [ 2 ], [ Ni ] II (NCCH 3 )(L)](L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide) was dissolved in 250mL of methanol, 15g of tetraethylammonium chloride was added, and the resulting solution was stirred at a rate of 200r/min at room temperature for 10 minutes, treated with an ultrasonic frequency of 20000Hz for 5 minutes, and allowed to stand at room temperature in a vacuum oven of-0.1 MPa for 1 hour. The solution was layered with 500mL of ether to form bright red crystals, which were filtered and recovered to give product 1, 20g in mass.
A solution of 10g of product 1 in acetone (0.3 mM, 20mL) was taken and cooled to the desired temperature in an Erlenmeyer flask (T = -40 ℃ C., for stabilization of the complex). Dissolving appropriate amount of newly prepared tris (4-bromophenyl) aminoacyl hexachloroantimonate in acetonitrile (10 mL) (concentration of 5 mol)L), adding into acetone cooling liquid of the product 1, stirring at 200r/min for 10 minutes at-40 deg.C and low temperature, and adjusting the power density (1 m W/cm) 2 ) Treating for 2 hours under the condition of microwave radiation, then centrifuging for 30 minutes under the condition of 50r/min, and standing for 30 minutes under the normal temperature condition of a vacuum oven with the pressure of-0.1 MPa to obtain a target product 2, wherein the nickel content of the prepared precursor is about 1g.
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of tetrabutyl phosphine tetrafluoroborate and trihexyl methyl ammonium bis (trifluoromethanesulfonic acid) imine salt in a mass ratio of 1:3, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after 8 hours of impregnation, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 3;
3) Application of catalyst 3 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial stage of the reaction, the conversion rate of acetylene is 72.52 percent, and the selectivity of vinyl chloride is 97.03 percent; after 1000 hours of reaction time, the acetylene conversion was 50.01% and the vinyl chloride selectivity was 96.37%.
Example 2
1) The same as example 1;
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of 1-hexyl-3-methylimidazolium hexafluorophosphate and 1-propyl-1-methylpiperidine bistrifluoromethylsulfonyl imide salt in a mass ratio of 1:5, fully stirring the mixture, adding 20g of activated carbon, completely soaking the activated carbon, completely absorbing the soaking solution, soaking for 8 hours, putting the mixture into an oven, and drying for 8 hours at 120 ℃ to obtain a catalyst 4;
3) Application of catalyst 4 in hydrochlorination of acetylene: evaluation of the hydrochlorination of acetylene in a fixed-bed reactor installationThe reaction conditions are as follows: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 99.90 percent, and the selectivity of chloroethylene is 99.91 percent; after 1000 hours of reaction time, the acetylene conversion was 97.81% and the vinyl chloride selectivity was 99.82%.
Comparative example 3: selecting glycol as dispersant to prepare catalyst
1) The same as example 1;
2) Preparation of the catalyst: adding ethylene glycol serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of 1-hexyl-3-methylimidazolium hexafluorophosphate and 1-propyl-1-methylpiperidine bistrifluoromethylsulfonyl imide salt in a mass ratio of 1:5, fully stirring the mixture, adding 20g of activated carbon, completely soaking the activated carbon, completely absorbing the soaking solution, soaking for 8 hours, putting the mixture into an oven, and drying for 8 hours at 120 ℃ to obtain a catalyst 5;
3) Application of catalyst 5 in acetylene hydrochlorination: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial stage of the reaction, the conversion rate of acetylene is 96.63 percent, and the selectivity of vinyl chloride is 95.93 percent; after 1000 hours of reaction time, the acetylene conversion was 85.51% and the vinyl chloride selectivity was 94.81%.
Comparative example 4: effect of non-sonication on catalyst
1) Will 30g [ 2 ], [ Ni ] II (NCCH 3 )(L)](L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide) was dissolved in 250mL of methanol, 15g of tetraethylammonium chloride was added, and the resulting solution was stirred at a rate of 200r/min at room temperature for 10 minutes and allowed to stand at room temperature in a vacuum oven at-0.1 MPa for 1 hour. The solution was layered with 500mL of ether to form bright red crystals, which were filtered and recovered to give product 1, 20g in mass.
10g of product 1 were dissolved in 20mL of acetone and the resulting solution was cooled in a conical flask to the desired temperature (T = -80 ℃ C., for stabilization of the complex). Taking 10mL of 1moL/L hypochlorous acid standard aqueous solution, adding the solution into acetone cooling liquid of the product 1, stirring the solution for 10 minutes at the speed of 200r/min under the condition of low temperature and constant temperature of 80 ℃ below zero, processing the solution for 2 hours under the condition of microwave radiation with low power density (1 m W/cm < 2 >), centrifuging the solution for 30 minutes under the condition of 50r/min, standing the solution for 30 minutes under the condition of normal temperature of a vacuum oven with pressure of 0.1MPa to obtain a target product 2, wherein the nickel content of the prepared precursor is about 1g.
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of 1-hexyl-3-methylimidazolium hexafluorophosphate and 1-propyl-1-methylpiperidine bistrifluoromethylsulfonyl imide salt in a mass ratio of 1:5, fully stirring the mixture, adding 20g of activated carbon, completely soaking the activated carbon, completely absorbing the soaking solution, soaking for 8 hours, putting the mixture into an oven, and drying for 8 hours at 120 ℃ to obtain a catalyst 6;
3) Application of the catalyst 6 in acetylene hydrochlorination: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 82.31 percent, and the selectivity of chloroethylene is 98.11 percent; after 1000 hours of reaction, the acetylene conversion was 58.01% and the vinyl chloride selectivity was 98.01%.
Example 3
1) The same as example 1;
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g 1-ethyl-2,3-dimethyl imidazole tetrafluoroborate and N-butyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide salt in a mass ratio of 1:2, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 7;
3) Application of catalyst 7 in hydrochlorination of acetylene: in a fixed bed reactorAnd (3) carrying out acetylene hydrochlorination evaluation under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 98.65%, and the selectivity of chloroethylene is 99.61%; after 1000 hours of reaction time, the acetylene conversion was 96.52% and the vinyl chloride selectivity was 99.55%.
Comparative example 5: preparation of catalyst by selecting n-propanol as dispersant
1) The same as example 1;
2) Preparation of the catalyst: adding the precursor prepared in the step 1) into N-propanol serving as a dispersing agent to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g 1-ethyl-2,3-dimethyl imidazole tetrafluoroborate and N-butyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide salt in a mass ratio of 1:2, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture for 8 hours at 120 ℃ to obtain a catalyst 8;
3) Application of catalyst 8 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 95.66 percent, and the selectivity of chloroethylene is 97.89 percent; after 1000 hours of reaction, the acetylene conversion was 90.97% and the vinyl chloride selectivity was 93.52%.
Comparative example 6: effect of non-microwave treatment on catalyst
1) Prepared from 30g [ 2 ], [ Ni ] II (NCCH 3 )(L)](L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide) was dissolved in 250mL of methanol, 15g of tetraethylammonium chloride was added, and the resulting solution was stirred at a rate of 200r/min at room temperature for 10 minutes, treated with an ultrasonic frequency of 20000Hz for 5 minutes, and allowed to stand at room temperature in a vacuum oven of-0.1 MPa for 1 hour. The solution was layered with 500mL of ether to form bright red crystals, which were filtered and recovered to give product 1, 20g in mass. 10g of product 1 are dissolved in 20mL of acetone and the resulting solution is taken up in a conical flaskCooling to the desired temperature (T = -80 ℃ for stabilization of the complex). Taking 10mL of 1moL/L hypochlorous acid standard aqueous solution, adding the solution into acetone cooling liquid of the product 1, stirring the solution for 10 minutes at the speed of 200r/min under the condition of low temperature and constant temperature of 80 ℃ below zero, then centrifuging the solution for 30 minutes under the condition of 50r/min, and standing the solution for 30 minutes under the condition of normal temperature of a vacuum oven of 0.1MPa to obtain a target product 2, wherein the nickel content of the prepared precursor is about 1g.
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of 1-ethyl-2,3-dimethylimidazole tetrafluoroborate and N-butyl-N-methylpyrrolidine bistrifluoromethanesulfonylimide salt in a mass ratio of 1:2, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after 8 hours of impregnation, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 9;
3) Application of catalyst 9 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial stage of the reaction, the conversion rate of acetylene is 85.30 percent, and the selectivity of vinyl chloride is 96.67 percent; after 1000 hours of reaction time, the acetylene conversion was 72.11% and the vinyl chloride selectivity was 95.76%.
Example 4
1) The same as example 1;
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of triphenyl ethylphosphine bistrifluoromethanesulfonimide salt and 1-propyl-3-butylimidazole tetrafluoroborate in a mass ratio of 1:1, fully stirring the mixture, adding 20g of activated carbon, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 10;
3) Application of the catalyst 10 in acetylene hydrochlorination: on a fixed bed reactor unitEvaluation of acetylene hydrochlorination was carried out under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 99.37 percent, and the selectivity of chloroethylene is 99.64 percent; after 1000 hours of reaction, the acetylene conversion was 96.88% and the vinyl chloride selectivity was 98.95%.
Comparative example 7: catalyst prepared by selecting isopropanol as dispersant
1) The same as example 1;
2) Preparation of the catalyst: adding isopropanol into the precursor prepared in the step 1) to serve as a dispersing agent to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of triphenyl ethylphosphine bistrifluoromethanesulfonimide salt and 1-propyl-3-butylimidazole tetrafluoroborate in a mass ratio of 1:1, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture for 8 hours at 120 ℃ to obtain a catalyst 11;
3) Application of the catalyst 11 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 97.13 percent, and the selectivity of chloroethylene is 98.44 percent; after 1000 hours of reaction time, the acetylene conversion was 95.77% and the vinyl chloride selectivity was 96.93%.
Comparative example 8: selecting different oxidants to treat the precursor
1) The same as comparative example 2;
2) Preparation of the catalyst: adding acetonitrile serving as a dispersing agent into the precursor prepared in the step 1) to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of triphenyl ethylphosphine bis (trifluoromethanesulfonimide) salt and 1-propyl-3-butylimidazole tetrafluoroborate in a mass ratio of 1:1, adding 20g of activated carbon after fully stirring, completely impregnating the activated carbon, completely absorbing the impregnating solution, putting the impregnated mixture into an oven after impregnating for 8 hours, and drying the impregnated mixture at 120 ℃ for 8 hours to obtain a catalyst 12;
3) Application of catalyst 12 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial stage of the reaction, the conversion rate of acetylene is 80.32 percent, and the selectivity of vinyl chloride is 90.21 percent; after 1000 hours of reaction time, the acetylene conversion was 71.94% and the vinyl chloride selectivity was 83.37%.
Comparative example 9: preparation of catalyst by single ionic liquid
1) The same as example 1;
2) Preparation of the catalyst: adding acetonitrile into the precursor prepared in the step 1) to serve as a dispersing agent to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of triphenyl ethyl phosphine bis (trifluoromethanesulfonimide) salt under the condition that a glass rod is slowly stirred, fully stirring, adding 20g of activated carbon, completely soaking the activated carbon, completely absorbing the soaking solution, soaking for 8 hours, putting the soaked activated carbon into an oven, and drying for 8 hours at 120 ℃ to obtain a catalyst 13;
3) Application of catalyst 13 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. At the initial stage of the reaction, the conversion rate of acetylene is 98.32%, and the selectivity of chloroethylene is 90.01%; after 1000 hours of reaction, the acetylene conversion was 70.94% and the vinyl chloride selectivity was 76.34%.
Comparative example 10: preparation of catalyst by single ionic liquid
1) The same as example 1;
2) Preparation of the catalyst: adding acetonitrile into the precursor prepared in the step 1) to be used as a dispersing agent to prepare 40ml of solution, pouring the solution into a clean culture dish, adding 2g of 1-propyl-3-butylimidazole tetrafluoroborate under the condition that a glass rod is slowly stirred, fully stirring, adding 20g of activated carbon, completely soaking the activated carbon, completely absorbing the soaking solution, soaking for 8 hours, putting the soaked activated carbon into an oven, and drying for 8 hours at 120 ℃ to obtain a catalyst 14;
3) Application of catalyst 14 in hydrochlorination of acetylene: acetylene hydrochlorination evaluation was carried out on a fixed bed reactor set-up under the following reaction conditions: the temperature is 170 ℃, and the space velocity of acetylene is 500h -1 ，n(HCl):n(C 2 H 2 ) 1.1 under the following conditions. In the initial reaction stage, the acetylene conversion rate is 88.99 percent, and the vinyl chloride selectivity is 95.51 percent; after 1000 hours of reaction, the acetylene conversion was 71.24% and the vinyl chloride selectivity was 83.37%.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a nickel catalyst for acetylene hydrochlorination is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) [ Ni ] represented by the formula (I) II (NCCH 3 )(L)]Dissolving with toluene, adding tetraethyl ammonium chloride, stirring the obtained solution at the speed of 100-300 r/min for 5-15 minutes at room temperature, carrying out ultrasonic treatment at the frequency of 15000 Hz-25000 Hz for 3-5 minutes, layering the solution with ether to form bright red crystals, and recovering to obtain a product 1;
said [ Ni ] II (NCCH 3 )(L)]In the formula, L represents N, N' - (2,6-dimethylphenyl) -2,6-pyridinedicarboxamide;
(2) Dissolving the product 1 obtained in the step (1) in acetone, and cooling to-80 to-40 ℃ to obtain acetone cooling liquid; adding oxidant solution into acetone cooling liquid, stirring for 5-20 minutes at the speed of 100-300 r/min under the condition of 1mW/cm 2 Performing microwave radiation for 1 to 3 hours at low power density, centrifuging and drying to obtain a product 2; the oxidant solution is tri (4-bromophenyl) aminoacyl hexachloroAcetonitrile solution of antimony salt or hypochlorous acid aqueous solution;
(3) Mixing the product 2 obtained in the step (2) with a dispersing agent, adding an ionic liquid, fully mixing, adding a carbon carrier for impregnation treatment, and drying after full impregnation to obtain a nickel catalyst for acetylene hydrochlorination; the dispersing agent is selected from at least one of alcohols, nitriles, ethers, ketones, alkanes and benzene solvents; the mass ratio of nickel, ionic liquid and carbon carrier in the product 2 is 4-10;
the ionic liquid is selected from one or more of ionic liquids shown in the following structural formulas (1) to (4);
in the structural formula (1),
R 1 、R 2 、R 3 、R 4 each independently is C n H 2n+1 Or phenyl, n is an integer and n is greater than or equal to 1 and less than or equal to 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenyl propionate;
in the structural formula (2),
R 1 、R 2 、R 3 、R 4 each independently is C n H 2n+1 N is an integer and n is not less than 1 and not more than 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenyl propionate;
in the structural formula (3),
R 1 is H, CH 3 Or C 2 H 5 ；
R 2 Is C n H 2n+1 N is an integer and n is not less than 1 and not more than 6;
R 3 is C k H 2k+1 K is an integer and is not less than 1 and not more than 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, trifluoromethanesulfonate, bistrifluoromethanesulfonate iminate or p-isobutylphenyl propionate;
in the structural formula (4),
R 1 、R 2 each independently is C n H 2n+1 N is an integer and n is not less than 1 and not more than 16;
R 3 is C n H 2n+1 Or O and n are integers, and n is more than or equal to 1 and less than or equal to 16;
X - selected from tetrafluoroborate or iminate, tetrachloroferrate, hexafluorophosphate, bistrifluoromethanesulfonate iminate or p-isobutylbenzene propionate.
2. The method of claim 1, wherein: in the step (1), the [ Ni ] II (NCCH 3 )(L)]The mass ratio of the ammonium chloride to the tetraethyl ammonium chloride is 1:0.5 to 10, more preferably 1:0.5-1.0.
3. The method of claim 1, wherein: in the step (2), the feeding ratio of the product 1 to the oxidant is 10g:0.01 to 0.2mol, more preferably 10g:0.01-0.05mol.
4. The method of claim 1, wherein: in the step (2), the alcohol solvent is at least one of methanol, ethanol, n-propanol, isopropanol, propylene glycol, ethylene glycol and 1,4-butanediol; the nitrile solvent is at least one of acetonitrile, propionitrile, malononitrile and acrylonitrile; the ether solvent is at least one of diphenyl ether, anisole, tetrahydrofuran and ethyl vinyl ether; the ketone solvent is at least one of acetylacetone and N-methylpyrrolidone; the alkane solvent is hexadecane; the benzene solvent is at least one of 1-ethoxy-4-toluene, hydroxymethyl phenol, o-diphenol, toluene, xylene and phenol.
5. The method of claim 4, wherein: the dispersant is selected from at least one of the following: methanol, ethanol, n-propanol, isopropanol, propylene glycol, ethylene glycol, 1,4-butanediol, acetonitrile, propionitrile, malononitrile, acrylonitrile.
6. The method of claim 1, wherein: the ionic liquid shown in the formula (1) is selected from one of the following substances:
tetrabutylphosphonium tetrafluoroborate, tetrabutylphosphonium tetrachloroferrite, trihexylhexadecylphosphonium trifluoromethanesulfonate, tributylmethylphosphonium p-toluenesulfonate, triphenylethylphosphonium bistrifluoromethanesulfonate;
the ionic liquid shown in the formula (2) is selected from one of the following substances:
N-methoxyethyl-N-methyl-N, N-diethylammonium tetrafluoroborate, trihexylmethylammonium bis (trifluoromethanesulfonic acid) imide salt, tetraethylammonium p-toluenesulfonate;
the ionic liquid shown in the formula (3) is selected from one of the following:
1-ethyl-2,3-dimethylimidazole hexafluorophosphate, 1-ethyl-2,3-dimethylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-propyl-3-butylimidazole tetrafluoroborate, 1-methyl-3-hexadecylimidazole bistrifluoromethanesulfonate, trimethylimidazole tetrafluoroborate, 1-methyl-3-octylimidazole hexafluorophosphate;
the ionic liquid shown in the formula (4) is selected from one of the following:
N-butyl-N-methylpyrrolidine bistrifluoromethanesulfonimide salt, N-butyl-N-methylpyrrolidine hexafluorophosphate salt.
7. The method of claim 6, wherein: the ionic liquid is selected from one of the following:
a mixture of tetrabutylphosphonium tetrafluoroborate and trihexylmethylammonium bis (trifluoromethanesulfonic acid) imide salt, most preferably in a mass ratio of 1:3;
1-hexyl-3-methylimidazolium hexafluorophosphate and 1-propyl-1-methylpiperidine bis (trifluoromethanesulfonimide) salt, most preferably in a mass ratio of 1:5;
1-ethyl-2,3-dimethylimidazolium tetrafluoroborate and N-butyl-N-methylpyrrolidine bistrifluoromethylsulfonyl imide salt, most preferably in a mass ratio of 1:2;
a mixture of triphenylethylphosphine bistrifluoromethanesulfonylimide and 1-propyl-3-butylimidazolium tetrafluoroborate, most preferably in a mass ratio of 1:1.
8. the method of claim 1, wherein: in the step (3), the dipping time is not less than 4-6 h, and the drying is carried out at the temperature of 100-150 ℃.
9. The method of claim 1, wherein: the carbon carrier is coconut shell activated carbon with the specific surface area of 800-1500 m 2 The mesh number is 200-400.
10. The use of the nickel catalyst prepared by the preparation method according to claim 1 in the hydrochlorination of acetylene.
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| CN110743616A (en) * | 2019-09-30 | 2020-02-04 | 浙江工业大学 | Environment-friendly acetylene hydrochlorination catalyst and preparation method thereof |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110743616A (en) * | 2019-09-30 | 2020-02-04 | 浙江工业大学 | Environment-friendly acetylene hydrochlorination catalyst and preparation method thereof |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| APPARAO DRAKSHARAPU ET AL.: "Spectroscopic Analyses on Reaction Intermediates Formed during Chlorination of Alkanes with NaOCl Catalyzed by a Nickel Complex", 《INORG. CHEM.》, vol. 54, pages 10656 * |
| PRASENJIT MONDAL ET AL.: "Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex", 《J. AM. CHEM. SOC.》, vol. 140, pages 1834 * |
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