CN115106093A - Preparation method and application of metal covalent organic framework catalyst - Google Patents
Preparation method and application of metal covalent organic framework catalyst Download PDFInfo
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- CN115106093A CN115106093A CN202210793686.9A CN202210793686A CN115106093A CN 115106093 A CN115106093 A CN 115106093A CN 202210793686 A CN202210793686 A CN 202210793686A CN 115106093 A CN115106093 A CN 115106093A
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- triazine
- organic framework
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 39
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 23
- 238000007598 dipping method Methods 0.000 claims description 19
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 11
- 239000012876 carrier material Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- FAAXSAZENACQBT-UHFFFAOYSA-N benzene-1,2,4,5-tetracarbonitrile Chemical compound N#CC1=CC(C#N)=C(C#N)C=C1C#N FAAXSAZENACQBT-UHFFFAOYSA-N 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 5
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- XNPMXMIWHVZGMJ-UHFFFAOYSA-N pyridine-2,6-dicarbonitrile Chemical compound N#CC1=CC=CC(C#N)=N1 XNPMXMIWHVZGMJ-UHFFFAOYSA-N 0.000 claims description 4
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- MYINLNBRJVGINA-UHFFFAOYSA-N thiophene-2,5-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)S1 MYINLNBRJVGINA-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 4
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- DARDYTBLZQDXBK-UHFFFAOYSA-N 1-(chloromethyl)-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(CCl)C([N+]([O-])=O)=C1 DARDYTBLZQDXBK-UHFFFAOYSA-N 0.000 claims description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical group C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 21
- 238000005303 weighing Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 108010018842 CTF-1 transcription factor Proteins 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013311 covalent triazine framework Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229960002523 mercuric chloride Drugs 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- CQVDKGFMVXRRAI-UHFFFAOYSA-J Cl[Au](Cl)(Cl)Cl Chemical compound Cl[Au](Cl)(Cl)Cl CQVDKGFMVXRRAI-UHFFFAOYSA-J 0.000 description 1
- 229910016347 CuSn Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 triazine structure compound Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a metal covalent organic framework catalyst, which adopts triazine framework material (CTF) as a carrier to prepare a highly dispersed triazine framework catalyst, namely a copper-tin monatomic catalyst, reduces the consumption of active components, improves the number of active sites, and macroscopically and obviously increases the catalytic reaction effect, wherein the reaction temperature is 100-120 ℃, and the acetylene airspeed is 30-50h ‑1 At normal pressure, the initial conversion per pass of acetylene can reach 95 percentThe selectivity of the chloroethylene is more than 98 percent, and the catalyst is not obviously deactivated after 500 hours of reaction.
Description
Technical Field
The invention belongs to the field of organic synthesis catalysts, and particularly relates to a preparation method of a triazine frame catalyst and application of the triazine frame catalyst in acetylene hydrochlorination.
Background
China is the first major world polyvinyl chloride (PVC) producing country, and the yield reaches 2500 million tons/year by 2020, wherein 70-80% of the yield of the monomer raw material vinyl chloride is produced by an acetylene hydrochlorination process, and a mercuric chloride catalyst is required for reaction. The mercury chloride is easy to sublimate and run off in the reaction process and has serious environmental pollution, the United nations environmental administration in 2013 passes "Water guarantee", and the convention stipulates that the mercury is completely prohibited from being used for PVC production by 2030. In recent years, scholars at home and abroad make great efforts on the development of mercury-free catalysts, and the research on the catalysts basically forms three directions: (1) a gold-based noble metal catalyst; (2) a base metal catalyst; (3) a carbon-based non-metallic catalyst.
At the earliest, noble metal chlorides such as gold tetrachloride and platinum chloride have very strong catalytic activity on acetylene hydrochlorination, but the noble metal catalysts are expensive, and no industrial application report is available. In recent years, there have been many developments of carbon-based non-metal catalysts and applications thereof in hydrochlorination of acetylene, such as institute of university of the Chinese academy of sciences, high research institute of Shanghai of China, university of Shihui, Tianjin university, Zhejiang university, etc., and the carbon-based non-metal catalysts are mainly used in the present invention because the catalyst activity is lower than that of metal catalysts. Compared with the defects of noble metal catalysts and non-metal catalysts, the non-noble metal (base metal) catalyst has better application prospect. Many researches and reports are made on the development of base metal mercury-free catalysts at home and abroad, but the base metal mercury-free catalysts are not really commercialized yet.
Chinese patents report many researches on base metal catalysts, such as copper, bismuth, tin and the like, and the activity and stability of the catalysts are improved to a certain extent, and pilot test is carried out, but the requirements of industrial application cannot be met; the main problems are that the activity and stability of the catalyst can not meet the industrial requirements, and the catalytic performance of the mercuric chloride catalyst is in gap.
Disclosure of Invention
Aiming at the defects in the prior art, the invention creates a preparation method of a metal Covalent organic framework catalyst, Covalent organic framework materials (COFs) arouse extensive attention in scientific research and industry due to the potential application value of the COFs in the aspects of gas separation, catalysis, photoelectricity, energy storage and sensors, the Covalent triazine framework materials (CTFs) are Covalent organic framework materials taking triazine rings as repeating units, the triazine framework materials become hot spots of research in the field of carbon-based porous materials due to the characteristic that chemical group structures and physical structures can be flexibly adjusted, reports that the triazine framework materials are used as catalysts in heterogeneous catalytic reactions are rare, particularly, metals are in the field of single-atom catalysis, the triazine framework materials are used as carriers to prepare metal single-atom catalysts, and the invention is invented based on the non-noble metal catalysts and the research of the carbon-based catalysts by the inventor, the invention takes triazine frame material (CTF) as a carrier and takes nonmetal catalysts such as copper and tin as main active components to synthesize and prepare the copper-tin monatomic catalyst, M @ CTF for short, by a certain process. The prepared M @ CTF catalyst shows high acetylene hydrochlorination activity and stability through the evaluation of the reaction activity of the catalyst and the characterization of materials. Compared with the copper-based catalyst reported before, the catalyst provided by the invention has the advantages of high catalytic activity, lower active component consumption, good stability and low production cost, compared with a mercury catalyst, the catalyst has the advantages of wide and easily available raw materials, and the catalyst cannot obviously damage the environment in production, use and aftertreatment.
In a first aspect of the present invention, there is provided a method for preparing a metal covalent organic framework catalyst, comprising the steps of:
preparing a triazine frame material (CTF) as a carrier material;
preparing a catalyst of a main catalytic component, a cocatalyst component and a coordination compound;
and (3) soaking the carrier material of the triazine framework material (CTF) obtained in the step (1) into the catalyst obtained in the step (2), and then drying, roasting, washing and drying the carrier material to obtain the metal covalent organic framework catalyst.
In the embodiment of the invention, the carrier material of the triazine frame material (CTF) is a triazine structure monomer for short, and the triazine structure is a porous material obtained by polymerizing a triazine structure compound serving as a monomer.
Further, the triazine structural monomers include, but are not limited to, 1, 4-terephthalonitrile (CAS: 622-75-3), isophthalonitrile (CAS: 626-17-5), 1, 2-dicyanobenzene (CAS: 91-15-6), 1,3, 5-benzenetricyano (CAS: 10365-94-3), 1,2,4, 5-tetracyanobenzene (CAS:712-74-3), 2, 6-pyridinedicarbonitrile (CAS:2893-33-6), 2, 5-dicyanothiophene (CAS: 18853-40-2), 4',4 "-nitrilotribenzonitrile (CAS: 51545-36-9), 4-biphenylcarbonitrile (CAS: 1591-30-6), 2' -bipyridine-5, 5' -dicyanobenzene (CAS: 1802-29-5).
In the embodiment of the present invention, the preparation method of the triazine based framework material (CTF) includes, but is not limited to:
A. in the presence of a zinc chloride catalyst, synthesizing a triazine structural monomer at the temperature of 400-600 ℃ to obtain a triazine frame material (CTF);
B. carrying out polymerization reaction on triazine structural monomers under the catalysis of trifluoromethanesulfonic acid to obtain the triazine framework material (CTF);
C. 4,4' -bipyridine and 2, 4-dinitrobenzyl chloride are reacted to synthesize a monomer containing a dimethyl nitrile group; the monomer of the dimethyl nitrile group is synthesized by using a triazine structural monomer at the temperature of 400-600 ℃ in the presence of a zinc chloride catalyst to obtain the triazine framework material (CTF).
In an embodiment of the invention, the main catalytic component comprises: one or more of copper chloride, cuprous chloride, copper sulfate, stannous chloride, stannic sulfate and organic tin.
Further, the mass percentage of the main catalytic component in the catalyst obtained in the step (2) is 5-30%.
In embodiments of the invention, the promoting component includes, but is not limited to, one or more of LiCl, KCl, NaCl, RbCl, CsCl, BaCl 2 ,CaCl 2 ,SrCl 2 ,MgCl 2 ，LaCl 3 ,CeCl 3 ,PrCl 3 ,EuCl 3 。
Furthermore, the mass percentage of the cocatalyst component in the catalyst obtained in the step (2) is 1-10%.
In embodiments of the present invention, coordination compounds include, but are not limited to, hydrochloric acid and triethyl phosphite, butyl phosphite, triphenyl phosphine, sulfur-containing species: thiourea, methyl pyrrolidone, N, N-diethyl acetamide and hydrochloride ionic liquid formed by one or more than two compounds of 1, 10-phenanthroline.
Further, the coordination compound accounts for 1-10% of the mass of the catalyst obtained in the step (2).
In an embodiment of the present invention, the method for preparing the metal covalent organic framework catalyst in the step (3) is:
A. dipping the carrier material of the triazine frame material (CTF) into the catalyst of the catalytic active component prepared in the step (2), keeping for 0.1-10 hours, carrying out auxiliary ultrasonic dipping with the ultrasonic frequency of 20-100KHZ, and removing excessive moisture by rotary evaporation pre-drying after the ultrasonic dipping is finished;
B. drying the sample subjected to rotary evaporation at 50-150 ℃, roasting at 500-1000 ℃ for 2 hours after drying, washing for 1-10 times by deionized water after roasting, and drying in vacuum at 100-200 ℃ for 8-10 hours to obtain the copper-tin monatomic catalyst, namely the metal covalent organic framework catalyst.
A metal covalent organic framework catalyst for use in the hydrochlorination of acetylene comprising: and (3) loading the metal covalent organic framework catalyst into a reaction tube, and introducing acetylene and hydrogen chloride to perform an addition reaction to obtain vinyl chloride.
Further, the molar ratio of acetylene to hydrogen chloride feed is in the range of 1: (1-1.5), and the volume space velocity of acetylene hydrochlorination reaction is 10-150h in terms of acetylene -1 The reaction is carried out under the acetylene hydrochlorination pressure of 0-1MPa and the acetylene hydrochlorination temperature of 80-180 ℃.
The invention has the advantages that: the invention adopts triazine frame material (CTF) as a carrier to prepare the highly dispersed triazine frame catalyst, namely the copper-tin monatomic catalyst, reduces the using amount of active components, improves the number of active sites, macroscopically and obviously increases the catalytic reaction effect, and the reaction temperature is 100-12 DEG0 ℃ and the acetylene space velocity of 30-50h -1 Under normal pressure, the initial conversion per pass of acetylene can reach 95%, the selectivity of chloroethylene is more than 98%, and the catalyst is not obviously inactivated after reacting for 500 hours.
Drawings
The above described and other features of the present disclosure will be more fully described when read in conjunction with the following drawings. It is appreciated that these drawings depict only several embodiments of the disclosure and are therefore not to be considered limiting of its scope. The present disclosure will be described more clearly and in detail by using the attached drawings.
FIG. 1 is a schematic diagram of the synthesis and structure of CTF.
FIG. 2 is a schematic diagram of the synthesis and structure of CTF.
Detailed Description
The following examples are described to aid in the understanding of the present application and are not, and should not be construed to, limit the scope of the present application in any way.
The specific embodiment comprises two parts:
first part preparation of 7 groups of triazine framework catalysts:
example 1
1) Preparing a polymerization monomer raw material 1, 4-terephthalonitrile and a zinc chloride catalyst;
2) uniformly mixing 2g of monomer raw material and 4g of zinc chloride, sealing the mixture by using an ampere bottle, and carbonizing the mixture in a 400 ℃ muffle furnace for 40 hours;
3) cooling the ampoule after the reaction is finished, taking out the reactant, soaking and washing the reactant for multiple times by using a 2N hydrochloric acid solution to remove most of zinc chloride salt, then changing deionized water for multiple times to wash the reactant to be neutral, placing the obtained triazine framework material in a drying oven, and drying the triazine framework material for 5 to 6 hours at 120 ℃, wherein the obtained triazine framework material is abbreviated as CTF-1;
4) weighing copper chloride, adding water to dissolve the copper chloride, and controlling the mass ratio of the copper chloride to the carrier CTF-1 to be 1:10 to obtain solution I, ZnCl 2 Controlling the mass and the CTF-1 ratio to be 1: 8, adding water to dissolve to obtain a solution II; weighing triethyl phosphite and a proper amount of hydrochloric acid, and controlling the mass ratio of the triethyl phosphite to CTF-1 to be 1:15, dissolving in water to obtain a solutionLiquid III;
5) mixing I, II and III solution, adding CTF-1 into the mixture for impregnation, firstly carrying out vacuum impregnation for 2 hours, then carrying out 50KHZ ultrasonic-assisted impregnation for 2 hours, and then removing water by rotary evaporation to obtain a primary dried sample;
6) the preliminarily dried sample is dried at 120 ℃ for 5 hours and then placed in a 500 ℃ tube furnace seed nitrogen atmosphere to be burnt for 2 hours to obtain the copper-tin bi-component composite catalyst Cu @ CTF-1.
Example 2
1) Preparing a polymerization monomer raw material namely isophthalonitrile and a zinc chloride catalyst;
2) uniformly mixing 2g of monomer raw material with 10g of zinc chloride, sealing the mixture by using an ampere bottle, and carbonizing the mixture in a 600 ℃ muffle furnace for 60 hours;
3) cooling the ampoule after the reaction is finished, taking out the reactant, soaking and washing the reactant for multiple times by using a 2N hydrochloric acid solution to remove most of zinc chloride salt, then changing deionized water for multiple times to wash the reactant to be neutral, placing the obtained triazine framework material in a drying oven, and drying the triazine framework material for 5 to 6 hours at 120 ℃, wherein the obtained triazine framework material is abbreviated as CTF-2;
4) weighing cuprous chloride, adding water to dissolve the cuprous chloride, and controlling the mass ratio of the cuprous chloride to the carrier CTF-1 to be 1:15 to obtain solution I and CoCl 3 Controlling the mass and the CTF-2 ratio to be 1:10, adding water to dissolve to obtain a solution II; weighing triphenylphosphine and a proper amount of hydrochloric acid, and controlling the mass ratio of the triphenylphosphine to CTF-2 to be 1:10, adding water to dissolve to obtain a solution III;
5) mixing I, II and III solution, adding CTF-2 into the mixture for impregnation, vacuumizing and impregnating for 2 hours, then impregnating for 1 hour under the assistance of 80KHZ ultrasonic waves, and removing moisture by rotary evaporation to obtain a primarily dried sample;
6) the preliminarily dried sample is dried at 110 ℃ for 6 hours and then placed in a tube furnace seed nitrogen atmosphere at 600 ℃ for 4 hours to obtain the copper-tin bi-component composite catalyst Cu @ CTF-2.
Example 3
1) Preparing a polymerization monomer raw material 1, 2-dicyanobenzene and a zinc chloride catalyst;
2) uniformly mixing 2g of monomer raw material and 20g of zinc chloride, sealing the mixture by using an ampere bottle, and carbonizing the mixture in a muffle furnace at 500 ℃ for 50 hours;
3) after the reaction is finished, cooling the ampoule, taking out a reactant, soaking and washing the reactant for multiple times by using a 2N hydrochloric acid solution to remove most zinc chloride salts, then changing deionized water for multiple times to wash until the reactant is neutral, placing the obtained triazine framework material in a drying oven, and drying the triazine framework material for 5-6 hours at 120 ℃, wherein the obtained triazine framework material is abbreviated as CTF-3;
4) weighing stannous chloride, adding water to dissolve the stannous chloride, and controlling the mass ratio of the stannous chloride to the carrier CTF-3 to be 1:10 to obtain solution I and FeCl 3 Controlling the mass and the CTF-3 ratio to be 1:15, adding water to dissolve to obtain a solution II; weighing N-methylpyrrolidone and a proper amount of hydrochloric acid, and controlling the mass ratio of N-methylpyrrolidone to CTF-3 to be 1: 12, adding water to dissolve to obtain a solution III;
5) mixing I, II and III solution, adding CTF-3 into the mixture for dipping, firstly carrying out vacuum dipping for 2 hours, then carrying out dipping for 2 hours under the assistance of 100KHZ ultrasonic waves, and then removing moisture by rotary evaporation to obtain a primarily dried sample;
6) and drying the preliminarily dried sample at 120 ℃ for 6 hours, and then placing the sample in a 800 ℃ tubular furnace under nitrogen atmosphere for burning for 4 hours to obtain the copper-tin bi-component composite catalyst Sn @ CTF-3.
Example 4
1) Preparing a polymerization monomer raw material 1,3, 5-benzene tricyano and trifluoromethanesulfonic acid as a catalyst;
2) placing 2g of monomer raw material in a hydrothermal reaction kettle, dropwise adding 20mL of trifluoromethanesulfonic acid into the monomer at low temperature, stirring until the trifluoromethanesulfonic acid is completely dissolved, purging with nitrogen, sealing, screwing, and placing in a drying oven at 100 ℃ for standing reaction for 24 hours;
3) and (3) after the reaction is finished and cooled, neutralizing trifluoromethanesulfonic acid in the reactant with dilute ammonia water, washing the reactant with deionized water for multiple times to remove residual salt, placing the obtained triazine framework material in an oven, and drying at 120 ℃ for 5-6 hours to obtain the triazine framework material which is abbreviated as CTF-4.
4) Weighing stannic chloride, adding water to dissolve the stannic chloride, and controlling the mass ratio of the stannic chloride to the carrier CTF-4 to be 1:10 to obtain solution I and LaCl 3 Controlling the ratio of quality to CTF-4 to be 1:15, adding water to dissolve to obtain a solution II; weighing pyrroleAnd (3) keton and a proper amount of hydrochloric acid, wherein the mass ratio of the keton to the CTF-4 is controlled to be 1: 12, adding water to dissolve to obtain a solution III;
5) mixing I, II and III solution, adding CTF-4 into the mixture for dipping, firstly carrying out vacuum dipping for 2 hours, then carrying out dipping for 2 hours under the assistance of 60KHZ ultrasonic waves, and then removing moisture by rotary evaporation to obtain a primarily dried sample;
6) and drying the preliminarily dried sample at 110 ℃ for 6 hours, and then placing the dried sample in a nitrogen atmosphere of a 500 ℃ tube furnace seed for burning for 2 hours to obtain the copper-tin bi-component composite catalyst Sn @ CTF-4.
Example 5
1) Preparing a polymerization monomer raw material 1,2,4, 5-tetracyanobenzene and trifluoromethanesulfonic acid as a catalyst;
2) placing 2g of monomer raw material into a glass bottle, placing a glass sheet into a hydrothermal reaction kettle, adding 4mL of trifluoromethanesulfonic acid into the other glass bottle, placing the bottle into the reaction kettle, after purging with nitrogen, screwing down the cover of the reaction kettle, placing the bottle into a drying oven at 100 ℃ and standing for reaction for 24 hours, wherein the solid-phase synthesis method is adopted;
3) and after the reaction is finished and cooled, neutralizing trifluoromethanesulfonic acid in the reactant by using dilute ammonia water, washing the reactant by using deionized water, removing residual salt by washing for multiple times, placing the obtained triazine framework material in an oven, and drying at 120 ℃ for 5-6 hours to obtain the triazine framework material which is abbreviated as CTF-5.
4) Weighing copper chloride and tin chloride, adding water to dissolve the copper chloride and the tin chloride, and controlling the mass ratio of the copper chloride and the tin chloride to the carrier CTF-5 to be 1:10 to obtain a solution I, SrCl 2 Controlling the ratio of quality to CTF-5 to be 1:10, adding water to dissolve to obtain a solution II; weighing caprolactam and a proper amount of hydrochloric acid, and controlling the mass ratio of caprolactam to CTF-5 to be 1: 12, adding water to dissolve to obtain a solution III;
5) mixing I, II and III solution, adding CTF-5 into the mixture for dipping, firstly carrying out vacuum dipping for 2 hours, then carrying out dipping for 2 hours under the assistance of 60KHZ ultrasonic waves, and then removing moisture by rotary evaporation to obtain a primarily dried sample;
6) and drying the preliminarily dried sample at 110 ℃ for 6 hours, and then placing the sample in a 500 ℃ tubular furnace under nitrogen atmosphere to be burnt for 2 hours to obtain the copper-tin bi-component composite catalyst CuSn @ CTF-5.
Comparative example 1
(1) Weighing 10g of 40-mesh active carbon, pretreating with a 2N hydrochloric acid solution at 60 ℃ for 6 hours, then washing with deionized water until the pH is neutral, and then drying at 120 ℃ for 5 hours for later use;
(2) mixing the pretreated activated carbon with pyridine and borax solution, and controlling the mass ratio of nitrogen and boron atoms to the activated carbon to be 1:15, ultrasonically dipping for 8 hours at 60KHZ, drying for 16 hours at 60 ℃ after ultrasonic dipping, placing in a tube furnace, and roasting for 2 hours under nitrogen atmosphere to obtain modified activated carbon;
(3) weighing CuCl 2 Controlling the ratio of the quality to the active carbon to be 1:10, adding water to dissolve to obtain a solution I;
(4) adding modified activated carbon into the impregnation solution I, firstly vacuumizing and impregnating for 5 hours, then impregnating for 4 hours under the assistance of 70KHZ ultrasonic waves, and then removing moisture by rotary evaporation to obtain a primary dried sample;
(5) drying the preliminarily dried sample at 120 ℃ for 6 hours, and then placing the dried sample in a nitrogen atmosphere of a 500 ℃ tube furnace seed for 2 hours to obtain a non-mercury catalyst C1;
comparative example 2
(1) Weighing 10g of 40-mesh active carbon, pretreating with a 2N hydrochloric acid solution at 60 ℃ for 6 hours, then washing with deionized water until the pH is neutral, and then drying at 120 ℃ for 5 hours for later use;
(2) mixing the pretreated activated carbon with pyridine and borax solution, and controlling the mass ratio of nitrogen and boron atoms to the activated carbon to be 1:10, ultrasonically dipping for 6 hours at 60KHZ, drying for 12 hours at 60 ℃ after ultrasonic dipping, placing in a tube furnace, and roasting for 2 hours under nitrogen atmosphere to obtain modified activated carbon;
(3) weighing SnCl 2 Controlling the ratio of the quality to the active carbon to be 1:10, adding water to dissolve to obtain a solution I;
(4) adding modified activated carbon into the solution I for impregnation, firstly vacuumizing for impregnation for 4 hours, then impregnating for 5 hours under the assistance of 60KHZ ultrasonic waves, and then removing moisture by rotary evaporation to obtain a primary dried sample;
(5) drying the preliminarily dried sample at 130 ℃ for 8 hours, and then placing the dried sample in a nitrogen atmosphere of a 500 ℃ tube furnace seed for burning for 2 hours to obtain a non-mercury catalyst C2;
second part the 7 groups of catalysts prepared in the first part were used for acetylene hydrochlorination evaluations.
1. Catalyzing acetylene hydrochlorination:
taking 1g of a C1-C7 catalyst sample, loading the sample into a reaction tube with the diameter of 10mm, introducing acetylene and hydrogen chloride to carry out addition reaction to obtain vinyl chloride, evaluating the activity and stability of the catalyst by using a fixed bed reactor, wherein the molar ratio of the acetylene to the hydrogen chloride is 1: (1-1.5) and the acetylene space velocity is 10-150h -1 The reaction temperature is 80-180 ℃, the reaction pressure is 0-1MPa, and the gas phase product is analyzed by gas chromatography. The catalyst evaluation results are shown in table 1 (acetylene conversion is the initial highest conversion in the table).
TABLE 1 evaluation results of catalysts
While various aspects and embodiments have been disclosed herein, it will be apparent to those skilled in the art that other aspects and embodiments can be made without departing from the spirit of the disclosure, and that several modifications and improvements can be made without departing from the spirit of the disclosure. The various aspects and embodiments disclosed herein are presented by way of example only and are not intended to limit the present disclosure, which is to be controlled in the spirit and scope of the appended claims.
Claims (10)
1. A preparation method of a metal covalent organic framework catalyst is characterized by comprising the following steps:
preparing a triazine frame material (CTF) as a carrier material;
preparing a catalyst of a main catalytic component, a cocatalyst component and a coordination compound;
and (3) soaking the carrier material of the triazine framework material (CTF) obtained in the step (1) into the catalyst obtained in the step (2), and then drying, roasting, washing and drying the carrier material to obtain the metal covalent organic framework catalyst.
2. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the carrier material of the triazine frame material (CTF) is referred to as triazine structure monomer for short, and the triazine structure is a porous material obtained by polymerizing triazine structure compounds serving as monomers.
3. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the triazine structural monomer includes, but is not limited to, 1, 4-terephthalonitrile (CAS: 622-75-3), isophthalonitrile (CAS: 626-17-5), 1, 2-dicyanobenzene (CAS: 91-15-6), 1,3, 5-benzenetricyano group (CAS: 10365-94-3), 1,2,4, 5-tetracyanobenzene (CAS:712-74-3), 2, 6-pyridinedicarbonitrile (CAS:2893-33-6), 2, 5-dicyanothiophene (CAS: 18853-40-2), 4 '-nitrilotribenzonitrile (CAS: 51545-36-9), 4-biphenylcarbonitrile (CAS: 1591-30-6), 2' -bipyridine-5, 5' -dicyanobenzene (CAS: 1802-29-5).
4. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the preparation method of the triazine frame material (CTF) comprises but is not limited to the following steps:
A. in the presence of a zinc chloride catalyst, synthesizing a triazine structural monomer at the temperature of 400-600 ℃ to obtain a triazine frame material (CTF);
B. carrying out polymerization reaction on triazine structural monomers under the catalysis of trifluoromethanesulfonic acid to obtain the triazine framework material (CTF);
C. 4,4' -bipyridine and 2, 4-dinitrobenzyl chloride are reacted to synthesize a monomer containing a dimethyl nitrile group; the monomer of the dinitrile group is synthesized by triazine structural monomer at 400-600 ℃ in the presence of zinc chloride catalyst to obtain the triazine framework material (CTF).
5. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the main catalytic component comprises: one or more of copper chloride, cuprous chloride, copper sulfate, stannous chloride, stannic sulfate and organic tin.
6. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the promoter component includes but is not limited to one or more of the following compounds, LiCl, KCl, NaCl, RbCl, CsCl, BaCl 2 ,CaCl 2 ,SrCl 2 ,MgCl 2 ，LaCl 3 ,CeCl 3 ,PrCl 3 ,EuCl 3 。
7. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: coordination compounds include, but are not limited to, hydrochloric acid and triethyl phosphite, butyl phosphite, triphenyl phosphine, sulfur-containing species: thiourea, methyl pyrrolidone, N, N-diethyl acetamide and hydrochloride ionic liquid formed by one or more than two compounds of 1, 10-phenanthroline.
8. The method of claim 1, wherein the metal covalent organic framework catalyst is prepared by: the method for preparing the metal covalent organic framework catalyst in the step (3) comprises the following steps:
A. dipping the carrier material of the triazine frame material (CTF) into the catalyst of the catalytic active component prepared in the step (2), keeping for 0.1-10 hours, carrying out auxiliary ultrasonic dipping with the ultrasonic frequency of 20-100KHZ, and removing excessive moisture by rotary evaporation pre-drying after the ultrasonic dipping is finished;
B. drying the sample subjected to rotary evaporation at 50-150 ℃, roasting at 500-1000 ℃ for 2 hours after drying, washing for 1-10 times by deionized water after roasting, and drying in vacuum at 100-200 ℃ for 8-10 hours to obtain the copper-tin monatomic catalyst, namely the metal covalent organic framework catalyst.
9. The metal covalent organic framework catalyst of claim 1 for use in acetylene hydrochlorination comprising: and (3) loading the metal covalent organic framework catalyst into a reaction tube, and introducing acetylene and hydrogen chloride to perform an addition reaction to obtain vinyl chloride.
10. The use of a metal covalent organic framework catalyst according to claim 9 for the hydrochlorination of acetylene, characterized in that: the molar ratio of acetylene to hydrogen chloride feed is in the range of 1: (1-1.5), and the volume space velocity of acetylene hydrochlorination reaction is 10-150h in terms of acetylene -1 The reaction is carried out under the acetylene hydrochlorination pressure of 0-1MPa and the acetylene hydrochlorination temperature of 80-180 ℃.
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