CN115106093B - Preparation method and application of metal covalent organic framework catalyst - Google Patents
Preparation method and application of metal covalent organic framework catalyst Download PDFInfo
- Publication number
- CN115106093B CN115106093B CN202210793686.9A CN202210793686A CN115106093B CN 115106093 B CN115106093 B CN 115106093B CN 202210793686 A CN202210793686 A CN 202210793686A CN 115106093 B CN115106093 B CN 115106093B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- triazine
- acetylene
- cas
- covalent organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 43
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 31
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 21
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002390 rotary evaporation Methods 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
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 239000012876 carrier material Substances 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 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
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- -1 butyl phosphite Chemical compound 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 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
- 239000011148 porous material Substances 0.000 claims description 2
- XNPMXMIWHVZGMJ-UHFFFAOYSA-N pyridine-2,6-dicarbonitrile Chemical compound N#CC1=CC=CC(C#N)=N1 XNPMXMIWHVZGMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009849 deactivation Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000004090 dissolution Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 108010018842 CTF-1 transcription factor Proteins 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 238000005470 impregnation Methods 0.000 description 4
- 238000004519 manufacturing process 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013311 covalent triazine framework Substances 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 229910052718 tin Inorganic materials 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 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
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-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
- 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 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 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
- 101710205482 Nuclear factor 1 A-type Proteins 0.000 description 1
- 101710170464 Nuclear factor 1 B-type Proteins 0.000 description 1
- 102100022162 Nuclear factor 1 C-type Human genes 0.000 description 1
- 101710113455 Nuclear factor 1 C-type Proteins 0.000 description 1
- 101710140810 Nuclear factor 1 X-type Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000011161 development Methods 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
- 238000007210 heterogeneous catalysis Methods 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
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- 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 monoatomic catalyst, reduces the consumption of active components, improves the number of active sites, macroscopically and obviously increases the catalytic reaction effect, and the acetylene airspeed is 30-50h at the reaction temperature of 100-120 DEG C ‑1 Under normal pressure, the initial conversion per pass of acetylene can reach 95%, the selectivity of vinyl chloride is more than 98%, and no obvious deactivation is seen in the reaction of the catalyst for 500 hours.
Description
Technical Field
The invention belongs to the field of organic synthesis catalysts, and particularly relates to a preparation method of a triazine framework catalyst and application of the triazine framework catalyst in hydrochlorination of acetylene.
Background
The production of polyvinyl chloride (PVC) in China is 2500 ten thousand tons/year in 2020, wherein 70-80% of the vinyl chloride as monomer is produced by acetylene hydrochlorination process, and mercuric chloride catalyst is needed for reaction. Mercury chloride is easy to sublimate and lose in the reaction process, serious environmental pollution is caused, the national environmental agency of the United nations in 2013 passes the "water protocol" which prescribes that mercury is thoroughly prohibited from being used for PVC production until 2030. In recent years, the scholars at home and abroad have made great efforts for developing mercury-free catalysts, and the research on the catalysts basically forms three directions: (1) a Jin Jigui metal catalyst; (2) a base metal catalyst; (3) a carbon-based nonmetallic catalyst.
In the earliest stage, precious metal chlorides such as gold tetrachloride, platinum chloride and the like have very strong catalytic activity on acetylene hydrochlorination, but precious metal catalysts are expensive and have not been reported for industrial application so far. In recent years, a lot of carbon-based nonmetallic catalysts have been developed and used for hydrochlorination of acetylene, such as the university of Chinese academy of sciences, shanghai higher institute of China, university of stone, tianjin university, zhejiang university and the like, and the main problem of the current application of the carbon-based nonmetallic catalysts is that the catalyst activity is low compared with that of the metallic catalysts. Compared with the defects of noble metal catalysts and non-metal catalysts, the non-noble metal (base metal) catalysts have more application prospects. Many researches and reports are made on the development of base metal mercury-free catalysts at home and abroad, but no real commercialization is made yet.
The Chinese patent reports that a lot of researches on base metal catalysts, such as copper, bismuth, tin and the like, improve the activity and stability of the catalysts to a certain extent, and perform pilot test, but cannot meet the requirements of industrial application; the main problem is that the activity and stability of the catalyst can not meet the industrial requirements, and the catalytic performance of the mercury chloride catalyst has a gap.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention creates a preparation method of a metal covalent organic framework catalyst, the covalent organic framework material (Covalent organic frameworks, COFs) brings wide attention to scientific research and industry due to potential application values of the covalent organic framework material (Covalent organic frameworks, COFs) in the aspects of gas separation, catalysis, photoelectricity, energy storage and sensors, the covalent triazine framework material (Covalent triazine frameworks, CTFs) is a covalent organic framework material taking triazine rings as repeated units, the triazine framework material becomes a hot spot for research in the field of carbon-based porous new materials due to the flexible adjustment of chemical group structures and physical structures, the triazine framework material is used as a catalyst in heterogeneous catalysis, particularly, metal is used as a carrier for preparing a metal single-atom catalyst in the field of single-atom catalysis, the invention is based on the basis of the research of a non-noble metal catalyst and a carbon-based catalyst by the inventor, the invention takes the triazine framework material (CTF) as a carrier, and the copper and tin non-metal catalyst as main active components, and the CTF is prepared by a certain single-atom synthesis process of copper@tin. The prepared M@CTF catalyst shows high acetylene hydrochlorination activity and stability through the evaluation of the reactivity of the catalyst and the material characterization. Compared with the copper-based catalyst reported before, the catalyst provided by the invention has the advantages of high catalytic activity, lower consumption of active components, good stability and low production cost, and compared with mercury catalyst, the catalyst has the advantages of wide and easily obtained raw materials, and no obvious damage to the environment during production, use and post-treatment of the catalyst.
The first part of the invention provides a preparation method of a metal covalent organic framework catalyst, which is characterized by comprising the following steps of:
preparing triazine frame materials (CTF) serving as carrier materials;
step (2), preparing a catalyst of a main catalytic component, a co-catalytic component and a coordination compound;
and (3) immersing the carrier material of the triazine frame material (CTF) obtained in the step (1) into the catalyst obtained in the step (2), and then drying, roasting, washing and drying to obtain the metal covalent organic frame catalyst.
In the embodiment of the invention, the carrier material of the triazine frame material (CTF) is referred to as a triazine structure monomer, and the triazine structure is a porous material obtained by polymerizing a triazine structure compound serving as a monomer.
Further, the triazine-based 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-benzene tricyano (CAS: 10365-94-3), 1,2,4, 5-tetracyanobenzene (CAS: 712-74-3), 2, 6-pyridine-dicyano (CAS: 2893-33-6), 2, 5-dicyanothiophene (CAS: 18853-40-2), 4',4 "-nitrilotriazonitrile (CAS: 51545-36-9), 4-biphenylcarbonitrile (CAS: 1591-30-6), 2' -bipyridine-5, 5' -dimethylnitrile (CAS: 1802-29-5).
In an embodiment of the present invention, the preparation method of the triazine frame material (CTF) includes, but is not limited to:
A. synthesizing a triazine structural monomer at 400-600 ℃ in the presence of a zinc chloride catalyst to obtain a triazine framework material (CTF);
B. polymerizing a triazine structural monomer under the catalysis of trifluoromethanesulfonic acid to obtain a triazine frame material (CTF);
C. 4,4' -bipyridine and 2, 4-dinitrobenzyl chloride react first to synthesize a monomer containing a dicyano group; and synthesizing a monomer of a dicyano group in the presence of a zinc chloride catalyst by using a triazine structural monomer at 400-600 ℃ to obtain the triazine frame material (CTF).
In an embodiment of the invention, the main catalyst component comprises: one or more of copper chloride, cuprous chloride, cupric sulfate, stannous chloride, stannic sulfate and organotin.
Further, the mass ratio of the main catalyst component in the catalyst obtained in the step (2) is 5-30%.
In embodiments of the present invention, the co-catalytic 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 。
Further, the mass ratio of the auxiliary catalytic component in the catalyst obtained in the step (2) is 1-10%.
In embodiments of the present invention, the complexing compound includes, but is not limited to, hydrochloric acid with triethyl phosphite, butyl phosphite, triphenylphosphine, sulfur-containing species: thiourea, methyl pyrrolidone, N, N-diethyl acetamide, and 1, 10-phenanthrene green, and the hydrochloride ionic liquid formed by one or more than two compounds.
Further, the mass ratio of the coordination compound in the catalyst obtained in the step (2) is 1-10%.
In an embodiment of the present invention, the method for preparing the metal-covalent organic framework catalyst in step (3) is:
A. soaking 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, assisting ultrasonic soaking, wherein the ultrasonic frequency is 20-100KHZ, and removing redundant water by rotary evaporation pre-drying after ultrasonic soaking is finished;
B. the spin-evaporated sample is dried at 50-150 ℃, baked for 2 hours at 500-1000 ℃, washed by deionized water for 1-10 times after baking, and dried in vacuum at 100-200 ℃ for 8-10 hours to obtain the copper-tin monoatomic catalyst, namely the metal covalent organic framework catalyst.
A metal-covalent organic framework catalyst for 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 raw material is 1: (1-1.5), the volume space velocity of the hydrochlorination reaction of acetylene is 10-150h calculated by acetylene -1 The acetylene hydrochlorination reaction pressure is 0-1MPa, and the acetylene hydrochlorination reaction temperature is 80-180 ℃.
The invention has the advantages that: the invention adopts triazine frame material (CTF) as a carrier, and prepares the highly dispersed triazine frame catalyst, namely the copper-tin monoatomic catalyst, reduces the consumption of active components, improves the number of active sites, macroscopically and obviously increases the catalytic reaction effect, and the acetylene airspeed is 30-50h at the reaction temperature of 100-120 DEG C -1 Under normal pressure, the initial conversion per pass of acetylene can reach 95%, the selectivity of vinyl chloride is more than 98%, and no obvious deactivation is seen in the reaction of the catalyst for 500 hours.
Drawings
The foregoing and other features of the present application 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 present application and are therefore not to be considered limiting of its scope. The present application will be described more specifically and in detail by using the accompanying drawings.
FIG. 1 is a schematic diagram of CTF synthesis and structure.
FIG. 2 is a schematic diagram of CTF synthesis and structure.
Detailed Description
The following examples are described to aid in the understanding of the present application and are not, nor should they be construed in any way to limit the scope of the present application.
The specific embodiment comprises two parts:
the first part prepares 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 materials with 4g of zinc chloride, sealing by using an ampere bottle, and carbonizing in a muffle furnace at 400 ℃ for 40 hours;
3) Cooling an ampere bottle after the reaction is finished, taking out reactants, soaking and washing the reactants with 2N hydrochloric acid solution for a plurality of times, removing most of zinc chloride salt, then changing deionized water for a plurality of times to wash the materials to be neutral, putting the obtained triazine frame materials into a baking oven, and drying the materials at 120 ℃ for 5-6 hours, wherein the obtained triazine frame materials are abbreviated as CTF-1;
4) Weighing copper chloride, adding water for dissolution, and controlling the mass ratio of the copper chloride to the carrier CTF-1 to be 1:10 to obtain a solution I, znCl 2 The ratio of control quality to CTF-1 is 1:8, adding water for dissolution 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, adding water for dissolution to obtain a solution III;
5) Mixing I, II with III solution, adding CTF-1 into the mixture, dipping for 2 hours under vacuum, dipping for 2 hours under the assistance of 50KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
6) And drying the primarily dried sample at 120 ℃ for 5 hours, and then placing the sample in a 500 ℃ tubular furnace for 2 hours under nitrogen atmosphere to obtain the copper-tin bi-component composite catalyst Cu@CTF-1.
Example 2
1) Preparing a polymerization monomer raw material isophthalonitrile and a zinc chloride catalyst;
2) Uniformly mixing 2g of monomer raw materials and 10g of zinc chloride, sealing by using an ampere bottle, and carbonizing in a muffle furnace at 600 ℃ for 60 hours;
3) Cooling an ampere bottle after the reaction is finished, taking out reactants, soaking and washing the reactants with 2N hydrochloric acid solution for a plurality of times, removing most of zinc chloride salt, then changing deionized water for a plurality of times to wash the materials to be neutral, putting the obtained triazine frame materials into a baking oven, and drying the materials at 120 ℃ for 5-6 hours, wherein the obtained triazine frame materials are abbreviated as CTF-2;
4) Weighing cuprous chloride, adding water for dissolution, and controlling the mass ratio of the cuprous chloride to the carrier CTF-1 to be 1:15 to obtain a solution I, coCl 3 The ratio of control quality to CTF-2 is 1:10, adding water for dissolution 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 for dissolution to obtain a solution III;
5) Mixing I, II with III solution, adding CTF-2 into the mixture, dipping for 2 hours under vacuum, dipping for 1 hour under the assistance of 80KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
6) And drying the primarily dried sample at 110 ℃ for 6 hours, and then placing the sample in a 600 ℃ tubular furnace for nitrogen atmosphere to burn 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 materials with 20g of zinc chloride, sealing by using an ampere bottle, and carbonizing in a muffle furnace at 500 ℃ for 50 hours;
3) Cooling an ampere bottle after the reaction is finished, taking out reactants, soaking and washing the reactants with 2N hydrochloric acid solution for a plurality of times, removing most of zinc chloride salt, then changing deionized water for a plurality of times to wash the materials to be neutral, putting the obtained triazine frame materials into a baking oven, and drying the materials at 120 ℃ for 5-6 hours, wherein the obtained triazine frame materials are abbreviated as CTF-3;
4) Weighing stannous chloride, adding water for dissolution, and controlling the mass ratio of the stannous chloride to the carrier CTF-3 to be 1:10 to obtain a solution I, feCl 3 The ratio of control quality to CTF-3 is 1:15, adding water for dissolution to obtain a solution II; weighing N-methyl pyrrolidone and a proper amount of hydrochloric acid, and controlling the mass ratio of the N-methyl pyrrolidone to CTF-3 to be 1:12, adding water for dissolution to obtain a solution III;
5) Mixing I, II with III solution, adding CTF-3 into the mixture, dipping for 2 hours under vacuum, dipping for 2 hours under the assistance of 100KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
6) And drying the primarily dried sample at 120 ℃ for 6 hours, and then placing the sample in a 800 ℃ tubular furnace for sintering under nitrogen atmosphere 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 taking trifluoromethanesulfonic acid as a catalyst;
2) 2g of monomer raw materials are placed in a hydrothermal reaction kettle, 20mL of trifluoromethanesulfonic acid is dripped into the monomer at low temperature, the mixture is stirred until the trifluoromethanesulfonic acid is completely dissolved, the mixture is sealed and screwed after nitrogen purging, and the mixture is placed in a drying oven at 100 ℃ for static reaction for 24 hours;
3) After the reaction is finished and cooled, the trifluoro methane sulfonic acid in the reactant is neutralized by dilute ammonia water, the reactant is washed by deionized water for a plurality of times to remove residual salt, and the obtained triazine frame material is placed in an oven and dried for 5-6 hours at 120 ℃, and is abbreviated as CTF-4.
4) Weighing tin chloride, adding water for dissolution, and controlling the mass ratio of the tin chloride to the carrier CTF-4 to be 1:10 to obtain a solution I, laCl 3 The ratio of control quality to CTF-4 is 1:15, adding water for dissolution to obtain a solution II; weighing pyrrolidone and a proper amount of hydrochloric acid, and controlling the mass ratio of the pyrrolidone to CTF-4 to be 1:12, adding water for dissolution to obtain a solution III;
5) Mixing I, II with III solution, adding CTF-4 into the mixture, dipping for 2 hours under vacuum, dipping for 2 hours under the assistance of 60KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
6) And drying the primarily dried sample at 110 ℃ for 6 hours, and then placing the sample in a 500 ℃ tubular furnace for 2 hours under nitrogen atmosphere 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, wherein trifluoromethanesulfonic acid is used as a catalyst;
2) Placing 2g of monomer raw materials into a glass bottle, placing glass sheets into a hydrothermal reaction kettle, adding 4mL of trifluoromethanesulfonic acid into the other glass bottle, placing the bottle into the reaction kettle, screwing a reaction kettle cover after nitrogen purging, and placing the reaction kettle cover into a drying box at 100 ℃ for standing reaction for 24 hours, thus obtaining a solid phase synthesis method;
3) After the reaction is finished and cooled, the trifluoro methane sulfonic acid in the reactant is neutralized by dilute ammonia water, the reactant is washed by deionized water for a plurality of times to remove residual salt, the obtained triazine frame material is placed in an oven and dried for 5 to 6 hours at 120 ℃, and the obtained triazine frame material is abbreviated as CTF-5.
4) Weighing copper chloride and tin chloride, adding water for dissolution, and controlling the mass ratio of the copper chloride to the tin chloride to the carrier CTF-5 to be 1:10 to obtain a solution I, srCl 2 The ratio of control quality to CTF-5 is 1:10, adding water for dissolution to obtain a solution II; weighing caprolactam and a proper amount of hydrochloric acid, and controlling the mass ratio of the caprolactam to CTF-5 to be 1:12, adding water for dissolution to obtain a solution III;
5) Mixing I, II with III solution, adding CTF-5 into the mixture, dipping for 2 hours under vacuum, dipping for 2 hours under the assistance of 60KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
6) And drying the primarily dried sample at 110 ℃ for 6 hours, and then placing the sample in a 500 ℃ tubular furnace for 2 hours under nitrogen atmosphere to obtain the copper-tin bi-component composite catalyst CuSn@CTF-5.
Comparative example 1
(1) Weighing 10g of 40-mesh active carbon, pretreating for 6 hours at 60 ℃ with 2N hydrochloric acid solution, washing with deionized water until the pH is neutral, and drying for 5 hours at 120 ℃ 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, carrying out ultrasonic impregnation for 8 hours at 60KHZ, drying at 60 ℃ for 16 hours after the ultrasonic impregnation is finished, and then placing the dried product in a tube furnace, and roasting for 2 hours in nitrogen atmosphere to obtain modified activated carbon;
(3) Weighing CuCl 2 The control quality and the ratio of the activated carbon are 1:10, adding water for dissolution to obtain a solution I;
(4) Adding modified activated carbon into the impregnating solution I, vacuumizing and impregnating for 5 hours, then impregnating for 4 hours under the assistance of 70KHZ ultrasonic waves, and removing water by rotary evaporation to obtain a primary dried sample;
(5) Drying the primarily dried sample at 120 ℃ for 6 hours, and then placing the sample in a 500 ℃ tubular furnace for 2 hours under nitrogen atmosphere to obtain a non-mercury catalyst C1;
comparative example 2
(1) Weighing 10g of 40-mesh active carbon, pretreating for 6 hours at 60 ℃ with 2N hydrochloric acid solution, washing with deionized water until the pH is neutral, and drying for 5 hours at 120 ℃ 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, carrying out ultrasonic impregnation for 6 hours at 60KHZ, drying at 60 ℃ for 12 hours after ultrasonic impregnation is finished, and then placing the dried product in a tube furnace, and roasting for 2 hours in nitrogen atmosphere to obtain modified activated carbon;
(3) Weighing SnCl 2 The control quality and the ratio of the active carbon are 1:10, adding water for dissolution to obtain a solution I;
(4) Adding modified activated carbon into the solution I for soaking, vacuumizing for soaking for 4 hours, then soaking for 5 hours under the assistance of 60KHZ ultrasonic waves, and then removing water by rotary evaporation to obtain a primary dried sample;
(5) Drying the primarily dried sample at 130 ℃ for 8 hours, and then placing the sample in a 500 ℃ tubular furnace for 2 hours under nitrogen atmosphere to obtain a non-mercury catalyst C2;
the second part 7 sets of catalysts prepared in the first part were used to conduct acetylene hydrochlorination evaluation.
1. Catalytic hydrochlorination of acetylene:
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 for addition reaction to obtain vinyl chloride, and evaluating the activity and stability of the catalyst by a fixed bed reactor, wherein the molar ratio of the acetylene to the hydrogen chloride is 1: (1-1.5), the space velocity of acetylene 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 results of catalyst evaluation
While various aspects and embodiments have been disclosed, other aspects and embodiments will be apparent to those skilled in the art, and many changes and modifications can be made without departing from the spirit of the application, which is intended to be within the scope of the invention. The various aspects and embodiments disclosed herein are for illustration only and are not intended to limit the application, the actual scope of which is subject to the claims.
Claims (5)
1. The preparation method of the metal covalent organic framework catalyst is characterized by comprising the following steps of:
preparing triazine frame materials as carrier materials;
step (2) preparing a mixture of a main catalytic component, a co-catalytic component and a coordination compound, wherein the main catalytic component is a mixture of copper chloride and tin chloride, the mass ratio of the copper chloride to the tin chloride to the carrier is controlled to be 1:10, and the co-catalytic component is one or more than two 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 The coordination compound is as follows: hydrochloric acid and triethyl phosphite, butyl phosphite,triphenylphosphine, sulfur-containing species: hydrochloride ionic liquid formed by one or more than two compounds of thiourea, methyl pyrrolidone, N, N-diethyl acetamide and 1, 10-phenanthrene green;
the preparation method of the triazine frame material comprises the steps of (3) dipping a carrier material of the triazine frame material obtained in the step (1) into a mixture obtained in the step (2), and then drying, roasting, washing and drying to obtain a metal covalent organic frame catalyst, wherein the metal covalent organic frame catalyst is a copper-tin bi-component composite catalyst, and the carrier material of the triazine frame material is a porous material obtained by polymerizing a triazine structure compound serving as a monomer, and the preparation method of the triazine frame material specifically comprises the following steps:
A. soaking the carrier material of the triazine frame material into the mixture of the catalytic active components prepared in the step (2), maintaining for 0.1-10 hours, assisting ultrasonic soaking, wherein the ultrasonic frequency is 20-100KHZ, and removing excessive water by rotary evaporation pre-drying after ultrasonic soaking is finished;
B. the spin-evaporated sample is dried at 50-150 ℃, baked for 2 hours at 500-1000 ℃, washed by deionized water for 1-10 times after baking, and dried in vacuum at 100-200 ℃ for 8-10 hours to obtain the copper-tin monoatomic catalyst, namely the metal covalent organic framework catalyst.
2. The method for preparing a metal-covalent organic framework catalyst according to claim 1, wherein: the triazine structural compound is as follows: 1, 4-terephthalonitrile (CAS: 622-75-3), isophthalonitrile (CAS: 626-17-5), 1, 2-dicyanobenzene (CAS: 91-15-6), 1,3, 5-benzene tricyano (CAS: 10365-94-3), 1,2,4, 5-tetracyanobenzene (CAS: 712-74-3), 2, 6-pyridine-dinitrile (CAS: 2893-6), 2, 5-dicyanothiophene (CAS: 18853-40-2), 4' -nitrilotriaconitrile (CAS: 51545-36-9), 4-biphenylcarbonitrile (CAS: 1591-30-6), 2' -bipyridine-5, 5' -dicyanonitrile (CAS: 1802-29-5).
3. The method for preparing a metal-covalent organic framework catalyst according to claim 1, wherein: the preparation method of the triazine frame material comprises one of the following steps:
A. synthesizing a triazine structural monomer at 400-600 ℃ in the presence of a zinc chloride catalyst to obtain a triazine frame material;
B. and (3) carrying out polymerization reaction on the triazine structural monomer under the catalysis of trifluoromethanesulfonic acid to obtain the triazine frame material.
4. The metal-covalent organic framework catalyst of claim 1 for 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.
5. The metal-covalent organic framework catalyst of claim 4 for hydrochlorination of acetylene, wherein: the reaction conditions of acetylene and hydrogen chloride are as follows: the mole ratio of acetylene to hydrogen chloride raw material is 1: (1-1.5), the volume space velocity of the hydrochlorination reaction of acetylene is 10-150h calculated as acetylene -1 The pressure of the hydrochlorination reaction of acetylene is 0-1MPa, and the temperature of the hydrochlorination reaction of acetylene is 80-180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210793686.9A CN115106093B (en) | 2022-07-05 | 2022-07-05 | Preparation method and application of metal covalent organic framework catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210793686.9A CN115106093B (en) | 2022-07-05 | 2022-07-05 | Preparation method and application of metal covalent organic framework catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115106093A CN115106093A (en) | 2022-09-27 |
| CN115106093B true CN115106093B (en) | 2023-12-22 |
Family
ID=83331470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210793686.9A Active CN115106093B (en) | 2022-07-05 | 2022-07-05 | Preparation method and application of metal covalent organic framework catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115106093B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116493046A (en) * | 2023-04-14 | 2023-07-28 | 东莞理工学院 | Halloysite compound supported SnO 2 -Au core-shell catalyst, preparation method and application |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB156117A (en) * | 1921-01-13 | 1922-03-30 | Otto Traun S Forschungslaborat | Manufacture of vinyl compounds and polymerisation products thereof |
| US2401850A (en) * | 1944-11-01 | 1946-06-11 | Du Pont | Preparation of fluorohydrocarbons |
| GB1416181A (en) * | 1972-01-17 | 1975-12-03 | Secr Defence | Processes for the manufacture of fluoroalkylaromatic compounds |
| CN110721743A (en) * | 2019-10-29 | 2020-01-24 | 福州大学 | Methane-producing atomic-level dispersed copper @ covalent triazine organic polymer composite photocatalyst and preparation and application thereof |
| CN111253214A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol by hydrogenating methyl glycolate |
| CN112619710A (en) * | 2019-09-24 | 2021-04-09 | 国家纳米科学中心 | Triazine-based covalent network loaded metal monoatomic composite material and preparation method and application thereof |
| CN113058644A (en) * | 2021-03-19 | 2021-07-02 | 山东大学 | Catalyst for catalyzing oxidative dehydrogenation and hydrogenation of organic compounds and application thereof |
| CN113634273A (en) * | 2021-07-28 | 2021-11-12 | 新疆至臻化工工程研究中心有限公司 | Cuprous catalyst and application of preparation method thereof in hydrochlorination of acetylene |
| CN114573418A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院上海有机化学研究所 | Method for preparing chloroethylene by reaction of acetylene and hydrogen chloride |
-
2022
- 2022-07-05 CN CN202210793686.9A patent/CN115106093B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB156117A (en) * | 1921-01-13 | 1922-03-30 | Otto Traun S Forschungslaborat | Manufacture of vinyl compounds and polymerisation products thereof |
| US2401850A (en) * | 1944-11-01 | 1946-06-11 | Du Pont | Preparation of fluorohydrocarbons |
| GB1416181A (en) * | 1972-01-17 | 1975-12-03 | Secr Defence | Processes for the manufacture of fluoroalkylaromatic compounds |
| CN111253214A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol by hydrogenating methyl glycolate |
| CN112619710A (en) * | 2019-09-24 | 2021-04-09 | 国家纳米科学中心 | Triazine-based covalent network loaded metal monoatomic composite material and preparation method and application thereof |
| CN110721743A (en) * | 2019-10-29 | 2020-01-24 | 福州大学 | Methane-producing atomic-level dispersed copper @ covalent triazine organic polymer composite photocatalyst and preparation and application thereof |
| CN114573418A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院上海有机化学研究所 | Method for preparing chloroethylene by reaction of acetylene and hydrogen chloride |
| CN113058644A (en) * | 2021-03-19 | 2021-07-02 | 山东大学 | Catalyst for catalyzing oxidative dehydrogenation and hydrogenation of organic compounds and application thereof |
| CN113634273A (en) * | 2021-07-28 | 2021-11-12 | 新疆至臻化工工程研究中心有限公司 | Cuprous catalyst and application of preparation method thereof in hydrochlorination of acetylene |
Non-Patent Citations (3)
| Title |
|---|
| Cationic Covalent Triazine Network: A Metal-Free Catalyst for Effective Acetylene Hydrochlorination;Zhaobing Shen等;catalysts;第1-10页 * |
| Direct Z-scheme copper cobaltite/covalent triazine-based framework heterojunction for efficient photocatalytic CO2 reduction under visible light;Guiyun Lin等;The Royal Society of Chemistry;第732-739页 * |
| 乙炔氢氯化反应无汞催化剂的制备及应用;张磊;姜恒;王红;董世伟;丁其维;宋丽娟;;石油化工高等学校学报(06);第11页结束语 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115106093A (en) | 2022-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109012722B (en) | Cerium dioxide/titanium nitride nanotube taking Ce-MOF as precursor and preparation method and application thereof | |
| CN115106093B (en) | Preparation method and application of metal covalent organic framework catalyst | |
| CN113210019A (en) | Preparation method and application of Cu-MOF catalyst for acetylene hydrochlorination | |
| CN108097251B (en) | Catalyst for fixed bed acetylene hydrochlorination and use method thereof | |
| CN108654693A (en) | A kind of hydrophobic palladium/metal-organic framework material and preparation method thereof and the application for synthesizing 2,5- dimethyl furans | |
| CN111715253A (en) | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination and preparation and use methods thereof | |
| CN110813336B (en) | Phosphorus-doped carbon-loaded transition metal catalyst and preparation method and application thereof | |
| CN113713841B (en) | Acetylene copper chloride-based catalyst and preparation method and application thereof | |
| CN102069000A (en) | Non-mercury catalyst for production of vinyl chloride and preparation method thereof | |
| CN114289048A (en) | Preparation method of polyvinyl chloride mercury-free catalyst | |
| CN111774094A (en) | Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof | |
| CN113797942B (en) | Phosphorus-modified copper-based catalyst for hydrochlorination of acetylene as well as preparation method and application thereof | |
| CN111744538A (en) | Molecular sieve non-noble metal catalyst for hydrochlorination of acetylene | |
| CN107754841A (en) | A kind of preparation method and application of modified ordered mesopore carbon copper-loading catalyst | |
| CN114100659A (en) | Nitrogen-boron co-doped metal-free catalyst and preparation method and application thereof | |
| CN103623837A (en) | Ru-Co-Cu catalyst used for synthesizing vinyl chloride by hydrochlorinating acetylene | |
| CN116899621A (en) | Preparation method of ZIF-8 coated supported palladium catalyst and application of ZIF-8 coated supported palladium catalyst in acetylene selective hydrogenation reaction | |
| CN115430425B (en) | High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, preparation and application thereof | |
| CN115155573B (en) | Method for preparing vinyl chloride by hydrochlorination of acetylene in fixed bed by using ultralow-content gold-based catalyst modified by nitrogen and sulfur | |
| CN110615895A (en) | Covalent triazine polymer and preparation method and application thereof | |
| CN115007214B (en) | Copper-based metal organic framework catalyst prepared by mechanochemical method and preparation method | |
| CN114618594B (en) | Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof | |
| CN112871207B (en) | Supported non-metal catalyst and preparation method and application thereof | |
| CN112774701B (en) | Acid radical intercalation hydrotalcite derived composite oxide and preparation method and application thereof | |
| CN115608415B (en) | Supported catalyst, preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240813 Address after: Room 401, Building 1, No. 88 Qixing Road, Meishan, Beilun District, Ningbo City, Zhejiang Province, China 315000 C0316, Zone C Patentee after: Ningbo Keyu Enterprise Management Partnership (Limited Partnership) Country or region after: China Address before: Room 616, 6th Floor, Building H5, Production and Research Base, Shanhe Road, High-tech Zone, Jining City, Shandong Province, 272000 Patentee before: Zhongke Lanhe (Shandong) New Materials Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |