CN112916049B - Oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination and its preparation method and application - Google Patents
Oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination and its preparation method and application Download PDFInfo
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- CN112916049B CN112916049B CN202110108031.9A CN202110108031A CN112916049B CN 112916049 B CN112916049 B CN 112916049B CN 202110108031 A CN202110108031 A CN 202110108031A CN 112916049 B CN112916049 B CN 112916049B
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- copper
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- oxygen
- acetylene
- activated carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- 150000001879 copper Chemical class 0.000 title claims abstract description 28
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003446 ligand Substances 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 claims description 4
- VXIXUWQIVKSKSA-UHFFFAOYSA-N 4-hydroxycoumarin Chemical compound C1=CC=CC2=C1OC(=O)C=C2O VXIXUWQIVKSKSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 3
- BPOVRAAUERBWFK-UHFFFAOYSA-N 1-hydroxycyclohexane-1-carboxylic acid Chemical compound OC(=O)C1(O)CCCCC1 BPOVRAAUERBWFK-UHFFFAOYSA-N 0.000 claims description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 3
- 229960002510 mandelic acid Drugs 0.000 claims description 3
- IAWVHZJZHDSEOC-UHFFFAOYSA-N 3,3-dimethyl-2-oxobutanoic acid Chemical compound CC(C)(C)C(=O)C(O)=O IAWVHZJZHDSEOC-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001431 copper ion Inorganic materials 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000005749 Copper compound Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OTUXCLKRSRDYPV-UHFFFAOYSA-N acetylene hydrochloride Chemical compound Cl.C#C OTUXCLKRSRDYPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TYEYBOSBBBHJIV-UHFFFAOYSA-N 2-oxobutanoic acid Chemical compound CCC(=O)C(O)=O TYEYBOSBBBHJIV-UHFFFAOYSA-N 0.000 description 1
- CQGDLUZXSAXPRC-UHFFFAOYSA-N Cl.[Cu].C#C Chemical compound Cl.[Cu].C#C CQGDLUZXSAXPRC-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PDOBNBXZWXCBGR-UHFFFAOYSA-M azanium tetraethylazanium dichloride Chemical compound [Cl-].[NH4+].[Cl-].C(C)[N+](CC)(CC)CC PDOBNBXZWXCBGR-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical group [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical group [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HDFZSPPOXSAVRI-UHFFFAOYSA-N n,n,n',n'-tetramethylethane-1,2-diamine;hydrochloride Chemical compound Cl.CN(C)CCN(C)C HDFZSPPOXSAVRI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明属于化工催化领域,特别是涉及一种用于乙炔氢氯化反应的含氧多齿配体改性的铜基催化剂及其制备方法和应用。The invention belongs to the field of chemical catalysis, in particular to an oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination reaction, and a preparation method and application thereof.
背景技术Background technique
聚氯乙烯(PVC)是世界五大通用树脂之一,被广泛应用于化工、建材、农业和医疗器械等多个行业。2018年,中国PVC总产能超过2400万吨,在全球PVC总产能中占比超过40%。预计到2026年,全球PVC总需求量预计达到5620万吨。聚氯乙烯(PVC)的生产需要氯乙烯单体(VCM),鉴于我国“富煤、贫油、少气”的特殊能源结构,我国选择技术成熟、耗水量少、生产成本低,以煤炭为基础的乙炔法生产路线,但是该生产路线的核心环节依赖于含汞催化剂,聚氯乙烯(PVC)生产已经成为我国用汞量最大的行业,占到了中国用汞总量的60%以上。Polyvinyl chloride (PVC) is one of the top five general-purpose resins in the world and is widely used in many industries such as chemical industry, building materials, agriculture and medical equipment. In 2018, China's total PVC production capacity exceeded 24 million tons, accounting for more than 40% of the global PVC production capacity. It is estimated that by 2026, the total global PVC demand is expected to reach 56.2 million tons. The production of polyvinyl chloride (PVC) requires vinyl chloride monomer (VCM). In view of my country's special energy structure of "rich coal, lean oil, and less gas", our country chooses mature technology, low water consumption and low production cost. The basic acetylene production route, but the core link of this production route relies on mercury-containing catalysts. Polyvinyl chloride (PVC) production has become the industry with the largest mercury consumption in my country, accounting for more than 60% of the total mercury consumption in China.
工业上乙炔氢氯化反应使用的含汞催化剂其主要活性成分为HgCl2,其在高温下极易升华流失,会造成严重的环境污染,严重危害人体健康。随着2017年《关于汞的水俣公约》在中国等缔约方正式生效,含汞产品的使用将受到严格限制,电石法制氯乙烯行业的无汞化成为行业发展必经之路。自上世纪70年代起,国内外相关科研工作者就已经开始了乙炔氢氯化无汞催化剂的研究。大量的研究结果表明,现阶段具备工业应用条件的无汞催化剂主要是以贵金属(如Au、Pt、Ru)为活性组分的催化剂和以非贵金属(如Cu、Sn、Bi)为活性组分的催化剂。基于经济性,近年来非贵金属无汞催化剂迎来一个研究热潮,特别是Cu基催化剂,出现了大量文献、专利报道。The main active component of mercury-containing catalysts used in acetylene hydrochlorination in industry is HgCl 2 , which is easily sublimated and lost at high temperatures, causing serious environmental pollution and serious harm to human health. With the official entry into force of the "Minamata Convention on Mercury" in China and other parties in 2017, the use of mercury-containing products will be strictly restricted. Since the 1970s, relevant researchers at home and abroad have started the research on mercury-free catalysts for acetylene hydrochloride. A large number of research results show that the mercury-free catalysts with industrial application conditions at this stage are mainly catalysts with noble metals (such as Au, Pt, Ru) as active components and non-precious metals (such as Cu, Sn, Bi) as active components. catalyst. Based on economy, non-precious metal mercury-free catalysts have ushered in a research upsurge in recent years, especially Cu-based catalysts, and a large number of literature and patent reports have appeared.
公告号为CN107008465B的发明专利公开了一种用于乙炔氢氯化反应的铜基催化剂,该催化剂以铜盐作为活性组分,并且加入稳定剂提高催化剂稳定性。铜盐选自氯化铜、硝酸铜、硫酸铜、磷酸铜中的一种或几种,稳定剂选自盐酸胍、四甲基乙二胺盐酸盐、四甲基氯化铵、四乙基氯化铵、三甲基苄基氯化铵、三乙基苄基氯化铵、四甲基氯化鏻、四丁基氯化鏻、甲基三苯基氯化鏻、1-丁基三苯基氯化鏻中的一种及几种,该发明虽然有效改善了铜基催化剂的稳定性,但在反应活性上未有提高,最高反应初活性仅为74%。The invention patent with the publication number CN107008465B discloses a copper-based catalyst for acetylene hydrochlorination. The catalyst uses copper salt as an active component, and adds a stabilizer to improve the stability of the catalyst. The copper salt is selected from one or more of copper chloride, copper nitrate, copper sulfate and copper phosphate, and the stabilizer is selected from guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethylammonium chloride, tetraethylammonium chloride ammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, methyltriphenylphosphonium chloride, 1-butyl One or several kinds of triphenylphosphonium chloride, although the invention effectively improves the stability of the copper-based catalyst, the reaction activity is not improved, and the highest initial reaction activity is only 74%.
申请201910933364.8提出了一种三价铜催化剂的制备方法及其在乙炔氢氯化反应中的应用。该催化剂制备方法为将含氮杂环化合物与铜盐加入到三氯甲烷溶液中混合得到含二价铜化合物的混合液;向所得的混合液中加入离子液体,在氧化剂的作用下,得到含三价铜化合物的混合液;将多孔固体载体浸渍于所得的含有三价铜化合物的混合液中0.5~5h,然后取出处理后的固体在蓝光照射的条件下加热烘干,即得三价铜催化剂。该催化剂虽然在反应中有一定活性和稳定性,但制备过程繁琐,不易工业化生产。Application 201910933364.8 proposes a preparation method of a trivalent copper catalyst and its application in acetylene hydrochlorination. The catalyst preparation method comprises the following steps: adding nitrogen-containing heterocyclic compounds and copper salts into a chloroform solution and mixing to obtain a mixed solution containing divalent copper compounds; adding ionic liquid to the obtained mixed solution, under the action of an oxidant, to obtain a mixed solution containing a divalent copper compound; The mixed solution of trivalent copper compound; the porous solid carrier is immersed in the obtained mixed solution containing the trivalent copper compound for 0.5 to 5 hours, and then the treated solid is taken out and heated and dried under the condition of blue light irradiation, that is, the trivalent copper is obtained. catalyst. Although the catalyst has certain activity and stability in the reaction, the preparation process is cumbersome and difficult to industrialize production.
目前乙炔氢氯化铜基催化剂主要存在的困境有活性、稳定性差或制备方法不易工业化生产。基于此背景,本申请公开了一种以活性炭为载体,铜盐为活性组分,通过含氧多齿配体来提高活性与稳定性的乙炔氢氯化无汞催化剂,该方法经济性高、绿色环保、工业可行性高。At present, the main difficulties of acetylene copper hydrochloride-based catalysts are that they have poor activity, poor stability or the preparation method is not easy for industrial production. Based on this background, the present application discloses a mercury-free catalyst for acetylene hydrochloride, which uses activated carbon as a carrier, copper salt as an active component, and uses oxygen-containing multidentate ligands to improve activity and stability. Green environmental protection, high industrial feasibility.
发明内容SUMMARY OF THE INVENTION
本发明针对以上所述技术存在的缺陷以及工业化应用方面的不足,提供了一种用于乙炔氢氯化反应的含氧多齿配体改性的铜基催化剂及其制备方法和应用。Aiming at the defects of the above-mentioned technologies and the deficiencies in industrial application, the present invention provides an oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination, and a preparation method and application thereof.
针对目前铜基催化剂普遍存在的活性不高、稳定性较差的问题,我们通过大量实验和研究发现,含氧多齿配体可使高价铜活性物种更稳定,减少催化过程中还原产物零价铜的生成。根据软硬酸碱理论,羧基、羟基等的电子给予体均为氧原子,难极化,属于硬碱,铜离子是较硬的酸,能与硬碱形成稳定的配合物,羧基、羟基等的电子给予体的氧原子可与作为交界酸的铜离子稳定配位,所以铜离子可以与含氧多齿配体牢固地结合,防止催化过程中被还原为无活性的零价铜,进而提高铜基催化剂的活性和稳定性。此外,若二者配位后形成五元环状络合物,可调控铜离子的电子趋向于对催化更有利的空间分布。In view of the common problems of low activity and poor stability of current copper-based catalysts, we have found through a large number of experiments and studies that oxygen-containing multidentate ligands can make high-valent copper active species more stable and reduce the zero valence of reduction products in the catalytic process. formation of copper. According to the theory of soft and hard acid-base, the electron donors of carboxyl and hydroxyl groups are oxygen atoms, which are difficult to polarize and belong to hard bases. Copper ions are hard acids and can form stable complexes with hard bases. The oxygen atom of the electron donor can stably coordinate with the copper ion as the junction acid, so the copper ion can be firmly combined with the oxygen-containing multidentate ligand, preventing it from being reduced to inactive zero-valent copper during the catalytic process, thereby improving Activity and stability of copper-based catalysts. In addition, if the two are coordinated to form a five-membered cyclic complex, the electrons of copper ions can be regulated to tend to a more favorable spatial distribution for catalysis.
含氧多齿配体是指一个配体中含两个或两个以上的氧作为配位原子的配体。氧周围有6个电子。其中两个与碳形成共价键后,还有两对孤对电子,可以与过渡金属配位。呋喃环中的氧原子、羰基氧以及羧基中的羟基氧都为sp2杂化,醇羟基的氧为sp3杂化,但都可作为配位原子。本专利涉及的含氧多齿配体不含除氧以外的其他杂原子。Oxygen-containing multidentate ligands refer to ligands containing two or more oxygens as coordination atoms in one ligand. There are 6 electrons around oxygen. After two of them form covalent bonds with carbon, there are also two lone pairs of electrons that can coordinate with transition metals. The oxygen atom in the furan ring, the carbonyl oxygen and the hydroxyl oxygen in the carboxyl group are all sp2 hybridized, and the oxygen of the alcoholic hydroxyl group is sp3 hybridized, but they can be used as coordination atoms. The oxygen-containing multidentate ligands involved in this patent do not contain heteroatoms other than oxygen.
本发明通过如下方法实现:The present invention is realized by the following method:
用于乙炔氢氯化反应的含氧多齿配体改性的铜基催化剂,所述催化剂由铜盐、含氧多齿配体和载体组成。将铜盐与一种或几种含氧配体负载于碳载体表面,其中所述的铜盐阳离子主要为Cu2+;所述的含氧配体的配位氧原子来自呋喃环、酯基、羧基、羟基中的一种或多种。An oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination, the catalyst is composed of a copper salt, an oxygen-containing multidentate ligand and a carrier. The copper salt and one or more oxygen-containing ligands are loaded on the surface of the carbon support, wherein the copper salt cation is mainly Cu 2+ ; the coordinating oxygen atom of the oxygen-containing ligand comes from furan ring, ester group , one or more of carboxyl group and hydroxyl group.
一种用于乙炔氢氯化反应的含氧多齿配体改性的铜基催化剂的制备方法如下:A preparation method of an oxygen-containing multidentate ligand-modified copper-based catalyst for acetylene hydrochlorination is as follows:
1)将铜盐与含氧多齿配体在一定温度下按一定比例溶于特定溶剂中得到混合溶液,在该温度下配体能够完全溶解,能获得均一稳定的混合溶液;1) Dissolve the copper salt and the oxygen-containing multidentate ligand in a specific solvent at a certain temperature in a certain proportion to obtain a mixed solution, at which the ligand can be completely dissolved and a uniform and stable mixed solution can be obtained;
2)在相同温度下,采用浸渍、喷涂、沉淀法、离子交换法、喷雾蒸干法等方法将混合溶液中的活性组分均匀负载到活性炭载体上;2) Under the same temperature, the active components in the mixed solution are evenly loaded on the activated carbon carrier by methods such as dipping, spraying, precipitation, ion exchange, spray evaporation and drying;
3)在一定温度及压力环境下干燥处理一定时间,即得所述催化剂。3) The catalyst is obtained by drying for a certain period of time under a certain temperature and pressure environment.
优选地,步骤1)中,还包括以下一项或多项特征:Preferably, in step 1), one or more of the following features are also included:
1)所述铜盐选自氯化铜、溴化铜、硝酸铜、硫酸铜中的一种或多种;更优选地,所述铜盐为氯化铜;1) the copper salt is selected from one or more of copper chloride, copper bromide, copper nitrate, copper sulfate; more preferably, the copper salt is copper chloride;
2)所述配体选自结构带有呋喃环(如2-乙酰基呋喃、糠醇、糠醛、羟甲基糠醛)、酯基(碳酸环乙酯、1,4-丁内酯、丙酮酸甲酯、马来酸二甲酯、草酸二乙酯、4-羟基香豆素)、羧基(扁桃酸、1-羟基环己基甲酸、三甲基丙酮酸、乳酸、丙二酸、2-四氢呋喃甲酸)的含氧有机物中的一种或多种;其中2-乙酰基呋喃、糠醇、糠醛、羟甲基糠醛、丙酮酸甲酯、草酸二乙酯、扁桃酸、1-羟基环己基甲酸、三甲基丙酮酸、乳酸、2-四氢呋喃甲酸等能与铜形成五元环的络合结构。2) The ligands are selected from structures with furan rings (such as 2-acetyl furan, furfuryl alcohol, furfural, hydroxymethyl furfural), ester groups (cycloethyl carbonate, 1,4-butyrolactone, methyl pyruvate); ester, dimethyl maleate, diethyl oxalate, 4-hydroxycoumarin), carboxyl (mandelic acid, 1-hydroxycyclohexylcarboxylic acid, trimethylpyruvic acid, lactic acid, malonic acid, 2-tetrahydrofurancarboxylic acid) ) one or more of the oxygen-containing organics; wherein 2-acetyl furan, furfuryl alcohol, furfural, hydroxymethyl furfural, methyl pyruvate, diethyl oxalate, mandelic acid, 1-hydroxycyclohexylcarboxylic acid, Methyl pyruvic acid, lactic acid, 2-tetrahydrofuran carboxylic acid, etc. can form complex structures with five-membered rings with copper.
3)所述混合溶液中铜盐与配体的摩尔比值为0.25~2;更优选地,所述混合溶液中铜盐与配体的摩尔比值为0.5~1;3) the molar ratio of copper salt to ligand in the mixed solution is 0.25-2; more preferably, the molar ratio of copper salt to ligand in the mixed solution is 0.5-1;
4)所述混合溶液溶剂为常见极性溶剂;更优选地,所述溶剂选自去离子水、无水乙醇、丙酮、二氯甲烷、乙腈、氯仿、N,N-二甲基甲酰胺的一种或多种;4) The mixed solution solvent is a common polar solvent; more preferably, the solvent is selected from deionized water, absolute ethanol, acetone, dichloromethane, acetonitrile, chloroform, N,N-dimethylformamide. one or more;
5)混合溶液中Cu元素质量占催化剂成品质量分数为2.5~16%,如2.5~5wt%、5~8.5wt%、12~15wt%;5) The mass fraction of Cu element in the mixed solution accounts for 2.5-16% of the catalyst product mass, such as 2.5-5wt%, 5-8.5wt%, 12-15wt%;
6)所述混合溶液搅拌溶解温度为15~80℃,如15℃~30℃、40℃~65℃、65℃~80℃。6) The stirring and dissolving temperature of the mixed solution is 15 to 80°C, such as 15°C to 30°C, 40°C to 65°C, and 65°C to 80°C.
优选地,步骤2)中应包含以下一种或几种特征:Preferably, the following one or more features should be included in step 2):
1)活性炭载体为椰壳活性碳、煤质活性炭、木质活性炭、沥青基活性炭中的一种或几种;1) The activated carbon carrier is one or more of coconut shell activated carbon, coal-based activated carbon, wood activated carbon, and pitch-based activated carbon;
2)所述活性炭的水容量60~130%,堆积密度为0.3~0.8g/mL;2) The water capacity of the activated carbon is 60-130%, and the bulk density is 0.3-0.8 g/mL;
3)负载温度同搅拌溶解温度,为15~80℃。3) The loading temperature is the same as the stirring and dissolving temperature, which is 15-80°C.
优选地,步骤3)中应包含以下一种或几种特征:Preferably, the following one or more features should be included in step 3):
1)催化剂烘干处理的过程为:在高于溶剂沸点5~20℃,0.1MPa条件下干燥6~20h。1) The drying process of the catalyst is as follows: drying for 6-20 hours at 5-20°C higher than the boiling point of the solvent and 0.1MPa.
更加优选地,步骤3)中在高于溶剂沸点15℃下干燥20h。More preferably, in step 3), drying is performed at 15° C. higher than the boiling point of the solvent for 20 h.
制得的含氧多齿配体改性铜基催化剂应用于乙炔氢氯化反应中。The prepared oxygen-containing multidentate ligand-modified copper-based catalyst is used in acetylene hydrochlorination.
优选地,反应条件为:温度为90~250℃、乙炔体积空速为5~200h-1,压力为0.01~0.2Mpa。Preferably, the reaction conditions are as follows: the temperature is 90-250° C., the volume space velocity of acetylene is 5-200 h −1 , and the pressure is 0.01-0.2 Mpa.
产物由气相色谱分析组成,反应活性由乙炔转化率表示。The product consisted of gas chromatographic analysis and the reactivity was represented by the acetylene conversion.
与已有技术相比,本发明的有益效果为:Compared with the prior art, the beneficial effects of the present invention are:
1)本发明催化剂在铜盐中添加中性含氧多齿配体,用于与铜形成稳定配合物,通过引入含氧多齿配体,与铜形成配合物,稳定了高价铜活性物种;1) The catalyst of the present invention adds neutral oxygen-containing multidentate ligands to copper salts to form stable complexes with copper, and forms complexes with copper by introducing oxygen-containing multidentate ligands to stabilize high-valent copper active species;
2)铜离子的稳定,可以减少催化过程中无活性的零价铜生成,以此来提高铜基催化剂的活性;2) The stability of copper ions can reduce the generation of inactive zero-valent copper in the catalytic process, thereby improving the activity of copper-based catalysts;
3)2-四氢呋喃甲酸、糠醇等含氧配体,与铜离子配位后形成五元环状络合物,调控铜离子的电子趋向于对催化更有利的空间分布,使催化活性更优。五元环状络合物结构如下所示:3) Oxygen-containing ligands such as 2-tetrahydrofurancarboxylic acid and furfuryl alcohol form a five-membered ring complex after coordination with copper ions, and the electrons of copper ions are adjusted to tend to be more favorable for catalysis. The spatial distribution makes the catalytic activity better. The structure of the five-membered cyclic complex is shown below:
4)该制备方法制得的含氧多齿配体改性铜基催化剂催化活性高、稳定性好,在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率在80%以上,稳定性较好,具备良好的工业应用潜力。4) The oxygen-containing multidentate ligand-modified copper-based catalyst prepared by the preparation method has high catalytic activity and good stability. When the reaction conditions are 130° C., the space velocity of acetylene is 40h -1 , and the volume ratio of hydrogen chloride to acetylene is 1.2:1, The acetylene conversion rate is above 80%, the stability is good, and it has good industrial application potential.
具体实施方式Detailed ways
以下通过特定的具体实例说明本发明的技术方案。以下实施例是为了本行业人员更详细地理解本发明而非限制本发明的保护范围。本发明的保护范围在附属的权利要求书中提出。The technical solutions of the present invention are described below through specific specific examples. The following examples are intended for those skilled in the art to understand the present invention in more detail and are not intended to limit the protection scope of the present invention. The scope of protection of the present invention is set forth in the attached claims.
实施例1Example 1
(1)在50℃下,将1.7g无水氯化铜、0.61g丙酮酸甲酯搅拌溶于5.5g无水乙醇中得到含铜离子和配体的浸渍液;(1) at 50 ° C, 1.7 g of anhydrous copper chloride and 0.61 g of methyl pyruvate were stirred and dissolved in 5.5 g of absolute ethanol to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在95℃下干燥20小时,即得到催化剂A1。(3) The activated carbon was dried at 95° C. for 20 hours to obtain catalyst A1.
A1在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为84.5%。When the reaction conditions of A1 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 84.5%.
对比例1Comparative Example 1
(1)在50℃下,将1.7g无水氯化铜搅拌溶于5.5g无水乙醇中得到仅含铜离子的浸渍液;(1) at 50 ° C, 1.7 g of anhydrous copper chloride was stirred and dissolved in 5.5 g of absolute ethanol to obtain an immersion solution containing only copper ions;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在95℃下干燥20小时,即得到催化剂A2。(3) The activated carbon was dried at 95° C. for 20 hours to obtain catalyst A2.
A2在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为80.6%。但同等条件下,仅以铜离子作为活性组分,稳定性及寿命等整体性能较差,远不能满足工业应用。When the reaction conditions of A2 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 80.6%. However, under the same conditions, only using copper ions as the active component has poor overall performance such as stability and lifespan, which is far from satisfying industrial applications.
实施例2Example 2
(1)50℃下,将1.7g无水氯化铜、0.54g乳酸搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) At 50°C, 1.7g of anhydrous copper chloride and 0.54g of lactic acid were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A3。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A3.
A3在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为87.1%。When the reaction conditions of A3 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 87.1%.
实施例3Example 3
(1)50℃下,将1.7g无水氯化铜、0.61g丙酮酸甲酯搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) At 50°C, 1.7g of anhydrous copper chloride and 0.61g of methyl pyruvate were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A4。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A4.
A4在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为86.9%。When the reaction conditions of A4 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 86.9%.
实施例4Example 4
(1)50℃下,将1.7g无水氯化铜、0.66g 2-乙酰基呋喃搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) at 50°C, 1.7g of anhydrous copper chloride and 0.66g of 2-acetylfuran were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A5。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A5.
A5在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为87.3%。When the reaction conditions of A5 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 87.3%.
实施例5Example 5
(1)50℃下,将1.7g无水氯化铜、0.59g糠醇搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) at 50°C, 1.7g of anhydrous copper chloride and 0.59g of furfuryl alcohol were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A6。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A6.
A6在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为87.7%。When the reaction conditions of A6 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 87.7%.
实施例6Example 6
(1)50℃下,将1.7g无水氯化铜、0.70g 2-四氢呋喃甲酸搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) at 50° C., 1.7g of anhydrous copper chloride and 0.70g of 2-tetrahydrofuran formic acid were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an impregnation solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A7。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A7.
A7在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为88.8%。When the reaction conditions of A7 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 88.8%.
实施例7Example 7
(1)50℃下,将1.7g无水氯化铜、0.53g碳酸环乙酯搅拌溶于5.5gN,N-二甲基甲酰胺中得到含铜离子和配体的浸渍液;(1) At 50°C, 1.7g of anhydrous copper chloride and 0.53g of cycloethyl carbonate were stirred and dissolved in 5.5g of N,N-dimethylformamide to obtain an immersion solution containing copper ions and ligands;
(2)采用等体积浸渍法将浸渍液浸渍到10g活性炭上,50℃密封静置1小时;(2) Immerse the immersion liquid on 10g of activated carbon by the equal volume immersion method, and seal and stand at 50°C for 1 hour;
(3)将活性炭在170℃下干燥20小时,即得到催化剂A8。(3) The activated carbon was dried at 170° C. for 20 hours to obtain catalyst A8.
A8在反应条件为130℃,乙炔空速40h-1,氯化氢乙炔体积比1.2:1时,乙炔转化率为88.1%。When the reaction conditions of A8 are 130℃, the acetylene space velocity is 40h -1 and the volume ratio of hydrogen chloride to acetylene is 1.2:1, the acetylene conversion rate is 88.1%.
使用气相色谱分析尾气组成,每隔0.5小时采样一次。以反应4小时的点为代表数据取样,比较引入不同含氧多齿配体的铜基催化剂的乙炔转化率和氯乙烯选择性,结果如表所示:The exhaust gas composition was analyzed using gas chromatography, with samples taken every 0.5 hours. The representative data was sampled at the point of reaction for 4 hours, and the acetylene conversion and vinyl chloride selectivity of copper-based catalysts introduced with different oxygen-containing multidentate ligands were compared. The results are shown in the table:
碳酸环乙酯活性较好可能是由于该结构具有特殊的电子效应,两个ɑ位上的氧,减小羰基碳上的电子云密度,使羰基氧亲核性增强,与铜配位比普通的羰基更稳定。The better activity of cycloethyl carbonate may be due to the special electronic effect of this structure. The oxygen on the two ɑ positions reduces the electron cloud density on the carbonyl carbon and enhances the nucleophilicity of the carbonyl oxygen. The coordination with copper is more common. The carbonyl group is more stable.
实施例1-6中的含氧配体,与铜离子配位后能形成五元环状络合物,同等条件下,相对于无含氧配体的铜催化剂乙炔转化率明显提高,且铜离子与含氧多齿配体牢固地结合使催化剂的稳定性及寿命也显著提高,表明含氧配体添加后有明显的增益效果。The oxygen-containing ligands in Examples 1-6 can form a five-membered cyclic complex after being coordinated with copper ions. Under the same conditions, the acetylene conversion rate is significantly improved compared to the copper catalyst without oxygen-containing ligands, and copper The strong binding of ions to oxygen-containing multidentate ligands also significantly improves the stability and life of the catalyst, indicating that the addition of oxygen-containing ligands has a significant gain effect.
本发明未述及之处适用于现有技术。What is not described in the present invention applies to the prior art.
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