CN113617393A - 一种乙炔氢氯化金属有机骨架材料催化剂 - Google Patents
一种乙炔氢氯化金属有机骨架材料催化剂 Download PDFInfo
- Publication number
- CN113617393A CN113617393A CN202110859221.4A CN202110859221A CN113617393A CN 113617393 A CN113617393 A CN 113617393A CN 202110859221 A CN202110859221 A CN 202110859221A CN 113617393 A CN113617393 A CN 113617393A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- organic framework
- framework material
- copper
- metal 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 34
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 29
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 19
- 239000013084 copper-based metal-organic framework Substances 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052753 mercury Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000005997 Calcium carbide Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- -1 structure Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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 1
- 229910015723 MoP Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种乙炔氢氯化金属有机骨架材料催化剂,特别适用于乙炔氢氯化反应合成氯乙烯的非汞催化剂,该催化剂采用铜基‑金属有机骨架材料为催化剂的主活性组分,以钾、钡、锌、镍、钴、银、铈、锡的化合物的一种及以上为辅活性组分,载体为二氧化硅、活性炭、分子筛、碳纳米管、石墨烯等多孔材料为载体,经过浸渍干燥后制得所需催化剂。铜基‑金属有机骨架材料自身也具有较好的乙炔氢氯化催化作用,用上述铜基‑金属有机骨架材料催化剂具有较好的综合性能,催化剂活性高、选择性好、绿色环保等优点。
Description
技术领域
本发明涉及一种乙炔氢氯化金属有机骨架材料催化剂,特别涉及一种适用于乙炔氢氯化合成氯乙烯的催化剂。
背景技术
氯乙烯单体是聚氯乙烯重要的合成的原料,聚氯乙烯是我国消费和产量最大的合成树脂之一,而我国多煤少油的基本国情决定了乙炔氢氯化法生产氯乙烯仍然在我国占有主导的地位。乙炔氢氯化法合成氯乙烯现在所面临的主要问题之一是汞触媒的使用所带来的环境污染以及汞资源的大量消耗。随着人们环保意识的日益增强和国际限汞条约谈判的日益紧张,无汞触媒的开发在近十年成为电石法聚氯乙烯行业的研究热点之一。
目前无汞催化剂的研究主要集中在非贵金属与贵金属无汞催化剂的研究开发。贵金属无汞催化剂的研究开发近十年来进入鼎盛时期,清华大学、南开大学、华东理工大学、新疆天业等很多研发单位和企业都对贵金属无汞催化剂的开发做了很多工作,使得贵金属无汞催化剂的开发也取得了很大的研究进展。贵金属无汞催化剂虽然转化率高,但是其一次性投入大,反应热点高,热点集中等问题限制了贵金属无汞催化剂的推广应用,贵金属无汞催化剂存在的这些问题使得价格低廉的非贵金属无汞催化剂越来越受人们的关注。
非贵金属催化剂的研发近期也取得了一定的进展,例如CN101497046、CN101671293、CN102151581A分别以Cu、Bi、MoP等非贵金属为主活性组分的催化体系;CN201710174566.X公开了贱金属盐和酰胺类溶剂协同作用的铜基催化剂;CN201910933364.8公开了一种三价铜催化剂及其制备方法在乙炔氢氯化中的应用。
乙炔氢氯化气固相法催化剂的开发和催化剂的活性中心、组成、结构、助剂、载体及载体改性等相辅相成,缺一不可。目前,上述非贵金属催化剂的综合性能并不理想,催化剂还存在寿命短、活性低、容易积炭,容易流失等等问题。
发明内容
针对以上电石法乙炔氢氯化给贵金属无汞催化剂存在寿命短、活性低、容易积炭,容易流失等的问题,本发明提出一种乙炔氢氯化金属有机骨架材料催化剂,该催化剂活性高,稳定性好,是一种金属有机骨架材料的催化剂。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂包括多孔性铜基-金属有机骨架材料(Cu-MOFs),铜基-金属有机骨架材料可以直接作为乙炔氢氯化催化剂。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂,铜基-金属有机骨架材料作为乙炔氢氯化催化剂的主活性组分,负载在活性炭、硅胶、分子筛、碳纳米管、石墨烯等载体上,获得乙炔氢氯化催化剂。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂,铜基-金属有机骨架材料和多孔硅胶、活性炭、分子筛等掺混使用。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂中铜基-金属有机骨架材料的制备方法为:称取一定量的1,3,5-均苯三甲酸(H3BTC)溶解于N,N-二甲基甲酰胺(DMF)和无水乙醇的混合溶液备用,称取一定量的铜化合物溶于去离子水中;将上述两溶液混合搅拌10分钟,超声2-30分钟;混合液倒入聚四氟乙烯内衬的晶化釜中密封,放入烘箱中,在30-100℃条件下晶化2-24小时,之后拿出静置自然冷却至室温;用离心机除去母液,并用N,N-二甲基甲酰胺(DMF)在离心机里洗涤2-5次,将上述晶体用无水乙醇再次萃取2-24小时,也即转入索氏提取器中,向圆底烧中加入的一定量的无水乙醇,提取洗涤2-24小时后移出,在真空烘箱中50-125℃、0.1MPa真空度真空干燥2-24小时,获得催化剂。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂铜基-金属有机骨架材料铜的含量为5-80%。
如上所述的一种乙炔氢氯化金属有机骨架材料催化剂,其特征在于如上所述的铜基-金属有机骨架材料的比表面积是50-2000m2/g。
本发明提供的一种乙炔氢氯化金属有机骨架材料催化剂具有转化率高,稳定性好,价格低廉等特点。在10~180h-1的空速反应时,初始转化率能达到30~99%,在反应12h后转化率仍能维持稳定,氯乙烯的选择性可达到60%以上,解决了电石乙炔法聚氯乙烯生产中使用高毒性的汞催化剂,生产中汞消耗量大,对环境污染严重,现有非贵金属催化剂活性低、稳定性较差等问题。
具体实施方式
为了更好的说明本发明,举出以下实例。但本发明的范围并不仅局限于实例,其要求保护的范围记载于权利要求的权项中。
多孔性铜基-金属有机骨架材料(Cu-MOFs)的制备:称取1.0561g的1,3,5-均苯三甲酸(H3BTC)溶解于20ml的N,N-二甲基甲酰胺(DMF)和20ml无水乙醇的混合溶液,称取1.4665g氯化铜溶于去离子水中;将上述两溶液混合搅拌10分钟,超声2-30分钟;混合液倒入聚四氟乙烯内衬的晶化釜中密封,放入烘箱中,30-100℃下晶化12小时,之后拿出静置自然冷却至室温20-25℃均可;用离心机除去母液,并用N,N-二甲基甲酰胺(DMF)在离心机里洗涤5次,将其转入索氏提取器中,向圆底烧中加入的一定量的无水乙醇,提取洗涤224小时后移出,在真空烘箱中105℃、0.1MPa真空度真空干燥24小时。
实施例1
将Cu-MOFs研磨成粉,过筛20-200目后,称取2g填装微反固定床,经过氮气干燥成为一种乙炔氢氯化金属有机骨架材料催化剂,氯化氢活化以后,催化剂的转化率达到95%。
实施例2
称量Cu-MOFs2g、氯化铈0.4g于烧杯中,随后加入20ml去离子水稀释。搅拌均匀后,加入10g活性炭载体,搅拌均匀,常温浸渍24h,然后50℃条件下干燥8h,在125℃条件下干燥12h自然降温后成为一种乙炔氢氯化金属有机骨架材料催化剂样品。经过氮气干燥,氯化氢活化以后,催化剂的转化率达到55%。
实施例3
称量Cu-MOFs4g、氯化亚锡2g于烧杯中,随后加入20ml乙醇。搅拌均匀后,加入10g硅胶载体,搅拌均匀,常温浸渍24h,然后50℃条件下干燥8h,在125℃条件下干燥12h自然降温后成为一种乙炔氢氯化金属有机骨架材料催化剂样品。经过氮气干燥,氯化氢活化以后,催化剂的转化率达到78%。
实施例4
称量Cu-MOFs6g、氯化钴1g、氯化钡1g于烧杯中,随后加入20ml乙醇。搅拌均匀陈化2小时,50℃蒸干,然后50℃条件下干燥8h,在125℃条件下干燥12h自然降温后成为一种乙炔氢氯化金属有机骨架材料催化剂样品。经过氮气干燥,氯化氢活化以后,催化剂的转化率达到85%。
实施例5
称量氯化锡3g,随后加入20ml去离子水,1ml盐酸,搅拌均匀后,加入10gCu-MOFs,搅拌均匀,常温浸渍24h,然后50℃条件下干燥8h,在125℃条件下干燥12h自然降温后成为一种乙炔氢氯化金属有机骨架材料催化剂样品。经过氮气干燥,氯化氢活化以后,催化剂的转化率达到95%。
Claims (6)
1.一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于该催化剂包括多孔性铜基-金属有机骨架材料。
2.如权利要求1所述的一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于制备方法为:1,3,5-均苯三甲酸溶解于N,N-二甲基甲酰胺和无水乙醇的混合溶液备用,铜化合物溶于去离子水中;将上述两种溶液均匀混合,形成混合液;混合液倒入晶化釜中密封,放入烘箱中,在30-100℃下晶化2-24小时,之后出釜静置自然冷却至室温;除去母液,并用N,N-二甲基甲酰胺洗涤2-5次,将上述晶体用无水乙醇再次萃取2-24小时,烘干后得到该催化剂。
3.如权利要求1所述的一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于所述的铜基-金属有机骨架材料还包括负载在活性炭、硅胶、分子筛、碳纳米管、石墨烯中的一种或任意几种的载体。
4.如权利要求1所述的一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于所述的铜基-金属有机骨架材料和多孔硅胶、活性炭、分子筛等载体掺混形成催化剂。
5.如权利要求1所述的一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于所述的铜基-金属有机骨架材料铜的含量为5-80%。
6.如权利要求1所述的一种乙炔氢氯化催化金属有机骨架材料催化剂,其特征在于所述的铜基-金属有机骨架材料的比表面积是50-2000m2/g。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110859221.4A CN113617393A (zh) | 2021-07-28 | 2021-07-28 | 一种乙炔氢氯化金属有机骨架材料催化剂 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110859221.4A CN113617393A (zh) | 2021-07-28 | 2021-07-28 | 一种乙炔氢氯化金属有机骨架材料催化剂 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113617393A true CN113617393A (zh) | 2021-11-09 |
Family
ID=78381336
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110859221.4A Pending CN113617393A (zh) | 2021-07-28 | 2021-07-28 | 一种乙炔氢氯化金属有机骨架材料催化剂 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113617393A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114939437A (zh) * | 2022-05-24 | 2022-08-26 | 鄂尔多斯市瀚博科技有限公司 | 一种Ru-MOF/AC乙炔氢氯化催化剂及其制备方法 |
CN115007214A (zh) * | 2022-06-20 | 2022-09-06 | 鄂尔多斯市瀚博科技有限公司 | 机械化学法制备的含铜基金属有机框架催化剂及制备方法 |
CN115212882A (zh) * | 2022-06-30 | 2022-10-21 | 浙江工业大学 | 一种多孔硅化铜金属间化合物材料及其制备和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102631947A (zh) * | 2012-04-01 | 2012-08-15 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化的金络合物催化剂 |
CN105521801A (zh) * | 2015-12-15 | 2016-04-27 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化合成氯乙烯的催化剂及其制备方法 |
CN106423287A (zh) * | 2016-09-10 | 2017-02-22 | 新疆大学 | 负载型无汞催化剂及其制备方法和在乙炔氢氯化制备氯乙烯中的应用 |
WO2018049820A1 (zh) * | 2016-09-18 | 2018-03-22 | 天津大学 | 负载季鏻盐和金属氯化物的催化剂在乙炔氢氯化中的用途 |
CN110743624A (zh) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | 一种乙炔氢氯化铜基催化剂及其制备方法与应用 |
-
2021
- 2021-07-28 CN CN202110859221.4A patent/CN113617393A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102631947A (zh) * | 2012-04-01 | 2012-08-15 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化的金络合物催化剂 |
CN105521801A (zh) * | 2015-12-15 | 2016-04-27 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | 一种用于乙炔氢氯化合成氯乙烯的催化剂及其制备方法 |
CN106423287A (zh) * | 2016-09-10 | 2017-02-22 | 新疆大学 | 负载型无汞催化剂及其制备方法和在乙炔氢氯化制备氯乙烯中的应用 |
WO2018049820A1 (zh) * | 2016-09-18 | 2018-03-22 | 天津大学 | 负载季鏻盐和金属氯化物的催化剂在乙炔氢氯化中的用途 |
CN110743624A (zh) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | 一种乙炔氢氯化铜基催化剂及其制备方法与应用 |
Non-Patent Citations (2)
Title |
---|
YIBO WU ET AL.: "Carbon-supported copper-organic framework as active catalysts for acetylene hydrochlorination" * |
YIBO WU ET AL.: "Synthesis and Characterization of X-MOF/AC (X=tin or copper) Catalysts for the Acetylene Hydrochlorination" * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114939437A (zh) * | 2022-05-24 | 2022-08-26 | 鄂尔多斯市瀚博科技有限公司 | 一种Ru-MOF/AC乙炔氢氯化催化剂及其制备方法 |
CN114939437B (zh) * | 2022-05-24 | 2024-01-09 | 鄂尔多斯市瀚博科技有限公司 | 一种Ru-MOF/AC乙炔氢氯化催化剂及其制备方法 |
CN115007214A (zh) * | 2022-06-20 | 2022-09-06 | 鄂尔多斯市瀚博科技有限公司 | 机械化学法制备的含铜基金属有机框架催化剂及制备方法 |
CN115007214B (zh) * | 2022-06-20 | 2024-01-09 | 鄂尔多斯市瀚博科技有限公司 | 机械化学法制备的含铜基金属有机框架催化剂及制备方法 |
CN115212882A (zh) * | 2022-06-30 | 2022-10-21 | 浙江工业大学 | 一种多孔硅化铜金属间化合物材料及其制备和应用 |
CN115212882B (zh) * | 2022-06-30 | 2023-12-19 | 浙江工业大学 | 一种多孔硅化铜金属间化合物材料及其制备和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113617393A (zh) | 一种乙炔氢氯化金属有机骨架材料催化剂 | |
CN112717953B (zh) | 一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法 | |
CN110560086A (zh) | 一种高分散钯-掺硫活性炭催化剂及其制备与应用 | |
CN115672316B (zh) | 生物质骨架炭-金属复合微纳结构催化材料及制备方法和应用 | |
CN102380380A (zh) | 一种用于乙炔氢氯化反应的非汞催化剂体系及其应用 | |
CN109384750B (zh) | 一种催化加氢5-羟甲基糠醛制备2,5-二甲基呋喃的方法 | |
CN110560085A (zh) | 一种原位硫掺杂介孔碳负载钯金属催化剂及其制备方法与应用 | |
CN113210019A (zh) | 一种用于乙炔氢氯化反应的Cu-MOF催化剂的制备方法和应用 | |
CN107670697B (zh) | 可见光催化环己烷选择性氧化的催化剂及其制备方法 | |
CN111087370B (zh) | 一种非贵金属负载氮掺杂碳催化糠醛转移氢化制备糠醇的方法 | |
CN113731465A (zh) | 一种Pd/N-CNTs催化剂及其制备方法与应用 | |
CN115555005B (zh) | 具有强吸附能力的无汞催化剂载体活性炭的生产方法 | |
CN114177940A (zh) | 一种单原子Cu锚定共价有机框架材料的制备及其应用 | |
CN111921543B (zh) | 一种高效乙炔氢氯化反应触媒的制备方法及用途 | |
CN111362887B (zh) | 催化氧化制备六氟环氧丙烷的方法 | |
CN111135848A (zh) | 木质基碳催化剂、其制备方法及苯酚加氢制备环己酮的方法 | |
CN113634273A (zh) | 一种一价铜催化剂及其制备方法在乙炔氢氯化中的应用 | |
CN115350724A (zh) | 一种用于合成恶唑烷酮的双功能聚离子液体催化剂的制备方法 | |
CN113600203B (zh) | 一种用于合成氯乙烯的钼酸铜催化剂及其制备方法 | |
CN111672525A (zh) | 一种活性炭上原位合成层状介孔磷酸锆改性铜基乙炔氢氯化催化剂及其制备方法 | |
CN115888816B (zh) | 一种离子型超交联多孔有机聚合物负载纳米钯材料的制备方法及应用 | |
CN114917931B (zh) | 一种铜-钯-硼/生物质炭催化剂、制备方法及其应用 | |
CN114805281B (zh) | 一种1,2-二氟代碳酸乙烯酯的制备方法 | |
CN113072416B (zh) | 一种制备氘代乙烯的方法 | |
CN113332984B (zh) | 一种聚合反应制备钴碳催化剂的制备方法及其应用 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211109 |
|
WD01 | Invention patent application deemed withdrawn after publication |