CN108043463B - A high-performance catalyst for carbon dioxide recycling and preparation method thereof - Google Patents
A high-performance catalyst for carbon dioxide recycling and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000004064 recycling Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 47
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- CZSOUHCUPOPPRC-UHFFFAOYSA-N 3-phenylphthalaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1C=O CZSOUHCUPOPPRC-UHFFFAOYSA-N 0.000 claims description 3
- AEKQNAANFVOBCU-UHFFFAOYSA-N benzene-1,3,5-tricarbaldehyde Chemical compound O=CC1=CC(C=O)=CC(C=O)=C1 AEKQNAANFVOBCU-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- LZDHIQDKAYUDND-UHFFFAOYSA-N biphenylene-1,2-diamine Chemical compound C1=CC=C2C3=C(N)C(N)=CC=C3C2=C1 LZDHIQDKAYUDND-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 15
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- DUVVGYBLYHSFMV-YGEZULPYSA-N 4-methyl-n-[[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]carbamoyl]benzamide Chemical compound C1=CC(C)=CC=C1C(=O)NC(=O)N[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DUVVGYBLYHSFMV-YGEZULPYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- -1 benzidine diamine Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- AETJTBDBQRMLLQ-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Cl AETJTBDBQRMLLQ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- 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]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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- 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
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- B01J2531/26—Zinc
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Abstract
本发明公开了一种用于二氧化碳资源化的高性能催化剂及其制备方法，制备方法为：将带有氨基的刚性单体、带有醛基的刚性单体和乳液稳定剂溶在极性有机溶剂中，再逐滴加入非极性有机溶剂，搅拌，形成高内相乳液，加热，反应，依次用丙酮，四氢呋喃，二氯乙烷和水洗，过滤，得到固体，浸泡在金属离子水溶液中18‑24小时，过滤，固体干燥，得到用于二氧化碳资源化的高性能催化剂。本发明的方法制备方法简单，原料便宜易得，本发明的用于二氧化碳资源化的高性能催化剂能够高效催化二氧化碳与环氧类单体的环化加成反应，制备成本低。
The invention discloses a high-performance catalyst for carbon dioxide resource utilization and a preparation method thereof. The preparation method is as follows: a rigid monomer with an amino group, a rigid monomer with an aldehyde group and an emulsion stabilizer are dissolved in a polar organic In the solvent, a non-polar organic solvent was added dropwise, stirred to form a high internal phase emulsion, heated, reacted, washed with acetone, tetrahydrofuran, dichloroethane and water in turn, filtered to obtain a solid, immersed in an aqueous solution of metal ions 18 ‑24 hours, filtration, and solid drying to obtain a high-performance catalyst for carbon dioxide recycling. The method of the invention has simple preparation method, cheap and readily available raw materials, and the high-performance catalyst for carbon dioxide resource utilization of the invention can efficiently catalyze the cycloaddition reaction of carbon dioxide and epoxy monomers, and the preparation cost is low.
Description
技术领域technical field
本发明属于催化剂制备领域，特别是涉及一种用于二氧化碳资源化的高性能催化剂及其制备方法。The invention belongs to the field of catalyst preparation, and particularly relates to a high-performance catalyst for carbon dioxide recycling and a preparation method thereof.
背景技术Background technique
随着经济的发展，人们对化石燃料、煤炭和天燃气的需求与日俱增，这导致了大量的二氧化碳被排放到空气中，并造成了诸如温室效应等严重的环境问题。二氧化碳，因具有易获取，可再生，以及低毒性等特点，是最常见的单碳碳源之一，并被广泛的用于化学合成中。因此，探索高效廉价的二氧化碳催化技术来制备合成有价值的化工原料具有重要价值，并受到国内外学者的广泛关注。在众多化工产品中，碳酸酯类物质，如碳酸丙烯酯，碳酸乙烯酯，氯代碳酸乙烯酯，氯代碳酸丙烯酯等，是一种重要的二氧化碳转换产物。其具有高沸点，高闪点，高极性，低蒸气压以及绿色环保等特性，常用于锂离子电池的电解液和聚合反应的介质溶剂等。With the development of economy, people's demand for fossil fuels, coal and natural gas is increasing day by day, which leads to a large amount of carbon dioxide being released into the air and causes serious environmental problems such as greenhouse effect. Carbon dioxide is one of the most common single-carbon carbon sources and is widely used in chemical synthesis due to its easy availability, reproducibility, and low toxicity. Therefore, it is of great value to explore efficient and cheap carbon dioxide catalysis technology to prepare and synthesize valuable chemical raw materials, and has received extensive attention from scholars at home and abroad. Among many chemical products, carbonates, such as propylene carbonate, ethylene carbonate, chloroethylene carbonate, chloropropylene carbonate, etc., are an important carbon dioxide conversion product. It has the characteristics of high boiling point, high flash point, high polarity, low vapor pressure and environmental protection, and is often used in the electrolyte of lithium ion batteries and the medium solvent of polymerization reaction.
在早期的研究中，通常采用带有金属中心离子的Salen类小分子催化剂进行二氧化碳和环氧丙烷的均相催化反应。该类方法的局限之处在于反应后小分子催化剂难于分离再生。另一方面，由于小分子催化剂对二氧化碳的吸附性能较差，限制了其催化活性。近年来在国内外的研究中，学者们采用含有金属中心的有机或无机微孔材料，如MOF，分子筛等材料作为非均相催化剂。相较于Salen类小分子催化剂，非均相催化剂可以通过过滤，离心等操作直接从产物中分离出来。然而，这些非均相催化剂的效率较低，且制备成本较高。In earlier studies, Salen-type small-molecule catalysts with metal central ions were usually used for the homogeneous catalytic reaction of carbon dioxide and propylene oxide. The limitation of this type of method is that it is difficult to separate and regenerate the small molecule catalyst after the reaction. On the other hand, the catalytic activity of small-molecule catalysts is limited due to their poor adsorption performance for carbon dioxide. In recent years, in research at home and abroad, scholars have used organic or inorganic microporous materials containing metal centers, such as MOF, molecular sieves and other materials as heterogeneous catalysts. Compared with Salen-based small molecule catalysts, heterogeneous catalysts can be directly separated from products by filtration, centrifugation and other operations. However, these heterogeneous catalysts are less efficient and expensive to prepare.
发明内容SUMMARY OF THE INVENTION
本发明针对现有技术的不足，提供一种用于二氧化碳资源化的高性能催化剂。Aiming at the deficiencies of the prior art, the present invention provides a high-performance catalyst for carbon dioxide resource utilization.
本发明的第二个目的是提供一种用于二氧化碳资源化的高性能催化剂的制备方法。The second object of the present invention is to provide a method for preparing a high-performance catalyst for carbon dioxide recycling.
本发明的技术方案概述如下：The technical scheme of the present invention is summarized as follows:
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1：0.4-1.6：1.5-4.5：5-13的比例，将带有氨基的刚性单体、带有醛基的刚性单体和乳液稳定剂溶在极性有机溶剂中，再逐滴加入非极性有机溶剂，所述极性有机溶剂和非极性有机溶剂的体积比为1：3-5，搅拌，形成高内相乳液，加热至140-170℃，反应72-96 小时，依次用丙酮，四氢呋喃，二氯乙烷和水洗，过滤，得到固体，浸泡在金属离子水溶液中18-24小时，过滤，固体干燥，得到用于二氧化碳资源化的高性能催化剂。According to the mass ratio of 1:0.4-1.6:1.5-4.5:5-13, the rigid monomer with amino group, the rigid monomer with aldehyde group and the emulsion stabilizer are dissolved in polar organic solvent, and then Add dropwise a non-polar organic solvent, the volume ratio of the polar organic solvent to the non-polar organic solvent is 1:3-5, stir to form a high internal phase emulsion, heat to 140-170 ° C, and react 72-96 hours, washed with acetone, tetrahydrofuran, dichloroethane and water in turn, filtered to obtain solid, soaked in metal ion aqueous solution for 18-24 hours, filtered, and dried to obtain a high-performance catalyst for carbon dioxide recycling.
优选地，带有氨基的刚性单体为三聚氰胺，对苯二胺，均苯三胺或联苯二胺。Preferably, the amino group-bearing rigid monomer is melamine, p-phenylenediamine, trimesyltriamine or biphenylenediamine.
优选地，带有醛基的刚性单体为多聚甲醛，对苯二甲醛，均苯三甲醛或联苯二甲醛。Preferably, the rigid monomer bearing an aldehyde group is paraformaldehyde, terephthalaldehyde, trimesaldehyde or biphenyldialdehyde.
优选地，乳液稳定剂为
优选地，极性有机溶剂为二甲基甲酰胺，二甲基乙酰胺或二甲亚砜。Preferably, the polar organic solvent is dimethylformamide, dimethylacetamide or dimethylsulfoxide.
优选地，非极性有机溶剂为石油醚，IsoparTMG或IsoparTMM。Preferably, the non-polar organic solvent is petroleum ether, Isopar ™ G or Isopar ™ M.
优选地，金属离子为锌，钴，铜或铁。Preferably, the metal ion is zinc, cobalt, copper or iron.
上述方法制备的用于二氧化碳资源化的高性能催化剂。The high-performance catalyst for carbon dioxide recycling prepared by the above method.
本发明的优点：Advantages of the present invention:
本发明的方法制备方法简单，原料便宜易得，本发明的用于二氧化碳资源化的高性能催化剂能够高效催化二氧化碳与环氧类单体的环化加成反应，制备成本低。The method of the invention has simple preparation method, cheap and readily available raw materials, and the high-performance catalyst for carbon dioxide resource utilization of the invention can efficiently catalyze the cycloaddition reaction of carbon dioxide and epoxy monomers, and the preparation cost is low.
附图说明Description of drawings
图1为实施例1制备的用于二氧化碳资源化的高性能催化剂形貌照片。其中，a为其扫面电子显微镜照片，b和c均为高分辨透射电子显微镜照片。FIG. 1 is a photograph of the morphology of the high-performance catalyst for carbon dioxide recycling prepared in Example 1. Among them, a is the scanning electron microscope image, and b and c are high-resolution transmission electron microscope images.
具体实施方式Detailed ways
通过以下实施例将有助于理解本发明，但并不限制本发明的内容。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The following examples will help to understand the present invention, but do not limit the content of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，多聚甲醛和
从图中可以看出，a图表明结构内具有大量的大孔结构，而在b图内可以看到在其孔壁内由同时存在介孔孔道。c图中的栅格结构则表明材料内还存在大量微孔结构。该结构是由带有氨基的单体与带有醛基的单体通过席夫碱反应聚合形成。As can be seen from the figure, a picture shows that there are a large number of macroporous structures in the structure, and in b picture, it can be seen that there are mesoporous channels in its pore walls at the same time. The grid structure in figure c shows that there are still a lot of microporous structures in the material. The structure is formed by the polymerization of monomers with amino groups and monomers with aldehyde groups through Schiff base reaction.
用于二氧化碳资源化的高性能催化剂催化性能表征：Characterization of catalytic performance of high-performance catalysts for carbon dioxide recycling:
将16.5mg用于二氧化碳资源化的高性能催化剂，0.414mg四丁基溴化铵与15mL环氧丙烷加入25mL反应釜中，向反应釜内通入二氧化碳并加压至2MPa。该反应在100℃下进行，反应时间为30min。反应结束后，向产物液中加入等体积的1,1,2,2-四氯乙烷作为内标溶剂，利用液体核磁共振光谱分析仪(NMR)表征该混合液成分，根据产物与内标溶剂峰强度来计算反应的转化率和TOF。反应中，每克环氧丙烷催化剂用量为0.75mg，测得碳酸丙烯酯其转化率为79.2％，其TOF值高达18430。16.5mg of high-performance catalyst for carbon dioxide recycling, 0.414mg of tetrabutylammonium bromide and 15mL of propylene oxide were added to a 25mL reaction kettle, and carbon dioxide was introduced into the reaction kettle and pressurized to 2MPa. The reaction was carried out at 100°C and the reaction time was 30 min. After the reaction, an equal volume of 1,1,2,2-tetrachloroethane was added to the product liquid as the internal standard solvent, and the liquid nuclear magnetic resonance spectrometer (NMR) was used to characterize the components of the mixed liquid. The solvent peak intensity was used to calculate the conversion and TOF of the reaction. In the reaction, the amount of catalyst per gram of propylene oxide was 0.75 mg, the conversion rate of propylene carbonate was measured to be 79.2%, and the TOF value was as high as 18430.
以下各实施例和对比例都采用这种方法测定。The following examples and comparative examples are all determined by this method.
对比例1Comparative Example 1
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，多聚甲醛和
测得其碳酸丙烯酯的转化率37.5％，TOF值为5431。The conversion rate of propylene carbonate was measured to be 37.5%, and the TOF value was 5431.
实施例2Example 2
用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the following steps:
按质量比为1:1.6:4.5:13的比例，将三聚氰胺，多聚甲醛和
测得碳酸丙烯酯的转化率为68.1％，TOF为13451。The conversion of propylene carbonate was found to be 68.1%, and the TOF was 13451.
实施例3Example 3
用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the following steps:
按质量比为1:0.4:1.5:5的比例，将三聚氰胺，多聚甲醛和
测得碳酸丙烯酯的转化率为67.2％，TOF为13642。The conversion of propylene carbonate was found to be 67.2%, and the TOF was 13642.
实施例4Example 4
用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the following steps:
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，多聚甲醛和
测得碳酸丙烯酯的转化率为70.1％，TOF为14453.5。The conversion of propylene carbonate was found to be 70.1% and the TOF was 14453.5.
实施例5Example 5
用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the following steps:
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，多聚甲醛和
测得碳酸丙烯酯的转化率为63.1％，TOF为10571。The conversion of propylene carbonate was found to be 63.1%, and the TOF was 10571.
实施例6Example 6
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，多聚甲醛和
测得碳酸丙烯酯的转化率为65.1％，TOF为11867.1。The conversion of propylene carbonate was found to be 65.1%, and the TOF was 11867.1.
实施例7Example 7
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:1.6:3.7:11.6的比例，将三聚氰胺，对苯二甲醛和
测得碳酸丙烯酯的转化率为64.8％，TOF为10952。The conversion of propylene carbonate was found to be 64.8% and the TOF was 10952.
实施例8Example 8
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:1.6:3.7:11.6的比例，将三聚氰胺，对苯二甲醛和
测得碳酸丙烯酯的转化率为63.2％，TOF为10543。The conversion of propylene carbonate was found to be 63.2% and the TOF was 10543.
实施例9Example 9
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1：0.43：4.1：11.6的比例，将三聚氰胺，对苯二甲醛和
测得碳酸丙烯酯的转化率为67.8％，TOF为14041。The conversion of propylene carbonate was found to be 67.8%, and the TOF was 14041.
实施例10Example 10
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:0.66:1.9:12.3的比例，将对苯二胺，均苯三甲醛和
测得碳酸丙烯酯的转化率为72.4％，TOF为15021。The conversion of propylene carbonate was found to be 72.4%, and the TOF was 15021.
实施例11Example 11
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:1.16:3.2:12.5的比例，将均苯三胺，联苯二甲醛和
测得碳酸丙烯酯的转化率为71.1％，TOF为14935.1。The conversion of propylene carbonate was found to be 71.1% and the TOF was 14935.1.
实施例12Example 12
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:0.6:1.5:6.5的比例，将联苯二胺，均苯三甲醛和
测得碳酸丙烯酯的转化率为73.4％，TOF为15871.4。The conversion of propylene carbonate was found to be 73.4%, and the TOF was 15871.4.
实施例13Example 13
一种用于二氧化碳资源化的高性能催化剂的制备方法，包括如下步骤：A preparation method of a high-performance catalyst for carbon dioxide recycling, comprising the steps of:
按质量比为1:0.6:1.5:6.5的比例，将联苯二胺，均苯三甲醛和
测得碳酸丙烯酯的转化率为75.2％，TOF为16125.4。The conversion of propylene carbonate was found to be 75.2%, and the TOF was 16125.4.
实验证明：实施例2-13制备的用于二氧化碳资源化的高性能催化剂形貌照片与图1的形貌照片相似。Experiments show that the morphology photos of the high-performance catalysts prepared in Examples 2-13 for carbon dioxide recycling are similar to the morphology photos in FIG. 1 .
Claims (6)
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