CN108043456A - A kind of polyacid class ionic-liquid catalyst, preparation method and the method for preparing cyclohexanol with its catalysis ethyl cyclohexyl ester hydrolysis - Google Patents
A kind of polyacid class ionic-liquid catalyst, preparation method and the method for preparing cyclohexanol with its catalysis ethyl cyclohexyl ester hydrolysis Download PDFInfo
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 ethyl cyclohexyl Chemical group 0.000 title claims description 6
- 238000010931 ester hydrolysis Methods 0.000 title claims 2
- 238000006555 catalytic reaction Methods 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 39
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 30
- 230000007062 hydrolysis Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011964 heteropoly acid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical class CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims 2
- 229910020628 SiW12O40 Inorganic materials 0.000 claims 2
- 239000011831 acidic ionic liquid Substances 0.000 claims 2
- 238000007306 functionalization reaction Methods 0.000 claims 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 claims 1
- 150000005837 radical ions Chemical class 0.000 claims 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- BZWQNMUGNDAMBX-UHFFFAOYSA-N butyl butane-1-sulfonate Chemical compound CCCCOS(=O)(=O)CCCC BZWQNMUGNDAMBX-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction 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
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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Abstract
本发明公开了一种多酸类离子液体催化剂、制备方法及用其催化乙酸环己酯水解制备环己醇的方法。该水解制备环己醇的方法以乙酸环己酯为原料，以双磺酸基功能化多酸类离子液体为催化剂，通过水解反应制备环己醇。本发明乙酸环己酯转化率高达91％，环己醇选择性高达95％，环己醇收率达到了87％。本发明所述的方法具有水解反应快，环己醇选择性高，反应条件温和，催化剂易于重复使用等优点。The invention discloses a multi-acid ionic liquid catalyst, a preparation method and a method for preparing cyclohexanol by catalyzing the hydrolysis of cyclohexyl acetate. The method for preparing cyclohexanol by hydrolysis uses cyclohexyl acetate as a raw material, uses a bissulfonic acid functionalized polyacid ionic liquid as a catalyst, and prepares cyclohexanol through a hydrolysis reaction. The conversion rate of cyclohexyl acetate in the invention is as high as 91%, the selectivity of cyclohexanol is as high as 95%, and the yield of cyclohexanol reaches 87%. The method of the invention has the advantages of fast hydrolysis reaction, high selectivity of cyclohexanol, mild reaction conditions, easy reuse of catalyst and the like.
Description
技术领域technical field
本发明涉及一种多酸类离子液体催化剂、制备方法及用其催化乙酸环己酯水解制备环己醇的方法，涉及环己醇的催化合成领域，以及离子液体领域。The invention relates to a multi-acid ionic liquid catalyst, a preparation method and a method for preparing cyclohexanol by catalyzing the hydrolysis of cyclohexyl acetate, and relates to the field of catalytic synthesis of cyclohexanol and the field of ionic liquid.
背景技术Background technique
环己醇是生产己二酸、己二胺、己内酰胺、环己酮等重要化工产品的中间原料，还广泛应用于有机化工、纺织、涂料、染料等领域。目前，环己醇的生产方法主要有环己烷氧化法、苯酚加氢法和环己烯直接水合法。工业上，主要用环己烷氧化法来生产环己醇。然而，由于原料易与空气形成爆炸混合物、环己烷转化率低、环己醇选择性差、能耗高、三废问题严重等缺陷限制了其发展。苯酚加氢法由于苯酚价格较高、反应中需要消耗大量氢气使其发展缓慢。其中，环己烯直接水合法是一种有发展前景的方法，该法原子利用率高、无废弃物和环境污染。但是由于环己烯和水互溶性极差，导致其反应速率慢、单程转化率低、产物分离循环使用增加能耗，而且生产工艺操作难度大，这都限制了其应用。为了克服环己烯直接水合法的种种缺陷，为此，国内外众多学者研究开发了环己烯间接法制备环己醇工艺，即环己烯与羧酸(如乙酸)先酯化，然后再水解制备环己醇。其中，水解作为整个反应的第二个步骤，其重要性不言而喻。Cyclohexanol is an intermediate raw material for the production of important chemical products such as adipic acid, hexamethylenediamine, caprolactam, and cyclohexanone, and is also widely used in the fields of organic chemicals, textiles, coatings, and dyes. At present, the production methods of cyclohexanol mainly include cyclohexane oxidation method, phenol hydrogenation method and cyclohexene direct hydration method. Industrially, cyclohexanol is mainly produced by cyclohexane oxidation. However, its development is limited by the disadvantages of raw materials that easily form explosive mixtures with air, low conversion rate of cyclohexane, poor selectivity of cyclohexanol, high energy consumption, and serious waste problems. Due to the high price of phenol and the need to consume a large amount of hydrogen in the reaction, the development of phenol hydrogenation is slow. Among them, the direct hydration method of cyclohexene is a promising method, which has high atom utilization rate, no waste and no environmental pollution. However, due to the extremely poor miscibility of cyclohexene with water, its reaction rate is slow, its single-pass conversion rate is low, product separation and recycling increase energy consumption, and the production process is difficult to operate, which limits its application. In order to overcome the various defects of the direct hydration method of cyclohexene, for this reason, many scholars at home and abroad have researched and developed the process of preparing cyclohexanol by the indirect method of cyclohexene, that is, cyclohexene and carboxylic acid (such as acetic acid) are first esterified, and then Hydrolysis to prepare cyclohexanol. Among them, hydrolysis is the second step of the whole reaction, and its importance is self-evident.
一些新型的催化剂已经应用于乙酸环己酯水解制备环己醇反应过程中，采用酸性阳离子交换树脂、分子筛等催化剂用于水解反应，均获得了一定的收率，但仍然达不到较好的理想反应效果，其转化率与环己醇的选择性较差。例如，酸性阳离子交换树脂催化剂显示出良好的催化活性，但同时也存在一些缺陷，如热稳定性差、易中毒和失活、存在传质等问题。Some novel catalysts have been applied in the reaction process of preparing cyclohexanol by the hydrolysis of cyclohexyl acetate. Catalysts such as acidic cation exchange resins and molecular sieves have been used for the hydrolysis reaction, and certain yields have been obtained, but still do not reach a good yield. Ideal reaction effect, its conversion rate and selectivity of cyclohexanol are poor. For example, acidic cation exchange resin catalysts show good catalytic activity, but there are also some defects, such as poor thermal stability, easy poisoning and deactivation, and mass transfer problems.
综上所述，如何将乙酸环己酯在水解反应中高效地转化为环己醇还存在着一些困难与挑战，如水解反应速率低、反应过程伴随副产物环己烯的产生及环己醇收率偏低等问题。因此，迫切需要开发活性高及可重复使用的环境友好型催化体系以及绿色合成工艺以解决上述关键问题。In summary, there are still some difficulties and challenges in how to efficiently convert cyclohexyl acetate into cyclohexanol in the hydrolysis reaction, such as the low rate of hydrolysis reaction, the generation of by-product cyclohexene and the generation of cyclohexanol during the reaction process. issues such as low yields. Therefore, there is an urgent need to develop highly active and reusable environmentally friendly catalytic systems and green synthesis processes to solve the above key problems.
本发明合成了一种双二甲氨基乙基醚丁基磺酸内酯杂多酸盐催化剂，并将其应用于乙酸环己酯水解合成环己醇。The invention synthesizes a bis-dimethylaminoethyl ether butyl sultone heteropolysalt catalyst, and applies it to the hydrolysis of cyclohexyl acetate to synthesize cyclohexanol.
发明内容Contents of the invention
本发明的目的是解决上述背景技术的不足，提出一种乙酸环己酯水解制备环己醇的新方法，其特点是采用双磺酸基功能化多酸类离子液体为催化剂，以乙酸环己酯为原料，经水解反应生成环己醇。The purpose of the present invention is to solve the deficiencies of the above-mentioned background technology, propose a kind of new method of preparing cyclohexanol by hydrolysis of cyclohexyl acetate, it is characterized in that adopting double sulfonic acid functionalized multi-acid ionic liquid as catalyst, with cyclohexyl acetate Esters are used as raw materials, and cyclohexanol is generated through hydrolysis.
为实现上述发明目的，本发明的技术方案如下：For realizing the above-mentioned purpose of the invention, the technical scheme of the present invention is as follows:
一种多酸类离子液体催化剂，其特征在于，所述催化剂为双磺酸基功能化多酸类离子液体，所述双磺酸基功能化多酸类离子液体为双二甲氨基乙基醚丁基磺酸内酯杂多酸盐，其结构式为：[Bis-Bs-BDMAEE]XA kind of multi-acid ionic liquid catalyst, it is characterized in that, described catalyst is two sulfonic acid functionalized multi-acid ionic liquids, and described disulfonic acid functional multi-acid ionic liquid is bis-dimethylaminoethyl ether Butyl sultone heteropoly acid salt, its structural formula is: [Bis-Bs-BDMAEE]X
上述式中X为以下杂多酸根离子的一种以上：HPW12O40 2-，HPMo12O40 2-，H2SiW12O40 2-，H2PW11VO40 2-，H2PMo11VO40 2-，或H3SiW11VO40 2-。In the above formula, X is one or more of the following heteropolyacid ions: HPW 12 O 40 2- , HPMo 12 O 40 2- , H 2 SiW 12 O 40 2- , H 2 PW 11 VO 40 2- , H 2 PMo 11 VO 40 2- , or H 3 SiW 11 VO 40 2- .
上述双磺酸基功能化多酸类离子液体包括：The above-mentioned disulfonic acid functionalized polyacid ionic liquids include:
[Bis-Bs-BDMAEE]HPW12O40、[Bis-Bs-BDMAEE] HPW 12 O 40 ,
[Bis-Bs-BDMAEE]HPMo12O40、[Bis-Bs-BDMAEE] HPMo 12 O 40 ,
[Bis-Bs-BDMAEE]H2SiW12O40、[Bis-Bs-BDMAEE]H 2 SiW 12 O 40 ,
[Bis-Bs-BDMAEE]H2PW11VO40、[Bis-Bs-BDMAEE]H 2 PW 11 VO 40 、
[Bis-Bs-BDMAEE]H2PMo11VO40、[Bis-Bs-BDMAEE]H 2 PMo 11 VO 40 ,
[Bis-Bs-BDMAEE]H3SiW11VO40等。[Bis-Bs-BDMAEE]H 3 SiW 11 VO 40 etc.
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：将一定体积比的乙酸环己酯和水的反应混合物及多酸类离子液体催化剂投入反应釜进行水解反应，反应完毕后，得到的环己醇混合物出料冷却静置，多酸类离子液体催化剂逐渐从料液中沉淀，经简单过滤即可实现多酸类离子液体催化剂的回收循环利用，液相混合物经进一步蒸馏得到产品环己醇。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: putting a reaction mixture of a certain volume ratio of cyclohexyl acetate and water and a multi-acid ionic liquid catalyst into a reactor for hydrolysis reaction, and the reaction is completed Finally, the obtained cyclohexanol mixture is cooled and left to stand, and the multi-acid ionic liquid catalyst gradually precipitates from the feed liquid, and the recovery and recycling of the multi-acid ionic liquid catalyst can be realized by simple filtration, and the liquid phase mixture is further distilled The product cyclohexanol is obtained.
上述的原料乙酸环己酯与水的体积比为1∶0.5～6；多酸类离子液体催化剂的质量占原料总质量的1～15％；水解反应温度为50～120℃；反应时间为1～12h。The volume ratio of the above-mentioned raw material cyclohexyl acetate to water is 1: 0.5-6; the mass of the multi-acid ionic liquid catalyst accounts for 1-15% of the total mass of the raw material; the hydrolysis reaction temperature is 50-120°C; the reaction time is 1 ~12h.
上述双磺酸基功能化多酸类离子液体的制备方法为：The preparation method of the above-mentioned disulfonic acid functionalized polyacid ionic liquid is:
取一定摩尔量的内鎓盐置于70-100℃水浴中，将杂多酸溶于蒸馏水中形成溶液，将所述溶液滴加到所述鎓盐中，搅拌并冷凝回流10-20h，反应结束后减压蒸馏除去水，洗涤，真空干燥后得到目标产品；所述内鎓盐与杂多酸的摩尔比为1∶1～1.5。Take a certain molar amount of ylide and place it in a water bath at 70-100°C, dissolve the heteropolyacid in distilled water to form a solution, add the solution dropwise to the onium salt, stir and condense to reflux for 10-20h, react After the end, the water is distilled off under reduced pressure, washed, and vacuum-dried to obtain the target product; the molar ratio of the ylide to the heteropolyacid is 1:1-1.5.
上述内鎓盐通过以下方法获得，取一定摩尔量双二甲氨基乙基醚与1，4-丁基磺酸内酯，置于50-80℃下搅拌快速反应，得到白色固体；将所述白色固体用乙酸乙酯洗涤3次过滤后，在60-100℃下真空干燥10-15h，得到内鎓盐；所述双二甲氨基乙基醚与1，4-丁基磺酸内酯的摩尔比为1∶2～3。The above-mentioned ylide is obtained by the following method, taking a certain molar amount of bis-dimethylaminoethyl ether and 1,4-butyl sultone, stirring and reacting rapidly at 50-80°C to obtain a white solid; The white solid was washed with ethyl acetate for 3 times and filtered, then dried under vacuum at 60-100°C for 10-15h to obtain the ylide; The molar ratio is 1:2-3.
上述述杂多酸选自磷钨酸(H3PW12O40)、磷钼酸(H3PMo12O40)、硅钨酸(H4SiW12O40)、磷钨钒酸(H4PW11VO40)、磷钼钒酸(H4PMo11VO40)及硅钨钒酸(H5SiW11VO40)的一种以上。The above-mentioned heteropoly acid is selected from phosphotungstic acid (H 3 PW 12 O 40 ), phosphomolybdic acid (H 3 PMo 12 O 40 ), silicotungstic acid (H 4 SiW 12 O 40 ), phosphotungstic vanadic acid (H 4 One or more of PW 11 VO 40 ), phosphomolybdovanadate (H 4 PMo 11 VO 40 ), and silicotungstovanadate (H 5 SiW 11 VO 40 ).
与现有方法相比，本发明的显著优点在于：Compared with existing methods, the remarkable advantage of the present invention is:
(1)新型双磺酸基功能化多酸类离子液体催化剂催化活性较高，反应条件温和，乙酸环己酯的转化率较及环己醇的选择性高；(1) The new bissulfonic acid group functionalized multi-acid ionic liquid catalyst has high catalytic activity, mild reaction conditions, and the conversion rate of cyclohexyl acetate is higher than that of cyclohexanol;
(2)本发明提供的双磺酸基功能化多酸类离子液体催化剂合成方法简单，稳定性好，绿色对环境友好，解决了无机液体酸催化剂易发生副反应，设备腐蚀严重，产生大量废酸水，造成环境污染等问题；(2) The synthesis method of the disulfonic acid functionalized multi-acid ionic liquid catalyst provided by the present invention is simple, good in stability, green and environmentally friendly, and solves the problem that the inorganic liquid acid catalyst is prone to side reactions, serious equipment corrosion, and a large amount of waste Acid water, causing environmental pollution and other problems;
(3)本发明提供的双磺酸基功能化多酸类离子液体催化剂为固态，反应后经简单过滤、洗涤、烘干处理后即可实现催化剂的回收循环利用，多次使用后仍可保持较高的催化活性，具有广阔的工业化应用前景。(3) The disulfonic acid functionalized multi-acid ionic liquid catalyst provided by the present invention is a solid state, and after the reaction, the recovery and recycling of the catalyst can be realized after simple filtration, washing, and drying treatment, and can still be maintained after multiple uses. It has high catalytic activity and has broad industrial application prospects.
具体实施方式Detailed ways
以下通过具体实施例对本发明做进一步的说明，但本发明的保护范围并不局限于这些实施例。The present invention will be further described through specific examples below, but the protection scope of the present invention is not limited to these examples.
实施例1：Example 1:
一种多酸类离子液体催化剂的制备方法，包括以下步骤：A kind of preparation method of multi-acid ionic liquid catalyst, comprises the following steps:
(1)取一定量双二甲氨基乙基醚(0.1mol)与1，4-丁基磺酸内酯(0.2mol)于圆底烧瓶中，将圆底烧瓶置于60℃下搅拌快速反应，得到白色固体。(1) Take a certain amount of bis-dimethylaminoethyl ether (0.1mol) and 1,4-butyl sultone (0.2mol) in a round-bottomed flask, and place the round-bottomed flask at 60°C for rapid reaction , to obtain a white solid.
(2)将所得固体用乙酸乙酯洗涤3次过滤后，在80℃下真空干燥12h，得到的白色固体为内鎓盐。然后取一定量的内鎓盐(0.1mol)置于圆底烧瓶中，并置于80℃水浴中。取0.1mol的磷钨酸(H3PW12O40)溶于蒸馏水中并逐滴加入圆底烧瓶中，搅拌并冷凝回流16h。反应结束后减压蒸馏除去水，得到淡黄色固体，将所得的固体使用乙醚和甲苯依次洗涤3次后，在80℃下真空干燥12h可得到催化剂[Bis-Bs-BDMAEE]HPW12O40。(2) The obtained solid was washed three times with ethyl acetate and filtered, then vacuum-dried at 80° C. for 12 h, and the obtained white solid was an ylide. Then a certain amount of ylide (0.1 mol) was placed in a round bottom flask and placed in a water bath at 80°C. Dissolve 0.1 mol of phosphotungstic acid (H 3 PW 12 O 40 ) in distilled water and add it dropwise into a round bottom flask, stir and reflux for 16 hours. After the reaction, the water was distilled off under reduced pressure to obtain a light yellow solid, which was washed three times with ether and toluene in sequence, and dried in vacuum at 80°C for 12 hours to obtain the catalyst [Bis-Bs-BDMAEE]HPW 12 O 40 .
将磷钨酸(H3PW12O40)替换为磷钼酸(H3PMo12O40)、硅钨酸(H4SiW12O40)、磷钨钒酸(H4PW11VO40)、磷钼钒酸(H4PMo11VO40)、硅钨钒酸(H5SiW11VO40)，用同样的方法可以制备Replace phosphotungstic acid (H 3 PW 12 O 40 ) with phosphomolybdic acid (H 3 PMo 12 O 40 ), silicotungstic acid (H 4 SiW 12 O 40 ), phosphotungstic vanadic acid (H 4 PW 11 VO 40 ) , phosphomolybdovanadate (H 4 PMo 11 VO 40 ), silicotungstovanadate (H 5 SiW 11 VO 40 ), can be prepared by the same method
[Bis-Bs-BDMAEE]HPMo12O40、[Bis-Bs-BDMAEE] HPMo 12 O 40 ,
[Bis-Bs-BDMAEE]H2SiW12O40、[Bis-Bs-BDMAEE]H 2 SiW 12 O 40 ,
[Bis-Bs-BDMAEE]H2PW11VO40、[Bis-Bs-BDMAEE]H 2 PW 11 VO 40 、
[Bis-Bs-BDMAEE]H2PMo11VO40、[Bis-Bs-BDMAEE]H 2 PMo 11 VO 40 ,
[Bis-Bs-BDMAEE]H3SiW11VO40等。[Bis-Bs-BDMAEE]H 3 SiW 11 VO 40 etc.
实施例2：Example 2:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯20mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]HPMo12O40催化剂8.74g(占原料总质量的11％)，搅拌加热升温至反应温度90℃，恒温反应6h，乙酸环己酯转化率为91％，环己醇选择性为95％，环己醇的收率为87％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 20mL, water 60mL and [Bis-Bs-BDMAEE] obtained in Example 1 HPMo 12 O 40 catalyst 8.74g (accounting for 11% of the total mass of raw materials), stirring and heating to a reaction temperature of 90°C, constant temperature reaction for 6h, the conversion rate of cyclohexyl acetate is 91%, the selectivity of cyclohexanol is 95%, and the cyclohexanol selectivity is 95%. The yield of hexanol was 87%.
实施例3：Example 3:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯40mL，水20mL和实施例1中制得的[Bis-Bs-BDMAEE]HPW12O40催化剂2.94g(占原料总质量的5％)，搅拌加热升温至反应温度120℃，恒温反应3h，乙酸环己酯转化率为34％，环己醇选择性为65％，环己醇的收率为22％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 40mL, [Bis-Bs-BDMAEE] obtained in water 20mL and embodiment 1 2.94g of HPW 12 O 40 catalyst (accounting for 5% of the total mass of raw materials), stirring and heating to a reaction temperature of 120°C, constant temperature reaction for 3h, the conversion rate of cyclohexyl acetate is 34%, the selectivity of cyclohexanol is 65%, and the cyclohexanol selectivity is 65%. The yield of hexanol was 22%.
实施例4：Example 4:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯10mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]H2SiW12O40催化剂10.46g(占原料总质量的15％)，搅拌加热升温至反应温度70℃，恒温反应12h，乙酸环己酯转化率为36％，环己醇选择性为84％，环己醇的收率为30％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 10mL, water 60mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 2 SiW 12 O 40 catalyst 10.46g (accounting for 15% of the total mass of raw materials), stirring and heating to a reaction temperature of 70°C, constant temperature reaction for 12 hours, the conversion rate of cyclohexyl acetate was 36%, and the selectivity of cyclohexanol was 84% , the yield of cyclohexanol was 30%.
实施例5：Example 5:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯20mL，水40mL和实施例1中制得的[Bis-Bs-BDMAEE]H2PW11VO40催化剂5.35g(占原料总质量的9％)，搅拌加热升温至反应温度100℃，恒温反应8h，乙酸环己酯转化率为81％，环己醇选择性为83％，环己醇的收率为67％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 20mL, water 40mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 2 PW 11 VO 40 catalyst 5.35g (accounting for 9% of the total mass of raw materials), stirring and heating to a reaction temperature of 100°C, constant temperature reaction for 8 hours, the conversion rate of cyclohexyl acetate is 81%, and the selectivity of cyclohexanol is 83% , the yield of cyclohexanol was 67%.
实施例6：Embodiment 6:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯15mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]H3SiW11VO40催化剂0.75g(占原料总质量的1％)，搅拌加热升温至反应温度100℃，恒温反应10h，乙酸环己酯转化率为33％，环己醇选择性为72％，环己醇的收率为24％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 15mL, water 60mL and the [Bis-Bs-BDMAEE] obtained in Example 1 H 3 SiW 11 VO 40 catalyst 0.75g (accounting for 1% of the total mass of raw materials), stirring and heating to a reaction temperature of 100°C, constant temperature reaction for 10 hours, the conversion rate of cyclohexyl acetate is 33%, and the selectivity of cyclohexanol is 72% , the yield of cyclohexanol was 24%.
实施例7：Embodiment 7:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯40mL，水40mL和实施例1中制得的[Bis-Bs-BDMAEE]H2PMo11VO40催化剂10.25g(占原料总质量的13％)，搅拌加热升温至反应温度50℃，恒温反应7h，乙酸环己酯转化率为64％，环己醇选择性为70％，环己醇的收率为45％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 40mL, water 40mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 2 PMo 11 VO 40 catalyst 10.25g (accounting for 13% of the total mass of raw materials), stirring and heating to a reaction temperature of 50°C, constant temperature reaction for 7 hours, the conversion rate of cyclohexyl acetate is 64%, and the selectivity of cyclohexanol is 70% , the yield of cyclohexanol was 45%.
实施例8：Embodiment 8:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯20mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]HPW12O40催化剂5.56g(占原料总质量的7％)，搅拌加热升温至反应温度80℃，恒温反应5h，乙酸环己酯转化率为65％，环己醇选择性为89％，环己醇的收率为58％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 20mL, water 60mL and [Bis-Bs-BDMAEE] obtained in Example 1 HPW 12 O 40 catalyst 5.56g (accounting for 7% of the total mass of raw materials), stirring and heating to a reaction temperature of 80°C, and constant temperature reaction for 5h, the conversion rate of cyclohexyl acetate was 65%, and the selectivity of cyclohexanol was 89%. The yield of hexanol was 58%.
实施例9：Embodiment 9:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯10mL，水50mL和实施例1中制得的[Bis-Bs-BDMAEE]H2SiW12O40催化剂1.79g(占原料总质量的3％)，搅拌加热升温至反应温度110℃，恒温反应1h，乙酸环己酯转化率为21％，环己醇选择性为75％，环己醇的收率为16％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 10mL, water 50mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 2 SiW 12 O 40 catalyst 1.79g (accounting for 3% of the total mass of raw materials), stirring and heating to a reaction temperature of 110°C, and constant temperature reaction for 1 hour, the conversion rate of cyclohexyl acetate is 21%, and the selectivity of cyclohexanol is 75% , the yield of cyclohexanol was 16%.
实施例10：Example 10:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯10mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]HPMo12O40催化剂6.27g(占原料总质量的9％)，搅拌加热升温至反应温度60℃，恒温反应10h，乙酸环己酯转化率为89％，环己醇选择性为85％，环己醇的收率为76％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 10mL, water 60mL and [Bis-Bs-BDMAEE] obtained in Example 1 HPMo 12 O 40 catalyst 6.27g (accounting for 9% of the total mass of raw materials), stirring and heating to a reaction temperature of 60°C, constant temperature reaction for 10h, the conversion rate of cyclohexyl acetate was 89%, the selectivity of cyclohexanol was 85%, and the cyclohexanol selectivity was 85%. The yield of hexanol was 76%.
实施例11：Example 11:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯15mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]H2PW11VO40催化剂11.18g(占原料总质量的15％)，搅拌加热升温至反应温度90℃，恒温反应7h，乙酸环己酯转化率为86％，环己醇选择性为88％，环己醇的收率为76％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 15mL, water 60mL and the [Bis-Bs-BDMAEE] obtained in Example 1 H 2 PW 11 VO 40 catalyst 11.18g (accounting for 15% of the total mass of raw materials), stirring and heating to a reaction temperature of 90°C, constant temperature reaction for 7 hours, the conversion rate of cyclohexyl acetate was 86%, and the selectivity of cyclohexanol was 88% , the yield of cyclohexanol was 76%.
实施例12：Example 12:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯10mL，水60mL和实施例1中制得的[Bis-Bs-BDMAEE]H3SiW11VO40催化剂6.27g(占原料总质量的9％)，搅拌加热升温至反应温度60℃，恒温反应12h，乙酸环己酯转化率为26％，环己醇选择性为82％，环己醇的收率为21％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 10mL, water 60mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 3 SiW 11 VO 40 catalyst 6.27g (accounting for 9% of the total mass of raw materials), stirring and heating to a reaction temperature of 60°C, constant temperature reaction for 12 hours, the conversion rate of cyclohexyl acetate was 26%, and the selectivity of cyclohexanol was 82% , the yield of cyclohexanol was 21%.
实施例13：Example 13:
一种多酸类离子液体催化乙酸环己酯水解的方法，包括以下步骤：在反应釜内，依次加入乙酸环己酯10mL，水50mL和实施例1中制得的[Bis-Bs-BDMAEE]H2PMo11VO40催化剂2.99g(占原料总质量的5％)，搅拌加热升温至反应温度120℃，恒温反应4h，乙酸环己酯转化率为63％，环己醇选择性为80％，环己醇的收率为50％。A method for the hydrolysis of cyclohexyl acetate catalyzed by a multi-acid ionic liquid, comprising the following steps: in the reactor, successively add cyclohexyl acetate 10mL, water 50mL and [Bis-Bs-BDMAEE] obtained in Example 1 H 2 PMo 11 VO 40 catalyst 2.99g (accounting for 5% of the total mass of raw materials), stirring and heating to a reaction temperature of 120°C, constant temperature reaction for 4 hours, the conversion rate of cyclohexyl acetate is 63%, and the selectivity of cyclohexanol is 80% , the yield of cyclohexanol was 50%.
以上所述，仅为本发明的较佳实施例而已，故不能以此限定本发明实施的范围，及依本发明申请的专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明专利涵盖的范围内。The above is only a preferred embodiment of the present invention, so the scope of the present invention cannot be limited with this, and the equivalent changes and modifications made according to the scope of the patent application for the present invention and the contents of the description should still belong to the present invention. within the scope of invention patents.
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| CN114933666A (en) * | 2022-05-31 | 2022-08-23 | 河南大学 | Metal-doped polyionic liquid catalyst for hydrogenation of cyclohexyl acetate, preparation method and application thereof |
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