CN116393167A - 一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂 - Google Patents
一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂 Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 41
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- 239000002815 homogeneous catalyst Substances 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 12
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
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- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- 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
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- WRHHVVPVKLLPFT-UHFFFAOYSA-N 2-o-ethyl 1-o-methyl oxalate Chemical compound CCOC(=O)C(=O)OC WRHHVVPVKLLPFT-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 231100000260 carcinogenicity Toxicity 0.000 description 1
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- 239000013064 chemical raw material Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-O dodecylazanium Chemical compound CCCCCCCCCCCC[NH3+] JRBPAEWTRLWTQC-UHFFFAOYSA-O 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011828 neutral ionic liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 150000003901 oxalic acid esters Chemical group 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229960002695 phenobarbital Drugs 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J31/0279—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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- 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
- B01J31/0298—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 the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,该催化剂为乙酸根离子液体,乙酸盐为含溴或含氯有机物与乙酸盐。酯交换反应的温度为70~100℃,其催化剂用量为草酸二甲酯质量的0.5~10%,本发明所制备的离子液体催化剂为均相催化剂,避免了固体催化剂易堵塞设备、固液分离困难的问题,是一种活性好、稳定性高的新型催化剂。
Description
技术领域
本发明属于化学工业催化领域,尤其涉及一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂。
背景技术
目前国内煤制乙二醇技术整体开工率呈逐年下降的趋势,急需拓宽乙二醇的下游产业,发展一头多尾的煤制乙二醇产业链。酯交换路径合成草酸烷基酯的关键技术,不仅可以解决传统草酸烷基酯工艺合成中存在能耗高、产品收率低、纯度低、精馏中使用含有致癌性的苯作为脱水剂伴生大量含VOC和含盐废水等问题,还是对煤制乙二醇技术的重大补充、突破和产业链高值化延展,对实现“一头多尾”的灵活生产要求有重要的现实意义。
草酸二乙酯可用作溶剂、染料中间体,及油漆、药物的合成,是一种重要的有机化工原料,主要应用在巴基卡丙二酸酯、三乙胺、新诺明药物、苯巴比妥的中间体,更是畅销药“新诺明”主要原料。亦可作为二棉胶化染料、塑料的中间体和纤维、香料的溶剂。在有机合成领域也有很大应用,如草酸二乙酯可以代替剧毒的氯乙酸氰化生产路线,一种新的路线合成丙二酸二乙酯。草酸二乙酯也可用于制造塑料促进剂,是电视机显像管喷涂阴极的溶液的组成成分。由于草酸二乙酯分子中含有羰基,乙氧基等官能团,故可用作染料的中间体、纤维素和香料的溶剂,与丙酮,乙醇混用可作为天然或合成树脂的溶剂、纺织工业中的助剂以及低温轴承耐高压的润滑剂等。
草酸二乙酯合成路线主要包括酸醇酯化法和CO氧化偶联法。酸醇酯化法在一般采用无机酸(如浓硫酸等)或强酸性离子交换树脂为催化剂,在过程中会产生大量含VOC和含盐的废水,存在能耗高、产品收率和纯度低且原料草酸易腐蚀设备等问题。如果以乙二酸自身为酯化催化剂,则存在反应时间长,反应不完全的问题。CO氧化羰化法采用Pd系贵金属催化剂,生产成本高,在反应过程中催化剂易流失,副产物会造成环境污染。而草酸二甲酯通过酯交换路径和乙醇合成草酸二乙酯,此工艺反应能耗低,副产物甲醇极易分离出反应体系,反应可以进行得十分彻底,无设备腐蚀等问题,且产品草酸二乙酯纯度高,是一个绿色高效的合成工艺。
酯交换法生产烷基酯的工艺中,催化剂是反应的关键要素。专利CN 109081779 A公开了一种由酯交换路径合成草酸对称酯的工艺,该工艺所用催化剂为一种多功能复合碱性材料,催化剂载体为具有介孔和微孔结构的分子筛,负载一种或多种金属元素作为活性组分;其使用量为所述原料总质量的0 .3%~5%。专利CN 111672493 A公开了一种碱性介孔催化剂及其制备方法及应用,所述催化剂为大比表面、大孔径以及高碱含量和中强碱中心介孔氧化镁,它是将镁盐乙酸盐与过饱和碳酸钠溶液控制pH值剧烈搅拌沉淀,老化后经去离子水洗涤至中性,经过滤、干燥和焙烧而成,镁盐乙酸盐包含硝酸镁、硫酸镁和氯化镁等可溶镁盐中的一种或多种。专利CN 108911975 A公开了一种由草酸二甲酯及醇类一步合成对称草酸酯的方法。采用的催化剂为介-微孔复合的多功能碱性催化剂,催化剂通式为X/Z,其中Z为不同拓扑结构的载体,包括拓扑结构为MOR、FAU、MFI、FER、BEA分子筛以及常规SiO2、Al2O3、ZrO2、MgO及ZnO载体中的一种或者多种氧化物;X为Li、Na、K、Ca、Cr、Fe、Al、La中一种或者多种金属的氧化物。但非均相催化剂容易失活,催化草酸酯交换反应稳定性较差。
离子液体是由有机阳离子和无机或有机阴离子构成的在室温下呈液态的有机盐,通常可称为室温离子液体。离子液体作为一种新型的极性溶剂,几乎没有蒸汽压、不可燃性、非挥发性、良好的化学稳定性和热稳定性、可循环利用及对环境友好,故称之为“绿色”化学溶剂,可以用来代替传统的易挥发有毒溶剂。此外,离子液体的高极性、疏水性及溶解性等均可以通过选用不同的阴阳离子和侧链取代基而改变,故又称之为“设计溶剂”。离子液体被认为是21世纪最有希望的绿色溶剂和催化剂之一,已应用于生物催化、分离科学及电化学等诸多领域。将乙酸盐离子液体用于草酸二甲酯与乙醇酯交换合成草酸烷基酯的催化剂尚无报道。
发明内容
为解决现有催化剂容易失活、反应稳定性差的问题,本发明提供一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,即一种均相高效催化草酸二甲酯与乙醇酯交换反应生成草酸甲乙酯和草酸二乙酯的中性离子液体催化剂,反应后又以非均相状态从混合草酸酯分离,并能够循环使用。所发明的离子液体特征是具有乙酸根阴离子的典型结构,该离子液体制备方法简单、酸碱性均较弱并呈中性、但对草酸酯交换反应催化活性高、反应后容易分离、能循环使用且对设备基本没有腐蚀。
如上所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,为乙酸根离子液体,其中碳元素含量为50%-80%,氢元素含量为5%-20%,氮元素含量为2%-20%,氧元素含量为5%-25%。
如上所述的乙酸根离子液体的制备方法为:将一定量的含溴有机物加入乙醇或甲醇中完全溶解,配制成含溴或含氯有机物的溶液A,将一定量的乙酸盐加入乙醇完全溶解,配制成含乙酸盐乙醇溶液,形成溶液B;将溶液A缓慢加入溶液B中,在30-60℃的条件下,充分搅拌1-20h后,过滤分离出固体,将最终得到的滤液进行旋蒸,减压抽滤,最后得到乙酸根离子液体催化剂。
如上所述含溴有机物与乙酸盐的摩尔比为1:1-2.5。
如上所述含溴有机物为含溴或氯有机物为季铵盐中的一种或多种。
如上所述乙酸盐为乙酸钠、乙酸钾等中的一种或两种。
如上所述旋蒸温度为30-50℃,压力为-0.1MPa,时间为1-8h。
如上所述催化剂完成酯交换的反应后,旋蒸出甲醇和乙醇后,催化剂经固液分离后循环使用。
本发明所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,该催化剂具有不可燃性、非挥发性、良好的化学稳定性和热稳定性、可循环利用及对环境友好等优点,是一种安全、绿色、稳定性优的用于草酸二甲酯与乙醇酯交换反应的催化剂。
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。
实施例
分别取70.23g、60.01g以及50.01g乙醇溶解32.24g四丁基溴化铵,配置成溶液A1、A2和A3。135.31g乙醇溶解14.72g乙酸钾,配置成溶液B。分别将A1、A2和A3溶液缓慢加入溶液B中,40℃的条件下充分搅拌10h后,过滤分离出固体溴化钾(KBr),将最终得到的滤液在50℃,转速为30r/min,压力为-0.1MPa的条件下旋蒸2h,得到四丁基乙酸铵离子液体催化剂四丁基乙酸铵-1、四丁基乙酸铵-2和四丁基乙酸铵-3。
上述获得的催化剂用于草酸二甲酯与乙醇酯交换反应中,称取15.00g草酸二甲酯、35.08g乙醇混合加热达到80℃条件下,将离子液体0.075-1.5g加入体系,进行反应考察催化剂性能。
实施例
分别取70.12g、60.11g以及50.15g甲醇溶解32.24g四丁基溴化铵,配置成溶液A4、A5和A6。96.11g甲醇溶解14.72g乙酸钾,配置成溶液B。分别将A4、A5和A6溶液缓慢加入溶液B中,40℃的条件下充分搅拌10h后,过滤分离出固体溴化钾(KBr),将最终得到的滤液在50℃,转速为30r/min,压力为-0.1MPa的条件下旋蒸2h,得到四丁基乙酸铵离子液体催化剂四丁基乙酸铵-4、四丁基乙酸铵-5和四丁基乙酸铵-6。
上述获得的催化剂用于草酸二甲酯与乙醇酯交换反应中,称取15.00g草酸二甲酯、35.08g乙醇混合加热达到80℃条件下,将离子液体0.075-1.5g加入体系,进行反应考察催化剂性能。
表2:制备过程中甲醇溶剂使用量的不同对离子液体催化剂性能的影响
实施例
称取70.03g乙醇溶解32.24g四丁基溴化铵,配置成溶液A7。110.02g乙醇溶解14.72g乙酸钾,配置成溶液B。分别将A7溶液缓慢加入溶液B中,分别在30℃、40℃、50℃、60℃的条件下充分搅拌10h后,过滤分离出固体溴化钾(KBr),将最终得到的滤液在分别在30℃、40℃、50℃、60℃,转速为30r/min,压力为-0.1MPa的条件下旋蒸2h,得到四丁基乙酸铵离子液体催化剂四丁基乙酸铵-7、四丁基乙酸铵-8、四丁基乙酸铵-9和四丁基乙酸铵-10。
上述获得的催化剂用于草酸二甲酯与乙醇酯交换反应中,称取15.00g草酸二甲酯、35.08g乙醇混合加热达到80℃条件下,将离子液体0.075-1.5g加入体系,进行反应考察催化剂性能。
表3:制备温度的不同对离子液体催化剂性能的影响
实施例
分别称取32.24g四丁基溴化铵、21.02g四乙基溴化铵,19.11g1-乙基-3-甲基咪唑溴、40.42g甲基三辛基氯化铵、27.22g苄基三乙基溴化铵、26.39g十二烷基三甲基氯化铵,加入70.20g乙醇使其完全溶解,配置成溶液A11、A12、A13、A14、A15、A16,再称量14.72g乙酸钾(或12.30g乙酸钠),并加入135.31g乙醇使其完全溶解,配置成溶液B,分别将A11、A12、A13、A14、A15、A16溶液缓慢加入溶液B中,40℃的条件下充分搅拌10h后,过滤分离出固体,将最终得到的滤液在40℃,转速为30r/min,压力为-0.1MPa的条件下旋蒸2h,得到四丁基乙酸铵-11、四丁基乙酸铵-12、1-乙基-3-甲基咪唑乙酸盐-13、甲基三辛基乙酸铵-14、苄基三乙基乙酸铵-15、十二烷基三甲基乙酸铵-16。
上述获得的催化剂用于草酸二甲酯与乙醇酯交换反应中,称取15.00g草酸二甲酯、35.08g乙醇混合加热达到80℃条件下,将离子液体0.075-1.5g加入体系,进行反应考察催化剂性能。
表4:乙酸盐的不同对离子液体催化剂性能的影响。
Claims (6)
1.一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于该催化剂为乙酸根离子液体,其中碳元素含量为50%-80%,氢元素含量为5%-20%,氮元素含量为2%-20%,氧元素含量为5%-25%。
2.按照权利要求1所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于将含溴或含氯有机物加入乙醇或甲醇中完全溶解,配制成含溴或含氯有机物的溶液A,将乙酸盐加入乙醇完全溶解,配制成含乙酸盐乙醇溶液,形成溶液B,将溶液A加入溶液B中,在30-60℃的条件下,充分搅拌1-20h后,过滤分离出固体,将最终得到的滤液进行旋蒸,减压抽滤,最后得到乙酸根离子液体催化剂。
3.按照权利要求1、2所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于其含溴或氯有机物与乙酸盐的摩尔比为1:1-2.5。
4.按照权利要求1、2所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于含溴或氯有机物为季铵盐中的一种或多种。
5.按照权利要求1、2所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于乙酸盐为乙酸钠、乙酸钾中的一种或两种。
6.按照权利要求2所述的一种用于草酸二甲酯与乙醇酯交换反应的离子液体催化剂,其特征在于所述旋蒸温度为30-60℃,压力为-0.1MPa,时间为1-8h。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060128996A1 (en) * | 2002-09-26 | 2006-06-15 | Michel Vaultier | Compositions containing Ionic liquids and uses thereof, especially in organic synthesis |
CN101397307A (zh) * | 2008-10-24 | 2009-04-01 | 广东工业大学 | 一种含硅氧烷基的硫酸氢盐离子液体的制备方法 |
CN103524341A (zh) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Brφnsted酸离子液体在制备草酸二苯酯中的应用 |
CN107473933A (zh) * | 2017-08-25 | 2017-12-15 | 如皋市福通纺织化学品有限公司 | 一种含离子性液体催化剂仲丁醇 |
CN109174176A (zh) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | 碱性离子液体催化剂及其制备方法 |
CN111018710A (zh) * | 2019-12-09 | 2020-04-17 | 沈阳化工大学 | 一种碳酸二甲酯的制备方法 |
-
2023
- 2023-03-09 CN CN202310220454.9A patent/CN116393167A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060128996A1 (en) * | 2002-09-26 | 2006-06-15 | Michel Vaultier | Compositions containing Ionic liquids and uses thereof, especially in organic synthesis |
CN101397307A (zh) * | 2008-10-24 | 2009-04-01 | 广东工业大学 | 一种含硅氧烷基的硫酸氢盐离子液体的制备方法 |
CN103524341A (zh) * | 2013-08-26 | 2014-01-22 | 中建安装工程有限公司 | Brφnsted酸离子液体在制备草酸二苯酯中的应用 |
CN107473933A (zh) * | 2017-08-25 | 2017-12-15 | 如皋市福通纺织化学品有限公司 | 一种含离子性液体催化剂仲丁醇 |
CN109174176A (zh) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | 碱性离子液体催化剂及其制备方法 |
CN111018710A (zh) * | 2019-12-09 | 2020-04-17 | 沈阳化工大学 | 一种碳酸二甲酯的制备方法 |
Non-Patent Citations (2)
Title |
---|
QING WANG ET AL.: ""Efficient synthesis of diethyl oxalate from transesterification of dimethyl oxalate and ethanol using alkaline catalysts and kinetic studies of transesterification"", 《NEW JOURNAL OF CHEMISTRY》, vol. 47, 7 February 2023 (2023-02-07), pages 5510 - 5518 * |
忻萍萍: ""室温离子液体中纤维素的溶解及改性研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 3, 15 March 2018 (2018-03-15), pages 014 - 202 * |
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