CN102234228A - Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid - Google Patents
Method for synthesizing trimethylolpropane fatty acid ester under catalysis of ionic liquid Download PDFInfo
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 67
- 239000000194 fatty acid Substances 0.000 title claims abstract description 67
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 67
- -1 trimethylolpropane fatty acid ester Chemical class 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title 1
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 9
- 239000008158 vegetable oil Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 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 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 24
- 239000002253 acid Substances 0.000 abstract description 18
- 239000006227 byproduct Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
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- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- FMNZBNCPTJEVDS-KVVVOXFISA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;(z)-octadec-9-enoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O FMNZBNCPTJEVDS-KVVVOXFISA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及一种离子液体催化合成三羟甲基丙烷脂肪酸脂的方法,它以三羟甲基丙烷和脂肪酸为原料,将三羟甲基丙烷与脂肪酸加入反应釜中,在酸性离子液体催化剂和带水剂作用下,进行脱水酯化反应,脱水酯化反应温度为120~180℃、反应时间为4~10小时,直至无水馏出,降温后,静置分离离子液体催化剂,得到三羟甲基丙烷脂肪酸酯,该方法具有合成简单,催化活性高,反应选择性高、无副产物生成,提高酯转化率、产品质量稳定,良好的水解稳定性,良好的生物降解性和低挥发性,且酸值低的优点及效果。The invention relates to a method for catalyzing and synthesizing trimethylolpropane fatty acid ester by ionic liquid, which uses trimethylolpropane and fatty acid as raw materials, adds trimethylolpropane and fatty acid into a reaction kettle, and reacts with acidic ionic liquid catalyst and Under the action of water-carrying agent, dehydration-esterification reaction is carried out. The dehydration-esterification reaction temperature is 120-180°C, and the reaction time is 4-10 hours, until anhydrous distills out. After cooling down, stand to separate the ionic liquid catalyst to obtain trihydroxy Methyl propane fatty acid ester, the method has the advantages of simple synthesis, high catalytic activity, high reaction selectivity, no by-product generation, improved ester conversion rate, stable product quality, good hydrolysis stability, good biodegradability and low volatility properties, and the advantages and effects of low acid value.
Description
技术领域 technical field
本发明涉及一种离子液体催化合成三羟甲基丙烷油酸脂的方法,特别是用酸性离子液体催化合成三羟甲基丙烷脂肪酸酯的方法,属化工材料领域。The invention relates to a method for catalyzing and synthesizing trimethylolpropane oleate with an ionic liquid, in particular to a method for catalyzing and synthesizing trimethylolpropane fatty acid ester with an acidic ionic liquid, belonging to the field of chemical materials.
背景技术 Background technique
三羟甲基丙烷脂肪酸酯的种类较多,应用领域比较广泛,它具有优异的润滑性能,良好的退火清净性,良好的水解稳定性和低挥发性,适用于金属加工和轧制用油、航空发动机润滑油、化纤油剂等领域。There are many types of trimethylolpropane fatty acid esters, and the application fields are relatively wide. It has excellent lubricating properties, good annealing cleanliness, good hydrolytic stability and low volatility, and is suitable for metal processing and rolling oils , aviation engine lubricants, chemical fiber oils and other fields.
现有三羟甲基丙烷脂肪酸酯的合成方法主要有酸醇酯化法和酯交换法,酸醇酯化法以三羟甲基丙烷和脂肪酸为原料,以对甲苯磺酸、硫酸、钛酸四丁醋等为催化剂或固体催化剂反应而成。使用该类酸性催化剂,需要水洗等过程,或需要过滤过程,工艺比较复杂,而且部分催化剂仍残留在产品中,致使产品在储存过程中质量易发生变化,影响产品稳定性。酯交换法以三羟甲基丙烷和脂肪酸甲酯或乙酯为原料,以碱性催化剂为主,其工艺复杂,反应速度慢,酯化率不高,引入碱性催化剂使后处理复杂。中国专利CN1379014A中公开了一种以固体氧化物为催化剂,采用三羟甲基丙烷和油酸先脱水缩合再加水水解制备三羟甲基丙烷油酸酯的方法,工艺流程复杂,而且还需过滤分离催化剂,对环境造成污染。The synthetic method of existing trimethylolpropane fatty acid ester mainly contains acid alcohol esterification method and transesterification method, acid alcohol esterification method is raw material with trimethylolpropane and fatty acid, with p-toluenesulfonic acid, sulfuric acid, titanic acid Tetrabutyl acetic acid is formed by reaction of catalyst or solid catalyst. The use of such acidic catalysts requires processes such as washing with water, or requires a filtration process. The process is relatively complicated, and some catalysts still remain in the product, resulting in easy changes in the quality of the product during storage and affecting product stability. The transesterification method uses trimethylolpropane and fatty acid methyl ester or ethyl ester as raw materials, and mainly uses basic catalysts. The process is complex, the reaction speed is slow, and the esterification rate is not high. The introduction of basic catalysts makes post-treatment complicated. Chinese patent CN1379014A discloses a method for preparing trimethylolpropane oleate by using solid oxide as a catalyst, using trimethylolpropane and oleic acid to dehydrate and condense and then hydrolyze to prepare trimethylolpropane oleate. Separation of the catalyst causes pollution to the environment.
发明内容 Contents of the invention
本发明的目的正是为了克服上述已有技术的缺点与不足而提供一种以酸性离子液体为催化剂,直接合成三羟甲基丙烷脂肪酸酯的方法,从而工艺方法更简单,反应速度快,酯化率高,得到的产品质量稳定,良好的水解稳定性、生物降解性和低挥发性。Purpose of the present invention provides a kind of with acidic ionic liquid as catalyzer in order to overcome above-mentioned shortcoming and deficiency of prior art, directly synthesizes the method for trimethylolpropane fatty acid ester, thereby process method is simpler, and reaction speed is fast, High esterification rate, stable product quality, good hydrolytic stability, biodegradability and low volatility.
本发明的目的是通过下列技术方案实现的:The purpose of the present invention is achieved through the following technical solutions:
一种离子液体催化合成三羟甲基丙烷脂肪酸酯的方法,它以三羟甲基丙烷和脂肪酸为原料,将三羟甲基丙烷与脂肪酸配比按摩尔比为1~1.2∶3比例加入反应釜中,在酸性离子液体催化剂和带水剂作用下,进行脱水酯化反应,脱水酯化反应温度为120~180℃、反应时间为4~10小时,直至无水馏出,降温后,静置分离离子液体催化剂,得到三羟甲基丙烷脂肪酸酯,A method for catalyzing and synthesizing trimethylolpropane fatty acid ester by ionic liquid, which uses trimethylolpropane and fatty acid as raw materials, and adds trimethylolpropane and fatty acid in a molar ratio of 1 to 1.2:3 In the reaction kettle, under the action of an acidic ionic liquid catalyst and a water-carrying agent, the dehydration esterification reaction is carried out. The dehydration esterification reaction temperature is 120-180 ° C, and the reaction time is 4-10 hours, until no water is distilled out. After cooling down, Stand to separate the ionic liquid catalyst to obtain trimethylolpropane fatty acid ester,
所述脂肪酸为动物油脂肪酸、植物油脂肪酸或两种任意比例混合的工业脂肪酸,The fatty acid is animal oil fatty acid, vegetable oil fatty acid or two kinds of industrial fatty acids mixed in any proportion,
所述的酸性离子液体催化剂为溶解有Lewis酸性的无机盐选自FeCl3、SnCl4、AlCl3、ZnCl2、Zn(NO3)2的离子液体[Hmim]+BF4-或[Heim]+BF4-和[Hbim]+BF4-,酸性离子液体催化剂的加入量为三羟甲基丙烷和脂肪酸总重量的5-20%,Described acidic ionic liquid catalyst is to be dissolved with Lewis acidic inorganic salt and is selected from FeCl3, SnCl4, AlCl3, ZnCl2, Zn(NO3) ionic liquid [Hmim]+BF4- or [Heim]+BF4-and [Hbim] +BF4-, the addition of acidic ionic liquid catalyst is 5-20% of the total weight of trimethylolpropane and fatty acid,
所述的带水剂为环己烷、甲苯或二甲苯的一种或两种或三种任意比例的混合物,带水剂用量与脂肪酸的质量比0.1~1∶1;The water-carrying agent is cyclohexane, toluene or xylene, or a mixture of two or three in any proportion, and the mass ratio of the water-carrying agent to fatty acid is 0.1 to 1:1;
所述的方法,按下述步骤进行:Described method, carry out according to the following steps:
(a)将三羟甲基丙烷与脂肪酸按摩尔比为1~1.2∶3的比例混合加入反应釜中,再加入带水剂,带水剂与脂肪酸的质量比为0.1~1∶1,(a) mixing trimethylolpropane and fatty acid in a ratio of 1 to 1.2:3 in molar ratio and adding to the reaction kettle, then adding water-carrying agent, the mass ratio of water-carrying agent and fatty acid is 0.1 to 1:1,
(b)将离子液体与溶解有Lewis酸性无机盐选自FeCl3、SnCl4、ZnCl2、Zn(NO3)2的配比,按质量比为1∶0.01-1比例混合,制备酸性离子液体催化剂,(b) the ionic liquid and the dissolved Lewis acidic inorganic salt are selected from the proportion of FeCl3, SnCl4, ZnCl2, Zn(NO3)2, mixed in a mass ratio of 1: 0.01-1 to prepare an acidic ionic liquid catalyst,
(c)再将(b)项的酸性离子液体催化剂按三羟甲基丙烷与脂肪酸总重量的5~20%比例加入(a)项物料中,在搅拌下升温至120~180℃,进行脱水酯化反应,馏出反应生成的水,反应4~10h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品。(c) Add the acidic ionic liquid catalyst of item (b) into the material of item (a) according to the ratio of 5-20% of the total weight of trimethylolpropane and fatty acid, and heat up to 120-180° C. under stirring for dehydration In the esterification reaction, the water generated by the reaction was distilled off. After 4-10 hours of reaction, the anhydrous distilled off, the temperature was lowered to 70°C, and the trimethylolpropane fatty acid ester product was obtained by standing and separating.
本发明的三羟甲基丙烷脂肪酸酯的合成方法,以三羟甲基丙烷和脂肪酸为原料,三羟甲基丙烷,别名三甲醇丙烷,分子式为CH3CH2(CH2OH)3,脂肪酸为动物油脂肪酸、植物油脂肪酸或两种任意比例混合的工业油脂肪酸,一般酸值209~235mgKOH/g,三羟甲基丙烷与脂肪酸按摩尔比为1~1.2∶3的比例混合,再将带水剂与脂肪酸的质量比为0.1~1∶1比例混合加入反应釜中,过量的三羟甲基丙烷,可将脂肪酸反应完全,生成部分二酯,既可改善产品的粘温特性,又可使反应进行完全,从而得到低酸值目标产品,简化工艺流程。The synthetic method of trimethylolpropane fatty acid ester of the present invention, take trimethylolpropane and fatty acid as raw material, trimethylolpropane, another name trimethylolpropane, molecular formula is CH3CH2(CH2OH)3, fatty acid is tallow fatty acid, Vegetable oil fatty acid or two kinds of industrial oil fatty acid mixed in any proportion, the general acid value is 209-235mgKOH/g, trimethylolpropane and fatty acid are mixed in a molar ratio of 1-1.2:3, and then the water-carrying agent and the fatty acid The mass ratio is 0.1-1:1 and mixed into the reaction kettle. Excessive trimethylolpropane can completely react the fatty acid and form some diesters, which can not only improve the viscosity-temperature characteristics of the product, but also make the reaction complete. Thereby obtaining the target product with low acid value and simplifying the technological process.
将离子液体与具有Lewis酸性无机盐选自FeCl3、SnCl4、ZnCl2、Zn(NO3)2的与离子液体配比,按质量比为1∶0.01-1比例混合,制备酸性离子液体催化剂,制备出的离子液体酸性强、酸强度均匀,而且无腐蚀性。The ionic liquid is mixed with the ionic liquid having a Lewis acidic inorganic salt selected from FeCl3, SnCl4, ZnCl2, Zn(NO3)2, and the mass ratio is 1: 0.01-1 to prepare an acidic ionic liquid catalyst, and the prepared Ionic liquids are highly acidic, have uniform acid strength, and are non-corrosive.
再将所制备的酸性离子液体催化剂按三羟甲基丙烷与脂肪酸总重量的5~20%比例加入配置的反应物料中,在搅拌下升温至120~180℃,进行脱水酯化反应,馏出反应生成的水,反应4~10h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品。由于离子液体酸性强、酸强度均匀,与原料和反应产物不互溶,可高酯转化率、高选择性生成目标产品,并经静置分离催化剂离子液体与产品。Then the prepared acidic ionic liquid catalyst is added to the prepared reaction material according to the ratio of 5-20% of the total weight of trimethylolpropane and fatty acid, and the temperature is raised to 120-180°C under stirring to carry out the dehydration esterification reaction, distilling The water generated by the reaction, after 4-10 hours of reaction, distilled out without water, cooled to 70°C, and stood to separate to obtain the trimethylolpropane fatty acid ester product. Because the ionic liquid has strong acidity and uniform acid strength, it is immiscible with the raw materials and reaction products, and can generate the target product with high ester conversion rate and high selectivity, and the catalyst ionic liquid and the product can be separated by standing.
由于采取上述技术方案使本发明技术与现有技术相比,具有如下优点及效:Owing to adopting above-mentioned technical scheme to make the technology of the present invention compare with prior art, have following advantage and effect:
(a)由于采用酸性离子液体催化剂合成简单,催化活性高,反应选择性高、无副产物生成,提高酯转化率、高选择性生成三羟甲基丙烷脂肪酸酯产品目标产品。(a) Due to the use of an acidic ionic liquid catalyst, the synthesis is simple, the catalytic activity is high, the reaction selectivity is high, no by-products are generated, the ester conversion rate is improved, and the target product of trimethylolpropane fatty acid ester product is generated with high selectivity.
(b)离子液体催化剂与反应产物容易分离,产品无需精制工序,工艺流程简单、能耗低,反应过程无污染物排放,过程清洁,离子液体催化剂可循环使用,腐蚀性低。(b) The ionic liquid catalyst is easily separated from the reaction product, the product does not require a refining process, the process flow is simple, the energy consumption is low, the reaction process has no pollutant discharge, the process is clean, the ionic liquid catalyst can be recycled, and the corrosion is low.
(c)由本发明合成的三羟甲基丙烷油酸酯,产品质量稳定,具有良好的水解稳定性,良好的生物降解性和低挥发性,且酸值低。(c) The trimethylolpropane oleate synthesized by the present invention has stable product quality, good hydrolysis stability, good biodegradability and low volatility, and low acid value.
具体实施方式 Detailed ways
下面的实例将对本发明提供的方法予以进一步说明,但并不因此限制本发明。The following examples will further illustrate the method provided by the invention, but do not limit the invention thereby.
实施例1:Example 1:
取三羟甲基丙烷134.17g,工业动物油脂肪酸(酸值209mgKOH/g)847.41g混合加入反应釜中,再加入环己烷84.74g,取FeCl3 0.491g与1-甲基咪唑氟硼酸盐[Hmim]+BF4-混合,制备酸性离子液体催化剂49.08g加反应釜中,在搅拌下升温至120℃,进行脱水酯化反应,馏出反应生成的水,反应10h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品922.51g,离子液体48.98g,脂肪酸转化率95%,产品酸值10.7mgKOH/g,无其它副产物。Get 134.17g of trimethylolpropane, 847.41g of industrial tallow fatty acid (acid value 209mgKOH/g) are mixed in the reaction kettle, then add cyclohexane 84.74g, get FeCl 0.491g and 1-methylimidazolium fluoroborate [ Hmim]+BF4- mix, prepare 49.08g of acidic ionic liquid catalyst, add it to the reaction kettle, heat up to 120°C under stirring, carry out dehydration esterification reaction, distill out the water generated by the reaction, and distill out anhydrous after reacting for 10 hours, then cool down After standing at 70°C, 922.51g of trimethylolpropane fatty acid ester product, 48.98g of ionic liquid, 95% conversion rate of fatty acid, 10.7mgKOH/g acid value and no other by-products were obtained.
实施例2:Example 2:
取三羟甲基丙烷161.00g,工业植物油脂肪酸(酸值243mgKOH/g) 847.41g混合加入反应釜中,再加入环己烷423.71g,取SnCl4 8.07g与1-丁基咪唑氟硼酸盐[Hbim]+BF4-混合,制备酸性离子液体催化剂80.67g加反应釜中,在搅拌下升温至140℃,进行脱水酯化反应,馏出反应生成的水,反应6h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品947.89g,离子液体80.52g,脂肪酸转化率97%,产品酸值4.25mgKOH/g,无其它副产物。Get 161.00g of trimethylolpropane, 847.41g of industrial vegetable oil fatty acid (acid value 243mgKOH/g) are mixed and added in the reaction kettle, then add cyclohexane 423.71g, get SnCl 8.07g and 1-butylimidazolium fluoroborate [ Hbim]+BF4- mix, prepare 80.67g of acidic ionic liquid catalyst, add it to the reaction kettle, heat up to 140°C under stirring, carry out dehydration esterification reaction, distill out the water generated by the reaction, after 6 hours of reaction, distill out anhydrous, and cool down After standing at 70°C, 947.89g of trimethylolpropane fatty acid ester product, 80.52g of ionic liquid, 97% conversion rate of fatty acid, 4.25mgKOH/g product acid value, and no other by-products were obtained.
实施例3:Example 3:
取三羟甲基丙烷147.58g,工业植物油脂肪酸(酸值243mgKOH/g) 847.41g混合加入反应釜中,再加入甲苯677.93g,取ZnCl2 49.97g与1-甲基咪唑氟硼酸盐[Hmim]+BF4-混合,制备酸性离子液体催化剂99.50g加反应釜中,在搅拌下升温至150℃,进行脱水酯化反应,馏出反应生成的水,反应10h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品935.18g,离子液体99.35g,脂肪酸转化率99.1%,产品酸值1.45mgKOH/g,无其它副产物。Get 147.58g of trimethylolpropane, 847.41g of industrial vegetable oil fatty acid (acid value 243mgKOH/g) are mixed and added in the reactor, then add toluene 677.93g, get ZnCl 49.97g and 1-methylimidazolium fluoroborate [Hmim] +BF4- mix, prepare 99.50g of acidic ionic liquid catalyst, add it to the reaction kettle, heat up to 150°C under stirring, carry out dehydration esterification reaction, distill out the water generated by the reaction, after 10 hours of reaction, distill out anhydrous, and cool down to 70°C °C, standing and separating to obtain 935.18g of trimethylolpropane fatty acid ester product, 99.35g of ionic liquid, fatty acid conversion rate of 99.1%, product acid value of 1.45mgKOH/g, and no other by-products.
实施例4:Example 4:
取三羟甲基丙烷134.17g,工业植物油脂肪酸与工业植物油脂肪酸按1∶1组合,(酸值224mgKOH/g) 847.41g混合加入反应釜中,再加入二甲苯与环己烷按1∶1组合847.41g,取En(CO3)2 147.24g与1-甲基咪唑氟硼酸盐[Hmim]+BF4-混合,制备酸性离子液体催化剂147.24g加反应釜中,在搅拌下升温至140℃,进行脱水酯化反应,馏出反应生成的水,反应8h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品922.65g,离子液体147.21g,脂肪酸酸转化率99.4%,产品酸值0.71mgKOH/g,无其它副产物。Take 134.17g of trimethylolpropane, industrial vegetable oil fatty acid and industrial vegetable oil fatty acid according to 1:1 combination, (acid value 224mgKOH/g) 847.41g are mixed into the reactor, then add xylene and cyclohexane according to 1:1 combination 847.41g, get En(CO3)2 147.24g mixed with 1-methylimidazolium fluoroborate [Hmim]+BF4-, prepare 147.24g of acidic ionic liquid catalyst and add it to the reaction kettle, heat up to 140°C under stirring, and carry out Dehydration esterification reaction, distilling the water generated by the reaction, after 8 hours of reaction, distilling out anhydrous, cooling to 70°C, standing and separating to obtain 922.65g of trimethylolpropane fatty acid ester product, 147.21g of ionic liquid, fatty acid conversion The yield is 99.4%, the acid value of the product is 0.71mgKOH/g, and there are no other by-products.
实施例5:Example 5:
取三羟甲基丙烷134.17g,工业植物油脂肪酸与工业植物油脂肪酸按1∶2组合,(酸值235mgKOH/g) 847.41g混合加入反应釜中,再加入甲苯与环己烷按1∶0.5组合)423.71g,取Zn(CO3)2 157.05g与1-丁基咪唑氟硼酸盐[Hbim]+BF4-混合,制备酸性离子液体催化剂196.32g加反应釜中,在搅拌下升温至180℃,进行脱水酯化反应,馏出反应生成的水,反应4h后,无水馏出,降温至70℃,静置分离得三羟甲基丙烷脂肪酸酯产品922.63g,离子液体196.29g,脂肪酸转化率99.6%,产品酸值0.65mgKOH/g,无其它副产物。Take 134.17g of trimethylolpropane, industrial vegetable oil fatty acid and industrial vegetable oil fatty acid according to 1:2 combination, (acid value 235mgKOH/g) 847.41g are mixed into the reaction kettle, then add toluene and cyclohexane according to 1:0.5 combination) 423.71g, get Zn(CO3)2 157.05g mixed with 1-butylimidazolium fluoroborate [Hbim]+BF4-, prepare 196.32g of acidic ionic liquid catalyst and add in the reaction kettle, heat up to 180°C under stirring, carry out Dehydration esterification reaction, distilling off the water generated by the reaction, after 4 hours of reaction, distilling off anhydrous, cooling to 70°C, standing and separating to obtain 922.63g of trimethylolpropane fatty acid ester product, 196.29g of ionic liquid, and the conversion rate of fatty acid 99.6%, product acid value 0.65mgKOH/g, no other by-products.
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