CN103145551A - Application of phosphotungstic acid serving as catalyst in mixed alcohol esterification - Google Patents
Application of phosphotungstic acid serving as catalyst in mixed alcohol esterification Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 13
- 230000032050 esterification Effects 0.000 title claims abstract description 11
- 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 title abstract description 34
- 239000003054 catalyst Substances 0.000 title abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 21
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims abstract description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract description 15
- 238000010992 reflux Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000010812 external standard method Methods 0.000 description 6
- 238000002309 gasification Methods 0.000 description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229940117955 isoamyl acetate Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- NDPUCEKMWKJTRO-UHFFFAOYSA-N 2-methylpropan-1-ol;pentan-1-ol Chemical compound CC(C)CO.CCCCCO NDPUCEKMWKJTRO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种磷钨酸作为催化剂在混合醇酯化中的应用，属于化工领域。所述应用步骤如下：在反应器中加入混合醇、乙酸、磷钨酸和溶剂并混合均匀，在搅拌下加热至95～120℃回流，反应1.5h～3h后，反应结束，停止搅拌，停止加热，冷却至室温，得到混合酯。所述磷钨酸的化学式为H3PO4﹒12WO3﹒xH2O，x为1～12的正整数；所述混合醇为正丁醇、仲丁醇或叔丁醇中任意两种混合物，或正戊醇和异戊醇两种的混合物；所述溶剂为甲苯或环己烷中的一种。所述磷钨酸作为催化剂能够使C4-C5混合醇同时与单一的酸进行良好的反应。The invention discloses the application of phosphotungstic acid as a catalyst in the esterification of mixed alcohols, belonging to the field of chemical industry. The application steps are as follows: add mixed alcohol, acetic acid, phosphotungstic acid and solvent into the reactor and mix evenly, heat to reflux at 95-120°C under stirring, react for 1.5h-3h, the reaction is over, stop stirring, stop Heated and cooled to room temperature to obtain mixed esters. The chemical formula of the phosphotungstic acid is H 3 PO 4 . 12 WO 3 ． xH 2 O, x is a positive integer of 1 to 12; the mixed alcohol is a mixture of any two of n-butanol, sec-butanol or tert-butanol, or a mixture of n-amyl alcohol and isoamyl alcohol; the solvent One of toluene or cyclohexane. The phosphotungstic acid as a catalyst can make C4-C5 mixed alcohols react well with a single acid at the same time.
Description
技术领域technical field
本发明涉及一种磷钨酸作为催化剂在混合醇酯化中的应用，具体涉及一种基于不同空间位阻结构的C4-C5醇的选择性酯化反应的催化剂的应用，该催化剂用于不同空间位阻结构的C4-C5醇与乙酸反应生成相应的酯，属于化工领域。The invention relates to the application of phosphotungstic acid as a catalyst in the esterification of mixed alcohols, in particular to the application of a catalyst for the selective esterification of C4-C5 alcohols based on different steric hindrance structures. The catalyst is used for different The invention relates to a C4-C5 alcohol with a steric hindrance structure reacting with acetic acid to generate a corresponding ester, which belongs to the field of chemical industry.
背景技术Background technique
酯类物质被广泛地用作溶剂、香料和防腐剂，在食品、工业、日用化工及药物生产中十分重要。酯化反应是有机合成中的一类重要反应，通常是由有机酸和醇反应，生成酯和水。目前，磷钨酸作为催化剂应用于C4-C5醇与乙酸的酯化反应时只涉及单一的醇和酸反应，而混合醇同时与酸反应还未见报道，混合醇同时与酸反应的反应规律对指导酯合成的工业化生产具有重要意义。此外，反应物醇羟基的位置不同和碳链的连接方式不同都可能对酯化反应具有很大的影响，探讨反应物醇羟基的位置不同和碳链的连接方式不同都对实际生产具有重要的指导意义。Esters are widely used as solvents, spices and preservatives, and are very important in food, industry, daily chemical and pharmaceutical production. Esterification is an important reaction in organic synthesis, usually by reacting organic acid and alcohol to generate ester and water. At present, when phosphotungstic acid is used as a catalyst in the esterification reaction of C4-C5 alcohols and acetic acid, only a single alcohol and acid reaction is involved, and mixed alcohols react with acids at the same time. It is of great significance to guide the industrial production of ester synthesis. In addition, the different positions of the alcoholic hydroxyl groups of the reactants and the different connection methods of the carbon chains may have a great impact on the esterification reaction. It is important to explore the different positions of the reactant alcoholic hydroxyl groups and the different connection methods of the carbon chains for actual production. Guiding significance.
发明内容Contents of the invention
本发明的目的在于提供一种磷钨酸作为催化剂在混合醇酯化中的应用，具体涉及一种基于不同空间位阻结构的C4-C5醇的选择性酯化反应的催化剂的应用。磷钨酸作为催化剂能够使C4-C5混合醇同时与单一的酸进行良好的反应。The purpose of the present invention is to provide an application of phosphotungstic acid as a catalyst in the esterification of mixed alcohols, in particular to the application of a catalyst for the selective esterification of C4-C5 alcohols based on different steric hindrance structures. As a catalyst, phosphotungstic acid can make C4-C5 mixed alcohols react well with a single acid at the same time.
本发明的目的由以下技术方案实现：The purpose of the present invention is achieved by the following technical solutions:
一种磷钨酸作为催化剂在混合醇酯化中的应用，步骤如下：A kind of application of phosphotungstic acid as catalyst in the esterification of mixed alcohols, the steps are as follows:
在反应器中加入混合醇、乙酸、磷钨酸和溶剂并混合均匀，在搅拌下加热至95～120℃回流，反应1.5h～3h后，反应结束，停止搅拌，停止加热，冷却至室温，得到混合酯；Add mixed alcohol, acetic acid, phosphotungstic acid and solvent into the reactor and mix evenly, heat to reflux at 95-120°C under stirring, react for 1.5h-3h, the reaction is over, stop stirring, stop heating, cool to room temperature, to obtain mixed esters;
所述磷钨酸的化学式为H3PO4﹒12WO3﹒xH2O，x为1～12的正整数；The chemical formula of the phosphotungstic acid is H 3 PO 4 . 12WO 3 . xH 2 O, x is a positive integer from 1 to 12;
所述混合醇、乙酸、磷钨酸和溶剂组成反应液，其中，磷钨酸的质量占反应液总质量的1.0%～2.0%；The mixed alcohol, acetic acid, phosphotungstic acid and solvent form a reaction solution, wherein the mass of phosphotungstic acid accounts for 1.0% to 2.0% of the total mass of the reaction solution;
所述混合醇为正丁醇、仲丁醇或叔丁醇中任意两种混合物，或正戊醇和异戊醇两种的混合物；The mixed alcohol is any two mixtures of n-butanol, sec-butanol or tert-butanol, or a mixture of n-amyl alcohol and isoamyl alcohol;
当所述混合醇为正丁醇、仲丁醇或叔丁醇中任意两种混合物时，两种醇的物质的量相等，混合醇的总物质的量与乙酸的物质的量比为0.8:1～1.1:1，溶剂的质量占反应液总质量的21%～31%；When the mixed alcohol is any two mixtures in n-butanol, sec-butanol or tert-butanol, the amount of substance of the two alcohols is equal, and the ratio of the total amount of substance of the mixed alcohol to the amount of substance of acetic acid is 0.8: 1～1.1:1, the mass of the solvent accounts for 21%～31% of the total mass of the reaction solution;
当所述混合醇为正戊醇和异戊醇两种的混合物时，两种醇的物质的量相等，混合醇的总物质的量与乙酸的物质的量比为0.8:1～1.2:1，溶剂的质量占反应液总质量的13%～22%；When the mixed alcohol is a mixture of n-amyl alcohol and isoamyl alcohol, the amount of substance of the two alcohols is equal, and the ratio of the total amount of substance of the mixed alcohol to the amount of acetic acid is 0.8:1～1.2:1, The mass of the solvent accounts for 13% to 22% of the total mass of the reaction solution;
所述溶剂为甲苯或环己烷中的一种。The solvent is one of toluene or cyclohexane.
有益效果Beneficial effect
磷钨酸作为催化剂能够使C4-C5混合醇同时与单一的酸进行良好的反应。正丁醇、仲丁醇、叔丁醇中任意两种组成的混合醇能够同时与乙酸充分的反应，产物的产率相差较大，此方法在工业生产中便于产物分离提纯；正戊醇和异戊醇也能够同时与乙酸充分反应，且二者的选择性和产率都较高，混合反应对产率几乎无影响。且磷钨酸具有很好的选择性和较高的催化活性，反应条件温和，对环境友好。可有效地避免催化剂本身对反应设备的腐蚀，催化剂本身对环境污染轻微，有效的促使羧酸酯的生产向绿色合成转变，大幅度减少化工生产的社会成本。As a catalyst, phosphotungstic acid can make C4-C5 mixed alcohols react well with a single acid at the same time. Mixed alcohols composed of any two of n-butanol, sec-butanol, and tert-butanol can fully react with acetic acid at the same time, and the yield of the product is quite different. This method is convenient for product separation and purification in industrial production; n-pentanol and iso-butanol Pentanol can also fully react with acetic acid at the same time, and the selectivity and yield of both are high, and the mixed reaction has almost no influence on the yield. Moreover, phosphotungstic acid has good selectivity and high catalytic activity, mild reaction conditions, and is environmentally friendly. It can effectively avoid the corrosion of the catalyst itself to the reaction equipment, the catalyst itself has slight environmental pollution, effectively promote the transformation of the production of carboxylate to green synthesis, and greatly reduce the social cost of chemical production.
此外，不同空间位阻结构的C4-C5醇的酯化程度与醇的结构即羟基的位置密切相关，酯化能力：伯醇>仲醇>叔醇。碳链的连接方式对酯生成产率影响小。这对工业生产具有重要的指导意义。In addition, the degree of esterification of C4-C5 alcohols with different steric hindrance structures is closely related to the structure of the alcohol, that is, the position of the hydroxyl group, and the esterification ability is: primary alcohol>secondary alcohol>tertiary alcohol. The connection mode of the carbon chain has little effect on the yield of ester formation. This has important guiding significance for industrial production.
具体实施方式Detailed ways
下面结合具体实施例来详述本发明，但不限于此。The present invention will be described in detail below in conjunction with specific examples, but is not limited thereto.
实施例1Example 1
将正丁醇和仲丁醇各0.11mol，乙酸0.20mol，环己烷8mL，磷钨酸0.504g，依次加入到带有回流分水器的三口烧瓶中，在搅拌下加热至95℃回流3小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒H2O。Add 0.11mol each of n-butanol and sec-butanol, 0.20mol of acetic acid, 8mL of cyclohexane, and 0.504g of phosphotungstic acid into a three-necked flask with a reflux water separator, and heat to 95°C under stirring for 3 hours. , the reaction is over, stop stirring, stop heating, cool to room temperature, and get the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12WO 3 . H2O .
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度230℃，检测器：FID，检测器温度：230℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 230°C, detector: FID, detector temperature: 230°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在50℃保持0min，以10℃/min的速度升到180℃，并在180℃保持0min。Separation conditions: keep at 50°C for 0min, raise to 180°C at a rate of 10°C/min, and keep at 180°C for 0min.
根据测试得到的气相色谱图计算选择性和产率，见表1，说明磷钨酸作为催化剂的情况下，正丁醇和仲丁醇能够同时与乙酸充分的反应，二者选择性和产率都较高，且产物便于分离提纯。Calculate selectivity and productive rate according to the gas chromatogram that test obtains, see table 1, under the situation that illustrates phosphotungstic acid as catalyst, n-butanol and sec-butanol can fully react with acetic acid simultaneously, and both selectivity and productive rate are high. Higher, and the product is easy to separate and purify.
表1Table 1
实施例2Example 2
将仲丁醇和叔丁醇各0.1mol，乙酸0.25mol，环己烷14mL，磷钨酸0.432g，依次加入到带有回流分水器的三口烧瓶中，在搅拌下加热至95℃回流2小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒8H2O。Add 0.1 mol of sec-butanol and tert-butanol, 0.25 mol of acetic acid, 14 mL of cyclohexane, and 0.432 g of phosphotungstic acid into a three-necked flask with a reflux separator, and heat to 95°C for 2 hours under stirring. , the reaction is over, stop stirring, stop heating, cool to room temperature, and get the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12WO 3 . 8H2O .
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度240℃，检测器：FID，检测器温度：240℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 240°C, detector: FID, detector temperature: 240°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在50℃保持0min，以10℃/min的速度升到180℃，并在180℃保持0min。Separation conditions: keep at 50°C for 0min, raise to 180°C at a rate of 10°C/min, and keep at 180°C for 0min.
根据测试得到的气相色谱图计算选择性和产率，见表2，说明磷钨酸作为催化剂的情况下，仲丁醇和叔丁醇能够同时与乙酸充分的反应，且产物便于分离提纯。The selectivity and yield were calculated according to the gas chromatogram obtained from the test, as shown in Table 2, which shows that when phosphotungstic acid is used as a catalyst, sec-butanol and tert-butanol can fully react with acetic acid at the same time, and the product is easy to separate and purify.
表2Table 2
实施例3Example 3
将正丁醇和仲丁醇各0.1mol，乙酸0.22mol，环己烷11mL，磷钨酸0.782g，依次加入到带有回流分水器的三口烧瓶中，在搅拌下加热至95℃回流1.5小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒12H2O。Add 0.1mol each of n-butanol and sec-butanol, 0.22mol of acetic acid, 11mL of cyclohexane, and 0.782g of phosphotungstic acid into a three-necked flask with a reflux water separator, and heat to 95°C under stirring for 1.5 hours. , the reaction is over, stop stirring, stop heating, cool to room temperature, and get the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12WO 3 . 12H 2 O.
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度230℃，检测器：FID，检测器温度：230℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 230°C, detector: FID, detector temperature: 230°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在50℃保持0min，以10℃/min的速度升到180℃，并在180℃保持0min。Separation conditions: keep at 50°C for 0min, raise to 180°C at a rate of 10°C/min, and keep at 180°C for 0min.
根据测试得到的气相色谱图计算选择性和产率，见表3，说明磷钨酸作为催化剂的情况下，正丁醇和仲丁醇能够同时与乙酸充分的反应，且产物便于分离提纯。The selectivity and yield were calculated according to the gas chromatogram obtained from the test, as shown in Table 3, which shows that when phosphotungstic acid is used as a catalyst, n-butanol and sec-butanol can fully react with acetic acid at the same time, and the product is easy to separate and purify.
表3table 3
实施例4Example 4
将正戊醇和异戊醇各0.1mol，乙酸0.2mol，甲苯5mL，磷钨酸0.503g，依次加入到带有回流分水器和温度计的三口烧瓶中，在搅拌下加热至120℃回流1.5小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒H2O。Add 0.1 mol each of n-amyl alcohol and isoamyl alcohol, 0.2 mol of acetic acid, 5 mL of toluene, and 0.503 g of phosphotungstic acid into a three-necked flask with a reflux separator and a thermometer, and heat to 120°C under stirring for 1.5 hours. , the reaction is over, stop stirring, stop heating, cool to room temperature, and get the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12 WO 3 ． H2O .
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度230℃，检测器：FID，检测器温度：230℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 230°C, detector: FID, detector temperature: 230°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在40℃保持1min，以10℃/min的速度升到170℃，并在170℃保持1min。Separation conditions: keep at 40°C for 1min, raise to 170°C at a rate of 10°C/min, and keep at 170°C for 1min.
根据测试得到的气相色谱图计算选择性和产率，见表4，说明磷钨酸作为催化剂的情况下，正戊醇和异戊醇能够同时与乙酸充分的反应，且二者的选择性都较高，得到的乙酸正戊酯和乙酸异戊酯的产率相等，说明混合反应并未影响二者的产率。Calculate selectivity and productive rate according to the gas chromatogram that test obtains, see table 4, under the situation that illustrates phosphotungstic acid as catalyst, n-amyl alcohol and isoamyl alcohol can fully react with acetic acid simultaneously, and the selectivity of both is all higher. High, the yields of n-amyl acetate and isoamyl acetate obtained are equal, indicating that the mixed reaction has not affected the yield of the two.
表4Table 4
实施例5Example 5
正戊醇和异戊醇各0.09mol，乙酸0.24mol，甲苯7mL，磷钨酸0.752g，依次加入到带有回流分水器和温度计的三口烧瓶中，在搅拌下加热至120℃回流2小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒8H2O。Add 0.09 mol of n-amyl alcohol and isoamyl alcohol, 0.24 mol of acetic acid, 7 mL of toluene, and 0.752 g of phosphotungstic acid into a three-necked flask with a reflux separator and a thermometer in sequence, and heat to reflux at 120°C for 2 hours while stirring. After the reaction is over, stop stirring, stop heating, and cool to room temperature to obtain the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12WO 3 . 8H2O .
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度230℃，检测器：FID，检测器温度：230℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 230°C, detector: FID, detector temperature: 230°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在40℃保持1min，以10℃/min的速度升到170℃，并在170℃保持1min。Separation conditions: keep at 40°C for 1min, raise to 170°C at a rate of 10°C/min, and keep at 170°C for 1min.
根据测试得到的气相色谱图计算选择性和产率，见表5，说明磷钨酸作为催化剂的情况下，正戊醇和异戊醇能够同时与乙酸充分的反应，且二者的选择性都较高，得到的乙酸正戊酯和乙酸异戊酯的产率相等，说明混合反应并未影响二者的产率。Calculate selectivity and productive rate according to the gas chromatogram that test obtains, see table 5, under the situation that illustrates phosphotungstic acid as catalyst, n-amyl alcohol and isoamyl alcohol can fully react with acetic acid simultaneously, and the selectivity of both is all higher. High, the yields of n-amyl acetate and isoamyl acetate obtained are equal, indicating that the mixed reaction has not affected the yield of the two.
表5table 5
实施例6Example 6
正戊醇和异戊醇各0.13mol，乙酸0.21mol，甲苯12mL，磷钨酸0.461g，依次加入到带有回流分水器和温度计的三口烧瓶中，在搅拌下加热至120℃回3小时，反应结束，停止搅拌，停止加热，冷却至室温，得到产物；所述磷钨酸的化学式为H3PO4﹒12WO3﹒12H2O。Add 0.13mol each of n-amyl alcohol and isoamyl alcohol, 0.21mol of acetic acid, 12mL of toluene, and 0.461g of phosphotungstic acid into a three-necked flask with a reflux separator and a thermometer, and heat to 120°C for 3 hours while stirring. After the reaction is over, stop stirring, stop heating, and cool to room temperature to obtain the product; the chemical formula of phosphotungstic acid is H 3 PO 4 . 12WO 3 . 12H 2 O.
采用外标法在气相色谱仪上对产物进行测试：Adopt external standard method to test product on gas chromatograph:
测试条件：气化室温度230℃，检测器：FID，检测器温度：230℃，载气：氮气（99.9%），分流比：30:1，N2000型色谱工作站处理数据。Test conditions: gasification chamber temperature 230°C, detector: FID, detector temperature: 230°C, carrier gas: nitrogen (99.9%), split ratio: 30:1, N2000 chromatography workstation to process data.
分离条件：在40℃保持1min，以10℃/min的速度升到170℃，并在170℃保持1min。Separation conditions: keep at 40°C for 1min, raise to 170°C at a rate of 10°C/min, and keep at 170°C for 1min.
根据测试得到的气相色谱图计算选择性和产率，见表6，说明磷钨酸作为催化剂的情况下，正戊醇和异戊醇能够同时与乙酸充分的反应，且二者的选择性都较高，得到的乙酸正戊酯和乙酸异戊酯的产率相等，说明混合反应并未影响二者的产率。Calculate selectivity and productive rate according to the gas chromatogram that test obtains, see table 6, under the situation that illustrates phosphotungstic acid as catalyst, n-amyl alcohol and isoamyl alcohol can fully react with acetic acid simultaneously, and the selectivity of both is all higher. High, the yields of n-amyl acetate and isoamyl acetate obtained are equal, indicating that the mixed reaction has not affected the yield of the two.
表6Table 6
本发明包括但不限于以上实施例，凡是在本发明精神的原则之下进行的任何等同替换或局部改进，都将视为在本发明的保护范围之内。The present invention includes but is not limited to the above embodiments, and any equivalent replacement or partial improvement under the principle of the spirit of the present invention will be considered within the protection scope of the present invention.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635929A (en) * | 2000-09-07 | 2005-07-06 | 昭和电工株式会社 | Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester |
| CN101108360A (en) * | 2007-07-05 | 2008-01-23 | 北京服装学院 | A silicon tungsten, phosphotungstic heteropolyacid supported catalyst for esterification, preparation method and application |
| CN101260039A (en) * | 2008-03-13 | 2008-09-10 | 中国烟草总公司郑州烟草研究院 | Method for preparing low grade aliphatic acid polyatomic alcohol mixing ester and application thereof in tobacco |
| CN102452933A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of carboxylic ester |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1635929A (en) * | 2000-09-07 | 2005-07-06 | 昭和电工株式会社 | Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester |
| CN101108360A (en) * | 2007-07-05 | 2008-01-23 | 北京服装学院 | A silicon tungsten, phosphotungstic heteropolyacid supported catalyst for esterification, preparation method and application |
| CN101260039A (en) * | 2008-03-13 | 2008-09-10 | 中国烟草总公司郑州烟草研究院 | Method for preparing low grade aliphatic acid polyatomic alcohol mixing ester and application thereof in tobacco |
| CN102452933A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of carboxylic ester |
Non-Patent Citations (1)
| Title |
|---|
| 荆涛等: "工业混醇催化合成混合酯的研究", 《齐齐哈尔大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557533A (en) * | 2015-01-22 | 2015-04-29 | 中国石油大学(华东) | Method for catalytic synthesis of acetoin short chain fatty acid ester by using phosphotungstic acid |
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