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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- CN103145551A CN103145551A CN201310076756XA CN201310076756A CN103145551A CN 103145551 A CN103145551 A CN 103145551A CN 201310076756X A CN201310076756X A CN 201310076756XA CN 201310076756 A CN201310076756 A CN 201310076756A CN 103145551 A CN103145551 A CN 103145551A
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Abstract
The invention discloses application of phosphotungstic acid serving as a catalyst in mixed alcohol esterification, and belongs to the field of chemical industries. The application steps are as follows: adding mixed alcohol, acetic acid, phosphotungstic acid and a solvent into a reactor and uniformly mixing; heating to 95-120 DEG C for performing reflux while stirring; stopping the reaction after the reaction is carried out for 1.5-3 hours; stopping the stirring and the heating; cooling to the room temperature to obtain mixed ester. A chemical formula of the phosphotungstic acid is H2PO4.12WO3.xH2O, wherein x is a positive integral from 1 to 12; the mixed alcohol is a mixture of any two of n-butyl alcohol, sec-butyl alcohol or tertiary butanol, or a mixture of n-amyl alcohol and isoamyl alcohol; and the solvent is one of methylbenzene or cyclohexane. Phosphotungstic acid is used as the catalyst, so that C4-C5 mixed alcohol can be reacted well with single acid.
Description
Technical field
The present invention relates to a kind of phospho-wolframic acid as the application of catalyzer in the alcohol mixture esterification, be specifically related to a kind of application of catalyzer of selective esterification reaction of the C4-C5 alcohol based on different spaces steric hindrance structure, the C4-C5 alcohol that this catalyzer is used for different spaces steric hindrance structure generates corresponding ester with acetic acidreaction, belongs to chemical field.
Background technology
Ester is widely used as solvent, spices and sanitas, and is very important in food, industry, daily-use chemical industry and drug manufacture.Esterification is the important reaction of class in organic synthesis, normally by organic acid and alcohol reaction, generates ester and water.At present, phospho-wolframic acid only relates to single pure and mild acid-respons when being applied to the esterification of C4-C5 alcohol and acetic acid as catalyzer, and alcohol mixture yet there are no report with acid-respons simultaneously, and alcohol mixture is significant to the suitability for industrialized production that instructs ester to synthesize with the reaction rule of acid-respons simultaneously.In addition, the different mode of connection with carbochain in the position of reactant alcoholic extract hydroxyl group are different all may be had a great impact the esterification tool, and the different mode of connection with carbochain in position of inquiring into the reactant alcoholic extract hydroxyl group are different all has important directive significance to actual production.
Summary of the invention
The object of the present invention is to provide a kind of phospho-wolframic acid as the application of catalyzer in the alcohol mixture esterification, be specifically related to a kind of application of catalyzer of selective esterification reaction of the C4-C5 alcohol based on different spaces steric hindrance structure.Phospho-wolframic acid can make the C4-C5 alcohol mixture carry out good reaction with single acid simultaneously as catalyzer.
Purpose of the present invention is realized by following technical scheme:
A kind of phospho-wolframic acid is as the application of catalyzer in the alcohol mixture esterification, and step is as follows:
Add alcohol mixture, acetic acid, phospho-wolframic acid and solvent and mix in reactor, under agitation being heated to 95～120 ℃ of backflows, after reaction 1.5h～3h, reaction finishes, and stops stirring, and stopped heating is cooled to room temperature, obtains mixed ester;
The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ xH
2O, x are 1～12 positive integer;
Described alcohol mixture, acetic acid, phospho-wolframic acid and solvent composition reaction solution, wherein, the quality of phospho-wolframic acid accounts for 1.0%～2.0% of reaction solution total mass;
Described alcohol mixture is any two kinds of mixtures in propyl carbinol, sec-butyl alcohol or the trimethyl carbinol, or the mixture of two kinds of Pentyl alcohol and primary isoamyl alcohol;
When described alcohol mixture is in propyl carbinol, sec-butyl alcohol or the trimethyl carbinol during any two kinds of mixtures, the amount of substance of two kinds of alcohol equates, total amount of substance of alcohol mixture and the molar ratio of acetic acid are 0.8:1～1.1:1, and the quality of solvent accounts for 21%～31% of reaction solution total mass;
When described alcohol mixture was the mixture of two kinds of Pentyl alcohol and primary isoamyl alcohol, the amount of substance of two kinds of alcohol equated, total amount of substance of alcohol mixture and the molar ratio of acetic acid are 0.8:1～1.2:1, and the quality of solvent accounts for 13%～22% of reaction solution total mass;
Described solvent is a kind of in toluene or hexanaphthene.
Beneficial effect
Phospho-wolframic acid can make the C4-C5 alcohol mixture carry out good reaction with single acid simultaneously as catalyzer.In propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, the alcohol mixture of any two kinds of compositions can react with acetic acid simultaneously fully, and the productive rate of product differs larger, and this method is convenient to the product separation purification in industrial production; Pentyl alcohol and primary isoamyl alcohol also can fully react with acetic acid simultaneously, and selectivity both and productive rate all higher, hybrid reaction on productive rate almost without affecting.And phospho-wolframic acid has good selectivity and higher catalytic activity, and reaction conditions is gentle, and is environmentally friendly.Can effectively avoid catalyzer itself to the corrosion of conversion unit, the environmental pollution of catalyzer own is slight, effectively impels the production of carboxylicesters to change to green is synthetic, significantly reduces the social cost of Chemical Manufacture.
In addition, the structure of the degree of esterification of the C4-C5 alcohol of different spaces steric hindrance structure and alcohol is that the position of hydroxyl is closely related, esterification ability: primary alconol〉secondary alcohol〉tertiary alcohol.It is little that the mode of connection of carbochain generates the productive rate impact to ester.This has important directive significance to industrial production.
Embodiment
Below in conjunction with specific embodiment in detail the present invention is described in detail, but is not limited to this.
Embodiment 1
With propyl carbinol and each 0.11mol of sec-butyl alcohol, acetic acid 0.20mol, hexanaphthene 8mL, phospho-wolframic acid 0.504g, join successively in the there-necked flask with the reflux water-dividing device, under agitation be heated to 95 ℃ and refluxed 3 hours, reaction finishes, and stops stirring, stopped heating is cooled to room temperature, obtains product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 230 ℃ of vaporizer temperature, detector: FID, detector temperature: 230 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 0min at 50 ℃, be raised to 180 ℃ with the speed of 10 ℃/min, and keep 0min at 180 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, sees Table 1, illustrates in the situation of phospho-wolframic acid as catalyzer, and propyl carbinol and sec-butyl alcohol can react with acetic acid simultaneously fully, and both selectivity and productive rate are all higher, and product is convenient to separating-purifying.
Table 1
Embodiment 2
With sec-butyl alcohol and each 0.1mol of the trimethyl carbinol, acetic acid 0.25mol, hexanaphthene 14mL, phospho-wolframic acid 0.432g, join successively in the there-necked flask with the reflux water-dividing device, under agitation be heated to 95 ℃ and refluxed 2 hours, reaction finishes, and stops stirring, stopped heating is cooled to room temperature, obtains product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ 8H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 240 ℃ of vaporizer temperature, detector: FID, detector temperature: 240 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 0min at 50 ℃, be raised to 180 ℃ with the speed of 10 ℃/min, and keep 0min at 180 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, sees Table 2, illustrates in the situation of phospho-wolframic acid as catalyzer, and sec-butyl alcohol and the trimethyl carbinol can react with acetic acid simultaneously fully, and product is convenient to separating-purifying.
Table 2
Embodiment 3
With propyl carbinol and each 0.1mol of sec-butyl alcohol, acetic acid 0.22mol, hexanaphthene 11mL, phospho-wolframic acid 0.782g, join successively in the there-necked flask with the reflux water-dividing device, under agitation be heated to 95 ℃ and refluxed 1.5 hours, reaction finishes, and stops stirring, stopped heating is cooled to room temperature, obtains product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ 12H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 230 ℃ of vaporizer temperature, detector: FID, detector temperature: 230 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 0min at 50 ℃, be raised to 180 ℃ with the speed of 10 ℃/min, and keep 0min at 180 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, sees Table 3, illustrates in the situation of phospho-wolframic acid as catalyzer, and propyl carbinol and sec-butyl alcohol can react with acetic acid simultaneously fully, and product is convenient to separating-purifying.
Table 3
Embodiment 4
With Pentyl alcohol and each 0.1mol of primary isoamyl alcohol, acetic acid 0.2mol, toluene 5mL, phospho-wolframic acid 0.503g joins in the there-necked flask with reflux water-dividing device and thermometer successively, under agitation being heated to 120 ℃ refluxed 1.5 hours, reaction finishes, and stops stirring stopped heating, be cooled to room temperature, obtain product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 230 ℃ of vaporizer temperature, detector: FID, detector temperature: 230 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 1min at 40 ℃, be raised to 170 ℃ with the speed of 10 ℃/min, and keep 1min at 170 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, see Table 4, illustrate in the situation of phospho-wolframic acid as catalyzer, Pentyl alcohol and primary isoamyl alcohol can react with acetic acid simultaneously fully, and selectivity both is all higher, the n-amyl acetate that obtains and the productive rate of Isoamyl Acetate FCC equate, illustrate that hybrid reaction does not affect productive rate both.
Table 4
Embodiment 5
Each 0.09mol of Pentyl alcohol and primary isoamyl alcohol, acetic acid 0.24mol, toluene 7mL, phospho-wolframic acid 0.752g, join successively in the there-necked flask with reflux water-dividing device and thermometer, under agitation be heated to 120 ℃ and refluxed 2 hours, reaction finishes, and stops stirring, stopped heating is cooled to room temperature, obtains product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ 8H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 230 ℃ of vaporizer temperature, detector: FID, detector temperature: 230 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 1min at 40 ℃, be raised to 170 ℃ with the speed of 10 ℃/min, and keep 1min at 170 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, see Table 5, illustrate in the situation of phospho-wolframic acid as catalyzer, Pentyl alcohol and primary isoamyl alcohol can react with acetic acid simultaneously fully, and selectivity both is all higher, the n-amyl acetate that obtains and the productive rate of Isoamyl Acetate FCC equate, illustrate that hybrid reaction does not affect productive rate both.
Table 5
Embodiment 6
Each 0.13mol of Pentyl alcohol and primary isoamyl alcohol, acetic acid 0.21mol, toluene 12mL, phospho-wolframic acid 0.461g, join successively in the there-necked flask with reflux water-dividing device and thermometer, under agitation be heated to 120 ℃ and returned 3 hours, reaction finishes, and stops stirring, stopped heating is cooled to room temperature, obtains product; The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ 12H
2O。
Adopt external standard method on gas chromatograph, product to be tested:
Test condition: 230 ℃ of vaporizer temperature, detector: FID, detector temperature: 230 ℃, carrier gas: nitrogen (99.9%), splitting ratio: 30:1, N2000 type chromatographic working station processing data.
Separation condition: keep 1min at 40 ℃, be raised to 170 ℃ with the speed of 10 ℃/min, and keep 1min at 170 ℃.
The gas chromatogram that obtains according to test calculates selectivity and productive rate, see Table 6, illustrate in the situation of phospho-wolframic acid as catalyzer, Pentyl alcohol and primary isoamyl alcohol can react with acetic acid simultaneously fully, and selectivity both is all higher, the n-amyl acetate that obtains and the productive rate of Isoamyl Acetate FCC equate, illustrate that hybrid reaction does not affect productive rate both.
Table 6
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the principle of spirit of the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (1)
1. a phospho-wolframic acid is as the application of catalyzer in the alcohol mixture esterification, and it is characterized in that: described applying step is as follows:
Add alcohol mixture, acetic acid, phospho-wolframic acid and solvent and mix in reactor, under agitation being heated to 95～120 ℃ of backflows, after reaction 1.5h～3h, reaction finishes, and stops stirring, and stopped heating is cooled to room temperature, obtains mixed ester;
The chemical formula of described phospho-wolframic acid is H
3PO
4﹒ 12WO
3﹒ xH
2O, x are 1～12 positive integer;
Described alcohol mixture, acetic acid, phospho-wolframic acid and solvent composition reaction solution, wherein, the quality of phospho-wolframic acid accounts for 1.0%～2.0% of reaction solution total mass;
Described alcohol mixture is any two kinds of mixtures in propyl carbinol, sec-butyl alcohol or the trimethyl carbinol, or the mixture of two kinds of Pentyl alcohol and primary isoamyl alcohol;
When described alcohol mixture is in propyl carbinol, sec-butyl alcohol or the trimethyl carbinol during any two kinds of mixtures, the amount of substance of two kinds of alcohol equates, total amount of substance of alcohol mixture and the molar ratio of acetic acid are 0.8:1～1.1:1, and the quality of solvent accounts for 21%～31% of reaction solution total mass;
When described alcohol mixture was the mixture of two kinds of Pentyl alcohol and primary isoamyl alcohol, the amount of substance of two kinds of alcohol equated, total amount of substance of alcohol mixture and the molar ratio of acetic acid are 0.8:1～1.2:1, and the quality of solvent accounts for 13%～22% of reaction solution total mass;
Described solvent is a kind of in toluene or hexanaphthene.
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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 |
Citations (4)
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|---|---|---|---|---|
| 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 | Silicon tungsten, phosphorus heteropoly tungstic acid load type catalyzer used for esterification reaction, manufacturing method and application thereof |
| 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 |
-
2013
- 2013-03-11 CN CN201310076756XA patent/CN103145551A/en active Pending
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 | Silicon tungsten, phosphorus heteropoly tungstic acid load type catalyzer used for esterification reaction, manufacturing method and application thereof |
| 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)
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|---|
| 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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Application publication date: 20130612 |