CN1541991A - Hydrolysis method of esters - Google Patents
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- CN1541991A CN1541991A CNA031228534A CN03122853A CN1541991A CN 1541991 A CN1541991 A CN 1541991A CN A031228534 A CNA031228534 A CN A031228534A CN 03122853 A CN03122853 A CN 03122853A CN 1541991 A CN1541991 A CN 1541991A
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Abstract
The ester hydrolyzing method includes hydrolyzing ester in water to produce C1-C10 fatty acid or aromatic acid and C1-C4 fatty alcohol under the presence of ammonium salt of heteropoly acid as catalyst. The ammonium salt of heteropoly acid is obtained through the reaction between heteropoly acid in Keggin structure and inorganic ammonium salt or organic amine, the heteropoly acid is selected from phosphotungstic acid, silicotungstic acid, silicomolybdic acid and phosphomolybdic acid; the inorganic ammonium salt is selected from ammonium carbonate, ammonium nitrate, ammonium sulfate, ammonium phosphate and diammonium hydrochloride; and the organic amine is selected from fatty amine, alicyclic amine and arylamine. The said ester hydrolyzing method can obtain high conversion rate in relatively lower water/ester ratio and relatively short time, and the catalyst is cheap and easy to separate from the product.
Description
Technical field
The present invention relates to the method for ester-type hydrolysis and the catalyzer of use.
Technical background
The hydrolysis of ester compound is the important reaction of a class, is widely used in all departments of national economy.For example the hydrolysis of ritalin is to realize the important step that acetic acid and Methanol Recovery recycle in the polyvinyl alcohol industry.Industrial annual a large amount of ritalin byproduct that produces needs that it is hydrolyzed to acetic acid and methanol loop is used, to reduce cost.Existing methyl acetate hydrolysis catalyzer has: resin, heteropolyacid and acidic cs salts of heteropolyacid etc.
Storng-acid cation exchange resin is the methyl acetate hydrolysis catalyzer of present industrial use.The advantage of this catalyzer is: catalyzer is the solid that is insoluble to reaction system, and post catalyst reaction and product are easily separated, 55 ℃, when water to ester ratio is 0.95-1, the reaction conversion ratio of catalyzer is 23-25%.The shortcoming of this catalyzer is: when temperature was higher than 56.9 ℃, this catalyzer swelling in reaction system lost activity.
Heteropolyacid (as phospho-wolframic acid) is another kind of ester-type hydrolysis catalyzer.This catalyzer can be divided into loading type and loading type not.The heteropolyacid catalyst of load is not a homogeneous catalyst, and catalyst dissolution is reacted the separation difficulty of after product and catalyzer in reaction system.Carried heteropoly acid catalyst is a heterogeneous catalyst, Applied catalysis A:General 189 (1999) 217-214 one civilian proposition is used for this catalyzer the hydrolysis reaction of ethyl acetate, be in temperature of reaction that 80 ℃, water to ester ratio are 87.8, catalyst levels is 0.05mmol, under 4 hours conditions of reaction, the reaction conversion ratio of this catalyzer is about 15%.
The heteropolyacid metal-salt mainly is that the phospho-wolframic acid cesium salt is to study a more class heteropolyacid salt catalyzer at present.Applied catalysis A:General 155 (1997) L9-L13 one civilian proposition is used for the hydrolysis reaction of ethyl acetate with this catalyzer, is that 60 ℃, water to ester ratio are that the reactive behavior of 94.7 o'clock these catalyzer is about 30.1 μ molg in temperature of reaction
-1Min
-1The shortcoming of this catalyzer is to cost an arm and a leg, industrial use cost height.
Summary of the invention
The method that the purpose of this invention is to provide a kind of ester-type hydrolysis, this method can be carried out under comparatively high temps, low water to ester ratio, and can obtain higher transformation efficiency.
The method of the ester-type hydrolysis that provides of the present invention comprises: in the presence of the heteropoly acid ammonium salt catalyst, make C1-C10 acid C1-C4 ester that hydrolysis reaction take place in water, generate C1-C10 acid and C1-C4 alcohol.
Said heteropoly acid ammonium salt catalyst is to be formed by the heteropolyacid with Keggin structure and inorganic ammonium salt or organic amine reaction.Wherein, the preferred phospho-wolframic acid of said heteropolyacid, silicotungstic acid, silicomolybdic acid or phospho-molybdic acid; Said inorganic ammonium salt can be volatile salt, ammonium nitrate, ammonium sulfate, ammonium phosphate, hydrochloric acid diammonium etc.; Said organic amine can be aliphatic amide, aliphatic cyclic amine or arylamine; Can be primary amine, secondary amine or tertiary amine; Can be monoamine, diamine or tertiary amine; Wherein the carbon number of the single alkyl that links to each other with amino is C1-C14, preferred C1-C12.For example, said organic amine can be methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, Tri-n-Propylamine, TERTIARY BUTYL AMINE, hexahydroaniline, hexanediamine, two n-octyl amine, amino dodecane, methyl amino dodecane etc.
Said heteropoly acid ammonium salt catalyst can not load, also can load, and available carrier has silicon-dioxide, gac, aluminum oxide etc.Ammonium heteropoly acids is a solid, is in suspended state in reaction solution, is convenient to separate.
Said catalyzer can prepare according to laxative remedy: take by weighing the heteropolyacid of an amount of oven dry earlier, be made into the solution A of about 5-30%; Take by weighing the inorganic ammonium salt or the organic amine of the amount of respective substance again, be made into the solution B of about 5-30%; Solution B is added drop-wise in the solution A, fully stirs; After dripping with products therefrom 50-200 ℃ of dry for standby.Also can carry out load to catalyzer according to usual method as required.Reacted catalyzer is recyclable to be recycled.
The acid that said ester-type hydrolysis generates is C1-C10 lipid acid or aromatic acid, and preferred C2-C8 lipid acid or aromatic acid can be monoprotic acid or diprotic acid; Can be saturated fatty acid, also can be unsaturated fatty acids.For example, the acid that hydrolysis generated can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, phenylformic acid, phthalic acid, toluylic acid, methacrylic acid, oxalic acid, Succinic Acid, or the like.
The alcohol that said ester-type hydrolysis generates is the C1-C4 Fatty Alcohol(C12-C14 and C12-C18), preferred C1-C3 Fatty Alcohol(C12-C14 and C12-C18), as, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, glycerol.
In the hydrolysis reaction, the ratio of water and ester (mol ratio) is 0.5: 1-100: 1, and water-content is high more, reaction conversion ratio is high more, but the energy of required consumption is also big more when separate purifying, and therefore will control the consumption of water, suitable water to ester ratio is 1-5: 1, and 1-3 preferably: 1.
Reaction formation of the present invention can be intermittent type, semibatch or continous way.Catalyst levels consumption routinely determines that for example, for rhythmic reaction, in 100 weight part raw materials (ester+water), catalyst levels is suitable with the 1-30 weight part, preferably the 5-15 weight part.
The inventive method can be carried out under room temperature or higher temperature, and actual temp is decided on each concrete reaction, and generally speaking, temperature is high more, and transformation efficiency is big more, but temperature of reaction should not be above 200 ℃; This reaction also can suitably be pressurizeed, and carries out under 1-4MPa pressure, from easy to operate angle, preferably depresses at saturated vapo(u)r and carries out.
The method of ester-type hydrolysis provided by the invention has the following advantages:
1. compare with the method that with the resin is catalyzer, the catalyzer that the present invention uses can use under comparatively high temps, and can obtain higher hydrolysis conversion;
2. compare with the method that with pure heteropolyacid is catalyzer, the inventive method is a heterogeneous reaction, the post catalyst reaction separate easily;
3. compare with the method that with the phospho-wolframic acid cesium salt is catalyzer, the catalyzer price that the present invention uses is more cheap, and cost is lower.
Embodiment
Below enumerate embodiment, illustrate in greater detail the inventive method.In these examples, the weight ratio of catalyzer and reactant (ester+water) is 1: 10, and analysis is to utilize gas chromatograph and totalizing instrument to carry out.When not specifying, it is the transformation efficiency of the ester of benchmark that transformation efficiency (%) all refers to acid.Concrete calculation formula is:
The amount of substance of transformation efficiency %=acid/(amount of substance of ester hydrolysis of amount of substance+not of acid) * 100%.
In this formula, the amount of substance of acid and ester is that external standard method measuring and calculating general in the chromatographically obtains.
Embodiment 1
Take by weighing 20g at 100 ℃ of phospho-wolframic acids of drying down, be dissolved in the 80g pure water, make solution A; Take by weighing the 0.67g volatile salt, be dissolved in the 6g water, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; 80 ℃ of oven dry, get following catalyzer: NH
4H
2PW
12O
40
This catalyzer of 10.00g, 67.25g ritalin, 32.75g water are packed in the 250ml batch reactor, be warming up to 100 ℃, carry out the hydrolysis of ritalin, reacted 90 minutes.Gather resultant of reaction and analyze, the result is that the transformation efficiency of ritalin is 47.8%.
Embodiment 2
Take by weighing 5g at 100 ℃ of phospho-wolframic acids of drying down, be dissolved in the 20g water, make solution A; Take by weighing the 0.10g quadrol, be dissolved in the 2g methyl alcohol, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; 80 ℃ of oven dry, get following catalyzer: NH
4CH
2CH
2NHH
2PW
12O
40
This catalyzer of 10.00g, 74.00g methyl-butyrate, 26.10g water are packed in the 250ml three-necked bottle.Be warming up to 80 ℃, carry out the hydrolysis of methyl-butyrate, reacted 150 minutes.Gather resultant of reaction and analyze, the result is that the transformation efficiency of methyl-butyrate is 24.4%.
Embodiment 3
Take by weighing 20g at 100 ℃ of silicotungstic acids of drying down, be dissolved in the 80g pure water, make solution A; Take by weighing 0.56g ammonium nitrate, be dissolved in the 5g water, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; In this mixture, add an amount of fine silica end, continued violent stirring 60 minutes; Oven dry, calcining gets following catalyzer: NH
4H
3SiW
12O
40/ SiO
2
This catalyzer of 10.00g, 81.00g ethyl benzoate, 19.30g water are packed in the 250ml batch reactor.Be warming up to 100 ℃, carry out the hydrolysis of ethyl benzoate, reacted 120 minutes.Gather resultant of reaction and analyze, the result is that the transformation efficiency of ethyl benzoate is 44.8%.
Embodiment 4
Take by weighing 5g at 100 ℃ of phospho-molybdic acids of drying down, be dissolved in the 20g pure water, make solution A; Take by weighing the 0.35g n-octyl amine, be dissolved in the 3g methyl alcohol, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; The SiO 2 powder that in this mixture, adds an amount of certain granules degree; Oven dry, calcining gets following catalyzer: NH
4C
8H
16H
2PMo
12O
40/ SiO
2
This catalyzer of 10.00g, 80.30g oxalic acid diethyl ester, 19.70g water are packed in the 250ml batch reactor.Be warming up to 100 ℃, reacted 120 minutes, carry out the hydrolysis of oxalic acid diethyl ester.Gather resultant of reaction and analyze, the result is that the transformation efficiency of oxalic acid diethyl ester is 46%.
Embodiment 5
Take by weighing 20g at 100 ℃ of phospho-molybdic acids of drying down, be dissolved in the 80g pure water, make solution A; Take by weighing 2.29g ammonium sulfate, be dissolved in the 18g water, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; 80 ℃ of oven dry, get following catalyzer: (NH
4)
2HPMo
12O
40
This catalyzer of 10.00g, 100g methyl acrylate, 32.75g water are packed in the 250ml batch reactor.Be warming up to 100 ℃, reacted 120 minutes, carry out the hydrolysis of methyl acrylate.Gather resultant of reaction and analyze, the result is that the transformation efficiency of ritalin is 21%.
Embodiment 6
Take by weighing 5g at 100 ℃ of silicotungstic acids of drying down, be dissolved in the 20g pure water, make solution A; Take by weighing the 0.10g methylamine, be dissolved in the 4g methyl alcohol, make solution B; In solution A, drip solution B, fully stir; Being added dropwise to complete the back continues to stir 40 minutes; 80 ℃ of oven dry, get following catalyzer: (CH
3NH
4)
2H
2SiW
12O
40
This catalyzer of 10.00g, 67.25g vinyl acetic monomer, 32.75g water are packed in the 250ml three-necked bottle.Be warming up to 70 ℃ (reaction mixture boiling points), violent stirring.Reacted 180 minutes, and carried out the hydrolysis of vinyl acetic monomer.Gather resultant of reaction and analyze, the result is that the transformation efficiency of vinyl acetic monomer is 76.6% (reactive behavior 403 μ molg
-1Min
-1).
Comparative example 1
As with the contrast of embodiment 6, the embedded heteropolyacid catalyst that Applied catalysis A:General 189 (1999) 217-214 are proposed is applied to the hydrolysis reaction of vinyl acetic monomer.
Record according to the document prepares catalyzer: an amount of heteropolyacid (phospho-wolframic acid) is dissolved in the 20ml water, stirred 1 hour at 40 ℃ with 0.23mol tetraethyl orthosilicate salt and 0.62mol ethanol, stirred 4 hours at 85 ℃.Product dewaters under 45 ℃, 3325Pa earlier, and again in 150 ℃, thermal treatment is 3 hours under the 3325Pa condition.Took out 3 hours at 80 ℃.Calcining 3 hours under 150 ℃, 3325Pa condition at last, 11% heteropolyacid.
The condition of hydrolysis reaction is: water to ester ratio 87.8 (0.527molH
2O, 6mmol ester), 80 ℃ of temperature of reaction, 4 hours reaction times, catalyst levels 0.05mmol, reaction conversion ratio be 40%.
Comparative example 2
As with the contrast of embodiment 6, the carried heteropoly acid catalyst that Applied catalysis A:General 189 (1999) 217-214 are proposed is applied to the hydrolysis reaction of vinyl acetic monomer.
Record according to the document prepares catalyzer: proper silica gel is injected 0.01mol heteropolyacid (phospho-wolframic acid) dilute solution, get 10% product, then with gained mud evaporate to dryness, 170 ℃ of calcinings 4 hours, promptly get required carried heteropoly acid catalyst at last.
The hydrolysis reaction condition is: water to ester ratio 87.8 (0.527molH
2O, the 6mmol ester), 80 ℃ of temperature of reaction, in 4 hours reaction times, catalyst levels 0.05mmol gets reaction conversion ratio 15%.
Comparative example 3
As with the contrast of embodiment 6, the catalyzer of Applied catalysis A:General 155 (1997) L9-L13 report is applied to the hydrolysis reaction of vinyl acetic monomer.
According to the record of the document, catalyzer is by H
3PW
12O
40And Cs
2CO
3Be prepared from.This catalyzer costs an arm and a leg.The hydrolysis reaction condition is: water to ester ratio 94.7 (1.6molH
2O, 16.9mmol ester), 60 ℃ of temperature of reaction, reactive behavior be 30.1 μ molg
-1Min
-1
According to the general knowledge of this area, in the ester-type hydrolysis reaction, water to ester ratio is more little, and the one way reaction conversion ratio is low more.Can find that by above contrast the inventive method still can obtain higher transformation efficiency at less water to ester ratio with in the reaction times than weak point.
Claims (13)
1. the method for an ester-type hydrolysis, comprise: in the presence of the heteropoly acid ammonium salt catalyst, make the ester class that hydrolysis reaction take place in water, generate C1-C10 lipid acid or aromatic acid and C1-C4 Fatty Alcohol(C12-C14 and C12-C18), wherein ammonium heteropoly acids is to be reacted with inorganic ammonium salt or organic amine by the heteropolyacid with Keggin structure to form.
2. in accordance with the method for claim 1, it is characterized in that said heteropolyacid is selected from phospho-wolframic acid, silicotungstic acid, silicomolybdic acid and phospho-molybdic acid.
3. in accordance with the method for claim 1, it is characterized in that said inorganic ammonium salt is selected from volatile salt, ammonium nitrate, ammonium sulfate, ammonium phosphate and hydrochloric acid diammonium.
4. in accordance with the method for claim 1, it is characterized in that said organic amine is selected from aliphatic amide, aliphatic cyclic amine and arylamine, wherein the carbon number of the single alkyl that links to each other with amino is C1-C14.
5. according to claim 1 or 4 described methods, it is characterized in that said organic amine is selected from methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, Tri-n-Propylamine, TERTIARY BUTYL AMINE, hexahydroaniline, hexanediamine, two n-octyl amine, amino dodecane and methyl amino dodecane.
6. in accordance with the method for claim 1, it is characterized in that the acid that said ester-type hydrolysis generates is C2-C8 lipid acid or aromatic acid.
7. according to claim 1 or 6 described methods, it is characterized in that the acid that said ester-type hydrolysis generates is selected from formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, phenylformic acid, phthalic acid, toluylic acid, methacrylic acid, oxalic acid and Succinic Acid.
8. in accordance with the method for claim 1, it is characterized in that the alcohol that said ester-type hydrolysis generates is the C1-C3 Fatty Alcohol(C12-C14 and C12-C18),
9. according to claim 1 or 8 described methods, it is characterized in that the alcohol that said ester-type hydrolysis generates is selected from methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol and glycerol.
10. in accordance with the method for claim 1, it is characterized in that the mol ratio of water and ester is 0.5-100: 1.
11. in accordance with the method for claim 1, it is characterized in that water to ester ratio is 1-5: 1.
12. in accordance with the method for claim 1, it is characterized in that in 100 weight part raw materials, catalyst levels is 1-30 part.
13. in accordance with the method for claim 1, it is characterized in that temperature of reaction is a room temperature to 200 ℃, reaction pressure is 1-4MPa.
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| CN 03122853 CN1224596C (en) | 2003-04-29 | 2003-04-29 | Hydrolysis method of esters |
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| CN1224596C CN1224596C (en) | 2005-10-26 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292578A1 (en) | 2009-09-03 | 2011-03-09 | BP Chemicals Limited | Process for producing acetic acid and dimethyl ether using a zeolite catalyst |
| CN101541891B (en) * | 2006-11-14 | 2012-07-18 | 旭化成化学株式会社 | Metal pigment composition |
| CN101641156B (en) * | 2007-06-13 | 2012-07-25 | Lg化学株式会社 | Method of preparing heteropoly acid catalyst |
| CN102641746A (en) * | 2012-04-05 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof |
| CN103420794A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN103588636A (en) * | 2013-11-14 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin |
| CN104588060A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN105642352A (en) * | 2014-12-02 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of heteropolyacid ammonium salt catalyst |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
-
2003
- 2003-04-29 CN CN 03122853 patent/CN1224596C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541891B (en) * | 2006-11-14 | 2012-07-18 | 旭化成化学株式会社 | Metal pigment composition |
| CN101641156B (en) * | 2007-06-13 | 2012-07-25 | Lg化学株式会社 | Method of preparing heteropoly acid catalyst |
| WO2011027105A1 (en) | 2009-09-03 | 2011-03-10 | Bp Chemicals Limited | Process for producing acetic acid and dimethyl ether using a zeolite catalyst |
| EP2292578A1 (en) | 2009-09-03 | 2011-03-09 | BP Chemicals Limited | Process for producing acetic acid and dimethyl ether using a zeolite catalyst |
| CN102641746A (en) * | 2012-04-05 | 2012-08-22 | 中国科学院青岛生物能源与过程研究所 | Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof |
| CN103420794A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN103420794B (en) * | 2012-05-16 | 2015-06-10 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through ethylene carbonate hydrolysis |
| CN104588060B (en) * | 2013-11-03 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of preparing dimethyl ether by dewatering methanol catalyst and preparation method thereof |
| CN104588060A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparing dimethyl ether through methanol dehydration, and preparation method thereof |
| CN103588636A (en) * | 2013-11-14 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin |
| CN105642352A (en) * | 2014-12-02 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of heteropolyacid ammonium salt catalyst |
| CN105642352B (en) * | 2014-12-02 | 2017-12-08 | 中国石油化工股份有限公司 | The preparation method of heteropoly acid ammonium salt catalyst |
| CN106008206A (en) * | 2016-05-31 | 2016-10-12 | 邵阳学院 | Method for dodecylamine phosphotungstate catalyzed synthesis of long-chain carboxylate |
| CN106008206B (en) * | 2016-05-31 | 2018-10-23 | 邵阳学院 | A kind of method that phosphotungstic acid lauryl amine salt catalyzes and synthesizes higher fatty ester |
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