CN101293210A - Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene - Google Patents
Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene Download PDFInfo
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- CN101293210A CN101293210A CNA2007100986970A CN200710098697A CN101293210A CN 101293210 A CN101293210 A CN 101293210A CN A2007100986970 A CNA2007100986970 A CN A2007100986970A CN 200710098697 A CN200710098697 A CN 200710098697A CN 101293210 A CN101293210 A CN 101293210A
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Abstract
The present invention relates to a composite catalyst for preparing sec-butyl acetate by direct esterification of ethyl ester and butylene, which takes heteropoly acid as the catalyst active component and porous carrier as the dispersant; the weight proportion of the heteropoly acid and the porous carrier is 0.01:1 to 10:1. The heteropoly acid is one with Keggin structure, which consists of phosphotungstic acid, silicotungstic acid, germanium tungstic acid, arsenowolframic acid, phosphomolybdate, germanomolybdate or arsenicomolybdate. The porous carrier comprises porous SiO2, Al2O3, SBA-15, MCM-41, white carbon black, porous SiC, corallite, andalusite, cordierite, meerschaum, Attapulgite or kaolin. The composite catalyst of the present invention solves the problem that the catalysis efficiency is low if the heteropoly acid is separated out from the reaction system.
Description
Technical field
The present invention relates to a kind of composite catalyst that is used to prepare sec-butyl acetate, refer in particular to composite catalyst by acetate and the direct prepared in reaction sec-butyl acetate of butylene.
The invention still further relates to above-mentioned catalyst and prepare application in the sec-butyl acetate reaction in ethyl ester and butylene direct esterification.
Background technology
Butyl acetate is a kind of good organic solvent, and it is widely used in nitrocellulose, coating, artificial leather, medicine, printing ink and the plastics industry.The method of traditional mode of production butyl acetate is to adopt the batch (-type) still reaction both at home and abroad, is the esterification of catalyst acetate and butanols with sulfuric acid.Chinese patent CN1844076A has reported to be the method for catalyst reaction rectification method large-scale production butyl acetate with sulfuric acid, and this method uses sulfuric acid to be catalyst, certainly will cause problems such as equipment corrosion, and needs discharging acid-bearing wastewater, serious environment pollution.Chinese patent CN1184187C adopts the fixed bed reaction mode, with super acids SO
4 2-/ Fe
2O
3-ZrO
2-SiO
2Be the reaction of catalyst acetate and butanols, because super acids is in course of reaction, especially under the situation that water exists, SO
4 2-Run off easily, cause catalysqt deactivation, and the catalyst behind the inactivation is difficult to regeneration.
U.S. Pat 6018076A and US5994578 report acetate and the isobutene method that butyl acetate is produced in esterification under the catalysis of acid-exchange resin.Butyl acetate is produced in Russ P RU2176239 report acetate and butylene direct esterification, use also be ion-exchange resin catalyst.In course of reaction, can occur problems such as sulfonic group loss, resin particle fragmentation owing to resin catalyst and cause catalysqt deactivation, and resin catalyst be difficult to regeneration, cause the discharging of solid waste, contaminated environment.Simultaneously, sulfur content is higher in the product of resin catalysis, makes to have peculiar smell in the product, and influence is used.
Heteropoly acid is owing to have high catalytic activity, and is difficult for inactivation and is applied in esterification.Produce water simultaneously in acetate and the esterified by butyl alcohol process, and water not only can cause the generation of esterification back reaction (ester hydrolysis reaction), because water and acetate azeotropic cause the difficulty in the separation, therefore present research mainly concentrates in the direct esterification of acetate and butylene simultaneously.Though the direct esterification of heteropoly acid catalysis acetate and butylene reaction has high catalytic activity, because in esterification process, along with the generation of ester, heteropoly acid is separated out from solution gradually, causes the reduction of catalyst efficient.
Summary of the invention
The purpose of this invention is to provide a kind of composite catalyst that is used to produce sec-butyl acetate, from reaction system, separate out the problem of the institute's catalytic efficiency that caused reduction to solve heteropoly acid.
For achieving the above object, composite catalyst provided by the invention, adopting heteropoly acid is the catalyst activity component, and porous carrier is as dispersant, and the weight ratio of heteropoly acid and porous carrier is 0.01: 1-10: 1, preferred weight ratio is 0.1: 1-2: 1.
Described composite catalyst, wherein, heteropoly acid is the heteropoly acid of Keggin structure, comprising: phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
Described composite catalyst, wherein, porous carrier is porous SiO
2, Al
2O
3, SBA-15, MCM-41, white carbon, porous SiC, corallite, andalusite, cordierite, sepiolite, attapulgite or kaolin, porous SiO wherein
2, Al
2O
3For having the carrier of regular meso-hole structure, or unformed carrier with loose structure.
Composite catalyst provided by the invention can be used for the reaction that ethyl ester and butylene direct esterification prepare sec-butyl acetate, its reaction temperature is 70-180 ℃, reaction pressure is 0.5-6MPa, and the mol ratio of butylene and acetate is 0.1-10, and the weight content of catalyst in acetate is 0.02-5%.
The specific embodiment
Composite catalyst of the present invention is to be used for acetate and butylene direct esterification to produce sec-butyl acetate, and adopting heteropoly acid is the catalyst activity component, and porous carrier has solved heteropoly acid and separate out the problem of the institute's catalytic efficiency that causes reduction from reaction system as dispersant.Wherein, heteropoly acid adds in the reaction system with the porous dispersant, in the starting stage of esterification, heteropoly acid is dissolved in the reaction solution, reacts to be homogeneous catalytic reaction, along with the generation of sec-butyl acetate, heteropoly acid is separated out from reactant liquor gradually, and be adsorbed on the porous material, becoming supported catalyst, reaction is transferred to heterogeneous by homogeneous phase.After reaction finished, the porous material catalyst that is adsorbed with heteropoly acid was by filtering and feed separation, and when isolated catalyst reacted at the new acetate of adding, heteropoly acid was dissolved in the reaction solution once more, becomes homogeneous catalytic reaction.
Esterification adopts still formula intermittent reaction.The heteropoly acid that reacts used mainly is the heteropoly acid of Keggin structure, comprises phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid, arsenic molybdic acid.Porous carrier is porous SiO
2, Al
2O
3, SBA-15, MCM-41, white carbon, porous SiC, corallite, andalusite, cordierite, sepiolite, attapulgite, kaolin, porous SiO
2, Al
2O
3Can be the carrier with regular meso-hole structure, also can be unformed carrier with loose structure.
Used acetate is industrial acetic in the reaction.Butylene in the reaction is a linear butenes, as 1-butylene and 2-butylene, and their mixture.
Esterification reaction temperature is 70-180 ℃, and preferably 100-140 ℃, the too high meeting of temperature causes increasing of butene polymerization product.Reaction pressure is 0.5-6MPa, is preferably 0.5-2MPa.The mol ratio of butylene and acetate is 0.1-10,0.2-2 preferably, though reaction selectivity height when butenes ratio is low, because a large amount of acetate unreacteds cause the efficient of device low, and high butylene consumption can generate a large amount of butene polymerization products.The heteropoly acid consumption is 0.02-5% (weight content in acetate), preferably 0.5-3%.The weight ratio of heteropoly acid and carrier is 0.01: 1-10: 1, preferably 0.1: 1-2: 1.
Detailed technology contents of the present invention will be described further in the following example.
Embodiment 1
98% industrial acetic 30g, 1-butylene (98% content) 30g, phosphotungstic acid 0.6g, SBA-151.2g pack in the 100ml autoclave, 120 ℃ of reactions, 2 hours reaction time.Reaction is chilled to room temperature with autoclave, emptying after finishing.Getting liquid phase material analyzes with gas-chromatography.Acetate conversion ratio 78.5%, sec-butyl acetate selectivity 98.6%, other is a butene dimer.
Embodiment 2-5
Do not add carrier among the embodiment 2,3～5 carrier is respectively white carbon, kaolin, the unformed Al of porous
2O
3, other is identical with embodiment 1.The results are shown in Table 1.
Table 1:
| Embodiment | Carrier/g | Acetate conversion ratio/% | Ester selectivity/% | Butene polymers selectivity/% |
| 2 | 0 | 68.6 | 98.2 | 1.8 |
| 3 | White carbon/1 | 74.1 | 98.5 | 1.5 |
| 4 | Kaolin/0.8 | 78.3 | 98.4 | 1.6 |
| 5 | The unformed Al of porous 2O 3/1.5 | 69.6 | 98.0 | 2.0 |
Reaction is separated out the brownish black thick liquid after finishing in the solution of embodiment 2, sticks on reactor wall and the stirrer, and the water-soluble and acetate of this thick liquid, it is heteropoly acid for an XRD analysis.Then do not occur this thick liquid among the embodiment 3-5, illustrate that the heteropoly acid of separating out is adsorbed on the porous carrier.
Embodiment 6-10
Operation is identical with embodiment 1.Reaction time is respectively 0,0.5,1,1.5 and 2 hour, and after reaction finished, the reaction solution clarification filtered out the SBA-15 that is adsorbed with heteropoly acid, and all the other liquid are at 200 ℃, evaporated under reduced pressure under the 100Pa, the quality of remaining heteropoly acid in the weighing liquid phase.The results are shown in Table 2.
Table 2:
| Embodiment | Reaction time/hour | Acetate conversion ratio/% | Ester selectivity/% | Remaining heteropoly acid/the g of liquid phase |
| 6 | 0 | 0 | 0 | 0.58 |
| 7 | 0.5 | 58.6 | 98.6 | 0.22 |
| 8 | 1 | 78.9 | 98.5 | 0.12 |
| 9 | 1.5 | 84.2 | 98.8 | 0.09 |
| 10 | 2 | 88.5 | 98.6 | 0.06 |
From the result of embodiment 6-10 as can be seen, when not reacting (embodiment 6), heteropoly acid is dissolved in liquid phase substantially, and along with the carrying out of reaction, the heteropoly acid of separating out increases gradually and is adsorbed on the carrier, and reaction transfers to heterogeneous gradually from homogeneous phase.
Embodiment 11
The reacted SBA-15 that is adsorbed with heteropoly acid among the embodiment 1 directly is used as catalyst, adds acetate and 1-butylene and carry out esterification.Operate identical with embodiment 1.Acetate conversion ratio 88.1%, sec-butyl acetate selectivity 98.9%, other is a butene dimer.
Claims (7)
1, a kind of ethyl ester and butylene direct esterification prepare the composite catalyst of sec-butyl acetate, and adopting heteropoly acid is the catalyst activity component, and porous carrier is as dispersant, and the weight ratio of heteropoly acid and porous carrier is 0.01: 1-10: 1.
2, according to the described composite catalyst of claim 1, wherein, described heteropoly acid is the heteropoly acid of Keggin structure.
3, according to the described composite catalyst of claim 2, wherein, the heteropoly acid of described Keggin structure is phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
4, according to the described composite catalyst of claim 1, wherein, described porous carrier is porous SiO
2, Al
2O
3, SBA-15, MCM-41, white carbon, porous SiC, corallite, andalusite, cordierite, sepiolite, attapulgite or kaolin.
5, according to the described composite catalyst of claim 4, wherein, described porous SiO
2, Al
2O
3For having the carrier of regular meso-hole structure, or unformed carrier with loose structure.
6, according to the described composite catalyst of claim 1, wherein, the weight ratio of heteropoly acid and carrier is 0.1: 1-2: 1.
7, a kind of ethyl ester and butylene direct esterification prepare the method for sec-butyl acetate, adopt the described composite catalyst of claim 1, reaction temperature is 70-180 ℃, and reaction pressure is 0.5-6MPa, the mol ratio of butylene and acetate is 0.1-10, and the weight content of catalyst in acetate is 0.02-5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100986970A CN101293210A (en) | 2007-04-25 | 2007-04-25 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
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|---|---|---|---|
| CNA2007100986970A CN101293210A (en) | 2007-04-25 | 2007-04-25 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862678A (en) * | 2010-06-28 | 2010-10-20 | 浙江树人大学 | Method for preparing tungstosilicic acid-supported catalyst for use in preparation of menthyl lactate |
| CN101869849A (en) * | 2010-06-28 | 2010-10-27 | 浙江树人大学 | Phosphomolybdic and tungstogermanate heteropoly acid supported catalyst for preparing menthyl lactate |
| CN101890357A (en) * | 2010-06-28 | 2010-11-24 | 浙江树人大学 | Preparation method and application of phosphotungstic acid-supported catalyst to preparation of menthyl lactate |
| CN103044246A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Synthesis method of sec-butyl acetate |
| CN103464216A (en) * | 2013-09-26 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene |
| CN103706398A (en) * | 2013-12-25 | 2014-04-09 | 西北大学 | supported vanadium-substituted phosphotungstic acid catalyst and preparation method and application of catalyst |
| CN103819296A (en) * | 2014-03-10 | 2014-05-28 | 河南理工大学 | Method for preparing surface active agent by using porous material adsorptive catalyst |
| CN105712877A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for sec-butyl acetate |
| CN110327989A (en) * | 2019-07-23 | 2019-10-15 | 西北化工研究院有限公司 | A kind of preparation method and applications of catalyst carrier |
| CN110369003A (en) * | 2019-07-25 | 2019-10-25 | 长春工业大学 | A kind of phosphotungstic acid titanium silicon composite and preparation method thereof with meso-hole structure |
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2007
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862678A (en) * | 2010-06-28 | 2010-10-20 | 浙江树人大学 | Method for preparing tungstosilicic acid-supported catalyst for use in preparation of menthyl lactate |
| CN101869849A (en) * | 2010-06-28 | 2010-10-27 | 浙江树人大学 | Phosphomolybdic and tungstogermanate heteropoly acid supported catalyst for preparing menthyl lactate |
| CN101890357A (en) * | 2010-06-28 | 2010-11-24 | 浙江树人大学 | Preparation method and application of phosphotungstic acid-supported catalyst to preparation of menthyl lactate |
| CN103044246A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Synthesis method of sec-butyl acetate |
| CN103464216A (en) * | 2013-09-26 | 2013-12-25 | 中国海洋石油总公司 | Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene |
| CN103706398A (en) * | 2013-12-25 | 2014-04-09 | 西北大学 | supported vanadium-substituted phosphotungstic acid catalyst and preparation method and application of catalyst |
| CN103819296A (en) * | 2014-03-10 | 2014-05-28 | 河南理工大学 | Method for preparing surface active agent by using porous material adsorptive catalyst |
| CN103819296B (en) * | 2014-03-10 | 2015-12-02 | 河南理工大学 | A kind of method of porous material absorption Catalyst Production tensio-active agent |
| CN105712877A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for sec-butyl acetate |
| CN110327989A (en) * | 2019-07-23 | 2019-10-15 | 西北化工研究院有限公司 | A kind of preparation method and applications of catalyst carrier |
| CN110327989B (en) * | 2019-07-23 | 2022-04-05 | 西北化工研究院有限公司 | Preparation method and application of catalyst carrier |
| CN110369003A (en) * | 2019-07-25 | 2019-10-25 | 长春工业大学 | A kind of phosphotungstic acid titanium silicon composite and preparation method thereof with meso-hole structure |
| CN110369003B (en) * | 2019-07-25 | 2022-02-01 | 长春工业大学 | Titanium-silicon phosphotungstate composite material with mesoporous structure and preparation method thereof |
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