CN102295556A - Method for preparing sec-butyl acetate by direct esterification of acetic acid and butylene - Google Patents

Method for preparing sec-butyl acetate by direct esterification of acetic acid and butylene Download PDF

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CN102295556A
CN102295556A CN2010102079664A CN201010207966A CN102295556A CN 102295556 A CN102295556 A CN 102295556A CN 2010102079664 A CN2010102079664 A CN 2010102079664A CN 201010207966 A CN201010207966 A CN 201010207966A CN 102295556 A CN102295556 A CN 102295556A
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acetate
sec
butylene
butyl acetate
carrier
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陈梁锋
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a method for preparing sec-butyl acetate by direct esterification of acetic acid and butylene. The method mainly solves the problem that the activity of a catalyst declines because heteropolyacid serving as an active ingredient of the catalyst is easily dissolved from a carrier. The acetic acid and the butylene are used as raw materials in the method; the reaction raw materials are in contact with the catalyst to generate the sec-butyl acetate under self-generated pressure and under the conditions that the reaction temperature is 60 to 190 DEG C, the molar ratio of the butylene to the acetic acid is (0.1-10): 1 and the weight content of the catalyst in the acetic acid is 0.01 to 10 percent; the catalyst comprises the following components in part by weight: a) 0.1 to 50 parts of heteropolyacid, and b) 50 to 99.9 parts of SiO2 carrier, wherein the SiO2 carrier is treated by nitrogen-containing silicate ester; and the nitrogen-containing silicate ester is CxHyNz-Si(OR)3, wherein x is 1 to 10, y is 4 to 26, z is 1 to 5, and R is CH3 or C2H5. According to the technical scheme, the problem is well solved, and the method can be used for industrial production of preparing the sec-butyl acetate by direct esterification of the acetic acid and the butylene.

Description

Acetate and butylene direct esterification prepare the method for sec-butyl acetate
Technical field
The present invention relates to the method that a kind of acetate and butylene direct esterification prepare sec-butyl acetate.
Background technology
Butylacetate, comprise n-butyl acetate, sec-butyl acetate, isobutyl acetate and tert.-butyl acetate, it is the important organic chemicals of a class, be the good organic solvent of a kind of preparation that is widely used as grease, resin, coating, paint and organic reaction process, extraction separation process etc., also can be used for preparing metal clean-out system and spices etc.Particularly in recent years, because the environmental requirement increasingly stringent, ester class environmentally friendly solvent consumption sharply increases.Butylacetate series products in the market is mainly based on n-butyl acetate, but because n-butyl acetate need be obtained by price higher propyl carbinol and acid esterification reaction, therefore domestic and international many companies are one after another at the sec-butyl acetate of exploitation in order to the positive butyl ester of substituted acetic acid.The character and the n-butyl acetate of sec-butyl acetate are close, and can use the method preparation of a large amount of by-products, low-cost butylene and the acetate direct addition of refinery, therefore can reduce cost greatly.
Prepare the technology of sec-butyl acetate about acetate and butylene direct addition, open in many pieces of patent applications and document, report, employed catalyzer mainly comprises sulfuric acid, tosic acid, strong-acid ion exchange resin, heteropolyacid (salt).Liquid acid catalyst such as sulfuric acid or tosic acid is replaced by solid acid catalysts such as ion exchange resin and heteropolyacids just gradually because it has stronger corrodibility.Document RU2176239 discloses the method for acetate and butylene direct esterification production sec-butyl acetate, and the catalyzer that uses is strong-acid ion exchange resin.In reaction process, can occur problems such as sulfonic group loss, resin particle fragmentation owing to resin catalyst and cause catalyst deactivation, and resin catalyst be difficult to regeneration, cause solid waste discharge, contaminate environment.Simultaneously, sulphur content is higher in the product of resin catalysis, makes to have peculiar smell in the product, and influence is used.
Heteropolyacid is owing to have advantages of high catalytic activity, and is difficult for inactivation, therefore obtained using widely in esterification.Loaded by heteropoly acid can be increased its surface-area and proper pore structure is provided on carrier, and can make the homogeneous catalysis agent carrierization.Document CN101293210A discloses the method that a kind of ethyl ester and butylene direct esterification prepare sec-butyl acetate, and adopting heteropolyacid is the catalyst activity component, and porous support is a dispersion agent.But the greatest problem of its existence is the easy solution-off of its active ingredient heteropolyacid, thereby causes catalytic activity to descend.
Summary of the invention
Technical problem to be solved by this invention is an easily solution-off from the carrier of the catalyst activity component heteropolyacid that exists in the conventional art, causes the problem of catalyst activity reduction, the method that provides a kind of new acetate and butylene direct esterification to prepare sec-butyl acetate.This method has heteropolyacid and is difficult for solution-off from the carrier, the characteristics that catalyst activity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of acetate and butylene direct esterification prepare the method for sec-butyl acetate, with acetate and butylene is raw material, under autogenous pressure, in temperature of reaction is 60～190 ℃, the mol ratio of butylene and acetate is (0.1～10): 1, and the weight content of catalyzer in acetate is under 0.01～10% condition, reaction raw materials contacts with catalyzer and generates sec-butyl acetate; Wherein used catalyzer comprises following component in parts by weight:
A) 0.1～50 part heteropolyacid;
B) 50～99.9 parts SiO 2Carrier;
Wherein, described SiO 2Carrier is handled through the nitrogenated silicon acid esters; Described nitrogenated silicon acid esters is C xH yN z-Si (OR) 3, x=1～10 wherein, y=4～26, z=1～5, R is CH 3Or C 2H 5
In the technique scheme, the treatment temp preferable range of nitrogenated silicon acid esters is 70～140 ℃, and more preferably scope is 90～120 ℃; The treatment time preferable range is 1～60 hour, and more preferably scope is 5～48 hours.Nitrogenated silicon acid esters and SiO 2The weight ratio preferable range of carrier is 0.005～0.15, and more preferably scope is 0.01～0.1.SiO 2The carrier preferred version is for being selected from porous SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or the diatomite, more preferably scheme is for being selected from porous SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS or the diatomite, SiO 2The preferred specific surface area of carrier is 100～1500 meters 2/ gram, more preferably 200～1000 meters 2/ gram.In parts by weight, the consumption preferable range of heteropolyacid is 1～40 part, SiO 2The consumption preferable range of carrier is 60～99 parts.Described heteropolyacid is the heteropolyacid of Keggin structure, and preferred version is for being selected from phospho-wolframic acid, silicotungstic acid, germanotungstic acid, arsenowolframic acid, phospho-molybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.The reaction conditions preferable range is: temperature of reaction is 80～200 ℃, and the mol ratio of butylene and acetate is (0.5～5): 1, and the weight content of catalyzer in acetate is 1～20%.
The Preparation of catalysts method is as follows among the present invention:
A) with carrier S iO 2With the nitrogenated silicon acid esters after handling 1～60 hour under 70～140 ℃ of temperature, filtration, washing, drying.
B) with the carrier S iO that handles through the nitrogenated silicon acid esters of step a) gained 2Place the heteropolyacid ethanolic soln of aequum, room temperature is placed, evaporate to dryness under 25～60 ℃ of temperature then, and last drying promptly gets catalyzer of the present invention.
In the inventive method, because after employed support of the catalyst is handled with the nitrogenated silicon acid esters, nitrogenous weakly alkaline group on the surface graft, utilize fixedly tart heteropolyacid molecule of this weakly alkaline group, thereby in immobilized heteropolyacid, also improved the stability of catalyzer, prevented the loss of heteropolyacid in reaction process.The present invention is under autogenous pressure, 120 ℃ of temperature of reaction, the mol ratio of 2-butylene and acetate is 1.5, and the weight content of catalyzer in acetate is under 6.5% condition, the transformation efficiency of acetate reaches as high as 89.5%, and the selectivity of sec-butyl acetate reaches as high as 98.4%; After catalyzer was reused 5 times, active not obviously decline had obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
With SiO 2(Degussa, Aerisol 200,210 meters of specific surface areas for carrier 2/ gram) 10.0 grams place 500 milliliters of three-necked bottles, add 200 milliliters of dry toluenes then respectively, 2.0 milliliters of 3-aminopropyltriethoxywerene werene (3-aminopropyltriethoxysilane, APTES, C 3H 8NSi (OC 2H 5) 3), at 110 ℃ of 24 hours after-filtration that reflux, with behind the absolute ethanol washing 3 times in 110 ℃ of baking ovens dry 12 hours, then resulting solid is added in 100 milliliters of ethanol solutions that contain phospho-wolframic acid 2.0 grams, after room temperature leaves standstill 3 hours, 50 ℃ of slow evaporates to dryness, dried overnight in 110 ℃ of baking ovens obtains catalyzer.
[embodiment 2～9]
With [embodiment 1], be the kind and the consumption of heteropolyacid, the kind of nitrogenated silicon acid esters, consumption, treatment temp and treatment time are different.Specifically see Table 1.
Figure BSA00000166994500041
[embodiment 10～18]
The catalyzer of 40.0 gram Glacial acetic acid, 56.0 gram 2-butylene and 2.6 gram [embodiment 1～9] preparations is placed 200 milliliters of autoclaves (mol ratio of 2-butylene and Glacial acetic acid is 1.5, and the weight content of catalyzer in acetate is 6.5%), and 120 ℃ were reacted 2 hours.Reaction is cooled to room temperature with autoclave, emptying after finishing.Get liquid product and carry out gas chromatographic analysis, the result is as shown in table 2.
Table 2
Embodiment The acetate transformation efficiency, % The sec-butyl acetate selectivity, % The butene dimer selectivity, %
10 75.9 95.6 4.4
11 8.5 94.1 5.9
12 89.5 98.4 1.6
13 78.4 89.5 10.5
14 71.2 95.4 4.6
15 65.8 91.3 8.7
16 6.3 95.6 4.4
17 72.3 88.4 11.6
18 68.9 96.3 3.7
[embodiment 19]
With [embodiment 10], just temperature of reaction is 140 ℃.Obtaining the acetate transformation efficiency is 88.1%, and the selectivity of sec-butyl acetate is 85.1%, and other is a butene dimer.
[embodiment 20]
With [embodiment 10], just temperature of reaction is 80 ℃.Obtaining the acetate transformation efficiency is 15.2%, and the selectivity of sec-butyl acetate is 93.4%, and other is a butene dimer.
[embodiment 21]
With [embodiment 10], just temperature of reaction is 180 ℃.Obtaining the acetate transformation efficiency is 94.2%, and the selectivity of sec-butyl acetate is 80.1%, and other is a butene dimer.
[embodiment 22]
With [embodiment 10], just the quality of 2-butylene is 40.0 grams (mol ratio of 2-butylene and Glacial acetic acid is 1.07).Obtaining the acetate transformation efficiency is 70.8%, and the selectivity of sec-butyl acetate is 96.9%, and other is a butene dimer.
[embodiment 23]
With [embodiment 10], just the quality of 2-butylene is 20.0 grams (mol ratio of 2-butylene and Glacial acetic acid is 0.53).Obtaining the acetate transformation efficiency is 38.9%, and the selectivity of sec-butyl acetate is 98.8%, and other is a butene dimer.
[embodiment 24]
With [embodiment 10], just the quality of 2-butylene is 160 grams (mol ratio of 2-butylene and Glacial acetic acid is 4.29).Obtaining the acetate transformation efficiency is 78.9%, and the selectivity of sec-butyl acetate is 85.2%, and other is a butene dimer.
[embodiment 25]
With [embodiment 10], just catalyzer is the catalyzer of [embodiment 1] preparation, and consumption is 1.3 grams (content of catalyzer in acetate is 3.3%).Obtaining the acetate transformation efficiency is 43.1%, and the selectivity of sec-butyl acetate is 94.2%, and other is a butene dimer.
[embodiment 26]
With [embodiment 10], just catalyzer is the catalyzer of [embodiment 1] preparation, and consumption is 0.5 gram (content of catalyzer in acetate is 1.3%).Obtaining the acetate transformation efficiency is 15.1%, and the selectivity of sec-butyl acetate is 96.4%, and other is a butene dimer.
[embodiment 26]
With [embodiment 10], just catalyzer is the catalyzer of [embodiment 1] preparation, and consumption is 7.5 grams (content of catalyzer in acetate is 18.8%).Obtaining the acetate transformation efficiency is 81.5%, and the selectivity of sec-butyl acetate is 95.9%, and other is a butene dimer.
[embodiment 27]
Catalyzer after [embodiment 12] reaction end is applied mechanically 5 times active unobvious decline by same reaction conditions.Reaction result is shown in Table 3.
Table 3
Apply mechanically number of times The acetate transformation efficiency, % The sec-butyl acetate selectivity, % The butene dimer selectivity, %
1 89.0 98.6 1.4
2 89.1 98.2 1.8
3 88.4 98.4 1.6
4 88.6 98.5 1.5
5 87.6 98.1 1.9
[Comparative Examples 1～9]
With used SiO in [embodiment 1～9] 2Material is handled without the nitrogenated silicon acid esters, checks and rates with [embodiment 10], and reaction result sees Table 4.
Table 4
Comparative Examples The acetate transformation efficiency, % The sec-butyl acetate selectivity, % The butene dimer selectivity, %
1 71.1 86.3 13.7
2 7.9 92.6 7.4
3 84.6 96.3 3.7
4 79.6 95.3 4.7
5 68.3 89.6 10.4
6 63.2 96.3 3.7
7 5.9 95.3 4.7
8 70.2 91.2 8.8
9 71.3 97.8 2.2
[Comparative Examples 10]
Catalyzer after reaction finishes in the Comparative Examples 3 is applied mechanically 5 times by same reaction conditions, and the reaction result of gained is as shown in table 5.
Table 5
Apply mechanically number of times The acetate transformation efficiency, % The sec-butyl acetate selectivity, % The butene dimer selectivity, %
1 75.1 97.5 2.5
2 65.4 93.8 6.2
3 59.6 92.1 7.9
4 45.4 95.3 4.7
5 35.2 94.1 5.9

Claims (10)

1. acetate and butylene direct esterification prepare the method for sec-butyl acetate, with acetate and butylene is raw material, under autogenous pressure, in temperature of reaction is 60～190 ℃, the mol ratio of butylene and acetate is (0.1～10): 1, the weight content of catalyzer in acetate is under 0.01～10% condition, and reaction raw materials contacts with catalyzer and generates sec-butyl acetate; Wherein used catalyzer comprises following component in parts by weight:
A) 0.1～50 part heteropolyacid;
B) 50～99.9 parts SiO 2Carrier;
Wherein, described SiO 2Carrier is handled through the nitrogenated silicon acid esters; Described nitrogenated silicon acid esters is C xH yN z-Si (OR) 3, x=1～10 wherein, y=4～26, z=1～5, R is CH 3Or C 2H 5
2. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, and the treatment temp that it is characterized in that the nitrogenated silicon acid esters is 70～140 ℃, and the treatment time is 1～60 hour, nitrogenated silicon acid esters and SiO 2The weight ratio of carrier is 0.005～0.15.
3. acetate according to claim 2 and butylene direct esterification prepare the method for sec-butyl acetate, and the treatment temp that it is characterized in that the nitrogenated silicon acid esters is 90～120 ℃, and the treatment time is 5～48 hours, nitrogenated silicon acid esters and SiO 2The weight ratio of carrier is 0.01～0.1.
4. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that described SiO 2Carrier is selected from porous SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or the diatomite.
5. acetate according to claim 4 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that described SiO 2Carrier is selected from porous SiO 2, a kind of in SBA-15, MCM-41, MCF, HMS or the diatomite.
6. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that SiO 2The specific surface area of carrier is 100～1500 meters 2/ gram.
7. acetate according to claim 6 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that SiO 2The specific surface area of carrier is 200～1000 meters 2/ gram.
8. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that in parts by weight, and the consumption of heteropolyacid is 1～40 part, SiO 2The consumption of carrier is 60～99 parts.
9. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that described heteropolyacid is selected from phospho-wolframic acid, silicotungstic acid, germanotungstic acid, arsenowolframic acid, phospho-molybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
10. acetate according to claim 1 and butylene direct esterification prepare the method for sec-butyl acetate, it is characterized in that temperature of reaction is 80～200 ℃, and the mol ratio of butylene and acetate is (0.5～5): 1, and the weight content of catalyzer in acetate is 1～20%.
CN2010102079664A 2010-06-24 2010-06-24 Method for preparing sec-butyl acetate by direct esterification of acetic acid and butylene Pending CN102295556A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293824A (en) * 2007-04-25 2008-10-29 中国科学院大连化学物理研究所 Method for preparing sec-butyl acetate with direct esterification of acetic acid and butylene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101293824A (en) * 2007-04-25 2008-10-29 中国科学院大连化学物理研究所 Method for preparing sec-butyl acetate with direct esterification of acetic acid and butylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周琰: "《介孔材料为载体的杂多酸催化剂的制备、表征及在非均相催化反应中的应用》", 《中国博士学位论文全文数据库》 *

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Application publication date: 20111228