CN102294270A - Catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene - Google Patents
Catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene Download PDFInfo
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- CN102294270A CN102294270A CN201010207958XA CN201010207958A CN102294270A CN 102294270 A CN102294270 A CN 102294270A CN 201010207958X A CN201010207958X A CN 201010207958XA CN 201010207958 A CN201010207958 A CN 201010207958A CN 102294270 A CN102294270 A CN 102294270A
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Abstract
The invention relates to a catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene, which is mainly used for solving the problem of the reduction in the catalyst activity caused by easiness of leaching of heteropoly acid serving as an active ingredient from a carrier existing in the prior art. The catalyst comprises the following components in parts by weight: (a) 0.1-50 parts of heteropoly acid and (b) 50-99.9 parts of SiO2 carrier, wherein the SiO2 carrier is treated with nitrogen-containing silicon ester; the nitrogen-containing silicon ester is CxHyNz-Si(OR)3; x=1-10; y=4-26; z=1-5; and R is CH3 or C2H5. By adopting the technical scheme, the problem is well solved; and the catalyst can be applied to industrial production of sec-butyl acetate prepared by directly esterifying acetic acid and butylene.
Description
Technical field
The present invention relates to the catalyst that a kind of acetate and butylene direct esterification prepare sec-butyl acetate.
Background technology
Butyl acetate, 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 cleaning agent and spices etc.Particularly in recent years, because the environmental requirement increasingly stringent, ester class environmentally friendly solvent consumption sharply increases.Butyl acetate series products in the market is mainly based on n-butyl acetate, but because n-butyl acetate need be obtained by price higher n-butanol 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 direct addition of acetate of refinery, therefore can reduce cost greatly.
Prepare the technology of sec-butyl acetate about acetate and the direct addition of butylene, open in many pieces of patent applications and document, report, employed catalyst mainly comprises sulfuric acid, p-methyl benzenesulfonic acid, strong-acid ion exchange resin, heteropoly acid (salt).Liquid acid catalyst such as sulfuric acid or p-methyl benzenesulfonic acid is replaced by solid acid catalysts such as ion exchange resin and heteropoly acids just gradually because it has stronger corrosivity.Document RU2176239 discloses the method for acetate and butylene direct esterification production sec-butyl acetate, and the catalyst that uses is strong-acid ion exchange resin.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 solid waste discharge, 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 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 composite catalyst that a kind of ethyl ester and butylene direct esterification prepare sec-butyl acetate, and adopting heteropoly acid is the catalyst activity component, and porous carrier is a dispersant.But the greatest problem of its existence is the easy solution-off of its active component heteropoly acid, 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 active component heteropoly acid that exists in the conventional art, causes the problem of catalyst activity reduction, the catalyst that provides a kind of new acetate and butylene direct esterification to prepare sec-butyl acetate.This catalyst has heteropoly acid 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 catalyst of sec-butyl acetate, comprise following component in parts by weight:
A) 0.1～50 part heteropoly acid;
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 temperature preferable range of nitrogenated silicon acid esters is 70～140 ℃, and more preferably scope is 90～120 ℃; The processing 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 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 heteropoly acid is 1～40 part, SiO
2The consumption preferable range of carrier is 60～99 parts.Described heteropoly acid is the heteropoly acid of Keggin structure, and preferred version is for being selected from phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
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 heteropoly acid ethanolic solution of aequum, room temperature is placed, evaporate to dryness under 25～60 ℃ of temperature then, and last drying promptly gets catalyst of the present invention.
The present invention is because after the processing of employed carrier usefulness nitrogenated silicon acid esters, nitrogenous alkalescent group on the surface graft, utilize this alkalescent group can fix acid heteropoly acid molecule, thereby in immobilized heteropoly acid, also improved the stability of catalyst, prevented the loss of heteropoly acid in course of reaction.Catalyst of the present invention is used for the reaction that acetate and the direct esterification of 2-butylene prepare sec-butyl acetate, under self-generated pressure, 120 ℃ of reaction temperatures, the mol ratio of 2-butylene and acetate is 1.5, the weight content of catalyst in acetate is under 6.5% condition, the conversion ratio of acetate reaches as high as 89.5%, and the selectivity of sec-butyl acetate reaches as high as 98.4%; After catalyst was reused 5 times, active not obviously decline had obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With SiO
2(Degussa, Aerisol 200,210 meters of specific 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), filter after 24 hours 110 ℃ of backflows, 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 phosphotungstic 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 catalyst.
[embodiment 2～9]
With [embodiment 1], be the kind and the consumption of heteropoly acid, the kind of nitrogenated silicon acid esters, consumption, treatment temperature and processing time are different.Specifically see Table 1.
[embodiment 10～18]
The catalyst 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, 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 conversion ratio, % | 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 reaction temperature is 140 ℃.Obtaining the acetate conversion ratio 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 the quality of 2-butylene is 40.0 grams.Obtaining the acetate conversion ratio is 70.8%, and the selectivity of sec-butyl acetate is 92.1%, and other is a butene dimer.
[embodiment 21]
With [embodiment 10], just catalyst is the catalyst of [embodiment 1] preparation, and consumption is 1.3 grams.Obtaining the acetate conversion ratio is 43.1%, and the selectivity of sec-butyl acetate is 94.2%, and other is a butene dimer.
[embodiment 22]
Catalyst 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 conversion ratio, % | 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 conversion ratio, % | 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]
Catalyst 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 conversion ratio, % | 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 (9)
1. acetate and butylene direct esterification prepare the catalyst of sec-butyl acetate, comprise following component in parts by weight:
A) 0.1～50 part heteropoly acid;
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 catalyst of sec-butyl acetate, and the treatment temperature that it is characterized in that the nitrogenated silicon acid esters is 70～140 ℃, and the processing 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 catalyst of sec-butyl acetate, and the treatment temperature that it is characterized in that the nitrogenated silicon acid esters is 90～120 ℃, and the processing 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 catalyst of 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 1 and butylene direct esterification prepare the catalyst of 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 catalyst of sec-butyl acetate, it is characterized in that described SiO
2The specific area of carrier is 100～1500 meters
2/ gram.
7. acetate according to claim 6 and butylene direct esterification prepare the catalyst of sec-butyl acetate, it is characterized in that described SiO
2The specific area of carrier is 200～1000 meters
2/ gram.
8. acetate according to claim 1 and butylene direct esterification prepare the catalyst of sec-butyl acetate, it is characterized in that in parts by weight, and the consumption of heteropoly acid 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 catalyst of sec-butyl acetate, it is characterized in that described heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, germanotungstic acid, arsenowolframic acid, phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid or arsenic molybdic acid.
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|---|---|---|---|
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|---|---|---|---|
| CN201010207958XA CN102294270A (en) | 2010-06-24 | 2010-06-24 | Catalyst applied to preparation of sec-butyl acetate by directly esterifying acetic acid and butylene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105861030A (en) * | 2014-12-24 | 2016-08-17 | 神华集团有限责任公司 | Gasoline alkylating and desulfurizing method based on modified heteropolyacid catalyst and product thereof |
| CN110201716A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | A kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst and its preparation method and application |
-
2010
- 2010-06-24 CN CN201010207958XA patent/CN102294270A/en active Pending
Non-Patent Citations (2)
| 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 工程科技Ⅰ辑》》 * |
| 李琴等: "负载型杂多酸催化2-丁烯与醋酸直接酯化", 《石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105861030A (en) * | 2014-12-24 | 2016-08-17 | 神华集团有限责任公司 | Gasoline alkylating and desulfurizing method based on modified heteropolyacid catalyst and product thereof |
| CN105861030B (en) * | 2014-12-24 | 2018-04-13 | 神华集团有限责任公司 | Gasoline alkylation desulfuration method based on modified heteropolyacid catalyst and products thereof |
| CN110201716A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | A kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst and its preparation method and application |
| CN110201716B (en) * | 2019-05-21 | 2022-04-19 | 南京工业大学 | Alcohol amine group modified ordered mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
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Application publication date: 20111228 |