CN102924251B - Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid - Google Patents
Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid Download PDFInfo
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Abstract
The invention discloses a method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid. The method comprises the following steps of: adding n-butyl aldehyde and a solid-acid catalyst into a high-pressure kettle, wherein the amount of the catalyst is 0.5 to 25 percent of the mass of added n-butyl aldehyde, replacing air in the kettle by using nitrogen, and performing a self-condensation reaction on n-butyl aldehyde to obtain 2-ethyl-2-hexenoic aldehyde at the temperature of 100 to 220 DEG C under the magnetic stirring reaction conditions for 0.5 to 8 hours. The researched solid-acid catalyst has high activity, selectivity and stability and is simple in post-treatment, and the catalyst can be repeatedly used; and compared with a solid base catalyst, the solid-acid catalyst has the advantage that the industrialization is easily realized. The conversion rate of n-butyl aldehyde is up to 87.5 percent, and the selectivity of 2-ethyl-2-hexenoic aldehyde is up to 92.3 percent.
Description
Technical field
The present invention relates to Green Chemical Technology field, be specially 2-ethyl-2-hexenoic aldehyde prepared by a kind of solid acid catalysis butyraldehyde-n processing method from condensation.
Background technology
Octanol (2-Ethylhexyl Alcohol), as important solvent and Organic Chemicals, is widely used in the production of lipid acid and various ester class, as Organic chemical products such as acrylic acid synthesizing monooctyl ester, dioctyl sebacate, dioctyl phthalate (DOP)s (DOP).Wherein DOP is the important softening agent of polyvinyl chloride.In addition, octanol or the solvent of excellent property are also the dewatering agents of washing composition simultaneously, the defoamer of the techniques such as photograph, papermaking, printing and dyeing, the dispersion agent of ceramic industry glaze slip, dressing agent, purification agent, petroleum additive etc.
The industrial production of octanol adopts the hydroformylation of propylene synthesis butyraldehyde-n, butyraldehyde-n to prepare 2-ethyl-2-hexenoic aldehyde (octenal), the acquisition of octenal hydrogenation three-step reaction from condensation.Butyraldehyde-n is one of important step of Octanol production technique from condensation octenal.This reaction is typical aldol reaction, has the universals of aldol condensation: both can be catalyzed by acids and also can be alkali catalyzed.Industrially carry out butyraldehyde-n self-condensation reaction, use sig water (NaOH) as catalyzer, carry out aldol condensation under certain temperature and pressure.Although higher butyraldehyde transformation efficiency and octenal yield can be obtained, but containing octenal and various organic acid sodium in the waste water of discharging, the organic acid sodium generated causes serious corrosion to equipment, direct discharging of waste water also can bring serious pollution to environment, and the waste water of process butyraldehyde condensation workshop section needs to consume a large amount of acid solutions, causes cost to improve.
Along with the development of Green Chemistry, people more and more pay attention to the exploitation of eco-friendly novel catalyzing technology process.Solid catalyst has high reactivity, highly selective, high stability, product are easy to the plurality of advantages such as separation, more and more receives publicity.Lou Hui etc. develop MgO catalyzer (CN102070419A respectively, 2011) and loaded catalyst (take oxide compound as carrier, an alkali metal salt and alkaline earth salt are active ingredient) (CN102093183A, 2011), when using solvent, the yield of 2-ethyl-2-hexenoic aldehyde is respectively 85% and about 70%.For aldol reaction, compared with use basic catalyst, use the reaction activity needed for an acidic catalyst lower, and the stability of solid acid catalyst is better.
The present invention adopts solid acid to be catalyzer, and catalysis butyraldehyde-n prepares the reaction of 2-ethyl-2-hexenoic aldehyde from condensation.
Summary of the invention
The invention provides a kind of solid acid catalyst generating the reaction of 2-ethyl-2-hexenoic aldehyde for butyraldehyde-n from condensation, avoid and use liquid alkali catalyst to there is the shortcoming that catalyzer can not be reused, wastewater discharge is large.This catalyzer has higher activity, selectivity and stability.
Technical scheme of the present invention is as follows:
A kind of solid acid catalysis butyraldehyde-n prepares the method for 2-ethyl-2-hexenoic aldehyde from condensation, comprise the following steps: in autoclave, add butyraldehyde-n and solid acid catalyst, the wherein 0.5%-25% of consumption quality added by butyraldehyde-n of catalyzer, with air in nitrogen replacement still, 100 DEG C-220 DEG C, under magnetic agitation reaction 0.5h-8h condition, butyraldehyde-n obtains 2-ethyl-2-hexenoic aldehyde through self-condensation reaction.
Described solid acid catalyst is: HY, HZSM-5, USY, H β, ALPO
4-11, ALPO
4-5, SAPO-34, Al
2o
3, Fe
2o
3, Nb
2o
5, AlPO
4, Al
2(SO
4)
3,cuSO
4, Fe
2(SO
4)
3, ZnSO
4, AlCl
3, CuCl
2, FeCl
3or ZnCl
2.
Beneficial effect of the present invention is as follows:
1. in the technique of industrial n butyraldehyde aldolization octenal, use sig water as catalyzer, not only can etching apparatus, discharge waste water can not be able to be reused environment but also catalyzer, cost is higher.The solid acid catalyst that the present invention studies has higher activity, selectivity and stability and aftertreatment is simple, and catalyzer is reusable, is easy to realize industrialization than solid base catalyst.
2. used solid acid catalyst, in butyraldehyde-n self-condensation reaction, without the need to using any solvent, the transformation efficiency of butyraldehyde-n is up to 87.5%, and the selectivity of product 2-ethyl-2-hexenoic aldehyde is up to 92.3%.
Embodiment
Embodiment 1
In 100ml autoclave, put into 40g butyraldehyde-n, and then add butyraldehyde-n quality 18.0% H β (40) catalyzer, use N
2displaced air, magnetic agitation, reacts 4h at 120 DEG C, and after reaction terminates, filtration under diminished pressure, carries out gas chromatographic analysis to production fluid, and the transformation efficiency of butyraldehyde-n is the selectivity of 75.5%, 2-ethyl-2-hexenoic aldehyde is 81.7%.
Embodiment 2-26 according to the operation steps of embodiment 1, the reaction conditions of change and the results are shown in summary sheet.
Embodiment 27
In 100ml autoclave, put into 30g butyraldehyde-n, and then add HZSM-5 (150) catalyzer of butyraldehyde-n quality 5%, use N
2displaced air, magnetic agitation, reacts 3h at 150 DEG C, and after reaction terminates, filtration under diminished pressure, carries out gas chromatographic analysis to filtrate, and the transformation efficiency of butyraldehyde-n is the selectivity of 80.7%, 2-ethyl-2-hexenoic aldehyde is 88.0%.By reacted HZSM-5 (150) catalyzer absolute ethanol washing three times, at 80 DEG C after dry 4h, put into retort furnace, roasting 4h at 500 DEG C.Then under identical reaction conditions, that investigates catalyzer reuses effect, the results are shown in following table.Along with the increase of reaction times, the activity of catalyzer declines to some extent, and after use 4 times, the selectivity of 2-ethyl-2-hexenoic aldehyde only have dropped 6.7%, and catalyzer still has very high activity.
| Number of times reused by catalyzer | Butyraldehyde-n transformation efficiency % | 2-ethyl-2-hexenoic aldehyde selectivity % |
| 1 | 80.7 | 88.0 |
| 2 | 77.9 | 86.5 |
| 3 | 73.3 | 82.1 |
| 4 | 72.6 | 81.3 |
Claims (1)
1. the method for 2-ethyl-2-hexenoic aldehyde prepared by a solid acid catalysis butyraldehyde-n from condensation, it is characterized by and comprise the following steps: in autoclave, add butyraldehyde-n and solid acid catalyst, the wherein 0.5%-25% of consumption quality added by butyraldehyde-n of catalyzer, with air in nitrogen replacement still, 100 DEG C-220 DEG C, under magnetic agitation reaction 0.5h-8h condition, butyraldehyde-n obtains 2-ethyl-2-hexenoic aldehyde through self-condensation reaction;
Described solid acid catalyst is: Al
2o
3, Fe
2o
3, Al
2(SO
4)
3, CuSO
4, Fe
2(SO
4)
3, ZnSO
4, AlCl
3, CuCl
2, FeCl
3or ZnCl
2.
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|---|---|---|---|
| CN201210507185.6A CN102924251B (en) | 2012-11-30 | 2012-11-30 | Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid |
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|---|---|---|---|
| CN201210507185.6A CN102924251B (en) | 2012-11-30 | 2012-11-30 | Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid |
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|---|---|
| CN102924251A CN102924251A (en) | 2013-02-13 |
| CN102924251B true CN102924251B (en) | 2015-03-11 |
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| CN113087605B (en) * | 2019-12-23 | 2023-05-26 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for preparing octenal |
| CN112961031B (en) * | 2021-02-23 | 2022-03-29 | 河北工业大学 | Method for preparing high-carbon alcohol based on low-carbon alcohol and acetal compound |
Citations (5)
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|---|---|---|---|---|
| CN101830785A (en) * | 2009-03-11 | 2010-09-15 | 上海隆瑞化工科技有限公司 | Method for generating octenal by reacting n-butyl aldehyde and application of polyethylene glycol |
| CN102019177A (en) * | 2009-09-18 | 2011-04-20 | 中国石油天然气股份有限公司 | Aldol condensation reaction solid base catalyst and application |
| CN102093178A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound by using reaction and rectification |
| CN102701926A (en) * | 2012-06-19 | 2012-10-03 | 河北工业大学 | Technical method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butyraldehyde with acidic ionic liquid |
| CN102746129A (en) * | 2012-07-23 | 2012-10-24 | 河北工业大学 | Process method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butanal with heteropoly acid |
-
2012
- 2012-11-30 CN CN201210507185.6A patent/CN102924251B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830785A (en) * | 2009-03-11 | 2010-09-15 | 上海隆瑞化工科技有限公司 | Method for generating octenal by reacting n-butyl aldehyde and application of polyethylene glycol |
| CN102019177A (en) * | 2009-09-18 | 2011-04-20 | 中国石油天然气股份有限公司 | Aldol condensation reaction solid base catalyst and application |
| CN102093178A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound by using reaction and rectification |
| CN102701926A (en) * | 2012-06-19 | 2012-10-03 | 河北工业大学 | Technical method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butyraldehyde with acidic ionic liquid |
| CN102746129A (en) * | 2012-07-23 | 2012-10-24 | 河北工业大学 | Process method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butanal with heteropoly acid |
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