CN103086856B - Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid - Google Patents
Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid Download PDFInfo
- Publication number
- CN103086856B CN103086856B CN201310050973.1A CN201310050973A CN103086856B CN 103086856 B CN103086856 B CN 103086856B CN 201310050973 A CN201310050973 A CN 201310050973A CN 103086856 B CN103086856 B CN 103086856B
- Authority
- CN
- China
- Prior art keywords
- solid acid
- ethyl
- potassium salt
- sylvite
- butyraldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process for preparing 2-ethyl-2-hexylenaldehyde from n-butyl aldehyde by self-condensation through catalysis of potassium salt-solid acid, which comprises the following steps: adding n-butyl aldehyde and a potassium salt-solid acid catalyst into a reaction kettle, wherein the ratio of components in the potassium salt-solid acid catalyst is as follows: the mass ratio of potassium salt to solid acid is (1-20):1, and the catalyst accounts for 0.5-15% of the mass of the n-butyl aldehyde; and reacting at 20-150 DEG C for 0.5-8 hours while stirring, and performing self-condensation reaction on the n-butyl aldehyde to obtain the 2-ethyl-2-hexylenaldehyde. According to the invention, the used potassium salt-solid acid catalyst has the advantages of high activity, favorable selectivity, no equipment corrosion, simple posttreatment and the like, and can overcome the defects of a liquid base catalyst. The maximum conversion rate of the n-butyl aldehyde can be up to 99.0%, and the maximum selectivity of the 2-ethyl-2-hexylenaldehyde can be up to 99.1%, thereby ensuring that the invention has favorable industrial application prospects.
Description
Technical field
The present invention relates to Green Chemical Technology field, be specially the processing method of employing sylvite-solid acid catalysis synthesis 2-ethyl-2-hexenoic aldehyde.
Background technology
Butyraldehyde-n is one of important step of industrial production octanol from condensation synthesis 2-ethyl-2-hexenoic aldehyde (octenal) reaction.Octanol is important basic organic chemical industry raw material, mainly for the production of softening agent such as dioctyl phthalate (DOP) (DOP), dioctyl terephthalate (DOTP), Octyl adipates (DOA), be widely used in the production of various plastics and rubber item, also can be used as the defoamer of the industry such as papermaking, paint, printing and dyeing simultaneously, be also widely used in solvent, tackiness agent, petroleum additive etc.
It is typical aldol reaction that butyraldehyde-n prepares 2-ethyl-2-hexenoic aldehyde from condensation.Aldol condensation refer to acid or alkali katalysis under, there is nucleophilic addition by the compound (as aldehyde, ketone, carboxylic acid and ester etc.) containing active alpha-hydrogen atom and obtain beta-hydroxy aldehyde or acid, or dehydration obtains α, the reaction of beta-unsaturated aldehyde ketone or acid esters further.
At present, the industrial production of 2-ethyl-2-hexenoic aldehyde obtains mainly through liquid base catalysis butyraldehyde-n self-condensation reaction.This technique is simple, and economic benefit is higher, but there is many shortcomings: (1), if liquid base concentration is too low, condensation reaction is complete not, low conversion rate; If liquid base excessive concentration, aldol reaction is violent, and easily generate trimer or polymer, by product is more, causes selectivity on the low side; (2) large containing alkali waste water quantity discharged, contaminate environment on the one hand, processing costs is high on the other hand; (3) production cost is high, and one is have a large amount of NaOH to run off along with waste water, causes catalyst consumption to remain high; Two is that reaction terminates to contain product in rear aqueous phase, needs to be extracted by techniques such as extractions, causes running cost to improve; Three is that process waste water needs to consume a large amount of acid solutions etc., causes running cost to improve.
In order to overcome the shortcoming that traditional liquid alkaline catalysts brings, research and development novel green catalyzer seems particularly important.In recent years, under enzymatic inspiration, the application of soda acid concerted catalysis is increasing.Compared to liquid alkali catalyst, sylvite-solid acid, as a class difunction catalyst, has high reactivity, highly selective, product is easy to the plurality of advantages such as separation.The present invention carries out butyraldehyde-n and prepares the reaction of 2-ethyl-2-hexenoic aldehyde from condensation using sylvite-solid acid as catalyzer.
Summary of the invention
The object of the invention is, production cost high deficiency large for the liquid alkali catalyst loss existed in current techniques, a kind of sylvite-solid acid catalyst preparing the reaction of 2-ethyl-2-hexenoic aldehyde for butyraldehyde-n from condensation is provided.This catalyzer have active high, selectivity good, non-corrosiveness and the advantage such as reaction conditions is gentle.
Technical scheme of the present invention is
Sylvite-solid acid catalysis butyraldehyde-n prepares a processing method for 2-ethyl-2-hexenoic aldehyde from condensation, comprises the following steps:
Add butyraldehyde-n and sylvite-solid acid catalyst in a kettle., the material proportion formed in sylvite-solid acid catalyst is: quality is than sylvite: solid acid=1 ~ 20:1, the consumption of catalyzer is the 0.5%-15% of butyraldehyde-n quality, stirring reaction 0.5h-8h at 20 DEG C-150 DEG C, butyraldehyde-n obtains 2-ethyl-2-hexenoic aldehyde through self-condensation reaction.
Described sylvite comprises: KHCO
3, K
2cO
3, K
2tiO
3, KNO
3, CH
3cOOK, KF, KCl, KBr or KI.
Described solid acid is: HZSM-5, H β, HY, USY, CRP-1, ALPO
4, γ-Al
2o
3, Fe
2o
3, Nb
2o
5, AlCl
3, FeCl
3or ZnCl
2.
Beneficial effect of the present invention is as follows:
1. for the self-condensation reaction of butyraldehyde-n, traditional liquid alkaline catalysts can bring a large amount of Industry Waste buck, needs a large amount of acid solutions to carry out neutralization washing, not only causes environmental pollution, also cause production cost to improve.Sylvite-solid acid catalyst has active high, the advantage such as selectivity good, etching apparatus, aftertreatment be not simple, can overcome the shortcoming of liquid alkali catalyst.
2. used sylvite-solid acid catalyst, in butyraldehyde-n self-condensation reaction, the selectivity that the transformation efficiency of butyraldehyde-n reaches as high as 99.0%, 2-ethyl-2-hexenoic aldehyde reaches as high as 99.1%, has good prospects for commercial application.
Embodiment
Embodiment 1
In 100mL reactor, put into 30g butyraldehyde-n, and then add the KF-H beta catalyst of butyraldehyde-n weight 10%, KF and H β mass ratio 5:1, adopt N
2displaced air, magnetic agitation, reacts 4h at 100 DEG C.After reaction terminates, carry out gas chromatographic analysis to reaction solution, the transformation efficiency of butyraldehyde-n is the selectivity of 89.9%, 2-ethyl-2-hexenoic aldehyde is 81.1%.
Sylvite-solid acid in the present invention is common commercial reagent.
Embodiment 2-20 according to the operation steps of embodiment 1, reaction conditions and the results are shown in summary sheet.
As can be seen from the above embodiments, sylvite-solid acid catalyst is applied to butyraldehyde-n self-condensation reaction by the present invention, and the selectivity that the transformation efficiency of butyraldehyde-n reaches as high as 99.0%, 2-ethyl-2-hexenoic aldehyde reaches as high as 99.1%.Sylvite-solid acid catalyst used in the present invention has active high, the advantage such as selectivity good, etching apparatus, aftertreatment be not simple.
Claims (1)
1. sylvite-solid acid catalysis butyraldehyde-n prepares a processing method for 2-ethyl-2-hexenoic aldehyde from condensation, it is characterized by and comprises the following steps:
Add butyraldehyde-n and sylvite-solid acid catalyst in a kettle., the material proportion formed in sylvite-solid acid catalyst is: quality is than sylvite: solid acid=1 ~ 20:1, the consumption of catalyzer is the 0.5%-15% of butyraldehyde-n quality, stirring reaction 0.5h-8h at 20 DEG C-150 DEG C, butyraldehyde-n obtains 2-ethyl-2-hexenoic aldehyde through self-condensation reaction;
Described sylvite is: KHCO
3, K
2tiO
3, CH
3cOOK, KCl, KBr or KI;
Described solid acid is: HZSM-5, H β, HY, USY, CRP-1, ALPO
4, Fe
2o
3, Nb
2o
5, AlCl
3, FeCl
3or ZnCl
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310050973.1A CN103086856B (en) | 2013-02-16 | 2013-02-16 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310050973.1A CN103086856B (en) | 2013-02-16 | 2013-02-16 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103086856A CN103086856A (en) | 2013-05-08 |
| CN103086856B true CN103086856B (en) | 2015-07-22 |
Family
ID=48200048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310050973.1A Active CN103086856B (en) | 2013-02-16 | 2013-02-16 | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103086856B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093183A (en) * | 2010-12-22 | 2011-06-15 | 浙江大学 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
| 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 |
-
2013
- 2013-02-16 CN CN201310050973.1A patent/CN103086856B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093183A (en) * | 2010-12-22 | 2011-06-15 | 浙江大学 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| A new approach to the synthesis of diacetals (diketals)pentaerythritol catalyzed by SO3H-functionalized ionic liquids;Yuan Yuan Wang等;《Chinese Chemical Letters》;20101231;第21卷;第524-528页 * |
| 正丁醛自缩合生产辛烯醛新型催化工艺研究;张媛媛;《中国优秀硕士学位论文全文数据库》;20100815(第8期);第1-62页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103086856A (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102701926B (en) | Technical method for preparing 2-ethyl-2-hexenal by catalyzing self-condensation of n-butyraldehyde with acidic ionic liquid | |
| CN107096551B (en) | A kind of double isobutyrate catalyst for esterification reaction of 2,2,4- trimethyl -1,3- pentanediol and preparation method and purposes | |
| CN110204422A (en) | A method of 1,3- propylene glycol is prepared by methacrylaldehyde | |
| CN102259025B (en) | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof | |
| CN105148990A (en) | Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst | |
| CN102557908B (en) | Preparation method of 2- (cyclohex-1' -enyl) cyclohexanone | |
| CN101869847B (en) | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof | |
| CN103342638A (en) | Preparation method of dibutyl succinate | |
| CN109794285A (en) | A kind of catalyst and the preparation method and application thereof preparing hydroxyacetic acid for formaldehyde carbonylation | |
| CN103086856B (en) | Process for synthesizing 2-ethyl-2-hexylenaldehyde through catalysis of potassium salt-solid acid | |
| CN104945238A (en) | Isocaprylic acid production process | |
| CN102259008B (en) | Solid acid catalyst for esterification reaction and preparation method thereof | |
| CN103012079A (en) | Method for synthesizing ethylene glycol allyl ether under catalysis of solid base catalyst | |
| CN106883087A (en) | A kind of Cu/TiO of volatile corrosion inhibitor film producing ethylene with ethyl alcohol, acetaldehyde and acetone2Catalyst and reaction process | |
| CN105906484A (en) | Method for preparing phenol by directly oxidizing benzene | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN109734722A (en) | A kind of method that sorb dehydration of alcohols prepares isobide | |
| CN111302981A (en) | Method for preparing taurine | |
| CN101745396B (en) | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof | |
| CN103665062A (en) | Method for producing alkyl glycoside by utilizing starch | |
| CN105712858A (en) | Method for catalyzing olefin oxidation to produce aromatic aldehyde with metalloporphyrin as catalyst | |
| CN102924251B (en) | Method for preparing 2-ethyl-2-hexenoic aldehyde through n-butyl aldehyde self-condensation under catalysis of solid acid | |
| CN109420510A (en) | A kind of preparing cyclohexane by hydrogenating benzene catalyst and preparation method thereof | |
| CN102285882B (en) | Method for synthesizing acetyl tributyl citrate (ATBC) by adopting composite ionic liquid catalyst | |
| CN102964244A (en) | Method for separating refined sec-butyl acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |