CN103936570B - The method of acetal is prepared in one-level fatty alcohol dehydrogenation coupling - Google Patents
The method of acetal is prepared in one-level fatty alcohol dehydrogenation coupling Download PDFInfo
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- CN103936570B CN103936570B CN201410194223.6A CN201410194223A CN103936570B CN 103936570 B CN103936570 B CN 103936570B CN 201410194223 A CN201410194223 A CN 201410194223A CN 103936570 B CN103936570 B CN 103936570B
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
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Abstract
A kind of method that acetal is prepared in photocatalysis one-level fatty alcohol dehydrogenation coupling is that commercial titanium dioxide P25 is added in alcohol reactant liquor, add noble metal source solution simultaneously, under magnetic agitation, vacuumize or pass into argon gas, remove after the oxygen in system, stop vacuumizing or passing into argon gas, open uviol lamp source, by original position photocatalysis, noble metal source is reduced into noble metal granule, load to titanium dioxide surface, catalytic alcohol dehydrogenation coupling forms acetal. Control reaction temperature 10-70 DEG C, reaction time 10-72 hour. After reaction finishes, by centrifugation, vacuum filtration or quiescent setting method separating catalyst, then alcohol is removed in decompression distillation, obtains acetal product. The present invention has high, the with low cost and advantages of environment protection of selective height, productive rate, and purity reaches more than 97%.
Description
Technical field
The present invention relates to the synthetic method of acetal, specifically under a kind of illumination condition, use semiconductor light-catalyst catalytic alcohol de-The method of the corresponding acetal of hydrogen coupling preparation.
Background technology
Acetal is a class oxygen-containing organic compound, is not only important pharmaceutical intermediate, spices, organic solvent, and is a kind ofImportant potential green fuel or fuel additive. For example acetal is added diesel oil can significantly reduce the row of particulate and nitrogen oxidePut, improve Cetane number; Acetal can be used as alcohol fuel additive and reduces burning-point.
The method of traditional synthetic acetal adopts two-step method: first alcohol be oxidized to corresponding aldehyde, then under acid catalysis condition by aldehydeWith alcohol condensation prepare acetal (bibliography: R.MorrisonandR.Boyd, ' Organicchemistry (4thed.) ', AllynandBacon,1983；F.Frusteri,L.Spadaro,C.Beatrice,andC.Guido,ChemicalEngineeringJournal,2007,134239-245.). Utilize oxygen that primary alcohol (methyl alcohol, ethanol, a normal propyl alcohol and n-butanol) step coupling is oxidized to phaseAnswer the research of acetal also to have report, under acid chloride, copper acetate and the acting in conjunction of p-methyl benzenesulfonic acid multicomponent catalyst, selectively canReach more than 90% (bibliography: A.C.Bueno, J.A.Goncalves, andE.V.Gusevskaya, AppliedCatalysisA:General, 2007,329,1-6). But these two kinds of processes all need acid catalyst, and environment is caused to severe contamination. Recently, MilsteinEtc. discovery utilize ruthenium homogeneous catalyst can be directly by n-amyl alcohol and n-hexyl alcohol oxidation be coupled be penta acetal and own acetal (bibliography:C.Gunanathan, L.J.W.Shimon, andD.Milstein, J.Am.Chem.Soc., 2009,131,3146-3147). But loseRegret be that the method not only needs higher temperature, and living beings ethanol and butanols can not generate acetal under this condition.
Photocatalysis is a kind of green synthesis techniques, is conventionally applied to the organic and inorganic pollution in degraded gas phase and liquid phase, oftenNormal temperature and pressure carries out, easy to operate, conventionally can not produce secondary pollution. At present existing a lot of photocatalysis technologies are applied to organic synthesisReport, but because the Characteristics of Free Radicals Produced of light-catalyzed reaction causes photocatalysis organic synthesis selectively low, be not used widely.Although the reports such as Yoshida utilize Ta2O5/SiO2And Nb2O5/SiO2For catalyst can be coupled as second by ethanol photochemical catalytic oxidationAcetal, but reaction generates acetaldehyde, acetic acid, ethene and CO2Deng accessory substance, productive rate very low (bibliography: T.Tanaka, S.Takenaka,T.Funabiki,andS.Yoshida,Chem.Lett.,1994,809；T.Tanaka,S.Takenaka,T.Funabiki,andS.Yoshida,Stud.Surf.Sci.Catal.,1994,90,485)。
Summary of the invention
The object of the present invention is to provide that a kind of yield is high, purity is high, cost is low, non-environmental-pollution, the simple photocatalysis of techniqueThe method of acetal is prepared in one-level fatty alcohol dehydrogenation coupling.
The present invention utilizes commercial titanium dioxide P25 for catalyst, supports co-catalyst, photocatalysis alcohol one step under UV-irradiationThe synthetic acetal of method highly selective dehydrogenation coupling, by-product hydrogen simultaneously. This invented technology method is simple, and catalyst is with low cost,Selectivity of product, up to more than 97%, is easy to separate, and is the technology of the synthetic acetal of an efficient green. Course of reaction is as follows:
The present invention is achieved through the following technical solutions:
Add 0.5-2.5g catalyst by every 100-500ml alcoholic solution, catalyst is added in alcoholic solution, press catalytic amount simultaneously0.5-1.0wt% add noble metal source solution, under magnetic agitation, vacuumize or pass into argon gas, remove after the oxygen in system, stopOnly vacuumize or pass into argon gas, open uviol lamp, by original position photocatalysis, noble metal source is reduced into noble metal granule and loads to and urgeAgent surface, carries out the reaction of photocatalysis alcohol dehydrogenase coupling formation acetal. Control reaction temperature 10-70 DEG C, reaction 10-72 hour,By centrifugation, vacuum filtration or quiescent setting method separating catalyst, then isolate alcohol by decompression distillation, producedThing acetal.
Described catalyst is commercial titanium dioxide P25.
Described noble metal source solution is the alcoholic solution of chloroplatinic acid or palladium bichloride, the chloroplatinic acid that specifically concentration is 100mg/ml orThe alcoholic solution of palladium bichloride.
Described alcohol is ethanol, normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol etc.
Described uviol lamp power is 10-2000W, preferably 300-2000W.
The present invention compared with prior art tool has the following advantages: the method that 1, adopts photocatalysis alcohol dehydrogenase to be coupled is prepared acetal, and light is urgedChange is a kind of synthetic route of green, and photocatalysis organic synthesis is carried out conventionally at normal temperatures and pressures, easy to operate, generally can not produceSecondary pollution. 2, raw material is one-level fatty alcohol, can reuse, and conversion ratio is high. 3 technical process are simple, having property of catalystStable, active high, cheap, the advantages of environment protection of matter. 4, product acetal is simple with separating of alcohol and catalyst, productSelective high, purity is up to more than 97%.
Brief description of the drawings
The gas chromatogram of Fig. 1 embodiment 1 ethanol light-catalyzed reaction liquid
The electron impact mass spectra figure of Fig. 2 embodiment 1 acetal
The gas chromatogram of Fig. 3 embodiment 2 propyl alcohol light-catalyzed reaction liquid
The electron impact mass spectra figure of Fig. 4 embodiment 2 propylal
The gas chromatogram of Fig. 5 embodiment 3 butanols light-catalyzed reaction liquid
The electron impact mass spectra figure of Fig. 6 embodiment 3 butyral
The gas chromatogram of Fig. 7 embodiment 4 amylalcohol light-catalyzed reaction liquid
The gas chromatogram of Fig. 8 embodiment 5 hexanol light-catalyzed reaction liquid
Detailed description of the invention
Below by embodiment, the present invention will be further described, and its object is only to understand better research contents of the present invention,But not limit the scope of the invention.
In embodiment, noble metal source solution used is that concentration is the chloroplatinic acid of 100mg/ml or the alcoholic solution of palladium bichloride, describedAlcohol is ethanol, normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol.
Embodiment 1
1gP25 photochemical catalyst is joined in 200ml ethanolic solution, add the chloroplatinic acid ethanol of catalytic amount 1wt% molten simultaneouslyLiquid, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out photocatalysisAlcohol dehydrogenase is coupled the reaction of synthetic acetal, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes, by quietPut and precipitate and isolate reactant liquor, solution distills and obtains product acetal. Gas chromatographic analysis shows, second contracting in liquid productAldehyde is selectively 99.3%, and ethanol conversion is 27.7%.
Embodiment 2
1gP25 photochemical catalyst is joined in 200ml normal propyl alcohol solution, add the chloroplatinic acid positive third of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis normal propyl alcohol is coupled the reaction of synthetic propylal, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product propylal. Gas chromatographic analysis shows, liquid productMiddle propylal is selectively 99.5%, and normal propyl alcohol conversion ratio is 24.8%.
Embodiment 3
1gP25 photochemical catalyst is joined in 200ml butanol solution, add the positive fourth of chloroplatinic acid of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-butanol is coupled the reaction of synthetic butyral, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.2%, and n-butanol conversion ratio is 22.2%.
Embodiment 4
1gP25 photochemical catalyst is joined in 200ml n-amyl alcohol solution, add the chloroplatinic acid positive penta of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-amyl alcohol is coupled the reaction of synthetic penta acetal, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product penta acetal. Gas chromatographic analysis shows, liquid productIn penta acetal be selectively 99.3%, n-amyl alcohol conversion ratio is 17.9%.
Embodiment 5
1gP25 photochemical catalyst is joined in 200ml n-hexyl alcohol solution, add the chloroplatinic acid of catalytic amount 1wt% just own simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-hexyl alcohol is coupled the reaction of synthetic own acetal, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains the own acetal of product. Gas chromatographic analysis shows, liquid productIn own acetal be selectively 97.2%, n-hexyl alcohol conversion ratio is 12.1%.
Embodiment 6
1gP25 photochemical catalyst is joined in 200ml butanol solution, add the positive fourth of palladium bichloride of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-butanol is coupled the reaction of synthetic butyral, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.3%, and n-butanol conversion ratio is 21.3%.
Embodiment 7
1gP25 photochemical catalyst is joined in 200ml butanol solution, just adding the chloroplatinic acid of catalytic amount 0.5wt% simultaneouslyButanol solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries outThe dehydrogenation of photocatalysis n-butanol is coupled the reaction of synthetic butyral, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.1%, and n-butanol conversion ratio is 20.5%.
Embodiment 8
1gP25 photochemical catalyst is joined in 200ml butanol solution, add the positive fourth of chloroplatinic acid of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 2000W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-butanol is coupled the reaction of synthetic butyral, controls 25 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.1%, and n-butanol conversion ratio is 31%.
Embodiment 9
1gP25 photochemical catalyst is joined in 200ml butanol solution, add the positive fourth of chloroplatinic acid of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 300W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-butanol is coupled the reaction of synthetic butyral, controls 70 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.2%, and n-butanol conversion ratio is 21.6%.
Embodiment 10
1gP25 photochemical catalyst is joined in 200ml butanol solution, add the positive fourth of chloroplatinic acid of catalytic amount 1wt% simultaneouslyAlcoholic solution, passes into argon gas under magnetic agitation, after the air in eliminating system, closes argon gas, opens 100W high-pressure sodium lamp and carries out lightThe dehydrogenation of catalysis n-butanol is coupled the reaction of synthetic butyral, controls 70 DEG C of reaction temperatures, reaction time 12h. After reaction finishes,Isolate reactant liquor by staticly settling, solution distills and obtains product butyral. Gas chromatographic analysis shows, liquid productMiddle butyral is selectively 99.5%, and n-butanol conversion ratio is 14.6%.
Claims (6)
1. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling, it is characterized in that, comprises the steps:
Add 0.5-2.5g catalyst by every 100-500ml alcoholic solution, catalyst is added in alcoholic solution, press catalytic amount simultaneously0.5-1.0wt% add noble metal source solution, under magnetic agitation, vacuumize or pass into argon gas, remove after the oxygen in system, stopOnly vacuumize or pass into argon gas, open uviol lamp, control reaction temperature 10-70 DEG C, reaction 10-72 hour, quiescent setting method is dividedFrom catalyst, then isolate alcohol by decompression distillation, obtain product acetal; Wherein said catalyst is commercial titanium dioxide;Described noble metal source solution is the alcoholic solution of chloroplatinic acid or palladium bichloride.
2. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling as claimed in claim 1, it is characterized in that your described goldGenus source solution is that concentration is the chloroplatinic acid of 100mg/ml or the alcoholic solution of palladium bichloride.
3. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling as claimed in claim 1, it is characterized in that, described alcohol isEthanol, normal propyl alcohol, n-butanol, n-amyl alcohol or n-hexyl alcohol.
4. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling as claimed in claim 1, it is characterized in that described ultravioletThe power of lamp is 10-2000W.
5. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling as claimed in claim 4, it is characterized in that described ultravioletThe power of lamp is 300-2000W.
6. the method for acetal is prepared in one-level fatty alcohol dehydrogenation coupling as claimed in claim 1, it is characterized in that, described is staticPrecipitation substitutes with centrifugation or vacuum filtration.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565429A (en) * | 1979-06-26 | 1981-01-20 | Ube Ind Ltd | Preparation of acetal |
| JPS5735535A (en) * | 1980-08-07 | 1982-02-26 | Daicel Chem Ind Ltd | Preparation of acetal |
| CN1911510A (en) * | 2006-08-24 | 2007-02-14 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl acetal and its preparation method and application |
| CN101322943A (en) * | 2007-06-15 | 2008-12-17 | 南京大学 | Ti2O nano tube supported V2O5 composite catalyst |
| CN101428211A (en) * | 2008-12-12 | 2009-05-13 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof |
| CN102731273A (en) * | 2012-07-09 | 2012-10-17 | 北京大学 | Preparation method of acetal |
-
2014
- 2014-05-08 CN CN201410194223.6A patent/CN103936570B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565429A (en) * | 1979-06-26 | 1981-01-20 | Ube Ind Ltd | Preparation of acetal |
| JPS5735535A (en) * | 1980-08-07 | 1982-02-26 | Daicel Chem Ind Ltd | Preparation of acetal |
| CN1911510A (en) * | 2006-08-24 | 2007-02-14 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl acetal and its preparation method and application |
| CN101322943A (en) * | 2007-06-15 | 2008-12-17 | 南京大学 | Ti2O nano tube supported V2O5 composite catalyst |
| CN101428211A (en) * | 2008-12-12 | 2009-05-13 | 中国科学院山西煤炭化学研究所 | Catalyst for producing dimethoxymethane with methanol selective oxidation and preparation method thereof |
| CN102731273A (en) * | 2012-07-09 | 2012-10-17 | 北京大学 | Preparation method of acetal |
Non-Patent Citations (1)
| Title |
|---|
| Photocatalflc Oxidation of Ethanol over Tantalum Oxide Supported on Silica;Tsunehiro Tanaka等;《Stud.Surf.Sci.Catal.》;19941231;第90卷;第486页2.实验和表1 * |
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