CN103265400A - Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives - Google Patents
Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives Download PDFInfo
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- CN103265400A CN103265400A CN2013102041656A CN201310204165A CN103265400A CN 103265400 A CN103265400 A CN 103265400A CN 2013102041656 A CN2013102041656 A CN 2013102041656A CN 201310204165 A CN201310204165 A CN 201310204165A CN 103265400 A CN103265400 A CN 103265400A
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Abstract
The invention provides a novel method for preparing middle/long-chain primary alcohol from furan or tetrahydrofuran derivatives. Specifically, a double-function catalyst is adopted, and such catalyst comprises two activity centers, namely, a hydrogenation activity center and an acid center; water is taken as a solvent in the reaction, the reaction is carried out in a batch reactor, and by utilizing the characteristic that the middle/long-chain primary alcohol is not dissolved in water, the generated primary alcohol is naturally separated from water and the catalyst, and alkane is prevented from being generated because of hydrogen over-addition or hydrogenolysis. Due to the characteristic that the primary alcohol and the water are not dissolved with each other, the primary alcohol can be conveniently separated, the separation cost is greatly lowered, and good industrial prospect is achieved.
Description
Technical field
The present invention relates to a kind ofly prepare the novel method of primary alconol by furans or tetrahydrofuran derivatives, belong to the catalytic chemistry field.
Background technology
In, long-chain (C
5-C
15) primary alconol is widely used in the essence and flavoring agent industry, can be used as solvent, tensio-active agent, defoamer, industrial auxiliary agent etc. again simultaneously, has very important use in fine chemistry industry.In traditional, the long-chain primary alconol is to be produced by the petrochemical complex method.Be example with the n-Octanol, present existing maturation process route is to be raw material with 1-heptene and synthetic gas, restores through oxo synthesis to make.Because fossil oil exhausted day by day and for the worry of environmental problems such as global warming utilizes green reproducible biomass resource to produce fuel and chemical has become the task of top priority.Through thermochemistry, catalyzed conversion can prepare furans or the tetrahydrofuran (THF) analog derivative of a series of cheapnesss by biomass, then by selective catalytic hydrogenation/hydrogenolysis can prepare a series of in, the long-chain primary alconol.2012, have bibliographical information with the furfural of biomass derived and condensation of acetone, saturated hydrogenation abroad after, use ionic liquid [EMIM] [NTf again
2] as solvent, at acid additives [BSO
3BIM] [NTf
2] and Ru/C exist down, selectivity deoxidation hydrogenation under 150 ℃ and 12MPa hydrogen pressure, reaction 60h, the highest obtain 48.8% n-Octanol yield (Angew.Chem.Int.Ed., 2012,51:1-6).This method has been started the beginning that biomass derivatives prepares primary alconol, but production cost is high, ionic liquid itself is relatively more expensive, and adopt ionic liquid to make the separation of product become very complicated as solvent, the introducing of acid additives makes the recovery difficult of ionic liquid and catalyzer increase greatly again in addition, does not have industrial prospect.
Summary of the invention
The object of the present invention is to provide in a kind of furans or tetrahydrofuran derivatives compound that can be obtained by biomass derived, the green novel method of long-chain primary alconol, its core is to have adopted to have shortening/dual-function catalyst of hydrogenolysis ability, this catalyzer comprises two kinds of active centre: hydrogenation sites and acid sites, be solvent with water, can be under the condition of gentleness catalysis furans or tetrahydrofuran (THF) analog derivative hydrogenation/hydrogenolysis obtain primary alconol.Its reaction equation can be expressed as:
This by in the preparation of five yuan of oxygen helerocyclics, the characteristics of the green novel method of long-chain primary alconol are: this reaction is solvent with water, in batch reactor, carry out, by dual-function catalyst selective catalytic hydrogenation/hydrogenolysis, two kinds of active centre synergies make hydrogenation/hydrogenolysis activation energy reduce greatly; In utilizing simultaneously, the water-fast characteristic of long-chain primary alconol, make primary alconol and water and the catalyzer natural separation of generation, reaction product is stopped to primary alconol, prevent hydrogenation/hydrogenolysis generation alkane exceedingly.This product also makes with the immiscible characteristic of solvent and becomes very convenient separating of product, greatly reduces separation costs, has good industrial prospect.
Wherein, R
1Can be hydrogen or methylol, R
2Can be hydrogen, C
1-C
10Alkyl, one or more C that replace arbitrarily of hydroxyl, carbonyl, ester group, carboxyl, halogen, aromatic ring, heterocycle
1-C
10Alkyl.R in the product
2' expression R
2Group behind hydrogenation/hydrogenolysis, may with R
2Identical, also may be different, decide on different groups, specifically referring to embodiment 1-10.
Described dual-function catalyst comprises two kinds of active ingredients: (I) have metal Pt, Pd, Ru, Rh, Ir, the Ni of hydrogenation activity, the mixture of the one or any ratio among Co, the Cu; (II) has the Al of acid sites
2O
3, SiO
2, unbodied silico-aluminate, zeolite molecular sieve, sulfonation charcoal, sulfonate resin, supported liquid acid, solid heteropoly acid or Ti, V, Cr, Mn, Zr, Nb, Mo, Ta, W, Re a kind of mixture of or their arbitrary proportions of oxide compound, oxyhydroxide, vitriol, phosphoric acid salt, sulfonic fluoropolymer salt; Catalyzer is that the metal in (I) is carried on the solid acid carrier of (II) by equi-volume impregnating or coprecipitation method.
Describedly prepare the green novel method of primary alconol by furans or tetrahydrofuran derivatives, reaction is preferably:
The reactive mode of the novel method of above-mentioned preparation primary alconol is batch reactor, and temperature of reaction is 80-300 ℃, preferred 130-230 ℃; Pressure is 0.1-10MPa, preferred 1-6MPa; Reaction times is 5min-60h, preferred 3-30h.
With embodiment technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Embodiment
Embodiment 1-10
Embodiment 1-10 adopts polyfunctional catalyst Pd/H-ZSM-5 catalysis differential responses substrate, reacts under the differential responses condition, and reaction substrate and corresponding primary alconol see Table 1
Table 1
| Embodiment | Five-membered ring | R 1 | R 2 | R 2′ |
| Embodiment 1 | Furans | -H | -CHO | -CH 3 |
| Embodiment 2 | Furans | -H | -CH＝CHCOCH 3 | -CH 2CH 2CH 2CH 3 |
| Embodiment 3 | Tetrahydrofuran (THF) | -H | -CH 2COHCH 3 | -CH 2CH 2CH 3 |
| Embodiment 4 | Tetrahydrofuran (THF) | -H | -CH 2CH 3 | -CH 2CH 3 |
| Embodiment 5 | Furans | -H | -CH＝CHCOCH＝CH-C 4H 3O | -(CH 2) 9-OH |
| Embodiment 6 | Furans | -CH 2OH | -CHO | -CH 3 |
| Embodiment 7 | Tetrahydrofuran (THF) | -CH 2OH | -CH 2CH 2COOH | -CH 2CH 2CH 3 |
| Embodiment 8 | Tetrahydrofuran (THF) | -CH 2OH | -CH 2CH 2-C 6H 5 | -CH 2CH 2-C 6H 11 |
| Embodiment 9 | Furans | -CH 2OH | -CH 2CH 2Cl | -CH 2CH 2Cl |
| Embodiment 10 | Tetrahydrofuran (THF) | -CH 2OH | -CH 2COOCH 3 | -CH 2CH 3 |
Embodiment 1-10 reaction conditions and reaction result see Table 2
Table 2
| Embodiment | Temperature (℃) | Pressure (MPa) | Time (h) | Primary alconol yield (%) |
| Embodiment 1 | 170 | 3 | 24 | 33 |
| Embodiment 2 | 190 | 2 | 16 | 52 |
| Embodiment 3 | 200 | 2.5 | 6 | 47 |
| Embodiment 4 | 150 | 6 | 30 | 26 |
| Embodiment 5 | 220 | 4 | 10 | 35 |
| Embodiment 6 | 200 | 3.5 | 15 | 30 |
| Embodiment 7 | 230 | 5 | 18 | 43 |
| Embodiment 8 | 170 | 3 | 24 | 18 |
| Embodiment 9 | 240 | 4.5 | 2 | 27 |
| Embodiment 10 | 210 | 2.5 | 4 | 37 |
Embodiment 11-20
Embodiment 11-20 selects that 4-(2-furyl)-3-butene-2-ketone is substrate for use, selects different polyfunctional catalyst catalysis for use, reacts under different condition, and reaction result sees Table 3
Table 3
Claims (2)
1. one kind prepares the green novel method of primary alconol by furans or tetrahydrofuran derivatives, it is characterized in that:
Be solvent with water, furans or tetrahydrofuran derivatives react in batch reactor, by dual-function catalyst selective catalytic hydrogenation/hydrogenolysis, temperature of reaction is 80-300 ℃, hydrogen pressure is 0.1-10MPa, and the reaction times is 5min-60h, and its general formula is expressed as:
R wherein
1Be hydrogen or methylol, R
2Can be hydrogen, C
1-C
10Alkyl, one or more C that replace arbitrarily of hydroxyl, carbonyl, ester group, carboxyl, halogen, aromatic ring, heterocycle
1-C
10Alkyl.
2. according to claims 1 described polyfunctional catalyst, it is characterized in that this catalyzer comprises two kinds of active ingredients: (I) have metal Pt, Pd, Ru, Rh, Ir, the Ni of hydrogenation activity, the mixture of the one or any ratio among Co, the Cu; (II) has the Al of acid sites
2O
3, SiO
2, unbodied silico-aluminate, zeolite molecular sieve, sulfonation charcoal, sulfonate resin, supported liquid acid, solid heteropoly acid or Ti, V, Cr, Mn, Zr, Nb, Mo, Ta, W, Re a kind of mixture of or their arbitrary proportions of oxide compound, oxyhydroxide, vitriol, phosphoric acid salt, sulfonic fluoropolymer salt; Catalyzer is that the metal in (I) is carried on the solid acid carrier of (II) by equi-volume impregnating or coprecipitation method.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106278889A (en) * | 2015-05-13 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method preparing 5-hydroxyl methyl |
| CN108409560A (en) * | 2018-04-11 | 2018-08-17 | 合肥利夫生物科技有限公司 | A kind of preparation method of 1,13- tridecane diols ester and its 1,13- tridecane diols |
| CN108484360A (en) * | 2018-04-04 | 2018-09-04 | 中国科学技术大学 | A kind of preparation method of alcohol compound |
| CN108484394A (en) * | 2018-04-11 | 2018-09-04 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol |
| CN108774135A (en) * | 2018-08-06 | 2018-11-09 | 朱友富 | A kind of preparation method of 5- hydroxyl methyls |
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
| CN110357782A (en) * | 2018-04-11 | 2019-10-22 | 中国科学技术大学 | A kind of preparation method of middle long-chain fatty alcohol and its ester |
| JP2020525280A (en) * | 2017-07-20 | 2020-08-27 | ワンファ ケミカル グループ カンパニー，リミテッド | Catalyst based on silicalite-1 molecular sieve and method for preparing 1,2-pentanediol using the catalyst |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106278889A (en) * | 2015-05-13 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of method preparing 5-hydroxyl methyl |
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| JP2020525280A (en) * | 2017-07-20 | 2020-08-27 | ワンファ ケミカル グループ カンパニー，リミテッド | Catalyst based on silicalite-1 molecular sieve and method for preparing 1,2-pentanediol using the catalyst |
| CN108484360A (en) * | 2018-04-04 | 2018-09-04 | 中国科学技术大学 | A kind of preparation method of alcohol compound |
| CN108409560A (en) * | 2018-04-11 | 2018-08-17 | 合肥利夫生物科技有限公司 | A kind of preparation method of 1,13- tridecane diols ester and its 1,13- tridecane diols |
| CN108484394A (en) * | 2018-04-11 | 2018-09-04 | 合肥利夫生物科技有限公司 | A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol |
| CN110357782A (en) * | 2018-04-11 | 2019-10-22 | 中国科学技术大学 | A kind of preparation method of middle long-chain fatty alcohol and its ester |
| CN108409560B (en) * | 2018-04-11 | 2021-04-06 | 合肥利夫生物科技有限公司 | 1, 13-tridecanediol ester and preparation method of 1, 13-tridecanediol thereof |
| CN110357782B (en) * | 2018-04-11 | 2022-03-01 | 中国科学技术大学 | Preparation method of medium-long chain fatty alcohol and ester thereof |
| CN108774135A (en) * | 2018-08-06 | 2018-11-09 | 朱友富 | A kind of preparation method of 5- hydroxyl methyls |
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
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