CN105797711A - Preparation method of catalyst for catalyzing glucose to generate 5-hydroxymethylfurfural through dehydration process - Google Patents
Preparation method of catalyst for catalyzing glucose to generate 5-hydroxymethylfurfural through dehydration process Download PDFInfo
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- CN105797711A CN105797711A CN201610227370.8A CN201610227370A CN105797711A CN 105797711 A CN105797711 A CN 105797711A CN 201610227370 A CN201610227370 A CN 201610227370A CN 105797711 A CN105797711 A CN 105797711A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention discloses a catalyst for catalyzing glucose to generate 5-hydroxymethylfurfural (5-HMF) through the dehydration process.The catalyst is an efficient catalyst prepared through the steps that alumina nanofibers are synthesized through a hydrothermal method, and then the alumina nanofibers are loaded with tungsten oxide through an equivalent-volume impregnation method, and the prepared catalyst can significantly increase the yield of 5-hydroxymethylfurfural.When dimethyl sulfoxide serves as a solvent, alumina loaded with 40 wt% of tungsten oxide serves as the catalyst, and glucose is catalyzed for 4 h at 150 DEG C, the yield of 5-hydroxymethylfurfural can reach 51.6% and is higher than that of 5-hydroxymethylfurfural obtained through alumina catalysis by 18.2%, and the catalyst is the efficient catalyst with a directional selectivity function.
Description
Technical field
The present invention relates to the preparation method of a kind of supported solid catalyst loading tungsten oxide on alumina host.
Background technology
Fossil energy is not only the important substance resource concerning economic development, or the important substance that human society is indispensable
Basis.However as the exhaustion day by day of the energy, the whole world is faced with the test of the energy crisis of sternness.On the other hand, fossil
The environment also depended on for existence to us of product of resource burning brings huge environmental effect, such as water pollutions, air pollution, entirely
Ball warms.Biomass energy mainly organism converts solar energy into, by photosynthesis, the energy that chemical energy is stored in organism
Amount.Biomass, as the one of regenerative resource, rich reserves, cheap, wide material sources, become ideal replacement
Resource and paid close attention to widely.
It is a kind of very important platform chemicals that saccharide prepares 5 hydroxymethyl furfural (5-HMF), is also effectively to utilize biomass
One of aspect, catalyst plays vital effect to product yield, in early days using mineral acid as catalyst, such as hydrochloric acid,
Sulphuric acid etc..But mineral acid has etching apparatus, and wastewater discharge is big, and byproduct of reaction is many, and aftertreatment technology complexity etc. lacks
Point, disagrees with the chemical industry greenization that nowadays society advocates；People attempted using organic acid and some salt compounds later,
Such as oxalic acid, ammonium salt etc., what research recently was relatively more is solid acid such as ion exchange resin and ionic liquid, and zeolite molecular sieve etc. is made
For catalyst, wherein solid acid makees catalyst and forms two-phase system with solvent, is more beneficial for separating with solvent and product.Tradition
Theory is thought, lewis acid beneficially glucose isomerase turns to fructose, and bronsted acid is then conducive to fructose dehydration to be converted into other
Compound.Owing to metal oxide surface has different acid basic sites, applied to glucose isomerization and dehydration is anti-
Ying Zhong, numerous researchs show, bimetallic oxide is more beneficial for biomass turning to 5-HMF compared to single metal-oxide
Change.
Summary of the invention
The invention provides and a kind of rapidly and efficiently can generate the synthetic method of catalyst of 5 hydroxymethyl furfural by catalysis biomass.
Can be used for improving biomass and be converted into the efficiency of 5 hydroxymethyl furfural.
Preparation process of the present invention is simple, it is not necessary to expensive device, and the good performance of products obtained therefrom quality is high, can quickly, efficient,
Directional catalyzing biomass are converted into 5 hydroxymethyl furfural.
In the present invention, the catalyst low cost, effective of preparation, is a kind of effective catalyst with orthoselection sexual function,
5 hydroxymethyl furfural can be converted into by catalysis biomass fast and efficiently.
A kind of biomass that the present invention proposes are converted into the preparation method of the catalyst of 5 hydroxymethyl furfural, comprise the following steps:
1) ammonia water titration Al (NO3)3·9H2O solution is to pH=5；Described Al (NO3)3·9H2In O solution
Al(NO3)3·9H2The mass ratio of O and water is 3: 5, and described ammonia concn is 10%；
2) with teflon-lined hydrothermal reaction kettle fill step 1) in mixture, carry out hydro-thermal reaction；
3) with distilled water and ethanol washing step 2 successively) in reacted precipitation, be dried afterwards；
4) in Muffle furnace, calcine 3) solid that obtains, obtain the matrix alumina nanofiber of catalyst；
5) step 4) alumina nano fiber that obtains adds phosphotungstic acid water incipient impregnation；Described phosphotungstic acid and aluminium oxide
Consumption according to the load capacity of tungsten oxide；
6) step 5) the mixture drying that obtains, obtain loading the alumina nano fiber catalyst of tungsten oxide.
7) test above-mentioned product catalyst glucose by high performance liquid chromatography and generate the productivity of 5-HMF, characterize its catalytic performance.
Described hydrothermal condition is 200 DEG C, and the response time is 48h.
Described drying condition is the vacuum drying at 55 DEG C or oven drying, and drying time is 12h.
Described calcination condition is 600 DEG C, and calcination time is 5h.
Described drying condition is the vacuum drying at 100 DEG C or oven drying, and drying time is 24h.
Described catalytic condition is 150 DEG C of reaction 4h.
The invention have the advantages that
The raw material that the present invention uses is mainly Al (NO3)3·9H2O and ammonia, wide material sources, low price, safety is high.
Catalyst prepared by the inventive method is effective catalyst, and with dimethyl sulfoxide as solvent, load 40wt% aoxidizes
The aluminium oxide of tungsten, as catalyst, is catalyzed glucose 4 hours at 150 DEG C, and the productivity of 5 hydroxymethyl furfural can reach
51.6%, the productivity of the 5 hydroxymethyl furfural obtained than alumina catalyzation is high 18.2%.
Catalyst prepared by the inventive method has easy separation, and this catalyst is solid catalyst, can pass through after having reacted
The simple operationss such as filtration washing are separated from reaction system.
Catalyst prepared by the inventive method can synthesize in a large number, it is not necessary to expensive device.
Accompanying drawing explanation
Fig. 1 be specific embodiment 1 obtain at γ-Al2O340%WO is loaded on nanofiber matrix3Catalyst
SEM schemes (long 300-400nm；Wide 30-50nm)；
Fig. 2 is the productivity that the different loads rate catalyst glucose obtained in specific embodiment 1,2 generates 5-HMF.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
30g Al(NO3)3·9H2O is dissolved in bis-water of 50mL and obtains Al (NO3)3Solution, 40mL 25% ammonia is fixed with secondary water
Hold to 100mL, shake up and titrate Al (NO with it3)3Solution is to pH=5.
Being poured in the hydrothermal reaction kettle that politef is liner by reactant liquor after titration, oven temperature is adjusted to 200 DEG C,
Temperature stabilization, to after 200 DEG C, puts into baking oven after being tightened by water heating kettle, the response time is 48h.
Wash successively with secondary water and dehydrated alcohol after precipitation after hydro-thermal reaction is collected, after being dried 12h at 55 DEG C
Obtain the AlOOH nanofiber of white.
Muffle furnace is adjusted to 600 DEG C, is loaded and puts into Muffle furnace after crucible by AlOOH nanofiber, response time 5h,
It is cooled to room temperature, obtains γ-Al2O3Nanofiber.
0.5gγ-Al2O3Nanofiber mixes with 0.3450g phosphotungstic acid, adds equivalent impregnation 48h under appropriate secondary hydroecium temperature,
Oven temperature is adjusted to 100 DEG C, after temperature stabilization to 100 DEG C, puts it into baking oven, is cooled to room temperature and obtains after 24h
40%WO3-Al2O3。
Above-mentioned obtained solid catalyst being used for be catalyzed glucose and is converted into the reaction of 5-HMF, end product is high
Effect liquid phase chromatogram measures its productivity, characterizes the catalytic performance of this kind of different-phase catalyst (aluminium oxide of load tungsten oxide).
Embodiment 2
30g Al(NO3)3·9H2O is dissolved in bis-water of 50mL and obtains Al (NO3)3Solution, 40mL 25% ammonia is fixed with secondary water
Hold to 100mL, shake up and titrate Al (NO with it3)3Solution is to pH=5.
Being poured in the hydrothermal reaction kettle that politef is liner by reactant liquor after titration, oven temperature is adjusted to 200 DEG C,
Temperature stabilization, to after 200 DEG C, puts into baking oven after being tightened by water heating kettle, the response time is 48h.
Wash successively with secondary water and dehydrated alcohol after precipitation after hydro-thermal reaction is collected, after being dried 12h at 55 DEG C
Obtain the AlOOH nanofiber of white.
Muffle furnace is adjusted to 600 DEG C, is loaded and puts into Muffle furnace after crucible by AlOOH nanofiber, response time 5h,
It is cooled to room temperature, obtains γ-Al2O3Nanofiber.
0.5gγ-Al2O3Nanofiber closes with 0.0891g, adds equivalent impregnation 48h under appropriate secondary hydroecium temperature, baking oven temperature
Degree is adjusted to 100 DEG C, after temperature stabilization to 100 DEG C, puts it into baking oven, is cooled to room temperature and obtains 15%WO after 24h3-
Al2O3。
Above-mentioned obtained solid catalyst being used for be catalyzed glucose and is converted into the reaction of 5-HMF, end product is high
Effect liquid phase chromatogram measures its productivity, characterizes the catalytic performance of this kind of different-phase catalyst (aluminium oxide of load tungsten oxide).
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted,
And all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (6)
1. the preparation method being catalyzed gluconate dehydratase generation 5 hydroxymethyl furfural catalyst:
1) ammonia water titration Al (NO3)3·9H2O solution is to pH=5；Described Al (NO3)3·9H2Al (NO in O solution3)3·
9H2The mass ratio of O and water is 3: 5, and described ammonia concn is 10%；
2) with teflon-lined hydrothermal reaction kettle fill step 1) in mixture, carry out hydro-thermal reaction；
3) with distilled water and ethanol washing step 2 successively) in reacted precipitation, be dried afterwards；
4) in Muffle furnace, calcine 3) solid that obtains, obtain the matrix alumina nanofiber of catalyst；
5) step 4) alumina nano fiber that obtains adds phosphotungstic acid water incipient impregnation；Described phosphotungstic acid and aluminium oxide
Consumption according to the load capacity of tungsten oxide；
6) step 5) the mixture drying that obtains, obtain loading the alumina nano fiber catalyst of tungsten oxide；
7) by 6) solid that obtains generates 5-HMF for being catalyzed glucose.
Preparation method the most according to claim 1, is characterized in that, step 2) described in hydrothermal condition be 200 DEG C, instead
It is 48 hours between Ying Shi.
Preparation method the most according to claim 1, is characterized in that, step 3) described in drying condition be at 55 DEG C
Vacuum drying or oven drying, drying time is 12 hours.
Preparation method the most according to claim 1, is characterized in that, step 4) described in calcination condition be 600 DEG C, forge
The burning time is 5 hours.
Preparation method the most according to claim 1, is characterized in that, step 6) described in drying condition be at 100 DEG C
Vacuum drying or oven drying, drying time is 24 hours.
Preparation method the most according to claim 1, is characterized in that, step 7) described in catalytic condition be solvent be dimethyl
Sulfoxide, 150 DEG C are reacted 4 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159174A (en) * | 2016-12-22 | 2017-09-15 | 青岛大学 | A kind of preparation method of metatitanic acid nanofiber and its application for being catalyzed fructose |
| CN107185510A (en) * | 2016-12-22 | 2017-09-22 | 青岛大学 | It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation |
| CN108610311A (en) * | 2018-05-30 | 2018-10-02 | 盐城工学院 | A kind of method that the low-temperature catalyzed glucose of boehmite prepares 5 hydroxymethyl furfural |
| CN109701639A (en) * | 2019-01-11 | 2019-05-03 | 江苏大学 | Difunctional solid catalyst of a kind of carbon-based soda acid of N doping and preparation method thereof |
| CN109908890A (en) * | 2019-04-01 | 2019-06-21 | 清华大学 | A kind of visible light nano composite catalyst and its preparation and application |
| CN110038547A (en) * | 2019-04-29 | 2019-07-23 | 南开大学 | A kind of preparation method of tin Supported alumina nanometer sheet |
| CN112827489A (en) * | 2021-01-06 | 2021-05-25 | 湖南大学 | Supported photocatalyst and application thereof |
| CN113600189A (en) * | 2021-08-24 | 2021-11-05 | 沈阳科技学院 | Hydroxymethyl furfural catalyst, preparation method and application thereof |
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| JPH11267459A (en) * | 1998-03-20 | 1999-10-05 | Mitsubishi Heavy Ind Ltd | Reducing method of nitrogen oxide and so3 in exhaust gas |
| CN102617287A (en) * | 2012-02-21 | 2012-08-01 | 北京大学 | Method for preparing hexitol or hydroxy-acetone |
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Patent Citations (2)
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| JPH11267459A (en) * | 1998-03-20 | 1999-10-05 | Mitsubishi Heavy Ind Ltd | Reducing method of nitrogen oxide and so3 in exhaust gas |
| CN102617287A (en) * | 2012-02-21 | 2012-08-01 | 北京大学 | Method for preparing hexitol or hydroxy-acetone |
Non-Patent Citations (1)
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| HUANFENG JIAO等: "Characterization and catalytic activity of WO3-Al2O3 on biomass conversion", 《NANO REPORTS》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107159174A (en) * | 2016-12-22 | 2017-09-15 | 青岛大学 | A kind of preparation method of metatitanic acid nanofiber and its application for being catalyzed fructose |
| CN107185510A (en) * | 2016-12-22 | 2017-09-22 | 青岛大学 | It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation |
| CN108610311A (en) * | 2018-05-30 | 2018-10-02 | 盐城工学院 | A kind of method that the low-temperature catalyzed glucose of boehmite prepares 5 hydroxymethyl furfural |
| CN108610311B (en) * | 2018-05-30 | 2021-12-10 | 盐城工学院 | Method for preparing 5-hydroxymethylfurfural by using boehmite to catalyze glucose at low temperature |
| CN109701639A (en) * | 2019-01-11 | 2019-05-03 | 江苏大学 | Difunctional solid catalyst of a kind of carbon-based soda acid of N doping and preparation method thereof |
| CN109701639B (en) * | 2019-01-11 | 2021-08-03 | 江苏大学 | Nitrogen-doped carbon-based acid-base bifunctional solid catalyst and preparation method thereof |
| CN109908890A (en) * | 2019-04-01 | 2019-06-21 | 清华大学 | A kind of visible light nano composite catalyst and its preparation and application |
| CN110038547A (en) * | 2019-04-29 | 2019-07-23 | 南开大学 | A kind of preparation method of tin Supported alumina nanometer sheet |
| CN110038547B (en) * | 2019-04-29 | 2023-01-17 | 南开大学 | Preparation method of tin-loaded aluminum oxide nanosheet |
| CN110038547B8 (en) * | 2019-04-29 | 2024-04-05 | 南开大学 | Preparation method of tin-loaded alumina nano-sheet |
| CN112827489A (en) * | 2021-01-06 | 2021-05-25 | 湖南大学 | Supported photocatalyst and application thereof |
| CN113600189A (en) * | 2021-08-24 | 2021-11-05 | 沈阳科技学院 | Hydroxymethyl furfural catalyst, preparation method and application thereof |
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Application publication date: 20160727 |