CN102101851A - Method for catalytic preparation of 5-hydroxymethyl furfural from carbohydrates - Google Patents
Method for catalytic preparation of 5-hydroxymethyl furfural from carbohydrates Download PDFInfo
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- CN102101851A CN102101851A CN2009102654521A CN200910265452A CN102101851A CN 102101851 A CN102101851 A CN 102101851A CN 2009102654521 A CN2009102654521 A CN 2009102654521A CN 200910265452 A CN200910265452 A CN 200910265452A CN 102101851 A CN102101851 A CN 102101851A
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Abstract
The invention relates to a niobium-containing compound catalyst for efficiently converting carbohydrates into 5-hydroxymethyl furfural, which has high activity and selectivity for preparing hydroxymethyl furfural (HMF) by dehydrolyzing saccharides and is an ideal catalyst for preparing HMF. When the reaction is performed under moderate conditions, the target product HMF can have a high yield. The catalyst is environment-friendly, is easy to separate and recycle, can be reused, is convenient and practical to operate, and can not corrode the equipment, thereby being an ideal solid acid catalyst for preparing HMF, and having significant industrial application meanings.
Description
Technical field
The present invention relates to prepare the method for 5 hydroxymethyl furfural (HMF) by the high-performance solid acid catalyst, promptly with the efficient conversion of biomass of solid acid catalyst sugar source (hexose or be rich in the biomass of hexose), the recyclable repeated use of catalyzer, equipment there is not corrosion, environmental protection has very strong industrial application meaning.
Background technology
5 hydroxymethyl furfural (HMF) is a kind of important furyl compounds, owing to contain reactive group aldehyde radical and methylol in its molecule, character is more active, can be used as the intermediate of many materials of preparation and chemical, is expected to become new hardware and software platform compound.And, HMF is a kind of key intermediate between biomass chemistry and petroleum base chemistry, with biomass is raw material preparing HMF, and then be converted into liquid fuel 2,5-dimethyl furan or alkane (Kunkes E L, Simonetti D A, DumesicJ A, et al.Catalytic Conversion of Biomass to Monofunctional Hydrocarbonsand Targeted Liquid-Fuel Classes[J] .Science 2008322:417-421), will great help be arranged to the petroleum resources of alleviating growing tension.It is reported 2, this biofuel of 5-dimethyl furan has better properties, all is higher than used alcohol fuel now as octane value and boiling point, and the great potential of alternative fossil oil is arranged.If can obtain 2 to the further oxidation of HMF, 5-two formyl furans and 2,5-furans dioctyl phthalate, 2,5-two formyl furans can be used as pharmaceutical intermediate or polymer precursor and antiseptic-germicide; And 2,5-furans dioctyl phthalate can be used as good substitute (Pentz K W.Br.Pat.2131014,1984 that produce polyester (as PET and PBT) raw material terephthalic acid and m-phthalic acid; Werpy T, Petersen G.Top Value Added Chemicals From Biomass, 2004); In addition, HMF can be used as odor additive in cosmetic industry, also can be used as medicine intermediate etc.
Because HMF as chemical intermediate, has important application prospects in a lot of industries, in recent years its research is also increased gradually.The preparation of HMF generally with hexose as reactant, obtain through acid-catalyzed dehydration.Wherein reactant can be a hexose, also can be some oligose and high glycan, or even the ecosystem biomass.The hexose molecule is transformed the research that generates HMF be tending towards ripe, can be divided into homogeneous acid catalysis, ionic liquid catalyst and solid acid catalyst catalysis with regard to its reaction system and used catalyzer.Homogeneous acid catalysis is promptly used some protonic acids such as HCl, H
3PO
4, H
2SO
4, and organic acid such as formic acid, levulinic acid etc.During with these protonic acid catalytic preparation HMF,, produce a large amount of waste liquids, cause equipment corrosion owing to consume a large amount of acid in the reaction process, environmental pollution, and also catalyzer and product are not easily separated yet.Ionic liquid is many compounds of Recent study, and it is during as reaction medium, and HMF can obtain very high yield.But when ionic liquid was used to react, because its price is high, its toxicity remained further to be studied, and aftertreatment is difficulty relatively, and these shortcomings have all limited the industrial application of ionic liquid.Have higher activity and selectivity during the solid acid catalyst catalyzed reaction, be easy to Separation and Recovery, can reuse, environmental friendliness is that the development of catalyzer is sent to.Yet, many solid acid molecular sieve catalysts are active unstable at aqueous phase, structure is caved in easily, cause its catalytic activity to reduce, be unfavorable for reusing, and the used catalyzer not only not loss of activity in Aquo System of the present invention, also have certain enhancing on the contrary, and water helps reducing cost as reaction medium with it as natural green solvent, promotes the suitability for industrialized production of HMF.
Summary of the invention
The object of the present invention is to provide a kind of easy method for preparing HMF by hexose or glycosyl carbohydrate, this process environment close friend, mild condition, catalyzer are reusable, to overcome cost height in the prior art, energy consumption height, shortcomings such as the difficult recovery of catalyzer.
For achieving the above object, the technical solution used in the present invention is:
The present invention relates to a kind of solid acid catalyst for preparing 5 hydroxymethyl furfural (HMF) by efficient catalytic conversion monose or polysaccharide, this catalyzer is for containing niobium compound, catalysis monose or polysaccharide and ecosystem biomass are during as reactant, react under 80-300 ℃ temperature, the HMF yield can reach 40%-100%.
Catalyst system therefor is compounds such as aqua oxidation niobium, niobate.Aqua oxidation niobium or niobium hydroxide mineral acid treatment; Mineral acid comprises: sulfuric acid, phosphoric acid, nitric acid etc.; Inorganic acid concentration is 0.1-10mol/L.Treatment time be 1 hour to 1 week.
Containing niobium compound is composite oxides with ad hoc structure or the salt that niobium and other metal form.It comprises nickel, tungsten, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, formation such as tin close oxide compound or salt.The percentage composition that other metallic compound accounts for niobium compound is: 0.1%-50%.Contain niobium compound and can load on some carriers, comprise each molecular sieve analog, silicon oxide, aluminum oxide, titanium dioxide, zirconium white etc.; The mass ratio of catalyzer and carrier is 0.001-1.Catalyzer is at 100-1000 ℃ of following calcination activation.
The jerusalem artichoke juice that described reactant is fructose, glucose, semi-lactosi, seminose, sucrose, starch, inulin, corn juice, squeeze the juice and obtain through the Mierocrystalline cellulose and the ecosystem biomass jerusalem artichoke stem tuber of pre-treatment.
The reaction system that adopts is two-phase system or the miscible system that water, water and organic solvent are formed, wherein organic solvent can be water insoluble but can dissolve the solvent of HMF, and it is mixture of methyl iso-butyl ketone (MIBK), propyl carbinol, 2-butanols, tetrahydrofuran (THF), ethyl acetate, methylene dichloride, chloroform, acetone and their any ratios etc.; The volume ratio of water and organic phase is 1: 20-20: 1.
Reaction can be carried out under anhydrous system, and solvent is the mixture of dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyrrolidone and their any ratios.
Temperature of reaction system is 80-300 ℃.Reaction times is 10min-300min.
Reactant concn is 0.5%-0%; The ratio of catalyzer and reactant is 1: 1-1: 10000.
Preparation HMF is in the autoclave of preheating, in reaction solvent water and/or organic solvent butanols, 2-butanols, methyl iso-butyl ketone (MIBK) or their mixture, raw material substrate hexose or hexose source biomass and catalyzer uniform mixing and reactor, reactor is sent into the reactor of heating, stir to promote the generation of HMF with certain speed.
During catalyzed reaction, service temperature is 80-300 ℃, and the reaction times is 10min-300min, and stirring velocity is 300-1000rpm, and described reactant is that hexose is: fructose, glucose, seminose, semi-lactosi; Described hexose source biomass is the biomass inulin that contains fructose, glucose, seminose, semi-lactosi, maize treacle, starch, Mierocrystalline cellulose, jerusalem artichoke powder etc., preferred fructose, inulin, jerusalem artichoke juice.
The present invention has following advantage:
1 compares with the method that the dehydration of traditional bronsted acid catalyst prepare HMF, and the solid acid catalyst that the present invention uses is active high, and HMF is had good selectivity, and environmental friendliness is water insoluble, is easy to separation, is difficult for causing equipment corrosion, and catalyzer is with low cost.
In 2 reactions with natural solvent water or aqueous mixture as reaction medium, and HMF has very high selectivity, the process green non-pollution, operational condition gentleness, the simple cost of technology are low.
In 3 reactions, sugar transforms production HMF to carry out at aqueous phase, HMF forms the back and in time is extracted in the organic phase by stirring action, so not only impel further carrying out of aqueous phase sugar dehydration preparation HMF reaction, can also avoid HMF in aqueous phase and water generation hydration and degrade, also reduce production of by-products such as rotten melanocyte, thereby reduced the inactivation of catalyzer, improved the transformation efficiency and the HMF yield of reactant.
4 the present invention can be directly with biomass material as reactant, the key intermediate that directly prepares biomass energy or biological material, process green, yield height, and production technique and existing petrochemical process have very big similarity, has very big industrial prospect and strategic importance.
In a word, reaction process HMF of the present invention has outside the highly selective, used solid acid environmental friendliness, the operational condition gentleness, technology is simple, and the repeated use of catalyzer has reduced cost, for providing new way from biomass sugar source suitability for industrialized production HMF, helping promoting with biomass is feedstock production petroleum base chemical and alternative fuel, has very strong industrialization meaning.
Embodiment
Embodiment 1
Get niobium hydroxide 1.5g, add the 1M phosphoric acid 20ml for preparing, stirring at room 52h leaves standstill aging 12h, centrifugation goes out white depositions, be washed with water to pH then and become neutral, 60 ℃ of dryings are ground, 110 ℃ of 2h in vacuum drying oven afterwards, slowly be warming up to 300 ℃ of activation 3h again in retort furnace, can obtain required catalyzer, it is the columbium oxide catalyst of handling through phosphoric acid.
Get and above-mentionedly after phosphoric acid is handled, obtain columbium oxide catalyst 0.01g, glucose 1.2g, add 20ml water and 30ml methyl iso-butyl ketone (MIBK), sealing, at 160 ℃ of reaction 30min, reacting liquid filtering is isolated catalyzer, remove reaction liquid with catalyst and detect with high performance liquid chromatography, recording the HMF yield is 78%.
Embodiment 2
Get columbium pentachloride 1g, be dissolved in the 10ml anhydrous methanol, after treating its dissolving, add zirconium oxychloride 0.2g, dropping ammonia is regulated pH to neutrality under the stirring state, continues to stir 4h, leave standstill aging 12h, be washed to not chloride ion-containing, the throw out that obtains is in 60 ℃ of dry 2h, and promptly obtaining charge capacity in 500 ℃ of calcination for activation is 20% ZrO/Nb
2O
5With XPS it is characterized and verifies.
Get this catalyzer 0.1g, fructose 2g adds entry 20ml, butanols 30ml, and 160 ℃ of reaction 60min isolate catalyzer with reacting liquid filtering, and sample detects with high performance liquid chromatography, and recording the HMF yield is 69%.
Embodiment 3
Get niobium chloride 0.2g, add the 20ml dehydrated alcohol, treat its dissolving after, add 2g silicon-dioxide, stir 3h, place the 5h after-filtration and obtain throw out, and be washed to not chloride ion-containing, dry then, it is 10% Nb that 450 ℃ of roastings obtain charge capacity
2O
5/ SiO
2
Get above-mentioned catalyzer 0.1g, fructose 1.4g, water 10ml, methyl iso-butyl ketone (MIBK) 40ml places autoclave, stops behind 160 ℃ of reaction 45min, takes out sample, and detecting the HMF yield is 82%.
Embodiment 4
Get inulin 2g, dimethyl sulfoxide (DMSO) 50ml, the aqua oxidation niobium catalytic 0.1g that embodiment 1 handles through phosphoric acid, place autoclave, 800rpm stirs down, 160 ℃ of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample detects with high performance liquid chromatography, and recording the HMF yield is 68%.
Embodiment 5
Get corn juice (total sugar concentration 50%) 10ml, water 10ml, 2-butanols 30ml, the aqua oxidation niobium catalytic 0.1g that embodiment 1 handles through phosphoric acid places autoclave, and 800rpm stirs down, 180 ℃ of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample detects with high performance liquid chromatography, and recording the HMF yield is 55%.
Embodiment 6
Get jerusalem artichoke juice (12wt%) 10ml, add water 10ml, 2-butanols 30ml, aqua oxidation niobium 0.1g places reactor, sealing, the autoclave of preheating 30min before placing, 800rpm stirs down, and 160 ℃ of reaction 90min isolate catalyzer with reacting liquid filtering, sample detects with high performance liquid chromatography, and recording the HMF yield is 71%.
Embodiment 7
Get niobium chloride 3g, add ammonia precipitation process, and transfer pH to stir 5h to neutral back with ammoniacal liquor, standing over night aging throw out, be not washed to and behind the chloride ion-containing 350 ℃ of roastings of drying precipitate obtained required niobium hydroxide catalyzer.
Get this catalyzer 0.1g, fructose 1.2g, water 20ml, butanols 30ml stops behind 160 ℃ of reaction 40min in autoclave, and high performance liquid phase detects HMF yield 89%.
Embodiment 8
Get niobic acid chromium potassium 0.2g, fructose 2.0g, pyrrolidone 30ml, 80 ℃ of reaction 2h stop, and it is 70% that high performance liquid phase detects yield.
Embodiment 9
Get starch 3g, 600 ℃ of niobium hydroxide catalyzer 0.1g that activatory is handled through phosphoric acid, 20ml water, the 30ml methyl iso-butyl ketone (MIBK), 180 ℃ of reaction 1.5h, the HMF yield can reach 42%.
Embodiment 10
Get inulin 3g, 450 ℃ of niobium hydroxide catalyzer 0.1g through the 1M nitric acid treatment, water 20ml, 2-butanols 30ml, 150 ℃ of reaction 2h, it is 54% that high performance liquid phase detects the HMF yield.
Embodiment 11
Get the jerusalem artichoke stem tuber 3g of pulverizing, 300 ℃ of Niobic Acid agent 0.05g that activatory is handled through phosphoric acid, N,N-dimethylacetamide 30ml, 100 ℃ of reaction 2h, it is 65% (with respect to the total sugar content in the jerusalem artichoke powder) that high performance liquid phase detects the HMF yield.
In the above-mentioned experiment, after reusing three times, do not see by catalyzer active decline.
By above embodiment as can be seen, the present invention be compound with a kind of solid acid niobium and tantalum as catalyzer, in the two-phase system that water and organic solvent are formed, realize hexose or contain the biomass highly selective dehydration preparation HMF of hexose.Be reflected under the comparatively gentle condition and carry out, target product HMF can obtain than higher yield, compare with the liquid acid catalysis technique with other solid acids, of the present invention have a remarkable advantage: the transformation efficiency height, and the selectivity height, catalyzer is cheap, be easy to Separation and Recovery, can reuse, and can not cause corrosion to equipment, be the solid acid catalyst that a kind of ideal prepares HMF; The gentle technology of operational condition is simple, and cost is low, environmental friendliness.
Claims (8)
1. a catalyzed carbon hydrate prepares the method for 5 hydroxymethyl furfural, it is characterized in that: it is a catalyzer to contain niobium compound, with the carbohydrate is raw material, reacts under 80-300 ℃ temperature, under liquid-phase condition the carbohydrate efficient catalytic is generated HMF.
2. according to the method for claim 1, it is characterized in that: the described niobium compound that contains is the composite oxides with ad hoc structure that form of aqua oxidation niobium, niobium hydroxide, niobate, niobium and other metals or in the salt one or more;
Composite oxides with ad hoc structure or salt that described niobium and other metal form; Other metal is nickel, tungsten, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, one or more in vanadium, the tin; The mol ratio of other metal and niobium is 1: 5～1: 100.
3. it is characterized in that in accordance with the method for claim 2: adopt mineral acid treatment before described aqua oxidation niobium or niobium hydroxide use; Mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid; Inorganic acid concentration is 0.1-10mol/L, the treatment time be 1 hour to 1 week.
4. in accordance with the method for claim 2, it is characterized in that: niobium hydroxide or niobium oxides can load on the solid carrier surface, form loading type and contain niobium catalytic, and carrier is molecular sieve, silicon oxide, aluminum oxide, titanium dioxide or zirconium white; The mass ratio of catalyzer and carrier is 0.001-1.
5. according to claim 2 or 4 described methods, it is characterized in that: described niobium hydroxide or loading type are preferably in 100-1000 ℃ of following calcination activation before containing the niobium catalytic use.
6. it is characterized in that in accordance with the method for claim 1: described carbohydrate is that fructose, glucose, semi-lactosi, seminose, sucrose, starch, inulin, corn juice or jerusalem artichoke stem tuber are squeezed the juice in the jerusalem artichoke juice that obtains one or more.
7. it is characterized in that in accordance with the method for claim 1: the reaction system of employing is two-phase system or the anhydrous system that miscible system, water and the organic solvent of water, water and organic solvent formed;
Two-phase system wherein: organic solvent is water insoluble but can dissolves the solvent of HMF, it is one or more the mixture of any ratio in methyl iso-butyl ketone (MIBK), propyl carbinol, 2-butanols, tetrahydrofuran (THF), ethyl acetate, methylene dichloride, N,N-dimethylacetamide, pyrrolidone, chloroform or the acetone; The volume ratio of water and organic phase is 1: 20-20: 1;
The miscible system of water and organic solvent wherein: organic solvent is water-soluble and can dissolves the solvent of HMF, it is: methyl iso-butyl ketone (MIBK), propyl carbinol, 2-butanols, tetrahydrofuran (THF), ethyl acetate, methylene dichloride, N,N-dimethylacetamide, pyrrolidone, chloroform, acetone;
The reaction system that adopts is carried out under anhydrous system, and solvent is the mixture of one or more any ratios in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, the pyrrolidone.
8. according to the method for claim 1, it is characterized in that: temperature of reaction system is 80-300 ℃.Reaction times is 10min-300min; The concentration of reactant feed is 0.5-70wt%; The mass ratio of catalyzer and reactant is 1: 1-1: 10000.
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| CN113845497A (en) * | 2021-11-01 | 2021-12-28 | 沈阳化工大学 | Method for synthesizing 5-hydroxymethylfurfural at low temperature |
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