CN103172599A - Method for catalyzing carbohydrate to prepare 5-(hydroxymethyl) furfural (5-HMF) and levulinic acid (LA) - Google Patents
Method for catalyzing carbohydrate to prepare 5-(hydroxymethyl) furfural (5-HMF) and levulinic acid (LA) Download PDFInfo
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Abstract
The invention relates to a tungsten and tantalum containing catalyst for efficiently converting a carbohydrate to prepare 5-(hydroxymethyl) furfural (5-HMF) and levulinic acid (LA). The catalyst has high activity of converting the carbohydrate to prepare the HMF and the LA, is environment-friendly, is easy to separate and recover, can be reused, can not corrode equipment, has important industrial application significance and is an ideal solid acid catalyst for converting the carbohydrate.
Description
Technical field
The present invention relates to be prepared by the high-performance solid acid catalyst method of 5 hydroxymethyl furfural (HMF) and levulinic acid (LA), namely use solid acid catalyst Efficient Conversion biomass sugar source (hexose or be rich in the biomass of hexose), catalyzer is recyclable to be reused, to equipment without corrosion, environmental protection has very strong industrial application meaning.
Background technology
5 hydroxymethyl furfural (HMF) and levulinic acid (LA) are a kind of important bio-based hardware and software platform compounds, it is a kind of key intermediate between biomass chemistry and petroleum base chemistry, prepare HMF and LA take biomass as starting material, and then be converted into liquid fuel or bulk chemical, will great help be arranged to the petroleum resources of alleviating growing tension.It is reported that HMF can be converted into 2,5-dimethyl furan, this biofuel has better properties, all higher than alcohol fuel used now, the great potential of substitute fossil fuels is arranged as octane value and boiling point.Can obtain 2,5-, two formyl furans and FDCAs to the further oxidation of HMF, 2,5-, two formyl furans can be used as pharmaceutical intermediate or polymer precursor and antiseptic-germicide; And FDCA 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 Valus 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.LA can be used as resin, medicine, spices, coating etc. and is widely used in the fields such as medicine, agricultural chemicals, dyestuff and tensio-active agent.
As chemical intermediate, in a lot of industries, important application prospect is arranged due to HMF and LA, also a lot of to its research.The preparation of these two kinds of compounds generally with hexose as reactant, obtain through acid-catalyzed dehydration.Wherein reactant can be hexose, can be also 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 catalyzer used.Homogeneous acid catalysis is namely used some protonic acids such as HCl, H
3PO
4, H
2SO
4, and organic acid such as formic acid, levulinic acid etc.When preparing HMF with these protonic acid catalysis, owing to consuming a large amount of acid in reaction process, produce a large amount of waste liquids, cause equipment corrosion, environmental pollution, and catalyzer and product 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 for reaction, because its price is high, its toxicity remained further to be studied, and aftertreatment is more difficult, and these shortcomings have all limited the industrial application of ionic liquid.At present, mostly LA is at protonic acid such as HCl, H
3PO
4, H
2SO
4Deng what prepare under catalysis, consume a large amount of acid in reaction process, produce a large amount of waste liquids, cause equipment corrosion, environmental pollution.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 unstable in the aqueous phase activity, structure is easily caved in, cause its catalytic activity to reduce, be unfavorable for reusing, and the present invention's catalyzer not only not loss of activity in Aquo System used, also have on the contrary certain enhancing, and water is conducive to reduce costs as reaction medium with it as natural green solvent, promotes the suitability for industrialized production of HMF.Searching close friend's method for transformation prepares important in inhibiting to the green of LA.
Summary of the invention
The object of the present invention is to provide a kind of easy method that is prepared HMF by hexose or glycosyl carbohydrate, this process environment close friend, mild condition, catalyzer are reusable, high to overcome in prior art cost, energy consumption is high, and catalyzer is difficult for the shortcomings such as recovery.
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 that is prepared 5 hydroxymethyl furfural (HMF) and levulinic acid (LA) by efficient catalytic conversion monose or polysaccharide, this catalyzer is for containing tantalum and tungsten compound, catalysis monose or polysaccharide and ecosystem biomass (carbohydrate) are during as reactant, react at the temperature of 80-300 ℃, LA and HMF yield can reach 40%-100%.
The catalyzer of described tantalum and tungsten is entrained in by both precursor tantalum chlorides, ethanol tantalum and muriate, metatungstate, tungstate etc. and obtains together, and after precipitation formed, aged at room temperature 24 hours was to a week.
Tungstenic and tantalum compound are the mixed oxide with ad hoc structure or the salt of tantalum and tungsten and the formation of other metals.It comprises nickel, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, the formation such as tin close oxide compound or salt.The percentage composition that other metallic compound accounts for tantalum compound is: 0.1%-50%.The tungstenic tantalum compound can load on some carriers, comprises 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 lower 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 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 and organic solvent form, 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.
Reaction process 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 the even mixing of catalyzer and reactor, reactor is sent into the reactor of heating, stirred 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 traditional bronsted acid catalyst dehydration transforms carbohydrate, the solid acid catalyst activity that the present invention uses is high, can be according to the selectivity of different doping modulations to LA and HMF, environmental friendliness, water insoluble, be easy to separate, be difficult for causing equipment corrosion, catalyzer is with low cost.
In 2 reactions with natural solvent water or aqueous mixture as reaction medium, the process green non-pollution, operational condition is gentle, the simple cost of technique is low.
In 3 reactions, sugar is converted into HMF to carry out at aqueous phase, in time is extracted in organic phase by stirring action after HMF forms, and so not only impels further carrying out of the standby HMF reaction of aqueous phase sugar Dehydration, is conducive to reaction and moves right.
4 the present invention can be directly with biomass material as reactant, directly prepare the key intermediate of biomass energy or biological material, process is green, yield is high, and production technique and existing petrochemical process have very large similarity, has very large industrial prospect and strategic importance.
In a word, reaction process of the present invention is gentle, solid acid environmental friendliness used, operational condition is gentle, technique is simple, and reusing of catalyzer reduced cost, for providing new way from biomass sugar source preparation of industrialization hardware and software platform compound HMF and LA, be conducive to promote to prepare petroleum base chemical and alternative fuel take biomass as raw material, have very strong industrialization meaning.
Description of drawings
Fig. 1 is 5%WO
3-Ta
2O
5The reaction of catalysis fructose, levulinic acid (LA) and 5 hydroxymethyl furfural (HMF) are with the variation relation trend map in reaction times.
Embodiment
Embodiment 1
The 2.44g ammonium metawolframate is dissolved in the 20ml deionized water, after ammonium metawolframate dissolves fully, the 5g tantalum chloride is slowly dropped in ammonium metatungstate solution, stirring at room 48h, ageing 12h, afterwards in 65 ℃ and 110 ℃ of dryings, 300 ℃ of activation got final product in 3 hours.With catalyzer obtained above catalysis fructose reaction in the two-phase system that 180 ℃, water and 2-butanols form, the reaction solution of removing after catalyzer detects with high performance liquid chromatography, and LA and HMF yield are respectively 86% and 8%.
Embodiment 2
Get metatungstic acid 1.35g, after being dissolved in water, add ethanol tantalum 5ml, stirring at room 52h, standing aging 12h, 65 ℃ of dryings, 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 tungsten tantalum catalyzer.
Get above-mentioned catalyzer (tungstic oxide content 5%) 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, and the reaction solution after the removal catalyzer detects with high performance liquid chromatography, and recording LA and HMF yield is 85% and 8%.
Embodiment 3
Get tungsten chloride 1g, soluble in water, after its dissolving, add tantalum hydroxide 5g, room temperature continues to stir 4h, and standing aging 12h is washed to not chloride ion-containing, and the throw out that obtains gets final product in 500 ℃ of calcination for activation in 60 ℃ of dry 2h.With XPS, catalyzer 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 LA and HMF yield is 69% and 17%.
Embodiment 4
Get tungsten chloride 0.2g, after adding water dissolution, add the 2g tantalum chloride, stir 3h, place to filter after 5h and be precipitated thing, and be washed to not chloride ion-containing, then dry, it is 10% WO that 450 ℃ of roastings obtain charge capacity
3/ Ta
2O
5
Get above-mentioned catalyzer 0.1g, fructose 1.4g, water 10ml, methyl iso-butyl ketone (MIBK) 40ml is placed in autoclave, stops after 160 ℃ of reaction 45min, takes out sample, and detecting LA and HMF yield is 72% and 25%.
Embodiment 5
Get metatungstic acid 0.2g, after adding water dissolution, then add ethanol tantalum 4ml and silica 1 0g, obtain loaded catalyst.Get this catalyzer 0.1g, fructose 2.4g, water 10ml, 2-butanols 40ml is placed in autoclave, stops after 160 ℃ of reaction 45min, takes out sample, and detecting LA and HMF yield is 68% and 23%.
Embodiment 6
Get inulin 2g, dimethyl sulfoxide (DMSO) 50ml, embodiment 4 catalyzer 0.1g, be placed in autoclave, stir under 800rpm, 160 ℃ of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample detects with high performance liquid chromatography, and recording LA and HMF yield is 69% and 6%.
Embodiment 7
Get corn juice (total Sugar concentration 50%) 10ml, water 10ml, 2-butanols 30ml, adopt the catalyzer 0.1g in embodiment 4, be placed in autoclave, stir under 800rpm, 180 ℃ of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample detects with high performance liquid chromatography, and recording LA and HMF yield is 55% and 12%.
Get jerusalem artichoke juice (total sugar concentration 12%) 10ml, add water 10ml, 2-butanols 30ml adopts the catalyzer 0.1g in embodiment 4 to be placed in reactor, sealing, the autoclave of preheating 30min before being placed in, stir under 800rpm, 160 ℃ of reaction 90min isolate catalyzer with reacting liquid filtering, sample detects with high performance liquid chromatography, and recording LA and HMF yield is 51% and 9%.
Embodiment 9
Get starch 3g, the WO of 600 ℃ of activation
3-Ta
2O
5Catalyzer 0.1g, 20ml water, the 30ml methyl iso-butyl ketone (MIBK), 180 ℃ of reaction 1.5h, LA and HMF yield can reach 42% and 15%.
Get inulin 3g, 450 ℃ of WO through the 1M nitric acid treatment
3-Ta
2O
5Catalyzer 0.1g, water 20ml, 2-butanols 30ml, 150 ℃ of reaction 2h, high performance liquid phase detects LA and the HMF yield is 54% and 11%.
Embodiment 11
Get the jerusalem artichoke stem tuber 3g of pulverizing, 300 ℃ of activation through the acid-treated tantalic acid catalyzer of phosphorus 0.05g, N,N-dimethylacetamide 30ml, 100 ℃ of reaction 2h, high performance liquid phase detects LA and the HMF yield is 25% and 32% (with respect to the total sugar content in the jerusalem artichoke powder).
As shown in Figure 1, levulinic acid and HMF are with the reaction times variation tendency:
Reaction conditions: WO
3-Ta
2O
5(5%): 0.1g, fructose: 1.2g, water: 20ml, 2-butanols: 30ml, 180 ℃, 800rpm.
In above-mentioned experiment, have no active after catalyzer is reused three times and descend.
Can find out by above embodiment, the present invention be compound with a kind of solid acid tantalum as catalyzer, in the two-phase system that water and organic solvent form, realize hexose or contain the standby HMF of biomass highly selective Dehydration of hexose.Compare with the liquid acid catalysis technique with other solid acids, of the present invention have a remarkable advantage: transformation efficiency is high, and selectivity is high, and catalyzer is cheap, and the operational condition mild process is simple, and cost is low, environmental friendliness.
Claims (7)
1. the method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate and levulinic acid, it is characterized in that: its take tungstenic and tantalum is compound or mixed oxide as catalyzer, take carbohydrate as raw material, react at the temperature of 80-300 ℃, under liquid-phase condition, the carbohydrate efficient catalytic is generated 5 hydroxymethyl furfural (HMF) and levulinic acid (LA), the LA yield can reach 40%-95%; In tungstic oxide and tantalum pentoxide, in catalyzer, the mass ratio of Tungsten oxide 99.999 and tantalum oxide is 0.5-20%.
2. according to the method for claim 1, it is characterized in that:
Described with tungstenic with tantalum is compound or mixed oxide adopts following precursor to form at 100-1000 ℃ of lower calcination activation;
Described precursor is: contain tantalum compound and be one or more in hydrated tantalum oxide, tantalum hydroxide, tantalate, tantalum oxide; Tungstenic compound is one or more in tungstic oxide, tungstate, ammonium metawolframate; Catalyzer is for above-mentioned tantalum compound and the Tungstenic compound oxide compound that contains tantalum and tungsten or the salt that forms that adulterates that contains is formed solid catalyst at 100-1000 ℃ of lower calcination activation, as: WO
3-Ta
2O
5Deng;
Or, also be added with also compound or mixed oxide or the salt of other metallic elements of load in the precursor that contains tantalum compound and Tungstenic compound; Other metallic elements comprise one or two or more kinds in nickel, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, tin;
Catalyzer be for above-mentioned contain tantalum compound and Tungstenic compound, and compound or mixed oxide or the salt of other metallic elements of load, the oxide compound that contains tantalum and tungsten or the salt that forms that adulterates form solid catalyst at 100-1000 ℃ of lower calcination activation, in solid catalyst, other metal oxygen compound accounts for the percentage composition of the total amount of tungsten and tantalum oxygenate and is: 0.1%-50%.
3. in accordance with the method for claim 2, it is characterized in that: one or two or more kinds is entrained in and obtains together the catalyzer of described tantalum and tungsten by both precursor tantalum chlorides, ethanol tantalum one or two or more kinds and tungsten chloride, metatungstic acid, metatungstate, tungstate, form precipitation in the aqueous solution, after precipitation forms, aged at room temperature was used front in 100-1000 ℃ of lower calcination activation to a week in 24 hours.
4. in accordance with the method for claim 2, it is characterized in that: tungsten and tantalum compound can load on the carrier surface of solid, form loaded catalyst, and carrier is molecular sieve, silicon oxide, aluminum oxide, titanium dioxide or zirconium white; The mass ratio of catalyzer and carrier is 0.0001-1; The catalyzer of described loading type tungstenic and tantalum compound uses front at 100-1000 ℃ of lower calcination activation.
5. it is characterized in that in accordance with the method for claim 1: described carbohydrate is fructose, glucose, semi-lactosi, seminose, sucrose, starch, inulin, corn juice, one or two or more kinds in the Mierocrystalline cellulose of pre-treatment and jerusalem artichoke stem tuber are squeezed the juice the jerusalem artichoke juice that obtains.
6. it is characterized in that in accordance with the method for claim 1: the reaction system of employing is the miscible system of water or water and organic solvent or two-phase system or the anhydrous system of water and organic solvent composition;
Two-phase system wherein: organic solvent is water insoluble but can dissolves the solvent of HMF, and it is one or two or more kinds the mixture of any ratio in methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), ethyl acetate, pyrrolidone, chloroform; The volume ratio of water and organic phase is 1: 20-20: 1;
Miscible system wherein: organic solvent is water-soluble and can dissolves the solvent of HMF, and it is: the mixture of any ratio of one or two or more kinds in ethanol, propyl carbinol, 2-butanols, methylene dichloride, N,N-dimethylacetamide or acetone.
The reaction system that adopts is carried out under anhydrous system, solvent be a kind of in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, pyrrolidone or they more than two kinds arbitrarily than mixture.
7. 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539766A (en) * | 2013-10-29 | 2014-01-29 | 中国科学技术大学 | Preparation method of furfural |
| CN104130223A (en) * | 2014-04-23 | 2014-11-05 | 中国科学院山西煤炭化学研究所 | Method for production of 5-hydroxymethylfurfural or levulinic acid from inulin biomass |
| CN104250237A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethylfurfural through catalyzing fructose conversion by solid catalyst |
| CN105859545A (en) * | 2016-04-07 | 2016-08-17 | 中国科学技术大学 | Preparation method of furfural and levulinic acid |
| CN106496166A (en) * | 2016-09-06 | 2017-03-15 | 安徽理工大学 | A kind of method that xylose high-efficiency dehydration prepares furfural |
| CN106540677A (en) * | 2016-11-07 | 2017-03-29 | 江苏理工学院 | A kind of porous charcoal supported nano-gold belongs to the preparation method and purposes of oxide material |
| CN106928168A (en) * | 2017-03-16 | 2017-07-07 | 南开大学 | A kind of method for converting glucose into 5 hydroxymethylfurfurals in a mild condition |
| CN108187674A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols |
| CN111841527A (en) * | 2020-07-14 | 2020-10-30 | 江苏理工学院 | Preparation method and application of composite bimetal oxide mesoporous material |
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| CN104250237A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethylfurfural through catalyzing fructose conversion by solid catalyst |
| CN104250237B (en) * | 2013-06-28 | 2017-02-08 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethylfurfural through catalyzing fructose conversion by solid catalyst |
| CN103539766A (en) * | 2013-10-29 | 2014-01-29 | 中国科学技术大学 | Preparation method of furfural |
| CN104130223A (en) * | 2014-04-23 | 2014-11-05 | 中国科学院山西煤炭化学研究所 | Method for production of 5-hydroxymethylfurfural or levulinic acid from inulin biomass |
| CN104130223B (en) * | 2014-04-23 | 2016-06-15 | 中国科学院山西煤炭化学研究所 | Inulin biolobic material is utilized to produce the method for 5 hydroxymethyl furfural or levulinic acid |
| CN105859545A (en) * | 2016-04-07 | 2016-08-17 | 中国科学技术大学 | Preparation method of furfural and levulinic acid |
| CN106496166A (en) * | 2016-09-06 | 2017-03-15 | 安徽理工大学 | A kind of method that xylose high-efficiency dehydration prepares furfural |
| CN106540677A (en) * | 2016-11-07 | 2017-03-29 | 江苏理工学院 | A kind of porous charcoal supported nano-gold belongs to the preparation method and purposes of oxide material |
| CN108187674A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols |
| CN106928168A (en) * | 2017-03-16 | 2017-07-07 | 南开大学 | A kind of method for converting glucose into 5 hydroxymethylfurfurals in a mild condition |
| CN111841527A (en) * | 2020-07-14 | 2020-10-30 | 江苏理工学院 | Preparation method and application of composite bimetal oxide mesoporous material |
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