CN103172599B - 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 the method being prepared 5 hydroxymethyl furfural (HMF) and levulinic acid (LA) by high-performance solid acid catalyst, namely solid acid catalyst Efficient Conversion biomass sugar source (hexose or be rich in the biomass of hexose) is used, catalyzer is recyclable to be reused, corrosion-free to equipment, 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 platform chemicals, it is a kind of key intermediate between biomass chemistry and petroleum-based chemical, be that HMF and LA prepared by starting material with biomass, and then be converted into liquid fuel or bulk chemical, there is great help by the petroleum resources alleviating growing tension.It is reported that HMF can be converted into 2,5-dimethyl furan, this biofuel has better properties, if octane value and boiling point are all higher than alcohol fuel now used, has the great potential of substitute fossil fuels.HMF is oxidized further and can obtains 2,5-Diformylfuran and FDCA, 2,5-Diformylfuran can as pharmaceutical intermediate or polymer precursor and antiseptic-germicide; And FDCA can as excellent substitute (Pentz K W.Br.Pat.2131014,1984 producing 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 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.
Because HMF and LA is as chemical intermediate, there is important application prospect in a lot of industry, also a lot of to its research.The preparation of these two kinds of compounds, generally using hexose as reactant, obtains through acid-catalyzed dehydration.Wherein reactant can be hexose, also can be some oligose and high glycan, or even ecosystem biomass.The research of hexose Molecular Cloning generation HMF is tending towards ripe, homogeneous acid catalysis, ionic liquid catalyst and solid acid catalyst catalysis can be divided into regard to its reaction system and catalyzer used.Homogeneous acid catalysis, namely with some protonic acids as HCl, H
3pO
4, H
2sO
4, and organic acid is as formic acid, levulinic acid etc.During with these Protic Acid Catalyzed preparation HMF, owing to consuming a large amount of acid in reaction process, produce a large amount of waste liquid, cause equipment corrosion, environmental pollution, and catalyzer and product not easily separated yet.Ionic liquid is many compounds of Recent study, and when it is as reaction medium, HMF can obtain very high yield.But when ionic liquid is for reacting, because its price is high, its toxicity needs to be studied further, and aftertreatment is more difficult, and these shortcomings all limit the industrial application of ionic liquid.At present, mostly LA is at protonic acid 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 liquid, cause equipment corrosion, environmental pollution.Having higher activity and selectivity during solid acid catalyst catalyzed reaction, be easy to Separation and Recovery, can reuse, environmental friendliness, is that the development of catalyzer is sent to.But, many solid acid molecular sieve catalysts are active unstable in aqueous phase, structure is easily caved in, cause its catalytic activity to reduce, be unfavorable for reusing, and the present invention's catalyzer activity in Aquo System used is not only lost, also have certain enhancing on the contrary, and water is as natural green solvent, be conducive to reducing costs as reaction medium using it, promote the suitability for industrialized production of HMF.Find friendly method for transformation to the Green synthesis important in inhibiting of LA.
Summary of the invention
The object of the present invention is to provide a kind of easy method being prepared HMF by hexose or glycosyl carbohydrate, this process environment close friend, mild condition, catalyzer are reusable, high to overcome cost in prior art, energy consumption is high, and catalyzer such as not easily to reclaim at the shortcoming.
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 being 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, when catalysis monose or polysaccharide and ecosystem biomass (carbohydrate) are as reactant, react at the temperature of 80-300 DEG C, LA and HMF yield can reach 40%-100%.
The catalyzer of described tantalum and tungsten obtains together with being entrained in muriate, metatungstate, tungstate etc. by both precursor tantalum chlorides, ethanol tantalum, and after precipitation is formed, aged at room temperature 24 is little of one week.
Tungstenic and tantalum compound are the mixed oxide with ad hoc structure that formed of tantalum and tungsten and other metals or salt.It comprises nickel, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, the conjunction oxide compound that tin etc. are formed or salt.The percentage composition that other metallic compound accounts for tantalum compound is: 0.1%-50%.Tungstenic tantalum compound 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 calcination activation at 100-1000 DEG C.
Described reactant is fructose, glucose, semi-lactosi, seminose, sucrose, starch, inulin, corn juice, the jerusalem artichoke juice obtained of squeezing the juice through the Mierocrystalline cellulose of pre-treatment and ecosystem biomass jerusalem artichoke stem tuber.
The reaction system adopted is the two-phase system that forms of water and organic solvent or miscible system, wherein organic solvent can be water insoluble but can dissolve the solvent of HMF, and it is the mixture etc. of methyl iso-butyl ketone (MIBK), propyl carbinol, 2-butanols, tetrahydrofuran (THF), ethyl acetate, methylene dichloride, chloroform, acetone and their any ratios; The volume ratio of aqueous phase 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 DEG C.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, by 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 Homogeneous phase mixing and reactor, reactor is sent into the reactor of heating, stir with the generation promoting HMF with certain speed.
During catalyzed reaction, service temperature is 80-300 DEG C, and the reaction times is 10min-300min, and stirring velocity is 300-1000rpm, and to be hexose be described reactant: fructose, glucose, seminose, semi-lactosi; Described hexose source biomass is biomass inulin, maize treacle, starch, Mierocrystalline cellulose, jerusalem artichoke powder etc. containing fructose, glucose, seminose, semi-lactosi, preferred fructose, inulin, jerusalem artichoke juice.
Tool of the present invention has the following advantages:
1 with traditional bronsted acid catalyst dewater transform carbohydrate method compared with, the solid acid catalyst activity that the present invention uses is high, can according to different doping modulations to the selectivity of LA and HMF, environmental friendliness, water insoluble, be easy to be separated, not easily cause equipment corrosion, catalyzer is with low cost.
Using natural solvent water or aqueous mixture as reaction medium in 2 reactions, 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 in aqueous phase, is extracted in time in organic phase after HMF is formed by stirring action, and that so not only impels sugared Dehydration in aqueous phase to react for HMF carries out further, is conducive to reaction and moves right.
4 the present invention can directly using biomass material as reactant, the key intermediate of direct preparation biomass energy or biological material, process is green, yield is high, and production technique and existing petrochemical process have very large similarity, have 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 reduces cost, for providing new way from biomass sugar source preparation of industrialization platform chemicals HMF and LA, being conducive to promoting with biomass is that raw material prepares petroleum-based chemical product and alternative fuel, has very strong industrialization meaning.
Accompanying drawing explanation
Fig. 1 is 5%WO
3-Ta
2o
5catalysis fructose reacts, and levulinic acid (LA) and 5 hydroxymethyl furfural (HMF) are with the variation relation trend map in reaction times.
Embodiment
Embodiment 1
Be dissolved in by 2.44g ammonium metawolframate in 20ml deionized water, after ammonium metawolframate dissolves completely, slowly dropped in ammonium metatungstate solution by 5g tantalum chloride, stirring at room temperature 48h, ageing 12h, afterwards in 65 DEG C and 110 DEG C of dryings, 300 DEG C activate 3 hours.By catalyzer obtained above 180 DEG C, catalysis fructose reaction in the two-phase system of water and 2-butanols composition, remove the reaction solution high performance liquid chromatography after catalyzer and detect, LA and HMF yield is respectively 86% and 8%.
Embodiment 2
Get metatungstic acid 1.35g, after being dissolved in water, add ethanol tantalum 5ml, stirring at room temperature 52h, leave standstill aging 12h, 65 DEG C of dryings, afterwards 110 DEG C of 2h in vacuum drying oven, in retort furnace, be slowly warming up to 300 DEG C of activation 3h again, 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 DEG C of reaction 30min, reacting liquid filtering is isolated catalyzer, and the reaction solution high performance liquid chromatography removed after catalyzer detects, and recording LA and HMF yield is 85% and 8%.
Embodiment 3
Get tungsten chloride 1g, soluble in water, until its dissolve after, add tantalum hydroxide 5g, room temperature continue stir 4h, leave standstill aging 12h, be washed to not chloride ion-containing, the throw out obtained in 60 DEG C of dry 2h, in 500 DEG C of calcination for activation.Carry out characterizing and verify to catalyzer with XPS.
Get this catalyzer 0.1g, fructose 2g, add water 20ml, butanols 30ml, 160 DEG C of reaction 60min, reacting liquid filtering is isolated catalyzer, and sample high performance liquid chromatography detects, and recording LA and HMF yield is 69% and 17%.
Embodiment 4
Get tungsten chloride 0.2g, after adding water dissolution, add 2g tantalum chloride, stir 3h, filter and be precipitated thing, and be washed to not chloride ion-containing after placing 5h, then dry, 450 DEG C of roastings obtain the WO that charge capacity is 10%
3/ Ta
2o
5.
Get above-mentioned catalyzer 0.1g, fructose 1.4g, water 10ml, methyl iso-butyl ketone (MIBK) 40ml, be placed in autoclave, and stop after 160 DEG C of reaction 45min, take out sample, 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, and stop after 160 DEG C of reaction 45min, take out sample, 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 DEG C of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample high performance liquid chromatography detects, 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 DEG C of reaction 150min, reacting liquid filtering is isolated catalyzer, and sample high performance liquid chromatography detects, and recording LA and HMF yield is 55% and 12%.
Embodiment 8
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 DEG C of reaction 90min, isolate catalyzer by reacting liquid filtering, sample high performance liquid chromatography detects, and recording LA and HMF yield is 51% and 9%.
Embodiment 9
Get starch 3g, the WO of 600 DEG C of activation
3-Ta
2o
5catalyzer 0.1g, 20ml water, 30ml methyl iso-butyl ketone (MIBK), 180 DEG C of reaction 1.5h, LA and HMF yields can reach 42% and 15%.
Embodiment 10
Get inulin 3g, 450 DEG C of WO through 1M nitric acid treatment
3-Ta
2o
5catalyzer 0.1g, water 20ml, 2-butanols 30ml, 150 DEG C of reaction 2h, it is 54% and 11% that high performance liquid phase detects LA and HMF yield.
Embodiment 11
Get the jerusalem artichoke stem tuber 3g of pulverizing, 300 DEG C activation through phosphorus acid-treated tantalic acid catalyzer 0.05g, N,N-dimethylacetamide 30ml, 100 DEG C of reaction 2h, it is 25% and 32% (total sugar content relative in jerusalem artichoke powder) that high performance liquid phase detects LA and HMF yield.
As shown in Figure 1, levulinic acid and HMF are with reaction times variation tendency:
Reaction conditions: WO
3-Ta
2o
5(5%): 0.1g, fructose: 1.2g, water: 20ml, 2-butanols: 30ml, 180 DEG C, 800rpm.
In above-mentioned experiment, catalyzer has no activity decrease after reusing three times.
Can be found out by above embodiment, the present invention is using a kind of compound of solid acid tantalum as catalyzer, in the two-phase system of water and organic solvent composition, realize hexose or containing the biomass highly selective Dehydration of hexose for HMF.Compare with liquid acid catalysis technique with other solid acids, of the present invention have remarkable advantage: transformation efficiency is high, and selectivity is high, and catalyzer is cheap, and operational condition mild process is simple, and cost is low, environmental friendliness.
Claims (5)
1. the method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate and levulinic acid, it is characterized in that: its with tungstenic and tantalum compound or mixed oxide for catalyzer, take carbohydrate as raw material, react at the temperature of 80-300 DEG C, under liquid-phase condition, carbohydrate efficient catalytic is generated 5 hydroxymethyl furfural (HMF) and levulinic acid (LA), 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%; Wherein, described liquid-phase condition is the mixed solvent of water and 2-butanols, water and the mixed solvent of methyl iso-butyl ketone (MIBK) or the mixed solvent of water and butanols;
Describedly following precursor calcination activation at 100-1000 DEG C is adopted to form with tungstenic and tantalum compound or mixed oxide;
Described precursor is: be one or more in hydrated tantalum oxide, tantalum hydroxide, tantalate, tantalum oxide containing tantalum compound; Tungstenic compound is one or more in tungstic oxide, tungstate, ammonium metawolframate; Catalyzer is for forming solid catalyst WO by above-mentioned containing tantalum compound and Tungstenic compound carry out the adulterating oxide compound containing tantalum and tungsten that formed or salt calcination activation at 100-1000 DEG C
3-Ta
2o
5;
Or, in the precursor containing tantalum compound and Tungstenic compound, be also added with the compound or mixed oxide of going back other metallic elements of load or salt; Other metallic elements comprise one or two or more kinds in nickel, titanium, zirconium, chromium, aluminium, cobalt, platinum, palladium, ruthenium, molybdenum, vanadium, tin;
Catalyzer is for the above-mentioned compound containing tantalum compound and Tungstenic compound and other metallic elements of load or mixed oxide or salt, carry out the adulterating oxide compound containing tantalum and tungsten that formed or salt calcination activation at 100-1000 DEG C are formed solid catalyst, and 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%.
2. in accordance with the method for claim 1, it is characterized in that: the catalyzer of described tantalum and tungsten by both precursor tantalum chlorides, ethanol tantalum one or two or more kinds with tungsten chloride, metatungstic acid, metatungstate, tungstate one or two or more kinds be entrained in together with obtain, precipitation is formed in the aqueous solution, after formation to be precipitated, aged at room temperature 24 is little of one week, use before at 100-1000 DEG C calcination activation.
3. in accordance with the method for claim 1, it is characterized in that: tungsten and tantalum compound can load at the carrier surface of solid, form loaded catalyst, carrier is molecular sieve, silicon oxide, aluminum oxide, titanium dioxide or zirconium white; The mass ratio of catalyzer and carrier is 0.0001-1; Before the catalyzer of described loading type tungstenic and tantalum compound uses at 100-1000 DEG C calcination activation.
4. in accordance with the method for claim 1, it is characterized in that: described carbohydrate is fructose, glucose, semi-lactosi, seminose, sucrose, starch, inulin, corn juice, squeeze the juice in the jerusalem artichoke juice that obtains through the Mierocrystalline cellulose of pre-treatment and jerusalem artichoke stem tuber one or two or more kinds.
5. in accordance with the method for claim 1, it is characterized in that: temperature of reaction system is 80-300 DEG C; 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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| 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 |
| 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 |
| CN106496166B (en) * | 2016-09-06 | 2018-09-28 | 安徽理工大学 | A kind of method that xylose high-efficiency dehydration prepares furfural |
| CN106540677B (en) * | 2016-11-07 | 2019-12-10 | 江苏理工学院 | preparation method and application of porous carbon-loaded nano metal 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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