CN103113215A - Method for preparing acetylpropionic acid by means of concerted catalysis effect of Lewis acid and Bronsted acid on degradation of hexahydric carbohydrate in high-temperature liquid water - Google Patents
Method for preparing acetylpropionic acid by means of concerted catalysis effect of Lewis acid and Bronsted acid on degradation of hexahydric carbohydrate in high-temperature liquid water Download PDFInfo
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Abstract
The invention discloses a method for preparing acetylpropionic acid by means of concerted catalysis effect of Lewis acid and Bronsted acid on degradation of hexahydric carbohydrate in high-temperature liquid water. The method comprises the following steps of: adding water, hexahydric carbohydrate, Lewis acid and Bronsted acid into a high-pressure reaction kettle in sequence to form a homogeneous phase mixed solution; stirring the mixed solution after sealing the solution, heating to 140-200 DEG C to have reaction for 1-7 hours, and finally cooling, wherein the mass concentration of the hexahydric carbohydrate in the mixed solution is 20-200g/L; molar concentration of the Lewis acid is 0.01-0.6 mol/L; and molar concentration of the Bronsted acid is 0.01-0.6 mol/L. By utilizing the concerted catalysis of the Lewis acid and Bronsted acid, the method disclosed by the invention greatly increases the yield of acetylpropionic acid and has good industrial application prospect, wherein the yield of the acetylpropionic acid is as high as 70% at most.
Description
Technical field
The present invention relates to the method that the hexa-atomic sugar degraded of Lewis acid and bronsted sour concerted catalysis in a kind of high temperature liquid water prepares levulinic acid.
Background technology
Along with the exhaustion gradually of the Nonrenewable resources such as oil, coal, the new recyclability resource of Devoting Major Efforts To Developing utilization has become the precondition of walking sustainable development path.Biomass resource is the renewable resources of most abundant on the earth, and the annual biomass that generated by photosynthesis in the whole world are up to 1,500 hundred million ~ 2,000 hundred million tons, but the utilization ratio of these resources is very low at present.Renewable biomass resource main component is Mierocrystalline cellulose, hemicellulose and xylogen, and wherein hemicellulose and Mierocrystalline cellulose are respectively take wood sugar as main five-carbon sugar and glucose forms as main hexose.
Levulinic acid has another name called 4-oxidation valeric acid, LA or LA, is a kind of very promising biomass-based hardware and software platform compound, and its outward appearance is white plates or needle-like crystal.Following formula is the molecular structural formula of levulinic acid, can find out from formula, levulinic acid contains a carboxyl and a carbonyl, therefore have good reactive behavior, can be widely used in: in the fields such as chiral reagent, biological active materials, polymkeric substance, lubricant, sorbent material, coating, battery, printing ink, electronic product.
Utilize Production of Levulinic Acid from Biomass can adopt two operational paths.A kind of is at first to obtain furfural with biomass, then hydrogenation of furfural generates furfuryl alcohol, the recycling furfuryl alcohol is under acid catalysis, generate levulinic acid by hydrolysis, open loop, rearrangement reaction, its representational technique mainly contains: the catalyzed hydrolysis of furfuryl alcohol of the companies such as large mound pharmaceutical chemicals, the emerging product of space section, French organic synthesis, U.S. Gu Te Ritchie etc., the method is more and complicated condition due to step, is eliminated gradually.Another kind method is the direct hydrolysis method of biomass, and namely biomass material under the catalysis of mineral acid, directly generates levulinic acid through pyrohydrolysis, and there is the problem of following two aspects in the method:
1. environmental pollution is more serious, in preparation process, generally uses sulfuric acid and hydrochloric acid as acid catalyst, and because mineral acid has severe corrosive, a large amount of acid waste residues and the waste liquid of generation have brought the severe contamination problem to environment protection;
2. yield is on the low side, and the yield of levulinic acid is generally lower than 60%.
Generating levulinic acid from glucose is a polystep reaction, and response path is shown below, and the first isomerization of glucose generates fructose, and then the fructose dehydration generates 5 hydroxymethyl furfural, and last 5 hydroxymethyl furfural hydration generates levulinic acid and formic acid.Wherein the first step reaction Lewis acid plays a major role, and the bronsted acid of rear two-step reaction plays a major role.The present invention is applied to Lewis acid and bronsted acid take high temperature liquid water as reaction medium, realize preparing with high yield levulinic acid from hexa-atomic sugar in the reaction of hexa-atomic sugar degraded preparation levulinic acid simultaneously.
Lewis acid refers to electron acceptor, also can regard the centrosome that forms coordinate bond as.Electrophilic reagent or electron acceptor(EA) are all Lewis acids.What it was different from bronsted acid is that Lewis acid might not need that proton (H is arranged
+) transfer.Common Lewis acid has the fluoroform sulphonate of aluminum chloride, columbium pentachloride and lanthanon etc.Bronsted acid also claims " proton theory of acid base ".All molecule or ions that can discharge proton are called acid; All molecule or the ions that can accept proton are called alkali.Common bronsted acid has HCl, H
2SO
4, trichoroacetic acid(TCA) etc.
High temperature liquid water (High temperature liquid water, HTLW) typically refers to the compressed liquid water of temperature between 150～350 ℃.Water has following three key properties in this zone:
1) self has the function of acid catalysis and base catalysis.Depress at saturated vapo(u)r, the ionization constant of high temperature liquid water has a maximum value to be about 10 near 275 ℃
-11(molkg)
2, its value is 1000 times of normal temperature and pressure water, and ionization constant increases with the increase of pressure, [H3O
+] and [OH
-] near weak acid or weak base, therefore can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt;
2) while dissolved organic matter and inorganics.Depress at saturated vapo(u)r, the specific inductivity of 20 ℃ of water is 80.1, and only has 23.5 275 ℃ the time.Although the specific inductivity of high temperature liquid water is still larger, solubilized is ionized salts even, and is enough little of dissolved organic matter.This can carry out the building-up reactions in many high-temperature liquid state water mediums in homogeneous phase, thereby eliminates resistance to mass transfer, improves speed of response, only need after simultaneous reactions simple cooling just can realize wax moisture from, water can be recycled;
3) physical property adjustability.The physicochemical property such as the specific inductivity of high temperature liquid water, ion-product constant, density, viscosity, spread coefficient, solubleness are adjustable continuously in wider scope with temperature, pressure, therefore as reaction medium, high temperature liquid water has different solvent properties and reactivity worth at different states.
Summary of the invention
The purpose of this invention is to provide the method that the hexa-atomic sugar degraded of Lewis acid and bronsted sour concerted catalysis in a kind of high temperature liquid water prepares levulinic acid.
The method that in high temperature liquid water, the hexa-atomic sugar degraded of Lewis acid and bronsted sour concerted catalysis prepares levulinic acid is: add successively entry, hexa-atomic sugar, Lewis acid and bronsted acid and form homogeneous mixed solution in autoclave, in mixing solutions, the mass concentration of hexa-atomic sugar is 20～200 g/L, lewis acidic volumetric molar concentration is 0.01～0.6 mol/L, the volumetric molar concentration of bronsted acid is 0.01～0.6 mol/L, open stirring after airtight, be warming up to 140～200 ℃ of reaction 1～7h, cooling.
Described hexa-atomic sugar is fructose, glucose or fructose_glucose mixture.
Described Lewis acid is zinc chloride, chromium chloride, iron(ic) chloride or cupric chloride.
Described bronsted acid is hydrochloric acid, sulfuric acid, phosphoric acid, potassium primary phosphate, dipotassium hydrogen phosphate, Phenylsulfonic acid, oxalic acid or trichoroacetic acid(TCA).
In described mixing solutions, the mass concentration of hexa-atomic sugar aqueous solution is 50～180 g/L.
In described mixing solutions, lewis acidic volumetric molar concentration is 0.02～0.5 mol/L.
In described mixing solutions, the volumetric molar concentration of bronsted acid is 0.02～0.5 mol/L.
Described temperature of reaction is 150～190 ℃.
The present invention utilizes Lewis acid and bronsted sour concerted catalysis effect, has greatly improved the yield of levulinic acid, has been up to 70%, has good industrial applications prospect.
Description of drawings
Accompanying drawing is the process flow diagram of Lewis acid and the hexa-atomic sugar degraded preparation levulinic acid of bronsted sour concerted catalysis in high temperature liquid water.
Embodiment
In the present invention, HPLC analyzes and measures yield of levulinic acid, and analysis condition is as follows:
Adopt Agilent 1100 high performance liquid chromatographs, chromatographic column is Sugar SH1011(Shodex, and 8mmID * 300mm), moving phase is 5 * 10
-4The aqueous sulfuric acid of mol/L, flow velocity are 0.5 mL/min; Column temperature is 60 ℃, and detector temperature is 40 ℃, adopts external standard method quantitative.
The mole number of the hexa-atomic sugar of the mole number of the levulinic acid that the yield %=(of levulinic acid generates/add) * 100%
Following examples employing mass concentration is 38% hydrochloric acid, and density is 1.19g/mL; Mass concentration is 98% sulfuric acid, and density is 1.84g/mL; Mass concentration is 85% phosphoric acid, and density is 1.68g/mL.
Embodiment 1
Add successively deionized water 300mL, fructose 15g, sulfuric acid 9.00g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 50g/L at this moment, and the volumetric molar concentration of sulfuric acid is 0.30mol/L, open stirring after airtight, be warming up to 180 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 25.6 %.
Embodiment 2
Add successively deionized water 300mL, glucose 15g, phosphoric acid 6.92g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 50g/L at this moment, and the volumetric molar concentration of phosphoric acid is 0.20mol/L, open stirring after airtight, be warming up to 190 ℃ of reaction 3h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 5.1%.
Embodiment 3
Add successively in the 500mL autoclave deionized water 300mL, fructose_glucose mixture 24 g(wherein fructose and glucose quality than being 3:5), chromium chloride 9.51 g, dipotassium hydrogen phosphate 10.45g, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 80g/L at this moment, the volumetric molar concentration of chromium chloride is 0.20mol/L, the volumetric molar concentration of dipotassium hydrogen phosphate is 0.20mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 61.1%.
Embodiment 4
Add successively deionized water 300mL, fructose 30g, iron(ic) chloride 2.43 g, sulfuric acid 12.00g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 100g/L at this moment, the volumetric molar concentration of iron(ic) chloride is 0.05mol/L, the volumetric molar concentration of sulfuric acid is 0.40mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 51.3%.
Embodiment 5
Add successively deionized water 300mL, glucose 60g, dipotassium hydrogen phosphate 2.61g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 200g/L at this moment, the volumetric molar concentration of dipotassium hydrogen phosphate is 0.05mol/L, open stirring after airtight, be warming up to 140 ℃ of reaction 7h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 0.5%.
Embodiment 6
Add successively deionized water 300mL, glucose 36g, Phenylsulfonic acid 9.49g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 120g/L at this moment, the volumetric molar concentration of Phenylsulfonic acid is 0.20mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 18.8 %.
Embodiment 7
Add successively deionized water 300mL, fructose 30g, zinc chloride 8.18 g, hydrochloric acid 5.76g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 100g/L at this moment, the volumetric molar concentration of zinc chloride is 0.20mol/L, the volumetric molar concentration of hydrochloric acid is 0.20mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 28.7 %.
Embodiment 8
Add successively in the 500mL autoclave deionized water 300mL, fructose_glucose mixture 30g(wherein the mass ratio of fructose and glucose be 1:1), chromium chloride 19.00 g, phosphatase 11 .73g, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 100g/L at this moment, the volumetric molar concentration of chromium chloride is 0.40mol/L, the volumetric molar concentration of phosphoric acid is 0.05mol/L, open stirring after airtight, be warming up to 200 ℃ of reaction 1h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 40.9 %.
Embodiment 9
Add successively deionized water 300mL, glucose 6g, oxalic acid 5.40g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 20g/L at this moment, and the volumetric molar concentration of oxalic acid is 0.20mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 10.4 %.
Embodiment 10
Add successively deionized water 300mL, fructose 54g, iron(ic) chloride 9.74 g, hydrochloric acid 8.65g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 180g/L at this moment, the volumetric molar concentration of iron(ic) chloride is 0.20mol/L, the volumetric molar concentration of hydrochloric acid is 0.30mol/L, open stirring after airtight, be warming up to 190 ℃ of reaction 2 h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 45.6 %.
Embodiment 11
Add successively deionized water 300mL, glucose 6 g, zinc chloride 0.41 g in 500 mL autoclaves, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 20g/L at this moment, the volumetric molar concentration of zinc chloride is 0.01mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 3.1%.
Embodiment 12
Add successively deionized water 300mL, glucose 30g, chromium chloride 9.50g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 100g/L at this moment, the volumetric molar concentration of chromium chloride is 0.20mol/L, open stirring after airtight, be warming up to 190 ℃ of reaction 3h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 12.8 %.
Embodiment 13
Add successively deionized water 300mL, fructose_glucose mixture 36 g (wherein the mass ratio of fructose and glucose is 7:5), cupric chloride 12.11 g, trichoroacetic acid(TCA) 29.41g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 120g/L at this moment, the volumetric molar concentration of cupric chloride is 0.30mol/L, the volumetric molar concentration of trichoroacetic acid(TCA) is 0.60mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 43.6 %.
Embodiment 14
Add successively deionized water 300mL, glucose 6 g, iron(ic) chloride 4.87 g, Phenylsulfonic acid 0.47g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 20g/L at this moment, the volumetric molar concentration of iron(ic) chloride is 0.05mol/L, the volumetric molar concentration of Phenylsulfonic acid is 0.01mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 5h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 26.7 %.
Embodiment 15
Add successively deionized water 300mL, fructose 36g, chromium chloride 4.75 g, potassium primary phosphate 8.17g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 120g/L at this moment, the volumetric molar concentration of chromium chloride is 0.10mol/L, the volumetric molar concentration of potassium primary phosphate is 0.20mol/L, open stirring after airtight, be warming up to 150 ℃ of reaction 6h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 52.7 %.
Embodiment 16
Add successively deionized water 300mL, glucose 30g, cupric chloride 24.22 g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 100g/L at this moment, the volumetric molar concentration of cupric chloride is 0.60mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 22.2 %.
Embodiment 17
Add successively deionized water 300mL, fructose 15g, cupric chloride 8.07g, oxalic acid 2.70g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 50g/L at this moment, the volumetric molar concentration of cupric chloride is 0.20mol/L, the volumetric molar concentration of oxalic acid is 0.10mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 38.9%.
Embodiment 18
Add successively deionized water 300mL, glucose 30g, chromium chloride 2.38g, hydrochloric acid 5.76g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 100g/L at this moment, the volumetric molar concentration of chromium chloride is 0.05mol/L, the volumetric molar concentration of hydrochloric acid is 0.20mol/L, open stirring after airtight, be warming up to 140 ℃ of reaction 7h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 35.6 %.
Embodiment 19
Add successively deionized water 300mL, fructose_glucose mixture 45 g (wherein the mass ratio of fructose and glucose is 1:2), chromium chloride 23.75g, phosphoric acid 3.46g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 150g/L at this moment, the volumetric molar concentration of chromium chloride is 0.50mol/L, the volumetric molar concentration of phosphoric acid is 0.10mol/L, open stirring after airtight, be warming up to 200 ℃ of reaction 3h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 60.9 %.
Embodiment 20
Add successively deionized water 300mL, fructose 15g, cupric chloride 8.07 g, trichoroacetic acid(TCA) 14.71g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 50g/L at this moment, the volumetric molar concentration of cupric chloride is 0.20mol/L, the volumetric molar concentration of trichoroacetic acid(TCA) is 0.30mol/L, open stirring after airtight, be warming up to 160 ℃ of reaction 6h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 39.5%.
Embodiment 21
Add successively deionized water 300mL, glucose 54 g, cupric chloride 8.07g, hydrochloric acid 5.76g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 180g/L at this moment, the volumetric molar concentration of cupric chloride is 0.20mol/L, the volumetric molar concentration of hydrochloric acid is 0.20mol/L, open stirring after airtight, be warming up to 200 ℃ of reaction 1h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 42.3%.
Embodiment 22
Add successively deionized water 300mL, fructose 30g, chromium chloride 14.25g, phosphatase 11 7.31g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 100g/L at this moment, the volumetric molar concentration of chromium chloride is 0.30mol/L, the volumetric molar concentration of phosphoric acid is 0.50mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 5h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 68.6 %.
Embodiment 23
Add successively deionized water 300mL, fructose_glucose mixture 54g (wherein the mass ratio of fructose and glucose is 5:13), chromium chloride 4.75g, phosphatase 11 0.38g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 180g/L at this moment, the volumetric molar concentration of chromium chloride is 0.10mol/L, the volumetric molar concentration of phosphoric acid is 0.30mol/L, open stirring after airtight, be warming up to 190 ℃ of reaction 3h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 62.3 %.
Embodiment 24
Add successively deionized water 300mL, glucose 30g, iron(ic) chloride 9.74g, Phenylsulfonic acid 9.49g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 100g/L at this moment, the volumetric molar concentration of iron(ic) chloride is 0.20mol/L, the volumetric molar concentration of Phenylsulfonic acid is 0.20mol/L, open stirring after airtight, be warming up to 200 ℃ of reaction 2h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 35.9%.
Embodiment 25
Add successively deionized water 300mL, fructose 30g, chromium chloride 19.01 g, phosphatase 11 0.38g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 100g/L at this moment, the volumetric molar concentration of chlorination chromic acid is 0.40mol/L, the volumetric molar concentration of phosphoric acid is 0.30mol/L, open stirring after airtight, be warming up to 180 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 70.1 %.
Embodiment 26
Add successively deionized water 300mL, glucose 6g, chromium chloride 4.75g, potassium primary phosphate 2.04g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 20g/L at this moment, the volumetric molar concentration of chromium chloride is 0.10mol/L, the volumetric molar concentration of potassium primary phosphate is 0.05mol/L, open stirring after airtight, be warming up to 150 ℃ of reaction 6h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 35.7%.
Embodiment 27
Add successively deionized water 300mL, fructose 45g, chromium chloride 9.50g, phosphoric acid 20.77g in 500 mL autoclaves, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 150g/L at this moment, the volumetric molar concentration of chromium chloride is 0.20mol/L, the volumetric molar concentration of phosphoric acid is 0.60mol/L, open stirring after airtight, be warming up to 140 ℃ of reaction 7h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 50.1%.
Embodiment 28
Add successively deionized water 300mL, glucose 15g, chromium chloride 23.75g, dipotassium hydrogen phosphate 0.52g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 50g/L at this moment, the volumetric molar concentration of chromium chloride is 0.50mol/L, the volumetric molar concentration of dipotassium hydrogen phosphate is 0.01mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 38.5 %.
Embodiment 29
Add successively deionized water 300mL, fructose 24g, chromium chloride 14.75g, phosphatase 11 0.38g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 80g/L at this moment, the volumetric molar concentration of chromium chloride is 0.30mol/L, the volumetric molar concentration of phosphoric acid is 0.30mol/L, open stirring after airtight, be warming up to 180 ℃ of reaction 3h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 64.7 %.
Embodiment 30
Add successively deionized water 300mL, glucose 45g, chromium chloride 19.01 g, potassium primary phosphate 16.33g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 150g/L at this moment, the volumetric molar concentration of chromium chloride is 0.40mol/L, the volumetric molar concentration of potassium primary phosphate is 0.40mol/L, open stirring after airtight, be warming up to 160 ℃ of reaction 4h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 58.6%.
Embodiment 31
Add successively in the 500mL autoclave deionized water 300mL, fructose_glucose mixture 30 g(wherein the mass ratio of fructose and glucose be 1:1), chromium chloride 19.01g, potassium primary phosphate 12.25g, form homogeneous mixed solution, in mixing solutions, the mass concentration of hexa-atomic sugar is 100g/L at this moment, the volumetric molar concentration of chromium chloride is 0.40mol/L, the volumetric molar concentration of potassium primary phosphate is 0.30mol/L, open stirring after airtight, be warming up to 190 ℃ of reaction 2h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 63.4%.
Embodiment 32
Add successively deionized water 300mL, glucose 54g, chromium chloride 23.75g, phosphatase 11 0.38g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 180g/L at this moment, the volumetric molar concentration of chromium chloride is 0.50mol/L, the volumetric molar concentration of phosphoric acid is 0.30mol/L, open stirring after airtight, be warming up to 150 ℃ of reaction 6h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 49.7%.
Embodiment 33
Add successively deionized water 300mL, fructose 45g, chromium chloride 23.75g, phosphoric acid 6.92g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 150g/L at this moment, the volumetric molar concentration of chromium chloride is 0.50mol/L, the volumetric molar concentration of phosphoric acid is 0.20mol/L, open stirring after airtight, be warming up to 160 ℃ of reaction 5h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 64.7%.
Embodiment 34
Add successively deionized water 300mL, glucose 60g, chromium chloride 28.49g, trichoroacetic acid(TCA) 24.51g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of glucose is 200g/L at this moment, the volumetric molar concentration of chromium chloride is 0.60mol/L, the volumetric molar concentration of trichoroacetic acid(TCA) is 0.50mol/L, open stirring after airtight, be warming up to 140 ℃ of reaction 7h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 47.5%.
Embodiment 35
Add successively deionized water 300mL, fructose 36g, chromium chloride 19.01 g, potassium primary phosphate 20.41g in the 500mL autoclave, form homogeneous mixed solution, in mixing solutions, the mass concentration of fructose is 120g/L at this moment, the volumetric molar concentration of chromium chloride is 0.40mol/L, the volumetric molar concentration of potassium primary phosphate is 0.50mol/L, open stirring after airtight, be warming up to 170 ℃ of reaction 5h; After reaction product is cooling reaction solution, reaction solution after filtration, HPLC after analyzing, calculating the levulinic acid molar yield be 62.3 %.
Claims (8)
1. in a high temperature liquid water, the hexa-atomic sugar degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that: add successively entry, hexa-atomic sugar, Lewis acid and bronsted acid and form homogeneous mixed solution in autoclave, in mixing solutions, the mass concentration of hexa-atomic sugar is 20～200 g/L, lewis acidic volumetric molar concentration is 0.01～0.6 mol/L, the volumetric molar concentration of bronsted acid is 0.01～0.6 mol/L, open stirring after airtight, be warming up to 140～200 ℃ of reaction 1～7h, cooling.
2. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that described hexa-atomic sugar is fructose, glucose or fructose_glucose mixture.
3. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that described Lewis acid is zinc chloride, chromium chloride, iron(ic) chloride or cupric chloride.
4. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that described bronsted acid is hydrochloric acid, sulfuric acid, phosphoric acid, potassium primary phosphate, dipotassium hydrogen phosphate, Phenylsulfonic acid, oxalic acid or trichoroacetic acid(TCA).
5. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, and the mass concentration that it is characterized in that hexa-atomic sugar aqueous solution in described mixing solutions is 50～180 g/L.
6. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that in described mixing solutions, lewis acidic volumetric molar concentration is 0.02～0.5 mol/L.
7. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, and the volumetric molar concentration that it is characterized in that bronsted acid in described mixing solutions is 0.02～0.5 mol/L.
8. in a kind of high temperature liquid water according to claim 1, hexa-atomic sugared degraded of Lewis acid and bronsted sour concerted catalysis prepares the method for levulinic acid, it is characterized in that described temperature of reaction is 150～190 ℃.
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| CN105859545A (en) * | 2016-04-07 | 2016-08-17 | 中国科学技术大学 | Preparation method of furfural and levulinic acid |
| CN106565453A (en) * | 2016-10-28 | 2017-04-19 | 华南理工大学 | Method for degradation of low-quality reused fibers through collaborative catalysis of metal chloride and proton acid to prepare levulinic acid |
| CN108373408A (en) * | 2018-02-09 | 2018-08-07 | 青岛科技大学 | A kind of preparation method of levulic acid |
| CN112851490A (en) * | 2021-01-15 | 2021-05-28 | 太原工业学院 | Method for producing levulinic acid by efficiently catalyzing saccharides |
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| CN101475543A (en) * | 2009-02-11 | 2009-07-08 | 中国科学院山西煤炭化学研究所 | Method for preparing hydroxymethyl-furfural from glucide under low temperature and normal pressure |
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| CN101092347A (en) * | 2007-06-05 | 2007-12-26 | 浙江大学 | Method for preparing levulinic acid from hexabasic sugar catalyzed and hydrolyzed by fire resistant and highly acidic resin |
| CN101475543A (en) * | 2009-02-11 | 2009-07-08 | 中国科学院山西煤炭化学研究所 | Method for preparing hydroxymethyl-furfural from glucide under low temperature and normal pressure |
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| CN105859545A (en) * | 2016-04-07 | 2016-08-17 | 中国科学技术大学 | Preparation method of furfural and levulinic acid |
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| CN108373408B (en) * | 2018-02-09 | 2022-09-27 | 青岛科技大学 | Preparation method of levulinic acid |
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| CN112851490B (en) * | 2021-01-15 | 2023-03-28 | 太原工业学院 | Method for producing levulinic acid by efficiently catalyzing saccharides |
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