CN104496797A - Method for preparing acetyl propionic acid by degrading hexamylose in ionic liquid-water medium - Google Patents
Method for preparing acetyl propionic acid by degrading hexamylose in ionic liquid-water medium Download PDFInfo
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Abstract
The invention discloses a method for preparing acetyl propionic acid by degrading hexamylose in an ionic liquid-water medium. The method comprises the following steps: mixing the hexamylose, ionic liquid and water; heating for reaction; carrying out decompression distillation on the reaction liquid to obtain the acetyl propionic acid; and simultaneously recycling the ionic liquid. The ionic liquid adopted by the method disclosed by the invention is relatively high in thermal stability chemical stability, relatively high in polarity adjustability, low in viscosity, high in dissolving capacity and relatively good in catalytic effect and has dual performances of a solvent and a catalyst; the target product acetyl propionic acid obtained by a catalytic reaction is high in yield which is as high as 78.7%. The ionic liquid adopted by the method disclosed by the invention is easy to recycle and can be used repeatedly, the amount of discharged wastewater is greatly reduced, and the ionic liquid is environment-friendly, so the method disclosed by the invention is quite good in industrial application prospect.
Description
Technical field
The present invention relates to organic synthesis field, particularly relate to hexa-atomic sugar degraded in a kind of ionic liquid-water medium and prepare the method for levulinic acid.
Background technology
Levulinic acid (Levulinic Acid, LA), No. CAS: 123-76-2, also known as LA, LA, LA, pure levulinic acid is white plates or thallus crystallization, nontoxic, has water absorbability.Containing a carboxyl and a carbonyl in levulinic acid molecule, there is good reactive behavior, the chemical reactions such as salify, esterification, halogenation, hydrogenation, oxidation, condensation can occur.Therefore utilize it can derive many high value-added products, be mainly used in the field such as additive of medicine, agricultural chemicals, organic synthesis intermediate, spices, plastic modifier, polymkeric substance, resin, coating.Levulinic acid is the very promising biomass-based platform chemicals of one, has a good application prospect.
According to the difference of raw material, the production method of levulinic acid can be divided into two large classes.One is catalyzed hydrolysis of furfuryl alcohol: as the furfuryl alcohol of starting raw material, be hydrolyzed in acidic medium, carries out open loop, rearrangement reaction, generation levulinic acid.The key of the method is open loop and rearrangement reaction, and reaction medium is very big on whole reaction impact, and step is more complicated, is eliminated gradually.Another kind is hydrolysis of biomass: be raw material mainly with the biomass such as cellulose and starch, high temperature heat altogether under the katalysis of mineral acid, biomass material is decomposed into monose, forms 5 hydroxymethyl furfural in dehydration, is then hydrolyzed further and generates levulinic acid.There is the problems such as yield is low, seriously polluted, production cost is high in the method.
Application number be 201310033470.3 application discloses 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.In autoclave, add water, hexa-atomic sugar, Lewis acid and bronsted acid successively form homogeneous mixed solution, airtight rear temperature reaction.This invention utilizes Lewis acid and bronsted sour concerted catalysis effect, substantially increases the yield of levulinic acid.Shortcoming is that reaction yield is lower, and reaction to terminate rear wastewater discharge large and difficult, cause environmental pollution.
Ionic liquid, also known as ionic liquid at room temperature or room temperature molten salt, also claims nonaqueous ionic liquid, organic ion liquid etc.Ionic liquid refers to do not have electriccenter molecule and 100% by negatively charged ion and cation composition, be the material of liquid under room temperature.The salt that it is made up of a kind of organic cation and a kind of inorganic anion of nitrogenous or phosphorus heterocycle, is in a liquid state under room temperature or near room temperature temperature.
Ionic liquid is replaced the green medium of traditional volatile organic solvent owing to having extremely low vapour pressure, higher thermostability and adjustable dissolving power by as a kind of and be widely used in organic synthesis, separating-purifying field; Catalytic chemistry and electrochemical research field is applied to as novel electrolytes and effective catalyst because specific conductivity is high, stablize the wide and adjustable acid-basicity of electrochemical window; Because its coordination ability is low, interfacial tension and interfacial energy is little and their easily form hydrogen bond and have higher order make them in the nano material preparation with special appearance, both can play the effect of template as medium.Therefore ionic liquid research to scientific basis research or practical application all has very important meaning.
Summary of the invention
The invention provides hexa-atomic sugar degraded in a kind of ionic liquid-water medium and prepare the method for levulinic acid.The method productive rate is higher, and used ionic liquid-catalyzed effective, environmental pollution is little.
In ionic liquid-water medium, a method for levulinic acid is prepared in hexa-atomic sugar degraded, hexa-atomic sugar, ionic liquid and water is formed mixing solutions reacting by heating, obtains levulinic acid after process.
Preferably, in mixing solutions, the massfraction of hexa-atomic sugar is 10% ~ 30%, and ionic liquid massfraction is 5% ~ 50%.The degradation rate of hexa-atomic sugar is fast with this understanding, and transformation efficiency is high, and product yield of levulinic acid is high.
Described hexa-atomic sugar is glucose, fructose or Glucose-Fructose mixture.
Glucose in described Glucose-Fructose mixture and the weight ratio of fructose are 1:1 ~ 2.
Described ionic liquid refers to the liquid salt system be only made up of ion under room temperature or a little higher than room temperature.Generally be made up of organic cation and inorganic anion, the imidazol ion that common positively charged ion has quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, alkyl to replace and alkyl pyrrolidinium ion etc.; Common Anions has halide-ions, sulfate ion, acetate ion, trifluoro sulfonate ion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions etc.
Ionic liquid of the present invention is acidic ion liquid, and ionic liquid-water mixed solution provides free proton hydrogen, the degraded of the free hexa-atomic sugar of proton hydrogen catalysis, and free protons hydrogen concentration is higher, and the degradation rate of hexa-atomic sugar is faster.
Preferably, described ionic liquid is bromination 1-carboxymethyl-3-Methylimidazole, chlorination 1-carboxymethyl-3-Methylimidazole, 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, N-propyl sulfonic acid pyridine villaumite, 1-propanesulfonic acid base-3-Methylimidazole villaumite, 1-sulfonic acid butyl-3-Methylimidazole villaumite, chlorination N-allyl pyridine, N-methylimidazolium hydrogen sulphate salt, chlorination 1-benzyl-3-Methylimidazole, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-amyl group-3-Methylimidazole hexafluorophosphate, 1-carboxymethyl-3-methyl imidazolium tetrafluoroborate and 1-butyl-3-Methylimidazole bromine salt, at least one in 1-allyl group-3-Methylimidazole bromine salt.
Further preferably, described ionic liquid is at least one of 1-propanesulfonic acid base-3-Methylimidazole villaumite, 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, N-propyl sulfonic acid pyridine villaumite and 1-sulfonic acid butyl-3-Methylimidazole villaumite.
Preferred Ionic Liquids Acidity is comparatively strong, excellent catalytic effect, and the degradation rate of hexa-atomic sugar is fast, and transformation efficiency is high and yield that is product levulinic acid is high.
Described temperature of reaction is 140 DEG C ~ 200 DEG C, and preferably, temperature of reaction is 170 DEG C ~ 190 DEG C.In this range of reaction temperature, hexa-atomic sugared degradation rate is fast, and transformation efficiency is high, and the productive rate of product levulinic acid is high.
The described reaction times is 0.5h ~ 3.5h, and substrate is different, and there is difference in the reaction times.
More preferably, reaction conditions is: described hexa-atomic sugar is fructose, in mixing solutions, the massfraction of fructose is 10% ~ 20%, described ionic liquid is 1-propanesulfonic acid base-3-Methylimidazole villaumite or 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, massfraction is 10% ~ 20%, temperature of reaction is 170 DEG C ~ 190 DEG C, and the reaction times is 0.5h ~ 2h.The degradation rate of fructose is fast under this condition, and transformation efficiency is high, and product yield of levulinic acid is high.
Reaction terminates rear reaction solution through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower reclaims and reuses.
The present invention's reaction can be carried out in high temperature and high pressure kettle, the mixing solutions that ionic liquid-water is formed has stronger corrodibility at high temperature under high pressure, thus require the high temperature and high pressure kettle protection against corrosion used, the high-temperature high-pressure reaction kettle etc. of zirconium alloy reactor or liner (tetrafluoroethylene, graphite, enamel) can be adopted.
Compared with prior art, the present invention has following beneficial effect:
The ionic liquid that the present invention adopts has higher thermostability and chemical stability, has the dual property of solvent and catalyzer, and dissolving power is strong, and ionic liquid-catalyzed effect is better, and the target product yield of levulinic acid that catalyzed reaction obtains is high.Ionic liquid of the present invention easily reclaims, and can reuse, and greatly reduces the quantity discharged of waste water, environmental protection, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
HPLC analytical test yield of levulinic acid in the present invention, analysis condition is as follows:
Adopt Agilent 1100 high performance liquid chromatograph, chromatographic column is SH1011 (Shodex, 8mmID × 300mm), and moving phase is 5 × 10
-4the aqueous sulfuric acid of mol/L, flow velocity is 0.5mL/min; Column temperature is 60 DEG C, and detector temperature is 40 DEG C, adopts quantified by external standard method.
The yield %=of levulinic acid (mole number of the hexa-atomic sugar of the mole number of the levulinic acid of generation/add) × 100%
Embodiment 1
30g fructose, 60g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 210g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 10%, ionic liquid massfraction is 20%, open stirring, be heated to 170 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 78.7%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 2
90g fructose, 30g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 30%, ionic liquid massfraction is 10%, open stirring, be heated to 160 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 56.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 3
30g glucose, 90g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 10%, ionic liquid massfraction is 30%, open stirring, be heated to 140 DEG C of reaction 3.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 22.5%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 4
60g glucose, 120g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 120g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose sugar massfraction is 20%, ionic liquid massfraction is 40%, open stirring, be heated to 150 DEG C of reaction 2.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 40.2%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 5
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 45g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 60g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 195g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 15%, ionic liquid massfraction is 20%, open stirring, be heated to 180 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 74.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 6
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 75g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:2), 150g 1-propanesulfonic acid base-3-Methylimidazole villaumite, 75g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 25%, ionic liquid massfraction is 50%, open stirring, be heated to 160 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 54.4%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 7
60g fructose, 15g N-propyl sulfonic acid pyridine villaumite, 225g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 20%, ionic liquid massfraction is 5%, open stirring, be heated to 200 DEG C of reaction 1.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 51.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 8
30g fructose, 60g N-propyl sulfonic acid pyridine villaumite, 210g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 10%, ionic liquid massfraction is 20%, opens stirring, is heated to 170 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 68.5%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 9
45g glucose, 90g N-propyl sulfonic acid pyridine villaumite, 165g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 15%, ionic liquid massfraction is 30%, open stirring, be heated to 150 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 50.6%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 10
90g glucose, 30g N-propyl sulfonic acid pyridine villaumite, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 30%, ionic liquid massfraction is 10%, open stirring, be heated to 160 DEG C of reaction 1.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 59.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 11
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 60g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 150g N-propyl sulfonic acid pyridine villaumite, 90g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 20%, ionic liquid massfraction is 50%, open stirring, be heated to 180 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 73.6%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 12
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 75g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:2), 120g N-propyl sulfonic acid pyridine villaumite, 105g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 25%, ionic liquid massfraction is 40%, open stirring, be heated to 140 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 21.9%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 13
30g fructose, 60g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 210g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 10%, ionic liquid massfraction is 20%, open stirring, be heated to 190 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 53.4%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 14
90g fructose, 15g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 195g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 30%, ionic liquid massfraction is 5%, open stirring, be heated to 180 DEG C of reaction 1.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 38.7%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 15
30g glucose, 90g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 10%, ionic liquid massfraction is 30%, open stirring, be heated to 160 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 20.3%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 16
60g glucose, 150g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 90g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 20%, ionic liquid massfraction is 50%, open stirring, be heated to 140 DEG C of reaction 2.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 10.5%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 17
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 45g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 60g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 195g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 15%, ionic liquid massfraction is 20%, open stirring, be heated to 190 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 46.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 18
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 75g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:2), 120g 1-sulfonic acid butyl-3-Methylimidazole villaumite, 105g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 25%, ionic liquid massfraction is 40%, open stirring, be heated to 200 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 47.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 19
60g fructose, 90g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 150g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 20%, ionic liquid massfraction is 30%, open stirring, be heated to 170 DEG C of reaction 3.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 56.9%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 20
30g fructose, 60g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 210g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 10%, ionic liquid massfraction is 20%, open stirring, be heated to 160 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 33.4%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 21
45g glucose, 30g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 225g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 15%, ionic liquid massfraction is 10%, open stirring, be heated to 140 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 18.6%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 22
90g glucose, 90g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 120g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 30%, ionic liquid massfraction is 30%, open stirring, be heated to 150 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 24.3%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 23
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 60g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 120g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 120g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 20%, ionic liquid massfraction is 40%, open stirring, be heated to 180 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 51.0%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 24
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 75g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:2), 60g 1-sulfonic acid butyl-3-methylimidazolium hydrogen sulphate salt, 165g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 25%, ionic liquid massfraction is 20%, open stirring, be heated to 160 DEG C of reaction 2.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 46.5%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 25
45g fructose, 150g chlorination-carboxymethyl-3-Methylimidazole, 105g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 15%, ionic liquid massfraction is 50%, open stirring, be heated to 200 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 68.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 26
90g fructose, 15g chlorination-carboxymethyl-3-Methylimidazole, 195g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 30%, ionic liquid massfraction is 5%, open stirring, be heated to 170 DEG C of reaction 1.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 45.6%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 27
60g glucose, 60g chlorination-carboxymethyl-3-Methylimidazole, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 20%, ionic liquid massfraction is 20%, open stirring, be heated to 150 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 33.5%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 28
75g glucose, 90g chlorination-carboxymethyl-3-Methylimidazole, 135g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 25%, ionic liquid massfraction is 30%, open stirring, be heated to 160 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 47.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 29
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 30g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 30g chlorination-carboxymethyl-3-Methylimidazole, 240g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 10%, ionic liquid massfraction is 10%, open stirring, be heated to 180 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 50.2%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 30
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 90g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:2), 150g chlorination-carboxymethyl-3-Methylimidazole, 60g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 30%, ionic liquid massfraction is 50%, open stirring, be heated to 140 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 16.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 31
30g fructose, 120g bromination-carboxymethyl-3-Methylimidazole, 150g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 10%, ionic liquid massfraction is 40%, open stirring, be heated to 190 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 58.0%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 32
60g glucose, 60g bromination-carboxymethyl-3-Methylimidazole, 180g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 20%, ionic liquid massfraction is 20%, open stirring, be heated to 180 DEG C of reaction 1.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 45.6%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 33
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 45g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 15g bromination-carboxymethyl-3-Methylimidazole, 240g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 15%, ionic liquid massfraction is 5%, open stirring, be heated to 160 DEG C of reaction 2.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 32.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 34
75g fructose, 90g chlorination N-allyl pyridine, 135g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 25%, ionic liquid massfraction is 30%, opens stirring, is heated to 140 DEG C of reaction 3.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 11.7%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 35
60g glucose, 150g chlorination N-allyl pyridine, 90g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 20%, ionic liquid massfraction is 50%, open stirring, be heated to 190 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 22.9%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 36
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 30g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 60g chlorination N-allyl pyridine, 210g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 10%, ionic liquid massfraction is 20%, open stirring, be heated to 200 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 26.4%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 37
45g fructose, 120g N-methylimidazolium hydrogen sulphate salt, 135g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 15%, ionic liquid massfraction is 40%, open stirring, be heated to 170 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 28.1%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 38
90g glucose, 90g chlorination 1-benzyl-3-Methylimidazole, 120g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 30%, ionic liquid massfraction is 30%, open stirring, be heated to 160 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 17.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 39
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 60g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 15g 1-ethyl-3-methylimidazole hexafluorophosphate, 225g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 20%, ionic liquid massfraction is 5%, open stirring, be heated to 140 DEG C of reaction 3h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 5.3%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 40
75g fructose, 90g 1-amyl group-3-Methylimidazole hexafluorophosphate, 135g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 25%, ionic liquid massfraction is 30%, open stirring, be heated to 150 DEG C of reaction 2.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 10.9%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 41
30g glucose, 150g 1-carboxymethyl-3-methyl imidazolium tetrafluoroborate, 120g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, glucose quality mark is 10%, ionic liquid massfraction is 50%, open stirring, be heated to 180 DEG C of reaction 0.5h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 9.8%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 42
In the high-temperature high-pressure reaction kettle that 500mL band stirs, add 45g Glucose-Fructose mixture (wherein the mass ratio of glucose and fructose is 1:1), 60g 1-butyl-3-Methylimidazole bromine salt, 195g deionized water form mixing solutions, now in mixing solutions, hexa-atomic sugared massfraction is 15%, ionic liquid massfraction is 20%, open stirring, be heated to 160 DEG C of reaction 2h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 7.2%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Embodiment 43
90g fructose, 120g 1-allyl group-3-Methylimidazole bromine salt, 90g deionized water formation mixing solutions is added in the high-temperature high-pressure reaction kettle that 500mL band stirs, now in mixing solutions, fructose massfraction is 30%, ionic liquid massfraction is 40%, open stirring, be heated to 200 DEG C of reaction 1h; Reaction cooling after, obtain reaction solution, reaction solution after filtration, HPLC analyze, calculate after levulinic acid molar yield be 15.3%.Reaction solution is through rectification under vacuum, and tower top obtains levulinic acid product, and the ionic liquid at the bottom of tower is reusable.
Claims (9)
1. in ionic liquid-water medium, the method for levulinic acid is prepared in hexa-atomic sugar degraded, it is characterized in that, by the reaction of hexa-atomic sugar, ionic liquid and water mixing post-heating, treatedly obtains levulinic acid.
2. the method for levulinic acid is prepared in hexa-atomic sugar degraded according to claim 1, and it is characterized in that, described hexa-atomic sugar is glucose, fructose or Glucose-Fructose mixture.
3. in ionic liquid-water medium according to claim 2, the method for levulinic acid is prepared in hexa-atomic sugar degraded, and it is characterized in that, the glucose in described Glucose-Fructose mixture and the weight ratio of fructose are 1:1 ~ 2.
4. in ionic liquid-water medium according to claim 1, the method for levulinic acid is prepared in hexa-atomic sugar degraded, it is characterized in that, described ionic liquid is bromination 1-carboxymethyl-3-Methylimidazole, chlorination 1-carboxymethyl-3-Methylimidazole, 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, N-propyl sulfonic acid pyridine villaumite, 1-propanesulfonic acid base-3-Methylimidazole villaumite, 1-sulfonic acid butyl-3-Methylimidazole villaumite, chlorination N-allyl pyridine, N-methylimidazolium hydrogen sulphate salt, chlorination 1-benzyl-3-Methylimidazole, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-amyl group-3-Methylimidazole hexafluorophosphate, 1-carboxymethyl-3-methyl imidazolium tetrafluoroborate, the at least one of 1-butyl-3-Methylimidazole bromine salt and 1-allyl group-3-Methylimidazole bromine salt.
5. in ionic liquid-water medium according to claim 4, the method for levulinic acid is prepared in hexa-atomic sugar degraded, it is characterized in that, described ionic liquid is at least one of 1-propanesulfonic acid base-3-Methylimidazole villaumite, 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, N-propyl sulfonic acid pyridine villaumite and 1-sulfonic acid butyl-3-Methylimidazole villaumite.
6. in ionic liquid-water medium according to claim 1, the method for levulinic acid is prepared in hexa-atomic sugar degraded, and it is characterized in that, in mixing solutions, the massfraction of hexa-atomic sugar is 10% ~ 30%; Ionic liquid massfraction is 5% ~ 50%.
7. in the ionic liquid-water medium according to claim 1 or 6, the method for levulinic acid is prepared in hexa-atomic sugar degraded, and it is characterized in that, temperature of reaction is 140 DEG C ~ 200 DEG C, and the reaction times is 0.5h ~ 3.5h.
8. in ionic liquid-water medium according to claim 6, the method for levulinic acid is prepared in hexa-atomic sugar degraded, it is characterized in that, hexa-atomic sugar in described mixing solutions is fructose, massfraction is 10% ~ 20%, described ionic liquid is 1-propanesulfonic acid base-3-Methylimidazole villaumite or 1-butyl sulfonic acid-3-methylimidazolium hydrogen sulphate salt, massfraction is 10% ~ 20%, and temperature of reaction is 170 DEG C ~ 190 DEG C, and the reaction times is 0.5h ~ 2h.
9. in ionic liquid-water medium according to claim 1, the method for levulinic acid is prepared in hexa-atomic sugar degraded, it is characterized in that, described in be treated to rectification under vacuum.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107935844A (en) * | 2017-11-22 | 2018-04-20 | 盐城师范学院 | The preparation method of ionic liquid-catalyzed methyl ester levulinate |
| CN108147958A (en) * | 2018-02-09 | 2018-06-12 | 青岛科技大学 | A kind of method that catalytic cellulose conversion prepares levulic acid |
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| CN103467419A (en) * | 2013-09-06 | 2013-12-25 | 中国科学院过程工程研究所 | Method for transforming monosaccharides into high-value-added chemicals through microwave-assisted ionic liquid catalysis |
| CN103804167A (en) * | 2014-03-11 | 2014-05-21 | 南开大学 | Method for extracting levulinic acid from biomass hydrolysate glucose |
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| CN103467419A (en) * | 2013-09-06 | 2013-12-25 | 中国科学院过程工程研究所 | Method for transforming monosaccharides into high-value-added chemicals through microwave-assisted ionic liquid catalysis |
| CN103804167A (en) * | 2014-03-11 | 2014-05-21 | 南开大学 | Method for extracting levulinic acid from biomass hydrolysate glucose |
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| HUIFANG REN ET AL.: "Selective and recyclable depolymerization of cellulose to levulinic acid catalyzed by acidic ionic liquid", 《CARBOHYDRATE POLYMERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935844A (en) * | 2017-11-22 | 2018-04-20 | 盐城师范学院 | The preparation method of ionic liquid-catalyzed methyl ester levulinate |
| CN108147958A (en) * | 2018-02-09 | 2018-06-12 | 青岛科技大学 | A kind of method that catalytic cellulose conversion prepares levulic acid |
| CN108147958B (en) * | 2018-02-09 | 2022-09-27 | 青岛科技大学 | Method for preparing levulinic acid by catalyzing cellulose conversion |
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