CN101591246A - Utilize the method for the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification - Google Patents
Utilize the method for the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification Download PDFInfo
- Publication number
- CN101591246A CN101591246A CNA200910040713XA CN200910040713A CN101591246A CN 101591246 A CN101591246 A CN 101591246A CN A200910040713X A CNA200910040713X A CN A200910040713XA CN 200910040713 A CN200910040713 A CN 200910040713A CN 101591246 A CN101591246 A CN 101591246A
- Authority
- CN
- China
- Prior art keywords
- acid
- reaction
- solid
- water
- glucose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification.This method comprises saccharic acid hydrolysis, hydrogenating reduction and three steps of esterification; Acid hydrolysis is that biomass sugar is joined in the reaction system of solid acid and water or solid acid, water and water-fast organic solvent, obtains formic acid and levulinic acid product after the reaction; After reaction product is cooled to, filter solid acid, feed hydrogen, synchronous hydrogenation reduction takes place in catalysis formic acid and levulinic acid under the solid hydrogenation catalyst, generates product methyl alcohol and 4-hydroxypentanoic acid; Hydrogenation reaction product cooled and filtered hydrogenation catalyst in the pure and mild 4-hydroxypentanoic acid of esterifying catalyst catalysis carapax et plastruw testudinis generation esterification, generates 4-hydroxypentanoic acid methyl esters.The inventive method can realize that the clean high-valued conversion of biomass sugar produces 4-hydroxypentanoic acid methyl esters, and the efficiency of pcr product height does not produce pollution, operational path is brief, helps promoting the heavy industrialization of biomass energy technology.
Description
Technical field
The present invention relates to biomass energy fuel compound 4-hydroxy base methyl valerate, particularly relate to the method for utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification, be specifically related to the method that a kind of biomass sugar acid hydrolysis lotus root is closed the synthetic 4-hydroxypentanoic acid methyl esters of esterification behind the hydrogenating reduction.
Background technology
After entering the nineties in 20th century, global energy consumption sharply increases, and limited petroleum resources are difficult to satisfy the demand of people to the energy.Therefore, various countries consider that from the angle of energy security and environmental protection begin to seek the substitute energy fuel of cleaning, wherein oxygenated fuel is particularly noticeable.Oxygenated fuel is many to be produced from Wood Adhesives from Biomass, is the reproducible energy, can not increase the CO in the atmosphere in the energy natural circulation process of biofuel
2Clean quantity discharged makes oxygenated fuel that development potentiality be arranged very much; Oxygenated fuel can reduce the noxious emission of oil engine, especially particulate emission.At present, synthetic oxygenated fuel kind is a lot, mainly contains ester class A fuel A, biomass pyrolytic fuel, Aalcohols fuel and ethers fuel.
The ester class A fuel A mainly is meant vegetables oil and ester thereof at present, mainly comprise the fatty acid monoester that lipid acid that the Vegetable oil lipoprotein hydrolysis obtains and common monohydroxy-alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols and amylalcohol etc. obtain by transesterification reaction, also comprise methylcarbonate, acetic acid-2-methoxy-ethyl ester, acetate-1-methoxyl group-2-propyl ester, carbonic acid methyl 2-methoxyl group ethyl ester, carbonic acid methyl-2-ethoxy ethyl ester, ethylene glycol monoethyl ether acetate etc.; Ester class A fuel A sulphur content is few, nontoxic, can be a kind of biomass fuel of environmental protection by biological degradation.But when directly using vegetables oil,, form gum deposit easily, stop up oil circuit because unsaturated fatty acids wherein is very many.When oil engine directly used vegetables oil, unburnt resistates was deposited on the combustion chamber, and made piston ring bonding, oil thrower coking, influenced the work-ing life of oil engine; In addition, also can cause in the cylinder formation of gas mixture second-rate, Ran fuel is sprayed onto behind the cylinder wall inflow crankcase easily, causes deterioration of lubricant, thus vegetables oil directly the application on diesel engine be restricted.For addressing the above problem, utilize esterification techniques to change vegetables oil character; Esterification process is exactly with the glycerine in the replacement macromolecular chain structure tri-glycerides such as methyl alcohol, ethanol, obtains the fatty acid ester of small molecules chain, common acid, enzyme, alkaline earth metal hydroxides such as KOH, NaOH, sodium methylate (CH in the esterification process
3ONa) etc. make catalyzer.But this process need consumes a large amount of acid, alkali cpd, can pollute; The reaction product yield is also lower; In addition, handle there to be other ester class A fuel A synthetic route long, improved production cost because the esterification process of vegetables oil and vegetables oil carry out depickling (as adding methanol esterification) decon; Simultaneously, utilize vegetables oil mass production ester class A fuel A, the grain security of entail dangers to country.
The biomass pyrolytic liquid fuel be with the hemicellulose in the biomass, Mierocrystalline cellulose, xylogen and on a small quantity other organism under high temperature, anaerobic environment, resolve into gaseous state thing, aerosol and charcoal, again with the condensation of gaseous state thing be condensed into auburn pyrolysis liquid fuel.What research was maximum at present is fast pyrolysis technology.The wherein output and the character of the structure of reactor, temperature of reaction and factor affecting biomass pyrolytic fuel such as pressure, heat rate.Though bio oil is suitable for storing and transportation, can be used as reserve fuel, composition is too complicated, and calorific value is low, needs the back treating process of a series of complexity, the Financial cost height; Simultaneously, still can produce a large amount of pollutents in the pyrolytic process.
What Aalcohols fuel production at present was maximum is methyl alcohol and ethanol.Brazil is to use the maximum country of alcohol fuel, just has 40% automobile to use the fuel of 95% ethanol+5% water in 1989, and 40% automobile uses 78% gasoline+22% alcoholic acid fuel.Alcohol can not generate carbon when burning, help organizing lean burn, reduce the CO discharging.A little less than the activity of the hydrocarbon polymer of discharging when the specific activity of alcohol is used diesel oil, favourable to the ozone that reduces in the atmosphere.And Aalcohols fuel sulfur-bearing not, can in atmosphere, not discharge SO
2But the cetane value of Aalcohols fuel is low, only could involuntary ignition under the temperature more than 530 ℃, make oil engine directly use Aalcohols fuel to encounter difficulties, and alcohol low volatility and high heat of gasification make its Low Temperature Steam pressure low, influence the cold cranking capacity of Aalcohols fuel oil engine.When alcohol was used as biofuel, it and diesel oil were difficult to dissolve each other, and therefore, diesel engine must solve when using Aalcohols fuel and catch fire and dissolve each other problem; Still there is more problem in the extensive lasting production of Aalcohols fuel, as low from the yield of Wood Adhesives from Biomass methyl alcohol, and the cost height; Ethanol mostly is that at present its mass production also directly endangers national grain and economic security from grain raw material such as starch, sucrose inversion.It is long to transform the alcoholic acid route from wood fibre, and the cost height is difficult to extensive industrialization.
Ethers fuel has dme, Methylal, ether, isopropyl ether, butyl ether, methylene diethyl ether, glycol dimethyl ether, Propanal dimethyl acetal, methyl ethyl ether, ethoxyethylether, glycol dimethyl ether, diethylene glycol dimethyl ether, tripropylene glycol dimethyl ether etc.; Produce and use more have dme and methyl tertiary butyl ether.There is not the C-C key in the dme molecule, and contain Sauerstoffatom, therefore, dme has from the oxygen supply ability when burning, can when big load, realize smokeless combustion, and the corresponding index of the energy consumption of total hydrocarbon discharging and unit power when all being better than using diesel oil, the discharging of CO also can obtain improvement to a certain degree.Dme is direct contaminate environment not generally, and to not corrosion of metal, and the material of fuel supply system is not had special requirement; Yet dme need be synthetic from methyl alcohol, and operational path is long; Methyl tertiary butyl ether is a kind of oxygenated fuel that is used to improve gasoline octane rating, is extensive use of as a kind of gasoline dope; It is difficult to spontaneous combustion, but can dissolve each other with diesel oil, can use on diesel engine.But ethers fuel production cost and price is very high; In addition, because methyl tertiary butyl ether has pollution to underground water, banned use of by more and more national.
4-hydroxypentanoic acid methyl esters is a kind of high-grade liquid fuel compound, and boiling point is suitable, be in 68-70 ℃ (during the 5mmHg normal atmosphere), and 76 ℃ of flash-points (＞be higher than 50 ℃ of ideal biofuel flash-points), the combustion heat value height, but be mainly derived from the petroleum base compound at present.As standing stock are the abundantest on the earth biomass carbon resource wood fibre such as agricultural stalk, timber etc. can be obtained glucose by suitable approach hydrolysis; further conversion of glucose is produced 4-hydroxypentanoic acid methyl esters; be expected to realize the large-scale production of 4-hydroxypentanoic acid methyl esters, significant for the development novel biological fuel.
Summary of the invention
The objective of the invention is to contain the shortcoming that oxygen biofuel technology exists, provide the biomass sugar acid hydrolysis lotus root of a kind of clearly cleaning, efficient, short flow process to close the method for the synthetic 4-hydroxypentanoic acid methyl esters fuel of esterification behind the hydrogenating reduction at existing.
At present, 4-hydroxypentanoic acid methyl esters mainly by the petroleum base pentane after oxidation and hydroxyl substitution reaction, generate the 4-hydroxypentanoic acid, generate then with after the methyl alcohol generation esterification.This synthetic route is long, and total yield is lower than 10%, and only derives from the petroleum base resource; Because the continuous minimizing of petroleum resources and the significantly rising of price thereof and fluctuation and petroleum base 4-hydroxypentanoic acid methyl esters synthetic are expensive, 4-hydroxypentanoic acid methyl esters is not applied as a kind of fuel product.The present invention is directed to the shortcoming that existing biofuel and petroleum base methyl ester levulinate are produced, provide the biomass carbohydrate material of a kind of cleaning, efficient, short flow process to be converted into high-grade liquid fuel compound methyl ester levulinate synthetic technological method that marketable value is arranged.Up to the present, still directly do not transform the open invention or the research report of the overall technology route that produces the methyl ester levulinate product both at home and abroad from biomass sugar.Biomass sugar of the present invention is a glucose.
The present invention is achieved through the following technical solutions:
A kind of method of utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification comprises the steps:
(1) acid hydrolytic reaction of biomass sugar: glucose is joined in two-phase or the heterogeneous reaction system, is 200～350rmin in stir speed (S.S.)
-1, temperature is under 125～175 ℃ of conditions, the acid hydrolytic reaction 1～4h of glucose obtains formic acid and levulinic acid; Described biphasic reaction system is made up of solid acid and water; Described heterogeneous system is made up of solid acid, water and water-fast organic solvent, and the volume ratio of wherein water-fast organic solvent and water is 1～20: 1; Described water-fast organic solvent is methyl iso-butyl ketone (MIBK) or butanols; Solid acid in described two-phase or the heterogeneous reaction system is SO
4 2-/ W
xO
yA kind of in type solid acid, heteropolyacid solid acid, the load metal oxide type solid acid; The weightmeasurement ratio of liquid phase is 1g: 5～20ml in glucose add-on and two-phase or the heterogeneous reaction system; By weight, the solid acid add-on is 1%～10% of a reactant glucose weight; Described liquid phase is water or water and organic solvent;
(2) hydrogenation reduction: with step (1) reaction product through being cooled to 95 ℃～room temperature, after filtering solid acid, joining in the reaction system that contains solid hydrogenation catalyst and hydrogen, is 95～155 ℃ in temperature, and hydrogen pressure is that 1～2.5MPa and stir speed (S.S.) are 250～400rmin
-1Under the condition, the reaction of reaction 1～3h catalytic hydrogenating reduction generates methyl alcohol and 4-hydroxypentanoic acid; Described solid hydrogenation catalyst is a kind of in Ru/C, Pt/C and the Pd/C catalyzer, solid hydrogenation catalyst add-on be this step reaction thing formic acid and levulinic acid weight and 1%～12%;
(3) esterification: step (2) products therefrom methyl alcohol and 4-hydroxypentanoic acid are through being cooled to 95 ℃～room temperature, cross the filter solid hydrogenation catalyst, joining in the reaction system of esterifying catalyst and hydrogen, is 125～210 ℃ in temperature, and hydrogen pressure is that 1.5～3.5MPa and stir speed (S.S.) are 250～350rmin
-1Under the condition, carry out catalytic esterification 2～4h, generate biofuel compound 4-hydroxy base methyl valerate; Described esterifying catalyst is Ru-Pd/ γ-AI
2O
3, a kind of in Ru/C and the Pd/C catalyzer, the esterifying catalyst add-on be this step reaction thing methyl alcohol and 4 hydroxypentanoic acid weight and 2%～10%.
Described SO
4 2-/ W
xO
yThe type solid acid is SO
4 2-/ Fe
2O
3Or SO
4 2-/ ZrO
2-Al
2O
3In a kind of; The heteropolyacid solid acid is H
3PW
12O
40Or H
3SiW
12O
40In a kind of; Load metal oxide type solid acid is SiO
2/ Al
2O
3Or TiO
2/ ZrO
3In a kind of.
Described step (1) glucose is obtained through acid or cellulase hydrolysis by the paper pulp of cotton fibre, agricultural stalk or wood chip preparation.Concrete preparation method is as follows:
1) cotton fibre produces glucose through acid hydrolysis or enzyme.During the cotton fibre acid hydrolysis, adopt solid acid SiO
2/ Al
2O
3Prehydrolysis obtains glucose; The solid acid add-on is 2%～8% of cotton fibre or a Microcrystalline Cellulose weight, and temperature of reaction is 100～120 ℃, and the reaction times is 1～3h, and stir speed (S.S.) is 100～350rmin
-1, the glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 90%～95% (weight); During the cotton fibre enzymic hydrolysis, adopt cellulase hydrolysis in damping fluid to obtain glucose; Enzymic hydrolysis pH value is 3.2～7.5; 40～55 ℃ of hydrolysis temperatures, reaction 40～100h; Described cellulase is cellulolytic enzyme, contains filter paper enzyme activity 200～320U/g, and cellobiohydrolase vigor 400～600U/g, endoglucanase vigor are 300～700U/g, and the beta-glucoside enzyme activity is 300～750U/g; Described damping fluid is a kind of in sodium hydrogen phosphate-Sodium phosphate dibasic, acetic acid-sodium-acetate or the citric acid-sodium citrate damping fluid; In weightmeasurement ratio, damping fluid is 0.05～0.5mol/L in the concentration of reaction system; Heavy with respect to the raw material over dry before the hydrolysis, total percent hydrolysis is 93.4%, and the glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 91%～95%.
2) acid hydrolysis of agricultural stalk or the slurrying of wood chip S-WAT and gained slurry or enzymic hydrolysis produce glucose.During S-WAT slurrying, reaction system is made of agricultural stalk or wood raw material, water, S-WAT, bases compound and catalyzer anthraquinone; Relative over dry raw material weight, the S-WAT consumption is 4%～15%; The bases compound amount is 8%～20%; Described bases compound is NaOH or NH
4A kind of among the OH; The pulping reaction temperature is 120～180 ℃, and the time that is raised to maximum temperature from room temperature is 1～2h, the soaking time 2～3.5h under the top temperature condition; The consumption of water is 4～8 times of cellulosic material weight in the reaction system; The consumption of inferior anthraquinone is the plain raw material weight 0%～1.0% of bone dry fiber; Adding cellulase and damping fluid carry out enzymic hydrolysis in the slurrying disposed slurry, cellulase contains filter paper enzyme activity 200～320U/g, cellobiohydrolase vigor 400～600U/g, endoglucanase vigor are 300～700U/g, and the beta-glucoside enzyme activity is 300～750U/g; Enzymic hydrolysis pH value is 3.2～7.5; 40～55 ℃ of enzymic hydrolysis temperature, reaction 40～100h; Described damping fluid is sodium hydrogen phosphate-Sodium phosphate dibasic, acetic acid-sodium-acetate or citric acid-sodium citrate damping fluid, and damping fluid is 0.05～0.5mol/L in the concentration of reaction system, and is heavy with respect to the raw material over dry before the hydrolysis, and total percent hydrolysis is 93.4%; The glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 65%～75%.The brown stock that is obtained after S-WAT slurrying by agricultural stalk or timber adopts SO
4 2-/ ZrO
2-Al
2O
3Solid acid prehydrolysis obtains, and temperature of reaction is 115～125 ℃, and the reaction times is 2～4h, and stir speed (S.S.) is 100～250rmin
-1, the glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 70%～80%.
3) acid hydrolysis of agricultural stalk or wood chip steam explosion pulping and gained slurry or enzymic hydrolysis produce glucose.When agricultural stalk or timber also adopt steam explosion pulping, treatment condition are: agricultural stalk or timber water preimpregnation 30～45min under the condition of normal pressure, in 2.5～5.0min, boost to 0.5～0.75Mpa then, keep this pressure 6～15min, pressure being risen to behind 1～1.4Mpa immediately again in 2～5min, the explosion blowing obtains slurry; Gained slurry adding cellulase and damping fluid lotus root are closed and carry out enzymic hydrolysis, cellulase contains filter paper enzyme activity 200～320U/g, cellobiohydrolase vigor 400～600U/g, endoglucanase vigor are 300～700U/g, and the beta-glucoside enzyme activity is 300～750U/g; Enzymic hydrolysis pH value is 3.2～7.5; 40～55 ℃ of enzymic hydrolysis temperature, reaction 40～100h; Described damping fluid is sodium hydrogen phosphate-Sodium phosphate dibasic, acetic acid-sodium-acetate or citric acid-sodium citrate damping fluid; Damping fluid is 0.05～0.5mol/L in the concentration of reaction system, and the glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 65%～75%; Steam explosion gained slurry also can pass through SO
4 2-/ TiO
2-Fe
2O
3Solid acid prehydrolysis obtains glucose, adopts SO
4 2-/ W
xO
yThe solid acid catalysis hydrolysis is 115～125 ℃ in temperature, and stir speed (S.S.) is 100～350rmin
-1The following reaction times of condition is 2～4h, and the glucose purity that hydrolyzed solution obtains behind the dehydration concentrate drying is 75%～85%.
Contain oxygen biofuel synthetic technology with respect to existing, the present invention has following advantage and beneficial effect:
(1) solid acid hydrolysis in the 4-hydroxypentanoic acid methyl esters building-up process, hydrogenating reduction and esterification reaction process transformation efficiency height, the efficiency of pcr product height; In weight ratio, the final total yield of conversion of glucose 4-hydroxypentanoic acid methyl esters product per ton can surpass 70%, transforms the yield of fuel Products such as ethanol (maximum yield is 51%) far above present biomass sugar.
(2) use free of contamination solid acid, solid hydrogenation catalyst and solid esterifying catalyst in the 4-hydroxypentanoic acid methyl esters building-up process, can reuse after filtration after the reaction, do not produce the pollution substance discharging, help ecological environmental protection.
(3) in the 4-hydroxypentanoic acid methyl esters synthetic reaction process, formic acid and the synchronous hydrogenation reduction of levulinic acid mixture have been realized, the decomposition of catalysis glucose molecule and structural changes and molecular recombination reaction are with synthetic purpose product, and the hydrogen that uses in the reaction process can be produced by reaction process intermediate product methyl alcohol hydrogenolysis; Whole process route is short, target product yield height, and technology is succinct, helps the industrialization that bioenergy technology of new generation was used and realized in large-scale promotion.
(4) the synthetic 4-of institute hydroxypentanoic acid methyl esters is a kind of high-grade oxygen-bearing liquid biofuel that can substitute petroleum base diesel oil on a large scale, boiling point and flash-point are suitable, the calorific value height, from reproducible biomass sugar, production process clean environment firendly, its scale operation with utilize the sustainable supply can drive liquid fuel.
(5) as the glucose wide material sources of 4-hydroxypentanoic acid methyl esters building-up reactions raw material, can obtain through acid or cellulase hydrolysis by the paper pulp of cotton fibre, agricultural stalk or timber preparation.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.Glucose, formic acid, levulinic acid, methyl alcohol, 4-hydroxypentanoic acid (existing) and 4-hydroxypentanoic acid methyl esters content ion chromatography and gas chromatography determination in the following embodiment reaction process with the γ-Wu Neizhi form.
Embodiment 1
(1) glucose is joined contains SO
4 2-/ W
xO
yIn the heterogeneous reaction system that solid acid, water and water-fast organic solvent are formed; Water-fast organic solvent is a butanols; The volume ratio of butanols and water is 1: 1.Volume ratio meter by weight, glucose add water and volume of organic solvent in weight and the reaction system and ratio be 1g: 5ml; SO
4 2-/ W
xO
yThe solid acid add-on is 1% of a glucose adding weight; The temperature of reaction of gluconic acid hydrolysis reaction is 175 ℃, and the reaction times is 1h, and stir speed (S.S.) is 350rmin
-1, SO
4 2-/ W
xO
ySolid acid is SO
4 2-/ ZrO
2-Al
2O
3Or SO
4 2-/ Fe
2O
3(available from brilliant pure chemistry technology company), the acid hydrolysis products of glucose is formic acid and levulinic acid.When using SO
4 2-/ ZrO
2-Al
2O
3During catalytic hydrolysis, in the weight ratio that glucose adds, inversion rate of glucose is 99%, and the formic acid efficiency of pcr product is 25%, and the levulinic acid product is 58%.When using SO
4 2-/ Fe
2O
3During catalytic hydrolysis, in the weight ratio to reactant glucose, inversion rate of glucose is 98%, and the formic acid efficiency of pcr product is 24%, and the levulinic acid product is 61%.
(2) step (1) gained glucose hydrolysis reaction product is when being cooled to 95 ℃, after filtering solid acid, join in the reaction system that contains solid hydrogenation catalyst and hydrogen, carry out the catalytic hydrogenating reduction reaction, generate product methyl alcohol and 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form); The temperature of hydrogenation reduction is 155 ℃, and the reaction times is 1h, and hydrogen pressure is 1MPa, and stir speed (S.S.) is 400rmin
-1The solid hydrogenation catalyst is Ru/C (available from a brilliant pure chemistry technology company), and solid hydrogenation catalyst add-on is 12% of this step reaction thing formic acid and a levulinic acid weight sum; In the weight ratio to reactant formic acid, the formic acid transformation efficiency is 99%, and the methanol product yield is 69%; In the weight to the reactant levulinic acid, the levulinic acid transformation efficiency is 90%, 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form) efficiency of pcr product 97% (weight).
(3) mixture of step (2) gained formic acid hydrogenation reduction product methyl alcohol and levulinic acid hydrogenation reduction product 4-hydroxypentanoic acid in reaction after during cool to room temperature, cross the filter solid hydrogenation catalyst, join in the reaction system of esterifying catalyst and hydrogen, carry out catalytic esterification, after the products therefrom cooling, the solid catalyst for esterification reaction promptly gets biofuel compound 4-hydroxy base methyl valerate after filtration; Esterification reaction temperature is 125 ℃, and the reaction times is 4h, and hydrogen pressure is 3.5MPa, and stir speed (S.S.) is 350rmin
-1The solid esterifying catalyst is Ru-Pd/ γ-AI
2O
3(available from brilliant pure chemistry technology company); Solid hydrogenation catalyst add-on is 2% of this step reaction thing methyl alcohol and a 4-hydroxypentanoic acid weight sum; In the weight to reactant, methanol conversion is 97%, and 4-hydroxypentanoic acid transformation efficiency is 98%, and 4-hydroxypentanoic acid methyl esters efficiency of pcr product is 88%.
By weight percentage, glucose is through above three acid hydrolysiss, hydrogenation and three reaction process of esterification, and conversion of glucose is that the final yield of 4-hydroxypentanoic acid methyl esters product is 70.9% (SO
4 2-/ ZrO
2-Al
2O
3During hydrolyzation of glucose) or 72.5% (SO
4 2-/ Fe
2O
3During hydrolyzation of glucose).As seen, flow process of the present invention is short, target product yield height, and solid catalyst and organic solvent are recyclable, do not produce pollution.
Embodiment 2
(1) glucose is joined in the biphasic reaction system that contains solid acid and water composition; The ratio that volume ratio meter by weight, glucose add volume of water in weight and the reaction system is 1g: 20ml; The temperature of reaction of gluconic acid hydrolysis reaction is 125 ℃, and the reaction times is 4h, and stir speed (S.S.) is 200rmin
-1, solid acid is heteropolyacid H
3PW
12O
40Or H
3SiW
12O
4(available from brilliant pure chemistry technology company); By weight, the heteropolyacid add-on is 10% of a glucose add-on; The acid hydrolysis products of glucose is formic acid and levulinic acid; If solid acid H
3PW
12O
40During catalytic hydrolysis, in the weight ratio that glucose adds, inversion rate of glucose is 90%, and the formic acid efficiency of pcr product is 23%, and the levulinic acid product is 64%; If solid acid H
3SiW
12O
4During catalytic hydrolysis, inversion rate of glucose is 93%, and the formic acid efficiency of pcr product is 24%, and the levulinic acid product is 63%.
(2) step (1) gained glucose hydrolysis reaction product is when cool to room temperature, after filtering solid acid catalyst, join in the reaction system that contains solid hydrogenation catalyst and hydrogen, carry out the catalytic hydrogenating reduction reaction, generate product methyl alcohol and 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form); The temperature of formic acid and levulinic acid hydrogenation reduction is 95 ℃, and the reaction times is 3h, and hydrogen pressure is 2.5MPa, and stir speed (S.S.) is 250rmin
-1The solid hydrogenation catalyst is Pt/C (available from a brilliant pure chemistry technology company), and solid hydrogenation catalyst add-on is 1% of this step reaction thing formic acid and a levulinic acid weight sum; In the weight to reactant formic acid, the formic acid transformation efficiency is 95%, and the methanol product yield is 65%; In the weight to the reactant levulinic acid, the levulinic acid transformation efficiency is 98%, 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form) efficiency of pcr product 101%;
(3) mixture of step (2) gained formic acid hydrogenation reduction product methyl alcohol and levulinic acid hydrogenation reduction product 4-hydroxypentanoic acid is when reacting after being cooled to 95 ℃, cross the filter solid hydrogenation catalyst, join in the reaction system that contains esterifying catalyst and hydrogen, carry out catalytic esterification, after the products therefrom cooling, the solid catalyst for esterification reaction promptly gets biofuel compound 4-hydroxy base methyl valerate after filtration; Esterification reaction temperature is 210 ℃, and the reaction times is 2h, and hydrogen pressure is 1.5MPa, and stir speed (S.S.) is 250rmin
-1The solid hydrogenation catalyst is Pd/C (available from a brilliant pure chemistry technology company), and solid esterifying catalyst add-on is 10% of this step reaction thing methyl alcohol and a 4-hydroxypentanoic acid weight sum; In the weight of this step reaction thing, methanol conversion is 99%, and 4-hydroxypentanoic acid transformation efficiency is 95%, and 4-hydroxypentanoic acid methyl esters efficiency of pcr product is 86%.
By weight percentage, glucose is through above three acid hydrolysiss, hydrogenation and three reaction process of esterification, and conversion of glucose is that the final yield of 4-hydroxypentanoic acid methyl esters product is 77.3% (H
3PW
12O
40During catalysis hydrolyzation of glucose) or 75.6% (H
3SiW
12O
4During catalysis hydrolyzation of glucose).As seen, flow process of the present invention is short, target product yield height, and solid catalyst and organic solvent are recyclable, do not produce pollution.
Embodiment 3
(1) glucose is joined in the heterogeneous reaction system that contains solid acid, water and water-fast organic solvent composition; The organic solvent immiscible with water is methyl iso-butyl ketone (MIBK); With water can not be miscible organic solvent and the volume ratio of water be 1: 20.In the gluconic acid hydrolytic process, volume ratio meter by weight, liquid phase in glucose add-on and the reaction system (water and water-fast organic solvent) volume and ratio be 15g: 100ml; The acid-hydrolyzed temperature of reaction of glucose is 155 ℃, and the reaction times is 2.5h, and stir speed (S.S.) is 300rmin
-1, solid acid is load metal oxide SiO
2/ Al
2O
3Or TiO
2/ ZrO
3(available from brilliant pure chemistry technology company), the load metal oxide add-on be glucose add weight 5%; The acid hydrolysis products of glucose is formic acid and levulinic acid; In the weight of glucose adding, if use SiO
2/ Al
2O
3During catalytic hydrolysis, inversion rate of glucose is 98%, and the formic acid efficiency of pcr product is 25%, and the levulinic acid product is 63%; If use TiO
2/ ZrO
3During catalytic hydrolysis, inversion rate of glucose is 98%, and the formic acid efficiency of pcr product is 22%, and the levulinic acid product is 64%.
(2) step (1) gained glucose hydrolysis reaction product is when being as cold as 85 ℃, after filtering solid acid catalyst, join in the reaction system that contains solid hydrogenation catalyst and hydrogen, carry out the catalytic hydrogenating reduction reaction, generate product methyl alcohol and 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form); The temperature of formic acid and levulinic acid hydrogenation reduction is 125 ℃, and the reaction times is 2.5h, and hydrogen pressure is 2.0MPa, and stir speed (S.S.) is 350rmin
-1The solid hydrogenation catalyst is Pd/C (available from a brilliant pure chemistry technology company), and solid hydrogenation catalyst add-on is 6% of this step reaction thing formic acid and a levulinic acid weight sum; In the weight of this step reaction thing formic acid, the formic acid transformation efficiency is 98%, and the methanol product yield is 68%; In the weight of this step reaction thing levulinic acid, the levulinic acid transformation efficiency is 96%, 4-hydroxypentanoic acid (the 4-hydroxypentanoic acid exists with the γ-Wu Neizhi form) efficiency of pcr product 99%.
(3) mixture of step (2) gained formic acid hydrogenation reduction product methyl alcohol and levulinic acid hydrogenation reduction product 4-hydroxypentanoic acid is when reacting after being cooled to 75 ℃, cross the filter solid hydrogenation catalyst, join in the reaction system that contains esterifying catalyst and hydrogen, carry out catalytic esterification, after the products therefrom cooling, the solid catalyst for esterification reaction promptly gets biofuel compound 4-hydroxy base methyl valerate after filtration; Esterification reaction temperature is 200 ℃, and the reaction times is 3h, and hydrogen pressure is 3.0MPa, and stir speed (S.S.) is 300rmin
-1The solid hydrogenation catalyst is Ru/C (available from a brilliant pure chemistry technology company), and solid esterifying catalyst add-on is 8% of this step reaction thing methyl alcohol and a 4-hydroxypentanoic acid weight sum.In the weight of this step reaction thing, methanol conversion is 98%, and 4-hydroxypentanoic acid transformation efficiency is 97%, and 4-hydroxypentanoic acid methyl esters efficiency of pcr product is 87%.
By weight percentage, glucose is through above three acid hydrolysiss, hydrogenation and three reaction process of esterification, and conversion of glucose is that the final yield of 4-hydroxypentanoic acid methyl esters product is 75.8% (SiO
2/ Al
2O
3During catalysis hydrolyzation of glucose) or 74.1% (TiO
2/ ZrO
3During catalysis hydrolyzation of glucose).As seen, flow process of the present invention is short, target product yield height, and solid catalyst and organic solvent are recyclable, do not produce pollution.
Claims (3)
1, a kind of method of utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification is characterized in that comprising the steps:
(1) acid hydrolytic reaction of biomass sugar: glucose is joined in two-phase or the heterogeneous reaction system, is 200～350rmin in stir speed (S.S.)
-1, temperature is under 125～175 ℃ of conditions, the acid hydrolytic reaction 1～4h of glucose obtains formic acid and levulinic acid; Described biphasic reaction system is made up of solid acid and water; Described heterogeneous system is made up of solid acid, water and water-fast organic solvent, and the volume ratio of wherein water-fast organic solvent and water is 1～20: 1; Described water-fast organic solvent is methyl iso-butyl ketone (MIBK) or butanols; Solid acid in described two-phase or the heterogeneous reaction system is SO
4 2-/ W
xO
yA kind of in type solid acid, heteropolyacid solid acid, the load metal oxide type solid acid; The weightmeasurement ratio of liquid phase is 1g: 5～20ml in glucose add-on and two-phase or the heterogeneous reaction system; By weight, the solid acid add-on is 1%～10% of a reactant glucose weight; Described liquid phase is water or water and organic solvent;
(2) hydrogenation reduction: with step (1) reaction product through being cooled to 95 ℃～room temperature, after filtering solid acid, joining in the reaction system that contains solid hydrogenation catalyst and hydrogen, is 95～155 ℃ in temperature, and hydrogen pressure is that 1～2.5MPa and stir speed (S.S.) are 250～400rmin
-1Under the condition, the reaction of reaction 1～3h catalytic hydrogenating reduction generates methyl alcohol and 4-hydroxypentanoic acid; Described solid hydrogenation catalyst is a kind of in Ru/C, Pt/C and the Pd/C catalyzer, solid hydrogenation catalyst add-on be this step reaction thing formic acid and levulinic acid weight and 1%～12%;
(3) esterification: step (2) products therefrom methyl alcohol and 4-hydroxypentanoic acid are through being cooled to 95 ℃～room temperature, cross the filter solid hydrogenation catalyst, joining in the reaction system of esterifying catalyst and hydrogen, is 125～210 ℃ in temperature, and hydrogen pressure is that 1.5～3.5MPa and stir speed (S.S.) are 250～350rmin
-1Under the condition, carry out catalytic esterification 2～4h, generate biofuel compound 4-hydroxy base methyl valerate; Described esterifying catalyst is Ru-Pd/ γ-AI
2O
3, a kind of in Ru/C and the Pd/C catalyzer, the esterifying catalyst add-on be this step reaction thing methyl alcohol and 4 hydroxypentanoic acid weight and 2%～10%.
2, the method for utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification according to claim 1 is characterized in that: described step (1) glucose is obtained through acid or cellulase hydrolysis by the paper pulp of cotton fibre and agricultural stalk or wood chip preparation.
3, the method for utilizing the synthetic 4-hydroxypentanoic acid methyl esters of biomass sugar hydrolysis hydrogenation and esterification according to claim 1 is characterized in that: described SO
4 2-/ W
xO
yThe type solid acid is SO
4 2-/ Fe
2O
3Or SO
4 2-/ ZrO
2-Al
2O
3In a kind of; The heteropolyacid solid acid is H
3PW
12O
40Or H
3SiW
12O
40In a kind of; Load metal oxide type solid acid is SiO
2/ Al
2O
3Or TiO
2/ ZrO
3In a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910040713XA CN101591246B (en) | 2009-06-30 | 2009-06-30 | Method for synthesizing 4-hydroxy methyl valerate through hydrolysis, hydrogenation and esterification of biomass sugar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910040713XA CN101591246B (en) | 2009-06-30 | 2009-06-30 | Method for synthesizing 4-hydroxy methyl valerate through hydrolysis, hydrogenation and esterification of biomass sugar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101591246A true CN101591246A (en) | 2009-12-02 |
| CN101591246B CN101591246B (en) | 2012-10-31 |
Family
ID=41406151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910040713XA Expired - Fee Related CN101591246B (en) | 2009-06-30 | 2009-06-30 | Method for synthesizing 4-hydroxy methyl valerate through hydrolysis, hydrogenation and esterification of biomass sugar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101591246B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277456A (en) * | 2011-06-16 | 2011-12-14 | 中国科学院广州能源研究所 | Fixed bed pipe type reaction device for realizing solid acid catalytic hydrolysis and concentration of liquid glycan |
| CN102533352A (en) * | 2012-01-06 | 2012-07-04 | 雷学军 | Alcohol base fuel and preparation method thereof |
| CN103194495A (en) * | 2013-04-18 | 2013-07-10 | 天津大学 | Method for preparing levulinic acid from starch type traditional Chinese medicine residues |
-
2009
- 2009-06-30 CN CN200910040713XA patent/CN101591246B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277456A (en) * | 2011-06-16 | 2011-12-14 | 中国科学院广州能源研究所 | Fixed bed pipe type reaction device for realizing solid acid catalytic hydrolysis and concentration of liquid glycan |
| CN102277456B (en) * | 2011-06-16 | 2013-01-23 | 中国科学院广州能源研究所 | Fixed bed pipe type reaction device for realizing solid acid catalytic hydrolysis and concentration of liquid glycan |
| CN102533352A (en) * | 2012-01-06 | 2012-07-04 | 雷学军 | Alcohol base fuel and preparation method thereof |
| CN103194495A (en) * | 2013-04-18 | 2013-07-10 | 天津大学 | Method for preparing levulinic acid from starch type traditional Chinese medicine residues |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101591246B (en) | 2012-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Okolie et al. | Next‐generation biofuels and platform biochemicals from lignocellulosic biomass | |
| Nanda et al. | Pathways of lignocellulosic biomass conversion to renewable fuels | |
| Nanda et al. | Lignocellulosic biomass: a review of conversion technologies and fuel products | |
| Abdulkhani et al. | Potential of Soya as a raw material for a whole crop biorefinery | |
| CN103013552B (en) | Method for preparing biological oil by liquefying biomass under atmospheric pressure by using solid acid catalyst | |
| CN101168679A (en) | Method for preparing liquid fuel by using biomass material | |
| CN101407727A (en) | Method for preparing biomass liquefied oil by biomass catalytic liquefaction | |
| Liu et al. | Preparation of carbonyl precursors for long-chain oxygenated fuels from cellulose ethanolysis catalyzed by metal oxides | |
| CN101591246B (en) | Method for synthesizing 4-hydroxy methyl valerate through hydrolysis, hydrogenation and esterification of biomass sugar | |
| CN102827108A (en) | Bio-based functional material as well as preparation method and application thereof | |
| Crocker et al. | The rationale for biofuels | |
| US20090203092A1 (en) | Liquid Biofuel Mixture and Method and Device for Producing The Same | |
| Lucia et al. | Chemicals, materials, and energy from biomass: a review | |
| CN108485748B (en) | Biofuel prepared from kitchen waste and preparation method thereof | |
| Shah et al. | Products and production routes for the catalytic conversion of seed oil into fuel and chemicals: a comprehensive review | |
| Dubey et al. | Biomass: sustainable energy solution from agriculture | |
| Quereshi et al. | Catalytic conversion of lignocellulosic biomass into fuels and value-added chemicals | |
| CN102533352A (en) | Alcohol base fuel and preparation method thereof | |
| CN102796573B (en) | Low-freezing biodiesel combined fuel and preparation method thereof | |
| Reshma et al. | Trends in valorization of biomass to biofuels: biobutanol | |
| CN111234887A (en) | Preparation method of long-chain oxygen-containing liquid fuel precursor | |
| CN214781691U (en) | Preparation facilities of low sulfur environmental protection oil tank detersive | |
| Elgharbawy et al. | Advances of bioethanol production using ionic liquids | |
| Kumar et al. | Second Generation Biofuels and Extraction Techniques | |
| Prasad et al. | Utilization of biomass from refineries as additional source of energy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121031 Termination date: 20150630 |
|
| EXPY | Termination of patent right or utility model |