CN102796573A - Low-freezing biodiesel combined fuel and preparation method thereof - Google Patents
Low-freezing biodiesel combined fuel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-freezing biodiesel combined fuel and a preparation method thereof, and the components of low-freezing biodiesel combined fuel comprise ethyl levulinate, methylfuroate, dibutyl carbonate, methyl oleate, solubilizing assistant and flash point improver. Each esters component in the low-freezing biodiesel combined fuel disclosed by the invention can be prepared from biomass materials, is simple in preparation technology, easy in separation and purification, pollution-free in production process, and can realize continuous operation with high preparation efficiency; and moreover, the prepared low-freezing biodiesel combined fuel is low in cost, environment-friendly and reproducible, particularly low in freezing point, and can well satisfy the demand for fuel in northern cold district.
Description
Technical field
The present invention relates to energy field, particularly a kind of low biofuel propellant combination and preparation method thereof that coagulates.
Background technology
Along with problems such as serious day by day global energy shortage and environmental degradations, the control motor vehicle exhaust, the human physical environment of depending on for existence of protection becomes present human urgent problem.Angle from environment protection and resource strategy; The energy research personnel of countries in the world are trying to explore to develop alternative fuel and renewable energy source; Biofuel is exactly one of them, and it is that raw oil is processed through ester exchange process with waterplant greases such as oil crops, wild oilseed plant and engineering microalgae and animal oil and fat, food garbage wet goods, is a kind of renewable energy source; Oilness, security, have good burning performance; Biodegradable, use postcure thing quantity discharged to significantly reduce, have good security and economic worth.
The preparation method of biofuel mainly contains direct mixing method, microemulsion method, high temperature pyrolytic cracking, ester-interchange method etc. at present.Direct mixing method mixes natural fats and oils to reduce its viscosity with diesel oil, solvent or alcohols, though technology is simple, be prone to problems such as charing, coking; Microemulsion method utilizes emulsifying agent that vegetables oil is distributed in the low viscosity solvent, though can satisfy the requirement of oil fuel, is vulnerable to environmental influence and demulsifying phenomenon occurs; High temperature pyrolytic cracking utilizes high temperature to make the vegetables oil molecular rupture, thereby forms hydrocarbon polymer simple in structure, that molecule is less, but its complex process, equipment are huge, with high costs, can't reach suitability for industrialized production; Ester-interchange method generally adopts grease and methyl alcohol or ethanol that transesterification reaction takes place under acidity or basic catalyst effect; Make biofuel through the washing drying again; Yet acid-catalyzed transesterification process reaction speed is slow, separation difficulty and be prone to produce the three wastes, and base-catalyzed transesterification also exists defectives such as productive rate is low, separation difficulty.
Although biofuel as a novel energy industry, can be brought the economy and the social benefit of many aspects, yet exists many problems also.Staple crop raw material like present production biofuel is a soybean, and its production cost is high, thereby has limited the widespread use of biofuel; And for example the HV of biofuel has limited its utilization ratio at low temperatures; High pour point has influenced its low-temperature startup; Glycerin soap easy blocking oil pipeline and oil nozzle, the Trace Methanol that it contained and glycerine can make degradeds gradually such as the rubber part that contacts with it such as rubber diaphragm, sealing-ring, fuelpipe; In addition; Also there is the handling problem of by-product glycerol in the biodiesel manufacture process; Incomplete like transesterification reaction; Be easy to generate impurity and cause engine operation undesired and exhaust gas emission is bad, the fatty ester methyl esters in the biofuel is vulnerable to oxidation and changes fuel performance, thereby the colloid or the dregs of fat that generate that cause burning block.
Publication number is that the Chinese invention patent of CN1818024A discloses a kind of process method of utilizing agricultural, forestry waste to produce biofuel; With being crushed to 120 orders after the waste seasoning; Add solvent, auxiliary agent and catalyzer then and stir, mix the back again with coal water slurry in 250-400 ℃, 10-28MPa reacted 30-120 minute down; Through distillation process, make biofuel.Although it adopts agriculture and forestry organic waste material as raw material, solved defectives such as with high costs to a certain extent, yet it still need be unfavorable for the renewable production of resources conservation and biofuel with coal as raw material.
Summary of the invention
Primary and foremost purpose of the present invention be to the problem that above-mentioned prior art exists provide that a kind of technology is simple, with low cost, environmental protection, reproducible low biofuel propellant combination and preparation method thereof that coagulates; Each component in the propellant combination all can obtain through reproducible biomass resource production; Preparation technology can realize continuous operation; Preparation efficiency is high, and production process is pollution-free, separates and purifies easily.
In order to achieve the above object, one aspect of the present invention provides a kind of low biofuel propellant combination that coagulates, and its component comprises ethyl levulinate, methylfuroate, dibutyl carbonate, Witconol 2301, solubility promoter and flash-point rising agent.
Particularly, the quality percentage composition of said each component is respectively: ethyl levulinate 30%-50%, methylfuroate 10%-25%, dibutyl carbonate 20%-40%, Witconol 2301 5%-10%, solubility promoter 0-5%, flash-point rising agent 0.1%-0.2%.
The effect of solubility promoter of the present invention is that each component is mixed, and is selected from methylcarbonate, ritalin, the vinyl acetic monomer one or more; The effect of flash-point rising agent of the present invention is to improve flash-point.
Further aspect of the present invention provides a kind of low preparation method who coagulates the biofuel propellant combination, comprises the steps:
A) biomass material is carried out acid hydrolytic reaction, make furfural and levulinic acid;
B) levulinic acid and ethanol are carried out the supercritical esterification reaction, make ethyl levulinate;
C) furfural and oxygen are carried out oxidizing reaction, make furancarboxylic acid;
D) furancarboxylic acid and methyl alcohol are carried out the supercritical esterification reaction, make the furfural methyl esters;
E) methylcarbonate and butanols are carried out transesterification reaction, make dibutyl carbonate;
F) ethyl levulinate, methylfuroate, dibutyl carbonate, Witconol 2301, solubility promoter and flash-point rising agent are mixed, make the low biofuel propellant combination that coagulates.
Wherein, steps A) abandoned biomass comprises soybean stalk, corn straw, corn cob, bagasse, oat shell, cottonseed chaff shell, rice bran shell, sunflower shell, reed, scrub growth stump thing etc. described in, is preferably scrub growth stump things such as caragana microphylla, salix monogolica.
Particularly; Steps A) after in biomass material being processed into biomass slurry; With formic acid biomass slurry is carried out described acid hydrolytic reaction, the mass percent concentration of wherein said formic acid is 4-10%, is preferably 6-8%; The water ratio of biomass slurry is 60-65%, and the weight proportion of biomass slurry and formic acid is 100:2-8.
Especially, steps A) biomass material is pulverized to behind the small-particle of 0.5-1cm, added the tap water stirring and evenly mixing, process described biomass slurry.
Wherein, steps A) acid hydrolytic reaction carries out in two steps described in, and wherein the acid-hydrolyzed temperature of the first step is 200-260 ℃; Be preferably 220-240 ℃, absolute pressure is 1.8-2.6Mpa, is preferably 2.2-2.4Mpa; Reaction times is 5-20 minute, is preferably 5-10 minute; Second step, acid-hydrolyzed temperature was 180-220 ℃, was preferably 190-200 ℃, and absolute pressure is 1.0-1.6Mpa, is preferably 1.2-1.4Mpa, and the reaction times is 15-20 minute; The first step acid hydrolysis mainly is that the semicellulose in the biomass material is converted into furfural, and the second step acid hydrolysis mainly is that the cellulose conversion in the biomass material is become levulinic acid, and two one-step hydrolysis help making full use of of biomass.
Wherein, step B) levulinic acid and alcoholic acid mol ratio are 1:2-20 described in, are preferably 1:2-8, further are preferably 1:4; The temperature of said supercritical esterification reaction is 220-350 ℃, is preferably 280-320 ℃, further is preferably 300 ℃, and absolute pressure is 10-20MPa, is preferably 15MPa, and the reaction times is 1-3 hour, is preferably 2 hours; Under these conditions, the Ethanol Treatment supercritical state, the reaction mass transfer resistance is little, and reactant is uniformly dispersed, the esterification mild condition, thus reduce corrosion to conversion unit.
Wherein, oxidizing reaction comprises the steps: step C)
C1) furfural is dissolved in the basic soln, makes furfurine solution;
C2) under the effect of copper silver cerium composite catalyst, furfurine solution and oxygen are carried out oxidizing reaction, make oxidation mixtures;
C3) with carrying out acidification after the oxidation mixtures filtration, make furancarboxylic acid.
Wherein, Step C1) basic soln described in is selected from a kind of in sodium hydroxide solution, sodium carbonate solution, sodium hydrogen carbonate solution, solution of potassium carbonate, potassium hydroxide solution, sodium acetate soln, the liquor kalii acetici, is preferably sodium hydroxide solution or sodium hydrogen carbonate solution; The volumetric molar concentration of said basic soln is 1-4mol/L, is preferably 1mol/L, and the mole proportioning of said basic soln and furfural is 2-8:1.
Wherein, The mol ratio of oxygen step C2) and furfural is 5-10:1; Said copper silver cerium composite catalyst comprises cupric oxide, silver suboxide and cerium oxide; Wherein the mass percentage content of cupric oxide is 80-90%, and the mass percentage content of silver suboxide is 3-5%, and the mass percentage content of cerium oxide is 5-15%; The weight proportion of copper silver cerium composite catalyst and furfural is 0.5-1.5:100; The temperature of said oxidizing reaction is 50-100 ℃, and absolute pressure is 0.1-0.2MPa, and the reaction times is 2-4 hour.
Wherein, step C3) acidification described in comprises that the pH value that will filter rear filtrate with acid transfers to 2.5-3, and said acid is the salpeter solution of 30-65% for mass percent concentration.
Particularly, use the CaCl of ice after the acidification
2Solution cools off, and separates out crystallization, makes furancarboxylic acid.
Wherein, step D) mol ratio of furancarboxylic acid and methyl alcohol is 1:2-20 described in, is preferably 1:2-8, further is preferably 1:4; The temperature of said supercritical esterification reaction is 220-350 ℃, is preferably 280-320 ℃, further is preferably 280 ℃, and absolute pressure is 10-20MPa, is preferably 15MPa, and the reaction times is 1-3 hour, is preferably 2 hours; Under these conditions, the methanol treatment supercritical state, the reaction mass transfer resistance is little, and reactant is uniformly dispersed, the esterification mild condition, thus reduce corrosion to conversion unit.
Wherein, Step e) methylcarbonate described in and butanols carry out transesterification reaction under the effect of metal-rare earth loaded catalyzer, the mol ratio of wherein said methylcarbonate and butanols is 0.2-0.4:1, and the temperature of said transesterification reaction is 200-300 ℃; Be preferably 240-260 ℃; Absolute pressure is 4-10MPa, is preferably 6-8MPa, and the reaction times is 2-4h.
Particularly, said transesterification reaction is carried out under the effect of metal-rare earth loaded catalyzer; Said supported catalyst refers to catalytic active component and is supported on the carrier surface, and said carrier is mainly used in the support active ingredient, make catalyzer have specific physical behavior, and carrier itself does not generally have catalytic activity.Carrier commonly used has alumina supporter, silica-gel carrier, absorbent charcoal carrier and some natural product such as float stone, zeyssatite etc.
Metal according to the invention-rare earth loaded catalyzer comprises active ingredient and carrier, and the weight proportion of wherein said active constituent and carrier is (10-20): (80-90); Said active ingredient comprises MOX and rare earth oxide, and the mole proportioning of said MOX and rare earth oxide is 2-8:1.
Particularly, said MOX is selected from alkalimetal oxide or alkaline earth metal oxide; Said basic metal is selected from one or more in sodium (Na), potassium (K), rubidium (Rb), the caesium (Cs), is preferably sodium and potassium; Said earth alkali metal is selected from one or more in magnesium (Mg), the calcium (Ca), is preferably magnesium; Said rare earth oxide is selected from cerium oxide (CeO
2), lanthanum trioxide (La
2O
3) in one or more; Said carrier is selected from Al
2O
3, C, TiO
2In one or more.
Especially, the weight proportion of methylcarbonate and metal-rare earth loaded catalyzer is 100:0.5-5, is preferably 100:1-3, further is preferably 100:2.
Compared with prior art, the present invention has following beneficial effect:
1, the low various ester class components of coagulating in the biofuel propellant combination of the present invention all can prepare through biomass material; Not only economic environmental protection; Reduced pollution; Also fully open up the availability of biomass resource, practiced thrift crop and other mineral wealth, had great economic worth and social benefit;
2, preparation technology of the present invention adopts supercritical esterification and transesterification reaction, and wherein the supercritical esterification reaction need not raw material is carried out pre-treatment, need not to use catalyzer; The reaction mass transfer resistance is little; RM is uniformly dispersed, and the reaction times is short, and reaction conversion ratio and selectivity are high; And the catalyst efficiency that adopts in the esterification is high, and speed of reaction is fast, and product yield is high; In addition, preparation technology of the present invention is pollution-free, and product separation is purified easily, and product purity is high, and can carry out continuous operation, helps large-scale industrial production;
3, low low, the environmental protection, renewable of biofuel propellant combination cost with fixed attention of the present invention's preparation; Has higher cetane value; And sulphur content is low, and product performance are stable, and quality meets the regulation of relevant national standard; Particularly can prepare the biofuel of various low condensation points, can satisfy the oily demand of using of northern China cold district preferably through adjusting each components contents.
Description of drawings
Fig. 1 is the low biofuel propellant combination preparation technology schema that coagulates of the present invention.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage of the present invention and characteristics will be more clear along with description.But these embodiment only are exemplary, scope of the present invention are not constituted any restriction.It will be understood by those skilled in the art that and down can make amendment with form or replace without departing from the spirit and scope of the present invention, but these modifications and replacing all fall within the scope of protection of the present invention the details of technical scheme of the present invention.
Embodiment 1
One, preparation furfural and levulinic acid
1, raw materials pretreatment:
With water ratio is that the salix monogolica stump thing of 15-20% is pulverized to behind the small-particle of 0.5-1cm, adds the tap water stirring and evenly mixing, makes water ratio and be 65% biomass slurry;
2, the first step acid hydrolytic reaction:
Above-mentioned biomass slurry is put into premixing tank, and the adding mass percent concentration is 8% formic acid solution in jar, mixes the back and with the plunger type high-pressure pump slurry formic acid mixed solution is sent into first reactor drum; Feed high temperature and high pressure steam at reactor bottom; Temperature and pressure in first reactor drum is raise, carry out the first step acid hydrolytic reaction, obtain the first step to the acid hydrolysis mixture; Wherein the weight proportion of biomass slurry and formic acid solution is 100:5; The temperature of the first step acid hydrolytic reaction is 220 ℃, and absolute pressure is 2.2Mpa, and the reaction times is 10 minutes;
The first step acid hydrolysis products is the mixed gas that contains furfural, a small amount of combustion gas and water vapor; And the solidliquid mixture that contains thick oil, wooden residue and unreacted biomass material; Wherein mixed gas is discharged from first reactor head, and solidliquid mixture gets into flashing tower and further handles;
The solidliquid mixture obtain is handled in the first step acid hydrolysis to be sent into and carries out flash distillation in the flashing tower and handle; The flash distillation mixture that obtains the furfural mixing steam and do not gasify; The furfural mixing steam is discharged from cat head; Carry out the second step acid hydrolytic reaction after the flash distillation mixture is discharged at the bottom of the tower, wherein flash distillation treatment temperature is 200 ℃, and absolute pressure is 0.1Mpa;
3, second one-step hydrolysis reaction
The flash distillation mixture is pumped into second reactor drum with plunger type high-pressure; Feed high temperature and high pressure steam at second reactor bottom, the temperature and pressure in first reactor drum is raise, carry out the second step acid hydrolytic reaction; Obtain the second step acid hydrolytic reaction mixture; Wherein the temperature of the second step acid hydrolytic reaction is 190 ℃, and absolute pressure is 1.4Mpa, and the reaction times is 15 minutes;
Contain furfural, formic acid, levulinic acid and lignin residue in the second step acid hydrolytic reaction product; The second step acid hydrolytic reaction product is cooled to 140 ℃ through cooling system; Sending into gravity separator carries out settlement separate; The volatile matters such as water, furfural and formic acid that discharge at the separator top form the furfural mixing steam, and residues such as the levulinic acid of separator bottom, xylogen form residue mixture;
4, refining furfural
Furfural mixing steam after the flash distillation, the furfural mixing steam after the gravity settling separation are merged into total mixed gas, and its composition mainly comprises water, furfural and formic acid;
Total mixed gas is removed the residue in the gas through the gas pulp separator, be cooled to 40-50 ℃ after, obtain the furfural mixed solution; The furfural mixed solution sent into distill processing in the distillation tower; The furfural that collection distillation tower cat head steams and the azeotropic steam of water to≤55 ℃, are removed the moisture in the furfural mixed solution with the azeotropic steam cooling; Make bullion aldehyde liquid, wherein the flow of furfural mixed solution entering distillation tower is 10m
3/ h, the temperature of control distillation tower is 103-105 ℃, and absolute pressure is 0.02MPa in the tower, and the volume ratio of mixed solution and distillation tower is 0.6:1, furfural content in the waste water at the bottom of the tower<0.05%;
Bullion aldehyde liquid is sent into branch aldehyde jar, in jar, leave standstill and carried out layering in 20 minutes, collect lower floor's liquid, obtain the furfural bullion, the mass percent concentration of furfural is 80% in the furfural bullion;
The furfural bullion is sent into neutralization tank through thick aldehyde test tank, and the adding mass percent concentration is 10% Na in neutralization tank
2CO
3Solution after adjusting furfural bullion pH is 7.0, is sent into vacuum tower with the furfural bullion under 60 ℃, the control tower top temperature is 97-99 ℃, and the temperature of tower still is 100-103 ℃, and vacuum tightness is 80-95Kpa; When temperature progressively rises to 100 ℃ by 60 ℃, when vacuum tightness progressively rose to 85Kpa by 65Kpa, extracting overhead distillate 10 minutes was collected in the branch aldehyde jar, and extracting collection of finished products then is in the finished product jar, made mass percentage content and be 99.2% furfural;
5, refining levulinic acid
The residue mixture of gravity separator bottom is sent into spiral decompression evaporator distill processing; Collect the steam that distiller steams; Make mass percentage content and be 65% levulinic acid bullion, wherein the relative pressure handled of distillation is-0.02MPa that temperature is 145 ℃;
After the levulinic acid bullion is preheated to 150 ℃; Send into the levulinic acid vacuum still and further distill processing; Collect the fraction of 135-140 ℃ of section, obtain mass percentage content and be 95% levulinic acid, wherein the relative pressure handled of underpressure distillation is-0.03MPa;
Two, preparation ethyl levulinate
After the levulinic acid of above-mentioned preparation and ethanol mixed, be driven into pump and carry out the supercritical esterification reaction in the overcritical tubular reactor, make ethyl levulinate; Wherein levulinic acid and alcoholic acid mol ratio are 1:4, and controlling said supercritical esterification treatment temperature is 300 ℃, and absolute pressure is 15MPa, and the treatment time is 2h; The transformation efficiency of levulinic acid is 98% in the esterification, and the selectivity of ethyl levulinate is 95%;
Three, preparation methylfuroate
1, preparation copper silver cerium composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), Silver Nitrate (AgNO
3) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed nitrate solution; Under 60 ℃, sodium carbonate solution and the drip of mixed nitrate solution and 1mol/L are gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed nitrate solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃,, make copper silver cerium composite catalyst again in 400 ℃ of roasting 4h; Wherein the content of cupric oxide is 80wt% (mass percentage content, down together), and the content of silver suboxide is 5wt%, and the content of cerium oxide is 15wt%;
Copper silver cerium composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 250 ℃, and the recovery time is 15 hours;
2, oxidizing reaction
In reaction kettle, add sodium hydrogen carbonate solution, add the furfural of above-mentioned preparation then, the back that stirs adds copper silver cerium composite catalyst; Aerating oxygen under agitation carries out oxidizing reaction, makes oxidation mixtures; Wherein the mole proportioning of sodium hydrogen carbonate solution and furfural is 4:1, and the mol ratio of oxygen and furfural is 8:1, and the weight proportion of copper silver cerium composite catalyst and furfural is 1:100; The volumetric molar concentration of sodium hydrogen carbonate solution is 1mol/L; The temperature of controlled oxidation reaction is 60 ℃, and absolute pressure is 0.1MPa, and the reaction times is 2h;
Oxidation mixtures is carried out suction strainer, reclaim catalyzer, it is that 30% salpeter solution is acidified to the pH value and is 2.5-3 that filtrating is used mass percent concentration, separates out furancarboxylic acid, makes acidizing fluid; Acidizing fluid is carried out suction strainer, with 3-5 back oven dry of deionized water washing filter residue, make the furancarboxylic acid bullion, wherein the temperature of oven dry is 60 ℃;
With the furancarboxylic acid dissolving crude product in 80 ℃ hot distilled water, be acidified to pH value 2.5-3 with concentrated nitric acid (mass percent concentration is 65%) after, add 15% gac and boiled 10 minutes, filter; Naturally cooling, the CaCl of usefulness ice again will filtrate
2Solution cooling, separate out crystallization after, dry for 3-5 time with deionized water wash, make mass percentage content and be 94.3% furancarboxylic acid;
3, supercritical esterification reaction
With furancarboxylic acid and methanol mixed evenly after, squeeze into pump and to carry out the supercritical esterification reaction in the overcritical tubular reactor, make methylfuroate; Wherein the mol ratio of furancarboxylic acid and methyl alcohol is 1:4, and controlling said supercritical esterification treatment temperature is 280 ℃, and absolute pressure is 15MPa, and the treatment time is 2h; The transformation efficiency of furancarboxylic acid is 95% in the esterification, and the selectivity of methylfuroate is 90%;
Four, preparation dibutyl carbonate
1, preparation metal-rare earth loaded catalyzer
At normal temperatures yellow soda ash and cerous nitrate are dissolved in the zero(ppm) water, make metal-mixed solution of rare earth of 1mol/L; Above-mentioned mixing solutions impregnated in Al
2O
3Behind the particle 24 hours,,, pulverize again in 500 ℃ of roastings 3 hours in 120 ℃ of dryings 12 hours, screening 20-40 order, make metal-rare earth loaded catalyzer, wherein the mole proportioning of sodium oxide and cerium oxide is 4:1 in metal-rare earth loaded catalyzer, said Al
2O
3Weight account for 80% of metal-rare earth loaded catalyzer, i.e. Al
2O
3With the weight proportion of active ingredient (sodium oxide and cerium oxide) be 80:20;
2, transesterification reaction
With joining transesterification reactor after methylcarbonate and the propyl carbinol mixing, in reactor drum, add above-mentioned metal-rare earth loaded catalyzer again, after mixing; Reactor drum is heated, pressurizeed, carry out transesterification reaction, make dibutyl carbonate; Wherein the mol ratio of methylcarbonate and propyl carbinol is 0.4:1, and the weight proportion of methylcarbonate and metal-rare earth loaded catalyzer is 100:2, and the temperature of controlling said transesterification reaction is 240 ℃; Absolute pressure is 4MPa, and the reaction times is 3h; The transformation efficiency of methylcarbonate is 95% in the transesterification reaction, and the selectivity of dibutyl carbonate is 92%;
Five, the low biofuel propellant combination that coagulates
Ethyl levulinate, methylfuroate, dibutyl carbonate and the Witconol 2301 of above-mentioned preparation is (common commercially available; Mass percentage content is 99%) mix after; Add solubility promoter methylcarbonate and flash-point rising agent (available from east wood gloomy science and technology difficult to understand (Tianjin) ltd) again; Mix; Promptly make the low biofuel propellant combination that coagulates, wherein the quality percentage composition of each component is respectively: ethyl levulinate 30%, methylfuroate 23%, dibutyl carbonate 35%, Witconol 2301 8%, solubility promoter 3.9%, flash-point rising agent 0.1%;
The low quality examination result who coagulates the biofuel propellant combination sees table 1.
Embodiment 2
One, preparation furfural and levulinic acid
1, raw materials pretreatment:
With water ratio is that the caragana microphylla stump thing of 15-20% is pulverized to behind the small-particle of 0.5-1cm, adds the tap water stirring and evenly mixing, makes water ratio and be 60% biomass slurry;
2, the first step acid hydrolytic reaction:
Above-mentioned biomass slurry is put into premixing tank, and the adding mass percent concentration is 4% formic acid solution in jar, mixes the back and with the plunger type high-pressure pump slurry formic acid mixed solution is sent into first reactor drum; Feed high temperature and high pressure steam at reactor bottom; Temperature and pressure in first reactor drum is raise, carry out the first step acid hydrolytic reaction, obtain the first step to the acid hydrolysis mixture; Wherein the weight proportion of biomass slurry and formic acid solution is 100:2; The temperature of the first step acid hydrolytic reaction is 200 ℃, and absolute pressure is 2.6Mpa, and the reaction times is 5 minutes;
The first step acid hydrolysis products is the mixed gas that contains furfural, a small amount of combustion gas and water vapor; And the solidliquid mixture that contains thick oil, wooden residue and unreacted biomass material; Wherein mixed gas is discharged from first reactor head, and solidliquid mixture gets into flashing tower and further handles;
The solidliquid mixture obtain is handled in the first step acid hydrolysis to be sent into and carries out flash distillation in the flashing tower and handle; The flash distillation mixture that obtains the furfural mixing steam and do not gasify; The furfural mixing steam is discharged from cat head; Carry out the second step acid hydrolytic reaction after the flash distillation mixture is discharged at the bottom of the tower, wherein flash distillation treatment temperature is 180 ℃, and absolute pressure is 0.2Mpa;
3, second one-step hydrolysis reaction
The flash distillation mixture is pumped into second reactor drum with plunger type high-pressure; Feed high temperature and high pressure steam at second reactor bottom, the temperature and pressure in first reactor drum is raise, carry out the second step acid hydrolytic reaction; Obtain the second step acid hydrolytic reaction mixture; Wherein the temperature of the second step acid hydrolytic reaction is 200 ℃, and absolute pressure is 1.6Mpa, and the reaction times is 20 minutes;
Contain furfural, formic acid, levulinic acid and lignin residue in the second step acid hydrolytic reaction product; The second step acid hydrolytic reaction product is cooled to 150 ℃ through cooling system; Sending into gravity separator carries out settlement separate; The volatile matters such as water, furfural and formic acid that discharge at the separator top form the furfural mixing steam, and residues such as the levulinic acid of separator bottom, xylogen form residue mixture;
4, refining furfural
Furfural mixing steam after the flash distillation, the furfural mixing steam after the gravity settling separation are merged into total mixed gas, and its composition mainly comprises water, furfural and formic acid;
Total mixed gas is removed the residue in the gas through the gas pulp separator, be cooled to 40-50 ℃ after, obtain the furfural mixed solution; The furfural mixed solution sent into distill processing in the distillation tower; The furfural that collection distillation tower cat head steams and the azeotropic steam of water to≤55 ℃, are removed the moisture in the furfural mixed solution with the azeotropic steam cooling; Make bullion aldehyde liquid, wherein the flow of furfural mixed solution entering distillation tower is 10m
3/ h, the temperature of control distillation tower is 103-105 ℃, and absolute pressure is 0.02MPa in the tower, and the volume ratio of mixed solution and distillation tower is 0.6:1, furfural content in the waste water at the bottom of the tower<0.05%;
Bullion aldehyde liquid is sent into branch aldehyde jar, in jar, leave standstill and carried out layering in 20 minutes, collect lower floor's liquid, obtain the furfural bullion, the mass percent concentration of furfural is 83% in the furfural bullion;
The furfural bullion is sent into neutralization tank through thick aldehyde test tank, and the adding mass percent concentration is 10% Na in neutralization tank
2CO
3Solution after adjusting furfural bullion pH is 7.0, is sent into vacuum tower with the furfural bullion under 60 ℃, the control tower top temperature is 97-99 ℃, and the temperature of tower still is 100-103 ℃, and vacuum tightness is 80-95Kpa; When temperature progressively rises to 100 ℃ by 60 ℃, when vacuum tightness progressively rose to 85Kpa by 65Kpa, extracting overhead distillate 10 minutes was collected in the branch aldehyde jar, and extracting collection of finished products then is in the finished product jar, made mass percentage content and be 99.1% furfural;
5, refining levulinic acid
The residue mixture of gravity separator bottom is sent into spiral decompression evaporator distill processing; Collect the steam that distiller steams; Make mass percentage content and be 62% levulinic acid bullion, wherein the relative pressure handled of distillation is-0.01MPa that temperature is 135 ℃;
After the levulinic acid bullion is preheated to 145 ℃; Send into the levulinic acid vacuum still and further distill processing; Collect the fraction of 135-140 ℃ of section, obtain mass percentage content and be 97% levulinic acid, wherein the relative pressure handled of underpressure distillation is-0.02MPa;
Two, preparation ethyl levulinate
After the levulinic acid of above-mentioned preparation and ethanol mixed, be driven into pump and carry out the supercritical esterification reaction in the overcritical tubular reactor, make ethyl levulinate; Wherein levulinic acid and alcoholic acid mol ratio are 1:8, and controlling said supercritical esterification treatment temperature is 350 ℃, and absolute pressure is 12MPa, and the treatment time is 1h; The levulinic acid transformation efficiency is 96% in the esterification, and the selectivity of ethyl levulinate is 93%;
Three, preparation methylfuroate
1, preparation copper silver cerium composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), Silver Nitrate (AgNO
3) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed nitrate solution; Under 60 ℃, sodium carbonate solution and the drip of mixed nitrate solution and 1mol/L are gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed nitrate solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃,, make copper silver cerium composite catalyst again in 500 ℃ of roasting 3h; Wherein the content of cupric oxide is 90wt% (mass percentage content, down together), and the content of silver suboxide is 3wt%, and the content of cerium oxide is 7wt%;
Copper silver cerium composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 220 ℃, and the recovery time is 20 hours;
2, oxidizing reaction
In reaction kettle, add sodium hydroxide solution, add the furfural of above-mentioned preparation then, the back that stirs adds copper silver cerium composite catalyst; Aerating oxygen under agitation carries out oxidizing reaction, makes oxidation mixtures; Wherein the mole proportioning of sodium hydroxide solution and furfural is 2:1, and the mol ratio of oxygen and furfural is 10:1, and the weight proportion of copper silver cerium composite catalyst and furfural is 1.5:100; The volumetric molar concentration of sodium hydroxide solution is 2mol/L; The temperature of controlled oxidation reaction is 80 ℃, and absolute pressure is 0.2MPa, and the reaction times is 3h;
Oxidation mixtures is carried out suction strainer, reclaim catalyzer, it is that 30% salpeter solution is acidified to the pH value and is 2.5-3 that filtrating is used mass percent concentration, separates out furancarboxylic acid, makes acidizing fluid; Acidizing fluid is carried out suction strainer, with 3-5 back oven dry of deionized water washing filter residue, make the furancarboxylic acid bullion, wherein the temperature of oven dry is 60 ℃;
With the furancarboxylic acid dissolving crude product in 80 ℃ hot distilled water, be acidified to pH value 2.5-3 with concentrated nitric acid (mass percent concentration is 65%) after, add 15% gac and boiled 10 minutes, filter; Naturally cooling, the CaCl of usefulness ice again will filtrate
2Solution cooling, separate out crystallization after, dry for 3-5 time with deionized water wash, make mass percentage content and be 95.0% furancarboxylic acid;
3, supercritical esterification reaction
With furancarboxylic acid and methanol mixed evenly after, squeeze into pump and to carry out the supercritical esterification reaction in the overcritical tubular reactor, make methylfuroate; Wherein the mol ratio of furancarboxylic acid and methyl alcohol is 1:8, and controlling said supercritical esterification treatment temperature is 320 ℃, and absolute pressure is 10MPa, and the treatment time is 3h; The furancarboxylic acid transformation efficiency is 96% in the esterification, and the selectivity of methylfuroate is 92%;
Four, preparation dibutyl carbonate
1, preparation metal-rare earth loaded catalyzer
At normal temperatures salt of wormwood and Lanthanum trinitrate are dissolved in the zero(ppm) water, make metal-mixed solution of rare earth of 1mol/L; Above-mentioned mixing solutions impregnated in activated carbon granule after 24 hours; In 120 ℃ of dryings 12 hours, again in 500 ℃ of roastings 3 hours, pulverize, screening 20-40 order; Make metal-rare earth loaded catalyzer; Wherein the mole proportioning of potassium oxide and lanthanum trioxide is 8:1 in metal-rare earth loaded catalyzer, and the weight of said gac accounts for 90% of metal-rare earth loaded catalyzer, and promptly the weight proportion of gac and active ingredient (potassium oxide and lanthanum trioxide) is 90:10;
2, transesterification reaction
With joining transesterification reactor after methylcarbonate and the propyl carbinol mixing; In reactor drum, add above-mentioned metal-rare earth loaded catalyzer again, after mixing, reactor drum is heated, pressurizeed; Carry out transesterification reaction; Make dibutyl carbonate, wherein the mol ratio of methylcarbonate and propyl carbinol is 0.2:1, and the weight proportion of methylcarbonate and metal-rare earth loaded catalyzer is 100:4; The temperature of controlling said transesterification reaction is 300 ℃, and absolute pressure is 6MPa, and the reaction times is 2h; The transformation efficiency of methylcarbonate is 93% in the transesterification reaction, and the selectivity of dibutyl carbonate is 90%;
Five, the low biofuel propellant combination that coagulates
Ethyl levulinate, methylfuroate, dibutyl carbonate and the Witconol 2301 of above-mentioned preparation is (common commercially available; Mass percentage content is 99%) mix after; Add solubility promoter ritalin and flash-point rising agent again; Mix, promptly make the low biofuel propellant combination that coagulates, wherein the quality percentage composition of each component is respectively: ethyl levulinate 40%, methylfuroate 20%, dibutyl carbonate 28%, Witconol 2301 10%, solubility promoter 1.8%, flash-point rising agent 0.2%;
The low quality examination result who coagulates the biofuel propellant combination sees table 1.
Embodiment 3
One, preparation furfural and levulinic acid
1, raw materials pretreatment:
With water ratio is that the salix monogolica stump thing of 15-20% is pulverized to behind the small-particle of 0.5-1cm, adds the tap water stirring and evenly mixing, makes water ratio and be 65% biomass slurry;
2, the first step acid hydrolytic reaction:
Above-mentioned biomass slurry is put into premixing tank, and the adding mass percent concentration is 10% formic acid solution in jar, mixes the back and with the plunger type high-pressure pump slurry formic acid mixed solution is sent into first reactor drum; Feed high temperature and high pressure steam at reactor bottom; Temperature and pressure in first reactor drum is raise, carry out the first step acid hydrolytic reaction, obtain the first step to the acid hydrolysis mixture; Wherein the weight proportion of biomass slurry and formic acid solution is 100:8; The temperature of the first step acid hydrolytic reaction is 260 ℃, and absolute pressure is 1.8Mpa, and the reaction times is 20 minutes;
The first step acid hydrolysis products is the mixed gas that contains furfural, a small amount of combustion gas and water vapor; And the solidliquid mixture that contains thick oil, wooden residue and unreacted biomass material; Wherein mixed gas is discharged from first reactor head, and solidliquid mixture gets into flashing tower and further handles;
The solidliquid mixture obtain is handled in the first step acid hydrolysis to be sent into and carries out flash distillation in the flashing tower and handle; The flash distillation mixture that obtains the furfural mixing steam and do not gasify; The furfural mixing steam is discharged from cat head; Carry out the second step acid hydrolytic reaction after the flash distillation mixture is discharged at the bottom of the tower, wherein flash distillation treatment temperature is 190 ℃, and absolute pressure is 0.2Mpa;
3, second one-step hydrolysis reaction
The flash distillation mixture is pumped into second reactor drum with plunger type high-pressure; Feed high temperature and high pressure steam at second reactor bottom, the temperature and pressure in first reactor drum is raise, carry out the second step acid hydrolytic reaction; Obtain the second step acid hydrolytic reaction mixture; Wherein the temperature of the second step acid hydrolytic reaction is 220 ℃, and absolute pressure is 1.0Mpa, and the reaction times is 18 minutes;
Contain furfural, formic acid, levulinic acid and lignin residue in the second step acid hydrolytic reaction product; The second step acid hydrolytic reaction product is cooled to 150 ℃ through cooling system; Sending into gravity separator carries out settlement separate; The volatile matters such as water, furfural and formic acid that discharge at the separator top form the furfural mixing steam, and residues such as the levulinic acid of separator bottom, xylogen form residue mixture;
4, refining furfural
Furfural mixing steam after the flash distillation, the furfural mixing steam after the gravity settling separation are merged into total mixed gas, and its composition mainly comprises water, furfural and formic acid;
Total mixed gas is removed the residue in the gas through the gas pulp separator, be cooled to 40-50 ℃ after, obtain the furfural mixed solution; The furfural mixed solution sent into distill processing in the distillation tower; The furfural that collection distillation tower cat head steams and the azeotropic steam of water to≤55 ℃, are removed the moisture in the furfural mixed solution with the azeotropic steam cooling; Make bullion aldehyde liquid, wherein the flow of furfural mixed solution entering distillation tower is 12m
3/ h, the temperature of control distillation tower is 103-105 ℃, and absolute pressure is 0.02MPa in the tower, and the volume ratio of mixed solution and distillation tower is 0.7:1, furfural content in the waste water at the bottom of the tower<0.05%;
Bullion aldehyde liquid is sent into branch aldehyde jar, in jar, leave standstill and carried out layering in 30 minutes, collect lower floor's liquid, obtain the furfural bullion, the mass percent concentration of furfural is 85% in the furfural bullion;
The furfural bullion is sent into neutralization tank through thick aldehyde test tank, and the adding mass percent concentration is 10% Na in neutralization tank
2CO
3Solution after adjusting furfural bullion pH is 7.5, is sent into vacuum tower with the furfural bullion under 60 ℃, the control tower top temperature is 97-99 ℃, and the temperature of tower still is 100-103 ℃, and vacuum tightness is 80-95Kpa; When temperature progressively rises to 100 ℃ by 60 ℃, when vacuum tightness progressively rose to 85Kpa by 65Kpa, extracting overhead distillate 15 minutes was collected in the branch aldehyde jar, and extracting collection of finished products then is in the finished product jar, made mass percentage content and be 99.5% furfural;
5, refining levulinic acid
The residue mixture of gravity separator bottom is sent into spiral decompression evaporator distill processing; Collect the steam that distiller steams; Make mass percentage content and be 65% levulinic acid bullion, wherein the relative pressure handled of distillation is-0.02MPa that temperature is 140 ℃;
After the levulinic acid bullion is preheated to 150 ℃; Send into the levulinic acid vacuum still and further distill processing; Collect the fraction of 135-140 ℃ of section, obtain mass percentage content and be 96% levulinic acid, wherein the relative pressure handled of underpressure distillation is-0.03MPa;
Two, preparation ethyl levulinate
After the levulinic acid of above-mentioned preparation and ethanol mixed, be driven into pump and carry out the supercritical esterification reaction in the overcritical tubular reactor, make ethyl levulinate; Wherein levulinic acid and alcoholic acid mol ratio are 1:2, and controlling said supercritical esterification treatment temperature is 280 ℃, and absolute pressure is 20MPa, and the treatment time is 3h; The levulinic acid transformation efficiency is 95% in the esterification, and the selectivity of ethyl levulinate is 92%;
Three, preparation methylfuroate
1, preparation copper silver cerium composite catalyst
With cupric nitrate (Cu (NO
3)
23H
2O), Silver Nitrate (AgNO
3) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the zero(ppm) water, make mixed nitrate solution; Under 60 ℃, sodium carbonate solution and the drip of mixed nitrate solution and 1mol/L are gone into to be equipped with in the container of zero(ppm) water, form vs; The rate of addition of regulating mixed nitrate solution and sodium carbonate solution is 7-8 with the pH value that keeps vs; After titration finishes,, wash then the aging 2h of vs deposition, suction filtration, after carrying out drying under 120 ℃,, make copper silver cerium composite catalyst again in 500 ℃ of roasting 4h; Wherein the content of cupric oxide is 85wt% (mass percentage content, down together), and the content of silver suboxide is 5wt%, and the content of cerium oxide is 10wt%;
Copper silver cerium composite catalyst reduces processing with hydrogen before use, and the treatment temperature of wherein reducing is 220 ℃, and the recovery time is 12 hours;
2, oxidizing reaction
In reaction kettle, add potassium bicarbonate solution, add the furfural of above-mentioned preparation then, the back that stirs adds copper silver cerium composite catalyst; Aerating oxygen under agitation carries out oxidizing reaction, makes oxidation mixtures; Wherein the mole proportioning of potassium bicarbonate solution and furfural is 8:1, and the mol ratio of oxygen and furfural is 5:1, and the weight proportion of copper silver cerium composite catalyst and furfural is 0.5:100; The volumetric molar concentration of potassium bicarbonate solution is 1mol/L; The temperature of controlled oxidation reaction is 100 ℃, and absolute pressure is 0.15MPa, and the reaction times is 4h;
Oxidation mixtures is carried out suction strainer, reclaim catalyzer, it is that 30% salpeter solution is acidified to the pH value and is 2.5-3 that filtrating is used mass percent concentration, separates out furancarboxylic acid, makes acidizing fluid; Acidizing fluid is carried out suction strainer, with 3-5 back oven dry of deionized water washing filter residue, make the furancarboxylic acid bullion, wherein the temperature of oven dry is 60 ℃;
With the furancarboxylic acid dissolving crude product in 80 ℃ hot distilled water, be acidified to pH value 2.5-3 with concentrated nitric acid (mass percent concentration is 65%) after, add 15% gac and boiled 10 minutes, filter; Naturally cooling, the CaCl of usefulness ice again will filtrate
2Solution cooling, separate out crystallization after, dry for 3-5 time with deionized water wash, make mass percentage content and be 95.8% furancarboxylic acid;
3, supercritical esterification reaction
With furancarboxylic acid and methanol mixed evenly after, squeeze into pump and to carry out the supercritical esterification reaction in the overcritical tubular reactor, make methylfuroate; Wherein the mol ratio of furancarboxylic acid and methyl alcohol is 1:10, and controlling said supercritical esterification treatment temperature is 220 ℃, and absolute pressure is 20MPa, and the treatment time is 1h; The furancarboxylic acid transformation efficiency is 94% in the esterification, and the selectivity of methylfuroate is 90%;
Four, preparation dibutyl carbonate
1, preparation metal-rare earth loaded catalyzer
At normal temperatures magnesium nitrate and cerous nitrate are dissolved in the zero(ppm) water, make metal-mixed solution of rare earth of 1mol/L; Above-mentioned mixing solutions impregnated in TiO
2Behind the particle 24 hours,,, pulverize again in 500 ℃ of roastings 3 hours in 120 ℃ of dryings 12 hours, screening 20-40 order, make metal-rare earth loaded catalyzer, wherein the mole proportioning of Natural manganese dioxide and cerium oxide is 2:1 in metal-rare earth loaded catalyzer, said TiO
2Weight account for 85% of metal-rare earth loaded catalyzer, i.e. TiO
2With the weight proportion of active ingredient (Natural manganese dioxide and cerium oxide) be 85:15;
2, transesterification reaction
With joining transesterification reactor after methylcarbonate and the propyl carbinol mixing; In reactor drum, add above-mentioned metal-rare earth loaded catalyzer again, after mixing, reactor drum is heated, pressurizeed; Carry out transesterification reaction; Make dibutyl carbonate, wherein the mol ratio of methylcarbonate and propyl carbinol is 0.3:1, and the weight proportion of methylcarbonate and metal-rare earth loaded catalyzer is 100:1; The temperature of controlling said transesterification reaction is 200 ℃, and absolute pressure is 10MPa, and the reaction times is 4; The transformation efficiency of methylcarbonate is 96% in the transesterification reaction, and the selectivity of dibutyl carbonate is 93%;
Five, the low biofuel propellant combination that coagulates
Ethyl levulinate, methylfuroate, dibutyl carbonate and the Witconol 2301 of above-mentioned preparation is (common commercially available; Mass percentage content is 99%) mix after; Add solubility promoter vinyl acetic monomer and flash-point rising agent again; Mix, promptly make the low biofuel propellant combination that coagulates, wherein the quality percentage composition of each component is respectively: ethyl levulinate 50%, methylfuroate 15%, dibutyl carbonate 25%, Witconol 2301 5%, solubility promoter 4.85%, flash-point rising agent 0.15%;
The low quality examination result who coagulates the biofuel propellant combination sees table 1.
The low quality examination result who coagulates the biofuel propellant combination of table 1
| Project | National standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | TP |
| Density (20 ℃)/(kg/m 3) | 820-900 | 856 | 869 | 872 | GB/T?2540 |
| Kinematic viscosity (40 ℃)/(mm 2/s） | 1.9-6.0 | 2.4 | 2.0 | 22 | GB/T?265 |
| Flash-point (remaining silent), ℃ | ≥130 | 136.2 | 140.6 | 138.5 | GB/T?261 |
| Cold filter clogging temperature/℃ | Report | -18 | -55 | -42 | SH/T?0248 |
| Sulphur content (massfraction)/% | ≤0.005 | 0.001 | 0.001 | 0.001 | SH/T0689 |
| 10% steams excess carbon residue (massfraction)/% | ≤0.3 | 0.1 | 0.1 | 0.1 | GB/T?17144 |
| Sulfated ash (massfraction)/% | ≤0.02 | 0.008 | 0.010 | 0.009 | GB/T?2433 |
| Water-content (massfraction)/% | ≤0.05 | 0.04 | 0.03 | 0.03 | SH/T0246 |
| Mechanical impurity | Do not have | Do not have | Do not have | Do not have | GB/T?511 |
| Copper corrosion (50 ℃, 3h)/level | ≤1 | 1a | 1a | 1a | GB/T?5096 |
| Cetane value | ≥49 | 65 | 60 | 62 | GB/T?386 |
| Oxidation stability (110 ℃)/hour | ≥6 | 15 | 15 | 15 | EN?14112 |
| Acid number/(mgKOH/g) | ≤0.80 | 0.32 | 0.30 | 0.33 | GB/T?264 |
| Free glycerol content (massfraction)/% | ≤0.02 | 0.001 | 0 | 0 | ASTMD?6584 |
| Total glycerol content (massfraction)/% | ≤0.240 | 0.009 | 0.005 | 0.005 | ASTMD?6584 |
| 90% recovered temperature | ≤360 | 318 | 320 | 316 | GB/T?6536 |
Can know by table 1 result:
The biofuel propellant combination cetane value of the present invention's preparation is high, and oxidation stability is good, and sulphur content is low; Product performance are stable; Quality meets the regulation of relevant national standard, and particularly its condensation point is low, low-temperature fluidity good, can satisfy the oily demand of using of north cold area preferably.
Claims (10)
1. one kind low is coagulated the biofuel propellant combination, and its component comprises ethyl levulinate, methylfuroate, dibutyl carbonate, Witconol 2301, solubility promoter and flash-point rising agent.
2. the low biofuel propellant combination that coagulates as claimed in claim 1; It is characterized in that the quality percentage composition of said each component is respectively: ethyl levulinate 30%-50%, methylfuroate 10%-25%; Dibutyl carbonate 20%-40%; Witconol 2301 5%-10%, solubility promoter 0-5%, flash-point rising agent 0.1%-0.2%.
3. according to claim 1 or claim 2 the low biofuel propellant combination that coagulates is characterized in that said solubility promoter is selected from one or more in methylcarbonate, ritalin, the vinyl acetic monomer.
4. the one kind low preparation method who coagulates the biofuel propellant combination comprises the steps:
A) biomass material is carried out acid hydrolytic reaction, make furfural and levulinic acid;
B) levulinic acid and ethanol are carried out the supercritical esterification reaction, make ethyl levulinate;
C) furfural and oxygen are carried out oxidizing reaction, make furancarboxylic acid;
D) furancarboxylic acid and methyl alcohol are carried out the supercritical esterification reaction, make the furfural methyl esters;
E) methylcarbonate and butanols are carried out transesterification reaction, make dibutyl carbonate;
F) ethyl levulinate, methylfuroate, dibutyl carbonate, Witconol 2301, solubility promoter and flash-point rising agent are mixed, make the low biofuel propellant combination that coagulates.
5. method as claimed in claim 4 is characterized in that steps A) described in acid hydrolytic reaction carry out in two steps, wherein the acid-hydrolyzed temperature of the first step is 200-260 ℃, absolute pressure is 1.8-2.6Mpa, the reaction times is 5-20 minute; Second step, acid-hydrolyzed temperature was 180-220 ℃, and absolute pressure is 1.0-1.6Mpa, and the reaction times is 15-20 minute.
6. method as claimed in claim 4 is characterized in that step B) described in levulinic acid and alcoholic acid mol ratio be 1:2-20, the temperature of said supercritical esterification reaction is 220-350 ℃, absolute pressure is 10-20MPa, the reaction times is 1-3 hour.
7. method as claimed in claim 4 is characterized in that step C) described in oxidizing reaction comprise the steps:
C1) furfural is dissolved in the basic soln, makes furfurine solution;
C2) under the effect of copper silver cerium composite catalyst, furfurine solution and oxygen are carried out oxidizing reaction, make oxidation mixtures;
C3) with carrying out acidification after the oxidation mixtures filtration, make furancarboxylic acid.
8. method as claimed in claim 7; It is characterized in that said copper silver cerium composite catalyst comprises cupric oxide, silver suboxide and cerium oxide, wherein the mass percentage content of cupric oxide is 80-90%; The mass percentage content of silver suboxide is 3-5%, and the mass percentage content of cerium oxide is 5-15%; The weight proportion of copper silver cerium composite catalyst and furfural is 0.5-1.5:100; The temperature of said oxidizing reaction is 50-100 ℃, and absolute pressure is 0.1-0.2MPa, and the reaction times is 2-4 hour.
9. method as claimed in claim 4 is characterized in that step D) described in the mol ratio of furancarboxylic acid and methyl alcohol be 1:2-20, the temperature of said supercritical esterification reaction is 220-350 ℃, absolute pressure is 10-20MPa, the reaction times is 1-3 hour.
10. method as claimed in claim 4; It is characterized in that; Step e) methylcarbonate described in and butanols carry out transesterification reaction under the effect of metal-rare earth loaded catalyzer, the mol ratio of wherein said methylcarbonate and butanols is 0.2-0.4:1, and the temperature of said transesterification reaction is 200-300 ℃; Absolute pressure is 4-10MPa, and the reaction times is 2-4 hour.
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