CN103058862B - A kind of novel method taking agriculture and forestry organic waste material as initial feed and produce dialkyl carbonate - Google Patents
A kind of novel method taking agriculture and forestry organic waste material as initial feed and produce dialkyl carbonate Download PDFInfo
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Abstract
The invention discloses a kind of method taking agriculture and forestry organic waste material as initial feed and produce dialkyl carbonate, is first that initial feed obtains 2-methyltetrahydrofuran with agriculture and forestry organic waste material; Then 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, obtained a kind of cyclic carbonate (i.e. Isosorbide-5-Nitrae-pentanediol carbonic ether); Again described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, obtained dialkyl carbonate.The inventive method with the agriculture and forestry organic waste material of cheapness and industrial gaseous waste carbonic acid gas for raw material production dialkyl carbonate, production technique also by-product high added value 1,4-pentanediol, not only save production cost, decrease environmental pollution, also for the high-efficiency comprehensive utilization of suitability for industrialized production dialkyl carbonate and agriculture and forestry organic waste material provides new way, there is significant economic and social benefit.
Description
Technical field
The present invention relates to a kind of preparation method of dialkyl carbonate, particularly relate to a kind of novel method and the application thereof that take agriculture and forestry organic waste material as initial feed and produce dialkyl carbonate.
Background technology
Dialkyl carbonate, also referred to as dialkyl carbonate, containing alkoxyl group and carbonyl in its molecule, can react with multiple alcohol, phenol, amine and ester, be a kind of purposes organic compound widely, have higher industrial application value and market outlook.The preparation method of dialkyl carbonate mainly comprises optical self-encoding method, oxidative carbonylation, ester-interchange method etc.Traditional Industrialization manufactures dialkyl carbonate and generally adopts optical self-encoding method, but in this method preparation process, phosgene and intermediate are hypertoxicity material, and by product has severe corrosive, and environmental pollution is serious, thus gradually replace by oxidative carbonylation of methanol method.
Authorization Notice No. is that the Chinese invention patent of CN101234965B discloses a kind of method manufacturing dialkyl carbonate, under alcohol compound, carbon monoxide and oxygen existent condition, the catalysis system that the promotor using organic halogenation metal catalyst collocation at least one to have nitrogen-atoms forms, carry out liquid-phase oxidative carbonylation reaction and generate dialkyl carbonate, this method reduces the corrodibility to reactor to a certain extent, however also exist that catalyzer is expensive also, transformation efficiency and the defect such as selectivity is limited.
Ester-exchange technology is that a kind of ester and another kind of lipid acid or alcohol or ester exchange the technology generating new ester under certain condition with acyl group, has that catalyzer is extensive, reaction conditions is gentle, is easy to control, the advantage such as transformation efficiency is high, good product quality.The Chinese invention patent being CN1699328A as publication number discloses a kind of method preparing dialkyl carbonate, adopt green chemical industry oxide spinel dimethyl ester and the aliphat single-alcohol Reactive Synthesis dialkyl carbonate of clean, nontoxic, environmental protection, this method reaction conditions is gentle, reproducible biomass resource particularly can be utilized to produce, and production process three-waste free pollution.But above-mentioned esterification adopts alcoholate or the oxyhydroxide of basic metal or alkaline-earth metal, alkaline carbonate, alkaline earth metal carbonate, organotin, organic zinc or basic resin are as catalyzer, and speed of reaction is slow, and activity and selectivity is limited.
Except adopting methylcarbonate, cyclic carbonate can also be adopted to prepare dialkyl carbonate as starting raw material.As the publication number Chinese invention patent that is CN102464587A discloses a kind of method of preparing small molecular carbonated dialkyl ester through ester exchange, it adopts cyclic carbonate (as NSC 11801, propylene carbonate, glycerol carbonate) and small molecular alcohol to be raw material, in the presence of a catalyst, under normal pressure or reduced pressure, small molecules dialkyl carbonate is prepared in reaction.This method has that reaction conditions is gentleer, catalyzer is easy to the advantages such as separation, has actual application value.
Summary of the invention
Primary and foremost purpose of the present invention be provide with low cost for above-mentioned prior art Problems existing, the method for production dialkyl carbonate that economic worth is high, the inventive method with the agriculture and forestry organic waste material of cheapness and industrial gaseous waste carbonic acid gas for raw material, production technique also by-product high added value 1,4-pentanediol, economic and social benefit is remarkable.
In order to achieve the above object, one aspect of the present invention provides a kind of method taking agriculture and forestry organic waste material as initial feed and produce dialkyl carbonate, comprises the step that following order is carried out:
A) be that initial feed obtains 2-methyltetrahydrofuran with agriculture and forestry organic waste material;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, obtained structural formula is
cyclic carbonate;
C) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, obtained dialkyl carbonate.
Wherein, described agriculture and forestry organic waste material comprises the scrub growth stump things such as Huang Liu, salix monogolica, caragana microphylla, the agricultural crop straw such as soybean stalk, maize straw, the agricultural wastes such as corn cob, bagasse, oat shell, cottonseed chaff shell, rice bran shell, sunflower shell, and discarded sugar and starch based etc.; Described cyclic carbonate called after Isosorbide-5-Nitrae-pentanediol carbonic ether.
Particularly, described steps A) in customary preparation methods of the prior art can be adopted to be that initial feed obtains 2-methyltetrahydrofuran with agriculture and forestry organic waste material, the Chinese invention patent being CN102558106A as publication number discloses a kind of method utilizing abandoned biomass to prepare 2-methyltetrahydrofuran, comprises the steps:
A1) abandoned biomass is carried out acid hydrolytic reaction, obtained furfural and levulinic acid;
A2) furfural and hydrogen are carried out hydrogenation, obtained 2-methyltetrahydrofuran.
Wherein, described steps A 1) in adopt the vitriol oil to carry out acid hydrolysis to biomass slurry, described acid hydrolytic reaction carries out in two steps, and wherein the acid-hydrolyzed temperature of the first step is 200-260 DEG C, and absolute pressure is 1.8-2.6Mpa, and the reaction times is 10-20 minute; The acid-hydrolyzed temperature of second step is 180-220 DEG C, and absolute pressure is 1.0-1.6Mpa, and the reaction times is 15-20 minute.
Wherein, described steps A 2) in hydrogenation carry out in two steps; In the first step hydrogenation, the mol ratio of hydrogen and furfural is 40-60:1, and the mass space velocity of hydrogen is 10-20h
-1, the temperature of reaction is 180-240 DEG C, and absolute pressure is 1-4MPa, and the hydrogen residence time is 1-3min; In second step hydrogenation, the mol ratio of hydrogen and furfural is 40-60:1, and the mass space velocity of hydrogen is 10-20h
-1, the temperature of reaction is 190-210 DEG C, and absolute pressure is 4-6MPa, and the hydrogen residence time is 1-3min.
Particularly, described the first step hydrogenation carries out under the effect of copper chromium cerium lanthanum composite catalyst, described copper chromium cerium lanthanum composite catalyst comprises cupric oxide, chromium sesquioxide, cerium dioxide and lanthanum sesquioxide, wherein the mass percentage of cupric oxide is 40-60%, the mass percentage of chromium sesquioxide is 30-40%, the mass percentage of cerium dioxide is 5-10%, and the mass percentage of lanthanum sesquioxide is 5-10%.
Particularly, described second step hydrogenation carries out under the effect of nickel aluminium composite catalyst, described nickel aluminium composite catalyst comprises nickel oxide and aluminium sesquioxide, and wherein the mass percentage of nickel oxide is 60-80%, and the mass percentage of aluminium sesquioxide is 20-40%.
Wherein, described step B) in cycloaddition reaction carry out under the effect of magnesium-zincium-rare earth oxide compound composite catalyst, described magnesium-zincium-rare earth oxide compound composite catalyst comprises magnesium oxide, zinc oxide and rare earth oxide, wherein the mol ratio of magnesium oxide and zinc oxide is 1-4:1, be preferably 1-3:1, more preferably 1.5:1, the mass percentage of rare earth oxide in magnesium-zincium-rare earth oxide compound composite catalyst is 0.1-1%, be preferably 0.6-1%, more preferably 0.8%.
Particularly, described rare earth oxide is preferably one or more in lanthanum trioxide, cerium oxide.
Wherein, described magnesium-zincium-rare earth oxide compound composite catalyst adopts the coprecipitation method of this area routine and pickling process to prepare, namely adopt coprecipitation method to prepare magnesium oxide-zinc oxide composites, then adopt pickling process further composite rare-earth oxide on magnesium oxide-zinc oxide composites; Described magnesium-zincium-rare earth oxide compound composite catalyst first uses hydrogen reducing before use, particularly reductase 12-10 hours at 200 DEG C, preferred 4-6 hour.
Particularly, the preparation method of described magnesium-zincium-rare earth oxide compound composite catalyst comprises the steps:
1) by after the mixing solutions heating containing magnesium nitrate and zinc nitrate, add precipitation agent wherein, adjust ph, then carry out insulation aging, after filtration, dry after obtain magnesium oxide-zinc oxide composites;
2) earth solution be impregnated on described magnesium oxide-zinc oxide composites, obtained magnesium-zincium-rare earth oxide compound composite catalyst after drying, roasting.
Wherein, the concentration of mixing solutions described in step 1) is preferably 1mol/L; The temperature of described heating is 40-60 DEG C, is preferably 45 DEG C; The described aging time is 1-4 hour, is preferably 2 hours; Regulate described pH value to 8-9; The temperature of described drying is 100-150 DEG C, and be preferably 110 DEG C, time of drying is 8-24 hour, is preferably 12 hours; Described precipitation agent is the Na of 1mol/L
2cO
3solution, and control the time that described precipitation agent adds and be about 30min.
Particularly, step 2) described in time of dipping be 8-24 hour, be preferably 12 hours; The temperature of described drying is 100-150 DEG C, and be preferably 110 DEG C, time of drying is 2-5 hour, is preferably 3 hours; The temperature of described roasting is 400-600 DEG C, and be preferably 500 DEG C, roasting time is 2-5 hour, is preferably 3 hours.
Wherein, in described cycloaddition reaction, carbonic acid gas is excessive relative to 2-methyltetrahydrofuran; Particularly in described cycloaddition reaction, the mol ratio of 2-methyltetrahydrofuran and carbonic acid gas is 1:1-20, is preferably 1:8-15, more preferably 1:10-12; The weight proportion of described magnesium oxide-zinc oxide composite rare-earth oxide and 2-methyltetrahydrofuran is 0.1-5:100, is preferably 0.1-2:100, more preferably 0.1-1:100.
Particularly, the temperature of described cycloaddition reaction is 80-150 DEG C, is preferably 110-130 DEG C; Reaction absolute pressure is 2-10MPa, is preferably 2-8MPa, more preferably 5-8MPa; Reaction times is 5-120 minute, is preferably 5-30 minute, more preferably 20-30 minute.
Wherein, step C) described in monohydroxy-alcohol be selected from C1-C8 straight chain alcohol, C3-C8 branched-chain alcoho, C3-C8 cyclic alcohol, mixture with one or more in the alcohol of furan nucleus.
Particularly, described C1-C8 straight chain alcohol is preferably ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol, n-Octanol, described C3-C8 branched-chain alcoho is preferably Virahol, isopropylcarbinol, and described C3-C8 cyclic alcohol is preferably ring propyl alcohol, cyclobutanol, and the described alcohol with furan nucleus is preferably furfuryl alcohol.
Especially, when described transesterification reaction adopts single monohydroxy-alcohol to carry out, generate symmetrical dialkyl carbonate; When described transesterification reaction adopts the monohydroxy-alcohol of mixing to carry out, generate the mixed carbonic acid dialkyl containing symmetrical dialkyl carbonate and asymmetric dialkyl carbonate.
Wherein, described transesterification reaction is carried out under the effect of metal-rare earth oxide compound composite catalyst, described metal-rare earth oxide compound composite catalyst comprises metal oxide and rare earth oxide, and wherein the weight proportion of metal oxide and rare earth oxide is (90-99): (1-10); Described metal oxide is one or more in zinc oxide, aluminum oxide, tin protoxide, described rare earth oxide be selected from lanthanum trioxide, cerium oxide one or more.Described metal-rare earth oxide compound composite catalyst first uses hydrogen reducing before use, particularly reductase 12-10 hours at 200 DEG C, preferred 4-6 hour.
Particularly, described metal oxide comprises zinc oxide, aluminum oxide and tin protoxide, and wherein zinc oxide, weight proportion between aluminum oxide and tin protoxide are (6-8): (1-2): (1-2); Described rare earth oxide comprises lanthanum trioxide and cerium oxide.
Wherein, described metal-rare earth oxide compound composite catalyst is prepared by the coprecipitation method of this area routine and pickling process; Particularly, the preparation method of described metal-rare earth oxide compound composite catalyst comprises the steps:
A) in metal-nitrate solutions/mixed solution, add precipitation agent form precipitation, then throw out is carried out drying or calcination process, obtained metal oxide;
B) described metal oxide is immersed rare earth nitrate solution, then carry out drying or calcination process, obtained metal-rare earth oxide compound composite catalyst.
Especially, described precipitation agent is carbonate solution, is preferably sodium carbonate solution, the more preferably sodium carbonate solution of 1mol/L; The temperature of described drying treatment is 100-150 DEG C, and be preferably 120 DEG C, the treatment time is 8-24 hour, is preferably 12 hours; The temperature of described calcination process is 400-600 DEG C, and be preferably 500 DEG C, the treatment time is 2-5 hour, is preferably 3 hours.
Wherein, in described transesterification reaction, monohydroxy-alcohol is excessive relative to cyclic carbonate; Particularly, the mol ratio of cyclic carbonate and monohydroxy-alcohol is 1:1-20, is preferably 1:4-10, more preferably 1:6-8; The described weight of metal-rare earth oxide compound composite catalyst and the proportioning of cyclic carbonate and monohydroxy-alcohol gross weight are 0.1-5:100, are preferably 0.1-2:100, more preferably 0.1-1:100; The temperature of described transesterification reaction is 120-180 DEG C, and be preferably 150-160 DEG C, reaction absolute pressure is 0.1-4MPa, and be preferably 2-3MPa, the reaction times is 5-120 minute, is preferably 5-30 minute, more preferably 20-30 minute.
Particularly, also comprise step D): distillation process is carried out to described dialkyl carbonate, obtained liquid fuel.
Wherein, be 0.01-0.02MPa in absolute pressure, temperature is 180-220 DEG C and carries out underpressure distillation to described dialkyl carbonate, collects 80-90 DEG C, the cut of 125-135 DEG C and 180-200 DEG C, i.e. obtained described liquid fuel.
Particularly, when carrying out underpressure distillation, collect the cut of 80-90 DEG C, the dialkyl carbonate ester mixture of obtained carbonatoms≤5; Collect the cut of 125-135 DEG C, obtained carbonatoms is the dialkyl carbonate ester mixture of 6-9; Collect the cut of 180-200 DEG C, obtained carbonatoms is the dialkyl carbonate ester mixture of 10-17.
The present invention provides a kind of preparation method of liquid fuel on the other hand, comprises the step that following order is carried out:
A) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, obtained structural formula is
cyclic carbonate;
B) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, obtained liquid fuel.
Particularly, described 2-methyltetrahydrofuran is that initial feed obtains with agriculture and forestry organic waste material.
The present invention provides a kind of preparation method of liquid fuel on the other hand, comprises the step that following order is carried out:
A) be that initial feed obtains 2-methyltetrahydrofuran with agriculture and forestry organic waste material;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, obtained structural formula is
cyclic carbonate;
C) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, obtained liquid fuel.
Wherein, in described liquid fuel preparation technology, the numerical range of associated control parameters can with reference to the above-mentioned correlation parameter numerical range prepared in dialkyl carbonate method.
The present invention provides on the other hand a kind of structural formula to be
cyclic carbonate.
The present invention provides on the other hand a kind of structural formula to be
cyclic carbonate preparing the application on liquid fuel, wherein described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, i.e. obtained described liquid fuel.
Application on the dialkyl carbonate liquid fuel within that the present invention provides a kind of aforesaid method to prepare on the other hand, such as, be used as gasoline or gasoline components, diesel oil or diesel oil component, aviation kerosene or aviation kerosene component.
The present invention provides a kind of liquid fuel on the other hand, and its composition comprises structural formula and is
dialkyl carbonate, wherein R and R ' is identical or different, and R, R ' be selected from C1-C8 straight chained alkyl, C3-C8 branched-chain alkyl, C3-C8 cycloalkyl or the alkyl with furan nucleus.
Particularly, R, R ' is preferably ethyl, propyl group, butyl, amyl group, octyl group, sec.-propyl, isobutyl-, cyclopropyl, cyclobutyl, furfuryl alcohol base.
Wherein, when described liquid fuel is used as gasoline or gasoline components, wherein the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 60-100%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 0-40%.
Wherein, when described liquid fuel is used as diesel oil or diesel oil component, wherein the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 10-20%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40-60%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20-30%.
Wherein, when described liquid fuel is used as aviation kerosene or aviation kerosene component, wherein the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 20-40%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40-60%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 10-20%.
The present invention provides a kind of carbonic acid two furfuryl alcohol ester utilizing aforesaid method to prepare on the other hand, and its structural formula is:
Particularly, methylcarbonate and furfuryl alcohol can also be adopted to carry out transesterification reaction and obtain described carbonic acid two furfuryl alcohol ester, described transesterification reaction is carried out under above-mentioned metal-rare earth oxide compound composite catalyst existent condition.Wherein, in described transesterification reaction, the mol ratio of methylcarbonate and furfuryl alcohol is 1:1-20, is preferably 1:2-8; The temperature of described transesterification reaction is 100-300 DEG C, is preferably 120-200 DEG C; Absolute pressure is 1.5-8MPa, is preferably 2-4MPa; Reaction times is 5-100 minute, is preferably 10-40 minute, more preferably 10-20 minute; Especially transformation efficiency >=85% of methylcarbonate in described transesterification reaction, preferably >=95%, yield >=80% of carbonic acid two furfuryl alcohol ester, preferably >=90%.
The present invention provides the application on a kind of above-mentioned carbonic acid two furfuryl alcohol ester liquid fuel within, lubricating oil and engineering plastics on the other hand.
Wherein, when described carbonic acid two furfuryl alcohol ester is applied to liquid fuel, there is higher oxygen level, burn more abundant; It can directly use as diesel oil, and quality meets the relevant regulations of standard GB/T/T19147-2003; It also can directly use as aviation kerosene, and quality meets the relevant regulations of ASTMD910; It as liquid fuel additive, when adding in gasoline or diesel oil, can also can improve octane value and the diesel-fuel cetane number of gasoline, and improve oil-fired oilness and emission performance.
Wherein, when described carbonic acid two furfuryl alcohol ester is applied to lubricating oil, performance and other bigh carbon alcohol carbonate class lubricating oil similar, have low frictional resistance, modest viscosity, oxidation and heat-resistant quality good, good with rubber packing material compatibleness, resistance to wear, the feature such as automatically cleaning, corrodibility are little, carbon residue is few, oil film strength is high, can be used for I. C. engine oil, compressor oil, refrigerator oil, hydraulic pressure wet goods.
Wherein, when described carbonic acid two furfuryl alcohol ester is applied to engineering plastics, can be used as engineering plastics monomer to prepare polycarbonate, its carbonic ether optical transparence prepared is good, excellent in cushion effect, and there is the features such as excellent thermostability, creep resistant, winter resistance, electrical insulating property and flame retardant resistance, the association areas such as building material industry, car industry, medicine equipment, aerospace, packaging, electronic apparatus, optical lens can be widely used in, also can be used for CD base mateiral.
Further aspect of the present invention provides a kind of liquid fuel or liquid fuel additive, and its composition comprises carbonic acid two furfuryl alcohol ester.Particularly, described liquid fuel comprises gasoline, diesel oil, aviation kerosene etc.
Further aspect of the present invention provides a kind of lubricating oil or lubricating oil component, and its composition comprises carbonic acid two furfuryl alcohol ester.Particularly, described lubricating oil comprises I. C. engine oil, compressor oil, refrigerator oil, hydraulic pressure wet goods.
Further aspect of the present invention provides a kind of engineering plastics monomer, and its composition comprises carbonic acid two furfuryl alcohol ester.Particularly, described engineering plastics are polycarbonate.
Compared with prior art, the present invention has the following advantages:
1, the present invention with the agriculture and forestry organic waste material of cheapness and industrial gaseous waste carbonic acid gas for raw material production dialkyl carbonate, production technique also by-product high added value 1,4-pentanediol, not only save production cost, decrease environmental pollution, also for the high-efficiency comprehensive utilization of suitability for industrialized production dialkyl carbonate and agriculture and forestry organic waste material provides new way, there is significant economic and social benefit;
2, preparation technology of the present invention is simple, with short production cycle, energy expenditure is low, is conducive to industrialization scale operation; Particularly adopt metal-rare earth oxide compound composite catalyst catalyzed transesterification, not only speed of reaction is fast, and transformation efficiency, selectivity and product yield are high;
3, the dialkyl carbonate that prepared by the present invention can be applicable to biological liquid fuel, there is the advantages such as nontoxic, biodegradable, it is better than fossil base liquid fuel in oilness, emission performance, noise reduction, volatility, security, environment friendly etc., in low temperature properties, sealing material consistency, heat and oxidation stability, corrodibility, price etc., be better than fatty acid methyl ester class and alcohol fuel class biological liquid fuel.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, these embodiments are only exemplary, do not form any restriction to scope of the present invention.It will be understood by those skilled in the art that and can modify to the details of technical solution of the present invention and form or replace down without departing from the spirit and scope of the present invention, but these amendments and replacement all fall within the scope of protection of the present invention.
Embodiment 1
One, 2-methyltetrahydrofuran is prepared
Add tap water after being pulverized by soybean stalk, obtained water ratio is the biomass slurry of 65%; Described biomass slurry and the vitriol oil are sent in a reactor, in 200 DEG C, carry out the first step acid hydrolytic reaction under 2.2Mpa, react and obtain the first step acid hydrolysis products after 20 minutes; The first step acid hydrolysis products enters in the second reactor after flash distillation process, in 180 DEG C, carry out second step acid hydrolytic reaction under 1.4Mpa, react and obtain second step acid hydrolytic reaction product after 15 minutes; Through refining, namely obtain the furfural that mass percentage content is 99.2%;
By copper chromium cerium lanthanum composite catalyst (wherein containing cupric oxide 50wt%, chromium sesquioxide 40wt%, cerium dioxide 5wt%, lanthanum sesquioxide 5wt%) and furfural add the first hydrogenation reactor, in reactor, pass into hydrogen, in 220 DEG C, carry out the first step hydrogenation under 3MPa, obtained 2-methyl furan; 2-methyl furan and nickel aluminium composite catalyst (are wherein contained nickel oxide 70wt%, aluminium sesquioxide 30wt%) join in the second hydrogenation reactor, in 200 DEG C, carry out second step hydrogenation under 6MPa, reaction product, after refining, obtains the 2-methyltetrahydrofuran that mass percentage is 96%;
Two, cycloaddition reaction
1, magnesium-zincium-rare earth oxide compound composite catalyst is prepared
Adopt coprecipitation method, the hybrid metal solution stirring containing magnesium nitrate and zinc nitrate is warming up to 45 DEG C, then slowly adds Na wherein
2cO
3solution, control Na
2cO
3the joining day of solution is about 30min, after regulating pH value to 8-9, and aging 2h at 45 DEG C, after leaving standstill, filter, washing, in 110 DEG C of dry 12h, obtained magnesium oxide-zinc oxide composites, wherein the mol ratio of magnesium oxide and zinc oxide is 1.5:1;
Adopt pickling process, mixed rare earth solution containing lanthanum nitrate and cerous nitrate is immersed on above-mentioned magnesium oxide-zinc oxide composites, flood after 12 hours in 110 DEG C of dry 3h, roasting 3h at 500 DEG C, i.e. obtained magnesium-zincium-rare earth oxide compound composite catalyst, wherein the mol ratio of lanthanum element and Ce elements is 1:1;
Obtained composite catalyst comprises magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide, wherein the mol ratio of magnesium elements and zinc element is 1.5:1, the mol ratio of lanthanum element and Ce elements is 1:1, and the gross weight of controlled oxidization lanthanum and cerium oxide accounts for 0.8% of whole composite catalyst weight; Described magnesium-zincium-rare earth oxide compound composite catalyst reduces 6 hours at 200 DEG C with hydrogen before use;
2, cycloaddition reaction
After the magnesium-zincium-rare earth oxide compound composite catalyst of 2-methyltetrahydrofuran and above-mentioned preparation is joined reactor according to the weight proportion of 100:0.5, open heating unit and make the homo(io)thermism of reactor at 120 DEG C, in reactor, pass into excessive CO
2, and to control absolute pressure in reactor constant be 8.0MPa, the 2-methyltetrahydrofuran in reactor and CO
2carry out cycloaddition reaction and obtain reaction product after 30 minutes, through distillation i.e. obtained Isosorbide-5-Nitrae-pentanediol carbonic ether; Wherein 2-methyltetrahydrofuran and the CO passed into
2mol ratio be 1:10, in cycloaddition reaction, the transformation efficiency of 2-methyltetrahydrofuran is 90%, and the yield of Isosorbide-5-Nitrae-pentanediol carbonic ether is 60%;
The reaction formula of described cycloaddition reaction is as follows:
Three, transesterification reaction
1, metal-rare earth oxide compound composite catalyst is prepared
Adopt coprecipitation method, sub-to zinc nitrate, aluminum nitrate and nitric acid tin is dissolved in distilled water, after mixing, obtained zinc-aluminium tin mixing solutions; Under agitation by above-mentioned zinc-aluminium tin mixing solutions and sodium carbonate solution and drip enters to be equipped with in the container of 60 DEG C of distilled water, form titrating solution; Regulate the rate of addition of zinc-aluminium tin mixing solutions and sodium carbonate solution to keep the pH value of titrating solution for 7-8; After titration terminates, titrating solution is precipitated aging 2h, then carries out washing, suction filtration, in 120 DEG C of dryings after 12 hours, then in 500 DEG C of roastings 3 hours, obtained ZnO-Al
2o
3-SnO
2metal catalyst;
Adopt pickling process, by lanthanum nitrate (La (NO
3)
36H
2and cerous nitrate (Ce (NO O)
3)
36H
2o) be dissolved in distilled water, obtained mixed solution of rare earth; Utilize pickling process, by above-mentioned ZnO-Al
2o
3-SnO
2immerse in metal catalyst in mixed solution of rare earth, obtain dip compound; By dip compound in 120 DEG C of dryings 12 hours, then in 500 DEG C of roastings 3 hours, pulverize, sieve 20-40 order, obtained metal-rare earth oxide compound composite catalyst;
In obtained metal-rare earth oxide compound composite catalyst, the mass percentage of each oxide compound is respectively: zinc oxide: 60%, aluminum oxide: 20%, tin protoxide: 15%, lanthanum trioxide: 2.5%, cerium oxide: 2.5%; Metal-rare earth oxide compound composite catalyst reduces 6 hours at 200 DEG C with hydrogen before use;
2, transesterification reaction
Isosorbide-5-Nitrae-pentanediol carbonic ether and furfuryl alcohol are joined in tubular type transesterification reactor, then add the metal-rare earth oxide compound composite catalyst of above-mentioned preparation, carry out transesterification reaction after mixing, reaction product is through distillation i.e. obtained carbonic acid two furfuryl alcohol ester; Wherein, the mol ratio 1:6 of Isosorbide-5-Nitrae-pentanediol carbonic ether and furfuryl alcohol, the proportioning of the weight of metal-rare earth oxide compound composite catalyst and Isosorbide-5-Nitrae-pentanediol carbonic ether and furfuryl alcohol gross weight is 0.5:100, and the temperature controlling transesterification reaction is 160 DEG C, absolute pressure is 3MPa, and the reaction times is 20 minutes; The transformation efficiency of Isosorbide-5-Nitrae in transesterification reaction-pentanediol carbonic ether is 100%, and the yield of carbonic acid two furfuryl alcohol ester is 92%;
The reaction formula of described transesterification reaction is as follows:
D4529 method is adopted to measure calorific value, D2700 method is adopted to measure cetane value, GB/T261 is adopted to measure close flash point, employing GB/T265 measures the kinematic viscosity at 40 DEG C, GB/T3535 is adopted to measure pour point, employing EN14112 method measures the oxidation stability at 110 DEG C, and employing D130 method measures the copper corrosion performance at 50 DEG C, adopts SH/T0305 method to measure seal compatibility energy index;
The calorific value of the carbonic acid two furfuryl alcohol ester of preparation is 39.8MJ/kg, and cetane value is 97, and close flash point is 158 DEG C, and the kinematic viscosity at 40 DEG C is 22.6mm
2/ s, pour point is-21 DEG C, and the oxidation stability at 110 DEG C is 30, and copper corrosion is 1 grade, and seal compatibility energy index is 4.
Embodiment 2
Methylcarbonate and furfuryl alcohol are joined in tubular type transesterification reactor, then add the metal-rare earth oxide compound composite catalyst of embodiment 1 preparation, carry out transesterification reaction after mixing, reaction product is through distillation i.e. obtained carbonic acid two furfuryl alcohol ester; Wherein, the mol ratio 1:6 of methylcarbonate and furfuryl alcohol, the weight of metal-rare earth oxide compound composite catalyst and the proportioning of methylcarbonate and furfuryl alcohol gross weight are 0.5:100, and the temperature controlling transesterification reaction is 160 DEG C, absolute pressure is 3MPa, and the reaction times is 20 minutes; In transesterification reaction, methylcarbonate transformation efficiency is 95%, and the yield of carbonic acid two furfuryl alcohol ester is 90%;
The calorific value of the carbonic acid two furfuryl alcohol ester of preparation is 39.6MJ/kg, and cetane value is 97, and close flash point is 156 DEG C, and the kinematic viscosity at 40 DEG C is 22.8mm
2/ s, pour point is-20 DEG C, and the oxidation stability at 110 DEG C is 30, and copper corrosion is 1 grade, and seal compatibility energy index is 4.
Embodiment 3
One, cycloaddition reaction
Adopt the co-precipitation of embodiment 1 and the obtained magnesium-zincium-rare earth oxide compound composite catalyst containing magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide of pickling process, wherein the mol ratio of controlled oxidization magnesium and zinc oxide is 1:1, the mol ratio of lanthanum element and Ce elements is 2:1, and the gross weight controlling lanthanum trioxide and cerium oxide in composite catalyst accounts for 1% of whole composite catalyst weight; Described composite catalyst uses hydrogen reducing before use;
After 2-methyltetrahydrofuran embodiment 1 prepared and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst join reactor according to the weight proportion of 100:1, open heating unit and make the homo(io)thermism of reactor at 80 DEG C, in reactor, pass into excessive CO
2, and to control absolute pressure in reactor constant be 6.0MPa, the 2-methyltetrahydrofuran in reactor and CO
2carry out cycloaddition reaction 20 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO passed into
2mol ratio be 1:15, in cycloaddition reaction, the transformation efficiency of 2-methyltetrahydrofuran is 86%, and Isosorbide-5-Nitrae-pentanediol carbonic ether yield is 54%;
Two, transesterification reaction
Adopt the coprecipitation method of embodiment 1 and pickling process to obtain metal-rare earth oxide compound composite catalyst, the mass content wherein controlling each oxide compound in described composite catalyst is respectively: zinc oxide 80%, aluminum oxide 10%, lanthanum trioxide 5%, cerium oxide 5%; Described composite catalyst uses hydrogen reducing before use;
Isosorbide-5-Nitrae-pentanediol carbonic ether and ethanol are joined in tubular type transesterification reactor, then add the metal-rare earth oxide compound composite catalyst of above-mentioned preparation, carry out transesterification reaction after mixing, reaction product is through distillation i.e. obtained diethyl carbonate; Wherein, the mol ratio 1:10 of Isosorbide-5-Nitrae-pentanediol carbonic ether and ethanol, the proportioning of the weight of metal-rare earth oxide compound composite catalyst and Isosorbide-5-Nitrae-pentanediol carbonic ether and total ethanol weight is 1:100, and the temperature controlling transesterification reaction is 180 DEG C, absolute pressure is 2MPa, and the reaction times is 10 minutes; The transformation efficiency of Isosorbide-5-Nitrae in transesterification reaction-pentanediol carbonic ether is 100%, and the yield of diethyl carbonate is 95%.
Embodiment 4
One, cycloaddition reaction
Adopt the co-precipitation of embodiment 1 and the obtained magnesium-zincium-rare earth oxide compound composite catalyst containing magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide of pickling process, wherein the mol ratio of controlled oxidization magnesium and zinc oxide is 2:1, the mol ratio of lanthanum element and Ce elements is 3:1, and the gross weight controlling lanthanum trioxide and cerium oxide in composite catalyst accounts for 0.2% of whole composite catalyst weight; Described composite catalyst uses hydrogen reducing before use;
After 2-methyltetrahydrofuran embodiment 1 prepared and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst join reactor according to the weight proportion of 100:3, open heating unit and make the homo(io)thermism of reactor at 150 DEG C, in reactor, pass into excessive CO
2, and to control absolute pressure in reactor constant be 2MPa, the 2-methyltetrahydrofuran in reactor and CO
2carry out cycloaddition reaction 100 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO passed into
2mol ratio be 1:3, in cycloaddition reaction, the transformation efficiency of 2-methyltetrahydrofuran is 83%, and Isosorbide-5-Nitrae-pentanediol carbonic ether yield is 50%;
Two, transesterification reaction
Adopt the coprecipitation method of embodiment 1 and pickling process to obtain metal-rare earth oxide compound composite catalyst, the mass content wherein controlling each oxide compound in described composite catalyst is respectively: zinc oxide 70%, aluminum oxide 15%, tin protoxide 14%, lanthanum trioxide 1%; Described composite catalyst uses hydrogen reducing before use;
Isosorbide-5-Nitrae-pentanediol carbonic ether and isopropylcarbinol are joined in tubular type transesterification reactor, then add the metal-rare earth oxide compound composite catalyst of above-mentioned preparation, carry out transesterification reaction after mixing, reaction product is through distillation i.e. obtained carbonic acid diisobutyl ester; Wherein, 1, the mol ratio 1:4 of 4-pentanediol carbonic ether and isopropylcarbinol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and isopropylcarbinol gross weight is 0.2:100, the temperature controlling transesterification reaction is 120 DEG C, and absolute pressure is 4MPa, and the reaction times is 60 minutes; The transformation efficiency of Isosorbide-5-Nitrae in transesterification reaction-pentanediol carbonic ether is 98%, and the yield of carbonic acid diisobutyl ester is 92%.
Embodiment 5
One, cycloaddition reaction
Adopt the co-precipitation of embodiment 1 and the obtained magnesium-zincium-rare earth oxide compound composite catalyst containing magnesium oxide, zinc oxide and lanthanum trioxide of pickling process, wherein the mol ratio of controlled oxidization magnesium and zinc oxide is 3:1, and control that the weight of lanthanum trioxide in composite catalyst accounts for whole composite catalyst weight 0.6%; Described composite catalyst uses hydrogen reducing before use;
After 2-methyltetrahydrofuran embodiment 1 prepared and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst join reactor according to the weight proportion of 100:0.1, open heating unit and make the homo(io)thermism of reactor at 100 DEG C, in reactor, pass into excessive CO
2, and to control absolute pressure in reactor constant be 10MPa, the 2-methyltetrahydrofuran in reactor and CO
2carry out cycloaddition reaction 60 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO passed into
2mol ratio be 1:8, in cycloaddition reaction, the transformation efficiency of 2-methyltetrahydrofuran is 85%, and Isosorbide-5-Nitrae-pentanediol carbonic ether yield is 52%;
Two, transesterification reaction
Isosorbide-5-Nitrae-pentanediol carbonic ether and ring propyl alcohol are joined in tubular type transesterification reactor, then add the metal-rare earth oxide compound composite catalyst of embodiment 1 preparation, carry out transesterification reaction after mixing, reaction product is through distillation i.e. obtained carbonic acid two ring propyl ester; Wherein, 1, the mol ratio 1:15 of 4-pentanediol carbonic ether and ring propyl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and ring propyl alcohol gross weight is 2:100, the temperature controlling transesterification reaction is 140 DEG C, and absolute pressure is 0.5MPa, and the reaction times is 120 minutes; The transformation efficiency of Isosorbide-5-Nitrae in transesterification reaction-pentanediol carbonic ether is 99%, and the yield of carbonic acid two ring propyl ester is 93%.
Embodiment 6
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing methyl alcohol and ethanol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 3-5; Wherein, 1, mol ratio 1:2:2 between 4-pentanediol carbonic ether, methyl alcohol, ethanol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature controlling transesterification reaction is 150 DEG C, and absolute pressure is 2MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, underpressure distillation is carried out at 200 DEG C, collect the cut of 80-90 DEG C, obtained liquid fuel (the i.e. dialkyl carbonate ester mixture of carbonatoms≤5, its volumn concentration is 100%), described liquid fuel can be used as formulated gasolines and uses, and quality measurements is in table 1.
Embodiment 7
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, n-propyl alcohol, propyl carbinol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-9; Wherein, 1, mol ratio 6:10:1:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, propyl carbinol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature controlling transesterification reaction is 160 DEG C, and absolute pressure is 3MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect the cut of 80-90 DEG C, the dialkyl carbonate ester mixture of obtained carbonatoms≤5; Collect the cut of 125-135 DEG C, obtained carbonatoms is the dialkyl carbonate ester mixture of 6-9, merges the cut i.e. obtained liquid fuel of above-mentioned 80-90 DEG C and 125-135 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 67%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 33%; Described liquid fuel can be used as formulated gasolines and uses, and quality measurements is in table 1.
Embodiment 8
By prepared by embodiment 31,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, ring propyl alcohol, isopropylcarbinol, the metal-rare earth oxide compound composite catalyst adding embodiment 3 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-9; Wherein, 1, mol ratio 9:18:1:1 between 4-pentanediol carbonic ether, ethanol, ring propyl alcohol, isopropylcarbinol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature controlling transesterification reaction is 160 DEG C, and absolute pressure is 3MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect the cut of 80-90 DEG C and the cut of 125-135 DEG C, obtained liquid fuel; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 80%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 20%; Described liquid fuel can be used as formulated gasolines and uses, and quality measurements is in table 1.
Embodiment 9
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, n-propyl alcohol, Pentyl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-11; Wherein, 1, mol ratio 5:10:3:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, Pentyl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature controlling transesterification reaction is 155 DEG C, and absolute pressure is 2.5MPa, reaction times is 40 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect the cut of 80-90 DEG C, the dialkyl carbonate mixture of obtained carbonatoms≤5; Collect the cut of 125-135 DEG C, obtained carbonatoms is the dialkyl carbonate mixture of 6-9; Collect the cut of 180-200 DEG C, obtained carbonatoms is the dialkyl carbonate mixture of 10-17; Merge above-mentioned 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 20%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as allotment diesel oil and uses, and quality measurements is in table 2.
Embodiment 10
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, Virahol, furfuryl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-11; Wherein, 1, mol ratio 10:20:5:3 between 4-pentanediol carbonic ether, ethanol, Virahol, furfuryl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.2:100, and the temperature controlling transesterification reaction is 180 DEG C, and absolute pressure is 4MPa, reaction times is 15 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 20%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 50%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 30%, it can be used as allotment diesel oil and uses, and quality measurements is in table 2.
Embodiment 11
By prepared by embodiment 41,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, isopropylcarbinol, n-Octanol, furfuryl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 4 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-17; Wherein, 1, mol ratio 10:18:6:1.5:1.5 between 4-pentanediol carbonic ether, ethanol, isopropylcarbinol, n-Octanol, furfuryl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.8:100, and the temperature controlling transesterification reaction is 160 DEG C, and absolute pressure is 3MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 10%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 30%, it can be used as allotment diesel oil and uses, and quality measurements is in table 2.
Embodiment 12
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, cyclobutanol, n-hexyl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-13; Wherein, 1, mol ratio 5:15:2:1 between 4-pentanediol carbonic ether, ethanol, cyclobutanol, n-hexyl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.2:100, and the temperature controlling transesterification reaction is 150 DEG C, and absolute pressure is 3MPa, reaction times is 20 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 40%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as allotment aviation kerosene and uses, and its quality measurements is in table 3.
Embodiment 13
By prepared by embodiment 31,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, n-propyl alcohol, primary isoamyl alcohol, furfuryl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 3 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-11; Wherein, 1, mol ratio 10:20:6:1:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, primary isoamyl alcohol, furfuryl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature controlling transesterification reaction is 160 DEG C, and absolute pressure is 3MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 20%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as allotment aviation kerosene and uses, and its quality measurements is in table 3.
Embodiment 14
By prepared by embodiment 11,4-pentanediol carbonic ether joins in tubular type transesterification reactor with the alcohol mixture containing ethanol, ring propyl alcohol, isooctyl alcohol, furfuryl alcohol, the metal-rare earth oxide compound composite catalyst adding embodiment 1 preparation again carries out transesterification reaction, i.e. the mixed carbonic acid dialkyl of obtained carbonatoms 5-17; Wherein, 1, mol ratio 10:18:5:1:1 between 4-pentanediol carbonic ether, ethanol, ring propyl alcohol, isooctyl alcohol, furfuryl alcohol, the weight and 1 of metal-rare earth oxide compound composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature controlling transesterification reaction is 160 DEG C, and absolute pressure is 3MPa, reaction times is 30 minutes, i.e. obtained mixed carbonic acid dialkyl;
By the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, at 200 DEG C, carry out underpressure distillation, collect 80-90 DEG C, the cut i.e. obtained liquid fuel of 125-135 DEG C and 180-200 DEG C; In described liquid fuel, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 30%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 50%, carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as allotment aviation kerosene and uses, and its quality measurements is in table 3.
Table 1 is as the quality measurements of the mixed carbonic acid dialkyl of formulated gasolines
Table 2 is as the quality measurements of the mixed carbonic acid dialkyl of allotment diesel oil
Table 3 is as the quality measurements of the mixed carbonic acid dialkyl of allotment aviation kerosene
| Project | ASTM D190 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Test method |
| Calorific value MJ/kg | ≥43.5 | 45.8 | 46.5 | 46.9 | D 4529 |
| Cetane value | ≥80.7 | 91 | 91 | 92 | D2700 |
| Density g/cm 3 | Report | 0.828 | 0.832 | 0.835 | D 1298 |
| Sulphur content % | ≤0.05 | 0.02 | 0.03 | 0.02 | D 1266 |
| Flash-point (remaining silent) DEG C | ≥55 | 81 | 81 | 80 | GB/T261 |
| Condensation point DEG C | ≤-58 | -76 | -73 | -71 | D 2386 |
| Oxidation stability (110 DEG C) h | ≥25 | 28 | 32 | 31 | EN14112 |
| Copper corrosion (50 DEG C, 3h -1) level | 1 | 1 | 1 | 1 | D 130 |
Claims (8)
1. be the method that initial feed produces as the dialkyl carbonate of liquid fuel with agriculture and forestry organic waste material, it is characterized in that, comprise the step that following order is carried out:
A) be that initial feed obtains 2-methyltetrahydrofuran with agriculture and forestry organic waste material;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, obtained structural formula is
cyclic carbonate;
C) by structural formula be
cyclic carbonate and monohydroxy-alcohol carry out transesterification reaction, the obtained dialkyl carbonate as liquid fuel;
Wherein: described cycloaddition reaction is carried out under the effect of magnesium-zincium-rare earth oxide compound composite catalyst, described magnesium-zincium-rare earth oxide compound composite catalyst comprises magnesium oxide, zinc oxide and rare earth oxide, wherein the mol ratio of magnesium oxide and zinc oxide is 1-4:1, and the mass percentage of rare earth oxide in magnesium-zincium-rare earth oxide compound composite catalyst is 0.1-1%;
Wherein, when described liquid fuel is used as gasoline or gasoline components, the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 is 60-100%, and carbonatoms is the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 0-40%.
2. the method for claim 1, it is characterized in that, in described cycloaddition reaction, the mol ratio of 2-methyltetrahydrofuran and carbonic acid gas is 1:1-20, and the weight proportion of described magnesium-zincium-rare earth oxide compound composite catalyst and 2-methyltetrahydrofuran is 0.1-5:100.
3. method as claimed in claim 2, it is characterized in that, the temperature of described cycloaddition reaction is 80-150 DEG C, and reaction absolute pressure is 2-10MPa, and the reaction times is 5-120 minute.
4. the method for claim 1, is characterized in that, described monohydroxy-alcohol is selected from C1-C8 straight chain alcohol, C3-C8 branched-chain alcoho, C3-C8 cyclic alcohol, mixture with one or more in the alcohol of furan nucleus.
5. the method for claim 1, it is characterized in that, described transesterification reaction is carried out under the effect of metal-rare earth oxide compound composite catalyst, described metal-rare earth oxide compound composite catalyst comprises metal oxide and rare earth oxide, and wherein the weight proportion of metal oxide and rare earth oxide is (90-99): (1-10).
6. method as claimed in claim 5, is characterized in that, described metal oxide be selected from zinc oxide, aluminum oxide, tin protoxide one or more, described rare earth oxide be selected from lanthanum trioxide, cerium oxide one or more.
7. method as claimed in claim 5, it is characterized in that, the mol ratio of described cyclic carbonate and monohydroxy-alcohol is 1:1-20, and the described weight of metal-rare earth oxide compound composite catalyst and the proportioning of described cyclic carbonate and monohydroxy-alcohol gross weight are 0.1-5:100.
8. method as claimed in claim 5, it is characterized in that, the temperature of described transesterification reaction is 120-180 DEG C, and reaction absolute pressure is 0.1-4MPa, and the reaction times is 5-120 minute.
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| CN102464587A (en) * | 2010-11-16 | 2012-05-23 | 中国科学院兰州化学物理研究所 | Method for preparing small molecular carbonated dialkyl ester through ester exchange |
| CN102531907A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Method for synthesizing dipropyl carbonate |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
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| CN102464587A (en) * | 2010-11-16 | 2012-05-23 | 中国科学院兰州化学物理研究所 | Method for preparing small molecular carbonated dialkyl ester through ester exchange |
| CN102531907A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Method for synthesizing dipropyl carbonate |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
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