CN103058862A - New method for producing dialkyl ester carbonate by using forestry and agricultural residues as initial raw materials - Google Patents
New method for producing dialkyl ester carbonate by using forestry and agricultural residues as initial raw materials Download PDFInfo
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Abstract
The invention discloses a method for producing dialkyl ester carbonate by using forestry and agricultural residues as initial raw materials. The method comprises the steps of: firstly, preparing 2-methyl tetrahydrofuran by using the forestry and agricultural residues as the initial raw materials; then performing cycloaddition reaction on the 2-methyl tetrahydrofuran and carbon dioxide to prepare a cyclic carbonate (namely, 1,4-pentanediol carbonic ester); and then performing ester exchange reaction on the cyclic carbonate and monohydric alcohol to prepare the dialkyl ester carbonate. As the low-cost forestry and agricultural residues and industrial waste gas carbon dioxide are used as the raw materials, and 1,4-pentanediol with high additional value is also produced in the production process, the method for producing the dialkyl ester carbonate by using the forestry and agricultural residues as the initial raw materials not only saves production cost, and reduces environment pollution, but also provides a new path for the efficient and comprehensive utilization of the forestry and agricultural residues and the industrial production of the dialkyl ester carbonate, and has remarkable economic and social benefits.
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 application thereof of producing dialkyl carbonate take agriculture and forestry organic waste material as initial feed.
Background technology
Dialkyl carbonate is also referred to as dialkyl carbonate, contains alkoxyl group and carbonyl in its molecule, can react with multiple alcohol, phenol, amine and ester, and be very widely organic compound of a kind of purposes, have higher industrial application value and market outlook.The preparation method of dialkyl carbonate mainly comprises phosgene synthesis method, oxidative carbonylation, ester-interchange method etc.Traditional Industrialization is made dialkyl carbonate and is generally adopted the phosgene synthesis method, yet phosgene and intermediate are the hypertoxicity material in the standby process of this legal system, and by product has severe corrosive, and environmental pollution is serious, thereby is replaced by oxidative carbonylation of methanol method gradually.
Granted publication number discloses a kind of method of making dialkyl carbonate for the Chinese invention patent of CN101234965B, alcohol compound, carbon monoxide, and the condition that exists of oxygen under, the catalysis system that uses at least a promotor with nitrogen-atoms of organic halogenation metal catalyst collocation to form, carry out the liquid-phase oxidative carbonylation reaction and generate dialkyl carbonate, this method has reduced the corrodibility to reactor to a certain extent, yet exists also that catalyzer is expensive, the defective such as transformation efficiency and selectivity are limited.
Ester-exchange technology is that a kind of ester and another kind of lipid acid or alcohol or ester follow the acyl group exchange to generate the technology of new ester under certain condition, has that catalyzer is extensive, reaction conditions is gentle, is easy to control, the advantages such as transformation efficiency is high, good product quality.Be that the Chinese invention patent of CN1699328A discloses a kind of method for preparing dialkyl carbonate such as publication number, adopt cleaning, green chemical industry material carbon dimethyl phthalate and aliphat single-alcohol nontoxic, environmental protection to react synthesis of dialkyl carbonates, this method reaction conditions is gentle, particularly can utilize reproducible biomass resource to produce, and the production process three-waste free pollution.Yet above-mentioned esterification adopts alcoholate or the oxyhydroxide of basic metal or alkaline-earth metal, and 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, can also adopt cyclic carbonate to prepare dialkyl carbonate as starting raw material.Be the method that the Chinese invention patent of CN 102464587A discloses a kind of preparing small molecular carbonated dialkyl ester through ester exchange such as publication number, it adopts cyclic carbonate (such as NSC 11801, propylene carbonate, glycerol carbonate) and small molecular alcohol is raw material, in the presence of catalyzer, reaction preparation small molecules dialkyl carbonate under normal pressure or the reduced pressure.This method has that reaction conditions is gentle, 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 is the method for the production dialkyl carbonate that problem provides with low cost, economic worth is high of above-mentioned prior art existence, the inventive method is take the agriculture and forestry organic waste material of cheapness and industrial gaseous waste carbonic acid gas as raw material, production technique also the by-product high added value 1, the 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 of producing dialkyl carbonate take agriculture and forestry organic waste material as initial feed, comprises following in sequence step:
A) make the 2-methyltetrahydrofuran take agriculture and forestry organic waste material as initial feed;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, make structural formula and be
Cyclic carbonate;
C) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, make 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) can adopt conventional preparation method of the prior art to make the 2-methyltetrahydrofuran take agriculture and forestry organic waste material as initial feed in, be that the Chinese invention patent of CN102558106A discloses a kind of method of utilizing abandoned biomass to prepare the 2-methyltetrahydrofuran such as publication number, comprise the steps:
A1) abandoned biomass is carried out acid hydrolytic reaction, make furfural and levulinic acid;
A2) furfural and hydrogen are carried out hydrogenation, make the 2-methyltetrahydrofuran.
Wherein, described steps A 1) adopt the vitriol oil that biomass slurry is carried out acid hydrolysis in, described acid hydrolytic reaction carries out in two steps, and wherein the acid-hydrolyzed temperature of the first step is 200-260 ℃, 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 ℃, and absolute pressure is 1.0-1.6Mpa, and the reaction times is 15-20 minute.
Wherein, hydrogenation carries out in two steps described steps A 2); The mol ratio of hydrogen and furfural is 40-60:1 in the first step hydrogenation, and the mass space velocity of hydrogen is 10-20h
-1, the temperature of reaction is 180-240 ℃, and absolute pressure is 1-4MPa, and the hydrogen residence time is 1-3min; The mol ratio of hydrogen and furfural is 40-60:1 in the second step hydrogenation, and the mass space velocity of hydrogen is 10-20h
-1, the temperature of reaction is 190-210 ℃, 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 quality percentage composition of cupric oxide is 40-60%, the quality percentage composition of chromium sesquioxide is 30-40%, the quality percentage composition of cerium dioxide is 5-10%, and the quality percentage composition 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 quality percentage composition of nickel oxide is 60-80%, and the quality percentage composition of aluminium sesquioxide is 20-40%.
Wherein, described step B) cycloaddition reaction is carried out under the effect of magnesium-zincium-rare earth oxide compound composite catalyst in, 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 1-3:1,1.5:1 more preferably, the quality percentage composition 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, the cerium oxide.
Wherein, described magnesium-zincium-rare earth oxide compound composite catalyst adopts coprecipitation method and the pickling process of this area routine to prepare, namely adopt coprecipitation method to prepare magnesium oxide-zinc oxide composites, adopt again pickling process further composite rare-earth oxide on magnesium oxide-zinc oxide composites; Described magnesium-zincium-rare earth oxide compound composite catalyst is used first hydrogen reducing before use, particularly at 200 ℃ of lower reductase 12s-10 hour, and preferred 4-6 hour.
Particularly, the preparation method of described magnesium-zincium-rare earth oxide compound composite catalyst comprises the steps:
1) will contain the mixing solutions heating of magnesium nitrate and zinc nitrate after, to wherein adding precipitation agent, regulate the pH value, then be incubated aging, after filtration, make magnesium oxide-zinc oxide composites after the drying;
2) earth solution be impregnated on described magnesium oxide-zinc oxide composites, make magnesium-zincium-rare earth oxide compound composite catalyst after drying, the roasting.
Wherein, the concentration of mixing solutions described in the step 1) is preferably 1mol/L; The temperature of described heating is 40-60 ℃, is preferably 45 ℃; 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 ℃, is preferably 110 ℃, and be 8-24 hour time of drying, 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) time of dipping is 8-24 hour described in, is preferably 12 hours; The temperature of described drying is 100-150 ℃, is preferably 110 ℃, and be 2-5 hour time of drying, is preferably 3 hours; The temperature of described roasting is 400-600 ℃, is preferably 500 ℃, and roasting time is 2-5 hour, is preferably 3 hours.
Wherein, carbonic acid gas is excessive with respect to the 2-methyltetrahydrofuran in the described cycloaddition reaction; Particularly the mol ratio of 2-methyltetrahydrofuran and carbonic acid gas is 1:1-20 in the described cycloaddition reaction, 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 ℃, is preferably 110-130 ℃; The 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, monohydroxy-alcohol step C) is selected from C1-C8 straight chain alcohol, C3-C8 branched-chain alcoho, C3-C8 cyclic alcohol, with one or more the mixture 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 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 that mixes to carry out, generate the mixed carbonic acid dialkyl that contains symmetrical dialkyl carbonate and asymmetric carbonic acid dialkyl.
Wherein, described transesterification reaction is carried out under the effect of metal-rare earth oxide composite catalyst, described metal-rare earth oxide 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, the tin protoxide, and described rare earth oxide is selected from one or more in lanthanum trioxide, the cerium oxide.Described metal-rare earth oxide composite catalyst is used first hydrogen reducing before use, particularly at 200 ℃ of lower reductase 12s-10 hour, and preferred 4-6 hour.
Particularly, described metal oxide comprises zinc oxide, aluminum oxide and tin protoxide, and wherein the weight proportion between zinc oxide, aluminum oxide and the tin protoxide is (6-8): (1-2): (1-2); Described rare earth oxide comprises lanthanum trioxide and cerium oxide.
Wherein, described metal-rare earth oxide composite catalyst prepares by coprecipitation method and the pickling process of this area routine; Particularly, the preparation method of described metal-rare earth oxide composite catalyst comprises the steps:
A) in metal-nitrate solutions/mixed solution, add precipitation agent formation precipitation, again throw out is carried out drying or calcination process, make metal oxide;
B) described metal oxide is immersed rare earth nitrate solution, carry out again drying or calcination process, make metal-rare earth oxide composite catalyst.
Especially, described precipitation agent is carbonate solution, is preferably sodium carbonate solution, more preferably the sodium carbonate solution of 1mol/L; The temperature of described drying treatment is 100-150 ℃, is preferably 120 ℃, and the treatment time is 8-24 hour, is preferably 12 hours; The temperature of described calcination process is 400-600 ℃, is preferably 500 ℃, and the treatment time is 2-5 hour, is preferably 3 hours.
Wherein, monohydroxy-alcohol is excessive with respect to cyclic carbonate in the described transesterification reaction; 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 proportioning of the weight of described metal-rare earth oxide composite catalyst and cyclic carbonate and monohydroxy-alcohol gross weight is 0.1-5:100, is preferably 0.1-2:100, more preferably 0.1-1:100; The temperature of described transesterification reaction is 120-180 ℃, is preferably 150-160 ℃, and the reaction absolute pressure is 0.1-4MPa, is preferably 2-3MPa, and the reaction times is 5-120 minute, is preferably 5-30 minute, more preferably 20-30 minute.
Particularly, also comprise step D): described dialkyl carbonate is distilled processing, make liquid fuel.
Wherein, be 0.01-0.02MPa in absolute pressure, temperature is 180-220 ℃ described dialkyl carbonate carried out underpressure distillation, collects the cut of 80-90 ℃, 125-135 ℃ and 180-200 ℃, namely makes described liquid fuel.
Particularly, when carrying out underpressure distillation, collect 80-90 ℃ cut, make the dialkyl carbonate ester mixture of carbonatoms≤5; Collect 125-135 ℃ cut, making carbonatoms is the dialkyl carbonate ester mixture of 6-9; Collect 180-200 ℃ cut, making 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 following in sequence step:
A) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, make structural formula and be
Cyclic carbonate;
B) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, make liquid fuel.
Particularly, described 2-methyltetrahydrofuran is to make take agriculture and forestry organic waste material as initial feed.
The present invention provides a kind of preparation method of liquid fuel on the other hand, comprises following in sequence step:
A) make the 2-methyltetrahydrofuran take agriculture and forestry organic waste material as initial feed;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, make structural formula and be
Cyclic carbonate;
C) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, make liquid fuel.
Wherein, the numerical range of relevant control parameter can be with reference to the correlation parameter numerical range in the above-mentioned preparation dialkyl carbonate method among the described liquid fuel preparation technology.
The present invention provides a kind of structural formula to be on the other hand
Cyclic carbonate.
The present invention provides a kind of structural formula to be on the other hand
The application of cyclic carbonate on prepare liquid fuel, wherein described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, namely make described liquid fuel.
The present invention provides the application on the dialkyl carbonate liquid fuel within of a kind of aforesaid method preparation on the other hand, for example as gasoline or gasoline component, 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 that structural formula is
Dialkyl carbonate, wherein R and R ' are identical or different, and R, R ' be selected from the C1-C8 straight chained alkyl, C3-C8 branched-chain alkyl, C3-C8 cycloalkyl or with the alkyl of furan nucleus.
Particularly, R, R ' are preferably ethyl, propyl group, butyl, amyl group, octyl group, sec.-propyl, isobutyl-, cyclopropyl, cyclobutyl, furfuryl alcohol base.
Wherein, when described liquid fuel was used as gasoline or gasoline component, wherein the cumulative volume percentage composition of the dialkyl carbonate of carbonatoms≤5 was 60-100%, and carbonatoms is that 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 that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40-60%, and carbonatoms is that 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 that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40-60%, and carbonatoms is that 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 esters that utilize the aforesaid method preparation on the other hand, and its structural formula is:
Particularly, can also adopt methylcarbonate and furfuryl alcohol to carry out transesterification reaction and make described carbonic acid two furfuryl alcohol esters, described transesterification reaction is carried out under the condition that above-mentioned metal-rare earth oxide composite catalyst exists.Wherein, the mol ratio of methylcarbonate and furfuryl alcohol is 1:1-20 in the described transesterification reaction, is preferably 1:2-8; The temperature of described transesterification reaction is 100-300 ℃, is preferably 120-200 ℃; 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 the transformation efficiency of methylcarbonate 〉=85% in the described transesterification reaction, preferred 〉=95%, the yield of carbonic acid two furfuryl alcohol esters 〉=80%, preferred 〉=90%.
The present invention provides the application on a kind of above-mentioned carbonic acid two furfuryl alcohol ester liquid fuel withins, lubricating oil and the engineering plastics on the other hand.
Wherein, when described carbonic acid two furfuryl alcohol esters are applied to liquid fuel, have 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 can also as liquid fuel additive, when adding in gasoline or the diesel oil, 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 esters are applied to lubricating oil, performance and other bigh carbon alcohol carbonate class lubricating oil are similar, have low frictional resistance, modest viscosity, oxidation and heat-resistant quality good, good with the rubber packing material compatibleness, resistance to wear, automatically cleaning, the feature such as corrodibility is 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 esters are applied to engineering plastics, can be used as the engineering plastics monomer and prepare polycarbonate, the carbonic ether optical transparence of its preparation is good, excellent in cushion effect, and have characteristics such as good thermostability, creep resistant, winter resistance, electrical insulating property and flame retardant resistance, can be widely used in the association areas such as building material industry, car industry, medicine equipment, aerospace, packing, electronic apparatus, optical lens, also can be used for the 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 esters.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 esters.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 esters.Particularly, described engineering plastics are polycarbonate.
Compared with prior art, the present invention has the following advantages:
1, the present invention is take the agriculture and forestry organic waste material of cheapness and industrial gaseous waste carbonic acid gas as the raw material production dialkyl carbonate, production technique also the by-product high added value 1, the 4-pentanediol, not only save production cost, reduced environmental pollution, also the high-efficiency comprehensive utilization for suitability for industrialized production dialkyl carbonate and agriculture and forestry organic waste material provides new way, has 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 large-scale industrialization production; Particularly adopt metal-rare earth oxide composite catalyst catalyzed transesterification, not only speed of reaction is fast, and transformation efficiency, selectivity and product yield are high;
3, the dialkyl carbonate of the present invention's preparation can be applicable to biological liquid fuel, have the advantages such as nontoxic, biodegradable, it is better than the fossil base liquid fuel at aspects such as oilness, emission performance, noise reduction, volatility, security, environment friendly, is better than fatty acid methyl ester class and alcohol fuel class biological liquid fuel at aspects such as low temperature properties, sealing material consistency, heat and oxidation stability, corrodibility, prices.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, these embodiment only are exemplary, scope of the present invention are not consisted of any restriction.It will be understood by those skilled in the art that lower without departing from the spirit and scope of the present invention and can make amendment or replace the details of technical solution of the present invention and form, but these modifications and replacing all fall within the scope of protection of the present invention.
Embodiment 1
One, preparation 2-methyltetrahydrofuran
Add tap water after soybean stalk pulverized, make water ratio and be 65% biomass slurry; Described biomass slurry and the vitriol oil are sent in the reactor, under 200 ℃, 2.2Mpa, carry out the first step acid hydrolytic reaction, react and obtain the first step acid hydrolysis products after 20 minutes; The first step acid hydrolysis products enters in the second reactor after processing through flash distillation, carries out the second step acid hydrolytic reaction under 180 ℃, 1.4Mpa, reacts to obtain second step acid hydrolytic reaction product after 15 minutes; Through refining, namely obtain mass percentage content and be 99.2% furfural;
Copper chromium cerium lanthanum composite catalyst (is wherein contained cupric oxide 50wt%, chromium sesquioxide 40wt%, cerium dioxide 5wt%, lanthanum sesquioxide 5wt%) and furfural add the first hydrogenation reactor, in reactor, pass into hydrogen, under 220 ℃, 3MPa, carry out the first step hydrogenation, make the 2-methyl furan; 2-methyl furan and nickel aluminium composite catalyst (are wherein contained nickel oxide 70wt%, aluminium sesquioxide 30wt%) joins in the second hydrogenation reactor, carry out the second step hydrogenation under 200 ℃, 6MPa, reaction product obtains the quality percentage composition and is 96% 2-methyltetrahydrofuran after refining;
Two, cycloaddition reaction
1, preparation magnesium-zincium-rare earth oxide compound composite catalyst
Adopt coprecipitation method, the hybrid metal solution stirring that will contain magnesium nitrate and zinc nitrate is warming up to 45 ℃, then to wherein slowly adding Na
2CO
3Solution, control Na
2CO
3The joining day of solution is about 30min, regulates pH value to 8-9, in 45 ℃ of lower aging 2h, after leaving standstill, filter, washing, in 110 ℃ of dry 12h, makes magnesium oxide-zinc oxide composites, and wherein the mol ratio of magnesium oxide and zinc oxide is 1.5:1;
Adopt pickling process, the mixed rare earth solution that will contain lanthanum nitrate and cerous nitrate is immersed on above-mentioned magnesium oxide-zinc oxide composites, flood after 12 hours in 110 ℃ of dry 3h, 500 ℃ of lower roasting 3h, namely make magnesium-zincium-rare earth oxide compound composite catalyst, wherein the mol ratio of lanthanum element and Ce elements is 1:1;
Comprise magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide in the composite catalyst that makes, 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 control lanthanum trioxide and cerium oxide accounts for 0.8% of whole composite catalyst weight; Described magnesium-zincium-rare earth oxide compound composite catalyst reduced 6 hours under 200 ℃ with hydrogen before use;
2, cycloaddition reaction
After the magnesium of 2-methyltetrahydrofuran and above-mentioned preparation-zincium-rare earth oxide compound composite catalyst joined reactor according to the weight proportion of 100:0.5, open homo(io)thermism that heating unit makes reactor at 120 ℃, in reactor, pass into excessive CO
2, and the absolute pressure of control in the reactor constant be 8.0MPa, 2-methyltetrahydrofuran and CO in the reactor
2Carry out cycloaddition reaction and obtain reaction product after 30 minutes, namely make Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO that passes into
2Mol ratio be 1:10, the transformation efficiency of 2-methyltetrahydrofuran is 90% in the cycloaddition reaction, 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, preparation metal-rare earth oxide composite catalyst
Adopt coprecipitation method, the inferior tin of zinc nitrate, aluminum nitrate and nitric acid is dissolved in the distilled water, after mixing, make zinc-aluminium tin mixing solutions; Under agitation condition, above-mentioned zinc-aluminium tin mixing solutions and sodium carbonate solution and drip are entered to be equipped with in the container of 60 ℃ of distilled water, form titrating solution; The rate of addition of regulating zinc-aluminium tin mixing solutions and sodium carbonate solution is take the pH value that keeps titrating solution as 7-8; After titration finishes, with the aging 2h of titrating solution precipitation, then wash, suction filtration, after 12 hours, in 500 ℃ of roastings 3 hours, make ZnO-Al in 120 ℃ of dryings again
2O
3-SnO
2Metal catalyst;
Adopt pickling process, with lanthanum nitrate (La (NO
3)
36H
2O) and cerous nitrate (Ce (NO
3)
36H
2O) be dissolved in the distilled water, make mixed solution of rare earth; Utilize pickling process, with above-mentioned ZnO-Al
2O
3-SnO
2Immerse in the mixed solution of rare earth in the metal catalyst, obtain dip compound; Dip compound in 120 ℃ of dryings 12 hours, again in 500 ℃ of roastings 3 hours, is pulverized, screening 20-40 order, made metal-rare earth oxide composite catalyst;
The quality percentage composition of each oxide compound is respectively in the metal that makes-rare earth oxide composite catalyst: zinc oxide: 60%, and aluminum oxide: 20%, tin protoxide: 15%, lanthanum trioxide: 2.5%, cerium oxide: 2.5%; Metal-rare earth oxide composite catalyst reduced 6 hours under 200 ℃ with hydrogen before use;
2, transesterification reaction
Isosorbide-5-Nitrae-pentanediol carbonic ether and furfuryl alcohol are joined in the tubular type transesterification reactor, add the metal of above-mentioned preparation-rare earth oxide composite catalyst again, carry out transesterification reaction after mixing, reaction product namely makes carbonic acid two furfuryl alcohol esters through distillation; 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 composite catalyst and Isosorbide-5-Nitrae-pentanediol carbonic ether and furfuryl alcohol gross weight is 0.5:100, and the temperature of control transesterification reaction is 160 ℃, absolute pressure is 3MPa, and the reaction times is 20 minutes; The transformation efficiency of Isosorbide-5-Nitrae in the transesterification reaction-pentanediol carbonic ether is 100%, and the yield of carbonic acid two furfuryl alcohol esters is 92%;
The reaction formula of described transesterification reaction is as follows:
Adopt the D4529 method to measure calorific value, adopt the D2700 method to measure cetane value, adopt GB/T261 to measure close flash point, kinematic viscosity under employing GB/T265 measures 40 ℃, adopt GB/T3535 to measure pour point, adopt the EN14112 method to measure 110 ℃ of lower oxidation stabilities, adopt the D130 method to measure 50 ℃ of lower copper corrosion performances, adopt SH/T0305 method mensuration seal compatibility energy index;
The calorific value of carbonic acid two furfuryl alcohol esters of preparation is 39.8MJ/kg, and cetane value is 97, and close flash point is 158 ℃, and the kinematic viscosity under 40 ℃ is 22.6mm
2/ s, pour point are-21 ℃, and the oxidation stability under 110 ℃ is 30, and copper corrosion is 1 grade, and seal compatibility can index be 4.
Embodiment 2
Methylcarbonate and furfuryl alcohol are joined in the tubular type transesterification reactor, add the metal of embodiment 1 preparation-rare earth oxide composite catalyst again, carry out transesterification reaction after mixing, reaction product namely makes carbonic acid two furfuryl alcohol esters through distillation; Wherein, the mol ratio 1:6 of methylcarbonate and furfuryl alcohol, the proportioning of the weight of metal-rare earth oxide composite catalyst and methylcarbonate and furfuryl alcohol gross weight is 0.5:100, the temperature of control transesterification reaction is 160 ℃, absolute pressure is 3MPa, and the reaction times is 20 minutes; The methylcarbonate transformation efficiency is 95% in the transesterification reaction, and the yield of carbonic acid two furfuryl alcohol esters is 90%;
The calorific value of carbonic acid two furfuryl alcohol esters of preparation is 39.6MJ/kg, and cetane value is 97, and close flash point is 156 ℃, and the kinematic viscosity under 40 ℃ is 22.8mm
2/ s, pour point are-20 ℃, and the oxidation stability under 110 ℃ is 30, and copper corrosion is 1 grade, and seal compatibility can index be 4.
Embodiment 3
One, cycloaddition reaction
The magnesium that adopts the co-precipitation of embodiment 1 and pickling process to make to contain magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide-zincium-rare earth oxide compound composite catalyst, the mol ratio of wherein controlling magnesium oxide and zinc oxide is 1:1, the mol ratio of lanthanum element and Ce elements is 2:1, and the gross weight of lanthanum trioxide and cerium oxide accounts for 1% of whole composite catalyst weight in the control composite catalyst; Described composite catalyst is used hydrogen reducing before use;
After the 2-methyltetrahydrofuran of embodiment 1 preparation and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst joined reactor according to the weight proportion of 100:1, open homo(io)thermism that heating unit makes reactor at 80 ℃, in reactor, pass into excessive CO
2, and the absolute pressure of control in the reactor constant be 6.0MPa, 2-methyltetrahydrofuran and CO in the reactor
2Carried out cycloaddition reaction 20 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO that passes into
2Mol ratio be 1:15, the transformation efficiency of 2-methyltetrahydrofuran is 86% in the cycloaddition reaction, Isosorbide-5-Nitrae-pentanediol carbonic ether yield is 54%;
Two, transesterification reaction
Adopt coprecipitation method and the pickling process of embodiment 1 to make metal-rare earth oxide composite catalyst, the mass content of wherein controlling each oxide compound in the described composite catalyst is respectively: zinc oxide 80%, aluminum oxide 10%, lanthanum trioxide 5%, cerium oxide 5%; Described composite catalyst is used hydrogen reducing before use;
Isosorbide-5-Nitrae-pentanediol carbonic ether and ethanol are joined in the tubular type transesterification reactor, add the metal of above-mentioned preparation-rare earth oxide composite catalyst again, carry out transesterification reaction after mixing, reaction product namely makes diethyl carbonate through distillation; 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 composite catalyst and Isosorbide-5-Nitrae-pentanediol carbonic ether and total ethanol weight is 1:100, and the temperature of control transesterification reaction is 180 ℃, absolute pressure is 2MPa, and the reaction times is 10 minutes; The transformation efficiency of Isosorbide-5-Nitrae in the transesterification reaction-pentanediol carbonic ether is 100%, and the yield of diethyl carbonate is 95%.
Embodiment 4
One, cycloaddition reaction
The magnesium that adopts the co-precipitation of embodiment 1 and pickling process to make to contain magnesium oxide, zinc oxide, lanthanum trioxide and cerium oxide-zincium-rare earth oxide compound composite catalyst, the mol ratio of wherein controlling magnesium oxide and zinc oxide is 2:1, the mol ratio of lanthanum element and Ce elements is 3:1, and the gross weight of lanthanum trioxide and cerium oxide accounts for 0.2% of whole composite catalyst weight in the control composite catalyst; Described composite catalyst is used hydrogen reducing before use;
After the 2-methyltetrahydrofuran of embodiment 1 preparation and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst joined reactor according to the weight proportion of 100:3, open homo(io)thermism that heating unit makes reactor at 150 ℃, in reactor, pass into excessive CO
2, and the absolute pressure of control in the reactor constant be 2MPa, 2-methyltetrahydrofuran and CO in the reactor
2Carried out cycloaddition reaction 100 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO that passes into
2Mol ratio be 1:3, the transformation efficiency of 2-methyltetrahydrofuran is 83% in the cycloaddition reaction, Isosorbide-5-Nitrae-pentanediol carbonic ether yield is 50%;
Two, transesterification reaction
Adopt coprecipitation method and the pickling process of embodiment 1 to make metal-rare earth oxide composite catalyst, the mass content of wherein controlling each oxide compound in the described composite catalyst is respectively: zinc oxide 70%, aluminum oxide 15%, tin protoxide 14%, lanthanum trioxide 1%; Described composite catalyst is used hydrogen reducing before use;
Isosorbide-5-Nitrae-pentanediol carbonic ether and isopropylcarbinol are joined in the tubular type transesterification reactor, add the metal of above-mentioned preparation-rare earth oxide composite catalyst again, carry out transesterification reaction after mixing, reaction product namely makes the carbonic acid diisobutyl ester through distillation; Wherein, 1, the mol ratio 1:4 of 4-pentanediol carbonic ether and isopropylcarbinol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and isopropylcarbinol gross weight is 0.2:100, the temperature of control transesterification reaction is 120 ℃, and absolute pressure is 4MPa, and the reaction times is 60 minutes; The transformation efficiency of Isosorbide-5-Nitrae in the transesterification reaction-pentanediol carbonic ether is 98%, and the yield of carbonic acid diisobutyl ester is 92%.
Embodiment 5
One, cycloaddition reaction
The magnesium that adopts the co-precipitation of embodiment 1 and pickling process to make to contain magnesium oxide, zinc oxide and lanthanum trioxide-zincium-rare earth oxide compound composite catalyst, the mol ratio of wherein controlling magnesium oxide and zinc oxide is 3:1, and the weight of lanthanum trioxide accounts for 0.6% of whole composite catalyst weight in the control composite catalyst; Described composite catalyst is used hydrogen reducing before use;
After the 2-methyltetrahydrofuran of embodiment 1 preparation and above-mentioned magnesium-zincium-rare earth oxide compound composite catalyst joined reactor according to the weight proportion of 100:0.1, open homo(io)thermism that heating unit makes reactor at 100 ℃, in reactor, pass into excessive CO
2, and the absolute pressure of control in the reactor constant be 10MPa, 2-methyltetrahydrofuran and CO in the reactor
2Carried out cycloaddition reaction 60 minutes, reaction product obtains Isosorbide-5-Nitrae-pentanediol carbonic ether through distillation; Wherein 2-methyltetrahydrofuran and the CO that passes into
2Mol ratio be 1:8, the transformation efficiency of 2-methyltetrahydrofuran is 85% in the cycloaddition reaction, 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 the tubular type transesterification reactor, add the metal of embodiment 1 preparation-rare earth oxide composite catalyst again, carry out transesterification reaction after mixing, reaction product namely makes carbonic acid two ring propyl ester through distillation; Wherein, 1,4-pentanediol carbonic ether and the mol ratio 1:15 that encircles propyl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and ring propyl alcohol gross weight is 2:100, the temperature of control transesterification reaction is 140 ℃, and absolute pressure is 0.5MPa, and the reaction times is 120 minutes; The transformation efficiency of Isosorbide-5-Nitrae in the transesterification reaction-pentanediol carbonic ether is 99%, and the yield of carbonic acid two ring propyl ester is 93%.
Embodiment 6
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains methyl alcohol and ethanol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 3-5 again; Wherein, 1, mol ratio 1:2:2 between 4-pentanediol carbonic ether, methyl alcohol, the ethanol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature of control transesterification reaction is 150 ℃, and absolute pressure is 2MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
With the mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, carry out underpressure distillation under 200 ℃, collect 80-90 ℃ cut, making liquid fuel (is the dialkyl carbonate ester mixture of carbonatoms≤5, its volumn concentration is 100%), described liquid fuel can be used as allotment gasoline and uses, and quality examination the results are shown in Table 1.
Embodiment 7
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, n-propyl alcohol, propyl carbinol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-9 again; Wherein, 1, mol ratio 6:10:1:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, the propyl carbinol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature of control transesterification reaction is 160 ℃, and absolute pressure is 3MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, collect 80-90 ℃ cut, make the dialkyl carbonate ester mixture of carbonatoms≤5; Collect 125-135 ℃ cut, making carbonatoms is the dialkyl carbonate ester mixture of 6-9, and the cut that merges above-mentioned 80-90 ℃ and 125-135 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 67%, and carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 33%; Described liquid fuel can be used as allotment gasoline and uses, and quality examination the results are shown in Table 1.
Embodiment 8
With 1 of embodiment 3 preparations, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, ring propyl alcohol, isopropylcarbinol, adding the metal of embodiment 3 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-9 again; Wherein, 1, mol ratio 9:18:1:1 between 4-pentanediol carbonic ether, ethanol, ring propyl alcohol, the isopropylcarbinol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature of control transesterification reaction is 160 ℃, and absolute pressure is 3MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, collect 80-90 ℃ cut and 125-135 ℃ cut, make liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 80%, and carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 20%; Described liquid fuel can be used as allotment gasoline and uses, and quality examination the results are shown in Table 1.
Embodiment 9
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, n-propyl alcohol, Pentyl alcohol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-11 again; Wherein, 1, mol ratio 5:10:3:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, the Pentyl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature of control transesterification reaction is 155 ℃, and absolute pressure is 2.5MPa, reaction times is 40 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, collect 80-90 ℃ cut, make the dialkyl carbonate ester mixture of carbonatoms≤5; Collect 125-135 ℃ cut, making carbonatoms is the dialkyl carbonate ester mixture of 6-9; Collect 180-200 ℃ cut, making carbonatoms is the dialkyl carbonate ester mixture of 10-17; The cut that merges above-mentioned 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 20%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is that 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 examination the results are shown in Table 2.
Embodiment 10
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, Virahol, furfuryl alcohol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-11 again; Wherein, 1, mol ratio 10:20:5:3 between 4-pentanediol carbonic ether, ethanol, Virahol, the furfuryl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.2:100, and the temperature of control transesterification reaction is 180 ℃, and absolute pressure is 4MPa, reaction times is 15 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, and the cut of collecting 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 20%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 50%, carbonatoms is that 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 examination the results are shown in Table 2.
Embodiment 11
With 1 of embodiment 4 preparations, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, isopropylcarbinol, n-Octanol, furfuryl alcohol, adding the metal of embodiment 4 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-17 again; Wherein, 1, mol ratio 10:18:6:1.5:1.5 between 4-pentanediol carbonic ether, ethanol, isopropylcarbinol, n-Octanol, the furfuryl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.8:100, and the temperature of control transesterification reaction is 160 ℃, and absolute pressure is 3MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, and the cut of collecting 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 10%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is that 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 examination the results are shown in Table 2.
Embodiment 12
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, cyclobutanol, n-hexyl alcohol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-13 again; Wherein, 1, mol ratio 5:15:2:1 between 4-pentanediol carbonic ether, ethanol, cyclobutanol, the n-hexyl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.2:100, and the temperature of control transesterification reaction is 150 ℃, and absolute pressure is 3MPa, reaction times is 20 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, and the cut of collecting 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 40%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 40%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as the allotment aviation kerosene and uses, and its quality examination the results are shown in Table 3.
Embodiment 13
With 1 of embodiment 3 preparations, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, n-propyl alcohol, primary isoamyl alcohol, furfuryl alcohol, adding the metal of embodiment 3 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-11 again; Wherein, 1, mol ratio 10:20:6:1:1 between 4-pentanediol carbonic ether, ethanol, n-propyl alcohol, primary isoamyl alcohol, the furfuryl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 0.5:100, and the temperature of control transesterification reaction is 160 ℃, and absolute pressure is 3MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, and the cut of collecting 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 20%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 60%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as the allotment aviation kerosene and uses, and its quality examination the results are shown in Table 3.
Embodiment 14
With 1 of embodiment 1 preparation, 4-pentanediol carbonic ether joins in the tubular type transesterification reactor with the alcohol mixture that contains ethanol, ring propyl alcohol, isooctyl alcohol, furfuryl alcohol, adding the metal of embodiment 1 preparation-rare earth oxide composite catalyst carries out transesterification reaction, namely makes the mixed carbonic acid dialkyl of carbonatoms 5-17 again; Wherein, 1, mol ratio 10:18:5:1:1 between 4-pentanediol carbonic ether, ethanol, ring propyl alcohol, isooctyl alcohol, the furfuryl alcohol, the weight and 1 of metal-rare earth oxide composite catalyst, the proportioning of 4-pentanediol carbonic ether and alcohol mixture gross weight is 1:100, and the temperature of control transesterification reaction is 160 ℃, and absolute pressure is 3MPa, reaction times is 30 minutes, namely makes the mixed carbonic acid dialkyl;
The mixed carbonic acid dialkyl of above-mentioned preparation at 0.01MPa, is carried out underpressure distillation under 200 ℃, and the cut of collecting 80-90 ℃, 125-135 ℃ and 180-200 ℃ namely makes liquid fuel; The cumulative volume percentage composition of the dialkyl carbonate of carbonatoms in the described liquid fuel≤5 is 30%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 6-9 is 50%, carbonatoms is that the cumulative volume percentage composition of the dialkyl carbonate of 10-17 is 20%, it can be used as the allotment aviation kerosene and uses, and its quality examination the results are shown in Table 3.
Table 1 is as the quality examination result of the mixed carbonic acid dialkyl of allotment gasoline
Table 2 is as the quality examination result of the mixed carbonic acid dialkyl of allotment diesel oil
Table 3 is as the quality examination result 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) ℃ | ≥55 | 81 | 81 | 80 | GB/T261 |
| Condensation point ℃ | ≤-58 | -76 | -73 | -71 | D 2386 |
| Oxidation stability (110 ℃) h | ≥25 | 28 | 32 | 31 | EN14112 |
| Copper corrosion (50 ℃, 3h -1) level | 1 | 1 | 1 | 1 | D 130 |
Claims (10)
1. a method of producing dialkyl carbonate take agriculture and forestry organic waste material as initial feed is characterized in that, comprises following in sequence step:
A) make the 2-methyltetrahydrofuran take agriculture and forestry organic waste material as initial feed;
B) 2-methyltetrahydrofuran and carbonic acid gas are carried out cycloaddition reaction, make structural formula and be
Cyclic carbonate;
C) described cyclic carbonate and monohydroxy-alcohol are carried out transesterification reaction, make dialkyl carbonate.
2. the method for claim 1, it is characterized in that, 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 quality percentage composition of rare earth oxide in magnesium-zincium-rare earth oxide compound composite catalyst is 0.1-1%.
3. method as claimed in claim 2, it is characterized in that, the mol ratio of 2-methyltetrahydrofuran and carbonic acid gas is 1:1-20 in the described cycloaddition reaction, and the weight proportion of described magnesium-zincium-rare earth oxide compound composite catalyst and 2-methyltetrahydrofuran is 0.1-5:100.
4. such as arbitrary described method in the claim 2, it is characterized in that, the temperature of described cycloaddition reaction is 80-150 ℃, and the reaction absolute pressure is 2-10MPa, and the reaction times is 5-120 minute.
5. 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, with one or more the mixture in the alcohol of furan nucleus.
6. method as claimed in claim 5, it is characterized in that, described transesterification reaction is carried out under the effect of metal-rare earth oxide composite catalyst, described metal-rare earth oxide 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).
7. method as claimed in claim 6 is characterized in that, described metal oxide is selected from one or more in zinc oxide, aluminum oxide, the tin protoxide, and described rare earth oxide is selected from one or more in lanthanum trioxide, the cerium oxide.
8. method as claimed in claim 6, it is characterized in that, the mol ratio of described cyclic carbonate and monohydroxy-alcohol is 1:1-20, and the proportioning of the weight of described metal-rare earth oxide composite catalyst and described cyclic carbonate and monohydroxy-alcohol gross weight is 0.1-5:100.
9. method as claimed in claim 6 is characterized in that, the temperature of described transesterification reaction is 120-180 ℃, and the reaction absolute pressure is 0.1-4MPa, and the reaction times is 5-120 minute.
10. the application on the dialkyl carbonate liquid fuel within of the described method preparation of claim 1.
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| US13/893,727 US9045707B2 (en) | 2012-05-17 | 2013-05-14 | Environmental-friendly liquid fuel and production process thereof |
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