CN109320419A - A kind of method of biomass-based furfural carbonate synthesis dialkyl - Google Patents
A kind of method of biomass-based furfural carbonate synthesis dialkyl Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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Abstract
The invention belongs to ester type compound synthetic method in organic chemistry, specifically a kind of method of biomass-based furfural carbonate synthesis dialkyl.It is reacted first using agriculture and forestry organic waste material as initial feed by sour water solution and cyclodehydration, purification obtains furfural；Then biomass-based furfural carries out oxidation reaction under the action of hydrogen peroxide and catalyst, synthesizes cis-butenedioic anhydride；The cis-butenedioic anhydride of synthesis is subjected to epoxidation reaction, synthesizing epoxy succinic acid under catalyst and hydrogen peroxide effect；Again by Epoxysuccinic acid and CO2Cycloaddition reaction is carried out, a kind of cyclic carbonate is made；The cyclic carbonate and monohydric alcohol or polyalcohol being finally synthesizing carry out ester exchange reaction, and dialkyl carbonate is made.The method of the present invention produces dialkyl carbonate by raw material of cheap agriculture and forestry organic waste material, the tartaric acid of high added value is also generated simultaneously, it not only saved production cost, reduced environmental pollution, high-efficiency comprehensive utilization also for industrialized production dialkyl carbonate, tartaric acid and agriculture and forestry organic waste material provides new way, has significant economic and social benefit sheet.
Description
Technical field
The present invention relates to a kind of preparation methods of dialkyl carbonate, more particularly to a kind of biomass-based furfural carbonate synthesis
The new method and its application of dialkyl.
Background technique
Dialkyl carbonate is a kind of nontoxic industrial chemicals, due to containing-CO ,-COOCH in its molecule3With-CH3, have
Good reactivity can be reacted with a variety of alcohol, phenol, amine and ester, be a kind of widely used organic compound and functional
Solvent, there are many dialkyl carbonate type, such as are used as nitrocellulose, cellulose ether, conjunction in diethyl carbonate Chemical Manufacture
At the solvent of resin and natural resin；A kind of solvent of excellent lithium-ion battery electrolytes of methyl ethyl carbonate；Pentaerythrite carbon
Acid esters and trimethylolpropane carbonic ester can make lubricating oil.Therefore dialkyl carbonate industrial application value with higher and good
Good market prospects.Wherein with dimethyl carbonate for most representative organic compound, it can replace phosgene and is carbonylated
Agent makees methylating agent instead of dimethyl suflfate, can do low poison solvent, and synthetic method mainly includes optical self-encoding method, oxygen
Change carbonyl process, ester-interchange method etc..
Traditional Industrialization manufacture dimethyl carbonate generally uses optical self-encoding method, however synthesis can only maintain Small Scale Industry
Metaplasia produces, and the method for these preparations needs phosgene, and safe operation requires height, and environmental pollution is serious, thus gradually by methanol
Replaced oxidation carbonylation method.However oxidative carbonylation of methanol method is divided into liquid phase method and vapor phase method: in the reaction process of liquid phase method,
Methanol had not only been raw material but also had been solvent, and oxygen concentration remains at explosion limit hereinafter, shortcoming is chloride in reaction process
Catalyst it is big to equipment corrosion, methanol loop amount is big in system, and catalyst easy in inactivation, vapor phase method needs fixed bed reaction
Device, the disadvantage is that catalyst activity is low.Ester-interchange method is that organic synthesis is common i.e. from a kind of more difficult ester produced of Lipase absobed being easy to get
One of method.The method is also applied in the synthesis of dimethyl carbonate.Imre Weisz it is proposed that with dimethyl suflfate with
Sodium carbonate reacts Synthesis of dimethyl carbonate in tank reactor, and using chlorobenzene as catalyst, flow back 6h at 150~210 DEG C, can
Obtain dimethyl carbonate (Weisz I, Havelka F, Pellek Z, the Dimethyl and diethyl that yield is 44%
Carbonates, Hung Teljes, 1977,14:221~226), but since the yield of this process is low, chlorobenzene, dimethyl suflfate
There is severe toxicity, therefore the method is not developed further.
Therefore, it is still necessary to which one kind can be improved conversion ratio and selectivity, and raw material is easy to get, and production cost is low, environmentally protective, work
Skill is simple, the synthetic method that low energy consumption.
Summary of the invention
In view of technical problem and deficiency existing for current dialkyl carbonate Lipase absobed, the present invention provides a kind of cheap agricultural
Waste furfural is raw material, the method for the tartaric acid of the costly dialkyl carbonate of production economy and high added value.
The present invention having the advantage that compared with prior art
1, the present invention produces dialkyl carbonate by starting material of agriculture and forestry organic waste material, not only raw material is easy to get, production cost is low,
Also create the tartaric acid of high added value simultaneously, and the high-efficiency comprehensive utilization of agriculture and forestry organic waste material reduces environmental pollution, also for
Production dialkyl carbonate provides new way, has significant economic and social benefit；
2, it is easily separated to prepare product by the present invention, simple process, with short production cycle, and synthetic method science environmental protection has fine
Industrialized production prospect；
3, the dialkyl carbonate for preparing of the present invention, can be applied to biological liquid fuel, volatility, safety,
Environment friendly, reproducibility etc. are superior to fossil base liquid fuel, low temperature properties, compatibility, heat and oxidation stability,
Corrosivity, price etc. are better than fatty acid methyl esters and alcohol fuel class biological liquid fuel；It also is used as lubricating oil and life
Object diesel oil.
Detailed description of the invention
Fig. 1 is the synthetic route chart of dialkyl carbonate provided in an embodiment of the present invention；
Specific embodiment
Below with reference to attached specific embodiment the present invention will be further explained explanation, but the present invention be not limited in it is as follows
Embodiment.
Embodiment 1
1) biomass-based furfural is prepared
100g maize cob meal is broken to 1mm or so, impregnates 2h at 120 DEG C in the aqueous sulfuric acid that mass fraction is 4%,
The liquid-solid ratio (V/W) of dilute sulfuric acid and agriculture and forestry organic waste material is 10:1.Pentose yield is 78.67% after hydrolysis.The pentose of acquisition is matched
It is fitted into reaction kettle at 0.4mol/L solution, loads onto condensation distilling apparatus, control sulfuric acid mass fraction 20% or so, vapo(u)rizing temperature
190 DEG C, distillation time 5h obtains 49% furfuryl aldehyde solution.
2) cis-butenedioic anhydride is synthesized
It is heteropoly acid MoWP/SiO first2The preparation of catalyst.The synthesis of MoWP heteropoly acid: the ammonium molybdate of 1mol/L is configured
Aqueous solution, after by the ratio between amount of molybdenum and phosphorus substance be 0.9 phosphoric acid to be slowly added dropwise in ammonium molybdate solution；Weigh tungsten and phosphorus substance
The wolframic acid that the ratio between amount is 0.038, is dissolved in wolframic acid and H2O2The ratio between amount of substance is that 0.074 mass fraction is 30%H2O2Solution
In；It is by volume that 2.3:1 is uniformly mixed to get MoWP heteropoly acid solution by two kinds of solution.Weigh pretreated SiO2Powder
End is added in MoWP heteropoly acid solution with the load capacity that mass fraction is 50%, impregnates 12h.After absorption completely to be impregnated, 120
DEG C dry 2h, 400 DEG C of roasting 5h obtain heteropoly acid MoWP/SiO2Catalyst.
Oxidation reaction carries out in a kettle, and reaction condition is catalyst MoWP/SiO2Mass ratio with furfural is 0.09,
The ratio between amount of solvent dichloroethanes and furfural substance is 3, oxidant H2O2Under the conditions of being 2.5,60 DEG C with the ratio between the amount of furfural substance
3h is reacted, the conversion ratio through detecting furfural reaches 82.33%, and the yield of cis-butenedioic anhydride and selectivity are respectively in lower layer's water phase
78.51% and 95.36%.
3) synthesizing epoxy succinic acid
Pretreated MCN-41 molecular sieve powder is weighed, Na is added with the load capacity that mass fraction is 50%2WO4Solution
In, it stirs evenly.Then ultrasound 1h then stands dipping for 24 hours.After absorption completely to be impregnated, 120 DEG C of dry 4h, 600 DEG C of roastings
5h obtains W/MCN-41 catalyst.
Epoxidation reaction carries out in a kettle, and reaction condition is catalyst W/MCN-41 and the mass ratio of cis-butenedioic anhydride is
0.05, oxidant H2O22h is reacted under the conditions of being 1.5,65 DEG C with the ratio between the amount of cis-butenedioic anhydride substance, the conversion ratio through detecting cis-butenedioic anhydride reaches
90.33%, the selectivity of Epoxysuccinic acid is 91.5%.
4) synthesizing annular carbonate
It is the preparation of metal oxide catalyst first, selecting magnesia, zinc oxide and cerium oxide mixed oxide is to urge
Agent, then mixed with the metal nitrate mixed salt solution of configuration metal ion molar ratio Mg:Zn:Ce=5:5:1, stirring is warming up to
It 80 DEG C, is added using the sodium carbonate liquor of 1mol/L as precipitating reagent after adjusting PH=8, is kept for 80 DEG C of bath temperature, and in continuous
Stirring.80 DEG C of standing aging 2h after co-precipitation, then deionized water is washed, and is filtered, 120 DEG C of dry 12h, 500 DEG C
4h is roasted, mixed metal oxide catalyst is obtained.
The mixed metal oxide catalyst of Epoxysuccinic acid and above-mentioned preparation is added in reactor, heating dress is opened
Setting keeps the temperature of reactor constant at 120 DEG C, and excessive CO is passed through into reactor2；Wherein mixed metal oxide catalyst
Weight accounts for the 0.5% of Epoxysuccinic acid weight, and the temperature for controlling cycloaddition reaction is 120 DEG C, pressure 8MPa, and the reaction time is
100min；Dimethyl carbonate is obtained through distillation；Wherein Epoxysuccinic acid and the CO being passed through2Molar ratio be 1:10, cycloaddition
The conversion ratio of Epoxysuccinic acid is 90% in reaction, and the yield of dimethyl carbonate is 48%；Tartaric acid yield is 47.2%.
5) transesterification prepares dialkyl carbonate
Ester exchange reaction equally uses the mixed-metal oxides in step 3) for catalyst, by dimethyl carbonate and ethyl alcohol
Be added in tubular type transesterification reactor, add it is above-mentioned prepare mixed metal oxide catalyst, carry out ester after mixing
Exchange reaction, reaction product obtain diethyl carbonate through distillation；Wherein, the molar ratio 1:10 of dimethyl carbonate and ethyl alcohol is mixed
It closes metal oxide catalyst weight and accounts for the 1% of dimethyl carbonate and ethyl alcohol total weight, the temperature for controlling ester exchange reaction is 120
DEG C, pressure 2MPa, reaction time 90min；The conversion ratio of dimethyl carbonate is 100% in ester exchange reaction, carbonic acid diethyl
The yield of ester is 97.2%, and the yield of methyl ethyl carbonate is 2.8%.
Embodiment 2
1) biomass-based furfural is prepared
100g is discarded into bamboo wood and is crushed to 1mm or so, is impregnated at 110 DEG C in the aqueous sulfuric acid that mass fraction is 5%
The liquid-solid ratio (V/W) of 2.5h, dilute sulfuric acid and agriculture and forestry organic waste material is 11:1.Pentose yield is 70.67% after hydrolysis.By the penta of acquisition
Sugar is made into 0.6mol/L solution and is fitted into reaction kettle, loads onto condensation distilling apparatus, controls sulfuric acid mass fraction 25% or so, distillation
180 DEG C of temperature, distillation time 6h obtains 46% furfuryl aldehyde solution.
2) cis-butenedioic anhydride is synthesized
It is heteropoly acid MoWP/SiO first2The preparation of catalyst.The synthesis of MoWP heteropoly acid: the ammonium molybdate of 1mol/L is configured
Aqueous solution, after by the ratio between amount of molybdenum and phosphorus substance be 0.85 phosphoric acid to be slowly added dropwise in ammonium molybdate solution；Weigh tungsten and phosphorus substance
The ratio between amount be 0.034 wolframic acid, be dissolved in wolframic acid and H2O2The ratio between amount of substance is that 0.074 mass fraction is 30%H2O2It is molten
In liquid；It is by volume that 2.3:1 is uniformly mixed to get MoWP heteropoly acid solution by two kinds of solution.Weigh pretreated SiO2Powder
End is added in MoWP heteropoly acid solution with the load capacity that mass fraction is 44%, impregnates 12h.After absorption completely to be impregnated, 120
DEG C dry 2h, 400 DEG C of roasting 5h obtain heteropoly acid MoWP/SiO2Catalyst.
Oxidation reaction carries out in a kettle, and reaction condition is catalyst MoWP/SiO2Mass ratio with furfural is 0.1,
The ratio between amount of solvent dichloroethanes and furfural substance is 2.8, oxidant H2O2Under the conditions of being 2,70 DEG C with the ratio between the amount of furfural substance
2h is reacted, the conversion ratio through detecting furfural reaches 85.33%, and the yield of cis-butenedioic anhydride and selectivity are respectively in lower layer's water phase
76.51% and 96.6%.
3) synthesizing epoxy succinic acid
Pretreated MCN-41 molecular sieve powder is weighed, Na is added with the load capacity that mass fraction is 45%2WO4Solution
In, it stirs evenly.Then ultrasound 1h then stands dipping for 24 hours.After absorption completely to be impregnated, 120 DEG C of dry 4h, 600 DEG C of roastings
5h obtains W/MCN-41 catalyst.
Epoxidation reaction carries out in a kettle, and reaction condition is catalyst W/MCN-41 and the mass ratio of cis-butenedioic anhydride is
0.06, oxidant H2O23h is reacted under the conditions of being 1.5,70 DEG C with the ratio between the amount of cis-butenedioic anhydride substance, the conversion ratio through detecting cis-butenedioic anhydride reaches
91.25%, the selectivity of Epoxysuccinic acid is 90.88%.
4) synthesizing annular carbonate
It is the preparation of metal oxide catalyst first, selecting magnesia, zinc oxide and cerium oxide mixed oxide is to urge
Agent, then mixed with the metal nitrate mixed salt solution of configuration metal ion molar ratio Mg:Zn:Ce=6:3:1, stirring is warming up to
It 80 DEG C, is added using the sodium carbonate liquor of 1mol/L as precipitating reagent after adjusting PH=8, is kept for 80 DEG C of bath temperature, and in continuous
Stirring.80 DEG C of standing aging 2h after co-precipitation, then deionized water is washed, and is filtered, 120 DEG C of dry 12h, 500 DEG C
4h is roasted, mixed metal oxide catalyst is obtained.
The mixed metal oxide catalyst of Epoxysuccinic acid and above-mentioned preparation is added in reactor, heating dress is opened
Setting keeps the temperature of reactor constant at 150 DEG C, and excessive CO is passed through into reactor2；Wherein mixed metal oxide catalyst
Weight accounts for the 10% of Epoxysuccinic acid weight, and the temperature for controlling cycloaddition reaction is 150 DEG C, pressure 8MPa, and the reaction time is
90min；Dimethyl carbonate is obtained through distillation；Wherein Epoxysuccinic acid and the CO being passed through2Molar ratio be 1:10, cycloaddition is anti-
The conversion ratio for answering middle Epoxysuccinic acid is 92.1%, and the yield of dimethyl carbonate is 45.9%；Tartaric acid yield is 49.2%.
5) transesterification prepares dialkyl carbonate
Ester exchange reaction equally uses the mixed-metal oxides in step 3) for catalyst, by dimethyl carbonate and three hydroxyls
Methylpropane is added in tubular type transesterification reactor, add it is above-mentioned prepare mixed metal oxide catalyst, be uniformly mixed
After carry out ester exchange reaction, reaction product obtains trimethylolpropane carbonic ester through distillation；Wherein, dimethyl carbonate and three hydroxyls
The molar ratio 1:5 of methylpropane, the weight and dimethyl carbonate and trimethylolpropane gross weight of mixed metal oxide catalyst
The proportion of amount is 1.2%, and the temperature for controlling ester exchange reaction is 170 DEG C, pressure 3MPa, reaction time 100min；Ester is handed over
Changing dimethyl carbonate conversion ratio in reaction is 99.1%, and the yield of trimethylolpropane carbonic ester is 95.2%, through Detection and Extraction
The performance indexes of trimethylolpropane carbonic ester meets the national standard that lubricating oil uses.
Embodiment 3
1) biomass-based furfural is prepared
100g waste wood is crushed to 1mm or so, is soaked at 130 DEG C in the aqueous sulfuric acid that mass fraction is 3.5%
The liquid-solid ratio (V/W) of stain 3h, dilute sulfuric acid and agriculture and forestry organic waste material is 13:1.Pentose yield is 75.25% after hydrolysis.By the penta of acquisition
Sugar is made into 0.5mol/L solution and is fitted into reaction kettle, loads onto condensation distilling apparatus, controls sulfuric acid mass fraction 30% or so, distillation
200 DEG C of temperature, distillation time 5.5h obtains 48.2% furfuryl aldehyde solution.
2) cis-butenedioic anhydride is synthesized
It is heteropoly acid MoWP/SiO first2The preparation of catalyst.The synthesis of MoWP heteropoly acid: the ammonium molybdate of 1mol/L is configured
Aqueous solution, after by the ratio between amount of molybdenum and phosphorus substance be 0.9 phosphoric acid to be slowly added dropwise in ammonium molybdate solution；Weigh tungsten and phosphorus substance
The wolframic acid that the ratio between amount is 0.038, is dissolved in wolframic acid and H2O2The ratio between amount of substance is that 0.074 mass fraction is 30%H2O2Solution
In；It is by volume that 2.3:1 is uniformly mixed to get MoWP heteropoly acid solution by two kinds of solution.Weigh pretreated SiO2Powder
End is added in MoWP heteropoly acid solution with the load capacity that mass fraction is 48%, impregnates 12h.After absorption completely to be impregnated, 120
DEG C dry 2h, 400 DEG C of roasting 5h obtain heteropoly acid MoWP/SiO2Catalyst.
Oxidation reaction carries out in a kettle, and reaction condition is catalyst MoWP/SiO2Mass ratio with furfural is 0.08,
The ratio between amount of solvent dichloroethanes and furfural substance is 2.7, oxidant H2O2It is 2.2,60 DEG C of conditions with the ratio between the amount of furfural substance
Lower reaction 2h, the conversion ratio through detecting furfural reach 85.33%, and the yield of cis-butenedioic anhydride and selectivity are respectively in lower layer's water phase
72.38% and 94.9%.
3) synthesizing epoxy succinic acid
Pretreated MCN-41 molecular sieve powder is weighed, Na is added with the load capacity that mass fraction is 35%2WO4Solution
In, it stirs evenly.Then ultrasound 1h then stands dipping for 24 hours.After absorption completely to be impregnated, 120 DEG C of dry 4h, 600 DEG C of roastings
5h obtains W/MCN-41 catalyst.
Epoxidation reaction carries out in a kettle, and reaction condition is catalyst W/MCN-41 and the mass ratio of cis-butenedioic anhydride is
0.05, oxidant H2O23h is reacted under the conditions of being 1.7,60 DEG C with the ratio between the amount of cis-butenedioic anhydride substance, the conversion ratio through detecting cis-butenedioic anhydride reaches
92.15%, the selectivity of Epoxysuccinic acid is 91.58%.
4) synthesizing annular carbonate
It is the preparation of metal oxide catalyst first, selecting magnesia, zinc oxide and cerium oxide mixed oxide is to urge
Agent, then mixed with the metal nitrate mixed salt solution of configuration metal ion molar ratio Mg:Zn:Ce=9:3:1, stirring is warming up to
It 80 DEG C, is added using the sodium carbonate liquor of 1mol/L as precipitating reagent after adjusting PH=8, is kept for 80 DEG C of bath temperature, and in continuous
Stirring.80 DEG C of standing aging 2h after co-precipitation, then deionized water is washed, and is filtered, 120 DEG C of dry 12h, 500 DEG C
4h is roasted, mixed metal oxide catalyst is obtained.
The mixed metal oxide catalyst of Epoxysuccinic acid and above-mentioned preparation is added in reactor, heating dress is opened
Setting keeps the temperature of reactor constant at 160 DEG C, and excessive CO is passed through into reactor2；Wherein mixed metal oxide catalyst
Weight accounts for the 10% of Epoxysuccinic acid weight, and the temperature for controlling cycloaddition reaction is 160 DEG C, pressure 8MPa, and the reaction time is
60min；Dimethyl carbonate is obtained through distillation；Wherein Epoxysuccinic acid and the CO being passed through2Molar ratio be 1:8, cycloaddition is anti-
The conversion ratio for answering middle Epoxysuccinic acid is 93.1%, and the yield of dimethyl carbonate is 48.9%；Tartaric acid yield is 46.2%.
4) transesterification prepares dialkyl carbonate
Ester exchange reaction equally uses the mixed-metal oxides in step 3) for catalyst, by dimethyl carbonate and season penta
Tetrol is added in tubular type transesterification reactor, add it is above-mentioned prepare mixed metal oxide catalyst, be uniformly mixed laggard
Row ester exchange reaction, reaction product obtain pentaerythrite carbonic ester through distillation；Wherein, dimethyl carbonate and pentaerythrite rub
, than 1:8, the weight and dimethyl carbonate of mixed metal oxide catalyst and the proportion of pentaerythrite total weight are 1.5% for you,
The temperature for controlling ester exchange reaction is 180 DEG C, pressure 2.5MPa, reaction time 120min；Carbonic acid two in ester exchange reaction
Methyl ester conversion rate is 99.2%, and the yield of pentaerythrite carbonic ester is 96.3%, the pentaerythrite carbonic ester through detection purification
Performance indexes meets the national standard that lubricating oil uses.
Claims (12)
1. a kind of method of biomass-based furfural carbonate synthesis dialkyl, which is characterized in that include the steps that following sequence carries out:
A it) is reacted using biomass-based agriculture and forestry organic waste material as initial feed by sour water solution and cyclodehydration, purification obtains biomass
Base furfural；
B) biomass-based furfural carries out oxidation reaction under the action of hydrogen peroxide and catalyst, synthesizes cis-butenedioic anhydride；
C) cis-butenedioic anhydride carries out epoxidation reaction, synthesizing epoxy succinic acid under catalyst and hydrogen peroxide effect；
D) Epoxysuccinic acid and CO2 carry out cycloaddition reaction, and a kind of cyclic carbonate is made；
E) cyclic carbonate and monohydric alcohol or polyalcohol carry out ester exchange reaction, and dialkyl carbonate is made.
2. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(A) in, acid used in the sour water solution is sulfuric acid；Hydrolysising condition is 110-130 DEG C of reaction temperature, soaking time 2-3h,
Sulfuric acid mass fraction is 3-5%, and the liquid-solid ratio (V/W) of dilute sulfuric acid and agriculture and forestry organic waste material is 8-15:1.
3. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(A) in, cyclodehydration reaction catalyst used is sulfuric acid, and condition is 180-210 DEG C of reaction temperature, and soaking time is
5-6h, sulfuric acid mass fraction are 20-30%.
4. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(B) in, the cis-butenedioic anhydride synthetic reaction is in heteropoly acid MoWP/SiO2It is carried out under the action of catalyst, in the catalyst
P, the mass ratio of the material of Mo and W is 1:0.8-0.9:0.03-0.04, and loaded by heteropoly acid is in SiO2Mass fraction be 40-50%.
5. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(B) in, the cis-butenedioic anhydride synthetic reaction condition are as follows: the mass ratio of catalyst and furfural is 0.09-0.1, solvent dichloroethanes and chaff
The ratio between amount of aldehyde substance is 2.5-3.5, oxidant H2O2It is 2-3 with the ratio between the amount of furfural substance, reaction temperature is 50-70 DEG C.
6. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(C) in, the reaction of the synthesizing epoxy succinic acid is carried out under W/MCM-41 catalyst action, w in the catalyst
Load capacity be 20-50%.
7. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(C) in, the synthesis reaction temperature of the Epoxysuccinic acid is 55-75 DEG C, reaction time 1.5-3h, wherein 30%H2O2With
The mass ratio of cis-butenedioic anhydride is 1:1.3-1.8, and catalyst accounts for the 4-6% of cis-butenedioic anhydride quality.
8. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(D) in, the reaction of the synthesizing annular carbonate is in magnesia, zinc oxide and oxidation ce composite oxidation catalyst effect
Lower progress, wherein cerium oxide accounts for the 0.1-1% of the quality of composite oxide catalysts, and the molar ratio of magnesia and zinc oxide is 1-
3:1。
9. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
(D) in, the synthesis reaction temperature of the cyclic carbonate is 90-160 DEG C, reaction time 1-2h, wherein Epoxysuccinic acid
Molar ratio with carbon dioxide is 1:5-20, and catalyst accounts for the 1-4% of Epoxysuccinic acid quality.
10. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: institute
State monohydric alcohol or polyalcohol be in C2-C8 straight chain alcohol, C3-C8 branched-chain alcoho, C3-C8 cyclic alcohol, the alcohol with furan nucleus one
Kind or a variety of mixtures.
11. a kind of method of biomass-based furfural carbonate synthesis dialkyl according to claim 1, it is characterised in that: step
Suddenly in (E), the ester exchange reaction is equally carried out under magnesia, zinc oxide and oxidation ce composite oxidation catalyst effect,
Wherein cerium oxide accounts for the 0.1-1% of the quality of composite oxide catalysts, and the molar ratio of magnesia and zinc oxide is 1-3:1.
12. a kind of method of Biomass Syngas carbonate synthesis dialkyl according to claim 1, it is characterised in that:
In step (D), the molar ratio of dimethyl carbonate and monohydric alcohol or polyalcohol is 1:1-10 in the ester exchange reaction, catalyst
Weight accounts for the 0.1-3% of dimethyl carbonate and monohydric alcohol or total polyol weight, and the temperature of reaction is 120-180 DEG C, reaction pressure
Power is 1-4MPa, reaction time 90-120min.
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| CN (1) | CN109320419A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286506A (en) * | 2022-07-04 | 2022-11-04 | 华南理工大学 | Method for synthesizing bifenthrin by one-step oxidation esterification with metal organic framework material as catalyst |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286506A (en) * | 2022-07-04 | 2022-11-04 | 华南理工大学 | Method for synthesizing bifenthrin by one-step oxidation esterification with metal organic framework material as catalyst |
| CN115286506B (en) * | 2022-07-04 | 2023-05-23 | 华南理工大学 | Method for synthesizing matrithrin by one-step oxidation esterification with metal organic framework material as catalyst |
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Application publication date: 20190212 |