CN108727194B - Method for synthesizing dialkyl carbonate from biomass-based synthesis gas - Google Patents

Method for synthesizing dialkyl carbonate from biomass-based synthesis gas Download PDF

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CN108727194B
CN108727194B CN201810478178.5A CN201810478178A CN108727194B CN 108727194 B CN108727194 B CN 108727194B CN 201810478178 A CN201810478178 A CN 201810478178A CN 108727194 B CN108727194 B CN 108727194B
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biomass
synthesis gas
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carbonate
dialkyl carbonate
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CN108727194A (en
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李学兵
王�忠
李青洋
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/48—Esters of carbonic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • C10M2207/325—Esters of carbonic acid used as base material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

The invention belongs to a method for synthesizing ester compounds in organic chemistry, and particularly relates to a method for synthesizing dialkyl carbonate from biomass-based synthesis gas. The method comprises the steps of further catalyzing biomass-based synthesis gas obtained by using biomass-based agricultural and forestry waste as an initial raw material to obtain dimethyl ether, further catalyzing the dimethyl ether to obtain dimethyl carbonate, and then carrying out ester exchange reaction on the dimethyl carbonate and monohydric alcohol or polyhydric alcohol to obtain dialkyl carbonate. The method of the invention uses cheap agriculture and forestry waste as raw materials to produce dialkyl carbonate, not only saves production cost and reduces environmental pollution, but also provides a new way for the industrial production of dialkyl carbonate and the efficient comprehensive utilization of the agriculture and forestry waste, and has obvious economic and social benefits.

Description

Method for synthesizing dialkyl carbonate from biomass-based synthesis gas
Technical Field
The invention relates to a preparation method of dialkyl carbonate, in particular to a method for synthesizing dialkyl carbonate by biomass-based synthesis gas.
Background
Dialkyl carbonate is a nontoxic chemical raw material, and contains-CO, -COOCH in its molecule3and-CH3The dialkyl carbonate has a plurality of varieties, some can be used as fuel, some can be used as lubricating oil, and some can be used as biodiesel, so the dialkyl carbonate has higher industrial application value and good market prospect. Wherein dimethyl carbonate is the most representative organic compound, and the synthesis method mainly comprises phosgene synthesis method and oxidative carbonylation methodAnd transesterification methods.
The traditional industrial preparation of dimethyl carbonate generally adopts a phosgene synthesis method, but the synthesis can only maintain small-scale industrial production, and the preparation methods need phosgene, have high operation safety requirements and serious environmental pollution, and are gradually replaced by a methanol oxidative carbonylation method. However, the methanol oxidative carbonylation process is classified into a liquid phase process and a gas phase process: in the reaction process of the liquid phase method, methanol is used as a raw material and a solvent, the oxygen concentration is always kept below the explosion limit in the reaction process, the defects are that the chloride catalyst has high corrosion to equipment, and the gas phase method needs a fixed bed reactor and has low catalyst activity. The ester exchange method, namely synthesizing the ester which is difficult to prepare from the easily obtained ester, is one of the commonly used methods for organic synthesis. The method is also applied to the synthesis of dimethyl carbonate. Imre Weisz proposed that Dimethyl carbonate was synthesized by reacting Dimethyl sulfate with sodium carbonate in a tank reactor, and refluxing the mixture at 150 to 210 ℃ for 6 hours using chlorobenzene as a catalyst to obtain Dimethyl carbonate with a yield of 44% (Weisz I, Havelka F, Pelek Z, Dimethyl and Dimethyl carbonates, Hung Teljes, 1977,14:221 to 226), but this method was not further developed because of its low yield and its severe toxicity.
Therefore, a synthesis method which can improve the conversion rate and selectivity, has easily obtained raw materials, low production cost, environmental protection, simple process and low energy consumption is still needed.
Disclosure of Invention
In view of the technical problems and disadvantages of the current dialkyl carbonate synthesis, the invention provides a method for synthesizing dialkyl carbonate from biomass-based synthesis gas.
In order to realize the purpose, the invention adopts the technical scheme that:
a method for synthesizing dialkyl carbonate from biomass-based synthetic gas comprises the steps of further catalyzing the biomass-based synthetic gas obtained by using biomass-based agricultural and forestry waste as an initial raw material to obtain dimethyl ether, further catalyzing the dimethyl ether to obtain dimethyl carbonate, and then carrying out ester exchange reaction on the dimethyl ether and monohydric alcohol or polyhydric alcohol to obtain the dialkyl carbonate.
The biomass-based synthesis gas is prepared by taking agricultural and forestry wastes as initial raw materials, performing pyrolysis gasification in a gasification furnace, controlling the temperature of a drying layer of the gasification furnace to be 110-245 ℃, the temperature of a pyrolysis layer to be 335-556 ℃, the temperature of a combustion layer to be 800-900 ℃, mixing the biomass-based synthesis gas with a gasification agent, performing gasification to obtain biomass crude synthesis gas, and performing reforming and purification to obtain the biomass-based synthesis gas (wherein the molar ratio of H2 to CO is 1.3-1.5).
The flow rate of the gasification agent steam is 1 percent g/min of the mass of the agricultural and forestry waste.
The dimethyl ether is synthesized by the biomass-based synthesis gas flow through a catalyst Cu-Zn-Mn/HZSM-5, the mass of the catalyst is 0.5-2% of the mass of the synthesis gas, the reaction temperature is 200-280 ℃, the reaction pressure is 2-4MPa, and the airspeed is 1500-2000/h.
In the Cu-Zn-Mn/HZSM-5 catalyst, Cu-Zn-Mn is a hydrogenation component, HZSM-5 is a dehydration component, the molar ratio of Cu to Zn plus Mn is 1:0.3-0.6, and the mass ratio of the hydrogenation component to the dehydration component is 2-3: 1.
The dimethyl carbonate is synthesized by reacting the dimethyl ether and the mixed gas in the presence of a catalyst at the temperature of 100-160 ℃ and the reaction pressure of 2-4MP a; wherein the mixed gas is oxygen and carbon monoxide, the molar ratio of the oxygen to the carbon monoxide to the dimethyl ether is 1:1.5-2.5:1.5-2.5, and the mass of the catalyst is 0.5-3% of that of the dimethyl ether; the catalyst is Pd-Cu/Ce1-xZrxO2Wherein the loading amounts of Pd and Cu are both 5-15%, and the value of x is 0.1-0.5.
Performing ester exchange reaction on dimethyl carbonate and monohydric alcohol or polyhydric alcohol under the action of a metal oxide catalyst at the temperature of 120-180 ℃, the reaction pressure of 1-4MPa and the reaction time of 90-120min to obtain dialkyl carbonate; wherein, the mol ratio of the dimethyl carbonate to the monohydric alcohol or the polyhydric alcohol is 1:1-10, and the weight of the catalyst accounts for 0.1-3% of the total weight of the dimethyl carbonate and the monohydric alcohol or the polyhydric alcohol.
The monohydric alcohol is selected from one of C2-C8 straight chain alcohol (preferably ethanol and butanol), C3-C8 branched chain alcohol (preferably isopropanol and secondary octanol) and C3-C8 cyclic alcohol (preferably cyclohexanol), and the polyalcohol is selected from one of trimethylolpropane, pentaerythritol and neopentyl glycol;
the formula of the transesterification of the dimethyl carbonate and the monohydric alcohol is as follows:
Figure BDA0001665044190000021
(Note: R ═ C)2H5,C3H7,C5H8，C5H10,C6H11，C8H17… …, etc., i.e., R is dependent on the alcohol selected)
The metal oxide is selected from two or more of aluminum oxide, magnesium oxide, zinc oxide, stannous oxide and cerium oxide, and is preferably the metal oxide formed by mixing one or two of aluminum oxide, magnesium oxide, zinc oxide and stannous oxide with cerium oxide.
Compared with the prior art, the invention has the following advantages:
1. the invention takes the agricultural and forestry waste as the initial raw material to produce the dialkyl carbonate, not only the raw material is easy to obtain, the production cost is low, no by-product is produced, but also the high-efficiency comprehensive utilization of the agricultural and forestry waste reduces the environmental pollution, and the invention also provides a new way for producing the dialkyl carbonate, and has obvious economic and social benefits;
2. the preparation method has the advantages of simple preparation process, short production period, low energy consumption, scientific and environment-friendly synthesis method and good industrial production prospect;
3. the dialkyl carbonate prepared by the method can be applied to biological liquid fuels, is superior to fossil-based liquid fuels in the aspects of volatility, safety, environmental friendliness, renewability and the like, and is superior to fatty acid methyl esters and fuel ethanol biological liquid fuels in the aspects of low temperature, compatibility, thermal and oxidative stability, corrosivity, price and the like; it can also be used as lubricating oil and biodiesel.
Drawings
Fig. 1 is a synthesis scheme of dialkyl carbonate provided by an embodiment of the present invention;
Detailed Description
The present invention will be further explained with reference to the following examples, but the present invention is not limited to the following embodiments.
The invention firstly takes the agricultural and forestry wastes as the initial raw materials to react with the gasifying agent steam at a higher temperature to generate CO and H2、CH4Biomass-based syngas of isoflammable gas; then the biomass-based synthesis gas can be directly synthesized into dimethyl ether through gas purification and reforming; then the synthesized dimethyl ether is mixed with CO and O2Directly synthesizing dimethyl carbonate by reaction; finally, the synthesized dimethyl carbonate and monohydric alcohol or polyhydric alcohol are subjected to ester exchange reaction to prepare dialkyl carbonate. The method of the invention uses cheap agriculture and forestry waste as raw materials to produce dialkyl carbonate, not only saves production cost and reduces environmental pollution, but also provides a new way for the industrial production of dialkyl carbonate and the efficient comprehensive utilization of the agriculture and forestry waste, and has obvious economic and social benefits.
Example 1
1) Preparation of Biomass-based syngas
Putting 100g of granulated wood chips into a gasification furnace, firstly controlling the temperature of a drying layer of the gasification furnace to be 200 ℃, and drying the wood chips for 2.5 hours; then regulating the temperature to carry out pyrolysis at 500 ℃, and then carrying out pyrolysis on the wood chips for 1.5 h; and finally, the temperature of wood chips entering a combustion layer is 900 ℃, gasifying agent steam is introduced into the combustion layer of the gasification furnace at the speed of 1g/min, gas discharged from the gasification furnace is recycled to prepare biomass crude synthesis gas, and the crude synthesis gas mainly comprises the following components: 35% H2，38％CO，11％CO2， 15％H2O。
Reforming H of crude synthesis gas by a steam shift reaction device2The molar ratio of the CO to the iron is 1.4, the iron is used as a catalyst, the pressure is 0.8MP a, and the reaction temperature is 250 ℃; then introducing the gas into a methanol solution at the temperature of-53 ℃ for purification so as to absorb CO2And collecting the synthesis gas.
2) Synthesis of dimethyl ether
Firstly, preparing a Cu-Zn-Mn/HZSM-5 catalyst, adopting a coprecipitation method, firstly preparing a mixed aqueous solution of nitrate according to the molar ratio of Cu (Zn + Mn) to 1:0.5, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator and adjusting the pH to 8, then keeping the water bath temperature at 80 ℃, and keeping the stirring state. And (3) after the coprecipitation is finished, standing and aging for 2h at 80 ℃, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the hydrogenation component. Mechanically mixing the hydrogenation component and the dehydration component HZSM-5 according to the mass ratio of 2:1, grinding, tabletting, crushing and sieving, and sieving to obtain 20-40 meshes for later use.
Then, the obtained 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst accounting for 1% of the mass of the synthesis gas is loaded into a high-pressure fixed bed reactor, the biomass synthesis gas is introduced into the high-pressure fixed bed reactor at the airspeed of 1500/h, the temperature is raised to 240 ℃, the pressure is raised to 2MP a, the mixed gas is collected, the temperature of the mixed gas is reduced to-25 ℃, and the dimethyl ether is collected.
3) Synthesis of dimethyl carbonate
Firstly Pd-Cu/Ce0.8Zr0.2O2The preparation of the catalyst comprises two steps:
the first step is Ce0.8Zr0.2O2The carrier is prepared by a citric acid method, and Ce (NO) with a molar ratio of 4:1 is prepared3)2And Zr (NO)3)2Adding a little excessive citric acid into the mixed solution, stirring and ultrasonically oscillating until the citric acid is completely dissolved, then evaporating to dryness on a water bath at 80 ℃, drying in an oven at 100 ℃ for 8 hours to obtain a white loose powder sample, and finally roasting the sample in a muffle furnace at 500 ℃ for 4 hours to obtain a composite oxide sample;
in the second step, the composite oxide load (Pd-Cu double active component catalyst) prepared in the first step is used for preparing Pd-Cu/Ce by adopting a conventional co-impregnation method0.8Zr0.2O2Catalyst: 10% in equimolar ratio H2PdC14And Cu (NO)3)2The solution is simultaneously dipped on the composite oxide, dried and finally roasted in air at 650 ℃ for 4h to obtain Pd (10%) -Cu (10%)/Ce0.8Zr0.2O2Grinding the catalyst, tabletting, crushing, sieving, and sieving to obtain 20-40 mesh catalyst
Then, 1.5 percent of 20-40 mesh Pd (10%) -Cu (10%)/Ce based on the mass of dimethyl ether0.8Zr0.2O2CatalysisThe agent is filled into a high-pressure fixed bed reactor, and then oxygen, carbon monoxide and dimethyl ether are introduced into the high-pressure fixed bed reactor according to the volume ratio of 1:2:2 for reaction. The temperature is raised to 120 ℃, the pressure is raised to 2MP a, and the dimethyl carbonate solution is collected at normal temperature.
4) Preparation of dialkyl carbonate by transesterification
Firstly, preparing a metal oxide catalyst, selecting a mixed oxide of aluminum oxide, zinc oxide and cerium oxide as the catalyst, mixing the mixed oxide with a mixed solution of metal nitrates with a metal ion molar ratio of Zn, Al and Ce being 8:1:1, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator to adjust the pH value to 8, keeping the water bath temperature at 80 ℃, and keeping the mixture in a continuous stirring state. And (3) standing and aging for 2h at 80 ℃ after the coprecipitation is finished, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the mixed metal oxide catalyst.
Then adding the dimethyl carbonate and ethanol synthesized in the step 3) in the embodiment 1 into a tubular ester exchange reactor, adding the prepared mixed metal oxide catalyst, uniformly mixing, carrying out ester exchange reaction, and distilling a reaction product to obtain diethyl carbonate; wherein the molar ratio of the dimethyl carbonate to the ethanol is 1:10, the weight of the mixed metal oxide catalyst accounts for 1% of the total weight of the dimethyl carbonate and the ethanol, the temperature of the ester exchange reaction is controlled to be 120 ℃, the pressure is 2MPa, and the reaction time is 90 min; the conversion of dimethyl carbonate in the ester exchange reaction was 100%, the yield of diethyl carbonate was 97.2%, and the yield of ethyl methyl carbonate was 2.8%.
Example 2
1) Preparation of Biomass-based syngas
150g of granulated wood chips are put into a gasification furnace, the temperature of a drying layer of the gasification furnace is controlled to be 180 ℃, and the wood chips are dried for 2.5 hours; then regulating the temperature to carry out pyrolysis at 400 ℃, and then carrying out pyrolysis on the wood chips for 1.5 h; and finally, the temperature of wood chips entering a combustion layer is 800 ℃, gasifying agent steam is introduced into the combustion layer of the gasification furnace at the speed of 1.5g/min, gas discharged from the gasification furnace is recycled to prepare biomass crude synthesis gas, and the crude synthesis gas mainly comprises the following components: 35% H2，30％CO，20％CO2， 15％H2O。
Regulating H of the crude synthesis gas by a steam shift reaction device2The ratio of the carbon dioxide to CO is 1.3, iron is used as a catalyst, the pressure is 0.8MP a, and the reaction temperature is 250 ℃; then introducing the gas into a methanol solution at the temperature of minus 53 ℃ to absorb CO2And collecting the synthesis gas.
2) Synthesis of dimethyl ether
Firstly, preparing a Cu-Zn-Mn/HZSM-5 catalyst, adopting a coprecipitation method, firstly preparing a mixed aqueous solution of nitrate according to the molar ratio of Cu (Zn + Mn) to 1:0.6, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator and adjusting the pH to 8, then keeping the water bath temperature at 80 ℃, and keeping the stirring state. And (3) after the coprecipitation is finished, standing and aging for 2h at 80 ℃, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the hydrogenation component. Mechanically mixing the hydrogenation component and the dehydration component HZSM-5 according to the mass ratio of 2:1, grinding, tabletting, crushing and sieving, and sieving to obtain 20-40 meshes for later use.
Then, the obtained 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst accounting for 1.5% of the mass of the synthesis gas is loaded into a high-pressure fixed bed reactor, the biomass synthesis gas is introduced into the high-pressure fixed bed reactor at the airspeed of 2000/h, the temperature is raised to 260 ℃, the pressure is raised to 3MP a, the mixed gas is collected, the temperature of the mixed gas is reduced to-25 ℃, and the dimethyl ether is collected.
3) Synthesis of dimethyl carbonate
Firstly Pd-Cu/Ce0.8Zr0.2O2The preparation of the catalyst comprises two steps:
the first step is Ce0.7Zr0.3O2The carrier is prepared by a citric acid method, and Ce (NO) with a molar ratio of 7:3 is prepared3)2And Zr (NO)3)2Adding a little excessive citric acid into the mixed solution, stirring and ultrasonically oscillating until the citric acid is completely dissolved, then evaporating to dryness on a water bath at 80 ℃, drying in an oven at 100 ℃ for 8 hours to obtain a white loose powder sample, and finally roasting the sample in a muffle furnace at 500 ℃ for 4 hours to obtain a composite oxide sample;
the second step is to prepare composite oxidationThe Pd-Cu/Ce is prepared by adopting a conventional co-impregnation method through material loading (Pd-Cu double-active component catalyst)0.7Zr0.3O2Catalyst: 10% in equimolar ratio H2PdC14And Cu (NO)3)2The solution is simultaneously dipped on the composite oxide, dried and finally roasted in air at 650 ℃ for 4h to obtain Pd (10%) -Cu (10%)/Ce0.7Zr0.3O2Grinding the catalyst, tabletting, crushing, sieving, and sieving to obtain 20-40 mesh catalyst
Then, 2% by mass of dimethyl ether of 20-40 mesh Pd (10%) -Cu (10%)/Ce0.7Zr0.3O2The catalyst is loaded into a high-pressure fixed bed reactor, and then oxygen, carbon monoxide and dimethyl ether are introduced into the high-pressure fixed bed reactor according to the volume ratio of 1:1.7:2.1 for reaction. Raising the temperature to 150 ℃, raising the pressure to 3MP a, and collecting the dimethyl carbonate solution at normal temperature.
4) Preparation of dialkyl carbonate by transesterification
Firstly, preparing a metal oxide catalyst, selecting a mixed oxide of magnesium oxide and cerium oxide as the catalyst, mixing the mixed oxide with a mixed solution of metal nitrate with a molar ratio of metal ions Mg: Ce ═ 2:1, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator to adjust the pH value to 8, keeping the water bath temperature at 80 ℃, and keeping the water bath in a continuous stirring state. And (3) standing and aging for 2h at 80 ℃ after the coprecipitation is finished, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the mixed metal oxide catalyst.
Then adding the dimethyl carbonate and the trimethylolpropane synthesized in the step 3) in the embodiment 2 into a tubular ester exchange reactor, adding the prepared mixed metal oxide catalyst, uniformly mixing, carrying out ester exchange reaction, and distilling a reaction product to obtain trimethylolpropane carbonate; wherein the molar ratio of the dimethyl carbonate to the trimethylolpropane is 1:5, the weight of the mixed metal oxide catalyst and the total weight of the dimethyl carbonate and the trimethylolpropane are 1.2 percent, the temperature of the ester exchange reaction is controlled to be 170 ℃, the pressure is 3MPa, and the reaction time is 100 min; the conversion rate of dimethyl carbonate in the ester exchange reaction is 99 percent, the yield of the trimethylolpropane carbonic ester is 95 percent, and various performance indexes of the trimethylolpropane carbonic ester extracted by detection meet the national standard of the use of lubricating oil.
Example 3
1) Preparation of Biomass-based syngas
Putting 120g of granulated wood chips into a gasification furnace, firstly controlling the temperature of a drying layer of the gasification furnace to be 230 ℃, and drying the wood chips for 2.5 hours; then regulating the temperature to carry out pyrolysis at 550 ℃, and then carrying out pyrolysis on the wood chips for 1.5 h; and finally, the temperature of wood chips entering a combustion layer is 850 ℃, gasifying agent steam is introduced into the combustion layer of the gasification furnace at the speed of 1.2g/min, gas discharged from the gasification furnace is recycled to prepare biomass crude synthesis gas, and the crude synthesis gas mainly comprises the following components: 36% H2，33％CO，19％CO2， 12％H2O。
Regulating H of the crude synthesis gas by a steam shift reaction device2The ratio of the carbon dioxide to CO is 1.5, iron is used as a catalyst, the pressure is 0.8MP a, and the reaction temperature is 250 ℃; then introducing the gas into a methanol solution at the temperature of minus 53 ℃ to absorb CO2And collecting the synthesis gas.
2) Synthesis of dimethyl ether
Firstly, preparing a Cu-Zn-Mn/HZSM-5 catalyst, adopting a coprecipitation method, firstly preparing a mixed aqueous solution of nitrate according to the molar ratio of Cu (Zn + Mn) to 1:0.4, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator and adjusting the pH to 8, then keeping the water bath temperature at 80 ℃, and keeping the stirring state. And (3) after the coprecipitation is finished, standing and aging for 2h at 80 ℃, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the hydrogenation component. Mechanically mixing the hydrogenation component and the dehydration component HZSM-5 according to the mass ratio of 2:1, grinding, tabletting, crushing and sieving, and sieving to obtain 20-40 meshes for later use.
Then, the obtained 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst accounting for 2% of the mass of the synthesis gas is loaded into a high-pressure fixed bed reactor, the biomass synthesis gas is introduced into the high-pressure fixed bed reactor at the airspeed of 1800/h, the temperature is raised to 200 ℃, the pressure is raised to 4MP a, the mixed gas is collected, the temperature of the mixed gas is reduced to-25 ℃, and the dimethyl ether is collected.
3) Synthesis of dimethyl carbonate
Firstly Pd-Cu/Ce0.8Zr0.2O2The preparation of the catalyst comprises two steps:
the first step is Ce0.6Zr0.4O2The carrier is prepared by a citric acid method, and Ce (NO) with a molar ratio of 3:2 is prepared3)2And Zr (NO)3)2Adding a little excessive citric acid into the mixed solution, stirring and ultrasonically oscillating until the citric acid is completely dissolved, then evaporating to dryness on a water bath at 80 ℃, drying in an oven at 100 ℃ for 8 hours to obtain a white loose powder sample, and finally roasting the sample in a muffle furnace at 500 ℃ for 4 hours to obtain a composite oxide sample;
in the second step, the composite oxide load (Pd-Cu double active component catalyst) prepared in the first step is used for preparing Pd-Cu/Ce by adopting a conventional co-impregnation method0.6Zr0.4O2Catalyst: 10% in equimolar ratio H2PdC14And Cu (NO)3)2The solution is simultaneously dipped on the composite oxide, dried and finally roasted in air at 650 ℃ for 4h to obtain Pd (10%) -Cu (10%)/Ce0.6Zr0.4O2Grinding the catalyst, tabletting, crushing, sieving, and sieving to obtain 20-40 mesh catalyst
Then, 20-40 mesh Pd (10%) -Cu (10%)/Ce0.6Zr0.4O2 catalyst accounting for 3% of the mass of the dimethyl ether is loaded into the high-pressure fixed bed reactor, and then oxygen, carbon monoxide and dimethyl ether are introduced into the high-pressure fixed bed reactor according to the volume ratio of 1:2.2:1.8 for reaction. The temperature is raised to 160 ℃, the pressure is raised to 2.5MP a, and the dimethyl carbonate solution is collected at normal temperature.
4) Preparation of dialkyl carbonate by transesterification
Firstly, preparing a metal oxide catalyst, selecting a mixed oxide of zinc oxide and cerium oxide as the catalyst, mixing the mixed oxide with a mixed solution of metal nitrate with a molar ratio of metal ions Mg to Ce being 6:1, stirring and heating to 80 ℃, adding 1mol/L sodium carbonate solution as a precipitator to adjust the pH value to 8, keeping the water bath temperature at 80 ℃, and keeping the mixture in a continuous stirring state. And (3) standing and aging for 2h at 80 ℃ after the coprecipitation is finished, then washing with deionized water, performing suction filtration, drying for 12h at 120 ℃, and roasting for 4h at 500 ℃ to obtain the mixed metal oxide catalyst.
Adding dimethyl carbonate and pentaerythritol synthesized in the step 3) in the embodiment 3 into a tubular ester exchange reactor, adding the prepared mixed metal oxide catalyst, uniformly mixing, carrying out ester exchange reaction, and distilling a reaction product to obtain pentaerythritol carbonate; wherein the molar ratio of dimethyl carbonate to pentaerythritol is 1:8, the ratio of the weight of the mixed metal oxide catalyst to the total weight of dimethyl carbonate and pentaerythritol is 1.5%, the temperature of the ester exchange reaction is controlled to be 180 ℃, the pressure is 2.5MPa, and the reaction time is 120 min; the conversion rate of dimethyl carbonate in the ester exchange reaction is 99%, the yield of pentaerythritol carbonate is 96%, and various performance indexes of the purified pentaerythritol carbonate are detected and accord with the national standard of the use of lubricating oil.

Claims (4)

1. A method for synthesizing dialkyl carbonate by biomass-based synthesis gas is characterized by comprising the following steps: the method comprises the following steps of (1) further catalyzing biomass-based synthesis gas obtained by taking biomass-based agricultural and forestry waste as an initial raw material to obtain dimethyl ether, further catalyzing the dimethyl ether to obtain dimethyl carbonate, and then carrying out ester exchange reaction on the dimethyl carbonate and monohydric alcohol or polyhydric alcohol to obtain dialkyl carbonate;
the biomass-based synthesis gas is prepared by taking agricultural and forestry wastes as initial raw materials, pyrolyzing and gasifying the agricultural and forestry wastes in a gasification furnace, controlling the temperature of a drying layer of the gasification furnace to be 110-DEG C and 245-DEG C, the temperature of a pyrolysis layer to be 335-DEG C and the temperature of a combustion layer to be 800-DEG C and 900-DEG C, mixing the biomass-based synthesis gas with a gasifying agent, gasifying the biomass-based synthesis gas to obtain biomass crude synthesis gas, and then reforming and purifying the biomass-based;
the dimethyl ether is synthesized by the biomass-based synthesis gas flow through a catalyst Cu-Zn-Mn/HZSM-5, the mass of the catalyst is 0.5-2% of the mass of the synthesis gas, the reaction temperature is 200-280 ℃, the reaction pressure is 2-4MPa, and the airspeed is 1500-2000/h;
dimethyl carbonate is synthesized by reacting the obtained dimethyl ether with mixed gas in the presence of a catalyst at the temperature of 100-160 ℃ and the reaction pressure of 2-4MP a; wherein the mixed gas is oxygen and carbon monoxide, and the molar ratio of the oxygen to the carbon monoxide to the dimethyl ether1:1.5-2.5:1.5-2.5, the mass of the catalyst is 0.5-3% of that of the dimethyl ether; the catalyst is Pd-Cu/Ce1-xZrxO2Wherein the loading amounts of Pd and Cu are both 5-15%, and the value of x is 0.1-0.5;
performing ester exchange reaction on dimethyl carbonate and monohydric alcohol or polyhydric alcohol under the action of a metal oxide catalyst at the temperature of 120-180 ℃, the reaction pressure of 1-4MPa and the reaction time of 90-120min to obtain dialkyl carbonate; wherein, the mol ratio of the dimethyl carbonate to the monohydric alcohol or the polyhydric alcohol is 1:1-10, and the weight of the catalyst accounts for 0.1-3% of the total weight of the dimethyl carbonate and the monohydric alcohol or the polyhydric alcohol.
2. The method for synthesizing dialkyl carbonate by using biomass-based synthesis gas according to claim 1, wherein the method comprises the following steps: the flow rate of the gasification agent is 1 percent g/min of the mass of the agricultural and forestry waste.
3. The method for synthesizing dialkyl carbonate by using biomass-based synthesis gas according to claim 1, wherein the method comprises the following steps: in the Cu-Zn-Mn/HZSM-5 catalyst, Cu-Zn-Mn is a hydrogenation component, HZSM-5 is a dehydration component, the molar ratio of Cu to Zn plus Mn is 1:0.3-0.6, and the mass ratio of the hydrogenation component to the dehydration component is 2-3: 1.
4. The method for synthesizing dialkyl carbonate by using biomass-based synthesis gas according to claim 1, wherein the method comprises the following steps: the monohydric alcohol is selected from one of C2-C8 straight-chain alcohol, C3-C8 branched-chain alcohol and C3-C8 cyclic alcohol, and the polyhydric alcohol is selected from one of trimethylolpropane, pentaerythritol and neopentyl glycol;
the metal oxide is two or more selected from aluminum oxide, magnesium oxide, zinc oxide, stannous oxide and cerium oxide.
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