CN108727194A - A kind of method of Biomass Syngas carbonate synthesis dialkyl - Google Patents
A kind of method of Biomass Syngas carbonate synthesis dialkyl Download PDFInfo
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- CN108727194A CN108727194A CN201810478178.5A CN201810478178A CN108727194A CN 108727194 A CN108727194 A CN 108727194A CN 201810478178 A CN201810478178 A CN 201810478178A CN 108727194 A CN108727194 A CN 108727194A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
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- 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
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- C10L1/00—Liquid carbonaceous fuels
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- 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
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Abstract
The invention belongs to ester type compound synthetic method in organic chemistry, specifically a kind of method of Biomass Syngas carbonate synthesis dialkyl.The Biomass Syngas obtained using biomass-based agriculture and forestry organic waste material as initial feed is further catalyzed to obtain dimethyl ether, and gained dimethyl ether, which is further catalyzed, obtains dimethyl carbonate, then carries out ester exchange reaction with monohydric alcohol or polyalcohol, obtains dialkyl carbonate.The method of the present invention produces dialkyl carbonate by raw material of cheap agriculture and forestry organic waste material, it not only saved production cost, reduced environmental pollution, high-efficiency comprehensive utilization also for industrialized production dialkyl carbonate 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, and carbon is synthesized more particularly to a kind of Biomass Syngas
The method of sour dialkyl.
Background technology
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, and what is had can do fuel, and what is had can make lubricating oil, and what is had can do biodiesel,
Therefore there are higher industrial application value and good market prospects.It is wherein most representative organic with dimethyl carbonate
Compound, synthetic method include mainly optical self-encoding method, oxidative carbonylation, ester-interchange method etc..
Traditional Industrialization manufactures dimethyl carbonate and generally uses optical self-encoding method, however synthesis can only maintain Small Scale Industry
Metaplasia is produced, and these methods prepared need phosgene, safe operation to require height, and environmental pollution is serious, to gradually by methanol
Oxidation carbonylation method is replaced.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, vapor phase method needs fixed bed reactors, the disadvantage is that catalyst activity is low.Ester-interchange method i.e. from
A kind of more difficult ester produced of the Lipase absobed being easy to get, is one of common method of organic synthesis.Synthesis of the method in dimethyl carbonate
In be also applied.Imre Weisz in tank reactor with dimethyl suflfate it is proposed that react carbonate synthesis two with sodium carbonate
Methyl esters, using chlorobenzene as catalyst, flow back 6h at 150~210 DEG C, can get the dimethyl carbonate (Weisz that yield is 44%
I,Havelka F,Pellek Z,Dimethyl and diethyl carbonates,Hung Teljes,1977,14:221
~226), but since the yield of this process is low, chlorobenzene, dimethyl suflfate have severe toxicity, therefore the method is not developed further.
Therefore, it is still necessary to which one kind can improve 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.
Invention content
In view of technical problem and deficiency existing for current dialkyl carbonate Lipase absobed, the present invention provides a kind of biomass-based conjunctions
At the method for gas carbonate synthesis dialkyl.
To make realization above-mentioned purpose, the invention adopts a technical scheme as：
A kind of method of Biomass Syngas carbonate synthesis dialkyl, using biomass-based agriculture and forestry organic waste material as initially
The Biomass Syngas that raw material obtains further is catalyzed to obtain dimethyl ether, and gained dimethyl ether, which is further catalyzed, obtains carbonic acid two
Methyl esters then carries out ester exchange reaction with monohydric alcohol or polyalcohol, obtains dialkyl carbonate.
The Biomass Syngas is pyrolytic gasification, control gasification in gasification furnace by initial feed of agriculture and forestry organic waste material
Stove drying layer temperature be 110-245 DEG C, pyrolytic layer temperature be 335-556 DEG C, burning zone temperature be 800-900 DEG C, and with gasification
Agent is mixed into promoting the circulation of qi and obtains biomass raw synthesis gas, then reform, purify Biomass Syngas (wherein, H2 with CO moles
Ratio is 1.3-1.5).
The flow velocity of the gasifying agent vapor is the 1%g/min of agriculture and forestry organic waste material quality.
The Biomass Syngas flows through catalyst Cu-Zn-Mn/HZSM-5 dimethyl ether synthesis, and catalyst quality is to close
At the 0.5-2% of makings amount, reaction temperature is 200-280 DEG C, reaction pressure 2-4MPa, air speed 1500-2000/h.
Cu-Zn-Mn is hydrogenation component in the Cu-Zn-Mn/HZSM-5 catalyst, and HZSM-5 is dehydration component, Cu and Zn
The molar ratio of+Mn is 1:The mass ratio of 0.3-0.6, hydrogenation component and dehydration component is 2-3:1.
The dimethyl carbonate be by above-mentioned acquisition dimethyl ether and mixed gas in the presence of a catalyst, in 100-160 DEG C,
Reaction pressure is 2-4Mpa, Synthesis of dimethyl carbonate；Wherein, mixed gas be oxygen and carbon monoxide, oxygen, carbon monoxide and
Dimethyl ether molar ratio is 1:1.5-2.5:1.5-2.5, catalyst quality are the 0.5-3% of dimethyl ether quality；The catalyst is
Pd-Cu/Ce1-xZrxO2, the load capacity of wherein Pd and Cu are 5-15%, and the value of x is 0.1-0.5.
By dimethyl carbonate and monohydric alcohol or polyalcohol, in 120-180 DEG C under the action of metal oxide catalyst, instead
It is 1-4MPa, reaction time 90-120min to answer pressure, carries out ester exchange reaction and obtains dialkyl carbonate；Wherein, dimethyl carbonate
It is 1 with the molar ratio of monohydric alcohol or polyalcohol:The weight of 1-10, catalyst account for dimethyl carbonate and monohydric alcohol or polyalcohol gross weight
The 0.1-3% of amount.
The monohydric alcohol is selected from C2-C8 straight chain alcohols (preferred alcohol, butanol), C3-C8 branched-chain alcohos (preferably isopropanol, Zhong Xin
Alcohol), one kind in C3-C8 cyclic alcohol (preferably cyclohexanol), polyalcohol is in trimethylolpropane, pentaerythrite, neopentyl glycol
One kind；
The dimethyl carbonate equation transesterification with monohydric alcohol be：
(note：R=C2H5,C3H7,C5H8, C5H10,C6H11, C8H17... etc., i.e. R depend on the alcohol being selected from)
Two or more of the metal oxide in aluminium oxide, magnesia, zinc oxide, stannous oxide, cerium oxide,
It is preferred that one or both of aluminium oxide, magnesia, zinc oxide, stannous oxide and the mixed metal oxide of cerium oxide.
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,
No coupling product generates, and the high-efficiency comprehensive utilization of agriculture and forestry organic waste material reduces environmental pollution, is also carried for production dialkyl carbonate
New way has been supplied, there is significant economic and social benefit；
2, preparation process of the present invention is simple, with short production cycle, energy expenditure is low, and synthetic method science environmental protection has fine
Industrialized production foreground；
3, the dialkyl carbonate for preparing of the present invention, can be applied to biological liquid fuel, volatility, safety,
Environment friendly, recyclability 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.
Description of the drawings
Fig. 1 is the synthetic route chart of dialkyl carbonate provided in an embodiment of the present invention；
Specific implementation mode
The present invention is further explained with reference to attached specific embodiment, but the present invention be not limited in it is as follows
Embodiment.
The present invention reacts generation at a higher temperature using agriculture and forestry organic waste material as initial feed with gasifying agent water vapour first
CO、H2、CH4The Biomass Syngas of equal fuel gas；Then Biomass Syngas can be direct by gas purification and reformation
Dimethyl ether synthesis；Again by dimethyl ether synthesis and CO, O2React Direct Synthesis of Dimethyl Carbonate；The dimethyl carbonate that is finally synthesizing with
Monohydric alcohol or polyalcohol carry out ester exchange reaction, and dialkyl carbonate is made.The method of the present invention is original with cheap agriculture and forestry organic waste material
Material production dialkyl carbonate, has not only saved production cost, has reduced environmental pollution, also for industrialized production dialkyl carbonate and
The high-efficiency comprehensive utilization of agriculture and forestry organic waste material provides new way, has significant economic and social benefit sheet.
Embodiment 1
1) Biomass Syngas is prepared
100g is made in the sawdust input gasification furnace of particle, it is 200 DEG C to control gasification furnace drying layer temperature first, to wood
2.5h is dried in bits；Then it is 500 DEG C to adjust temperature and carry out pyrolytic layer temperature, then carries out pyrolysis 1.5h to sawdust；Last wood
It is 900 DEG C to consider to be worth doing into people's burning zone temperature, and gasifying agent vapor is imported to the burning zone of gasification furnace with 1g/min, recycles gasification furnace
Gas out is that biomass raw synthesis gas is made, and the main component of crude synthesis gas is：35%H2, 38%CO, 11%CO2, 15%
H2O。
Crude synthesis gas reforms H through vapor transformationreation device2Molar ratio with CO is 1.4, uses iron for catalyst,
Pressure 0.8Mpa, reaction temperature are 250 DEG C；Gas is passed through again in -53 DEG C of methanol solution and is purified to absorb CO2, collect and close
At gas.
2) dimethyl ether synthesis
It is the preparation of Cu-Zn-Mn/HZSM-5 catalyst first, using the method for co-precipitation, first, in accordance with Cu:(Zn+Mn)
=1:0.5 molar ratio configures the mixed aqueous solution of nitrate, and stirring is warming up to 80 DEG C, the sodium carbonate liquor with 1mol/L is heavy
After adjusting pH=8 is added in shallow lake agent, 80 DEG C of bath temperature is kept, and be in and be stirred continuously state.80 DEG C of standings after co-precipitation
Aging 2h, then deionized water washing, filters, 120 DEG C of dry 12h, and 500 DEG C of roasting 4h obtain hydrogenation component.Hydrogenation component and
Dehydration component HZSM-5 in mass ratio 2:1 ratio mechanical mixture, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare.
Then, the 1% 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst that above-mentioned acquisition accounts for synthesis gas quality is taken to be packed into height
It presses in fixed bed reactors, then biomass synthesis gas is passed through in high pressure fixed bed reactors, air speed 1500/h, increases temperature
To 240 DEG C, pressure is increased to 2Mpa, collects mixed gas, mixed gas is cooled to -25 DEG C, collects dimethyl ether.
3) Synthesis of dimethyl carbonate
It is Pd-Cu/Ce first0.8Zr0.2O2The preparation of catalyst is divided into two steps：
The first step is Ce0.8Zr0.2O2The preparation of carrier is prepared using citric acid method, and it is 4 to prepare molar ratio:1 Ce (NO3)2
With Zr (NO3)2Mixed solution, is added slightly excessive citric acid, then stirring and sonic oscillation are steamed to being completely dissolved in 80 DEG C of water-baths
It is sent to dry, then dries 8h in 100 DEG C of baking ovens, obtain the powder sample of white fluffy, sample finally 500 DEG C of roastings in Muffle furnace
It burns 4h and obtains composite oxides sample；
The first step is prepared composite oxide supported (Pd-Cu double activateds component catalyst) using conventional co-impregnation by second step
Method prepare Pd-Cu/Ce0.8Zr0.2O2Catalyst：By 10% equimolar ratio H2PdC14With Cu (NO3)2Solution is immersed in simultaneously
After on composite oxides, through drying, finally, 4h is roasted in 650 DEG C of air, obtain Pd (10%)-Cu (10%)/
Ce0.8Zr0.2O2Catalyst, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare
Then, 1.5% 20-40 mesh Pd (10%)-Cu (10%)/Ce of dimethyl ether quality will be accounted for0.8Zr0.2O2Catalyst
It is fitted into high pressure fixed bed reactors, then by oxygen, carbon monoxide, dimethyl ether according to volume ratio 1:2:2, which are passed through high pressure, fixes
It is reacted in bed reactor.Temperature is increased to 120 DEG C, increases pressure to 2Mpa, room temperature collects dimethyl carbonate solution.
4) transesterification prepares dialkyl carbonate
It is the preparation of metal oxide catalyst first, it is to urge to select aluminium oxide, zinc oxide and cerium oxide mixed oxide
Agent, then with configuration metal ion molar ratio Zn:Al:Ce=8:1:1 metal nitrate mixed salt solution mixing, stirring are warming up to
It 80 DEG C, is added using the sodium carbonate liquor of 1mol/L as precipitating reagent after adjusting PH=8, keeps 80 DEG C of bath temperature, and in continuous
Stirring.80 DEG C of standing aging 2h after co-precipitation, then deionized water washing filter, 120 DEG C of dry 12h, 500 DEG C
4h is roasted, mixed metal oxide catalyst is obtained.
Then the dimethyl carbonate and ethyl alcohol that 3) are synthesized in embodiment 1 are added in tubular type transesterification reactor, then added
Enter it is above-mentioned prepare mixed metal oxide catalyst, carry out ester exchange reaction after mixing, reaction product is obtained through distillation
Diethyl carbonate；Wherein, the molar ratio 1 of dimethyl carbonate and ethyl alcohol:10, mixed metal oxide catalyst weight accounts for carbonic acid two
The 1% of methyl esters and ethyl alcohol total weight, the temperature for controlling ester exchange reaction are 120 DEG C, pressure 2MPa, reaction time 90min；
The conversion ratio of dimethyl carbonate is 100% in ester exchange reaction, and the yield of diethyl carbonate is 97.2%, the receipts of methyl ethyl carbonate
Rate is 2.8%.
Embodiment 2
1) Biomass Syngas is prepared
150g is made in the sawdust input gasification furnace of particle, it is 180 DEG C to control gasification furnace drying layer temperature first, to wood
2.5h is dried in bits；Then it is 400 DEG C to adjust temperature and carry out pyrolytic layer temperature, then carries out pyrolysis 1.5h to sawdust；Last wood
It is 800 DEG C to consider to be worth doing into people's burning zone temperature, and gasifying agent vapor is imported to the burning zone of gasification furnace with 1.5g/min, recycling gasification
The gas that stove comes out is that biomass raw synthesis gas is made, and the main component of crude synthesis gas is：35%H2, 30%CO, 20%CO2,
15%H2O。
Crude synthesis gas adjusts H through vapor transformationreation device2Ratio with CO is 1.3, uses iron for catalyst, pressure
0.8Mpa, reaction temperature are 250 DEG C；Gas is passed through again in -53 DEG C of methanol solution to absorb CO2, collect synthesis gas.
2) dimethyl ether synthesis
It is the preparation of Cu-Zn-Mn/HZSM-5 catalyst first, using the method for co-precipitation, first, in accordance with Cu:(Zn+Mn)
=1:0.6 molar ratio configures the mixed aqueous solution of nitrate, and stirring is warming up to 80 DEG C, the sodium carbonate liquor with 1mol/L is heavy
After adjusting pH=8 is added in shallow lake agent, 80 DEG C of bath temperature is kept, and be in and be stirred continuously state.80 DEG C of standings after co-precipitation
Aging 2h, then deionized water washing, filters, 120 DEG C of dry 12h, and 500 DEG C of roasting 4h obtain hydrogenation component.Hydrogenation component and
Dehydration component HZSM-5 in mass ratio 2:1 ratio mechanical mixture, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare.
Then, the 1.5% 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst that above-mentioned acquisition accounts for synthesis gas quality is taken to be packed into
In high pressure fixed bed reactors, then biomass synthesis gas is passed through in high pressure fixed bed reactors, air speed 2000/h, increases temperature
Degree increases pressure to 3Mpa, collects mixed gas, mixed gas is cooled to -25 DEG C, collects dimethyl ether to 260 DEG C.
3) Synthesis of dimethyl carbonate
It is Pd-Cu/Ce first0.8Zr0.2O2The preparation of catalyst is divided into two steps：
The first step is Ce0.7Zr0.3O2The preparation of carrier is prepared using citric acid method, and it is 7 to prepare molar ratio:3 Ce (NO3)2
With Zr (NO3)2Mixed solution, is added slightly excessive citric acid, then stirring and sonic oscillation are steamed to being completely dissolved in 80 DEG C of water-baths
It is sent to dry, then dries 8h in 100 DEG C of baking ovens, obtain the powder sample of white fluffy, sample finally 500 DEG C of roastings in Muffle furnace
It burns 4h and obtains composite oxides sample；
The first step is prepared composite oxide supported (Pd-Cu double activateds component catalyst) using conventional co-impregnation by second step
Method prepare Pd-Cu/Ce0.7Zr0.3O2Catalyst：By 10% equimolar ratio H2PdC14With Cu (NO3)2Solution is immersed in simultaneously
After on composite oxides, through drying, finally, 4h is roasted in 650 DEG C of air, obtain Pd (10%)-Cu (10%)/
Ce0.7Zr0.3O2Catalyst, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare
Then, 2% 20-40 mesh Pd (10%)-Cu (10%)/Ce of dimethyl ether quality will be accounted for0.7Zr0.3O2Catalyst fills
Enter in high pressure fixed bed reactors, then by oxygen, carbon monoxide, dimethyl ether according to volume ratio 1:1.7:2.1 are passed through high pressing
It is reacted in fixed bed reactor.Temperature is increased to 150 DEG C, increases pressure to 3Mpa, room temperature collects dimethyl carbonate solution.
4) transesterification prepares dialkyl carbonate
It is the preparation of metal oxide catalyst first, it is catalyst to select magnesia and cerium oxide mixed oxide, then
With configuration metal ion molar ratio Mg:Ce=2:1 metal nitrate mixed salt solution mixing, stirring is warming up to 80 DEG C, with 1mol/
The sodium carbonate liquor of L is after adjusting PH=8 is added in precipitating reagent, to keep 80 DEG C of bath temperature, and be in and be stirred continuously state.It is coprecipitated
80 DEG C of standing aging 2h after shallow lake, then deionized water washing filter, 120 DEG C of dry 12h, and 500 DEG C of roasting 4h are mixed
Close metal oxide catalyst.
Then by 3) dimethyl carbonate and trimethylolpropane of synthesis are added to tubular type transesterification reactor in embodiment 2
In, add it is above-mentioned prepare mixed metal oxide catalyst, carry out ester exchange reaction after mixing, reaction product is through distillation
Obtain trimethylolpropane carbonic ester；Wherein, the molar ratio 1 of dimethyl carbonate and trimethylolpropane:5, mixed metal oxygen
The weight of compound catalyst is 1.2% with the proportioning of dimethyl carbonate and trimethylolpropane total weight, controls ester exchange reaction
Temperature be 170 DEG C, pressure 3MPa, reaction time 100min；Dimethyl carbonate conversion ratio is 99% in ester exchange reaction,
The yield of trimethylolpropane carbonic ester is 95%, extracts the property indices of trimethylolpropane carbonic ester, symbol after testing
Close the national standard that lubricating oil uses.
Embodiment 3
1) Biomass Syngas is prepared
120g is made in the sawdust input gasification furnace of particle, it is 230 DEG C to control gasification furnace drying layer temperature first, to wood
2.5h is dried in bits；Then it is 550 DEG C to adjust temperature and carry out pyrolytic layer temperature, then carries out pyrolysis 1.5h to sawdust；Last wood
It is 850 DEG C to consider to be worth doing into people's burning zone temperature, and gasifying agent vapor is imported to the burning zone of gasification furnace with 1.2g/min, recycling gasification
The gas that stove comes out is that biomass raw synthesis gas is made, and the main component of crude synthesis gas is：36%H2, 33%CO, 19%CO2,
12%H2O。
Crude synthesis gas adjusts H through vapor transformationreation device2Ratio with CO is 1.5, uses iron for catalyst, pressure
0.8Mpa, reaction temperature are 250 DEG C；Gas is passed through again in -53 DEG C of methanol solution to absorb CO2, collect synthesis gas.
2) dimethyl ether synthesis
It is the preparation of Cu-Zn-Mn/HZSM-5 catalyst first, using the method for co-precipitation, first, in accordance with Cu:(Zn+Mn)
=1:0.4 molar ratio configures the mixed aqueous solution of nitrate, and stirring is warming up to 80 DEG C, the sodium carbonate liquor with 1mol/L is heavy
After adjusting pH=8 is added in shallow lake agent, 80 DEG C of bath temperature is kept, and be in and be stirred continuously state.80 DEG C of standings after co-precipitation
Aging 2h, then deionized water washing, filters, 120 DEG C of dry 12h, and 500 DEG C of roasting 4h obtain hydrogenation component.Hydrogenation component and
Dehydration component HZSM-5 in mass ratio 2:1 ratio mechanical mixture, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare.
Then, the 2% 20-40 mesh Cu-Zn-Mn/HZSM-5 catalyst that above-mentioned acquisition accounts for synthesis gas quality is taken to be packed into height
It presses in fixed bed reactors, then biomass synthesis gas is passed through in high pressure fixed bed reactors, air speed 1800/h, increases temperature
To 200 DEG C, pressure is increased to 4Mpa, collects mixed gas, mixed gas is cooled to -25 DEG C, collects dimethyl ether.
3) Synthesis of dimethyl carbonate
It is Pd-Cu/Ce first0.8Zr0.2O2The preparation of catalyst is divided into two steps：
The first step is Ce0.6Zr0.4O2The preparation of carrier is prepared using citric acid method, and it is 3 to prepare molar ratio:2 Ce (NO3)2
With Zr (NO3)2Mixed solution, is added slightly excessive citric acid, then stirring and sonic oscillation are steamed to being completely dissolved in 80 DEG C of water-baths
It is sent to dry, then dries 8h in 100 DEG C of baking ovens, obtain the powder sample of white fluffy, sample finally 500 DEG C of roastings in Muffle furnace
It burns 4h and obtains composite oxides sample；
The first step is prepared composite oxide supported (Pd-Cu double activateds component catalyst) using conventional co-impregnation by second step
Method prepare Pd-Cu/Ce0.6Zr0.4O2Catalyst：By 10% equimolar ratio H2PdC14With Cu (NO3)2Solution is immersed in simultaneously
After on composite oxides, through drying, finally, 4h is roasted in 650 DEG C of air, obtain Pd (10%)-Cu (10%)/
Ce0.6Zr0.4O2Catalyst, polished, tabletting are crushed sieving, and sieve takes 20-40 mesh spare
Then, 3% 20-40 mesh Pd (10%)-Cu (10%)/Ce0.6Zr0.4O2 catalyst of dimethyl ether quality will be accounted for
It is fitted into high pressure fixed bed reactors, then by oxygen, carbon monoxide, dimethyl ether according to volume ratio 1:2.2:1.8 are passed through high pressure
It is reacted in fixed bed reactors.Temperature is increased to 160 DEG C, increases pressure to 2.5Mpa, room temperature collects dimethyl carbonate solution.
4) transesterification prepares dialkyl carbonate
It is the preparation of metal oxide catalyst first, it is catalyst to select zinc oxide and cerium oxide mixed oxide, then
With configuration metal ion molar ratio Mg:Ce=6:1 metal nitrate mixed salt solution mixing, stirring is warming up to 80 DEG C, with 1mol/
The sodium carbonate liquor of L is after adjusting PH=8 is added in precipitating reagent, to keep 80 DEG C of bath temperature, and be in and be stirred continuously state.It is coprecipitated
80 DEG C of standing aging 2h after shallow lake, then deionized water washing filter, 120 DEG C of dry 12h, and 500 DEG C of roasting 4h are mixed
Close metal oxide catalyst.
The dimethyl carbonate and pentaerythrite that 3) are synthesized in embodiment 3 are added in tubular type transesterification reactor, then added
Enter it is above-mentioned prepare mixed metal oxide catalyst, carry out ester exchange reaction after mixing, reaction product is obtained through distillation
Pentaerythrite carbonic ester；Wherein, the molar ratio 1 of dimethyl carbonate and pentaerythrite:8, the weight of mixed metal oxide catalyst
Amount is 1.5% with the proportioning of dimethyl carbonate and pentaerythrite total weight, and the temperature for controlling ester exchange reaction is 180 DEG C, pressure
For 2.5MPa, reaction time 120min；Dimethyl carbonate conversion ratio is 99% in ester exchange reaction, pentaerythrite carbonic ester
Yield is 96%, the property indices of the pentaerythrite carbonic ester purified after testing, meets the national standard that lubricating oil uses.
Claims (8)
1. a kind of method of Biomass Syngas carbonate synthesis dialkyl, it is characterised in that：It is discarded with biomass-based agricultural
The Biomass Syngas that object is obtained as initial feed, is further catalyzed to obtain dimethyl ether, and gained dimethyl ether is further catalyzed
Dimethyl carbonate is obtained, then ester exchange reaction is carried out with monohydric alcohol or polyalcohol, obtains dialkyl carbonate.
2. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 1, it is characterised in that：The biology
Matter base synthesis gas is that pyrolytic gasification, control gasification furnace drying layer temperature are in gasification furnace by initial feed of agriculture and forestry organic waste material
110-245 DEG C, pyrolytic layer temperature is 335-556 DEG C, and burning zone temperature is 800-900 DEG C, and is mixed into promoting the circulation of qi with gasifying agent
Biomass raw synthesis gas is obtained, then reforms, purify to obtain Biomass Syngas.
3. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 1, it is characterised in that：The gasification
The flow velocity of agent vapor is the 1%g/min of agriculture and forestry organic waste material quality.
4. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 1, it is characterised in that：The biology
Matter base synthesis gas flows through catalyst Cu-Zn-Mn/HZSM-5 dimethyl ether synthesis, and catalyst quality is the 0.5- of synthesis gas quality
2%, reaction temperature is 200-280 DEG C, reaction pressure 2-4MPa, air speed 1500-2000/h.
5. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 4, it is characterised in that：The Cu-
Cu-Zn-Mn is hydrogenation component in Zn-Mn/HZSM-5 catalyst, and HZSM-5 is dehydration component, and the molar ratio of Cu and Zn+Mn are 1:
The mass ratio of 0.3-0.6, hydrogenation component and dehydration component is 2-3:1.
6. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 1, it is characterised in that：The carbonic acid
Dimethyl ester be by above-mentioned acquisition dimethyl ether and mixed gas in the presence of a catalyst, in 100-160 DEG C, reaction pressure 2-
4Mpa, Synthesis of dimethyl carbonate；Wherein, mixed gas is oxygen and carbon monoxide, oxygen, carbon monoxide and dimethyl ether molar ratio
It is 1:1.5-2.5:1.5-2.5, catalyst quality are the 0.5-3% of dimethyl ether quality；The catalyst is Pd-Cu/Ce1- xZrxO2, the load capacity of wherein Pd and Cu are 5-15%, and the value of x is 0.1-0.5.
7. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 1, it is characterised in that：By carbonic acid two
Methyl esters and monohydric alcohol or polyalcohol, in 120-180 DEG C, reaction pressure 1-4MPa under the action of metal oxide catalyst,
Reaction time is 90-120min, carries out ester exchange reaction and obtains dialkyl carbonate；Wherein, dimethyl carbonate and monohydric alcohol or polynary
The molar ratio of alcohol is 1:1-10, the weight of catalyst account for the 0.1-3% of dimethyl carbonate and monohydric alcohol or total polyol weight.
8. the method for Biomass Syngas carbonate synthesis dialkyl as described in claim 7, it is characterised in that：The unitary
The one kind of alcohol in C2-C8 straight chain alcohols, C3-C8 branched-chain alcohos, C3-C8 cyclic alcohol, polyalcohol are selected from trimethylolpropane, Ji Wusi
One kind in alcohol, neopentyl glycol；
Two or more of the metal oxide in aluminium oxide, magnesia, zinc oxide, stannous oxide, cerium oxide.
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