CN103525874B - Method for preparing dimethyl carbonate - Google Patents
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- CN103525874B CN103525874B CN201210226548.9A CN201210226548A CN103525874B CN 103525874 B CN103525874 B CN 103525874B CN 201210226548 A CN201210226548 A CN 201210226548A CN 103525874 B CN103525874 B CN 103525874B
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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Abstract
The invention discloses a method for preparing dimethyl carbonate by using ionic liquid as a cocatalyst of lipase for catalysis. The method comprises the following steps of adding ionic liquid in a reaction device; adding reactants methyl alcohol and ethylene carbonate or methyl alcohol and propylene carbonate into a reaction device in sequence; adding the lipase into the reactants; and stirring to carry out transesterification, thereby obtaining a product dimethyl carbonate after the reaction. According to the method of preparing dimethyl carbonate, the dimethyl carbonate is prepared by using ionic liquid as the cocatalyst of lipase to catalyze the methyl alcohol and ethylene carbonate or methyl alcohol and propylene carbonate, so that not only are conversation rate, selectivity and universality high, but also the process is simple, reaction conditions are gentle, cost is cost, environment is friendly, the lipase can be recycled and application prospect is wide.
Description
Technical field
The present invention relates to biological chemical field, particularly relate to a kind of method taking ionic liquid as the cocatalyst catalysis of lipase and prepare methylcarbonate.
Background technology
Methylcarbonate (Dimethyl Carbonate, DMC), is a kind of water white transparency, slightly smell, micro-sweet liquid during DMC normal temperature, is insoluble in water, but immiscible organic solvent that can be nearly all with alcohol, ether, ketone etc.DMC toxicity is very low, just non-toxic product is classified as by Europe in 1992, it is a kind of environmental protective type chemical raw material meeting modern cleaning procedure requirement, therefore the synthetic technology of DMC receives the extensive attention (J.H.Clements of domestic and international chemical circles, Ind.Eng.Chem.Res., 42 (2003): 663; S.Fukuoka et al., GreenChem.5 (2003): 497; J.Bayarydon et al., Angew.Chem.Int.Ed., 46 (2007): 5971).
The initial production method of DMC is phosgenation, succeed in developing, but the toxicity of phosgene and corrodibility limits the application of this method in 1918, and particularly along with environmental protection is by the raising day by day of whole world attention degree, phosgenation is eliminated.From the eighties in 20th century, the research for DMC production technique starts to receive general concern, according to the statistics of Michael A.Pacheco and ChristopherL.Marshall, about the patent of DMC production technique just exceeded 200 from 1980 ~ 1996 years.Early 1980s, it is the commercialization of being synthesized DMC technique by methanol oxidation carbonylation of catalyzer that gondola EniChem company achieves with CuCl, this is first technique realizing industrialized non-phosgene synthesis DMC, also be most widely used technique, when the defect of this technique is high conversion, the deactivation phenomenom of catalyzer is serious, and therefore its per pass conversion is only 20%.In the nineties in 20th century, the research of DMC synthesis technique obtains and develops rapidly, the technique of Ube to EniChem company methanol oxidation carbonylation synthesis DMC of Japan is improved, selection NO is catalyzer, this avoid the inactivation of catalyzer, makes transformation efficiency almost reach 100%, this technique achieves industrialization, but this technique take CO as raw material, and CO is a kind of poisonous gas, and the safety problem that therefore CO causes limits the application of this technique; Texaco company of the U.S. develops first by oxyethane and carbon dioxide reaction Formed vinyl acetate, produce the technique of DMC again through transesterify with methyl alcohol, this technique coproduction ethylene glycol, industrialization is achieved in 1992, this process quilt thinks that productive rate is lower, production cost is higher, only has when DMC annual production just can be competed with additive method higher than its investment and cost during 55kt; In addition also have a kind of emerging technique, i.e. urea alcoholysis reaction, carry out reducing costs if combine with urea production, this technique is expected to realize industrialization.
In recent years, the research of synthesis DMC is subject to the extensive concern of domestic and international investigator, synthetic route just towards simplifying, the future development of Non-toxic and pollution-freeization.The green method of current synthesis DMC mainly contains CO
2with methyl alcohol direct synthesis technique, ester-interchange method and alcoholysis of urea.Wherein, with NSC 11801 or propylene carbonate for raw material, by preparing the economic benefits of methylcarbonate and glycol with methyl alcohol transesterify and industrial requirement increases day by day, various countries scientist is caused to pay close attention to widely.US Patent No. 430703 discloses a kind of preparation method of dialkyl carbonate, the catalyzer using thallium compound as transesterification reaction is disclosed in this patent, under relative low temperature, low catalyst concentration, high speed of reaction can be obtained, and inhibit the generation of side reaction forcefully.Such as at 150 DEG C, 1.92 × 10
-4under mol thallium carbonate exists, after reaction 30min, (methyl alcohol: NSC 11801=5: transformation efficiency 1) reaches 7%, the selectivity generating DMC reaches 90% to NSC 11801.Removed the azeotrope (about 70% methyl alcohol) of DMC and methyl alcohol by distillation after, residue continues and methyl alcohol reaction under identical conditions, can obtain the transformation efficiency of 80%, its by product is still little, and this reaction also can be carried out in the fixed-bed reactor that thallium catalyzer is housed.US Patent No. 4661609 discloses a kind of method of coproduction ethylene glycol and methylcarbonate, the soluble salt that uses titanium and zirconium or its complex compound homogeneous catalyst as transesterification reaction is disclosed in this patent, temperature of reaction is at 20 DEG C ~ 200 DEG C, and joining of methyl alcohol and NSC 11801 is smaller.Such as 130 DEG C of zirconium make catalyzer, and when methyl alcohol and NSC 11801 mol ratio are 4.7, the transformation efficiency of ethylene carbonate vinegar is 89%.The selectivity of DMC counts 80% with NSC 11801, counts 76% with methyl alcohol, and the selectivity of ethylene glycol is all more than 95%.Alkaline earth metal silicate is as Na2SiO3, KHSiO3, Li2SiO3 even load on silica gel as reaction catalyzer, at 80 DEG C ~ 125 DEG C, 0.7Mpa, LHSV=1.0, time CH3OH/EC (mol)=4, its active order is: Na2SiO3 > KHSiO3 > Li2SiO3, wherein, water glass supported on silica gel as catalyzer time, the transformation efficiency of NSC 11801 is about 30%.But the catalytic life of this type of material is not long, and with the prolongation in reaction times, catalytic activity declines gradually (Liu Zongjian, Cai Ye, the catalyst research of ester-interchange method synthesis DMC, Chemical Manufacture and technology, 1998,5 (4), 13-15).
There is catalyst activity or the shortcoming such as selectivity is not high, productive rate is low in methyl alcohol direct synthesis technique, ester-interchange method and alcoholysis of urea synthesis DMC, therefore finds more suitable catalyzer and carrier, the activity and selectivity of raising catalyzer is key problem in technology and the study hotspot of producing DMC.
Enzyme is as a kind of biological catalyst, and oneself is widely used in the field such as foodstuff production and detection, green technology, biotechnology, biological medicine by people in recent years.Current investigation and application is lipase (Lipase the most widely, EC 3.1.1.3) be the biological catalyst that a class energy catalysis grease and short chain alcohol carry out that transesterification generates fatty acid methyl ester, the reaction that lipase mediates has reaction conditions gentleness, alcohol consumption is little, product easily collecting purifying, the advantages such as non-pollutant discharge, the domestic and international lipase for transesterification research is mainly the Novozym435 that Novozymes Company produces at present, this enzyme is resin immobilized enzyme, carrier is macroporous acrylic resin, price is high, be unfavorable for that enzyme process prepares the suitability for industrialized production of industrial chemicals.In addition, when enzyme carries out transesterification as catalyst grease and short chain alcohol, short chain alcohol can reduce the activity of enzyme, and therefore, the cocatalyst that the enzyme finding a kind of energy stabilized enzyme is lived becomes the study hotspot of people with the productive rate improving transesterification.In recent years, a kind of novel Green Chemistry solvent-ionic liquid (ionic liquid) causes the extensive concern of people.Ionic liquid is made up of organic cation and inorganic or organic anion, salt in liquid state below 100 DEG C, compared with ordinary organic solvents, ionic liquid has the following advantages: ionic liquid can not volatilize, environmentally friendly, relatively safe for industrial production, by the design of zwitterion adjustable its to the solvability of material; Ionic liquid and some organic solvents immiscible, organic solvent-ionic liquid biphasic system or organic solvent-water-ionic liquid three-phase system can be formed.Generally speaking, ionic liquid is applied to biocatalysis process using 3 kinds of forms: (1) is as neat solvent; (2) in aqueous phase system as cosolvent; (3) in biphasic system as cosolvent.Lipase is in ionic liquid, carry out the maximum class of enzymes of biocatalytic reaction research report at present, and it can exist and the polytype reaction of catalysis in different kinds of ions liquid, as transesterification reaction, ammonolysis reaction, hydrolysis reaction and epoxidation reaction etc.R.M.Lau etc. utilize antarctic candidia lipase (Candida antarcticalipase B first, CALB) potentiality that it carries out biocatalytic reaction in ionic liquid are demonstrated, as the transesterification reaction of lipase-catalyzed ethyl butyrate and butanols.Lipase catalysis vinyl butyrate and propyl carbinol in ionic liquid such as P.Lazano pass through transesterification reaction synthetic butyric acid butyl ester, result shows that the catalytic activity of lipase in ionic liquid is higher than its activity in organic solvent, the catalytic activity of enzyme raises along with the enhancing of ionic liquid polarity, and lipase has very high stability in operate continuously process.S.J.Nara etc. also confirm that ionic liquid has the effect that enzymatic activity is improved.But the method that methylcarbonate is prepared in the cocatalyst catalysis that employing ionic liquid is lipase have not been reported.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of method taking ionic liquid as the cocatalyst catalysis of lipase and prepare methylcarbonate, not only there is high conversion, highly selective, high universality, and technique is simple, reaction conditions is gentle, reduce costs, environmental friendliness, lipase reusable edible, have a extensive future.
For solving the problems of the technologies described above, the technical solution used in the present invention is: provide a kind of method preparing methylcarbonate, said method comprising the steps of:
1) in reaction unit, ionic liquid is added;
2) in described reaction unit, add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate successively;
3) in described reactant, lipase is added;
4) transesterification reaction is carried out in stirring, obtains product methylcarbonate after reaction.
Preferably, described step 1) in add ionic liquid 2ml/g based on described NSC 11801 or described propylene carbonate weight, described ionic liquid selects the one in 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate.
Preferably, described step 2) in add methyl alcohol and NSC 11801 or methyl alcohol and the propylene carbonate that alcohol ester mol ratio is 4: 1 ~ 50: 1.
Most preferably, described step 2) in add methyl alcohol and NSC 11801 or methyl alcohol and the propylene carbonate that alcohol ester mol ratio is 16: 1.
Preferably, described step 3) in add the lipase of 0.1% ~ 25% of described reactant massfraction.
Most preferably, described step 3) in add the lipase of 0.3% of described reactant massfraction.
Preferably, described step 4) in add the water of described NSC 11801 or described propylene carbonate massfraction 1%, the temperature of reaction of described transesterification reaction is 25 DEG C ~ 75 DEG C, and the reaction times is 1 ~ 160 hour, and reaction pressure is 0.1Mpa.In the present invention, the activity of content to enzyme of water has material impact.
Most preferably, the temperature of reaction of described transesterification reaction is 55 DEG C, and the reaction times is 72 hours.
Lipase can derive from animal, plant or microorganism.
Preferably, described lipase is Penicillium lipase.
Most preferably, described lipase is penicillium expansum lipase.
The invention has the beneficial effects as follows: be different from the low conversion rate existed in the preparation of existing methylcarbonate, selectivity is low, complex process, the situation of contaminate environment, the cocatalyst catalysis methanol that the present invention uses ionic liquid to be lipase and NSC 11801 or methyl alcohol and propylene carbonate carry out transesterification reaction and prepare methylcarbonate, because ionic liquid physical efficiency reduces methyl alcohol to the disadvantageous effect of lipase activity, the enzyme of stabilised fat enzyme is lived, and the single-minded catalytic activity of lipase and nontoxicity, the inventive method is made not only to have high conversion, highly selective, high universality, and technique is simple, reaction conditions is gentle, reduce costs, environmental friendliness, lipase reusable edible, have a extensive future.
Accompanying drawing explanation
The cocatalyst catalysis methanol of Fig. 1 to be the present invention with ionic liquid be lipase and NSC 11801 or methyl alcohol and propylene carbonate react the reaction formula preparing methylcarbonate;
Cocatalyst catalysis methanol and the NSC 11801 of Fig. 2 to be the present invention with ionic liquid be lipase react the relation schematic diagram preparing methylcarbonate and reaction times;
Cocatalyst catalysis methanol and the propylene carbonate of Fig. 3 to be the present invention with ionic liquid be lipase react the relation schematic diagram preparing methylcarbonate and reaction times;
Cocatalyst catalysis methanol and the NSC 11801 of Fig. 4 to be the present invention with ionic liquid be lipase react the relation schematic diagram preparing methylcarbonate and temperature of reaction;
Cocatalyst catalysis methanol and the NSC 11801 of Fig. 5 to be the present invention with ionic liquid be lipase react the relation schematic diagram preparing methylcarbonate and molar ratio of material;
Cocatalyst catalysis methanol and the propylene carbonate of Fig. 6 to be the present invention with ionic liquid be lipase react the relation schematic diagram preparing methylcarbonate and lipase consumption.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Refer to Fig. 1, the present invention is that lipase cocatalyst catalysis methanol and NSC 11801 or methyl alcohol and propylene carbonate react the reaction formula preparing carbon ester dimethyl ester with ionic liquid.The preparation process of methylcarbonate: first add ionic liquid in reaction unit; Then in described reaction unit, add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate successively; In described reactant, add lipase again, stir and carry out transesterification reaction, after reaction, obtain product methylcarbonate.Ionic liquid selects the one in 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate.Lipase can derive from animal, plant or microorganism, especially Penicillium lipase.
Be that the cocatalyst catalysis methanol of lipase and NSC 11801 or methyl alcohol and propylene carbonate react in the process preparing carbon ester dimethyl ester with ionic liquid, reaction preference Finnigan TraceDSQ type gas chromatography mass spectrometry chromatographic instrument measures, and chromatographic column used is HP 5MS type.
Be that the cocatalyst catalysis methanol of lipase and NSC 11801 or methyl alcohol and propylene carbonate react in the process preparing carbon ester dimethyl ester with ionic liquid, DMC addition analytical procedure is: get the centrifugal layering of 50 μ L reaction solution, get upper liquid sample 10 μ L, dissolve with 290 μ L hexanaphthenes, shake up, then add 300 μ L dodecanes (2mg/ml) as interior mark; Get 1 μ L sample feeding, by the methylcarbonate amount in gas Chromatographic Determination reactant.The SP-6890 type gas chromatograph for determination of transformation efficiency Shandong LuNan Chemical Engineering Instrument Plant, chromatographic column is SE-54 type.Concrete test condition is: column compartment adopts temperature programming: 100 DEG C maintain 6 minutes, heat-up rate 40 DEG C/min, maintain 15 minutes, vaporizer 320 DEG C, sensing chamber 320 DEG C to 200 DEG C.Calculated the transformation efficiency of NSC 11801 or propylene carbonate by the carbon ester dimethyl ester gauge measured, method of calculation are as follows:
The quality of methylcarbonate, residual carbon vinyl acetate or residual carbon acid acrylic acid is obtained (marker method, dodecane is as interior mark) by gas-chromatography calculated by peak area.
Embodiment 1
In containing the reaction unit of ionic liquid 1-ethyl-3-methylimidazole hexafluorophosphate, add reactant methanol and NSC 11801 successively, the mol ratio of methyl alcohol and NSC 11801 is 16: 1, ionic liquid 2ml/g (based on ester weight, v/w); Then the penicillium expansum lipase of reactant massfraction 0.3% is added; Add water again, water-content 1% (based on ester weight, w/w), stir and carry out transesterification reaction, temperature of reaction 55 DEG C, the reaction times is 1 ~ 120h, and reaction pressure is 0.1Mpa.Timing extracts reaction solution for DMC addition analysis.Refer to Fig. 2, the present invention is that the cocatalyst catalysis methanol of lipase and NSC 11801 react the relation schematic diagram preparing methylcarbonate and reaction times with ionic liquid, as shown in Figure 2, along with the prolongation in reaction times, the transformation efficiency of NSC 11801 improves gradually, when being when reacted 72h, the transformation efficiency of NSC 11801 culminates, and is 91%; Afterwards, along with the prolongation in reaction times, the transformation efficiency of NSC 11801 tends towards stability.
Embodiment 2
Reactant methanol and propylene carbonate is added successively, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, ionic liquid 2ml/g (based on ester weight, v/w)) in containing the reaction unit of ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate; Then the penicillium expansum lipase of reactant massfraction 0.3% is added; Add water again, water-content 1% (based on ester weight, w/w)), stir and carry out transesterification reaction, temperature of reaction 55 DEG C, reaction times 1 ~ 160h, reaction pressure is 0.1Mpa.Timing extracts reaction solution for DMC addition analysis.Refer to Fig. 3, the present invention is that the cocatalyst catalysis methanol of lipase and propylene carbonate react the relation schematic diagram preparing methylcarbonate and reaction times with ionic liquid, as shown in Figure 3, along with the prolongation in reaction times, the transformation efficiency of propylene carbonate improves gradually, when being when reacted 72h, the transformation efficiency of propylene carbonate culminates, and is 81%; Afterwards, along with the prolongation in reaction times, the transformation efficiency of propylene carbonate tends towards stability.
Embodiment 3
Reactant methanol and NSC 11801 is added successively, the mol ratio 16: 1 of methyl alcohol and NSC 11801, ionic liquid 2ml/g (based on ester weight, v/w) in containing the reaction unit of ionic liquid 1-ethyl-3-methylimidazole a tetrafluoro borate; Then the penicillium expansum lipase of reactant massfraction 0.3% is added; Add water again, water-content 1% (based on ester weight, w/w), stir and carry out transesterification reaction, temperature of reaction 25 DEG C ~ 75 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Extract reaction solution for DMC addition analysis when differing temps.Refer to Fig. 4, the present invention is that the cocatalyst catalysis methanol of lipase and NSC 11801 react the relation schematic diagram preparing methylcarbonate and temperature of reaction containing ionic liquid, as shown in Figure 4, along with the raising of temperature, the transformation efficiency of NSC 11801 improves gradually, when temperature of reaction is 55 DEG C, the transformation efficiency of NSC 11801 reaches the highest, is 85%; When temperature of reaction is 60 DEG C, the transformation efficiency of NSC 11801 still reaches 84%; Afterwards, along with the raising of temperature, the transformation efficiency of NSC 11801 reduces gradually.
Embodiment 4
Reactant methanol and NSC 11801 is added successively, the mol ratio 4: 1 ~ 50: 1 of methyl alcohol and NSC 11801, ionic liquid 2ml/g (based on ester weight, v/w) in containing the reaction unit of ionic liquid 1-butyl-3-methyl imidazolium a tetrafluoro borate; Then the penicillium expansum lipase of reactant massfraction 0.3% is added; Add water again, water-content 1% (based on ester weight, w/w), stir and carry out transesterification reaction, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Extract reaction solution for DMC addition analysis.Refer to Fig. 5, ionic liquid of the present invention is that the cocatalyst catalysis methanol of lipase and NSC 11801 react the relation schematic diagram preparing methylcarbonate and molar ratio of material, as shown in Figure 5, along with the raising of alcohol ester mol ratio, the transformation efficiency of NSC 11801 improves gradually; When alcohol ester mol ratio is 16: 1, the transformation efficiency of NSC 11801 is the highest, reaches 81%; Afterwards, along with the raising of alcohol ester mol ratio, the transformation efficiency of NSC 11801 reduces gradually.
Embodiment 5
Reactant methanol and propylene carbonate is added successively, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, ionic liquid 2ml/g (based on ester weight, v/w) in containing the reaction unit of ionic liquid 1-ethyl-3-methylimidazole hexafluorophosphate; Then the penicillium expansum lipase of reactant massfraction 0.1% ~ 25% is added; Add water again, water-content 1% (based on ester weight, w/w), stir and carry out transesterification reaction, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Extract reaction solution for DMC addition analysis.Refer to Fig. 6, the present invention is that the cocatalyst catalysis methanol of lipase and propylene carbonate react the relation schematic diagram preparing methylcarbonate and lipase consumption with ionic liquid, as shown in Figure 6, when lipase consumption is 0.3% of reactant massfraction, the transformation efficiency of propylene carbonate is the highest, up to 92%; After lipase consumption exceedes 0.3% of reactant massfraction, along with the increase of lipase consumption, the transformation efficiency of propylene carbonate reduces gradually.
Above in each embodiment, the selectivity of reaction preference methylcarbonate after reaction 72h is all greater than 90%.
Above in each embodiment, after completion of the reaction, cross and filter lipase, remove excessive methyl alcohol by fractionation and obtain product methylcarbonate, lipase is through washing with acetone, and 40 DEG C of dryings, reusable, catalytic activity can not reduce.
Comparative example
Comply with in not containing the reaction unit of ionic liquid into adding reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate, the mol ratio 16: 1 of methyl alcohol and NSC 11801 or methyl alcohol and carbon ester propylene; Then the penicillium expansum lipase of reactant massfraction 0.3% is added; Add water again, water-content 1% (based on ester weight, w/w), stir and carry out transesterification reaction, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa, obtains product methylcarbonate after reaction.
After reaction 72h, extract reaction solution for DMC addition analysis, and the transformation efficiency calculating NSC 11801 by the carbon ester dimethyl ester gauge determined is 65%, the transformation efficiency of propylene carbonate is 63%.
From above each embodiment and comparative example, be not that lipase cocatalyst catalysis methanol and NSC 11801 or methyl alcohol and propylene carbonate are prepared in the reaction of carbon ester dimethyl ester with ionic liquid, the transformation efficiency of NSC 11801 is 65%, the transformation efficiency of propylene carbonate is about 63%, and under the same conditions, be that the cocatalyst catalysis methanol of lipase and NSC 11801 or methyl alcohol and propylene carbonate are prepared in the reaction of carbon ester dimethyl ester with ionic liquid, the transformation efficiency of NSC 11801 is up to 81% ~ 91%, the transformation efficiency of propylene carbonate is up to 81% ~ 92%, the transformation efficiency of NSC 11801 improves 16% ~ 26%, the transformation efficiency of propylene carbonate improves 18% ~ 29%.
Those skilled in the art do not depart from essence of the present invention and spirit, and various deformation scheme can be had to realize the present invention, the foregoing is only the better feasible embodiment of the present invention, not thereby limit to interest field of the present invention.In addition, should be appreciated that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Claims (8)
1. prepare a method for methylcarbonate, it is characterized in that, said method comprising the steps of:
1) in reaction unit, ionic liquid is added;
2) in described reaction unit, add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate successively;
3) in described reactant, penicillium expansum lipase is added;
4) transesterification reaction is carried out in stirring, obtains product methylcarbonate after reaction.
2. prepare the method for methylcarbonate as claimed in claim 1, it is characterized in that, described step 1) in add ionic liquid 2ml/g based on described NSC 11801 or described propylene carbonate weight, described ionic liquid selects the one in 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate.
3. prepare the method for methylcarbonate as claimed in claim 1, it is characterized in that, described step 2) in add the methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate that alcohol ester mol ratio is 4:1 ~ 50:1.
4. prepare the method for methylcarbonate as claimed in claim 3, it is characterized in that, described step 2) in add the methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate that alcohol ester mol ratio is 16:1.
5. prepare the method for methylcarbonate as claimed in claim 1, it is characterized in that, described step 3) in add the penicillium expansum lipase of 0.1% ~ 25% of described reactant massfraction.
6. prepare the method for methylcarbonate as claimed in claim 5, it is characterized in that, described step 3) in add the penicillium expansum lipase of 0.3% of described reactant massfraction.
7. prepare the method for methylcarbonate as claimed in claim 1, it is characterized in that, described step 4) in add the water of described NSC 11801 or described propylene carbonate massfraction 1%, the temperature of reaction of described transesterification reaction is 25 DEG C ~ 75 DEG C, reaction times is 1 ~ 160 hour, and reaction pressure is 0.1Mpa.
8. prepare the method for methylcarbonate as claimed in claim 7, it is characterized in that, the temperature of reaction of described transesterification reaction is 55 DEG C, and the reaction times is 72 hours.
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| CN201210226548.9A CN103525874B (en) | 2012-07-03 | 2012-07-03 | Method for preparing dimethyl carbonate |
| PCT/CN2013/000236 WO2014005417A1 (en) | 2012-07-03 | 2013-03-06 | Method for preparing dimethyl carbonate |
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| CN201210226548.9A CN103525874B (en) | 2012-07-03 | 2012-07-03 | Method for preparing dimethyl carbonate |
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| WO2015087341A1 (en) | 2013-12-12 | 2015-06-18 | Council Of Scientific & Industrial Research | An improved process for the preparation of dimethyl carbonate using ionic liquids as catalyst |
| CN105669366A (en) * | 2015-12-31 | 2016-06-15 | 天津中福工程技术有限公司 | Method for synthesizing diethyl carbonate by adopting alkaline ionic liquid as catalyst |
| CN110878020B (en) * | 2019-12-04 | 2021-11-30 | 大连理工大学 | Method for directly preparing dimethyl carbonate under low pressure |
| CN112961871A (en) * | 2021-02-26 | 2021-06-15 | 源创核新(北京)新材料科技有限公司 | Recombinant plasmid, genetic engineering bacterium containing recombinant plasmid and application of recombinant plasmid in preparation of dimethyl carbonate |
| CN115108911A (en) * | 2022-05-26 | 2022-09-27 | 南京工业大学 | Method for preparing dimethyl carbonate by directly esterifying alkylene oxide |
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| US4661609A (en) * | 1986-07-31 | 1987-04-28 | Texaco Inc. | Process for cosynthesis of ethylene glycol and dimethyl carbonate |
| JP4000912B2 (en) * | 2002-05-30 | 2007-10-31 | 三菱化学株式会社 | Method for producing dimethyl carbonate |
| CN102126956B (en) * | 2010-11-30 | 2013-10-16 | 中国科学院过程工程研究所 | Catalytic method for preparing dimethyl cabonate along with ethylene glycol |
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