CN103525872B - Method for preparing dimethyl carbonate through lipase catalysis - Google Patents
Method for preparing dimethyl carbonate through lipase catalysis Download PDFInfo
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- CN103525872B CN103525872B CN201210226238.7A CN201210226238A CN103525872B CN 103525872 B CN103525872 B CN 103525872B CN 201210226238 A CN201210226238 A CN 201210226238A CN 103525872 B CN103525872 B CN 103525872B
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Abstract
The invention discloses a method for preparing dimethyl carbonate through lipase catalysis. The method comprises the following steps of sequentially adding reactants, namely methanol and ethylene carbonate or methanol and propylene carbonate into a reaction device, then adding lipase into the reactants, and finally, stirring for a transesterification reaction to obtain a product, namely dimethyl carbonate. According to the method disclosed by the invention, the transesterification reaction between methanol and ethylene carbonate or methanol and propylene carbonate is catalyzed by the lipase to obtain dimethyl carbonate; due to the specific catalysis activity and no toxicity of the lipase, the method realizes high conversion rate, high selectivity and high universality; moreover, the technology is simple, the reaction conditions are mild, the cost is lowered, the method is environment-friendly, the lipase can be recycled, and the application prospect is broad.
Description
Technical field
The present invention relates to biological chemical field, particularly relate to a kind of lipase-catalyzed method preparing 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 CO2 and 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 70%, 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 of 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 the selectivity of 76% ethylene glycol all more than 95% with methyl alcohol.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, as a kind of biological catalyst, 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.The lipase-catalyzed method preparing methylcarbonate is adopted to have not been reported.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of lipase-catalyzed method preparing methylcarbonate, because lipase has single-minded catalytic activity and nontoxicity, make the inventive method not only 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.
For solving the problems of the technologies described above, the technical solution used in the present invention is: provide a kind of lipase-catalyzed method preparing methylcarbonate, said method comprising the steps of:
1) in reaction unit, add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate successively;
2) in described reactant, lipase is added;
3) transesterification reaction is carried out in stirring, obtains product methylcarbonate after reaction.
Preferably, described step 1) in add methyl alcohol and NSC 11801 or methyl alcohol and the propylene carbonate that alcohol ester mol ratio is 10: 1 ~ 30: 1.
Most preferably, described step 1) 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 water of described NSC 11801 or described propylene carbonate massfraction 1%, the temperature of reaction of described transesterification reaction is 45 DEG C ~ 60 DEG C, and the reaction times is 1 ~ 160 hour, and reaction pressure is 0.1Mpa.
Most preferably, the temperature of reaction of described transesterification reaction is 55 DEG C, and the reaction times is 72 hours.
Preferably, described step 2) in add the lipase of 0.3% ~ 15% of described reactant massfraction.
Most preferably, described step 2) in add the lipase of 0.3% of described reactant massfraction.
Wherein, described lipase derives 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 that the low conversion rate, the selectivity that exist in the preparation of existing methylcarbonate are low, the situation of complex process, contaminate environment, the present invention uses lipase-catalyzed methyl alcohol and propylene carbonate or NSC 11801 to carry out transesterification reaction to prepare methylcarbonate, due to single-minded catalytic activity and the nontoxicity of lipase, make the inventive method not only 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
Fig. 1 is that the lipase-catalyzed methyl alcohol of the present invention and NSC 11801 or methyl alcohol and propylene carbonate react the reaction formula preparing carbon ester dimethyl ester.
Fig. 2 is that the lipase-catalyzed methyl alcohol of the present invention and NSC 11801 react the relation schematic diagram preparing methylcarbonate and reaction times;
Fig. 3 is that the lipase-catalyzed methyl alcohol of the present invention and propylene carbonate react the relation schematic diagram preparing methylcarbonate and reaction times;
Fig. 4 is that the lipase-catalyzed methyl alcohol of the present invention and NSC 11801 react the relation schematic diagram preparing methylcarbonate and temperature of reaction;
Fig. 5 is that the lipase-catalyzed methyl alcohol of the present invention and propylene carbonate react the relation schematic diagram preparing methylcarbonate and molar ratio of material;
Fig. 6 is that the lipase-catalyzed methyl alcohol of the present invention and NSC 11801 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 lipase-catalyzed methyl alcohol of the present invention and NSC 11801 or methyl alcohol and propylene carbonate react the reaction formula preparing carbon ester dimethyl ester.The preparation process of methylcarbonate: first add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate in reaction unit successively; Lipase is added in reactant; Transesterification reaction is carried out in stirring, obtains product methylcarbonate after reaction.Lipase can derive from animal, plant or microorganism, especially Penicillium lipase.
React in the process preparing carbon ester dimethyl ester at lipase-catalyzed methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate, reaction preference Finnigan Trace DSQ type gas chromatography mass spectrometry chromatographic instrument measures, and chromatographic column used is HP 5MS type.
React in the process preparing carbon ester dimethyl ester at lipase-catalyzed methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate, 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 content of the methylcarbonate 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 reaction unit, add reactant methanol and NSC 11801 successively, the mol ratio of methyl alcohol and NSC 11801 is 16: 1; 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 lipase-catalyzed methyl alcohol of the present invention and NSC 11801 react the relation schematic diagram preparing methylcarbonate and reaction times, 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 67%; 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 in reaction unit; 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 lipase-catalyzed methyl alcohol of the present invention and propylene carbonate react the relation schematic diagram preparing methylcarbonate and reaction times, 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 65%; 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 in reaction unit; 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 lipase-catalyzed methyl alcohol of the present invention and NSC 11801 react the relation schematic diagram preparing methylcarbonate and temperature of reaction, 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 66%; When temperature of reaction is 60 DEG C, the transformation efficiency of NSC 11801 still reaches 65%; Afterwards, along with the raising of temperature, the transformation efficiency of NSC 11801 reduces gradually.
Embodiment 4
Reactant methanol and propylene carbonate is added successively, the mol ratio 4: 1 ~ 50: 1 of methyl alcohol and propylene carbonate in reaction unit; 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, the lipase-catalyzed methyl alcohol of the present invention and propylene carbonate react the relation schematic diagram preparing methylcarbonate and molar ratio of material, and as shown in Figure 5, along with the raising of alcohol ester mol ratio, the transformation efficiency of propylene carbonate improves gradually; When alcohol ester mol ratio is 16: 1, the transformation efficiency of propylene carbonate is the highest, reaches 64%; Afterwards, along with the raising of alcohol ester mol ratio, the transformation efficiency of propylene carbonate reduces gradually.
Embodiment 5
Reactant methanol and NSC 11801 is added successively, the mol ratio 16: 1 of methyl alcohol and NSC 11801 in reaction unit; 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 lipase-catalyzed methyl alcohol of the present invention and NSC 11801 react the relation schematic diagram preparing methylcarbonate and lipase consumption, as shown in Figure 6, when lipase consumption is 0.3% of reactant massfraction, the transformation efficiency of NSC 11801 is the highest, up to 67%; After lipase consumption exceedes 0.3% of reactant massfraction, along with the increase of lipase consumption, the transformation efficiency of NSC 11801 reduces gradually.
Above in each embodiment, the selectivity of reaction preference methylcarbonate after reaction 72h is all greater than 80%.
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.
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 (7)
1. the lipase-catalyzed method preparing methylcarbonate, is characterized in that, said method comprising the steps of:
1) in reaction unit, add reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate successively;
2) in described reactant, penicillium expansum lipase is added;
3) transesterification reaction is carried out in stirring, obtains product methylcarbonate after reaction.
2. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 1, is characterized in that, described step 1) in add the methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate that alcohol ester mol ratio is 10:1 ~ 30:1.
3. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 2, is characterized in that, described step 1) in add the methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate that alcohol ester mol ratio is 16:1.
4. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 1, it is characterized in that, described step 3) in add the water of described NSC 11801 or described propylene carbonate massfraction 1%, the temperature of reaction of described transesterification reaction is 45 DEG C ~ 60 DEG C, reaction times is 1 ~ 160 hour, and reaction pressure is 0.1Mpa.
5. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 4, it is characterized in that, the temperature of reaction of described transesterification reaction is 55 DEG C, and the reaction times is 72 hours.
6. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 1, is characterized in that, described step 2) in add the penicillium expansum lipase of 0.3% ~ 15% of described reactant massfraction.
7. the lipase-catalyzed method preparing methylcarbonate as claimed in claim 6, is characterized in that, described step 2) in add the penicillium expansum lipase of 0.3% of described reactant massfraction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829554A (en) * | 2010-03-26 | 2010-09-15 | 中国科学院化学研究所 | Repeatedly used catalyst for synthesizing dimethyl carbonate |
| CN102126956A (en) * | 2010-11-30 | 2011-07-20 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829554A (en) * | 2010-03-26 | 2010-09-15 | 中国科学院化学研究所 | Repeatedly used catalyst for synthesizing dimethyl carbonate |
| CN102126956A (en) * | 2010-11-30 | 2011-07-20 | 中国科学院过程工程研究所 | Catalytic method for preparing dimethyl cabonate along with ethylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| Understanding Structure Stability Relationships of Candida antartica Lipase B in Ionic Liquids;Teresa De Diego et al.;《Biomacromolecules》;20050302;第6卷(第3期);摘要，第1458页左栏第4段 * |
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