CN103525798B - For the preparation of the biological enzyme agent and preparation method thereof of methylcarbonate - Google Patents
For the preparation of the biological enzyme agent and preparation method thereof of methylcarbonate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/16—Hydrolases (3) acting on ester bonds (3.1)
- C12N9/18—Carboxylic ester hydrolases (3.1.1)
- C12N9/20—Triglyceride splitting, e.g. by means of lipase
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Y—ENZYMES
- C12Y301/00—Hydrolases acting on ester bonds (3.1)
- C12Y301/01—Carboxylic ester hydrolases (3.1.1)
- C12Y301/01003—Triacylglycerol lipase (3.1.1.3)
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
Abstract
The invention discloses a kind of biological enzyme agent for the preparation of methylcarbonate and preparation method thereof, described biological enzyme agent comprises ionic liquid and lipase, wherein, containing 0.003 gram ~ 0.75 gram lipase in every milliliter of ionic liquid.The present invention uses the biological enzyme agent formed for main component with ionic liquid and lipase, prepare catalytic efficiency in the process of methylcarbonate high, and described biological enzyme agent can recycle at catalytic esterification, environmentally friendly.
Description
Technical field
The present invention relates to biological chemical field, particularly relate to a kind of biological enzyme agent for the preparation of methylcarbonate and preparation method thereof.
Background technology
Methylcarbonate (DimethylCarbonate, 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.Fukuokaetal., GreenChem.5 (2003): 497; J.Bayarydonetal., 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 MichaelA.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 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, EC3.1.1.3) be that a class energy catalysis grease and short chain alcohol are carried out transesterification and generated the biological catalyst of fatty acid methyl ester, the reaction that lipase mediates has the advantages such as reaction conditions gentleness, alcohol consumption are little, product easily collecting purifying, non-pollutant discharge.The biological enzyme agent formed for main component with ionic liquid and lipase have not been reported preparing the application on methylcarbonate.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of biological enzyme agent for the preparation of methylcarbonate and preparation method thereof, and not only catalytic efficiency is high in described biological enzyme agent, and can recycle, environmentally friendly.
For solving the problems of the technologies described above, the technical solution used in the present invention is: provide a kind of biological enzyme agent for the preparation of methylcarbonate, described biological enzyme agent comprises ionic liquid and lipase, wherein, containing 0.003 gram ~ 0.75 gram lipase in every milliliter of ionic liquid.
Preferably, 0.01 gram ~ 0.3 gram lipase is contained in every milliliter of ionic liquid.
Most preferably, 0.01 gram of lipase is contained in every milliliter of ionic liquid.
Wherein, described lipase derives from animal, plant or microorganism.
Preferably, described lipase is Penicillium lipase.
Most preferably, described lipase is penicillium expansum lipase.
Preferably, described ionic liquid is 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.
Biological enzyme agent can also comprise methyl alcohol, preparing in the reaction of methylcarbonate by reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate, the content of methyl alcohol is determined according to the mol ratio of reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate.
Biological enzyme agent can also comprise water, is preparing in the reaction of methylcarbonate by reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate, and the content of water is determined according to the quality of carbon reactant vinyl acetate or propylene carbonate.
For solving the problems of the technologies described above, another technical scheme that the present invention adopts is: the preparation method providing a kind of biological enzyme agent for the preparation of methylcarbonate, namely lipase is added at ionic liquid, described biological enzyme agent is obtained after mixing, wherein, 0.003 gram ~ 0.75 gram lipase is added in every milliliter of ionic liquid.
Preferably, 0.01 gram ~ 0.3 gram lipase is added in every milliliter of ionic liquid.
Most preferably, 0.01 gram of lipase is added in every milliliter of ionic liquid.
Wherein, the lipase added derives from animal, plant or microorganism.
Preferably, the lipase added is Penicillium lipase.
Most preferably, the lipase added is penicillium expansum lipase.
Preferably, 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.
The invention has the beneficial effects as follows: be different from that the existing catalyst efficiency for the preparation of methylcarbonate is low, the situation of contaminate environment, the present invention uses the biological enzyme agent formed for main component with ionic liquid and lipase, ionic liquid is lived by the enzyme of the interaction stabilised fat enzyme with lipase, catalytic efficiency in the process of methylcarbonate is prepared high at catalytic esterification, and described biological enzyme agent can recycle, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is the content of lipase and the relation schematic diagram of transformation efficiency in every milliliter of ionic liquid in biological enzyme agent of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Add ionic liquid in a reservoir, then add lipase, after mixing, obtain biological enzyme agent, wherein, in every milliliter of ionic liquid, add 0.003 gram ~ 0.75 gram.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, selects Penicillium lipase in the present invention, especially penicillium expansum lipase.
When biological enzyme agent is for the preparation of carbon ester dimethyl ester, the add-on of biological enzyme agent is mol ratio according to reactant and determines.
Biological enzyme agent can also comprise methyl alcohol, and preparing in the reaction of methylcarbonate by methyl alcohol and NSC 11801 or methyl alcohol and propylene carbonate, methyl alcohol is one of component forming biological enzyme agent, is again reactant.When biological enzyme agent comprises methyl alcohol, in biological enzyme agent, the content of methyl alcohol is determined according to the mol ratio of reactant methanol and NSC 11801 or methyl alcohol and propylene carbonate.
Biological enzyme agent can also comprise water, prepare in the reaction of methylcarbonate when this biological enzyme agent is used for catalysis methanol and NSC 11801 or methyl alcohol and propylene carbonate, in biological enzyme agent, the content of water is determined according to the quality of carbon reactant vinyl acetate or propylene carbonate.
Embodiment 1
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.003 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 25%.
Embodiment 2
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.01 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 92%.
Embodiment 3
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.03 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 85%.
Embodiment 4
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.06 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 69%.
Embodiment 5
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.12 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 66%.
Embodiment 6
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.18 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 61%.
Embodiment 7
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.24 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 60%.
Embodiment 8
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.3 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 59%.
Embodiment 9
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.36 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 55%.
Embodiment 10
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.45 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 55%.
Embodiment 11
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.54 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 41%.
Embodiment 12
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.6 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 30.5%.
Embodiment 13
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme agent is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.66 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 28%.
Embodiment 14
Reactant methanol and propylene carbonate is added successively in reaction unit, the mol ratio 16: 1 of methyl alcohol and propylene carbonate, then biological enzyme profit is added, add water again, water-content 1% (based on ester weight, w/w), transesterification reaction is carried out in stirring, temperature of reaction 55 DEG C, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, ionic liquid 2ml/g (based on ester weight, v/w); In biological enzyme agent, lipase is penicillium expansum lipase, adds 0.75 gram of penicillium expansum lipase in every milliliter of ionic liquid.Extract reaction solution for DMC addition analysis, the transformation efficiency being calculated propylene carbonate by the carbon ester dimethyl ester gauge measured is 24.5%.
Above in each embodiment, after the reaction, remove excessive methyl alcohol and obtain product methylcarbonate by fractionation, remaining biological enzyme agent is reusable, and catalytic activity can not reduce.
Above in each embodiment, DMC addition analytical procedure is: get the centrifugal layering of 50 μ L reaction solution, get upper liquid sample 10 μ L, dissolves, shake up, then add 300 μ L dodecanes (2mg/ml) as interior mark with 290 μ L hexanaphthenes; 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 propylene carbonate by the carbon ester dimethyl ester gauge measured, method of calculation are as follows:
The quality of methylcarbonate, residual carbon acid acrylic acid is obtained (marker method, dodecane is as interior mark) by gas-chromatography calculated by peak area.
Refer to Fig. 1, the content of lipase and the relation schematic diagram of transformation efficiency in every milliliter of ionic liquid in biological enzyme agent of the present invention, as shown in Figure 1, when the enzyme amount in every milliliter of ionic liquid is 0.01 gram, the transformation efficiency of propylene carbonate is the highest, up to 92%; When the enzyme amount in every milliliter of ionic liquid is more than 0.01 gram, along with the increase of enzyme amount, propylene carbonate ester conversion rate reduces gradually; When the enzyme amount in every milliliter of ionic liquid reaches 0.3 gram, the transformation efficiency of propylene carbonate still reaches 59%; After this, along with the increase of enzyme amount, the transformation efficiency of propylene carbonate declines rapidly, and when the enzyme amount in every milliliter of ionic liquid is 0.75 gram, the transformation efficiency of propylene carbonate is down to 24.5%.Therefore, the fatty enzyme amount in every milliliter of ionic liquid is 0.01 gram ~ 0.3 gram is preferred version of the present invention, and the fatty enzyme amount in every milliliter of ionic liquid is 0.01 gram is the present invention's most preferably scheme.
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 (2)
1. the biological enzyme agent for the preparation of methylcarbonate, it is characterized in that, described biological enzyme agent comprises ionic liquid and penicillium expansum lipase, described ionic liquid is 1-ethyl-3-methylimidazole hexafluorophosphate, wherein, 0.01 gram of penicillium expansum lipase is contained in every milliliter of ionic liquid; Described biological enzyme agent catalysis methanol and propylene carbonate react Formed dimethyl phthalate.
2. as claimed in claim 1 for the preparation of the preparation method of the biological enzyme agent of methylcarbonate, it is characterized in that, penicillium expansum lipase is added in ionic liquid 1-ethyl-3-methylimidazole hexafluorophosphate, described biological enzyme agent is obtained after mixing, wherein, 0.01 gram of penicillium expansum lipase is added in every milliliter of ionic liquid.
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| CN101619329A (en) * | 2009-07-29 | 2010-01-06 | 华东理工大学 | Technical method for preparing biodiesel by biocatalysis one-pot method |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619329A (en) * | 2009-07-29 | 2010-01-06 | 华东理工大学 | Technical method for preparing biodiesel by biocatalysis one-pot method |
Non-Patent Citations (5)
| Title |
|---|
| enicillium expansum lipase-catalyzed production of biodiesel in ionic liquids;Kai-Pei et al.;《Bioresource Technology》;20111231;第2767页摘要，第2768页右栏2.3-2.4部分 * |
| Lipase-Catalyzed Reactions in Ionic Liquids;R. Madeira Lau et al.;《ORGANIC LETTERS》;20001231;4-6 * |
| 功能化离子液体的合成及其在非水相催化中的应用;欧光南;《中国博士学位论文全文数据库 工程科技I辑》;20090815;全文 * |
| 固定化扩展青霉脂肪酶的制备及其在玉米油转酯反应中的应用;李南薇等;《催化学报》;20070430;全文 * |
| 离子液体中脂肪酶催化酯化、转酯反应;杜海枫;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》;20060915;第11页 * |
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| Publication number | Publication date |
|---|---|
| CN103525798A (en) | 2014-01-22 |
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