CN103525798A - Biological enzyme catalyst for preparing dimethyl carbonate and preparation method thereof - Google Patents
Biological enzyme catalyst for preparing dimethyl carbonate and preparation method thereof Download PDFInfo
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- 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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- 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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- 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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- 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 biological enzyme catalyst for preparing dimethyl carbonate and a preparation method thereof. The biological enzyme catalyst comprises ionic liquid and lipase, wherein every milliliter of ionic liquid contains 0.003-0.75g of lipase. By adopting the biological enzyme catalyst taking the ionic liquid and lipase as main components, the catalysis efficiency in a process of preparing dimethyl carbonate through a catalytic esterification reaction is high, and the biological enzyme catalyst can be recycled, thereby being environment-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 (Dimethyl Carbonate, DMC), is a kind of water white transparency during DMC normal temperature, omits scent of, micro-sweet liquid, is insoluble in water, but immiscible organic solvent that can be nearly all with alcohol, ether, ketone etc.DMC toxicity is very low, in 1992, just by Europe, classified as nontoxic product, it is a kind of environmental protective type chemical raw material that meets modern cleaning procedure requirement, therefore the synthetic technology of DMC has been subject to the extensive attention (J.H.Clements of domestic and international chemical circles, Ind.Eng.Chem.Res., 42 (2003): 663; S.Fukuoka et al., Green Chem.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 has limited the application of this method in 1918, particularly along with environmental protection, is subject to the raising day by day of whole world attention degree, and phosgenation is eliminated.From the eighties in 20th century, for the research of DMC production technique, start to be subject to general concern, according to the statistics of Michael A.Pacheco and ChristopherL.Marshall, the patent of relevant DMC production technique just surpassed 200 from 1980～1996 years.Early 1980s, gondola EniChem company has realized take the commercialization by the synthetic DMC technique of methanol oxidation carbonylation that CuCl is catalyzer, this is first technique that realizes the synthetic DMC of industrialized non-phosgene, also be most widely used technique, when the defect of this technique is high conversion, the deactivation phenomenom of catalyzer is serious, so its per pass conversion is only 20%.In the nineties in 20th century, the research of DMC synthesis technique has obtained development rapidly, the technique of the synthetic DMC of UbeDui EniChem company methanol oxidation carbonylation of Japan is improved, selection NO is catalyzer, has avoided like this inactivation of catalyzer, makes transformation efficiency almost reach 100%, this technique has realized industrialization, but this technique be take CO as raw material, CO is a kind of poisonous gas, so the safety problem that causes of CO limits the application of this technique; U.S. Texaco company has developed first by oxyethane and carbon dioxide reaction Formed vinyl acetate, through transesterify, produce again the technique of DMC with methyl alcohol, this technique coproduction ethylene glycol, in 1992, realized industrialization, this process quilt thinks that productive rate is lower, production cost is higher, only have when DMC annual production during higher than 55kt its investment and cost just can compete with additive method; In addition also have a kind of emerging technique, i.e. urea alcoholysis reaction, carries out reducing costs if combine with urea production, and this technique is expected to realize industrialization.
In recent years, the research of synthetic DMC is subject to domestic and international investigator's extensive concern, synthetic route just towards simplifying, without poisoning and the future development of pollution-freeization.The green method of at present synthetic DMC mainly contains CO2 and methyl alcohol direct synthesis technique, ester-interchange method and alcoholysis of urea.Wherein, take NSC 11801 or propylene carbonate as raw material, by economic benefits and the industrial requirement that methylcarbonate and glycol are prepared in transesterify with methyl alcohol, day by day increase, cause that various countries scientist pays close attention to widely.US Patent No. 430703 discloses a kind of preparation method of dialkyl carbonate, in this patent, disclose and used thallium compound as the catalyzer of transesterification reaction, under relative low temperature, low catalyst concentration, can obtain high speed of reaction, and suppress forcefully the generation of side reaction.For example, at 150 ℃, 1.92 * 10
-4under mol thallium carbonate exists, after reaction 30min, (methyl alcohol: NSC 11801=5: transformation efficiency 1) reaches 70%, the selectivity that generates DMC reaches 90% to NSC 11801.By distillation, remove after the azeotrope (approximately 70% methyl alcohol) of DMC and methyl alcohol, residue continues and methyl alcohol reaction under identical conditions, can obtain 80% transformation efficiency, its by product still seldom, also can carry out in the fixed-bed reactor that thallium catalyzer is housed by this reaction.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 are disclosed in this patent as the homogeneous catalyst of transesterification reaction, temperature of reaction is at 20 ℃-200 ℃, and joining of methyl alcohol and NSC 11801 is smaller.For example 130 ℃ of zirconium are made catalyzer, and methyl alcohol and NSC 11801 mol ratio are 4.7 o'clock, and the transformation efficiency of ethylene carbonate vinegar is 89%.The selectivity of DMC counts 80% with NSC 11801, with methyl alcohol, counts 76%, and the selectivity of ethylene glycol is all more than 95%.Alkaline earth metal silicate is as Na2SiO3, KHSiO3, the catalyzer of Li2SiO3 even load conduct reaction on silica gel, at 80 ℃～125 ℃, 0.7Mpa, LHSV=1.0, CH3OH/EC (mol)=4 o'clock, its active order is: Na2SiO3 > KHSiO3 > Li2SiO3, wherein water glass supported on silica gel during as catalyzer, the transformation efficiency of NSC 11801 is about 30%.But the catalytic life of this type of material is not long, with the prolongation in reaction times, catalytic activity decline gradually (Liu Zongjian, Cai Ye, the catalyst research of the synthetic DMC of ester-interchange method, Chemical Manufacture and technology, 1998,5 (4), 13-15).
There is the shortcomings such as catalyst activity or selectivity are not high, productive rate is low in the synthetic DMC of methyl alcohol direct synthesis technique, ester-interchange method and alcoholysis of urea, the activity and selectivity of therefore finding more suitable catalyzer and carrier, 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 fields such as foodstuff production and detection, green technology, biotechnology, biological medicine by people in recent years.Study at present and most widely used lipase (Lipase, EC 3.1.1.3) be that a class energy catalysis grease and short chain alcohol are carried out the biological catalyst that transesterification generates 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 that ionic liquid and lipase is that main component forms of take have not been reported in the application of preparing 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: a kind of biological enzyme agent for the preparation of methylcarbonate is provided, described biological enzyme agent comprises ionic liquid and lipase, wherein, contains 0.003 gram～0.75 gram lipase in every milliliter of ionic liquid.
Preferably, in every milliliter of ionic liquid, contain 0.01 gram～0.3 gram lipase.
Most preferably, in every milliliter of ionic liquid, contain 0.01 gram of lipase.
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 a kind of 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, by reactant methanol, prepared in reacting of methylcarbonate with propylene carbonate with NSC 11801 or methyl alcohol, 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, by reactant methanol, is being prepared in reacting of methylcarbonate with propylene carbonate with NSC 11801 or methyl alcohol, 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 that a kind of biological enzyme agent for the preparation of methylcarbonate is provided, at ionic liquid, add lipase, after mixing, obtain described biological enzyme agent, wherein, in every milliliter of ionic liquid, add 0.003 gram～0.75 gram lipase.
Preferably, in every milliliter of ionic liquid, add 0.01 gram～0.3 gram lipase.
Most preferably, in every milliliter of ionic liquid, add 0.01 gram of lipase.
Wherein, the lipase adding derives from animal, plant or microorganism.
Preferably, the lipase adding is Penicillium lipase.
Most preferably, the lipase adding is penicillium expansum lipase.
Preferably, described ionic liquid is selected a kind of 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 that to take ionic liquid and lipase be the biological enzyme agent that main component forms, ionic liquid is lived by the enzyme of the interaction stabilised fat enzyme with lipase, at catalytic esterification, prepare in the process of methylcarbonate catalytic efficiency high, and described biological enzyme agent can recycle, environmentally friendly.
Accompanying drawing explanation
Fig. 1 be in biological enzyme agent of the present invention in every milliliter of ionic liquid the content of lipase and transformation efficiency be related to schematic diagram.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
In container, add ionic liquid, 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 is selected a kind of 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, especially penicillium expansum lipase in the present invention.
Biological enzyme agent is during for the preparation of carbon ester dimethyl ester, and the add-on of biological enzyme agent is to determine according to the mol ratio of reactant.
Biological enzyme agent can also comprise methyl alcohol, by methyl alcohol, is being prepared in reacting of methylcarbonate with propylene carbonate with NSC 11801 or methyl alcohol, and 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, when this biological enzyme agent, for catalysis methanol, prepare reacting of methylcarbonate with NSC 11801 or methyl alcohol with 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
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 25%.
Embodiment 2
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 92%.
Embodiment 3
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 85%.
Embodiment 4
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 69%.
Embodiment 5
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 66%.
Embodiment 6
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 61%.
Embodiment 7
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 60%.
Embodiment 8
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 59%.
Embodiment 9
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 55%.
Embodiment 10
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 55%.
Embodiment 11
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 41%.
Embodiment 12
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 30.5%.
Embodiment 13
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme agent, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 28%.
Embodiment 14
In reaction unit, add successively reactant methanol and propylene carbonate, the mol ratio of methyl alcohol and propylene carbonate 16: 1, then add biological enzyme profit, add water, water-content 1% is (based on ester weight, w/w) again, transesterification reaction is carried out in stirring, 55 ℃ of temperature of reaction, reaction times 72h, reaction pressure is 0.1Mpa.Ionic liquid in biological enzyme agent is 1-ethyl-3-methylimidazole hexafluorophosphate, and ionic liquid 2ml/g is (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 that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring is 24.5%.
In each embodiment, after reaction, by fractionation, removed excessive methyl alcohol and obtained product methylcarbonate above, remaining biological enzyme agent is reusable, and catalytic activity can not reduce.
In each embodiment, DMC addition analytical procedure is above: get the centrifugal layering of 50 μ L reaction solution, get upper strata liquid sample 10 μ L, with 290 μ L hexanaphthenes, dissolve, shake up, then add 300 μ L dodecanes (2mg/ml) as interior mark; Get 1 μ L sample feeding, the methylcarbonate amount in gas Chromatographic Determination reactant.The SP-6890 type gas chromatograph for determination of Shandong LuNan Chemical Engineering Instrument Plant for transformation efficiency, chromatographic column is SE-54 type.Concrete test condition is: column compartment adopts temperature programming: 100 ℃ maintain 6 minutes, and 40 ℃/min of heat-up rates maintain 15 minutes, 320 ℃ of vaporizer 320℃， sensing chamber to 200 ℃.The transformation efficiency that is calculated propylene carbonate by the carbon ester dimethyl ester amount of measuring, method of calculation are as follows:
The quality of methylcarbonate, residual carbon acid acrylic acid obtains (marker method, dodecane is as interior mark) by gas-chromatography calculated by peak area.
Refer to Fig. 1, in biological enzyme agent of the present invention in every milliliter of ionic liquid the content of lipase and transformation efficiency be related to schematic diagram, 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 surpasses 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, it is preferred version of the present invention that the lipase amount in every milliliter of ionic liquid is 0.01 gram～0.3 gram, and it is most preferably scheme of the present invention that the lipase amount in every milliliter of ionic liquid is 0.01 gram.
Those skilled in the art do not depart from essence of the present invention and spirit, can have various deformation scheme 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 after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. for the preparation of a biological enzyme agent for methylcarbonate, it is characterized in that, described biological enzyme agent comprises ionic liquid and lipase, wherein, contains 0.003 gram～0.75 gram lipase in every milliliter of ionic liquid.
2. the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 1, is characterized in that, contains 0.01 gram～0.3 gram lipase in every milliliter of ionic liquid.
3. the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 2, is characterized in that, contains 0.01 gram of lipase in every milliliter of ionic liquid.
4. the biological enzyme agent for the preparation of methylcarbonate as described in claim 1～3 any one, is characterized in that, described lipase derives from animal, plant or microorganism.
5. the biological enzyme agent for the preparation of methylcarbonate as described in claim 4 any one, is characterized in that, described lipase is Penicillium lipase.
6. the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 5, is characterized in that, described lipase is penicillium expansum lipase.
7. the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 1, it is characterized in that, described ionic liquid is a kind of in 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate.
8. the preparation method of the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 1, it is characterized in that, at ionic liquid, add lipase, after mixing, obtain described biological enzyme agent, wherein, in every milliliter of ionic liquid, add 0.003 gram～0.75 gram lipase.
9. the preparation method of the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 8, is characterized in that, adds 0.01 gram～0.3 gram lipase in every milliliter of ionic liquid.
10. the preparation method of the biological enzyme agent for the preparation of methylcarbonate as claimed in claim 9, is characterized in that, adds 0.01 gram of lipase in every milliliter of ionic liquid.
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| CN201210226569.0A CN103525798B (en) | 2012-07-03 | 2012-07-03 | For the preparation of the biological enzyme agent and preparation method thereof of methylcarbonate |
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Non-Patent Citations (5)
| Title |
|---|
| KAI-PEI ET AL.: "enicillium expansum lipase-catalyzed production of biodiesel in ionic liquids", 《BIORESOURCE TECHNOLOGY》, 31 December 2011 (2011-12-31), XP027582914 * |
| R. MADEIRA LAU ET AL.: "Lipase-Catalyzed Reactions in Ionic Liquids", 《ORGANIC LETTERS》, 31 December 2000 (2000-12-31) * |
| 李南薇等: "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", 《催化学报》, 30 April 2007 (2007-04-30) * |
| 杜海枫: "离子液体中脂肪酶催化酯化、转酯反应", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》, 15 September 2006 (2006-09-15), pages 11 * |
| 欧光南: "功能化离子液体的合成及其在非水相催化中的应用", 《中国博士学位论文全文数据库 工程科技I辑》, 15 August 2009 (2009-08-15) * |
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| CN117802070A (en) * | 2024-02-29 | 2024-04-02 | 山东德普新材料科技有限公司 | Composite biological enzyme catalyst and preparation method and application thereof |
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