CN1456674A - Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester - Google Patents
Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester Download PDFInfo
- Publication number
- CN1456674A CN1456674A CN02117614A CN02117614A CN1456674A CN 1456674 A CN1456674 A CN 1456674A CN 02117614 A CN02117614 A CN 02117614A CN 02117614 A CN02117614 A CN 02117614A CN 1456674 A CN1456674 A CN 1456674A
- Authority
- CN
- China
- Prior art keywords
- reaction
- lipase
- acid
- alcohol
- enzyme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A process for catalytic synthesis of the low-carbon alcohol ester of fatty acid from immobilized lipase includes such steps as immobilizing lipase to inertial carrier membrane or fabric, combining it with metallic wire mesh to form novel reactor, and catalytic esterifying reaction between fatty acid and alcohol at 20-60 deg.C for 14-24 hr. Its advantages are high esterifying rate up to 90-97%, less by-product and low energy consumption.
Description
(1) technical field
The present invention relates to biochemical industry, specifically a kind of with the method for immobilized microorganism lipase at non-aqueous system catalysis lipid acid and the synthetic ester of alcohol reaction.
(2) background technology
Fatty acid ester is common chemical materials such as the many industries of daily-use chemical industry such as food, weaving, plastics, makeup.Fatty acid ester of low-carbon alcohol is important industrial additive and the tensio-active agent of a class wherein.The short chain fatty acid aromatic ester is the important component part of synthetic perfume and the main raw material of liquor blending.The ester of low-carbon alcohol of longer chain fatty acids such as iso-octyl palmitate, isopropyl ester, Isopropyl myristate and octyl stearate then is the important oiliness raw material of the cosmetics of super quality.This type of long chain fatty acid ester and skin-friendliness are good, have good moistening and ramollescence, and be widely used in to bathe and use goods, hair preparation, cosmetics, the product that shave, skin care product, the sweat inhibiting and odour repellent agent is in the personal-care supplies such as sunscreen.Wherein iso-octyl palmitate also can be used as softening agent in the plastic industry, lubricant etc.Fatty acid methyl ester, fatty-acid ethyl ester then are biodegradable, that air pollutant emission is low reproducible " biofuel " or the like.But for a long time, industrial fatty acid ester all is to produce by chemical method.Promptly the esterification of catalysis acid alcohol under High Temperature High Pressure is finished with organic catalyst such as the vitriol oil, Phenylsulfonic acid etc.Though productive rate is higher, also there are many shortcomings that are difficult to overcome.Many as: high-temperature high-voltage reaction energy consumption height, side reaction, the product color and luster is dark, separation and refining difficulty etc., and acid is serious to equipment corrosion, is unfavorable for producing.Along with development of biology, the particularly research of enzyme engineering is for the biological catalyst Acrawax provides new method.Compare with traditional chemical method, enzyme process is synthetic to have the reaction conditions gentleness, high specificity, and side reaction is few, characteristics such as product quality height.Particularly fatty enzymatic reaction in the nonaqueous phase, the range of application and the field of having widened enzyme, the focus of enzymology over becoming year.
Numerous research reports and general survey have showed that all the enzyme in the nonaqueous phase is better than the enzyme in the water.Organic solvent can keep a lower water-activity, can reduce the thermokinetics and the kinetics obstacle of esterification and hydrolysis reaction.And organic substrates higher solubleness in organic solvent can improve speed of response.Therefore, the esterification in non-aqueous system can realize high conversion, thereby simplifies separating technology.
According to domestic and international lipase-catalyzed fatty acid ester synthetic technology report, " synthesizing of microbial lipase catalysis ester ", CN 1223300A (1999) reported that with Fatty Alcohol(C12-C14 and C12-C18), lipid acid be substrate, the lipase of free is catalyzer, under 15 ℃～40 ℃ conditions, the catalysis fatty acid ester is synthetic in organic solvent.The used lipase of this method is to use zhizopchin production, reacts to be batchwise operation, carries out in stirred pot.10～36hr substrate conversion efficiency can reach 95%.After reaction finishes, filtering separation lipase and reaction solution, underpressure distillation obtains the product ester.Compare with using immobilized enzyme, resolvase is easily assembled caking in organic solvent, and repeating utilization factor is low, the big shortcoming of enzyme loss alive.This method uses heptane to improve production cost as organic solvent simultaneously.In addition, CN 1308129 has reported in solvent-free system, synthetic with immobilization rizolipase, lipase from candida sp catalysis sorbitan monooleate, but solvent-free system is for insoluble substrate such as immiscible acid and pure then can influence mass transfer and reduce the efficient of reaction.
EP 0383405A1 (1990) has reported with commercialization lipase as using the immobilized lipase from candida sp NOVO of particulate resins CP382, the mould lipase NOVO of immobilization rice black wool SP392, catalysis fatty acid ester synthetic method.The characteristics of this method are to carry out at condition of no solvent, utilize the alcohol of one of the water that generates in the esterification and reaction substrate to form the character of azeotrope, be lower than under 80 ℃ of conditions in 5000～50000Pa pressure, temperature, the water that generates in the reaction is shifted out, the 24hr substrate conversion efficiency can reach more than 97%.But also there is weak point,, causes substrate minimizing in the reaction system, must in reaction system, add alcohol as owing to alcohol in the reaction process also constantly is moved out of.And for the alcohol-water azeotrope that forms higher azeotropic point, the rising of temperature can cause the reduction of enzymic activity and stability, and this method is separated the enzyme reaction post with distillation plant, operate under different temperature, has increased the complicacy of energy consumption and equipment and operation.
People such as Liu Junkang (2000) have studied the reverse micelle system immobilized lipase of forming with AOT (two (2-ethylhexyl))/succinate sodium sulfonate/normal heptane/water/gelatin, immobilized enzyme is filled in the synthetic of catalysis long chain fatty acid ester in the chromatography column of internal diameter 1.8cm, used organic solvent is a heptane.Under 25 ℃, the reaction esterification yield can reach 90%.The reverse micelle activity of the immobilized enzyme hold-time is long, but for the strong ethanol of wetting ability, propyl alcohol etc. can and water miscible, and enter in the micro emulsion drop of gel, the structure and the activity of enzyme molecule exerted an influence, cause speed of response slow, transformation efficiency is low.And tubular reactor also exists the substrate flow velocity low, the deficiency that treatment capacity is little.
People such as Leite (1998) have studied the mould lipase-catalyzed esterification of immobilization rice black wool.With the octane-iso is that solvent is removed the water that generates in the reaction by osmotic evaporation film.People such as Bufeiend (1999) have studied hollow fiber membrane reactor, are solvent with the octane, by the substrate circulating reaction is synthesized long chain fatty acid ester.Membrane reactor catalytic efficiency height can selectivity remove the water that generates in the reaction, but also there is the cost height in membrane reactor, problems such as complicated operation, the easy obstruction of film.
(3) summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the immobilized lipase synthesis of fatty acid low carbon alcohol ester.
Technical scheme of the present invention comprise with lipase and altogether fixing agent be fixed on jointly on inert support film or the textiles film and make immobilized enzyme, be fixed in immobilized enzyme in the Stainless Steel Cloth again and place the synthetic of catalysis fatty acid ester in the enzyme reactor.
Effect of the present invention is: the existence of (1) fixed film carrier has prevented the congregation of enzyme molecule in organic solvent, has improved the diffusion effect of enzyme molecule, has increased the catalysis area.(2) altogether fixing agent has improved the hydrophilic and hydrophobic property of fixation support effectively, for the effect between enzyme and the substrate provides good microenvironment, from having improved the catalytic activity of enzyme greatly.(3) by immobilized enzyme is fixed in the wire cloth, wire cloth is curled into that spiral is tabular to have increased the catalysis area in the enzyme reactor, can in time add water-retaining agent and remove the water that dereaction generates in reaction process.(4) after reaction finished, immobilized enzyme also was easy to separate with water-retaining agent with reaction solution, helped reclaiming multiplexing and serialization production.(5) the present invention adopts inexpensive petroleum cuts to make solvent for solid substrate, has reduced production cost.
Shallow by the product color that the present invention obtains, the quality height, low cost, thus provide a kind of novel method for the suitability for industrialized production of fatty acid ester.
Major technique thes contents are as follows:
1. lipase immobilization: fixation support is earlier with fixing agent activation altogether.With fixation support and altogether fixing agent press mass volume ratio 1: 1～1: 3 mixed (W: V), room temperature is dried.Lipase solution is mixed with fixation support after the activation in the ratio of 1000～30000 units/gram carriers, dries stand-by.
2. fatty acid ester is synthetic: substrate lipid acid and the adding of 1: 1 in molar ratio～1: 3 ratio of alcohol are contained in the enzyme reactor of organic solvent.Add immobilized enzyme and begin reaction.Under 20-60 ℃ condition, vibrate or stirring reaction 14-24 hour, transformation efficiency can reach 90-97%, adds molecular sieve or discolour silica gel except that the water that generates in the dereaction when reaction 4-10hr, can accelerate reaction arrival balance time.After reaction finished, immobilized enzyme can directly separate with reaction solution, with reusing behind a spot of organic solvent washing.Reaction solution is through 5%NaCO
3Dilute solution washing, filtration back underpressure distillation under vacuum tightness 0.05-0.08MPa condition evaporate the reaction media organic solvent, obtain the product ester.The solvent that evaporates is through recyclable multiplexing after the condensation.
3. used common fixture comprised materials such as macromolecular compound, grease, tensio-active agent, protein and mineral ion when carrier activated.Its composition comprises: polyoxyethylene glycol, Tween and span series, gelatin, Yelkin TTS etc.
4. the used lipase of the present invention is immobilization lipase from candida sp, immobilization Penicillium lipase and esterase.The fixation support of selecting for use is a textiles, as film etc.Fixed enzyme membrane has that surface-area is big, adsorptivity is strong, low price, good stability and with the characteristics of recycling.
5. in enzyme reactor, the fixed film carrier is fixed in the Stainless Steel silk screen.Stainless Steel Cloth places in the reactor or is curled into the tabular reactor that places of spiral, and reaction can directly separate with reaction solution after finishing, and behind organic solvent washing, can be used for catalyzed reaction once more.
The esterification equation that the present invention finishes in organic solvent is:
Enzyme is lived and is defined as: under 40 ℃ of conditions, the enzyme amount that hydrolysis sweet oil in the phosphate buffer solution of pH8.0, per minute discharge 1 μ mol lipid acid is an enzyme unit alive.
Compare with traditional chemical synthesis, reaction conditions gentleness of the present invention, energy consumption are low, greatly reduce production cost.The present invention simultaneously uses biological catalyst, and atopic is strong, by product is few.Product has lighter color, characteristics that quality is high.
Compare with similar biosynthetic means, advance of the present invention is (seeing Table 1):
1. selected novel fixation support for use, as fixed enzyme membrane, thereby the active area that has increased enzyme has reduced enzyme dosage.Fixing altogether by material such as macromolecular compound, albumen, tensio-active agent and grease and mineral ion and enzyme, fixing agent can well improve the hydrophilic and hydrophobic property of carrier altogether, strengthened contacting and diffusion effect of substrate and enzyme, for enzyme provides good and microenvironment substrate-function, thereby the catalytic activity and the thermodynamic stability of enzyme have been improved greatly.Above factor degree has reduced the use cost of enzyme.
2. immobilized enzyme is fixed in the Stainless Steel Cloth, has increased the catalysis area.Compare with resolvase or granular immobilized enzyme, be easier to separate, and it is multiplexing to help the recovery of serialization production and enzyme with reaction solution.Its corresponding enzyme reactor and other reactors such as tubular type, membrane reactor are compared, structure and simple to operate, and equipment interoperability is strong.And in reactor, the enzyme catalysis area is big, catalytic efficiency is high.
3. use cheap petroleum distillate to be reaction solvent for solid-state substrate, reduced production cost.
The every index of product that is obtained by the present invention all reaches company standard, is better than commercially available chemical products.Can be applicable in the fields such as the energy, agricultural and food, makeup, textile industry.
Table 1. the present invention with the comparison of class methods
| Same class methods | The present invention | |
| Enzyme | Resolvase: easily assemble immobilized enzyme: particulate resins, reverse micelle immobilization, complicated operation, cost height | Enzymatic activity height after the immobilization, consumption is few, and carrier is a textiles, and the catalysis area is big, the source is abundant, inexpensive |
| Reactor | The equipment complexity, the process cost height | Simply, catalytic efficiency height, enzyme are easily separated |
| Solvent | Hexane, heptane, octane-iso | Solvent-free or petroleum distillate, cost is low |
(4) embodiment
Embodiment 1:
0.12g immobilized enzyme (9000U/g) joins in the 5mL organic solvent that contains 1g palmitinic acid (0.54mol/L) and 0.5g2-ethylhexanol (0.7mol/L).Under 40 ℃ of conditions, oscillatory reaction (190r/min) 24hr, reaction conversion ratio reaches 91%.
Embodiment 2:
0.12g immobilized enzyme (9000U/g) joins in the 5mL organic solvent that contains 1g palmitinic acid (0.54mol/L) and 0.67g2-ethylhexanol (0.7mol/L).Under 40 ℃ of conditions, oscillatory reaction (190r/min), the 22hr reaction conversion ratio reaches 96.7%.Transformation period reaches 150hr.
Embodiment 3:
0.12g immobilized enzyme (9000U/g) joins in the 5mL organic solvent that contains 1g stearic acid (mol/L) and 0.62g2-ethylhexanol (0.65mol/L).Under 37 ℃ of conditions, oscillatory reaction (190r/min), the 24hr reaction conversion ratio reaches 95%.
Embodiment 4:
20g immobilized enzyme (9000U/g) adds in the organic solvent of the 690mL that contains 138g palmitinic acid (0.54mol) and 92g isooctyl alcohol (0.706mol), stirring reaction under 40 ℃ of conditions.Immobilized enzyme is fixed on Stainless Steel Wire and places on the net in the reactor, and reaction 24hr transformation efficiency can reach 95%.Reaction solution evaporates organic solvent under 0.05～0.08 Mpa vacuum tightness after 5% sodium carbonate solution washs, filters, obtain product palmitinic acid isooctyl.Product color is shallow, and acid number is 0.251mgKOH/g.
Embodiment 5:
0.085g lipase (16000u/g) adds in the organic solvent of the 5ml that contains 0.85mol/L concentration oleic acid and methyl alcohol, under 40 ℃ of conditions, behind the reaction 24hr, the transformation efficiency of reaction reaches 95%.Obtain the product Witconol 2301 through underpressure distillation under-0.05Mpa pressure.
Embodiment 6:
0.048g lipase (16000u/g) adds in the organic solvent of the 5ml that contains 0.75mol/L concentration palmitinic acid and methyl alcohol, under 40 ℃ of conditions, behind the reaction 24hr, the transformation efficiency of reaction reaches 92%.Obtain the product Uniphat A60 through underpressure distillation under-0.05Mpa pressure.
Embodiment 7:
0.05g lipase (16000u/g) adds in the organic solvent of the 5ml that contains 0.7mol/L concentration stearic acid and butanols, under 40 ℃ of conditions, behind the reaction 24hr, the transformation efficiency of reaction reaches 96%.Obtain the product butyl stearate through underpressure distillation under-0.05Mpa pressure.
Embodiment 8:
0.085g lipase (16000u/g) adds and contains in the organic solvent of 0.85mol/L concentration oleic acid and alcoholic acid 5ml, under 40 ℃ of conditions, behind the reaction 24hr, the transformation efficiency of reaction reaches 95%.Obtain the product ethyl oleate through underpressure distillation under-0.05Mpa pressure.
Embodiment 9:
0.05g lipase (16000u/g) adds in the organic solvent of the 5ml that contains 0.7mol/L concentration stearic acid and methyl alcohol, under 40 ℃ of conditions, behind the reaction 24hr, the transformation efficiency of reaction reaches 96%.Obtain the product methyl stearate through underpressure distillation under-0.05Mpa pressure.
Claims (8)
1. the step of fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester:
(1) lipase immobilization: it is characterized in that fixation support is earlier with fixing agent activation altogether.With fixation support and altogether fixing agent press mass volume ratio 1: 1～1: 3 mixed (W: V), room temperature is dried.Lipase solution is mixed with fixation support after the activation in the ratio of 1000～30000 units/gram carriers, dries stand-by.
(2) fatty acid ester is synthetic: it is characterized in that substrate lipid acid and the adding of 1: 1 in molar ratio～1: 5 ratio of alcohol are contained in the enzyme reactor of organic solvent, add immobilized enzyme and begin reaction.Under 20-60 ℃ condition, vibrate or stirring reaction 14-24 hour, transformation efficiency can reach 90-97%.In reaction process, add water-retaining agent and can shorten reaction arrival balance time.After reaction finished, immobilized enzyme can directly separate, with reusing behind a spot of organic solvent washing.Reaction solution underpressure distillation after alkali liquid washing, filtration evaporates the reaction media organic solvent, obtains the product ester.The solvent that evaporates is through recyclable multiplexing after the condensation.
2. according to method described in the right 1. (1), it is characterized in that used lipase is immobilization Penicillium lipase, immobilization lipase from candida sp and esterase.Used fixation support is yarn fabric such as film and cloth etc.
3. according to right 1. (1) described methods, the common fixing agent composition that it is characterized in that fixation support comprises macromolecular compound, grease, protein, tensio-active agent and inorganic salt and other material, comprising: polyoxyethylene glycol, Tween and span series, gelatin, Yelkin TTS.
4. according to right 1. (2) described methods, it is characterized in that in stirred reactor, the fixation support film is fixed in the Stainless Steel silk screen, and Stainless Steel Cloth places in the reactor or is curled into the tabular reactor that places of spiral, and reaction can directly separate with reaction solution after finishing.
5. according to right 1. (2) described methods, it is characterized in that the organic solvent that reacts used is cheap petroleum distillate, boiling range is 40 ℃-150 ℃, can directly adopt solvent-free system for the substrate of liquid state.
6. according to right 1. (2) described methods, it is characterized in that used water-retaining agent is silica gel and molecular sieve.
7. according to right 1. (2) described methods, it is characterized in that used washing alkali liquid is NaCO
3Or NaOH solution, concentration is 5-10%.
8. according to right 1. (2) described methods, it is characterized in that lipid acid is the lipid acid of C10～C18, as certain herbaceous plants with big flowers acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid etc.Alcohol is the primary alconol of C1～C8, and as methyl alcohol, hexanol, propyl alcohol, butanols, hexanol, isooctyl alcohol etc., the secondary alcohol of C3～C5 is as Virahol, isopropylcarbinol etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02117614 CN1279174C (en) | 2002-05-10 | 2002-05-10 | Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02117614 CN1279174C (en) | 2002-05-10 | 2002-05-10 | Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1456674A true CN1456674A (en) | 2003-11-19 |
| CN1279174C CN1279174C (en) | 2006-10-11 |
Family
ID=29410321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02117614 Expired - Fee Related CN1279174C (en) | 2002-05-10 | 2002-05-10 | Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1279174C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363482C (en) * | 2005-12-09 | 2008-01-23 | 清华大学 | Method for immobilizing lipase using microstructure in hydrophilic/ hydrophobic composite membrane |
| CN100424170C (en) * | 2005-10-11 | 2008-10-08 | 北京化工大学 | Lipase, its gene, yalulipolytic geast for producing said enzyme and its application |
| CN102492741A (en) * | 2011-12-22 | 2012-06-13 | 江南大学 | Synthesizing method of chloropropanol ester |
| CN1752185B (en) * | 2004-09-20 | 2012-10-24 | 三合生物柴油公司 | Devices and Methods for producing fuel |
| CN101613691B (en) * | 2008-06-27 | 2013-08-14 | 北京化工大学 | Method for immobilizing lipase |
| CN103865917A (en) * | 2012-12-12 | 2014-06-18 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Preparation method for atom transfer radical polymerization modified-metal wire immobilized enzyme reactor |
| CN104704125A (en) * | 2012-10-10 | 2015-06-10 | 巴斯夫欧洲公司 | Three-stage method for the enzymatic synthesis of fatty acid esters |
| CN104884630A (en) * | 2012-12-31 | 2015-09-02 | 转换生物柴油有限公司 | Enzymatic transesterification/esterification processing systems and processes employing lipases immobilized on hydrophobic resins |
| CN105463036A (en) * | 2016-01-12 | 2016-04-06 | 南京工业大学 | Method for utilizing micro-reaction device for preparing long-chain fatty acid |
| CN107034205A (en) * | 2017-06-08 | 2017-08-11 | 江南大学 | A kind of method that utilization surfactant prepares high esterification active lipase |
| CN109266699A (en) * | 2018-09-21 | 2019-01-25 | 北京化工大学 | A kind of transesterification method for preparing isobutyl palmitate |
| CN109486874A (en) * | 2018-11-30 | 2019-03-19 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of high esterification degree lacquer tree fat base isopropyl ester |
| CN112029754A (en) * | 2020-08-13 | 2020-12-04 | 浙江工业大学 | Imprinted lipase and application thereof in synthesis of sucrose-6-ethyl ester |
| CN113969151A (en) * | 2020-07-22 | 2022-01-25 | 中石化石油工程技术服务有限公司 | Biomass main emulsifier, preparation method and application thereof |
| CN114736739A (en) * | 2022-03-21 | 2022-07-12 | 中国农业科学院油料作物研究所 | Method for deacidifying by lipid enzyme method and synchronously preparing functional lipid |
| CN115747266A (en) * | 2023-01-05 | 2023-03-07 | 苏州丰倍生物科技股份有限公司 | Method for producing fatty acid methyl ester by lipase catalysis |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812485B (en) * | 2010-04-20 | 2012-01-18 | 北京化工大学 | New process for producing biodiesel by free enzyme catalysis |
-
2002
- 2002-05-10 CN CN 02117614 patent/CN1279174C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752185B (en) * | 2004-09-20 | 2012-10-24 | 三合生物柴油公司 | Devices and Methods for producing fuel |
| CN100424170C (en) * | 2005-10-11 | 2008-10-08 | 北京化工大学 | Lipase, its gene, yalulipolytic geast for producing said enzyme and its application |
| CN100363482C (en) * | 2005-12-09 | 2008-01-23 | 清华大学 | Method for immobilizing lipase using microstructure in hydrophilic/ hydrophobic composite membrane |
| CN101613691B (en) * | 2008-06-27 | 2013-08-14 | 北京化工大学 | Method for immobilizing lipase |
| CN102492741A (en) * | 2011-12-22 | 2012-06-13 | 江南大学 | Synthesizing method of chloropropanol ester |
| CN102492741B (en) * | 2011-12-22 | 2014-04-09 | 江南大学 | Synthesizing method of chloropropanol ester |
| CN104704125B (en) * | 2012-10-10 | 2018-07-17 | 巴斯夫欧洲公司 | The three-step approach of enzymatic synthesis aliphatic ester |
| CN104704125A (en) * | 2012-10-10 | 2015-06-10 | 巴斯夫欧洲公司 | Three-stage method for the enzymatic synthesis of fatty acid esters |
| CN103865917B (en) * | 2012-12-12 | 2016-08-17 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | The preparation method of the tinsel immobilized enzyme reactor that a kind of atom transfer radical polymerization is modified |
| CN103865917A (en) * | 2012-12-12 | 2014-06-18 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Preparation method for atom transfer radical polymerization modified-metal wire immobilized enzyme reactor |
| CN104884630A (en) * | 2012-12-31 | 2015-09-02 | 转换生物柴油有限公司 | Enzymatic transesterification/esterification processing systems and processes employing lipases immobilized on hydrophobic resins |
| CN105463036A (en) * | 2016-01-12 | 2016-04-06 | 南京工业大学 | Method for utilizing micro-reaction device for preparing long-chain fatty acid |
| CN107034205A (en) * | 2017-06-08 | 2017-08-11 | 江南大学 | A kind of method that utilization surfactant prepares high esterification active lipase |
| CN109266699A (en) * | 2018-09-21 | 2019-01-25 | 北京化工大学 | A kind of transesterification method for preparing isobutyl palmitate |
| CN109266699B (en) * | 2018-09-21 | 2021-10-08 | 北京化工大学 | Method for preparing isooctyl palmitate by transesterification |
| CN109486874A (en) * | 2018-11-30 | 2019-03-19 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of high esterification degree lacquer tree fat base isopropyl ester |
| CN113969151A (en) * | 2020-07-22 | 2022-01-25 | 中石化石油工程技术服务有限公司 | Biomass main emulsifier, preparation method and application thereof |
| CN112029754A (en) * | 2020-08-13 | 2020-12-04 | 浙江工业大学 | Imprinted lipase and application thereof in synthesis of sucrose-6-ethyl ester |
| CN114736739A (en) * | 2022-03-21 | 2022-07-12 | 中国农业科学院油料作物研究所 | Method for deacidifying by lipid enzyme method and synchronously preparing functional lipid |
| CN114736739B (en) * | 2022-03-21 | 2023-08-25 | 中国农业科学院油料作物研究所 | Method for synchronously preparing deacidification and functional lipid by using oil enzymatic method |
| CN115747266A (en) * | 2023-01-05 | 2023-03-07 | 苏州丰倍生物科技股份有限公司 | Method for producing fatty acid methyl ester by lipase catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1279174C (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1456674A (en) | Fixed lipase catalyzed synthesis of fatty acid low carbon alcohol ester | |
| Rodrigues et al. | Lipase from Rhizomucor miehei as an industrial biocatalyst in chemical process | |
| CN102757988B (en) | Preparation method of 1,3-dioleoyl-2-palmitoyl triglyceride | |
| Lee et al. | Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent | |
| Kamiya et al. | Surfactant‐coated lipase suitable for the enzymatic resolution of menthol as a biocatalyst in organic media | |
| US11208672B2 (en) | Method for enzymatic deacidification of polyunsaturated fatty acid-rich oil | |
| Mu et al. | A combined bioprocess of biodiesel production by lipase with microbial production of 1, 3-propanediol by Klebsiella pneumoniae | |
| CN101200740A (en) | Method for preparing vitamin A fatty acid ester by lipase catalysis | |
| Tan et al. | Preparation of PVA/chitosan lipase membrane reactor and its application in synthesis of monoglyceride | |
| CN104046662A (en) | Transesterification preparation method for 1,3-dioleic acid-2-triglyceride palmitate | |
| Zhao et al. | Efficient production of diltiazem chiral intermediate using immobilized lipase from Serratia marcescens | |
| CN105441494B (en) | A kind of method of enzymatic clarification 1,2- diglyceride | |
| Szczęsna-Antczak et al. | Catalytic properties of membrane-bound Mucor lipase immobilized in a hydrophilic carrier | |
| CN1085252C (en) | Process for synthesizing ester from Rhizopus chinensis by using enzyme method | |
| JPH08294394A (en) | Production of diglyceride | |
| CN101104861B (en) | Method for preparing S-ibuprofen and S-ibuprofen ester by biological catalysis | |
| Ader et al. | Hydrolases in organic synthesis: Preparation of enantiomerically pure compounds | |
| Egwim et al. | Optimization of Lipase immobilised on Chitosan Beads for Biodiesel Production | |
| CN1260368C (en) | Method for catalytic synthesis of vitamin A fatty acid ester using immobilized lipase | |
| Kovalenko et al. | Heterogeneous biocatalytic processes of the low-temperature synthesis of esters: selecting an organic solvent | |
| Ishak et al. | Kojic acid esters: comparative review on its methods of synthesis | |
| CN1242067C (en) | Method for preparing intermidiate of VE | |
| CN113684230A (en) | Method for preparing structured fat by enzyme method | |
| JP2749034B2 (en) | Production of symmetric triglycerides by high molecular weight lipase. | |
| Gunawan et al. | Enzyme-catalysed synthesis of palm-based wax esters-A kinetic study |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061011 Termination date: 20160510 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |