CN115747266A - Method for producing fatty acid methyl ester by lipase catalysis - Google Patents
Method for producing fatty acid methyl ester by lipase catalysis Download PDFInfo
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Abstract
The invention relates to a method for producing fatty acid methyl ester by lipase catalysis, which comprises the steps of carrying out catalytic reaction on deodorized distillate of vegetable oil in the presence of methanol by using lipase in three steps under the protection of nitrogen circulation to obtain a mixture containing the fatty acid methyl ester, and then carrying out post-treatment to obtain the fatty acid methyl ester. The method can obtain fatty acid methyl ester and natural vitamin E with high yield, the acid value of the methyl ester is low, and in the catalytic reaction process, the nitrogen assists in dispersion and simultaneously plays a role in reducing the oxidation loss of raw materials and finished products.
Description
Technical Field
The invention belongs to the technical field of fatty acid methyl ester synthesis, and particularly relates to a method for producing fatty acid methyl ester by lipase catalysis.
Background
China is a large country for producing and consuming edible vegetable oil, and the yield of the vegetable oil is thousands of tons every year. The deodorized distillate of the vegetable oil is produced in the deodorizing step of the vegetable oil refining process of the vegetable oil manufacturer, and is generally 0.2-0.5% of the vegetable oil, so that nearly 10 ten thousand tons of deodorized distillate of the vegetable oil are produced in China every year. The deodorized distillate of vegetable oil is rich in natural vitamin E and phytosterol, and is the only source of natural vitamin E for domestic food additives at present.
At present, the main method for producing fatty acid methyl ester and natural vitamin E by using the deodorized distillate of vegetable oil in China is an acid-base two-step catalytic method: using sulfuric acid and sodium hydroxide as catalysts to convert fatty substances into fatty acid methyl ester, and separating the fatty acid methyl ester by molecular distillation to obtain a concentrated solution of natural vitamin E. The production process uses strong acid and strong base for catalysis, which inevitably causes partial oxidative denaturation of fat substances and natural vitamin E and generation of other fatty acid ester substances. Meanwhile, the use of strong acid and strong base catalysts leads to high sulfur content (more than 50 ppm) in the obtained fatty acid methyl ester and also brings adverse effects on food safety.
The reaction conditions for catalytically synthesizing the fatty acid methyl ester by the biological enzyme method are mild, the pollutant discharge is less, and the method becomes a new research direction for producing the fatty acid methyl ester and the natural vitamin E. However, in industrial application, the problems of complicated process and rapid enzyme inactivation caused by raw material impurities still exist in the enzymatic catalytic production of fatty acid methyl ester, and the yield and acid value of fatty acid methyl ester are difficult to control, so that the industrial mass production of the fatty acid methyl ester by biological enzyme catalytic synthesis is difficult to realize at present. The acid value is one of important indexes for evaluating the quality of the generated fatty acid methyl ester, at the present stage, the standard for enterprise production is to control the acid value to be less than or equal to 5.0mgKOH/g, if the acid value is higher, the quality of the fatty acid methyl ester is reduced, certain damage is caused to the health of a human body when the method is applied to the field of food, and the problems of reduction of plasticizing performance, engine abrasion and the like are caused when the method is applied to other fields.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for producing fatty acid methyl ester by lipase catalysis, which is suitable for industrial mass production, and can prepare fatty acid methyl ester with high yield and lower acid value of the fatty acid methyl ester product.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for producing fatty acid methyl ester by lipase catalysis comprises the steps of carrying out catalytic reaction on deodorized distillate of vegetable oil in the presence of methanol by using lipase in three steps under the protection of nitrogen circulation to obtain a mixture containing the fatty acid methyl ester, and then carrying out aftertreatment to obtain the fatty acid methyl ester.
Preferably, the second catalytic reaction is carried out in a system containing an emulsifier and glycerol, thereby further reducing the acid value of the fatty acid methyl ester to meet the increasingly stringent market demand for fatty acid methyl esters.
Preferably, both the emulsifier and the glycerol are food grade.
Further, the feeding mass ratio of the glycerol to the emulsifier is (17 to 23): 1; more preferably (18 to 22): 1; more preferably (19 to 21): 1.
preferably, the emulsifier is span and tween.
Further, the charging mass ratio of the span to the Tween is (1 to 5): 1; preferably (1 to 4): 1; more preferably (2 to 3): 1.
further, the span can be span 40, span 60, span 80, span 85, etc., and the tween can be tween 20, tween 40, tween 60, tween 80, etc.
In some preferred embodiments, the glycerol is added in an amount of 1 to 5wt% of the vegetable oil deodorizer distillate; preferably 1 to 4wt%; more preferably 1.5 to 2.5wt%.
Preferably, the lipase to be subjected to the second catalytic reaction is dispersed in the system comprising the emulsifier and glycerol, and then added to the reaction system obtained by the first catalytic reaction to carry out the second catalytic reaction.
Further, the specific steps of dispersing the lipase subjected to the second catalytic reaction in the system comprising the emulsifier and the glycerol are as follows:
(a) Preparing the emulsifier;
(b) Mixing the emulsifier and the glycerol;
(c) And (c) adding the lipase subjected to the second-step catalytic reaction into the system obtained by mixing in the step (b), and uniformly stirring.
In some specific and preferred embodiments, the catalytic reaction carried out in three steps using lipase comprises the following steps carried out in sequence:
(1) Adding the deodorized distillate of the vegetable oil, lipase and methanol into a reaction kettle to carry out a first-step catalytic reaction;
(2) Adding lipase, emulsifier and glycerol into the reaction kettle to perform a second step of catalytic reaction;
(3) Adding lipase and methanol into the reaction kettle to carry out a third step of catalytic reaction;
the steps (1) to (3) are carried out under the protection of nitrogen circulation.
In the step (1), the step (c),
preferably, the addition amount of the lipase in the reaction system of the step (1) is controlled to be 380 to 450IU/g; further preferably 380 to 420IU/g; more preferably 390 to 415IU/g.
Preferably, the feeding mass ratio of the methanol to the vegetable oil deodorizer distillate is 1: (2 to 3); preferably 1: (2 to 2.5).
Preferably, the reaction temperature is controlled to be 35 to 45 ℃; more preferably from 35 to 40 ℃.
Preferably, the reaction time is controlled to be 15 to 23h; more preferably 18 to 22h.
In the step (2),
preferably, the addition amount of the lipase is controlled to be 0.1-1wt% of the addition amount of the vegetable oil deodorizer distillate; more preferably 0.2 to 0.8wt%; more preferably 0.4 to 0.7wt%.
Preferably, the reaction temperature is controlled to be 40 to 60 ℃; further preferably 40 to 55 ℃; further preferably 45 to 50 ℃.
Preferably, the reaction time is controlled to be 10 to 15h; preferably 12 to 15h.
In the step (3), the step (c),
preferably, the mass ratio of the methanol to the vegetable oil deodorized distillate in the step (1) is 1: (1.5 to 2); more preferably 1: (1.7 to 2).
Preferably, the addition amount of the lipase in the reaction system of the step (3) is controlled to be 420-450IU/g; further preferably 430 to 450IU/g; more preferably 440 to 450IU/g.
Preferably, the reaction temperature is controlled to be 40 to 50 ℃; further preferably 40 to 45 ℃.
Preferably, the reaction time is controlled to be 15 to 20h; more preferably 18 to 20h.
Preferably, the lipase adopted in the first step of catalytic reaction and the third step of catalytic reaction is candida lipase, and the lipase adopted in the second step of catalytic reaction is lipase Novozyme435.
According to a specific and preferred embodiment, the vegetable oil deodorized distillate and methanol are catalyzed by candida lipase to carry out a first-step catalytic reaction, the mixture obtained by the reaction is mixed with a dispersion system containing lipase Novozyme435 to carry out a second-step catalytic reaction to generate fatty acid glycerol mixed ester, then the candida lipase is added to carry out a third-step catalytic reaction to catalytically convert the fatty acid glycerol mixed ester into fatty acid methyl ester, finally the generated fatty acid methyl ester is distilled through multi-stage molecules, and then the natural vitamin E and the biological heavy oil are separated through freezing and squeezing, and the glycerol in the system can be centrifugally recovered and reused. In the whole catalytic reaction process, under the protection of nitrogen circulation, water generated in the ester exchange reaction process is taken away from the system, so that the occurrence of side reactions is reduced, the yield of the product is further improved, the acid value of the fatty acid methyl ester product is reduced, and the quality of the fatty acid methyl ester is further improved.
Preferably, the vegetable oil deodorized distillate comprises one or more of a soybean oil deodorized distillate, a corn oil deodorized distillate, a sunflower oil deodorized distillate, a rapeseed oil deodorized distillate.
Preferably, the work-up process is a multistage molecular distillation.
The separation of fatty acid methyl esters by multistage molecular distillation in the present invention is a conventional means in the art for the separation and purification of fatty acid methyl esters.
Preferably, the multistage molecular distillation comprises at least 2, more preferably 3 stages, operating in particular: and (3) carrying out crude separation on the mixture containing the fatty acid methyl ester obtained by the catalytic reaction, and then carrying out multi-stage molecular distillation treatment on the obtained liquid phase.
Preferably, the crude separation mode can be suction filtration, cooling crystallization, centrifugation and the like.
Further, in the multistage molecular distillation treatment, the vacuum degree of primary molecular distillation is 100-700 Pa, the distillation temperature is 110-130 ℃, and the cycle number is 2-4; the vacuum degree of the secondary molecular distillation is 50 to 150Pa, the distillation temperature is 120 to 140 ℃, and the cycle time is 2 to 4; the vacuum degree of the three-stage molecular distillation is 1-5 Pa, the distillation temperature is 240-270 ℃, and the cycle time is 2-4.
Furthermore, the heavy phase substance obtained by multistage molecular distillation treatment is frozen and squeezed to separate out natural vitamin E and biological heavy oil, and the glycerol is recycled after centrifugation.
The catalytic reaction is carried out in a reaction kettle with a coil type air injection device.
Specifically, the coil pipe type air injection device comprises a coil pipe and a plurality of air injection devices, wherein the coil pipe is installed on the inner wall of the reaction kettle and spirally wound from the bottom end to the top end of the reaction kettle, and the air injection devices are installed on the coil pipe at intervals.
Further, the coil pipe is provided with an air inlet, and the air inlet of the coil pipe is communicated with an air inlet pipeline so as to convey nitrogen into the coil pipe; the reaction kettle is provided with an air outlet, and the air outlet of the reaction kettle is communicated with an exhaust pipeline.
Furthermore, a stirring device is arranged in the reaction kettle, the air injection device can only discharge air in one direction, and the air discharge direction faces to the axial lead of the stirring device.
Preferably, the number of turns of the coiled pipe is 8 to 10; the distance between two adjacent circles of coil pipes is 15 to 25 centimeters; the length of the coil between every two adjacent air injection devices is 25-35 cm.
In some preferred embodiments, the nitrogen pressure in the control disk tube is 3 to 7 kg; preferably 4 to 6 kg.
Preferably, the gas injection device comprises a one-way gas valve arranged on the coil pipe and a spray head communicated with the one-way gas valve, and a plurality of holes for gas to pass through are formed in the spray head.
Furthermore, an air inlet pump is arranged on the air inlet pipeline, a storage tank is arranged on the exhaust pipeline, the air inlet pipeline is communicated with the exhaust pipeline, and a connection point of the air inlet pipeline and the exhaust pipeline is located on the air inlet side of the air inlet pump.
Preferably, a drain pipe is arranged on the air inlet pipeline and/or the exhaust pipeline; furthermore, the air inlet pipeline and the exhaust pipeline are both provided with drain pipes.
Preferably, the gas inlet is positioned at the lower part of the reaction kettle, and the gas outlet is positioned at the upper part of the reaction kettle; and a material outlet is formed in the bottom of the reaction kettle.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) The method for producing the fatty acid methyl ester by the lipase catalysis can realize industrial production, can obtain the fatty acid methyl ester with high yield, has low acid value of the fatty acid methyl ester, and greatly meets the quality requirement of the fatty acid methyl ester in the industrial production.
(2) The invention uses lipase as catalyst, which has low energy consumption and no waste water and waste residue.
(3) In the invention, a sulfuric acid catalyst is not used, so that the introduction of sulfur element is reduced, and the reduction of the sulfur content in the fatty acid methyl ester is facilitated.
(4) In the catalytic reaction process, nitrogen assists in dispersing and simultaneously plays a role in reducing the oxidation loss of raw materials and finished products.
Drawings
FIG. 1 is a schematic view of a coil type air-jet apparatus;
FIG. 2 is a top view of a coil air jet unit;
description of reference numerals: 1. a reaction kettle; 11. a coil pipe; 111. an air injection device; 12. a stirring device; 2. an air intake duct; 21. an intake pump; 3. an exhaust duct; 31. a storage tank; 4. a drain pipe; A. an air inlet; B. an air outlet; C. and (5) material outlet.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations where mutually exclusive features or steps are mutually exclusive.
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The method for producing the fatty acid methyl ester by the lipase in the invention can obtain the fatty acid methyl ester and the natural vitamin E in high yield in industrial production, and the fatty acid methyl ester has low acid value and high quality.
Further, the lipase dispersion system in the second catalytic reaction is a glycerol-emulsifier-lipase dispersion system, and is formed by adding an emulsifier into glycerol, uniformly mixing, adding lipase, and uniformly mixing. The emulsifier and the glycerol are both food-grade, so that the safety of the product is ensured, and the addition of the emulsifier increases the contact area of a glycerol system and a grease system, further improves the reaction rate and promotes the esterification reaction to be more complete.
Furthermore, the catalytic reaction is carried out in a reaction kettle with a coil type air injection device, so that the nitrogen circulation protection is realized. The design of the spiral coiled coil and the air injection device is beneficial to the generation of turbulence in liquid, so that the catalytic acceleration effect is achieved, and the reaction time is shortened. In addition, the nitrogen circulating system is added from the lower part and recycled from the upper part, and plays a role in assisting in increasing the contact area of the lipase and the reactant below the liquid level, thereby accelerating the reaction.
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not noted are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used, unless otherwise specified, were all purchased from conventional biochemical manufacturers.
In the following examples, the deodorized distillate of vegetable oil is soybean oil deodorized distillate with natural vitamin E content of 8%, food grade span is a mixture of food grade span 60 and food grade span 80, and food grade tween is a mixture of food grade tween 20 and food grade tween 40.
Example 1
The present embodiment provides a reaction kettle 1 with a coil type air injection device, and fig. 1 and fig. 2 are only schematic structural diagrams, for example, the height of the coil type air injection device coiled in fig. 1 is only schematic, and in practice, it is only necessary to ensure that the coil type air injection device is provided below the liquid level of the material to realize the auxiliary mixing of the material, and the coil type air injection device may be provided above the liquid level or may not be provided.
The coil pipe type air injection device comprises a coil pipe 11 which is arranged on the inner wall of the reaction kettle 1 and spirally coiled from the bottom end to the top end of the reaction kettle 1, and a plurality of air injection devices 111 which are arranged on the coil pipe 11 at intervals. The bottom of coil pipe 11 has air inlet A, the top is sealed, can make nitrogen gas get into coil pipe 11 back from air inlet A of bottom, self-blowing device 111 spouts and forms the torrent in order to promote the material mixture in reation kettle 1 in to reation kettle 1, the position that reation kettle 1's upper portion is close to the top has gas outlet B, gas mixture such as nitrogen gas in reation kettle 1 discharges reation kettle 1 from gas outlet B, thereby realize the nitrogen gas circulation protection in the reaction sequence, simultaneously can take out the moisture that the reaction produced by bigger degree at the in-process that nitrogen gas rises, promote the reaction to go on.
The reaction vessel 1 in the present application is capable of allowing a ton-scale reaction, and the reaction vessel 1 used in the present embodiment has an inner diameter of 3 m and a height of 6.5 m.
In this embodiment, the number of turns of the coil pipe 11 is 10; the distance between two adjacent circles of coil pipes 11 is 25 cm; the length of the coil 11 between two adjacent air jet devices 111 is 30 cm. The bottom of the coil 11 is located about 50 cm above the bottom of the reactor 1.
The air inlet A of the coil 11 is communicated with the air inlet pipeline 2 to convey nitrogen into the coil 11, and the pressure of the nitrogen in the coil 11 is controlled to be 5 kilograms.
The air outlet B of the reaction kettle 1 is communicated with an exhaust pipeline 3.
The reaction kettle 1 is internally provided with a stirring device 12, the gas injection device 111 can only discharge gas in one direction, and the gas discharge direction faces to the axial lead of the stirring device 12. By controlling the gas outlet direction of the gas injection device 111, the circulating nitrogen can play a role in assisting in increasing the contact area of the lipase and the reactant below the liquid level, so that the reaction is accelerated, the occurrence of oxidation side reactions in the reaction process is reduced, and the yield is improved.
In this embodiment, the gas injection device 111 includes a one-way gas valve installed on the coil 11, and a nozzle connected to the one-way gas valve, and a plurality of holes for gas to pass through are formed on the nozzle, so that nitrogen gas enters the reaction kettle 1 from the coil 11 through the one-way gas valve and the holes on the nozzle. The shape of the spray head can be any shape such as a disk shape, a square shape and the like, and the holes are uniformly distributed on the surface of the spray head.
The stirring device 12 is positioned on the spiral central line of the coil pipe 11, and the height of the stirring device in the reaction kettle 1 is adjusted according to the addition amount of the reaction materials.
A material outlet C is formed in the lower bottom of the reaction kettle 1, so that the materials can be conveniently collected after the reaction is finished.
An air inlet pump 21 is arranged on the air inlet pipeline 2 and used for the air pressure of the nitrogen in the coil pipe 11.
The exhaust pipeline 3 is provided with a storage tank 31, which is convenient for collecting moisture generated in the reaction process and nitrogen in the reaction kettle 1 so as to maintain the stability of the air pressure in the reaction kettle 1.
The air inlet pipeline 2 is communicated with the exhaust pipeline 3, and the connecting point of the air inlet pipeline 2 and the exhaust pipeline 3 is positioned on the air inlet side of the air inlet pump 21, so that the cyclic utilization of nitrogen is realized, and the raw material cost is further saved.
All be provided with drain pipe 4 on admission line 2 and the exhaust duct 3, be provided with the drain valve on drain pipe 4, the moisture that contains in the nitrogen gas of guaranteeing to get into in the reaction system is few, has avoided the influence to reaction rate behind the trace moisture entering system that exists in the nitrogen gas, and can realize moisture through the drain valve and regularly discharge.
The catalytic reactions in the following examples and comparative examples were carried out in reaction vessel 1 of example 1 equipped with a coil jet device.
Example 2
The embodiment provides a method for producing fatty acid methyl ester by lipase catalysis, which comprises the following specific production steps:
(1) 15 tons of soybean oil deodorized distillate was charged into the reaction tank 1 of example 1, and the nitrogen circulation was turned on while stirring.
(2) Adding 7.5 tons of methanol and simultaneously adding candida lipase, controlling the enzyme amount to be 400IU/g, controlling the temperature of the reaction kettle 1 to be 35 ℃, and reacting for 20 hours.
(3) Adding the glycerase disperse system to continue the catalytic reaction. The addition amount of the glycerol enzyme dispersion system is 0.45 ton, the temperature is controlled at 50 ℃, and the reaction is carried out for 15 hours.
Wherein, the preparation of the glycerol enzyme disperse system comprises the following steps:
(3.1) according to the mass ratio of food-grade span to food-grade Tween 3:1 to obtain the mixed emulsifier.
(3.2) mixing the components in a mass ratio of 20:1 mixing food-grade glycerol and a mixed emulsifier to obtain a glycerol emulsifier system.
(3.3) adding lipase Novozyme435 which accounts for 0.5% of the mass of the soybean oil deodorized distillate into a glycerin emulsifier system, and uniformly stirring.
(4) 7.5 tons of methanol are continuously added into the reaction kettle 1, candida lipase is added, the enzyme amount is controlled to be 450IU/g, the temperature is controlled to be 40 ℃, and the reaction lasts 20 hours.
(5) Discharging a mixture containing fatty acid methyl ester obtained by catalytic reaction out of the reaction kettle 1, then carrying out coarse separation by adopting cooling crystallization, and carrying out multistage molecular distillation treatment on the obtained liquid phase to obtain the fatty acid methyl ester, wherein the three-stage treatment specifically comprises three stages. Wherein, the vacuum degree of the first-stage molecular distillation is 300Pa, the distillation temperature is 120 ℃, and the cycle times are 3 times; the vacuum degree of the secondary molecular distillation is 75Pa, the distillation temperature is 130 ℃, and the cycle times are 2 times; the vacuum degree of the three-stage molecular distillation is 3Pa, the distillation temperature is 255 ℃, and the cycle time is 2 times.
(6) And (3) carrying out freezing and squeezing operation on the heavy phase substance obtained by the multistage molecular distillation treatment to obtain the natural vitamin E.
Example 3
This example provides a method for producing fatty acid methyl ester by lipase catalysis, which is substantially the same as example 2, except that:
in step (3), the lipase Novozyme435 is not pre-dispersed by a glycerol-emulsifier system. Namely: directly after step (2) the lipase Novozyme435 was added.
Comparative example 1
This example provides a method for producing fatty acid methyl ester by lipase catalysis, which is substantially the same as example 2, except that: step (3) is omitted.
Comparative example 2
This example provides a method for producing fatty acid methyl esters catalyzed by lipase, which is substantially the same as that of example 2, except that: and nitrogen circulation protection is not started in the reaction process.
The yields of the fatty acid methyl esters and natural vitamin E synthesized using the production processes in the examples and comparative examples were calculated, and the methyl ester acid value and the sulfur content in the fatty acid methyl esters were measured, wherein,
content determination of fatty acid methyl ester: according to GB/T-23801-2021 infrared spectroscopy for determining the content of fatty acid methyl ester in middle distillate oil;
measurement of acid value: according to GB5009.229-2016 (determination of acid value in food safety national standard food);
and (3) measuring the content of vitamin E: according to GB 1886.233-2016 national food safety Standard food additive vitamin E;
and (3) measuring the sulfur content: determination of the sulfur content of automotive fuels according to ISO 20846;
the test results are shown in table 1.
By comparing comparative example 1 and the examples, it is found that the lipase-catalyzed production by the two-step method not only results in the yield of fatty acid methyl ester and natural vitamin E being reduced, but also results in the unpredictable increase of the acid value of the methyl ester.
Through comparative analysis of comparative example 2 and the examples, it is found that the yield of fatty acid methyl ester and natural vitamin E is obviously reduced and the acid value of methyl ester is increased to a certain extent because nitrogen circulation protection is not used in the whole catalytic reaction process.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent variations made in accordance with the spirit of the present invention are intended to be covered by the scope of the present invention.
Claims (15)
1. A method for producing fatty acid methyl ester by lipase catalysis is characterized in that: under the protection of nitrogen circulation, the vegetable oil deodorized distillate is subjected to catalytic reaction in three steps by using lipase in the presence of methanol to obtain a mixture containing fatty acid methyl ester, and then the fatty acid methyl ester is obtained through post-treatment.
2. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 1, wherein: the second catalytic reaction is carried out in a system containing an emulsifier and glycerol.
3. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 2, wherein: the mass ratio of the glycerol to the emulsifier is (17-23): 1; and/or the emulsifier is span and tween, and the mass ratio of the span to the tween is (1 to 5): 1; and/or the addition amount of the glycerol is 1-5wt% of the addition amount of the vegetable oil deodorizer distillate.
4. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 2, wherein: dispersing the lipase subjected to the second-step catalytic reaction in the system containing the emulsifier and the glycerol, and then adding the lipase into the reaction system obtained through the first-step catalytic reaction to perform the second-step catalytic reaction.
5. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 4, wherein the lipase-catalyzed production comprises the following steps: the specific steps of dispersing the lipase for the second catalytic reaction in the system containing the emulsifier and the glycerol are as follows:
(a) Preparing the emulsifier;
(b) Mixing the emulsifier and the glycerol;
(c) And (c) adding the lipase subjected to the second-step catalytic reaction into the mixed system obtained in the step (b), and uniformly stirring.
6. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 2, wherein the method comprises the following steps: the emulsifier and the glycerin are both food grade.
7. The method for lipase-catalyzed production of fatty acid methyl esters according to any of claims 1 to 6, characterized in that: the catalytic reaction is carried out by adopting lipase in three steps, which comprises the following steps in sequence:
(1) Adding the deodorized distillate of the vegetable oil, lipase and methanol into a reaction kettle to carry out a first-step catalytic reaction;
(2) Adding lipase, emulsifier and glycerol into the reaction kettle to perform a second step of catalytic reaction;
(3) Adding lipase and methanol into the reaction kettle to carry out a third step of catalytic reaction;
the steps (1) to (3) are carried out under the protection of nitrogen circulation.
8. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 7, wherein the method comprises the following steps: in the step (1), the addition amount of the lipase in the reaction system in the step (1) is controlled to be 380-450IU/g; and/or in the step (2), controlling the addition amount of the lipase to be 0.1-1wt% of the addition amount of the vegetable oil deodorized distillate; and/or in the step (3), controlling the addition amount of the lipase in the reaction system in the step (3) to be 420-450IU/g.
9. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 7, wherein the method comprises the following steps: in the step (1), the reaction temperature is controlled to be 35-45 ℃, and/or the reaction time is controlled to be 15-23h; and/or the presence of a gas in the gas,
in the step (2), the reaction temperature is controlled to be 40-60 ℃, and/or the reaction time is controlled to be 10-15h;
in the step (3), the reaction temperature is controlled to be 40-50 ℃, and/or the reaction time is controlled to be 15-20h.
10. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 7, wherein the method comprises the following steps: in the step (1), the feeding mass ratio of the methanol to the vegetable oil deodorized distillate is 1: (2 to 3); and/or the presence of a gas in the gas,
in the step (3), the feeding mass ratio of the methanol to the plant oil deodorized distillate in the step (1) is 1: (1.5 to 2).
11. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 1, wherein: the lipase adopted in the first step of catalysis and the third step of catalytic reaction is candida lipase, and the lipase adopted in the second step of catalytic reaction is lipase Novozyme435; and/or the presence of a gas in the gas,
the vegetable oil deodorized distillate comprises one or more of soybean oil deodorized distillate, corn oil deodorized distillate, sunflower seed oil deodorized distillate, and rapeseed oil deodorized distillate.
12. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 1, wherein the method comprises the following steps: catalytic reaction goes on in the reation kettle who has coil formula air jet system, coil formula air jet system is including installing on reation kettle's the inner wall and certainly reation kettle's bottom is installed to coil pipe, the interval that top spiral coiled and set up a plurality of air jet system on the coil pipe, the coil pipe has the air inlet, the air inlet and the admission line of coil pipe be linked together in order to be used for to carry nitrogen gas in the coil pipe, reation kettle has the gas outlet, reation kettle's gas outlet and exhaust duct are linked together, be provided with agitating unit in the reation kettle, air jet system only can give vent to anger in one way and give vent to anger the direction towards agitating unit's axial lead.
13. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 12, wherein: the number of turns of the coiled pipe is 8 to 10; and/or the distance between two adjacent circles of the coil pipes is 15 to 25 centimeters; and/or the length of the coil between two adjacent air injection devices is 25 to 35 centimeters; and/or controlling the nitrogen pressure in the coil pipe to be 3-7 kg; and/or the gas spraying device comprises a one-way gas valve arranged on the coil pipe and a spray head communicated with the one-way gas valve, and a plurality of holes for gas to pass through are formed in the spray head.
14. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 12, wherein the method comprises the following steps: an air inlet pump is arranged on the air inlet pipeline, a storage tank is arranged on the exhaust pipeline, the air inlet pipeline is communicated with the exhaust pipeline, a connecting point of the air inlet pipeline and the exhaust pipeline is positioned on the air inlet side of the air inlet pump, and a drain pipe is arranged on the air inlet pipeline and/or the exhaust pipeline; and/or the air inlet is positioned at the lower part of the reaction kettle, and the air outlet is positioned at the upper part of the reaction kettle.
15. The method for lipase-catalyzed production of fatty acid methyl esters according to claim 1, wherein the method comprises the following steps: the post-treatment method is multi-stage molecular distillation; the method also comprises the step of carrying out freezing and squeezing operation on the heavy phase substance obtained after the multistage molecular distillation to obtain the natural vitamin E.
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