CN113684231B - Method for synthesizing esters by multi-liquid-phase enzymatic esterification - Google Patents
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Abstract
The invention belongs to the field of bioengineering, and discloses a method for synthesizing esters by esterification through a multi-liquid-phase enzymatic method, which comprises the following steps: (1) adding a hydrophilic solvent and soluble salt into a lipase liquid, and fully mixing; (2) adding organic alcohol and organic acid with the carbon number of more than 4 into the mixed solution to form a three-liquid-phase system, and carrying out esterification reaction under the stirring condition; (3) after the reaction is finished, standing or centrifugally layering, and collecting the upper-layer product ester. Different from the serious inhibition reaction of water generated in the traditional esterification process, the water rich in the three liquid phases has no obvious inhibition effect on the esterification reaction, and unnecessary water molecules are not required to be removed under the conditions of adding a water removal agent or vacuum and the like in the esterification process, so that the operation complexity is reduced. The invention has faster catalytic esterification and shorter esterification equilibrium time, generally only 6 hours, while the traditional enzyme method generally needs more than 12 hours. Furthermore, in a three-liquid phase system, the enzyme may be concentrated in one of the phases for ease of separation and reuse.
Description
Technical Field
The invention belongs to the field of bioengineering, relates to a separation and application technology of enzyme, and particularly relates to a method for esterifying organic alcohol and organic acid by using lipase.
Background
Organic esters are important chemical raw materials and intermediates, and play an important role in the fields of solvents, fuels, additives and the like. For example, fatty acid alkyl esters are used as synthetic high-grade surfactants, additives for high-grade lubricating oils and fuels, emulsifier products, solvents for perfumes, and the like, and contribute significantly to the daily chemical industry. For another example, fatty acid methyl ester or ethyl ester, i.e., biodiesel, has the characteristics of good fuel performance, biodegradability, wide raw material source and the like, and can be used as a renewable green energy source for reducing the emission of air pollutants. Further, sucrose fatty acid ester and the like can be used as a food emulsifier; esters having a specific structure such as flavonoid fatty acid esters and daidzein fatty acid esters have an important role in the field of medicine.
Esterification is generally the process of dehydrating an alcohol and an acid to form an ester, and generally occurs relatively easily in an alcohol, while the esterification yield is reduced in a water-rich environment. The traditional method for chemical esterification needs concentrated acid or alkali and some acid salts such as hydrochloride, sulfonate and the like as catalysts. The adoption of concentrated acid or concentrated alkali as catalyst has high environmental pollution, complex production process and serious corrosion to equipment. Meanwhile, the reaction also needs high temperature conditions, such as esterification of acid and alcohol at 200-350 ℃ disclosed in CN105555920B, which causes serious energy loss. Most of the acid-base catalyst added in the reaction process can not be recycled, the production cost is high, a large amount of waste gas and waste residue are generated in the catalysis process, the environmental pollution is easy to cause, and the industrial application is greatly influenced.
Compared with the esterification by a chemical method, the enzyme catalysis esterification has the advantages of mild reaction conditions, strong specificity, high catalysis efficiency and the like. However, since enzymatic esterification is more susceptible to product water, the overall yield is not high. Water-rich environments tend to inhibit forward esterification and promote reverse hydrolysis (Biocatalysis and Agricultural Biotechnology, 20: 101221-. In order to increase the esterification rate, it is usually necessary to remove the water generated in the reaction in time, for example, to remove water continuously under vacuum, or to add molecular sieves to the reaction to remove water, so as to reduce the side reaction ester hydrolysis, which is complicated to operate and easy to inactivate enzymes, making its industrial application extremely difficult. Therefore, in recent years, the development of the application of enzyme esterification in high water environment has been the focus of research, but the overall progress is very little, and a great deal of research points to that in high water environment, the enzyme tends to hydrolyze esters rather than synthesize at high speed. As a result of previous studies in this group, a three-liquid phase system was developed as a novel, highly efficient, enzyme-recyclable enzyme catalysis system, but in this system, much water was contained, and it was considered that it could only be used for high-speed hydrolysis of esters (CN109295030A, Chemical Communications, 2015, 51(65): 12943-12946).
Disclosure of Invention
The invention develops a synthetic method for efficiently catalyzing organic esters by lipase in a high-water environment aiming at the problem that the catalytic efficiency is influenced by byproduct water in the esterification process of organic acid and organic alcohol to cause reverse hydrolysis reaction.
In a three-liquid-phase system of a polymer or an ionic liquid, when the acid participating in the reaction is an organic acid with the carbon number of more than 4, the enzyme can realize the high-efficiency catalysis of the enzyme-catalyzed esterification reaction in the high-water environment. The system reaction not only can reduce the inhibition of water and improve the esterification efficiency, but also can realize the high-efficiency recycling of the catalyst enzyme.
The purpose of the invention is realized by the following technical scheme:
a method for synthesizing esters by multi-liquid-phase enzymatic esterification comprises the following steps:
(1) adding a hydrophilic solvent and soluble salt into a lipase liquid, and fully mixing;
(2) adding organic alcohol and organic acid with the carbon number of more than 4 into the mixed solution to form a three-liquid-phase system, and carrying out esterification reaction under the stirring condition;
(3) after the reaction is finished, standing or centrifugally layering, and collecting the upper-layer product ester.
Preferably, the hydrophilic solvent in step (1) is PEG-200, PEG-400, PEG-600, PEG-2000, polypropylene glycol, [ BMIM ]]PF6One or more than two of them.
Preferably, the Lipase in the step (1) is Lipase AYS, Lipase AY30, CALB, TL100L, with the concentration of 100-; the soluble salt is one or more than two of sodium sulfate, ammonium sulfate, sodium carbonate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.
The organic acid does not comprise formic acid, acetic acid and propionic acid with carbon number of 1-3. Preferably, the esterification effect of the long-chain fatty acid with strong hydrophobicity is better than that of the fatty acid with low carbon number. The organic acid above C4 in the step (2) is butyric acid, caprylic acid, capric acid, lauric acid, oleic acid, linoleic acid, palmitic acid and stearic acid; the organic alcohol is methanol, ethanol, isopropanol, butanol, octanol or lauryl alcohol.
Preferably, the mass ratio of the soluble salt, the hydrophilic solvent and the enzyme solution in the step (1) is 0.2-0.6 and 0.2-0.6 respectively. More preferably, the mass ratio of the soluble salt, the hydrophilic solvent and the enzyme solution in the step (1) is 0.2-0.4 and 0.2-0.3.
Preferably, the molar ratio of the organic acid to the organic alcohol in the step (2) is 0.3-3; the mass ratio of the organic alcohol to the mixed solution is 1-20%, and more preferably 5-10%.
Preferably, in the step (2), the adding amount of the organic alcohol with the carbon number of C <4 is not more than 15% of the mass of the mixed solution. The addition of alcohols below C4 will dissolve partially or completely in the middle and lower phases, and excessive addition will precipitate out and eventually become only two liquid phases, thereby affecting the formation of three liquid phases. Therefore, in the present invention, the amount of the alcohol having a carbon number of C <4 is limited, and the addition of an excessive amount of the hydrophilic alcohol can be prevented from causing the destruction of the system phase.
Preferably, the organic acid and the organic alcohol in the step (2) are firstly dissolved in a hydrophobic solvent, and then are added into the mixed solution, wherein the hydrophobic solvent is n-hexane, isooctane or petroleum ether.
Preferably, the esterification reaction in the step (2) is carried out at the temperature of 20-50 ℃, the rotating speed of 100-; more preferably, the reaction temperature is 25-40 ℃, the rotation speed is 100-300 r/min, and the reaction time is 0.5-5 h.
The woody oil refers to oil produced by woody plants such as camellia oil, walnut oil and the like; the oleic acid, linoleic acid, palmitic acid, stearic acid and the like are common medium-long chain fatty acids in the woody oil. The method esterifies the mixed fatty acid generated by hydrolyzing the woody oil, has higher esterification efficiency, and shows that the method has universality for esterification of medium-chain and long-chain fatty acids in the woody oil.
Compared with the prior art, the invention has the beneficial effects that:
(1) different from the serious inhibition reaction of water generated in the traditional esterification process, the water rich in the three liquid phases has no obvious inhibition effect on the esterification reaction, redundant water molecules are not required to be removed under the conditions of adding a water removal agent or vacuum and the like in the esterification process, and the operation complexity is reduced;
(2) the invention has faster catalytic esterification and shorter esterification equilibrium time, generally only 6 hours, while the traditional enzyme method generally needs more than 12 hours. Furthermore, in a three-liquid phase system, the enzyme may be concentrated in one of the phases for ease of separation and reuse.
Drawings
FIG. 1 is a diagram showing the phase formation effect of methanol with different mass fractions, wherein the mass fractions of methanol corresponding to a-f are respectively 0, 5%, 10%, 13%, 16% and 20%.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Lipase AYS, Lipase AY30(Candida rugosa lipases) used in this example were purchased from Tianye, Japan, acids and alcohols are commercially available, CALB is purchased from Googlison, Beijing, and TL100L is purchased from Novoxin.
Example 1
0.3g of (NH) was added to 0.90g of AYS enzyme solution (200U/ml)4)2SO4 and 0.3g PEG400, mixed well. To the above solution was added 0.1g of free mixed fatty acids produced from fully hydrolyzed walnut oil, and 2 times the molar amount of methanol, 0.032g, to form a three liquid phase system. The reaction is carried out for 2 hours in a shaking table at the temperature of 37 ℃ and the rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency is 32.67 percent.
Comparative example 1
0.90g of AYS enzyme solution (200U/ml), 0.1g of free mixed fatty acid produced by fully hydrolyzed walnut oil and 2 times the molar amount of methanol were added, 0.032g were reacted in a shaker at 37 ℃ and 200rpm for 2 hours, and the esterification efficiency was only 7.21%.
Example 2
To 3.9g of AY30 enzyme solution (200U/ml) was added 0.96g of Na2SO4And 1.14g PEG600, mixed well. To the above solution was added 0.4g of free mixed fatty acids produced by the fully hydrolyzed camellia oil, and equimolar n-butanol to form a three liquid phase system. The reaction is carried out for 2 hours in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency is 75.80%.
Comparative example 2
3.90g AY30 enzyme solution (200U/ml), 0.4g free mixed fatty acid produced by the camellia oil after complete hydrolysis and an equal molar amount of n-butanol, 0.032g were added and reacted in a shaker at 37 ℃ and 200rpm for 2h, and the esterification efficiency was only 21.16%.
Example 3
0.96g of Na was added to 3.9g of AYS enzyme solution (400U/ml)2SO4And 1.14g PEG600, mixed well. To the above solution 8% (w/w) conjugated linoleic acid, i.e. 0.48g, was added, together with an equimolar amount of butanol, to form a three liquid phase system. The reaction is carried out for 2h in a shaker at the temperature of 37 ℃ and the rpm of 200, and the product ester is recovered by centrifugation or standing, and the esterification efficiency of the single isomer c9 and t 11-is 84.18 percent.
Comparative example 3
3.9g of AYS enzyme solution (400U/ml), 0.5g of conjugated linoleic acid and equal mol of butanol are added to react for 2 hours in a shaker at the temperature of 37 ℃ and the rpm of 200, and the esterification efficiency of a single isomer c9 and t 11-is only 61.86 percent.
Example 4
To 3.9g of AYS enzyme solution (600U/ml), 0.96g of (NH) was added4)2SO4And 1.14g PEG600, mixed well. To the above solution was added 8% (w/w) octanol, i.e. 0.48g, and equimolar conjugated linoleic acid to form a three liquid phase system. The reaction is carried out for 2h in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency of the single isomer c9 and t 11-is 89.74 percent.
Comparative example 4
3.9g AY30 enzyme solution (600U/ml), 0.48g octanol and equimolar conjugated linoleic acid are added to react for 2 hours in a shaker at 37 ℃ and 200rpm, and the esterification efficiency of a single isomer c9 and t 11-is only 45.30 percent.
Example 5
To 3.6g of CALB enzyme solution (600U/ml), 1.2g of Na was added2SO4And 1.2g PEG400, mixed well. To the above solution, about 7% (w/w) of dodecanol, i.e., 0.4g, and 0.28g of butyric acid in a 1.5-fold molar amount were added to form a three-liquid phase system. The reaction is carried out for 3 hours in a shaking table at the temperature of 37 ℃ and the rpm of 200, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency is 80.45 percent.
Comparative example 5
The esterification efficiency was only 11.71% under the same conditions when the same amounts of CALB enzyme, 0.4g of dodecanol and 0.28g of butyric acid as those of example 5 above were added.
Example 6
0.24g of (NH) was added to 0.9g of AY30 enzyme solution (400U/ml)4)2SO4And 0.285g [ BMIM ]]PF6And mixing the components completely. To the above solution was added 0.2g of conjugated linoleic acid, and an equimolar amount of octanol to form a three liquid phase system. The reaction is carried out for 0.5h in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency of the single isomer c9 and t 11-is 58.21 percent.
Comparative example 6
When the same amount of AY30 lipase as in example 6 above, 50. mu.L of ultrapure water, 0.2g of conjugated linoleic acid, and equimolar octanol were added, the esterification efficiency of the individual isomers c9, t 11-was only 9.62% under the same conditions.
Example 7
To 3.6g of CALB enzyme solution (500U/ml) was added 1.2g of (NH)4)2SO4And 1.2g PEG600, mixed well. To the above solution was added 1mL of n-hexane (in which 0.3g of dodecanol, 0.15g of butyric acid was dissolved) to form a three-liquid phase system. The reaction is carried out for 3 hours in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency is 84.83%.
Comparative example 7
With the addition of 1mL of n-hexane, 0.3g of dodecanol, 0.15g of butyric acid, and the same amount of CALB lipase as in example 7 above, the esterification efficiency was only 30.92% under the same conditions.
Example 8
0.24g of (NH) was added to 0.975gAY30 enzyme solution (400U/ml)4)2SO4And 0.285g PEG2000, mixed well. To the above solution was added 6.5% (w/w) octanol, i.e. about 0.1g, and equimolar conjugated linoleic acid to form a three liquid phase system. The reaction is carried out for 0.5h in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, wherein the esterification efficiency of the single isomer c9 and t 11-is 61.6 percent.
Example 9
This example differs from example 4 in that:
the alcohol used was isopropanol and the esterification efficiency of the single isomer c9, t 11-was 63.58%.
Example 10
This example differs from example 4 in that:
the alcohol used was ethanol, and the esterification efficiency of the single isomer c9, t 11-was 59.85%.
Example 11
This example differs from example 4 in that:
the alcohol used was methanol, and the esterification efficiency of the single isomer c9, t 11-was 51.78%.
Example 12
0.3g of (NH) was added to 0.9gAY30 enzyme solution (400U/ml)4)2SO4And 0.3g PEG600, mixed well. To make the phase interface and phase change more clear, the mesophase was stained with bromocresol green to observe the phase change. For example, the amount of methanol added is for C<4 was investigated for the upper limit of the mass fraction of the organic alcohol. As shown in FIG. 1, when methanol was added in an amount of 0, 5%, 10%, or 13%, a three-liquid phase system was formed. As shown in e and f in fig. 1, when methanol was added in an amount of 16% and 20% by mass of the system, precipitates had precipitated. Thus, the present invention defines the carbon number C<4, the organic alcohol does not exceed 15 percent of the mass of the mixed solution, and if the organic alcohol exceeds the upper limit, the organic alcohol does not form a three-liquid-phase system, and does not meet the requirement of the invention.
Comparative example 8
0.24g of (NH) was added to 0.9g of AY30 enzyme solution (400U/ml)4)2SO4And 0.285g [ BMIM ]]BF4And mixing the components completely. To the above solution was added 0.2g of conjugated linoleic acid, and an equimolar amount of octanol to form a three liquid phase system. The reaction is carried out for 0.5h in a shaker at 37 ℃ and 200rpm, and the product ester is recovered by centrifugation or standing, and the esterification efficiency of the single isomer c9, t 11-is only 5.13 percent.
Comparative example 9
0.24g of (NH) was added to 0.9g of AY30 enzyme solution (400U/ml)4)2SO4And 0.285g PEG400, mixed well. To the above solution was added 0.2g octanol, and equimolar acetic acid to form a three liquid phase system. The reaction is carried out for 2 hours in a shaking table at the temperature of 37 ℃ and the rpm, the product ester is recovered by centrifugation or standing, the esterification efficiency is only 1.62 percent, and the reaction is basically not reacted.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for synthesizing esters by multi-liquid-phase enzymatic esterification is characterized by comprising the following steps:
(1) adding a hydrophilic solvent and soluble salt into a lipase liquid, and fully mixing;
(2) adding organic alcohol and organic acid with the carbon number of more than 4 into the mixed solution to form a three-liquid-phase system, and carrying out esterification reaction under the stirring condition;
(3) after the reaction is finished, standing or centrifugally layering, and collecting the upper-layer product ester.
2. The method according to claim 1, wherein the hydrophilic solvent in step (1) is PEG-200, PEG-400, PEG-600, PEG-2000, polypropylene glycol, [ BMIM ]]PF6One or more than two of them.
3. The method as claimed in claim 2, wherein the Lipase in step (1) is Lipase AYS, Lipase AY30, CALB, TL100L, concentration 100-; the soluble salt is one or more than two of sodium sulfate, ammonium sulfate, sodium carbonate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate.
4. The method according to claim 3, wherein the organic acid having C4 or more in step (2) is one or more selected from butyric acid, caprylic acid, capric acid, lauric acid, oleic acid, linoleic acid, palmitic acid and stearic acid; the organic alcohol is methanol, ethanol, isopropanol, butanol, octanol or lauryl alcohol.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the soluble salt, the hydrophilic solvent and the enzyme solution in step (1) is 0.2 to 0.6, and 0.2 to 0.6, respectively.
6. The method according to claim 5, wherein the mass ratio of the soluble salt, the hydrophilic solvent and the enzyme solution in the step (1) is 0.2-0.4, 0.2-0.3.
7. The method according to claim 5, wherein the molar ratio of the organic acid to the organic alcohol in the step (2) is 0.3 to 3; the mass ratio of the organic alcohol to the mixed solution is 1-20%.
8. The method according to claim 7, wherein in the step (2), the organic alcohol having a carbon number of C <4 is added in an amount of not more than 15% by mass based on the mass of the mixed solution.
9. The method as claimed in claim 8, wherein the organic acid and the organic alcohol in step (2) are dissolved in a hydrophobic solvent, and then added to the mixed solution, wherein the hydrophobic solvent is n-hexane, isooctane, petroleum ether.
10. The method as claimed in any one of claims 1 to 4, wherein the esterification reaction in step (2) is carried out at a temperature of 20-50 ℃, a rotation speed of 100-.
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