WO2022227123A1 - 一种联产l-抗坏血酸棕榈酸酯和生物柴油的工艺方法 - Google Patents

一种联产l-抗坏血酸棕榈酸酯和生物柴油的工艺方法 Download PDF

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WO2022227123A1
WO2022227123A1 PCT/CN2021/093558 CN2021093558W WO2022227123A1 WO 2022227123 A1 WO2022227123 A1 WO 2022227123A1 CN 2021093558 W CN2021093558 W CN 2021093558W WO 2022227123 A1 WO2022227123 A1 WO 2022227123A1
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enzyme
catalyzed
reaction
ascorbic acid
palm oil
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French (fr)
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杜伟
刘德华
刘剑波
张圆满
湛东锐
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东莞深圳清华大学研究院创新中心
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/62—Three oxygen atoms, e.g. ascorbic acid
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to the field of biochemical industry, in particular to a process method for co-producing L-ascorbyl palmitate and biodiesel.
  • L-ascorbic acid (L-ascorbic acid) is a commonly used natural antioxidant. Its molecular structure has active alkene diol, which is easily oxidized by external factors such as light and temperature, so it has strong antioxidant capacity. However, because L-ascorbic acid has strong hydrophilicity and is not easily dissolved in hydrophobic liquids such as oils and fats, its application is greatly limited, and this problem can be solved by converting L-ascorbic acid into its fatty acid ester. L-ascorbic acid fatty acid ester not only maintains the antioxidant properties and physiological activity of L-ascorbic acid, but also significantly improves the solubility and stability in non-aqueous systems, and increases the scavenging ability of free radicals. It has become a kind of A highly effective, safe and non-toxic antioxidant.
  • fatty acids such as palmitic acid, stearic acid and lauric acid
  • the biological enzymatic reaction conditions are mild, the specificity is strong, and the product separation and purification method
  • the simple, enzyme-catalyzed synthesis of L-ascorbic acid fatty acid ester has good development and application prospects.
  • the present invention discloses a process method for co-producing L-ascorbyl palmitate and biodiesel.
  • a process for co-producing L-ascorbyl palmitate and biodiesel comprising the following steps:
  • Step 1 L-ascorbic acid and palm oil are subjected to an enzyme-catalyzed reaction to obtain an enzyme-catalyzed mixture;
  • step 2 the primary enzyme catalyzed mixture is subjected to layering and vacuum distillation to obtain a primary enzyme catalyzed product
  • Step 3 subjecting the primary enzyme-catalyzed product to a secondary enzyme-catalyzed reaction to obtain a secondary enzyme-catalyzed mixture;
  • step 4 the secondary enzyme-catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel (ie, palm oil short-chain alcohol ester).
  • L-ascorbyl palmitate and biodiesel ie, palm oil short-chain alcohol ester
  • step 1 the primary enzyme-catalyzed reaction is carried out by reacting with a short-chain alcohol under the catalysis of lipase; the lipase is Liquid lipase or immobilized lipase.
  • the above-mentioned process method for co-producing L-ascorbyl palmitate and biodiesel wherein said step 1 adopts liquid lipase catalysis; the condition of said primary enzyme catalysis reaction is: the liquid lipase consumption is 300-3000 % of the palm oil quality A standard enzyme activity unit, the amount of L-ascorbic acid is 0.2 to 0.8 times the number of moles of palm oil, the amount of short-chain alcohol is 3 to 5 times the number of moles of palm oil, and the water content is 2 to 5% of the mass of palm oil; the An enzyme-catalyzed reaction is carried out in a one-stage or multi-stage enzyme reactor, the temperature is controlled at 35-60 DEG C, and the reaction is carried out for 6-18 hours. Usually, the conversion rate of L-ascorbic acid is over 80%, and the yield of palm oil short-chain alcohol ester is over 90% of the theoretical yield.
  • the above-mentioned process method for co-producing L-ascorbyl palmitate and biodiesel wherein the step 1 adopts immobilized lipase catalysis; the condition of the primary enzyme catalysis reaction is: the immobilized lipase consumption is 300% of the palm oil quality. -2000 standard enzyme activity units, the amount of L-ascorbic acid is 0.2-0.8 times the mole number of palm oil, and the amount of short-chain alcohol is 3-65 times the mole number of palm oil; the one enzyme catalyzed reaction in one or more stages It is carried out in a loop reactor, the temperature is controlled at 35-60 °C, and the reaction is carried out for 5-18 hours. Usually, the conversion rate of L-ascorbic acid is over 90%, and the yield of palm oil short-chain alcohol ester is over 95% of the theoretical yield.
  • step 2 centrifugation or static stratification can be selected for the layering treatment to separate the heavy phase containing lipase and the light phase containing crude biodiesel, and the light phase is further reduced.
  • the pot liquid is taken by pressure distillation for the subsequent step 3, and the purpose of vacuum distillation is to remove excess short-chain alcohol.
  • step 3 the secondary enzyme-catalyzed reaction is carried out under the catalysis of immobilized lipase, and the immobilized lipase is
  • the dosage is 300-2000 standard enzyme activity units of the quality of palm oil; the secondary enzyme catalytic reaction is carried out in a one-stage or multi-stage loop reactor, the temperature is controlled at 35-60°C, and the reaction is performed for 10-18 hours.
  • the one-stage or multi-stage loop reactor is coupled with an online dehydration device to remove moisture in the reaction system online; usually, the conversion rate of L-ascorbic acid reaches more than 95%, and the palm oil short-chain alcohol ester is obtained. The rate is more than 98% of the theoretical yield.
  • the above-mentioned process method for co-producing L-ascorbyl palmitate and biodiesel wherein the lipase includes lipase derived from yeast cells, mold cells, bacteria or other microorganisms.
  • L-ascorbic acid As a common natural antioxidant, L-ascorbic acid has strong hydrophilicity and is not easy to dissolve in hydrophobic liquids such as oil, which greatly limits its application in fat-soluble hydrophobic systems.
  • hydrophobic liquids such as oil
  • fatty acids such as palmitic acid, stearic acid and lauric acid are directly used as acyl donors, but in the preparation process, the acyl donors are difficult to dissolve with L-ascorbic acid, so it is usually necessary to introduce a hydrophobic solvent to improve the degree of hydrophobicity in the reaction system , the traditional hydrophobic solvent can optionally include tert-butanol, acetone, etc., but if the above-mentioned solvent is introduced, the operating cost will be increased, and the product obtained from the reaction has a single type.
  • biocatalysts can be selected, including a variety of lipases, including liquid lipase, immobilized lipase, and lipase-containing bacteria or immobilized bacteria; lipase catalysts It has the advantages of wide adaptability of raw materials and mild reaction conditions, and is especially suitable for the enzyme-catalyzed reaction of high-acid-value oils and fats; liquid lipase is free liquid, relatively cheap, usually contains high moisture content, and its enzymatic catalysis of oils and fats Compared with liquid lipase, immobilized lipase has the advantages of good stress resistance and easy recovery.
  • a two-step enzymatic catalysis reaction including the catalysis of liquid lipase or immobilized lipase in the first enzymatic catalysis reaction, and the catalysis of immobilized lipase in the second enzymatic catalysis reaction, wherein the catalysis of liquid lipase is Under the oil-water emulsification system, the liquid lipase is dispersed on the oil-water two-phase interface to catalyze the reaction, thereby promoting the enzyme catalytic efficiency.
  • the protein of the immobilized lipase prepared by the adsorption method falls off and is inactivated, resulting in a decrease in the apparent enzymatic activity.
  • the present invention adopts the immobilized lipase to catalyze the reaction system as a solvent-free system, that is, without adding an organic solvent such as water as a reaction medium , the reaction system is homogeneous at this time, and there is no emulsification phenomenon. It should be noted that water is generated in the esterification reaction between L-ascorbic acid and palm oil, palm oil and short-chain alcohol, and the esterification reaction is an equilibrium reaction.
  • the reaction system in order to further promote the reaction to the esterification reaction, when the secondary enzyme catalyzed reaction is carried out, the reaction system can be coupled with an online dehydration device to remove the water in the system online, which can quickly promote the reaction to reach an equilibrium state, and then effectively Improve the conversion rate and product yield of L-ascorbic acid.
  • the present invention utilizes the solubility of L-ascorbic acid in short-chain alcohols, promotes the mutual solubility of L-ascorbic acid and palm oil, adopts two-step enzyme catalysis reaction to react under mild conditions, and realizes the reaction of L-ascorbic acid and palm oil catalyzed by lipase to generate At the same time of L-ascorbyl palmitate, it catalyzes the reaction of palm oil and short-chain alcohol to generate biodiesel, which realizes the integrated co-production of various high value-added products, and significantly improves the added value of palm oil and the comprehensive economic benefits of the reaction process.
  • the whole reaction process is mild and friendly, which can not only retain the biological activity of L-ascorbic acid to the maximum extent, but also make full use of the raw material components, which greatly improves the enzyme catalytic efficiency and product yield;
  • the alcohol replaces the conventional organic solvent, and there is no need to additionally introduce organic solvents such as tert-butanol and acetone used in the conventional process, solve the problem that L-ascorbic acid is insoluble in palm oil and need to add an additional organic solvent, eliminating the need for conventional L-ascorbic acid.
  • the cumbersome process of additionally adding an organic solvent in the preparation process of the palmitate the comprehensive economic benefit is significantly improved, and the process has a good market promotion and application prospect.
  • Fig. 1 is the reaction process schematic diagram of processing method in the present invention
  • Fig. 2 is the main flow schematic diagram of the technological method in the present invention.
  • Embodiment 1 provides a process for co-producing L-ascorbyl palmitate and biodiesel, comprising the following steps:
  • Step 1 mix 10 g of palm oil, 2% water based on oil mass, L-ascorbic acid based on 0.2 times the mole number of oil, liquid lipase derived from Aspergillus oryzae based on 400 standard enzyme activity units based on oil mass, based on oil Methanol with 3 times the mole number is placed in a one-stage or multi-stage enzyme reactor and reacted at 35° C. for 10 hours to obtain a primary enzyme-catalyzed mixture; wherein, the conversion rate of L-ascorbic acid in the primary enzyme-catalyzed mixture reaches 80%, and the palm The yield of oleyl methyl ester is 90%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • Step 3 placing the primary enzyme catalyzed product in a one-stage or multi-stage loop reactor, adding immobilized lipase from Aspergillus oryzae based on 300 standard enzyme activity units based on oil quality, and controlling the reaction temperature at 55°C , and reacted for 12 hours to obtain the secondary enzyme catalyzed mixture;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 95%, and the yield of palm oil methyl ester is 98%.
  • Embodiment 2 provides a process for co-producing L-ascorbyl palmitate and biodiesel, comprising the following steps:
  • Step 1 the liquid lipase derived from Candida antarctica based on 20 g of palm oil, 5% water based on oil mass, L-ascorbic acid based on 0.5 times the mole number of oil, and 2000 standard enzyme activity units based on oil mass, Ethanol with 4 times the mole number of oil is placed in a one-stage or multi-stage enzyme reactor to react at 45°C for 18 hours to obtain a primary enzyme-catalyzed mixture; wherein, the conversion rate of L-ascorbic acid in the primary enzyme-catalyzed mixture reaches 85% , the yield of palm oil ethyl ester is 90%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • Step 3 placing the primary enzyme catalyzed product in a one-stage or multi-stage loop reactor, adding immobilized lipase from Aspergillus oryzae based on 2000 standard enzyme activity units based on oil quality, and the reaction temperature is controlled at 45°C , and reacted for 12 hours to obtain the secondary enzyme catalyzed mixture;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 98%, and the yield of palm oil ethyl ester is 98%.
  • Embodiment 3 This embodiment provides a kind of technological method of co-production L-ascorbyl palmitate and biodiesel, and it comprises the following steps:
  • Step 1 using 30 g of palm oil, 0.8 times of L-ascorbic acid based on the number of moles of oil, 1500 standard enzyme activity units based on the quality of oil and the immobilized lipase derived from Rhizomucor miehei, 5 times of the number of moles of oil based on the immobilized lipase derived from Rhizomucor miehei.
  • Methanol is placed in a one-stage or multi-stage loop reactor and reacted at 55 ° C for 10 hours to obtain a primary enzyme-catalyzed mixture; wherein, the conversion rate of L-ascorbic acid in the primary enzyme-catalyzed mixture reaches 91%, and the yield of palm oil methyl ester 96%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • step 3 the primary enzyme catalyzed product is placed in a one-stage or multi-stage loop reactor, and the immobilized lipase from Candida antarctica based on 1000 standard enzyme activity units of oil quality is added, and the reaction temperature is controlled at 55°C for 10 hours to obtain a secondary enzyme-catalyzed mixture;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 96%, and the yield of palm oil methyl ester is 98%.
  • Embodiment 4 This embodiment provides a kind of technological method of co-production L-ascorbyl palmitate and biodiesel, and it comprises the following steps:
  • Step 1 the immobilized lipase derived from Rhizomucor miehei based on 50 g of palm oil, 0.2 times of L-ascorbic acid based on the number of moles of oil, and 5 times of the number of moles of oil based on the immobilized lipase derived from Rhizomucor miehei based on 2000 standard enzyme activity units of the oil quality.
  • Butanol is placed in a one-stage or multi-stage loop reactor and reacted at 50°C for 15 hours to obtain a primary enzyme-catalyzed mixture, wherein butanol is added to the reactor in a uniform flow within the first 2 hours; the primary enzyme-catalyzed mixture is The conversion rate of L-ascorbic acid reaches 90%, and the yield of butyl palm oil is 95%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • Step 3 placing the primary enzyme catalyzed product in a one-stage or multi-stage loop reactor, adding immobilized lipase from Aspergillus oryzae based on 1000 standard enzyme activity units based on oil quality, and the reaction temperature is controlled at 55°C , and reacted for 12 hours to obtain a secondary enzyme-catalyzed mixture; during the reaction, the on-line dehydration as shown in Figure 2 was adopted;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 96%, and the yield of butyl palm oil is 98%.
  • Embodiment 5 This embodiment provides a kind of technological method of co-production L-ascorbyl palmitate and biodiesel, and it comprises the following steps:
  • Step 1 the liquid lipase derived from Candida antarctica based on 30 g of palm oil, 4% water based on oil mass, L-ascorbic acid based on 0.8 times the number of moles of oil, and 1800 standard enzyme activity units based on oil mass, Ethanol with 6 times the mole number of oil is placed in a one-stage or multi-stage enzyme reactor to react at 45°C for 16 hours to obtain a primary enzyme-catalyzed mixture; wherein, the conversion rate of L-ascorbic acid in the primary enzyme-catalyzed mixture reaches 80% , the yield of palm oil ethyl ester is 92%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • Step 3 the primary enzyme catalyzed product is placed in a one-stage or multi-stage loop reactor, and the immobilized lipase from Candida antarctica based on 1,800 standard enzyme activity units based on oil quality is added, and the reaction temperature is controlled at 55 ° C, the reaction was carried out for 18 hours to obtain the secondary enzyme catalyzed mixture;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 97%, and the yield of palm oil ethyl ester is 99%.
  • Embodiment 6 provides a process for co-producing L-ascorbyl palmitate and biodiesel, comprising the following steps:
  • Step 1 put 2g palm oil, 0.3 times L-ascorbic acid based on the number of moles of oil, 900 standard enzyme activity units based on the quality of the oil and the immobilized lipase derived from Aspergillus oryzae, and 4 times the methanol based on the mole number of oil and put it in the lipase.
  • the reaction is carried out at 45° C. for 12 hours in a one-stage or multi-stage loop reactor to obtain a primary enzyme-catalyzed mixture; wherein, the conversion rate of L-ascorbic acid in the primary enzyme-catalyzed mixture reaches 92%, and the yield of palm oil methyl ester is 95%;
  • Step 2 after the primary enzyme catalyzed mixture is centrifuged and stratified, the heavy phase and the light phase are separated, and the light phase is further removed by distillation under reduced pressure to remove excess short-chain alcohols to obtain a primary enzyme catalyzed product;
  • Step 3 the primary enzyme catalyzed product is placed in a one-stage or multi-stage loop reactor, and the immobilized lipase from Candida antarctica based on 2000 standard enzyme activity units based on the oil quality is added, and the reaction temperature is controlled at 50°C for 18 hours to obtain a secondary enzyme-catalyzed mixture; during the reaction, the online dehydration as shown in Figure 2 was adopted;
  • step 4 the secondary enzyme catalyzed mixture is subjected to distillation treatment under on-line dehydration conditions to obtain L-ascorbyl palmitate and biodiesel; wherein the conversion rate of L-ascorbic acid reaches 97%, and the yield of palm oil methyl ester is 99%.
  • the present invention utilizes the solubility of L-ascorbic acid in short-chain alcohols, promotes the mutual solubility of L-ascorbic acid and palm oil, adopts two-step enzyme catalysis reaction to react under mild conditions, and realizes the reaction of L-ascorbic acid and palm oil catalyzed by lipase to generate At the same time of L-ascorbyl palmitate, it catalyzes the reaction of palm oil and short-chain alcohol to generate biodiesel, which realizes the integrated co-production of various high value-added products and significantly improves the comprehensive economic benefits of the process; the whole reaction process is mild and friendly.
  • the present invention utilizes the solubility of L-ascorbic acid in short-chain alcohols, promotes the mutual solubility of L-ascorbic acid and palm oil, adopts two-step enzyme catalysis reaction to react under mild conditions, and realizes the reaction of L-ascorbic acid and palm oil catalyzed by lipase to generate At the same time of L-ascorbyl palmitate, it catalyzes the reaction of palm oil and short-chain alcohol to generate biodiesel, which realizes the integrated co-production of various high value-added products, and significantly improves the added value of palm oil and the comprehensive economic benefits of the reaction process.
  • the whole reaction process is mild and friendly, which can not only retain the biological activity of L-ascorbic acid to the maximum extent, but also make full use of the raw material components, which greatly improves the enzyme catalytic efficiency and product yield;
  • the alcohol replaces the conventional organic solvent, and there is no need to additionally introduce organic solvents such as tert-butanol and acetone used in the conventional process, solve the problem that L-ascorbic acid is insoluble in palm oil and need to add an additional organic solvent, eliminating the need for conventional L-ascorbic acid.
  • the cumbersome process of additionally adding an organic solvent in the preparation process of the palmitate the comprehensive economic benefit is significantly improved, and the process has a good market promotion and application prospect.

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Abstract

本发明公开了一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：将L-抗坏血酸和棕榈油进行一次酶催化反应，得到一次酶催化混合物；将一次酶催化混合物进行分层和减压蒸馏处理，得到一次酶催化产物；将一次酶催化产物进行二次酶催化反应，得到二次酶催化混合物；将二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；本发明利用L-抗坏血酸在短链醇里的溶解性，促进L-抗坏血酸与棕榈油互溶，采用两步式酶催化反应在温和条件下反应，实现以脂肪酶催化L-抗坏血酸和棕榈油反应生成L-抗坏血酸棕榈酸酯的同时，催化棕榈油和短链醇反应生成生物柴油，实现了多种高附加值产品的一体化联产。

Description

一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法 技术领域
本发明涉及生物化工领域，具体涉及一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法。
背景技术
L-抗坏血酸(L-ascorbic acid)是一种常用的天然抗氧化剂，其分子结构中具有活性连烯二醇，易受光线和温度等外界因素影响而氧化，从而具有强抗氧化能力。然而，由于L-抗坏血酸的亲水性强，不易溶解于油脂等疏水性液体中，故极大地限制了它的应用，而将L-抗坏血酸转化为其脂肪酸酯则可解决该难题。L-抗坏血酸脂肪酸酯不仅保持了L-抗坏血酸的抗氧化性能和生理活性，而且在非水体系中的溶解性和稳定性均有显著提高，增加了对自由基的清除能力，已成为一种高效、安全、无毒的抗氧化剂。
目前，采用棕榈酸、硬脂酸和月桂酸等脂肪酸直接作为酰基供体，通过化学法制备L-抗坏血酸脂肪酸酯的研究较为广泛；生物酶法反应条件温和，特异性强，产物分离纯化方法简单，酶催化合成L-抗坏血酸脂肪酸酯具有很好的开发应用前景。
在生物酶法制备L-抗坏血酸脂肪酸酯的过程中，由于L-抗坏血酸的亲水性强，在长链脂肪酸酯的制备过程中难与酰基供体互溶，使得过程中常常需要引入包括叔丁醇、丙酮在内的疏水性溶剂，以促进反应的进行，此种方式需额外引入有机溶剂，直接增加操作成本，且反应过程产品单一。
技术问题
如何采用两步式酶催化反应促进原材料的转化率，进而在温和条件下实现多种高附加值产品的一体化联产。
技术解决方案
为了克服上述技术问题，本发明公开了一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法。
本发明为实现上述目的所采用的技术方案是：
一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将L-抗坏血酸和棕榈油进行一次酶催化反应，得到一次酶催化混合物；
步骤2，将所述一次酶催化混合物进行分层和减压蒸馏处理，得到一次酶催化产物；
步骤3，将所述一次酶催化产物进行二次酶催化反应，得到二次酶催化混合物；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油(即棕榈油短链醇酯)。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中在步骤1中，所述一次酶催化反应是在脂肪酶的催化作用下与短链醇反应进行的；所述脂肪酶为液体脂肪酶或固定化脂肪酶。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中所述步骤1采用液体脂肪酶催化；所述一次酶催化反应的条件为：液体脂肪酶用量为棕榈油质量的300-3000个标准酶活单位，L-抗坏血酸用量为棕榈油摩尔数的0.2～0.8倍，短链醇用量为棕榈油摩尔数的3～5倍，水含量为棕榈油质量的2～5％；所述一次酶催化反应于一级或多级酶反应器中进行，温度控制在35～60℃，反应6～18小时。通常情况下，L-抗坏血酸的转化率达到80％以上，棕榈油短链醇酯得率为理论得率的90％以上。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中所述步骤1采用固定化脂肪酶催化；所述一次酶催化反应的条件为：固定化脂肪酶用量为棕榈油质量的300-2000个标准酶活单位，L-抗坏血酸用量为棕榈油摩尔数的0.2～0.8倍，短链醇用量为棕榈油摩尔数的3～65倍；所述一次酶催化反应于一级或多级环流反应器中进行，温度控制在35～60℃，反应5～18小时。通常情况下， L-抗坏血酸的转化率达到90％以上，棕榈油短链醇酯得率为理论得率的95％以上。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中在所述一次酶催化反应中的短链醇以分步添加的方式加入，分步添加条件为短链醇在2个小时内匀速加入。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中经过一次酶催化反应后获得的一次酶催化混合物在进行二次酶催化反应之前，需要去除当中残余的短链醇等物质，以便于后续获得较纯的生物柴油；在步骤2中，所述分层处理可选取离心或静止分层，以分离出含脂肪酶的重相和含有粗生物柴油的轻相，轻相进一步减压蒸馏取釜液以备进行后续的步骤3，且减压蒸馏的目的在于去除多余的短链醇。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中在步骤3中，所述二次酶催化反应是在固定化脂肪酶的催化作用下反应进行的，所述固定化脂肪酶用量为棕榈油质量的300-2000个标准酶活单位；所述二次酶催化反应于一级或多级环流反应器中进行，温度控制在35～60℃，反应10～18小时。优选地，一级或多级环流反应器与在线脱水设备相偶联，以在线除去反应体系中的水分；通常情况下，L-抗坏血酸的转化率达到95％以上，棕榈油短链醇酯得率为理论得率的98％以上。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中在步骤4的反应过程中，引入分子筛、膜等在线脱水条件下进行，以在线除去反应体系中的水分，进而可获得质量合格的L-抗坏血酸棕榈酸酯和生物柴油；蒸馏所得馏出液为棕榈油短链醇酯，即为生物柴油，釜液为L-抗坏血酸棕榈酸酯。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中所述短链醇为甲醇、乙醇、丙醇或丁醇。
上述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其中所述脂肪酶包括来源于酵母细胞、霉菌细胞、细菌或其它微生物的脂肪酶。
L-抗坏血酸作为一种常用的天然抗氧化剂，因其亲水性强，不易溶解于油脂等疏水性液体，极大地限制了其于脂溶性疏水体系中的应用。为了提高L-抗 坏血酸的应用性能，如何提高生物酶法对其的催化转化率是制备L-抗坏血酸脂肪酸酯的关键。目前，棕榈酸、硬脂酸和月桂酸等脂肪酸直接作为酰基供体，但在制备过程中，酰基供体难与L-抗坏血酸互溶，故通常需要引入疏水性溶剂以改善反应体系中的疏水程度，传统的疏水性溶剂可选包括叔丁醇、丙酮等，但若引入上述溶剂则增加操作成本，同时反应所得产品种类单一。
在进行一次酶催化反应或二次酶催化反应时，可选用生物催化剂，包括多种脂肪酶，包括液体脂肪酶、固定化脂肪酶以及含有脂肪酶的菌体或固定化菌体；脂肪酶催化剂具有原料适应性广、反应条件温和等优点，特别适用于高酸价油脂的酶催化反应；液体脂肪酶为游离液态，价格相对低廉，通常含有较高的水分含量，且其对油脂的酶催化具有较高的反应速率；固定化脂肪酶相比于液体脂肪酶具有抗逆性好、易于回收等优点。本发明中采用两步式酶催化反应，包括一次酶催化反应采用的是液体脂肪酶或固定化脂肪酶催化，二次酶催化反应采用的是固定化脂肪酶催化，其中采用液体脂肪酶催化是在油水的乳化体系下进行，液态脂肪酶分散于油水两相界面上催化反应进行，进而促进酶催化效率，此外，由于油水的不互溶性会造成反应体系的乳化，而这种乳化作用会导致由吸附法制得的固定化脂肪酶的蛋白脱落和失活，致使表观酶活降低，故本发明采用固定化脂肪酶催化时反应体系为无溶剂体系，即不添加如水等有机溶剂作为反应介质，此时反应体系为均相，不存在乳化现象，需特别说明的是由于L-抗坏血酸和棕榈油、棕榈油和短链醇之间的酯化反应中生成水，而酯化反应为平衡反应，为进一步促进反应向酯化反应进行，在进行二次酶催化反应时，反应体系可与在线脱水设备相偶联，以在线除去体系中的水分，可快速推动反应达到平衡状态，进而有效地提高L-抗坏血酸的转化率和产物得率。
有益效果
本发明利用L-抗坏血酸在短链醇里的溶解性，促进L-抗坏血酸与棕榈油互溶，采用两步式酶催化反应在温和条件下反应，实现以脂肪酶催化L-抗坏血酸和棕榈油反应生成L-抗坏血酸棕榈酸酯的同时，催化棕榈油和短链醇反应生成生物柴油，实现了多种高附加值产品的一体化联产，显著提高了棕榈油的附加 值和反应过程的综合经济效益；整个反应过程环境温和友好，既能最大限度地保留L-抗坏血酸的生物活性，又能充分利用了原材料组分，极大地提高酶催化效率和产物得率；同时，反应过程中直接以短链醇代替常规的有机溶剂，不需要额外引入常规工艺中采用的叔丁醇、丙酮等有机溶剂，解决L-抗坏血酸在棕榈油里难溶需额外加入有机溶剂的问题，省去了常规L-抗坏血酸棕榈酸酯制备过程中额外加入有机溶剂的繁琐工艺，综合经济效益显著提高，该工艺具有很好的市场推广应用前景。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1为本发明中工艺方法的反应过程示意图；
图2为本发明中工艺方法的主要流程示意图。
本发明的实施方式
下面通过具体实施例对本发明作进一步说明，以使本发明技术方案更易于理解、掌握，而非对本发明进行限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段，所用原料均为市售商品。
实施例1：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将10g棕榈油、基于油脂质量2％的水、基于油脂摩尔数0.2倍的L-抗坏血酸，基于油脂质量400个标准酶活单位的来源于米曲霉Aspergillus oryzae的液体脂肪酶，基于油脂摩尔数3倍的甲醇置于一级或多级酶反应器中于35℃下反应10小时，得到一次酶催化混合物；其中，所述一次酶催化混合物中L-抗坏血酸转化率达到80％，棕榈油甲酯得率90％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量300个标准酶活单位的来自米曲霉Aspergillus oryzae的固定化脂肪酶， 反应温度控制在55℃，反应12小时，得到二次酶催化混合物；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到95％，棕榈油甲酯得率98％。
实施例2：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将20g棕榈油、基于油脂质量5％的水、基于油脂摩尔数0.5倍的L-抗坏血酸，基于油脂质量2000个标准酶活单位的来源于南极假丝酵母Candida antarctica的液体脂肪酶，基于油脂摩尔数4倍的乙醇置于一级或多级酶反应器中于45℃下反应18小时，得到一次酶催化混合物；其中，所述一次酶催化混合物中L-抗坏血酸转化率达到85％，棕榈油乙酯得率90％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量2000个标准酶活单位的来自米曲霉Aspergillus oryzae的固定化脂肪酶，反应温度控制在45℃，反应12小时，得到二次酶催化混合物；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到98％，棕榈油乙酯得率98％。
实施例3：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将30g棕榈油、基于油脂摩尔数0.8倍的L-抗坏血酸，基于油脂质量1500个标准酶活单位的来源于米黑根毛霉Rhizomucor miehei的固定化脂肪酶，基于油脂摩尔数5倍的甲醇置于一级或多级环流反应器中于55℃下反应10小时，得到一次酶催化混合物；其中，所述一次酶催化混合物中L-抗坏血酸转化率达到91％，棕榈油甲酯得率96％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量1000个标准酶活单位的来自南极假丝酵母Candida antarctica的固定化脂肪酶，反应温度控制在55℃，反应10小时，得到二次酶催化混合物；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到96％，棕榈油甲酯得率98％。
实施例4：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将50g棕榈油、基于油脂摩尔数0.2倍的L-抗坏血酸、基于油脂质量2000个标准酶活单位的来源于米黑根毛霉Rhizomucor miehei的固定化脂肪酶，基于油脂摩尔数5倍的丁醇置于一级或多级环流反应器中于50℃下反应15小时，得到一次酶催化混合物，其中，丁醇在前2个小时内匀速流加入反应器中；所述一次酶催化混合物中L-抗坏血酸转化率达到90％，棕榈油丁酯得率95％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量1000个标准酶活单位的来自米曲霉Aspergillus oryzae的固定化脂肪酶，反应温度控制在55℃，反应12小时，得到二次酶催化混合物；反应过程中采取如图2所示的在线脱水；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到96％，棕榈油丁酯得率98％。
实施例5：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将30g棕榈油、基于油脂质量4％的水、基于油脂摩尔数0.8倍的L-抗坏血酸，基于油脂质量1800个标准酶活单位的来源于南极假丝酵母Candida antarctica的液体脂肪酶，基于油脂摩尔数6倍的乙醇置于一级或多级酶反应器中于45℃下反应16小时，得到一次酶催化混合物；其中，所述一次酶催化混合 物中L-抗坏血酸转化率达到80％，棕榈油乙酯得率92％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量1800个标准酶活单位的来自南极假丝酵母Candida antarctica的固定化脂肪酶，反应温度控制在55℃，反应18小时，得到二次酶催化混合物；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到97％，棕榈油乙酯得率99％。
实施例6：本实施例提供一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其包括以下步骤：
步骤1，将2g棕榈油、基于油脂摩尔数0.3倍的L-抗坏血酸、基于油脂质量900个标准酶活单位的来源于米曲霉Aspergillus oryzae的固定脂肪酶、基于油脂摩尔数4倍的甲醇置于一级或多级环流反应器中于45℃下反应12小时，得到一次酶催化混合物；其中，所述一次酶催化混合物中L-抗坏血酸转化率达到92％，棕榈油甲酯得率95％；
步骤2，将所述一次酶催化混合物经离心分层后，分离出重相和轻相，取轻相进一步经过减压蒸馏除去里面多余的短链醇，得到一次酶催化产物；
步骤3，将所述一次酶催化产物置于一级或多级环流反应器中，加入基于油脂质量2000个标准酶活单位的来自南极假丝酵母Candida antarctica的固定化脂肪酶，反应温度控制在50℃，反应18小时，得到二次酶催化混合物；反应过程中采取如图2所示的在线脱水；
步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油；其中L-抗坏血酸转化率达到97％，棕榈油甲酯得率99％。
本发明利用L-抗坏血酸在短链醇里的溶解性，促进L-抗坏血酸与棕榈油互溶，采用两步式酶催化反应在温和条件下反应，实现以脂肪酶催化L-抗坏血酸和棕榈油反应生成L-抗坏血酸棕榈酸酯的同时，催化棕榈油和短链醇反应生成 生物柴油，实现了多种高附加值产品的一体化联产，显著提高了过程的综合经济效益；整个反应过程环境温和友好，既能最大限度地保留L-抗坏血酸的生物活性，又能充分利用了原材料组分，极大地提高酶催化效率和产物得率；同时，反应过程中不需要额外引入常规工艺中采用的叔丁醇、丙酮等有机溶剂，综合经济效益显著提高，该工艺具有很好的市场推广应用前景。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制。任何熟悉本领域的技术人员，在不脱离本发明技术方案范围情况下，都可利用上述揭示的技术手段和技术内容对本发明技术方案做出许多可能的变动和修饰，或修改为等同变化的等效实施例。故凡是未脱离本发明技术方案的内容，依据本发明之形状、构造及原理所作的等效变化，均应涵盖于本发明的保护范围。
工业实用性
本发明利用L-抗坏血酸在短链醇里的溶解性，促进L-抗坏血酸与棕榈油互溶，采用两步式酶催化反应在温和条件下反应，实现以脂肪酶催化L-抗坏血酸和棕榈油反应生成L-抗坏血酸棕榈酸酯的同时，催化棕榈油和短链醇反应生成生物柴油，实现了多种高附加值产品的一体化联产，显著提高了棕榈油的附加值和反应过程的综合经济效益；整个反应过程环境温和友好，既能最大限度地保留L-抗坏血酸的生物活性，又能充分利用了原材料组分，极大地提高酶催化效率和产物得率；同时，反应过程中直接以短链醇代替常规的有机溶剂，不需要额外引入常规工艺中采用的叔丁醇、丙酮等有机溶剂，解决L-抗坏血酸在棕榈油里难溶需额外加入有机溶剂的问题，省去了常规L-抗坏血酸棕榈酸酯制备过程中额外加入有机溶剂的繁琐工艺，综合经济效益显著提高，该工艺具有很好的市场推广应用前景。

Claims (10)

  1. 一种联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，其包括以下步骤：
    步骤1，将L-抗坏血酸和棕榈油进行一次酶催化反应，得到一次酶催化混合物；
    步骤2，将所述一次酶催化混合物进行分层和减压蒸馏处理，得到一次酶催化产物；
    步骤3，将所述一次酶催化产物进行二次酶催化反应，得到二次酶催化混合物；
    步骤4，将所述二次酶催化混合物于在线脱水条件下进行蒸馏处理，获得L-抗坏血酸棕榈酸酯和生物柴油。
  2. 根据权利要求1所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，在步骤1中，所述一次酶催化反应是在脂肪酶的催化作用下与短链醇反应进行的；
    所述脂肪酶为液体脂肪酶或固定化脂肪酶。
  3. 根据权利要求2所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述步骤1采用液体脂肪酶催化；
    所述一次酶催化反应的条件为：液体脂肪酶用量为棕榈油质量的300-3000个标准酶活单位，L-抗坏血酸用量为棕榈油摩尔数的0.2～0.8倍，短链醇用量为棕榈油摩尔数的3～5倍，水含量为棕榈油质量的2～5％。
  4. 根据权利要求3所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述一次酶催化反应于一级或多级酶反应器中进行，温度控制在35～60℃，反应6～18小时。
  5. 根据权利要求2所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述步骤1采用固定化脂肪酶催化；
    所述一次酶催化反应的条件为：固定化脂肪酶用量为棕榈油质量的300～2000个标准酶活单位，L-抗坏血酸用量为棕榈油摩尔数的0.2～0.8倍，短链醇用量为 棕榈油摩尔数的3～65倍。
  6. 根据权利要求5所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述一次酶催化反应于一级或多级环流反应器中进行，温度控制在35～60℃，反应5～18小时。
  7. 根据权利要求3-6任一所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，在所述一次酶催化反应中的短链醇以分步添加的方式加入，分步添加条件为短链醇在2个小时内匀速加入。
  8. 根据权利要求7所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，在步骤3中，所述二次酶催化反应是在固定化脂肪酶的催化作用下反应进行的，所述固定化脂肪酶用量为棕榈油质量的300-2000个标准酶活单位；
    所述二次酶催化反应于一级或多级环流反应器中进行，温度控制在35～60℃，反应10～18小时。
  9. 根据权利要求8所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述短链醇为甲醇、乙醇、丙醇或丁醇。
  10. 根据权利要求9所述的联产L-抗坏血酸棕榈酸酯和生物柴油的工艺方法，其特征在于，所述脂肪酶包括来源于酵母细胞、霉菌细胞、细菌或其它微生物的脂肪酶。
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