阅读说明：本技术 一种用加酶洗衣粉催化烯烃环氧化的方法 (Method for catalyzing olefin epoxidation by using enzymatic laundry powder ) 是由 张�杰 高凌 李伏坤 张佳颖 于 2019-09-18 设计创作，主要内容包括：本发明属于生物催化技术领域,特别涉及一种用加酶洗衣粉催化烯烃环氧化的方法。本发明方法以市售加酶洗衣粉和烯烃为原料,经反应液配制、环氧化反应、加酶洗衣粉回收、环氧化合物粗品制备等步骤实现用加酶洗衣粉催化烯烃环氧化。本发明提供的方法具有步骤简便,烯烃转化率高,加酶洗衣粉可重复使用,成本低廉,绿色环保等特点。采用本发明方法制备的产品,可广泛应用于医药、食品、化工等行业。(The invention belongs to the technical field of biocatalysis, and particularly relates to a method for catalyzing olefin epoxidation by using enzymatic laundry powder. The method takes commercial enzymatic laundry powder and olefin as raw materials, and the epoxidation of the olefin is catalyzed by the enzymatic laundry powder through the steps of reaction liquid preparation, epoxidation reaction, enzymatic laundry powder recovery, crude epoxy compound preparation and the like. The method provided by the invention has the characteristics of simple steps, high olefin conversion rate, reusable enzyme-added washing powder, low cost, environmental friendliness and the like. The product prepared by the method can be widely applied to the industries of medicine, food, chemical industry and the like.)

1. A method for catalyzing olefin epoxidation by using enzymatic laundry powder comprises the following specific steps:

(1) preparation of reaction solution

Taking commercially available olefin as a raw material, adding olefin into toluene or n-hexane according to the volume ratio of the olefin to the toluene or n-hexane of 1: 20-100, uniformly mixing to obtain an olefin reaction solution, and collecting the reaction solution;

(2) epoxidation reaction

After the step (1) is finished, dispersing the enzymatic laundry powder into the olefin reaction liquid according to the mass ratio of the commercially available enzymatic laundry powder to the volume ratio of the olefin reaction liquid collected in the step (1) of 1 g: 50-200 mL, carrying out catalytic reaction for 72-120 h at the temperature of 50-70 ℃ and the stirring speed of 200-400 r/min, and collecting a mixture after the reaction is finished;

(3) enzyme added washing powder recovery

After the step (2) is finished, placing the mixture collected in the step (2) in a centrifuge, centrifuging for 20-60 min at the rotating speed of 2000-5000 r/min, and respectively collecting supernatant and precipitate; drying the collected precipitate at 25-40 ℃, and then continuously using the precipitate as enzyme-added washing powder for the epoxidation reaction in the step (2), wherein the precipitate can be repeatedly used for 10-20 times;

(4) preparation of crude epoxy compound

After the step (3) is finished, pumping the supernatant collected in the step (3) into a vacuum concentrator, carrying out vacuum concentration under the conditions that the vacuum degree is 0.07-0.09 MPa and the temperature is 40-60 ℃, stopping when the supernatant is reduced to 0.1-0.5% of the original volume, and respectively collecting an evaporated liquid and a concentrated liquid; and the yield of the collected concentrated solution, namely the crude epoxy compound is 70.6-84.3%.

Technical Field

The invention belongs to the technical field of biocatalysis, and particularly relates to a method for catalyzing olefin epoxidation by using enzymatic laundry powder.

Background

The enzymatic laundry powder as a synthetic detergent contains components including a surfactant, a foaming agent, a solubilizer, phosphate, silicate, a fluorescent agent, an enzyme preparation and the like, and has a very important position in the daily life of people. The enzyme preparation mainly comprises protease, lipase, cellulase, amylase, etc., and can effectively and rapidly remove stains (such as milk, fruit juice, oil stain, sweat stain, blood stain, tea, chocolate, etc.) by using a small amount of enzyme, and has no toxic action on human body. In addition, the enzymes and the decomposition products thereof can be decomposed by microorganisms, thereby meeting the requirements of the modern society on environmental protection and sustainable development. The enzyme is used as a biocatalyst and added into the washing powder in an embedding or adsorption mode, and is actually an enzyme immobilization process. Therefore, the enzymatic laundry powder is also an immobilized enzyme.

The epoxide is an important organic synthesis intermediate, and is widely applied to the fields of petrochemical industry, fine chemical industry, organic synthesis, pharmacy, spice and the like. The lipase can catalyze carboxylic acid and hydrogen peroxide to perform a peroxyhydrolysis reaction to generate peroxy acid, and the peroxy acid spontaneously performs an epoxidation reaction with a carbon-carbon double bond to generate epoxide. The enzymatic washing powder contains carboxylic acid, hydrogen peroxide and lipase, so that the epoxidation of olefin can be realized. However, enzymatic laundry detergents are not currently used in epoxidation reactions in the form of catalysts. The application of the enzymatic laundry powder in the epoxidation reaction not only can expand the application of the laundry powder, but also has important significance for reducing the epoxidation cost and protecting the environment.

An existing olefin epoxidation method, for example, an invention patent with publication number CN 108473453a "olefin epoxidation method" published on 31/8/2018, discloses a method comprising: the chelating agent is first added to an aqueous hydrogen peroxide solution to reduce or prevent the formation of deposits on the catalyst and the clogging of the pores of the liquid distributor, and then the olefin, the aqueous hydrogen peroxide solution, the solvent and the like are mixed, and then the epoxidation reaction is continuously carried out through a fixed bed containing the titanium zeolite catalyst, and finally the product is separated by distillation or extractive distillation. The method has the following disadvantages: the method has the advantages that the production needs a plurality of reagents, the cost is high, the subsequent products are difficult to separate, and the energy consumption is high; secondly, the adopted chemical catalyst has toxicity and high price, and is not beneficial to actual production; and thirdly, in the production process, the chelating agent is added into the reaction system, so that the formation of deposits is avoided, but the production process is complicated and the route is long.

Disclosure of Invention

The invention aims to provide a method for catalyzing olefin epoxidation by using enzymatic laundry detergent, aiming at the defects of the existing olefin epoxidation method.

The mechanism of the invention is as follows: the enzymatic laundry powder contains Lipase (EC 3.1.1.3), hydrogen peroxide, carboxylic acid and the like, which provide necessary conditions for the epoxidation of olefin. When the enzymatic washing powder is added into a solvent containing olefin, lipase can catalyze carboxylic acid and hydrogen peroxide to perform a peroxyhydrolysis reaction to generate peroxy acid, then the peroxy acid is released out of enzyme molecules and then performs an epoxidation reaction with olefin containing carbon-carbon double bonds to generate epoxide, and the peroxy acid is reduced into carboxylic acid to be recycled for the next reaction. Soda ash, sodium silicate, sodium tripolyphosphate and the like contained in the enzymatic washing powder provide an alkaline environment required by lipase catalysis. In addition, because the lipase exists in the form of immobilized enzyme, the lipase can be recovered by centrifugal separation, thereby realizing the repeated use of the enzymatic laundry powder.

The purpose of the invention is realized as follows: the method takes commercially available enzymatic laundry powder and olefin as raw materials, and the epoxidation of olefin is catalyzed by the enzymatic laundry powder through the steps of reaction liquid preparation, epoxidation reaction, enzymatic laundry powder recovery, crude epoxy compound preparation and the like. The method comprises the following specific steps:

(1) preparation of reaction solution

The method comprises the steps of taking commercially available olefin as a raw material, adding olefin into toluene (or n-hexane) according to the volume ratio of the olefin to the toluene (or n-hexane) of 1: 20-100, uniformly mixing to obtain an olefin reaction liquid, collecting the reaction liquid, and using the reaction liquid for next treatment.

(2) Epoxidation reaction

After the step (1) is finished, dispersing the enzymatic laundry powder into the olefin reaction liquid according to the mass (g) of the commercial enzymatic laundry powder to the volume ratio (mL) of the olefin reaction liquid collected in the step (1) of 1: 50-200, carrying out catalytic reaction for 72-120 h at the temperature of 50-70 ℃ and the stirring speed of 200-400 r/min, and collecting a mixture after the reaction is finished for next treatment.

(3) Enzyme added washing powder recovery

And (3) after the step (2) is finished, placing the mixture collected in the step (2) in a centrifuge, centrifuging for 20-60 min under the condition that the rotating speed is 2000-5000 r/min, and respectively collecting supernatant and precipitate. Drying the collected precipitate at 25-40 ℃, and then continuously using the precipitate as enzyme-added washing powder for the epoxidation reaction in the step (2), wherein the precipitate can be repeatedly used for 10-20 times; the collected supernatant was used for the next step.

(4) Preparation of crude epoxy compound

And (4) after the step (3) is finished, pumping the supernatant collected in the step (3) into a vacuum concentrator, carrying out vacuum concentration under the conditions that the vacuum degree is 0.07-0.09 MPa and the temperature is 40-60 ℃, stopping when the volume of the supernatant is reduced to 0.1-0.5% of the original volume, and respectively collecting an evaporated liquid and a concentrated liquid. The collected evaporation liquid, which is mainly toluene (or n-hexane), can be continuously used for preparing the reaction liquid in the step (1); and the yield of the collected concentrated solution, namely the crude epoxy compound is 70.6-84.3%.

After the technical scheme is adopted, the invention mainly has the following effects:

1. the method of the invention takes the enzyme-added washing powder as the catalyst, not only provides the substances such as hydrogen peroxide, carboxylic acid and the like required by the lipase catalytic epoxidation reaction, but also provides a microenvironment for the reaction, improves the reaction stability and further improves the reaction efficiency.

2. The method has the advantages of simple process, mild reaction conditions, simple and convenient operation and easy control, thereby having safe production and reducing the production cost.

3. The method has the advantages of simple and easily obtained required reagent, easy separation of subsequent products, low energy consumption and accordance with a green sustainable development process route.

4. The enzymatic laundry powder has the advantages of low price, easy obtaining, convenient recovery, good continuous use stability, high repeated use stability and the like, further reduces the production cost, and provides reference for the catalytic application of other enzymes in the enzymatic laundry powder.

The product prepared by the method can be widely applied to the industries of medicine, food, chemical industry and the like.

Fourth, detailed description of the invention

The present invention will be further described with reference to the following specific embodiments.

Example 1

A method for catalyzing olefin epoxidation by using enzymatic laundry powder comprises the following specific steps:

(1) preparation of reaction solution

Taking styrene as a raw material, adding the styrene into toluene according to the volume ratio of the styrene to the toluene of 1: 20, uniformly mixing to obtain a styrene reaction solution, and collecting the reaction solution for further treatment.

(2) Epoxidation reaction

After the step (1), dispersing the enzymatic laundry powder into the styrene reaction liquid according to the mass (g) of the commercial enzymatic laundry powder to the volume ratio (mL) of the styrene reaction liquid collected in the step (1) of 1: 50, carrying out catalytic reaction for 72 hours at the temperature of 50 ℃ and the stirring speed of 200r/min, and collecting the mixture after the reaction is finished for next treatment.

(3) Enzyme added washing powder recovery

And (3) after the step (2), placing the mixture collected in the step (2) in a centrifuge, centrifuging for 20min at the rotating speed of 2000r/min, and respectively collecting supernatant and precipitate. The collected precipitate can be continuously used as enzyme-added washing powder for the epoxidation reaction in the step (2) after being dried at 25 ℃, and can be repeatedly used for 10 times; the collected supernatant was used for the next step.

(4) Preparation of crude epoxy compound

And (4) after the step (3) is finished, pumping the supernatant collected in the step (3) into a vacuum concentrator, carrying out vacuum concentration under the conditions that the vacuum degree is 0.09MPa and the temperature is 60 ℃, stopping when the supernatant is reduced to 0.1 percent of the original volume, and respectively collecting an evaporated solution and a concentrated solution. The collected evaporated liquid, mainly toluene, can be continuously used for preparing the reaction liquid in the step (1); the yield of the collected concentrated solution, i.e., the crude epoxy compound (epoxidized styrene), was 70.6%.

Example 2

A method for catalyzing olefin epoxidation by using enzymatic laundry powder comprises the following specific steps:

(1) preparation of reaction solution

Taking oleic acid as a raw material, adding the oleic acid into n-hexane according to the volume ratio of the oleic acid to the n-hexane of 1: 60, uniformly mixing to obtain an oleic acid reaction solution, and collecting the reaction solution for further treatment.

(2) Epoxidation reaction

After the step (1), dispersing enzyme-added washing powder into the oleic acid reaction solution according to the mass (g) of the commercially available enzyme-added washing powder to the volume ratio (mL) of the oleic acid reaction solution collected in the step (1) of 1: 120, carrying out catalytic reaction for 100 hours at the temperature of 60 ℃ and the stirring speed of 300r/min, and collecting a mixture after the reaction is finished for next treatment.

(3) Enzyme added washing powder recovery

And (3) after the step (2) is finished, placing the mixture collected in the step (2) in a centrifuge, centrifuging for 40min at the rotation speed of 3500r/min, and respectively collecting supernatant and precipitate. The collected precipitate can be continuously used as enzyme-added washing powder for the epoxidation reaction in the step (2) after being dried at 30 ℃, and can be repeatedly used for 15 times; the collected supernatant was used for the next step.

(4) Preparation of crude epoxy compound

And (4) after the step (3) is finished, pumping the supernatant collected in the step (3) into a vacuum concentrator, carrying out vacuum concentration under the conditions that the vacuum degree is 0.08MPa and the temperature is 50 ℃, stopping when the supernatant is reduced to 0.3 percent of the original volume, and respectively collecting an evaporated solution and a concentrated solution. The collected evaporation liquid, mainly n-hexane, can be continuously used for preparing the reaction liquid in the step (1); the yield of the collected concentrated solution, i.e., the crude epoxy compound (epoxy oleic acid), was 80.9%.

Example 3

A method for catalyzing olefin epoxidation by using enzymatic laundry powder comprises the following specific steps:

(1) preparation of reaction solution

Cyclohexene is used as a raw material, cyclohexene is added into normal hexane according to the volume ratio of cyclohexene to normal hexane of 1: 100, the cyclohexene is uniformly mixed to obtain cyclohexene reaction liquid, and the reaction liquid is collected for further treatment.

(2) Epoxidation reaction

After the step (1), dispersing enzyme-added washing powder in the cyclohexene reaction liquid according to the mass (g) of the commercially available enzyme-added washing powder to the volume ratio (mL) of the cyclohexene reaction liquid collected in the step (1) of 1: 200, carrying out catalytic reaction for 120 hours at the temperature of 70 ℃ and the stirring speed of 400r/min, and collecting the mixture after the reaction is finished for next treatment.

(3) Enzyme added washing powder recovery

And (3) after the step (2), placing the mixture collected in the step (2) in a centrifuge, centrifuging for 60min at the rotation speed of 5000r/min, and respectively collecting supernatant and precipitate. The collected precipitate can be continuously used as enzyme-added washing powder for the epoxidation reaction in the step (2) after being dried at 40 ℃, and can be repeatedly used for 20 times; the collected supernatant was used for the next step.

(4) Preparation of crude epoxy compound

And (4) after the step (3) is finished, pumping the supernatant collected in the step (3) into a vacuum concentrator, carrying out vacuum concentration under the conditions that the vacuum degree is 0.07MPa and the temperature is 40 ℃, stopping when the supernatant is reduced to 0.5 percent of the original volume, and respectively collecting an evaporated solution and a concentrated solution. The collected evaporation liquid, mainly n-hexane, can be continuously used for preparing the reaction liquid in the step (1); the yield of the collected concentrate, i.e., crude epoxy compound (epoxycyclohexane), was 84.3%.