阅读说明：本技术 微反应器用于制备乙蒜素的用途及其生产工艺 (Application of microreactor in preparing ethylicin and production process thereof ) 是由 薛照先 何昆明 林光东 于 2019-10-25 设计创作，主要内容包括：本发明涉及微反应器用于制备乙蒜素的用途及其生产工艺,所述微反应器用于制备乙蒜素的用途及工艺采用液体原料、气体原料,或气体原料和液体原料的混合物作为进入微反应器的乙蒜素原料,其中液体原料包括二乙基二硫醚、催化剂、液体氧化性原料,气体原料为气体氧化性原料,将原料输入到微反应器,然后进行气液分离或气液分离后继续反应制备得到乙蒜素。本发明首次将微反应器用于制备乙蒜素,并且开发了应用微反应器制备乙蒜素的各种可行的工艺,而且制备乙蒜素的效率提升,乙蒜素产物的浓度提高,最主要的是通过反应过程中条件的控制,能够实现乙蒜素生产的时间缩短,不同方式生产乙蒜素具有独特的工艺特点和工艺优势。(The invention relates to an application of a microreactor for preparing ethylicin and a production process thereof, wherein the application and the process of the microreactor for preparing the ethylicin adopt a liquid raw material, a gas raw material or a mixture of the gas raw material and the liquid raw material as the ethylicin raw material entering the microreactor, wherein the liquid raw material comprises diethyl disulfide, a catalyst and a liquid oxidizing raw material, the gas raw material is the gas oxidizing raw material, the raw material is input into the microreactor, and then the reaction is continued after gas-liquid separation or gas-liquid separation to prepare the ethylicin. The invention firstly uses the microreactor for preparing the ethylicin, develops various feasible processes for preparing the ethylicin by applying the microreactor, improves the efficiency for preparing the ethylicin, improves the concentration of the ethylicin product, can realize the shortening of the production time of the ethylicin mainly by controlling the conditions in the reaction process, and has unique process characteristics and process advantages for producing the ethylicin in different modes.)

1. The use of the microreactor for preparing the ethylicin is characterized in that the raw material for preparing the ethylicin by the microreactor is a liquid raw material or a gas raw material or a mixture of the gas raw material and the liquid raw material, wherein the liquid raw material comprises diethyl disulfide, a catalyst and a liquid oxidizing raw material, and the gas raw material is a gas oxidizing raw material.

2. The use according to claim 1, characterized in that the liquid oxidizing raw material is one or more of a nitric acid solution, a hydrogen peroxide solution, or a mixed solution of a nitric acid solution and a sulfuric acid solution, the gaseous oxidizing raw material is one or both of oxygen and ozone, and the catalyst is acetic acid.

3. The use according to claim 1, wherein the raw materials are separately or together fed into the microreactor to react, and then the product discharged from the microreactor is subjected to gas-liquid separation to obtain ethylicin, or the reaction is continued while the gas-liquid separation is carried out to obtain ethylicin, or the reaction is carried out again after the gas-liquid separation to obtain ethylicin.

4. The use according to claim 3, wherein the step of continuing the reaction again after the gas-liquid separation to obtain ethylicin comprises: and the ethylicin raw material passes through the microreactor, and then enters the tubular reactor for re-reaction to obtain ethylicin, or the liquid obtained after gas-liquid separation enters the microreactor again to obtain the ethylicin.

5. Use according to claim 4, characterized in that the microreactor is the same microreactor or a further microreactor when re-entering a microreactor, said further microreactor being the same or different from the microreactor from which the reaction was initiated when entering a further microreactor.

6. Use according to claim 1, wherein the gas or liquid feed is passed through a check valve before entering the microreactor and/or the gas or liquid feed is compressed by a compressor before entering the microreactor to increase the pressure of the gas or liquid feed.

7. The use according to claim 5, wherein the microreactor used for the initial reaction and the microreactor used for the subsequent reaction after the initial reaction are the same microreactor, and the product obtained from the initial reaction circulates through the same microreactor for 1-12 times, and the gas oxidizing raw material and/or the liquid oxidizing raw material for preparing the ethylicin are/is added when the product circulates through the same microreactor.

8. A method for preparing ethylicin by using a microreactor is characterized by comprising the following steps: introducing a raw material for preparing ethylicin into a microreactor, and introducing a product generated by the microreactor for gas-liquid separation, wherein the raw material for preparing the ethylicin is a liquid raw material or a gas raw material, or a mixture of the gas raw material and the liquid raw material, the liquid raw material comprises diethyl disulfide, a catalyst and a liquid oxidizing raw material, and the gas raw material is a gas oxidizing raw material.

9. The method according to claim 8, wherein the liquid oxidizing raw material is one or more of a nitric acid solution, a hydrogen peroxide solution, or a mixed solution of a nitric acid solution and a sulfuric acid solution, the gaseous oxidizing raw material is one or both of oxygen and ozone, and the catalyst is acetic acid, preferably glacial acetic acid.

10. The method of claim 8, wherein the raw materials are separately or together fed into the microreactor to react, and then the product discharged from the microreactor is subjected to gas-liquid separation to produce ethylicin, or the reaction is continued while the gas-liquid separation is performed to produce ethylicin, or the reaction is performed again after the gas-liquid separation to produce ethylicin.

11. The method according to claim 10, wherein the step of continuing the reaction again after the gas-liquid separation to obtain ethylicin comprises: and the ethylicin raw material passes through the microreactor, and then enters the tubular reactor for re-reaction to obtain ethylicin, or the liquid obtained after gas-liquid separation enters the microreactor again to obtain the ethylicin.

12. Method according to claim 10, characterized in that when re-entering a microreactor, the microreactor is the same microreactor or is a further microreactor, and when entering a further microreactor, the further microreactor is the same as or different from the microreactor from which the reaction was initiated.

13. The method according to claim 12, wherein the microreactor used for the initial reaction and the microreactor used for the subsequent reaction after the initial reaction are the same microreactor, and the product obtained from the initial reaction circulates through the same microreactor 1-12 times, and the gas oxidizing raw material and/or the liquid oxidizing raw material for preparing the ethylicin are/is added when the product circulates through the same microreactor.

14. The method of claim 8, wherein the gas or liquid feed is passed through a check valve before entering the microreactor and/or the gas or liquid feed is compressed by a compressor before entering the microreactor to increase the pressure of the gas or liquid feed.

15. The method according to claim 13, wherein the microreactor used for the initial reaction and the microreactor used for the subsequent reaction after the initial reaction are the same microreactor, and the product obtained from the initial reaction circulates through the same microreactor for 1-12 times, and the gas oxidizing raw material and/or the liquid oxidizing raw material for preparing the ethylicin are/is added when the product circulates through the same microreactor.

16. The use according to claim 1 or the process according to claim 8, wherein when the oxidic starting material is nitric acid and the catalyst is glacial acetic acid, the ratio of the molar speed X of diethyl disulfide entering the microreactor for the solution comprising diethyl disulfide to the molar speed Y of nitric acid entering the microreactor is 1 { (1.3-2)/(1-12) }, wherein the weight percentage of nitric acid in the solution comprising nitric acid is 35-65%, the weight percentage of diethyl disulfide in the solution comprising diethyl disulfide is 60-100%, and glacial acetic acid is contained in the solution of diethyl disulfide or in the solution of nitric acid.

17. Use according to claim 1 or method according to claim 8, characterized in that the microreactor is a microchannel reactor, the cross-sectional area of the flow channel in the microchannel reactor being 100 to 1000000 square micrometers, preferably the cross-sectional area of the flow channel being 100 to 100000 square micrometers, especially preferably the cross-sectional area of the flow channel being 100 to 20000 square micrometers, and the total volume of the flow channel being 50 to 500 ml.

Technical Field

The invention belongs to the field of pesticide preparation, and particularly relates to an application of a microreactor for preparing ethylicin and a production process thereof.

Background

The pure product of ethylicin (ethyl thiosulfonate) is colorless oily transparent liquid, and is heated to 130-140 ℃ for decomposition. Is easily dissolved in organic solvents such as ether, chloroform, ethanol, glacial acetic acid, etc., and has a solubility of 1.2% in water at room temperature. The industrial product is yellowish oily transparent liquid with garlic odor. Moderate toxicity to warm-blooded animals. The acute oral administration of LD50 mice was 80 mg/kg, and the rats were 140 mg/kg. Has stimulating effect on rabbit and guinea pig skin. The bactericidal composition has broad bactericidal spectrum, and can inhibit various fungi and bacteria such as cotton anthracnose bacteria, rhizoctonia solani, fusarium wilt bacteria, verticillium wilt bacteria, rice bacterial blight bacteria, rice blast bacteria, bakanae bacteria, sweet potato black spot bacteria, wheat gibberella, striped bacteria, stinking smut bacteria, apple anthracnose bacteria, cucumber tendrilled bacteria and the like under the concentration of 1-100 mg/L.

CN105523980A discloses a method for preparing ethylicin, which comprises the following steps: preparing 65% aqueous solution from sodium sulfide, injecting the aqueous solution into a reaction kettle, adding sulfur powder, continuously stirring, rapidly increasing the temperature of the reaction kettle to 70-90 ℃ by adopting a water bath heating mode, continuously stirring, keeping the temperature for 2-4 hours, and forming a disodium disulfide solution after the reaction is finished when sulfur is completely dissolved. And (3) cooling the reaction kettle to 50-60 ℃, injecting chloroethane into the solution, continuously stirring, and simultaneously heating the temperature in the reaction kettle to 80-90 ℃. And after the ethyl chloride is injected, keeping the temperature and continuously stirring for reacting for 1-2 hours. And (3) cooling the reaction kettle to 40-50 ℃ by oxidation, adding glacial acetic acid into the solution, uniformly mixing, slowly adding 98% nitric acid, carrying out oxidation reaction for 0.5-1 h, cooling to normal temperature, and standing for separation to obtain ethylicin.

Microreactors are widely used in chemical and medical fields, and include a wide variety of microchannel devices such as micromixers, micro heat exchangers, and micro separators, and these microchannel devices are generally referred to as microreactors abroad. The micro-reactor has the advantages of increased specific area, strengthened heat transfer process and mass transfer process, safe reaction and easy amplification of quantity, but in different chemical production, some micro-reactors are difficult to realize industrial effect, and some micro-reactors can realize the industrial production but cannot achieve the aim.

The present invention relates to a method for preparing ethylicin by using microreactor, and is characterized by that it utilizes the microreactor to prepare ethylicin, and utilizes the microreactor to make research on the preparation of ethylicin, so that it can obtain the requirements for quality and yield of ethylicin.

Disclosure of Invention

In order to solve the technical problems, the invention provides an application of a microreactor for preparing ethylicin, which is characterized in that a raw material for preparing the ethylicin by the microreactor is a liquid raw material or a gas raw material or a mixture of the gas raw material and the liquid raw material, wherein the liquid raw material comprises diethyl disulfide, a catalyst and a liquid oxidizing raw material, and the gas raw material is a gas oxidizing raw material.

Preferably, in the application of the microreactor for preparing ethylicin, the liquid oxidizing raw material is one or more of a nitric acid solution, a hydrogen peroxide solution or a mixed solution of the nitric acid solution and a sulfuric acid solution.

Preferably, in the application of the microreactor for preparing ethylicin, the gas oxidizing raw material is one or two of oxygen and ozone. The catalyst is acetic acid, preferably glacial acetic acid.

Preferably, the microreactor is used for preparing ethylicin, and the raw materials are respectively or mixedly introduced into the microreactor for reaction, and then the product discharged from the microreactor is subjected to gas-liquid separation to prepare the ethylicin, or the reaction is continued while the gas-liquid separation is carried out to prepare the ethylicin, or the reaction is carried out again after the gas-liquid separation to prepare the ethylicin.

Preferably, in the application of the microreactor for preparing ethylicin, the step of continuing the reaction again after gas-liquid separation to prepare the ethylicin comprises: and the ethylicin raw material passes through the microreactor, and then enters the tubular reactor for re-reaction to obtain ethylicin, or the liquid obtained after gas-liquid separation enters the microreactor again to obtain the ethylicin.

Preferably, the microreactor is used for preparing ethylicin, and when entering the microreactor again, the microreactor is the same as or different from the microreactor of the initial reaction.

Preferably, in the use of the microreactor for preparing ethylicin, the gas raw material or the liquid raw material is passed through a check valve before entering the microreactor, and/or the gas raw material or the liquid raw material is compressed by a compressor before entering the microreactor to increase the pressure of the gas raw material or the liquid raw material.

Preferably, in the application of the microreactor for preparing ethylicin, the product obtained by the first reaction is subjected to subsequent reaction again through the microreactor for 1-12 times to obtain a liquid product containing ethylicin

Preferably, the microreactor is used for preparing ethylicin, and is characterized in that the microreactor used for the initial reaction and the microreactor used for the subsequent reaction after the initial reaction are the same microreactor, the product obtained by the initial reaction circulates through the same microreactor for 1-12 times, and gas oxidizing raw materials and/or liquid oxidizing raw materials for preparing the ethylicin are added when the product circulates through the same microreactor.

Preferably, the microreactor is used for preparing ethylicin, and is characterized in that the microreactor used for the first reaction and the microreactor used for the subsequent reaction after the first reaction are different microreactors, a product obtained by the first reaction is subjected to 2-time reaction through a 2 nd microreactor, a product obtained after the 2-time reaction is subjected to an nth microreactor, and then n microreactors are used for reaction to obtain a liquid product containing ethylicin, wherein n is a positive integer of 0-11, and raw materials entering the microreactor at each subsequent time are subjected to gas-liquid separation treatment.

Preferably, the microreactor is used for preparing ethylicin, and is characterized in that a gas oxidizing raw material and/or a liquid oxidizing raw material for preparing the ethylicin are added when entering the 2 nd and nth microreactors.

Preferably, the microreactor is used for preparing ethylicin, and is characterized in that a product obtained after the first reaction of a1 st microreactor sequentially passes through 2 nd to m th reactors for first-round reaction, a product obtained after the first-round reaction of the m-th microreactor enters the 1 st microreactor, then passes through 2 nd to m-th reactors for 2-round reaction, and so on, and K-round reaction is performed to obtain a liquid product containing ethylicin, wherein m is a positive integer of 0-10, K is a positive integer of 0-5, and gas-liquid separation treatment is performed after each reaction.

Preferably, the microreactor is used for preparing ethylicin, and is characterized in that a gas raw material and/or a liquid raw material for preparing the ethylicin is added in the 2 nd and m nd microreactors.

The invention provides a method for preparing ethylicin by using a microreactor, which is characterized by comprising the following steps: introducing a raw material for preparing ethylicin into a microreactor, and introducing a product generated by the microreactor for gas-liquid separation, wherein the raw material for preparing the ethylicin is a liquid raw material or a gas raw material, or a mixture of the gas raw material and the liquid raw material, the liquid raw material comprises diethyl disulfide, a catalyst and a liquid oxidizing raw material, and the gas raw material is a gas oxidizing raw material.

Preferably, in the above method for preparing ethylicin by using a microreactor, the liquid oxidizing material is one or more of a nitric acid solution, a hydrogen peroxide solution, or a mixed solution of a nitric acid solution and a sulfuric acid solution.

Preferably, in the application of the microreactor for preparing ethylicin, the gas oxidizing raw material is one or two of oxygen and ozone.

Preferably, in the above method for preparing ethylicin by using a microreactor, the catalyst is acetic acid, preferably glacial acetic acid.

Preferably, in the above method for preparing ethylicin by using a microreactor, the raw materials are separately or mixed and introduced into the microreactor for reaction, and then the product discharged from the microreactor is subjected to gas-liquid separation to obtain ethylicin, or the reaction is continued while the gas-liquid separation is carried out to obtain ethylicin, or the reaction is carried out again after the gas-liquid separation to obtain ethylicin.

Preferably, in the method for preparing ethylicin by using the microreactor, the step of continuing the reaction again after the gas-liquid separation to prepare the ethylicin comprises the following steps: and the ethylicin raw material passes through the microreactor, and then enters the tubular reactor for re-reaction to obtain ethylicin, or the liquid obtained after gas-liquid separation enters the microreactor again to obtain the ethylicin.

Preferably, in the above method for preparing ethylicin by using a microreactor, when entering the microreactor again, the microreactor is the same as or different from the microreactor of the initial reaction.

Preferably, in the above method for preparing ethylicin by using a microreactor, the gas or liquid feedstock is passed through a check valve before entering the microreactor, and/or the gas or liquid feedstock is compressed by a compressor before entering the microreactor to increase the pressure of the gas or liquid feedstock.

Preferably, in the method for preparing ethylicin by using the microreactor, the product obtained by the first reaction is subjected to subsequent reaction again by using the microreactor for 1-12 times to obtain the liquid product containing ethylicin

Preferably, in the method for preparing ethylicin by using the microreactor, the microreactor used for the initial reaction and the microreactor used for the subsequent reaction after the initial reaction are the same microreactor, and the product obtained from the initial reaction circulates through the same microreactor for 1-12 times, and the gas oxidizing raw material and/or the liquid oxidizing raw material for preparing ethylicin are/is added when the product circulates through the same microreactor.

Preferably, in the method for preparing ethylicin by using the microreactor, the microreactor used for the first reaction and the microreactor used for the subsequent reaction after the first reaction are different microreactors, at this time, a product obtained by the first reaction is subjected to 2-time reaction through a 2 nd microreactor, a product obtained after the 2-time reaction is subjected to an nth microreactor, and then a liquid product containing ethylicin is prepared by reaction through n microreactors, wherein n is a positive integer of 0-11, and the raw materials entering the microreactor at each subsequent time are subjected to gas-liquid separation treatment.

Preferably, in the above method for preparing ethylicin by using microreactors, a gas oxidizing raw material and/or a liquid oxidizing raw material for preparing ethylicin are added when entering the 2 nd and nth microreactors.

Preferably, in the method for preparing ethylicin by using the microreactor, a product obtained after the first reaction of the 1 st microreactor sequentially passes through the 2 nd to the mth reactors for the first round reaction, a product obtained after the first round reaction of the mth microreactor enters the 1 st microreactor, then passes through the 2 nd to the mth reactors for the 2 nd round reaction, and so on, and then the K round reaction is performed to obtain a liquid product containing ethylicin, wherein m is a positive integer of 0-10, K is a positive integer of 0-5, and gas-liquid separation treatment is performed after each reaction.

Preferably, in the above method for preparing ethylicin by using microreactors, the gas oxidizing raw material and/or the liquid oxidizing raw material for preparing ethylicin are added at the 2 nd and m nd microreactors.

Preferably, in the above use and method, when the oxidizing feedstock is nitric acid and the catalyst is glacial acetic acid, the ratio of the molar speed X of diethyl disulfide entering the first microreactor for the solution comprising diethyl disulfide to the molar speed Y of nitric acid entering the microreactor is X: y is 1 { (1.3-2)/(1-12) }.

Preferably, when the reaction solution obtained from the previous microreactor reaction enters the subsequent microreactor again through the subsequent 1-12 cycles to perform parallel reaction or through the subsequent microreactor to perform series reaction, the ratio of the molar speed K calculated by the diethyl disulfide raw material of the reaction solution obtained from the previous microreactor reaction to the molar speed Z of the nitric acid of the solution containing the nitric acid entering the subsequent microreactor is 1 { (1.3-2)/(1-12) }, wherein the weight percentage of the nitric acid in the solution containing the nitric acid is 35-65%, the weight percentage of the diethyl disulfide in the solution containing the diethyl disulfide is 60-100%, and the glacial acetic acid is contained in the solution of the diethyl disulfide or in the nitric acid solution.

In the above-mentioned uses and methods, the microreactor used, i.e. the microchannel reactor, is a microreactor manufactured by precision machining techniques with characteristic microchannel dimensions of between 10 and 1000 microns, the "micro" of the microreactor indicating channels for process fluids on the micron scale, and not indicating a small physical size of the microreactor or a small product yield. The microreactors may contain millions of microchannels, and thus achieve high throughput, with the microchannels having cross-sectional areas in the shape of squares, rectangles, trapezoids, circles, or ovals.

Preferably, in the above uses and methods, the microreactor is a microchannel reactor, and the cross-sectional area of a fluid channel in the microchannel reactor is 100 to 1000000 square micrometers, preferably, the cross-sectional area of the fluid channel is 100 to 100000 square micrometers, and particularly preferably, the cross-sectional area of the fluid channel is 100 to 20000 square micrometers, and the total volume of the fluid channel is 50 to 500 ml.

The invention has the advantages of

1. The invention firstly uses the microreactor for preparing the ethylicin, develops various feasible processes for preparing the ethylicin by applying the microreactor, improves the efficiency for preparing the ethylicin, improves the concentration of the ethylicin product, can realize the shortening of the production time of the ethylicin mainly by controlling the conditions in the reaction process, and has unique process characteristics and process advantages for producing the ethylicin in different modes.

2. The microreactor is used for preparing the ethylicin, the production process is safe, and the risk of pot explosion or explosion caused by unbalanced reaction can be avoided in the process of producing the ethylicin by using the microreactor.

Detailed Description