CN111825589A - Method for preparing anhydrous peroxyacetic acid solution by using microchannel reactor - Google Patents
Method for preparing anhydrous peroxyacetic acid solution by using microchannel reactor Download PDFInfo
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- CN111825589A CN111825589A CN201910310585.XA CN201910310585A CN111825589A CN 111825589 A CN111825589 A CN 111825589A CN 201910310585 A CN201910310585 A CN 201910310585A CN 111825589 A CN111825589 A CN 111825589A
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- peroxyacetic acid
- acid solution
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- acetaldehyde
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Abstract
The invention provides a method for preparing anhydrous peroxyacetic acid solution by using a microchannel reactor. The method comprises the steps of dissolving acetaldehyde and a catalyst in an organic solvent to serve as a material 1, introducing oxygen or air to serve as a material 2 into a microchannel reactor at a temperature of 60-90 DEG CoAnd C, continuously synthesizing the anhydrous peroxyacetic acid solution, wherein the reaction time is 10-50 s, and the pressure is 2-6 bar. Compared with the conventional kettle type reactor, the process has small liquid holding volume, and greatly reduces the potential danger of peroxyacetic acid; the reaction time is greatly shortened, the mass transfer and heat transfer are uniform, the amplification effect is avoided, the yield and the concentration are greatly improved compared with those of the kettle type reaction, and the production efficiency and the safety of the process are improved to a great extent.
Description
Technical Field
The invention relates to the technical field of synthesis of peroxyacetic acid, in particular to the technical field of preparation of anhydrous peroxyacetic acid solution by a microchannel reactor.
Background
Peracetic acid is a colorless liquid with a strong pungent odor. Since peracetic acid is a strong oxidizer, it is extremely unstable. The explosion is caused by slightly high temperature, or more than 45% concentration, or the presence of reducing agent and metal ions, so the production and the use need to be careful.
The industrial product peroxyacetic acid is generally a solution containing 18-23% of water and acetic acid, is mainly used as a bactericide, can be used for sterilizing infectious diseases, sterilizing drinking water, sterilizing fabrics, in the food industry and the like, and is a bactericide with a good popularization prospect. The peroxyacetic acid is also an important chemical raw material, and can be used in a series of reactions such as olefin epoxidation, oxidation of aromatic condensed rings, N-oxidation of pyridine and the like. Especially anhydrous peroxyacetic acid, can be used in more special oxidation reactions; however, peroxyacetic acid is potentially dangerous, and the conventional kettle-type preparation method limits the application range of the peroxyacetic acid due to the safety problem of the peroxyacetic acid.
The peroxyacetic acid is generally prepared by the following two methods:
1. the most common method is to mix acetic acid with 30-90% hydrogen peroxide and react for 4-36 hours under the catalysis of sulfuric acid or strong acid resin, so as to prepare aqueous solution of peroxyacetic acid, which generally contains substances such as acetic acid, strong acid, water and the like. Due to the potential danger of the tank reaction, CN103204793A reports a method for preparing peroxyacetic acid by using a continuous flow reactor, and CN103539770B, CN108250163A and the like also report application examples of the method for preparing peroxyacetic acid; although the method replaces a kettle type reactor with continuous flow, the obtained peroxyacetic acid is still aqueous solution and cannot meet the requirements of some anhydrous reactions.
2. Prepared by direct oxidation of acetaldehyde. Cobalt acetate and tartrate are generally used as catalysts, acetone or ethyl acetate is used as a solvent, and air or oxygen is directly introduced into an acetaldehyde solution to be oxidized to generate peroxyacetic acid. Also, the production and use of the kettle reaction is limited by its potential hazard.
Disclosure of Invention
In order to avoid the disadvantages of the above-mentioned production processes and to better prepare and use anhydrous peroxyacetic acid, the present invention proposes a process for preparing anhydrous peroxyacetic acid solutions using microchannel reactors, as shown in FIG. 1. Dissolving acetaldehyde and a catalyst in an organic solvent to serve as a material 1, introducing oxygen or air to serve as a material 2 into a microchannel reactor at a temperature of 60-90 DEG CoAnd C, continuously synthesizing the anhydrous peroxyacetic acid solution, wherein the reaction time is 10-50 s, and the pressure is 2-6 bar. Compared with the conventional kettle type reactor, the process has small liquid holding volume, and greatly reduces the potential danger of peroxyacetic acid; the reaction time is greatly shortened, the mass transfer and heat transfer are uniform, the amplification effect is avoided, and the yield and the concentration are higher than those of the kettle type reactionThe production efficiency and the safety of the process are improved to a great extent.
Preferably, the catalyst comprises cobalt acetate and ferric acetylacetonate. The molar quantity and the number of moles of acetaldehyde are 3-6 ppm.
Preferably, the flow rate of the liquid material 1 is 1-5 mL/min, and the flow rate of the gas material 2 is 100-1000 mL/min under the standard condition.
Preferably, the suitable temperature is 60-90 deg.CoC。
Preferably, the reaction time is 10 to 50s and the pressure is 2 to 6 bar.
The invention has the advantages that:
1. compared with the conventional kettle type reactor, the continuous flow synthesis of the microchannel reactor is adopted, so that the reaction liquid holding volume is small, the potential danger of the peroxyacetic acid is greatly reduced, and the intrinsic safety is realized.
2. The reaction time is greatly shortened from 1 to 2 hours of the kettle type reaction to 10 to 50 seconds; the yield is improved from about 50 percent of the kettle type reaction to about 70 percent. The mass transfer and heat transfer are uniform, the continuous production can be realized, and the amplification effect is avoided.
3. Provides a new continuous flow reaction method for the reaction of anhydrous peroxyacetic acid.
Description of the drawings:
FIG. 1 is a schematic diagram of the feed and discharge of an anhydrous peracetic acid solution prepared by using a microchannel reactor
Detailed Description
For a better understanding of the present invention, reference will now be made to the following examples. It should be understood that the following specific examples are illustrative of the invention only and are not limiting.
Example 1: preparation of an ethyl acetate solution of anhydrous peracetic acid
Adding 150g acetaldehyde into ethyl acetate to obtain 1000mL solution, adding 5.0mg catalyst, and stirring to dissolveAnd (5) solving. The microreactor was turned on and the reactor temperature set at 80 deg.foAnd C, opening an oxygen cylinder valve, adjusting the pressure to 8-10 bar, adjusting the flow rate of oxygen to 150mL/min, adjusting the backup pressure of the microreactor to 5bar, opening a feeding pump, and adjusting the flow to 1.8 mL/min. The outlet needs to be cooled to 0oAnd C, the prepared peroxyacetic acid can be collected after being stabilized for 5 minutes, the content is calibrated to be 2.4mol/L by adopting a method provided by the supplementary notes, and the yield is 75.4%.
The conditions of reaction solvent, temperature, flow rate, catalyst, gas type and the like are changed, and the obtained micro-reactor experimental results are as follows:
| serial number | Reaction temperature (C)oC) | Solvent(s) | Catalyst and process for preparing same | Liquid flow rate (mL/min) | Type of gas | Gas flow rate (mL/min) | Retention time(s) | Peroxyacetic acid concentration (mol/L) | Yield of |
| 1 | 80 | EtOAc | Co(OAc)2 | 1.8 | Oxygen gas | 150 | 24 | 2.4 | 75.4% |
| 2 | 80 | EtOAc | Co(OAc)2 | 5.0 | Oxygen gas | 500 | 10 | 2.2 | 69.1% |
| 3 | 80 | EtOAc | Co(OAc)2 | 1.0 | Oxygen gas | 100 | 38 | 2.0 | 62.0% |
| 4 | 60 | EtOAc | Co(OAc)2 | 1.8 | Oxygen gas | 150 | 24 | 1.6 | 50.3% |
| 5 | 90 | EtOAc | Co(OAc)2 | 1.8 | Oxygen gas | 150 | 24 | 2.1 | 66.0% |
| 6 | 80 | EtOAc | Fe(acac)2 | 1.8 | Air (a) | 750 | 20 | 2.3 | 72.3% |
| 7 | 80 | acetone | Fe(acac)2 | 1.8 | Air (a) | 750 | 20 | 2.0 | 62.0% |
| 8 | 80 | acetone | Co(OAc)2 | 1.8 | Air (a) | 750 | 20 | 2.3 | 72.3% |
| 9 | 80 | CHCl3 | Fe(acac)2 | 1.8 | Air (a) | 750 | 20 | 2.3 | 72.3% |
| 10 | 80 | CHCl3 | Co(OAc)2 | 1.8 | Air (a) | 750 | 20 | 2.5 | 78.5% |
And (4) supplementary notes: method for measuring concentration of peroxyacetic acid
Solution preparation:
1. starch indicator fluid: adding water 5mL of 0.5 g of soluble starch, stirring, slowly pouring into 100mL of boiling water, stirring with water, boiling for 2 min, cooling, and collecting supernatant
2. Sulfuric acid solution: 1mL of sulfuric acid was measured and slowly added to 10mL of water, followed by mixing.
The determination process comprises the following steps:
accurately measuring a liquid to be measured by using a 1mL pipette, transferring the liquid to a 50mL volumetric flask, adding about 30mL of distilled water at 4 ℃, shaking up, adding the distilled water to the scale mark of the volumetric flask, and then shaking up; adding 5mL of the diluent into an iodometry bottle, adding about 40mL of distilled water and about 1 g of potassium iodide, adding 10mL of the sulfuric acid solution, covering and placing in the dark; after 5 minutes, the iodophor bottle was taken out and the bottle cap and the surrounding were rinsed with distilled water, titrated with 0.1mol/L sodium thiosulfate standard solution to yellowish color, 2 drops of starch indicator were added, and titration was continued until the solution was colorless.
The concentration of peracetic acid in the solution to be tested was calculated as follows:
C(mol/L)=N×V×5
wherein N is the concentration of the substance amount of the sodium thiosulfate standard solution; v is the volume mL of standard solution of sodium thiosulfate consumed.
Comparative example 1:
adding 0.5mg cobalt acetate into 1mL acetic acid to dissolve, adding 200mL ethyl acetate and 20g acetaldehyde, adding the mixed solution into autoclave, cooling to 5%oC, introducing oxygen at a pressure of 4.5bar, and slowly raising the temperature to 15-20 DEG CoC, reacting for 80 minutes, and cooling the system to 0oAnd C, relieving pressure to obtain an ethyl acetate solution of the peroxyacetic acid, wherein the nominal content is 1.01mol/L, and the yield is 48.9%.
Comparative example 2:
adding 0.6mg of iron acetylacetonate into 200mL of ethyl acetate to dissolve, adding 20g of acetaldehyde, adding the mixed solution into an autoclave, and cooling to 5%oC, introducing oxygen at a pressure of 4.5bar, and slowly raising the temperature to 15-20 DEG CoC, reacting for 80 minutes, and cooling the system to 0oAnd C, decompressing to obtain an ethyl acetate solution of the peroxyacetic acid, wherein the nominal content is 1.12mol/L, and the yield is 54.3%.
In this specification, the invention has been described with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The description is thus to be regarded as illustrative instead of limiting.
Claims (6)
1. A process for preparing anhydrous peroxyacetic acid solution by using microchannel reactor includes dissolving acetaldehyde and catalyst in organic solvent as material 1, introducing oxygen or air as material 2 into microchannel reactor, and continuous flow synthesizing anhydrous peroxyacetic acid solution at proper temp.
2. The method of claim 1, wherein the organic solvent comprises ethyl acetate, acetone, chloroform.
3. The method of claim 1, wherein the catalyst comprises cobalt acetate and iron acetylacetonate in a molar amount of 3 to 6ppm based on the moles of acetaldehyde.
4. The method according to claim 1, wherein the flow rate of the liquid material 1 is 1-5 mL/min and the flow rate of the gas material 2 is 100-1000 mL/min under standard conditions.
5. The method of claim 1, wherein the suitable temperature is 60-90 deg.CoC。
6. The process according to claim 1, wherein the reaction time is 10 to 50s and the pressure is 2 to 6 bar.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105380A (en) * | 2021-04-16 | 2021-07-13 | 河北载和新材料科技有限公司 | Novel process for preparing peroxyacetic acid by using acetic acid as raw material through microreactor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087772A (en) * | 2005-01-07 | 2007-12-12 | 大赛璐化学工业株式会社 | High-purity alicyclic diepoxy compound and process for producing the same |
| JP2009263240A (en) * | 2008-04-22 | 2009-11-12 | Showa Denko Kk | Process for producing peracetic acid and process for producing epoxy compound using the peracetic acid |
| CN105503685A (en) * | 2016-01-19 | 2016-04-20 | 黎明化工研究设计院有限责任公司 | Method and device for preparing anhydrous peroxyacetic acid solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087772A (en) * | 2005-01-07 | 2007-12-12 | 大赛璐化学工业株式会社 | High-purity alicyclic diepoxy compound and process for producing the same |
| JP2009263240A (en) * | 2008-04-22 | 2009-11-12 | Showa Denko Kk | Process for producing peracetic acid and process for producing epoxy compound using the peracetic acid |
| CN105503685A (en) * | 2016-01-19 | 2016-04-20 | 黎明化工研究设计院有限责任公司 | Method and device for preparing anhydrous peroxyacetic acid solution |
Non-Patent Citations (1)
| Title |
|---|
| YI WANG等: "Investigations on Catalytic Oxidation of Acetaldehyde into Peracetic Acid in a Trickle Bed Reactor", 《J.CHEM.SOC.PAK.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105380A (en) * | 2021-04-16 | 2021-07-13 | 河北载和新材料科技有限公司 | Novel process for preparing peroxyacetic acid by using acetic acid as raw material through microreactor |
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