CN111333559A - Method for rapidly preparing peroxyacetic acid by continuous flow - Google Patents
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Abstract
The invention provides a method for rapidly preparing peroxyacetic acid by continuous flow, which utilizes a continuous flow microchannel reactor to carry out reaction and comprises the following steps of 1) mixing acetic acid, hydrogen peroxide solution, catalyst and stabilizer and then introducing the mixture into a microchannel reaction preheating module; 2) continuously feeding the preheated mixture obtained in the step 1) into a microchannel reaction module, wherein the reaction temperature is 80-150 ℃, the pressure is maintained at 0.5-2.0 MPa, and the retention time is 10-200 seconds; 3) and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step 2) to enter a cooling module. The method can realize continuous flow rapid preparation of the peroxyacetic acid by utilizing the characteristics of the microchannel reactor, greatly shortens the reaction time, improves the production efficiency, effectively reduces the safety risk and is easy to carry out industrial amplification and production compared with the traditional process.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and pharmaceutical chemical engineering, and particularly relates to a method for rapidly preparing peroxyacetic acid by continuous flow.
Background
Peroxyacetic acid (CH)3COOOH) is colorless transparent liquid, has strong oxidizability, and can be widely applied to material synthesis in chemical industry, diesel oil desulfurization in petroleum industry, fabric bleaching in light textile industry, and sterilization and disinfection in the field of medical treatment and health. More specifically, in chemical synthesis, peracetic acid can be used as an epoxidizing agent to perform olefin epoxidation to prepare an epoxy monomer for synthesizing propylene oxide, caprolactam, glycerol, an epoxy plasticizer, valerolactone, caprolactone and the like; in the medical field, the peracetic acid is an efficient broad-spectrum chemical disinfectant, has the advantages of low use concentration, strong bactericidal effect, short disinfection time, no toxicity of decomposed products and the like, is widely applied to disinfection and sterilization of medical instruments and disinfection of epidemic sources such as environment, object surfaces, air and the like and is mainly used as a disinfectant for disinfection and sterilization in hospitals and other public places during the classical epidemic situation in 2003.
There are two main methods for synthesizing peroxyacetic acid: acetaldehyde air/oxygen oxidation and hydrogen peroxide processes. Although the acetaldehyde air/oxygen oxidation method has relatively low cost, the required equipment is complex, the investment is large, the safety risk is high, and meanwhile, the acetaldehyde monoperacetate generated in the production process is a temperature-sensitive explosive substance and has high explosion risk; if a heavy metal acid catalyst is used to inhibit the formation of acetaldehyde monoperacetate, the heavy metal acid catalyst needs to be removed at a later stage, otherwise the stability of peracetic acid is affected. The hydrogen peroxide is prepared by reacting 30-90 wt% of hydrogen peroxide with glacial acetic acid in the presence of a strong acid catalyst (sulfuric acid or sulfonic acid type ion exchange resin) for 4-36 h, and the reaction formula is shown in (I). In addition, acetic anhydride can be used as a raw material instead of acetic acid, although the concentration of the peroxyacetic acid can be increased, an explosive diacyl peroxide byproduct is generated in the reaction process, so that the acetic acid-hydrogen peroxide reaction is still frequently used in the industrial production for producing the peroxyacetic acid.
The acetic acid-hydrogen peroxide method also presents a great challenge in terms of process synthesis: first, the reaction system exothermed very significantly. In the reaction process, materials need to be added slowly and the reaction heat needs to be removed by continuous strong stirring, so that production accidents such as explosion and the like caused by reaction temperature runaway are prevented, and the slow feeding inevitably leads to prolonged reaction time and low production efficiency; second, hydrogen peroxide is unstable with peroxyacetic acid. The traditional process is generally carried out at a lower temperature (40-60 ℃), the reaction approaches the equilibrium time for at least several hours, and a larger reactor volume is required to be occupied. The concentration of hydrogen peroxide is increased, although the reaction speed can be accelerated, the production efficiency is still very low; increasing the reaction temperature increases the reaction rate and increases the production efficiency, but hydrogen peroxide starts to decompose exothermically at temperatures above 35 ℃.
The traditional kettle type reactor has the mass transfer and heat transfer difference (liquid-liquid mass transfer coefficient is 0.05-0.1 s)-1The total heat transfer coefficient is 1-10 KW/m3K), the backflow phenomenon cannot be avoided, the liquid holdup is large, the local material concentration and temperature are uneven, and a huge safety risk exists in the process of synthesizing peroxyacetic acid; the heat exchange area of the static mixer or the tubular reactor is greatly increased compared with that of a kettle type reactor (the liquid-liquid mass transfer coefficient is 0.1-10 s)-1The total heat transfer coefficient is 200-800 KW/m3K), the reflux problem is solved, but the mixing is still finished in a dispersion-turbulence mode, the uniform mixing needs a long time, the requirement on the mass transfer is high for some materials, and the reaction of two-phase materials cannot achieve the ideal mass transfer effect and reaction selectivity;the continuous flow microchannel reactor refers to a small reaction system manufactured by micro-processing and precision processing technologies, and comprises a mixer, a heat exchanger, a reactor, a controller and the like required by chemical unit reaction, but the size of the pipeline of the continuous flow microchannel reactor is far smaller than that of a conventional tubular reactor, and is generally in the micrometer to millimeter level. The separation effect of a phase interface on fluid and the friction effect of a microchannel on the fluid exist in the continuous flow microchannel reactor, so that strong internal circulation and secondary flow exist in the reactor, the important effect on the enhancement of mass transfer between reactants is achieved, and the reaction can be promoted to be completed in millisecond to second grade (the liquid-liquid mass transfer coefficient is 1-41 s) by means of enhanced mixing, such as separation and remixing, laminar diffusion and the like-1) (ii) a Meanwhile, the reaction channel of the microchannel reactor has small size, shortens the molecular diffusion distance and increases the mass transfer efficiency, and simultaneously, the liquid holdup of the reaction zone is very small, the specific surface area with the heat exchange zone is very large, and the heat transfer capacity is very strong (the total heat transfer coefficient is 1500 KW/m)3K or more), the temperature rise effect is not obvious, the 'number increase amplification' can be realized, the amplification effect is not generated, and the safety coefficient is high. Therefore, the microchannel reactor can be used for quickly finishing the reaction in a short retention time, the selectivity of the obtained product is higher than that of the traditional process, the by-product is lower, and the microchannel reactor is particularly suitable for reactions with violent heat release, unstable reactants or products, strict requirements on the proportion of the reactants, higher danger coefficients, flammability and explosiveness, and the like.
How to realize the aim of rapidly preparing peroxyacetic acid by continuous flow becomes a problem to be solved urgently.
Disclosure of Invention
In view of the above, the present invention aims to provide a continuous flow method for rapidly preparing peroxyacetic acid, which overcomes the problems of long reaction time, low production efficiency, relatively complex process, large equipment investment, high manufacturing cost, high safety risk, etc. in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing peroxyacetic acid by continuous flow and fast speed utilizes a continuous flow micro-channel reactor to carry out reaction, which comprises the following steps,
1) mixing acetic acid, a hydrogen peroxide solution, a catalyst and a stabilizer, and then introducing the mixture into a micro-channel reaction preheating module;
2) continuously feeding the preheated mixture obtained in the step 1) into a microchannel reaction module, wherein the reaction temperature is 80-150 ℃, the pressure is maintained at 0.5-2.0 MPa, and the retention time is 10-200 seconds;
3) and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step 2) to enter a cooling module.
By utilizing the characteristics of small reaction channel size, low liquid holdup, no back mixing, fast mass and heat transfer, narrow residence time distribution and the like of the microchannel reactor, the reaction efficiency and stability are greatly improved, and the safety risk caused by the out-of-control reaction temperature is greatly reduced.
Preferably, the mass transfer coefficient of the continuous flow microchannel reactor is 1-41 s-1The total heat transfer coefficient is 1500KW/m3K or more.
Preferably, the catalyst is one or more than two of concentrated sulfuric acid, methanesulfonic acid and benzenesulfonic acid, preferably concentrated sulfuric acid; the stabilizer is one or more than two of sodium phosphate, sodium pyrophosphate, hydroxyethylidene diphosphonic acid, ethylenediamine tetraacetic acid, 8-hydroxyquinoline and pyridine-2, 6-dicarboxylic acid, preferably one or a mixture of two of 8-hydroxyquinoline and ethylenediamine tetraacetic acid.
Preferably, in the step 1), the molar ratio of acetic acid to hydrogen peroxide is (1-10): 1, preferably the proportion is (1.5-4): 1; the concentration of the hydrogen peroxide solution is 25-75 wt%, preferably 30-70 wt%; the addition amount of the catalyst is 0.5-10 wt% of the total reaction materials, preferably 1-5 wt%; the addition amount of the stabilizer is 0.01-0.5 wt% of the total reaction materials; preferably 0.15 to 0.3 wt%.
Preferably, in the step 2), the reaction temperature of the microchannel reaction module is 100-130 ℃, the reaction pressure is 1.2-1.5 MPa, and the residence time is 15-45 seconds.
Preferably, in the step 1), the preheating temperature of the microchannel reaction preheating module is 80-150 ℃, and preferably 100-130 ℃; in the step 3), the cooling temperature of the cooling module is 0-30 ℃, and preferably 5-20 ℃.
Preferably, the continuous flow microchannel reactor is an enhanced hybrid microchannel reactor, a thin-layer continuous cut microchannel reactor, a micro-pore array microchannel reactor, a fin microchannel reactor, a capillary microchannel reactor or a multi-strand parallel flow microreactor.
Preferably, the microchannel structure in the reaction module of the microchannel reactor is a direct-flow type channel structure or an enhanced mixed type channel structure; preferably, the straight-flow type channel structure is a tubular structure, the reinforced mixed type channel structure is a T-shaped structure, a spherical baffle structure, a water drop structure, a heart-shaped structure, a sawtooth structure or an umbrella-shaped structure, and the diameter of the channel is 0.5-10 mm.
The invention also provides the application of the method in the preparation of the peroxyacetic acid.
According to the method provided by the invention, the oxidation reaction of the acetic acid and the hydrogen peroxide is carried out in the continuous microchannel reactor, and the preheating module, the reaction module, the cooling module and the heat transfer module can be connected as required. After the microchannel reactor is connected, heat conduction oil can be adopted for heat transfer, and ethanol/glycol is adopted for cooling.
Compared with the prior art, the method for rapidly preparing the peroxyacetic acid by the continuous flow has the following advantages:
(1) the method adopts acetic acid and hydrogen peroxide to react in a continuous flow microchannel reactor. By utilizing the characteristics of the microchannel reactor, namely the dimension of a reaction channel is micron to millimeter, the diffusion distance of molecules is short, back mixing is avoided, the mass and heat transfer is fast, the residence time distribution is narrow, the reaction temperature of the traditional process can be greatly increased to 80-150 ℃ in the reaction for preparing peroxyacetic acid, the reaction efficiency is greatly improved, the residence time is reduced to 10-200 s, the hydrogen peroxide cannot be decomposed before the reaction is finished due to the extremely short residence time, and the trends of decomposition and heat release of the hydrogen peroxide at high temperature are greatly reduced. The heat emitted by the reaction module with extremely small liquid holdup is quickly removed under the action of overlarge specific surface area of unit volume and ultra-fast heat transfer speed, so that the safety risk caused by the out-of-control reaction temperature is greatly reduced, and the intrinsic safety production is realized.
(2) The method of the invention utilizes the characteristics that the microchannel reactor can simultaneously realize the combination of 'size amplification' and 'number amplification', has no amplification effect, is easy to carry out industrialized amplification and production, and simultaneously has small occupied area of equipment, small investment, high production flexibility and safety.
(3) The method provided by the invention enables the conversion rate of hydrogen peroxide to reach more than 99%, and the prepared peracetic acid has high concentration which is between 20 and 35%. Meanwhile, due to the existence of the stabilizer, the peroxyacetic acid is stably stored at normal temperature and high concentration, the degradation rate is low, and the defects that the peroxyacetic acid is easy to decompose and cannot be stored in the prior art are overcome. The peroxyacetic acid solution prepared by the invention can be directly used as a medical disinfectant after being diluted to a specified concentration by distilled water.
Drawings
FIG. 1 is a diagram of a continuous flow microchannel reactor system, an example of an enhanced hybrid microchannel reactor used in the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
Selecting 1 reinforced mixed microchannel module as a pre-mixing preheating module, 6 reinforced mixed microchannel modules as a reaction module, and 1 reinforced mixed microchannel module as a cooling module, and forming a continuous flow microchannel reaction system according to a reaction flow.
The micro-channel structure of each module is a reinforced mixed type channel heart-shaped structure, and the diameter of the channel is 0.5-10 mm; as for the number setting of the modules, it is mainly sufficient to ensure that sufficient residence time is available.
The heat exchange media of the preheating module and the reaction module adopt heat conduction oil, and the heat exchange media of the cooling module adopt ethylene glycol/ethanol. According to the principle of forced heat transfer of the microchannel reactor, two temperature measuring points are arranged at the feed inlet and the discharge outlet of the reactor. Before the reaction, the micro-channel reaction system and the connecting pipeline are respectively subjected to water removal and oil removal treatment, and the system is subjected to 1.0MPa air tightness inspection by adopting nitrogen.
Step (1): mixing acetic acid and 50 wt% of hydrogen peroxide solution according to the molar ratio of the acetic acid to the hydrogen peroxide of 2:1, then respectively adding 98 wt% concentrated sulfuric acid and 0.2 wt% 8-hydroxyquinoline into the reaction solution with the mass concentration of 1 wt% of the total mass of the reaction solution, uniformly mixing, continuously and stably pumping the reaction solution mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 100 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 100 ℃, adjusting a back pressure valve to maintain the pressure of a reaction system to be 1.0MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 15 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 10 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid reaches 24wt percent by adopting an iodometry method.
Example 2
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 70 wt% of hydrogen peroxide according to the molar ratio of the acetic acid to the hydrogen peroxide of 1.1:1, then respectively adding 98 wt% concentrated sulfuric acid and 0.3 wt% ethylene diamine tetraacetic acid, wherein the mass fraction of the concentrated sulfuric acid is 0.5 wt% of the total mass of the reaction liquid, uniformly mixing, continuously and stably pumping the reaction liquid mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 80 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 80 ℃, adjusting a back pressure valve to maintain the pressure of a reaction system to be 0.5MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 33 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 15 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid reaches 32wt percent by iodometry.
Example 3
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 30 wt% of hydrogen peroxide according to a molar ratio of the acetic acid to the hydrogen peroxide of 4:1, then respectively adding methanesulfonic acid accounting for 5 wt% of the total mass of the reaction liquid and sodium phosphate accounting for 0.5 wt% of the total mass of the reaction liquid, uniformly mixing, continuously and stably pumping the reaction liquid mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a preheating module heat exchanger to be 148 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 148 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 1.3MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 10 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 18 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid is measured to reach 16.5wt percent by an iodometry method.
Example 4
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 30 wt% of hydrogen peroxide according to a molar ratio of 10:1, then respectively adding 10 wt% of benzenesulfonic acid and 0.01 wt% of sodium pyrophosphate in the total mass of the reaction solution, uniformly mixing, continuously and stably pumping the reaction solution mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 130 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 130 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 1.9MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 162 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 25 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid is measured by an iodometry method to reach 10 wt%.
Example 5
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 50 wt% of hydrogen peroxide according to a molar ratio of 1.5:1, then respectively adding 98% concentrated sulfuric acid and 0.15 wt% of hydroxyethylidene diphosphonic acid, wherein the mass of the concentrated sulfuric acid is 2 wt% of the total mass of the reaction liquid, uniformly mixing, continuously and stably pumping the reaction liquid mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 120 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 120 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 0.9MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 44 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 5 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid is measured to reach 25.6wt percent by an iodometry method.
Example 6
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 70 wt% of hydrogen peroxide according to the molar ratio of the acetic acid to the hydrogen peroxide of 2.5:1, then respectively adding 98% concentrated sulfuric acid and 0.2 wt% pyridine-2, 6-dicarboxylic acid, wherein the mass of the concentrated sulfuric acid is 1.3 wt% of the total mass of the reaction liquid, uniformly mixing, continuously and stably pumping the reaction liquid mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 125 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 125 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 1.5MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 20 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 15 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid is measured by an iodometry method to reach 30.8 wt%.
Example 7
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 50 wt% of hydrogen peroxide according to the molar ratio of the acetic acid to the hydrogen peroxide of 2:1, then respectively adding 1 wt% of methanesulfonic acid and 0.2 wt% of 8-hydroxyquinoline in the total mass of the reaction solution, uniformly mixing, continuously and stably pumping the reaction solution mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 110 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 110 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 0.8MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 18 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 20 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid reaches 22wt percent by iodometry.
Example 8
The same microchannel reactor as in example 1 was used, and the same connection method and control method were followed. This example varied the reaction conditions.
Step (1): mixing acetic acid and 70 wt% of hydrogen peroxide according to the molar ratio of the acetic acid to the hydrogen peroxide of 2:1, then respectively adding 1 wt% of benzenesulfonic acid and 0.08 wt% of ethylenediamine tetraacetic acid in the total mass of the reaction solution, uniformly mixing, continuously and stably pumping the reaction solution mixture into a microchannel reaction system through a plunger pump, and setting the temperature of a heat exchanger of a preheating module to be 110 ℃.
Step (2): and (2) continuously feeding the reaction mixture preheated in the step (1) into a microchannel reaction module, setting the temperature of a heat exchanger of the reaction module to be 110 ℃, adjusting a backpressure valve to maintain the pressure of a reaction system to be 1.1MPa, and setting the flow of a plunger pump to ensure that the reaction residence time is 26 s.
And (3): and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step (2) to enter a cooling module, wherein the heat exchange temperature of the cooling module is 30 ℃, and finally collecting the reaction product.
The content of the peroxyacetic acid is measured to reach 28.7wt percent by an iodometry method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing peroxyacetic acid by continuous flow fast is characterized in that: the reaction is carried out by utilizing a continuous flow microchannel reactor, which comprises the following steps,
1) mixing acetic acid, a hydrogen peroxide solution, a catalyst and a stabilizer, and then introducing the mixture into a microchannel reaction preheating module;
2) continuously feeding the preheated mixture obtained in the step 1) into a microchannel reaction module, wherein the reaction temperature is 80-150 ℃, the pressure is maintained at 0.5-2.0 MPa, and the retention time is 10-200 seconds;
3) and (3) enabling the product obtained at the outlet of the microchannel reaction module in the step 2) to enter a cooling module.
2. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: the mass transfer coefficient of the continuous flow microchannel reactor is 1-41 s-1The total heat transfer coefficient is 1500KW/m3K or more.
3. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: the catalyst is one or more than two of concentrated sulfuric acid, methanesulfonic acid and benzenesulfonic acid, preferably concentrated sulfuric acid; the stabilizer is one or more than two of sodium phosphate, sodium pyrophosphate, hydroxyethylidene diphosphate, ethylenediamine tetraacetic acid, 8-hydroxyquinoline and pyridine-2, 6-dicarboxylic acid, and is preferably one or a mixture of two of 8-hydroxyquinoline and ethylenediamine tetraacetic acid.
4. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: in the step 1), the molar ratio of acetic acid to hydrogen peroxide is (1-10): 1, preferably in the ratio of (1.5-4): 1; the concentration of the hydrogen peroxide solution is 25-75 wt%, preferably 30-70 wt%; the addition amount of the catalyst is 0.5-10 wt% of the total reaction materials, preferably 1-5 wt%; the addition amount of the stabilizer is 0.01-0.5 wt% of the total reaction materials; preferably 0.15 to 0.3 wt%.
5. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: in the step 2), the reaction temperature of the microchannel reaction module is 100-130 ℃, the reaction pressure is 1.2-1.5 MPa, and the residence time is 15-45 seconds.
6. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: in the step 1), the preheating temperature of the microchannel reaction preheating module is 80-150 ℃, and preferably 100-130 ℃; in the step 3), the cooling temperature of the cooling module is 0-30 ℃, and preferably 5-20 ℃.
7. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: the continuous flow microchannel reactor is an enhanced mixed microchannel reactor, a thin-layer continuous cutting microchannel reactor, a micropore array microchannel reactor, a fin type microchannel reactor, a capillary microchannel reactor or a multi-strand parallel flow microreactor.
8. The continuous-flow rapid peroxyacetic acid process of claim 1, wherein: the microchannel structure in the reaction module of the microchannel reactor is a direct-current channel structure or an enhanced mixed channel structure; preferably, the straight-flow type channel structure is a tubular structure, the reinforced mixed type channel structure is a T-shaped structure, a spherical baffle structure, a water drop-shaped structure, a heart-shaped structure, a sawtooth structure or an umbrella-shaped structure, and the diameter of the channel is 0.5-10 mm.
9. Use of a process according to any one of claims 1 to 8 in the preparation of peroxyacetic acid.
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Cited By (4)
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| CN112825856A (en) * | 2021-02-09 | 2021-05-25 | 中国天辰工程有限公司 | Method for quickly preparing peroxyacetic acid disinfectant by using low-concentration hydrogen peroxide |
| CN112958079A (en) * | 2021-02-09 | 2021-06-15 | 中国天辰工程有限公司 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
| 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 |
| CN114100527A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Reactive distillation device and method for producing peroxycarboxylic acid |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1117337A (en) * | 1964-11-03 | 1968-06-19 | Fmc Corp | Apparatus for production of peracetic acid |
| EP1016657A1 (en) * | 1998-12-15 | 2000-07-05 | Akzo Nobel N.V. | Method for producing peracetic acid |
| JP2006089472A (en) * | 2004-08-27 | 2006-04-06 | Asahi Glass Co Ltd | Method for producing organic peroxide |
| JP2006219379A (en) * | 2005-02-08 | 2006-08-24 | Mitsubishi Gas Chem Co Inc | Method for preparing solution containing percarboxylic acid |
| CN101023058A (en) * | 2004-07-28 | 2007-08-22 | 佩雷根系统有限公司 | Continuous process for on-site and on-demand production of aqueous peracetic acid |
| KR20100048261A (en) * | 2008-10-30 | 2010-05-11 | 이진태 | Manufacturing method for peracetic acid solution using column-type reactor and coil-tube-type aging reactor |
| CN103204793A (en) * | 2013-03-05 | 2013-07-17 | 嘉兴学院 | Process and device for synthesizing peroxyacetic acid |
| WO2017196373A1 (en) * | 2016-05-13 | 2017-11-16 | Eltron Research & Development, LLC | Process for the continuous on-site production of percarboxycilic acid solutions and device for its implementation |
| CN207727006U (en) * | 2017-11-30 | 2018-08-14 | 黎明化工研究设计院有限责任公司 | A kind of serialization prepares the device of Peracetic acid |
| CN109384699A (en) * | 2017-08-12 | 2019-02-26 | 上海惠和化德生物科技有限公司 | A kind of online Total continuity stream production technology directly preparing organic peroxide using hydrogen peroxide as raw material |
-
2020
- 2020-03-18 CN CN202010192877.0A patent/CN111333559A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1117337A (en) * | 1964-11-03 | 1968-06-19 | Fmc Corp | Apparatus for production of peracetic acid |
| EP1016657A1 (en) * | 1998-12-15 | 2000-07-05 | Akzo Nobel N.V. | Method for producing peracetic acid |
| CN101023058A (en) * | 2004-07-28 | 2007-08-22 | 佩雷根系统有限公司 | Continuous process for on-site and on-demand production of aqueous peracetic acid |
| JP2006089472A (en) * | 2004-08-27 | 2006-04-06 | Asahi Glass Co Ltd | Method for producing organic peroxide |
| JP2006219379A (en) * | 2005-02-08 | 2006-08-24 | Mitsubishi Gas Chem Co Inc | Method for preparing solution containing percarboxylic acid |
| KR20100048261A (en) * | 2008-10-30 | 2010-05-11 | 이진태 | Manufacturing method for peracetic acid solution using column-type reactor and coil-tube-type aging reactor |
| CN103204793A (en) * | 2013-03-05 | 2013-07-17 | 嘉兴学院 | Process and device for synthesizing peroxyacetic acid |
| WO2017196373A1 (en) * | 2016-05-13 | 2017-11-16 | Eltron Research & Development, LLC | Process for the continuous on-site production of percarboxycilic acid solutions and device for its implementation |
| CN109384699A (en) * | 2017-08-12 | 2019-02-26 | 上海惠和化德生物科技有限公司 | A kind of online Total continuity stream production technology directly preparing organic peroxide using hydrogen peroxide as raw material |
| CN207727006U (en) * | 2017-11-30 | 2018-08-14 | 黎明化工研究设计院有限责任公司 | A kind of serialization prepares the device of Peracetic acid |
Non-Patent Citations (6)
| Title |
|---|
| F. EBRAHIMI 等: "Determination of kinetics of percarboxylic acids synthesis in a microreactor by mathematical modeling", 《CHEMICAL ENGINEERING SCIENCE》 * |
| F. EBRAHIMIA 等: "Production of unstable percarboxylic acids in a microstructured reactor", 《CHEMICAL ENGINEERING JOURNAL》 * |
| SE´BASTIEN LEVENEUR 等: "Green process technology for peroxycarboxylic acids:Estimation of kinetic and dispersion parameters aided by RTD measurements:Green synthesis of peroxycarboxylic acids", 《CHEMICAL ENGINEERING SCIENCE》 * |
| 上海桃浦化工厂主编: "《过氧乙酸的生产和应用》", 30 September 1975 * |
| 吴巍 等: "微通道内连续合成过氧乙酸", 《化学反应工程与工艺》 * |
| 张志炳 著: "《有机过氧化合物的合成》", 31 January 1995 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100527A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Reactive distillation device and method for producing peroxycarboxylic acid |
| CN112825856A (en) * | 2021-02-09 | 2021-05-25 | 中国天辰工程有限公司 | Method for quickly preparing peroxyacetic acid disinfectant by using low-concentration hydrogen peroxide |
| CN112958079A (en) * | 2021-02-09 | 2021-06-15 | 中国天辰工程有限公司 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
| 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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