CN114984878A - Micro-reaction continuous synthesis method and device for peroxyacetic acid - Google Patents
Micro-reaction continuous synthesis method and device for peroxyacetic acid Download PDFInfo
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Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a micro-reaction continuous synthesis method and a device of peroxyacetic acid. Mixing acetic acid and concentrated sulfuric acid in a micro-reaction continuous synthesis device, then fully mixing the acetic acid and concentrated sulfuric acid uniformly, reacting for 3-10min at 60-95 ℃ after mixing uniformly, reacting for 1-3min at 0-5 ℃, and cooling to obtain high-content peracetic acid. The micro-reactor of the invention utilizes the excellent mass transfer and heat transfer characteristics and smaller liquid holding volume of the continuous flow micro-reaction technology, improves the mixing effect of acetic acid and hydrogen peroxide, and simultaneously reduces the pressure of the whole reaction process, thereby improving the product quality and simultaneously improving the safety of the peroxyacetic acid synthesis process.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a micro-reaction continuous synthesis method and a device of peroxyacetic acid.
Background
Peracetic acid is a green and environment-friendly oxidant, has attracted more and more attention in recent years due to high oxidizability and excellent antibacterial capacity, and is widely applied to the industries of food processing, medical treatment, chemical industry, pulping and papermaking and the like. Because the commercial peracetic acid solution also contains hydrogen peroxide, and the oxidation mechanism of organic substances by peracetic acid and hydrogen peroxide is the same. Peroxyacetic acid, however, has a much stronger oxidizing power for most organic compounds than hydrogen peroxide.
The production process of the peroxyacetic acid mainly comprises three methods, namely an acetaldehyde oxidation method, an acetic anhydride oxidation method and an acetic acid oxidation method.
(1) The acetaldehyde oxidation method adopts oxygen to oxidize acetaldehyde into peracetic acid, and the mixed gas of acetaldehyde and oxygen is easy to reach the explosion limit, so that the danger is high.
(2) The acetic anhydride oxidation method adopts acetic anhydride and hydrogen peroxide to react at room temperature in the presence of a strong acid catalyst to obtain a peroxyacetic acid solution. The reaction of acetic anhydride with water is highly exothermic and if heat is not removed in a timely manner, it can lead to decomposition of hydrogen peroxide, which can produce explosive diacyl peroxides, which is not safe.
(3) The acetic acid oxidation method is a classical process for synthesizing peroxyacetic acid, and is characterized in that glacial acetic acid and a hydrogen peroxide solution with the mass fraction of 30% or more are mixed and react for a long time under the catalysis of a strong acid substance to obtain the peroxyacetic acid solution. The reaction formula is as follows:
the acetic acid oxidation method is safer by combining the three synthesis methods of the peroxyacetic acid. However, peroxyacetic acid belongs to peroxide, the peroxide contains a peroxy bond (-O-O-), belongs to energetic substances, and has weak bonding force due to the peroxy bond, small energy required by fracture, extremely sensitive to heat, vibration, impact or friction and the like, and extremely easy decomposition and even explosion; the peroxide is easy to oxidize and generate fire when contacting with organic matters and fibers; the composition of the reaction gas phase is easy to reach the explosion limit, and has the explosion danger. In the production process of peroxyacetic acid, if high temperature caused by other external reasons or improper operation is met, heat is not removed in time, heat accumulation occurs, peroxybond breakage easily occurs under the condition, peroxyacetic acid is decomposed, and a large amount of heat is generated in the decomposition process and a large amount of gas is evaporated at the same time. If the heat generated by a runaway reaction is not removed in time and the pressure increases, the reactor or vessel may thermally explode.
From the life cycle of the product, improper operation in the production, storage, transportation and use links of the peracetic acid is likely to cause accidents. Although peroxyacetic acid is excellent in performance, it suffers from its instability and is severely limited in mass production and use. Therefore, the production of peroxyacetic acid requires new techniques or methods to solve the above problems.
Chemical Engineering Journal 276(2015) 91-96 peroxyacetic acid was prepared using a continuous flow, mini-packed bed reactor packed with solid acid catalyst Amberlite IR-120H under sonication. Using acetic acid and hydrogen peroxide to prepare peroxyacetic acid under the action of ultrasonic wave. The results show that the molar ratio of acetic acid to hydrogen peroxide is 1:1, the flow rate is 30mL/h, and the temperature is 40 DEG CThe dosage of the catalyst is 471mg/cm 3 Reaction time<After 10min, the mass fraction of the obtained peroxyacetic acid is 5.125 mol/L. The method adopts a solid acid packed bed as a catalyst, assists ultrasonic waves, and has higher process complexity.
Organic Process Research&Development 202125 (7),1648-1657 adopts T-type micromixer and tubular reactor connected in series, 50% of hydrogen peroxide and catalytic amount of H are added 2 SO 4 And the acetic acid of the EDTA is introduced into a T-shaped mixer to be mixed and then enters a tubular reactor to be reacted. The retention time is 10min, the reaction temperature is 55 ℃, and the content of the peroxyacetic acid is 20 percent. The method has longer retention time, can increase the equipment cost to a certain extent, and the mass fraction of the peroxyacetic acid in the final product is only 20 percent, and has lower content.
Although there are studies on the continuous synthesis of peracetic acid, most processes are complicated or the mass fraction of peracetic acid in the product is low. Therefore, a continuous synthesis process with mild reaction conditions, simple process and high peroxyacetic acid content in the product is needed to be developed, so that the continuous synthesis and continuous application of the peroxyacetic acid are facilitated, the generation and consumption of the peroxyacetic acid are realized, and the safety risk of synthesis and application of the peroxyacetic acid is thoroughly solved.
Disclosure of Invention
The invention aims to provide a micro-reaction continuous synthesis method and a device of peroxyacetic acid.
In order to realize the purpose, the invention adopts the technical scheme that:
a micro-reaction continuous synthesis method of peroxyacetic acid comprises the steps of mixing acetic acid and concentrated sulfuric acid in a micro-reaction continuous synthesis device, then fully and uniformly mixing the acetic acid and concentrated sulfuric acid with hydrogen peroxide, quickly and efficiently mixing the materials to reduce the pressure of the whole reaction process, reacting at 60-95 ℃ for 3-10min after uniform mixing, reacting at 0-5 ℃ for 1-3min after reaction, wherein the pressure in the reaction system is 0.05-0.5MPa, and cooling to obtain the high-content peroxyacetic acid.
The molar ratio of acetic acid to hydrogen peroxide in the reaction process is 1.2-2.5: 1; the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the concentration of the hydrogen peroxide solution is 30-50 wt%.
When the acetic acid and the concentrated sulfuric acid are mixed, the concentrated sulfuric acid accounts for 1-6% of the mass of the acetic acid.
A device adopted by the synthesis method comprises an acetic acid input pipeline (9), a hydrogen peroxide input pipeline (10), a micro-reactor (1), a first water bath chamber (4) and a second water bath chamber (7) in a micro-reaction continuous synthesis device, wherein the micro-reactor (1) comprises a disperse phase inlet pipeline (101), a continuous phase inlet pipeline (102), a reactor outlet pipeline (103) and a mixing channel (106), the disperse phase inlet pipeline (101), the continuous phase inlet pipeline (102) and the reactor outlet pipeline (103) are all connected with the mixing channel (106), a micropore channel (105) is arranged between the disperse phase inlet pipeline (101) and the mixing channel (106), the acetic acid input pipeline (9) is connected with the disperse phase inlet pipeline (101), the hydrogen peroxide input pipeline (10) is connected with the continuous phase inlet pipeline (102), a reaction pipeline group is arranged in the first water bath chamber (4), a cooling metal pipeline (8) is arranged in the second water bath chamber (7), and the reactor outlet pipeline (103), the reaction pipeline group and the cooling metal pipeline (8) are sequentially connected in series.
One end of the mixing channel (106) is connected with the continuous phase inlet pipeline (102), the other end of the mixing channel is connected with the reactor outlet pipeline (103), the tail end of the dispersed phase inlet pipeline (101) is provided with a fluid expanding cavity (104) which is connected with one end of the micropore channel (105), and the other end of the micropore channel (105) is connected with the mixing channel (106).
A plurality of microporous channels (105) are arranged between the fluid expansion chamber (104) and the mixing channel (106).
The acetic acid input pipeline (9) is provided with a first constant flow pump (3), and the hydrogen peroxide input pipeline (10) is provided with a second constant flow pump (2).
The reaction pipeline set comprises a reaction metal pipeline (5) and a polymer pipeline (6), a reactor outlet pipeline (103) of the microreactor (1) is connected with the reaction metal pipeline (5), and the reaction metal pipeline (5), the polymer pipeline (6) and a cooling metal pipeline (8) are sequentially connected in series.
The constant flow pump 1 and the constant flow pump 2 are one of a plunger pump, a diaphragm pump and an injection pump. The material of the micro-reactor is one of 316L stainless steel, hastelloy, titanium alloy or tantalum material. The temperature of the water bath 1 is 60-95 ℃, and the temperature of the water bath 2 is 0-5 ℃. The inner diameter of the metal tube 1 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-10 m, and the metal tube is made of one of hastelloy, titanium alloy or tantalum material. The inner diameter of the polymer pipe 1 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-50 m, and the material is PEEK or PTFE. The inner diameter of the metal tube 2 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-10 m, and the material is Hastelloy, titanium alloy or tantalum material.
The continuous synthesis process of the peroxyacetic acid microreactor has the advantages that:
the synthesis process of the peroxyacetic acid is safe, the cost of the micro-reaction process is reduced, and the established continuous flow micro-reaction device is adopted in the synthesis process to continuously synthesize the peroxyacetic acid by taking the hydrogen peroxide solution and the glacial acetic acid as raw materials and concentrated sulfuric acid as a catalyst. The invention utilizes the excellent mass transfer and heat transfer characteristics of the continuous flow micro-reaction technology and smaller liquid holding volume, reduces the reaction safety risk, improves the reaction yield and reduces the reaction energy consumption. In the reaction process, after peroxyacetic acid is continuously synthesized from hydrogen peroxide and acetic acid, the peroxyacetic acid can be used for the oxidation reaction of organic matters in situ, so a novel microreactor is needed to quickly and efficiently mix the hydrogen peroxide and the acetic acid so as to reduce the pressure drop of the whole reaction process; further, the following steps are carried out:
1. the micro-reactor of the invention utilizes the excellent mass transfer and heat transfer characteristics and smaller liquid holding volume of the continuous flow micro-reaction technology, improves the mixing effect of acetic acid and hydrogen peroxide, and simultaneously reduces the pressure of the whole reaction process, thereby improving the product quality and simultaneously improving the safety of the peroxyacetic acid synthesis process.
2. The reaction device has lower pressure and lower reaction temperature, and adopts the polymer pipeline to be matched with the reaction metal pipeline to realize material reaction, thereby reducing the cost and energy consumption of the device.
3. The continuous reaction of the invention improves the mixing effect of acetic acid and hydrogen peroxide; thereby improving the content of the peroxyacetic acid in the product; the safety risk in the synthesis process of the peroxyacetic acid is reduced.
Drawings
Figure 1 is a schematic structural view of the present invention,
FIG. 2 is a schematic diagram of the microreactor structure in FIG. 1,
fig. 3 is an enlarged view of a portion a in fig. 2.
The system comprises a reactor 1, a dispersion phase inlet pipeline 101, a continuous phase inlet pipeline 102, a reactor outlet pipeline 103, a fluid expansion cavity 104, a micropore channel 105, a mixing channel 106, a second constant flow pump 2, a first constant flow pump 3, a first water bath chamber 4, a reaction metal pipeline 5, a polymer pipeline 6, a second water bath chamber 7, a cooling metal pipeline 8, an acetic acid input pipeline 9 and a hydrogen peroxide input pipeline 10.
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 all conventional methods unless otherwise specified.
The solvent mentioned in the following embodiments is prepared in advance, concentrated sulfuric acid accounting for 1-6% of the mass of acetic acid is prepared and mixed with the acetic acid for standby, the temperature of a water bath 1 in a reaction device is set to be 60-95 ℃, and the temperature of a water bath 2 is 0-5 ℃; the flow rates of the constant flow pump 1 and the constant flow pump 2 are set to be 5-20 ml/min, and the specific set value is determined according to the molar ratio of glacial acetic acid to hydrogen peroxide.
Example 1
The device used in the present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1 to 3, the apparatus includes an acetic acid input pipeline 9, a hydrogen peroxide input pipeline 10, a microreactor 1, a first water bath chamber 4 and a second water bath chamber 7, wherein as shown in fig. 2, the microreactor 1 is provided with a dispersed phase inlet pipeline 101, a continuous phase inlet pipeline 102 and a reactor outlet pipeline 103, wherein the acetic acid input pipeline 9 is connected with the dispersed phase inlet pipeline 101, the hydrogen peroxide input pipeline 10 is connected with the continuous phase inlet pipeline 102, the acetic acid input pipeline 9 is provided with a first constant flow pump 3, the hydrogen peroxide input pipeline 10 is provided with a second constant flow pump 2, the first water bath chamber 4 is provided with a reaction pipeline group, the reaction pipeline group includes a reaction metal pipeline 5 and a polymer pipeline 6, the second water bath chamber 7 is provided with a cooling metal pipeline 8, the reactor outlet pipeline 103 of the microreactor 1 is connected with the reaction metal pipeline 5, the reaction metal pipe 5, the polymer pipe 6 and the cooling metal pipe 8 are connected in series in this order. When the device works, an acetic acid solution with a certain mass fraction of concentrated sulfuric acid needs to be prepared in advance for standby, the temperature of the first water bath room 4 is set to be 60-95 ℃, the temperature of the second water bath room 7 is set to be 0-5 ℃, the flow rates of the first constant flow pump 3 and the second constant flow pump 2 are set according to the molar ratio of the acetic acid to the hydrogen peroxide, then the acetic acid solution enters the micro-reactor 1 through the acetic acid input pipeline 9 under the action of the first constant flow pump 3, the hydrogen peroxide solution enters the microreactor 1 through the hydrogen peroxide input pipeline 10 under the action of the second constant flow pump 2, after being uniformly mixed in the microreactor 1, the materials enter a reaction metal pipeline 5 for heat exchange and reaction, then enters a polymer pipeline 6 for continuous reaction, enters a cooling metal pipeline 8 for cooling after the reaction is finished, then sampling is carried out at the outlet of the end of the pipeline, and the product peroxyacetic acid content is titrated and analyzed by the method of GB/T19104-2021. The first constant flow pump 3 and the second constant flow pump 2 are one of a plunger pump, a diaphragm pump and an injection pump.
As shown in fig. 2 to 3, the microreactor 1 includes a fluid expansion chamber 104, a microporous channel 105 and a mixing channel 106, wherein one end of the mixing channel 106 is connected to the continuous phase inlet pipeline 102, the other end is connected to the reactor outlet pipeline 103, the dispersed phase inlet pipeline 101, the fluid expansion chamber 104 and the microporous channel 105 are connected in sequence, and the microporous channel 105 is connected to the middle of the mixing channel 106. The micro-reactor 1 is made of one of 316L stainless steel, Hastelloy, titanium alloy or tantalum material.
In order to efficiently mix materials, the device comprises a micro-reactor with micro-pore channels 105, the micro-pore channels 105 are arranged in a line in a direction perpendicular to the direction of the mixing channels, when the device works, acetic acid enters a disperse phase inlet pipeline 101 of the micro-reactor 1, is divided into a plurality of strands through a fluid expansion cavity 104 and enters the mixing channels 106 through 4-12 micro-pore channels 105, then is mixed with hydrogen peroxide entering through a continuous phase inlet pipeline 102, then flows out of the micro-reactor 1 through a reactor outlet pipeline 103 and enters a reaction metal pipeline 5, rapid heat exchange is carried out in the reaction metal pipeline 5 to reach a reaction temperature, then enters a polymer pipeline 6 to prolong the reaction time, and after the reaction is finished, enters a cooling metal pipeline 8 to be rapidly cooled so as to be applied subsequently.
As shown in fig. 1, the reaction metal pipe 5, the polymer pipe 6 and the cooling metal pipe 8 are all helical to ensure the fluid reaction and heat exchange time, wherein the polymer pipe 6 can reduce the material cost. The inner diameter of the reaction metal pipeline 5 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-10 m, the material is one of Hastelloy, titanium alloy or tantalum material, the inner diameter of the polymer pipeline 6 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-50 m, and the material is one of PEEK or PTFE. The inner diameter of the cooling metal pipeline 8 is 1-5 mm, the wall thickness is 1-3 mm, the length is 1-10 m, and the cooling metal pipeline is made of one of hastelloy, titanium alloy or tantalum material.
Example 2
The synthesis of peroxyacetic acid is: the molar ratio of the glacial acetic acid to the hydrogen peroxide is 1.2-2.5: 1 (preferably 2.0:1), and the flow rates of the constant flow pump 1 and the constant flow pump 2 are determined according to the mass fraction of the hydrogen peroxide and the molar ratio of the glacial acetic acid to the hydrogen peroxide. The materials are firstly dispersed by the holes at room temperature and the micro-reactants are mixed evenly. Then enters the metal tube 1 for heat exchange and reaction, then enters the polymer tube for reaction, enters the metal tube 2 for cooling after the reaction is finished, samples are taken at an outlet, and the product peroxyacetic acid content is titrated and analyzed by GB/T19104-.
Specifically, acetic acid with the concentration of 99.5 wt% and 98% of concentrated sulfuric acid accounting for 1-6% of the mass of the acetic acid are mixed to form an acetic acid solution, then the acetic acid solution enters the microreactor 1 through the action of the first constant flow pump 3, the second constant flow pump 2 conveys a hydrogen peroxide solution with the mass fraction of 30-50% into the microreactor 1, the molar ratio of the acetic acid to the hydrogen peroxide is adjusted by setting the flow rates of the first constant flow pump 3 and the second constant flow pump 2, two streams of the acetic acid solution are uniformly mixed in the microreactor 1, wherein the acetic acid solution is divided into a plurality of streams through the fluid expansion cavity 104 of the microreactor 1, enters the mixing channel 106 through 4-12 microporous channels 105, and is mixed with the hydrogen peroxide solution entering through the continuous phase inlet pipeline 102, the hydrogen peroxide and the acetic acid can be rapidly and efficiently mixed to reduce the pressure drop of the whole reaction process, the temperature of the first water 4 is adjusted to be 60-95 ℃, and adjusting the temperature of the second water bath chamber 7 to be 0-5 ℃, enabling the mixed material to flow out of the microreactor 1 and then enter the reaction metal pipeline 5, carrying out rapid heat exchange in the reaction metal pipeline 5 to reach the reaction temperature, then entering the polymer pipeline 6 to prolong the reaction time, entering the cooling metal pipeline 8 to carry out rapid cooling after the reaction is finished, and finally collecting the product at an outlet at the tail end of the pipeline.
The device in the embodiment 1 can improve the mixing effect of acetic acid and hydrogen peroxide according to the reaction, improve the content of peroxyacetic acid in the product, reduce the pressure of the reaction device, relatively lower the reaction temperature, reduce the liquid holding volume of the reaction liquid in the whole reaction process, reduce the safety risk in the synthesis process of peroxyacetic acid, and reduce the device cost and energy consumption.
Example 3
Mixing 99.5 wt% acetic acid and 98% concentrated sulfuric acid 6% of the acetic acid to form an acetic acid solution, and preparing an acetic acid solution containing 6% concentrated sulfuric acid by mass fraction, wherein the mass fraction of hydrogen peroxide is 30%, and the molar ratio of the acetic acid to the hydrogen peroxide is 2: 1. The temperature of the water bath 1 is set to 85 ℃ and the temperature of the water bath 2 is set to 5 ℃ by utilizing the micro-reaction continuous synthesis device. Setting the flow rate of a constant flow pump 1 to be 12.8ml/min and the flow rate of a constant flow pump 2 to be 10.3ml/min, adopting a micropore mixing reactor to rapidly and efficiently mix two mixed materials to reduce the pressure of the whole reaction process, uniformly mixing the two materials, allowing the mixed solution to enter a tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for heating and reaction, allowing the mixed solution to enter a PTFE tube with the length of 20m, the inner diameter of 2mm and the wall thickness of 1mm for reaction, and allowing the mixed solution to enter a subsequent tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for cooling, wherein the reaction retention time is 4.1min, the pressure of the whole reaction system is 0.1Mpa, and the mass fraction of the final product peracetic acid is 15.41%.
Example 4
Mixing 99.5 wt% acetic acid and 98% concentrated sulfuric acid accounting for 5% of the acetic acid to form an acetic acid solution, and preparing an acetic acid solution containing 5% concentrated sulfuric acid by mass fraction, wherein the mass fraction of hydrogen peroxide is 35%, and the molar ratio of the acetic acid to the hydrogen peroxide is 2: 1. The temperature of the water bath 1 is set to 80 ℃ and the temperature of the water bath 2 is set to 5 ℃ by utilizing the micro-reaction continuous synthesis device. Setting the flow rate of a constant flow pump 1 to be 13.1ml/min and the flow rate of a constant flow pump 2 to be 9.8ml/min, adopting a micropore mixing reactor to rapidly and efficiently mix two mixed materials to reduce the pressure of the whole reaction process, uniformly mixing the two materials, allowing the mixed solution to enter a tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for heating and reaction, allowing the mixed solution to enter a PTFE tube with the length of 20m, the inner diameter of 2mm and the wall thickness of 1mm for reaction, and allowing the mixed solution to enter a subsequent tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for cooling, wherein the reaction retention time is 4.1min, the pressure of the whole reaction system is 0.11Mpa, and the mass fraction of the final product, namely peracetic acid, is 18.23%.
Example 5
Mixing 99.5 wt% acetic acid and 98% concentrated sulfuric acid 4% of acetic acid to form acetic acid solution, and preparing acetic acid solution containing 4% concentrated sulfuric acid in a mass fraction of 50% hydrogen peroxide in a molar ratio of 2: 1. The temperature of the water bath 1 is set to 80 ℃ and the temperature of the water bath 2 is set to 5 ℃ by utilizing the micro-reaction continuous synthesis device. Setting the flow rate of a constant flow pump 1 to be 15.3ml/min and the flow rate of a constant flow pump 2 to be 7.6ml/min, adopting a micropore mixing reactor to rapidly and efficiently mix two mixed materials to reduce the pressure of the whole reaction process, uniformly mixing the two materials, allowing the mixed solution to enter a tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for heating and reaction, allowing the mixed solution to enter a PTFE tube with the length of 20m, the inner diameter of 2mm and the wall thickness of 1mm for reaction, and allowing the mixed solution to enter a subsequent tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for cooling, wherein the reaction retention time is 4.1min, the pressure of the whole reaction system is 0.13Mpa, and the mass fraction of the final product, namely the peroxyacetic acid is 25.86%.
Comparative example 1
Mixing 99.5 wt% acetic acid and 98% concentrated sulfuric acid accounting for 5% of the acetic acid to form an acetic acid solution, and preparing an acetic acid solution containing 5% concentrated sulfuric acid by mass fraction, wherein the mass fraction of hydrogen peroxide is 35%, and the molar ratio of the acetic acid to the hydrogen peroxide is 2: 1. The temperature of the water bath 1 was set to 40 ℃ and the temperature of the water bath 2 was set to 5 ℃ using the above-mentioned micro-reaction continuous synthesis apparatus. Setting the flow of a constant flow pump 1 to be 13.1ml/min and the flow of a constant flow pump 2 to be 9.8ml/min, adopting a micropore mixing reactor to rapidly and efficiently mix two mixed materials to reduce the pressure of the whole reaction process, uniformly mixing the two materials, allowing the mixed solution to enter a tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for heating and reaction, allowing the mixed solution to enter a PTFE tube with the length of 20m, the inner diameter of 2mm and the wall thickness of 1mm for reaction, and allowing the mixed solution to enter a subsequent tantalum tube with the length of 10m, the inner diameter of 2mm and the wall thickness of 1mm for cooling, wherein the reaction retention time is 4.1min, the pressure of the whole reaction system is 0.11Mpa, and the mass fraction of the final product, namely peroxyacetic acid is 8.56%.
The embodiment shows that the peroxyacetic acid is continuously synthesized from the hydrogen peroxide and the acetic acid in the micro-reaction continuous synthesis device, the hydrogen peroxide and the acetic acid can be quickly and efficiently mixed, the pressure of the whole reaction process can be further reduced, the reaction time is shortened, the retention time of the embodiments 3 to 5 is about 4.1min, and the final peroxyacetic acid has a high mass fraction. When the hydrogen peroxide as the raw material is 30 wt%, the content of the product peracetic acid is 15.41 wt%; when the raw material hydrogen peroxide is 35 wt%, the content of the product peracetic acid is 18.23 wt%.
The documents Organic Process Research & Development 202125 (7),1648-1657 use 50 wt% of hydrogen peroxide as raw material, the residence time is 10min, the reaction temperature is 55 ℃, the peroxyacetic acid content is only 20 wt%. In example 5, the product peracetic acid content of 25.86 wt% is significantly higher than the literature value when the starting material hydrogen peroxide is 50 wt%.
By adopting the device, under other conditions, when the concentration of the raw material hydrogen peroxide is 35 wt%, the content of the product peracetic acid is only 8.56 wt%. The device is proved to be matched with the process to achieve good effect.
Claims (8)
1. A micro-reaction continuous synthesis method of peroxyacetic acid is characterized in that: mixing acetic acid and concentrated sulfuric acid in a micro-reaction continuous synthesis device, then fully mixing the acetic acid and concentrated sulfuric acid uniformly, reacting for 3-10min at 60-95 ℃ after mixing uniformly, reacting for 1-3min at 0-5 ℃, and cooling to obtain high-content peracetic acid.
2. A process for the micro-reactive continuous synthesis of peroxyacetic acid according to claim 1, wherein: the molar ratio of acetic acid to hydrogen peroxide in the reaction process is 1.2-2.5: 1.
3. A process for the micro-reactive continuous synthesis of peroxyacetic acid according to claim 1, wherein: when the acetic acid and the concentrated sulfuric acid are mixed, the concentrated sulfuric acid accounts for 1-6% of the mass of the acetic acid.
4. An apparatus for use in the synthesis method of claim 1, wherein: the micro-reaction continuous synthesis device comprises an acetic acid input pipeline (9), a hydrogen peroxide input pipeline (10), a micro-reactor (1), a first water bath chamber (4) and a second water bath chamber (7), wherein the micro-reactor (1) comprises a dispersed phase inlet pipeline (101), a continuous phase inlet pipeline (102), a reactor outlet pipeline (103) and a mixing channel (106), the dispersed phase inlet pipeline (101), the continuous phase inlet pipeline (102) and the reactor outlet pipeline (103) are all connected with the mixing channel (106), a micropore channel (105) is arranged between the dispersed phase inlet pipeline (101) and the mixing channel (106), the acetic acid input pipeline (9) is connected with the dispersed phase inlet pipeline (101), the hydrogen peroxide input pipeline (10) is connected with the continuous phase inlet pipeline (102), and a reaction pipeline group is arranged in the first water bath chamber (4), a cooling metal pipeline (8) is arranged in the second water bath chamber (7), and the reactor outlet pipeline (103), the reaction pipeline group and the cooling metal pipeline (8) are sequentially connected in series.
5. The apparatus of claim 4, wherein: one end of the mixing channel (106) is connected with the continuous phase inlet pipeline (102), the other end of the mixing channel is connected with the reactor outlet pipeline (103), the tail end of the dispersed phase inlet pipeline (101) is provided with a fluid expanding cavity (104) which is connected with one end of the micropore channel (105), and the other end of the micropore channel (105) is connected with the mixing channel (106).
6. The apparatus of claim 4, wherein: a plurality of microporous channels (105) are arranged between the fluid expansion chamber (104) and the mixing channel (106).
7. The apparatus of claim 4, wherein: the acetic acid input pipeline (9) is provided with a first constant flow pump (3), and the hydrogen peroxide input pipeline (10) is provided with a second constant flow pump (2).
8. The apparatus of claim 4, wherein: the reaction pipeline set comprises a reaction metal pipeline (5) and a polymer pipeline (6), a reactor outlet pipeline (103) of the microreactor (1) is connected with the reaction metal pipeline (5), and the reaction metal pipeline (5), the polymer pipeline (6) and a cooling metal pipeline (8) are sequentially connected in series.
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