CN111250012A - Continuous flow micro-channel reactor and method for preparing imidazole by using same - Google Patents
Continuous flow micro-channel reactor and method for preparing imidazole by using same Download PDFInfo
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Abstract
The invention provides a continuous flow microchannel reactor, which comprises a first reaction group and a second reaction group, wherein the first reaction group comprises a first material mixing channel, a first feeding channel and a second feeding channel are arranged outside the first material mixing channel, the first material mixing channel is connected with a second material mixing channel of the second reaction group through a straight pipe microchannel, the straight pipe microchannel is connected with a third feeding channel, and the second material mixing channel is provided with a material outlet connected with a storage tank. The invention also provides a process for preparing imidazole by adopting the continuous flow microchannel reactor. The microchannel reactor can reduce the reaction time from more than ten hours to several minutes of the traditional intermittent reaction by accurately controlling the flow rate and the residence time, so that the reaction time is greatly reduced; the method has the advantages of no need of high temperature and high pressure, mild reaction conditions, simple operation, less time consumption and improvement of production efficiency, thereby providing a foundation for industrial production of imidazole.
Description
Technical Field
The invention belongs to the technical field of organic compound synthesis, and particularly relates to a method for preparing imidazole by adopting a continuous flow microchannel reactor.
Background
Imidazole is mainly used as a medicine raw material and a pesticide raw material, is one of main raw materials of azole, econazole, ketoconazole, clotrimazole and other medicines, is widely used as a fruit and vegetable preservative, is used as an epoxy resin curing agent, accounts for more than 90 percent, and is a very important organic synthesis intermediate.
The method for industrially producing imidazole at home and abroad at present mainly adopts α -dicarbonyl compound (glyoxal), ammonia and aldehyde as raw materials, and an imidazole ring is formed through condensation reaction, the reaction is usually carried out in an indirect kettle type reactor, a dropwise adding mode is adopted in an intermittent kettle type reactor, a mixed solution of glyoxal and formaldehyde is slowly dropwise added into an ammonia source solution within hours or more under continuous stirring, and heat preservation is continuously carried out for tens of hours after dropwise adding is finished to ensure that the reaction is complete, the traditional intermittent process has the defects of high production cost, more byproducts and low safety, the intermittent operation in the reaction process ensures that the efficiency of the whole process is low, the residence time and the temperature distribution range of a reaction system in a kettle are wide, the yield is generally low, and the synthesis yield of imidazole generally does not exceed 50-60% in Qianmen and the like (chemical intermediates, 2012,09(4): 49-52).
The reaction is as follows:
patent CN104529902 adopts continuous tubular gas phase catalytic reaction to prepare imidazole, so that the purity of the product can reach 91.7%, and the conversion rate is 94%.
The continuous flow microchannel reactor is essentially a continuous flow pipeline reactor, a channel in the reactor is manufactured by using a precision processing technology, the size of the channel reaches the micron level, the continuous flow microchannel reactor has excellent heat transfer and mass transfer capabilities, and the instantaneous uniform mixing and the efficient heat transfer of materials can be realized; because the diameter of the pore channel is small, the accurate temperature control can be realized, and the product selectivity is higher. With the implementation of the national green environmental protection concept and the requirement of new and old kinetic energy conversion, the continuous flow microchannel reactor technology will become an irreplaceable emerging chemical production technology.
Patent CN109422693A discloses a method for continuously preparing imidazole by using a micro-reaction technology, wherein the imidazole is prepared by using micro-channel reaction continuous flow, but the reaction temperature of the method exceeds 100 ℃, a large amount of byproducts are generated, and the concentration, rectification and separation of the imidazole are not facilitated; moreover, the reaction of the invention is a pressure reaction, which is not favorable for safe production.
The invention provides a continuous flow micro-channel reactor and a method for synthesizing imidazole by using the micro-channel reactor.
Disclosure of Invention
Aiming at the problems of the imidazole preparation process, the invention provides a simple and efficient continuous flow microchannel reactor and provides a continuous imidazole preparation technology with high yield, low equipment requirement, high safety and short reaction time.
The above object of the present invention is achieved by the following technical solutions:
the invention provides a continuous flow microchannel reactor, which comprises a first reaction group and a second reaction group, wherein the first reaction group comprises a first material mixing channel, a first feeding channel and a second feeding channel are arranged outside the first material mixing channel, the first material mixing channel is connected with a second material mixing channel of the second reaction group through a straight pipe microchannel, the straight pipe microchannel is connected with a third feeding channel, the second material mixing channel is provided with a material outlet which is connected with a storage tank, and microchannels are arranged in the first material mixing channel and the second material mixing channel.
Furthermore, temperature sensors are arranged in the first material mixing channel and the second material mixing channel, heat exchange pipelines are arranged outside the channels, and the temperature sensors and the heat exchange pipelines are connected with an intelligent temperature control system.
Furthermore, the first feeding channel, the second feeding channel and the third feeding channel are respectively provided with a metering pump.
Furthermore, the diameter of the micro-channel in the first material mixing channel and the diameter and the length of the straight tube micro-channel are both 1-10mm, and the reaction liquid can be prevented from blocking the micro-channel in the diameter range.
Furthermore, the material mixing channel of the continuous flow micro-channel reactor is made of one or more of stainless steel 316, silicon carbide and hastelloy.
The invention also provides a method for preparing imidazole by adopting the continuous flow microchannel reactor, which comprises the following steps:
1) enabling a formaldehyde solution and a glyoxal solution to respectively enter a first material mixing channel through a first feeding channel and a second feeding channel, and controlling the flow rate of the aldehyde mixing solution to be 0.1-10 mL/min through a high-pressure pump;
2) enabling ammonia water and a catalyst solution to enter a second material mixing channel through a third feeding channel, mixing with mixed aldehyde entering the second material mixing channel through a straight pipe micro-channel, controlling the flow rate of the ammonia water and the catalyst solution to be 0.1-30 mL/min through a high-pressure pump, setting the reaction temperature of each material mixing channel, and controlling the material residence time to enable the materials to fully react;
3) discharging the mixture from a discharge port of the second material mixing channel into a storage tank, and concentrating and rectifying the product to obtain the pure imidazole product.
Further, the mass fractions of the formaldehyde solution and the glyoxal solution are both 10-50%; the molar ratio of the formaldehyde to the glyoxal is 1: 1-1: 2. The material concentration of formaldehyde and glyoxal is not suitable to be too low, and when the concentration is too low, the material water which does not participate in the reaction needs to be subjected to reduced pressure concentration during post-treatment, so that a large amount of energy is wasted, and the treatment capacity of wastewater is increased; excessive formaldehyde is not suitable to react with excessive ammonia water to generate urotropin, so that a large amount of byproducts are generated, and the yield of the imidazole product is reduced.
Further, the mass fraction of the ammonia water solution is 10% -25%, the catalyst is ammonium sulfate, and the molar ratio of the catalyst to the ammonia water is 1: 10-1: 40.
Furthermore, the molar ratio of the formaldehyde to the ammonia water is 1: 2-1: 10.
Furthermore, the total reaction residence time in the first material mixing channel and the second material mixing channel is 10-500 s, and the reaction temperature is controlled at 30-80 ℃.
Further, the residence time of the first material mixing channel is 30s, the reaction temperature is 30 ℃, the residence time of the second material mixing channel is 200-400s, and the reaction temperature is 50-80 ℃.
Advantageous effects
The continuous flow micro-channel reactor provided by the invention is provided with the first material mixing channel for mixing aldehyde materials, so that the mass transfer and heat transfer among the materials are enhanced, the occurrence of side reactions is reduced, and the selectivity and yield of the product are improved. In addition, the microchannel reactor can reduce the reaction time from more than ten hours to several minutes of the traditional intermittent reaction by accurately controlling the flow rate and the residence time, so that the reaction time is greatly reduced, and the reaction efficiency is effectively improved. The process for preparing the imidazole in the continuous flow microchannel reactor does not need high temperature and high pressure, has mild reaction conditions, simple operation and less time consumption, and improves the production efficiency, thereby providing a foundation for the industrial production of the imidazole.
Drawings
FIG. 1 is a schematic diagram of the structure of a continuous flow microchannel reactor of the present invention.
Detailed Description
In order to make the technical problems and advantages of the present invention better and clearer, the present invention is further described in detail with reference to the following embodiments. In addition, the specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting of the invention.
Example 1
As shown in figure 1, a continuous flow microchannel reactor comprises a first reaction group and a second reaction group, wherein the first reaction group comprises a first material mixing channel 1, a first feeding channel and a second feeding channel (3 and 4) are arranged outside the first material mixing channel 1, the second material mixing channel 2 of the second reaction group is connected through a straight pipe microchannel 6, the first straight pipe microchannel 6 is connected with a third feeding channel 5, a material outlet of the second material mixing channel 2 is connected with a storage tank 8, and microchannels are arranged in the first material mixing channel 1 and the second material mixing channel 2. And temperature sensors are arranged in the first material mixing channel and the second material mixing channel, heat exchange pipelines are arranged outside the channels, and the temperature sensors and the heat exchange pipelines are connected with an intelligent temperature control system 7. And the first feeding channel, the second feeding channel and the third feeding channel are respectively provided with a metering pump. The diameter and length of the micro-channel and the straight tube micro-channel are 1-10 mm.
The following microchannel reactions all used the continuous flow microchannel reactor described in example 1.
Example 2 method for preparing imidazole Using continuous flow Microchannel reactor
Mixing 25 mass percent of formaldehyde solution and 31 mass percent of glyoxal solution according to a molar ratio n (formaldehyde): and (2) enabling n (glyoxal) to be 1:1 to enter a first reaction group through a 3 rd metering pump and a 4 th metering pump, setting the flow rate of mixed aldehyde to be 7ml/min, and enabling an ammonia water solution with the mass fraction of 15% and ammonium sulfate as a catalyst to be mixed according to the molar ratio n (catalyst): and (3) allowing n (ammonia water) to enter a second reaction group through a third feeding channel 5 at a ratio of 1:15, setting the feeding flow rate to be 8ml/min, setting the temperature of a first reaction group temperature channel to be 30 ℃, setting the temperatures of a 2 nd reaction group channel and a 3 rd reaction group channel to be 70 ℃, controlling the residence time of the reaction in a first material mixing channel to be 30s, and controlling the residence time of the materials in a 2 nd material mixing channel to be 400s so as to enable the materials to fully react.
The reaction solution is concentrated, dewatered and rectified to obtain the imidazole pure product with the yield of 83.5 percent and the purity of 99.05 percent.
Example 3 method for preparing imidazole Using continuous flow Microchannel reactor
Mixing a formaldehyde solution with the mass fraction of 27% and a glyoxal solution with the mass fraction of 32% according to a molar ratio n (formaldehyde): n (glyoxal) ═ 1:1.2 enters a first reaction group through a 3 rd metering pump and a 4 th metering pump, the flow rate of mixed aldehyde is set to be 5ml/min, and an ammonia water solution with the mass fraction of 15% and ammonium sulfate serving as a catalyst are mixed according to the molar ratio n (catalyst): and (3) allowing n (ammonia water) to enter a second reaction group through a third feeding channel 5 at a ratio of 1:20, setting a feeding flow rate of 10ml/min, setting the temperature of a first reaction group temperature channel to be 30 ℃, setting the temperatures of a 2 nd reaction group channel and a 3 rd reaction group channel to be 60 ℃, controlling the residence time of the reaction in a first material mixing channel to be 30s, and controlling the residence time of the material in a 2 nd material mixing channel to be 350s so as to enable the material to fully react.
The reaction solution is concentrated, dewatered and rectified to obtain the imidazole pure product with the yield of 85 percent and the purity of 99.58 percent.
Example 4 method for preparing imidazole Using continuous flow Microchannel reactor
Mixing 29% by mass of formaldehyde solution and 35% by mass of glyoxal solution according to a molar ratio n (formaldehyde): n (glyoxal) ═ 1:1.5 enters a first reaction group through a 3 rd metering pump and a 4 th metering pump, the flow rate of mixed aldehyde is set to be 9ml/min, and an ammonia water solution with the mass fraction of 17% and ammonium sulfate serving as a catalyst are mixed according to the molar ratio n (catalyst): and (3) allowing n (ammonia water) to enter a second reaction group through a third feeding channel 5 at a ratio of 1:17, setting the feeding flow rate to be 12ml/min, setting the temperature of a first reaction group temperature channel to be 30 ℃, setting the temperatures of a 2 nd reaction group channel and a 3 rd reaction group channel to be 75 ℃, controlling the residence time of the reaction in a first material mixing channel to be 30s, and controlling the residence time of the materials in a 2 nd material mixing channel to be 260s so as to enable the materials to fully react.
The reaction solution is concentrated, dewatered and rectified to obtain the imidazole pure product with the yield of 87 percent and the purity of 99.86 percent.
Example 5 method for preparing imidazole Using continuous flow Microchannel reactor
Mixing a formaldehyde solution with the mass fraction of 37% and a glyoxal solution with the mass fraction of 41% according to the molar ratio n (formaldehyde): n (glyoxal) ═ 1:1.2 enters a first reaction group through a 3 rd metering pump and a 4 th metering pump, the flow rate of mixed aldehyde is set to be 10ml/min, and an ammonia water solution with the mass fraction of 17% and ammonium sulfate serving as a catalyst are mixed according to the molar ratio n (catalyst): and (3) allowing n (ammonia water) to enter a second reaction group from a third feeding channel 5 at a ratio of 1:20, setting a feeding flow rate of 15ml/min, setting the temperature of a first reaction group temperature channel to be 30 ℃, setting the temperatures of a 2 nd reaction group channel and a 3 rd reaction group channel to be 55 ℃, controlling the residence time of the reaction in a first material mixing channel to be 30s, and controlling the residence time of the material in a 2 nd material mixing channel to be 220s so as to enable the material to fully react.
The reaction solution is concentrated, dewatered and rectified to obtain the imidazole pure product with the yield of 86.5 percent and the purity of 99.07 percent.
Example 6 method for preparing imidazole Using continuous flow Microchannel reactor
Mixing a formaldehyde solution with the mass fraction of 37% and a glyoxal solution with the mass fraction of 39% according to a molar ratio n (formaldehyde): n (glyoxal) ═ 1:1.8 enters a first reaction group through a 3 rd metering pump and a 4 th metering pump, the flow rate of mixed aldehyde is set to be 10ml/min, and an ammonia water solution with the mass fraction of 20% and ammonium sulfate serving as a catalyst are mixed according to the molar ratio n (catalyst): and (3) allowing n (ammonia water) to enter a second reaction group through a third feeding channel 5 at a ratio of 1:22, setting a feeding flow rate of 19ml/min, setting the temperature of a first reaction group temperature channel to be 30 ℃, setting the temperatures of a 2 nd reaction group channel and a 3 rd reaction group channel to be 58 ℃, controlling the residence time of the reaction in a first material mixing channel to be 30s, and controlling the residence time of the material in a 2 nd material mixing channel to be 200s so as to enable the material to fully react.
The reaction solution is concentrated, dewatered and rectified to obtain the imidazole pure product with the yield of 88 percent and the purity of 99.92 percent.
Comparative example 1
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of 25% by mass of formaldehyde solution and 31% by mass of glyoxal 77.9 solution are mixed according to a molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.0, mixing 47.53g of 15% ammonia water solution and the molar ratio n: (ammonium sulfate): mixing the catalyst with n (ammonia water) ═ 1:15 for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 70 ℃, dropwise adding 15% of mixed solution of ammonia water and ammonium sulfate under the condition, stirring at the speed of 100r/min, and controlling the reaction time of the materials to be 8.5h after the dropwise adding is finished so as to enable the materials to fully react.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 65 percent, and the purity is more than 95 percent.
Comparative example 2
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of formaldehyde solution with the mass fraction of 27 percent and 97.8g of glyoxal solution with the mass fraction of 32 percent are mixed according to the molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.2, mixing 83.19g of 15% ammonia water solution and the molar ratio n: (ammonium sulfate): mixing the catalyst with n (ammonia water) ═ 1:20 for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 60 ℃, dropwise adding 15% of mixed solution of ammonia water and ammonium sulfate under the condition, stirring at the speed of 80r/min, and controlling the reaction time of the materials to be 6 hours after the dropwise adding is finished so as to enable the materials to fully react.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 68 percent, and the purity is more than 95 percent.
Comparative example 3
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of formaldehyde solution with the mass fraction of 29 percent and 120.1g of glyoxal with the mass fraction of 35 percent are mixed according to the molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.5, mixing 53.91g of 17% ammonia water solution, and mixing the mixture according to the molar ratio of n: (ammonium sulfate): mixing the catalyst with n (ammonia water) ═ 1:17 for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 75 ℃, dropwise adding 17% of ammonia water and ammonium sulfate mixed solution under the condition, stirring at the speed of 80r/min, and controlling the reaction time of the materials for 5 hours after the dropwise adding is finished so as to enable the materials to fully react.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 72 percent, and the purity is more than 95 percent.
Comparative example 4
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of formaldehyde solution with the mass fraction of 37 percent and 104.7g of glyoxal with the mass fraction of 41 percent are mixed according to the molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.2, adding 59.62g of 17% ammonia water solution, and mixing the mixture according to a molar ratio of n: (ammonium sulfate): mixing the catalyst with n (ammonia water) ═ 1:20 for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 55 ℃, dropwise adding 17% of ammonia water and ammonium sulfate mixed solution under the condition, stirring at the speed of 90r/min, and controlling the reaction time of the materials for 10 hours after the dropwise adding is finished so as to enable the materials to fully react.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 74 percent, and the purity is more than 95 percent.
Comparative example 5
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of formaldehyde solution with the mass fraction of 37 percent and 165.0g of glyoxal with the mass fraction of 39 percent are mixed according to the molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.8, mixing 74.86g of 20% ammonia water solution and the molar ratio n: (ammonium sulfate): mixing the catalyst with n (ammonia water) ═ 1:22 for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 58 ℃, dropwise adding 20% of mixed solution of ammonia water and ammonium sulfate under the condition, stirring at the speed of 80r/min, and controlling the reaction time of the materials for 10 hours after the dropwise adding is finished so as to enable the materials to fully react.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 75 percent, and the purity is more than 95 percent.
Comparative example 6
1) Preparing mixed aldehyde and ammonia water materials: 50.0g of 25 mass percent formaldehyde solution and 77.9g of 31 mass percent glyoxal solution are mixed according to a molar ratio n (formaldehyde): mixing n (glyoxal) 1:1.1, preparing 47.53g of ammonia water solution with the mass fraction of 15%, and adding no catalyst for later use.
2) The feeding mode is as follows: and (3) placing the mixed aldehyde solution into a cyclization kettle, setting the kettle temperature to be 70 ℃, dropwise adding 15% ammonia water solution under the condition, stirring at the speed of 100r/min, and controlling the reaction time of the materials to be 8.5h to enable the materials to fully react after the dropwise adding is finished.
3) And (3) post-reaction treatment: after the reaction is finished, the reaction liquid is concentrated and rectified to obtain the imidazole product, the yield is 64 percent, and the purity is more than 95 percent.
In the invention, the parallel condition for preparing imidazole by adopting the continuous flow micro-channel is compared with the condition for preparing imidazole by adopting the traditional batch method, and the result shows that the yield of the imidazole product prepared by adopting the continuous flow micro-channel is higher than that of the imidazole prepared by the batch method under the same condition, and the yield is correspondingly improved. The catalyst is added in the examples 2-6 and the comparative examples 1-5, but the yield is almost improved by 10 percent, which plays an extremely important role in industrial production; comparative example 6, no catalyst was added, and it was found that the catalyst may have a positive effect on the yield of imidazole compared to comparative examples 1-5, where catalyst was added. The inventor surprises that the yield is greatly improved by using the continuous flow microchannel, the reaction time is reduced to be within a few minutes from ten hours to several minutes, the quality of the product is improved, compared with the 95 percent content of a kettle type reactor, the imidazole content prepared by a continuous kettle exceeds 99 percent, and the inventor considers that the possible reason is that in the traditional reaction, a large amount of materials participate in the reaction to generate a large amount of heat, so that the heat release in unit time is severe, the heat can not be dissipated in time, the environment is provided for side reaction, and the yield is reduced; and the continuous flow microchannel reactor is adopted, so that the mixing efficiency is high, the material retention time is short, the heat is efficiently transferred, and the side reaction is greatly avoided, thereby improving the yield and the quality.
In the description of the present specification, reference to the description of the terms "one embodiment", "some embodiments", "example", "comparative example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or comparative example is included in at least one embodiment or comparative example of the present invention. In the present specification, a schematic expression of the above terms does not necessarily refer to the same embodiment or comparative example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more of the embodiments or comparative examples. Furthermore, the combination and combination of features of different embodiments or comparative examples and of different embodiments or comparative examples described in this specification may be made by those skilled in the art without contradiction.
Claims (10)
1. The utility model provides a continuous flow microchannel reactor, includes first reaction group and second reaction group, first reaction group includes first material mixing channel, first material mixing channel is provided with first and second feed channel outward, connects the second material mixing channel of second reaction group through straight tube microchannel, the straight tube microchannel is connected with third feed channel, second material mixing channel is equipped with the material export and links to each other with the storage tank, be equipped with the microchannel in first material mixing channel and the second material mixing channel.
2. The reactor of claim 1, wherein the first and second material mixing channels are provided with temperature sensors therein, and heat exchange lines are provided outside the channels, and the temperature sensors and the heat exchange lines are connected to an intelligent temperature control system.
3. The reactor of claim 1, wherein the first, second and third feed channels are each provided with a metering pump.
4. A reactor according to claim 1, wherein the diameter of the microchannels in the first and second material mixing channels and the diameter of the straight tube microchannels are each 1 to 10mm in length.
5. A process for preparing imidazole using the continuous flow microchannel reactor of claim 1, comprising the steps of:
1) enabling a formaldehyde solution and a glyoxal solution to respectively enter a first material mixing channel through a first feeding channel and a second feeding channel, and controlling the flow rate of the aldehyde mixing solution to be 0.1-10 mL/min through a high-pressure pump;
2) enabling ammonia water and a catalyst solution to enter a second material mixing channel through a third feeding channel, mixing with mixed aldehyde entering the second material mixing channel through a first straight tube micro-channel, controlling the flow rate of the ammonia water and the catalyst solution to be 0.1-30 mL/min through a high-pressure pump, setting the reaction temperature of each material mixing channel, and controlling the material residence time to enable the materials to fully react;
3) discharging the mixture from a discharge port of the second material mixing channel into a storage tank, and concentrating and rectifying the product to obtain the pure imidazole product.
6. The method according to claim 5, wherein the mass fractions of the formaldehyde solution and the glyoxal solution are 10% to 50%; the molar ratio of the formaldehyde to the glyoxal is 1: 1-1: 2.
7. The method according to claim 5, wherein the mass fraction of the ammonia water solution is 10-25%, the catalyst is ammonium sulfate, and the molar ratio of the catalyst to the ammonia water is 1: 10-1: 40.
8. The method according to claim 5, wherein the molar ratio of formaldehyde to ammonia is 1:2 to 1: 10.
9. The method according to claim 5, wherein the total reaction residence time in the first material mixing channel and the second material mixing channel is 10-500 s, and the reaction temperature is controlled to be 30-80 ℃.
10. The method as claimed in claim 9, wherein the residence time of the first material mixing channel is 30s, the reaction temperature is 30 ℃, the residence time of the second material mixing channel is 200s and 400s, and the reaction temperature is 50-80 ℃.
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