CN110862293A - Continuous method for preparing dihalogenated alkane from diol compound - Google Patents
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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Abstract
The invention discloses a continuous method for preparing dihalogenated alkane from diol compounds, which takes the diol compounds and halogen acid as substrates and utilizes a microchannel reactor to continuously synthesize the dihalogenated alkane, and the synthesis of the dihalogenated alkane comprises the following steps: under the condition of room temperature, respectively inputting a diol compound and halogen acid into a mixer by using a metering pump, and feeding the premixed materials into a microchannel reactor at a high temperature section for reaction, wherein the reaction temperature is controlled by an external circulation heat exchange system; after the reaction is finished, the product flows out from the outlet of the microchannel reactor and enters a cooling section, the cooled material enters a liquid separating kettle for standing and liquid separation, and an organic layer is collected; the organic layer is preheated and then sent into a rectifying tower by a metering pump, the temperature and reflux ratio of a reboiler are controlled, and the fraction with specific temperature is collected to obtain a target product in a product collecting tank. The invention has high reaction efficiency, safety, environmental protection, convenience and rapidness.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a continuous method for preparing dihalogenated alkane from diol compounds.
Background
Dihalogenated alkanes have very wide application in the field of traditional fine chemical engineering, and particularly have irreplaceable effects as hydrophobic groups and alkylation groups in molecules of medicines, pesticides and surfactants. With the development of biomedical technology, visual diagnostic reagents for preoperative diagnosis, operation planning or intermediate evaluation gradually become pets of surgeons, wherein the development of near-infrared fluorescence molecular diagnosis technology is particularly rapid, and the near-infrared fluorescence technology has the advantages of good tissue penetrability, small scattering and low background fluorescence, and is very suitable for clinical in-vivo imaging.
Indocyanine green is currently approved for clinical use as a liver cancer imaging and sentinel lymph node imaging agent. However, fluorescent molecules, such as indocyanine green, do not have biological targeting properties. In order to target fluorescent molecules, a targeting group (or called a recognition group) and a luminescent group (or called a reporter group) are usually connected by a small molecule, so that the connected molecule is called a linker. Dihaloalkanes are currently the most widely enabled linkers, and it is anticipated that the use of dihaloalkanes will be more and more widespread.
The common method for producing dihalo-alkane is nucleophilic substitution reaction of diol and thionyl chloride, but this method has large pollution, poor atom economy, high cost and is not suitable for production of other halogenated hydrocarbons except chloro-substituted hydrocarbon.
With the increasing awareness of environmental protection, attempts have been made to produce dihaloalkanes by using hydrochloric acid and diols, which are economical and environmentally friendly, but have low reaction efficiency, low yield and long reaction time, and thus cannot meet the requirements of industrial production. In order to enhance the reaction process and also to take into account the safety risks associated with high temperature, high pressure and high concentration during the process enhancement, we have developed a process for the synthesis of concentrated hydrochloric acid and diol in a microchannel reactor.
The microchannel reactor, also called as micro reactor, is one of the most important directions for the development of chemical engineering technology in this century. The microchannel reactor has very high-efficient mass transfer and heat transfer performance, can accelerate the reaction, reduce back mixing, improve reaction selectivity and yield, and has reliable intrinsic safety because of small liquid holdup and large surface heat exchange area. Because the capacity expansion of the microreactor mainly depends on the increase of the number of reactors and the extension of the running time, the whole process has no amplification effect, the method is safe and reliable, the rapid industrialization can be realized, the switching of varieties in the microreactor is very convenient and rapid, and the characteristics and advantages of the microreactor are very suitable for the industrial production of the dihalogenated alkane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a continuous method for preparing dihalogenated alkane from diol compounds, which has high reaction efficiency, safety, environmental protection, convenience and rapidness.
In order to achieve the above object, the present invention provides a continuous process for producing a dihaloalkane from a diol compound, which comprises continuously synthesizing a dihaloalkane using a microchannel reactor with the diol compound and a hydrohalogenoic acid as substrates, wherein the synthesis formula for producing the dihaloalkane by reacting the diol compound with the hydrohalogenoic acid is:
the continuous method comprises the following steps:
s1, under the condition of room temperature, respectively inputting a diol compound and halogen acid into a mixer by using a metering pump for mixing, preheating, and then, allowing the materials to enter a microchannel reactor at a high temperature section for reaction, wherein the reaction temperature is controlled by an external circulation heat exchange system, and the reaction pressure is controlled by a back pressure valve;
s2, after the reaction is finished, enabling a product to flow out of an outlet of the microchannel reactor, enabling the product to enter a cooling section, enabling the cooled material to enter a liquid separation kettle for standing and liquid separation, and collecting an organic layer;
s3, preheating the organic layer by a metering pump, then feeding the organic layer into a rectifying tower, controlling the temperature and reflux ratio of a reboiler, and collecting fractions at specific temperature to obtain a target product in a product collecting tank.
Further, the diol compounds include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, etc., and in the diol structural formula, n includes but is not limited to 1, 2, 3, 4;
the hydrohalic acid comprises hydrochloric acid, hydrobromic acid and hydroiodic acid, and the weight percentage concentration of the hydrohalic acid is as follows: 20 to 38 percent of hydrochloric acid, 10 to 47 percent of hydrobromic acid and 10 to 45 percent of hydroiodic acid.
Further, the molar ratio of the diol compound to the hydrohalic acid is 1: 1.2-1: 5, with a preferred range of 1: 2.4-1: 4.
further, the total flow rate of the diol compound and the halogen acid after mixing is in the range of 10 to 100ml/min, and preferably in the range of 20 to 50 ml/min.
Further, the reaction residence time in the microchannel reactor is 5-40min, and the preferable range is 12-15min of hydrochloric acid, 8-13min of hydrobromic acid and 5-7min of hydriodic acid.
Further, the reaction temperature in the microchannel reactor is 190 ℃ at 120-.
Further, the reaction pressure in the microchannel reactor is 1.5 to 5.0MPa, and the preferable range thereof is 2.0 to 3.0 MPa.
Further, the microchannel reactor used in the synthesis method includes, but is not limited to, a straight-flow type microchannel chip reactor, a microchannel chip reactor with a pulse diameter changing type, a microchannel chip reactor with a Heart Cell structure of Corning, a capillary coil reactor with a diameter of 0.2-1.0mm, and a fixed bed reactor with an inner diameter of 1-3cm and filled with inert filler.
Furthermore, the materials of the microchannel reactor adopted by the synthesis method are glass, silicon carbide, stainless steel coated with a corrosion-resistant coating and various corrosion-resistant metal alloys.
The method comprises a mixing section, a preheating section, a reaction section, a cooling section and other different functional areas, wherein all functions are continuously completed in microchannel equipment, the microchannel equipment comprises a metering pump, a mixer, a preheating device, a microchannel reactor, a back pressure valve, a liquid separating kettle, a rectifying tower and a product collecting tank, the metering pump is sequentially connected with the mixer, the preheating device, the microchannel reactor, the back pressure valve, the liquid separating kettle, the rectifying tower and the product collecting tank, and the metering pump and the preheating device are arranged between the liquid separating kettle and the rectifying tower.
Compared with the prior art, the invention has the beneficial effects that:
the reaction time in the tank reactor is generally 48 hours, the process is strengthened by using the microchannel reactor, the reaction time is greatly shortened, the energy consumption is saved, and side reactions such as ring formation, polymerization and the like which are inevitable in the conventional reactor can be effectively avoided.
The method has the greatest advantages that only common hydrochloric acid or hydrobromic acid and hydroiodic acid are needed, expensive reagents such as thionyl chloride and the like are avoided, the method can be continuously applied, the cost is reduced, and the emission of acid tail gas and waste acid is reduced.
In addition, the invention is a continuous process, can easily realize continuous and automatic production, and is a real, safe, green and economic industrialized production method.
Drawings
FIG. 1 is a schematic flow diagram of the present invention:
wherein 1 metering pump, 2 blenders, 3 microchannel reactors, 4 back pressure valves, 5 liquid separating kettles, 6 metering pumps, 7 rectifying columns, 8 product collecting tanks, 9 raw material tanks and 10 raw material tanks.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a continuous method for preparing dihalogenated alkane from diol compounds, which takes the diol compounds and halogen acid as substrates and utilizes a microchannel reactor to continuously synthesize the dihalogenated alkane, wherein the synthesis formula of the dihalogenated alkane generated by the reaction of the diol compounds and the halogen acid is as follows:
as shown in fig. 1, the continuous process comprises the following steps:
s1, under the condition of room temperature, feeding a diol compound in a raw material tank 9 and halogen acid in a raw material tank 10 into a mixer 2 by using a metering pump 1 respectively for mixing, preheating, feeding the materials into a microchannel reactor 3 at a high temperature section for reaction, controlling the reaction temperature by an external circulation heat exchange system, and controlling the reaction pressure by a back pressure valve 4;
s2, after the reaction is finished, enabling the product to flow out of an outlet of the microchannel reactor 3, entering a cooling section, enabling the cooled material to enter a liquid separation kettle 5 for standing and liquid separation, and collecting an organic layer;
s3, preheating the organic layer by a metering pump 6, then feeding the organic layer into a rectifying tower 7, controlling the temperature and reflux ratio of a reboiler, and collecting fractions at specific temperature to obtain a target product in a product collecting tank 8.
Example 1:
a reaction device: the reactor used in this embodiment is a chip-type reactor, and the interior of the chip-type reactor has an umbrella-shaped pulse diameter-changing structure. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
1, 2-glycol is filled in a raw material tank 9, 35% concentrated hydrochloric acid is filled in a raw material tank 10, the two raw materials are directly pumped into a micro reactor 3 for reaction at 6.8mL/min and 35.3mL/min respectively through a high-pressure constant flow pump 1, the temperature of the reactor is controlled to be 135 ℃, the pressure of a back pressure valve 4 is adjusted to be 2.5MPa, and the reaction residence time is 9.5 min. And cooling the emulsion reaction solution to 40 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute hydrochloric acid and can be recycled after thickening.
The reaction was sampled at the outlet of microreactor 2 for a conversion of 1, 2-dichloroethane of 92.7%.
Table 1 shows the reaction in a microreactor to produce dichloroethane under different conditions:
table 1: production of dichloroethane in microreactors
| Diol compound | 1, 2-ethanediol | 1, 2-ethanediol | 1, 2-ethanediol | 1, 2-ethanediol |
| Halogen acid | 28% hydrochloric acid | 35% hydrochloric acid | 35% hydrochloric acid | 28% hydrochloric acid |
| Molar ratio of the two | 1：4 | 1：2.4 | 1：4 | 1：5 |
| Reaction temperature | 160℃ | 170℃ | 180℃ | 190℃ |
| Reaction pressure | 3.0MPa | 2.0MPa | 3MPa | 1.5MPa |
| Residence time of the reaction | 15min | 10min | 15min | 30min |
| Conversion rate | 96.5％ | 74.7％ | 99.3％ | 76.4％ |
Example 2:
a reaction device: the reactor used in this embodiment is a chip-type microreactor, and has an umbrella-shaped pulse diameter-changing structure inside. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
The raw material tank 9 is filled with 1, 3-propanetriol, the raw material tank 10 is filled with 35% concentrated hydrochloric acid, the two raw materials are respectively pumped into the mixer 2 by a high-pressure constant flow pump 1 at a rate of 5.3mL/min and 24.1 mL/min, the two raw materials pass through the tubular preheating module, the temperature of the materials reaches 100 ℃, the materials enter the microreactor 3 for reaction, the temperature of the reactor is controlled to be 140 ℃, the pressure of the back pressure valve 4 is adjusted to be 3.0MPa, and the reaction retention time is 11.7 min. Cooling the emulsion reaction solution to 70 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute hydrochloric acid and can be recycled after being reconcentrated.
The reaction was carried out at the outlet of the microreactor 3 with a conversion of 1, 3-dichloropropane of 96.6% by sampling.
Table 2 shows the preparation of 1, 3-dichloropropane under different conditions, reacted in a microreactor:
table 2: preparation of 1, 3-dichloropropane in a microreactor
| Diol compound | 1, 3-propanetriol | 1, 3-propanetriol | 1, 3-propanetriol | 1, 3-propanetriol |
| Halogen acid | 28% hydrochloric acid | 35% hydrochloric acid | 35% hydrochloric acid | 28% hydrochloric acid |
| Molar ratio of the two | 1：4 | 1：2.4 | 1：4 | 1：5 |
| Reaction temperature | 170℃ | 150℃ | 180℃ | 190℃ |
| Reaction pressure | 5.0MPa | 5.0MPa | 3MPa | 1.5MPa |
| Residence time of the reaction | 12min | 12min | 15min | 30min |
| Conversion rate | 83.5％ | 93.2％ | 75.7％ | 62.6％ |
Example 3:
a reaction device: the reactor used in this embodiment is a chip-type microreactor, and has an umbrella-shaped pulse diameter-changing structure inside. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
1, 4-butanediol is filled in a raw material tank 9, 35% concentrated hydrochloric acid is filled in a raw material tank 10, the two raw materials are respectively pumped into a micro mixer 2 by a high-pressure constant flow pump 1 at a rate of 5.9mL/min and 20.3mL/min, the temperature of the materials reaches 120 ℃ after passing through a tubular preheating module, the materials enter a micro reactor 3 for reaction, the temperature of the reactor is controlled to be 170 ℃, the pressure of a back pressure valve 4 is adjusted to be 3.0MPa, and the reaction residence time is 15.3 min. Cooling the emulsion reaction solution to 70 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute acid and can be recycled after re-concentration.
The conversion rate of the reaction at the outlet of the microreactor by sampling is 98.7%.
Example 4:
a reaction device: the reactor used in this embodiment is a chip-type microreactor, and has an umbrella-shaped pulse diameter-changing structure inside. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
The raw material tank 9 is filled with 1, 4-butanediol, the raw material tank 10 is filled with 40% hydrobromic acid, the two raw materials are respectively pumped into the mixer 2 by a high-pressure constant flow pump 1 at a rate of 7.3mL/min and 40.0mL/min, the temperature of the materials reaches 120 ℃ after passing through the tubular preheating module, the materials enter the microreactor 3 for reaction, the temperature of the reactor is controlled to be 150 ℃, the pressure of a back pressure valve is adjusted to be 3.0MPa, and the reaction residence time is 8.3 min. Cooling the emulsion reaction solution to 70 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute acid and can be recycled after re-concentration.
The reaction was sampled at the outlet of microreactor 3 for a 1, 4-dibromobutane conversion of 85.8%.
Table 3 shows the preparation of 1, 4-dibromobutane in a microreactor under different conditions:
table 3: preparation of 1, 4-dibromobutane in a microreactor
| Diol compound | 1, 4-butanediol | 1, 4-butanediol | 1, 4-butanediol | 1, 4- |
| Halogen acid | ||||
| 10% hydrobromic acid | 25% hydrobromic acid | 40% hydrobromic acid | 47% hydrobromic acid | |
| Molar ratio of the two | 1：2.4 | 1：2.4 | 1：4 | 1：5 |
| Reaction temperature | 120℃ | 150℃ | 160℃ | 190℃ |
| Reaction pressure | 5.0MPa | 2.0MPa | 3MPa | 1.5MPa |
| Residence time of the reaction | 5min | 5min | 13min | 30min |
| Conversion rate | 84.3％ | 91.8％ | 80.5％ | 74.5％ |
Example 5:
a reaction device: the reactor used in this embodiment is a chip-type microreactor, and has an umbrella-shaped pulse diameter-changing structure inside. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
The raw material tank 9 is filled with 1, 4-butanediol, the raw material tank 10 is filled with 45% hydroiodic acid, the two raw materials are respectively and directly pumped into the microreactor 3 for reaction at 10.1mL/min and 51.4mL/min by the high-pressure constant flow pump 1, the temperature of the reactor is controlled to be 120 ℃, the pressure of the back pressure valve 4 is adjusted to be 3.0MPa, and the reaction residence time is 6.5 min. Cooling the emulsion reaction solution to 70 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase 4 into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute hydrochloric acid and can be recycled after being reconcentrated.
The reaction was sampled at the outlet of microreactor 3 for a 1, 4-diiodobutane conversion of 62.7%.
Table 4 shows the reaction in microreactors, preparation of 1, 4-diiodobutane under different conditions:
table 4: preparation of 1, 4-diiodobutane in microreactors
| Diol compound | 1, 4-butanediol | 1, 4-butanediol | 1, 4-butanediol | 1, 4- |
| Halogen acid | ||||
| 10% hydriodic acid | 20% hydriodic acid | 35% hydriodic acid | 45% hydriodic acid | |
| Both of them are rubbed togetherMole ratio of | 1：1.2 | 1：2.4 | 1：4 | 1：5 |
| Reaction temperature | 120℃ | 130℃ | 110℃ | 110℃ |
| Reaction pressure | 5.0MPa | 2.0MPa | 3MPa | 1.5MPa |
| Residence time of the reaction | 12min | 5min | 7min | 7min |
| Conversion rate | 78.2％ | 64.7％ | 81.6％ | 73.2％ |
Example 6:
a reaction device: the reactor used in this example was a packed bed type straight tube reactor having a tube inner diameter of 10mm, glass beads having a diameter of 2mm were packed inside the reactor, and a jacket was provided outside the reactor. The reaction residence time is calculated according to the liquid holdup of the reactor and the flow rate data of the materials. The heat exchange medium is heat conducting oil.
The raw material tank 9 is filled with 1, 4-butanediol, the raw material tank 10 is filled with 35% concentrated hydrochloric acid, the two raw materials are respectively pumped into a tubular preheating module by a high-pressure constant flow pump 1 at a rate of 12mL/min and 40mL/min, the materials directly enter a packed bed type straight tube reactor 3 for reaction after the temperature of the materials reaches 120 ℃, the temperature of the reactor is controlled to be 170 ℃, the pressure of a back pressure valve 4 is adjusted to be 2.8MPa, and the reaction retention time is 35 min. Cooling the emulsion reaction solution to 70 ℃ through a coil pipe, then feeding the emulsion reaction solution into a standing and liquid separating kettle 5 for liquid separation, feeding the lower organic phase into a rectifying tower 7 for rectification, and feeding the upper aqueous phase which is dilute hydrochloric acid and can be recycled after being reconcentrated.
The reaction was sampled at the outlet of microreactor 3 for a 1, 4-dichlorobutane conversion of 91.8%.
Table 5 is a reaction in a microreactor to prepare 1, 4-dichlorobutane under different conditions:
table 5: preparation of 1, 4-dichlorobutane in microreactors
| Diol compound | 1, 4-butanediol | 1, 4-butanediol | 1, 4-butanediol | 1, 4-butanediol |
| Halogen acid | 28% hydrochloric acid | 35% hydrochloric acid | 35% hydrochloric acid | 28% hydrochloric acid |
| Molar ratio of the two | 1：4 | 1：2.4 | 1：4 | 1：5 |
| Reaction temperature | 170℃ | 170℃ | 180℃ | 190℃ |
| Reaction pressure | 5.0MPa | 2.0MPa | 3MPa | 1.5MPa |
| Residence time of the reaction | 30min | 30min | 15min | 30min |
| Conversion rate | 94.5％ | 83.2％ | 64.9％ | 73.3％ |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should be considered within the scope of the present invention.
Claims (9)
1. A continuous process for producing a dihaloalkane from a diol compound, characterized in that the dihaloalkane is continuously synthesized by a microchannel reactor using the diol compound and a hydrohalic acid as substrates, and the synthesis formula for producing the dihaloalkane by the reaction of the diol compound and the hydrohalic acid is:
the continuous method comprises the following steps:
s1, under the condition of room temperature, respectively inputting a diol compound and halogen acid into a mixer by using a metering pump for mixing, preheating, and then, allowing the materials to enter a microchannel reactor at a high temperature section for reaction, wherein the reaction temperature is controlled by an external circulation heat exchange system, and the reaction pressure is controlled by a back pressure valve;
s2, after the reaction is finished, enabling a product to flow out of an outlet of the microchannel reactor, enabling the product to enter a cooling section, enabling the cooled material to enter a liquid separation kettle for standing and liquid separation, and collecting an organic layer;
s3, preheating the organic layer by a metering pump, then feeding the organic layer into a rectifying tower, controlling the temperature and reflux ratio of a reboiler, and collecting fractions at specific temperature to obtain a target product in a product collecting tank.
2. The continuous process for preparing dihaloalkanes according to claim 1, wherein said diol compounds include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, etc., and n includes but is not limited to 1, 2, 3, 4;
the hydrohalic acid comprises hydrochloric acid, hydrobromic acid and hydroiodic acid, and the weight percentage concentration of the hydrohalic acid is as follows: 20 to 38 percent of hydrochloric acid, 10 to 47 percent of hydrobromic acid and 10 to 45 percent of hydroiodic acid.
3. The continuous process for producing a dihaloalkane according to claim 1, wherein the molar ratio of the diol compound to the hydrohalic acid is 1: 1.2-1: 5.
4. the continuous process for producing a dihaloalkane according to claim 1, wherein the diol compound is mixed with a hydrohalic acid at a total flow rate in the range of 10 to 100 ml/min.
5. The continuous process for producing a dihaloalkane according to claim 1, wherein the residence time of the reaction in the microchannel reactor is 5 to 40 min.
6. The continuous process for producing a dihaloalkane according to claim 1, wherein the reaction temperature in the microchannel reactor is 120-190 ℃.
7. The continuous process for producing a dihaloalkane according to claim 1, wherein the reaction pressure in the microchannel reactor is 1.5 to 5.0 MPa.
8. The continuous process for preparing dihaloalkanes according to claim 1, wherein said microchannel reactor is selected from the group consisting of a once-through microchannel chip reactor, a chip reactor with a pulse diameter variable microchannel, a Heart Cell structure microchannel chip reactor with Corning, a capillary coil reactor with a diameter of 0.2-1.0mm, and a fixed bed reactor with an inner diameter of 1-3cm and an inert filler.
9. The continuous process for preparing dihalo-alkane from diol compound as claimed in claim 1, wherein the microchannel reactor material used in the process is polytetrafluoroethylene, glass, silicon carbide, stainless steel coated with corrosion-resistant coating, and various corrosion-resistant metal alloys.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113480400A (en) * | 2021-06-08 | 2021-10-08 | 山东同成医药股份有限公司 | Chloralkane micro-channel continuous reaction method |
| WO2022057220A1 (en) * | 2020-09-17 | 2022-03-24 | 苏州昊帆生物股份有限公司 | Ethionine ester continuous preparation device and method for preparing ethionine ester |
| CN115301172A (en) * | 2022-07-04 | 2022-11-08 | 中国科学院大连化学物理研究所 | System and method for continuously preparing carbamide peroxide by using microreactor |
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| CN115301172A (en) * | 2022-07-04 | 2022-11-08 | 中国科学院大连化学物理研究所 | System and method for continuously preparing carbamide peroxide by using microreactor |
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