CN109400554B - Method and device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate - Google Patents
Method and device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of chemical products, in particular to a method and a device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate, and the method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate comprises the following steps of mixing α -acetyl-gamma-butyrolactone and a sodium formate aqueous solution, introducing chlorine gas for reaction, and then layering the reaction solution, wherein the lower layer material is α -chloro- α -acetyl-gamma-butyrolactone, and the upper layer material is subjected to esterification reaction with methanol to obtain methyl formate.
Description
Technical Field
The invention relates to the technical field of preparation of chemical products, in particular to a method and a device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate.
Background
α -chloro- α -acetyl-gamma-butyrolactone is one of the important synthesis steps for synthesizing vitamin B1. in the prior art, α -chloro- α -acetyl-gamma-butyrolactone is synthesized by adopting a batch reaction, α -acetyl-gamma-butyrolactone, water and sodium bicarbonate are reacted by controlling the temperature under the condition of stirring and introducing chlorine gas.
Then, in the existing synthesis process, a large amount of carbon dioxide is generated in the reaction process, so that the raw material chlorine is carried, the raw material waste is caused, the utilization rate of the chlorine is low, and the safety risk is large. Meanwhile, the obtained carbon dioxide and chlorine tail gas has high treatment difficulty. In addition, in the reaction process, the obtained by-product hydrochloric acid cannot be comprehensively utilized, and a large amount of sodium bicarbonate is consumed, so that the waste of raw and auxiliary materials is caused.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate, which avoids generating a large amount of carbon dioxide in the reaction process, avoids carrying chlorine by the carbon dioxide, avoids collecting carbon dioxide and chlorine by flash evaporation at the same time, can not be recycled, improves the utilization rate of the chlorine, can produce methyl formate by continuously reacting the by-products with methanol after a certain reaction, fully utilizes the by-products generated in the production process to provide the own process requirements, greatly reduces the production cost and improves the environmental protection property.
The second purpose of the invention is to provide a device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate, which has the advantages of simple structure, high device utilization rate and low energy consumption.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and coproducing methyl formate comprises the following steps:
α -acetyl-gamma-butyrolactone and sodium formate water solution, introducing chlorine gas to react, and then layering the reaction solution, wherein the lower layer is α -chloro- α -acetyl-gamma-butyrolactone, and the upper layer is esterified with methanol to obtain methyl formate.
According to the synthetic method, no carbon dioxide is generated in the reaction process, the byproduct hydrochloric acid reacts with sodium formate to generate sodium chloride and formic acid, and the formic acid continuously reacts with methanol to produce methyl formate.
In the method, α -acetyl-gamma-butyrolactone reacts with complete chlorine to obtain reaction liquid containing a main product α -chloro- α -acetyl-gamma-butyrolactone, water, formic acid and sodium chloride, the reaction liquid is sent into a continuous layering unit, the α -chloro- α -acetyl-gamma-butyrolactone is insoluble in water and has high density, the lower layer reaction liquid is collected to be the main product α -chloro- α -acetyl-gamma-butyrolactone, the upper layer reaction liquid contains formic acid and water, the formic acid and water are sent into a reactor, and the esterification reaction is carried out on the upper layer reaction liquid and methanol to obtain a co-product methyl formate.
In the whole process, no carbon dioxide gas is generated, the problem of carrying chlorine and reducing the utilization rate is solved, the utilization rate of the chlorine can reach 99.8%, and meanwhile, even if the chlorine is slightly excessive in order to improve the conversion rate of α -acetyl-gamma-butyrolactone, the chlorine can be independently collected and recovered, and no additional separation treatment is needed.
Preferably, α -acetyl-gamma-butyrolactone and the aqueous solution of sodium formate are mixed in the microreactor and chlorine is introduced into the microreactor.
By carrying out the reaction in the microreactor, the heat exchanger has excellent heat transfer effect and high heat exchange efficiency, maintains stable reaction temperature and effectively avoids the phenomenon of local overtemperature; meanwhile, the method has excellent mass transfer effect, so that chlorine is uniformly distributed in the microreactor, and the polychlorinated side reaction caused by overlarge local chlorine concentration is avoided, thereby further improving the utilization rate of the chlorine and improving the reaction safety. In addition, in the reaction process of the invention, no solid particles are generated, and the micro-channel of the microreactor can not be blocked.
Preferably, after the reaction with chlorine gas, the reaction solution is separated into layers after recovering the chlorine gas by flash evaporation. In the synthesis method, other gas products are not generated, slightly excessive chlorine can be recovered by flash evaporation recovery, the influence of the excessive chlorine on the subsequent steps is avoided, and the chlorine is recovered and then sent into the reactor again for reaction, so that the utilization rate of the chlorine is improved.
Preferably, the flash conditions are: flashing at 10-20 deg.C under negative pressure. More preferably, the negative pressure is from-0.05 MPa to-0.1 MPa. After the reaction is finished, directly feeding the reaction mixture into a negative pressure condition for flash evaporation, wherein the flash evaporation temperature is the reaction temperature.
Preferably, the temperature for the reaction by introducing chlorine is 10-20 ℃. The synthesis method has good reaction uniformity, can properly improve the reaction temperature, can be carried out at the temperature of 20 ℃, and has higher yield of the target product.
When the reaction temperature is properly increased, the temperature of the externally used refrigerant such as condensed circulating water can be correspondingly increased, the utilization rate of equipment is increased, and the energy consumption is reduced.
Preferably, the mole ratio of α -acetyl-gamma-butyrolactone to chlorine is 1: 1.05, the utilization rate of chlorine can reach 99.8%, the chlorine is slightly excessive, so that the reactant α -acetyl-gamma-butyrolactone can completely react, and the excessive chlorine can be recovered without waste.
Preferably, the mass fraction of the sodium formate in the sodium formate aqueous solution is 30-45%, preferably 35-45%, more preferably 40-45%, the mass fraction of the sodium formate in the sodium formate aqueous solution is increased as much as possible, water in a reaction system is reduced, the amount of α -chloro- α -acetyl-gamma-butyrolactone possibly mixed into a water layer in a layering process is reduced, and the yield of a main product is increased.
Preferably, the mole ratio of α -acetyl-gamma-butyrolactone to sodium formate is 1: 1.05-1.2.
Preferably, the temperature of the esterification reaction is 50 to 95 ℃.
Preferably, the mass ratio of the upper layer reaction solution to methanol is 1: 0.18 to 0.3, preferably 1: 0.2 to 0.25. In the synthesis step, the content of formic acid in the obtained upper layer reaction liquid is about 25 wt%, methanol with slight excess is added to ensure that the formic acid is completely reacted, and the rest formic acid can be separated and recovered by a rectifying tower.
Preferably, after the esterification reaction of the upper layer reaction liquid and methanol, methyl formate is collected by primary rectification, and the residual liquid is subjected to secondary rectification, and methanol is collected and recovered.
Preferably, the bottom temperature of the primary rectification is 85-90 ℃, and the top temperature is 32-36 ℃.
Preferably, the bottom temperature of the secondary rectification is 90-95 ℃.
The invention also provides a device for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate, which comprises a chlorination unit and an esterification unit;
the chlorination unit comprises a chlorination reactor and a delayer, and the discharge end of the chlorination reactor is communicated with the delayer; the esterification unit comprises an esterification reactor, a first rectifying tower and a second rectifying tower which are connected in sequence; the upper outlet of the delaminating device is connected with the feed inlet of the esterification reactor.
According to the device, an upper outlet of a layering device of a chlorination reaction unit is connected with a feeding hole of an esterification reactor, formic acid obtained in the chlorination reaction process is fed into the esterification reactor to react with methanol, and the co-production of methyl formate is realized. The device has the advantages of simple structure, high utilization rate of the device and low energy consumption.
Preferably, the chlorination reactor is a microreactor, preferably a microchannel reactor. The feed end of the chlorination reactor is provided with a liquid inlet and a chlorine inlet. As in the different embodiments, a microreactor of the G1 platform device from corning incorporated may be used.
The micro-reactor has excellent heat transfer effect, high heat exchange efficiency, stable reaction temperature maintenance and effective avoidance of local overtemperature; meanwhile, the method has excellent mass transfer effect, so that chlorine is uniformly distributed in the microreactor, and the polychlorinated side reaction caused by overlarge local chlorine concentration is avoided, thereby further improving the utilization rate of the chlorine and improving the reaction safety.
Preferably, the esterification reactor is a microreactor, preferably a microchannel reactor. The feeding end of the esterification reactor is provided with a feeding inlet.
The esterification reactor adopts a micro-reactor, and can accurately regulate and control the temperature of the esterification reaction, so that the esterification reaction is rapid and sufficient, and the reaction efficiency is improved.
Preferably, a flash evaporator is arranged between the discharge end of the chlorination reactor and the feed end of the delaminator. More preferably, the flash vessel is provided with a reaction liquid discharge port and a chlorine gas discharge port, and the reaction liquid discharge port is connected to the fractionator.
Through the setting of flash vessel, can effectively collect excessive chlorine, improve the utilization ratio of raw materials, also avoided the influence of chlorine to follow-up reaction, effectively avoided environmental pollution and improved the security simultaneously.
The chlorine gas discharge port is preferably communicated with a chlorine gas inlet of the micro-pipeline reactor, so that the recycling of excessive chlorine gas is realized, the pollution to the environment is reduced, the utilization rate of raw materials is improved, and the continuous production process is also realized.
Preferably, the top outlet of the second rectification column is connected to the feed inlet of the esterification reactor. Therefore, the excessive methanol can be recycled and used as the raw material of the methyl formate, the utilization rate of the raw material is improved, and the continuous production process is realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the synthetic method, no carbon dioxide is generated in the reaction process, the byproduct hydrochloric acid reacts with sodium formate to generate sodium chloride and formic acid, and the formic acid continuously reacts with methanol to generate methyl formate;
(2) in the invention, because no carbon dioxide gas is generated, the problem of carrying chlorine and reducing the utilization rate is solved, the utilization rate of the chlorine can reach 99.8 percent, and meanwhile, even if the chlorine is slightly excessive in order to improve the conversion rate of α -acetyl-gamma-butyrolactone, the chlorine can be separately collected and recovered without additional separation treatment;
(3) the invention has excellent heat transfer effect, high heat exchange efficiency, stable reaction temperature maintenance and effective avoidance of local overtemperature phenomenon by carrying out reaction in the microreactor; meanwhile, the method has excellent mass transfer effect, so that chlorine is uniformly distributed in the microreactor, and polychlorinated side reactions caused by overlarge local chlorine concentration are avoided, so that the utilization rate of the chlorine and the yield of a main product are further improved, and the reaction safety can be improved;
(4) the device has the advantages of simple structure, high utilization rate and low energy consumption; and an upper outlet of a layering device of the chlorination reaction unit is connected with a feed inlet of the esterification reactor, and formic acid obtained in the chlorination reaction process is fed into the esterification reactor to react with methanol, so that the co-production of methyl formate is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of an apparatus for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to an embodiment of the present invention.
Reference numerals:
1-a chlorination unit; 2-an esterification unit; 11-a chlorination reactor;
12-a flash evaporator; 13-a delayer; 21-an esterification reactor;
22-a first rectification column; 23-a second rectification column; 111-a liquid inlet;
112-chlorine inlet; 121-reaction liquid discharge port; 122-chlorine gas exhaust;
211-feed inlet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Fig. 1 is a schematic structural diagram of an apparatus for synthesizing α -chloro- α -acetyl- γ -butyrolactone and co-producing methyl formate according to an embodiment of the present invention, as shown in fig. 1, the apparatus for synthesizing α -chloro- α -acetyl- γ -butyrolactone and co-producing methyl formate according to the embodiment includes a chlorination unit 1 and an esterification unit 2.
The chlorination unit 1 comprises a chlorination reactor 11 and a delayer 13, wherein the discharge end of the chlorination reactor 11 is communicated with the delayer 13; the esterification unit 2 comprises an esterification reactor 21, a first rectifying tower 22 and a second rectifying tower 23 which are connected in sequence; the upper outlet of the delaminator 13 is connected to the feed inlet of the esterification reactor 21. In the device in the embodiment, an upper outlet of the delayer 13 of the chlorination unit 1 is connected with a feed inlet of the esterification reactor 21, and formic acid obtained in the chlorination reaction process is fed into the esterification reactor 21 to react with methanol, so that co-production of methyl formate is realized. The device has simple structure, high utilization rate and low energy consumption.
In a preferred embodiment of the invention, the chlorination reactor 11 is a microreactor, preferably a microchannel reactor. The micro-reactor has excellent heat transfer effect, high heat exchange efficiency, stable reaction temperature maintenance and effective avoidance of local overtemperature; meanwhile, the method has excellent mass transfer effect, so that chlorine is uniformly distributed in the microreactor, and the polychlorinated side reaction caused by overlarge local chlorine concentration is avoided, thereby further improving the utilization rate of the chlorine and improving the reaction safety.
The feeding end of the chlorination reactor 11 is provided with a liquid inlet 111 and a chlorine inlet 112, wherein the liquid inlet 111 can be used for feeding α -acetyl-gamma-butyrolactone, sodium formate aqueous solution and the like, and the chlorine inlet 112 can be used for introducing chlorine.
In a preferred embodiment of the present invention, esterification reactor 21 is a microreactor, preferably a microchannel reactor. The feed end of esterification reactor 21 is provided with a feed inlet 211. The esterification reactor 21 adopts a micro-reactor, and can accurately regulate and control the esterification reaction temperature, so that the esterification reaction is rapid and sufficient, and the reaction efficiency is improved.
In a preferred embodiment of the invention, a flash evaporator 12 is arranged between the discharge end of the chlorination reactor 11 and the feed end of the delaminator 13. More preferably, the flash evaporator 12 is provided with a reaction liquid discharge port 121 and a chlorine gas discharge port 122, and the reaction liquid discharge port 121 is connected to the delayer 13.
Through the arrangement of the flash evaporator 12, excessive chlorine gas can be effectively collected, the utilization rate of raw materials is improved, the influence of the chlorine gas on subsequent reaction is also avoided, meanwhile, the environmental pollution is effectively avoided, and the safety is improved. After the reaction liquid obtained after the reaction in the chlorination reactor 11 is sent to the flash evaporator 12, as no other gas is generated in the reaction process, chlorine gas is effectively separated and discharged through a flash evaporation process, and is discharged through a chlorine gas discharge port 122 so as to be recovered; the remaining reaction liquid is sent to the delayer 13 through the reaction liquid discharge port 121 for separation of products and other substances.
The chlorine gas outlet 122 is preferably communicated with the chlorine gas inlet 112 of the chlorination reactor 11, and the chlorine gas collected by the flash evaporation process is directly sent to the chlorination reactor 11, so that the recycling of the excessive chlorine gas is realized, the pollution to the environment is reduced, the utilization rate of raw materials is improved, and the continuous production process is also realized.
In a preferred embodiment of the present invention, the specific connection relationship among the esterification reactor 21, the first rectifying tower 22 and the second rectifying tower 23 is that a reaction liquid outlet of the esterification reactor 21 is connected to the middle part of the first rectifying tower 22, methyl formate is continuously produced at the top of the first rectifying tower 22, a bottom outlet of the first rectifying tower 22 is connected to the middle part of the second rectifying tower 23, the remaining liquid is sent to the second rectifying tower 22 for rectification, methanol is recovered at the top of the second rectifying tower 22, and the remaining liquid at the bottom of the second rectifying tower 22 is continuously discharged.
In a preferred embodiment of the present invention, the top outlet of second rectification column 22 is connected to the feed inlet 211 of esterification reactor 21. Therefore, the excessive methanol can be recycled and used as the raw material of the methyl formate, the utilization rate of the raw material is improved, and the continuous production process is realized.
Example 1
The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate comprises the following steps:
(1) α -acetyl-gamma-butyrolactone in 96g, 180g of sodium formate aqueous solution with the mass fraction of 45% and chlorine in 54g are continuously introduced into a micro-pipeline reactor to react at 15-16 ℃, the residence time of reactants in the micro-pipeline reactor is controlled to be 20-30s, and after the reaction is finished, the obtained reaction liquid contains a main product α -chloro- α -acetyl-gamma-butyrolactone, water, formic acid and sodium chloride;
(2) the reacted reaction liquid is sent into a flash evaporator from the discharge end of the micro-pipeline reactor, and is subjected to flash evaporation treatment directly under the negative pressure condition of-0.05 to-0.1 MPa, so that slight excess chlorine gas can be separated out, and 330g of reaction liquid after chlorine discharge is obtained after chlorine discharge is continuously carried out;
(3) feeding the reaction liquid after chlorine discharge into a delayer for continuous delamination, wherein the lower layer substance is α -chloro- α -acetyl-gamma-butyrolactone, and the lower layer substance is discharged and collected to obtain 121g of main product α -chloro- α -acetyl-gamma-butyrolactone and 210g of upper layer substance (containing 52g of formic acid);
(4) mixing the upper-layer substance with 50g of methanol, feeding the mixture into a micro-pipeline reactor for esterification, heating the mixture to 70 ℃ for reaction, controlling the retention time of reactants in the micro-pipeline reactor to be 20-30s, feeding the mixture into a first rectifying tower after the reaction is finished, controlling the tower bottom temperature of the first rectifying tower to be 85 ℃ and the tower top temperature to be 32 ℃, continuously producing 74.5g of methyl formate from the tower top of the first rectifying tower and collecting the methyl formate, feeding liquid at the bottom of the first rectifying tower into a second rectifying tower, controlling the tower bottom temperature of the second rectifying tower to be 95 ℃, continuously collecting methanol from the tower top of the second rectifying tower for recycling and applying, and directly and continuously discharging and collecting residual liquid collected at the tower bottom of the second rectifying tower.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 99.2%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine can reach 99.8%, and the yield of methyl formate is 74.5g and 97%.
Example 2
The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate comprises the following steps:
(1) α -acetyl-gamma-butyrolactone in 96g, 231g of sodium formate aqueous solution with the mass fraction of 35% and chlorine in 54g are continuously introduced into the micro-pipeline reactor to react at 15-16 ℃, the residence time of reactants in the micro-pipeline reactor is controlled to be 20-30s, and after the reaction is finished, the obtained reaction liquid contains main products α -chloro- α -acetyl-gamma-butyrolactone, water, formic acid and sodium chloride;
(2) the reacted reaction liquid is sent into a flash evaporator from the discharge end of the micro-pipeline reactor, and is subjected to flash evaporation treatment directly under the negative pressure condition of-0.05 Pa to-0.1 MPa, so that the slight excess chlorine gas can be separated out, and the reaction liquid after chlorine discharge is obtained after continuous chlorine discharge;
(3) feeding the reaction liquid after chlorine discharge into a delayer for continuous layering, wherein the lower layer substance is α -chloro- α -acetyl-gamma-butyrolactone, and discharging and collecting the lower layer substance to obtain 119g of a main product α -chloro- α -acetyl-gamma-butyrolactone;
(4) mixing the upper-layer substance obtained by separation in the delayer with 50g of methanol, sending the mixture into a micro-pipeline reactor for esterification, heating to 70 ℃ for reaction, controlling the retention time of reactants in the micro-pipeline reactor to be 20-30s, sending the mixture into a first rectifying tower after the reaction is finished, controlling the tower bottom temperature of the first rectifying tower to be 85 ℃ and the tower top temperature to be 32 ℃, continuously producing 73g of methyl formate from the tower top of the first rectifying tower and collecting the methyl formate, sending liquid at the bottom of the first rectifying tower into a second rectifying tower, controlling the tower bottom temperature of the second rectifying tower to be 95 ℃, continuously collecting methanol from the tower top of the second rectifying tower for recycling, and directly and continuously discharging and collecting residual liquid collected at the tower bottom of the second rectifying tower.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 97.5%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of 73g methyl formate is 95%.
Example 3
The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate comprises the following steps:
(1) continuously introducing α -acetyl-gamma-butyrolactone, 270g of sodium formate aqueous solution with the mass fraction of 30% and 54g of chlorine into a micro-pipeline reactor, reacting at 15-16 ℃, controlling the retention time of reactants in the micro-pipeline reactor to be 20-30s, and obtaining reaction liquid containing a main product α -chloro- α -acetyl-gamma-butyrolactone, water, formic acid and sodium chloride after the reaction is finished;
(2) the reacted reaction liquid is sent into a flash evaporator from the discharge end of the micro-pipeline reactor, and is subjected to flash evaporation treatment directly under the negative pressure condition of-0.05 to-0.1 MPa, so that the slight excess chlorine gas can be separated out, and the reaction liquid after chlorine discharge is obtained after continuous chlorine discharge;
(3) feeding the reaction liquid after chlorine discharge into a delayer for continuous layering, wherein the lower layer substance is α -chloro- α -acetyl-gamma-butyrolactone, and discharging and collecting the lower layer substance to obtain 118g of a main product α -chloro- α -acetyl-gamma-butyrolactone;
(4) mixing the upper-layer substance obtained by separation in the delayer with 50g of methanol, sending the mixture into a micro-pipeline reactor for esterification, heating to 70 ℃ for reaction, controlling the retention time of reactants in the micro-pipeline reactor to be 20-30s, sending the mixture into a first rectifying tower after the reaction is finished, controlling the tower bottom temperature of the first rectifying tower to be 85 ℃ and the tower top temperature to be 32 ℃, continuously producing 72.2g of methyl formate from the tower top of the first rectifying tower and collecting the methyl formate, sending liquid at the bottom of the first rectifying tower into a second rectifying tower, controlling the tower bottom temperature of the second rectifying tower to be 95 ℃, continuously collecting the methanol from the tower top of the second rectifying tower for recycling, and directly and continuously discharging and collecting residual liquid collected at the tower bottom of the second rectifying tower.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 96.7%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate is 72.2g and is 94%.
Example 4
This example refers to the method of example 1, with the only difference that: the amount of chlorine used was 56 g.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 99.3%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate 74.5g is 97%.
Example 5
This example refers to the method of example 1, with the only difference that: the amount of chlorine used was 53.5 g.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 99.0%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate 74.5g is 97%.
Example 6
This example refers to the preparation of example 1, with the only difference that: the amount of the sodium formate aqueous solution with the mass fraction of 45 percent is 136 g.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 95%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate is 55g and is 95%.
Example 7
This example refers to the preparation of example 1, with the only difference that: the amount of the sodium formate aqueous solution with the mass fraction of 45 percent is 119 g.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 93%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate is 48.2g and is 95%.
Example 8
This example refers to the preparation of example 1, with the only difference that: the amount of the sodium formate aqueous solution with the mass fraction of 45 percent is 158 g.
The yield of the main product α -chloro- α -acetyl-gamma-butyrolactone in the embodiment is 95.8%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine is high, and the yield of methyl formate is 64g, which is 95%.
Example 9
This example refers to the preparation of example 1, with the only difference that: the amount of methanol used was 42 g. 69g of methyl formate was obtained in this example, and the yield was 90%.
Example 10
This example refers to the preparation of example 1, with the only difference that: the amount of methanol used was 52.5 g. 74.5g of methyl formate was obtained in this example, and the yield was 97%.
Example 11
This example refers to the preparation of example 1, with the only difference that: the amount of methanol used was 38 g. 65g of methyl formate was obtained in this example, and the yield was 85%.
Example 12
This example refers to the preparation of example 1, with the only difference that: the flash evaporation process in step (2) was not performed.
Comparative example 1
Comparative example 1 referring to steps (1) to (3) of example 1 of the present invention, the difference is that: replacing the sodium formate aqueous solution with a saturated aqueous solution of sodium bicarbonate, wherein the mass of the sodium bicarbonate is 100g and step (4) is not included.
Comparative example 2
Comparative example 2 reference is made to steps (1) to (3) of example 1 of the invention, with the difference that the aqueous sodium formate solution is replaced by aqueous sodium bicarbonate (62g of sodium bicarbonate, 192m L of water).
Comparative example 3
Comparative example 2 referring to steps (1) to (3) of example 1 of the present invention, except that an aqueous sodium formate solution was replaced with an aqueous sodium bicarbonate solution (62g of sodium bicarbonate, 192m L of water) and the reaction was carried out in a conventional reaction vessel at a temperature of 15 to 16 ℃.
Experimental example 1
In order to comparatively illustrate the processes of the examples of the present invention and the comparative examples, the yield of the main product (α -chloro- α -acetyl- γ -butyrolactone), the yield of the co-produced product (methyl formate), the utilization rate of the raw material chlorine gas, and the like in each process were tested, and the test results are shown in table 1.
TABLE 1 test results of different methods
In the method, the yield of the main product α -chloro- α -acetyl-gamma-butyrolactone is high and can reach 99.3%, compared with the traditional process, the yield is greatly improved, the utilization rate of chlorine can reach 99.8%, and the yield of the co-production product methyl formate can reach 97%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (27)
1. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and coproducing methyl formate is characterized by comprising the following steps:
α -acetyl-gamma-butyrolactone and sodium formate water solution, introducing chlorine gas to react, and then layering the reaction solution, wherein the lower layer is α -chloro- α -acetyl-gamma-butyrolactone, and the upper layer is esterified with methanol to obtain methyl formate.
2. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 1, wherein the α -acetyl-gamma-butyrolactone and the aqueous solution of sodium formate are mixed in a microreactor, and chlorine gas is introduced into the microreactor.
3. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 1, wherein after the chlorine gas is introduced for reaction, and after the chlorine gas is recovered by flash evaporation, the reaction solution is separated into layers.
4. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 3, wherein the flash evaporation is carried out under negative pressure and at 10-20 ℃.
5. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 4, wherein the negative pressure is-0.05 MPa to-0.1 MPa.
6. The process of claim 1 for the synthesis of α -chloro- α -acetyl- γ -butyrolactone with co-production of methyl formate, wherein the molar ratio of α -acetyl- γ -butyrolactone to chlorine gas is 1: 1 (1-1.05).
7. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 1, wherein the temperature of the reaction of introducing chlorine gas is 10-20 ℃.
8. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 1, wherein the mass fraction of sodium formate in the sodium formate aqueous solution is 30-45%.
9. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 1, wherein the mass fraction of sodium formate in the sodium formate aqueous solution is 35-45%.
10. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone with co-production of methyl formate according to claim 9, wherein the mass fraction of sodium formate in the sodium formate aqueous solution is 40-45%.
11. The process of claim 1 for the synthesis of α -chloro- α -acetyl- γ -butyrolactone with co-production of methyl formate, wherein the molar ratio of α -acetyl- γ -butyrolactone to sodium formate is 1: 1.05-1.2.
12. The method for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduced with methyl formate according to claim 1, wherein the temperature of the esterification reaction is 50-95 ℃.
13. The method for the synthesis α -chloro- α -acetyl- γ -butyrolactone coproduction of methyl formate according to claim 1, wherein the mass ratio of the upper layer material to the methanol is 1: 0.18-0.3.
14. The method for synthesizing α -chloro- α -acetyl- γ -butyrolactone coproduced methyl formate according to claim 13, wherein the mass ratio of the upper layer material to methanol is 1: 0.2-0.25.
15. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and coproducing methyl formate according to claim 1, wherein the esterification reaction of the upper substance and methanol is followed by primary rectification to collect methyl formate, secondary rectification of the residual liquid to collect methanol and recovery.
16. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 15, wherein the temperature of the bottom of the primary rectification is 85-90 ℃ and the temperature of the top of the primary rectification is 32-36 ℃.
17. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and co-producing methyl formate according to claim 15, wherein the bottom temperature of the secondary rectification is 90-95 ℃.
18. The method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and coproducing methyl formate according to claim 1, wherein the device for implementing the method for synthesizing α -chloro- α -acetyl-gamma-butyrolactone and coproducing methyl formate comprises a chlorination unit and an esterification unit;
the chlorination unit comprises a chlorination reactor and a delayer, and the discharge end of the chlorination reactor is communicated with the delayer; the esterification unit comprises an esterification reactor, a first rectifying tower and a second rectifying tower which are connected in sequence; the upper outlet of the delaminating device is connected with the feed inlet of the esterification reactor.
19. The method for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduction methyl formate of claim 18, wherein the chlorination reactor is a microreactor.
20. The process for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduct methyl formate according to claim 19, wherein the chlorination reactor is a microchannel reactor.
21. The process for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduction methyl formate according to claim 19, wherein the feed end of the chlorination reactor is provided with a liquid inlet and a chlorine inlet.
22. The method for synthesizing α -chloro- α -acetyl- γ -butyrolactone with co-production of methyl formate according to claim 18, wherein the esterification reactor is a microreactor.
23. The process for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduct methyl formate according to claim 22, wherein the esterification reactor is a microchannel reactor.
24. The process for the synthesis α -chloro- α -acetyl- γ -butyrolactone coproduction methyl formate of claim 21, wherein a flash vessel is disposed between the discharge end of the chlorination reactor and the feed end of the stratifier.
25. The method for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduction of methyl formate according to claim 24, wherein the flash evaporator is provided with a reaction liquid discharge port and a chlorine gas discharge port, the reaction liquid discharge port being connected to the stratifier.
26. The method for synthesizing α -chloro- α -acetyl- γ -butyrolactone with co-production of methyl formate according to claim 25, wherein the chlorine gas outlet is connected to the chlorine gas inlet of the chlorination reactor.
27. The process for the synthesis of α -chloro- α -acetyl- γ -butyrolactone coproduct methyl formate according to claim 25, wherein the overhead outlet of the second rectification column is connected to the feed inlet of the esterification reactor.
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| CN111116523B (en) * | 2019-12-30 | 2021-09-07 | 浙江新和成股份有限公司 | System and process for producing alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN112480041A (en) * | 2020-12-09 | 2021-03-12 | 京博农化科技有限公司 | Chlorination process of prothioconazole intermediate |
| CN112979461B (en) * | 2021-02-26 | 2022-03-18 | 复旦大学 | Full continuous flow preparation method of 3-chloro-4-oxoacetic acid amyl ester |
| CN115925655B (en) * | 2022-11-29 | 2024-06-21 | 江苏兄弟维生素有限公司 | Process method for synthesizing and co-producing sodium bicarbonate solution by using alpha-chloro-alpha-acetyl-gamma-butyrolactone and application thereof |
| CN115850211B (en) * | 2022-11-29 | 2024-06-21 | 江苏兄弟维生素有限公司 | Process method for synthesizing and co-producing acetamidine hydrochloride by using alpha-chloro-alpha-acetyl-gamma-butyrolactone and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387557A (en) * | 2012-05-08 | 2013-11-13 | 江苏兄弟维生素有限公司 | Continuous synthesis process of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN106008412A (en) * | 2016-05-27 | 2016-10-12 | 江苏兄弟维生素有限公司 | Novel synthesis process for alpha-chloro-alpha-ethanoyl-gamma-butyrolactone |
| CN106588832A (en) * | 2016-12-02 | 2017-04-26 | 连云港市金囤农化有限公司 | Preparation method of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN106966897A (en) * | 2017-03-29 | 2017-07-21 | 江苏兄弟维生素有限公司 | One kind is used for methyl formate continuous esterification synthetic method and device |
-
2018
- 2018-12-25 CN CN201811593983.9A patent/CN109400554B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387557A (en) * | 2012-05-08 | 2013-11-13 | 江苏兄弟维生素有限公司 | Continuous synthesis process of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN106008412A (en) * | 2016-05-27 | 2016-10-12 | 江苏兄弟维生素有限公司 | Novel synthesis process for alpha-chloro-alpha-ethanoyl-gamma-butyrolactone |
| CN106588832A (en) * | 2016-12-02 | 2017-04-26 | 连云港市金囤农化有限公司 | Preparation method of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN106966897A (en) * | 2017-03-29 | 2017-07-21 | 江苏兄弟维生素有限公司 | One kind is used for methyl formate continuous esterification synthetic method and device |
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