CN114425239B - Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt - Google Patents
Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt Download PDFInfo
- Publication number
- CN114425239B CN114425239B CN202011105080.9A CN202011105080A CN114425239B CN 114425239 B CN114425239 B CN 114425239B CN 202011105080 A CN202011105080 A CN 202011105080A CN 114425239 B CN114425239 B CN 114425239B
- Authority
- CN
- China
- Prior art keywords
- gasification
- pyrrolidone
- reaction
- alkali metal
- infiltration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/263—Chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00822—Metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00824—Ceramic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00831—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00869—Microreactors placed in parallel, on the same or on different supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00905—Separation
- B01J2219/00907—Separation using membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a micro-channel infiltration gasification device, which comprises one or more groups of infiltration gasification assembly units; wherein, each infiltration vaporization subassembly unit stacks gradually the reaction base plate, infiltration vaporization membrane and vaporization base plate. The invention also discloses a method for synthesizing pyrrolidone alkali metal salt by using the device.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis processes, and particularly relates to a process for continuously synthesizing pyrrolidone alkali metal salt by taking alkali solid containing alkali metal and 2-pyrrolidone as raw materials.
Background
N-vinylpyrrolidone (NVP) is mainly used for producing polyvinylpyrrolidone (PVP). PVP is a nonionic water-soluble high-molecular fine chemical, has excellent solubility, chemical stability, film forming property, physiological inertia, adhesive capacity and protective adhesive effect, and is internationally considered as one of the most important pharmaceutical synthetic new auxiliary materials. Because of these characteristics, PVP has wide application in industries such as medicine and health, daily chemical industry, pigment coating, office stationery, beverage and food, and the like, and along with the gradual expansion of application fields and market space, the demand of the PVP for the PVP product is also increasingly large, so that the PVP product is in short supply in domestic and foreign markets.
NVP synthesis is a key part of PVP industry chain, and acetylene method is a main process for industrially producing NVP at present. The catalyst used in the synthesis of NVP by acetylene is an alkali metal salt of pyrrolidone, and US5665889 teaches that such catalysts are very sensitive to water and alcohol and that the water and alcohol produced need to be removed in time during the catalyst synthesis to avoid deactivation of the catalyst after contact with trace amounts of water or alcohol during subsequent processes. At present, most processes adopt an intermittent stirred tank process to synthesize the catalyst, and in order to reach the use standard of the catalyst (the content of water or alcohol is below 50 ppm), a long-time reduced pressure distillation process is adopted to synthesize the catalyst and remove the water and the alcohol, so that the process has high energy consumption and poor batch stability. Meanwhile, in order to ensure the activity and stability of the catalyst, a large amount of auxiliary agents are often introduced in the subsequent NVP synthesis process, so that the NVP synthesis cost is further increased.
The osmotic gasification technology has a plurality of successful industrial application examples in the dehydration and dealcoholization of an organic system, and the continuous synthesis of the pyrrolidone alkali metal salt can be realized by combining the micro-channel technology with the osmotic gasification technology, so that the reaction time is greatly shortened, the process energy consumption is reduced, and the batch stability of the NVP synthesis catalyst is ensured. Chinese patent CN101701009a reports a dehydration method of caprolactam potassium salt system, which introduces the dehydration agent into the traditional reduced pressure distillation process, and increases the material consumption and energy consumption of the process itself although obtaining better effect. To date, no technological research report of continuously synthesizing pyrrolidone alkali metal salt has been seen, the invention provides a process strengthening technology based on the coupling of a micro-channel technology and an osmotic gasification technology for synthesizing the pyrrolidone alkali metal salt, the content of water or alcohol in the pyrrolidone alkali metal salt is greatly reduced by a reaction separation coupling method, the dosage of auxiliary agents in the subsequent NVP synthesis process can be reduced, and finally the economy of the NVP synthesis process is improved.
Disclosure of Invention
The invention aims to provide a micro-channel infiltration gasification device and a process for continuously synthesizing pyrrolidone alkali metal salt by using alkali metal-containing alkaline solid and 2-pyrrolidone as raw materials by using the device.
The invention performs continuous synthesis of pyrrolidone alkali metal salt. The technical process adopts a micro-channel permeation gasification device, the 2-pyrrolidone dissolved with alkaline solids is subjected to a reaction process of coupling by-product water or alcohol real-time separation in the micro-channel permeation gasification device, and the pyrrolidone alkali metal salt homogeneous catalyst directly used for NVP synthesis can be obtained after the reaction.
The first aspect of the invention provides a microchannel osmotic gasification device: comprises one or more groups of infiltration gasification assembly units; wherein each infiltration and gasification assembly unit is sequentially laminated with a reaction substrate, an infiltration and gasification membrane and a gasification substrate;
the reaction substrate includes:
a distribution zone, a reaction zone and a collection zone;
the distribution area and the collection area are arranged at two ends of the reaction area and are respectively used for distributing and sending reactants into the reaction area and collecting the reactants in the reaction area;
the reaction zone is formed by one or more sets of fluid channels;
the distribution area is connected with a reactant inlet of the micro-channel infiltration gasification device through a pipeline;
the collecting area is connected with an outlet of the micro-channel infiltration gasification device through a pipeline
A vaporization chamber is formed between the pervaporation membrane and the vaporization substrate, and is configured to allow small molecules generated after reacting the reactants in the fluid channel to enter the vaporization chamber through the pervaporation membrane and to be discharged out of the microchannel pervaporation device.
In a preferred embodiment of the invention, the pervaporation module units can be used alone or in parallel by stacking 2-10 units. The high-throughput pyrrolidone alkali metal salt synthesis process can be realized by superposing and parallel connection of a plurality of permeation and gasification assembly units, each reaction substrate is provided with an independent liquid phase inlet and an independent liquid phase outlet, and a plurality of gasification chambers share a gas phase outlet.
In some preferred embodiments of the present invention, the reaction substrate and the vaporization substrate are made of stainless steel, silicon carbide ceramic, glass, or hastelloy.
In some preferred embodiments of the invention, the pervaporation membrane is selected from GFT polymer membranes, ionic polymer membranes, silicone polymer membranes or cellulose derivative membranes. The organosilicon polymer film is at least one of polydimethylsiloxane, polytrimethylsilane propyne, polyvinyl trimethylsilane, polyvinyl dimethylsilane or polymethyl methacrylate; the fluorine-containing high polymer film is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene or Nafion; the cellulose derivative film is at least one selected from ethyl cellulose, cellulose acetate and cellulose acetate butyrate.
In some preferred embodiments of the present invention, the reaction substrate comprises three main body regions of a distribution region, a reaction region and a collection region, wherein the channel length of the distribution region and the collection region is 10-50mm, the channel width is 1-10mm, the channel length of the reaction region (11) is 300-500mm, the width is 50-500 μm, preferably 100-300 μm, the channel depth is 50-500 μm, preferably 100-300 μm, the length of the reaction substrate is 300-800mm, the width is 200-500mm, and the thickness is 1-5mm.
In some preferred embodiments of the present invention, the pervaporation membrane is only covered over the reaction zone of the reaction substrate, and the pervaporation membrane has a length-width dimension consistent with the reaction zone and a thickness of 100 to 500 μm, preferably 300 to 500 μm.
In some preferred embodiments of the present invention, the vaporization chamber in the inner cavity of the vaporization substrate is consistent with the reaction area of the reaction substrate, the height of the vaporization chamber is 500-800 μm, and the thickness of the vaporization substrate is 1-5mm.
In a second aspect, the invention provides a method for the continuous synthesis of an alkali metal salt of anhydrous pyrrolidone comprising:
(1) Providing the micro-channel infiltration gasification device;
(2) Premixing 2-pyrrolidone with an alkali metal-containing alkaline solid;
(3) Conveying the dissolved liquid-phase material in the step (1) into the fluid channel of the micro-channel permeation gasification device through a reactant inlet of the micro-channel permeation gasification device, and carrying out a synthesis reaction of pyrrolidone alkali metal salt to obtain a 2-pyrrolidone solution containing the pyrrolidone alkali metal salt; meanwhile, negative pressure is formed in the gasification chamber of the infiltration gasification device, so that water or alcohol generated in the synthesis reaction process of the pyrrolidone alkali metal salt is gasified through the infiltration gasification membrane and then separated from reaction products; thus, an alkali metal pyrrolidone salt having a water content of less than 100ppm was obtained.
In a preferred embodiment of the present invention, the alkali metal-containing alkaline solid is selected from at least one of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-amyl alcohol and sodium tert-amyl alcohol.
In a preferred embodiment of the invention, the mass fraction of the alkali metal-containing alkaline solid after mixing with 2-pyrrolidone is between 0.5 and 50%, preferably between 0.5 and 10%. The temperature of the mixing process is 40-90 ℃, preferably 60-80 ℃. For the mass fraction of the alkali metal-containing alkaline solid, too high a concentration is not preferable because the viscosity becomes large and is not suitable for the apparatus of the present invention.
In a preferred embodiment of the invention, the residence time of the liquid phase material in the microchannel osmotic gasifying device is from 10 to 30min, the reaction temperature is from 90 to 140 ℃, preferably from 100 to 120 ℃.
In a preferred embodiment of the invention, the negative pressure formed in the gasification chamber has a pressure of 5-200mbar
In a preferred embodiment of the invention, the negative pressure formed in the gasification chamber has a pressure of 10-50mbar. The pressure is in the range, so that the water gasification in the system can be better promoted, and a more efficient dehydration separation effect is realized.
Compared with the prior art, the technology of the invention adopts the micro-channel infiltration gasification device to continuously synthesize the pyrrolidone alkali metal salt, the reaction time is greatly shortened, the quality and stability of the product are greatly improved, the atom economy is high, the three wastes are less discharged, the process economy is greatly improved, the process safety is also improved, and the production of the pyrrolidone alkali metal salt with high space-time yield can be realized by a multi-unit parallel connection mode. In addition, the water content of the pyrrolidone alkali metal salt obtained by the process is extremely low, the use amount of the auxiliary agent can be greatly reduced in the NVP synthesis process, and the cost of the subsequent NVP synthesis process is reduced.
Drawings
FIG. 1 is a process flow diagram of a method for continuously synthesizing an alkali metal salt of anhydrous pyrrolidone according to the present invention.
Fig. 2 is a schematic structural diagram of a reaction substrate in the micro-channel infiltration gasification apparatus according to the present invention.
Fig. 3 is an assembled schematic diagram of the micro-channel infiltration gasification device provided by the invention.
In the figure: 1-2-pyrrolidone; 2-an alkali metal-containing alkaline solid; 3-premixing a kettle; 4-a advection pump; 5-micro-channel infiltration gasification device; 6-a recovery tank; 7-a vacuum pump; alkali metal 8-pyrrolidone salts; 9-liquid phase inlet; 10-distribution area; 11-reaction zone; 12-a collection zone; 13-a liquid phase outlet; 14-a gas phase outlet; 15-a gasification chamber; 16-fluid channel; 17-a reaction substrate; 18-infiltrating a gasification membrane; 19-vaporizing the substrate.
Detailed Description
The present invention will be further described in detail with reference to examples, but the scope of the present invention is not limited to the scope of the examples.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As shown in fig. 1 and 2 of the present invention, the method for continuously synthesizing an alkali metal pyrrolidone salt of the present invention comprises:
1) Premixing and dissolving raw materials: adding 2-pyrrolidone and alkali metal-containing alkaline solid into a premixing stirring kettle (3), and dissolving the alkaline solid into the 2-pyrrolidone under the condition of a certain temperature and a certain residence time by continuous stirring.
2) Synthesis of pyrrolidone alkali metal salt: and (2) conveying the liquid-phase material dissolved in the step (1) into a fluid channel (16) of a micro-channel permeation gasification device (5) through a liquid-phase inlet (9) by a advection pump (4), and carrying out a synthesis reaction of pyrrolidone alkali metal salt at a certain temperature to obtain a 2-pyrrolidone solution containing the pyrrolidone alkali metal salt, wherein a liquid-phase product collected through a liquid-phase outlet (13) can be directly used for synthesizing N-vinyl pyrrolidone. The micro-channel infiltration gasification device forms a negative pressure environment in a gasification chamber (15) of the infiltration gasification membrane through a gas phase outlet (14), a large amount of water or alcohol can be generated in the synthesis reaction process of the pyrrolidone alkali metal salt, and small molecules can be gasified after passing through the infiltration gasification membrane and separated from a liquid phase reaction main body, and are collected in a recovery tank (6) after being cooled.
In the continuous synthesis of alkali metal pyrrolidones, alkali metal-containing alkaline solids in the preparation step of alkali metal pyrrolidones include potassium hydroxide, sodium hydroxide, potassium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-amyl alcohol, sodium tert-amyl alcohol. The mass fraction of the alkali metal-containing alkaline solid after mixing with 2-pyrrolidone is between 0.5 and 10%, the temperature during mixing is between 40 and 90 ℃, preferably between 60 and 80 ℃. The residence time in the microchannel permeation gasification device in the synthesis process of the pyrrolidone alkali metal salt is 10-30min, and the reaction temperature is 90-140 ℃, preferably 100-120 ℃. During the synthesis of the alkali metal pyrrolidone salts, the pressure on the negative pressure side of the osmotic vaporization membrane is 5-200mbar, preferably 10-50mbar.
As shown in fig. 2 and 3, the micro-channel infiltration gasification device of the invention is of a plate-type laminated structure, an infiltration gasification assembly unit is formed by a reaction substrate (17), an infiltration gasification membrane (18) and a gasification substrate (19), a high-flux pyrrolidone alkali metal salt synthesis process can be realized by superposing and parallel connection of a plurality of infiltration gasification assembly units, each reaction substrate is provided with an independent liquid phase inlet (9) and a liquid phase outlet (13), and a plurality of gasification chambers (15) share one gas phase outlet (14). The infiltration gasification assembly unit can be singly used or can be overlapped and connected in parallel by 2-10 units, the reaction substrate (17) and the gasification substrate (19) can be made of various materials such as stainless steel, silicon carbide ceramics, special glass, hastelloy and the like, and the infiltration gasification membrane (18) can be a GFT polymer membrane, an ionic polymer membrane, an organosilicon polymer membrane (polydimethylsiloxane, polytrimethylsilpropyne, polyvinyltrimethylsilane, polyvinyldimethylsilane, polymethyl methacrylate), a fluorine-containing high polymer membrane (polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, nafion), a cellulose derivative membrane (ethylcellulose, cellulose acetate butyrate) and the like. The reaction substrate (17) comprises three main body areas of a distribution area (10), a reaction area (11) and a collection area (12), wherein the channel length of the distribution area (10) and the collection area (11) is 10-50mm, the channel width is 1-10mm, the channel length of the reaction area (11) is 300-500mm, the width is 50-500 mu m, preferably 100-300 mu m, the channel depth is 50-500 mu m, preferably 100-300 mu m, the length of the reaction substrate is 300-800mm, the width is 200-500mm, and the thickness is 1-5mm. The infiltration and vaporization film (18) is only covered on the upper part of the reaction zone (11) of the reaction substrate (17), and the length and width dimensions of the infiltration and vaporization film are consistent with those of the reaction zone (11), and the thickness is 100-500 mu m, preferably 300-500 mu m. The inner cavity vaporizing chamber (15) of the vaporizing substrate (19) is consistent with the reaction area (11) of the reaction substrate, the height of the vaporizing chamber (15) is 500-800 mu m, and the thickness of the vaporizing substrate is 1-5mm.
Example 1 device construction
The micro-channel infiltration gasification device (5) is characterized in that a main body is formed by machining stainless steel 316L, micron-sized grooves are manufactured on a reaction substrate (17) through precision machining, a GFT polymer film is selected as an infiltration gasification film (18), the reaction substrate (17), the infiltration gasification film (18) and a gasification substrate (19) are sequentially pressed and sealed to form a fluid channel (16) and a gasification chamber (15) which are divided into the middle by the infiltration gasification film (18), wherein the thickness of the reaction substrate (17) is 2mm, the thickness of the infiltration gasification film (18) is 300 mu m, the thickness of the gasification substrate (19) is 2mm, the whole width is 400mm, the length is 600mm, and the specific arrangement and the specific size in the reaction substrate (17) are as follows: the width of the channels of the distribution area (10) and the collection area (12) is 1mm, the length is 20mm, the width of the channels of the reaction area (11) is 300 mu m, and the length is 500mm.
Referring to the schematic diagram of the device shown in fig. 1, a device for continuously synthesizing pyrrolidone alkali metal salt is constructed, potassium hydroxide is dissolved in 2-pyrrolidone in a premixing kettle (3), the potassium hydroxide is conveyed into a micro-channel permeation gasification device (5) from a liquid phase inlet through a advection pump (4), water generated in the process of the reaction is pumped out in a gasification chamber (15) to form a negative pressure environment through a vacuum pump (7), the micro-channel permeation gasification device (5) is subjected to temperature control through an external circulation oil bath, and pyrrolidone potassium salt can be collected from a liquid phase outlet (13) of the device.
EXAMPLE 2 Synthesis of alkali metal pyrrolidone salts
Using the apparatus set up in example 1, dissolution of potassium hydroxide in 2-pyrrolidone was carried out in a premix tank (3) at 80 ℃ for a residence time of 10min, wherein the mass fraction of potassium hydroxide was 5%; a advection pump (4) is used for conveying liquid-phase raw materials to enter a micro-channel permeation gasification device (5) from a liquid-phase inlet (9), the reaction temperature is 120 ℃, the reaction residence time is 20min, the pressure of a gasification chamber (15) is 50mbar, moisture is collected in a recovery tank after being cooled through a gas-phase outlet (14), pyrrolidone containing pyrrolidone potassium salt is collected by a liquid-phase outlet (13), a product analysis result shows that the water content of the pyrrolidone potassium salt is 10ppm, and the pyrrolidone potassium salt can be used as a catalyst to realize the NVP yield of 76.5% in the NVP synthesis reaction process (180 ℃,1.2MPa and 2 h).
EXAMPLE 3 Synthesis of alkali metal pyrrolidone salts
Using the apparatus set up in example 1, dissolution of potassium hydroxide in 2-pyrrolidone was carried out in a premix tank (3) at 80 ℃ for a residence time of 10min, wherein the mass fraction of potassium hydroxide was 5%; a advection pump (4) is used for conveying liquid-phase raw materials to enter a micro-channel permeation gasification device (5) from a liquid-phase inlet (9), the reaction temperature is 100 ℃, the reaction residence time is 15min, the pressure of a gasification chamber (15) is 80mbar, moisture is collected in a recovery tank after being cooled through a gas-phase outlet (14), pyrrolidone containing pyrrolidone potassium salt is collected by a liquid-phase outlet (13), a product analysis result shows that the water content of the pyrrolidone potassium salt is 50ppm, and the pyrrolidone potassium salt can be used as a catalyst to realize the NVP yield of 74.2% in the NVP synthesis reaction process (180 ℃,1.2MPa and 2 h).
EXAMPLE 4 Synthesis of alkali metal pyrrolidone salts
Using the apparatus set up in example 1, dissolution of potassium hydroxide in 2-pyrrolidone was carried out in a premix tank (3) at 80 ℃ for a residence time of 10min, wherein the mass fraction of potassium hydroxide was 5%; a advection pump (4) is used for conveying liquid-phase raw materials to enter a micro-channel permeation gasification device (5) from a liquid-phase inlet (9), the reaction temperature is 140 ℃, the reaction residence time is 10min, the pressure of a gasification chamber (15) is 150mbar, moisture is collected in a recovery tank after being cooled through a gas-phase outlet (14), pyrrolidone containing pyrrolidone potassium salt is collected by a liquid-phase outlet (13), a product analysis result shows that the water content of the pyrrolidone potassium salt is 80ppm, and the pyrrolidone potassium salt can be used as a catalyst to realize the NVP yield of 68.2% in the NVP synthesis reaction process (180 ℃,1.2MPa and 2 h).
EXAMPLE 5 Synthesis of alkali metal pyrrolidone salts
Using the apparatus set up in example 1, dissolution of potassium hydroxide in 2-pyrrolidone was carried out in a premix tank (3) at 80 ℃ for a residence time of 10min, wherein the mass fraction of potassium hydroxide was 5%; a advection pump (4) is used for conveying liquid-phase raw materials to enter a micro-channel permeation gasification device (5) from a liquid-phase inlet (9), the reaction temperature is 90 ℃, the reaction residence time is 30min, the pressure of a gasification chamber (15) is 200mbar, moisture is collected in a recovery tank after being cooled through a gas-phase outlet (14), pyrrolidone containing pyrrolidone potassium salt is collected by a liquid-phase outlet (13), a product analysis result shows that the water content of the pyrrolidone potassium salt is 500ppm, and the pyrrolidone potassium salt can be used as a catalyst to realize the NVP yield of 46.4% in the NVP synthesis reaction process (180 ℃,1.2MPa and 2 h).
EXAMPLE 6 Synthesis of alkali metal salt of pyrrolidone
Using the apparatus set up in example 1, dissolution of potassium hydroxide in 2-pyrrolidone was carried out in a premix tank (3) at 80 ℃ for a residence time of 10min, wherein the mass fraction of potassium hydroxide was 5%; a advection pump (4) is used for conveying liquid-phase raw materials to enter a micro-channel permeation gasification device (5) from a liquid-phase inlet (9), the reaction temperature is 120 ℃, the reaction residence time is 20min, the pressure of a gasification chamber (15) is 100mbar, moisture is collected in a recovery tank after being cooled through a gas-phase outlet (14), pyrrolidone containing pyrrolidone potassium salt is collected by a liquid-phase outlet (13), a product analysis result shows that the water content of the pyrrolidone potassium salt is 200ppm, and the pyrrolidone potassium salt can be used as a catalyst to realize the NVP yield of 54.7% in the NVP synthesis reaction process (180 ℃,1.2MPa and 2 h).
Comparative example 1
The synthesis of the alkali metal pyrrolidone salts was carried out using prior art equipment.
The synthesis of pyrrolidone alkali metal salt is carried out by using a reduced pressure distillation device, potassium hydroxide is added into a kettle to dissolve the pyrrolidone alkali metal salt in 2-pyrrolidone, the reaction temperature is 120 ℃, the reaction residence time is 120min, the reaction pressure is 50mbar, the analysis result of the product shows that the water content of the pyrrolidone potassium salt is 100ppm, and the pyrrolidone potassium salt can realize the NVP yield of 63.2 percent in the NVP synthesis reaction process (180 ℃,1.2MPa,2 h) by taking the pyrrolidone potassium salt as a catalyst
TABLE 1
As can be seen from examples and comparative examples, the reaction time required for the synthesis of pyrrolidone alkali metal salt using a reduced pressure distillation apparatus in the prior art is much longer than that required for the synthesis of pyrrolidone alkali metal salt using the microchannel permeation gasification apparatus of the present invention.
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present invention is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (9)
1. A method of synthesizing an anhydrous alkali metal pyrrolidone salt comprising:
(1) Providing a microchannel infiltration gasification device comprising one or more groups of infiltration gasification assembly units; wherein each infiltration and gasification assembly unit comprises a reaction substrate, an infiltration and gasification membrane and a gasification substrate which are sequentially laminated;
the reaction substrate includes:
a distribution zone, a reaction zone and a collection zone;
the distribution area and the collection area are arranged at two ends of the reaction area and are respectively used for distributing and sending reactants into the reaction area and collecting the reactants in the reaction area;
the reaction zone is formed by one or more sets of fluid channels;
the distribution area is connected with a reactant inlet of the micro-channel infiltration gasification device through a pipeline;
the collecting area is connected with an outlet of the micro-channel infiltration gasification device through a pipeline;
a gasification chamber is formed between the infiltration gasification membrane and the gasification substrate, and small molecules generated after the reaction of reactants in the fluid channel enter the gasification chamber through the infiltration gasification membrane and are discharged out of the micro-channel infiltration gasification device;
(2) Premixing 2-pyrrolidone with an alkali metal-containing alkaline solid;
(3) Conveying the liquid-phase material dissolved in the step (2) into the fluid channel of the micro-channel permeation gasification device through a reactant inlet of the micro-channel permeation gasification device, and carrying out a synthesis reaction of pyrrolidone alkali metal salt to obtain a 2-pyrrolidone solution containing the pyrrolidone alkali metal salt; meanwhile, negative pressure is formed in the gasification chamber of the infiltration gasification device, so that water or alcohol generated in the synthesis reaction process of the pyrrolidone alkali metal salt is gasified through the infiltration gasification membrane and then separated from reaction products; thus, an alkali metal pyrrolidone salt having a water content of less than 100ppm was obtained.
2. The method of claim 1, wherein the pervaporation module units are used alone or in parallel by stacking 2-10 units.
3. The method of claim 1 or 2, wherein the reaction substrate and the vaporization substrate are made of stainless steel, silicon carbide ceramic, glass, or hastelloy.
4. The method of claim 1 or 2, wherein the pervaporation membrane is selected from GFT polymer membranes, ionic polymer membranes, silicone polymer membranes or cellulose derivative membranes.
5. The method of claim 1, wherein the alkali metal-containing alkaline solid is selected from at least one of potassium hydroxide, sodium hydroxide, potassium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, and sodium tert-butoxide.
6. The method according to claim 1 or 5, wherein the mass fraction of the alkali metal-containing alkaline solid after mixing with 2-pyrrolidone is between 0.5 and 50% and the temperature of the mixing process is 40-90 ℃.
7. The process of claim 1, wherein the liquid phase material has a residence time of 10-30min in the microchannel osmotic gasification device and a reaction temperature of 90-140 ℃.
8. The method according to claim 1, wherein the negative pressure formed in the gasification chamber has a pressure of 5-200mbar.
9. The method of claim 8, wherein the negative pressure formed in the gasification chamber is at a pressure of 10-50mbar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011105080.9A CN114425239B (en) | 2020-10-15 | 2020-10-15 | Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011105080.9A CN114425239B (en) | 2020-10-15 | 2020-10-15 | Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114425239A CN114425239A (en) | 2022-05-03 |
| CN114425239B true CN114425239B (en) | 2023-05-02 |
Family
ID=81308882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011105080.9A Active CN114425239B (en) | 2020-10-15 | 2020-10-15 | Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114425239B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635117A (en) * | 2015-10-30 | 2017-05-10 | 中国石油化工股份有限公司 | A fischer-tropsch synthetic reaction method |
| CN109293525A (en) * | 2018-09-26 | 2019-02-01 | 山东新和成精化科技有限公司 | A kind of micro passage reaction and the method for preparing N- alkyloxy oxalyl alanine ester using the micro passage reaction |
| CN110903229A (en) * | 2019-12-19 | 2020-03-24 | 清华大学 | Synthesis method of N-vinyl pyrrolidone |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4115399A (en) * | 1976-03-22 | 1978-09-19 | Chevron Research Company | Preparation of catalyst for the polymerization of 2-pyrrolidone |
| CN105013417B (en) * | 2015-06-04 | 2017-04-19 | 南京工业大学 | Continuous esterification micro-reaction device and micro-reaction system composed of same |
| CN106432028B (en) * | 2016-08-26 | 2019-10-25 | 衢州建华东旭助剂有限公司 | A kind of preparation method and its usage of the 2-Pyrrolidone solution of alkali metal 2-Pyrrolidone salt |
| CN110283056A (en) * | 2019-07-08 | 2019-09-27 | 万华化学集团股份有限公司 | A kind of method that micro passage reaction continuously synthesizes 4- ketoisophorone |
-
2020
- 2020-10-15 CN CN202011105080.9A patent/CN114425239B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635117A (en) * | 2015-10-30 | 2017-05-10 | 中国石油化工股份有限公司 | A fischer-tropsch synthetic reaction method |
| CN109293525A (en) * | 2018-09-26 | 2019-02-01 | 山东新和成精化科技有限公司 | A kind of micro passage reaction and the method for preparing N- alkyloxy oxalyl alanine ester using the micro passage reaction |
| CN110903229A (en) * | 2019-12-19 | 2020-03-24 | 清华大学 | Synthesis method of N-vinyl pyrrolidone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114425239A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102101847B (en) | Method for preparing N-methyl-N'-(2-chloroethyl)piperazine | |
| CN113117618B (en) | Continuous flow reaction device and method for synthesizing bis (fluorosulfonyl) imide through flow based on same | |
| CN114425239B (en) | Microchannel permeation gasification device and method for synthesizing pyrrolidone alkali metal salt | |
| CN111484537A (en) | Method for preparing Rudesiwei key intermediate by using microchannel reaction device | |
| CN111440215A (en) | Method for preparing Reidesvir by using microchannel reaction device | |
| CN104130198B (en) | 2-amino-4,6-dimethoxypyridin and preparation method thereof | |
| CN113149989A (en) | Method for preparing medicine and medicine intermediate by continuous solid-liquid-gas three-phase reaction | |
| CN113943252A (en) | Pyrazolidinesulfonyl fluoride compounds and preparation method thereof | |
| CN110256334A (en) | A kind of process for catalytic synthesis and preparation facilities of penta chloropyridine | |
| CN109607920A (en) | UF membrane-hydrolysis process waste water ethamine production system and technique | |
| CN102863361A (en) | Chiral catalytic synthesis method of thiamphenicol | |
| CN109082450B (en) | Method for producing sitagliptin free base by using continuous flow technology | |
| CN111825553A (en) | Preparation method of methyl acetoacetate | |
| CN113603575A (en) | Synthetic method of 4, 4-dimethoxy-2-butanone | |
| CN1911901A (en) | Production technology of formamide | |
| CN111793084B (en) | Microchannel reactor and preparation method of high-content dichlorvos | |
| CN111116520B (en) | Process for producing epichlorohydrin by oxidizing chloropropene with titanium-silicon molecular sieve as catalyst | |
| CN112552245B (en) | Synthesis method of Favipiravir | |
| CN112812071A (en) | Method for continuously synthesizing 1H-1,2, 3-triazole by using microchannel reactor | |
| CN107216241B (en) | Optically active 1, 5-pentanediol derivative and synthetic method and application thereof | |
| CN111056915A (en) | Synthesis method of 1, 2-dialkyl-1, 2-diaryl acetylene cyclobutane | |
| CN113461607B (en) | Method for preparing dortefravir intermediate DTG-4-2 based on continuous flow micro-reaction technology | |
| CN115784894B (en) | Refining method of ultra-high purity sodium p-nitrophenolate | |
| CN111732533B (en) | Method for preparing N- (6-chloro-3-picolyl) methylamine by micro-channel reactor | |
| CN112979560B (en) | Method for preparing uracil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |