CN111841403A - Solution preparation device for solid materials, and removing method and removing system for peroxide in caprolactone synthesis system - Google Patents
Solution preparation device for solid materials, and removing method and removing system for peroxide in caprolactone synthesis system Download PDFInfo
- Publication number
- CN111841403A CN111841403A CN202010767285.7A CN202010767285A CN111841403A CN 111841403 A CN111841403 A CN 111841403A CN 202010767285 A CN202010767285 A CN 202010767285A CN 111841403 A CN111841403 A CN 111841403A
- Authority
- CN
- China
- Prior art keywords
- kettle
- reduction reaction
- volatile
- caprolactone
- solid
- 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.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/60—Safety arrangements
- B01F35/605—Safety devices concerning the operation of the mixer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F21/00—Dissolving
- B01F21/10—Dissolving using driven stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/70—Mixers specially adapted for working at sub- or super-atmospheric pressure, e.g. combined with de-foaming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/181—Preventing generation of dust or dirt; Sieves; Filters
- B01F35/184—Preventing generation of dust
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/181—Preventing generation of dust or dirt; Sieves; Filters
- B01F35/189—Venting, degassing or ventilating of gases, fumes or toxic vapours during 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a solution preparation system of a solid material, which can avoid dust generation in the preparation process of the solution of the reducing solid material, reduce labor intensity and reduce health injury of operators and is suitable for continuous and automatic production; and can utilize a vacuum system, realize multiple material, a plurality of mixing apparatus's automatic material loading and stirring, when improving mixing efficiency, can reduce equipment purchase and running cost. The peroxide reduction equipment module reduces the loss of caprolactone products while removing residual peroxide, and reduces the emission of polluting gases by utilizing a volatile material recovery system, so that the peroxide reduction equipment module is more economic and environment-friendly. The invention also provides a method and a device for removing peroxide in the caprolactone synthesis system.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a solution preparation device for solid materials, a method and a device for removing peroxide in a caprolactone synthesis system.
Background
As an important fine chemical product, caprolactone has wide application. On one hand, the polycaprolactone material has excellent biocompatibility and absorbability, is approved by the FDA in the United states to be implanted into a human body for use, and has wide application prospect in the fields of high-added-value medical materials such as drug controlled release carriers, absorbable sutures, artificial cartilages, artificial skins, blood vessels and the like. With the continuous expansion of the application field of caprolactone, the research on the synthesis method is continuously innovated.
At present, the method for synthesizing caprolactone suitable for large-scale production and application is mainly a cyclohexanone catalytic oxidation method. In this method, a certain amount of peroxide usually remains in the reaction system after the reaction is completed. The residual peroxide is mixed with unreacted cyclohexanone and produced-caprolactone, which brings great potential safety hazard to the subsequent processes of distillation, rectification and purification of-caprolactone. Therefore, the method has important significance in developing safe, efficient and environment-friendly residual peroxide removing equipment and a removing method aiming at a caprolactone synthesis reaction system.
Disclosure of Invention
The invention aims to provide a solution preparation device for solid materials, a method and a device for removing peroxide in a caprolactone synthesis system.
The invention provides a solution preparation system of a solid material, which comprises a weighing and feeding system, a material mixing kettle, a volatile material recovery system, a tail gas treatment system and a vacuum system which are sequentially communicated;
a solid feeding hole is formed in the bottom of the material mixing kettle, and a volatile matter outlet is formed in the top of the material mixing kettle;
the volatile material recovery system comprises a heat exchanger, an inlet of the volatile material recovery system is communicated with the volatile matter outlet, an outlet of the volatile material recovery system is communicated with the tail gas treatment system, and the volatile material recovery system is provided with a backflow port for backflow of recovered volatile materials to the material mixing kettle;
the weighing and feeding system comprises weighing equipment and a suction pipe, wherein the suction pipe is communicated with a solid feeding hole in the bottom of the material mixing kettle through an inverse U-shaped raising pipeline.
Preferably, a stirring device and a bubble cutting sieve plate are arranged in the material mixing kettle;
the aperture of the bubble cutting sieve plate is 0.1-10 mm.
Preferably, the material mixing kettle is internally provided with a coil pipe, and the outside of the material mixing kettle is provided with a jacket for introducing a refrigerant or a heating medium to perform heat exchange with materials in the kettle.
Preferably, a filter screen is arranged at the pipe orifice of the material suction pipe.
The invention provides a device for removing peroxide in a caprolactone synthesis system, which comprises a reduction reaction kettle, a reflux condenser and a vacuum system;
the top of the reduction reaction kettle is provided with a reducing solution feeding port which is communicated with a reducing solution preparation system; the reducing solution preparation system is a solution preparation system of the solid material according to any one of claims 1 to 4;
the top of the reduction reaction kettle is provided with a volatile matter outlet which is communicated with a reflux condenser;
the reduction reaction kettle is internally provided with a coil pipe, and the outside of the reduction reaction kettle is provided with a jacket for introducing a refrigerant or a heating medium to carry out heat exchange with materials in the kettle.
The invention provides a method for removing peroxide in a caprolactone synthesis system, which comprises the following steps:
A) the removing device of claim 5 is used for feeding liquid materials into a material mixing kettle, wherein under the vacuum condition, a solid reducing agent is sucked into the material mixing kettle from a solid feeding hole at the bottom through a weighing and feeding system and is mixed with the liquid materials under the cooling environment to obtain a reducing solution;
B) adding the reducing solution into a reduction reaction kettle through a reducing solution adding port, mixing with a caprolactone synthesis reaction solution, and carrying out reduction reaction;
C) separating the reduction reaction solution obtained in the step B) to obtain a caprolactone organic phase.
Preferably, the solid reducing agent is one or more of sodium sulfide, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfate, potassium sulfide, potassium sulfite, potassium bisulfite, potassium metabisulfite, potassium thiosulfate, ammonium sulfide, ammonium sulfite, ammonium bisulfite, ammonium metabisulfite and ammonium thiosulfate;
the mass concentration of the reducing solution is 0.1-50%.
Preferably, the vacuum degree in the step A) is 0.02-0.1 MPa.
Preferably, the temperature of the reduction reaction is-5 to 20 ℃; the time of the reduction reaction is 1-5 hours.
Preferably, in the volatile material recovery system, the inlet temperature of a refrigerant is-20 to 10 ℃, and the outlet temperature is-15 to 30 ℃;
the temperature of the refrigerant in the reflux condenser is-20-30 ℃.
The invention provides a solution preparation system of a solid material, which comprises a weighing and feeding system, a material mixing kettle, a volatile material recovery system, a tail gas treatment system and a vacuum system which are sequentially communicated; a solid feeding hole is formed in the bottom of the material mixing kettle, and a volatile matter outlet is formed in the top of the material mixing kettle; the volatile material recovery system comprises a heat exchanger, an inlet of the volatile material recovery system is communicated with the volatile matter outlet, an outlet of the volatile material recovery system is communicated with the tail gas treatment system, and the volatile material recovery system is provided with a backflow port for backflow of recovered volatile materials to the material mixing kettle; the weighing and feeding system comprises weighing equipment and a material sucking pipe arranged above the weighing equipment, wherein the material sucking pipe is communicated with a solid feeding hole in the bottom of the material mixing kettle through an inverse U-shaped raising pipeline. The reductive solution preparation system is utilized, so that dust generated in the reductive solid material solution preparation process can be avoided, the labor intensity is reduced, the health injury of operators is reduced, and the reductive solution preparation system is suitable for continuous and automatic production; and can utilize a vacuum system, realize multiple material, a plurality of mixing apparatus's automatic material loading and stirring, when improving mixing efficiency, can reduce equipment purchase and running cost. The peroxide reduction equipment module reduces the loss of caprolactone products while removing residual peroxide, and reduces the emission of polluting gases by utilizing a volatile material recovery system, so that the peroxide reduction equipment module is more economic and environment-friendly.
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, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of the solution preparation system for solid materials according to the present invention;
FIG. 2 is a schematic diagram of a solution dispensing system for solid materials in accordance with the present invention;
FIG. 3 is a schematic view of the composition of the tail gas treatment system of the present invention;
FIG. 4 is a schematic view of the structure of a reduction reaction apparatus according to the present invention;
among them, in fig. 1, fig. 2, fig. 3, fig. 4:
the system comprises a weighing and feeding system (1), a material mixing kettle (2), a volatile material recovery system (3), a tail gas treatment system (4), a vacuum system (5) and a remote control system (6);
the device comprises a material mixing kettle (7), a solid material inlet (8), a liquid material (9), a weighing device (10), an automatic control material suction valve (11), a material suction pipe (12), a remote control system host (13), a filter screen (14), an inverted U-shaped raising pipeline (15), a bubble cutting sieve plate (16), a stirring paddle (17), a jacket (18), a coil pipe (19), a heat exchanger (20), a tail gas treatment device (21) and a vacuum pump (22);
an acid gas treatment module (23), an alkaline gas treatment module (24) and an activated carbon adsorption treatment module (25);
a reducing solution feed inlet (26), -caprolactone synthesis reaction solution (27), a reflux condenser (28), a reduction reaction temperature regulating system (29) and a vacuum system (30).
Detailed Description
The invention provides a solution preparation system of a solid material, which comprises a weighing and feeding system, a material mixing kettle, a volatile material recovery system, a tail gas treatment system and a vacuum system which are sequentially communicated;
a solid feeding hole is formed in the bottom of the material mixing kettle, and a volatile matter outlet is formed in the top of the material mixing kettle;
the volatile material recovery system comprises a heat exchanger, an inlet of the volatile material recovery system is communicated with the volatile matter outlet, an outlet of the volatile material recovery system is communicated with the tail gas treatment system, and the volatile material recovery system is provided with a backflow port for backflow of recovered volatile materials to the material mixing kettle;
the weighing and feeding system comprises weighing equipment and a material sucking pipe arranged above the weighing equipment, wherein the material sucking pipe is communicated with a solid feeding hole in the bottom of the material mixing kettle through an inverse U-shaped raising pipeline.
In the invention, the solution preparation system of the solid materials is suitable for the solution preparation of most solid materials, in particular to granular solid materials or powdery solid materials which are easy to generate dust.
In the invention, the solution preparation system of the solid material comprises a weighing and feeding system, the weighing and feeding system comprises a weighing device and a material suction pipe, and the material suction pipe is provided with a material suction valve with automatic control. The weighing information of the weighing equipment can be remotely transmitted to a remote control system, and the on-off operation of the material suction valve can be realized through the remote control system, so that the automatic control of the material suction process is realized. The filter screen is arranged at the pipe orifice end of the material sucking pipe, so that automatic screening of materials is realized, and solid particles with overlarge particle sizes are prevented from being sucked into the pipeline to cause pipeline blockage. The aperture of the filter screen is not specially limited, and the filter screen can be selected according to the diameter of a pipeline and the particle size of solid materials. The weighing and feeding system is connected with the material mixing kettle through a pipeline, the pipeline is provided with a section of inverted U-shaped raising pipeline, and liquid materials in the mixing kettle are prevented from leaking through the pipeline.
In the invention, the material mixing kettle is used for providing a mixing place and environment for the solid raw material and the liquid raw material, and in the invention, the liquid raw material can be water or an organic solution. In the invention, the bottom of the material mixing kettle is provided with a solid feeding hole which is communicated with the inverted U-shaped raising pipeline.
And a bubble cutting sieve plate is arranged in the material mixing kettle, so that severe bubbling is avoided, and the material is prevented from splashing. The aperture of the bubble cutting sieve plate is preferably 0.1-10 mm, more preferably 1-8 mm, and most preferably 3-6 mm. Under the drive of vacuum negative pressure, solid materials are pushed by airflow and enter the mixing kettle through the material suction pipeline, and in the process of contacting and mixing with liquid materials, gas enters to form large bubbles. If the control is not added, severe splashing is easily formed, so that the solution is splashed to the inner wall of the upper part of the mixing kettle; difficult to dissolve; even the explosive boiling can be carried out and the volatile materials are flushed into a volatile material recovery system and a tail gas treatment system, so that the pipeline is blocked. The design of the bubble cutting sieve plate can divide large bubbles into a plurality of small bubbles in the floating process of the bubbles, and the control reduces the intensity of splashing.
Furthermore, for a material system with higher solubility and difficult sedimentation and a mixed system with lower viscosity of the mixed material, the uniform mixing of the material can be realized only by evacuating and bubbling, and a material mixing kettle does not need to be provided with a mechanical stirring paddle, so that the equipment cost is saved. For a mixing system with low solubility, slow dissolution, easy sedimentation and hardening in the mixing process or high viscosity of the mixed materials, a speed reducer and a stirring paddle need to be prepared in the material mixing kettle to accelerate the diffusion speed of the solid materials entering the kettle and prevent the materials from silting at an inlet to cause the blockage of a feeding pipeline. The stirring speed of the stirring paddle is preferably controlled between 10 rpm and 300rpm, more preferably between 50rpm and 250rpm, and most preferably between 100rpm and 200 rpm.
In the invention, the material mixing kettle is preferably provided with a jacket and/or a coil pipe for introducing a heating medium (hot water, steam and the like) for heating the system or introducing a cooling medium (circulating water, refrigerating fluid and the like) for cooling the system, so that the material mixing kettle is suitable for a mixing system which needs heating in a mixing process or has large heat release in a dissolving process.
In the invention, under the condition of vacuum pumping to form negative pressure, the liquid material in the mixing kettle is volatile, and if the control is not carried out, the material is lost, and the efficiency and the service life of the vacuum equipment are influenced. In order to avoid the loss of volatile materials, the volatile material recovery system is arranged and communicated with a volatile matter outlet at the top of the material mixing kettle; the volatile material recovery system is designed in a heat exchanger mode, one end of the volatile material recovery system is communicated with the mixing kettle, and the other end of the volatile material recovery system is connected with a subsequent tail gas treatment system and a vacuum system. The refrigerant (circulating water, refrigerating fluid and the like) and the volatile material are subjected to heat exchange to realize the condensation and then return to the mixing kettle. The inlet temperature of refrigerant circulating water, refrigerating fluid and the like in the heat exchanger is preferably-20-10 ℃, and the outlet temperature is preferably-15-30 ℃.
The solution preparation system is also provided with a tail gas treatment system, and a corresponding tail gas processor is arranged for treating toxic, harmful and polluting gases generated by the reaction of a specific mixed system. The tail gas processor comprises an acid gas processing module (which is used for absorbing acid gases such as acetic acid, sulfur dioxide and hydrogen sulfide by using a filling column of calcium oxide, caustic soda, sodium carbonate, sodium bicarbonate and the like), an alkaline gas (which is used for processing ammonia gas alkaline gas by using a dilute sulfuric acid solution spraying device) processing module and an active carbon adsorption processing module (which is used for adsorbing cyclohexanone, a gas organic solvent and the like). Aiming at the different compositions and physical and chemical properties of the tail gas generated by the material mixing system, one treatment module can be selected or a plurality of treatment modules can be combined and prepared to form a tail gas treatment system for treating harmful gas.
The solution preparation system for the solid materials can utilize one vacuum system to be connected with a plurality of material mixing kettles, each material mixing kettle can be connected with a plurality of material suction pipes, so that the feeding and stirring of various materials and a plurality of mixing devices are realized, the mixing efficiency is improved, and the equipment purchase and operation cost is reduced.
The invention also provides a device for removing peroxide in the caprolactone and finished system, which comprises a reduction reaction kettle, a reflux condenser and a vacuum system;
the top of the reduction reaction kettle is provided with a reducing solution feeding port which is communicated with a reducing solution preparation system; the reducing solution preparation system is the solution preparation system of the solid material;
the top of the reduction reaction kettle is provided with a volatile matter outlet which is communicated with a reflux condenser;
the reduction reaction kettle is internally provided with a coil pipe, and the outside of the reduction reaction kettle is provided with a jacket for introducing a refrigerant or a heating medium to carry out heat exchange with materials in the kettle.
In the invention, the device for removing peroxide in the caprolactone synthesis system comprises a reduction reaction device and a reducing solution preparation device, wherein the reducing solution preparation device adopts the solution preparation system of the solid material.
In the present invention, the tail gas treatment system in the reducing solution configuration system comprises an acid gas treatment device, such as a packed column of calcium oxide, caustic soda, sodium carbonate, sodium bicarbonate, etc., for absorbing water vapor and sodium bisulfite to decompose and generate acid sulfur dioxide gas.
In the invention, the reduction reaction device comprises a reduction reaction kettle, a reflux condenser and a vacuum system;
and a stirring device is arranged in the reduction reaction kettle and is used for fully mixing the solution after the reduction solution and the caprolactone react. The reduction reaction kettle is also provided with a temperature regulating device, specifically, a coil pipe arranged inside and a jacket arranged outside, and the like, which can be filled with refrigerants (circulating water and refrigerating fluid), so that the reduction reaction in the reduction reaction kettle can be cooled, the ring-opening polymerization phenomenon of caprolactone caused by reaction heat release is prevented, and the product loss of caprolactone is reduced.
In the invention, the top of the reduction reaction kettle is provided with a reducing solution feeding port which is communicated with the reducing solution preparation system.
The method aims at the problems that partial volatile substances in a caprolactone synthesis reaction system are easy to diffuse into the air due to heat release of an oxidation-reduction reaction, so that the environment is polluted and economic loss is caused. The top of the reduction reaction kettle is also provided with a volatile matter outlet which is communicated with a reflux condenser, the inlet end of the reflux condenser is communicated with the reduction reaction kettle, and the outlet end of the reflux condenser is communicated with a vacuum system. After the volatile materials enter the reflux condenser, the refrigerant exchanges heat with the volatile materials to realize condensation and reflux of the volatile materials to the reduction reaction kettle.
The invention also provides a method for removing peroxide in a caprolactone and system, which comprises the following steps:
A) the removing device of claim 5 is used for feeding liquid materials into a material mixing kettle, wherein under the vacuum condition, a solid reducing agent is sucked into the material mixing kettle from a solid feeding hole at the bottom through a weighing and feeding system and is mixed with the liquid materials under the cooling environment to obtain a reducing solution;
B) adding the reducing solution into a reduction reaction kettle through a reducing solution adding port, mixing with a caprolactone synthesis reaction solution, and carrying out reduction reaction;
C) separating the reduction reaction solution obtained in the step B) to obtain a caprolactone organic phase.
The method for removing peroxide in the caprolactone synthesis system in the present invention is based on the above-described device for removing peroxide in the caprolactone synthesis system.
Specifically, the method utilizes a vacuum system to extract the weighed reductive solid material into the material mixing kettle, and the solid material enters from the position below the liquid level of the liquid material which is added into the mixing kettle in advance, so that solid dust can be effectively prevented from being formed, and the environmental pollution and the health hazard to field operators are reduced. Adding the prepared reducing solution with a certain concentration into a reduction reaction kettle with a temperature regulating system and a volatile substance recovery device, controlling the solution to react with a caprolactone synthesis reaction system material with residual peroxide under a certain temperature condition, and reducing and removing the residual peroxide in the reaction system. The addition amount of the reducing solution is preferably controlled so that the molar weight of the reducing agent is 1 to 5 times of the residual molar weight of the peroxide in the reaction system. Part of volatile substances in the system in the reaction process, including unreacted cyclohexanone, volatile solvent and the like, are recycled by the volatile material recycling system and then flow back to the reduction reaction kettle, so that environmental pollution and material loss are avoided.
According to the invention, a certain amount of water or other liquid materials are preferably injected or sucked into the material mixing kettle, so that the water or other liquid materials form a liquid seal for the reducing solid material inlet, then the reducing materials are sucked into the material mixing kettle by using the weighing and feeding system, and if the concentration of the reducing solution needs to be adjusted, water or liquid materials can be supplemented subsequently.
In the invention, vacuum negative pressure is formed in the material mixing kettle, and the vacuum degree of the vacuum negative pressure is preferably 0.02-0.1 MPa, more preferably 0.03-0.08 MPa, more preferably 0.04-0.07 MP, and most preferably 0.05-0.06 MPa; the stirring speed in the material mixing kettle is preferably 10-300 rpm, more preferably 50-250 rpm, and most preferably 100-200 rpm.
In the invention, in a volatile material recovery system in the reducing solution preparation system, the inlet temperature of the refrigerant is preferably-20-10 ℃, and more preferably-10-0 ℃; the outlet temperature of the refrigerant is preferably-15 to 30 ℃, and more preferably-10 to 20 ℃.
In the invention, the solid reducing agent is one or more of sodium sulfide, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfate, potassium sulfide, potassium sulfite, potassium bisulfite, potassium metabisulfite, potassium thiosulfate, ammonium sulfide, ammonium sulfite, ammonium bisulfite, ammonium metabisulfite and ammonium thiosulfate; the mass concentration of the reducing solution is 0.1-50%, preferably 1-40%, more preferably 10-30%, and most preferably 15-25%.
In the invention, the caprolactone synthesis system refers to a reaction solution prepared by a method of preparing caprolactone by a cyclohexanone oxidation method and through a caprolactone reaction, and the reaction solution contains caprolactone, cyclohexanone, peroxyacetic acid, acetic acid and water.
In the invention, the temperature of the reduction reaction is preferably-5-20 ℃, more preferably 0-15 ℃, and most preferably 5-10 ℃; the time of the reduction reaction is preferably 1 to 5 hours, more preferably 2 to 4 hours, and most preferably 3 hours. In the invention, the reduction reaction is preferably carried out under the condition of stirring, and the stirring speed is preferably 50-150rpm, more preferably 80-100 rpm.
In the reduction reaction process, volatile substances such as cyclohexanone and acetic acid are condensed and refluxed to the reduction reaction kettle through the reflux condenser, so that the environmental pollution and the material loss are avoided.
After the reduction reaction is finished, the solution in the reduction reaction kettle is subjected to liquid separation, and the water phase is separated from the organic phase containing the caprolactone.
The invention provides a solution preparation system of a solid material, which comprises a weighing and feeding system, a material mixing kettle, a volatile material recovery system, a tail gas treatment system and a vacuum system which are sequentially communicated; a solid feeding hole is formed in the bottom of the material mixing kettle, and a volatile matter outlet is formed in the top of the material mixing kettle; the volatile material recovery system comprises a heat exchanger, an inlet of the volatile material recovery system is communicated with the volatile matter outlet, an outlet of the volatile material recovery system is communicated with the tail gas treatment system, and the volatile material recovery system is provided with a backflow port for backflow of recovered volatile materials to the material mixing kettle; the weighing and feeding system comprises weighing equipment and a material sucking pipe arranged above the weighing equipment, wherein the material sucking pipe is communicated with a solid feeding hole in the bottom of the material mixing kettle through an inverse U-shaped raising pipeline. The reductive solution preparation system is utilized, so that dust generated in the reductive solid material solution preparation process can be avoided, the labor intensity is reduced, the health injury of operators is reduced, and the reductive solution preparation system is suitable for continuous and automatic production; and can utilize a vacuum system, realize multiple material, a plurality of mixing apparatus's automatic material loading and stirring, when improving mixing efficiency, can reduce equipment purchase and running cost. The peroxide reduction equipment module reduces the loss of caprolactone products while removing residual peroxide, and reduces the emission of polluting gases by utilizing a volatile material recovery system, so that the peroxide reduction equipment module is more economic and environment-friendly.
In order to further illustrate the present invention, the following will describe in detail a solution preparation device for solid materials, a method for removing peroxide in a caprolactone synthesis system and a device for removing peroxide provided by the present invention with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparing a reducing solution:
firstly, 2kg of water is injected or sucked into a mixing kettle barrel (7) with the volume of 20L, so that liquid seal is formed on a reducing solid material inlet (8) by liquid. And (3) starting a vacuum system (5), sucking 1.5kg of sodium bisulfite solid powder weighed by a weighing system into a feeding pipe through a suction pipe (12) provided with a filter screen (14), contacting with a liquid seal solution after passing through an inverted U-shaped raising pipeline (15), and further sucking the solution into a mixing kettle barrel (7). Adding 11.5kg of water, starting a stirring paddle, controlling the stirring speed at 50-150RPM, and stirring for 2h to obtain the reducing sodium bisulfite aqueous solution with the concentration of 10%. Stirring dissolving process, because dissolve exothermic, have a certain amount of vapor and sodium bisulfite to decompose and produce acid sulfur dioxide gas, for avoiding acid gas to get into the vacuum pump and corrode the pump body or polluted environment, set up the adsorption column that the calcium oxide was filled before vacuum system (5) and regard as tail gas processing system (4), absorb vapor and the sulfur dioxide of volatilizing.
Peroxide removal: 10kg of reaction solution prepared by the oxidation method of cyclohexanone and caprolactone reaction is transferred into a peroxide removal reaction kettle with the volume of 30L. The reaction solution contains 40% of caprolactone, 2% of cyclohexanone, 8% of peroxyacetic acid, 30% of acetic acid and 20% of water. And dropwise adding the prepared sodium bisulfite reducing solution into a caprolactone synthesis reaction solution. Introducing chilled water into a jacket of the reaction kettle and a coil pipe, controlling the reaction at a certain temperature (-5-20 ℃), and controlling the stirring paddle to stir at a rotating speed of 50-150RPM for reaction. During the reaction, volatile matters such as cyclohexanone, acetic acid and the like are condensed and refluxed by a volatile material condenser to enter a reduction reaction kettle, and the temperature of a refrigerant in the condenser is controlled to be between-5 and 15 ℃. After the reaction is continuously stirred for 3 hours, liquid is separated, and the content of the peroxyacetic acid in an organic phase in which caprolactone and cyclohexanone are positioned is measured according to an iodometry method described in GB-T32102-2015, wherein the peroxyacetic acid content is 0.4 percent.
Example 2
Preparing a reducing solution: firstly, 2kg of water is injected or sucked into a mixing kettle barrel (7) with the volume of 20L, so that liquid seal is formed on a reducing solid material inlet (8) by liquid. And (3) starting a vacuum system (5), sucking 2kg of sodium bisulfite solid powder weighed by the weighing system into a feeding pipe through a suction pipe (12) provided with a filter screen (14), contacting with a liquid seal solution after passing through an inverted U-shaped raising pipeline (15), and further sucking the powder into a mixing kettle barrel (7). Adding 12kg of water, starting a stirring paddle, controlling the stirring speed at 50-150RPM, and stirring for 4h to obtain the reducing sodium bisulfite aqueous solution with the concentration of 12.5%. Stirring dissolving process, because dissolve exothermic, have a certain amount of vapor and sodium bisulfite to decompose and produce acid sulfur dioxide gas, for avoiding acid gas to get into the vacuum pump and corrode the pump body or polluted environment, set up the adsorption column that the calcium oxide was filled before vacuum system (5) and regard as tail gas processing system (4), absorb vapor and the sulfur dioxide of volatilizing.
Peroxide removal: 10kg of reaction solution prepared by the oxidation method of cyclohexanone and caprolactone reaction is transferred into a peroxide removal reaction kettle with the volume of 30L. The reaction solution contains 40% of caprolactone, 2% of cyclohexanone, 8% of peroxyacetic acid, 30% of acetic acid and 20% of water. And dropwise adding the prepared sodium bisulfite reducing solution into a caprolactone synthesis reaction solution. Introducing chilled water into a jacket of the reaction kettle and a coil pipe, controlling the reaction at a certain temperature (-5-15 ℃), and controlling the stirring paddle to stir at a rotating speed of 50-150RPM for reaction. During the reaction, volatile matters such as cyclohexanone, acetic acid and the like are condensed and refluxed by a volatile material condenser to enter a reduction reaction kettle, and the temperature of a refrigerant in the condenser is controlled to be between-5 and 15 ℃. After continuously stirring and reacting for 4 hours, liquid separation is carried out, and the content of peracetic acid in an organic phase in which caprolactone and cyclohexanone are positioned is measured according to an iodometry method described in GB-T32102-2015, wherein the content of peracetic acid is 0.2%.
Example 3
Preparing a reducing solution: firstly, 2kg of water is injected or sucked into a mixing kettle barrel (7) with the volume of 20L, so that liquid seal is formed on a reducing solid material inlet (8) by liquid. And (3) starting a vacuum system (5), sucking 2kg of potassium bisulfite solid powder weighed by the weighing system into a feeding pipe through a material sucking pipe (12) provided with a filter screen (14), contacting with a liquid seal solution after passing through an inverted U-shaped raising pipeline (15), and further sucking the solution into a mixing kettle barrel (7). And adding 12kg of water, starting a stirring paddle, controlling the stirring speed at 50-150RPM, and stirring for 4 hours to obtain the reducing potassium bisulfite aqueous solution with the concentration of 12.5 percent. Stirring dissolving process, because dissolve exothermic, have a certain amount of vapor and potassium bisulfite to decompose and produce acid sulfur dioxide gas, for avoiding acid gas to get into the vacuum pump and corrode the pump body or polluted environment, set up the adsorption column that calcium oxide was filled before vacuum system (5) and regard as tail gas processing system (4), absorb the vapor and the sulfur dioxide of volatilizing.
Peroxide removal: 10kg of reaction solution prepared by the oxidation method of cyclohexanone and caprolactone reaction is transferred into a peroxide removal reaction kettle with the volume of 30L. The reaction solution contains 40% of caprolactone, 2% of cyclohexanone, 8% of peroxyacetic acid, 30% of acetic acid and 20% of water. And dropwise adding the prepared potassium bisulfite reducing solution into a caprolactone synthesis reaction solution. Introducing chilled water into a jacket of the reaction kettle and a coil pipe, controlling the reaction at a certain temperature (-5-15 ℃), and controlling the stirring paddle to stir at a rotating speed of 50-150RPM for reaction. During the reaction, volatile matters such as cyclohexanone, acetic acid and the like are condensed and refluxed by a volatile material condenser to enter a reduction reaction kettle, and the temperature of a refrigerant in the condenser is controlled to be between-5 and 15 ℃. After the reaction is continuously stirred for 2 hours, liquid is separated, and the content of the peroxyacetic acid in an organic phase in which caprolactone and cyclohexanone are positioned is measured according to an iodometry method described in GB-T32102-2015, wherein the peroxyacetic acid content is 0.25 percent.
Example 4
Preparing a reducing solution: firstly, 2kg of water is injected or sucked into a mixing kettle barrel (7) with the volume of 20L, so that liquid seal is formed on a reducing solid material inlet (8) by liquid. And (3) starting a vacuum system (5), sucking 2kg of ammonium bisulfite solid powder weighed by the weighing system into a feeding pipe through a material sucking pipe (12) provided with a filter screen (14), contacting with a liquid seal solution after passing through an inverted U-shaped raising pipeline (15), and further sucking the powder into a mixing kettle barrel (7). And adding 12kg of water, starting a stirring paddle, controlling the stirring speed at 50-150RPM, and stirring for 2 hours to obtain the reducing ammonium bisulfite aqueous solution with the concentration of 12.5 percent. Stirring dissolving process, because dissolve exothermic, have a certain amount of vapor and ammonium bisulfite decompose and produce acid sulfur dioxide gas, for avoiding acid gas to get into the vacuum pump and corrode the pump body or polluted environment, set up the adsorption column that calcium oxide was filled before vacuum system (5) and regard as tail gas treatment system (4), absorb the vapor and the sulfur dioxide of volatilizing.
Peroxide removal: 10kg of reaction solution prepared by the oxidation method of cyclohexanone and caprolactone reaction is transferred into a peroxide removal reaction kettle with the volume of 30L. The reaction solution contains 40% of caprolactone, 2% of cyclohexanone, 9% of peroxyacetic acid, 30% of acetic acid and 20% of water. And dropwise adding the prepared ammonium bisulfite reducing solution into a caprolactone synthesis reaction solution. Introducing chilled water into a jacket of a reaction kettle and a coil pipe, controlling the reaction at a certain temperature (-5-15 ℃), and controlling the stirring paddle to stir at a rotating speed of 50-150RPM for reaction. During the reaction, volatile matters such as cyclohexanone, acetic acid and the like are condensed and refluxed by a volatile material condenser to enter a reduction reaction kettle, and the temperature of a refrigerant in the condenser is controlled to be between-5 and 15 ℃. After the reaction is continuously stirred for 2 hours, liquid is separated, and the content of the peroxyacetic acid in an organic phase in which caprolactone and cyclohexanone are positioned is measured according to an iodometry method described in GB-T32102-2015, wherein the peroxyacetic acid content is 0.2 percent.
Example 5
Preparing a reducing solution: firstly, 2kg of water is injected or sucked into a mixing kettle barrel (7) with the volume of 20L, so that liquid seal is formed on a reducing solid material inlet (8) by liquid. And (3) starting a vacuum system (5), sucking 1.5kg of sodium thiosulfate solid powder weighed by a weighing system into a feeding pipe through a suction pipe (12) provided with a filter screen (14), contacting with a liquid seal solution after passing through an inverted U-shaped raising pipeline (15), and further sucking the sodium thiosulfate solid powder into a mixing kettle barrel (7). Adding 11.5kg of water, starting a stirring paddle, controlling the stirring speed at 50-150RPM, and stirring for 2h to obtain a 10% reducing sodium thiosulfate aqueous solution. Stirring dissolving process, because dissolve exothermic, have a certain amount of vapor and sodium thiosulfate to decompose and produce acid sulfur dioxide gas, for avoiding acid gas to get into the vacuum pump and corrode the pump body or polluted environment, set up the adsorption column that the calcium oxide was filled before vacuum system (5) and regard as tail gas processing system (4), absorb vapor and the sulfur dioxide of volatilizing.
Peroxide removal: 10kg of reaction solution prepared by the oxidation method of cyclohexanone and caprolactone reaction is transferred into a peroxide removal reaction kettle with the volume of 30L. The reaction solution contains 50% of caprolactone, 4% of cyclohexanone, 8% of peroxyacetic acid, 18% of acetic acid and 20% of water. And dropwise adding the prepared sodium thiosulfate reducing solution into a caprolactone synthesis reaction solution. Introducing chilled water into a jacket of a reaction kettle and a coil pipe, controlling the reaction at a certain temperature (-5-15 ℃), and controlling the stirring paddle to stir at a rotating speed of 50-150RPM for reaction. During the reaction, volatile matters such as cyclohexanone, acetic acid and the like are condensed and refluxed by a volatile material condenser to enter a reduction reaction kettle, and the temperature of a refrigerant in the condenser is controlled to be between-5 and 15 ℃. After the reaction is continuously stirred for 2 hours, liquid is separated, and the content of the peroxyacetic acid in an organic phase in which caprolactone and cyclohexanone are positioned is measured according to an iodometry method described in GB-T32102-2015, wherein the peroxyacetic acid content is 0.1 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A solution preparation system for solid materials comprises a weighing and feeding system, a material mixing kettle, a volatile material recovery system, a tail gas treatment system and a vacuum system which are sequentially communicated;
a solid feeding hole is formed in the bottom of the material mixing kettle, and a volatile matter outlet is formed in the top of the material mixing kettle;
the volatile material recovery system comprises a heat exchanger, an inlet of the volatile material recovery system is communicated with the volatile matter outlet, an outlet of the volatile material recovery system is communicated with the tail gas treatment system, and the volatile material recovery system is provided with a backflow port for backflow of recovered volatile materials to the material mixing kettle;
the weighing and feeding system comprises weighing equipment and a suction pipe, wherein the suction pipe is communicated with a solid feeding hole in the bottom of the material mixing kettle through an inverse U-shaped raising pipeline.
2. The deployment system of claim 1 wherein a stirring device and a bubble cutting screen plate are disposed within the material mixing tank;
the aperture of the bubble cutting sieve plate is 0.1-10 mm.
3. The system for preparing the materials of claim 1, wherein the materials mixing kettle is internally provided with a coil pipe, and externally provided with a jacket for introducing a cooling medium or a heating medium to exchange heat with the materials in the kettle.
4. The dispensing system of claim 1, wherein the nozzle of the aspiration tube is provided with a filter screen.
5. A device for removing peroxide in a caprolactone synthesis system comprises a reduction reaction kettle, a reflux condenser and a vacuum system;
the top of the reduction reaction kettle is provided with a reducing solution feeding port which is communicated with a reducing solution preparation system; the reducing solution preparation system is a solution preparation system of the solid material according to any one of claims 1 to 4;
the top of the reduction reaction kettle is provided with a volatile matter outlet which is communicated with a reflux condenser;
the reduction reaction kettle is internally provided with a coil pipe, and the outside of the reduction reaction kettle is provided with a jacket for introducing a refrigerant or a heating medium to carry out heat exchange with materials in the kettle.
6. A method for removing peroxide in a caprolactone synthesis system comprises the following steps:
A) the removing device of claim 5 is used for feeding liquid materials into a material mixing kettle, wherein under the vacuum condition, a solid reducing agent is sucked into the material mixing kettle from a solid feeding hole at the bottom through a weighing and feeding system and is mixed with the liquid materials under the cooling environment to obtain a reducing solution;
B) adding the reducing solution into a reduction reaction kettle through a reducing solution adding port, mixing with a caprolactone synthesis reaction solution, and carrying out reduction reaction;
C) separating the reduction reaction solution obtained in the step B) to obtain a caprolactone organic phase.
7. The removal method according to claim 6, wherein the solid reducing agent is one or more of sodium sulfide, sodium sulfite, sodium metabisulfite, sodium bisulfite, sodium thiosulfate, potassium sulfide, potassium sulfite, potassium bisulfite, potassium metabisulfite, potassium thiosulfate, ammonium sulfide, ammonium sulfite, ammonium bisulfite, ammonium metabisulfite, and ammonium thiosulfate;
the mass concentration of the reducing solution is 0.1-50%.
8. The method according to claim 6, wherein the degree of vacuum in step A) is 0.02 to 0.1 MPa.
9. The removing method according to claim 6, wherein the temperature of the reduction reaction is-5 to 20 ℃; the time of the reduction reaction is 1-5 hours.
10. The removing method of claim 6, wherein in the volatile material recovery system, the inlet temperature of the refrigerant is-20 to 10 ℃, and the outlet temperature is-15 to 30 ℃;
the temperature of the refrigerant in the reflux condenser is-20-30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010767285.7A CN111841403B (en) | 2020-08-03 | 2020-08-03 | Solution preparation device for solid material, and removal method and removal system for peroxide in epsilon-caprolactone synthesis system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010767285.7A CN111841403B (en) | 2020-08-03 | 2020-08-03 | Solution preparation device for solid material, and removal method and removal system for peroxide in epsilon-caprolactone synthesis system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111841403A true CN111841403A (en) | 2020-10-30 |
| CN111841403B CN111841403B (en) | 2021-11-09 |
Family
ID=72952905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010767285.7A Active CN111841403B (en) | 2020-08-03 | 2020-08-03 | Solution preparation device for solid material, and removal method and removal system for peroxide in epsilon-caprolactone synthesis system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111841403B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113623546A (en) * | 2021-06-30 | 2021-11-09 | 江苏华电昆山热电有限公司 | Corrosive liquid medicine adding system |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781263A (en) * | 2010-03-02 | 2012-11-14 | 埃科莱布美国股份有限公司 | Method for processing peroxygen solutions |
| CN103933922A (en) * | 2014-04-21 | 2014-07-23 | 太仓塑料助剂厂有限公司 | Reduction and condensation combined reaction device |
| CN203790920U (en) * | 2014-02-14 | 2014-08-27 | 黄山贝诺科技有限公司 | Online metering and feeding device |
| WO2014207472A2 (en) * | 2013-06-28 | 2014-12-31 | Colormatrix Holdings, Inc. | Polymeric materials |
| CN104353211A (en) * | 2014-09-25 | 2015-02-18 | 中国石油化工股份有限公司 | Scavenging agent for butadiene peroxide at bottom of butadiene storing tank |
| US20160144337A1 (en) * | 2013-06-21 | 2016-05-26 | Samsung Sdi Co., Ltd.. | Continuous Solid-State Polymerisation Device and Method |
| CN206483478U (en) * | 2017-01-25 | 2017-09-12 | 湖南聚仁化工新材料科技有限公司 | A kind of reaction unit for preparing ε caprolactones |
| CN107573256A (en) * | 2017-09-26 | 2018-01-12 | 安徽国星生物化学有限公司 | A kind of p-hydrochloride continuous production method and its device |
| CN208275315U (en) * | 2018-04-27 | 2018-12-25 | 山东希诚新材料科技有限公司 | Bottom feed system for the conveying of ultralight nano-powder |
| CN111420585A (en) * | 2019-07-16 | 2020-07-17 | 镇江市思泰智能装备技术有限公司 | Automatic preparation system and preparation method of catalyst slurry |
-
2020
- 2020-08-03 CN CN202010767285.7A patent/CN111841403B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781263A (en) * | 2010-03-02 | 2012-11-14 | 埃科莱布美国股份有限公司 | Method for processing peroxygen solutions |
| US20160144337A1 (en) * | 2013-06-21 | 2016-05-26 | Samsung Sdi Co., Ltd.. | Continuous Solid-State Polymerisation Device and Method |
| WO2014207472A2 (en) * | 2013-06-28 | 2014-12-31 | Colormatrix Holdings, Inc. | Polymeric materials |
| CN203790920U (en) * | 2014-02-14 | 2014-08-27 | 黄山贝诺科技有限公司 | Online metering and feeding device |
| CN103933922A (en) * | 2014-04-21 | 2014-07-23 | 太仓塑料助剂厂有限公司 | Reduction and condensation combined reaction device |
| CN104353211A (en) * | 2014-09-25 | 2015-02-18 | 中国石油化工股份有限公司 | Scavenging agent for butadiene peroxide at bottom of butadiene storing tank |
| CN206483478U (en) * | 2017-01-25 | 2017-09-12 | 湖南聚仁化工新材料科技有限公司 | A kind of reaction unit for preparing ε caprolactones |
| CN107573256A (en) * | 2017-09-26 | 2018-01-12 | 安徽国星生物化学有限公司 | A kind of p-hydrochloride continuous production method and its device |
| CN208275315U (en) * | 2018-04-27 | 2018-12-25 | 山东希诚新材料科技有限公司 | Bottom feed system for the conveying of ultralight nano-powder |
| CN111420585A (en) * | 2019-07-16 | 2020-07-17 | 镇江市思泰智能装备技术有限公司 | Automatic preparation system and preparation method of catalyst slurry |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113623546A (en) * | 2021-06-30 | 2021-11-09 | 江苏华电昆山热电有限公司 | Corrosive liquid medicine adding system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111841403B (en) | 2021-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5243530B2 (en) | Equipment for removing carbon dioxide from combustion gases | |
| CN202080917U (en) | Circulating closed-loop type ammonia nitrogen stripping system | |
| CN206103690U (en) | Acyl chlorides chemical industry preface sulfur dioxide exhaust purification recovery unit | |
| CN106039969A (en) | Sulfur dioxide absorption method and device | |
| CN207042222U (en) | Chlorine dioxide gaseous oxidation denitration integrated device | |
| CN111841403B (en) | Solution preparation device for solid material, and removal method and removal system for peroxide in epsilon-caprolactone synthesis system | |
| WO2014017654A1 (en) | Carbon dioxide recovery method and carbon dioxide recovery device | |
| TWI740458B (en) | Abstract of description nitrogen oxide absorption slurry and its preparation and use method thereof | |
| CN110813027A (en) | Method and device for removing carbon dioxide from gas flow | |
| JP3664867B2 (en) | PCB decomposition reaction vessel | |
| CN107694293A (en) | A kind of hypergravity ammonia removal device and ammonia-removal method | |
| CN105566188A (en) | Solid SDD (Sodium Dimethyl Dithiocarbamate) synthetic technology with short drying time | |
| CN109012093A (en) | Processing system for containing hydrogen chloride industrial waste gas purifying | |
| CN105439096B (en) | Environment-friendly type peroxide passivation chlorine dioxide technique prepares the method and apparatus of sodium chlorite | |
| JP2024501820A (en) | Continuous preparation system and method for vinylidene chloride | |
| CN110482506A (en) | A kind of process intensification removes the device and method of hydrogen sulfide in industrial phosphoric acid | |
| CN114230071A (en) | Treatment method of DMF (dimethyl formamide) -containing wastewater | |
| CN105920995A (en) | Harmless recovery and treatment method for metallurgical industry chlorine-containing tail gas | |
| CN105439091B (en) | The peroxide passivation chlorine dioxide preparation method and equipment of environment-friendly type | |
| CN108636066A (en) | A kind of exhaust treatment system | |
| CN109289744B (en) | Metronidazole production method, device and application for improving nitric acid utilization rate | |
| CN112076609A (en) | Device and method for removing carbon dioxide in tail gas generated in reaction of urea and polyhydric alcohol | |
| JP5769112B2 (en) | Gas separation method and apparatus and gas treatment method and apparatus | |
| CN112742185A (en) | Flue gas desulfurization reactor, flue gas treatment system and process method | |
| JPH11243985A (en) | Recovery of carbon dioxide in fermentation of l-glutamic acid |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20201030 Assignee: Shandong Jilu Caprolactone Special Materials Co.,Ltd. Assignor: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES Contract record no.: X2022220000009 Denomination of invention: A solution preparation device for solid materials, a method for removing peroxides in an e-caprolactone synthesis system, and a removal system Granted publication date: 20211109 License type: Exclusive License Record date: 20220826 |