CN116606219A - Production method and system of 1,2, 3-tri (cyanoethoxy) propane - Google Patents

Production method and system of 1,2, 3-tri (cyanoethoxy) propane Download PDF

Info

Publication number
CN116606219A
CN116606219A CN202310662814.0A CN202310662814A CN116606219A CN 116606219 A CN116606219 A CN 116606219A CN 202310662814 A CN202310662814 A CN 202310662814A CN 116606219 A CN116606219 A CN 116606219A
Authority
CN
China
Prior art keywords
acrylonitrile
cyanoethoxy
propane
glycerol
product
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
Application number
CN202310662814.0A
Other languages
Chinese (zh)
Other versions
CN116606219B (en
Inventor
苟永霞
牛超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Yonghao New Material Technology Co ltd
Original Assignee
Shandong Yonghao New Material Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong Yonghao New Material Technology Co ltd filed Critical Shandong Yonghao New Material Technology Co ltd
Priority to CN202310662814.0A priority Critical patent/CN116606219B/en
Publication of CN116606219A publication Critical patent/CN116606219A/en
Application granted granted Critical
Publication of CN116606219B publication Critical patent/CN116606219B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • 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
    • 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
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the technical field of production of lithium ion battery electrolyte additives, in particular to a method and a system for producing 1,2, 3-tri (cyanoethoxy) propane. The preparation method of 1,2, 3-tri (cyanoethoxy) propane in the prior art cannot obtain a high-purity and low-color product. The invention comprises mixing glycerol and catalyst, heating, and stirring to dissolve; then, a three-stage reaction method under specific conditions is adopted, and the obtained product is dissolved in a solvent, washed and purified to obtain the 1,2, 3-tri (cyanoethoxy) propane. Under the condition that both the primary substituted product and the secondary substituted product exist, the primary substituted product and the secondary substituted product are mutually matched, so that the three-section acrylonitrile tends to be dissolved and react with glycerol after being added, and the self-polymerization of a large amount of acrylonitrile is avoided, thereby improving the purity and the yield of the 1,2, 3-tri (cyanoethoxy) propane, reducing the color value and simplifying the production process.

Description

Production method and system of 1,2, 3-tri (cyanoethoxy) propane
Technical Field
The invention relates to the technical field of production of lithium ion battery electrolyte additives, in particular to a method and a system for producing 1,2, 3-tri (cyanoethoxy) propane.
Background
The bond energy of the carbon-nitrogen triple bond in the cyano group of the 1,2, 3-tri (cyanoethoxy) propane is high, the bond is not easy to oxidize, the bond has good stability on the positive electrode, and the bond has stronger coordination capacity, can be combined with metal ions such as nickel/cobalt/manganese on the surface of the electrode, masks active ions on the surface of the positive electrode, and reduces the decomposition effect of the electrode on electrolyte; ether linkage will be with HF and PF in non-aqueous electrolyte 6 And the like, thereby preventing the formation of an acidic solution to limit the acceleration of oxidation and decomposition reactions of the nonaqueous electrolytic solution and eliminate high-temperature flatulence caused by solvolysis of the electrolytic solution. Therefore, 1,2, 3-tri (cyanoethoxy) propane is used as an electrolyte additive, so that the initial capacity reduction of the battery can be restrained, the expansion of the battery after high-temperature placement is reduced, and the charge-discharge performance and the high-voltage resistance performance of the battery are improved.
Patent CN114195681a discloses a preparation method of 1,2, 3-tris (cyanoethoxy) propane, which discloses a preparation method of obtaining 1,2, 3-tris (cyanoethoxy) propane by reacting glycerol with a small amount of acrylonitrile and then reacting with the rest of acrylonitrile, wherein according to the embodiment part of the disclosure, the liquid prepared by the method is still yellow viscous liquid, and it is known that under the preparation method, a large amount of yellow acrylonitrile impurities generated by self-polymerization of acrylonitrile still cannot be avoided, namely, the purity of the product is limited, and when the chromaticity of the electrolyte additive used as a lithium battery electrolyte additive is too high, the performance of the electrolyte is seriously affected.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: overcomes the defects of the prior art and provides a production method and a system of 1,2, 3-tri (cyanoethoxy) propane with low color value and high purity.
The technical scheme adopted for solving the technical problems is as follows: a method for producing 1,2, 3-tri (cyanoethoxy) propane, which is characterized in that: the method comprises the following steps:
1) Mixing glycerol and a catalyst, heating to 30-80 ℃, and stirring until the glycerol and the catalyst are dissolved;
2) The temperature of the reaction system is controlled at 60-70 ℃, a section of acrylonitrile is added, and the mole ratio of the section of acrylonitrile to the glycerol is 0.5-1.5: 1, uniformly adding a section of acrylonitrile into a reaction system for 0.8-1 h, and reacting for 1-1.5 h after the addition is finished;
3) The temperature of the reaction system is controlled at 40-50 ℃, and secondary acrylonitrile is added, wherein the molar ratio of the secondary acrylonitrile to the glycerol is 0.5-1.5: 1, uniformly adding the second-stage acrylonitrile into a reaction system for 1.5-2 hours, and reacting for 1.5-2 hours after the addition is finished;
4) The temperature of the reaction system is controlled at 25-30 ℃, three sections of acrylonitrile are added, the molar ratio of the three sections of acrylonitrile to the glycerol is 1.0-1.4:1, the three sections of acrylonitrile are uniformly added into the reaction system for 2-4 hours, and the reaction is carried out for 3-8 hours after the addition is completed;
5) And (3) dissolving, washing and purifying the product obtained in the step (4) by using a solvent to obtain the 1,2, 3-tri (cyanoethoxy) propane.
Under the production method, the yield of the obtained 1,2, 3-tri (cyanoethoxy) propane reaches more than 90 percent, the purity reaches more than 99 percent, the chromaticity is less than 50, and the principle is as follows: the method adopts a three-section type acrylonitrile adding method, a large number of primary substituted products are firstly generated, a large number of secondary substituted products are regenerated, and finally the products are generated; in the synthesis process, the self-polymerization of acrylonitrile is reduced as much as possible, and glycerol and intermediate products are promoted to react with the acrylonitrile to generate products. The principle of the two-stage reaction method in the prior art is that the dissolution property of the primary substituted product is more similar to that of glycerol, namely, the primary substituted product is more easily mutually dissolved with a reaction system, so that the reaction efficiency of acrylonitrile and glycerol is improved in the second-stage reaction. However, it was found in the course of the present invention that simply reducing the amount of acrylonitrile added in the first stage reaction does not allow an excessively high amount of acrylonitrile in the second stage to react effectively with glycerol. The stock of the primary substituted product can not support a large amount of second-stage acrylonitrile to react with glycerol quickly, so that the second-stage acrylonitrile is self-polymerized to generate nitrile vinyl impurities, and meanwhile, the invention discovers that the acrylonitrile which is not dissolved in the glycerol is easier to self-polymerize to generate impurities at an excessively low temperature under the condition of longer adding time and reaction time, and the color value reaches hundreds of Hazen. Therefore, the invention is based on that the adding amount of the acrylonitrile is smaller in the first-stage reaction, the dissolving process of the first-stage acrylonitrile in the glycerol is accelerated through the higher first-stage reaction temperature and the faster first-stage acrylonitrile adding speed, instead of simply promoting the generation of the first-stage substituted product, and then the second-stage acrylonitrile is utilized to participate in the reaction as soon as possible, so that the second-stage reaction obtains the di-substituted product which is closer to the dissolving property of the acrylonitrile, and the tri-stage acrylonitrile is dissolved and reacted with the glycerol after being added under the condition that the first-stage substituted product and the di-substituted product exist, thereby avoiding the self-polymerization of a large amount of acrylonitrile, improving the purity and the yield of the 1,2, 3-tri (cyanoethoxy) propane and reducing the color value. Under the production method, the product with low color value can be obtained without extraction step, and the production process is simplified.
Further preferably, the solvent dissolving step adopts an organic solvent such as dichloromethane, the dosage of the solvent is generally 0.3-1 times of the volume of the reaction product, the reaction product is dispersed and diluted, and the viscous product is convenient to transfer and wash.
Preferably, the weight of the catalyst is 0.5-3% of the weight of glycerol.
Preferably, the weight of the catalyst is 1-2% of the weight of glycerol.
Under the higher reaction temperature and adding speed of the first-stage reaction and the second-stage reaction, the preferable catalyst dosage has better matching effect with the dosage, the temperature and the adding speed of the first-stage acrylonitrile and the second-stage acrylonitrile, ensures that the primary substituted product and the secondary substituted product are generated, and avoids the self-polymerization of the acrylonitrile under the high catalytic condition.
The catalyst is more preferably sodium methoxide, the matching effect of sodium methoxide with the first-stage acrylonitrile and the second-stage acrylonitrile is better, and the color value is lower.
Preferably, the ratio of the total mole amount of the primary acrylonitrile to the secondary acrylonitrile to the mole amount of the glycerol is 2:1.
it is further preferred that the mole ratio of primary acrylonitrile to glycerol is 1:1, the mole ratio of the two-stage acrylonitrile to the glycerol is 1:1. an excessively high amount of primary acrylonitrile may result in certain acrylonitrile autopolymerization, while an excessively low amount may result in insufficient amounts of primary and secondary substituted products, and a preferable reaction molar ratio may result in sufficient coordination of the primary and secondary substituted products, thereby avoiding the autopolymerization of the acrylonitrile by the three-stage reaction and improving the reaction efficiency.
Preferably, the washing and purifying in the step 5) sequentially comprises acid washing, water washing and reduced pressure distillation; stirring, standing and layering after acid washing, taking an upper product phase, washing to be neutral, and carrying out reduced pressure distillation to obtain 1,2, 3-tri (cyanoethoxy) propane.
The invention provides an acid washing step in the product treatment process, and the acid washing method has the advantages that part of oily heavy components such as polyacrylonitrile and the like of yellow polymers can be removed by acid washing, and the heavy components are distributed into sulfuric acid solution and layered with the product during acid washing. The product is washed to be neutral by water after acid washing, so that nitrile decomposition caused in the high-temperature distillation process is prevented.
Further preferably, the vacuum distillation is performed under a vacuum degree of 300Pa, and a fraction at 250-270 ℃ is collected to obtain 1,2, 3-tri (cyanoethoxy) propane.
Further preferably, the acid washing adopts sulfuric acid solution with the concentration of 5-60% by weight, and the addition amount of the sulfuric acid solution is 2-10% by weight of the product phase.
Further preferably, the acid washing adopts a sulfuric acid solution with the concentration of 60% by weight, and the addition amount of the sulfuric acid solution is 3-5% of the weight of the product phase. The sulfuric acid solution with specific conditions is used for contact with the product for acid washing, so that the color value of the product can be further reduced under the condition of lower color value, and the quality of the product is obviously improved.
A system for producing 1,2, 3-tris (cyanoethoxy) propane, characterized in that: comprises a glycerol raw material tank, an acrylonitrile raw material tank, a reaction kettle, a heat exchanger, an acid washing tower, a water washing tower, a flash evaporation tower, a solvent tank, a light component tank and a product tank; the glycerol raw material tank is connected with the acrylonitrile raw material tank by a reaction kettle, the heat exchanger is connected with the outer wall of the reaction kettle, the discharge end of the reaction kettle, the acid washing tower, the water washing tower and the flash evaporation tower are sequentially connected in series, and the flash evaporation tower is respectively connected to the solvent tank, the light component tank and the product tank.
Preferably, a stirrer and a distributor are arranged in the reaction kettle, and the distributor is connected with a glycerol raw material tank.
The distributor is connected with an acrylonitrile raw material tank, so that the acrylonitrile can be uniformly distributed in the glycerol solution, the acrylonitrile is promoted to be more mixed with the glycerol, and the self-polymerization of the acrylonitrile is reduced.
Compared with the prior art, the invention has the following beneficial effects: based on the fact that the adding amount of the acrylonitrile is small in the first-stage reaction, the dissolving process of the first-stage acrylonitrile in the glycerol is accelerated through the high first-stage reaction temperature and the high first-stage acrylonitrile adding speed, instead of simply promoting the generation of the first-stage substituted product, the second-stage acrylonitrile is utilized to participate in the reaction as soon as possible, so that the second-stage reaction obtains the di-substituted product which is closer to the dissolving property of the acrylonitrile, and the tri-stage acrylonitrile is dissolved and reacted with the glycerol after being added under the condition that the first-stage substituted product and the di-substituted product exist, the self-polymerization of a large amount of acrylonitrile is avoided, the purity and the yield of the 1,2, 3-tri (cyanoethoxy) propane are improved, and the color value is reduced. Under the production method, the product with low color value can be obtained without extraction step, and the production process is simplified.
Drawings
FIG. 1 is a schematic diagram of a system for producing 1,2, 3-tris (cyanoethoxy) propane.
Wherein, 1, glycerol raw material tank; 2. an acrylonitrile raw material tank; 3. a reaction kettle; 4. a heat exchanger; 5. a pickling tower; 6. a water washing tower; 7. a flash evaporation kettle; 8. a solvent tank; 9. a light component tank; 10. and (5) a product tank.
Detailed Description
The present invention will be further described with reference to the following examples, with example 1 being the best mode of carrying out the invention.
Referring to fig. 1: the production system used in the following examples is a production system of 1,2, 3-tris (cyanoethoxy) propane, comprising a glycerol feed stock tank 1, an acrylonitrile feed stock tank 2, a reaction kettle 3, a heat exchanger 4, a pickling tower 5, a water washing tower 6, a flash tower 7, a solvent tank 8, a light component tank 9 and a product tank 10; the glycerol feed tank 1 is connected with the acrylonitrile feed pipe 2 to the reaction kettle 3, the heat exchanger 4 is connected with the outer wall of the reaction kettle 4, the discharge end of the reaction kettle 3, the pickling tower 5, the washing tower 6 and the flash evaporation tower 7 are sequentially connected in series, and the flash evaporation tower 7 is respectively connected to the solvent tank 8, the light component tank 9 and the product tank 10. Wherein, stirred tank 301 and distributor 302 are arranged in reactor 3, and distributor 302 is connected with acrylonitrile raw material tank 2. The glycerol raw material tank 1 and the acrylonitrile raw material tank 2 are fed into the reaction kettle 3, the heat exchanger 4 controls the temperature in the reaction kettle 3 through medium circulation, a reaction product obtained in the reaction kettle 3 enters the pickling tower 5 for pickling, the pickling tower 5 is stirred and kept stand for layering, an upper product phase enters the water washing tower 6, a product obtained in the water washing tower 6 enters the flash evaporation tower 7, and the flash evaporation tower 7 is distilled and separated to obtain a solvent, a light component and a product 1,2, 3-tri (cyanoethoxy) propane, and the solvent, the light component and the product respectively enter the solvent tank 8, the light component tank 9 and the product tank 10.
Example 1
A process for the production of 1,2, 3-tris (cyanoethoxy) propane comprising the steps of:
1) Adding 200mol (18.42 kg) of glycerol into a 100L reaction kettle 3, adding sodium methoxide serving as a catalyst with the weight of 1% of glycerol, heating to 60 ℃, stirring for 1h for dissolution, and stirring at the speed of 300r/min;
2) Cooling to 60 ℃, adding 200mol (10.61 kg) of a section of acrylonitrile under stirring, uniformly adding the acrylonitrile within 1h (the adding speed is 10.61 kg/h), and reacting for 1h at 60 ℃ after the adding is completed;
3) Cooling to 40 ℃, adding 200mol (10.61 kg) of two-stage acrylonitrile under stirring, uniformly adding the two-stage acrylonitrile within 1.5h (the adding speed is 7.047 kg/h), and reacting for 1.5h at 40 ℃ after the adding is completed;
4) Reducing the temperature to 30 ℃, adding 220mol (11.67 kg) of three sections of acrylonitrile under stirring, uniformly adding the three sections of acrylonitrile within 4 hours (the adding speed is 2.92 kg/h), and reacting for 8 hours at 30 ℃ after the adding is completed;
5) After the reaction is finished, adding 30L of dichloromethane, stirring and dissolving to obtain a product phase, entering an acid washing tower 5, adding sulfuric acid (60% weight concentration) with the total weight of 5% (2.5 kg) of the product phase, stirring uniformly, standing and layering, washing an upper product into a water washing tower 6 until the upper product is neutral, distilling under reduced pressure, collecting components with the vacuum degree of 300Pa and the temperature of 30-40 ℃ into a solvent tank, and collecting components with the temperature of 250-270 ℃ into a product tank to obtain 1,2, 3-tri (cyanoethoxy) propane.
The calculated yield was 93.1%, the product purity was 99.7%, and the chroma was 15.2Hazen. The method for detecting the purity is liquid chromatography, and the detection conditions are as follows: the liquid chromatographic column is Shimadzu C18 column, and the mobile phase is 100% acetonitrile.
Example 2
A method for producing 1,2, 3-tri (cyanoethoxy) propane, wherein on the basis of the example 1, the amount of acrylonitrile in one stage is set to be 0.5 times of the molar amount of glycerol, and the temperature of the step 2) is set to be 70 ℃; the dosage of the second-stage acrylonitrile is set to be 1.5 times of the molar weight of the glycerol; other conditions were the same as in example 1.
The yield was calculated to be 92.0%, the product purity was 99.4% and the chroma was 18.7Hazen.
Example 3
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with a single acrylonitrile stage in an amount of 1.5 times the molar amount of glycerol; the dosage of the second-stage acrylonitrile is set to be 0.5 times of the molar quantity of the glycerol, and the temperature of the step 2) is set to be 50 ℃; other conditions were the same as in example 1.
The yield was calculated to be 92.0%, the product purity was 99.3% and the chroma was 19.2Hazen.
Example 4
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with the catalyst amount in step 1 set to 2% by weight of glycerol, with the other conditions being the same as in example 1.
The calculated yield was 93.0%, the product purity was 99.6% and the chroma was 18.5Hazen.
Example 5
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with the catalyst amount in step 1 set to 3% by weight of glycerol, with the other conditions being the same as in example 1.
The calculated yield was 90.0%, the product purity was 99.1% and the chroma was 36.4Hazen.
Example 6
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, in which the catalyst amount in step 1 was set to 0.5% by weight of glycerol, with the other conditions being the same as in example 1.
The calculated yield was 90.0%, the product purity was 99.0% and the chroma was 45.2Hazen.
Example 7
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with a single acrylonitrile stage in an amount of 1.5 times the molar amount of glycerol; other conditions were the same as in example 1.
The calculated yield was 89.4%, the product purity was 99.1% and the chroma was 62.8Hazen.
Example 8
A method for producing 1,2, 3-tri (cyanoethoxy) propane, wherein the amount of the second acrylonitrile is 1.5 times of the molar amount of glycerol based on the example 1; other conditions were the same as in example 1.
The calculated yield was 89.4%, the product purity was 99.1% and the chroma was 57.3Hazen.
Example 9
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with a three-stage acrylonitrile amount set to 280mol (1.4 times the molar amount of glycerol); other conditions were the same as in example 1.
The calculated yield was 93.0%, the product purity was 99.6% and the chroma was 40.1Hazen.
Comparative example 1
A method for producing 1,2, 3-tri (cyanoethoxy) propane, based on example 1, wherein the addition time of step 2) is set to 2 hours, and the addition temperature and the reaction temperature are set to 30 ℃; the second acrylonitrile and the first acrylonitrile are combined and added in the step 3), the adding time of the step 3) is set to be 3 hours, the adding temperature and the reaction temperature are set to be 25-30 ℃ (the fluctuation occurs with the increasing of the adding amount), and other conditions are the same as in the example 1.
The yield was calculated to be 89%, the product purity was 97.1% and the chroma was 210.3Hazen.
Comparative example 2
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on comparative example 1, in which step 2) the amount of acrylonitrile used is set to 100mol; step 3) the addition time was set to 5 hours, the addition temperature and the reaction temperature were set to 30℃and the other conditions were the same as in comparative example 1.
The yield was calculated to be 90.5%, the product purity 98.2% and the color 186.2Hazen.
Comparative example 3
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with the addition temperature and reaction temperature of step 2) set to 30℃and the other conditions being the same as in example 1.
The yield was calculated to be 85.5%, the product purity was 95.2% and the chroma was 175.5Hazen.
Comparative example 4
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, with the addition temperature and reaction temperature of step 3) set to 30℃and the other conditions being the same as in example 1.
The calculated yield was 90.5%, the product purity was 97.0% and the color was 130.3Hazen.
Comparative example 5
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, was carried out in 2h with the addition of step 2) and the other conditions were the same as in example 1.
The calculated yield was 90.1%, the product purity was 97.7% and the chroma was 120.9Hazen.
Comparative example 6
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on example 1, was carried out in step 3) with the addition of 2.5h, the other conditions being the same as in example 1.
The calculated yield was 90.9%, the product purity was 97.1% and the chroma was 132.3Hazen.
Comparative example 7
A process for the production of 1,2, 3-tris (cyanoethoxy) propane comprising the steps of:
1) Adding 200mol (18.42 kg) of glycerol into a 100L reaction kettle 3, adding sodium methoxide serving as a catalyst with the weight of 1% of glycerol, heating to 60 ℃, stirring for 1h for dissolution, and stirring at the speed of 300r/min;
2) Cooling to 60 ℃, adding 400mol (21.22 kg) of a section of acrylonitrile under stirring, uniformly adding (the adding speed is 10.61 kg/h) in 2h, and reacting for 2h at 60 ℃ after the adding is completed;
3) Reducing the temperature to 30 ℃, adding 220mol (11.67 kg) of three sections of acrylonitrile under stirring, uniformly adding the three sections of acrylonitrile within 4 hours (the adding speed is 2.918 kg/h), and reacting for 8 hours at 30 ℃ after the adding is completed;
4) After the reaction is finished, adding 30L of dichloromethane, stirring and dissolving to obtain a product phase, entering an acid washing tower 5, adding sulfuric acid (60% weight concentration) with the total weight of 5% (2.5 kg) of the product phase, stirring uniformly, standing and layering, washing an upper product into a water washing tower 6 until the upper product is neutral, distilling under reduced pressure, collecting components with the vacuum degree of 300Pa and the temperature of 30-40 ℃ into a solvent tank, and collecting components with the temperature of 250-270 ℃ into a product tank to obtain 1,2, 3-tri (cyanoethoxy) propane.
The yield was calculated to be 89%, the product purity was 97.1% and the chroma was 210.3Hazen.
Comparative example 8
A process for the production of 1,2, 3-tris (cyanoethoxy) propane, based on comparative example 7, in which the product phase from step 4) is directly fed to a water scrubber 6 for washing to neutrality, with the other conditions being identical to those of example 1.
The yield was calculated to be 89.1%, the product purity 96.8% and the chroma 485.6Hazen.
According to the experimental results of the above examples and comparative examples, it can be seen that the addition amount of the first-stage acrylonitrile and the second-stage acrylonitrile will affect the reaction effect of the third-stage acrylonitrile and further affect the chromaticity, and the addition amounts of the first-stage acrylonitrile and the second-stage acrylonitrile have a matching relationship; the comparison of the experimental results of example 1 with examples 5 and 6 can prove that the catalyst dosage has a certain effect of the three-stage reaction, and the comparison of the experimental results of example 1 with examples 7 and 8 can prove that the total acrylonitrile dosage of the first two stages has a certain effect on the final total chromaticity.
Comparison of comparative example 1 with example 1 shows that the two-stage reaction, which only uses one-stage reaction to produce one-stage substitution product, is not sufficient to effectively reduce the chromaticity of the final product, while comparative example 2 shows that even if the dropping time is prolonged, 1,2, 3-tris (cyanoethoxy) propane with low color value cannot be obtained, and further shows that the above-mentioned examples are not simple elongation reaction stages, but the products of the one-stage reaction and the two-stage reaction produce synergistic cooperation to improve the selectivity of the three-stage reaction, and avoid the self-polymerization of acrylonitrile. The experimental results of comparative examples 3 and 4 prove that the temperature and the adding speed of the first-stage reaction and the second-stage reaction have specific coordination relation with the adding amount and the adding speed, the self-polymerization of the acrylonitrile cannot be avoided simply by reducing the reaction temperature and slowing down the adding speed, and the reaction temperature which is too low is under the condition of the catalyst consumption and the acrylonitrile consumption, but the reaction efficiency of the final three-stage acrylonitrile and the glycerol cannot be improved to cause the increase of the chromaticity of the product. Comparative example 3 the reaction conditions of the two-stage method of comparative example 1 were employed to separate the two-stage acrylonitrile into three-stage acrylonitrile for the three-stage reaction, which corresponds to a simple reaction step of the two-stage method of elongation, and the reaction effect of the examples could not be obtained.
From the examples and comparative examples, it can be demonstrated that the examples utilize the combination of the added amount, total amount, temperature and addition rate of acrylonitrile for specific primary and secondary reactions to avoid the self-polymerization of the addition of the tertiary acrylonitrile and reduce the color of 1,2, 3-tris (cyanoethoxy) propane.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. A method for producing 1,2, 3-tri (cyanoethoxy) propane, which is characterized in that: the method comprises the following steps:
1) Mixing glycerol and a catalyst, heating to 30-80 ℃, and stirring until the glycerol and the catalyst are dissolved;
2) The temperature of the reaction system is controlled at 60-70 ℃, a section of acrylonitrile is added, and the mole ratio of the section of acrylonitrile to the glycerol is 0.5-1.5: 1, uniformly adding a section of acrylonitrile into a reaction system for 0.8-1 h, and reacting for 1-1.5 h after the addition is finished;
3) The temperature of the reaction system is controlled at 40-50 ℃, and secondary acrylonitrile is added, wherein the molar ratio of the secondary acrylonitrile to the glycerol is 0.5-1.5: 1, uniformly adding the second-stage acrylonitrile into a reaction system for 1.5-2 hours, and reacting for 1.5-2 hours after the addition is finished;
4) The temperature of the reaction system is controlled at 25-30 ℃, three sections of acrylonitrile are added, the molar ratio of the three sections of acrylonitrile to the glycerol is 1.0-1.4:1, the three sections of acrylonitrile are uniformly added into the reaction system for 2-4 hours, and the reaction is carried out for 3-8 hours after the addition is completed;
5) And (3) dissolving, washing and purifying the product obtained in the step (4) by using a solvent to obtain the 1,2, 3-tri (cyanoethoxy) propane.
2. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, wherein: the weight of the catalyst is 0.5-3% of the weight of glycerol.
3. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, wherein: the weight of the catalyst is 1-2% of that of glycerol.
4. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, wherein: the ratio of the total mole amount of the primary acrylonitrile to the secondary acrylonitrile to the mole amount of the glycerol is 2:1.
5. the process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 1, wherein: the washing and purifying of the step 5) sequentially comprises acid washing, water washing and reduced pressure distillation; stirring, standing and layering after acid washing, taking an upper product phase, washing to be neutral, and carrying out reduced pressure distillation to obtain 1,2, 3-tri (cyanoethoxy) propane.
6. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 5, wherein: the vacuum distillation is carried out at a vacuum degree of 300Pa, and fractions at 250-270 ℃ are collected to obtain 1,2, 3-tri (cyanoethoxy) propane.
7. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 5, wherein: the pickling is carried out by adopting a sulfuric acid solution with the concentration of 5-60% by weight, and the addition amount of the sulfuric acid solution is 2-10% of the weight of the product phase.
8. The process for producing 1,2, 3-tris (cyanoethoxy) propane according to claim 5, wherein: the pickling is carried out by adopting a sulfuric acid solution with the concentration of 60% by weight, and the addition amount of the sulfuric acid solution is 3-5% of the weight of the product phase.
9. A system for producing 1,2, 3-tris (cyanoethoxy) propane, characterized in that: the device comprises a glycerol raw material tank (1), an acrylonitrile raw material tank (2), a reaction kettle (3), a heat exchanger (4), an acid washing tower (5), a water washing tower (6), a flash evaporation tower (7), a solvent tank (8), a light component tank (9) and a product tank (10); the glycerol feed tank (1) is connected with the acrylonitrile feed tank (2) and is connected with the reaction kettle (3), the heat exchanger (4) is connected with the outer wall of the reaction kettle (4), the discharge end of the reaction kettle (3), the acid washing tower (5), the water washing tower (6) and the flash evaporation tower (7) are sequentially connected in series, and the flash evaporation tower (7) is respectively connected to the solvent tank (8), the light component tank (9) and the product tank (10).
10. The production system of 1,2, 3-tris (cyanoethoxy) propane according to claim 9, wherein: the reaction kettle (3) is internally provided with a stirrer (301) and a distributor (302), and the distributor (302) is connected with the glycerol raw material tank (1).
CN202310662814.0A 2023-06-06 2023-06-06 Production method and system of 1,2, 3-tri (cyanoethoxy) propane Active CN116606219B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310662814.0A CN116606219B (en) 2023-06-06 2023-06-06 Production method and system of 1,2, 3-tri (cyanoethoxy) propane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310662814.0A CN116606219B (en) 2023-06-06 2023-06-06 Production method and system of 1,2, 3-tri (cyanoethoxy) propane

Publications (2)

Publication Number Publication Date
CN116606219A true CN116606219A (en) 2023-08-18
CN116606219B CN116606219B (en) 2024-02-23

Family

ID=87674553

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310662814.0A Active CN116606219B (en) 2023-06-06 2023-06-06 Production method and system of 1,2, 3-tri (cyanoethoxy) propane

Country Status (1)

Country Link
CN (1) CN116606219B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005263716A (en) * 2004-03-19 2005-09-29 Mitsubishi Chemicals Corp Method for producing cyanoalkoxy compound
JP2005263717A (en) * 2004-03-19 2005-09-29 Mitsubishi Chemicals Corp Method for producing cyanoalkoxy compound
US20120249700A1 (en) * 2011-03-31 2012-10-04 Fujifilm Corporation Ink composition and image forming method
US20130316252A1 (en) * 2012-05-22 2013-11-28 Lg Chem, Ltd. Non-Aqueous Electrolyte Solution For Lithium Secondary Battery And Lithium Secondary Battery Comprising The Same
WO2013176421A1 (en) * 2012-05-22 2013-11-28 주식회사 엘지화학 Nonaqueous electrolyte solution for lithium secondary battery, and lithium secondary battery containing same
JP2014069156A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Functional polymer membrane, and method for producing the same
KR20150105790A (en) * 2014-03-10 2015-09-18 에스케이이노베이션 주식회사 Novel etheramine polyisobutenyl succinimide based compounds, process for preparing thereof and lubricating oil compositions comprising the same as dispersant
CN112898181A (en) * 2019-11-18 2021-06-04 石家庄圣泰化工有限公司 Preparation method of 1,2, 3-tri (2-cyanoxy) propane
CN114195681A (en) * 2020-09-18 2022-03-18 浙江蓝天环保高科技股份有限公司 Preparation method of 1,2, 3-tri (cyanoethoxy) propane

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005263716A (en) * 2004-03-19 2005-09-29 Mitsubishi Chemicals Corp Method for producing cyanoalkoxy compound
JP2005263717A (en) * 2004-03-19 2005-09-29 Mitsubishi Chemicals Corp Method for producing cyanoalkoxy compound
US20120249700A1 (en) * 2011-03-31 2012-10-04 Fujifilm Corporation Ink composition and image forming method
JP2012214561A (en) * 2011-03-31 2012-11-08 Fujifilm Corp Ink composition and image forming method
US20130316252A1 (en) * 2012-05-22 2013-11-28 Lg Chem, Ltd. Non-Aqueous Electrolyte Solution For Lithium Secondary Battery And Lithium Secondary Battery Comprising The Same
WO2013176421A1 (en) * 2012-05-22 2013-11-28 주식회사 엘지화학 Nonaqueous electrolyte solution for lithium secondary battery, and lithium secondary battery containing same
JP2014069156A (en) * 2012-09-28 2014-04-21 Fujifilm Corp Functional polymer membrane, and method for producing the same
KR20150105790A (en) * 2014-03-10 2015-09-18 에스케이이노베이션 주식회사 Novel etheramine polyisobutenyl succinimide based compounds, process for preparing thereof and lubricating oil compositions comprising the same as dispersant
CN112898181A (en) * 2019-11-18 2021-06-04 石家庄圣泰化工有限公司 Preparation method of 1,2, 3-tri (2-cyanoxy) propane
CN114195681A (en) * 2020-09-18 2022-03-18 浙江蓝天环保高科技股份有限公司 Preparation method of 1,2, 3-tri (cyanoethoxy) propane

Also Published As

Publication number Publication date
CN116606219B (en) 2024-02-23

Similar Documents

Publication Publication Date Title
CN101717348B (en) Synthesis method of diisopropyl azodiformate
CN105111079A (en) Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol
CN108570021B (en) Vulcanization accelerator CBS and continuous production method thereof
CN108059586B (en) Method for preparing dichloropropanol by glycerol chlorination
CN113024376A (en) Production process of hexadecanediester
CN112479808B (en) Method for preparing cyclohexanol by directly hydrating cyclohexene
CN116606219B (en) Production method and system of 1,2, 3-tri (cyanoethoxy) propane
CN103848739A (en) Production method of high-purity dimethyl fumarate
CN100537521C (en) Method for synthesizing N,N dimethyl acetamide in high purity
CN106518620B (en) A kind of method and device preparing sec-butyl alcohol
CN109721496B (en) Synthetic method of 3-nitro-o-xylene
CN112778094B (en) Preparation process of high-purity tetrabromobisphenol A
CN115626910A (en) Preparation method of vinyl sulfate
CN114409555A (en) Utilization method of bromamine acid by-product
CN102040479B (en) System for preparing dichloropropanol by autocatalytic reaction of glycerol and hydrogen chloride
CN116239496A (en) Method for continuously preparing heptafluoroisobutyronitrile
CN113735703A (en) Method for effectively recovering dibasic acid and nitric acid from adipic acid wastewater
CN106478402A (en) The method that ethanol acid crystal is prepared by methyl glycollate
CN108080027B (en) Resin catalyst treatment process for preparing caprolactam through liquid phase Beckmann rearrangement
CN104230764A (en) Preparation method of 2-acrylamide-2-methyl propanesulfonic acid
CN111072473A (en) Preparation method of dimethyl adipate
CN114456069B (en) Energy-saving process and system for producing and separating ethyl methyl carbonate
CN113999086B (en) Preparation method of 1-chloromethyl naphthalene
CN113845426B (en) Method and device for preparing ester compound
CN219631290U (en) Production system of glutaronitrile

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