CN116003362A - Method for treating acetic anhydride dehydration waste liquid generated by 3,3', 4' -diphenyl ether dianhydride dehydration process - Google Patents
Method for treating acetic anhydride dehydration waste liquid generated by 3,3', 4' -diphenyl ether dianhydride dehydration process Download PDFInfo
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 230000018044 dehydration Effects 0.000 title claims abstract description 52
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 52
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- RZKIRKYGCBPVJA-UHFFFAOYSA-N 9H-fluorene-1,2,3,4-tetracarboxylic acid Chemical compound C1(=C(C(=C(C=2C3=CC=CC=C3CC12)C(=O)O)C(=O)O)C(=O)O)C(=O)O RZKIRKYGCBPVJA-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 diphenyl ether tetracarboxylic acid Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 22
- 150000007529 inorganic bases Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 38
- 235000017281 sodium acetate Nutrition 0.000 abstract description 34
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 30
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 18
- 239000001632 sodium acetate Substances 0.000 abstract description 18
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 abstract description 16
- 229940087562 sodium acetate trihydrate Drugs 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 9
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 abstract description 7
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- SQAYGZJIWUVYKU-UHFFFAOYSA-N C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)OC1=CC=CC=C1 Chemical compound C(=O)O.C(=O)O.C(=O)O.C(=O)O.C1(=CC=CC=C1)OC1=CC=CC=C1 SQAYGZJIWUVYKU-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of resource recovery, and provides a method for treating acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process. According to the invention, through a first heat preservation reaction and a first cooling crystallization, 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride in acetic anhydride dehydration waste liquid can be respectively converted into 9-oxo (hetero) fluorene tetracarboxylic acid and biphenyl ether tetracarboxylic acid for recycling; meanwhile, the 9-oxo (hetero) fluorene tetracarboxylic acid and the diphenyl ether tetracarboxylic acid are easy to be converted into 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride, can be used for producing 3,3', 4' -diphenyl ether dianhydride, has low treatment energy consumption, has higher economic benefit and environmental benefit, and has extremely high popularization value. Adding inorganic alkali aqueous solution into the filtrate obtained by the first cooling crystallization, recovering acetic anhydride and acetic acid in the form of sodium acetate trihydrate and sodium acetate aqueous solution, wherein sodium acetate can be used for biochemically providing a carbon source.
Description
Technical Field
The invention relates to the technical field of resource recovery, in particular to a method for treating acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process.
Background
3,3', 4' -diphenyl ether dianhydride is an important monomer for manufacturing polyimide polymer materials (PI). Polyimide polymer material has wide application in the fields of aerospace, motor wrapping, automobile industry, mechanical industry, light industry, electric appliance industry, precision mechanical industry, electronic industry and the like. With the increase of polyimide polymer material types, the industrial demand is increased, and especially the large-scale application of the OLED on the smart phone, so that the explosive demand of the polyimide polymer film is increased, and the demand of the basic monomers of 3,3', 4' -diphenyl ether dianhydride is also increased year by year. Some problems which are easy to solve and even neglect in the prior small-batch production of 3,3', 4' -diphenyl ether dianhydride are prominent in the continuous mass production process, especially the problem of environmental protection.
A large amount of acetic anhydride dehydration waste liquid is generated in the dehydration process of 3,3', 4' -diphenyl ether dianhydride, and contains a large amount of acetic anhydride and acetic acid, and contains a small amount of 3,3', 4' -diphenyl ether dianhydride and 9-oxy (hetero) fluorene dianhydride, wherein the acetic anhydride and the acetic acid account for about 97wt%, and the 9-oxy (hetero) fluorene dianhydride accounts for about 3wt% of the 3,3', 4' -diphenyl ether dianhydride. At present, acetic anhydride and acetic acid are directly distilled from acetic anhydride dehydration waste liquid generated in the process of producing 3,3', 4' -diphenyl ether dianhydride at home and abroad, kettle residues are treated as solid waste, environmental protection cost is generated in the treatment process, pressure is increased for environmental protection work, and meanwhile, 3', 4' -diphenyl ether dianhydride and 9-oxo (hetero) fluorene dianhydride in residues are also treated as solid waste to cause material loss.
Therefore, a method for recovering 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride from acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process and effectively utilizing the waste acid anhydride is sought, and the method for reducing environmental protection pressure of enterprises has important significance for improving economic benefit of enterprises and reducing environmental protection pressure.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for treating acetic anhydride dehydration waste liquid generated by a dehydration process of 3,3', 4' -diphenyl ether dianhydride. The treatment method can recycle 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride in the waste liquid, and convert the 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid into 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid respectively for recycling; meanwhile, acetic anhydride and acetic acid are recovered in the form of sodium acetate trihydrate and sodium acetate aqueous solution, so that the effective recovery of raw materials in waste liquid is realized, the environmental protection pressure of enterprises is reduced, and the economic benefit of the enterprises is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for treating acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process, which comprises the following steps:
mixing acetic anhydride dehydration waste liquid and water, and sequentially carrying out a first heat preservation reaction and a first cooling crystallization to obtain solid and filtrate; the solid comprises 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid;
dropwise adding inorganic alkaline water solution into the filtrate, and controlling the temperature in the dropwise adding process to be not more than 95-105 ℃; and after the dropwise adding of the inorganic alkali water solution is finished, performing second cooling crystallization to obtain a trihydrate acetate and an acetate water solution.
Preferably, the mass ratio of the acetic anhydride dehydration waste liquid to water is 100: 40-50.
Preferably, the means for mixing the acetic anhydride dehydration waste liquid and water comprises: dropwise adding water into the acetic anhydride dehydration waste liquid, wherein the dropwise adding temperature of the water is 95-105 ℃; the water addition was completed within 1 h.
Preferably, the temperature of the first heat preservation reaction is 95-105 ℃ for 6-10 hours.
Preferably, the temperature of the first cooling crystallization is 20-30 ℃ and the time is 1-2 h.
Preferably, the inorganic base in the aqueous inorganic base solution comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the mass concentration of the inorganic alkaline aqueous solution is 30-50%.
Preferably, the mass ratio of the inorganic base in the filtrate and the inorganic base aqueous solution is 100:72 to 76.
Preferably, the inorganic alkaline aqueous solution is added dropwise over 1-2 hours.
Preferably, the temperature of the second cooling crystallization is 5-15 ℃ and the time is 1-2 h.
The invention provides a method for treating acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process, which comprises the following steps: mixing acetic anhydride dehydration waste liquid and water, and sequentially carrying out a first heat preservation reaction and a first cooling crystallization to obtain solid and filtrate; the solid comprises 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid; dropwise adding inorganic alkaline water solution into the filtrate, and controlling the temperature in the dropwise adding process to be not more than 95-105 ℃; and after the dropwise adding of the inorganic alkali water solution is finished, performing second cooling crystallization to obtain sodium acetate trihydrate and a sodium acetate water solution. According to the invention, through a first heat preservation reaction and a first cooling crystallization, 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride in acetic anhydride dehydration waste liquid can be respectively converted into 9-oxo (hetero) fluorene tetracarboxylic acid and biphenyl ether tetracarboxylic acid for recycling; meanwhile, the 9-oxo (hetero) fluorene tetracarboxylic acid and the diphenyl ether tetracarboxylic acid are easy to be converted into 9-oxo (hetero) fluorene dianhydride and 3,3', 4' -diphenyl ether dianhydride, can be used for producing 3,3', 4' -diphenyl ether dianhydride, has low treatment energy consumption, has higher economic benefit and environmental benefit, and has extremely high popularization value. Adding inorganic alkali aqueous solution into the filtrate, recovering acetic anhydride and acetic acid in the form of sodium acetate trihydrate and sodium acetate aqueous solution, wherein sodium acetate can be used for biochemically providing carbon sources. The treatment method provided by the invention realizes effective recovery of raw materials in the waste liquid, reduces environmental protection pressure of enterprises, and improves economic benefits of the enterprises.
Detailed Description
The invention provides a method for treating acetic anhydride dehydration waste liquid generated by a 3,3', 4' -diphenyl ether dianhydride dehydration process, which comprises the following steps:
mixing acetic anhydride dehydration waste liquid and water, and sequentially carrying out a first heat preservation reaction and a first cooling crystallization to obtain solid and filtrate; the solid comprises 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid;
dropwise adding inorganic alkaline water solution into the filtrate, and controlling the temperature in the dropwise adding process to be not more than 95-105 ℃; and after the dropwise adding of the inorganic alkali water solution is finished, performing second cooling crystallization to obtain a trihydrate acetate and an acetate water solution.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
Mixing acetic anhydride dehydration waste liquid and water, and sequentially carrying out a first heat preservation reaction and a first cooling crystallization to obtain solid and filtrate; the solids include 9-oxo (hetero) fluorene tetracarboxylic acid and biphenyl ether tetracarboxylic acid.
In the invention, the acetic anhydride dehydration waste liquid comprises acetic anhydride, acetic acid, 3', 4' -diphenyl ether dianhydride and 9-oxo (hetero) fluorene dianhydride; the anhydride dehydration waste liquid contains 40-80% of acetic anhydride by mass, 20-50% of acetic acid by mass, 0-10% of 3,3', 4' -diphenyl ether dianhydride by mass and 0-10% of 9-oxo (hetero) fluorene dianhydride by mass.
In the present invention, the water is preferably pure water.
In the invention, the mass ratio of the acetic anhydride dehydration waste liquid to water is preferably 100:40 to 50, more preferably 100:42 to 48, more preferably 100: 44-46.
In the present invention, the means for mixing the acetic anhydride dehydration waste liquid with water preferably comprises: and (3) dropwise adding water into the acetic anhydride dehydration waste liquid. In the present invention, the dropping temperature of the water is preferably 95 to 105 ℃, and more preferably 97 to 98 ℃. In the present invention, the water is preferably added dropwise over 1 hour.
In the present invention, the temperature of the first heat-retaining reaction is preferably 95 to 105 ℃; the time is preferably 6 to 10 hours, more preferably 8 hours.
In the invention, the temperature of the first cooling crystallization is preferably 20-30 ℃ and the time is preferably 1-2 h. In the present invention, the rate of lowering the temperature from the first thermal insulation reaction to the temperature of the first reduced temperature crystallization is preferably 1 to 2 ℃/min.
After the first cooling crystallization, the invention preferably further comprises centrifugation to obtain solids and filtrate. In the present invention, the temperature of the centrifugation is preferably consistent with the temperature of the first cooling crystallization, and will not be described herein.
After filtrate is obtained, inorganic alkaline water solution is dripped into the filtrate, and the temperature in the dripping process is controlled to be not more than 95-105 ℃; and after the dropwise adding of the inorganic alkali water solution is finished, performing second cooling crystallization to obtain a trihydrate acetate and an acetate water solution.
In the present invention, the inorganic base in the aqueous inorganic base solution preferably includes sodium hydroxide and/or potassium hydroxide, and more preferably sodium hydroxide. In the present invention, the mass concentration of the inorganic alkaline aqueous solution is preferably 30 to 50%, more preferably 40%. In the invention, the mass ratio of the inorganic base in the filtrate and the inorganic base aqueous solution is preferably 100:72 to 76. In the present invention, the inorganic alkaline aqueous solution is added to the filtrate in its entirety, and the pH of the resulting system is preferably 9.2 to 9.7.
In the present invention, the inorganic aqueous alkali is preferably completely added in 1 to 2 hours, more preferably 1.8 hours.
In the invention, the reaction of acetic acid and acetic anhydride in the filtrate with inorganic base is exothermic; with the addition of the inorganic alkaline water solution, the temperature of the filtrate is gradually increased; preferably, when the temperature of the system is raised to 98 ℃ with the addition of the inorganic alkaline aqueous solution, the system starts to be cooled, and the temperature of the system is controlled to be 95-105 ℃.
In the present invention, the temperature of the second cooling crystallization is preferably 5 to 15 ℃, and the time is preferably 1 to 2 hours.
In the present invention, the rate of cooling from 95 to 105 ℃ to the temperature of the second cooling crystallization is preferably 0.5 to 2 ℃/min.
The method for treating the acetic anhydride dehydration waste liquid generated by the 3,3', 4' -diphenyl ether dianhydride dehydration process provided by the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
100g of acetic anhydride dehydration waste liquid (wherein the content of acetic anhydride is 65wt percent, the content of acetic acid is 32wt percent, the content of 9-oxo (hetero) fluorene dianhydride is 0.7wt percent) generated in the 3,3', 4' -diphenyl ether dianhydride dehydration process is heated to 97 ℃, 50g of pure water is dripped, the temperature is kept for 1 hour after dripping, the temperature is kept at 105 ℃ for 6 hours, then the temperature is kept at 1 ℃/min to 20 ℃, the temperature is kept for 1 hour, the centrifugation is carried out, and 3.55g of 9-oxo (hetero) fluorene tetracarboxylic acid and 3.33g of biphenyl ether tetracarboxylic acid are obtained after drying.
And (3) dropwise adding a 40wt% sodium hydroxide aqueous solution into the filtrate at 31 ℃, when the temperature reaches 98 ℃, starting to cool, maintaining the temperature at 95-105 ℃, and after the dropwise adding of 180.9g sodium hydroxide aqueous solution is finished, the pH of the system is 9.25, starting to cool, cooling to 10 ℃ at 1 ℃/min, preserving heat for 1h, and centrifuging to obtain 160.27g of sodium acetate trihydrate and 166.28g of sodium acetate aqueous solution.
And (3) detecting: the mass content of sodium acetate trihydrate in the sodium acetate trihydrate is 99.4%, and the tetra-sodium salt of 9-oxo (hetero) fluorene tetra-formate and the tetra-sodium salt of diphenyl ether tetra-formate are not detected; the mass content of sodium acetate in the sodium acetate aqueous solution was 31.37%, and the mass content of the tetra-sodium salt of 9-oxo (hetero) fluorene tetracarboxylic acid and the tetra-sodium salt of diphenyl ether tetracarboxylic acid was 120ppm.
Example 2
100g of acetic anhydride dehydration waste liquid (wherein the content of acetic anhydride is 65wt percent, the content of acetic acid is 32wt percent, the content of 9-oxo (hetero) fluorene dianhydride is 0.7wt percent) produced by a 3,3', 4' -diphenyl ether dianhydride dehydration process is heated to 98 ℃, 40g of pure water is dripped, the temperature is kept for 10 hours at 105 ℃ after the dripping is finished, then the temperature is reduced to 20 ℃ at 20 ℃/15min, the temperature is kept for 1 hour, and the centrifugation is carried out, so as to obtain 3.6g of 9-oxo (hetero) fluorene tetracarboxylic acid and 3.32g of biphenyl ether tetracarboxylic acid after drying.
And (3) dropwise adding a 40% sodium hydroxide aqueous solution into the filtrate at 31 ℃, when the temperature reaches 98 ℃, starting to cool, maintaining the temperature at 95-105 ℃, dropwise adding 185g sodium hydroxide aqueous solution for 1.8 hours, after the dropwise adding is finished, reducing the pH of the system to 9.7, starting to cool, cooling to 10 ℃ at 1 ℃/min, preserving heat for 1h, and centrifuging to obtain 176.31g of sodium acetate trihydrate and 144.33g of sodium acetate aqueous solution.
And (3) detecting: the mass content of sodium acetate trihydrate in the sodium acetate trihydrate is 99.3%, and the tetra-sodium salt of 9-oxo (hetero) fluorene tetra-formate and the tetra-sodium salt of diphenyl ether tetra-formate are not detected; in the sodium acetate aqueous solution, the mass content of sodium acetate was 29.58%, and the mass content of the tetra-sodium salt of 9-oxo (hetero) fluorene tetracarboxylic acid and the tetra-sodium salt of diphenyl ether tetracarboxylic acid was 198ppm.
Example 3
100g of acetic anhydride dehydration waste liquid (wherein the content of acetic anhydride is 65wt percent, the content of acetic acid is 32wt percent, the content of 9-oxo (hetero) fluorene dianhydride is 0.7wt percent) produced by a 3,3', 4' -diphenyl ether dianhydride dehydration process is heated to 95 ℃, 50g of pure water is dripped, the temperature is kept for 1 hour at 105 ℃ after the dripping is finished, the temperature is kept for 8 hours, then the temperature is reduced to 20 ℃ at 25 ℃/15min, the temperature is kept for 1 hour, and the centrifugation is carried out, so that 3.54g of 9-oxo (hetero) fluorene tetracarboxylic acid and 3.34g of biphenyl ether tetracarboxylic acid are obtained after drying.
And (3) dropwise adding a 40% sodium hydroxide aqueous solution into the filtrate at 31 ℃, when the temperature reaches 98 ℃, starting to cool, maintaining the temperature at 95-105 ℃, keeping the pH of the system at 9.51 after the dropwise adding of 183.8g sodium hydroxide aqueous solution for 1.8 hours, starting to cool, cooling to 9 ℃ at 2 ℃/min, preserving heat for 1 hour, and centrifuging to obtain 166.32g of sodium acetate trihydrate and 162.28g of sodium acetate aqueous solution.
And (3) detecting: the mass content of sodium acetate trihydrate in the sodium acetate trihydrate is not 99.4%, and the tetra-sodium salt of 9-oxo (hetero) fluorene tetra-formate and the tetra-sodium salt of diphenyl ether tetra-formate are not detected; the sodium acetate aqueous solution contains 29.92% by mass of sodium acetate and 65ppm by mass of the tetra-sodium salt of 9-oxo (hetero) fluorene tetra-carboxylic acid and the tetra-sodium salt of diphenyl ether tetra-carboxylic acid.
Comparative example 1
The comparative example provides a method for treating waste anhydride from dehydration of 3,3', 4' -diphenyl ether dianhydride, which comprises the following steps:
taking 100g of acetic anhydride dehydration waste liquid (wherein the content of acetic anhydride is 65wt%, the content of acetic acid is 32wt%, the content of 9-oxo (hetero) fluorene dianhydride is 0.7wt%, the content of 3,3', 4' -diphenyl ether dianhydride is 2.3 wt%) produced by a 3,3', 4' -diphenyl ether dianhydride dehydration process, dropwise adding 40% sodium hydroxide aqueous solution and 50g of pure water at 25 ℃, when the temperature reaches 98 ℃, starting to cool, maintaining the temperature at 95-105 ℃, dropwise adding 184.9g of sodium hydroxide aqueous solution for 1.8 hours, after dropwise adding, the pH value of the system is 9.45, starting to cool, cooling to 10 ℃ at 15 ℃/15min, preserving heat for 1h, and centrifuging to obtain 163.54g of sodium acetate trihydrate and 170.26g of sodium acetate aqueous solution.
And (3) detecting: the mass content of sodium acetate trihydrate in the sodium acetate trihydrate is 97.4 percent, and the mass content of the 9-oxo (hetero) fluorene tetra-carboxylic acid tetrasodium salt and the biphenyl ether tetra-carboxylic acid tetrasodium salt is 0.46 percent; the mass content of sodium acetate in the sodium acetate aqueous solution is 30.65%, and the mass content of the 9-oxo (hetero) fluorene tetra-carboxylic acid tetrasodium salt and the mass content of the diphenyl ether tetra-carboxylic acid tetrasodium salt are 2.03%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for treating the acetic anhydride dehydration waste liquid generated by the 3,3', 4' -diphenyl ether dianhydride dehydration process is characterized by comprising the following steps:
mixing acetic anhydride dehydration waste liquid and water, and sequentially carrying out a first heat preservation reaction and a first cooling crystallization to obtain solid and filtrate; the solid comprises 9-oxo (hetero) fluorene tetracarboxylic acid and diphenyl ether tetracarboxylic acid;
dropwise adding inorganic alkaline water solution into the filtrate, and controlling the temperature in the dropwise adding process to be not more than 95-105 ℃; and after the dropwise adding of the inorganic alkali water solution is finished, performing second cooling crystallization to obtain a trihydrate acetate and an acetate water solution.
2. The treatment method according to claim 1, wherein the mass ratio of the acetic anhydride dehydration waste liquid to water is 100: 40-50.
3. The method according to claim 1 or 2, wherein the means for mixing the acetic anhydride dehydration waste liquid and water comprises: dropwise adding water into the acetic anhydride dehydration waste liquid, wherein the dropwise adding temperature of the water is 95-105 ℃; the water addition was completed within 1 h.
4. The method according to claim 1, wherein the temperature of the first heat-retaining reaction is 95 to 105 ℃ for 6 to 10 hours.
5. The method according to claim 1, wherein the temperature of the first cooling crystallization is 20-30 ℃ for 1-2 hours.
6. The process according to claim 1, wherein the inorganic base in the aqueous inorganic base solution comprises sodium hydroxide and/or potassium hydroxide.
7. The method according to claim 6, wherein the inorganic alkaline aqueous solution has a mass concentration of 30 to 50%.
8. The method according to claim 1, 6 or 7, wherein the mass ratio of the inorganic base in the filtrate and the aqueous inorganic base solution is 100:72 to 76.
9. The method according to claim 1, wherein the dropwise addition of the aqueous inorganic alkali solution is completed within 1 to 2 hours.
10. The process of claim 1, wherein the second reduced temperature crystallization is at a temperature of 5 to 15 ℃ for a time of 1 to 2 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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