CN117024384A - Treatment method for mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production - Google Patents
Treatment method for mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production Download PDFInfo
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- CN117024384A CN117024384A CN202310785245.9A CN202310785245A CN117024384A CN 117024384 A CN117024384 A CN 117024384A CN 202310785245 A CN202310785245 A CN 202310785245A CN 117024384 A CN117024384 A CN 117024384A
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- biphenyl tetracarboxylic
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- tetracarboxylic acid
- sublimation
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- 239000002910 solid waste Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000859 sublimation Methods 0.000 claims abstract description 48
- 230000008022 sublimation Effects 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 45
- 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 claims abstract description 29
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- 230000006837 decompression Effects 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DBIOVBYLTPWVSW-UHFFFAOYSA-N 2-ethylpiperidin-4-one;hydrochloride Chemical compound Cl.CCC1CC(=O)CCN1 DBIOVBYLTPWVSW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Abstract
The invention belongs to the technical field of solid waste treatment, and provides a method for treating mixed solid waste in the production of 3,3', 4' -biphenyl tetracarboxylic acid. The first decompression sublimation can remove phthalic anhydride and chloro-phthalic anhydride in mixed solid waste generated in 3,3', 4' -biphenyl tetracarboxylic acid production. The alkali dissolution can remove carbonized substances generated during the first reduced pressure sublimation. The second pressure reducing and lifting can purify and dewater the crude 3,3', 4' -biphenyl tetracarboxylic acid to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the refined 3,3', 4' -biphenyl tetracarboxylic dianhydride can be sold as a product. The treatment method provided by the invention can recover 3,3', 4' -biphenyl tetracarboxylic dianhydride, realizes the resource utilization of the solid waste of the mixture, and has the advantages of low cost, low energy consumption and no generation of dioxin secondary pollutants.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for treating mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production.
Background
3,3', 4' -biphenyl dianhydride (BPDA) can be used as a polyimide monomer to be polymerized with various amines to generate polyimide, and the polyimide generated by the polyimide is an indispensable material for wearable equipment, folding screen mobile phones and folding screen computers. In recent years, with the rapid development of hot technology 5G, wearable devices, folding screen mobile phones, folding screen computers and the like, the demand for polyimide has increased significantly.
At present, 3', 4' -biphenyl dianhydride is obtained by dehydrating 3,3', 4' -biphenyl tetracarboxylic acid, the industrial synthesis method of 3,3', 4' -biphenyl tetracarboxylic acid mainly comprises the steps of using phthalic anhydride for chlorination to obtain a 4-chlorophthalic acid monosodium salt mixture, then dechlorinating, coupling and acid separating under the catalysis of noble metal to obtain crude biphenyl tetracarboxylic acid, and refining about 1.1t of crude biphenyl tetracarboxylic acid to obtain 1t of fine biphenyl tetracarboxylic acid; meanwhile, 90kg of 3,3', 4' -biphenyl tetracarboxylic acid and mixed solid waste of chlorophthalic acid and phthalic acid can be recovered after treatment of refining mother liquor generated in the refining process of the 3,3', 4' -biphenyl tetracarboxylic acid crude product; in the mixed solid waste, the content of 3,3', 4' -biphenyl tetracarboxylic acid is 63-65wt%, the content of phthalic acid is 34-36 wt%, and the content of chlorophthalic acid is 1-1.4wt%.
At present, mixed solid waste is mainly treated by adopting an incineration method. The incineration method directly carries out combustion treatment on the mixture solid waste, but because the mixture solid waste contains organic chlorine, dioxin can be generated in the incineration process, the dioxin can be completely decomposed only at about 1100 ℃ after being generated, the treatment cost and the energy consumption are high, and the recycling utilization of 3,3', 4' -biphenyl tetracarboxylic acid in the mixture solid waste can not be realized.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for treating mixed solid waste in the production of 3,3', 4' -biphenyltetracarboxylic acid. The treatment method provided by the invention can recover 3,3', 4' -biphenyl tetracarboxylic dianhydride, realizes the resource utilization of the solid waste of the mixture, and has the advantages of low cost, low energy consumption and no generation of dioxin secondary pollutants.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for treating mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production, which comprises the following steps:
carrying out first decompression sublimation on mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid to obtain pretreated solid waste;
alkali dissolution is carried out on the pretreated solid waste, and alkali insoluble matters are removed to obtain alkali solution;
adjusting the pH value of the alkali solution to be acidic, and obtaining a crude product of 3,3', 4' -biphenyl tetracarboxylic acid through hot filtration;
performing second reduced pressure sublimation on the 3,3', 4' -biphenyl tetracarboxylic acid crude product, discarding an initial fraction, and collecting a middle-section fraction to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride;
the mass of the initial fraction is 5-10% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid;
the mass of the middle-section fraction is 70-80% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid.
Preferably, the temperature of the first reduced pressure sublimation is 110-120 ℃ and the vacuum degree is 3-5 mmHg.
Preferably, the pH value of the alkali is 12-14, and the temperature is 80-105 ℃.
Preferably, the alkali solution used for the alkali dissolution has a mass concentration of 20-30%.
Preferably, the mode of removing the alkali insoluble matters is solid-liquid separation.
Preferably, the acidic pH is between 0.5 and 1.5.
Preferably, the temperature of the hot filtration is 70-80 ℃.
Preferably, the temperature of the second reduced pressure sublimation is 230-240 ℃, and the vacuum degree is less than or equal to 1mmHg.
The invention provides a method for treating mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production, which comprises the following steps: carrying out first decompression sublimation on mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid to obtain pretreated solid waste; alkali dissolution is carried out on the pretreated solid waste, and alkali insoluble matters are removed to obtain alkali solution; adjusting the pH value of the alkali solution to be acidic, and obtaining a crude product of 3,3', 4' -biphenyl tetracarboxylic acid through hot filtration; performing second reduced pressure sublimation on the 3,3', 4' -biphenyl tetracarboxylic acid crude product, discarding an initial fraction, and collecting a middle-section fraction to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride; the mass of the initial fraction is 5-10% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid; the mass of the middle-section fraction is 70-80% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid. The first decompression sublimation can remove phthalic anhydride (phthalic acid can remove one molecule of water to form phthalic anhydride during sublimation) in mixed solid waste generated in 3,3', 4' -biphenyl tetracarboxylic acid production and chlorophthalic anhydride (chlorophthalic acid can remove one molecule of water to form chlorophthalic anhydride during sublimation); meanwhile, phthalic anhydride and chlorophthalic dianhydride can be used for preparing 4-chlorophthalic monosodium salt, so that the resource utilization rate is improved. The alkali dissolution can remove carbonized substances generated during the first reduced pressure sublimation. The second decompression sublimation can purify and dehydrate the crude 3,3', 4' -biphenyl tetracarboxylic acid to obtain refined 3,3', 4' -biphenyl tetracarboxylic acid dianhydride, and the refined 3,3', 4' -biphenyl tetracarboxylic acid dianhydride can be sold as a product, thereby reducing the raw material cost for producing 3,3', 4' -biphenyl tetracarboxylic acid dianhydride. The treatment method provided by the invention can recover 3,3', 4' -biphenyl tetracarboxylic dianhydride, realizes the resource utilization of the solid waste of the mixture, and has the advantages of low cost, low energy consumption and no generation of dioxin secondary pollutants.
Detailed Description
The invention provides a method for treating mixed solid waste in 3,3', 4' -biphenyl tetracarboxylic acid production, which comprises the following steps:
carrying out first decompression sublimation on mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid to obtain pretreated solid waste;
alkali dissolution is carried out on the pretreated solid waste, and alkali insoluble matters are removed to obtain alkali solution;
adjusting the pH value of the alkali solution to be acidic, and obtaining a crude product of 3,3', 4' -biphenyl tetracarboxylic acid through hot filtration;
performing second reduced pressure sublimation on the 3,3', 4' -biphenyl tetracarboxylic acid crude product, discarding an initial fraction, and collecting a middle-section fraction to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride;
the mass of the initial fraction is 5-10% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid;
the mass of the middle-section fraction is 70-80% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid is subjected to first decompression sublimation, and pretreated solid waste is obtained.
In the invention, the mixed solid waste in the production of 3,3', 4' -biphenyl tetracarboxylic acid preferably comprises the following components in percentage by mass:
the content of 3,3', 4' -biphenyl tetracarboxylic acid is 63-65 wt%, the content of phthalic acid is 34-36 wt%, and the content of chlorophthalic acid is 1-1.4 wt%.
In the present invention, the temperature of the first reduced pressure sublimation is preferably 110 to 120 ℃, and the vacuum degree is preferably 3 to 5mmHg.
After the first reduced pressure sublimation, the present invention preferably further comprises pulverizing the obtained residue. In the present invention, the particle size of the pulverized material obtained after the pulverization is preferably not more than 3mm.
In the invention, the first decompression and sublimation can remove phthalic anhydride and chloro-o-phthalic anhydride in mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid.
After the pretreated solid waste is obtained, the pretreated solid waste is subjected to alkali dissolution, and alkali insoluble matters are removed to obtain an alkali solution.
In the present invention, the pH value of the alkali is preferably 12 to 14; the temperature is preferably 80 to 105 ℃, more preferably 85 to 100 ℃, still more preferably 90 to 95 ℃; the time is preferably 1h.
In a specific embodiment of the present invention, the alkali solution used for the alkali dissolution is specifically preferably an inorganic alkali solution, more preferably an aqueous sodium hydroxide solution.
In the present invention, the alkali solution used in the alkali dissolution is preferably 20 to 30% by mass. In the invention, the mass ratio of alkali liquor of alkali dissolution to pretreatment solid waste is preferably 1:0.4 to 0.6.
In the invention, the mode of removing the alkali insoluble matters is solid-liquid separation; the solid-liquid separation is preferably performed by filtration.
In the present invention, the alkali dissolution is capable of removing carbide formed by the first reduced pressure sublimation in the pretreated solid waste.
After the alkali solution is obtained, the pH value of the alkali solution is regulated to be acidic, and the 3,3', 4' -biphenyl tetracarboxylic acid crude product is obtained through hot filtration.
In the present invention, the acidic pH is preferably 0.5 to 1.5. In the present invention, the temperature of the thermal filtration is preferably 70 to 80 ℃.
After the hot filtration, the present invention preferably further comprises drying the resulting solid.
In the invention, the mass percentage of the 3,3', 4' -biphenyl tetracarboxylic acid in the 3,3', 4' -biphenyl tetracarboxylic acid crude product is more than or equal to 99.5 percent.
After obtaining 3,3', 4' -biphenyl tetracarboxylic acid crude products, carrying out second decompression sublimation on the 3,3', 4' -biphenyl tetracarboxylic acid crude products, discarding initial fractions, and collecting middle-section fractions to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride.
In the present invention, the temperature of the second reduced pressure sublimation is preferably 230 to 240℃and the vacuum degree is preferably 1mmHg or less.
In the invention, the mass of the initial fraction is 5-10% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid; the mass of the middle-section fraction is 70-80% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid.
In the invention, the collection mode of the refined 3,3', 4' -biphenyltetracarboxylic acid is specifically as follows: for example, 100g of crude 3,3', 4' -biphenyl tetracarboxylic acid is put into the reactor, the second decompression sublimation is carried out, and 5 to 10g of initial fraction is collected (discarded); then switching the sublimation condensing pipe to continuously collect 70-80 g of interruption fraction; the remaining fraction is disposed of as hazardous waste.
In the invention, the mass percentage of the refined 3,3', 4' -biphenyl tetracarboxylic dianhydride is more than or equal to 99.9 percent.
The method for treating the mixed solid waste in the production of 3,3', 4' -biphenyltetracarboxylic acid according to 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
Taking 100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid, and detecting that the mixed solid waste dry products comprise the following substances in percentage by mass: 63.5% of 3,3', 4' -biphenyltetracarboxylic acid, 35.1% of phthalic acid and 1.4% of chlorophthalic acid.
100g of mixed solid waste products produced by 3,3', 4' -biphenyl tetracarboxylic acid are put into a sublimation kettle, a vacuum pump is started, the vacuum degree is controlled to be 3.5mmHg, the temperature is raised to 120 ℃ for sublimation, the temperature is reduced after the sublimation is finished, 65.3g of kettle residues are obtained, and the kettle residues are crushed until the particle size is less than or equal to 3mm, so that pretreated solid waste is obtained; adding the pretreated solid waste into 135g of sodium hydroxide solution with the mass concentration of 20%, heating to 95 ℃, preserving heat for 1h, and filtering to remove insoluble matters to obtain an alkali solution; the pH value of the alkaline solution is regulated to 0.95 by using hydrochloric acid with the mass concentration of 30 percent, the temperature is reduced to 80 ℃, the hot filtration and the drying are carried out, 61.5g of 3,3', 4' -biphenyltetracarboxylic acid crude product is obtained, and the mass content of the 3,3', 4' -biphenyltetracarboxylic acid is detected to be 99.52 percent.
61.5g of 3,3', 4' -biphenyl tetracarboxylic dianhydride is put into a sublimator, a vacuum pump is started, the vacuum degree is controlled to be 0.8mmHg, the temperature is raised to 230 ℃ for sublimation, 4.2g of a front cut fraction is collected (discarded), then the collection of products is started, the temperature is reduced after the sublimation is finished, 48.3g of white refined 3,3', 4' -biphenyl tetracarboxylic dianhydride is obtained, and the mass content of the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 99.91 percent according with the product quality standard in T/CIEP 010-2022 through detection.
Example 2
Taking 100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid, and detecting that the mixed solid waste dry products comprise the following substances in percentage by mass: 63.5% of 3,3', 4' -biphenyltetracarboxylic acid, 35.1% of phthalic acid and 1.4% of chlorophthalic acid.
100g of mixed solid waste products produced by 3,3', 4' -biphenyl tetracarboxylic acid are put into a sublimation kettle, a vacuum pump is started, the vacuum degree is controlled to be 3mmHg, the temperature is raised to 120 ℃ for sublimation, the temperature is reduced after the sublimation is finished, 67.3g of kettle residues are obtained, and the kettle residues are crushed until the particle size is less than or equal to 3mm, so that pretreated solid waste is obtained; adding the pretreated solid waste into 145g of sodium hydroxide solution with the mass concentration of 20%, heating to 100 ℃, preserving heat for 1h, and filtering to remove insoluble matters to obtain an alkali solution; the pH of the alkaline solution is regulated to 1.22 by using hydrochloric acid with the mass concentration of 30 percent, the temperature is reduced to 75 ℃, the thermal filtration and the drying are carried out, 62.4g of crude 3,3', 4' -biphenyltetracarboxylic acid product is obtained, and the mass content of the 3,3', 4' -biphenyltetracarboxylic acid product is detected to be 99.50 percent.
62.3g of 3,3', 4' -biphenyl tetracarboxylic dianhydride is put into a sublimator, a vacuum pump is started, the vacuum degree is controlled to be 0.8mmHg, the temperature is raised to 230 ℃ for sublimation, 5.1g of a pre-fraction is collected (discarded), then the collection of products is started, the temperature is reduced after the sublimation is finished, 47.6g of white refined 3,3', 4' -biphenyl tetracarboxylic dianhydride is obtained, and the mass content of the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 99.92 percent according with the product quality standard in T/CIEP 010-2022 through detection.
Example 3
Taking 100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid, and detecting that the mixed solid waste dry products comprise the following substances in percentage by mass: 63.5% of 3,3', 4' -biphenyltetracarboxylic acid, 35.1% of phthalic acid and 1.4% of chlorophthalic acid.
100g of mixed solid waste products produced by 3,3', 4' -biphenyl tetracarboxylic acid are put into a sublimation kettle, a vacuum pump is started, the vacuum degree is controlled to be 3mmHg, the temperature is raised to 110 ℃ for sublimation, the temperature is reduced after the sublimation is finished, 64.3g of kettle residues are obtained, and the kettle residues are crushed until the particle size is less than or equal to 3mm, so that pretreated solid waste is obtained; adding the pretreated solid waste into 108g of sodium hydroxide solution with the mass concentration of 30%, heating to 95 ℃, preserving heat for 1h, and filtering to remove insoluble matters to obtain an alkali solution; adjusting the pH of the alkaline solution to 0.68 by using hydrochloric acid with the mass concentration of 30%, cooling to 70 ℃, thermally filtering, and drying to obtain 60.9g of 3,3', 4' -biphenyl tetracarboxylic acid crude product; the mass content of the 3,3', 4' -biphenyl tetracarboxylic acid is 99.50 percent.
60.5g of 3,3', 4' -biphenyl tetracarboxylic acid crude product is put into a sublimator, a vacuum pump is started, the vacuum degree is controlled to be 0.8mmHg, the temperature is raised to 235 ℃ for sublimation, 4.5g of a pre-fraction is collected (discarded), then the collection of products is started, the temperature is reduced after the sublimation is finished, 44.9g of white refined 3,3', 4' -biphenyl tetracarboxylic dianhydride is obtained, and the mass content of the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 99.93 percent according with the product quality standard in T/CIEP 010-2022 through detection.
Comparative example 1
Taking 100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid, and detecting that the mixed solid waste dry products comprise the following substances in percentage by mass: 63.5% of 3,3', 4' -biphenyltetracarboxylic acid, 35.1% of phthalic acid and 1.4% of chlorophthalic acid.
100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid are put into a sublimation kettle, a vacuum pump is started, the vacuum degree is controlled to be 3.5mmHg, the temperature is increased to 120 ℃ for sublimation, and the kettle residue is obtained by cooling after the sublimation is finished. And (3) continuing sublimating the residue in the 65.3 kettle, controlling the vacuum degree to be 0.8mmHg, heating to 220 ℃ for sublimating, collecting 4.8g of front distillate, then starting collecting the product, and cooling after sublimating to obtain 51.3g of white 3,3', 4' -biphenyl tetracarboxylic dianhydride, wherein the mass content of the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 98.9% after detection, and does not meet the product quality standard in T/CIEP 010-2022.
Comparative example 2
Taking 100g of mixed solid waste dry products produced by 3,3', 4' -biphenyl tetracarboxylic acid, and detecting that the mixed solid waste dry products comprise the following substances in percentage by mass: 63.5% of 3,3', 4' -biphenyltetracarboxylic acid, 35.1% of phthalic acid and 1.4% of chlorophthalic acid.
100g of mixed solid waste dry product of 3,3', 4' -biphenyl tetracarboxylic acid production is added into 250g of sodium hydroxide solution with mass concentration of 20%, the temperature is raised to 95 ℃, the temperature is kept for 1h, insoluble matters are removed by filtration, and an alkali solution is obtained; the pH value of the alkaline solution is regulated to 0.95 by using hydrochloric acid with the mass concentration of 30 percent, the temperature is reduced to 80 ℃, the filtration and the drying are carried out, 94.1g of crude 3,3', 4' -biphenyltetracarboxylic acid product is obtained, and the mass content of the 3,3', 4' -biphenyltetracarboxylic acid product is 67.1 percent through detection.
94g of 3,3', 4' -biphenyl tetracarboxylic acid crude product is put into a sublimator, a vacuum pump is started, the vacuum degree is controlled to be 0.8mmHg, the temperature is raised to 220 ℃ for sublimation, 4.2g of a front cut fraction is collected (discarded), then the collection of products is started, the temperature is reduced after the sublimation is finished, and 74.1g of white 3,3', 4' -biphenyl tetracarboxylic acid dianhydride is obtained, and the mass content of the 3,3', 4' -biphenyl tetracarboxylic acid dianhydride is 72.1 percent and does not accord with the product quality standard in T/CIEP 010-2022 through detection.
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 (8)
1. The method for treating the mixed solid waste in the production of the 3,3', 4' -biphenyl tetracarboxylic acid is characterized by comprising the following steps:
carrying out first decompression sublimation on mixed solid waste generated in the production of 3,3', 4' -biphenyl tetracarboxylic acid to obtain pretreated solid waste;
alkali dissolution is carried out on the pretreated solid waste, and alkali insoluble matters are removed to obtain alkali solution;
adjusting the pH value of the alkali solution to be acidic, and obtaining a crude product of 3,3', 4' -biphenyl tetracarboxylic acid through hot filtration;
performing second reduced pressure sublimation on the 3,3', 4' -biphenyl tetracarboxylic acid crude product, discarding an initial fraction, and collecting a middle-section fraction to obtain refined 3,3', 4' -biphenyl tetracarboxylic dianhydride;
the mass of the initial fraction is 5-10% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid;
the mass of the middle-section fraction is 70-80% of the weight of 3,3', 4' -biphenyl tetracarboxylic acid.
2. The method according to claim 1, wherein the temperature of the first reduced pressure sublimation is 110 to 120 ℃ and the vacuum degree is 3 to 5mmHg.
3. The process according to claim 1, wherein the alkali is at a pH of 12 to 14 and a temperature of 80 to 105 ℃.
4. A process according to claim 1 or 3, wherein the alkali is used in a concentration of 20 to 30% by mass of alkali solution.
5. The process of claim 1, wherein the means for removing alkali insolubles is solid liquid separation.
6. The process of claim 1, wherein the acidic pH is from 0.5 to 1.5.
7. The process of claim 1, wherein the temperature of the hot filtration is 70-80 ℃.
8. The method according to claim 1, wherein the temperature of the second reduced pressure sublimation is 230 to 240 ℃ and the vacuum degree is not more than 1mmHg.
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