CN112028366B - Method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride - Google Patents

Method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride Download PDF

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CN112028366B
CN112028366B CN202010908321.7A CN202010908321A CN112028366B CN 112028366 B CN112028366 B CN 112028366B CN 202010908321 A CN202010908321 A CN 202010908321A CN 112028366 B CN112028366 B CN 112028366B
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biphenyl tetracarboxylic
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CN112028366A (en
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刘少华
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Shanghai Guchuang New Chemical Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to the technical field of organic matter synthesis, and discloses a method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, wherein sodium hydroxide is added into the production wastewater of the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride to generate water-soluble biphenyl tetracarboxylic acid sodium, impurities in the wastewater are insoluble in water, and can be removed by filtering, so that subsequent recovery is facilitated; hydrochloric acid is added into the filtrate after the impurities are removed, so that the biphenyl tetracarboxylic acid can be formed and is insoluble in water, and the biphenyl tetracarboxylic acid and water are separated by filtering, so that the biphenyl tetracarboxylic acid and the water are conveniently separated out for washing and high-temperature anhydride formation to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, and the COD value in the wastewater is reduced; further reducing the COD value in the wastewater by using hydrogen peroxide; ferrous sulfate is used as a flocculating agent for flocculation and purification of water; and finally, the wastewater is treated by a wastewater treatment system, so that the discharged water meets the discharge standard and the environment is prevented from being polluted.

Description

Method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride
Technical Field
The invention belongs to the technical field of organic matter synthesis, and particularly relates to a method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride.
Background
In the prior art, 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA) is one of important monomers for synthesizing plastic Polyimide (PI), polyimide synthesized by the monomer and diamine such as 1,4 '-p-phenylenediamine, 4,4' -diaminodiphenyl ether and the like has excellent heat resistance, mechanical property and electrical insulation property, and is widely applied to the fields of aviation, aerospace, electronics, laser, new energy sources and the like.
The 5% thermogravimetric temperature (in nitrogen atmosphere) of Polyimide (PI) synthesized from 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine is over 600 ℃, which is very high in the known polyimides. Polyimide (PI) synthesized from 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) and diamine has a water absorption reduced by about 50% as compared with Polyimide (PI) synthesized from pyromellitic dianhydride and diamine.
The traditional industrial production process of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA) mainly comprises the steps of halogenated phthalic anhydride catalytic coupling, hydrolysis, acidification, water washing, high-temperature anhydride formation and the like. Wherein, the medium of the coupling reaction is water, 32 percent of sodium hydroxide is used for hydrolysis reaction, 30 percent of hydrochloric acid is used for acidification, and a large amount of pure water is used for washing. About 10 tons of wastewater is generated when 1 ton of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA) is produced, the production wastewater contains 1-2% of 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), the COD value is as high as 8000 ppm, the wastewater cannot be directly discharged, the environment is polluted, and 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA) is wasted; and can not be directly treated by the existing sewage treatment system because the COD value of the waste water before entering the sewage treatment system needs to be controlled below 1000ppm, otherwise the bacteria in the biochemical pool of the sewage treatment system die.
Therefore, a treatment method is needed to treat the production wastewater, which can recover 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA) to avoid waste, and the treated wastewater can reach the discharge standard to avoid environmental pollution.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for treating production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride, which can recover 3,3', 4,4' -biphenyltetracarboxylic dianhydride and reduce the COD value of the production wastewater, and the treated wastewater can meet the discharge standard through the existing sewage treatment system, thereby avoiding environmental pollution.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
dewatering, namely heating and decompressing the production wastewater of the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride to dewater;
removing impurities, namely adding sodium hydroxide into the residual production wastewater after dehydration, adjusting the pH value of the residual production wastewater to be more than or equal to 10, and filtering after reaction to remove impurities;
separating, adding hydrochloric acid solution into the filtrate after removing impurities, adjusting the pH value of the filtrate to be less than or equal to 2.5, filtering after reaction to obtain 3,3', 4,4' -biphenyltetracarboxylic acid as a solid phase, and keeping the filtrate for later use;
washing with water, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid, washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride;
and (3) wastewater treatment, namely adding hydrogen peroxide into the filtrate for standby in the separation treatment, adding ferrous sulfate after reaction, and then putting the mixture into the conventional sewage treatment system for treatment.
In the invention, sodium hydroxide is added into the production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride to generate water-soluble biphenyl tetracarboxylic acid sodium, while impurities in the wastewater are insoluble in water, and can be removed by filtering, thereby facilitating subsequent recovery; hydrochloric acid is added into the filtrate after the impurities are removed, so that the biphenyl tetracarboxylic acid can be formed and is insoluble in water, and the biphenyl tetracarboxylic acid and water are separated by filtering, so that the biphenyl tetracarboxylic acid and the water are conveniently separated out for washing and high-temperature anhydride formation to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, and the COD value in the wastewater is reduced; further reducing the COD value in the wastewater by using hydrogen peroxide; ferrous sulfate is used as a flocculating agent for flocculation and purification of water; the wastewater with the reduced COD value can enter a sewage treatment system for treatment, so that the discharged water meets the discharge standard and the environment is prevented from being polluted; therefore, the method has certain economic value and environmental protection value for treating the wastewater generated in the production of the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride.
Further, in the dehydration treatment step, the production wastewater is heated to boiling and decompressed to 40-50% of the original weight. In the invention, the purpose of decompression dehydration is to reduce the addition of alkali and acid in the subsequent wastewater treatment process, thereby reducing the salt in the wastewater, wherein the salt is sodium chloride.
Further, in order to enable the biphenyltetracarboxylic acid to be fully reacted to form the water-soluble sodium biphenyltetracarboxylic acid, in the impurity removal treatment step, after adding sodium hydroxide, heating to reflux, keeping the temperature for 2-3 hours in a reflux state, cooling to 85 ℃ after reaction, and then filtering.
Further, in order to facilitate the separation of the biphenyltetracarboxylic acid and the water, in the separation treatment step, after adding a hydrochloric acid solution, heating to reflux, keeping the temperature for 2-3 hours in a reflux state, cooling to 85 ℃, and performing centrifugal filtration to obtain the solid phase of the 3,3', 4,4' -biphenyltetracarboxylic acid.
Further, in order to facilitate the separation of biphenyltetracarboxylic acid from water, the concentration of the hydrochloric acid solution added in the separation treatment step was 30%.
Further, in the step of wastewater treatment, when adding hydrogen peroxide, controlling the temperature to be below 50 ℃, stirring for 2-3 hours under heat preservation, then adding ferrous sulfate, stirring for 2-3 hours, and then placing into a sewage treatment system for treatment.
Further, in order to further reduce the COD value in the wastewater, the mass concentration of the added hydrogen peroxide in the wastewater treatment step is 30%.
Furthermore, in the step of wastewater treatment, when the wastewater treatment system is placed into the existing wastewater treatment system, the wastewater firstly passes through one sedimentation tank of the wastewater treatment system, stands for more than 3 hours, takes supernatant fluid to enter a biochemical tank of the wastewater treatment system, and after biochemical treatment, the supernatant fluid is precipitated in the other sedimentation tank of the wastewater treatment system, so that the discharge requirement is met, and the supernatant fluid is directly discharged.
Furthermore, the mass ratio of the hydrogen peroxide to the wastewater subjected to reduced pressure dehydration is 100: 0.4-0.6, so that the COD value in the wastewater can be reduced better, and the emission requirement can be met after subsequent treatment.
Further, the mass ratio of the ferrous sulfate to the wastewater subjected to reduced pressure dehydration is 100: 0.08-0.12. Can better flocculate and purify the waste water.
The invention has the beneficial effects that: compared with the prior art, in the invention, sodium hydroxide is added into the production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride to generate water-soluble biphenyltetracarboxylic acid sodium, while impurities in the wastewater are insoluble in water, and can be removed by filtering, thereby facilitating subsequent recovery; hydrochloric acid is added into the filtrate after the impurities are removed, so that the biphenyl tetracarboxylic acid can be formed and is insoluble in water, and the biphenyl tetracarboxylic acid and water are separated by filtering, so that the biphenyl tetracarboxylic acid and the water are conveniently separated out for washing and high-temperature anhydride formation to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, and the COD value in the wastewater is reduced; further reducing the COD value in the wastewater by using hydrogen peroxide; ferrous sulfate is used as a flocculating agent for flocculation and purification of water; the wastewater with the reduced COD value can enter a sewage treatment system for treatment, so that the discharged water meets the discharge standard and the environment is prevented from being polluted; therefore, the method has certain economic value and environmental protection value for treating the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride production wastewater.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, dehydration treatment, namely heating the production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride to boil, and reducing the pressure to about 40-50% of the original weight;
step 2, impurity removal treatment, namely adding sodium hydroxide into the residual production wastewater after dehydration to adjust the pH value of the residual wastewater to be more than or equal to 10, heating to reflux, preserving heat for 2-3 hours in a reflux state, cooling to 85 ℃ after reaction, and then filtering to remove impurities;
step 3, performing separation treatment, namely adding a 30% hydrochloric acid solution into the filtrate after removing impurities, adjusting the pH value of the filtrate to be less than or equal to 2.5, heating to reflux, preserving the heat for 2-3 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration to obtain a solid phase of 3,3', 4,4' -biphenyltetracarboxylic acid, and keeping the filtrate for later use;
step 4, water washing treatment, namely collecting 3,3', 4,4' -biphenyl tetracarboxylic acid, washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride;
step 5, treating the wastewater, namely adding 30% hydrogen peroxide into the filtrate for later use in the separation treatment, controlling the temperature to be below 50 ℃, keeping the temperature and stirring for 2-3 hours, then adding ferrous sulfate, stirring for 2-3 hours, reducing the COD value in the wastewater to be below 1000ppm, and putting the wastewater into a sewage treatment system for treatment; firstly, the supernatant liquor is taken to enter a biochemical tank of the sewage treatment system after standing for more than 3 hours in one sedimentation tank of the sewage treatment system, and after biochemical treatment and sedimentation in the other sedimentation tank of the sewage treatment system, the discharge requirement is met and the supernatant liquor is directly discharged.
Wherein the mass ratio of the hydrogen peroxide to the wastewater subjected to reduced pressure dehydration is 100: 0.4-0.6; the mass ratio of the ferrous sulfate to the wastewater subjected to reduced pressure dehydration is 100: 0.08-0.12.
Wherein, the flocculated liquid at the bottom of the first sedimentation tank, through which the wastewater passes, is collected in a centralized way, and is subjected to plate-and-frame filter pressing, so that solid is solid waste, and the solid is treated in a centralized way;
wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
In the research process, the inventor considers that 3,3', 4,4' -biphenyl tetracarboxylic dianhydride in the wastewater is a main factor for high COD value in the wastewater, so that the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride in the recovered wastewater can not only generate certain economic value, but also reduce COD value of the wastewater;
because the wastewater contains impurities and biphenyltetracarboxylic acid, the biphenyltetracarboxylic acid sodium can be generated by adding sodium hydroxide and dissolved in water, while the impurities are not dissolved in water, and can be removed by filtering; adding hydrochloric acid to form biphenyl tetracarboxylic acid which is insoluble in water, filtering to separate the biphenyl tetracarboxylic acid from water, not only facilitating the separation of the biphenyl tetracarboxylic acid from the water, but also reducing the COD value of the wastewater by recycling 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, and further reducing the COD value in the wastewater to be below 1000ppm by using hydrogen peroxide; ferrous sulfate is used as a flocculating agent for flocculation and purification of water; then biochemical treatment is carried out, namely the COD value is reduced by bacteria, and finally the waste water is discharged.
Wherein, the hydrogen peroxide is a strong oxidant and can oxidize organic molecules into small molecules with smaller molecular weight and even gas small molecules. The organic matter is reduced, thereby further reducing the COD value in the wastewater.
The method for treating production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to the present invention will be specifically described below with reference to specific examples.
Example 1
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, feeding 5m equipped with a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, the wastewater is heated to boiling, 50% of wastewater is dehydrated under reduced pressure, the rest 2 tons of wastewater can enter a production cooling water system for reuse.
And 2, adding 98Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 3 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 300Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the temperature for 2.5 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 8Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 3 hours, then adding 2.4Kg of industrial ferrous sulfate, stirring for 2 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
Measuring the COD value of supernatant liquor of the buffer sedimentation tank to be 920ppm, taking the supernatant liquor to enter a biochemical tank, carrying out aerobic biochemical treatment, then carrying out sedimentation in the sedimentation tank, and measuring the COD value of the supernatant liquor to be less than or equal to 300ppm, thereby meeting the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise addition of the industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.4; the mass ratio of the industrial ferrous sulfate to the wastewater subjected to reduced pressure dehydration is 100: 0.12.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, and the solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
Example 2
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, feeding 5m equipped with a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, heated to boiling, decompressed and dehydrated by 50 percent, and the rest 2 tons,the dehydrated water can enter a production cooling water system for reuse.
And 2, adding 95Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 2.5 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 290Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the heat for 3 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 10Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 2.5 hours, then adding 2Kg of industrial ferrous sulfate, stirring for 2 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
Measuring the COD value of supernatant liquor of the buffer sedimentation tank to be 930ppm, taking the supernatant liquor to enter a biochemical tank, carrying out aerobic biochemical treatment, then carrying out sedimentation in the sedimentation tank, and measuring the COD value of the supernatant liquor to be less than or equal to 300ppm so as to meet the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise addition of the industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.5; the mass ratio of the industrial ferrous sulfate to the wastewater subjected to reduced pressure dehydration is 100: 0.1.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, so that solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
Example 3
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, feeding 5m equipped with a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, the wastewater is heated to boiling, 50% of wastewater is dehydrated under reduced pressure, the rest 2 tons of wastewater can enter a production cooling water system for reuse.
And 2, adding 100Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 2 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 310Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the temperature for 2 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 12Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 2 hours, then adding 1.6Kg of industrial ferrous sulfate, stirring for 2 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
Measuring the COD value of supernatant liquor in the buffer sedimentation tank to be 900ppm, taking the supernatant liquor to enter a biochemical tank, carrying out aerobic biochemical treatment, then carrying out sedimentation in the sedimentation tank, and measuring the COD value of the supernatant liquor to be less than or equal to 300ppm, thereby meeting the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise addition of the industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.6; the mass ratio of the industrial ferrous sulfate to the wastewater after the reduced pressure dehydration is 100: 0.08.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, so that solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
Example 4
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, adding 5m of solution containing a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, the wastewater is heated to boiling, 50% of wastewater is dehydrated under reduced pressure, the rest 2 tons of wastewater can enter a production cooling water system for reuse.
And 2, adding 98Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 3 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 300Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the heat for 3 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 9Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 2 hours, then adding 1.8Kg of industrial ferrous sulfate, stirring for 3 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
The COD value of the supernatant liquor in the buffer sedimentation tank is 922ppm by measurement, the supernatant liquor is taken to enter a biochemical tank and is precipitated in a sedimentation tank after aerobic biochemical treatment, and the COD value of the supernatant liquor is measured to be less than or equal to 300ppm, thereby meeting the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise addition of the industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.45; the mass ratio of the industrial ferrous sulfate to the wastewater after the reduced pressure dehydration is 100: 0.09.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, so that solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
Example 5
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, feeding 5m equipped with a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, the wastewater is heated to boiling, 50% of wastewater is dehydrated under reduced pressure, the rest 2 tons of wastewater can enter a production cooling water system for reuse.
And 2, adding 95Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 2 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 300Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the temperature for 2.5 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 11Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 2 hours, then adding 2.2Kg of industrial ferrous sulfate, stirring for 2 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
Measuring the COD value of supernatant in the buffer sedimentation tank to be 925ppm, taking the supernatant to enter a biochemical tank, carrying out aerobic biochemical treatment, and then carrying out sedimentation in the sedimentation tank, and measuring the COD value of the supernatant to be less than or equal to 300ppm, thereby meeting the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise addition of the industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.55; the mass ratio of the industrial ferrous sulfate to the wastewater after the reduced pressure dehydration is 100: 0.11.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, so that solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
Example 6
A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps:
step 1, adding 5m of solution containing a thermometer, a stirrer and a reflux condenser34 tons of wastewater generated in the process of producing 3,3', 4,4' -biphenyltetracarboxylic dianhydride (BPDA) is added into a reaction kettle, the wastewater is heated to be boiled, 60% of wastewater is dehydrated under reduced pressure, and the rest 1.6 tons of wastewater can enter a production cooling water system for reuse.
And 2, adding 98Kg of sodium hydroxide flake caustic soda into the reaction kettle, adjusting the pH value to be more than or equal to 10, preserving the heat for 2.5 hours in a reflux state, cooling to 85 ℃, filtering, returning filtrate to the reaction kettle, collecting filter residues which are solid waste impurities, and performing centralized treatment.
And 3, adding 300Kg of hydrochloric acid solution with the concentration of 30% into the reaction kettle, adjusting the pH value to be less than or equal to 2.5, preserving the temperature for 2 hours in a reflux state, cooling to 85 ℃, performing centrifugal filtration, returning the filtrate to the reaction kettle, wherein the solid phase is 3,3', 4,4' -biphenyltetracarboxylic acid (BPTA).
And 4, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid (BPTA), then intensively washing with water, and forming anhydride at high temperature to obtain industrial 3,3', 4,4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the purity is more than or equal to 99.5 percent.
And 5, dropwise adding 8Kg of industrial hydrogen peroxide (with the concentration of 30%) into the reaction kettle at normal temperature, controlling the temperature to be not more than 50 ℃, keeping the temperature and stirring for 2 hours, then adding 1.6Kg of industrial ferrous sulfate, stirring for 2.5 hours, then placing the mixture into a buffer sedimentation tank of a sewage treatment system, and standing for more than 3 hours.
Measuring the COD value of supernatant liquor of the buffer sedimentation tank to be 928ppm, taking the supernatant liquor to enter a biochemical tank, carrying out aerobic biochemical treatment, then carrying out sedimentation in the sedimentation tank, and measuring the COD value of the supernatant liquor to be less than or equal to 300ppm, thus meeting the discharge requirement of a chemical industrial park.
Wherein, the mass ratio of the dropwise adding industrial hydrogen peroxide (with the concentration of 30%) to the wastewater after the reduced pressure dehydration is 100: 0.5; the mass ratio of the industrial ferrous sulfate to the wastewater after decompression and dehydration is 100: 0.1.
Wherein, the flocculation liquid at the bottom of the buffer sedimentation tank is collected in a centralized way, and is subjected to plate and frame filter pressing, so that solid is solid waste and is treated in a centralized way.
Wherein, after the filtrate enters a biochemical tank for treatment, sludge at the bottom of the biochemical tank is collected in a centralized manner and is subjected to plate-and-frame filter pressing, and the solid is solid waste and is treated in a centralized manner; and returning the filtrate to the biochemical pool for treatment.
As shown in examples 1 to 6, the method for treating production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to the present invention enables industrial 3,3', 4,4' -biphenyltetracarboxylic dianhydride to be recovered from production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride, and also enables COD value in the wastewater to be reduced; further reducing the COD value in the wastewater to below 1000ppm by using hydrogen peroxide; ferrous sulfate is used as a flocculating agent for flocculation and purification of water; finally, through the precipitation and biochemical treatment of a sewage treatment system, the COD value is further reduced to be less than or equal to 300ppm, the discharge standard is reached, and the environmental pollution is avoided; therefore, the treatment of the wastewater from the production of 3,3', 4,4' -biphenyltetracarboxylic dianhydride has certain economic value and environmental protection value.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for treating production wastewater of 3,3', 4,4' -biphenyl tetracarboxylic dianhydride, which is characterized by comprising the following steps:
dewatering, namely heating and decompressing the production wastewater of the 3,3', 4,4' -biphenyl tetracarboxylic dianhydride to dewater;
removing impurities, namely adding sodium hydroxide into the residual production wastewater after dehydration, adjusting the pH value of the residual production wastewater to be more than or equal to 10, and filtering after reaction to remove impurities;
separating, adding hydrochloric acid solution into the filtrate after removing impurities, adjusting the pH value of the filtrate to be less than or equal to 2.5, filtering after reaction to obtain 3,3', 4,4' -biphenyltetracarboxylic acid as a solid phase, and reserving the filtrate for later use;
washing with water, collecting 3,3', 4,4' -biphenyl tetracarboxylic acid, washing with water, and forming anhydride at high temperature to obtain 3,3', 4,4' -biphenyl tetracarboxylic dianhydride;
and (3) wastewater treatment, namely adding hydrogen peroxide into the filtrate for standby in the separation treatment, adding ferrous sulfate after reaction, and then putting the mixture into a sewage treatment system for treatment.
2. The method for treating production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein in the dehydration treatment step, the production wastewater is heated to boiling and depressurized to 40 to 50% by weight of the original.
3. The method for treating the production wastewater of the 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein in the step of removing impurities, after adding sodium hydroxide, heating to reflux, keeping the temperature for 2-3 hours in a reflux state, cooling to 85 ℃ after reaction, and then filtering.
4. The method for treating the production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein in the separation treatment step, after adding a hydrochloric acid solution, heating to reflux, maintaining the temperature for 2-3 hours in a reflux state, cooling to 85 ℃, and performing centrifugal filtration to obtain the solid phase of 3,3', 4,4' -biphenyltetracarboxylic dianhydride.
5. The method for treating waste water from the production of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein the concentration of the hydrochloric acid solution added in the separation treatment step is 30%.
6. The method for treating the production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein in the step of wastewater treatment, when hydrogen peroxide is added, the temperature is controlled to be below 50 ℃, after stirring for 2-3 hours under heat preservation, ferrous sulfate is added, and after stirring for 2-3 hours, the mixture is placed into a wastewater treatment system for treatment.
7. The method for treating the production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein the concentration by mass of the added hydrogen peroxide in the wastewater treatment step is 30%.
8. The method for treating the production wastewater of 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein in the wastewater treatment step, when the wastewater treatment system is placed in the wastewater treatment system, the wastewater is firstly passed through one of the sedimentation tanks of the wastewater treatment system, is allowed to stand for more than 3 hours, and the supernatant is taken to enter a biochemical tank of the wastewater treatment system, is subjected to biochemical treatment, is precipitated in the other sedimentation tank of the wastewater treatment system, and is then discharged.
9. The method for treating the production wastewater of the 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein the mass ratio of the hydrogen peroxide to the wastewater after the reduced pressure dehydration is 100: 0.4-0.6.
10. The method for treating the production wastewater of the 3,3', 4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein the mass ratio of the ferrous sulfate to the wastewater subjected to the reduced-pressure dehydration is 100: 0.08-0.12.
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