CN113912240B - Extracting agent and method for treating 4,4' -diphenyl ether dianhydride production wastewater by using same - Google Patents
Extracting agent and method for treating 4,4' -diphenyl ether dianhydride production wastewater by using same Download PDFInfo
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- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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Abstract
The invention relates to the technical field of industrial wastewater treatment, and particularly discloses an extracting agent and a method for treating 4,4' -diphenyl ether dianhydride production wastewater by using the extracting agent. The extracting agent comprises an ester compound with 3-6 carbon atoms and halogenated hydrocarbon with 1-6 carbon atoms, and the mass ratio of the ester compound to the halogenated hydrocarbon is 1: 2-4. According to the invention, the production wastewater is extracted by adopting the extracting agent, and then the oil phase obtained by extraction and separation is distilled to recover the extracting agent, the reaction solvent, the reaction raw material and other substances respectively, so that the obtained high-purity extracting agent, reaction solvent, reaction raw material and the like can be directly recycled, the wastewater treatment cost and the production cost of 4,4' -diphenyl ether dianhydride are reduced, the problems of serious hazardous waste disposal and resource waste caused by the fact that a large amount of hazardous waste is generated by a direct distillation method and needs secondary incineration treatment, and the raw material cannot be recycled are solved, and the method has high economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to an extracting agent and a method for treating 4,4' -diphenyl ether dianhydride production wastewater by using the extracting agent.
Background
The 4,4' -diphenyl ether dianhydride is an important intermediate for producing polyimide, can be polymerized with various amine compounds to generate polyimide, and the prepared polyimide is an indispensable material for wearable equipment, folding screen mobile phones, folding screen computers and the like. In recent years, with the development of hot technologies such as 5G devices, wearable devices, folding screen mobile phones, folding screen computers and the like, the demand of polyimide is increasing.
At present, 4,4 '-diphenyl ether dianhydride is prepared from 4-nitrophthalimide serving as a raw material through catalytic coupling, hydrolysis, acidification and refining to obtain 4,4' -diphenyl ether tetracarboxylic acid, and then the 4,4 '-diphenyl ether tetracarboxylic acid is subjected to anhydrous treatment to obtain the 4,4' -diphenyl ether dianhydride. The process has low selectivity, only about 75 percent of 4-nitrophthalimide participates in the coupling reaction of the oxo-bis- (N-methylphthalimide) to obtain the oxo-bis- (N-methylphthalimide), and the rest 25 percent of unreacted raw materials, a small amount of reaction products or byproducts and catalysts cannot be recovered, so that the unreacted raw materials, the reaction products or byproducts and the catalysts enter production wastewater, the environment-friendly treatment cost and the raw material price are high, and the development of the polyimide functional materials is limited.
The traditional process is to treat the production wastewater of the 4,4' -diphenyl ether dianhydride by a distillation method, namely, the distillation method is adopted to distill the mother liquor after crystallization and filtration, redundant water and organic solvent in the mother liquor are evaporated, and the residual mixture residue is treated as hazardous waste. The method can generate a large amount of harmful and dangerous waste to cause a serious problem of dangerous waste disposal, and the main raw materials cannot be recycled, so that the production cost is still high. With the obvious increase of the demand of polyimide, an environment-friendly and safe treatment method is urgently needed to treat byproducts in the production process of 4,4' -diphenyl ether dianhydride, so that the environment protection and raw material cost are reduced, and the rapid development requirement of polyimide functional materials is met.
Disclosure of Invention
The invention provides an extracting agent and a method for treating 4,4 '-diphenyl ether dianhydride production wastewater by using the same, aiming at the problems that a large amount of harmful waste is generated and raw materials cannot be recycled in the existing method for treating 4,4' -diphenyl ether dianhydride production wastewater, the extracting agent mainly comprises esters and halogenated alkane to extract reaction raw materials and reaction products in the wastewater, then materials such as the reaction raw materials, the reaction products and the extracting agent are respectively recovered by distillation, and finally the wastewater is treated by a wastewater treatment system, so that the discharged water meets the discharge standard, the purposes of raw material recycling and clean production are realized, and the method has higher economic benefit and environmental benefit.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the extracting agent comprises an ester compound with 3-6 carbon atoms and halogenated hydrocarbon with 1-6 carbon atoms, wherein the mass ratio of the ester compound to the halogenated hydrocarbon is 1: 2-4.
Compared with the prior art, the extracting agent provided by the invention can completely separate the main reaction raw material (4-nitrophthalimide), the reaction solvent (dimethylformamide), the reaction intermediate product (oxo-bis- (N-methylphthalimide)) and the like in the production wastewater of the 4,4 '-diphenyl ether dianhydride, the substances such as the extracting agent, the reaction solvent, the reaction raw material and the like can be respectively recovered from the oil phase obtained by extraction separation through distillation, and the obtained high-purity extracting agent, the reaction solvent, the reaction raw material and the like can be directly recycled, so that the wastewater treatment cost and the production cost of the 4,4' -diphenyl ether dianhydride are reduced, the problems of large amount of harmful and dangerous waste generated by a direct distillation method, secondary incineration treatment, serious dangerous waste disposal and resource waste caused by the fact that the raw material cannot be recycled are solved, has higher economic benefit and environmental benefit.
Preferably, the mass ratio of the ester compound to the halogenated hydrocarbon is 1: 2-3.
Preferably, the ester compound is at least one of methyl acetate, n-butyl acetate or isobutyl acetate.
Further preferably, the ester compound is isobutyl acetate.
Preferably, the halogenated hydrocarbon is at least one of dichloromethane, dichloroethane or 1,2, 4-trichlorobenzene.
Further preferably, the halogenated hydrocarbon is a mixture of dichloromethane and 1,2, 4-trichlorobenzene in a mass ratio of 1.5-2.0: 0.5-1.0.
More preferably, the extractant is isobutyl acetate, dichloromethane and 1,2, 4-trichlorobenzene in a mass ratio of 1:1.5-2.0: 0.5-1.0.
The optimized extracting agent can realize synchronous extraction of various organic substances such as reaction main raw materials, reaction solvents, reaction intermediate products and the like in the 4,4' -diphenyl ether dianhydride production wastewater, has high extraction rate, and can realize effective separation of various organic substances from the wastewater, thereby improving the recovery rates of the reaction main raw materials and the reaction solvents, realizing the recycling of the reaction main raw materials and the reaction solvents, and reducing the production cost of the diphenyl ether dianhydride; and the preferred extractant has low solubility in water and low loss in the extraction process, and the extractant can be effectively recovered through subsequent distillation, so that the recycling value is high.
The invention also provides application of the extracting agent in treatment of wastewater generated in production of 4,4' -diphenyl ether dianhydride.
The 4,4 '-diphenyl ether dianhydride production wastewater in the invention refers to crystallization mother liquor obtained after crystallization and filtration in the process for preparing 4,4' -diphenyl ether dianhydride, and the crystallization mother liquor contains 81% of water, 14% of dimethylformamide, 1.5% of potassium carbonate, 2% of 4-nitrophthalimide, 1% of oxybis- (N-methylphthalimide) and 0.5% of other side reaction products through detection and analysis.
The invention also provides a method for treating the 4,4' -diphenyl ether dianhydride production wastewater by using the extracting agent, which comprises the following steps:
step a, adding the extracting agent into the 4,4' -diphenyl ether dianhydride production wastewater, stirring, standing, separating liquid, extracting a water layer for 1-2 times by using the extracting agent, and respectively combining a water phase and an oil phase to obtain a first oil phase and a first water phase;
b, distilling the first oil phase at normal pressure, collecting fraction 1 with the boiling range of 30-145 ℃, heating, continuing to collect fraction 2 with the boiling range of 145-165 ℃, stopping distillation, cooling, crystallizing, and filtering to obtain a recovered raw material and a distillation mother liquor;
c, distilling the first water phase at normal pressure, and stopping distillation when the evaporation amount is 5-15% of the mass of the first wastewater to obtain a fraction 3; standing and separating the fraction 3 to obtain a second oil phase and a second water phase;
and d, treating the second water phase by a sewage treatment system and discharging.
Compared with the prior art, the method for treating the 4,4' -diphenyl ether dianhydride production wastewater provided by the invention comprises the steps of firstly adopting an extracting agent consisting of specific ester and halogenated alkane to synchronously extract and separate substances such as reaction main raw materials, reaction solvents, reaction intermediate products and the like in the production wastewater, realizing the complete separation of organic matters and water, distilling an oil phase obtained by extraction and separation at normal pressure to obtain fraction 1 (namely an extracting agent component), then heating and continuously distilling to obtain fraction 2 (namely the reaction solvents), and after the fraction 2 is collected and finished, cooling and crystallizing the bottom of a distillation kettle to obtain the reaction main raw materials and the reaction intermediate products; distilling the water phase obtained by extraction separation to recover a small amount of extractant components, and treating by a sewage system to reach the standard and discharging; the high-purity reaction solvent, the reaction raw materials and the reaction intermediate product obtained by recycling and separating can be directly recycled to the synthesis process of the 4,4' -diphenyl ether dianhydride, and the extractant obtained by recycling can also be recycled and used for extracting and treating the production wastewater next time. The invention realizes the recycling of various raw materials, effectively reduces the production cost of the 4,4' -diphenyl ether dianhydride and the wastewater treatment cost, and does not cause secondary pollution.
Preferably, in the step a, the mass ratio of the 4,4' -diphenyl ether dianhydride production wastewater to the extracting agent is 1: 0.2-1.0.
In the step a, when the aqueous phase obtained by the first extraction and separation is extracted for multiple times by using the extracting agent, the mass ratio of the extracting agent to the aqueous phase obtained by the separation is 1: 0.2-1.0.
The addition amount of the preferred extracting agent can fully extract substances such as reaction main raw materials, reaction solvents, reaction intermediate products, byproducts and the like in the wastewater, thereby being beneficial to recycling the components through distillation in the subsequent process.
Preferably, in the step a, the rotation speed of stirring is 150 rpm-200 rpm, and the standing time is 30 min-60 min.
The preferred conditions of agitation allow the extractant to sufficiently extract various organic substances in the wastewater.
Preferably, in step d, the sewage treatment system is an A/O sewage treatment system.
Preferably, the fraction 1, the distillation mother liquor and the second oil phase are combined and recycled to be used as a preparation raw material of the extracting agent.
Preferably, the fraction 2 and the recovered raw material are recycled as a raw material for producing 4,4' -biphenyl ether dianhydride.
The method for treating the 4,4' -diphenyl ether dianhydride production wastewater provided by the invention has the advantages that the process operation is simple, the wastewater treatment effect is stable, the problems of secondary pollution and the like caused by a large amount of harmful waste generated by the traditional treatment process are solved, the recycling of reaction raw materials and reaction solvents is realized, the comprehensive treatment and resource utilization of the wastewater are realized, the COD (chemical oxygen demand) of the treated water reaches below 200mg/L, the method accords with the discharge standard of chemical synthesis pharmaceutical industry water pollutants, the treatment energy consumption is low, and the economic benefit and the environmental benefit are higher.
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 are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
In this example, the 4,4 '-diphenyl ether dianhydride production wastewater is a crystallization mother liquor generated after crystallization and centrifugation in the 4,4' -diphenyl ether dianhydride synthesis process, and it was detected that the crystallization mother liquor contains 80% of water, 15% of dimethylformamide, 1.5% of potassium carbonate, 2.3% of 4-nitrophthalimide, 1% of oxybis- (N-methylphthalimide), and 0.2% of other side reaction products.
The method for treating the wastewater generated in the production of 4,4' -diphenyl ether dianhydride comprises the following steps:
step a, adding 500g of an extractant (isobutyl acetate: dichloromethane: 1,2, 4-trichlorobenzene =1:2:0.8) into 1000g of 4,4' -diphenyl ether dianhydride production wastewater, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then separating to obtain 871.5g of a first water phase and 628g of a first oil phase;
adding 500g of the extracting agent into the first water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and separating to obtain 834.5g of a second water phase and 538g of a second oil phase;
adding 500g of the extracting agent into the second water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and separating to obtain 827.5g of a third water phase and 506g of a third oil phase;
step b, combining the three oil phases to obtain 1672g of mixed oil phase, distilling the combined oil phase at normal pressure, collecting 11176.5 g of fraction obtained by collecting at 145 ℃ of kettle temperature, and detecting that the content of isobutyl acetate is 32.9% and the content of dichloromethane is 66.5%; continuously heating to 165 ℃ to collect fraction 2 to obtain 2143.4 g of fraction, and detecting the content of Dimethylformamide (DMF) to be 98.6%; when the temperature of the kettle is reduced to 135 ℃, crystals begin to precipitate, the temperature is reduced to 35 ℃, the crystals are filtered, 34.9g of filter cake is dried to obtain 32.7g of dry product, 0.13g of potassium carbonate is detected, the total content of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is detected to be 98.32 percent by high performance liquid detection, and the total recovery rate of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is 97.04 percent;
and c, heating 827.5g of the third aqueous phase obtained in the step a to 104 ℃ for distillation, collecting 90g of fraction, standing and separating the fraction to obtain 2.7g of oil phase, detecting that the content of isobutyl acetate is 99.5%, cooling the aqueous phase, and then feeding the aqueous phase into an A/O sewage treatment system for treatment, wherein the COD after treatment is 79.5mg and meets the standard of less than or equal to 200mg/L in the discharge Standard of pollutants for pharmaceutical industry Water of chemical Synthesis class.
And c, detecting the water content of the third water phase obtained in the step a to be 98.45%, 120ppm of dimethylformamide, 1.5% of potassium carbonate, 2ppm of 4-nitrophthalimide, 2ppm of oxo-bis- (N-methylphthalimide) and other side reaction products to be undetected.
Example 2
In this example, the 4,4 '-diphenyl ether dianhydride production wastewater is a crystallization mother liquor generated after crystallization and centrifugation in the 4,4' -diphenyl ether dianhydride synthesis process, and it was detected that the crystallization mother liquor contains 80% of water, 15% of dimethylformamide, 1.5% of potassium carbonate, 2.3% of 4-nitrophthalimide, 1% of oxybis- (N-methylphthalimide), and 0.2% of other side reaction products.
The method for treating the wastewater generated in the production of 4,4' -diphenyl ether dianhydride comprises the following steps:
step a, adding 1000g of an extractant (isobutyl acetate: dichloromethane: 1,2, 4-trichlorobenzene =1:2:0.8) into 1000g of 4,4' -diphenyl ether dianhydride production wastewater, stirring and mixing at 35 ℃ and 150rpm for 30min, standing for 1h, and then separating to obtain 867.4g of a first water phase and 1132g of a first oil phase;
adding 500g of the extracting agent into the first water phase, stirring and mixing at 35 ℃ and 150rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 830.4g of a second water phase and 537g of a second oil phase;
step b, combining the 2 parts of oil phase to obtain 1669g of mixed oil phase, distilling the combined oil phase at normal pressure, collecting at 145 ℃ to obtain 11177 g of fraction, and detecting the content of isobutyl acetate and dichloromethane to obtain 66.5%; continuously heating to 165 ℃ to collect fraction 2 to obtain 2145.2 g of fraction, and detecting the content of Dimethylformamide (DMF) to be 98.5%; when the temperature of the kettle is reduced to 135 ℃, crystals begin to precipitate, the temperature is reduced to 35 ℃, the filtration is carried out, a filter cake is 33.9, a dried product is obtained after drying, the detection is carried out on 0.12g of potassium carbonate, the total content of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is 98.92 percent and the total recovery rate of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is 94.96 percent through the detection and high performance liquid detection
And c, heating 830.4g of the second aqueous phase obtained in the step a to 104 ℃ for distillation, collecting 86g of fraction, standing and separating the obtained fraction to obtain 2.8g of oil phase, detecting the content of isobutyl acetate to be 99.7%, cooling the aqueous phase, and then feeding the aqueous phase into an A/O sewage treatment system for treatment, wherein the COD after treatment is 132.5mg and meets the standard of less than or equal to 200mg/L in the discharge standard of chemical synthesis pharmaceutical industry water pollutants.
Example 3
In this example, the 4,4 '-diphenyl ether dianhydride production wastewater is a crystallization mother liquor generated after crystallization and centrifugation in the 4,4' -diphenyl ether dianhydride synthesis process, and it was detected that the crystallization mother liquor contains 80% of water, 15% of dimethylformamide, 1.5% of potassium carbonate, 2.3% of 4-nitrophthalimide, 1% of oxybis- (N-methylphthalimide), and 0.2% of other side reaction products.
The method for treating the wastewater generated in the production of 4,4' -diphenyl ether dianhydride comprises the following steps:
step a, adding 200g of an extractant (isobutyl acetate: dichloromethane: 1,2, 4-trichlorobenzene =1:2:0.8) into 1000g of 4,4' -diphenyl ether dianhydride production wastewater, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then separating to obtain 897.4g of a first water phase and 302g of a first oil phase;
adding 200g of the extracting agent into the first water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and separating to obtain 843.4g of a second water phase and 254g of a second oil phase;
adding 200g of the extracting agent into the second water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and separating to obtain 828.4g of a third water phase and 215g of a third oil phase;
step b, combining the three oil phases to obtain 771g of mixed oil phase, distilling the combined oil phase at normal pressure, collecting 1469.5 g of fraction obtained by collecting at 145 ℃ of kettle temperature, and detecting that the content of isobutyl acetate is 33.5% and the content of dichloromethane is 66.1%; continuously heating to 165 ℃ to collect fraction 2 to obtain 2142 g of fraction, and detecting the content of Dimethylformamide (DMF) to be 98.7%; when the temperature of the kettle is reduced to 128 ℃, crystals begin to precipitate, the temperature is reduced to 35 ℃, the filtration is carried out, 32.4g of filter cake is dried, 30.5g of dry product is obtained, 0.1g of potassium carbonate is detected, the total content of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is detected to be 98.31 percent by high performance liquid detection, and the total recovery rate of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is 90.56 percent;
and c, heating 828.4g of the third aqueous phase obtained in the step a to 104 ℃ for distillation, collecting 90g of fraction, standing and separating the obtained fraction to obtain 2.6g of oil phase, detecting the content of isobutyl acetate to be 99.4%, cooling the aqueous phase, and then feeding the aqueous phase into an A/O sewage treatment system for treatment, wherein the COD after treatment is 185.5mg and meets the standard of less than or equal to 200mg/L in the discharge standard of chemical synthesis pharmaceutical industry water pollutants.
Example 4
In this example, the 4,4 '-diphenyl ether dianhydride production wastewater is a crystallization mother liquor generated after crystallization and centrifugation in the 4,4' -diphenyl ether dianhydride synthesis process, and it was detected that the crystallization mother liquor contains 80% of water, 15% of dimethylformamide, 1.5% of potassium carbonate, 2.3% of 4-nitrophthalimide, 1% of oxybis- (N-methylphthalimide), and 0.2% of other side reaction products.
The method for treating the wastewater generated in the production of 4,4' -diphenyl ether dianhydride comprises the following steps:
step a, adding 500g of an extracting agent (ethyl acetate: dichloroethane: 1,2, 4-trichlorobenzene =1:2:0.8) into 1000g of 4,4' -diphenyl ether dianhydride production wastewater, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 922g of a first water phase and 578g of a first oil phase;
adding 500g of the extracting agent into the first water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 885g of a second water phase and 537g of a second oil phase;
adding 500g of the extracting agent into the second water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 884g of a third water phase and 501g of a third oil phase;
step b, combining the three oil phases to obtain 1616g of mixed oil phase, distilling the combined oil phase at normal pressure, collecting at 145 ℃ to obtain 11129.2 g of fraction, and detecting the ethyl acetate content of 29.82%, the dichloroethane content of 69.78% and the DMF content of 0.4%; continuously heating to 165 ℃ to collect fraction 2 to obtain 2140.1 g of fraction with DMF content of 99.0%; when the temperature of the kettle is reduced to 121 ℃, crystals begin to precipitate, the temperature is reduced to 35 ℃, the crystals are filtered, 29.1g of filter cake is dried to obtain 26.9g of dry product, 0.12g of potassium carbonate is detected, the total content of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is detected to be 99.1 percent by high performance liquid detection, and the total recovery rate of 4-nitrophthalimide and oxo-bis- (N-methylphthalimide) is 80.42 percent;
and c, heating 884g of the third aqueous phase obtained in the step a to 104 ℃ for distillation, collecting 90g of fraction, standing and separating the obtained fraction to obtain 56.1g of oil phase, detecting the ethyl acetate content to be 91.5%, cooling the aqueous phase, and then feeding the aqueous phase into an A/O sewage treatment system for treatment, wherein the COD after treatment is 197mg and meets the standard that the COD is less than or equal to 200mg/L in the discharge standard of chemical synthesis pharmaceutical industry water pollutants.
Comparative example 1
The comparative example provides a treatment method of 4,4' -diphenyl ether dianhydride production wastewater, the used wastewater has the same composition as the wastewater of the embodiment, and the specific treatment method comprises the following steps:
step a, adding 500g of an extracting agent (aviation kerosene: isobutyl ketone: n-octanol: ethyl acetate =1:1: 1) into 1000g of 4,4' -diphenyl ether dianhydride production wastewater, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 1015g of a first water phase and 486g of a first oil phase;
adding 500g of the extracting agent into the first water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 1014g of a second water phase and 501g of a second oil phase;
adding 500g of the extracting agent into the second water phase, stirring and mixing at 35 ℃ and 180rpm for 30min, standing for 1h, and then carrying out liquid separation to obtain 1014g of a third water phase and 500g of a third oil phase;
the composition of the water phase after three times of detection and extraction is as follows: 76.4 percent of water, 8.8 percent of dimethylformamide, 1.5 percent of potassium carbonate, 2.2 percent of 4-nitrophthalimide, 0.8 percent of oxo-bis- (N-methylphthalimide), 0.1 percent of other side reaction products, 3.1 percent of isobutyl ketone, 2.5 percent of N-octanol, 4.6 percent of ethyl acetate, and toxic and harmful substances in water are not effectively removed.
As can be seen from the above comparative examples, the use of the extractant of comparative example 1 does not effectively extract and separate the organic substances in the wastewater, but rather introduces additional organic pollutants into the wastewater due to the added extractant.
The extractant in the above examples 1-3 can also adopt isobutyl acetate, dichloromethane and 1,2, 4-trichlorobenzene with other proportions defined by the invention, and can achieve the technical effect basically equivalent to that of the corresponding examples 1-3.
The extractant in the above example 4 may be replaced with an extractant of another composition defined in the present invention, and as long as the ratio of each extractant component is within the ratio defined in the present invention, a technical effect substantially equivalent to that of example 4 can be achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A method for treating 4,4' -diphenyl ether dianhydride production wastewater by using an extractant is characterized in that the extractant comprises isobutyl acetate, dichloromethane and 1,2, 4-trichlorobenzene in a mass ratio of 1:1.5-2.0:0.5-1.0, and further comprises the following steps:
step a, adding the extracting agent into the 4,4' -diphenyl ether dianhydride production wastewater, stirring, standing, separating liquid, extracting a water layer for 1-2 times by using the extracting agent, and respectively combining a water phase and an oil phase to obtain a first oil phase and a first water phase; the 4,4' -diphenyl ether dianhydride production wastewater comprises three components of a reaction main raw material 4-nitrophthalimide, a reaction solvent dimethylformamide and a reaction intermediate product oxo-bis- (N-methylphthalimide);
b, distilling the first oil phase at normal pressure, collecting fraction 1 with the boiling range of 30-145 ℃, heating, continuing to collect fraction 2 with the boiling range of 145-165 ℃, stopping distillation, cooling, crystallizing, and filtering to obtain a recovered raw material and a distillation mother liquor;
c, distilling the first water phase at normal pressure, and stopping distillation when the evaporation amount is 5-15% of the mass of the first water phase to obtain a fraction 3; standing and separating the fraction 3 to obtain a second oil phase and a second water phase;
and d, treating the second water phase by a sewage treatment system and discharging.
2. The method for treating wastewater from 4,4 '-diphenyl ether dianhydride production by using an extracting agent according to claim 1, wherein in the step a, the mass ratio of the wastewater from 4,4' -diphenyl ether dianhydride production to the extracting agent is 1: 0.2-1.0.
3. The method for treating 4,4' -diphenyl ether dianhydride production wastewater by using the extractant according to claim 1, wherein in the step a, the stirring rotation speed is 150rpm to 200rpm, and the standing time is 30min to 60 min.
4. The method for treating wastewater from the production of 4,4' -diphenyl ether dianhydride with an extractant according to claim 1, wherein in the step d, the wastewater treatment system is an A/O wastewater treatment system.
5. The method for treating wastewater from the production of 4,4' -diphenyl ether dianhydride with an extractant according to claim 1, wherein the fraction 1, the distillation mother liquor and the second oil phase are combined and recycled as raw materials for the preparation of the extractant.
6. The method for treating wastewater from the production of 4,4 '-biphenylether dianhydride with an extractant according to claim 1, wherein the fraction 2 and the recovered raw material are recycled as raw materials for preparing 4,4' -biphenylether dianhydride.
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