CN110330189B - Treatment method of wastewater containing benzoic acid - Google Patents
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Abstract
The invention discloses a method for treating wastewater containing benzoic acid, which is characterized in that the benzoic acid wastewater is treated by an adjusting tank, a filter, a reduced pressure recycling acid steaming system, a Fenton and coagulation system, a biochemical oxidation process and an ozone oxidation process, so that pollutants with high indexes such as refractory organic matters, inorganic salts, chromaticity and the like in the wastewater are efficiently removed, COD (chemical oxygen demand) of the finally treated effluent is less than or equal to 100mg/L, the chromaticity of the effluent is less than or equal to 75, and the pH range of the effluent is 6-9.
Description
Technical Field
The invention belongs to the technical field of chemical wastewater treatment, and particularly relates to a treatment method of wastewater containing benzoic acid.
Background
Benzoic acid is an important organic chemical raw material, and has wide application in the aspects of medicines, foods, chemical industry and the like. With the rapid development of industry and agriculture, a large amount of benzoic acid acidic wastewater is generated in some production, and the wastewater contains complex components, a large amount of nitric acid, inorganic salts, organic matters and the like. In the production, manufacturers can add a large amount of nitric acid, so that the nitric acid is a necessary additive in the production, the benzoic acid content of the wastewater is about 1-2%, the high benzoic acid content seriously affects the biological treatment of the wastewater, and causes great harm to the survival of animals, plants and human beings, especially organic pollutants such as phenol, aniline and the like with teratogenic, carcinogenic and mutagenic small molecules, so that the wastewater discharge often exceeds the national specified standard, the environment is polluted, and waste in the process production is caused.
The prior methods for treating and recycling the benzoic acid wastewater mainly comprise solvent extraction, adsorption, a liquid membrane method and the like, but the methods respectively have corresponding advantages and have some disadvantages. For example: solvent extraction has solvent loss, needs secondary treatment and has complex process; in the adsorption method, the adsorbent needs to be regenerated, so that the regeneration equipment is large and the cost is high; the liquid membrane method has high operation requirements, and has the defects of instability, secondary pollution and the like; in general, the benzoic acid wastewater treatment method is to perform neutralization reaction and then enter a biochemical system, but the biochemical reaction needs to control the concentration of inorganic salt, and dilution water needs to be added for diluting the salt to be more than 10 times of the water quantity of the wastewater, so that the subsequent treatment cost is greatly increased, and the purpose of saving the cost is not achieved; for the chromaticity of the benzoic acid wastewater, the final chromaticity removal standard can not be reached by adopting an electro-Fenton method in the traditional process, so that the innovation and the modification of the technology are finally needed.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the method for treating the wastewater containing the benzoic acid is provided.
The technical scheme adopted by the invention is as follows:
a method for treating wastewater containing benzoic acid comprises the following steps:
s1, enabling the wastewater containing benzoic acid to enter an adjusting tank, and uniformly stirring;
s2, the wastewater uniformly stirred in the step S1 enters a filter to be filtered;
s3, feeding the wastewater filtered in the step S2 into a reduced pressure recycling acid rectification system for acid distillation;
s4, the wastewater subjected to acid steaming in the step S3 enters a Fenton and coagulation system, and FeSO is added firstly4·7H2O and H2O2Performing Fenton reaction, filtering, adjusting pH to 6-9, adding PAM andPAC is subjected to coagulation reaction to remove flocculation and precipitation;
s5, the wastewater treated in the step S4 enters a biochemical oxidation reaction device, is diluted by adding water with the volume 3-4 times of that of the wastewater, enters an anoxic tank for stirring, and enters an aerobic tank for aeration stirring;
s6, the wastewater treated in the step S5 enters an ozone oxidation reaction device, and ozone is introduced for oxidation.
After being discharged in a centralized manner in a factory, the wastewater containing the benzoic acid enters a regulating tank and is uniformly stirred by using a stirrer, so that the wastewater achieves the effect of homogenizing and uniform amount; the wastewater treated in the step S1 enters a filter, and suspended matters and flocculation pollutants in the water are filtered; the wastewater treated in the step S2 enters a reduced pressure recycling acid steaming system, the evaporation temperature is not more than 200 ℃, the temperature is automatically controlled, the vacuum degree is not less than 2000mbar, the acid steaming device has the functions of high temperature resistance, quick heat conduction, strong acid corrosion prevention and the like, the evaporation efficiency of the nitric acid is high, 80-90% of the nitric acid can be recycled, the recycling concentration is 20-30%, the nitric acid can be directly recycled to a production workshop for use, the purpose of saving the cost is achieved, and the waste recycling and the recycling are realized; meanwhile, the acid evaporation system can evaporate most of nitric acid, reduce the content of inorganic salt in the wastewater, reduce the dilution water added in the biochemical oxidation reaction after the Fenton and coagulation system reaction by more than 6 times, replace the increased dilution water with domestic wastewater, further treat the domestic wastewater together to reach the standard, reduce the treatment equipment of the domestic wastewater, minimize the cost and maximize the utilization rate; the wastewater treated in the step S3 enters a Fenton and coagulation system, a Fenton reaction is carried out firstly, the COD degradation rate of the reaction reaches 60%, and meanwhile, the concentration of BOD is increased, and the ratio of BOD/COD is increased, so that the biodegradability of a subsequent biochemical system is improved, the biochemical pressure is reduced, the biochemical time is shortened, and the cost of a biochemical process is reduced; the filtered wastewater is subjected to coagulation reaction after pH adjustment to generate flocculent precipitate, so that a large amount of inorganic salt and the flocculent precipitate are removed, and the subsequent biochemical oxidation reaction can smoothly react; the wastewater treated in the step S4 is subjected to biochemical oxidation reaction, i.e. anoxic-aerobic reaction, and is firstly diluted by water to ensure that the biochemical reaction can be smoothly carried out and the wastewater can be subjected toThe domestic wastewater is used without increasing other water quantity, and the denitrifying bacteria in the anoxic pond utilize organic matters in the wastewater as carbon sources to bring a large amount of NO into the reflux mixed liquor3-N and NO2Reduction of-N to N2Released to the air, so that the BOD5 concentration is reduced, NO3The N concentration is greatly reduced, the organic matters in the aerobic tank are biochemically degraded by aerobic microorganisms and continuously reduced, the organic nitrogen is ammoniated and then nitrified, and NH is generated3The N concentration is reduced remarkably, and the reaction process can remove a large amount of total nitrogen and more than 90% of COD; the wastewater treated in the step S5 enters into an ozone oxidation reaction to further remove COD in the wastewater and simultaneously remove pigments in the wastewater. And finally, the COD of the discharged water can reach below 100mg/L, and the wastewater reaches the discharge standard.
Further, the wastewater containing benzoic acid in the step S1 stays in the regulating reservoir for 1-2 h.
Further, the filter pore size of the filter in step S2 is 12 to 100 μm.
Furthermore, in step S3, the acid steaming temperature is less than or equal to 200 ℃, and the vacuum degree is more than or equal to 2000 mbar.
Further, the retention time of the fenton reaction in step S4 is 2.5 to 3 hours.
Further, FeSO4·7H2O and H2O2The amount of the added water is obtained according to the COD value of the wastewater, the COD value and the H value of the wastewater2O2In a mass ratio of 1:1.5, the ratio of H to2O2With FeSO4·7H2The mass ratio of O is 1: 2-4.
Further, the mass ratio of PAC to PAM in step S4 is 150-: 5-50; preferably, the mass concentration of PAC and PAM in the wastewater is 200mg/L and 10mg/L respectively.
Further, in the step S5, the wastewater stays in the anoxic tank for 1-2h, the wastewater is stirred in the anoxic tank, the denitrifying bacteria in the anoxic tank utilize organic matters in the wastewater as carbon sources, and a large amount of NO is brought into the reflux mixed liquor3-N and NO2Reduction of-N to N2Released to the air, so that the BOD5 concentration is reduced, NO3The concentration of N is reduced and then stays in an aerobic tank for 3 to 4 hours, and the aerobic tank is provided with a microporous aeratorThe waste water is aerated and stirred aerobically, the organic matter is degraded biochemically by aerobic microbe in the aerobic pool and then descends continuously, the organic nitrogen is ammoniated and then nitrified, and NH is generated3The N concentration decreased and reached the standard.
Further, in step S5, domestic wastewater is used for dilution.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, the wastewater containing benzoic acid enters a reduced-pressure reflux acid steaming system through a filtering device, so that nitric acid is recycled in factory production workshops, the aim of saving cost is achieved, and waste recycling and recycling are realized;
2. the acid steaming system can evaporate most of acid, reduce the inorganic salt content of the wastewater, reduce the water for dilution added in the biochemical reaction after the Fenton and coagulation reaction, replace the added water for dilution with domestic wastewater, further treat the domestic wastewater together to reach the standard, reduce the treatment equipment of the domestic wastewater, minimize the cost and maximize the utilization rate;
3. in the Fenton coagulation system, the Fenton oxidation can increase the ratio of BOD/COD, and the coagulating sedimentation further removes inorganic salts and flocculates in water, thereby improving the biodegradability of a subsequent biochemical system, reducing the biochemical pressure, shortening the biochemical time and reducing the cost of the biochemical process;
4. in the invention, the wastewater finally passes through an ozone oxidation system, so that COD (chemical oxygen demand) is further reduced, pigments in the wastewater are removed, and the wastewater is ensured to be discharged after reaching standards;
5. the whole system device for treating the wastewater containing the benzoic acid has the advantages of low cost, high efficiency, waste recycling and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a process flow diagram of the treatment of wastewater containing benzoic acid in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Through measurement, the wastewater containing benzoic acid to be treated has the COD of 7142mg/L, the BOD of 1051mg/L, the chroma of more than 10000, deep red color, the salt content of 98500mg/L, the pH value of 1.3 and a small amount of total nitrogen.
The method for treating the wastewater containing the benzoic acid provided by the invention is used for treating the wastewater containing the benzoic acid, and comprises the following specific steps:
introducing wastewater containing benzoic acid to be treated into a regulating reservoir, and staying for 1.5 hours; introducing the treated wastewater into a bag filter, and removing micro suspended matters and flocculation precipitates in the wastewater; introducing the effluent water passing through the bag filter into a reduced-pressure recycling acid steaming system, wherein the salt content is 19900mg/L, and the salt content is reduced by about 80000 mg/L; directly feeding the wastewater into a reaction tank of a Fenton and coagulation system, adding 17.3g/L ferrous sulfate heptahydrate and 6.3g/L hydrogen peroxide, adding a stirrer, keeping the time for 2.5 hours, wherein COD (chemical oxygen demand) of effluent of the sedimentation tank subjected to the Fenton reaction is 2892mg/L, BOD is 1541mg/L, the value of BOD/COD is increased, and the biodegradability of a subsequent biochemical system is improved; performing coagulation reaction on the wastewater after the Fenton reaction, adding a proper amount of alkali to adjust the pH value to 7.5, and then adding 150mg/LPAC and 50mg/LPAM to further remove COD, inorganic salts and flocculates in the wastewater; after the Fenton and coagulation system react, domestic wastewater is added to dilute the salt concentration in the wastewater, at the moment, the salt concentration is 4787mg/L, the wastewater enters a biochemical oxidation process, firstly, the wastewater enters an anoxic tank, a stirrer is added into the anoxic tank, the retention time is 1 hour, the aerobic tank is provided with a microporous aerator, the wastewater is subjected to aerobic aeration and stirring, the retention time is 3 hours, part of sludge is refluxed, and the COD value of the effluent is 148 mg/L; the effluent of the biochemical oxidation process enters an ozone oxidation tank, the pH value of the effluent is 8.4 after ozone oxidation, the chromaticity of the effluent is clear, the COD of the effluent reaches 84mg/L, and the quality of the effluent can reach the standard for discharge.
Example 2
Through measurement, the wastewater containing benzoic acid to be treated has the COD of 8031mg/L, the BOD of 1202mg/L, the chroma of more than 10000, deep red color, the salt content of 99800mg/L, the pH value of 1.1 and a small amount of total nitrogen.
The method for treating the wastewater containing the benzoic acid provided by the invention is used for treating the wastewater containing the benzoic acid, and comprises the following specific steps:
introducing wastewater containing benzoic acid to be treated into a regulating reservoir, and staying for 1.8 hours; introducing the treated wastewater into a bag filter, and removing micro suspended matters and flocculation precipitates in the wastewater; the effluent water passing through the bag filter is introduced into a reduced-pressure recycling acid steaming system, the salt content is 20500mg/L, and the salt content is reduced by about 80000 mg/L; directly sending the wastewater into a reaction tank of a Fenton and coagulation system, adding 18.3g/L ferrous sulfate heptahydrate and 6.3g/L hydrogen peroxide, adding a stirrer, keeping the time for 2.8 hours, wherein COD (chemical oxygen demand) of effluent of the sedimentation tank subjected to the Fenton reaction is 2873mg/L, BOD is 1601mg/L, the value of BOD/COD is increased, and the biodegradability of a subsequent biochemical system is improved; performing coagulation reaction on the wastewater after the Fenton reaction, adding a proper amount of alkali to adjust the pH value to 7.5, and then adding 200mg/LPAC and 10mg/LPAM to further remove COD, inorganic salts and flocculates in the wastewater; after the Fenton and coagulation system react, domestic wastewater is added to dilute the salt concentration in the wastewater, the salt concentration is 5270mg/L, the wastewater enters a biochemical oxidation process, the wastewater firstly enters an anoxic tank, a stirrer is added into the anoxic tank, the retention time is 2 hours, the aerobic tank is provided with a microporous aerator, the wastewater is subjected to aerobic aeration and stirring, the retention time is 4 hours, part of sludge is refluxed, and the COD value of the effluent is 159 mg/L; the effluent of the biochemical oxidation process enters an ozone oxidation tank, the pH value of the effluent is 8.1 after ozone oxidation, the chromaticity of the effluent is clear, the COD of the effluent reaches 93mg/L, and the quality of the effluent can reach the standard for discharge.
Example 3
Through measurement, the wastewater containing benzoic acid to be treated has the COD of 7850mg/L, the BOD of 1138mg/L, the chroma of more than 10000, the deep red color, the salt content of 98900mg/L, the pH value of 1.2 and a small amount of total nitrogen.
The method for treating the wastewater containing the benzoic acid provided by the invention is used for treating the wastewater containing the benzoic acid, and comprises the following specific steps:
introducing wastewater containing benzoic acid to be treated into a regulating reservoir, and staying for 1.6 hours; introducing the treated wastewater into a bag filter, and removing micro suspended matters and flocculation precipitates in the wastewater; introducing the effluent water passing through the bag filter into a reduced-pressure recycling acid steaming system, wherein the salt content is 20000mg/L, and the salt content is reduced by about 80000 mg/L; directly feeding the wastewater into a reaction tank of a Fenton and coagulation system, adding 19.3g/L ferrous sulfate heptahydrate and 6.3g/L hydrogen peroxide, adding a stirrer, keeping the time for 2.5 hours, wherein COD (chemical oxygen demand) of effluent of the sedimentation tank subjected to the Fenton reaction is 2892mg/L, BOD is 1541mg/L, the value of BOD/COD is increased, and the biodegradability of a subsequent biochemical system is improved; performing coagulation reaction on the wastewater after the Fenton reaction, adding a proper amount of alkali to adjust the pH value to 7.5, and then adding 200mg/LPAC and 10mg/LPAM to further remove COD, inorganic salts and flocculates in the wastewater; after the Fenton and the coagulation system react, domestic wastewater is added to dilute the salt concentration in the wastewater, at the moment, the salt concentration is 4787mg/L, the wastewater enters a biochemical oxidation process, firstly enters an anoxic tank, a stirrer is added into the anoxic tank, the retention time is 1.5 hours, a microporous aerator is arranged in the aerobic tank, the wastewater is subjected to aerobic aeration and stirring, the retention time is 3 hours, part of sludge is refluxed, and the COD value of the effluent is 148 mg/L; the effluent of the biochemical oxidation process enters an ozone oxidation tank, the pH value of the effluent is 8.2 after ozone oxidation, the chromaticity of the effluent is clear, the COD of the effluent reaches 88mg/L, and the quality of the effluent can reach the standard for discharge.
As will be understood by those skilled in the art, the filter and the reduced-pressure acid distilling device in the scheme of the invention belong to the prior art, and products with different models and specifications can be purchased in the market according to specific requirements. For example, the filter used in the scheme is multipurpose filtering equipment with small volume, simple and flexible operation, energy conservation, high efficiency, closed work and strong applicability, such as a bag filter which is customized and purchased by a company for producing the filter, and the filtering precision is 12-100 μm so as to remove micron-sized micro suspended matters; the pressure-reducing acid steaming device used in the scheme is an automatic temperature-control pressure-reducing acid steaming device customized by professional equipment companies, the evaporation temperature is not more than 200 ℃, the vacuum degree is not less than 2000mbar, and the pressure-reducing acid steaming device has the functions of high temperature resistance, quick heat conduction, strong acid corrosion prevention and the like.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A method for treating wastewater containing benzoic acid is characterized by comprising the following steps:
s1, enabling the wastewater containing benzoic acid to enter an adjusting tank, and uniformly stirring;
s2, the wastewater uniformly stirred in the step S1 enters a filter to be filtered;
s3, feeding the wastewater filtered in the step S2 into a reduced pressure recycling acid steaming system for acid steaming;
s4, the wastewater subjected to acid steaming in the step S3 enters a Fenton and coagulation system, and FeSO is added firstly4·7H2O and H2O2Performing Fenton reaction, filtering, adjusting the pH to 6-9, adding PAM and PAC to perform coagulation reaction, and removing flocculation precipitation;
s5, the wastewater treated in the step S4 enters a biochemical oxidation reaction device, is diluted by adding domestic wastewater with the volume 3-4 times of that of the wastewater, enters an anoxic tank for stirring, and enters an aerobic tank for aeration stirring;
s6, allowing the wastewater treated in the step S5 to enter an ozone oxidation reaction device, and introducing ozone for oxidation;
wherein, the acid steaming temperature in the step S3 is less than or equal to 200 ℃, and the vacuum degree is more than or equal to 2000 mbar; the FeSO4·7H2O and H2O2The amount of the added water is obtained according to the COD value of the wastewater, the COD value and the H value of the wastewater2O2In a mass ratio of 1:1.5, the ratio of H to2O2With FeSO4·7H2The mass ratio of O is 1: 2-4.
2. The method for treating wastewater containing benzoic acid according to claim 1, characterized in that: and the wastewater containing the benzoic acid in the step S1 stays in the regulating reservoir for 1-2 h.
3. The method for treating wastewater containing benzoic acid according to claim 1, characterized in that: the filter pore size of the filter in the step S2 is 12-100 μm.
4. The method for treating wastewater containing benzoic acid according to claim 1, characterized in that: the retention time of the fenton reaction in the step S4 is 2.5 to 3 hours.
5. The method for treating wastewater containing benzoic acid according to claim 1, characterized in that: the mass ratio of PAC to PAM in step S4 is 150-: 5-50.
6. The method for treating wastewater containing benzoic acid according to claim 1, characterized in that: in the step S5, the wastewater stays in the anoxic tank for 1-2h at first and then stays in the aerobic tank for 3-4 h.
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