CN111847789A - Process for treating wastewater generated in production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation - Google Patents
Process for treating wastewater generated in production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- MOAJBSFIZZIIFV-UHFFFAOYSA-N OS(O)(=O)=O.C1=CC(N)=CC=C1C(O)CS(=O)(=O)CC(O)C1=CC=C(N)C=C1 Chemical compound OS(O)(=O)=O.C1=CC(N)=CC=C1C(O)CS(=O)(=O)CC(O)C1=CC=C(N)C=C1 MOAJBSFIZZIIFV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000003311 flocculating effect Effects 0.000 claims abstract 3
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- 229910052603 melanterite Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229960001413 acetanilide Drugs 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 4-aminophenyl-beta-hydroxyethyl sulfone sulfate ester Chemical class 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- QQNXPCCFPQRLMK-UHFFFAOYSA-N S(O)(O)(=O)=O.OCCS(=O)(=O)CCO Chemical compound S(O)(O)(=O)=O.OCCS(=O)(=O)CCO QQNXPCCFPQRLMK-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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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
- 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
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- C02F2101/30—Organic compounds
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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
- C02F2101/00—Nature of the contaminant
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- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a process for treating wastewater generated in the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation, which comprises the following steps: adding ferrous sulfate according to the amount of residual hydrogen peroxide in the wastewater, stirring for reaction, adding a polyacrylamide solution after the reaction is finished, flocculating and filtering; adjusting the pH value of the filtered wastewater by using a sulfuric acid solution, adding reduced iron powder, stirring for reaction, adding a sodium hydroxide solution to adjust the pH value to be neutral, adding a polyacrylamide solution, flocculating and filtering; mixing and homogenizing the filtered wastewater and equipment washing water, and carrying out anaerobic biological treatment; adopting an A-O biological treatment process for the wastewater after anaerobic biological treatment; the wastewater after biological treatment is subjected to advanced oxidation advanced treatment. The invention adopts ferrous sulfate to catalyze and decompose residual hydrogen peroxide, and the reduced iron powder reduces and degrades nitrobenzene into aniline or aniline salt under the acidic condition, thereby improving the biodegradability and creating conditions for subsequent biological treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment and environmental protection, in particular to a wastewater treatment process for producing 4-aminophenyl-beta-hydroxyethyl sulfone sulfate through catalytic hydrogenation.
Background
4-aminophenyl-beta-hydroxyethyl sulfone sulfate, wherein beta-hydroxyethyl sulfone sulfate is a temporary water-soluble group, which not only can improve the solubility of the dye in application, but also has lower affinity to fiber during dyeing, can achieve level dyeing effect, can react with fiber to generate dye-fiber ether bond, has better acid resistance and thermal stability of the ether bond, is favorable for improving washing efficiency and wet strength of printing and dyeing products, is an intermediate of KN type and M type reactive dyes, and is also the most important reactive group of vinyl sulfone.
The conventional production process adopts acetanilide synthesis, and the technological processes are chlorosulfonation reaction, reduction reaction, condensation reaction and esterification reaction. The specific reaction is as follows:
chlorosulfonation:
the main raw materials are acetanilide and chlorosulfonic acid, and a large amount of dilute sulfuric acid and hydrogen chloride are generated in the reaction process. Reduction reaction:
a large amount of sodium chloride and sodium sulfate generated in the reduction reaction is in the wastewater.
③ condensation reaction:
in the condensation reaction, a large amount of sodium hydroxide is produced, and a large amount of sodium chloride is produced in the waste water during neutralization.
Esterification reaction:
the synthesis process of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by acetanilide method has complex reaction and many byproducts, especially the waste water contains a large amount of Na2SO4And NaCl and other mixed salt with concentration as high as 6-10% and waste water output of 15-20 ton, and this results in high waste water and waste gas treating difficulty and high operation cost.
Under the circumstances, a synthesis process has been developed in recent years in which nitrochlorobenzene is used as a raw material, condensed with mercaptoethanol, subjected to oxidation reduction, and then esterified to produce 4-aminophenyl- β -hydroxyethyl sulfone sulfate. In the synthetic reaction process, the byproducts in each reaction process are few, the oxidation reaction is convenient to operate, particularly, in the hydrogenation reduction process, no salt byproduct is generated, compared with the acetanilide synthetic process, the production cost of the hydrogenation reduction process is low, the salt content in the wastewater is only 5% of that of the original process, and the production amount of the wastewater per ton is only 10% of that of the original process.
The production process of the 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation comprises the following steps:
condensation reaction:
the waste water generated in the reaction process contains a certain amount of sodium chloride, p-nitrochlorobenzene, and residual dimethylformamide, dimethylamine and the like in an organic phase.
Oxidation reaction:
in the reaction process, unreacted hydrogen peroxide exists in the wastewater, and intermediates of reactants, such as p-nitro-ethylhydroxy-ethyl sulfide and a product of the reactants, i.e. p-nitro-ethylhydroxy-ethyl sulfone, remain.
③ catalytic hydrogenation reaction:
in the reaction process, a p-nitro-ethylhydroxyethysulfone intermediate and a product p-amino-2-hydroxyethylsulfone remain in the produced wastewater.
Esterification reaction:
in the reaction process, 4-aminophenyl-beta-hydroxyethyl sulfone sulfate ester products which are not completely extracted from the p-amino-ethylhydroxyethyl sulfone intermediate remain in the wastewater.
In summary, the production process of 4-aminophenyl- β -hydroxyethyl sulfone sulfate by catalytic hydrogenation produces a small amount of wastewater, has low salt content, but has relatively many kinds of pollutants, such as a large amount of aniline, p-nitrobenzene, benzene, ethylbenzene, dimethylformamide, dimethylamine, various aromatic hydrocarbon intermediates, incompletely extracted 4-aminophenyl- β -hydroxyethyl sulfone sulfate, and the like.
In recent years, with the progress of technology, the production process of producing 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation is mature, but the production wastewater contains a large amount of biological toxic substances and has poor biodegradability, so that no mature treatment process exists at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a treatment process for producing 4-aminophenyl-beta-hydroxyethyl sulfone sulfate ester wastewater by catalytic hydrogenation, which aims to solve the problems of strong biological toxicity and poor biodegradability of organic compounds containing nitroarene in the wastewater, and realize clean production and standard-reaching discharge of the wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to a process for treating wastewater generated in the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation, which comprises the following steps:
(1) the wastewater of the production process is weakly acidic and has pH value of 5-6, ferrous sulfate is added for stirring reaction, and polyacrylamide solution is added for flocculation and filtration after the reaction is finished;
(2) adjusting the pH value of the filtered wastewater by using a sulfuric acid solution, adding reduced iron powder, stirring for reaction, reacting for a period of time, adding a sodium hydroxide solution, adjusting the pH value to be neutral, adding a polyacrylamide solution for flocculation, and filtering;
(3) mixing and homogenizing the filtered wastewater and equipment washing water, and carrying out anaerobic biological treatment;
(4) adopting an A-O biological treatment process for the wastewater after anaerobic biological treatment;
(5) the wastewater after biological treatment is discharged after advanced oxidation advanced treatment.
Further, the pH value of the production wastewater obtained in the step (1) is 5-6, and the amount of the hydrogen peroxide residual in the wastewater is H2O2:FeSO4·7H2Adding ferrous sulfate in a molar ratio of 0: 10-1-10, stirring and reacting for 3-4 hours, adjusting the pH value to be neutral by using a sodium hydroxide solution after the reaction is finished, adding a polyacrylamide solution for flocculation, and filtering by adopting a plate-and-frame filter pressing mode after flocculation. In the step, ferrous sulfate and residual hydrogen peroxide in the wastewater are added to form a Fenton-like advanced oxidation system so as to decompose the residual hydrogen peroxide, reduce the inhibition on subsequent biological treatment, oxidize organic pollutants in the wastewater and reduce the content of toxic and harmful substances in the wastewaterAmount of the compound (A).
Further, the step (2) is that the pH value of the wastewater treated in the step (1) is adjusted to 3-4 by using a sulfuric acid solution, 1.5-2.5g of reduced iron powder is added into 100mg/L of nitrobenzene according to the amount of nitrobenzene in the wastewater, the mixture is stirred and reacted for 3-5 hours, a sodium hydroxide solution is added after the reaction is finished, the pH value is adjusted to be neutral, and the mixture is filtered by adopting a plate-and-frame filter pressing mode after being flocculated by adding a polyacrylamide solution. The method adopts reduced iron powder to reduce the nitroaromatic compound under the acidic condition, degrades the biotoxicity of the nitroaromatic compound and creates conditions for subsequent biological treatment.
Further, the step (3) is that the wastewater treated in the step (2) is mixed and homogenized with equipment washing water, moderate-temperature anaerobic treatment is carried out, a UASB (upflow anaerobic sludge blanket) anaerobic reactor is adopted for anaerobic treatment, and the volume load of the anaerobic treatment is 1-2 kgCOD/(m)3D), after anaerobic biological treatment, most organic matters are degraded and mineralized to generate methane and carbon dioxide, organic nitrogen is converted into ammonia nitrogen, and nitro aromatic hydrocarbon organic matters which are not completely reacted are converted into easily biodegradable aniline and aniline salt.
Further, the step (4) is that the wastewater after anaerobic biological treatment in the step (3) is biologically treated by an A-O method, the TN sludge load of the A tank is 0.03-0.08kgTN/(kg MLSS. d), and the COD load of the O tank is 0.1-0.2kg COD/(kg MLSS. d), and pollutants such as total nitrogen, ammonia nitrogen, COD and the like in the wastewater are degraded through an A-O biological treatment process.
Further, the step (5) is that the wastewater after the A-O biological treatment in the step (4) is subjected to advanced oxidation advanced treatment to further remove residual aniline substances and COD in the wastewater, the Fenton method is adopted for the advanced oxidation advanced treatment, and H is adopted for the advanced oxidation advanced treatment2O2:FeSO4·7H2Stirring and reacting for 3-4 hours at a molar ratio of 0: 3-2, and adjusting the pH value to be neutral by using a sodium hydroxide solution.
The invention has the beneficial effects that: the invention adopts ferrous sulfate to catalyze and decompose residual hydrogen peroxide, and the reduced iron powder reduces and degrades nitrobenzene into aniline or aniline salt under an acidic condition, thereby improving biodegradability and creating conditions for subsequent biological treatment. The pretreated process wastewater is mixed and homogenized with equipment washing water, and then a biological treatment process is adopted. And (3) carrying out advanced treatment on the effluent after biological treatment by adopting a Fenton oxidation method, wherein the treated effluent is discharged after reaching the standard.
Drawings
FIG. 1 is a flow diagram of a wastewater treatment process of the present invention.
Detailed Description
The present invention is further described with reference to the following specific embodiments, which should be construed as merely illustrative and not limitative of the remainder of the disclosure, and it is understood that modifications and variations can be made by those skilled in the art in light of the above teachings.
The production waste water produced in the process of hydrogenating 4-aminophenyl-beta-hydroxyethyl sulfone sulfate has very high chemical oxygen demand (0.5-1X 10)5mg/L) of the waste water, and simultaneously contains a large amount of aniline, p-nitrochlorobenzene, nitrobenzene, ethylbenzene, dimethylformamide, dimethylamine, 4-aminophenyl-beta-hydroxyethyl sulfone sulfate products which are not completely extracted and residual hydrogen peroxide generated in oxidation reaction, so that the waste water has strong biological toxicity and poor biodegradability.
The invention is described in one step with reference to the accompanying drawings:
the process flow diagram of the invention for the treatment of wastewater from the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation is shown in figure 1, and comprises the following process steps:
step 1: the pH value of the process wastewater is 5.3, the content of hydrogen peroxide is 1.47 percent, and H2O2:FeSO4·7H20 molar ratio of 2:1, FeSO4·7H20 dosage of 60g/L, stirring and reacting for 3.2 hours, adjusting the pH value of a sodium hydroxide solution to 7.5 after the reaction is finished, adding a polyacrylamide solution for flocculation, and performing plate-and-frame filter pressing.
Step 2: the process wastewater after plate-and-frame filter pressing has the nitrobenzene content of 210mg/L, the pH of the process wastewater is adjusted to 3.7 by using a sulfuric acid solution, 2g of reduced iron powder is added according to 100mg/L of nitrobenzene, the reduced iron powder is added, the addition amount of the reduced iron powder is 4.2g/L, the mixture is stirred and reacted for 4 hours, after the reaction is finished, the pH is adjusted to 7.5 by using a sodium hydroxide solution, a polyacrylamide solution is added for flocculation, and the plate-and-frame filter pressing is carried out.
And step 3: mixing the process wastewater filtered by the plate frame with the equipment washing water to perform homogeneous regulation of water quantity and water quality, and regulating COD (chemical oxygen demand) to 11470mg/L, TN 416mg/L, NH3-N371 mg/L, adopting moderate temperature UASB anaerobic process, heating the wastewater to 35.3 deg.C, allowing the wastewater to enter UASB anaerobic reactor for anaerobic reaction, wherein the volume load of the UASB anaerobic reactor is 1.2 kgCOD/(m)3D). After anaerobic treatment, the COD of the wastewater is reduced to 4631mg/L, the removal rate of the COD is 59.63 percent, TN is reduced to 391mg/L, and NH is added3N was reduced to 356.2 mg/L.
And 4, step 4: after the anaerobic biological treatment in the step 3, the wastewater is biologically treated by an A-O treatment process, wherein the load of TN sludge in the tank A is 0.04kgTN/(kg MLSS. d), the load of COD in the tank O is 0.1kg COD/(kg MLSS. d), the COD of the wastewater after the A-O biological treatment is reduced to 648mg/L, the removal rate is 86 percent, the TN is reduced to 36mg/L, the removal rate of TN is 90.8 percent, and the NH of the wastewater after the A-0 biological treatment is treated3-N is reduced to 4.3mg/L, NH3the-N removal rate was 95.8%.
And 5: and 4, performing advanced oxidation treatment on the wastewater subjected to biological treatment in the steps 4A-O, wherein the advanced oxidation is performed by a Fenton method. Adjusting the pH value of the wastewater to 3.2, H by using sulfuric acid solution2O2:FeSO4·7H20 mol ratio of 3:1, namely the adding amount of 27.5 percent hydrogen peroxide is 5.5g/L, FeSO4·7H20 was added in an amount of 1.82g/L, and the reaction was stirred for 3.5 hours, and the pH was adjusted to 6.5 with sodium hydroxide solution. COD of the waste water after Fenton oxidation is reduced to 227mg/L, and the removal rate reaches 65%. The aniline content in the waste water is less than 1.0 mg/L.
| Inflow (mg/L) | Anaerobic effluent (mg/L) | A-O Water (mg/L) | Fenton effluent (mg/L) | |
| COD | 11470 | 4631 | 648 | 227 |
| TN | 416 | 391 | 36 | |
| NH3-N | 371 | 356.2 | 4.3 |
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A process for treating wastewater generated in the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation is characterized by comprising the following steps:
(1) adding ferrous sulfate according to the amount of residual hydrogen peroxide in the wastewater, stirring for reaction, and adding a polyacrylamide solution for flocculation and filtration after the reaction is finished;
(2) adjusting the pH value of the filtered wastewater by using a sulfuric acid solution, adding reduced iron powder, stirring for reaction, reacting for a period of time, adding a sodium hydroxide solution to adjust the pH value to be neutral, adding a polyacrylamide solution for flocculation, and filtering;
(3) mixing and homogenizing the filtered wastewater and equipment washing water, and carrying out anaerobic biological treatment;
(4) adopting an A-O biological treatment process for the wastewater after anaerobic biological treatment;
(5) the wastewater after biological treatment is subjected to advanced oxidation advanced treatment.
2. The process for treating wastewater from the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation according to claim 1, wherein: the pH of the wastewater obtained in the step (1) is 5-6 according to the residual hydrogen peroxide content in the wastewater and the H2O2:FeSO4·7H2Adding ferrous sulfate in the molar ratio of 0 to 10 (1-10), stirring for reaction for 3-4 hr, regulating pH value to neutrality with sodium hydroxide solution, adding polyacrylamide solution, flocculating and filtering.
3. The process for treating wastewater from the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation according to claim 1, wherein: in the step (2), the pH value is adjusted to 3-4 by using a sulfuric acid solution, 1.5-2.5g of reduced iron powder is added into 100mg/L of nitrobenzene according to the amount of the nitrobenzene in the wastewater, the mixture is stirred and reacted for 3-5 hours, a sodium hydroxide solution is added after the reaction is finished, the pH value is adjusted to be neutral, and a polyacrylamide solution is added for flocculation and filtration.
4. The process for treating wastewater from the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation according to claim 1, wherein: in the step (3), a moderate-temperature UASB anaerobic reactor is adopted for anaerobic biological treatment, and the volume load is 1-2 kgCOD/(m-d).
5. The process for treating wastewater from the production of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate by catalytic hydrogenation according to claim 1, wherein: in the step (4) A-O biological treatment process, the TN sludge load of the tank A is 0.03-0.08 kgTN/(kgMLSS.d), and the COD load of the tank O is 0.1-0.2 kgCOD/(kgMLSS.d).
6. The process for treating wastewater from the catalytic hydrogenation production of 4-aminophenyl- β -hydroxyethyl sulfone sulfate according to claim 1, wherein: the advanced oxidation advanced treatment in the step (5) adopts a Fenton oxidation method, H2O2:FeSO4·7H20 mol ratio of 3 (1-2), stirring and reacting for 3-4 hours, and adjusting the pH value to be neutral by sodium hydroxide solution.
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