CN110835178A - Method for directly oxidizing and degrading aniline organic pollutants in water - Google Patents
Method for directly oxidizing and degrading aniline organic pollutants in water Download PDFInfo
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 35
- 230000000593 degrading effect Effects 0.000 title claims abstract description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 85
- 239000000843 powder Substances 0.000 claims abstract description 46
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 27
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 34
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 34
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 31
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 7
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- 230000003647 oxidation Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 15
- 239000003344 environmental pollutant Substances 0.000 abstract description 14
- 231100000719 pollutant Toxicity 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000009303 advanced oxidation process reaction Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 10
- -1 sulfate radicals Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007344 nucleophilic reaction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-IDEBNGHGSA-N 4-bromoaniline Chemical group N[13C]1=[13CH][13CH]=[13C](Br)[13CH]=[13CH]1 WDFQBORIUYODSI-IDEBNGHGSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
A method for directly oxidizing and degrading aniline organic pollutants in water, which relates to the technical field of wastewater treatment. The invention aims to solve the problems that the prior method for removing aniline organic pollutants in wastewater has high selectivity to pollutants, is greatly influenced by environmental factors and has very limited pollutant removal effect, an advanced oxidation process represented by ozone and Fenton (Fenton) oxidation in a chemical method has more limiting factors, and the prior persulfate method based on sulfate radicals needs external energy or an environmental catalyst, has high cost and causes secondary pollution to the environment. The method comprises the following steps: regulating and controlling the pH value of wastewater to be treated containing aniline organic pollutants to 5-10, adding persulfate powder, and stirring for reaction to complete direct oxidative degradation of the aniline organic pollutants in water. The invention can obtain a method for directly oxidizing and degrading aniline organic pollutants in water.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for oxidative degradation of aniline organic pollutants.
Background
With the rapid development of the industry, the composition of wastewater generated in human production and life tends to be complex. The waste water generated in the industries of printing and dyeing, pharmacy, chemical industry and the like often contains a large amount of toxic and harmful substances, wherein the biodegradability of organic pollutants containing benzene rings is poor. The traditional biochemical treatment mainly depends on the metabolic process of microorganisms, but organic pollutants contained in the wastewater are difficult to be utilized by the microorganisms, the direct treatment effect is poor, and COD in the water is difficult to reach the standard. Therefore, trace organic chemicals are often detected in the effluent of sewage treatment plants, causing potential impact on human health.
Aniline is an important organic chemical raw material and is mainly applied to rubber industry, dye industry, pharmaceutical industry, pesticide industry and other industries. Aniline wastewater is mainly generated in petrochemical, printing and dyeing, pharmaceutical processes and the like, belongs to high-toxicity wastewater, has negative effects of carcinogenesis, teratogenesis and cell mutation, and can cause great influence on organisms and human bodies if being treated improperly and discharged into the environment. The existing sewage discharge standard has higher requirements on the discharge content of aniline pollutants.
The prior method for removing aniline organic pollutants in wastewater mainly comprises a biological method and a chemical method. The biological method is to degrade pollutants in water by utilizing the metabolic process of microorganisms, is environment-friendly and low in operation cost, can be applied to low-toxicity wastewater such as domestic sewage in a large scale, and has a very limited effect of removing toxic and harmful pollutants in the sewage. In addition, the method has high selectivity on pollutants, and a proper amount of carbon source, phosphorus source and the like are often added externally. Meanwhile, the biological method is greatly influenced by environmental factors such as temperature, pH and oxygen content, and the degradation of the microorganisms to pollutants has a limit value of minimum concentration. The chemical method mainly utilizes advanced oxidation methods (AOPs) to treat toxic and harmful organic pollutants in water. AOPs are based on strong oxidizers and their active species generated in situ to effectively degrade organic compounds. The main technique among these is the Fenton (Fenton) method based on OH radicals, which constitutes the most useful AOPs; in addition, degradation processes based on other oxidizing substances are also included, for exampleBased on sulfate radicals (SO)4 ·-) And sodium hypochlorite based on chlorine radicals (Cl). In drinking water treatment systems and reuse water systems, technologies such as ozone oxidation and ultraviolet irradiation are mainly used. In addition, there are a number of new research on water treatment processes using AOPs, such as electrochemical, plasma, electron beam, ultrasonic, or microwave AOPs.
Advanced oxidation processes, represented by ozone and Fenton (Fenton) oxidation, have been applied in large scale for advanced treatment and pretreatment of sewage. However, there are still more limiting factors, such as the requirement for ozone oxidation to have an electron donor and to use it in neutral water; fenton (Fenton) oxidation is only suitable for an acidic system, the pH value of the system needs to be adjusted, a large amount of waste such as iron mud is generated at the same time, and the subsequent effective treatment is needed.
In recent years, persulfate-based Advanced Oxidation Processes (AOPs) have received increasing attention because of their advantages such as high oxidizing ability, low cost, and high utilization efficiency. Persulfates (PS, S)2O8 2-) And peroxymonosulfate (PMS, HSO)5 -) Can be heated, alkali, ultraviolet light, activated carbon, transition metal (such as FeO, Fe)2+、Cu2+、Co2+、Ag+) Activation of mediators such as ultrasound and hydrogen peroxide to form sulfate radicals (SO)4 ·-) It has strong oxidizing power and can effectively degrade a large amount of organic pollutants. In contrast to OH, with sulfate radicals (SO)4 ·-) The persulfate process based on this method has a series of advantages such as high oxidation potential and wide pH range. Therefore, the persulfate process based on sulfate radicals can be used as an organic wastewater pretreatment or advanced treatment technology for future large-scale application. However, the currently applied technologies require activation of persulfate by external energy or environmental catalysts, which is relatively expensive, and introduction of the catalyst causes secondary environmental pollution.
In conclusion, effective degradation of toxic and harmful organic pollutants in wastewater is a great challenge for development of efficient and green water treatment technology, and a safe, stable and efficient treatment technology for treating harmful organic pollutants in water is urgently needed.
Disclosure of Invention
The invention aims to solve the problems that the prior method for removing aniline organic pollutants in wastewater has high selectivity to pollutants, is greatly influenced by environmental factors and has very limited pollutant removal effect, an advanced oxidation process represented by ozone and Fenton (Fenton) oxidation in a chemical method has more limiting factors, and the prior persulfate method based on sulfate radicals needs external energy or an environmental catalyst, has high cost and causes secondary pollution to the environment, and provides a method for directly oxidizing and degrading aniline organic pollutants in water.
A method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
firstly, measuring the pH value of wastewater to be treated containing aniline organic pollutants and the molar concentration of the aniline organic pollutants in the wastewater to be treated, if the pH value is less than 5, regulating the pH value to 5-10, and if the pH value is 5-10, regulating the pH value is not needed; adding persulfate powder into the wastewater to be treated containing the aniline organic pollutants, and stirring and reacting for 1.5-3 h at the temperature of 20-30 ℃ to complete direct oxidative degradation of the aniline organic pollutants in the water; the molar equivalent ratio of the persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
the invention has the beneficial effects that:
the invention relates to a method for directly oxidizing and degrading aniline organic pollutants in water, which utilizes persulfate powder to directly carry out nucleophilic reaction with amino groups of aniline substances so as to degrade the aniline substances. Free radicals are not generated in the reaction, the persulfate powder is not required to be activated and catalyzed, the oxidizing capability to the aniline substances is strong, the oxidizing and removing efficiency of pollutants is high, and the using efficiency of the persulfate powder is high. The method is suitable for directly oxidizing and degrading aniline organic pollutants in a wide concentration range and is also suitable for directly oxidizing and degrading water bodies jointly polluted by a plurality of aniline pollutants. The invention is suitable for a wide pH range (pH is 5-10), and is particularly suitable for treating pollutants under alkaline conditions. The invention can be used for the pretreatment of petrochemical wastewater, printing and dyeing wastewater, medical wastewater, garbage percolate and other wastewater. The method has no strict limit value on the water quality characteristics, transmittance, inorganic salt and chromaticity of the treated water, and has wider application range; and the process flow is simple, the dosage is less, and the running treatment cost is greatly reduced.
Secondly, according to the method for directly oxidizing and degrading aniline organic pollutants in water, when the pH value of the wastewater to be treated is less than 5, the oxidizing effect is sharply reduced. The main reason is that under the acidic condition, the charge density of the amino structure of the substituent group is changed due to dissociation, so that the overall nucleophilic reaction is influenced;
the method for directly oxidizing and degrading aniline organic pollutants in water optimizes the reaction process, greatly reduces the use and consumption of persulfate powder in the treatment process, reduces the input of external energy, is simple to operate and convenient to manage, and can perform full-automatic accurate control.
The invention can obtain a method for directly oxidizing and degrading aniline organic pollutants in water.
Drawings
FIG. 1 is a diagram showing the effect of removing parachloroaniline in wastewater to be treated by direct oxidation with sodium persulfate powder in the example, wherein a is parachloroaniline;
FIG. 2 is a diagram showing the effect of comparative example one (1) in removing p-chloroaniline, aniline, phenol and nitrobenzene from wastewater to be treated by direct oxidation with sodium persulfate powder, b is phenol, c is nitrobenzene, d is aniline, and e is p-chloroaniline;
FIG. 3 is a graph showing the effect of different ions of different concentrations on the removal of p-chloroaniline contaminants by direct oxidation of sodium persulfate in comparative example one (2),indicating calcium ions at a concentration of 5mmol/L,
indicating a calcium ion concentration of 20mmol/L,
indicates magnesium ions at a concentration of 5mmol/L,
indicating a magnesium ion concentration of 20mmol/L,
indicating a potassium ion concentration of 5mmol/L,
indicating a potassium ion concentration of 20mmol/L,
represents bicarbonate ion at a concentration of 5mmol/L,
represents bicarbonate ion at a concentration of 20mmol/L,
indicating a chloride ion concentration of 5mmol/L,
represents chloride ion with a concentration of 20 mmol/L;
FIG. 4 is a graph of the effect of quenching agents methanol and sodium azide on the removal of chloroaniline contaminants by direct oxidation of sodium persulfate in the first (3) comparative example, f is sodium azide at a concentration of 5mmol/L, g is methanol at a concentration of 500mmol/L, h is methanol at a concentration of 100mmol/L, and i is no addition of methanol;
FIG. 5 is a diagram showing the effect of example using sodium persulfate powder to directly oxidize and remove 4-bromoaniline, aniline, parachloroaniline and parachloroaniline in wastewater to be treated, j is ortho-chloroaniline, k is meta-chloroaniline, l is aniline, m is 4-bromoaniline, and n is parachloroaniline.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a method for directly oxidizing and degrading aniline organic pollutants in water, which comprises the following steps:
firstly, measuring the pH value of wastewater to be treated containing aniline organic pollutants and the molar concentration of the aniline organic pollutants in the wastewater to be treated, if the pH value is less than 5, regulating the pH value to 5-10, and if the pH value is 5-10, regulating the pH value is not needed; adding persulfate powder into the wastewater to be treated containing the aniline organic pollutants, and stirring and reacting for 1.5-3 h at the temperature of 20-30 ℃ to complete direct oxidative degradation of the aniline organic pollutants in the water; the molar equivalent ratio of the persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
after the mixture is fully stirred and mixed, the oxidation pretreatment of aniline organic pollutants in the wastewater to be treated can be realized, and the biodegradability of the aniline organic pollutants is improved; the persulfate powder is used as an oxidant to directly carry out oxidation reaction with aniline organic pollutants, and is a nucleophilic reaction which is not a free radical reaction.
The beneficial effects of the embodiment are as follows:
the method for directly oxidizing and degrading aniline organic pollutants in water utilizes persulfate powder to directly perform nucleophilic reaction with amino groups of aniline substances, so that the aniline substances are degraded. Free radicals are not generated in the reaction, the persulfate powder is not required to be activated and catalyzed, the oxidizing capability to the aniline substances is strong, the oxidizing and removing efficiency of pollutants is high, and the using efficiency of the persulfate powder is high. The embodiment is suitable for directly oxidizing and degrading aniline organic pollutants in a wide concentration range and is also suitable for directly oxidizing and degrading water bodies jointly polluted by a plurality of aniline pollutants. This embodiment is suitable for a wide pH range (pH 5-10), especially for the treatment of contaminants under alkaline conditions. The embodiment can be used for the pretreatment of wastewater such as petrochemical wastewater, printing and dyeing wastewater, medical wastewater, garbage leachate and the like. The method has no strict limit value on the water quality characteristics, transmittance, inorganic salt and chromaticity of the treated water, and has wider application range; and the process flow is simple, the dosage is less, and the running treatment cost is greatly reduced.
Secondly, in the method for directly oxidizing and degrading aniline organic pollutants in water, when the pH value of the wastewater to be treated is less than 5, the oxidizing effect is sharply reduced. The main reason is that under the acidic condition, the charge density of the amino structure of the substituent group is changed due to dissociation, so that the overall nucleophilic reaction is influenced;
the method for directly oxidizing and degrading the aniline organic pollutants in the water optimizes the reaction process, greatly reduces the use and consumption of persulfate powder in the treatment process, reduces the input of external energy, is simple to operate and convenient to manage, and can perform full-automatic accurate control.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the wastewater to be treated containing the aniline organic pollutants contains one or more of aniline, parachloroaniline, para-bromoaniline, benzidine, ortho-tolidine, para-nitroaniline, ortho-chloroaniline and meta-chloroaniline.
The aniline organic pollutant has aniline and similar structures, such as an amino group connected to a benzene ring.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the first or second differences from the present embodiment are as follows: the concentration of the parachloroaniline in the wastewater to be treated containing the aniline organic pollutants is 0.3 mmol/L.
The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: and adjusting the pH value of the wastewater to be treated containing the aniline organic pollutants to 5-10 by using 1mol/L sodium hydroxide solution or 1mol/L hydrochloric acid solution.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and adjusting the pH value of the wastewater to be treated containing the aniline organic pollutants to 7.5.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the persulfate powder is sodium persulfate powder or potassium persulfate powder.
The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the chemical reaction series of the persulfate powder and the aniline organic pollutants is two stages, and the reaction rate is jointly controlled by the concentrations of the persulfate powder and the aniline organic pollutants in the wastewater to be treated.
The other steps are the same as those in the first to sixth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
preparing 95mL of wastewater to be treated, wherein aniline organic pollutants in the wastewater to be treated are parachloroaniline, the initial concentration of the parachloroaniline is 0.3mmol/L, measuring the molar concentration of the aniline organic pollutants in the wastewater to be treated, regulating the pH value of the wastewater to be treated containing the aniline organic pollutants to 7.5, adding 5mL of 0.2mol/L phosphate buffer solution, and adding sodium persulfate powder into the wastewater to be treated to ensure that the pH value in the wastewater to be treated does not change greatly. After adding sodium persulfate powder, the concentration of sodium persulfate in the wastewater to be treated is 5mmol/L, stirring and reacting for 2h at the temperature of 25 ℃, and completing the direct oxidative degradation of aniline organic pollutants in water; the molar equivalent ratio of the sodium persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
FIG. 1 is a diagram showing the effect of removing parachloroaniline in wastewater to be treated by direct oxidation with sodium persulfate powder; as shown in FIG. 1, the removal rate of p-chloroaniline from the wastewater to be treated was 58.05%.
Comparative example one (1): a method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
preparing four kinds of wastewater to be treated, wherein each amount of the wastewater to be treated is 95mL, aniline organic pollutants in the four kinds of wastewater to be treated are p-chloroaniline, aniline, phenol and nitrobenzene respectively, the initial concentrations of the p-chloroaniline, the aniline, the phenol and the nitrobenzene are 0.3mmol/L, measuring the molar concentration of the aniline organic pollutants in the four kinds of wastewater to be treated, regulating and controlling the pH values of the four kinds of wastewater to be treated to 7.5, then adding 5mL and 0.2mol/L phosphate buffer solutions respectively, and then adding sodium persulfate powder into the four kinds of wastewater to be treated respectively to ensure that the pH value in the wastewater to be treated does not change greatly. After adding sodium persulfate powder, enabling the concentration of sodium persulfate in the wastewater to be treated to be 5mmol/L, stirring and reacting for 2h at the temperature of 25 ℃, and completing the direct oxidative degradation of aniline organic pollutants in water; the molar equivalent ratio of the sodium persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
FIG. 2 is a diagram showing the effect of removing p-chloroaniline, aniline, phenol and nitrobenzene from wastewater to be treated by direct oxidation with sodium persulfate powder; as shown in FIG. 2, sodium persulfate powder can not degrade phenols and nitrobenzenes without activation, i.e., the method is not suitable for degrading phenols. In 120min, the removal rate of phenol is almost zero, the removal rate of nitrobenzene is 18.53%, the removal rate of aniline is 45.19%, and the removal rate of parachloroaniline is 58.05%.
Comparative example one (2): a method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
preparing 95mL of wastewater to be treated, wherein aniline organic pollutants in the wastewater to be treated are parachloroaniline, the initial concentration of the parachloroaniline is 0.3mmol/L, firstly measuring the molar concentration of the aniline organic pollutants in the wastewater to be treated, regulating and controlling the pH value of the wastewater to be treated to 7.5, then adding 5mL of 0.2mol/L phosphate buffer solution, and then adding sodium persulfate powder into the wastewater to be treated to ensure that the pH value in the wastewater to be treated does not change greatly. After adding sodium persulfate powder, the concentration of sodium persulfate in the wastewater to be treated is made to be 5mmol/L, then calcium chloride, magnesium chloride, potassium chloride, sodium bicarbonate and sodium chloride solution are added, the reaction is stirred for 2 hours under the temperature condition of 25 ℃, and the influence of different concentrations (5mmol/L and 20mmol/L) of anions/cations on the oxidation reaction is observed respectively. The molar equivalent ratio of the sodium persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
FIG. 3 is a graph showing the effect of different ions on the removal of parachloroaniline contaminants by direct oxidation of sodium persulfate; as shown in fig. 3, calcium ions, magnesium ions, potassium ions, bicarbonate ions, and chloride ions have less influence on the reaction.
Comparative example one (3): a method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
preparing 95mL of wastewater to be treated, wherein aniline organic pollutants in the wastewater to be treated are parachloroaniline, the initial concentration of the parachloroaniline is 0.3mmol/L, firstly measuring the molar concentration of the aniline organic pollutants in the wastewater to be treated, regulating and controlling the pH value of the wastewater to be treated to 7.5, then adding 5mL of 0.2mol/L phosphate buffer solution, and then adding sodium persulfate powder into the wastewater to be treated to ensure that the pH value in the wastewater to be treated does not change greatly. After the addition of sodium persulfate powder, the concentration of sodium persulfate in the wastewater to be treated was made 5mmol/L, methanol at concentrations of 100mmol/L and 500mmol/L as a quencher and sodium azide at a concentration of 5mmol/L were added, respectively, and the effect on the reaction was observed. The molar equivalent ratio of the sodium persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3. 0.2
FIG. 4 is a graph showing the effect of quenching agents methanol and sodium azide on the direct oxidation of sodium persulfate to remove parachloroaniline contaminants; as shown in FIG. 4, methanol and sodium azide have no influence on the reaction rate, so that sodium persulfate is a non-radical reaction when directly oxidizing parachloroaniline, and active substances such as singlet oxygen are not generated.
Example two: a method for directly oxidizing and degrading aniline organic pollutants in water comprises the following steps:
preparing four kinds of wastewater to be treated, wherein each amount of the wastewater to be treated is 95mL, the aniline organic pollutants in the four kinds of wastewater to be treated are respectively 4-bromoaniline, aniline, parachloroaniline and m-chloroaniline, the initial concentrations of the 4-bromoaniline, the aniline, the parachloroaniline and the m-chloroaniline are respectively 0.3mmol/L, firstly measuring the molar concentrations of the aniline organic pollutants in the four kinds of wastewater to be treated, regulating and controlling the pH values of the four kinds of wastewater to be treated to 7.5, then respectively adding 5mL and 0.2mol/L of phosphate buffer solution, and then respectively adding sodium persulfate powder into the four kinds of wastewater to be treated, so as to ensure that the pH value in the wastewater to be treated does not change greatly. After adding sodium persulfate powder, enabling the concentration of sodium persulfate in the wastewater to be treated to be 5mmol/L, stirring and reacting for 2h at the temperature of 25 ℃, and verifying the oxidation universality of the aniline substances; the molar equivalent ratio of the sodium persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
FIG. 5 is a diagram showing the effect of removing 4-bromoaniline, aniline, parachloroaniline and m-chloroaniline from wastewater to be treated by direct oxidation with sodium persulfate powder; as shown in FIG. 5, in the reaction time of 120min, the removal rate of 4-bromoaniline reached 46.97%, the removal rate of aniline reached 45.19%, the removal rate of p-chloroaniline reached 58.1%, the removal rate of o-chloroaniline reached 22.4%, and the removal rate of chloroaniline reached 29.52%.
Claims (6)
1. A method for directly oxidizing and degrading aniline organic pollutants in water is characterized by comprising the following steps:
firstly, measuring the pH value of wastewater to be treated containing aniline organic pollutants and the molar concentration of the aniline organic pollutants in the wastewater to be treated, if the pH value is less than 5, regulating the pH value to 5-10, and if the pH value is 5-10, regulating the pH value is not needed; adding persulfate powder into the wastewater to be treated containing the aniline organic pollutants, and stirring and reacting for 1.5-3 h at the temperature of 20-30 ℃ to complete direct oxidative degradation of the aniline organic pollutants in the water; the molar equivalent ratio of the persulfate powder to the aniline organic pollutants in the water to be treated is 50: 3.
2. the method for directly oxidatively degrading aniline organic pollutant in water according to claim 1, wherein the wastewater to be treated containing aniline organic pollutant contains one or more of aniline, parachloroaniline, para-bromoaniline, benzidine, ortho-tolidine, para-nitroaniline, ortho-chloroaniline and meta-chloroaniline.
3. The method for directly oxidatively degrading aniline organic pollutants in water according to claim 2, wherein the concentration of parachloroaniline in the wastewater to be treated containing aniline organic pollutants is 0.3 mmol/L.
4. The method for directly oxidatively degrading aniline organic pollutants in water according to claim 1, wherein the pH value of the wastewater to be treated containing the aniline organic pollutants is adjusted to 5-10 by using 1mol/L sodium hydroxide solution or 1mol/L hydrochloric acid solution.
5. The method for directly oxidatively degrading aniline organic pollutants in water as claimed in claim 1, wherein the pH value of the wastewater to be treated containing aniline organic pollutants is adjusted to 7.5.
6. The method for directly oxidatively degrading aniline organic pollutants in water according to claim 1, wherein the persulfate powder is sodium persulfate powder or potassium persulfate powder.
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