CN111484158A - Pretreatment method of glyphosate production wastewater - Google Patents
Pretreatment method of glyphosate production wastewater Download PDFInfo
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- CN111484158A CN111484158A CN202010257459.5A CN202010257459A CN111484158A CN 111484158 A CN111484158 A CN 111484158A CN 202010257459 A CN202010257459 A CN 202010257459A CN 111484158 A CN111484158 A CN 111484158A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 31
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000002203 pretreatment Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 230000003647 oxidation Effects 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 16
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 12
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007844 bleaching agent Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 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
- 238000001914 filtration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 4
- -1 sulfate free radical Chemical class 0.000 description 4
- 244000005700 microbiome Species 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 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
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/61—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- 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
-
- 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
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The invention discloses a pretreatment method of glyphosate production wastewater, which comprises the following steps: (1) adding hydrogen peroxide and persulfate into the glyphosate wastewater, uniformly stirring, and adjusting the pH of the wastewater to 3-4; (2) introducing the wastewater with the pH adjusted in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of layers of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activity is highThe carbon catalyst layer is a double catalytic adsorption layer formed by activated carbon adsorbing ferrous sulfate; (3) adding bleaching powder into the wastewater subjected to oxidation pretreatment in the step (2), and removing precipitates after full reaction to obtain pretreated wastewater; the method combines the oxidation of hydrogen peroxide and the oxidation of sodium persulfate, treats the glyphosate wastewater under the condition of synergistic oxidation, has short treatment time, reduces the dosage of ferric salt, and overcomes the defect of a single oxidation mode; the ferrous sulfate is fixed in the micropores of the activated carbon to reduce the Fe content of the catalyst2+Loss of while the active carbon is in synergy with Fe2+And the catalytic action on the wastewater is enhanced together.
Description
Technical Field
The invention relates to the technical field of microbial wastewater treatment, in particular to a pretreatment method of glyphosate production wastewater.
Background
The environment is the basis for human beings to live and develop, however, with the acceleration of the industrialization and urbanization process, the sewage components are increasingly complex, the glyphosate wastewater is organic high-concentration heavy metal-containing wastewater discharged in the process of producing glyphosate powder and water agent in the chemical pesticide industry, and the main characteristics are as follows: the method has the advantages of high alkalinity, high COD concentration and high salt content, contains organic matters such as glyphosate, glyphosine, glycine, phosphite and the like which are difficult to degrade, becomes one of organic wastewater difficult to treat, and the common treatment method of the glyphosate production wastewater at present comprises the following steps: the traditional physical and chemical method, biological method and advanced oxidation technology, the physical and chemical method mainly destroys or converts toxic and harmful substances by some strong oxidants or precipitators; the biological method is a method with higher purification effect, aims at certain organic substances and toxic substances which are difficult to degrade, utilizes the condition that the sewage has the growth and the reproduction of microorganisms, utilizes the life activity of the microorganisms to ensure that the microorganisms can obtain nutrients from the sewage, and has the degradation effect on organic pollutants in a dissolved state or a colloidal state in the wastewater, thereby purifying the wastewater.
The advanced oxidation technology is also called as deep oxidation technology, and can directly mineralize or improve the biodegradability of pollutants through oxidation aiming at high-concentration organic wastewater; the traditional advanced oxidation technology is to take hydrogen peroxide as a raw materialOxidizing agent by chemical oxidation, hydrogen peroxide in Fe2+Hydroxyl free radicals with extremely strong oxidizability are generated under catalysis, and organic pollutants can be degraded into harmless small molecular substances; however, hydrogen peroxide is unstable and has too high decomposition speed, so that the oxidation efficiency of hydrogen peroxide is greatly influenced; another oxidizing agent commonly used is sodium persulfate, which is stable in the environment, but has the disadvantage of being too stable and requiring specific activation conditions; at present, the reports on a double oxidation system of hydrogen peroxide and sodium persulfate are less, the utilization rate of the catalyst is not high, and the secondary pollution is caused by easy loss.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for pretreating glyphosate production wastewater, which comprises the following steps:
(1) adding hydrogen peroxide and persulfate into the glyphosate wastewater respectively, stirring uniformly, and adjusting the pH of the wastewater to 3-4, wherein the adding mass ratio of the hydrogen peroxide to the persulfate is 1:5-1:2 (g/L) relative to the volume of the glyphosate wastewater;
(2) introducing the wastewater subjected to pH adjustment in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activated carbon catalyst layers are double catalytic adsorption layers formed by activated carbon adsorbing ferrous sulfate;
the preparation method of the activated carbon catalyst layer comprises the following steps: mixing an activated carbon raw material with acid, treating for 2-4h under an ultrasonic condition, adding a polyvinyl alcohol solution, treating for 5-12h at 30-60 ℃, and then placing in a tubular furnace for activation to obtain activated carbon; the activation reaction temperature is 700-850 ℃, a gradient heating mode is adopted, and the heating rate is 4-7 ℃/min; the reaction time is 2-6 h; then putting activated carbon into ferrous sulfate solution for adsorption, wherein the adsorption temperature is 20-30 ℃, the adsorption time is 1-3d, and the pH value of the solution after adsorption balance is 5.5-6.5;
(3) adding the bleaching powder 3Ca (ClO) 2.2 Ca (OH)2 into the wastewater subjected to the oxidation pretreatment in the step (2), fully reacting, fully filter-pressing the wastewater with the precipitate, and removing the precipitate to obtain the pretreated wastewater.
Preferably, the persulfate is one of sodium persulfate, potassium persulfate and ammonium persulfate.
Preferably, the weight part ratio of the bleaching powder to the wastewater in the step (3) is 1:12-1: 15.
Preferably, the mass concentration of the polyvinyl alcohol solution is 14-26%.
Preferably, the concentration of the ferrous sulfate solution is 0.8-2.5 mol/L.
Under acidic conditions, H2O2In Fe2+OH with high reaction activity is generated under the catalytic action of the catalyst, the oxidation potential of the OH is as high as 2.8V, the catalyst has extremely strong oxidation performance, and most of difficultly-degraded macromolecular organic matters can be degraded to form micromolecular organic matters; the persulfate can make up for the deficiency of hydrogen peroxide oxidation due to good stability, water solubility, strong oxidizing property and reaction product friendliness, and can generate an active substance sulfate free radical SO4 by decomposing the persulfate under neutral or acidic conditions-·The sulfate free radical has a pair of lone pair electrons, the oxidation potential of the sulfate free radical is as high as 2.6V, is close to the oxidation potential of the hydroxyl free radical, and also has stronger oxidation potential;
furthermore, the surface of the activated carbon contains a large amount of hydroxyl and phenolic hydroxyl, so that the activated carbon not only has adsorption capacity, but also has catalytic action, the reaction equation is shown as follows, the activated carbon has larger specific surface area, and can be used as a catalyst Fe2+The vector of (1);
AC+H2O2→AC++OH-+·OH
AC++H2O2→AC+HO2·+H+
AC+S2O8 2-→AC++·SO4 -+SO4 -
the invention has the following beneficial effects:
(1) the method combines the oxidation of hydrogen peroxide and the oxidation of sodium persulfate to form a system with stronger oxidability, treats the glyphosate wastewater under the condition of synergistic oxidation, has short treatment time, reduces the dosage of ferric salt, overcomes the defect of a single oxidation mode, reduces the sensitivity of the single oxidation mode to acidity and alkalinity, and enlarges the pH application range of a pretreatment system, and can ensure that the wastewater of the glyphosate with the inlet water COD of more than 2000 mg/L and TP of more than 200 mg/L is pretreated to reach the effluent COD of less than 210mg/L of less than 28.3 mg/L;
(2) a plurality of layers of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and activated carbon is not only a carrier of the catalyst, but also the catalyst; activated carbon is activated, the pore diameter and pore volume distribution of the activated carbon are increased, the specific surface area of the activated carbon is improved, and the catalytic efficiency of the activated carbon is increased; then putting the activated carbon into ferrous sulfate solution for adsorption, fixing the ferrous sulfate in micropores of the activated carbon, and reducing the catalyst Fe2+Loss of, and at the same time synergize with Fe2+And the catalytic action on the wastewater is enhanced together.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example 1
A pretreatment method of glyphosate production wastewater is characterized by comprising the following steps:
(1) respectively adding hydrogen peroxide and persulfate into glyphosate wastewater (COD is 2736mg/l, TP is 235mg/l), uniformly stirring, and then adjusting the pH of the wastewater to 3, wherein the adding mass ratio of the hydrogen peroxide to the sodium persulfate is 1:3 (g/L) relative to the volume of the glyphosate wastewater;
(2) introducing the wastewater subjected to pH adjustment in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activated carbon catalyst layers are double catalytic adsorption layers formed by activated carbon adsorbing ferrous sulfate;
the preparation method of the activated carbon catalyst layer comprises the steps of mixing an activated carbon raw material with acid, treating for 2 hours under an ultrasonic condition, adding a polyvinyl alcohol solution with the mass concentration of 16%, treating for 8 hours at 45 ℃, and then placing in a tubular furnace for activation to obtain activated carbon, wherein the activation reaction temperature is 700-850 ℃, the temperature rise rate is 7 ℃/min in a gradient temperature rise mode, the reaction time is 5 hours, then putting the activated carbon into a ferrous sulfate solution with the concentration of 1 mol/L for adsorption, the adsorption temperature is 25 ℃, the adsorption time is 1d, and the pH value of the solution after adsorption balance is 6;
adding the bleaching powder 3Ca (ClO) into the wastewater after the oxidation pretreatment in the step (2)2·2Ca(OH)2Wherein, the weight ratio of the bleaching powder to the wastewater is 1:12, after full reaction, the wastewater with precipitate is fully pressed and filtered, the precipitate is removed to obtain the pretreated wastewater, and the effluent indexes are COD:196mg/l, TP: 26.3 mg/l.
Example 2
A pretreatment method of glyphosate production wastewater is characterized by comprising the following steps:
(1) respectively adding hydrogen peroxide and persulfate into glyphosate wastewater (COD is 2504mg/l, TP is 209mg/l), uniformly stirring, and then adjusting the pH of the wastewater to 3.5, wherein the adding mass ratio of the hydrogen peroxide to the sodium persulfate is 1:4 (g/L) relative to the volume of the glyphosate wastewater;
(2) introducing the wastewater subjected to pH adjustment in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activated carbon catalyst layers are double catalytic adsorption layers formed by activated carbon adsorbing ferrous sulfate;
the preparation method of the activated carbon catalyst layer comprises the steps of mixing an activated carbon raw material with acid, treating for 3 hours under an ultrasonic condition, adding a polyvinyl alcohol solution with the mass concentration of 20%, treating for 6 hours at 40 ℃, and then placing in a tubular furnace for activation to obtain activated carbon, wherein the activation reaction temperature is 700-850 ℃, the temperature rise rate is 5 ℃/min in a gradient temperature rise mode, the reaction time is 6 hours, then putting the activated carbon into a ferrous sulfate solution with the concentration of 1.5 mol/L for adsorption, the adsorption temperature is 30 ℃, the adsorption time is 2d, and the pH of the solution after adsorption balance is 6.5;
(3) adding the bleaching powder 3Ca (ClO) into the wastewater after the oxidation pretreatment in the step (2)2·2Ca(OH)2Wherein the weight ratio of the bleaching powder to the wastewater is 1:14, after full reaction, the wastewater with precipitates is fully pressed and filtered, the precipitates are removed to obtain pretreated wastewater, and the effluent indexes are COD:179mg/l and TP: 25.9 mg/l.
Example 3
A pretreatment method of glyphosate production wastewater is characterized by comprising the following steps:
(1) respectively adding hydrogen peroxide and persulfate into glyphosate wastewater (COD is 2931mg/l and TP is 246mg/l), uniformly stirring, and then adjusting the pH of the wastewater to 4, wherein the adding mass ratio of the hydrogen peroxide to the sodium persulfate is 1:2 (g/L) relative to the volume of the glyphosate wastewater;
(2) introducing the wastewater subjected to pH adjustment in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activated carbon catalyst layers are double catalytic adsorption layers formed by activated carbon adsorbing ferrous sulfate;
the preparation method of the activated carbon catalyst layer comprises the steps of mixing an activated carbon raw material with acid, treating for 4 hours under an ultrasonic condition, adding a polyvinyl alcohol solution with the mass concentration of 25%, treating for 10 hours at 60 ℃, then placing in a tubular furnace for activation to obtain activated carbon, wherein the activation reaction temperature is 700-850 ℃, the temperature rise rate is 7 ℃/min in a gradient temperature rise mode, the reaction time is 4.5 hours, then putting the activated carbon into a ferrous sulfate solution with the concentration of 2.5 mol/L for adsorption, the adsorption temperature is 30 ℃, the adsorption time is 3d, and the pH of the solution after adsorption balance is 5.5;
(3) adding the bleaching powder 3Ca (ClO) into the wastewater after the oxidation pretreatment in the step (2)2·2Ca(OH)2Wherein, the weight ratio of the bleaching powder to the wastewater is 1:15, after full reaction, the wastewater with precipitate is fully pressed and filtered, the precipitate is removed to obtain the pretreated wastewater, and the effluent indexes are COD:210mg/l and TP: 28.3 mg/l.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A pretreatment method of glyphosate production wastewater is characterized by comprising the following steps:
(1) adding hydrogen peroxide and persulfate into the glyphosate wastewater respectively, stirring uniformly, and adjusting the pH of the wastewater to 3-4, wherein the adding mass ratio of the hydrogen peroxide to the persulfate is 1:5-1:2 (g/L) relative to the volume of the glyphosate wastewater;
(2) introducing the wastewater subjected to pH adjustment in the step (1) into a catalytic oxidation tower for oxidation pretreatment, wherein a plurality of activated carbon catalyst layers are arranged in the catalytic oxidation tower, and the activated carbon catalyst layers are double catalytic adsorption layers formed by activated carbon adsorbing ferrous sulfate;
the preparation method of the activated carbon catalyst layer comprises the following steps: mixing an activated carbon raw material with acid, treating for 2-4h under an ultrasonic condition, adding a polyvinyl alcohol solution, treating for 5-12h at 30-60 ℃, and then placing in a tubular furnace for activation to obtain activated carbon; the activation reaction temperature is 700-850 ℃, a gradient heating mode is adopted, and the heating rate is 4-7 ℃/min; the reaction time is 2-6 h; then putting activated carbon into ferrous sulfate solution for adsorption, wherein the adsorption temperature is 20-30 ℃, the adsorption time is 1-3d, and the pH value of the solution after adsorption balance is 5.5-6.5;
(3) adding the bleaching powder 3Ca (ClO) into the wastewater after the oxidation pretreatment in the step (2)2·2Ca(OH)2And after full reaction, fully press-filtering the wastewater with the precipitate, and removing the precipitate to obtain the pretreated wastewater.
2. The method for pretreating wastewater from glyphosate production according to claim 1, wherein the persulfate is one of sodium persulfate, potassium persulfate and ammonium persulfate.
3. The method for pretreating glyphosate production wastewater according to claim 1, wherein the weight part ratio of the bleaching powder to the wastewater in the step (3) is 1:12-1: 15.
4. The method for pretreating glyphosate production wastewater according to claim 1, wherein the mass concentration of the polyvinyl alcohol solution is 14-26%.
5. The method for pretreating waste water generated in glyphosate production according to claim 1, wherein the concentration of the ferrous sulfate solution is 0.8-2.5 mol/L.
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