CN108585280B - Treatment process of chromium-copper-nickel-containing wastewater - Google Patents
Treatment process of chromium-copper-nickel-containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 21
- XRBURMNBUVEAKD-UHFFFAOYSA-N chromium copper nickel Chemical compound [Cr].[Ni].[Cu] XRBURMNBUVEAKD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 43
- 239000011651 chromium Substances 0.000 claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004062 sedimentation Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 238000005345 coagulation Methods 0.000 claims description 38
- 230000015271 coagulation Effects 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229920002401 polyacrylamide Polymers 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- HIOOFBBNJCVVJZ-UHFFFAOYSA-N 5-methyl-2-sulfanylbenzoic acid Chemical compound CC1=CC=C(S)C(C(O)=O)=C1 HIOOFBBNJCVVJZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 12
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 12
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012629 purifying agent Substances 0.000 claims description 11
- 238000004073 vulcanization Methods 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012028 Fenton's reagent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910000570 Cupronickel Inorganic materials 0.000 claims 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000005486 sulfidation Methods 0.000 claims 1
- 230000001112 coagulating effect Effects 0.000 abstract description 12
- 229910018487 Ni—Cr Inorganic materials 0.000 abstract description 10
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 239000003513 alkali Substances 0.000 description 4
- 230000009920 chelation Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
-
- 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
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment process for chromium-copper-nickel-containing wastewater, which comprises the following steps: the method comprises the following steps of primary Fenton oxidation, chromium reduction, primary copper and nickel chromium removal, primary coagulating sedimentation, secondary copper and nickel chromium removal, secondary coagulating sedimentation, secondary Fenton oxidation, deep purification and tertiary coagulating sedimentation.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a treatment process of chromium-copper-nickel-containing wastewater.
Background
The wastewater generated in the electroplating industry generally contains various heavy metals such as Cu, Ni and Cr, and the heavy metals are high in content, turbidity and salt content, and the nickel exists in a complex state, so that the wastewater containing Cu, Ni and Cr is processed more complexly and is difficult to reach the discharge standard.
Patent 200810052298.5 discloses a method for treating waste water from electroplating, which mainly uses chemical precipitation method, wherein cyanide-containing waste water is broken, chromium-containing waste water is reduced by chromium, then the cyanide-containing waste water and the comprehensive waste water are treated by adjusting pH value and adding coagulant, polymer coagulant aid and the like to remove metal ions, suspended matters and COD.
Patent 201510940747.X discloses a method for treating comprehensive electroplating wastewater, which removes metals by online adding high sodium ferrite for oxidative decomplexation and twice flocculation, and although the treatment system is simple and the input cost is low, the wastewater containing various heavy metals such as Cu, Ni and Cr, especially the nickel-containing wastewater existing in a complex state, is extremely difficult to reach the discharge standard.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a treatment process of chromium-copper-nickel-containing wastewater, which is simple and easy to control and can treat wastewater simultaneously containing heavy metals such as Cu, Ni, Cr and the like, so that the concentration of various heavy metals such as Cu, Ni, Cr and the like existing in a complex state in the wastewater is less than 0.1 ppm.
The purpose of the invention is realized by the following technical scheme: a treatment process of chromium-copper-nickel-containing wastewater comprises the following steps:
(1) primary Fenton oxidation: adding acid liquor into the wastewater to adjust the pH value to 3.5-4, then adding a Fenton reagent, and adjusting the ORP value to 650-750mv for oxidation and decomplexation;
(2) and (3) chromium reduction: adding a reducing agent into the wastewater after oxidation and decomplexing to reduce hexavalent chromium into trivalent chromium;
(3) first-stage copper and nickel removal: adding alkali liquor into the wastewater after the chromium reduction to adjust the pH value to 10-10.5, and then adding a vulcanization precipitator to carry out a vulcanization reaction;
(4) primary coagulating sedimentation: adding polyaluminium and polyacrylamide into the wastewater after the primary copper and nickel chromium removal for coagulation, wherein the mass percentage concentration of the polyaluminium in the wastewater is 1-2%, and the mass percentage concentration of the polyacrylamide in the wastewater is 0.2-0.8%, and performing mud-water separation on the wastewater after the primary coagulation reaction;
(5) secondary copper and nickel removal: adjusting the pH value of the wastewater after the first-stage precipitation to 11.0-11.5, and then vulcanizing a precipitator to perform a vulcanization reaction;
(6) secondary coagulating sedimentation: adding polyaluminium and polyacrylamide into the wastewater after the secondary copper and nickel chromium removal for coagulation and mud-water separation, wherein the mass percentage concentration of the polyaluminium in the wastewater is 1-2%, and the mass percentage concentration of the polyacrylamide in the wastewater is 0.2-0.8%;
(7) and (3) secondary Fenton oxidation: adjusting the pH value of the wastewater after the secondary coagulation sedimentation to 3.5-4.5, performing Fenton oxidation, controlling the ORP at 600-700mv, and reacting for 1.5-2.5 hours;
(8) deep purification: adjusting the pH value to 9-10, and adding a purifying agent which can perform a chelation reaction with nickel into the wastewater after the secondary Fenton oxidation for nickel removal and deep purification;
(9) third-stage coagulating sedimentation: adding polyaluminium and polyacrylamide into the wastewater after deep purification for coagulation, and precipitating after coagulation, wherein the mass percent concentration of the polyaluminium in the wastewater is 1-3%, and the mass percent concentration of the polyacrylamide in the wastewater is 0.3-1%.
The invention simply enables the wastewater containing chromium, copper and nickel to be deeply purified simultaneously through the mutual matching of two times of Fenton oxidation, one time of chromium reduction, two times of copper and nickel removal, one time of deep purification of nickel and three times of coagulating sedimentation, finally enables the concentration of heavy metal in the discharged wastewater to be less than 0.1ppm, has low treatment cost, carries out oxidation and decomplexing through one time of Fenton reaction, then carries out chromium reduction, reduces hexavalent chromium into trivalent chromium to achieve the aim of chromium removal, carries out two times of vulcanization and two times of sedimentation on the wastewater to remove copper and most of nickel, and then carries out Fenton oxidation and deep purification nickel treatment, saves the using amount of a medicament while deeply removing copper and nickel, in addition, no concentrated water is generated in the whole treatment process, the concentration of heavy metal in the discharged water is less than 0.1ppm and far exceeds the national discharge standard requirement, and provides an aftercare treatment process for enterprises.
Further, the molar ratio of the ferrous sulfate to the hydrogen peroxide in the step (1) is 1: 10-15.
The molar ratio of the ferrous sulfate to the hydrogen peroxide in the step (1) is 1: 10-15, on one hand, the oxidation atmosphere in the wastewater is strengthened, the oxidation time is effectively shortened, and on the other hand, the hypophosphorous acid and phosphorous in the chemical nickel wastewater can be effectively removed.
Further, the reducing agent in the step (2) is sodium metabisulfite.
According to the invention, hexavalent chromium is reduced to trivalent chromium by using sodium metabisulfite, and the pH value is low during hydrolysis of the trivalent chromium, so that the pH value does not need to be adjusted in the process, treatment agents and treatment procedures are effectively saved, the wastewater treatment efficiency can be effectively improved, and the sodium metabisulfite has strong reducibility and low toxicity and is safer during use.
Further, the mass percentage concentration of the sodium metabisulfite is 3-5%.
Further, the concentration of the sodium sulfide in the wastewater in the step (3) and the step (5) is 2-4% by mass.
Further, the purifying agent in the step (8) is a mixture of 5-methyl-2-mercaptobenzyl alcohol and 5-methyl-2-mercaptobenzoic acid.
Further, in the step (8), the molar ratio of the 5-methyl-2-mercaptobenzyl alcohol to the 5-methyl-2-mercaptobenzoic acid is 1: 1-3.
Further, in the step (8), the concentration of the mixture of the 5-methyl-2-mercaptobenzyl alcohol and the 5-methyl-2-mercaptobenzoic acid in the wastewater is 1-4 per thousand in percentage by mass.
The invention has the beneficial effects that: the treatment process provided by the invention has the advantages that through the mutual cooperation of twice Fenton oxidation, once chromium reduction, twice copper and nickel removal, once deep purification of nickel and three times of coagulating sedimentation, the wastewater containing chromium, copper and nickel is deeply purified at the same time, and finally the concentration of heavy metal in the discharged water is less than 0.1ppm, the wastewater reaches the standard and is low in treatment cost.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to facilitate understanding of those skilled in the art, the present invention will be further described with reference to the following examples and fig. 1, which are not intended to limit the present invention.
Example 1
A treatment process of chromium-copper-nickel-containing wastewater comprises the following steps:
(1) performing primary Fenton oxidation, adding acid liquor into the wastewater to adjust the pH value to 3.5, then adding a Fenton reagent consisting of ferrous sulfate and hydrogen peroxide, adjusting the ORP value to 650mv to perform oxidation and complex breaking, and reacting for 1.5 hours;
(2) reducing chromium, namely adding a reducing agent into the wastewater after oxidation and complex breaking to reduce hexavalent chromium into trivalent chromium;
(3) removing copper and nickel and chromium at the first stage, adding alkali liquor into the wastewater after chromium reduction to adjust the pH value to 10, and then adding 2% of sodium sulfide for carrying out vulcanization reaction for 2 hours;
(4) performing primary coagulation sedimentation, namely adding polyaluminium with the mass percentage concentration of 1% and polyacrylamide with the mass percentage concentration of 0.2% into the wastewater after primary copper and nickel chromium removal for coagulation, and performing mud-water separation on the wastewater after primary coagulation reaction;
(5) removing copper and nickel and chromium in the second stage, adjusting the pH value of the wastewater after the first-stage precipitation to 11.0, and adding sodium sulfide with the mass percent concentration of 2-4% to perform a vulcanization reaction for 1.5 hours;
(6) performing secondary coagulating sedimentation, namely adding polyaluminium with the mass percent concentration of 1% and polyacrylamide with the mass percent concentration of 0.2% into the wastewater after secondary copper and nickel chromium removal for coagulation and mud-water separation;
(7) performing secondary Fenton oxidation, namely adjusting the pH value of the wastewater subjected to secondary coagulation and precipitation to 3.5, performing Fenton oxidation, controlling the ORP to be 600mv, and reacting for 1.5 hours;
(8) deep purification, namely adding a purifying agent which can perform chelation reaction with nickel into the wastewater after the secondary Fenton oxidation for nickel removal and deep purification, and reacting for 0.5 hour;
(9) and (3) performing three-stage coagulation precipitation, namely adding 1% by mass of polyaluminium and 0.3% by mass of polyacrylamide into the deeply purified wastewater for coagulation, and precipitating after coagulation.
Wherein the molar ratio of the ferrous sulfate to the hydrogen peroxide in the step (1) is 1: 10.
wherein the reducing agent in the step (2) is sodium metabisulfite, and the mass percentage concentration of the sodium metabisulfite is 3%.
Wherein, the mass percentage concentration of the sodium sulfide in the wastewater in the steps (3) and (5) is 2%.
Wherein the purifying agent in the step (8) is a mixture of 5-methyl-2-mercaptobenzyl alcohol and 5-methyl-2-mercaptobenzoic acid.
Wherein the molar ratio of the 5-methyl-2-mercaptobenzyl alcohol to the 5-methyl-2-mercaptobenzoic acid in the step (8) is 1: 1.
wherein, the mass percentage concentration of the mixture of the 5-methyl-2-mercaptobenzyl alcohol and the 5-methyl-2-mercaptobenzoic acid in the wastewater in the step (8) is 1 per mill.
Example 2
A treatment process of chromium-copper-nickel-containing wastewater comprises the following steps:
(1) performing primary Fenton oxidation, adding acid liquor into the wastewater to adjust the pH to 4, then adding a Fenton reagent consisting of ferrous sulfate and hydrogen peroxide, and adjusting the ORP value to 700mv to perform oxidation and decomplexation for 1 hour;
(2) reducing chromium, namely adding a reducing agent into the wastewater after oxidation and complex breaking to reduce hexavalent chromium into trivalent chromium;
(3) removing copper and nickel and chromium at the first stage, adding alkali liquor into the wastewater after chromium reduction to adjust the pH value to 10.5, and then adding sodium sulfide with the mass percentage concentration of 2% to perform vulcanization reaction for 1 hour;
(4) performing primary coagulation sedimentation, namely adding polyaluminium with the mass percent concentration of 1.5% and polyacrylamide with the mass percent concentration of 0.5% into the wastewater after the primary copper and nickel chromium removal for coagulation, and performing mud-water separation on the wastewater after the primary coagulation reaction;
(5) removing copper and nickel and chromium in the second stage, adjusting the pH value of the wastewater after the first-stage precipitation to 11.0, and adding sodium sulfide with the mass percentage concentration of 3% to perform a vulcanization reaction for 0.5 hour;
(6) secondary coagulating sedimentation, namely adding polyaluminium with the mass percentage concentration of 2% and polyacrylamide with the mass percentage concentration of 0.5% into the wastewater after secondary copper and nickel chromium removal for coagulation and mud-water separation;
(7) performing secondary Fenton oxidation, namely adjusting the pH value of the wastewater subjected to secondary coagulation precipitation to 4, performing Fenton oxidation, controlling the ORP to be 650mv, and reacting for 2 hours;
(8) deep purification, namely adding a purifying agent which can perform chelation reaction with nickel into the wastewater after the secondary Fenton oxidation to perform nickel removal deep purification;
(9) and (3) three-stage coagulation and precipitation, namely adding 2% by mass of polyaluminium and 0.5% by mass of polyacrylamide into the deeply purified wastewater for coagulation, and precipitating after coagulation.
Wherein the molar ratio of the ferrous sulfate to the hydrogen peroxide in the step (1) is 1: 12.
wherein the reducing agent in the step (2) is sodium metabisulfite, and the mass percentage concentration of the sodium metabisulfite is 4%.
Wherein, the mass percentage concentration of the sodium sulfide in the wastewater in the steps (3) and (5) is 3%.
Wherein the purifying agent in the step (8) is a mixture of 5-methyl-2-mercaptobenzyl alcohol and 5-methyl-2-mercaptobenzoic acid.
Wherein the molar ratio of the 5-methyl-2-mercaptobenzyl alcohol to the 5-methyl-2-mercaptobenzoic acid in the step (8) is 1: 2.
wherein, the mass percentage concentration of the mixture of the 5-methyl-2-mercaptobenzyl alcohol and the 5-methyl-2-mercaptobenzoic acid in the wastewater in the step (8) is 2 per mill.
Example 3
A treatment process of chromium-copper-nickel-containing wastewater comprises the following steps:
(1) performing primary Fenton oxidation, adding acid liquor into the wastewater to adjust the pH to 4, then adding a Fenton reagent consisting of ferrous sulfate and hydrogen peroxide, and adjusting the ORP value to 750mv to perform oxidation and decomplexing;
(2) reducing chromium, namely adding a reducing agent into the wastewater after oxidation and complex breaking to reduce hexavalent chromium into trivalent chromium;
(3) removing copper and nickel and chromium at the first stage, adding alkali liquor into the wastewater after chromium reduction to adjust the pH value to 10.5, and then adding sodium sulfide with the mass percent concentration of 4% to perform a vulcanization reaction for 1 hour;
(4) primary coagulating sedimentation, namely adding polyaluminium with the mass percentage concentration of 2% and polyacrylamide with the mass percentage concentration of 0.8% into the wastewater after primary copper and nickel chromium removal for coagulation, and performing mud-water separation on the wastewater after primary coagulation reaction;
(5) removing copper and nickel and chromium in the second stage, adjusting the pH value of the wastewater after the first-stage precipitation to 11.5, and adding sodium sulfide with the mass percent concentration of 4% to perform a vulcanization reaction for 1 hour;
(6) secondary coagulating sedimentation, namely adding polyaluminium with the mass percentage concentration of 2% and polyacrylamide with the mass percentage concentration of 0.8% into the wastewater after secondary copper and nickel chromium removal for coagulation and mud-water separation;
(7) performing secondary Fenton oxidation, namely adjusting the pH value of the wastewater subjected to secondary coagulation and precipitation to 4.5, performing Fenton oxidation, controlling the ORP to be 700mv, and reacting for 2.5 hours;
(8) deep purification, namely adding a purifying agent which can perform chelation reaction with nickel into the wastewater after the secondary Fenton oxidation to perform nickel removal deep purification;
(9) and (3) three-stage coagulation precipitation, namely adding 2% of polyaluminium and 1% of polyacrylamide in percentage by mass into the deeply purified wastewater for coagulation, and precipitating after coagulation.
Wherein the molar ratio of the ferrous sulfate to the hydrogen peroxide in the step (1) is 1: 15.
wherein the reducing agent in the step (2) is sodium metabisulfite, and the concentration of the sodium metabisulfite is 5 percent.
Wherein, the mass percentage concentration of the sodium sulfide in the wastewater in the steps (3) and (5) is 4%.
Wherein the purifying agent in the step (8) is a mixture of 5-methyl-2-mercaptobenzyl alcohol and 5-methyl-2-mercaptobenzoic acid.
Wherein the molar ratio of the 5-methyl-2-mercaptobenzyl alcohol to the 5-methyl-2-mercaptobenzoic acid in the step (8) is 1: 3.
wherein, the mass percentage concentration of the mixture of the 5-methyl-2-mercaptobenzyl alcohol and the 5-methyl-2-mercaptobenzoic acid in the wastewater in the step (8) is 4 per mill.
In the above embodiment, the concentration of heavy metals in the final discharged water is less than 0.1ppm, which far exceeds the regulation of national standard GB3838-2002 'surface water environmental quality Standard'.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
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| CN201810468211.6A CN108585280B (en) | 2018-05-16 | 2018-05-16 | Treatment process of chromium-copper-nickel-containing wastewater |
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