CN114956369B - Method for removing heavy metal nickel copper zinc from ammonium-containing wastewater - Google Patents
Method for removing heavy metal nickel copper zinc from ammonium-containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 31
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 23
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 title claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 claims abstract description 18
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 238000004062 sedimentation Methods 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 14
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 14
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 14
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 14
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 14
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 13
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010494 dissociation reaction Methods 0.000 abstract description 4
- 230000005593 dissociations Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 4
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 210000003462 vein Anatomy 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 3
- -1 platinum group metals Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 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
-
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal 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
- C02F1/66—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
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for removing heavy metal nickel, copper and zinc from ammonium-containing wastewater, which comprises the steps of pre-treating, regulating the PH of the ammonium-containing wastewater, adding a strong oxidation decomplexing agent, and dissociating Cu by utilizing the reaction of the strong oxidation decomplexing agent and complex metal ions of Cu, ni and Zn in a solution 2+ 、Ni 2+ 、Zn 2+ Further make Cu 2+ 、Ni 2+ 、Zn 2+ Ion vulcanization to generate metal sulfide, thereby achieving the effect of removing heavy metal precipitation, and FeO in sodium ferrate 4 2‑ The synergistic effect of the strong oxidizing property and the alkaline medium can inhibit and absorb the release of toxic hydrogen sulfide gas in the use process of calcium sulfide, and the moderate treatment can always maintain the decomplexed Cu by the complex metal ions such as Cu, ni, zn and the like through sodium hypochlorite 2+ 、Ni 2+ 、Zn 2+ The dissociation state of the ions so as to ensure whether the heavy metal removal effect of the ammonium-containing wastewater is correct; the iron-based sedimentation agent is added after severe treatment, and the polymeric ferric sulfate and ferrous chloride in the iron-based sedimentation agent can further strengthen the sedimentation effect, wherein sodium carboxymethyl cellulose can play a role in promoting sedimentation.
Description
Technical Field
The invention belongs to the field of methods for removing heavy metals from ammonium-containing wastewater, and particularly relates to a method for removing heavy metals nickel, copper and zinc from ammonium-containing wastewater.
Background
The main raw materials for refining and purifying the platinum group metals in Chinese minerals are copper-nickel smelting tailings, the refining process comprises the steps of chloridizing and dissolving, copper powder replacement, zinc-magnesium powder replacement, platinum-palladium refining and the like, and one of the representative wastewater produced in the refining process is ammonium-containing wastewater with higher nickel-copper-zinc content.
At present, the conventional neutralization hydrolysis sedimentation method and ferric salt sedimentation method are mainly adopted for the treatment of the ammonium-containing wastewater, but in the conventional neutralization and hydrolysis treatment process, NH 3+ Can be combined with OH - The reaction releases a large amount of ammonia gas, which causes severe operation environment and air pollution. Meanwhile, the traditional treatment method has the defects of large reagent consumption and difficult filter pressing, and most importantly, the method cannot meet the index requirement of industrial wastewater discharge. This is because copper and nickel ions in the wastewater exist in the form of complex ions, and the conventional neutralization sedimentation method is difficult to achieve the removal effect. In order to further solve the defects and the shortcomings of the prior art, reduce the content of heavy metal nickel copper zinc ions in the ammonium-containing wastewater to enable the heavy metal nickel copper zinc ions to reach the emission standard, and the prior art is urgently needed to be improved and broken through.
Disclosure of Invention
The invention aims at: provided is a method for removing heavy metals nickel copper zinc from ammonium-containing wastewater, which can remove complex ions in the wastewater without releasing ammonia gas.
The technical scheme adopted by the invention is as follows:
the method for removing the heavy metal nickel copper zinc from the ammonium-containing wastewater comprises the following steps of:
step one: pretreating, regulating the pH value of the ammonium-containing wastewater to 8-9, adding a strong oxidation decomplexant accounting for 1.5% -2% of the total volume of the wastewater, and stirring after adding;
step two: performing moderate treatment, namely adding sodium hypochlorite accounting for 0.5-1% of the total volume of the wastewater into the pretreated liquid for treatment, stirring after adding, and completely performing slag-liquid separation;
step three: heavy treatment, namely adding an iron-based sedimentation agent accounting for 2% -3% of the total volume of the wastewater into the moderately treated liquid; stirring, and separating slag from liquid after the reaction is completed;
the strong oxidation decomplexer in the first step is a mixed solution of sodium ferrate and calcium sulfide;
and in the third step, the iron-based settling agent is a mixed solution of polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose.
The further technical scheme is that the iron-based settling agent is prepared by mixing polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose according to the mass ratio of 3:1:1 and adding water to prepare a solution with the mass fraction of 10% -15%.
The further technical scheme is that the strong oxidation decomplexer is formed by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1 to prepare a mixed solution with the mass fraction of 10-15%, and adding hydrogen peroxide accounting for 0.5-1% of the mass of the mixed solution.
The further technical scheme is that the strong oxidation decomplexer is a mixed solution prepared by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1, wherein the mass fraction of the mixed solution is 10% -15%.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
the method comprises the following steps: pretreating, regulating the pH value of the ammonium-containing wastewater to 8-9, adding a strong oxidation decomplexant accounting for 1.5% -2% of the total volume of the wastewater, and stirring after adding; the strong oxidation decomplexing agent is utilized to react with complex metal ions such as Cu, ni, zn and the like in the solution to dissociate Cu 2+ 、Ni 2+ 、Zn 2+ Further make Cu 2+ 、Ni 2+ 、Zn 2+ Ion vulcanization to generate metal sulfide, thereby achieving the effect of removing heavy metal precipitation, and FeO in sodium ferrate 4 2- The synergistic effect of the strong oxidizing property and the alkaline medium can inhibit and absorb the release of toxic hydrogen sulfide gas in the use process of calcium sulfide;
the method comprises the following steps: moderately treating, adding sodium hypochlorite accounting for 0.5-1% of the total volume of the wastewater into the pretreated liquid for treatment, stirring after adding, and completely reactingSlag-liquid separation, the complex state metal ions such as Cu, ni, zn and the like can be always kept to break the complex Cu by sodium hypochlorite 2+ 、Ni 2+ 、Zn 2+ The dissociation state of the ions so as to ensure whether the heavy metal removal effect of the ammonium-containing wastewater is correct;
the method comprises the following steps: heavy treatment, namely adding an iron-based sedimentation agent accounting for 2% -3% of the total volume of the wastewater into the moderately treated liquid; stirring, and separating slag from liquid after the reaction is completed, wherein the polymeric ferric sulfate and ferrous chloride in the iron-based settling agent can further strengthen the settling effect, and the sodium carboxymethyl cellulose can play a role in promoting the settling.
Drawings
FIG. 1 is a graph showing the effects of the invention before and after wastewater treatment in example 1;
FIG. 2 is a graph showing the effects of the invention before and after wastewater treatment in example 2.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent.
As shown in fig. 1-2.
Example 1: the method for removing the heavy metal nickel copper zinc from the ammonium-containing wastewater comprises the following steps of: step one: pretreating, regulating the pH value of the ammonium-containing wastewater to 8, adding a strong oxidation decomplexer accounting for 1.5% of the total volume of the wastewater, and stirring for reaction for 30 min after adding;
step two: performing moderate treatment, namely adding sodium hypochlorite accounting for 0.5-1% of the total volume of the wastewater into the pretreated liquid for treatment, and stirring for reaction for 15 min after adding, wherein the reaction is completely performed for slag-liquid separation;
step three: heavy treatment, namely adding an iron-based sedimentation agent accounting for 2% of the total volume of the wastewater into the moderately treated liquid; stirring and reacting for 60 min, and separating slag from liquid after the reaction is completed;
the strong oxidation decomplexer in the first step is a mixed solution of sodium ferrate and calcium sulfide;
the three iron-based settling agents in the step are mixed solutions of polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose.
The iron-based settling agent is prepared by mixing polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose according to the mass ratio of 3:1:1 and adding water to prepare a solution with the mass fraction of 10%.
The strong oxidation decomplexer is formed by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1 to prepare a mixed solution with the mass fraction of 10 percent and adding hydrogen peroxide accounting for 0.5-1 percent of the mass of the mixed solution.
The strong oxidation decomplexer is a mixed solution prepared by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1, wherein the mass fraction of the mixed solution is 10%.
By adopting the method, 20mL of improved vein breaker is prepared according to the requirement, 1.5g of sodium ferrate and 1.5g of calcium sulfide are mixed, added with water to 20mL and stirred uniformly, so as to prepare the improved strong oxidation vein breaker; taking 1000 mL of ammonium-containing wastewater, adding 20mL of improved vein breaker for pretreatment after PH=8 adjustment, and stirring for 30 min after the pretreatment; adding 5g of sodium hypochlorite into the pretreated liquid for oxidation neutral treatment, stirring for 15 min after adding, and filtering by a filter after the reaction is completed to realize slag-liquid separation; preparing an iron-based coagulant of 20mL according to the requirement, adding 1.2 g polymeric ferric sulfate, 0.4g ferrous chloride and 0.4g sodium carboxymethyl cellulose into a container, adding water until the total volume is 20mL, uniformly stirring, and adding 0.2mL hydrogen peroxide to prepare the efficient iron-based sedimentation agent; uniformly adding 20mL high-efficiency macromolecular iron-based coagulant into the moderately treated wastewater, stirring for 60 min, filtering with a filter after the reaction is completed to realize slag-liquid separation,
the method comprises the following steps: pretreating, regulating the pH value of the ammonium-containing wastewater to 8, adding a strong oxidation decomplexer accounting for 1.5% of the total volume of the wastewater, and stirring for reaction for 30 min after adding; the strong oxidation decomplexing agent is utilized to react with complex metal ions such as Cu, ni, zn and the like in the solution to dissociate Cu 2+ 、Ni 2+ 、Zn 2+ Further make Cu 2+ 、Ni 2+ 、Zn 2+ Ion vulcanization to generate metal sulfide, thereby achieving the effect of removing heavy metal precipitation, and FeO in sodium ferrate 4 2- The synergistic effect of the strong oxidizing property and the alkaline medium can inhibit and absorb the release of toxic hydrogen sulfide gas in the use process of calcium sulfide.
The method comprises the following steps: adding sodium hypochlorite accounting for 0.5% of the total volume of the wastewater into the pretreated liquid for treatment, stirring after adding, completely separating slag and liquid after the reaction, and always maintaining the dissociation state of the complex-broken Cu2+, ni2+ and Zn2+ ions through sodium hypochlorite to ensure that the heavy metal removal effect of the ammonium-containing wastewater is correct;
the method comprises the following steps: heavy treatment, namely adding an iron-based sedimentation agent accounting for 2% of the total volume of the wastewater into the moderately treated liquid; stirring, and carrying out slag-liquid separation after the reaction is completed, wherein the polymeric ferric sulfate and ferrous chloride in the iron-based settling agent can further strengthen the precipitation effect, and the sodium carboxymethyl cellulose can play a role in promoting the precipitation.
Example 2: the method for removing the heavy metal nickel copper zinc from the ammonium-containing wastewater comprises the following steps of: step one: pretreating, regulating the pH value of the ammonium-containing wastewater to 9, adding a strong oxidation decomplexer accounting for 2% of the total volume of the wastewater, and stirring for reacting for 45 min after adding;
step two: performing moderate treatment, namely adding sodium hypochlorite accounting for 0.5-1% of the total volume of the wastewater into the pretreated liquid for treatment, and stirring for reaction for 25min after adding, wherein the reaction is completely performed for slag-liquid separation;
step three: heavy treatment, namely adding an iron-based sedimentation agent accounting for 3% of the total volume of the wastewater into the moderately treated liquid; stirring and reacting for 60 min, and separating slag from liquid after the reaction is completed;
the strong oxidation decomplexer in the first step is a mixed solution of sodium ferrate and calcium sulfide;
the three iron-based settling agents in the step are mixed solutions of polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose.
The iron-based settling agent is prepared by mixing polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose according to the mass ratio of 3:1:1 and adding water to prepare a solution with the mass fraction of 15%.
The strong oxidation decomplexer is formed by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1 to prepare a mixed solution with the mass fraction of 15 percent and adding hydrogen peroxide accounting for 1 percent of the mass of the mixed solution.
The strong oxidation decomplexer is a mixed solution prepared by mixing sodium ferrate and calcium sulfide according to the mass ratio of 1:1, wherein the mass fraction of the mixed solution is 15%.
By adopting the method, 200L of improved vein breaker is prepared according to the requirement, 12kg of sodium ferrate and 12kg of calcium sulfide are mixed, added with water to 200L and stirred uniformly, so as to prepare the improved strong oxidation vein breaker; 10000 liters of ammonium-containing wastewater is pumped into a wastewater treatment kettle, after PH=9 is adjusted, 200L of improved vein breaker is added for pretreatment, and after the pretreatment is added, stirring is carried out for 45 min; adding 100kg of sodium hypochlorite into the pretreated liquid for oxidation and neutralization treatment, stirring for 25min after adding, and realizing slag-liquid separation by a filter press after the reaction is completed; preparing 250L of high-efficiency macromolecule iron-based coagulant according to the requirement, adding 15kg of polymeric ferric sulfate, 5kg of ferrous chloride and 5kg of sodium carboxymethyl cellulose into a dissolving tank, adding water until the total volume is 250L, uniformly stirring, and adding 12.5L of hydrogen peroxide to prepare the high-efficiency iron-based sedimentation agent; 275L of high-efficiency iron-based settling agent is evenly added into the ammonium-containing wastewater after the intermediate treatment, stirred for 60 min, and after the reaction is completed, a filter press is used for realizing slag-liquid separation,
the method comprises the following steps: pretreating, regulating the pH value of the ammonium-containing wastewater to 9, adding a strong oxidation decomplexer accounting for 2% of the total volume of the wastewater, and stirring after adding; the strong oxidation decomplexing agent is utilized to react with complex metal ions such as Cu, ni, zn and the like in the solution to dissociate Cu 2+ 、Ni 2+ 、Zn 2+ Further make Cu 2+ 、Ni 2+ 、Zn 2+ Ion vulcanization to generate metal sulfide, thereby achieving the effect of removing heavy metal precipitation, and FeO in sodium ferrate 4 2- The synergistic effect of the strong oxidizing and alkaline mediums (whether in the wastewater or not) can inhibit and absorb the release of toxic hydrogen sulfide gas during the use of calcium sulfide.
The method comprises the following steps: adding sodium hypochlorite accounting for 1% of the total volume of the wastewater into the pretreated liquid for treatment, stirring after adding, completely separating slag and liquid after reaction, and keeping dissociation state of complex-broken Cu2+, ni2+ and Zn2+ ions through sodium hypochlorite all the time so as to ensure heavy metal removal effect of the ammonium-containing wastewater;
the method comprises the following steps: heavy treatment, namely adding an iron-based sedimentation agent accounting for 3% of the total volume of the wastewater into the moderately treated liquid; stirring, and carrying out slag-liquid separation after the reaction is completed, wherein the polymeric ferric sulfate and ferrous chloride in the iron-based settling agent can further strengthen the precipitation effect, and the sodium carboxymethyl cellulose can play a role in promoting the precipitation.
The foregoing is only illustrative of the preferred embodiments of the present invention.
Claims (4)
1. The method for removing the heavy metal nickel copper zinc from the ammonium-containing wastewater is characterized by comprising the following steps of:
step one: pretreating, regulating the pH value of the ammonium-containing wastewater to 8-9, adding a strong oxidation decomplexant accounting for 1.5% -2% of the total volume of the wastewater, and stirring after adding;
step two: performing moderate treatment, namely adding sodium hypochlorite accounting for 0.5-1% of the total volume of the wastewater into the pretreated liquid for treatment, stirring after adding, and completely performing slag-liquid separation;
step three: heavy treatment, namely adding an iron-based sedimentation agent accounting for 2% -3% of the total volume of the wastewater into the moderately treated liquid; stirring, and separating slag from liquid after the reaction is completed;
the strong oxidation decomplexer in the first step is a mixed solution of sodium ferrate and calcium sulfide;
and in the third step, the iron-based settling agent is a mixed solution of polymeric ferric sulfate, ferrous chloride and sodium carboxymethyl cellulose.
2. The method for removing heavy metal nickel, copper and zinc from ammonium-containing wastewater according to claim 1, wherein the iron-based sedimentation agent is prepared by mixing polymeric ferric sulfate, ferrous chloride and sodium carboxymethylcellulose according to the mass ratio of 3:1:1 and adding water to prepare a solution with the mass fraction of 10% -15%.
3. The method for removing heavy metal nickel, copper and zinc from ammonium-containing wastewater according to claim 2, wherein the strong oxidation decomplexer is formed by mixing sodium ferrate and calcium sulfide according to a mass ratio of 1:1 to prepare a mixed solution with a mass fraction of 10-15%, and adding hydrogen peroxide accounting for 0.5-1% of the mass of the mixed solution.
4. The method for removing heavy metal nickel, copper and zinc from ammonium-containing wastewater according to claim 1, wherein the strong oxidation decomplexer is a mixed solution prepared by mixing sodium ferrate and calcium sulfide according to a mass ratio of 1:1, wherein the mass fraction of the mixed solution is 10% -15%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153108A (en) * | 1998-06-11 | 2000-11-28 | Texaco Inc. | Method for removal of heavy metals from water |
| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
| CN108249613A (en) * | 2016-12-29 | 2018-07-06 | 南京源泉环保科技股份有限公司 | A kind of alkaline zinc-nickel alloy wastewater treatment method |
| CN111995167A (en) * | 2020-07-07 | 2020-11-27 | 广西夏阳环保科技有限公司 | Treatment method of acidic heavy metal wastewater |
| CN114275868A (en) * | 2022-01-18 | 2022-04-05 | 长沙千河环保科技有限责任公司 | Heavy metal targeted remover and preparation method and application thereof |
-
2022
- 2022-04-25 CN CN202210437657.9A patent/CN114956369B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153108A (en) * | 1998-06-11 | 2000-11-28 | Texaco Inc. | Method for removal of heavy metals from water |
| WO2010017652A1 (en) * | 2008-08-11 | 2010-02-18 | Hernandez Pavez Jose Octavio | Process and system for separation, recycling and sustainable environmental stabilisation of acid effluents with arsenic (as) and/or heavy metals which form insoluble sulphides |
| CN108249613A (en) * | 2016-12-29 | 2018-07-06 | 南京源泉环保科技股份有限公司 | A kind of alkaline zinc-nickel alloy wastewater treatment method |
| CN111995167A (en) * | 2020-07-07 | 2020-11-27 | 广西夏阳环保科技有限公司 | Treatment method of acidic heavy metal wastewater |
| CN114275868A (en) * | 2022-01-18 | 2022-04-05 | 长沙千河环保科技有限责任公司 | Heavy metal targeted remover and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张兴儒等.《油气田环境保护》.石油工业出版社,1995,第161页. * |
| 陈家镛等.《湿法冶金手册》.冶金工业出版社,2005,第76页. * |
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