CN115028293A - Method for treating cyanide-containing wastewater by using manganese dioxide in synergistic oxidation mode - Google Patents
Method for treating cyanide-containing wastewater by using manganese dioxide in synergistic oxidation mode Download PDFInfo
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- CN115028293A CN115028293A CN202210846585.3A CN202210846585A CN115028293A CN 115028293 A CN115028293 A CN 115028293A CN 202210846585 A CN202210846585 A CN 202210846585A CN 115028293 A CN115028293 A CN 115028293A
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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- 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
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- Engineering & Computer Science (AREA)
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Abstract
The invention belongs to the technical field of cyanide-containing wastewater treatment, and particularly discloses a method for treating cyanide-containing wastewater by using manganese dioxide for synergetic oxidation. Firstly, adjusting the pH value of cyanide-containing wastewater to 8-9 to obtain pretreated cyanide-containing wastewater; then mixing with manganese dioxide to obtain a mixed solution; then introducing an oxidizing atmosphere for reaction to finish the treatment of the cyanide-containing wastewater. The treatment method disclosed by the invention is simple in process and easy to operate; the treatment cost is low; the reaction can be carried out at normal pressure; heavy metal and other ions are prevented from entering a system as a catalyst or an oxidant in the decyanation process, and secondary pollution to the wastewater containing cyanogen is avoided.
Description
Technical Field
The invention relates to the technical field of cyanide-containing wastewater treatment, in particular to a method for treating cyanide-containing wastewater by using manganese dioxide for synergetic oxidation.
Background
In the gold production process, a large amount of cyanide-containing wastewater is generated by adopting a cyanidation method gold extraction process, and cyanide is extremely toxic, pollutes the environment and seriously harms life health and must be removed. The high-concentration cyanide-containing wastewater can be returned to the cyaniding process for secondary utilization, finally, the cyanide-containing wastewater with medium and low concentration is generated, and the cyanide-containing wastewater with medium and low concentration can be discharged or recycled after the decyanation process. The prior traditional chemical decyanation method for treating wastewater containing cyanogen has the problems of low stability or high cost, and agents (such as chlorine series oxidation agents and Cu) added in certain methods 2+ Catalyst) can also cause secondary pollution to cyanide-containing wastewater.The method has important significance for the development of environmental protection and gold industry by carrying out high-efficiency cyanogen breaking treatment on the cyanide-containing wastewater with medium and low concentration.
Therefore, how to provide a wastewater treatment method, which improves the removal effect of cyanide in cyanide-containing wastewater, reduces the treatment cost, and simultaneously avoids secondary pollution of drugs is a difficult problem to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a method for treating cyanide-containing wastewater by using manganese dioxide in cooperation with oxidation, so as to solve the problems of instability or high cost of the conventional cyanide-containing wastewater treatment method and the problem of secondary pollution of an oxidation agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating cyanide-containing wastewater by manganese dioxide synergistic oxidation comprises the following steps:
1) adjusting the pH value of the cyanide-containing wastewater to obtain pretreated cyanide-containing wastewater;
2) mixing the pretreated cyanide-containing wastewater with manganese dioxide to obtain a mixed solution;
3) introducing an oxidizing atmosphere into the mixed solution for reaction to finish the treatment of the cyanide-containing wastewater;
wherein the pH value of the cyanide-containing wastewater pretreated in the step 1) is 8-9.
Preferably, the cyanide content in the cyanide-containing wastewater is less than or equal to 400 mg/L.
Preferably, the pH value of the cyanide-containing wastewater is adjusted in step 1) by using a sodium hydroxide solution or a sulfuric acid solution.
Preferably, the purity of the manganese dioxide in the step 2) is more than or equal to 80%, and the particle size of the manganese dioxide is 20-40 μm.
Preferably, the mass volume ratio of the manganese dioxide to the pretreated cyanide-containing wastewater in the step 2) is 2-10 g: 1L of the total amount of the active ingredients.
Preferably, the oxidizing atmosphere in step 3) includes an air atmosphere and/or an oxygen atmosphere.
Preferably, the introduction amount of the oxidizing atmosphere in the step 3) is 5-10L/min.
Preferably, the reaction temperature in the step 3) is 20-40 ℃, and the reaction time is 60-180 min;
the reaction in the step 3) is carried out under the stirring condition, and the stirring speed is 400-600 rpm.
Preferably, the reaction in step 3) is completed and then a filtering step is further included, and filter residue and filtrate are obtained through filtering.
Preferably, when the cyanide content in the filtrate is more than 0.5mg/L and less than or equal to 20mg/L, the cyanide-containing waste liquid is recycled as washing water of the cyanide slag cyanide breaking process; the content of cyanide in the filtrate is less than or equal to 0.5mg/L and can be directly discharged.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the manganese dioxide adopted by the invention is an amphoteric substance, is insoluble in water, weak acid and weak base solution, has strong adsorption capacity, and can effectively adsorb free cyanide and metal complex cyanide in cyanide-containing wastewater; meanwhile, manganese dioxide has the function of catalytic oxidation, and can be used as a catalyst to promote cyanide to be oxidized into cyanate under the condition of ensuring sufficient oxygen supply in a system, so that the cyanide is converted into a nontoxic substance. Manganese dioxide has certain oxidation capacity and strong oxidizability under the condition of low pH value. However, the pH value is too low, cyanide easily forms hydrocyanic acid to overflow, and serious harm is caused, so that the pH value of the ore pulp is adjusted within the range of 8.0-9.0, the oxidation effect of manganese dioxide can be exerted as far as possible on the premise of ensuring safe production, the cyanide-containing wastewater is treated by cooperating with oxygen oxidation, and the content of the cyanide is reduced to below the national emission standard.
The method has simple process and easy operation; the reaction can be carried out at normal pressure; in the decyanation process, heavy metals and other ions are prevented from entering a system as a catalyst or an oxidant to generate secondary pollution on the wastewater containing cyanogen; the catalytic action and the oxidability of manganese dioxide are utilized to cooperate with oxygen to oxidize cyanide-containing wastewater, so that cyanide is converted into nontoxic substances, and the adsorption performance of manganese dioxide is exerted to remove a part of cyanide. The manganese dioxide is used for treating the cyanide-containing wastewater in cooperation with the oxidative decyanation, a high-power reactor is not needed, and the production energy consumption is greatly reduced. The treated filtrate can be recycled as washing water of the cyanogen slag decyanation process, so that the comprehensive utilization of resources is realized, and the cyanide content of less than 0.5mg/L can meet the national discharge standard and can be directly discharged. The manganese dioxide obtained by filtering after decyanation treatment can be desorbed after drying for recycling, so that the treatment cost is reduced.
Detailed Description
The invention provides a method for treating cyanide-containing wastewater by manganese dioxide synergistic oxidation, which comprises the following steps:
1) adjusting the pH value of the cyanide-containing wastewater to 8-9, preferably 8.2-8.7, and further preferably 8.5; obtaining pretreated cyanide-containing wastewater;
2) mixing the pretreated cyanide-containing wastewater with manganese dioxide to obtain a mixed solution;
3) and introducing an oxidizing atmosphere into the mixed solution for reaction to finish the treatment of the cyanide-containing wastewater.
In the invention, the cyanide content in the cyanide-containing wastewater is less than or equal to 400mg/L, preferably 20-200 mg/L, and more preferably 150 mg/L.
In the invention, sodium hydroxide solution or sulfuric acid solution is adopted for adjusting the pH value of the cyanide-containing wastewater in the step 1); the concentration of the sodium hydroxide solution is 10-40 g/L, preferably 15-30 g/L, and further preferably 20 g/L; the concentration of the sulfuric acid solution is 10-40 g/L, preferably 15-30 g/L, and more preferably 20 g/L.
In the invention, the particle size of the manganese dioxide in the step 2) is 20-40 μm, preferably 24-35 μm, and more preferably 30 μm. In a specific embodiment of the invention, the manganese dioxide used is technical grade manganese dioxide, and the purity of the manganese dioxide is greater than or equal to 80%, preferably greater than or equal to 85%, and more preferably greater than or equal to 88%.
In the invention, the mass volume ratio of manganese dioxide to the pretreated cyanide-containing wastewater in the step 2) is 2-10 g: 1L, preferably 4-8: 1, more preferably 6: 1.
in the present invention, the oxidizing atmosphere in the step 3) includes an air atmosphere and/or an oxygen atmosphere.
In the invention, the introduction amount of the oxidizing atmosphere in the step 3) is 5-10L/min, preferably 6-9L/min, and more preferably 8L/min.
In the invention, the reaction temperature in the step 3) is 20-40 ℃, preferably 25-35 ℃, and further preferably 30 ℃; the reaction time is 60-180 min, preferably 80-150 min, and more preferably 120 min.
In the present invention, the reaction in step 3) is performed under stirring conditions, and the stirring rate is 400 to 600rpm, preferably 450 to 550rpm, and more preferably 500 rpm.
In the present invention, the oxidation reaction equation is
2CN - +O 2 ＝2CNO -
CN - +MnO 2 +H 2 O＝2CNO - +Mn 2+ +2OH - In the invention, the step 3) of filtering after the reaction is finished further comprises the step of filtering to obtain filter residue and filtrate.
In the present invention, the filtration pore size is preferably 400 to 800 mesh, and more preferably 600 mesh.
In the invention, when the cyanide content in the filtrate is more than 0.5mg/L and less than or equal to 20mg/L, the cyanide is recycled as washing water of the cyanide slag cyanide breaking process; the content of cyanide in the filtrate is less than or equal to 0.5mg/L and can be directly discharged.
In the invention, the cyanide content in the manganese dioxide filter residue is less than or equal to 100 mg/kg.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment of the invention, the sulfuric acid solution and the sodium hydroxide solution are used as analytical reagents, and the water is deionized water.
The manganese dioxide adopted in the embodiment of the invention is a commercial product, and the purity of the manganese dioxide is 80 percent of industrial grade manganese dioxide.
In the embodiment of the invention, a thunder magnetic PHBJ-260 type portable pH meter is adopted for measuring the pH value.
The discharge standard of the cyanide-containing wastewater obtained in the embodiment of the invention is in accordance with GB8978-1996 Integrated wastewater discharge Standard.
Example 1
In the embodiment of the invention, the cyanide content in the cyanide-containing wastewater to be treated is 326.6mg/L, and the initial pH of the stock solution is 11.23.
(1) Adding cyanide-containing wastewater into a reaction tank, and adjusting the pH value of the solution to 9.0 by using dilute sulfuric acid;
(2) adding manganese dioxide powder (the particle size is 25-30 mu m) into the solution after the pH is adjusted, wherein the addition amount is 10g per liter of solution;
(3) introducing air into the cyanide-containing wastewater at the temperature of 25 ℃, stirring (the stirring speed is 600rpm) and carrying out oxidation reaction, wherein the air filling amount is 10L/min, and the oxidation reaction time is 180min, so as to obtain a reaction material;
(4) filtering the reaction material by 800 meshes to obtain filter residue and filtrate; the content of cyanide in the filtrate is 16.9mg/L, and the cyanide can be recycled as washing water of the cyanide slag decyanation process.
Example 2
In the embodiment of the invention, the cyanide content in the cyanide-containing wastewater to be treated is 195.2mg/L, and the initial pH of the stock solution is 12.09.
The method is the same as example 1, except that:
(1) adjusting the pH value of the solution to 8.5;
(2) the adding amount of the manganese dioxide powder is 5g (the particle size range is 25-35 mu m) per liter of solution;
(3) the oxidation reaction temperature is 30 ℃, the air charging amount is 10L/min, the oxidation reaction time is 120min, and the stirring speed in the reaction is 500 rpm;
(4) the aperture of the filter screen is 600 meshes, the content of cyanide in the filtrate is 10.5mg/L, and the filter screen enters the cyanogen slag decyanation process to be used as washing water for recycling.
Example 3
In the embodiment of the invention, the cyanide content in the cyanide-containing wastewater to be treated is 106.4mg/L, and the initial pH of the stock solution is 8.7.
The method is the same as example 1, except that:
(1) sodium hydroxide solution or sulfuric acid solution is not required to be added;
(2) the adding amount of the manganese dioxide powder is 4g (the particle size range is 30-40 mu m) added into each liter of solution;
(3) the oxidation reaction temperature is 40 ℃, the air charging amount is 5L/min, the oxidation reaction time is 60min, and the stirring speed in the reaction is 500 rpm;
(4) the aperture of the filter screen is 400 meshes, the content of cyanide in the filtrate is 5.8mg/L, and the filter screen enters the cyanogen slag decyanation process to be used as washing water for recycling.
Example 4
In the embodiment of the invention, the cyanide content in the cyanide-containing wastewater to be treated is 25.9mg/L, and the initial pH of the stock solution is 10.26.
The method is the same as example 1, except that:
(1) adjusting the pH value of the solution to 8.0;
(2) the adding amount of the manganese dioxide powder is 2g (the particle size range is 20-30 mu m) added into each liter of solution;
(3) the oxidation reaction temperature is 20 ℃, the air charging amount is 5L/min, the oxidation reaction time is 60min, and the stirring speed in the reaction is 400 rpm;
(4) the aperture of the filter screen is 800 meshes, the content of cyanide in the filtrate is 0.45mg/L and less than 0.5mg/L, and the filter screen can be directly discharged.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for treating cyanide-containing wastewater by using manganese dioxide for synergetic oxidation is characterized by comprising the following steps:
1) adjusting the pH value of the cyanide-containing wastewater to 8-9 to obtain pretreated cyanide-containing wastewater;
2) mixing the pretreated cyanide-containing wastewater with manganese dioxide to obtain a mixed solution;
3) and introducing an oxidizing atmosphere into the mixed solution to perform an oxidation decyanation reaction, thereby finishing the treatment of the cyanide-containing wastewater.
2. The method for treating cyanide-containing wastewater by manganese dioxide synergistic oxidation as claimed in claim 1, wherein the cyanide content in the cyanide-containing wastewater is less than or equal to 400 mg/L.
3. The method for treating cyanide-containing wastewater by manganese dioxide synergistic oxidation according to claim 2, wherein the pH value of the cyanide-containing wastewater in step 1) is adjusted by using sodium hydroxide solution or sulfuric acid solution.
4. The method for treating cyanide-containing wastewater by using manganese dioxide synergistic oxidation according to any one of claims 1 to 3, wherein the purity of manganese dioxide in the step 2) is not less than 80%, and the particle size of manganese dioxide is 20 to 40 μm.
5. The method for treating cyanide-containing wastewater by using manganese dioxide synergistic oxidation as claimed in claim 4, wherein the mass volume ratio of manganese dioxide to pretreated cyanide-containing wastewater in the step 2) is 2-10 g: 1L of the compound.
6. The method for treating cyanide-containing wastewater by manganese dioxide synergistic oxidation according to claim 5, wherein the oxidation atmosphere in step 3) comprises an air atmosphere and/or an oxygen atmosphere.
7. The method for treating cyanide-containing wastewater by using manganese dioxide synergistic oxidation as claimed in claim 5 or 6, wherein the amount of the introduced oxidizing atmosphere in the step 3) is 5-10L/min.
8. The method for treating cyanide-containing wastewater by using manganese dioxide in cooperation with oxidation according to claim 7, wherein the reaction temperature in the step 3) is 20-40 ℃ and the reaction time is 60-180 min.
9. The method for treating cyanide-containing wastewater by using manganese dioxide for synergetic oxidation according to claim 8, wherein the step 3) of filtering after the reaction is completed further comprises filtering to obtain filter residue and filtrate.
10. The method for treating cyanide-containing wastewater by using manganese dioxide synergistic oxidation as claimed in claim 9, wherein the filtrate is recycled as washing water of the cyanide slag cyanide breaking process when the cyanide content is greater than 0.5mg/L and less than or equal to 20 mg/L;
when the cyanide content in the filtrate is less than or equal to 0.5mg/L, directly discharging.
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Citations (8)
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| JPS63291690A (en) * | 1987-05-25 | 1988-11-29 | Tanaka Kikinzoku Kogyo Kk | Treatment of waste water separated from metal cyanide |
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| CN113101591A (en) * | 2021-03-17 | 2021-07-13 | 东北大学 | Cyanide tailing decyanation method based on activated carbon catalytic oxidation |
-
2022
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Patent Citations (8)
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|---|---|---|---|---|
| JPS63291690A (en) * | 1987-05-25 | 1988-11-29 | Tanaka Kikinzoku Kogyo Kk | Treatment of waste water separated from metal cyanide |
| AU5551696A (en) * | 1995-04-21 | 1996-11-07 | Apyron Technologies, Inc. | Enhanced adsorbent and room temperature catalyst particle and method of making and using therefor |
| JPH11165180A (en) * | 1997-12-02 | 1999-06-22 | Ngk Insulators Ltd | Method for treating scrubber drainage |
| CN101549916A (en) * | 2008-03-31 | 2009-10-07 | 李成心 | Method for treating electroplating cyanide waste water |
| CN102030436A (en) * | 2009-09-30 | 2011-04-27 | 北京中科国益环保工程有限公司 | Method for treating sulfite-containing wastewater |
| CN110980916A (en) * | 2019-11-14 | 2020-04-10 | 东北大学 | Method for degrading thiocyanate in cyanogen-containing barren solution under acidic condition |
| CN113101591A (en) * | 2021-03-17 | 2021-07-13 | 东北大学 | Cyanide tailing decyanation method based on activated carbon catalytic oxidation |
| CN113087115A (en) * | 2021-04-19 | 2021-07-09 | 广东工业大学 | Method for removing heavy metal complex in wastewater |
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