CN115417482B - Method for reducing secondary pollutants generated by degradation of collecting agent in sulfide mine wastewater - Google Patents
Method for reducing secondary pollutants generated by degradation of collecting agent in sulfide mine wastewater Download PDFInfo
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- CN115417482B CN115417482B CN202211129379.7A CN202211129379A CN115417482B CN 115417482 B CN115417482 B CN 115417482B CN 202211129379 A CN202211129379 A CN 202211129379A CN 115417482 B CN115417482 B CN 115417482B
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- wastewater
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- secondary pollutants
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- 239000002351 wastewater Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 41
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 27
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 27
- 230000015556 catabolic process Effects 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 title description 7
- 239000011028 pyrite Substances 0.000 claims abstract description 34
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 34
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 10
- 239000012991 xanthate Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 5
- -1 thiamine ester Chemical class 0.000 claims description 3
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 claims description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 2
- 229960003495 thiamine Drugs 0.000 claims description 2
- 235000019157 thiamine Nutrition 0.000 claims description 2
- 239000011721 thiamine Substances 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 33
- 229910052500 inorganic mineral Inorganic materials 0.000 description 10
- 239000011707 mineral Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZCUFTCUMEDALHC-UHFFFAOYSA-N CC[K] Chemical compound CC[K] ZCUFTCUMEDALHC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for reducing secondary pollutants generated by degradation of a collector in sulfide mine wastewater. The method comprises the following steps: firstly, crushing and grinding pyrite, then adding the obtained pyrite particles into the wastewater, adjusting the pH value of the wastewater to 7.0-12.0, and fully contacting and reacting for a period of time, thereby accelerating the degradation of a sulfide ore collector in the wastewater and simultaneously reducing secondary pollutants generated in the wastewater. The method innovatively takes pyrite as a wastewater treatment material, and controls the pH value of a reaction system to accelerate the degradation of a sulfide ore collector in wastewater and simultaneously obviously reduce secondary pollutants generated in the degradation process.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for reducing secondary pollutants generated by degradation of a collector in sulfide mine wastewater.
Background
Nonferrous metal minerals are usually present in the form of polymetallic sulphide ores, and prior to wet or pyrogenic extraction of the nonferrous metal, it is often necessary to beneficiate the desired sulphide mineral to separate it from other sulphide minerals or gangue. The surface properties of different sulphide minerals differ and can therefore be separated by flotation. Mineral separation wastewater generated in the flotation process is one of main sources of sulfide mine wastewater, contains a large amount of residual mineral separation agents, particularly sulfide collecting agents, and if discharged into the nature, not only causes waste of water resources, but also causes a series of ecological environment problems; if the untreated materials are directly recycled in the beneficiation process, flotation recovery or flotation separation of the vulcanized minerals can be affected, and adverse effects on flotation indexes are generated.
Current methods for treating collectors in sulphide mine wastewater include physical, chemical and biological methods, with chemical methods being the dominant. The acidification degradation method, natural degradation method and chemical oxidation method of sulphide ore collector in the waste water belong to chemical methods, and the instability and chemical reaction activity of the sulphide ore collector are utilized, and acid, strong oxidant or aeration is added to degrade the sulphide ore collector in the waste water under the action of hydrogen ions, redox agents or oxygen. In the chemical method treatment process, secondary pollutants such as carbon disulfide and the like are usually generated by degrading a sulfide ore collector in the wastewater, if the secondary pollutants are released into the atmosphere, the secondary pollutants have potential toxicity risks to organisms around a mining area, and the secondary environmental problems such as acid rain and the like can be caused by further decomposition of the secondary pollutants. The existing chemical method for treating the mine wastewater of the sulphide ores is faced with the problem of high cost on one hand and secondary pollutant release on the other hand. Therefore, the development of the sulfide mine wastewater treatment technology which is low in cost and good in effect and can avoid secondary pollutants in the degradation process of the collector as much as possible is a long-term requirement in the field of mine industrial wastewater treatment.
Pyrite is a common iron-containing sulphide mineral, and in the prior art, in methods related to the treatment of wastewater with pyrite, pyrite must be used in combination with persulfates, hydrogen peroxide, and other peroxides, or with microorganisms. When the catalyst is combined with peroxide, ferrous ions added in Fenton reaction are replaced, the catalyst plays a role, and the catalyst is still a high-grade oxidative degradation method in nature and mainly consumes peroxide, so that the process is complex, the peroxide used in combination is high in cost and severe in reaction, and secondary products are complex; when the microbial acid is combined with microorganisms, the pH of the wastewater is reduced by utilizing microbial ferric oxide mineral acid, the microbial acid still belongs to an acidification degradation method, and the microbial acid is difficult to culture and has more condition limitations, and similar to a direct acidification method, a large amount of secondary pollutants are generated. At present, no method for treating mine wastewater by using single pyrite exists, and no treatment method for generating secondary pollutants by degrading residual medicaments in sulfide mine wastewater is specially adopted.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for reducing secondary pollutants generated by degrading mine wastewater containing a sulphide ore collector, which innovatively takes pyrite as a wastewater treatment material, utilizes substances such as active oxygen generated in the self oxidation process of pyrite and the like to react with residual agents in the mine wastewater so as to promote the degradation of the mine wastewater, accelerates the degradation of the sulphide ore collector in the wastewater, and simultaneously controls the pH of a reaction system to inhibit the natural degradation of a flotation agent, thereby remarkably reducing the secondary pollutants generated in the degradation process.
According to the method for reducing secondary pollutants generated by degrading the collecting agent in the sulphide ore mine wastewater, pyrite is crushed and ground, then the obtained pyrite particles are added into the wastewater, the pH value of the wastewater is regulated to 7.0-12.0, and the wastewater is fully contacted and reacted for a period of time, so that the degradation of the sulphide ore collecting agent in the wastewater is accelerated, and the secondary pollutants generated in the wastewater are reduced.
Further, the pyrite is natural pyrite or artificially synthesized pyrite.
Further, the sulfide ore collector includes 1 or more of a xanthate collector containing carbon-sulfur bonds, a sulfur-nitrogen collector, a thiamine ester collector, a thiol collector, and derivatives thereof.
Further, the pyrite is crushed and ground into pyrite powder until the granularity is below 1 mm.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts pyrite as sulfide mine wastewater treatment material, has wide sources and low cost, and for most nonferrous metal sulfide mines, pyrite is usually valuable sulfide mineral symbiotic mineral, is a low-value beneficiation product, can be obtained locally, does not need to be purchased externally, basically has no loss in the use process, and can be sold and utilized continuously. Compared with the traditional chemical treatment methods such as a natural degradation method, an acidification degradation method, a high-grade oxidation method and the like, the method can obviously improve the degradation rate of the sulfide ore collector in the wastewater, shortens the degradation period, does not need a special site, has low cost, greatly reduces the production of secondary pollutants, is a green and high-efficiency method, and is suitable for large-scale popularization and application.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
The wastewater solution contains 165mg/L of sulphide ore collector ethyl potassium xanthate, and 2.0g/L of pyrite with granularity of-0.038 mm is added. The pH of the wastewater is regulated to 7.2+/-0.1, and under the condition of room temperature, the degradation rate of xanthate reaches 99.5 percent after standing for 48 hours, and the yield of carbon disulfide is 4.49 percent. Compared with the method without adding pyrite, the production amount of secondary pollutant carbon disulfide is reduced by 88.6 percent. The carbon disulphide yield was reduced by 49.19% compared to the pyrite addition but at a pH of 4.5.+ -. 0.1.
Example 2
The wastewater solution contains 161mg/L of sulphide ore collector ethyl potassium xanthate, and 2.0g/L of pyrite with granularity of-0.038 mm is added. The pH of the wastewater is regulated to 8.5+/-0.1, and under the condition of room temperature, the degradation rate of xanthate reaches 99.3 percent after standing for 48 hours, and the yield of carbon disulfide is 3.85 percent. Compared with the method without adding pyrite, the production amount of secondary pollutant carbon disulfide is reduced by 89.2 percent. The carbon disulphide yield was reduced by 50.08% compared to the pyrite addition but at a pH of 4.5.+ -. 0.1.
Example 3
The wastewater solution contains 102mg/L of sulphide ore collector butyl potassium xanthate, 5.0g/L of pyrite with granularity of-0.09 mm is added, the pH value of the wastewater is regulated to 8.0+/-0.1, and under the condition of room temperature, the degradation rate of the xanthate reaches 99.2% after stirring for 48 hours, and the yield of carbon disulfide is 6.01%. Compared with the method without adding pyrite, the production amount of secondary pollutant carbon disulfide is reduced by 85.2 percent. The reduction in carbon disulphide production was 16.29% compared to the pyrite addition but at a pH of 6.2.+ -. 0.1.
Example 4
The wastewater solution contains 141mg/L of sulfide ore collector ethion, 10.0g/L of pyrite with granularity of-0.074 mm is added, the pH value of the wastewater is regulated to 9.5+/-0.2, and under the condition of room temperature, the degradation rate of ethion reaches 98.1% after stirring for 48 hours, and the yield of carbon disulfide is 5.11%. Compared with the method without adding pyrite, the production amount of secondary pollutant carbon disulfide is reduced by 84.5 percent.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.
Claims (3)
1. A method for reducing secondary pollutants generated by degrading a collector in wastewater of a sulphide mine is characterized in that pyrite is crushed and ground to a particle size of less than 1mm, then the obtained pyrite particles are added into the wastewater, the pH value of the wastewater is regulated to be always between 7.0 and 12.0 by using alkaline substances, and the wastewater is fully contacted and reacted for a period of time, so that the degradation of the collector in the sulphide mine in the wastewater is accelerated, and the secondary pollutants generated in the wastewater are reduced.
2. The method for reducing secondary pollutants produced by degradation of collectors in sulphide ore mine wastewater of claim 1, wherein the pyrite is natural pyrite or artificially synthesized pyrite.
3. The method of reducing secondary pollutants produced by degradation of collectors in sulphide ore mine wastewater of claim 1, wherein the sulphide ore collectors comprise 1 or more of xanthate collectors, sulfur nitrogen collectors, thiamine ester collectors, thiol collectors, and derivatives thereof, containing carbon-sulfur bonds.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211129379.7A CN115417482B (en) | 2022-09-16 | 2022-09-16 | Method for reducing secondary pollutants generated by degradation of collecting agent in sulfide mine wastewater |
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| CN202211129379.7A CN115417482B (en) | 2022-09-16 | 2022-09-16 | Method for reducing secondary pollutants generated by degradation of collecting agent in sulfide mine wastewater |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584097A (en) * | 1984-08-17 | 1986-04-22 | American Cyanamid Company | Neutral hydrocarboxycarbonyl thionocarbamate sulfide collectors |
| US5853571A (en) * | 1996-06-17 | 1998-12-29 | Harris; Guy H. | Pyrite depressant useful in flotation separation |
| JP2007209824A (en) * | 2005-10-04 | 2007-08-23 | Dowa Holdings Co Ltd | Method for cleaning contaminated soil or contaminated groundwater |
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-
2022
- 2022-09-16 CN CN202211129379.7A patent/CN115417482B/en active Active
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