CN104445750A - Cyanide waste water recovery treatment method - Google Patents
Cyanide waste water recovery treatment method Download PDFInfo
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- CN104445750A CN104445750A CN201510003443.0A CN201510003443A CN104445750A CN 104445750 A CN104445750 A CN 104445750A CN 201510003443 A CN201510003443 A CN 201510003443A CN 104445750 A CN104445750 A CN 104445750A
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- waste water
- resin
- cyanide
- treatment
- flocculation agent
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
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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)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a cyanide waste water recovery treatment method. The method is composed of a resin adsorption method, an advanced oxidation process, a coagulant-sedimentation method and an active carbon adsorption method. When cyanide waste water is treated, firstly, resin is selected and used for adsorbing and recovering cyanide in the waste water, an oxidizing agent and a catalyst are added to the adsorbed waste water for advanced oxidation treatment, coagulant-sedimentation is conducted on the oxidized waste water so as to remove pollutants such as suspended particulate matter and heavy metal ions in the waste water, active carbon adsorption is conducted on supernate obtained after sedimentation, and therefore remaining pollutants in the waste water are removed. According to the characteristics that the concentration of cyanide in the cyanide waste water generated in the gold production process is high, pollutant types are complex, and the pollutants are difficult to treat, the resin adsorption method, the advanced oxidation process, the coagulant-sedimentation method and the active carbon adsorption method are combined together to collaboratively conduct deep treatment on the cyanide waste water, the cyanide waste water recovery treatment method has the advantages of being good in treatment effect, high in treatment efficiency, stable in system operation, simple in technological process, capable of facilitating industrial application and the like, and the treated waste water can return to the production technological process and serve as reuse water to be used or can be drained when reaching the standard.
Description
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly a kind of cyanide wastewater recycling and administration method.
Background technology
Gold manufacturing enterprises is in process of production owing to using Cyanide Process, a large amount of cyanide wastewater can be produced, not only containing a large amount of hypertoxic prussiates in these waste water, but also contain the heavy metal ion of thiocyanate-and copper, zinc, lead and so on, if can not get effective process, great environmental protection hidden danger will be produced.At present, the method of conventional Treatment of Cyanide-containing Wastewater has acidifying absorption method, Pomolio-Celdecor process, Yin Kefa, sulfurous gas method etc. both at home and abroad, although adopt acidifying absorption method can reclaim a certain amount of prussiate, but because recovery of cyanide is not thorough, the remaining a certain amount of prussiate of meeting in waste water, thiocyanate ion and some heavy metal ion are not all effectively removed simultaneously.Chlorine residue that can be remaining a large amount of after Pomolio-Celdecor process process, produces ClCN product, causes secondary pollution problem, and the heavy metal ion such as copper, zinc, lead simultaneously in waste water fails effectively to be administered.Although Yin Kefa and sulfurous gas method can make cyanid up to standard, the thiocyanate-in waste water fails to be processed, and in addition, the waste residue produced in process heavy metal process is also more, easily causes secondary pollution.Therefore, also still lack more satisfactory method in cyanide wastewater process, if resolve this problem, have important meaning by the Sustainable development of China's gold industry and the environment protection of gold mine.
Summary of the invention
Object of the present invention is exactly the problems referred to above existed for existing treatment process, and provides a kind of cyanide wastewater recycling and administration method that technical process is simple, treatment effect good, processing efficiency is high, stable.The present invention is according to the feature containing multiple pollutants such as prussiate, thiocyanate-and heavy metals in gold manufacturing enterprises cyanide wastewater, first select resin to carry out absorption to the prussiate in waste water to reclaim, waste water after absorption adds oxygenant and catalyzer carries out advanced oxidation process, waste water after oxidation removes the pollutent such as suspended particulate, heavy metal ion in waste water by coagulating sedimentation, and the supernatant liquor after precipitation adopts charcoal absorption to remove pollutent remaining in waste water.Concrete technology step of the present invention is as follows:
(1), by cyanide wastewater pump into resin absorbing column and carry out adsorption treatment, adsorbent hydroxyl aluminum is 0.5 ~ 20h;
(2), adsorb saturated after resin send in pickling post, add pickle solution, under temperature 30 ~ 40 DEG C of conditions, pass into air and carry out the process of acidifying stripping, the gas sodium hydroxide solution of stripping absorbs, absorption liquid returns in golden production technical process, and the resin after pickling carries out manipulation of regeneration, then sends in resin absorbing column;
(3) cyanide wastewater, after resin absorption enters advanced oxidation treatment system, adds oxygenant and catalyzer carries out oxide treatment, and the treatment time is 0.25 ~ 2h;
(4) waste water, after oxidizing reaction adds flocculation agent successively under whipped state and flocculation agent carries out coagulating sedimentation, and after coagulation, waste water enters settling tank and staticly settles 0.25 ~ 2h;
(5), precipitation after supernatant liquor enter activated carbon treatment system, carry out charcoal absorption process, the treatment time is 0.5 ~ 3h;
(6) waste water after, having processed returns in the technological process of production or qualified discharge.
In described step (1), resin is strongly basic anionic resin.
In described step (2), pickle solution is sulfuric acid or hydrochloric acid soln, and pH value is between 2 ~ 3, and the gas-liquid-solid of air, pickle solution and resin is than being (100 ~ 5000): (2 ~ 10): 1.
In described step (3), oxygenant is hydrogen peroxide solution and the ozone of 30% ~ 50%, catalyzer is copper-bath, the dosage of oxygenant is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, oxygenant dosage is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of oxygenant dosage.
In described step (4), flocculation agent is polymer-inorganic salt flocculation agent, and flocculation agent is polyacrylamide, and flocculation agent and flocculation agent are all mixed with solution state and add.
Beneficial effect of the present invention:
The present invention is high according to the Cyanide in Cyanide Wastewater concentration produced in golden production process, pollutant kind is complicated, unmanageable feature, resin adsorption method, advanced oxidation processes, coagulant sedimentation and active carbon adsorption are combined, work in coordination with and advanced treatment is carried out to cyanide wastewater, have that treatment effect is good, processing efficiency is high, system run all right, technical process are simple, be convenient to realize the advantages such as industrial application, the waste water after process can return the technological process of production and use or qualified discharge as reuse water.
Embodiment
The present invention includes following steps:
(1), by cyanide wastewater pump into resin absorbing column and carry out adsorption treatment, adsorbent hydroxyl aluminum is 0.5 ~ 20h;
(2), adsorb saturated after resin send in pickling post, add pickle solution, under temperature 30 ~ 40 DEG C of conditions, pass into air and carry out the process of acidifying stripping, the gas sodium hydroxide solution of stripping absorbs, absorption liquid returns in golden production technical process, and the resin after pickling carries out manipulation of regeneration, then sends in resin absorbing column;
(3) cyanide wastewater, after resin absorption enters advanced oxidation treatment system, adds oxygenant and catalyzer carries out oxide treatment, and the treatment time is 0.25 ~ 2h;
(4) waste water, after oxidizing reaction adds flocculation agent successively under whipped state and flocculation agent carries out coagulating sedimentation, and after coagulation, waste water enters settling tank and staticly settles 0.25 ~ 2h;
(5), precipitation after supernatant liquor enter activated carbon treatment system, carry out charcoal absorption process, the treatment time is 0.5 ~ 3h;
(6) waste water after, having processed returns in the technological process of production or qualified discharge.
In described step (1), resin is strongly basic anionic resin.
In described step (2), pickle solution is sulfuric acid or hydrochloric acid soln, and pH value is between 2 ~ 3, and the gas-liquid-solid of air, pickle solution and resin is than being (100 ~ 5000): (2 ~ 10): 1.
In described step (3), oxygenant is hydrogen peroxide solution and the ozone of 30% ~ 50%, catalyzer is copper-bath, the dosage of oxygenant is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, oxygenant dosage is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of oxygenant dosage.
In described step (4), flocculation agent is polymer-inorganic salt flocculation agent, and flocculation agent is polyacrylamide, and flocculation agent and flocculation agent are all mixed with solution state and add.
Specific examples 1:
Certain gold mine cyanide wastewater, pH is 10.8, CN
tfor 657.26mg/L, SCN
-for 176.56mg/L, Cu
2+for 123.42mg/L, Fe
3+for 48.45mg/L, COD are 870.28mg/L, other heavy metal ion in addition containing trace.5L cyanide wastewater is pumped into resin absorbing column and carries out adsorption treatment, strongly basic anion polymeric adsorbent is filled in resin absorbing column, waste water adsorbent hydroxyl aluminum is 2h, waste water after absorption is placed in advanced oxidation treatment unit, advanced oxidation treatment unit interior bottom portion is provided with ceramic micropore aerator, top is provided with chemical feed pipe, the hydrogen peroxide solution 20mL of 30% is added in advanced oxidation treatment unit, open ozonizer, ozone reaction 30min is passed into from ceramic micropore aerator, ozone intake is 450mg, reaction terminates rear stopping and passing into ozone, waste water is moved in steel basin, open and stir, the polymeric aluminum chlorides solution 15mL adding 10g/L under stirring linear velocity is 0.8m/s condition stirs 5min, then 0.5 ‰ anionic polyacrylamide solution 5mL are added, regulate after continuing to stir 2min and stir linear velocity 0.1m/s stirring 5min, stop stirring, leave standstill 30min, with peristaltic pump supernatant liquor is moved in activated carbon treatment system and carries out adsorption treatment, gac is particulate coal activated carbon, adsorption time is 30min.The water outlet of waste water after system process through assay pH between 8 ~ 9, CN
t< 0.1mg/L, SCN
-< 0.5mg/L, Cu
2+< 0.5mg/L, COD < 20mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after process, water quality can reach reuse or emission standard.
Specific examples 2:
Certain gold mine is containing cyanogen, and pH is 10.2, CN
tfor 365.42mg/L, SCN
-for 123.78mg/L, Cu
2+for 25.43mg/L, Fe
3+for 57.55mg/L, Zn
2+for 14.43mg/L, COD are 498.69mg/L, other heavy metal ion in addition containing trace.5L cyanide wastewater is pumped into resin absorbing column and carries out adsorption treatment, strongly basic anion polymeric adsorbent is filled in resin absorbing column, waste water adsorbent hydroxyl aluminum is 2h, waste water after absorption is placed in advanced oxidation treatment unit, advanced oxidation treatment unit interior bottom portion is provided with ceramic micropore aerator, top is provided with chemical feed pipe, the hydrogen peroxide solution 20mL of 30% is added in advanced oxidation treatment unit, the copper-bath 1mL of 5%, open ozonizer, ozone reaction 30min is passed into from ceramic micropore aerator, ozone intake is 350mg, reaction terminates rear stopping and passing into ozone, waste water is moved in steel basin, open and stir, the polymeric aluminum chlorides solution 15mL adding 10g/L under stirring linear velocity is 0.8m/s condition stirs 5min, then 0.5 ‰ anionic polyacrylamide solution 5mL are added, regulate after continuing to stir 2min and stir linear velocity 0.1m/s stirring 5min, stop stirring, leave standstill 30min, with peristaltic pump supernatant liquor is moved in activated carbon treatment system and carries out adsorption treatment, gac is particulate coal activated carbon, adsorption time is 30min.The water outlet of waste water after system process through assay pH between 8 ~ 9, CN
t< 0.1mg/L, SCN
-< 0.5mg/L, Cu
2+< 0.5mg/L, Zn
2+< 1mg/L, COD < 20mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after process, water quality can reach reuse or emission standard.
Claims (6)
1. a cyanide wastewater recycling and administration method, the step of the method is as follows:
(1), by cyanide wastewater pump into resin absorbing column and carry out adsorption treatment, adsorbent hydroxyl aluminum is 0.5 ~ 20h;
(2), adsorb saturated after resin send in pickling post, add pickle solution, under temperature 30 ~ 40 DEG C of conditions, pass into air and carry out the process of acidifying stripping, the gas sodium hydroxide solution of stripping absorbs, absorption liquid returns in golden production technical process, and the resin after pickling carries out manipulation of regeneration, then sends in resin absorbing column;
(3) cyanide wastewater, after resin absorption enters advanced oxidation treatment system, adds oxygenant and catalyzer carries out oxide treatment, and the treatment time is 0.25 ~ 2h;
(4) waste water, after oxidizing reaction adds flocculation agent successively under whipped state and flocculation agent carries out coagulating sedimentation, and after coagulation, waste water enters settling tank and staticly settles 0.25 ~ 2h;
(5), precipitation after supernatant liquor enter activated carbon treatment system, carry out charcoal absorption process, the treatment time is 0.5 ~ 3h;
(6) waste water after, having processed returns in the technological process of production or qualified discharge.
2. a kind of cyanide wastewater recycling and administration method according to claim 1, it is characterized in that: in described step (1), resin is strongly basic anionic resin.
3. a kind of cyanide wastewater recycling and administration method according to claim 1, it is characterized in that: in described step (2), pickle solution is sulfuric acid or hydrochloric acid soln, and pH value is between 2 ~ 3, and the gas-liquid-solid ratio of air, pickle solution and resin is 100 ~ 5000:2 ~ 10:1.
4. a kind of cyanide wastewater recycling and administration method according to claim 1, is characterized in that: in described step (3), and oxygenant is hydrogen peroxide solution and the ozone of 30% ~ 50%, and catalyzer is copper-bath.
5. a kind of cyanide wastewater recycling and administration method according to claim 1, it is characterized in that: in described step (3), the dosage of oxygenant is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, oxygenant dosage is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of oxygenant dosage.
6. a kind of cyanide wastewater recycling and administration method according to claim 1, it is characterized in that: in described step (4), flocculation agent is polymer-inorganic salt flocculation agent, and flocculation agent is polyacrylamide, and flocculation agent and flocculation agent are all mixed with solution state and add.
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| CN201510003443.0A CN104445750B (en) | 2015-01-01 | 2015-01-01 | A kind of cyanide wastewater recycling and administration method |
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| CN201510003443.0A CN104445750B (en) | 2015-01-01 | 2015-01-01 | A kind of cyanide wastewater recycling and administration method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923557A (en) * | 2015-07-08 | 2015-09-23 | 长春黄金研究院 | Cyanide contaminated soil restoring method |
| CN104926036A (en) * | 2015-06-12 | 2015-09-23 | 长春黄金研究院 | Cyanogen-containing tailing slag treatment method |
| CN107973451A (en) * | 2017-12-29 | 2018-05-01 | 广西生富锑业科技股份有限公司 | A kind of wastewater zero discharge system |
| CN109020037A (en) * | 2018-09-18 | 2018-12-18 | 中钢集团鞍山热能研究院有限公司 | A kind of needle coke waste water pretreatment system and processing method |
| CN111377566A (en) * | 2018-12-27 | 2020-07-07 | 山东新海表面技术科技有限公司 | Method for surface treatment of cyanide in wastewater |
| CN112047525A (en) * | 2020-08-31 | 2020-12-08 | 营创三征(营口)精细化工有限公司 | Method and system for breaking cyanogen in resin |
| CN112456441A (en) * | 2020-11-05 | 2021-03-09 | 江苏永葆环保科技有限公司 | Purification pretreatment method of chemical byproduct hydrochloric acid |
| CN112645489A (en) * | 2020-12-07 | 2021-04-13 | 江苏国创新材料研究中心有限公司 | High-salinity wastewater treatment method based on adsorption and oxidation of temperature swing desorption resin |
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| CN1141886A (en) * | 1996-06-11 | 1997-02-05 | 高大明 | Technology for treatment of waste liquid containing cyanogen by ion exchange method |
| CN101157509A (en) * | 2007-09-04 | 2008-04-09 | 南京南大表面和界面化学工程技术研究中心有限责任公司 | Electroplating wastewater zero-discharge or low-discharge handling method |
| CN104058560A (en) * | 2014-07-16 | 2014-09-24 | 长春黄金研究院 | Nonferrous mine wastewater treatment method |
| CN104193123A (en) * | 2014-09-29 | 2014-12-10 | 长春黄金研究院 | Gold mine cyanide-containing wastewater system treating method |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4189381A (en) * | 1978-09-07 | 1980-02-19 | Amax Inc. | Waste water treatment |
| CN1141886A (en) * | 1996-06-11 | 1997-02-05 | 高大明 | Technology for treatment of waste liquid containing cyanogen by ion exchange method |
| CN101157509A (en) * | 2007-09-04 | 2008-04-09 | 南京南大表面和界面化学工程技术研究中心有限责任公司 | Electroplating wastewater zero-discharge or low-discharge handling method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926036A (en) * | 2015-06-12 | 2015-09-23 | 长春黄金研究院 | Cyanogen-containing tailing slag treatment method |
| CN104923557A (en) * | 2015-07-08 | 2015-09-23 | 长春黄金研究院 | Cyanide contaminated soil restoring method |
| CN107973451A (en) * | 2017-12-29 | 2018-05-01 | 广西生富锑业科技股份有限公司 | A kind of wastewater zero discharge system |
| CN109020037A (en) * | 2018-09-18 | 2018-12-18 | 中钢集团鞍山热能研究院有限公司 | A kind of needle coke waste water pretreatment system and processing method |
| CN111377566A (en) * | 2018-12-27 | 2020-07-07 | 山东新海表面技术科技有限公司 | Method for surface treatment of cyanide in wastewater |
| CN112047525A (en) * | 2020-08-31 | 2020-12-08 | 营创三征(营口)精细化工有限公司 | Method and system for breaking cyanogen in resin |
| CN112047525B (en) * | 2020-08-31 | 2021-11-02 | 营创三征(营口)精细化工有限公司 | Method and system for breaking cyanogen in resin |
| CN112456441A (en) * | 2020-11-05 | 2021-03-09 | 江苏永葆环保科技有限公司 | Purification pretreatment method of chemical byproduct hydrochloric acid |
| CN112645489A (en) * | 2020-12-07 | 2021-04-13 | 江苏国创新材料研究中心有限公司 | High-salinity wastewater treatment method based on adsorption and oxidation of temperature swing desorption resin |
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