CN104071953A - Cyanide-containing wastewater treating method for gold mine - Google Patents

Cyanide-containing wastewater treating method for gold mine Download PDF

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Publication number
CN104071953A
CN104071953A CN201410339685.2A CN201410339685A CN104071953A CN 104071953 A CN104071953 A CN 104071953A CN 201410339685 A CN201410339685 A CN 201410339685A CN 104071953 A CN104071953 A CN 104071953A
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treatment
gold mine
cyanogen
activated carbon
described step
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李哲浩
降向正
刘强
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Changchun Gold Research Institute
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Changchun Gold Research Institute
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Abstract

The invention discloses a cyanide-containing wastewater treating method for a gold mine. The treating method comprises four steps as follows: sulfur dioxide-air oxidation treatment, coagulating sedimentation treatment, ozone or activated carbon catalytic oxidation treatment and biological activated carbon treatment; in the cyanide-containing wastewater treatment, firstly, the sulfur dioxide-air oxidation method is adopted to remove easily removed cyanide; a coagulant is added in the treated wastewater for coagulating sedimentation to remove heavy metal ions in the wastewater; then ozone and the activated carbon are adopted for catalytic oxidation and contaminants such as residual cyanide that is hard to be treated and rhodanate are removed; lastly, through a biological activated carbon treatment system, contaminants that cannot be removed through chemical methods in the wastewater are removed by biological and physical adsorption methods. According to the invention, as technologies of the sulfur dioxide-air oxidation treatment, the coagulating sedimentation treatment, the ozone or activated carbon catalytic oxidation treatment and the biological activated carbon treatment are integrated and coordinated to conduct an advanced treatment on the cyanide-containing wastewater in the gold mine, the treatment efficiency is high, the treated wastewater can return to manufacturing technology processes and serve as renovated water for using or can be emitted up to standard.

Description

A kind of gold mine Treatment of cyanogen-contained wastewater
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly a kind for the treatment of process of gold mine cyanide wastewater.
Background technology
Gold mine is in process of production owing to using Cyanide Process, can produce a large amount of cyanide wastewater, this part cyanide wastewater not only contains a certain amount of hypertoxic prussiate, but also contain thiocyanate-and copper, zinc, plumbous and so on heavy metal ion, if can not get effective processing, will produce great environmental protection hidden danger.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.Pomolio-Celdecor process can remaining a large amount of chlorine residue after processing, and produces ClCN product, causes secondary pollution problem, and the heavy metal ion such as the copper in waste water, zinc, lead fails effectively to be administered simultaneously.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, processes the waste residue producing in heavy metal process also more, easily causes secondary pollution.Therefore, aspect cyanide wastewater processing, also still lacking more satisfactory method, if resolve this problem, the gold production of development China and environmental protection development will had to important meaning.
Summary of the invention
Object of the present invention is exactly the problems referred to above that exist for existing treatment process, and the Treatment of cyanogen-contained wastewater that a kind of technical process is simple, treatment effect good, processing efficiency is high, stable is provided.The present invention is according to containing prussiate in gold mine cyanide wastewater, the feature of the multiple pollutant such as thiocyanate-and heavy metal, particularly in prussiate, also comprise unmanageable metal cyano complex, as iron cyano complex etc., select Yin Kefa first tractable prussiate to be removed, waste water after treatment carries out coagulating sedimentation by dosing coagulant, remove the heavy metal ion in waste water, then adopt ozone and gac to carry out catalyzed oxidation, by the difficult prussiate of waste water remnants, the pollutant removals such as thiocyanate-fall, the pollutent that finally by biological activated carbon treatment system, chemical process in waste water is difficult to remove is got rid of by the method for biological and physical adsorption.Concrete technology step is as follows:
(1) under stirring and aeration state, in waste water, add acid-base reagent, pyrosulphite sodium reagent and catalyzer, ensure that the pH value of reaction process is controlled between 8~10, the reaction times is 30min~90min;
(2) reacted waste water adds successively flocculation agent and flocculation agent carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min~120min;
(3) supernatant liquor after precipitation, under gac existence condition, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min~60min;
(4) reacted waste water enters biological activated carbon treatment system, under the condition of active carbon filler, biofilm bacterial classification and air aeration, carries out biological activated carbon processing, and the treatment time is 30min~120min;
(5) supernatant liquor after treatment returns in the technological process of production or qualified discharge.
In described step (1), stirring linear velocity is 0.01m/s~10m/s; The vapour-liquid ratio that when aeration, air passes into is 3~50:1; Acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime; Pyrosulphite sodium reagent is 5%~30% sodium metabisulfite solution, catalyzer is 5%~30% copper-bath, the dosage of pyrosulphite sodium reagent is determined with processing index request according to the cyanide content in waste water quality is how many, cyanide content is high, processing index request is tight, corresponding the increasing of dosage of pyrosulphite sodium reagent, otherwise cyanide content is low, processing index request pine, the corresponding minimizing of dosage of pyrosulphite sodium reagent; The dosage of catalyzer is determined according to the content of bivalent cupric ion in the dosage of pyrosulphite sodium reagent and cyanide wastewater, the dosage of catalyzer becomes positive line sexual intercourse with the dosage of pyrosulphite sodium reagent, and the bivalent cupric ion content in cyanide wastewater can partly or entirely replace the dosage of catalyzer.
In described step (2), stirring linear velocity is 0.01m/s~10m/s, and 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.
In described step (3), gac is coconut husk charcoal or ature of coal charcoal, loadings accounts for 1/10~2/3 of reactor volume, ozone intake is determined according to number and the processing requirements of the remaining prussiate in influent quality and COD content, prussiate and COD content are high, processing index request is tight, corresponding the increasing of intake of ozone, otherwise, prussiate and COD content are low, processing index request pine, the corresponding minimizing of intake of ozone.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, and gac is coconut husk charcoal or ature of coal charcoal, and dress charcoal amount accounts for 1/5~4/5 of reactor volume, biofilm bacterial classification is nitrococcus and nitrobacteria, be collected near the topsoil of Tailings Dam, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and vapour-liquid ratio is set as 1~15:1.
Beneficial effect of the present invention:
The present invention is according to containing pollutent complexity, unmanageable feature in gold mine cyanide wastewater, Yin Kefa, coagulant sedimentation, ozone and active carbon catalytic oxidation and biological activated carbon treatment technology are combined, work in coordination with gold mine cyanide wastewater is carried out to advanced treatment, treatment effect is good, processing efficiency is high, system run all right, technical process is simple, is convenient to realize industrial application, and waste water after treatment can return to the technological process of production and use or qualified discharge as reuse water.
Embodiment
The present invention includes following steps:
(1) under stirring and aeration state, in waste water, add acid-base reagent, pyrosulphite sodium reagent and catalyzer, ensure that the pH value of reaction process is controlled between 8~10, the reaction times is 30min~90min;
(2) reacted waste water adds successively flocculation agent and flocculation agent carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min~120min;
(3) supernatant liquor after precipitation, under gac existence condition, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min~60min;
(4) reacted waste water enters biological activated carbon treatment system, under the condition of active carbon filler, biofilm bacterial classification and air aeration, carries out biological activated carbon processing, and the treatment time is 30min~120min;
(5) supernatant liquor after treatment returns in the technological process of production or qualified discharge.
In described step (1), stirring linear velocity is 0.01m/s~10m/s; The vapour-liquid ratio that when aeration, air passes into is 3~50:1; Acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime; Pyrosulphite sodium reagent is 5%~30% sodium metabisulfite solution, catalyzer is 5%~30% copper-bath, the dosage of pyrosulphite sodium reagent is determined with processing index request according to the cyanide content in waste water quality is how many, cyanide content is high, processing index request is tight, corresponding the increasing of dosage of pyrosulphite sodium reagent, otherwise cyanide content is low, processing index request pine, the corresponding minimizing of dosage of pyrosulphite sodium reagent; The dosage of catalyzer is determined according to the content of bivalent cupric ion in the dosage of pyrosulphite sodium reagent and cyanide wastewater, the dosage of catalyzer becomes positive line sexual intercourse with the dosage of pyrosulphite sodium reagent, and the bivalent cupric ion content in cyanide wastewater can partly or entirely replace the dosage of catalyzer.
In described step (2), stirring linear velocity is 0.01m/s~10m/s, and 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.
In described step (3), gac is coconut husk charcoal or ature of coal charcoal, loadings accounts for 1/10~2/3 of reactor volume, ozone intake is determined according to number and the processing requirements of the remaining prussiate in influent quality and COD content, prussiate and COD content are high, processing index request is tight, corresponding the increasing of intake of ozone, otherwise, prussiate and COD content are low, processing index request pine, the corresponding minimizing of intake of ozone.
In described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, and gac is coconut husk charcoal or ature of coal charcoal, and dress charcoal amount accounts for 1/5~4/5 of reactor volume, biofilm bacterial classification is nitrococcus and nitrobacteria, be collected near the topsoil of Tailings Dam, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and vapour-liquid ratio is set as 1~15:1.
Specific examples 1:
Certain gold mine cyanide wastewater, pH is 7.8, CN tfor 113.47mg/L, SCN -for 35.24mg/L, Cu 2+for 82.56mg/L, COD is 187.25mg/L, NH 3-N is 26.55mg/L, contains in addition other heavy metal ion of trace.Getting 3L waste water is placed in the oxidizing reaction groove that stirring system and aerating system are housed, open stirring system, be that under 0.8m/s condition, the sodium hydroxide solution with 1% regulates wastewater pH to 9.0 stirring linear velocity, open aerating system, aeration rate is adjusted into 1L/min, slowly add 10% sodium metabisulfite solution 20mL, reaction 30min, stop aeration, the polymeric aluminum chlorides solution 8mL that adds 10g/L stirs 5min, then add 0.5 ‰ anionic polyacrylamide solution 4mL, after continuing to stir 2min, regulate stirring linear velocity 0.1m/s to stir 5min, stop stirring, leave standstill 15min, the supernatant liquor of 2.8L is pumped in the reactor that gac and ozonation aerated device are housed with peristaltic pump, gac is coconut husk charcoal, loadings is 50g, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, after starting, reaction passes into ozone reaction 30min, ozone intake is 150mg, after finishing, reaction stops passing into ozone, reacted ozone catalytic waste water is pumped in biological activated carbon reactor and is processed with peristaltic pump, biological activated carbon reactor is upflowing bio-reactor, gac adopts column ature of coal charcoal, amount of fill is 2kg, air adopts Ti-alloyed filter element micro-pore aeration, be placed in reactor bottom, vapour-liquid ratio is set as 5:1, bacterial classification adopts and manually adds biofilm, reaction time is 60min.Waste water through system water outlet after treatment through assay pH between 8~9, CN t< 0.1mg/L, SCN -< 0.5mg/L, Cu 2+< 0.5mg/L, COD < 20mg/L, NH 3-N < 1.0mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after processing, water quality can reach reuse or emission standard.
Specific examples 2:
Certain gold mine cyanide wastewater, pH is 7.5, CN tfor 79.58mg/L, SCN -for 83.45mg/L, Cu 2+for 6.39mg/L, Zn 2+for 24.25mg/L, COD is 275.45mg/L, NH 3-N is 32.74mg/L, contains in addition other heavy metal ion of trace.Getting 3L waste water is placed in the oxidizing reaction groove that stirring system and aerating system are housed, open stirring system, be that under 0.8m/s condition, the sodium hydroxide solution with 1% regulates wastewater pH to 9.0 stirring linear velocity, open aerating system, aeration rate is adjusted into 1L/min, slowly add 10% sodium metabisulfite solution 18mL simultaneously, 10% copper-bath 1mL, reaction 30min, stop aeration, the polymeric aluminum chlorides solution 8mL that adds 10g/L stirs 5min, then add 0.5 ‰ anionic polyacrylamide solution 4mL, after continuing to stir 2min, regulate stirring linear velocity 0.1m/s to stir 5min, stop stirring, leave standstill 15min, the supernatant liquor of 2.8L is pumped in the reactor that gac and ozonation aerated device are housed with peristaltic pump, gac is coconut husk charcoal, loadings is 50g, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, after starting, reaction passes into ozone reaction 30min, ozone intake is 180mg, after finishing, reaction stops passing into ozone, reacted ozone catalytic waste water is pumped in biological activated carbon reactor and is processed with peristaltic pump, biological activated carbon reactor is upflowing bio-reactor, gac adopts column ature of coal charcoal, amount of fill is 2kg, air adopts Ti-alloyed filter element micro-pore aeration, be placed in reactor bottom, vapour-liquid ratio is set as 5:1, bacterial classification adopts and manually adds biofilm, reaction time is 60min.Waste water through system water outlet after treatment through assay pH between 8~9, CN t< 0.1mg/L, SCN -< 0.5mg/L, Cu 2+< 0.5mg/L, COD < 20mg/L, NH 3-N < 1.0mg/L, first kind pollutent is all within the highest permission emission concentration limit value, and after processing, water quality can reach reuse or emission standard.

Claims (12)

1. a gold mine Treatment of cyanogen-contained wastewater, the step of the method is as follows:
(1) under stirring and aeration state, in waste water, add acid-base reagent, pyrosulphite sodium reagent and catalyzer, ensure that the pH value of reaction process is controlled between 8~10, the reaction times is 30min~90min;
(2) reacted waste water adds successively flocculation agent and flocculation agent carries out coagulating sedimentation under whipped state, and after coagulation, waste water enters settling tank and staticly settles 15min~120min;
(3) supernatant liquor after precipitation, under gac existence condition, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min~60min;
(4) reacted waste water enters biological activated carbon treatment system, under the condition of active carbon filler, biofilm bacterial classification and air aeration, carries out biological activated carbon processing, and the treatment time is 30min~120min;
(5) supernatant liquor after treatment returns in the technological process of production or qualified discharge.
2. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (1), stirring linear velocity is 0.01m/s~10m/s.
3. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (1), the vapour-liquid ratio that when aeration, air passes into is 3~50:1.
4. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (1), acid-base reagent is sulfuric acid, hydrochloric acid, sodium hydroxide solution or milk of lime.
5. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (1), the sodium metabisulfite solution that pyrosulphite sodium reagent is 5%~30%.
6. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (1), the copper-bath that catalyzer is 5%~30%.
7. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (2), stirring linear velocity is 0.01m/s~10m/s.
8. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (2), 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.
9. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (3), gac is coconut husk charcoal or ature of coal charcoal, and loadings accounts for 1/10~2/3 of reactor volume.
10. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (4), biological activated carbon treatment system is upflowing or downflow system reaction tank, at the bottom of pond, be provided with water-distributing device and aerating apparatus, aerating apparatus top is active carbon filler layer, gac is coconut husk charcoal or ature of coal charcoal, and dress charcoal amount accounts for 1/5~4/5 of reactor volume.
11. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (4), biofilm bacterial classification is nitrococcus and nitrobacteria, be collected near the topsoil of Tailings Dam, bacterial classification biofilm mode takes manually to add bacterial classification biofilm or Biofilmculturing.
12. according to a kind of gold mine Treatment of cyanogen-contained wastewater described in claims 1, it is characterized in that: in described step (4), biological activated carbon treatment system vapour-liquid ratio is set as 1~15:1.
CN201410339685.2A 2014-07-16 2014-07-16 Cyanide-containing wastewater treating method for gold mine Pending CN104071953A (en)

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CN105399237A (en) * 2015-11-11 2016-03-16 紫金矿业集团股份有限公司 Treatment method for copper-containing gold ore cyaniding waste water
CN105502628A (en) * 2015-12-03 2016-04-20 湖南城市学院 Cycling treatment system for low-concentration cyanide-containing wastewater
CN106746065A (en) * 2015-11-24 2017-05-31 湖南衡阳新澧化工有限公司 A kind of method for the treatment of electroplating wastewater by microwave
CN108588439A (en) * 2018-04-09 2018-09-28 中南大学 A kind of method of cyanide in removal cyanide residue
CN109160776A (en) * 2018-09-21 2019-01-08 宁波纯恒固废科技有限公司 A kind of integrated conduct method of the tailing containing arsenic
CN113101591A (en) * 2021-03-17 2021-07-13 东北大学 Cyanide tailing decyanation method based on activated carbon catalytic oxidation

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105000720A (en) * 2015-08-23 2015-10-28 长春黄金研究院 Method for treating cyaniding tailing slurry in gold smelting industry
CN105399237A (en) * 2015-11-11 2016-03-16 紫金矿业集团股份有限公司 Treatment method for copper-containing gold ore cyaniding waste water
CN106746065A (en) * 2015-11-24 2017-05-31 湖南衡阳新澧化工有限公司 A kind of method for the treatment of electroplating wastewater by microwave
CN105502628A (en) * 2015-12-03 2016-04-20 湖南城市学院 Cycling treatment system for low-concentration cyanide-containing wastewater
CN108588439A (en) * 2018-04-09 2018-09-28 中南大学 A kind of method of cyanide in removal cyanide residue
CN109160776A (en) * 2018-09-21 2019-01-08 宁波纯恒固废科技有限公司 A kind of integrated conduct method of the tailing containing arsenic
CN109160776B (en) * 2018-09-21 2021-06-08 宁波纯力固废科技有限责任公司 Comprehensive treatment method of arsenic-containing tailings
CN113101591A (en) * 2021-03-17 2021-07-13 东北大学 Cyanide tailing decyanation method based on activated carbon catalytic oxidation

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