CN104445842A - Cyanide waste water comprehensive recovery treatment method - Google Patents
Cyanide waste water comprehensive recovery treatment method Download PDFInfo
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- CN104445842A CN104445842A CN201510003424.8A CN201510003424A CN104445842A CN 104445842 A CN104445842 A CN 104445842A CN 201510003424 A CN201510003424 A CN 201510003424A CN 104445842 A CN104445842 A CN 104445842A
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Abstract
The invention discloses a cyanide waste water comprehensive recovery treatment method. The method is composed of a resin adsorption method, an ozone oxidation method, a coagulant-sedimentation method and the biological filter treatment technology. When cyanide waste water is treated, firstly, resin is selected and used for adsorbing and recovering cyanide in the waste water, ozone is delivered to the adsorbed waste water for 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, supernate obtained after sedimentation is treated through a biological filter treatment system, 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 ozone oxidation method, the coagulant-sedimentation method and the biological filter treatment technology are combined together to collaboratively conduct deep treatment on the cyanide waste water of a gold production enterprise, the cyanide waste water comprehensive 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 synthetical recovery treatment process.
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 the cyanide wastewater synthetical recovery treatment process that a kind of 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 passes into ozone and carries out oxide treatment, 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 biological filter chamber treatment system 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 ozone treating system, and pass into ozone and carry out oxide treatment, 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 biological filter chamber treatment system, under the condition of biologic packing material, biofilm bacterial classification and air aeration, carry out a biological disposal upon;
(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), ozone intake is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of intake of ozone.
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.
In described step (5), biological filter chamber treatment system is upflowing reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, be gac, zeolite or biological potsherd filling layer above aerating apparatus, loadings accounts for 1/5 ~ 4/5 of reactor volume, biofilm bacterial classification is for falling cyanogen flora, comprise Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocardia bacteria, genus bacillus etc., to be collected near Tailings Dam in topsoil, 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 high according to the Cyanide in Cyanide Wastewater concentration produced in golden production process, pollutant kind is complicated, unmanageable feature, resin adsorption method, Ozonation, coagulant sedimentation and biological filter treatment technology 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 ozone treating system, and pass into ozone and carry out oxide treatment, 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 biological filter chamber treatment system, under the condition of biologic packing material, biofilm bacterial classification and air aeration, carry out a biological disposal upon;
(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), ozone intake is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of intake of ozone.
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.
In described step (5), biological filter chamber treatment system is upflowing reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, be gac, zeolite or biological potsherd filling layer above aerating apparatus, loadings accounts for 1/5 ~ 4/5 of reactor volume, biofilm bacterial classification is for falling cyanogen flora, comprise Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocardia bacteria, genus bacillus etc., to be collected near Tailings Dam in topsoil, 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 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 ozone-oxidizing device, ozone-oxidizing device interior bottom portion is provided with ceramic micropore aerator, open ozonizer, pass into ozone reaction 30min, ozone intake is 850mg, 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 biological filter chamber treatment system and processes, biological filter chamber treatment system adopts upflowing, filling filler is particulate coal activated carbon, loadings is 5kg, air aeration device adopts Ti-alloyed filter element, be placed in reactor bottom, vapour-liquid ratio is set as 3:1, reactor carries out biofilm by manually adding bacterial classification, the waste water reaction residence time is 60min.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 ozone-oxidizing device, ozone-oxidizing device interior bottom portion is provided with ceramic micropore aerator, open ozonizer, pass into ozone reaction 30min, ozone intake is 550mg, 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 biological filter chamber treatment system and processes, biological filter chamber treatment system adopts upflowing, filling filler is particulate coal activated carbon, loadings is 5kg, air aeration device adopts Ti-alloyed filter element, be placed in reactor bottom, vapour-liquid ratio is set as 3:1, reactor carries out biofilm by manually adding bacterial classification, the waste water reaction residence time is 60min.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 (7)
1. a cyanide wastewater synthetical recovery treatment process, 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 ozone treating system, and pass into ozone and carry out oxide treatment, 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 biological filter chamber treatment system, under the condition of biologic packing material, biofilm bacterial classification and air aeration, carry out a biological disposal upon;
(6) waste water after, having processed returns in the technological process of production or qualified discharge.
2. a kind of cyanide wastewater synthetical recovery treatment process 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 synthetical recovery treatment process 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 synthetical recovery treatment process according to claim 1, it is characterized in that: in described step (3), ozone intake is determined according to the number of the prussiate in waste liquid and COD content, prussiate and COD content high, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content low, the corresponding minimizing of intake of ozone.
5. a kind of cyanide wastewater synthetical recovery treatment process 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.
6. a kind of cyanide wastewater synthetical recovery treatment process according to claim 1, it is characterized in that: in described step (5), biological filter chamber treatment system is upflowing reaction tank, water-distributing device and aerating apparatus is provided with at the bottom of pond, be gac, zeolite or biological potsherd filling layer above aerating apparatus, loadings accounts for 1/5 ~ 4/5 of reactor volume, biofilm bacterial classification is for falling cyanogen flora, to be collected near Tailings Dam in topsoil, bacterial classification biofilm mode is taked manually to add bacterial classification biofilm or Biofilmculturing, and vapour-liquid ratio is set as 1 ~ 15:1.
7. a kind of cyanide wastewater synthetical recovery treatment process according to claim 6, is characterized in that: the described cyanogen flora that falls includes Pseudomonas fluorescens, pseudomonas putida, Pseudomonas stutzeri, Nocardia bacteria and genus bacillus.
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Cited By (5)
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|---|---|---|---|---|
| CN104944695A (en) * | 2015-06-12 | 2015-09-30 | 长春黄金研究院 | Emergency treatment method for goldmine tailing pond accident wastewater |
| CN106242188A (en) * | 2016-08-31 | 2016-12-21 | 南京河海环境研究院有限公司 | Effluent treatment plant |
| CN110683720A (en) * | 2019-11-21 | 2020-01-14 | 重庆化医长寿化工集团有限公司 | Method for treating sulfanilamide mother liquor |
| CN111494866A (en) * | 2020-05-10 | 2020-08-07 | 浙江澄宇环保新材料股份有限公司 | Process for screening and repairing tailing slag |
| CN114011843A (en) * | 2021-11-12 | 2022-02-08 | 长春黄金研究院有限公司 | Method for treating cyanide-containing wastewater by utilizing cyanide tailings |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944695A (en) * | 2015-06-12 | 2015-09-30 | 长春黄金研究院 | Emergency treatment method for goldmine tailing pond accident wastewater |
| CN106242188A (en) * | 2016-08-31 | 2016-12-21 | 南京河海环境研究院有限公司 | Effluent treatment plant |
| CN110683720A (en) * | 2019-11-21 | 2020-01-14 | 重庆化医长寿化工集团有限公司 | Method for treating sulfanilamide mother liquor |
| CN111494866A (en) * | 2020-05-10 | 2020-08-07 | 浙江澄宇环保新材料股份有限公司 | Process for screening and repairing tailing slag |
| CN111494866B (en) * | 2020-05-10 | 2021-07-23 | 浙江澄宇环保新材料股份有限公司 | Process for screening and repairing tailing slag |
| CN114011843A (en) * | 2021-11-12 | 2022-02-08 | 长春黄金研究院有限公司 | Method for treating cyanide-containing wastewater by utilizing cyanide tailings |
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