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CN104961272A - Method for treating cyaniding tailing pulp in gold industry - Google Patents

Method for treating cyaniding tailing pulp in gold industry Download PDF

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Publication number
CN104961272A
CN104961272A CN201510330891.1A CN201510330891A CN104961272A CN 104961272 A CN104961272 A CN 104961272A CN 201510330891 A CN201510330891 A CN 201510330891A CN 104961272 A CN104961272 A CN 104961272A
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China
Prior art keywords
dosage
hydrogen peroxide
ozone
reagent
cyanogens
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CN201510330891.1A
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Chinese (zh)
Inventor
兰馨辉
迟崇哲
丁成
邱陆明
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Changchun Gold Research Institute
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Changchun Gold Research Institute
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Priority to CN201510330891.1A priority Critical patent/CN104961272A/en
Publication of CN104961272A publication Critical patent/CN104961272A/en
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Abstract

The invention discloses a method for treating cyaniding tailing pulp in a gold industry. The method comprises the following steps of recycling cyanide which is easy to treat by using an acidizing recovery method; feeding hydrogen peroxide reagent and ferrous reagent in the treated tailing pulp containing cyanogens so as to perform oxidation treatment on the treated tailing pulp; feeding coagulant in the tailing pulp containing the cyanogens; removing heavy metal ions; and performing catalytic oxidation by using ozone and activated carbon so as to remove residual pollutants such as cyanide difficult to treat and thiocyanate in the pulp. The tailing pulp containing the cyanogens in a gold mine is treated deeply by using the acidizing recovery method, a fenton method, a coagulation-sedimentation method and an ozone/activated carbon catalytic oxidation method cooperatively, the treatment effect is high, the treatment efficiency is also high, a system runs stably, a technological process is simple, industrial application is convenient to implement, treated wastewater can return to a technological process of production to serve as reclaimed water or is drained on a standard, and the tailing pulp containing the cyanogens reaches a standard of a class I of common solid wastes.

Description

A kind of gold industry cyaniding tailing slurry treatment process
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly a kind for the treatment of process of gold industry cyaniding tailing slurry.
Background technology
Gold industry is in process of production owing to using Cyanide Process, a large amount of cyaniding tailing slurries can be produced, this part cyaniding tailing slurry is not only containing a certain amount of hypertoxic prussiate, 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 process cyaniding tailing slurry has acidifying absorption method, Pomolio-Celdecor process, Yin Kefa 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 ore pulp, and thiocyanate ion is not all effectively removed with some heavy metal ion.Can remaining a large amount of chlorine residue after Pomolio-Celdecor process process, produce ClCN product, cause secondary pollution problem, the heavy metal ion such as the copper in waste water, zinc, lead fail effectively to be administered, and liquid chlorine etc. has very large environmental risk.Although Yin Kefa 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 lacking more satisfactory method in sludge containing cyanogens process, if resolve this problem, will important meaning had to development China's golden production and environmental protection development.
Summary of the invention
Object of the present invention is exactly the problems referred to above existed for existing treatment process, and provides the sludge containing cyanogens 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 industry sludge containing cyanogens, particularly also comprise unmanageable metal top cradle in prussiate, as iron cyano complex etc., acidifying absorption method is selected first to be reclaimed by tractable prussiate; Sludge containing cyanogens after process carries out oxide treatment by throwing hydrogen peroxide reagent, ferrous iron reagent, then to dosing coagulant in sludge containing cyanogens, and heavy-metal ion removal; Finally adopt ozone and gac to carry out catalyzed oxidation, the pollutant removal such as difficult prussiate, thiocyanate-remaining in ore pulp is fallen.
The present invention includes following steps:
(1) under aeration state, in ore pulp, add the vitriol oil, ensure that the pH value of reaction process controls 2.0 ~ 3.0, the reaction times is 30min ~ 90min;
(2) reacted ore pulp adds alkali conditioning agent, hydrogen peroxide reagent and ferrous iron reagent successively under whipped state, and ensure that in reaction process, pH value controls 3 ~ 4, the reaction times is 5min ~ 10min;
(3) reacted ore pulp adds alkali conditioning agent, flocculation agent successively under whipped state, and ensure that in reaction process, pH value controls 8.0 ~ 9.0, the reaction times is 10min ~ 30min;
(4) reacted ore pulp is under whipped state, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min ~ 60min;
(5) sludge containing cyanogens after process carries out press filtration, and filtrate returns in the technological process of production or qualified discharge, and mine tailings reach Ordinary solid waste I class standard.
In described step (1), the vapour-liquid ratio that during aeration, air passes into is 200 ~ 400:1;
In described step (2), stirring linear velocity is 0.01m/s ~ 10m/s, alkali conditioning agent is milk of lime or sodium hydroxide, hydrogen peroxide reagent is the hydrogen peroxide solution of mass percent 30%, and the dosage of hydrogen peroxide reagent is how many and process index request and determine according to the cyanide content in ore pulp, and cyanide content is high, it is tight to process index request, the dosage of hydrogen peroxide reagent is corresponding to be increased, otherwise cyanide content is low, process index request pine, the corresponding minimizing of dosage of hydrogen peroxide reagent; Ferrous iron reagent is copperas solution, ferrous dosage is determined according to the content of ferrous ion in the dosage of hydrogen peroxide reagent and sludge containing cyanogens, ferrous dosage becomes positive line sexual intercourse with the dosage of hydrogen peroxide reagent, and the ferrous ion content in sludge containing cyanogens partly or entirely can replace the dosage of ferrous iron reagent.
In described step (3), alkali conditioning agent is milk of lime or sodium hydroxide, and flocculation agent is zinc sulfate or ferrous sulfate.
In described step (4), gac is coconut husk charcoal or ature of coal charcoal, activated carbon dosage becomes positive correlation with the content of prussiate in sludge containing cyanogens, ozone intake is determined according to the number of the remaining prussiate in sludge containing cyanogens and COD content and processing requirements, prussiate and COD content is high, process index request is tight, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content is low, process index request pine, the corresponding minimizing of intake of ozone.
Beneficial effect of the present invention:
The present invention is according to, unmanageable feature complicated containing pollutent in gold industry sludge containing cyanogens, acidifying absorption method, Fenton process, coagulant sedimentation and ozone and active carbon catalytic oxidation are combined, work in coordination with and advanced treatment is carried out to gold mine sludge containing cyanogens, treatment effect is good, processing efficiency is high, system run all right, technical process is simple, be convenient to realize industrial application, waste water after process can return the technological process of production and use or qualified discharge as reuse water, and cyanogen-containing tailing slag reaches Ordinary solid waste I class standard.
Embodiment
The present invention includes following steps:
(1) under aeration state, in ore pulp, add the vitriol oil, ensure that the pH value of reaction process controls 2.0 ~ 3.0, the reaction times is 30min ~ 90min;
(2) reacted ore pulp adds alkali conditioning agent, hydrogen peroxide reagent and ferrous iron reagent successively under whipped state, and ensure that in reaction process, pH value controls 3 ~ 4, the reaction times is 5min ~ 10min;
(3) reacted ore pulp adds alkali conditioning agent, flocculation agent successively under whipped state, and ensure that in reaction process, pH value controls 8.0 ~ 9.0, the reaction times is 10min ~ 30min;
(4) reacted ore pulp is under whipped state, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min ~ 60min;
(5) sludge containing cyanogens after process carries out press filtration, and filtrate returns in the technological process of production or qualified discharge, and mine tailings reach Ordinary solid waste I class standard.
In described step (1), the vapour-liquid ratio that during aeration, air passes into is 200 ~ 400:1;
In described step (2), stirring linear velocity is 0.01m/s ~ 10m/s, alkali conditioning agent is milk of lime or sodium hydroxide, hydrogen peroxide reagent is the hydrogen peroxide solution of mass percent 30%, and the dosage of hydrogen peroxide reagent is how many and process index request and determine according to the cyanide content in ore pulp, and cyanide content is high, it is tight to process index request, the dosage of hydrogen peroxide reagent is corresponding to be increased, otherwise cyanide content is low, process index request pine, the corresponding minimizing of dosage of hydrogen peroxide reagent; Ferrous iron reagent is copperas solution, ferrous dosage is determined according to the content of ferrous ion in the dosage of hydrogen peroxide reagent and sludge containing cyanogens, ferrous dosage becomes positive line sexual intercourse with the dosage of hydrogen peroxide reagent, and the ferrous ion content in sludge containing cyanogens partly or entirely can replace the dosage of ferrous iron reagent.
In described step (3), alkali conditioning agent is milk of lime or sodium hydroxide, and flocculation agent is zinc sulfate or ferrous sulfate.
In described step (4), gac is coconut husk charcoal or ature of coal charcoal, activated carbon dosage becomes positive correlation with the content of prussiate in sludge containing cyanogens, ozone intake is determined according to the number of the remaining prussiate in sludge containing cyanogens and COD content and processing requirements, prussiate and COD content is high, process index request is tight, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content is low, process index request pine, the corresponding minimizing of intake of ozone.
Specific examples 1:
Certain gold mining enterprises sludge containing cyanogens, pH is 11.8, CN tfor 1113.47mg/L, SCN -for 1035.24mg/L, Fe 2+for 12.56mg/L, COD are 2587.25mg/L, other heavy metal ion in addition containing trace.Get 3L sludge containing cyanogens to be placed in and to be equipped with in the acidification reaction groove of aerating system, open aerating system, aeration rate is adjusted to 0.9m 3/ h, slowly adds vitriol oil 54mL, reaction times 60min; Stop aeration, adding concentration is that 10% sodium hydroxide solution 15mL stirs 5min, then add the hydrogen peroxide 60mL/L of concentration 30%, concentration is the copperas solution 40mL/L stirring 5min of 10%, and then adding concentration is that 10% sodium hydroxide solution 30mL, zinc sulfate 3g stir 30min; Then with peristaltic pump sludge containing cyanogens is pumped in the reactor that gac and ozonation aerated device are housed, gac is coconut husk charcoal, loadings is 50g, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, pass into ozone reaction 30min after reaction starts, ozone intake is 150mg, and reaction terminates rear stopping and passing into ozone.The water outlet of sludge containing cyanogens 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, and cyanogen-containing tailing slag reaches Ordinary solid waste I class standard.
Specific examples 2:
Certain gold mining enterprises sludge containing cyanogens, pH is 8.5, CN tfor 179.58mg/L, SCN -for 183.45mg/L, Fe 2+for 6.39mg/L, Zn 2+for 24.25mg/L, COD are 475.45mg/L, other heavy metal ion in addition containing trace.Get 3L sludge containing cyanogens to be placed in and to be equipped with in the acidification reaction groove of aerating system, open aerating system, aeration rate is adjusted to 0.9m 3/ h, slowly adds vitriol oil 45mL, reaction times 60min; Stop aeration, adding concentration is that 10% sodium hydroxide solution 15mL stirs 5min, then add the hydrogen peroxide 15mL/L of concentration 30%, concentration is the copperas solution 10mL/L stirring 5min of 10%, and then adding concentration is that 10% sodium hydroxide solution 30mL, zinc sulfate 1g stir 30min; Then with peristaltic pump sludge containing cyanogens is pumped in the reactor that gac and ozonation aerated device are housed, gac is coconut husk charcoal, loadings is 50g, ozonation aerated device adopts titanium alloy micro-hole aerator, be placed in the bottom in reactor, pass into ozone reaction 30min after reaction starts, ozone intake is 100mg, and reaction terminates rear stopping and passing into ozone.The water outlet of sludge containing cyanogens 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, and cyanogen-containing tailing slag reaches Ordinary solid waste I class standard.

Claims (7)

1. a gold industry cyaniding tailing slurry treatment process, the method comprises the following steps:
(1) under aeration state, in ore pulp, add the vitriol oil, ensure that the pH value of reaction process controls 2.0 ~ 3.0, the reaction times is 30min ~ 90min;
(2) reacted ore pulp adds alkali conditioning agent, hydrogen peroxide reagent and ferrous iron reagent successively under whipped state, and ensure that in reaction process, pH value controls 3 ~ 4, the reaction times is 5min ~ 10min;
(3) reacted ore pulp adds alkali conditioning agent, flocculation agent successively under whipped state, and ensure that in reaction process, pH value controls 8.0 ~ 9.0, the reaction times is 10min ~ 30min;
(4) reacted ore pulp is under whipped state, passes into ozone and carries out ozone and active carbon catalytic oxidation, and the reaction times is 15min ~ 60min;
(5) sludge containing cyanogens after process carries out press filtration, and filtrate returns in the technological process of production or qualified discharge, and mine tailings reach Ordinary solid waste I class standard.
2. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, it is characterized in that: in described step (1), the vapour-liquid ratio that during aeration, air passes into is 200 ~ 400:1.
3. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, it is characterized in that: in described step (2), stirring linear velocity is 0.01m/s ~ 10m/s, alkali conditioning agent is milk of lime or sodium hydroxide, hydrogen peroxide reagent is the hydrogen peroxide solution of mass percent 30%, and ferrous iron reagent is copperas solution.
4. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, it is characterized in that: in described step (2), the dosage of hydrogen peroxide reagent is how many and process index request and determining according to the cyanide content in ore pulp, cyanide content is high, process index request is tight, the dosage of hydrogen peroxide reagent is corresponding to be increased, otherwise cyanide content is low, process index request pine, the corresponding minimizing of dosage of hydrogen peroxide reagent; Ferrous dosage is determined according to the content of ferrous ion in the dosage of hydrogen peroxide reagent and sludge containing cyanogens, ferrous dosage becomes positive line sexual intercourse with the dosage of hydrogen peroxide reagent, and the ferrous ion content in sludge containing cyanogens partly or entirely can replace the dosage of ferrous iron reagent.
5. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, it is characterized in that: in described step (3), alkali conditioning agent is milk of lime or sodium hydroxide, and flocculation agent is zinc sulfate or ferrous sulfate.
6. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, is characterized in that: in described step (4), and gac is coconut husk charcoal or ature of coal charcoal.
7. a kind of gold industry cyaniding tailing slurry treatment process according to claim 1, it is characterized in that: in described step (4), activated carbon dosage becomes positive correlation with the content of prussiate in sludge containing cyanogens, ozone intake is determined according to the number of the remaining prussiate in sludge containing cyanogens and COD content and processing requirements, prussiate and COD content is high, process index request tight, the intake of ozone is corresponding to be increased, otherwise, prussiate and COD content is low, process index request pine, the corresponding minimizing of intake of ozone.
CN201510330891.1A 2015-06-16 2015-06-16 Method for treating cyaniding tailing pulp in gold industry Pending CN104961272A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106800332A (en) * 2017-01-16 2017-06-06 东北大学 A kind of method for treating water of utilization slag catalysis ozone
CN106977015A (en) * 2017-04-30 2017-07-25 长春黄金研究院 A kind of sulphur-bearing ore Cyanided gold tailings slurry harmless treatment and tail washings purification method
CN108149027A (en) * 2017-12-08 2018-06-12 长春黄金研究院 A kind for the treatment of agent and take off processing method using the cyanogen-containing tailing wash heat of the medicament
CN110090385A (en) * 2019-05-23 2019-08-06 东北大学 A kind of method of Catalytic Thermal Decomposition removing zinc cyano complex
CN110090386A (en) * 2019-05-23 2019-08-06 东北大学 A kind of method of low-temperature catalytic oxidation Cymag

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030505A (en) * 2014-06-26 2014-09-10 长春黄金研究院 Non-ferrous metal mine flotation wastewater treatment method
CN104445751A (en) * 2015-01-01 2015-03-25 长春黄金研究院 Method for recycling and treating cyanide waste water

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030505A (en) * 2014-06-26 2014-09-10 长春黄金研究院 Non-ferrous metal mine flotation wastewater treatment method
CN104445751A (en) * 2015-01-01 2015-03-25 长春黄金研究院 Method for recycling and treating cyanide waste water

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106800332A (en) * 2017-01-16 2017-06-06 东北大学 A kind of method for treating water of utilization slag catalysis ozone
CN106977015A (en) * 2017-04-30 2017-07-25 长春黄金研究院 A kind of sulphur-bearing ore Cyanided gold tailings slurry harmless treatment and tail washings purification method
CN108149027A (en) * 2017-12-08 2018-06-12 长春黄金研究院 A kind for the treatment of agent and take off processing method using the cyanogen-containing tailing wash heat of the medicament
CN110090385A (en) * 2019-05-23 2019-08-06 东北大学 A kind of method of Catalytic Thermal Decomposition removing zinc cyano complex
CN110090386A (en) * 2019-05-23 2019-08-06 东北大学 A kind of method of low-temperature catalytic oxidation Cymag

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Application publication date: 20151007