CN104445750B - A kind of cyanide wastewater recycling and administration method - Google Patents
A kind of cyanide wastewater recycling and administration method Download PDFInfo
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- CN104445750B CN104445750B CN201510003443.0A CN201510003443A CN104445750B CN 104445750 B CN104445750 B CN 104445750B CN 201510003443 A CN201510003443 A CN 201510003443A CN 104445750 B CN104445750 B CN 104445750B
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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
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
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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
- 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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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of cyanide wastewater recycling and administration method, the method is made up of resin adsorption method, advanced oxidation processes, coagulant sedimentation and active carbon adsorption, cyanide wastewater is when processing, first select resin that the cyanide in waste water carries out absorption to reclaim, waste water after absorption adds oxidant and catalyst carries out advanced oxidation process, waste water after oxidation removes the pollutant such as suspended particulate substance, heavy metal ion in waste water by coagulating sedimentation, and the supernatant after precipitation uses activated carbon adsorption to remove pollutant remaining in waste water.The present invention is high according to the Cyanide in Cyanide Wastewater concentration produced during golden production, pollutant kind feature complicated, intractable, resin adsorption method, advanced oxidation processes, coagulant sedimentation and active carbon adsorption are combined, collaborative cyanide wastewater carries out advanced treating, have high treating effect, treatment effeciency height, system run all right, technological process is simple, facilitate implementation the advantages such as commercial Application, and the waste water after process can return to the technological process of production and uses as recycled water or qualified discharge.
Description
Technical field
The present invention relates to field of Environment Protection Pollutant Treatment method, particularly to a kind of cyanide wastewater recycling and administration
Method.
Background technology
Gold manufacturing enterprises owing to using Cyanide Process, can produce substantial amounts of containing cyanogen in process of production
Waste water, does not contain only substantial amounts of severe toxicity cyanide in these waste water, but also containing rhodanate and copper,
The heavy metal ion of zinc, lead etc, if can not get effectively processing, it will produce great environmental protection hidden
Suffer from.At present, both at home and abroad the method for conventional Treatment of Cyanide-containing Wastewater have acidifying absorption method, Pomolio-Celdecor process, Yin Kefa,
Sulfur dioxide methods etc., although using acidifying absorption method can reclaim a certain amount of cyanide, but owing to reclaiming
Cyanide is not thorough, can remaining a certain amount of cyanide, simultaneously thiocyanate radical and some heavy metals in waste water
Ion is the most effectively removed.The remaining substantial amounts of chlorine residue of meeting after Pomolio-Celdecor process process, produces ClCN and produces
Thing, causes secondary pollution problem, and the heavy metal ion such as the copper in waste water, zinc, lead fails to be had simultaneously
The improvement of effect.Although Yin Kefa and sulfur dioxide method can make cyanid up to standard, but the sulfur cyanogen in waste water
Hydrochlorate fails to be processed, additionally, the waste residue produced during processing heavy metal is the most more, easily causes
Secondary pollution.Therefore, in terms of to cyanide wastewater process, the most still lack more satisfactory method, if solving
This problem the best, will have weight to the sustainable development of China's gold industry and the environmental conservation of gold mine
The meaning wanted.
Summary of the invention
The purpose of the present invention is aiming at the problems referred to above that existing processing method exists, and provides a kind of technique
The cyanide wastewater recycling and administration method that flow process is simple, high treating effect, treatment effeciency are high, stable.
The present invention is according to multiple containing cyanide, rhodanate and heavy metal etc. in gold manufacturing enterprises cyanide wastewater
The feature of pollutant, first selects resin that the cyanide in waste water carries out absorption and reclaims, giving up after absorption
Water adds oxidant and catalyst carries out advanced oxidation process, and the waste water after oxidation is removed by coagulating sedimentation
The pollutant such as suspended particulate substance, heavy metal ion in waste water, the supernatant after precipitation uses activated carbon adsorption
Remove pollutant remaining in waste water.Concrete technology step of the present invention is as follows:
(1), by cyanide wastewater pumping 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, at temperature 30～40 DEG C of bars
Under part, being passed through air and carry out being acidified stripping process, the gas sodium hydroxide solution of stripping absorbs,
Absorbing liquid returns in golden production technological process, and the resin after pickling carries out Regeneration Treatment, is then fed into tree
In fat adsorption column；
(3) cyanide wastewater, after resin absorption enters advanced oxidation processing system, adds oxidant and urges
Agent carries out oxidation processes, and the process time is 0.25～2h；
(4), the waste water after oxidation reaction adds flocculating agent under stirring successively and flocculant mixes
Retrogradation is formed sediment, and after coagulation, waste water enters sedimentation tank and staticly settles 0.25～2h；
(5), precipitation after supernatant enter activated carbon processing system, carry out activated carbon adsorption process, place
The reason 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 is sulphuric acid or hydrochloric acid solution, pH value between 2～3, air,
The gas-liquid-solid of pickle and resin is than being (100～5000): (2～10): 1.
In described step (3), oxidant is hydrogen peroxide solution and the ozone of 30%～50%, and catalyst is
Copper-bath, depending on the dosage of the oxidant number according to the cyanide in waste liquid and COD content,
Cyanide and COD content are high, and oxidant dosage increases accordingly, otherwise, cyanide and COD content
Low, oxidant dosage reduces accordingly.
In described step (4), flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is polyacrylamide,
Flocculating agent and flocculant are all configured to solution state and add.
Beneficial effects of the present invention:
The present invention is high according to the Cyanide in Cyanide Wastewater concentration produced during golden production, pollute species
Class feature complicated, intractable, by resin adsorption method, advanced oxidation processes, coagulant sedimentation and activated carbon
Absorption method combines, and works in coordination with and cyanide wastewater is carried out advanced treating, have high treating effect, process
Efficiency height, system run all right, technological process is simple, facilitate implementation the advantages such as commercial Application, after process
Waste water can return to the technological process of production and use as recycled water or qualified discharge.
Detailed description of the invention
The present invention comprises the following steps:
(1), by cyanide wastewater pumping 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, at temperature 30～40 DEG C of bars
Under part, being passed through air and carry out being acidified stripping process, the gas sodium hydroxide solution of stripping absorbs,
Absorbing liquid returns in golden production technological process, and the resin after pickling carries out Regeneration Treatment, is then fed into tree
In fat adsorption column；
(3) cyanide wastewater, after resin absorption enters advanced oxidation processing system, adds oxidant and urges
Agent carries out oxidation processes, and the process time is 0.25～2h；
(4), the waste water after oxidation reaction adds flocculating agent under stirring successively and flocculant mixes
Retrogradation is formed sediment, and after coagulation, waste water enters sedimentation tank and staticly settles 0.25～2h；
(5), precipitation after supernatant enter activated carbon processing system, carry out activated carbon adsorption process, place
The reason 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 is sulphuric acid or hydrochloric acid solution, pH value between 2～3, air,
The gas-liquid-solid of pickle and resin is than being (100～5000): (2～10): 1.
In described step (3), oxidant is hydrogen peroxide solution and the ozone of 30%～50%, and catalyst is
Copper-bath, depending on the dosage of the oxidant number according to the cyanide in waste liquid and COD content,
Cyanide and COD content are high, and oxidant dosage increases accordingly, otherwise, cyanide and COD content
Low, oxidant dosage reduces accordingly.
In described step (4), flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is polyacrylamide,
Flocculating agent and flocculant are all configured to solution state and add.
Instantiation 1:
Certain gold mine cyanide wastewater, pH is 10.8, CNTFor 657.26mg/L, SCN—For 176.56mg/L,
Cu2+For 123.42mg/L, Fe3+It is 870.28mg/L for 48.45mg/L, COD, additionally contains trace
Other heavy metal ion.5L cyanide wastewater is pumped into resin absorbing column and carries out adsorption treatment, in resin absorbing column
Filling strong alkalinity anion adsorbent resin, waste water adsorbent hydroxyl aluminum is 2h, and the waste water after absorption is placed in senior
In oxidation treatment device, advanced oxidation processing means interior bottom portion is provided with ceramic micropore aerator, and top is provided with and adds
Pencil, adds the hydrogen peroxide solution 20mL of 30% in advanced oxidation processing means, opens ozonator,
Being passed through ozone reaction 30min from ceramic micropore aerator, ozone intake is 450mg, and reaction stops after terminating
It is passed through ozone, waste water is moved in agitator tank, open stirring, add under the conditions of stirring linear velocity is 0.8m/s
The polymeric aluminum chlorides solution 15mL of 10g/L stirs 5min, then adds 0.5 ‰ PAMA solution
5mL, continues regulation stirring linear velocity 0.1m/s stirring 5min after stirring 2min, stops stirring, stand 30min,
Being moved in activated carbon processing system by supernatant with peristaltic pump and carry out adsorption treatment, activated carbon is that granule ature of coal is lived
Property charcoal, adsorption time is 30min.Waste water through system process after water outlet through assay pH 8～9 it
Between, CNT＜ 0.1mg/L, SCN—＜ 0.5mg/L, Cu2+＜ 0.5mg/L, COD ＜ 20mg/L, the first kind
Pollutant are all within the highest permission concentration of emission limit value, and after process, water quality can reach reuse or discharge standard.
Instantiation 2:
Certain gold mine contains cyanogen, and pH is 10.2, CNTFor 365.42mg/L, SCN—For 123.78mg/L,
Cu2+For 25.43mg/L, Fe3+For 57.55mg/L, Zn2+It is 498.69mg/L for 14.43mg/L, COD,
Additionally contain other heavy metal ion of trace.5L cyanide wastewater is pumped into resin absorbing column carry out at absorption
Reason, fills strong alkalinity anion adsorbent resin in resin absorbing column, waste water adsorbent hydroxyl aluminum is 2h, absorption
After waste water be placed in advanced oxidation processing means, advanced oxidation processing means interior bottom portion be provided with ceramic capillary expose
Gas device, top is provided with chemical feed pipe, adds the hydrogen peroxide solution 20mL of 30% in advanced oxidation processing means,
The copper-bath 1mL of 5%, opens ozonator, is passed through ozone reaction 30min from ceramic micropore aerator,
Ozone intake is 350mg, and reaction stops being passed through ozone after terminating, and is moved into by waste water in agitator tank, and unlatching is stirred
Mixing, the polymeric aluminum chlorides solution 15mL adding 10g/L under the conditions of stirring linear velocity is 0.8m/s stirs 5min,
Then add 0.5 ‰ PAMA solution 5mL, continue regulation stirring linear velocity after stirring 2min
0.1m/s stirs 5min, stops stirring, stands 30min, with peristaltic pump, supernatant is moved into activated carbon and processes
Carrying out adsorption treatment in system, activated carbon is particulate coal activated carbon, and adsorption time is 30min.Waste water passes through
System process after water outlet through assay pH between 8～9, CNT＜ 0.1mg/L, SCN—＜ 0.5mg/L,
Cu2+＜ 0.5mg/L, Zn2+＜ 1mg/L, COD ＜ 20mg/L, first kind pollutant all allow discharge the highest
Within concentration limit, after process, water quality can reach reuse or discharge standard.
Claims (4)
1. a cyanide wastewater recycling and administration method, the step of the method is as follows:
(1), by cyanide wastewater pumping 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, at temperature 30～40 DEG C of bars
Under part, being passed through air and carry out being acidified stripping process, the gas sodium hydroxide solution of stripping absorbs,
Absorbing liquid returns in golden production technological process, and the resin after pickling carries out Regeneration Treatment, is then fed into tree
In fat adsorption column；
(3), the cyanide wastewater after resin absorption enters advanced oxidation processing system, advanced oxidation process dress
Putting interior bottom portion and be provided with ceramic micropore aerator, top is provided with chemical feed pipe, opens ozonator, from pottery
Porcelain micro-hole aerator is passed through oxidant, adds catalyst and carry out oxidation processes in advanced oxidation processing means；
The process time is 0.25～2h；
(4), the waste water after oxidation reaction adds flocculating agent and flocculation under stirring successively to agitator tank
Agent carries out coagulating sedimentation, and after coagulation, waste water enters sedimentation tank and staticly settles 0.25～2h；
(5), precipitation after supernatant with peristaltic pump move into activated carbon processing system, carry out activated carbon adsorption
Processing, the process time is 0.5～3h；
(6) waste water after, having processed returns in the technological process of production or qualified discharge.
A kind of cyanide wastewater recycling and administration method the most according to claim 1, it is characterised in that: institute
Stating in step (1), resin is strongly basic anionic resin.
A kind of cyanide wastewater recycling and administration method the most according to claim 1, it is characterised in that: institute
State in step (3), the dosage of oxidant according to the cyanide in waste liquid and the number of COD content and
Fixed, cyanide and COD content are high, and oxidant dosage increases accordingly, otherwise, cyanide and COD
Content is low, and oxidant dosage reduces accordingly.
A kind of cyanide wastewater recycling and administration method the most according to claim 1, it is characterised in that: institute
Stating in step (4), flocculating agent is polymer-inorganic salt flocculating agent, and flocculant is polyacrylamide, flocculating agent
All it is configured to solution state to add with flocculant.
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| 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 |
| 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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| US4189381A (en) * | 1978-09-07 | 1980-02-19 | Amax Inc. | Waste water treatment |
| CN1055903C (en) * | 1996-06-11 | 2000-08-30 | 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 |
| CN104193123B (en) * | 2014-09-29 | 2016-05-18 | 长春黄金研究院 | A kind of gold mine cyanide wastewater system processing method |
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