CN102464414A - Method of removing total cyanide in sewage by using ionic transformation and oxidative disassembling - Google Patents
Method of removing total cyanide in sewage by using ionic transformation and oxidative disassembling Download PDFInfo
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- CN102464414A CN102464414A CN2010105317240A CN201010531724A CN102464414A CN 102464414 A CN102464414 A CN 102464414A CN 2010105317240 A CN2010105317240 A CN 2010105317240A CN 201010531724 A CN201010531724 A CN 201010531724A CN 102464414 A CN102464414 A CN 102464414A
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Abstract
The invention discloses a method of removing total cyanide in sewage and especially relates to a method of removing total cyanide in sewage by using ionic transformation and oxidative disassembling, which belongs the field of environmental protection. According to the method, based on chemical characteristics of different cyanogen compounds, different removing technologies are used for a variety of cyanides of different forms; that is, a two-stage progressive SIF method of strong ionic transformation and targeted breaking is adopted for free cyanogen, high-concentration complicated cyano complexes, complex derivatives hard to degrade and coupled cyanogen; the method enables a breaking rate of total cyanogen in cyanogen-containing waste water produced by industries related to cyanogen to reach 99.99%, thereby allowing the cyanogen-containing waste water to stably meet or be superior to level 1 discharge standard as prescribed in Integrated Wastewater Discharge Standard (GB8978-1996). The method is applicable to treatment of cyanide pollutants in waste water produced and discharged in a plurality of industries, e.g., mining and mineral separation, metallurgy, mechanical processing, electroplating, chemical engineering and leather making, and has industrial popularization and application prospects.
Description
Technical field
The present invention relates to a kind of method of removing total cyanogen in the sewage, relate in particular to a kind of ion that utilizes and transform the method for disassembling total cyanogen in the method removal sewage with oxidation, belong to field of environment protection.
Background technology
Although prussiate belongs to hypertoxic acute harmful substances, very harmful with production waste discharge entering water or air ambient to people and animals' living safety, belong to national strict control Chemicals.But reality also has quite a lot of industry such as metallurgy in producing at present, and selecting and purchasing is electroplated, chemical industry, and machining, rubber, process hides, many industries such as pharmacy are owing to the waste that production needs to contain prussiate enters in the water.Utilization to water when producing such as the choosing gold is 1: 3 approximately, promptly when one ton of Gold Ore entering selecting and purchasing process, just needs 3 tons of water.The small-sized factory that selects with 500 tons in day ore dressing stone estimates that producing needed fresh water every day is 1500 tons at least just.Because production process does not have the damage by water consumption basically, is 1500 tons basically so discharge cyanide wastewater every day.When cyanogen content is 90mg/L in detecting such water, contain the about 135000mg of cyanogen total amount in the 1500L water, get into sewage and receive the sewage body.Accumulation harm is self-evident to water body safety.Along with people's is thoroughly handled very urgent to the pay attention to day by day of environment protection to it.In recent years, people take multiple measure that prussiate is administered, like natural degradation method, acid volatilization method, alkaline chlorination process, flocculent precipitation, Yin Kefa, ozone method, hypochlorite oxidation method, biological oxidation process etc.Although above-mentioned many technological methods have his own strong points, in practical application, there are many defectives.Be summarized as follows: the simple cyanogen under the unbound state can only be handled in (1), and high density, difficult degradation, the complicated component cyanogen that various ways is existed then is difficult to thoroughly, overall treatment.Especially of a great variety to the complex compound of cyanogen, conjugates, verivate etc., in conjunction with closely, the prussiate that is difficult to abolish is powerless basically, makes treatment effect be difficult to satisfy the actual needs of national environmental protection emission request and enterprise governance pollution.For example: 1. owing to the complicacy and the polytropy of prussiate kind, its reductibility and oxidisability have huge difference, simple oxidation style (alkaline liquid chlorine method, H
2O
2, NaClO, O
3Deng) can only abolish the stronger prussiate of partial reduction property, final oxidation effectiveness is often undesirable also unstable; 2. the ferrous sulfate flocculent precipitation cyanogen root that dissociates out easily; 3. Yin Kefa is to the verivate poor of sulphur cyanogen and cyanogen; 4. the immature instability of biochemical process.
(2) working cost is high, and treatment facility is built up with not rising, and is difficult to satisfy the dual needs that industry energy conservation reduces discharging.
(3) technological adaptability is poor, generally is difficult to cyaniding Pollutant levels in the water yield and the water, composition is different changes.In case cyaniding Pollutant levels, composition change in water displacement and the water, it is unstable operation promptly to occur, and emission concentration changes increasing.Formed thus and contained the technical bottleneck that the processing of cyanogen pollutant effluents is difficult to crack.Make such waste water can not get better processing for a long time, serious environment pollution, harm people and animals living safety.Also restrict the development of such enterprise thus.What application was comparatively general at present is alkali formula chlorination facture; Although possible in theory, research trial result and application practice prove that this technical finesse cost is up to 30 yuan/ton; The total cyanogen content of water outlet surpasses state emission standard value 5-20 doubly still at 3-10mg/l.
Technological deficiencies such as (4) prior art ubiquity facility floor space is big, and technical process is long, and level of automation is low, and is not easy to operate.
Therefore, the technology that breaks traditions thoroughly becomes and changes, and it is extremely urgent to research and develop out that processing is effective, cost is low, easy to operate, stable cyanide wastewater is efficiently handled new technology.
Summary of the invention
To the prior art situation, the object of the invention is to provide that a kind of treatment effect is good, expense is low, stable, reliable, efficiently, meets the cyanide wastewater New Method for Processing of energy-saving and emission-reduction developing direction.Thoroughly break cyanide wastewater Treatment Technology bottleneck, effectively protect water surrounding and edatope to avoid cyanide pollution.
For realizing the object of the invention, choose following technical scheme:
Chemical property according to different cyanogen binding substancess in the waste water; Prussiate to various multi-form existence adopts different removal technology, and the unique new design of promptly taking " powerful ion conversion " and " abolishing targetedly " secondary to go forward one by one to free cyanogen, the complicated complexing cyanogen of high density, the complicated verivate of difficult degradation and coupling cyanogen is the SIF method.
At first adopt one-level ion conversion method that free cyanogen, complicated cyanogen, complexing cyanogen and difficult cyanogen verivate, the conjugates that cracks in the sewage are carried out pre-treatment: to add 0.3-0.5kg aluminium salt in the sewage per ton; And adjustment sewage pH value is to 8.0-9.5; The cyanide ion that mainly is different shape in aluminum ion and the sewage that utilizes in the aluminium salt generates the aluminium cyano complex, accomplishes the conversion process to different shape cyanogen complicated and changeable.On the other hand, reaction such as aluminum ion and complexing cyanogen generates deposition and removes; Next utilizes aluminium salt compression double electric layer, adsorption bridging and net to catch that volume such as sweeps at principle and the verivate, conjugates etc. of removing the cyanogen that difficulty cracks carry out brute force and sink altogether.Adopting second stage sulfurous gas air method pointedly the aluminium cyano complex to be carried out oxidation then disassembles: add S-WAT or Sodium Pyrosulfite; Dosage is 0.2-0.5g/l, is exactly need not add expensive heavy metal ion copper sulfate as catalyzer with the important different of traditional sulfurous gas air method.Adopting the blast aeration mode to carry out the catalyzed oxidation completion at last finally cracks.Water outlet can reach below the 0.5mg/l, reaches the GB requirement.
Described aluminium salt is flocculation agents such as Tai-Ace S 150, aluminium chlorohydroxide.
This SIF technological method innovative point is: the aluminium salt action that is added is to utilize aluminum ion and cyanogen root to react, and forms new aluminium cyano complex, accomplishes the IX to most cyanogen roots in the sewage.Impelling the cyanogen root of multiple different shape to change into the aluminium cyano complex through the ion conversion process, is present technique core place.Whole exchange process only needs the one-level deposition to accomplish.Then utilize the sulfurous gas atmospheric oxidation to abolish the aluminium cyano complex in the sewage pointedly; And need not add expensive catalyst sulfuric acid copper; And the consumption of sulfurous gas is descended significantly; (consumption is about the half the of traditional oxidizing sulfur dioxide technology), its effect inverse ratio traditional technology is obviously good a lot.SIF method Treatment of Cyanide-containing Wastewater two-stage process is inseparable.The leading portion conversion is prerequisite and the basis that back segment is thoroughly abolished, and back segment is that the strong of leading portion replenishes.
Beneficial effect of the present invention: (1) makes and relates to the cyanogen industry and produce in the cyanide wastewater total cyanogen and abolish rate and reach 99.99%, stable reach or excellent being better than " integrated wastewater discharge standard " (GB8978-1996) first discharge standard.Standard value: 0.5mg/l, best water outlet result is superior to 10 times of standard values;
(2) saving energy and cost is handled 28 yuan/t of average cost by conventional art at present and is dropped to about 3.62 yuan/t, is merely 1/5 of conventional art; Some technological range of decrease can be up to 90% relatively;
(3) compared with prior art, can reduce power-equipment 3/4, reduce construction investment 1/3, reduce power consumption 90%.
(4) adopt the waste water after this method is handled to meet the process water specification of quality fully, be back to use production technique, reach waste water " zero " discharging, practice thrift the fresh water of equivalent simultaneously.
This method can be applicable to selecting and purchasing, metallurgy, and mechanical workout is electroplated chemical industry, the improvement of cyaniding pollutent in the multiple industry production waste discharge such as process hides, environmental protection.
The present invention and existing various technological method comparative results such as following table:
Description of drawings
Fig. 1 process flow diagram of the present invention;
Embodiment
For the present invention is better explained, it is following to lift embodiment:
100 tons of cyanide wastewater of certain Mining Limited Company are handled; At first adding yellow soda ash adjustment pH is 8.5; Add 30kg Tai-Ace S 150, through the heavy altogether scheduling theory of IX, chemical precipitation and flocculation, the heavy altogether triple role of performance IX and chemical precipitation, flocculation; Most of prussiate is changed into the aluminium cyano complex get into the second stage; Add S-WAT 30kg then, targetedly the water inlet prussiate is carried out deep oxidation and handle, reach the purpose of removing residue cyanogen; Adopting the blast aeration mode to carry out the catalyzed oxidation completion at last finally cracks.The result shows: handle the total sewage draining exit cyanide content 0.089-0.256mg/l (excellent standard value one one magnitude that is better than) in back, show that fully this Technology is stable except that the good and effluent quality of cyanogen effect.Has the industrialization promotion application prospect.
Before and after cyanide wastewater is handled, composition, content detection comparison result such as following table:
| Period | Contain cyanogen concentration (mg/L) | Clearance |
| Before the processing | 94.4 | —— |
| After the processing | 0.089-0.256 | More than 99.7% |
Claims (3)
1. one kind is utilized ion to transform the method for disassembling total cyanogen in the method removal sewage with oxidation; It is characterized in that; At first adjust sewage pH value to 8.0-9.5, adopt one-level ion conversion method to add free cyanogen in the aluminium salt pair sewage, complicated cyanogen, complexing cyanogen and difficult cyanogen verivate, the conjugates that cracks and carry out pre-treatment; Add S-WAT or Sodium Pyrosulfite then, adopt second stage sulfurous gas air method pointedly the aluminium cyano complex to be carried out oxidation and disassemble; Adopting the blast aeration mode to carry out the catalyzed oxidation completion at last finally cracks.
2. the method for total cyanogen is characterized in that described aluminium salt is Tai-Ace S 150, aluminium chlorohydroxide in the removal sewage as claimed in claim 1; Add 0.3-0.5kg aluminium salt in the sewage per ton.
3. the method for total cyanogen in according to claim 1 or claim 2 the removal sewage is characterized in that S-WAT or Sodium Pyrosulfite dosage are 0.2-0.5g/l.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935240A (en) * | 2017-11-28 | 2018-04-20 | 贵州锦丰矿业有限公司 | A kind of SO2The method of/Air method complexed-precipitation method Combined Treatment cyanide gold-leaching Tailings Slurries and waste water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085192A (en) * | 1992-09-29 | 1994-04-13 | 赵永新 | The preparation of high-efficiency compound water purifying agent and application thereof |
| CN101186405A (en) * | 2007-12-04 | 2008-05-28 | 甘晓明 | Closed circulation processing technique for cyanide-containing waste water |
| JP2008273994A (en) * | 2006-10-18 | 2008-11-13 | Murakashi Sekkai Kogyo Kk | Composition for insolubilizing harmful substance |
| CN101723503A (en) * | 2009-12-16 | 2010-06-09 | 暨南大学 | Organic-inorganic compound high-efficient decolorizing flocculant and preparation method and application thereof |
-
2010
- 2010-11-04 CN CN201010531724.0A patent/CN102464414B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085192A (en) * | 1992-09-29 | 1994-04-13 | 赵永新 | The preparation of high-efficiency compound water purifying agent and application thereof |
| JP2008273994A (en) * | 2006-10-18 | 2008-11-13 | Murakashi Sekkai Kogyo Kk | Composition for insolubilizing harmful substance |
| CN101186405A (en) * | 2007-12-04 | 2008-05-28 | 甘晓明 | Closed circulation processing technique for cyanide-containing waste water |
| CN101723503A (en) * | 2009-12-16 | 2010-06-09 | 暨南大学 | Organic-inorganic compound high-efficient decolorizing flocculant and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935240A (en) * | 2017-11-28 | 2018-04-20 | 贵州锦丰矿业有限公司 | A kind of SO2The method of/Air method complexed-precipitation method Combined Treatment cyanide gold-leaching Tailings Slurries and waste water |
| CN107935240B (en) * | 2017-11-28 | 2023-10-24 | 贵州锦丰矿业有限公司 | SO (SO) device 2 Method for treating cyanide gold leaching tailing pulp and wastewater by combining Air method and complex precipitation method |
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