CN109534556A - A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency - Google Patents
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency Download PDFInfo
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- CN109534556A CN109534556A CN201811592231.0A CN201811592231A CN109534556A CN 109534556 A CN109534556 A CN 109534556A CN 201811592231 A CN201811592231 A CN 201811592231A CN 109534556 A CN109534556 A CN 109534556A
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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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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/545—Silicon compounds
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- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
Abstract
The invention discloses a kind of processing methods of the cyanide wastewater of iron content Zn-ef ficiency, the ferrous sulfate of 7-8 times of cyanogen root weight is added in the cyanide wastewater containing iron, Zn-ef ficiency, acid adding adjusts wastewater pH to 5-6.5, adds flocculant stirring 0.5-2h, filtering, takes filtrate；Mantoquita and modification infusorial earth or modified zeolite are added in filtrate, stirs 0.5-2h, filtering, gained filter residue is acidified through sulfuric acid again, stripping, and remaining waste residue is stacked or recycling copper again after recovery of cyanide；Filtrate adjusts pH to 7.5-8.5, and flocculant is added, and stirs, and after separation of solid and liquid, waste water can be discharged.This method is in faintly acid and under the conditions of containing existing for the reducing substances such as inferior sulfate radical, combine the cyanogen root in ferrous ion and waste water sufficiently, generate precipitating, a small amount of remaining iron cyanide, by the collective effect that a small amount of mantoquita and modification infusorial earth or modified zeolite is added, it generates precipitating to achieve the purpose that through being separated by solid-liquid separation except cyanogen, total cyanogen content is lower than 0.5mg/L in the waste water that can make that treated.
Description
Technical field
The present invention relates to metallurgy waste water treatment technical field, the processing of the cyanide wastewater of specifically a kind of iron content Zn-ef ficiency
Method.
Background technique
Extraction of gold by cyanidation is current main Gold Extracting Methods, and the 80% of world's gold output is using this according to statistics
Technique obtains.Cyanidation gold-extracted to generate a large amount of cyanide wastewater, cyanide wastewater toxicity is very big, just discharges if not carrying out processing to it,
Very serious contamination accident will certainly be caused to environment.Various countries using and discharging to cyanide, there is stringent management and control measures.
Also generally make cyanide gold-leaching method in golden production industry at present, similarly generally using cyanide in electroplating industry
Carry out electroplating activity.At present to the processing method of cyanide, there are many kinds of, in short, two major classes can be divided into, one kind is to destroy
Property processing method, such as Inco method, hypochlorite oxidation method, chlorine oxidation process, Fenton oxidation method, Ozonation etc.；This
Kind mode is at high cost and technics comparing is cumbersome, is unfavorable for the comprehensive utilization of cyanide in the cyaniding gold extraction waste water of high concentration, and
Due to the presence of the iron cyanogen complex ion of strong combination, it frequently can lead to cyanide and metal ion in processed waste water and be difficult
It reaches.Another kind of is non-destructive processing method, is such as acidified absorption method, although such method can recycle a certain amount of cyanide,
But since recovery of cyanide is not thorough, the remaining a large amount of cyanide of meeting in waste water, while thiocyanate radical and some heavy metal ion
All do not removed effectively.
In conclusion although each method all respectively has excellent there are many kinds of the methods handled at present cyanide wastewater
Disadvantage, single use a certain kind method, remaining cyanogen root concentration generally all reaches ten milligrams per liter or more in treated waste water, past
It is past that handled waste water stably reaching standard cannot all discharged.Therefore, seek a kind of side at low cost, that cyanide can be effectively removed
Method is current metallurgy industry urgent problem.
The disclosure of background above technology contents is only used for auxiliary and understands inventive concept and technical solution of the invention, not
The prior art for necessarily belonging to present patent application shows above content in the applying date of present patent application in no tangible proof
In the case where having disclosed, above-mentioned background technique should not be taken to the novelty and creativeness of evaluation the application.
Summary of the invention
The present invention is in view of the above-mentioned problems, provide a kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency.This method exists
Faintly acid and containing the reducing substances such as inferior sulfate radical it is existing under the conditions of, make the cyanogen root in ferrous ion and waste water abundant first
In conjunction with generating precipitating, a small amount of remaining iron cyanide, by the way that being total to for a small amount of copper ion and modification infusorial earth or modified zeolite is added
Same-action generates precipitating and achievees the purpose that through being separated by solid-liquid separation except cyanogen.
In order to achieve the goal above, The technical solution adopted by the invention is as follows:
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, includes the following steps:
(1) ferrous sulfate of 7-8 times of cyanogen root weight is added in the cyanide wastewater of Yu Hanyou iron, Zn-ef ficiency, acid adding adjusts wastewater pH
To 5-6.5, flocculant stirring 0.5-2h is added, filtering takes filtrate；
(2) mantoquita and modification infusorial earth or modified zeolite are added in filtrate, stirs 0.5-2h, filtering, gained filter residue is again through sulphur
Acid acidification, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide；
(3) step (2) filters remaining filtrate and adjusts pH to 7.5-8.5, and flocculant is added, and stirs, after separation of solid and liquid, Ji Kepai
Waste water out.
Further, the mantoquita is one or more combinations of copper sulphate, copper chloride, copper nitrate.
Further, the mantoquita usage amount is every liter of waste water >=0.01g.
Further, step (1) the acid adding adjusting is adjusted with sulfuric acid or hydrochloric acid.
Further, the usage amount of the modification infusorial earth or modified zeolite is that 1-10g is added in every liter of waste water.
Further, the modification infusorial earth or modified zeolite are by diatomite or zeolite via phosphoric acid, thiocarbamide and second two
Amine tetrem acid dianhydride composition modifier modification and obtain.
Further, the usage amount of the modifying agent is the 2-4% of diatomite or weight zeolite.
Further, the weight ratio of phosphoric acid, thiocarbamide and ethylenediamine tetra-acetic acid dianhydride is 1-3:1:2-4 in the modifying agent.
Further, the flocculant is made of polyacrylamide, chitosan and eight aminophenyl silsesquioxanes.
Further, the flocculant the ratio of each component is polyacrylamide, chitosan and eight aminophenyl sesquialter silicon
Oxygen alkane 2-4:1-2:1.
Compared with prior art, it advantages of the present invention and has the beneficial effect that
1, this method makes in ferrous ion and waste water in faintly acid and under the conditions of containing existing for the reducing substances such as inferior sulfate radical
Cyanogen root sufficiently combine, generate precipitating, a small amount of remaining iron cyanide passes through and a small amount of mantoquita and modification infusorial earth or modification is added
The collective effect of zeolite generates precipitating and achievees the purpose that through being separated by solid-liquid separation except cyanogen, total in this method can make that treated waste water
Cyanogen content is lower than 0.5mg/L, reaches the discharge standard of national environmental protection defined.
2, adsorbent diatomite or zeolite of the present invention change through peroxophosphoric acid, thiocarbamide and ethylenediamine tetra-acetic acid dianhydride
Property, the specific surface area and adsorption capacity of diatomite can be improved, improve the adsorbance to cyanide, so that the waste water cyanogen of discharge contains
Amount is substantially reduced, and can also adsorb the metal ions such as gold, silver, cadmium, chromium, copper in waste water.
3, the flocculant that the present invention is added is made of polyacrylamide, chitosan and eight aminophenyl silsesquioxanes, with
Conventional flocculant is compared, and flocculation ability is stronger, good effect of separating solid from liquid.
4, the method for the present invention also has at low cost, not high to equipment requirement, easy to operate, high-efficient, cyanide wastewater processing
After can do industrial water use, with good economic efficiency, ecological benefits and social benefit, be suitble to large-scale promotion.
Specific embodiment
Invention is further described in detail With reference to embodiment.It is emphasized that following the description is only
It is merely exemplary, the range and its application being not intended to be limiting of the invention.
Embodiment 1
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, includes the following steps:
(1) the present embodiment handles the cyanide wastewater containing iron, Zn-ef ficiency, CN in the cyanide wastewatert2816.8mg/L Zn
689.1mg/L, Fe 358.7mg/L, CN-1243.4mg/L, PH=11.0 take cyanide wastewater 2500mL, and addition contains sulfuric acid
The solution 900mL of ferrous 200g/L and 0.1% sodium sulfite add flocculant 3g with 3% sulfuric acid of concentration adjusting wastewater pH to 6,
The flocculant is made of polyacrylamide, chitosan and the eight aminophenyl silsesquioxanes that mass ratio is 3:2:1, is stirred
60min, filtering, takes filtrate；
(2) copper sulphate 0.1g and modification infusorial earth 5g is added in filtrate, stirs 60min, filtering, gained filter residue is again through sulfuric acid acid
Change, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide.The modification infusorial earth the preparation method comprises the following steps:
The modifying agent that its quality 3% is added in diatomite stirs evenly, the modifying agent by weight ratio be 2:1:2 phosphoric acid, thiocarbamide and
Ethylenediamine tetra-acetic acid dianhydride composition.
(3) step (2) filters remaining filtrate sulphur acid for adjusting pH to 7.5, and flocculant 2g is added, and stirs, and is separated by solid-liquid separation
Afterwards, waste water can be discharged.By taking the wastewater sample of discharge, remaining cyanogen is carried out by the cyanogen method of surveying of HJ484-2009 defined
It measures, the main component comparison before and after wastewater treatment is as shown in table 1.
Table 1: the main component of 1 cyanide wastewater of embodiment before and after the processing
| CNt(mg/L) | CN- (mg/L) | PH | |
| Before processing | 2816.8 | 1243.4 | 11.0 |
| After processing | 0.15 | 0 | 7.5 |
Embodiment 2
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, includes the following steps:
(1) the present embodiment handles the cyanide wastewater containing iron, Zn-ef ficiency, CN in the cyanide wastewatert542.8mg/L, Zn
113.2mg/L, Fe 87.6mg/lL, CN-225.7mg/L, PH=10.0 take cyanide wastewater 2500mL, are added sub- containing sulfuric acid
Iron 200g/L solution 20mL adds flocculant 5g, the flocculation with the adjusting wastewater pH that concentration is 3% sulfuric acid of concentration to 6.5
Agent is made of polyacrylamide, chitosan and the eight aminophenyl silsesquioxanes that mass ratio is 2:2:1, stirs 30min, mistake
Filter, takes filtrate；
(2) copper sulphate 0.2g and modified zeolite 8g is added in filtrate, stirs 30min, filtering, gained filter residue is again through sulfuric acid acid
Change, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide.The modification infusorial earth the preparation method comprises the following steps:
The modifying agent that its quality 4% is added in zeolite stirs evenly, and the modifying agent is 3:1:1 phosphoric acid, thiocarbamide and second by weight ratio
Ethylenediamine tetraacetic acid (EDTA) dianhydride composition.
(3) step (2) filters remaining filtrate sulphur acid for adjusting pH to 7.5, and flocculant 3g is added, and stirs, and is separated by solid-liquid separation
Afterwards, waste water can be discharged.By taking the wastewater sample of discharge, remaining cyanogen is carried out by the cyanogen method of surveying of HJ484-2009 defined
It measures, the main component comparison before and after wastewater treatment is as shown in table 2.
Table 2: the main component of 2 cyanide wastewater of embodiment before and after the processing
| CNt(mg/l) | CN- (mg/l) | PH | |
| Before processing | 542.8 | 225.7 | 11.0 |
| After processing | 0.06 | 0 | 7.5 |
Embodiment 3
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, includes the following steps:
(1) the present embodiment handles the cyanide wastewater containing iron, Zn-ef ficiency, CN in the cyanide wastewatert1239.6mg/L Zn
257.1mg/L, Fe 108.2mg/L, CN-712.9mg/L, PH=11.0 take cyanide wastewater 2500mL, and addition contains sulfuric acid
Ferrous 200g/L solution 18mL adjusts wastewater pH to 5.5 with 5% hydrochloric acid of concentration, adds flocculant 4g, the flocculant is by matter
Amount stirs 120min than polyacrylamide, chitosan and eight aminophenyl the silsesquioxanes composition for being 3:1:1, and filtering takes filter
Liquid；
(2) copper sulphate 0.05g and modification infusorial earth 10g is added in filtrate, stirs 30min, filtering, gained filter residue is again through sulfuric acid
Acidification, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide.The modification infusorial earth the preparation method comprises the following steps:
The modifying agent that its quality 3% is added in diatomite stirs evenly, and the modifying agent is 3:1:2 phosphoric acid, thiocarbamide by weight ratio
It is formed with ethylenediamine tetra-acetic acid dianhydride.
(3) step (2) filters remaining filtrate sulphur acid for adjusting pH to 7.0, and flocculant 5g is added, and stirs, and is separated by solid-liquid separation
Afterwards, waste water can be discharged.By taking the wastewater sample of discharge, remaining cyanogen is carried out by the cyanogen method of surveying of HJ484-2009 defined
It measures, the main component comparison before and after wastewater treatment is as shown in table 3.
Table 3: the main component of 3 cyanide wastewater of embodiment before and after the processing
| CNt(mg/l) | CN- (mg/l) | PH | |
| Before processing | 1239.6 | 712.9 | 11.0 |
| After processing | 0.08 | 0 | 7.0 |
Comparative example 1
A kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, includes the following steps:
(1) the present embodiment handles the cyanide wastewater containing iron, Zn-ef ficiency, CN in the cyanide wastewatert1239.6mg/L Zn
257.1mg/L, Fe 108.2mg/L, CN-712.9mg/L, PH=11.0 take cyanide wastewater 2500mL, and addition contains sulfuric acid
Ferrous 200g/L solution 18mL adjusts wastewater pH to 5.5 with 5% hydrochloric acid of concentration, adds flocculant 4g, the flocculant is by matter
Amount stirs 120min than polyacrylamide, chitosan and eight aminophenyl the silsesquioxanes composition for being 3:1:1, and filtering takes filter
Liquid；
(2) copper sulphate 0.05g and diatomite 10g is added in filtrate, stirs 30min, filtering, gained filter residue is again through sulfuric acid acid
Change, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide.
(3) step (2) filters remaining filtrate sulphur acid for adjusting pH to 7.0, and flocculant 5g is added, and stirs, and is separated by solid-liquid separation
Afterwards, waste water can be discharged.By taking the wastewater sample of discharge, remaining cyanogen is carried out by the cyanogen method of surveying of HJ484-2009 defined
It measures, the main component comparison before and after wastewater treatment is as shown in table 4.
Table 4: the main component of 4 cyanide wastewater of embodiment before and after the processing
| CNt(mg/l) | CN- (mg/l) | PH | |
| Before processing | 1239.6 | 712.9 | 11.0 |
| After processing | 0.12 | 0.02 | 7.0 |
It is learnt from above-mentioned test result, handles the cyanide wastewater containing iron, Zn-ef ficiency, treated waste water using the method for the present invention
In total cyanogen content be lower than 0.5mg/L, reach the discharge standard of national environmental protection defined.
The above content is combine it is specific/further detailed description of the invention for preferred embodiment, cannot
Assert that specific implementation of the invention is only limited to these instructions.General technical staff of the technical field of the invention is come
It says, without departing from the inventive concept of the premise, some replacements or modifications can also be made to the embodiment that these have been described,
And these substitutions or variant are regarded as belonging to the scope of protection of the present invention.
Claims (10)
1. a kind of processing method of the cyanide wastewater of iron content Zn-ef ficiency, characterized by the following steps:
(1) ferrous sulfate of 7-8 times of cyanogen root weight is added in the cyanide wastewater of Yu Hanyou iron, Zn-ef ficiency, acid adding adjusts wastewater pH
To 5-6.5, flocculant stirring 0.5-2h is added, filtering takes filtrate；
(2) mantoquita and modification infusorial earth or modified zeolite are added in filtrate, stirs 0.5-2h, filtering, gained filter residue is again through sulphur
Acid acidification, stripping, remaining waste residue is stacked or recycling copper again after recovery of cyanide；
(3) step (2) filters remaining filtrate and adjusts pH to 7.5-8.5, and flocculant is added, and stirs, after separation of solid and liquid, Ji Kepai
Waste water out.
2. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: the mantoquita is
One or more combinations of copper sulphate, copper chloride, copper nitrate.
3. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 2, it is characterised in that: the mantoquita makes
Dosage is every liter of waste water >=0.01g.
4. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: step (1) institute
Stating the acid adding adjusting is adjusted with sulfuric acid or hydrochloric acid.
5. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: the modified silicon
Diatomaceous earth or the usage amount of modified zeolite are that 1-10g is added in every liter of waste water.
6. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: the modified silicon
Diatomaceous earth or modified zeolite are the modifier modifications for forming diatomite or zeolite via phosphoric acid, thiocarbamide and ethylenediamine tetra-acetic acid dianhydride
And it obtains.
7. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 6, it is characterised in that: the modifying agent
Usage amount be diatomite or weight zeolite 2-4%.
8. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 7, it is characterised in that: the modifying agent
The weight ratio of middle phosphoric acid, thiocarbamide and ethylenediamine tetra-acetic acid dianhydride is 1-3:1:2-4.
9. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: the flocculant
It is made of polyacrylamide, chitosan and eight aminophenyl silsesquioxanes.
10. the processing method of the cyanide wastewater of iron content Zn-ef ficiency according to claim 1, it is characterised in that: the flocculation
Agent the ratio of each component is polyacrylamide, chitosan and eight aminophenyl silsesquioxane 2-4:1-2:1.
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| CN111101000A (en) * | 2019-12-27 | 2020-05-05 | 山东中城宏业矿业技术有限公司 | Device and method for removing zinc and iron in gold leaching barren solution of gold ore |
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| CN111101000A (en) * | 2019-12-27 | 2020-05-05 | 山东中城宏业矿业技术有限公司 | Device and method for removing zinc and iron in gold leaching barren solution of gold ore |
| CN111392848A (en) * | 2020-04-08 | 2020-07-10 | 甘肃稀土新材料股份有限公司 | Accurate oxidation flocculation treatment method for reducing total phosphorus concentration in mixed wastewater in rare earth industry |
| CN114180753A (en) * | 2021-12-01 | 2022-03-15 | 湖南邦普循环科技有限公司 | Method for treating wastewater containing cyanide and oxalate |
| WO2023098190A1 (en) * | 2021-12-01 | 2023-06-08 | 湖南邦普循环科技有限公司 | Treatment method for wastewater containing cyanide and oxalate |
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