CN105331820A - Method for recovering copper from copper and cyanogen-contained waste water of mine - Google Patents
Method for recovering copper from copper and cyanogen-contained waste water of mine Download PDFInfo
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Abstract
The invention relates to a method for recovering copper from copper and cyanogen-contained waste water of a mine. The method comprises the following steps: activated carbon absorption: the copper and cyanogen-contained waste water of the mine is fed to an activated carob absorbing system for inflating and stirring to absorb copper and cyanogen complex ions in the waste water; desorption reaction: A-grade desorption liquid is added in copper-contained carbons of a desorption column for leaching and powerful desorption; and replacement reaction: desorbed copper-enriched liquid is added in iron powder for replacement and solid-liquid separation to obtain sponge copper and post-replacement liquid. The method has such advantages as simple equipment, simple operation, low investment, low cost, strong adaptability and environmental protection, relieves more and more prominent contradiction of supply and demands of high-quality copper ore resources, realizes efficient treatment of amount reduction, reclamation and harmlessness of harmful wastes, and is suitable for treating and applying the copper and cyanogen-contained waste water of the mine.
Description
Technical field
The present invention relates to a kind of method of utilization of wastewater resource, particularly relate to a kind of from mine containing the method reclaiming copper Effluent of cuprous cyanide, be suitable for mine cupric cyanogen waste water treatment applications.
Background technology
Prussiate carries gold T&B, is that gold mine puies forward golden topmost method so far always.Along with the fast development of gold industry is simple and easy to along with the whole world minimizing day by day processing gold ore resource amount, and national environmental protection policy is increasingly strict, cupric difficult-treating gold mine resource one of main raw material becoming golden production.But this type of gold mine is in cyanidation-leaching process, your liquid copper is entered in by a large amount of leaching, this your liquid replaced by zinc or charcoal absorption carry gold after, a large amount of copper cyanogen complex ions is still had to be trapped in tail washings, if this tail washings is directly returned Cyanide Leaching operation, cupric ion will be caused to accumulate in systems in which always, give the leaching of gold, absorption and gold mud purification etc. all can cause extremely detrimentally affect, for eliminating copper to the detrimentally affect proposing gold generation, usually part open circuit is carried out to the tail washings after zinc displacement gold or charcoal ADSORPTION OF GOLD, if open circuit tail washings out does not process directly outer row, certainly will to environment particularly water resources pollute, to human health, animals and plants and the whole ecosystem cause serious harm.In addition, Faced In Sustainable Development the problem of the various energy, shortage of resources, metal should arouse enough attention as a kind of Nonrenewable resources, containing Effluent of cuprous cyanide as a kind of cheapness, huge secondary renewable resources, recycling is carried out to this waste water, not only having reclaimed copper but also also reduced environmental pollution, is achieve many things at one stroke.
At present, mine cupric cyanogen method of wastewater treatment is mainly divided into two classes: a class is destructive treatment process, prussiate is destroyed mainly through method for oxidation, there are Pomolio-Celdecor process, sulfurous gas-air method, By Ozone and hydrogen peroxide method etc., this class methods treatment process is simple, but there is the low-grade copper-containing residue that reagent consumption is large, cost is high and produce in treating processes and easily cause secondary pollution etc.As Chinese patent CN104016508A discloses " a kind for the treatment of process of cyanide wastewater ", it is characterized in that: first add sodium hydroxide and regulate waste water ph to 10.5 ~ 11.5, next adds clorox and carries out first paragraph oxidation broken cyanide, salt adding acid for adjusting pH value to 7.0 ~ 8.0 again, the last clorox that adds again carries out second segment oxidation broken cyanide, this technique has the following disadvantages: 1. clorox adds by more than 30 times of total cyanogen root quality usually, and clorox consumption is large, cost is high; 2. labour intensity is large, operating environment is poor; 3. Treatment of Copper cyanogen waste water forms low-grade copper-containing residue, easily causes secondary pollution.And for example Chinese patent CN103014368A discloses " a kind of method being separated also gold recovering and copper from cupric noble liquid cyanide ", it is characterized in that: first add alkali and your liquid is adjusted to pH=8.0 ~ 11.5, secondly adopt By Ozone to carry out oxidation broken cyanide to liquid after alkali tune and sink Copper treatment, last solid-liquid separation obtains liquid after heavy copper ashes and heavy copper, and send charcoal absorption system ADSORPTION OF GOLD by liquid after heavy copper, this technique exists that facility investment is large, system energy consumption is high and the high deficiency of processing costs.Equations of The Second Kind is recovery of cyanide method, as acidifying absorption method, extraction and recovery method and acidifying recovery+direct oxidation combined method etc., such recovery method meets the current energy-saving and emission-reduction policy of China, but have that technical process is long, floor space large, capital construction and the high deficiency of working cost.As Chinese CN104876361A discloses " a kind of method of synthetical recovery cyanide wastewater ", the method comprises: 1. in the acidifying tower that cyanide wastewater is housed, add non-oxidizing acid adjusted to ph, metal complex in cyanide wastewater is precipitated, with acidifying activation cyanide wastewater; 2. solid-liquid separation is carried out, to reclaim valuable metal to the cyanide wastewater after acidifying activation; 3. again utilize being separated the rear cyanogen filtered liquid that contains obtained, adjustment, containing the pH value of cyanogen filtered liquid, then will be put in Industrial processes containing cyanogen filtered liquid and again utilize; 4. if desired outer row, containing cyanogen filtered liquid, needs to send into stripping-absorption equipment containing cyanogen filtered liquid, make HCN remove from containing cyanogen filtered liquid and reclaim.5. deep oxidation is carried out to the filtrate after stripping, reach emission standard to make filtrate.This technical process running cost is low, efficiency is high, and reagent consumption is low, can reclaim most of prussiate and the synthetical recovery valuable metals such as copper, lead, zinc, and make that waste water is innoxious, resource utilization, but have the following disadvantages: 1. operation is loaded down with trivial details, long flow path, floor space are large, operational condition is harsh; 2. equipment material requirement is high, project investment is large, processing cost is high.
Seek that a kind of investment is little, processing cost is low for this reason, strong adaptability, environment amenablely just seem particularly urgent from mine cupric cyanogen waste water high-efficiency resource utilization process.
Summary of the invention
Task of the present invention is the deficiency existed for prior art, proposes that a kind of investment is little, processing cost is low, strong adaptability, environment amenable from mine cupric cyanogen waste water high-efficiency resource utilization process.
Task of the present invention has been come by the following technical programs:
From mine containing the method reclaiming copper Effluent of cuprous cyanide, processing step and condition realize in the following order successively:
The first step charcoal absorption: send charcoal absorption system to carry out air agitation containing Effluent of cuprous cyanide in mine, copper cyanogen complex ion in absorption waste water, described charcoal absorption system is made up of 5 ~ 7 grades of air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.10 ~ 0.20 times of bucket, after this every grade of dress charcoal height bound increases progressively 0.05 times respectively successively, respectively be 20 ~ 40min and every 1 ~ 2h at different levels air agitation bucket stirring 3 ~ 5min containing Effluent of cuprous cyanide in the stirrings residence time at different levels containing mine, after final stage absorption out, liquid is directly transported to gold mine cyaniding and is leached operation reuse, the cupric charcoal of chopped-off head air agitation bucket is first proposed when carrying charcoal, then step by step next stage charcoal carried to upper level air agitation bucket and add new gac at final stage air agitation bucket,
Second step desorb is reacted: send in desorption column by the cupric charcoal of the first step charcoal absorption, add A level desorbed solution and leaching desorb 3 ~ 5h is carried out to cupric charcoal, described A level desorbed solution is water in mass ratio: 98% sulfuric acid: mixed solution prepared by 30% hydrogen peroxide=1000:15 ~ 30:2 ~ 5, the quality controlling A level desorbed solution used per hour is the quality 1 ~ 2 times of cupric charcoal in desorption column, control to separate A level desorbed solution simultaneously and exceed charcoal face 10 ~ 20cm, obtain rich copper liquid;
3rd step replacement(metathesis)reaction: the rich copper liquid that second step desorb is reacted is added iron powder and carries out replacement(metathesis)reaction, described iron powder consumption needs 1.05 ~ 1.3 times of 0.88kg iron powder amount by displacement 1kg copper and carry out replacement(metathesis)reaction 30 ~ 60min to rich copper liquid under mechanical agitation, then solid-liquid separation obtains copper sponge and displaced liquid, and reaction to be replaced terminates rear solid-liquid separation and obtains copper sponge and displaced liquid.
Per-cent described in specification sheets is all weight percentage.
Advantage of the present invention:
1. adopting charcoal absorption and inhaling what use to the strong solution of cupric charcoal is core of the present invention by the A level desorbed solution of sulfuric acid+hydrogen peroxide+water.This technology exists that technical process is loaded down with trivial details, operational condition is harsh, project investment is large when solving present stage China's cupric cyanogen utilization of wastewater resource and the shortcoming such as processing cost is high, for the efficient process containing Effluent of cuprous cyanide provides the transformation of wide space and existing relevant enterprise to provide technical support.
2. the charcoal absorption rate of copper is up to 94% ~ 97%, and during the desorb of cupric charcoal, the desorption efficiency of copper can reach 92% ~ 94%, and during rich copper liquid employing iron replacement, the rate of recovery of copper can reach 94% ~ 97%, and the total yield of copper is 84% ~ 88%.In addition, after charcoal absorption, the copper ion concentration of liquid is lower than 10mg/L, can directly return gold mine cyaniding leaching section, can not cause detrimentally affect, achieve cycling utilization of wastewater to the leaching of gold, absorption and gold mud purification etc.
3. equipment is brief, simple to operate, less investment, cost are low, strong adaptability, environmentally friendly, both alleviated the contradiction that the supply and demand of high-quality copper ore resource is given prominence to increasingly, achieved again the minimizing of harmful waste, resource utilization and innoxious efficient process.
Accompanying drawing explanation
Fig. 1 contains from mine the method process flow sheet reclaiming copper Effluent of cuprous cyanide according to a kind of of the present invention's proposition.
In accompanying drawing, each sign represents respectively:
1. adsorb rear liquid containing Effluent of cuprous cyanide 2. cupric charcoal 3. rich copper liquid 4. iron powder 5. copper sponge 6. displaced liquid 7.A level desorbed solution 8.
Below in conjunction with accompanying drawing, explanation is described in further detail, not as limiting the scope of the present invention.
Embodiment
As shown in Figure 1, of the present invention a kind of from mine containing the method reclaiming copper Effluent of cuprous cyanide, processing step and condition are carried out in the following order successively:
The first step charcoal absorption: send charcoal absorption system to carry out air agitation containing Effluent of cuprous cyanide 1 in mine, copper cyanogen complex ion in absorption waste water, described charcoal absorption system is made up of 5 ~ 7 grades of air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.10 ~ 0.20 times of bucket, after this every grade of dress charcoal height bound increases progressively 0.05 times respectively successively, respectively be 20 ~ 40min and every 1 ~ 2h at different levels air agitation bucket stirring 3 ~ 5min containing Effluent of cuprous cyanide 1 in the stirrings residence time at different levels containing mine, after final stage absorption out, liquid 8 is directly transported to gold mine cyaniding and is leached operation reuse, the cupric charcoal 2 of chopped-off head air agitation bucket is first proposed when carrying charcoal, then step by step next stage charcoal carried to upper level air agitation bucket and add new gac at final stage air agitation bucket,
Second step desorb is reacted: send in desorption column by the cupric charcoal 2 of the first step charcoal absorption, add A level desorbed solution 7 pairs of cupric charcoals 2 and carry out leaching desorb 3 ~ 5h, described A level desorbed solution 7 is water in mass ratio: 98% sulfuric acid: mixed solution prepared by 30% hydrogen peroxide=1000:15 ~ 30:2 ~ 5, the quality controlling A level desorbed solution 7 used per hour is the quality 1 ~ 2 times of cupric charcoal 2 in desorption column, control to separate A level desorbed solution 7 simultaneously and exceed charcoal face 10 ~ 20cm, obtain rich copper liquid 3;
3rd step replacement(metathesis)reaction: the rich copper liquid 3 that second step desorb is reacted is added iron powder 4 and carries out replacement(metathesis)reaction, described iron powder 4 consumption needs 1.05 ~ 1.3 times of 0.88kg iron powder amount by displacement 1kg copper and carry out replacement(metathesis)reaction 30 ~ 60min to rich copper liquid 3 under mechanical agitation, then solid-liquid separation obtains copper sponge and displaced liquid, and reaction to be replaced terminates rear solid-liquid separation and obtains copper sponge 5 and displaced liquid 6.
Displaced liquid 6 part for the 3rd described step replacement(metathesis)reaction is back to second step desorb reaction reuse.
The displaced liquid 6 remainder dispensing Waste Water Treatment of the 3rd described step replacement(metathesis)reaction carries out qualified discharge process.
The desorb charcoal of described second step desorb reaction returns the first step charcoal absorption reuse.
Embodiment 1
Contain Effluent of cuprous cyanide for handling object with what produce in the cyanidation gold-extracted process of the low-grade copper gold in Fujian, its waste water Principle components analysis the results are shown in Table 1.
Table 1 Fujian is containing Effluent of cuprous cyanide Principle components analysis result (%)
Containing in Effluent of cuprous cyanide, copper is reclaimed to this mine, comprises following step and condition successively:
The first step charcoal absorption: send charcoal absorption system containing Effluent of cuprous cyanide by mine, adopt the copper cyanogen complex ion in charcoal absorption waste water, charcoal absorption system is made up of 7 grades of iron air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.15 times of bucket, 2nd grade of dress charcoal height is high 0.20 times of bucket, 3rd level dress charcoal height is high 0.25 times of bucket, 4th grade of dress charcoal height is high 0.30 times of bucket, 5th grade of dress charcoal height is high 0.35 times of bucket, 6th grade of dress charcoal height is high 0.40 times of bucket, 7th grade of dress charcoal height is high 0.45 times of bucket, control be 30min in the residence time at different levels containing Effluent of cuprous cyanide and carry out air agitation 3min every 1h at different levels, after most rear class absorption out, liquid is made to produce backwater and is directly transported to gold mine cyaniding and leach operation reuse, when carrying charcoal, first first step charcoal is proposed, obtain cupric charcoal, then second stage charcoal is carried to the first step, third stage charcoal is carried to the second stage, fourth stage charcoal is carried to the third stage, level V charcoal is carried to the fourth stage, 6th grade of charcoal is carried to level V, 7th grade of charcoal is carried to the 6th grade, and add new gac at the 7th grade,
Second step desorb is reacted: send in desorption column by the cupric charcoal of the first step gained, adopt sulfuric acid concentration to be 30g/L and hydrogen peroxide concentration be the A level desorbed solution of 3g/L to carry out leaching desorb 10h to cupric charcoal, the quality controlling A level stripping liquid used per hour is 2 times of the quality of cupric charcoal in desorption column, A level stripping liquid exceeds 20cm than cupric charcoal face, obtains desorb charcoal and rich copper liquid.Desorb charcoal returns charcoal absorption;
3rd step replacement(metathesis)reaction: the rich copper liquid that second step desorb is reacted is sent in iron replacement system, in rich copper liquid, need the amount of 1.2 times of 0.88kg iron powder amount to add iron powder by displacement 1kg copper, and 60min is reacted under mechanical agitation, then solid-liquid separation obtains copper sponge and displaced liquid, a displaced liquid part returns second step desorb reaction reuse, and remainder dispensing Waste Water Treatment carries out qualified discharge process.Copper reclaims Testing index in table 2.
Table 2 embodiment 1 bronze medal reclaims Testing index
Embodiment 2
Contain Effluent of cuprous cyanide for handling object with what produce in the cyanidation gold-extracted process of Huichun Station of Jilin Province copper gold, its waste water Principle components analysis the results are shown in Table 3.
Table 3 Huichun Station of Jilin Province is containing Effluent of cuprous cyanide Principle components analysis result (%)
The first step charcoal absorption: send charcoal absorption system containing Effluent of cuprous cyanide by mine, adopt the copper cyanogen complex ion in charcoal absorption waste water, charcoal absorption system is made up of 6 grades of iron air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.15 times of bucket, 2nd grade of dress charcoal height is high 0.20 times of bucket, 3rd level dress charcoal height is high 0.25 times of bucket, 4th grade of dress charcoal height is high 0.30 times of bucket, 5th grade of dress charcoal height is high 0.35 times of bucket, 6th grade of dress charcoal height is high 0.40 times of bucket, be 25min containing Effluent of cuprous cyanide in the residence time at different levels and carried out air agitation 4min every 1.5 hours at different levels, after most rear class absorption out, liquid is made to produce backwater and is directly transported to gold mine cyaniding and leach operation reuse, when carrying charcoal, first first step charcoal is proposed, obtain cupric charcoal, then second stage charcoal is carried to the first step, third stage charcoal is carried to the second stage, fourth stage charcoal is carried to the third stage, level V charcoal is carried to the fourth stage, 6th grade of charcoal is carried to level V, and add new gac at the 6th grade,
Second step desorb is reacted: send in desorption column by the cupric charcoal of the first step gained, adopt sulfuric acid concentration to be 20g/L and hydrogen peroxide concentration be the A level stripping liquid of 4g/L to carry out leaching desorb 7h to cupric charcoal and the quality controlling stripping liquid used per hour is 2 times of the quality of cupric charcoal in desorption column, control stripping liquid simultaneously and exceed about 20cm than charcoal face, obtain desorb charcoal and rich copper liquid, desorb charcoal returns the first step charcoal absorption reuse;
3rd step replacement(metathesis)reaction: the rich copper liquid that second step desorb is reacted is sent in iron replacement system, in rich copper liquid, need 1.1 times of 0.88kg iron powder amount to add iron powder by displacement 1kg copper, under mechanical agitation, replacement(metathesis)reaction 50min is carried out to rich copper liquid, then solid-liquid separation obtains copper sponge and displaced liquid, a displaced liquid part returns second step desorb reaction reuse, and remainder dispensing Waste Water Treatment carries out qualified discharge process.Copper reclaims Testing index in table 4.
Table 4 embodiment 2 bronze medal reclaims Testing index
Embodiment 3
Contain Effluent of cuprous cyanide for handling object with what produce in the cyanidation gold-extracted process of the low-grade copper gold in Guizhou, its waste water Principle components analysis the results are shown in Table 5.
Table 5 Guizhou is low-grade containing Effluent of cuprous cyanide Principle components analysis result (%)
The first step charcoal absorption: send charcoal absorption system containing Effluent of cuprous cyanide by mine, charcoal absorption system is made up of 5 grades of iron air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.20 times of bucket, 2nd grade of dress charcoal height is high 0.25 times of bucket, 3rd level dress charcoal height is high 0.30 times of bucket, 4th grade of dress charcoal height is high 0.35 times of bucket, 5th grade of dress charcoal height is high 0.40 times of bucket, be 40min containing Effluent of cuprous cyanide in the residence time at different levels, and carried out air agitation 3min every 1 hour at different levels, after most rear class absorption out, liquid is made to produce backwater and is directly returned gold mine cyaniding and leach operation reuse, when carrying charcoal, first first step charcoal is proposed, obtain cupric charcoal, then second stage charcoal is carried to the first step, third stage charcoal is carried to the second stage, fourth stage charcoal is carried to the third stage, level V charcoal is carried to the fourth stage, and add new gac charcoal at level V.
Second step desorb is reacted: send in desorption column by the cupric charcoal of the first step charcoal absorption, then sulfuric acid concentration is adopted to be 15g/L and hydrogen peroxide concentration is the A level stripping liquid leaching desorb 9h of 5g/L, the quality controlling stripping liquid used per hour is 1.5 times of the quality of cupric charcoal in desorption column, control stripping liquid and exceed charcoal face 10cm, obtain desorb charcoal and rich copper liquid, desorb charcoal returns the first step charcoal absorption reuse;
3rd step replacement(metathesis)reaction: the rich copper liquid that second step desorb is reacted is sent in iron replacement system, in rich copper liquid, need 1.05 times of 0.88kg iron powder amount to add iron powder by displacement 1kg copper, and under mechanical agitation, replacement(metathesis)reaction 30min is carried out to rich copper liquid, then solid-liquid separation obtains copper sponge and displaced liquid.A displaced liquid part returns second step desorb reaction reuse, and remainder dispensing Waste Water Treatment carries out qualified discharge process.Copper reclaims Testing index in table 6.
Table 6 embodiment 3 bronze medal reclaims Testing index
Shown by embodiment 1 to 3 result shown in table 2, table 4, table 6, adopt the inventive method, the charcoal absorption rate of copper is up to 94% ~ 97%, during the desorb of cupric charcoal, the desorption efficiency of copper can reach 92% ~ 94%, during rich copper liquid employing iron replacement, the rate of recovery of copper can reach 94% ~ 97%, and the total yield of copper is 84% ~ 88%.
As mentioned above, just the present invention can be realized preferably.Above-described embodiment is only the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; other changes made under not deviating from spirit of the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (4)
1. contain from mine the method reclaiming copper Effluent of cuprous cyanide, processing step and condition are carried out in the following order successively:
The first step charcoal absorption: send charcoal absorption system to carry out air agitation containing Effluent of cuprous cyanide [1] in mine, copper cyanogen complex ion in absorption waste water, described charcoal absorption system is made up of 5 ~ 7 grades of air agitation buckets, during absorption, chopped-off head dress charcoal height is high 0.10 ~ 0.20 times of bucket, after this every grade of dress charcoal height bound increases progressively 0.05 times respectively successively, respectively be 20 ~ 40min and every 1 ~ 2h at different levels air agitation bucket stirring 3 ~ 5min containing Effluent of cuprous cyanide [1] in the stirrings residence time at different levels containing mine, after final stage absorption out, liquid [8] is directly transported to gold mine cyaniding and is leached operation reuse, the cupric charcoal [2] of chopped-off head air agitation bucket is first proposed when carrying charcoal, then step by step next stage charcoal carried to upper level air agitation bucket and add new gac at final stage air agitation bucket,
Second step desorb is reacted: send in desorption column by the cupric charcoal [2] of the first step charcoal absorption, add A level desorbed solution [7] and leaching desorb 3 ~ 5h is carried out to cupric charcoal [2], described A level desorbed solution [7] is water in mass ratio: 98% sulfuric acid: mixed solution prepared by 30% hydrogen peroxide=1000:15 ~ 30:2 ~ 5, the quality controlling A level desorbed solution [7] used per hour is the quality 1 ~ 2 times of cupric charcoal [2] in desorption column, control to separate A level desorbed solution [7] simultaneously and exceed charcoal face 10 ~ 20cm, obtain rich copper liquid [3];
3rd step replacement(metathesis)reaction: the rich copper liquid [3] that second step desorb is reacted is added iron powder [4] and carries out replacement(metathesis)reaction, described iron powder [4] consumption needs 1.05 ~ 1.3 times of 0.88kg iron powder amount by displacement 1kg copper and carry out replacement(metathesis)reaction 30 ~ 60min to rich copper liquid [3] under mechanical agitation, then solid-liquid separation obtains copper sponge and displaced liquid, and reaction to be replaced terminates rear solid-liquid separation and obtains copper sponge [5] and displaced liquid [6].
2. method according to claim 1, is characterized in that displaced liquid [6] part for the 3rd described step replacement(metathesis)reaction is back to second step desorb reaction reuse.
3. method according to claim 1 and 2, is characterized in that displaced liquid [6] the remainder dispensing Waste Water Treatment of the 3rd described step replacement(metathesis)reaction carries out qualified discharge process.
4. method according to claim 1, is characterized in that the desorb charcoal of described second step desorb reaction returns the first step charcoal absorption reuse.
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| CN107841622A (en) * | 2017-11-10 | 2018-03-27 | 陈鹏 | A kind of method of cyanidation tailings comprehensive utilization and harmless treatment |
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| CN105331820B (en) | 2017-07-25 |
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