CN103233117B - Method for removing chlorine from zinc electrolytic waste liquid by utilizing floatation silver concentrate in oxygen pressure acid leaching process - Google Patents
Method for removing chlorine from zinc electrolytic waste liquid by utilizing floatation silver concentrate in oxygen pressure acid leaching process Download PDFInfo
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- CN103233117B CN103233117B CN201310153181.7A CN201310153181A CN103233117B CN 103233117 B CN103233117 B CN 103233117B CN 201310153181 A CN201310153181 A CN 201310153181A CN 103233117 B CN103233117 B CN 103233117B
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Abstract
The invention relates to a method for removing chlorine from zinc electrolytic waste liquid by utilizing floatation silver concentrate in an oxygen pressure acid leaching process. The floatation silver concentrate is a product obtained by performing floatation on the conventional zinc hydrometallurgy acid leaching residue. Based on the characteristic that the floatation silver concentrate contains more elemental silver, the method comprises the following steps of: transforming the elemental silver into silver oxide through oxygen pressure acid leaching in the oxygen pressure acid leaching process of the floatation silver concentrate; transforming the silver oxide into sulfuric acid; and combining free silver ions with chlorine in the zinc electrolytic waste liquid to form silver chloride so as to fulfill the chlorine removing aim.
Description
Technical field
The present invention relates to Metal smelting field, particularly a kind of method utilizing flotation of silver concentrate to remove chlorine in zinc electrolytic waste liquid in oxygen pressure acidleach process.
Background technology
At present, the zinc electrolytic waste liquid cl content obtained from zinc abstraction is constantly accumulated, zinc electrolytic waste liquid cl content is accumulated to a certain degree can affect Zinc electrolysis process afterwards, makes lead anode and equipment worsened by the leaded rising of burn into electric effusion, the reduction of negative electrode precipitation zinc quality, Zinc electrolysis Working environment.Therefore, the content of Zn system Chlorine in Solution must be reduced by every means.
The method dechlorinated in zinc hydrometallurgy is more, and wherein pyrogenic process employing multiple hearth furnace roasting method removes the chlorine in raw material, and wet method often adopts the dechlorination of the Sulfuric acid disilver salt precipitator method, chlorine removal from copper residue method, bismuthous oxide bismuth trioxide method, ion exchange method and alkali cleaning dechlorination method etc.Wherein multiple hearth furnace dechlorinating process energy consumption is high, and Sulfuric acid disilver salt, the bismuthous oxide bismuth trioxide dechlorination method prices of raw and semifnished materials are expensive, and ion exchange method resin regeneration can produce chloride higher dilute sulfuric acid solution and a large amount of wash water, and alkali cleaning dechlorinating process water consumption is large, energy consumption is also high.Be exactly that aforesaid method all needs independent operation in addition, all need fund input newly constructed facility or purchased materials, all can increase the cost of zinc hydrometallurgy.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art and a kind of method utilizing flotation of silver concentrate to remove chlorine in zinc electrolytic waste liquid in oxygen pressure acidleach process is provided.
Technical scheme of the present invention is: a kind of method utilizing flotation of silver concentrate to remove chlorine in zinc electrolytic waste liquid in oxygen pressure acidleach process, described flotation of silver concentrate is the product of conventional wet lay zinc metallurgy acid leaching residue through flotation, it utilizes the feature containing more elemental silver in flotation of silver concentrate, in the oxygen pressure acidleach process of flotation of silver concentrate, by the acidleach of oxygen pressure, elemental silver is first converted into silver suboxide, again silver suboxide is converted into Sulfuric acid disilver salt, then utilize the chloropexia in free silver ions and zinc electrolytic waste liquid to form silver nitride precipitation, reach the object of dechlorination.
Size mixing as follows with the processing condition in oxygen pressure acidleach dechlorination process:
Adopt zinc electrolytic waste liquid and flotation of silver concentrate to carry out mixing sizing mixing in A, process of sizing mixing, the ratio of flotation of silver concentrate and zinc electrolytic waste liquid is 1:6 ~ 10, and the chlorinity in zinc electrolytic waste liquid is 0.1 ~ 0.5g/L;
B, size mixing after flotation of silver concentrate by High Temperature High Pressure be dispersed in autoclave carry out oxygen pressure acidleach, compressed oxygen is passed in oxygen pressure acidleach process, pressure is 10 ~ 15 normal atmosphere, temperature in autoclave is 140 ~ 180 DEG C, sulfuric acid concentration is 180 ~ 250g/L, and chemical time is 5.5 ~ 6 hours.
In oxygen pressure acidleach process, main chemical reactions formula is as follows:
Ag
2O+H
2SO
4=Ag
2SO
4+H
2O
Ag
2SO
4→2Ag
++ SO
4 2-
Ag
++Cl
-=AgCl↓
Flotation of silver concentrate after the acidleach of oxygen pressure is by filtering separation, and obtain leach liquor and leached mud, the leach liquor after dechlorination enters electric Zn system and reclaims valuable element, and part silver is stayed in leached mud with the form of silver chloride, and leached mud is sent to lead system and reclaims valuable element.
The present invention compared with prior art has following features:
The present invention is the series of chemical utilizing the elemental silver in flotation of silver concentrate to produce in oxygen pressure acidleach process, elemental silver in flotation of silver concentrate is converted into Sulfuric acid disilver salt as much as possible, then the silver chloride making the silver ions dissociated become solubility product lower with chloride binding and being precipitated out, incidentally dechlorination is realized while synthetical recovery valuable element, without the need to increasing input, without the need to adding additive, the dechlorination rate of zinc electrolytic waste liquid is 30 ~ 75%, this dechlorination method dechlorination rate is higher, reduces the cost of zinc hydrometallurgy.
Below in conjunction with embodiment, detailed construction of the present invention is further described.
Embodiment
Embodiment: a kind of method utilizing flotation of silver concentrate to remove chlorine in zinc electrolytic waste liquid in oxygen pressure acidleach process, described flotation of silver concentrate is the product of conventional wet lay zinc metallurgy acid leaching residue through flotation, it utilizes the feature containing more elemental silver in flotation of silver concentrate, in the oxygen pressure acidleach process of flotation of silver concentrate, by the acidleach of oxygen pressure, elemental silver is first converted into silver suboxide, again silver suboxide is converted into Sulfuric acid disilver salt, then utilize the chloropexia in free silver ions and zinc electrolytic waste liquid to form silver nitride precipitation, reach the object of dechlorination.
Size mixing as follows with the processing condition in oxygen pressure acidleach dechlorination process:
Adopt zinc electrolytic waste liquid and flotation of silver concentrate to carry out mixing sizing mixing in A, process of sizing mixing, the ratio of flotation of silver concentrate and zinc electrolytic waste liquid is 1:6 ~ 10, and the chlorinity in zinc electrolytic waste liquid is 0.1 ~ 0.5g/L;
B, size mixing after flotation of silver concentrate by High Temperature High Pressure be dispersed in autoclave carry out oxygen pressure acidleach, compressed oxygen is passed in oxygen pressure acidleach process, pressure is 10 ~ 15 normal atmosphere, temperature in autoclave is 140 ~ 180 DEG C, sulfuric acid concentration is 180 ~ 250g/L, and chemical time is 5.5 ~ 6 hours.
In oxygen pressure acidleach process, main chemical reactions formula is as follows:
Ag
2O+H
2SO
4=Ag
2SO
4+H
2O
Ag
2SO
4→2Ag
++ SO
4 2-
Ag
++Cl
-=AgCl↓
Flotation of silver concentrate after the acidleach of oxygen pressure is by filtering separation, and obtain leach liquor and leached mud, the leach liquor after dechlorination enters electric Zn system and reclaims valuable element, and part silver is stayed in leached mud with the form of silver chloride, and leached mud is sent to lead system and reclaims valuable element.
In above-mentioned silver preparation concentrate, silver-colored thing phase composition is as shown in table 1:
Silver-colored thing phase composition in table 1 silver preparation concentrate
After dechlorination result of laboratory test as shown in table 2:
Result of laboratory test after table 2 dechlorination
Claims (1)
1. the method utilizing flotation of silver concentrate to remove chlorine in zinc electrolytic waste liquid in oxygen pressure acidleach process, it is characterized in that: described flotation of silver concentrate is the product of conventional wet lay zinc metallurgy acid leaching residue through flotation, it utilizes the feature containing more elemental silver in flotation of silver concentrate, in the oxygen pressure acidleach process of flotation of silver concentrate, by the acidleach of oxygen pressure, elemental silver is first converted into silver suboxide, again silver suboxide is converted into Sulfuric acid disilver salt, then utilize the chloropexia in free silver ions and zinc electrolytic waste liquid to form silver nitride precipitation, reach the object of dechlorination;
Size mixing as follows with the processing condition in oxygen pressure acidleach dechlorination process:
Adopt zinc electrolytic waste liquid and flotation of silver concentrate to carry out mixing sizing mixing in A, process of sizing mixing, the ratio of flotation of silver concentrate and zinc electrolytic waste liquid is 1:6 ~ 10, and the chlorinity in zinc electrolytic waste liquid is 0.1 ~ 0.5g/L;
B, size mixing after flotation of silver concentrate by High Temperature High Pressure be dispersed in autoclave carry out oxygen pressure acidleach, compressed oxygen is passed in oxygen pressure acidleach process, pressure is 10 ~ 15 normal atmosphere, temperature in autoclave is 140 ~ 180 DEG C, sulfuric acid concentration is 180 ~ 250g/L, chemical time is 5.5 ~ 6 hours
In oxygen pressure acidleach process, main chemical reactions formula is as follows:
Ag
2O+H
2SO
4=Ag
2SO
4+H
2O
Ag
2SO
4→2Ag
++ SO
4 2-
Ag
++Cl
-=AgCl↓
Flotation of silver concentrate after the acidleach of oxygen pressure is by filtering separation, and obtain leach liquor and leached mud, the leach liquor after dechlorination enters electric Zn system and reclaims valuable element, and part silver is stayed in leached mud with the form of silver chloride, and leached mud is sent to lead system and reclaims valuable element.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310153181.7A CN103233117B (en) | 2013-04-27 | 2013-04-27 | Method for removing chlorine from zinc electrolytic waste liquid by utilizing floatation silver concentrate in oxygen pressure acid leaching process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310153181.7A CN103233117B (en) | 2013-04-27 | 2013-04-27 | Method for removing chlorine from zinc electrolytic waste liquid by utilizing floatation silver concentrate in oxygen pressure acid leaching process |
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| Publication Number | Publication Date |
|---|---|
| CN103233117A CN103233117A (en) | 2013-08-07 |
| CN103233117B true CN103233117B (en) | 2015-04-15 |
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| CN103952553A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method for removing chloride ions from zinc hydrometallurgy solution |
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| CN102337391B (en) * | 2011-11-07 | 2012-12-12 | 云南东昌金属加工有限公司 | Process method for recovering indium, germanium and other valuable metals from indium concentrate |
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