CN104846211B - Method for separating zinc, cadmium, copper, lead and silver from zinc smelting copper slag - Google Patents
Method for separating zinc, cadmium, copper, lead and silver from zinc smelting copper slag Download PDFInfo
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- CN104846211B CN104846211B CN201510315608.8A CN201510315608A CN104846211B CN 104846211 B CN104846211 B CN 104846211B CN 201510315608 A CN201510315608 A CN 201510315608A CN 104846211 B CN104846211 B CN 104846211B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for separating zinc, cadmium, copper, lead and silver from zinc smelting copper slag and belongs to the field of wet-process metallurgy of nonferrous metals. The method comprises the following steps: directly slurrying mixed copper slag without ore grinding; leaching by adopting a pressure reactor; controlling the technical parameters of acid volume, temperature, oxygen partial pressure, reaction time, terminal pH value and the like; dissolving out zinc and cadmium from the copper slag into a solution; dissolving out copper, and hydrolyzing the copper into copper hydroxide which is added into the slag again; performing liquid-solid separation and washing on a leached ore pulp, and then adding the filtrate containing zinc and cadmium and a washing solution into a zinc smelting system to recover zinc and cadmium; adding sulfuric acid to a filter cake, and controlling the leaching terminal pH value at a normal temperature and a normal pressure to ensure that copper is leached out; and performing liquid-solid separation on a copper leaching ore pulp, and then adding the obtained lead and silver slag into a lead smelting system to recover lead and silver. By adopting the technical scheme of the invention, zinc, cadmium and copper can be completely separated, copper is completely separated from lead and silver, the valuable metals of Cu, Zn, Cd, Pb, Ag and the like in the copper slag can be completely recycled, the whole process avoids the generation of 'three wastes', and the production is clean and efficient.
Description
Technical field
The invention belongs to non-ferrous metal field of hydrometallurgy, specifically, be related to a kind of zinc abstraction copper ashes separation of Zinc, cadmium,
The method of copper and lead silver.
Background technology
When using the conventional zinc wet method smelting process such as lixiviation process or direct leaching, copper, cadmium in zinc concentrate etc. are entered
Solution, when clean unit is with zinc powder purification and impurity removal, copper, cadmium in solution etc. enter purification slag, while lead, silver that zinc powder is brought into
Deng metal also into purification slag；Purification slag leaches most of zinc, cadmium in purification slag using dilute sulfuric acid or Zinc electrolysis waste liquid, and liquid is solid
Copper ashes is obtained after separation.
Because each enterprise's zinc concentrate Cu, Cd content differs, leach, purify different with cadmium recovery process from technical conditions difference,
The fluctuation of copper ashes composition is larger, and copper ashes composition is：Cu10～50%, Zn5～10%, Cd2～10%, Pb10～20%, Ag200～
600g/t.Due to the element such as Cd, Pb containing high poison in copper ashes, therefore, 2008 editions have been included into《Country's danger waste register》In,
Code is：331-008-48.
But containing valuable metals such as Cu, Zn, Cd, Pb, Ag in copper ashes, with higher economic worth.Therefore, cause wide
The great attention of big researcher.Chinese invention patent CN100572573C is wet using copper ashes is spread out stacking autoxidation
The element such as normal pressure leaching Cu, Zn, Cd again after formula ball milling, leachate direct electrowinning tough cathode reclaims Zn, Cd after waste liquid is purified,
There are a large amount of Zn, Cd in copper ashes and be leached and enter solution, cause copper electrodeposition effluent purifying amount big, copper during purification in copper waste liquid is again
Into copper ashes, the problem that need to be leached again again.Chinese invention patent CN102634668B first stores up copper ashes after pre-oxidation, normal pressure
The elements such as Cu, Zn, Cd are leached in air blast, and leachate direct crystallization production cupric sulfate pentahydrate exists and stores up oxidation occupied ground, leaches
When compress wind and low-pressure steam consumption it is big, need to be from crystalline mother solution the problems such as separation of Zinc, cadmium.Peng Jianrong etc. is published in《There is coloured gold
Category》(Smelting Part) the 8th phase paper in 2013《The pressure acidleach of copper ashes oxygen prepares the research of copper sulphate》In, processed using oxygen pressure acidleach
Copper ashes, makes the element dissolution such as Cu, Zn, Cd in copper ashes, filtrate prepare copper sulfate crystal using direct crystallization method, stays Zn, Cd etc.
In crystalline mother solution, zinc dust precipitation copper is added, make copper enter slag and zinc, cadmium separation again, zinc powder consumption is big when there is displacement copper, copper
The problem that need to be leached again.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of zinc abstraction copper ashes separation of Zinc, cadmium, copper and lead silver
Method, presses acidleach to make the most of zinc in copper ashes, cadmium enter solution using oxygen, and copper is converted into Kocide SD form and lead silver is common
Enter slag, oxygen leaching ore pulp Jing after solid-liquor separation, the filtrate containing Zn, Cd individually process or into zinc abstraction flow process reclaim Zn,
Cd, after filter cake is scrubbed, can use as nertralizer, and also can add makes Kocide SD dissolution, ore pulp under dilute sulfuric acid, normal temperature and pressure
After solid-liquor separation, filtrate (copper-bath) can prepare sulfuric acid copper products or electrodeposition negative electrode copper products, drastically reduce the area crystallization
The treating capacity of mother liquor or copper electrodeposition waste liquid, filter cake (lead smelting gas) enters lead and smelts flow process recovery lead silver, can all recycle copper ashes
In the valuable metal such as Cu, Zn, Cd, Pb, Ag.
In order to achieve the above object, the present invention proposes following technical scheme：
A kind of method of zinc abstraction copper ashes separation of Zinc, cadmium, copper and lead silver, concretely comprises the following steps：
1) copper ashes Jing grab-cranes carry out batch mixing, the clear water pulp of mixed copper ashes；
2) copper ashes ore pulp and leaching agent are continuously pumped into respectively in autoclave pressure；
3) oxygen is continuously passed through in autoclave pressure, when 80～120 DEG C of controlling reaction temperature, 0.2～0.6Mpa of partial pressure of oxygen, reaction
Between 1.0～2.0h, terminal pH be 5.0～5.4, hydrolyze again after copper dissolution in copper ashes into slag, zinc, cadmium enter solution；
4) ore pulp is entered after flash tank and regulating tank pressure release cooling, and using chamber filter press solid-liquor separation, filter cake slurry are carried out
Carry out solid-liquor separation after change again, the filtrate that press filtration twice is obtained individually processes or reclaims Zn, Cd into zinc abstraction system；
5) Jing after the filter cake that press filtration twice is obtained is sized mixing, dilute sulfuric acid, normal temperature and pressure is added to leach copper, chamber filter press liquid is consolidated
After separation, filtrate is copper-bath, and filter cake is lead smelting gas, and filter cake contains Cu≤1.5%, Pb20～50%, Zn≤3.0%, Cd
≤ 0.2%, Ag400～1000g/t, filter cake enters lead smelting system and reclaims lead silver.
Preferably, step 1) in, after copper ashes batch mixing, without ore grinding pulp is directly carried out.
Preferably, step 2) in, leaching agent is dilute sulfuric acid, cupric sulphate crystal mother liquor or copper electrodeposition waste liquid, and acid adding amount is
0.8～1.0 times of Zn, Cd reaction acid consumption in copper ashes.
Preferably, step 5) in, filter cake as nertralizer, or can add sulfuric acid, and copper is leached at normal temperatures and pressures, soak
Go out terminal pH for 1.0～3.0.
Beneficial effects of the present invention：The present invention presses acidleach to make the most of zinc in copper ashes, cadmium enter solution using oxygen, and copper turns
Turn to Kocide SD form and lead silver enters slag jointly, Jing after solid-liquor separation, the filtrate containing Zn, Cd is individually processed oxygen leaching ore pulp
Or Zn, Cd are reclaimed into zinc abstraction flow process, and after filter cake is scrubbed, can use as nertralizer, can also add dilute sulfuric acid, normal temperature
Kocide SD dissolution is made under normal pressure, after pulp liquid-solid isolation, filtrate (copper-bath) can prepare sulfuric acid copper products or electrodeposition is cloudy
Pole copper products, drastically reduce the area the treating capacity of crystalline mother solution or copper electrodeposition waste liquid, and filter cake (lead smelting gas) enters lead and smelts flow process time
Receive lead silver, separate can zinc, cadmium and copper thorough, copper and lead silver separate it is thorough, all recycle Cu in copper ashes, Zn, Cd,
The valuable metals such as Pb, Ag, produce without " three wastes ", produce clean and effective.
Description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
As shown in figure 1, a kind of method of zinc abstraction copper ashes separation of Zinc, cadmium, copper and lead silver, concretely comprises the following steps：
1) Jing after grab-crane batch mixing, mixed copper ashes directly uses clear water pulp to copper ashes without ore grinding.
2) copper ashes ore pulp and leaching agent are distinguished into continuous pump to autoclave pressure with diaphragm metering pump, leaching agent be dilute sulfuric acid,
Cupric sulphate crystal mother liquor or copper electrodeposition waste liquid, acid adding amount is 0.8～1.0 times of Zn, Cd reaction acid consumption in copper ashes.
3) continuously it is passed through industrial oxygen in autoclave pressure, 80～120 DEG C of control pressure temperature in the kettle, partial pressure of oxygen 0.2～
0.6Mpa, 1.0～2.0h of reaction time, terminal pH are 5.0～5.4.In autoclave pressure, Zn, the Cd in copper ashes first reacts difference
Generate ZnSO4And CdSO4Into solution, there is following reaction in copper and oxygen afterwards in copper ashes, sulfuric acid：
Cu+1/2O2+H2SO4=CuSO4+H2O (1)
As the copper in copper ashes is dissolved, ore pulp acid content declines in kettle, and pH value is raised, molten when pH values of pulp >=4.0
The CuSO for going out4Hydrolyze, copper is entered in slag with the hydrolysis of Kocide SD form：
The reaction that copper of the sulfuric acid that reaction equation (2) is discharged again and in slag reacts in formula (1), makes copper constantly molten
Go out, and be constantly hydrolyzed precipitation, until the metallic copper almost all in copper ashes is converted into Kocide SD.By reaction equation (1) and instead
Answer formula (2) as follows after merging：
Cu+1/2O2+H2O=Cu (OH)2 (3)
The free letter of reaction equation (3) such as table 1.
The free letter of the reaction equation of table 1 (3)
As can be seen from Table 1, as long as oxygen supply is sufficient, reaction equation (3) can be carried out at 25 DEG C.
4) ore pulp is entered after flash tank and regulating tank pressure release cooling, and using chamber filter press solid-liquor separation, filter cake slurry are carried out
Carry out solid-liquor separation after change again, the filtrate that press filtration twice is obtained individually processes or reclaims Zn, Cd into zinc abstraction system.
5) Jing after the filter cake that press filtration twice is obtained is sized mixing, dilute sulfuric acid is added, controls terminal pH for the box pressures of 1.0～3.0, Jing
Filter solid-liquor separation, filtrate is copper-bath, and filter cake is lead smelting gas, and filter cake contains Cu≤1.5%, Pb20～50%, Zn≤
3.0%, Cd≤0.2%, Ag400～1000g/t, filter cake enters lead smelting system and reclaims lead silver.
Below in conjunction with the embodiment of the present invention and accompanying drawing, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on this
Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example is applied, the scope of protection of the invention is belonged to.
Embodiment 1
1) by the copper ashes 20t after batch mixing, composition is：Zn 5.65%, Cd 2.51%, Cu 49.19%, directly uses water slurry
Change.
2) pulp copper ashes, dilute sulfuric acid are continuously pumped into respectively in autoclave pressure, dilute sulfuric acid addition is Zn, Cd reaction in copper ashes
0.8 times of acid consumption.
3) industrial oxygen is continuously passed through, and controls 120 DEG C of temperature in the kettle, partial pressure of oxygen 0.6Mpa, reaction time 2.0h, terminal
PH is 5.4.
4) autoclave pressure leaches ore pulp Jing after flash tank, regulating tank step-down cooling, chamber filter press press filtration, after filter cake pulp again
Secondary press filtration, the filtrate that press filtration twice is obtained enters zinc abstraction system and reclaims Zn, Cd.
5) Jing after the filter cake that press filtration twice is obtained is sized mixing, dilute sulfuric acid, normal temperature and pressure is added to leach copper, terminal pH is leached in control
For 1.0, after chamber filter press solid-liquor separation, filtrate is copper-bath, and filter cake is lead smelting gas, and composition is：Cu 1.45%, Zn
2.90%, Cd 0.11%, Pb 48.93%, Ag 920g/t, enters lead smelting system and reclaims lead silver.
Embodiment 2
1) by the copper ashes 24t after batch mixing, composition is：Zn 7.39%, Cd 6.11%, Cu 24.33%, directly uses water slurry
Change.
2) pulp copper ashes, dilute sulfuric acid are continuously pumped into respectively in autoclave pressure, sulphuric acid is Zn, Cd reaction consumption in copper ashes
0.9 times of acid amount.
3) oxygen is continuously passed through, and controls 100 DEG C of temperature in the kettle, partial pressure of oxygen 0.4Mpa, reaction time 1.5h, terminal pH and be
5.2。
4) autoclave pressure leaches ore pulp Jing after flash tank, regulating tank step-down cooling, chamber filter press press filtration, after filter cake pulp again
Secondary press filtration, the filtrate that press filtration twice is obtained enters zinc abstraction system and reclaims Zn, Cd.
5) Jing after the filter cake that press filtration twice is obtained is sized mixing, dilute sulfuric acid, normal temperature and pressure is added to leach copper, terminal pH is leached in control
For 2.0, after chamber filter press solid-liquor separation, filtrate is copper-bath, and filter cake is lead smelting gas, and composition is：Cu 1.25%, Zn
2.69%, Cd 0.14%, Pb 40.49%, Ag 780g/t, enters lead smelting system and reclaims lead silver.
Embodiment 3
1) by the copper ashes 21t after batch mixing, composition is：Zn 9.67%, Cd 10.09%, Cu 10.93%, directly uses water slurry
Change.
2) pulp copper ashes, dilute sulfuric acid respectively, are continuously squeezed in autoclave pressure, sulphuric acid is Zn, Cd reaction in copper ashes
1.0 times of acid consumption.
3) oxygen is continuously passed through, and controls 80 DEG C of temperature in the kettle, partial pressure of oxygen 0.2Mpa, reaction time 1.0h, terminal pH and be
5.0。
4) autoclave pressure leaches ore pulp Jing after flash tank, regulating tank step-down cooling, chamber filter press press filtration, after filter cake pulp again
Secondary press filtration, the filtrate that press filtration twice is obtained enters zinc abstraction system and reclaims Zn, Cd.
5) Jing after the filter cake that press filtration twice is obtained is sized mixing, dilute sulfuric acid, normal temperature and pressure is added to leach copper, terminal pH is leached in control
For 3.0, after chamber filter press solid-liquor separation, filtrate is copper-bath, and filter cake is lead smelting gas, and composition is：Cu 1.44%, Zn
2.93%, Cd 0.17%, Pb 36.52%, Ag 481g/t, enters lead smelting system and reclaims lead silver.
Effect analysis
Can be clear that according to above example, Jing after press filtration twice, twice Zn, Cd, the Cu in filtrate is separated back
Receive, Zn, Cd, Cu content is substantially reduced in filter cake, and Pb, Ag content is improved, filter cake enters lead smelting system and reclaims lead silver, so
The valuable metals such as Cu, Zn, Cd, Pb, Ag in zinc abstraction copper ashes can be all recycled, crystalline mother solution or copper is drastically reduce the area
The treating capacity of electrodeposition waste liquid, produces without " three wastes ", produces clean and effective.
The present invention presses acidleach to make the most of zinc in copper ashes, cadmium enter solution using oxygen, and copper is converted into Kocide SD form
Enter slag jointly with lead silver, Jing after solid-liquor separation, the filtrate containing Zn, Cd is individually processed or into zinc abstraction stream oxygen leaching ore pulp
Cheng Huishou Zn, Cd, after filter cake is scrubbed, can use as nertralizer, and also can add make Kocide SD under dilute sulfuric acid, normal temperature and pressure
Dissolution, after pulp liquid-solid isolation, filtrate (copper-bath) can prepare sulfuric acid copper products or electrodeposition negative electrode copper products, significantly subtract
Lacked the treating capacity of crystalline mother solution or copper electrodeposition waste liquid, filter cake (lead smelting gas) enters lead to be smelted flow process and reclaim lead silver, can make zinc, cadmium and
Copper is separated thoroughly, and copper and lead silver are separated thoroughly, all the valuable metal such as Cu, Zn, Cd, Pb, Ag in recycling copper ashes, nothing
" three wastes " are produced, and produce clean and effective.
Finally, above example and accompanying drawing are only unrestricted to illustrate technical scheme, although by above-mentioned
Embodiment is described in detail to the present invention, it is to be understood by those skilled in the art that can in form and carefully
Various changes are made to it on section, without departing from claims of the present invention limited range.
Claims (1)
1. a kind of zinc abstraction copper ashes separation of Zinc, cadmium, copper and lead silver method, it is characterised in that concretely comprise the following steps：
1) copper ashes Jing grab-cranes carry out batch mixing, and mixed copper ashes directly uses clear water pulp without ore grinding；
2) copper ashes ore pulp and leaching agent are continuously pumped into respectively in autoclave pressure, wherein leaching agent is dilute sulfuric acid, cupric sulphate crystal mother
Liquid or copper electrodeposition waste liquid, acid adding amount is 0.8～1.0 times of Zn, Cd reaction acid consumption in copper ashes；
3) oxygen, 80～120 DEG C of controlling reaction temperature, 0.2～0.6Mpa of partial pressure of oxygen, reaction time are continuously passed through in autoclave pressure
1.0～2.0h, terminal pH are 5.0～5.4, are hydrolyzed again after copper dissolution in copper ashes into slag, and zinc, cadmium enter solution；
4) ore pulp is entered after flash tank and regulating tank pressure release cooling, solid-liquor separation is carried out using chamber filter press, after filter cake pulp
Solid-liquor separation is carried out again, and the filtrate that press filtration twice is obtained individually processes or reclaims Zn, Cd into zinc abstraction system；
5) filter cake that Jing press filtrations twice are obtained adds dilute sulfuric acid, normal temperature and pressure to leach copper as nertralizer, leaches terminal pH1.0
～3.0, after chamber filter press solid-liquor separation, filtrate is copper-bath, and filter cake is lead smelting gas, and filter cake contains Cu≤1.5%, Pb20
～50%, Zn≤3.0%, Cd≤0.2%, Ag400～1000g/t, filter cake enters lead smelting system and reclaims lead silver.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510315608.8A CN104846211B (en) | 2015-06-10 | 2015-06-10 | Method for separating zinc, cadmium, copper, lead and silver from zinc smelting copper slag |
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|---|---|---|---|
| CN201510315608.8A CN104846211B (en) | 2015-06-10 | 2015-06-10 | Method for separating zinc, cadmium, copper, lead and silver from zinc smelting copper slag |
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| CN104846211A CN104846211A (en) | 2015-08-19 |
| CN104846211B true CN104846211B (en) | 2017-04-19 |
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| CN112126795A (en) * | 2020-10-18 | 2020-12-25 | 赤峰中色锌业有限公司 | Method for recovering zinc from clean liquid poor copper slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168969A (en) * | 1978-04-17 | 1979-09-25 | Texasgulf Inc. | Recovery of silver, copper, zinc and lead from partially roasted pyrite concentrate by acid chloride leaching |
| CN101538646A (en) * | 2009-04-28 | 2009-09-23 | 云南驰宏锌锗股份有限公司 | Process method for producing copper sulfate by intensified leaching of copper-containing materials |
| CN104060099A (en) * | 2014-06-23 | 2014-09-24 | 贵州顶效开发区宏达金属综合回收有限公司 | Method for extracting Zn, In, Cd and Tl from lead and zinc smelting smoke dust |
-
2015
- 2015-06-10 CN CN201510315608.8A patent/CN104846211B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168969A (en) * | 1978-04-17 | 1979-09-25 | Texasgulf Inc. | Recovery of silver, copper, zinc and lead from partially roasted pyrite concentrate by acid chloride leaching |
| CN101538646A (en) * | 2009-04-28 | 2009-09-23 | 云南驰宏锌锗股份有限公司 | Process method for producing copper sulfate by intensified leaching of copper-containing materials |
| CN104060099A (en) * | 2014-06-23 | 2014-09-24 | 贵州顶效开发区宏达金属综合回收有限公司 | Method for extracting Zn, In, Cd and Tl from lead and zinc smelting smoke dust |
Non-Patent Citations (2)
| Title |
|---|
| 赵宏等.西北铅锌冶炼厂铜镉渣提取技术.《甘肃冶金》.2002,(第4期), * |
| 锌冶炼铜渣提取铜、锌、镉的试验研究";纪武仁等;《甘肃冶金》;20120831(第34期);第53页第2节，图1 * |
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