CN107574305A - A kind of high concn. arsenic and lead matte Recovering Copper and sulphur technique - Google Patents
A kind of high concn. arsenic and lead matte Recovering Copper and sulphur technique Download PDFInfo
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- CN107574305A CN107574305A CN201710686842.0A CN201710686842A CN107574305A CN 107574305 A CN107574305 A CN 107574305A CN 201710686842 A CN201710686842 A CN 201710686842A CN 107574305 A CN107574305 A CN 107574305A
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Abstract
The invention discloses the technique of a kind of high concn. arsenic and lead matte Recovering Copper and sulphur, the technique is by high concn. arsenic and lead matte raw material and troilite dispensing, is crushed, ore grinding；Gained miberal powder mixes with sulfuric acid and dispersing additive size mixing after, carry out pressure oxidation acidleach, solid-liquor separation, obtain cupric leachate and leached mud containing arsenic；The cupric leachate obtains copper products by eddy flow electrodeposition；The leached mud containing arsenic reclaims elemental sulfur product by being evaporated in vacuo；This method can eliminate whole process arsenic pollution problem, realize efficiently separating and reclaiming for copper, and cupric leachate carries copper using eddy flow electrodeposition technology, reduces direct current consumption, improves production efficiency；In this method removal process, sulphur exists in the form of elemental sulfur, during only relate to physical aspects change, realize efficiently separating and reclaiming for sulphur, whole process clean environment firendly, be advantageous to industrialized production.
Description
Technical field
The invention discloses a kind of handling process of high concn. arsenic and lead matte, more particularly to a kind of high concn. arsenic and lead matte is taken with troilite
The technique that the synthetical recovery of copper, sulphur etc. in high concn. arsenic and lead matte is realized with progress wet-treating, belongs to Non-ferrous Metallurgy field.
Background technology
Lead copper matte, be lead pyrometallurgical smelting system in a kind of caused byproduct, main component be copper, lead, iron vulcanization
Thing, and with the composition transfer of upstream lead concentrate, be often accompanied by the valuable metals such as gold, silver, still containing a small amount of scattered metals indium, germanium,
Tin, bismuth etc., and contain the poisonous and harmful metal impurities such as arsenic, iron.
At present, enterprise mainly sells to copper smelting plant to the processing mode of lead copper matte or voluntarily handled.It is domestic
Most of smeltery is using thermal process processing lead copper matte, and when cupric is higher, the converter for being directly entered copper carries out oxidation blowing,
Blister copper is obtained, lead voloxidation is separated；The process energy consumption is high, SO2And lead contamination is serious, lead, antimony, bismuth, arsenic in matte are made
Flue dust is evaporated into for impurity to remove, because this flue dust contains, arsenic is too high to be unable to efficient resource.When lead copper matte is high concn. arsenic and lead matte,
Converting process arsenic can disperse everywhere in smelting system, and arsenic pollution is more serious.
Conventional wet technique need to be by obtaining copper-bath after oxidizing roasting with sulfuric acid leaching.Roasting process equally exists
Low concentration SO2Pollution, and sulfide is difficult that roasting is thorough, copper recovery is not high.The pressure of this leachate removal of impurities simultaneously is big, electrodeposition production
Product are difficult to up to standard；It is if big using the copper cost height in iron powder replacement leachate, wastewater treatment pressure.Handled using wet processing
Arsenic partly can enter solution, whole process arsenic pollution is tight again in the volatilization of roasting link part leaching link during high concn. arsenic and lead matte
Weight.
Prior art, still using wet processing processing high concn. arsenic and lead matte, can not solve arsenic either using thermal process
The problem of pollution, and follow-up sulfur product recovery and a great problem, therefore, high concn. arsenic and lead matte treatment technology still needs to open up newly
Approach.
The content of the invention
For prior art exist during handling high concn. arsenic and lead matte the problem of, the purpose of the present invention aims to provide one kind
It can effectively prevent arsenic from leaching, simplify dearsenification step, realize selective copper leaching and the high concn. arsenic and lead of recovery and high efficiente callback sulphur
Matte comprehensive recycling process, the technique is inexpensive, step is simple, without arsenic evil, clean and effective, is advantageous to popularization and application.
, should the invention provides a kind of high concn. arsenic and lead matte Recovering Copper and sulphur technique in order to realize above-mentioned technical purpose
Technique is by high concn. arsenic and lead matte raw material and troilite dispensing, is crushed, ore grinding；Gained miberal powder mixes with sulfuric acid and dispersing additive
After conjunction is sized mixing, pressure oxidation acidleach is carried out, solid-liquor separation, obtains cupric leachate and leached mud containing arsenic；The cupric leachate
By eddy flow electrodeposition, copper products are obtained；The leached mud containing arsenic reclaims elemental sulfur product by being evaporated in vacuo.
In the prior art, high concn. arsenic and lead matte due to arsenic content it is high, no matter high concn. arsenic and lead matte be using hydrometallurgy or
Pyrometallurgical smelting, all it is difficult to the murder by poisoning for departing from arsenic, during traditional pyrogenic process oxidation blowing processing high concn. arsenic and lead matte, arsenic can smelted
System is disperseed everywhere, and arsenic pollution is serious；During traditional wet processing processing high concn. arsenic and lead matte, arsenic is waved in roasting link part
Hair, partly it can enter solution again leaching link, whole process arsenic pollution is serious.And technical solution of the present invention successfully passes through wet method
Efficient selective leaches copper from high concn. arsenic and lead matte, and obtains the cupric leachate for being used directly for eddy flow electro deposited copper.This
Inventive technique scheme key is to realize during high concn. arsenic and lead matte wet-treating from the solid arsenic in source, using troilite raw material with
The collocation of high concn. arsenic and lead matte is handled, and troilite is made full use of to realize solid arsenic, so as to effectively prevent the leaching of the arsenic in leaching process
Go out, while iron has also obtained effective fixation, selective copper is entered solution system, content of copper ion reaches 20g/L in leachate
More than, the impurity content such as iron ion in below 3g/L, complies fully with eddy flow electrodeposition requirement, so as to directly obtain high-purity
Electro deposited copper.This method effectively prevent conventional wet and smelt and need to it also avoid pyrogenic process smelting to the process of leachate dearsenification, deferrization
The process of refining process arsenic pollution, simplifies processing step.
Technical scheme contains substantial amounts of elemental sulfur in leached mud containing arsenic, mainly troilite and high concn. arsenic and lead is white
Sulphur lead ore and troilite in matte are mainly oxidized to elemental sulfur during Oxidation Leaching, and its arsenic is by ferropexy, Bu Huisui
Sulphur volatilizees together, and therefore, the present patent application technical scheme can realize the recovery of elemental sulfur well using vacuum distillation method, obtain
Obtain high-purity sublimed sulfur.And the generation of subsequent metal removal process sulphur oxide will be avoided after sulfur recovery.
Technical scheme reaches the impurity contents such as more than 20g/L, iron ion in 3g/ in acquisition content of copper ion
Under the precondition of below L cupric leachate, using eddy flow electrodeposition technology, eddy flow electrolytic deposition process can eliminate concentration polarization to electricity
Long-pending adverse effect, whole process can be carried out under the conditions of relatively low tank voltage and higher current density, reduce direct current consumption,
Improve production efficiency；Liquid concentration can be fallen too low after electrodeposition, the increase of unit electric effusion METAL EXTRACTION amount, be also increased simultaneously
Production efficiency；Electrolytic deposition process is carried out in totally-enclosed pipe-type rotary-flow electrolytic cell, completely eliminates the generation of electrolytic deposition process acid mist, clearly
Clean environmental protection.
Preferable scheme, the high concn. arsenic and lead matte raw material and troilite dispensing are 1~1.2 by iron arsenic mass ratio:1 dispensing.
More preferably scheme, the arsenic content of the high concn. arsenic and lead matte is 5~25%.
Preferable scheme, the high concn. arsenic and lead matte raw material and troilite dispensing ore grinding to below granularity satisfaction -0.074mm grains
The mass percentage content of degree is not less than 90%.
Preferable scheme, the condition sized mixing are：The liquid-solid ratio of miberal powder and sulfuric acid is 4~6:1mL/g, sulfuric acid concentration are
100~120g/L, temperature are 75~95 DEG C, and dispersing additive is the 1%~2% of powdered ore quality.In technical solution of the present invention
The main function for process of sizing mixing is that ore pulp is pre-processed, and is homogenized slurry, while the process of sizing mixing makes temperature reach pressurised oxygen
Change the start-up temperature of reaction, pressure leaching process need to only be passed through oxygen, avoid the need for compressive reaction kettle while heat
Be passed through oxygen, simplify equipment, harm reduction.
More preferably scheme, the dispersing additive are sodium lignin sulfonate.
Preferable scheme, the condition of the pressure oxidation acidleach are：Extraction temperature is 130~170 DEG C, extraction time 2
~3h, 0.6~1.8MPa of pressure, leaching process are passed through oxygen in system.
Preferable scheme, the condition of the vacuum distillation are：Relative degree of vacuum is not less than -0.1MPa, temperature 200~300
DEG C, 40~50min of distillation time, steam extracts 2~3L/S of speed control out.
Preferable scheme, the condition of the eddy flow electrodeposition are：The acidity of cupric leachate is 90~110g/L, one section of electric current
Density is 400~600A/m2, two sections of current densities are 200~300A/m2, the electrodeposition cycle is 10h.
More preferably scheme, liquid is used to size mixing after electrodeposition caused by the eddy flow electrodeposition.Copper ion concentration in liquid after electrodeposition
In below 5g/L, the process of sizing mixing can be directly returned to, for pressure oxidation acidleach.
Preferable scheme, leached mud containing arsenic by washing, dry, grinding, screening, take particle diameter less than 0.074mm's successively
Powder is added in vacuum drying oven stove, and vacuum drying oven is furnished with extract system, and the sulphur in leached mud containing arsenic is by distilling, volatilizing, and constantly
Extract sulphur steam out vacuum drying oven, cooled down under inert gas shielding, finally give qualified sulfur product.
Remaining solid residue discharge vacuum drying oven in the solution of the present invention vacuum drying oven, into lead smelting system synthetical recovery
Other valuable metals such as lead, gold, silver, antimony, bismuth.
Preferable scheme, the high concn. arsenic and lead matte arsenic content are 5~25%, and other main components include Cu：10~65%；
Pb：5~40%；Ag：0.1~0.4%；Fe：2~25%；S:1~30%.
Sulphur is mainly elemental sulfur in the slag of lead copper matte oxygen leaching described in technical scheme.
Leached mud containing arsenic preferably passes through carrying out washing treatment in technical scheme, goes in deoxygenation pressure acid leaching residue what is remained
Sulfuric acid.
Preferable scheme, after the drying process, moisture is not higher than 9% in leached mud containing arsenic.
Preferable scheme, leached mud containing arsenic are ground, and are sized to the mass percent of the following granularities of granularity satisfaction -0.074mm
70%~85%.
The main function of vacuum distillation process in technical solution of the present invention be allow leached mud sulphur in the form of elemental sulfur
It is enriched with, rather than is discharged in the form of sulphur dioxide, pollutes environment.
The rate of recovery of sulphur is up to more than 98% in technical scheme leached mud containing arsenic, and sulfur purity is up to 99%
More than, comply fully with commercial Application standard.
In technical scheme, the pressure oxidation in sulfuric acid of high concn. arsenic and lead matte raw material and the collocation of troilite dispensing is leached
Key reaction principle：By the way that under oxygen pressure condition, in sulfuric acid solution, the copper in lead copper matte is leached into the form of copper sulphate
Solution, sulphur are entered in leached mud by elemental sulfur, iron in the form of bloodstone, and arsenic can also be entered in a manner of ferric arsenate in matte
To leached mud, whole process realizes the Selectively leaching of copper and solid arsenic.Specific reaction is as follows：
2CuS+2H2SO4+O2=2CuSO4+2S↓+2H2O(1-1)
2Cu2S+4H2SO4+O2=4CuSO4+2S↓+2H2O(1-2)
2PbS+2H2SO4+O2=2PbSO4↓+2S↓+2H2O(1-3)
Ag2S+H2SO4+1/2O2=Ag2SO4↓+S↓+H2O(1-4)
4FeS+6H2SO4+3O2=2Fe2(SO4)3+6H2O+4S↓(1-5)
CuxAsy+H2SO4+O2→xCuSO4+yH3AsO4+H2O(1-6)
Fe2(SO4)3+2H3AsO4=2FeAsO4↓+3H2SO4(1-7)
In the slag raw material of lead copper matte oxygen leaching described in technical solution of the present invention beyond sulphur removal, other several elements are all high
Boiling point element, and the sulfide of this several element and the boiling point of sulfate are significantly larger than the boiling point of sulphur, and belong to non-volatile
Material, the difference of the vapour pressure of sulphur and other components is also very big.The difference of the above property is vacuum distillation Recovered sulphur,
Unclassified stores stays provides basic theoretical foundation in residue.
Compared with prior art, the advantageous effects that technical solution of the present invention is brought：
1) technical scheme realizes the solid arsenic in source in high concn. arsenic and lead matte leaching process, effectively avoids leaching in copper
During leaching arsenic simultaneously, leachate need not carry out purification and impurity removal after solid-liquor separation, so that it may directly progress eddy flow electrodeposition
Obtain acceptable cathodic copper products；The step of needing to carry out dearsenification processing to leachate this solution simplifies existing wet processing, disappear
Except arsenic pollution problem.
2) technical scheme is fixed simultaneously using troilite as solid arsenical, arsenic and iron, mainly with stable
Ferric arsenate form fix, copper leaching rate reaches more than 95%, and arsenic enters slag rate more than 99%, and iron enters slag rate more than 90%；Realize
The Selectively leaching of copper, it is the impurity content such as 20~80g/L, iron ion in below 3g/L leaching that can obtain content of copper ion
Go out liquid, meet eddy flow electrodeposition requirement.
3) technical scheme uses eddy flow electrodeposition technology during electro deposited copper, and eddy flow electrolytic deposition process can eliminate dense
The adverse effect that difference polarizes to electrodeposition, whole process can be carried out under the conditions of relatively low tank voltage and higher current density, be reduced
Direct current consumption, improve production efficiency；Liquid concentration can be fallen too low after electrodeposition, the increase of unit electric effusion METAL EXTRACTION amount,
Also increase production efficiency simultaneously；Electrolytic deposition process is carried out in totally-enclosed pipe-type rotary-flow electrolytic cell, completely eliminates electrolytic deposition process
The generation of acid mist, clean environment firendly.
4) eddy flow electrodeposition technology of the present invention can control after electrodeposition liquid copper ion concentration to effectively increase list in below 5g/L
The METAL EXTRACTION amount of position electrolyte, improves production efficiency, reduces power consumption.
5) technical scheme is by the mainly output in the form of elemental sulfur, rather than with sulfur dioxide of the sulphur in mineral
Form output, and vacuum distillation process is carried out in the vacuum drying oven of sealing, no toxic gas discharge, pollution-free, environmentally friendly height
Effect.
6) technical scheme is using the sulphur in vacuum distillation technique recovery lead copper matte leached mud, either leached mud
The rate of recovery of middle sulphur, or the purity of Recovered sulphur reach commercial Application demand；And the residue obtained after handling can be straight
Connect and return to lead smelting system synthetical recovery other valuable metals.
Brief description of the drawings
【Fig. 1】For the process chart of the present invention.
Embodiment
The present invention is further illustrated with reference to embodiment, but does not therefore limit the present invention to described embodiment model
Among enclosing.
Embodiment 1：
The present invention is using the high concn. arsenic and lead matte of Chenzhou, Hunan Province lead smeltery output as research object, by 500g lead copper mattes (Cu
41.08%；Pb14.14%；Ag0.35%；Fe1.576%；S3.23%；As14.25% iron arsenic mass ratio 1) is pressed:1 supplying sulphur
Iron ore, then crush, the levigate material to more than 90% is sized mixing after below 0.074mm with additive, sulfuric acid, liquid-solid ratio
5:1, initial sulfuric acid concentration 120g/L, the lignin sulfonic acid sodium additives for adding 2% are sized mixing, and the material after sizing mixing adds
In autoclave, moulding pressure 1.6MPa, now oxidation reaction start to start, can just controlling reaction temperature in 130-
160 DEG C, decrease temperature and pressure after heat-insulation pressure keeping 2h, to normal pressure and 90 DEG C or so blankings, terminal acidity 60g/L is leached in control, consolidate
Liquid separates, and copper enters leachate in the form of bivalent cupric ion, and the leaching rate that copper is obtained through assay is 95.7%, and leached mud returns
Return the valuable metals such as lead smelting system comprehensive recovery of lead, gold, silver, antimony, bismuth.Leaching liquid acidity is adjusted to 90g/L and directly revolved
Electrodeposition is flowed, controls one section of current density 500A/m2, two sections of current density 260A/m2, electrodeposition time 10h, finally give tough cathode
Product, its purity are 99.997%, meet the requirement of national standard tough cathode product quality.
Obtained leached mud is washed again, dried, ground, sieved, obtained powder particles meet below 0.074mm
The mass percent of granularity is 75%.Material is added in vacuum distillation furnace, seal, be evacuated to relative degree of vacuum for-
0.1MPa, 200 DEG C are heated to, keeping temperature is constant, and sulfur vapor is extracted and passes through B-grade condensation, and after distilling 40min, cooling is cold
But, recover to normal pressure, open distillation equipment, obtain sulphur and residue.The rate of recovery that sulphur is obtained after calculating reaches
98.2%, sulfur purity 99.23%, comply fully with commercial Application standard.It is valuable that residue return lead smelting system reclaims other
Metal.
Embodiment 2：
The present invention is using the high concn. arsenic and lead matte of Chenzhou, Hunan Province lead smeltery output as research object, by 500g lead copper mattes (Cu
31.57%；Pb15.22%；Ag0.41%；Fe10.53%；S1.13%；As17.31% iron arsenic mass ratio 1.2) is pressed:1 supplying
Troilite, then crush, it is levigate to more than 90% material after below the 0.074mm and lignin sulfonic acid sodium additives, sulfuric acid
Sized mixing, liquid-solid ratio 4:1, initial sulfuric acid concentration 100g/L, the additive for adding 1% carries out normal pressure leaching, by normal pressure leaching
Material afterwards is added in autoclave, moulding pressure 1.4MPa, and now oxidation reaction starts to start, and can just control reaction
Temperature decrease temperature and pressure after 140-170 DEG C, heat-insulation pressure keeping 3h, to normal pressure and 90 DEG C or so blankings, terminal acidity is leached in control
40g/L, separation of solid and liquid is carried out, copper enters leachate in the form of bivalent cupric ion, and the leaching rate that copper is obtained through assay is
95.53%, leached mud returns to the valuable metals such as lead smelting system comprehensive recovery of lead, gold, silver, antimony, bismuth.Liquid acidity is leached to be adjusted to
110g/L directly carries out eddy flow electrodeposition, controls one section of current density 600A/m2, two sections of current density 300A/m2, the electrodeposition time
10h, negative electrode copper products are finally given, its purity is 99.998%, meets the requirement of national standard tough cathode product quality.
Obtained leached mud is washed again, dried, ground, sieved, obtained powder particles meet below 0.074mm
The mass percent of granularity is 85%.Material is added in vacuum distillation furnace, seal, be evacuated to relative degree of vacuum for-
0.2MPa, 300 DEG C are heated to, keeping temperature is constant, and sulfur vapor is extracted and passes through B-grade condensation, and after distilling 50min, cooling is cold
But, recover to normal pressure, open distillation equipment, obtain sulphur and residue.The rate of recovery that sulphur is obtained after calculating reaches
98.1%, sulfur purity 99.01%, comply fully with commercial Application standard.It is valuable that residue return lead smelting system reclaims other
Metal.
Comparative example 1
Embodiment step such as embodiment 1, high concn. arsenic and lead matte presses iron arsenic mass ratio with troilite during simply testing
0.8:1 dispensing, other steps keep constant, then the cupric leachate arsenic concentration for testing to obtain is more than 600mg/L, finally gives
Tough cathode product purity is 99.8%, does not meet the requirement of national standard tough cathode product quality.
Comparative example 2
Embodiment step such as embodiment 2, is simply reduced to 40min by process distillation time, and other steps keep constant, then real
The sulfur product rate of recovery for testing to obtain is 88.31%, and sulfur product purity is 99.02%, and experiment products obtained therefrom purity is substantially not
Become, meet industrial requirements, and the sulfur product rate of recovery then declines by a big margin.
Claims (10)
1. a kind of high concn. arsenic and lead matte Recovering Copper and sulphur technique, it is characterised in that：High concn. arsenic and lead matte raw material and troilite are matched somebody with somebody
Material, is crushed, ore grinding；Gained miberal powder mixes with sulfuric acid and dispersing additive size mixing after, carry out pressure oxidation acidleach, liquid divides admittedly
From obtaining cupric leachate and leached mud containing arsenic；The cupric leachate obtains copper products by eddy flow electrodeposition；It is described to contain arsenic
Leached mud reclaims elemental sulfur product by being evaporated in vacuo.
2. high concn. arsenic and lead matte Recovering Copper according to claim 1 and sulphur technique, it is characterised in that：The high concn. arsenic and lead ice
It is 1~1.2 that copper raw material and troilite dispensing, which press iron arsenic mass ratio,:1 dispensing.
3. high concn. arsenic and lead matte Recovering Copper according to claim 2 and sulphur technique, it is characterised in that：The high concn. arsenic and lead ice
The arsenic content of copper is 5~25%.
4. high concn. arsenic and lead matte Recovering Copper and sulphur technique according to any one of claims 1 to 3, it is characterised in that：Institute
State high concn. arsenic and lead matte raw material and troilite dispensing ore grinding to the following granularities of granularity satisfaction -0.074mm mass percentage content not
Less than 90%.
5. high concn. arsenic and lead matte Recovering Copper and sulphur technique according to any one of claims 1 to 3, it is characterised in that：Institute
Stating the condition sized mixing is：The liquid-solid ratio of miberal powder and sulfuric acid is 4~6:1mL/g, sulfuric acid concentration are 100~120g/L, temperature 75
~95 DEG C, dispersing additive is the 1%~2% of powdered ore quality.
6. high concn. arsenic and lead matte Recovering Copper according to claim 5 and sulphur technique, it is characterised in that：The scattered addition
Agent is sodium lignin sulfonate.
7. high concn. arsenic and lead matte Recovering Copper and sulphur technique according to claims 1 to 3 or 6, it is characterised in that：It is described to add
Pressure oxidation acid leaching condition be：Extraction temperature is 130~170 DEG C, and extraction time is 2~3h, 0.6~1.8MPa of pressure, is leached
Process is passed through oxygen in system.
8. high concn. arsenic and lead matte Recovering Copper and sulphur technique according to claims 1 to 3 or 6, it is characterised in that：It is described true
Sky distillation condition be：Relative degree of vacuum is not less than -0.1MPa, 200~300 DEG C, 40~50min of distillation time of temperature, steam
Extract 2~3L/S of speed control out.
9. high concn. arsenic and lead matte Recovering Copper and sulphur technique according to claims 1 to 3 or 6, it is characterised in that：The rotation
Stream electrodeposition condition be：The acidity of cupric leachate is 90~110g/L, and one section of current density is 400~600A/m2, two sections of electricity
Current density is 200~300A/m2, the electrodeposition cycle is 10h.
10. high concn. arsenic and lead matte Recovering Copper according to claim 9 and sulphur technique, it is characterised in that：The eddy flow electricity
Liquid is used to size mixing after electrodeposition caused by product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108220618A (en) * | 2018-01-19 | 2018-06-29 | 中国地质科学院矿产综合利用研究所 | Arsenic-fixing and copper-extracting method for high-arsenic copper sulfide ore |
| CN112941563A (en) * | 2021-01-29 | 2021-06-11 | 昆明理工大学 | Method for recovering residual copper of cyclone electrodeposition cathode cylinder |
| CN114561547A (en) * | 2022-03-14 | 2022-05-31 | 昆明理工大学 | Method for comprehensively recovering valuable metals in high-zinc copper smelting smoke dust |
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| CN105349791A (en) * | 2015-10-28 | 2016-02-24 | 郴州市金贵银业股份有限公司 | Method for selectively extracting copper from iron-copper-matte materials |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108220618A (en) * | 2018-01-19 | 2018-06-29 | 中国地质科学院矿产综合利用研究所 | Arsenic-fixing and copper-extracting method for high-arsenic copper sulfide ore |
| CN112941563A (en) * | 2021-01-29 | 2021-06-11 | 昆明理工大学 | Method for recovering residual copper of cyclone electrodeposition cathode cylinder |
| CN114561547A (en) * | 2022-03-14 | 2022-05-31 | 昆明理工大学 | Method for comprehensively recovering valuable metals in high-zinc copper smelting smoke dust |
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Application publication date: 20180112 |