CN106191450A - Process the method and system of zinc leaching residue - Google Patents
Process the method and system of zinc leaching residue Download PDFInfo
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- CN106191450A CN106191450A CN201610693441.3A CN201610693441A CN106191450A CN 106191450 A CN106191450 A CN 106191450A CN 201610693441 A CN201610693441 A CN 201610693441A CN 106191450 A CN106191450 A CN 106191450A
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Abstract
The invention discloses the method and system processing zinc leaching residue, the method includes: zinc leaching residue is carried out drying and processing by (1), obtains zinc leaching residue siccative；(2) described zinc leaching residue siccative is mixed with anthracite, obtain mixed material；(3) supply of described mixed material is carried out pre-reduction treatment to rotary kiln, obtain hot kiln slag and zinc smoke；(4) described hot kiln slag is carried out hot wafering process with semi-coke and limestone, obtain hot pressing pelletizing；(5) supply of described hot pressing pelletizing is carried out secondary reduction process to rotary hearth furnace, obtain granular metal and containing zinc oxide, lead oxide and the flue dust of silver；(6) described granular metal is carried out dry separation process, obtain metallic iron and tailings.The method can realize the synthetical recovery of ferrum in zinc leaching residue, silver, zinc and lead, and the volatility of sulfur reaches more than 80%, and the response rate of ferrum reaches more than 90%, and Zinc volatilization rate reaches more than 99%, and lead volatility rate reaches more than 98%, and silver volatility reaches more than 85%.
Description
Technical field
The invention belongs to metallurgical technology field, specifically, the present invention relates to a kind of method processing zinc leaching residue and be
System.
Background technology
The smelting of zinc mainly has pyrogenic process and wet method two ways.Pyrogenic process is to volatilize with high temperature fuming, with the form of ZnO flue dust
Return to leach and reclaim zinc therein；Wet method is high temperature high acidic oils, makes zinc enter solution, and the most substantial amounts of ferrum enters molten the most therewith
Liquid, uses jarosite process, goethite process or hematite process except ferrum subsequently, makes the liquid containing zinc again return to neutral leaching and reclaim wherein
Zinc.For many years it was verified that with neutral leaching, high temperature height acid treatment leached mud, except ferrum, the zinc hydrometallurgy that purifies, be electrolysed,
The response rate of zinc, comprehensively recovering valuable metal, in energy-conservation and environmental protection, relatively pyrogenic process has certain advantage.So far zinc hydrometallurgy becomes
Producing the main method of zinc, in the total output of world's zinc, about 80% is to use wet production.
In Zinc Hydrometallurgy Process, using two sections of neutral cadmias obtained that leach typically to have two kinds of techniques to reclaim, one is
Pyrogenic process, i.e. uses rotary kiln evaporation method；Another kind is wet method, i.e. hot acid solvent extraction method.Rotary kiln evaporation method is China's zinc hydrometallurgy
The typical process that Slag treatment uses, the domestic development through more than 30 years, its technology is the most ripe, existing with strain smelting as representative
More zine-smelting plant uses.Leached mud when zinc kiln slag is zinc hydrometallurgy again with addition of 40%～50% coke powder, operating condition difference
Need to allocate into the coke powder of 80%～100%, in rotary kiln, under high temperature, extract the residue after the metal such as zinc, lead.By by kiln
Slag leaches again, and acid consumption is huge.It addition, 92～94% zinc and 82～84% lead can be reclaimed by rotary kiln fuming volatilization
With the silver of about 10%, Zn content about 2～3% in kiln slag, lead 1%, ferrum 35～40%, the especially content of silver can reach 200
～350g/t, C content 12～18%, also have the highest value.
Rotary kiln technology, during processing zinc leaching residue, also has additive owing to adding substantial amounts of coke, causes
The yield of kiln slag is relatively big, and owing to content of beary metal still exceeds standard, major part is directly stored up, and also has and transports on a small quantity cement plant, cause
The waste of resource.Ferrum recovery, silver recovery and the lead zinc recycling difficulty of kiln slag are relatively big, and multiple technologies process route is feasible, but warp
Ji property is poor.
Therefore, the technology of existing process zinc leaching residue is further improved.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the present invention
One purpose is to propose a kind of method and system processing zinc leaching residue, and the method can realize ferrum in zinc leaching residue, silver, zinc
With the synthetical recovery of lead, and the volatility of sulfur reaches more than 80%, and the response rate of ferrum reaches more than 90%, Zinc volatilization rate reach 99% with
On, lead volatility rate reaches more than 98%, and silver volatility reaches more than 85%.
In one aspect of the invention, the present invention proposes a kind of method processing zinc leaching residue.Reality according to the present invention
Executing example, the method includes:
(1) zinc leaching residue is carried out drying and processing, in order to obtain zinc leaching residue siccative；
(2) described zinc leaching residue siccative is mixed with anthracite, in order to obtain mixed material；
(3) supply of described mixed material is carried out pre-reduction treatment to rotary kiln, in order to obtain hot kiln slag and containing zinc
Flue dust；
(4) described hot kiln slag is carried out hot wafering process with semi-coke and limestone, in order to obtain hot pressing pelletizing；
(5) supply of described hot pressing pelletizing is carried out secondary reduction process to rotary hearth furnace, in order to obtain granular metal and contain
There is the flue dust of zinc oxide, lead oxide and silver；
(6) described granular metal is carried out dry separation process, in order to obtain metallic iron and tailings.
Thus, the method processing zinc leaching residue according to embodiments of the present invention is by mixing zinc leaching residue siccative with anthracite
Supply after conjunction to rotary kiln, carry out pre-reduction treatment, and by reducing the anthracitic amount of allocating into, it is ensured that preheating in rotary kiln
Section is oxidizing atmosphere, thus promotes the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, in ensureing kiln is simultaneously
Pre-reduction stage is weak reducing atmosphere, thus reduces the generation of zinc sulfide so that most of zinc and lead in zinc leaching residue are waved
Send out and carry out flue is recovered with the form of zinc oxide and lead oxide, secondly by hot for gained in rotary kiln kiln slag and semi-coke and stone
Lime stone carries out hot wafering process, is possible not only to make full use of the sensible heat of hot kiln slag, and the addition of semi-coke can ensure that and turns the end
Be reducing atmosphere in stove, more of the prior art hot for gained kiln slag is carried out Water Quenching after carry out drying and processing phase again
Ratio, the application not only eliminates the water quenching technology in original technique, and the drying cost of kiln slag after eliminating shrend, and blue
The addition of charcoal can realize in kiln slag remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price, thus is reducing
Improve ferrum in secondary reduction processing procedure, silver, zinc and the reduction efficiency of lead while energy consumption, additionally limestone be added in follow-up
During be possible not only to play the effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted, thus
Ensure while reducing energy consumption that gained granular metal has higher degree of metalization, and by hot pressing form being used to obtain
The supply of hot pressing pelletizing carries out secondary reduction process to rotary hearth furnace, can significantly improve the utilization rate of reducing agent, and again through dry
Choosing processes can realize slag sluicing system.Thus, the present processes is used can to realize ferrum in zinc leaching residue, silver, zinc and lead
Synthetical recovery, and the volatility of sulfur reaches more than 80%, and the response rate of ferrum reaches more than 90%, and Zinc volatilization rate reaches more than 99%, lead
Volatility reaches more than 98%, and silver volatility reaches more than 85%.
It addition, the method for process zinc leaching residue according to the above embodiment of the present invention can also have following additional technology
Feature:
In some embodiments of the invention, in step (1), described zinc leaching residue is dried water content in material and is not higher than
10wt%.Thus, it is possible to significantly improve the volatility of lead zinc-silver and the response rate of ferrum.
In some embodiments of the invention, in step (2), by described zinc leaching residue siccative and described anthracite according to
Mass ratio is 100:(20～30) mix.Thus, it is possible to improve volatility and the response rate of ferrum of lead zinc-silver further.
In some embodiments of the invention, in step (3), the temperature of described pre-reduction treatment is 800～1150 to take the photograph
Family name's degree.Thus, it is possible to improve volatility and the response rate of ferrum of lead zinc-silver further.
In some embodiments of the invention, in step (4), the temperature of described hot kiln slag is not higher than 500 degrees Celsius.
Thus, it is possible to avoid the scaling loss of semi-coke.
In some embodiments of the invention, in step (4), by described hot kiln slag and described semi-coke and described Calx
Stone is 100:(10～20 according to mass ratio): (5～25) mix.Thus, while reducing energy consumption, gained metal is improved
The degree of metalization of agglomerate.
In some embodiments of the invention, in step (5), the temperature that described secondary reduction processes is 1250～1400
Degree Celsius, the time is 15～40 minutes.Thus, it is possible to improve the degree of metalization of gained granular metal further.
In some embodiments of the invention, the method for described process zinc leaching residue farther includes: (7) by described containing zinc
Flue dust and the described flue dust containing zinc oxide, lead oxide and silver carry out waste heat recovery, in order to obtain flue dust of lowering the temperature；(8) by described
Cooling flue dust carries out cooling process, in order to cooling flue dust；(9) described cooling flue dust is carried out bag collection, in order to collect dust.
In another aspect of the invention, what the present invention proposed a kind of method implementing above-mentioned process zinc leaching residue is
System.According to embodiments of the invention, this system includes:
Drying unit, described drying unit has zinc leaching residue entrance and zinc leaching residue drier outlet；
Mixing arrangement, described mixing arrangement has zinc leaching residue siccative entrance, anthracite entrance and mixed material outlet, institute
State zinc leaching residue siccative entrance to be connected with described zinc leaching residue drier outlet；
Rotary kiln, described rotary kiln has mixed material entrance, the outlet of hot kiln slag and zinc smoke outlet, described mixing
Material inlet is connected with the outlet of described mixed material；
Hot wafering device, described hot wafering device has hot kiln slag entrance, semi-coke entrance, limestone entrance and hot pressing ball
Group's outlet, described hot kiln slag entrance is connected with the outlet of described hot kiln slag；
Rotary hearth furnace, described rotary hearth furnace have hot pressing pelletizing entrance, granular metal outlet and containing zinc oxide, lead oxide and
The flue dust outlet of silver, described hot pressing pelletizing entrance is connected with the outlet of described hot pressing pelletizing；
Dry separation device, described dry separation device has granular metal entrance, metallic iron outlet and tailings outlet, described metal group
Block entrance is connected with the outlet of described granular metal.
Thus, the system processing zinc leaching residue according to embodiments of the present invention is by mixing zinc leaching residue siccative with anthracite
Supply after conjunction to rotary kiln, carry out pre-reduction treatment, and by reducing the anthracitic amount of allocating into, it is ensured that preheating in rotary kiln
Section is oxidizing atmosphere, thus promotes the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, in ensureing kiln is simultaneously
Pre-reduction stage is weak reducing atmosphere, thus reduces the generation of zinc sulfide so that most of zinc and lead in zinc leaching residue are waved
Send out and carry out flue is recovered with the form of zinc oxide and lead oxide, secondly by hot for gained in rotary kiln kiln slag and semi-coke and stone
Lime stone carries out hot wafering process, is possible not only to make full use of the sensible heat of hot kiln slag, and the addition of semi-coke can ensure that and turns the end
Be reducing atmosphere in stove, more of the prior art hot for gained kiln slag is carried out Water Quenching after carry out drying and processing phase again
Ratio, the application not only eliminates the water quenching technology in original technique, and the drying cost of kiln slag after eliminating shrend, and blue
The addition of charcoal can realize in kiln slag remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price, thus is reducing
Improve ferrum in secondary reduction processing procedure, silver, zinc and the reduction efficiency of lead while energy consumption, additionally limestone be added in follow-up
During be possible not only to play the effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted, thus
Ensure while reducing energy consumption that gained granular metal has higher degree of metalization, and by hot pressing form being used to obtain
The supply of hot pressing pelletizing carries out secondary reduction process to rotary hearth furnace, can significantly improve the utilization rate of reducing agent, and again through dry
Choosing processes can realize slag sluicing system.Thus, the present processes is used can to realize ferrum in zinc leaching residue, silver, zinc and lead
Synthetical recovery, and the volatility of sulfur reaches more than 80%, and the response rate of ferrum reaches more than 90%, and Zinc volatilization rate reaches more than 99%, lead
Volatility reaches more than 98%, and silver volatility reaches more than 85%.
In some embodiments of the invention, the system of described process zinc leaching residue farther includes: waste-heat recovery device,
Described waste-heat recovery device has flue dust entrance and cooling flue dust outlet, and described flue dust entrance exports with described zinc smoke respectively
And described containing zinc oxide, lead oxide and silver flue dust outlet be connected；Chiller, described chiller has cooling flue dust
Entrance and cooling flue dust outlet, described cooling flue dust entrance is connected with the outlet of described cooling flue dust；Bagroom, described cloth bag
Dust-precipitator has cooling flue dust entrance, dust outlet and gas outlet, and described cooling flue dust entrance exports with described cooling flue dust
It is connected.
The additional aspect of the present invention and advantage will part be given in the following description, and part will become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage are from combining the accompanying drawings below description to embodiment and will become
Substantially with easy to understand, wherein:
Fig. 1 is the method flow schematic diagram processing zinc leaching residue according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram processing zinc leaching residue according to further embodiment of the present invention；
Fig. 3 is the system structure schematic diagram processing zinc leaching residue according to an embodiment of the invention；
Fig. 4 is the system structure schematic diagram processing zinc leaching residue according to further embodiment of the present invention.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most from start to finish
Same or similar label represents same or similar element or has the element of same or like function.Below with reference to attached
The embodiment that figure describes is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In the present invention, unless otherwise clearly defined and limited, term " install ", " being connected ", " connection ", " fixing " etc.
Term should be interpreted broadly, and connects for example, it may be fixing, it is also possible to be to removably connect, or integral；Can be that machinery connects
Connect, it is also possible to be electrical connection；Can be to be joined directly together, it is also possible to be indirectly connected to by intermediary, in can being two elements
The connection in portion or the interaction relationship of two elements, unless otherwise clear and definite restriction.For those of ordinary skill in the art
For, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
In one aspect of the invention, the present invention proposes a kind of method processing zinc leaching residue.Reality according to the present invention
Executing example, with reference to Fig. 1 and 2, the method includes:
S100: zinc leaching residue is carried out drying and processing
According to embodiments of the invention, zinc leaching residue is carried out drying and processing, obtain zinc leaching residue siccative.Thus, it is possible to
Significantly improve the volatilization efficiency of follow-up pre-reduction stage sulfur and zinc and the organic efficiency of lead.Concrete, gained zinc leaching residue is done
In material, water content is not higher than 10wt%.
S200: zinc leaching residue siccative is mixed with anthracite
According to embodiment, zinc leaching residue siccative obtained above is mixed with anthracite, obtains mixed material.Tool
Body, zinc leaching residue siccative can be mixed in disk feeder with anthracite.
According to one embodiment of present invention, zinc leaching residue siccative is not particularly restricted with anthracite mixed proportion, this
Skilled person can select according to actual needs, according to a particular embodiment of the invention, and zinc leaching residue siccative and nothing
Bituminous coal is 100:(20～30 according to mass ratio) mix.Inventor finds, if the anthracite amount of allocating into is too high, it is impossible to ensure back
In rotary kiln, preheating section is oxidizing atmosphere, thus is unfavorable for the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, and
And the too high meeting of the anthracite amount of allocating into causes surplus carbon in the hot kiln slag of follow-up gained too high and increases reducing agent cost, and rotary kiln
In fuel availability low, be not suitable for adding too much anthracite in this stage, and if the anthracite amount of allocating into is too low, do not have
The effect of prereduction.Thus, by being 100:(20～30 with anthracite according to mass ratio by zinc leaching residue siccative) mix,
It is possible not only to save reducing agent cost, and can ensure that in kiln as pre-reduction stage is weak reducing atmosphere, thus reduce sulfur
Change the generation of zinc so that most of zinc in zinc leaching residue and lead volatilize after reducing and carries out in flue with zinc oxide and oxidation
The form of lead is recovered.
S300: mixed material supply is carried out pre-reduction treatment to rotary kiln
According to embodiments of the invention, mixed material obtained above supply is carried out pre-reduction treatment to rotary kiln,
Obtain hot kiln slag and zinc smoke.Concrete, by reducing the anthracitic amount of allocating into, it is ensured that in rotary kiln, preheating section is oxidation
Property atmosphere, thus promote the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, ensure in kiln as prereduction rank simultaneously
Section is weak reducing atmosphere, thus reduces the generation of zinc sulfide so that after most of zinc in zinc leaching residue and lead reduce
Volatilization carries out being recovered with the form of zinc oxide and lead oxide in flue, i.e. obtain containing zinc oxide and lead oxide containing zinc cigarette
Dirt.According to a particular embodiment of the invention, the temperature of pre-reduction treatment can be 800～1150 degrees Celsius.Thus, further
Effectively prevent the bonding fusing of material while improving the volatilization efficiency of pre-reduction stage sulfur and the organic efficiency of zinc and lead and return
Rotary kiln ring formation, makes the hot wafering technique that material caking is less, follow-up.And through detection, the volatility of sulfur reaches 80%
Above, Zinc volatilization rate reaches more than 99%, and lead volatility rate reaches more than 98%, and silver volatility reaches more than 85%.
S400: hot kiln slag is carried out hot wafering process with semi-coke and limestone
According to embodiments of the invention, hot kiln slag obtained above is carried out hot wafering process with semi-coke and limestone,
Obtain hot pressing pelletizing.Inventor finds, by being carried out at hot wafering with semi-coke and limestone by hot for gained in rotary kiln kiln slag
Reason, is possible not only to make full use of the sensible heat of hot kiln slag, and the addition of semi-coke is reducing atmosphere in can ensure that rotary hearth furnace,
More of the prior art hot for gained kiln slag is carried out Water Quenching after carry out drying and processing again and compare, the application not only eliminates
Water quenching technology in original technique, and the drying cost of kiln slag after eliminating shrend, and the addition of semi-coke can realize kiln
Remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price in slag, thus while reducing energy consumption, improve secondary
The reduction efficiency of ferrum, silver, zinc and lead in reduction treatment process, additionally being added in subsequent process of limestone is possible not only to play
The effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted, thus ensure while reducing energy consumption
Gained granular metal has higher degree of metalization, and is supplied to turning the end by the hot pressing pelletizing that hot pressing form will be used to obtain
Stove carries out secondary reduction process, the utilization rate of reducing agent can be significantly improved, and slag ferrum can be realized through dry separation process again
Separate.In this step, concrete, in rotary kiln the hot kiln slag of gained 800 DEG C after air-cooled being cooled to below 500 DEG C again with orchid
Charcoal and limestone carry out hot wafering, such that it is able to be prevented effectively from the scaling loss of semi-coke.
According to one embodiment of present invention, hot kiln slag is limited the most especially with the mixed proportion of semi-coke and limestone
System, those skilled in the art can select according to actual needs, and according to a particular embodiment of the invention, hot kiln slag is with blue
Charcoal and limestone can be 100:(10～20 according to mass ratio): (5～25) mix.Thus, this mixed proportion is used, no
Only can significantly improve the utilization ratio of reducing agent, and can realize remaining zinc in kiln slag and at a low price iron oxides reduction with
And the reduction of silver and volatilization, thus while reducing energy consumption, improve ferrum, silver, zinc and the reduction of lead in secondary reduction processing procedure
Efficiency, and then obtain the granular metal of higher metal rate.
S500: the supply of hot pressing pelletizing is carried out secondary reduction process to rotary hearth furnace
According to embodiments of the invention, hot pressing pelletizing obtained above supply is carried out secondary reduction process to rotary hearth furnace,
Obtain granular metal and containing zinc oxide, lead oxide and the flue dust of silver.Inventor finds, by the supply of hot pressing pelletizing extremely being turned
Carrying out reduction treatment in end stove, semi-coke therein can realize in kiln slag remaining zinc and the reduction of iron oxides and silver at a low price
Reduction and volatilization, (wherein silver thing in flue dust is mutually to obtain granular metal and the flue dust containing zinc oxide, lead oxide and silver
Silver oxide, Argentous sulfide. and silver simple substance), thus while reducing energy consumption, improve ferrum, silver, zinc and lead in secondary reduction processing procedure
Reduction efficiency, additionally limestone be added in subsequent process the effect being possible not only to play flux, and can promote
The agglomeration of ferrum granule in reduction process, thus while reducing energy consumption, ensure that gained granular metal has higher metal
Rate, and by the hot pressing pelletizing using hot pressing form to obtain supply is carried out secondary reduction process to rotary hearth furnace, permissible
Significantly improve the utilization rate of reducing agent, and slag sluicing system can be realized through dry separation process again.After testing, the volatility of sulfur reaches
More than 80%, Zinc volatilization rate reaches more than 99%, and lead volatility rate reaches more than 98%, and silver volatility reaches more than 85%.According to the present invention
Specific embodiment, the temperature of secondary reduction processing procedure can be 1250～1400 DEG C, and the time can be 15～40 minutes.By
This, can significantly improve the reduction efficiency of secondary reduction processing procedure.
S600: granular metal is carried out dry separation process, in order to obtain metallic iron and tailings
According to embodiments of the invention, granular metal obtained above is carried out dry separation process, obtain metallic iron and tailings.
Concrete, will can realize dividing of metal iron powder and mine tailing after cooled for gained granular metal, broken, dry type magnetic separation
From.After testing, the response rate of metallic iron reaches more than 90%.
After the method processing zinc leaching residue according to embodiments of the present invention is by mixing zinc leaching residue siccative with anthracite
Supply to rotary kiln, carry out pre-reduction treatment, and by reducing the anthracitic amount of allocating into, it is ensured that in rotary kiln, preheating section is
Oxidizing atmosphere, thus promote the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, it is pre-going back in ensureing kiln simultaneously
The former stage is weak reducing atmosphere, thus reduces the generation of zinc sulfide so that most of zinc and lead volatility in zinc leaching residue enter
Row flue is recovered with the form of zinc oxide and lead oxide, secondly by hot for gained in rotary kiln kiln slag and semi-coke and limestone
Carry out hot wafering process, be possible not only to make full use of the sensible heat of hot kiln slag, and in the addition of semi-coke can ensure that rotary hearth furnace
For reducing atmosphere, more of the prior art hot for gained kiln slag is carried out Water Quenching after carry out drying and processing again and compare, this
Application not only eliminates the water quenching technology in original technique, and the drying cost of kiln slag after eliminating shrend, and semi-coke
Addition can realize in kiln slag remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price, thus is reducing energy consumption
While improve ferrum in secondary reduction processing procedure, silver, zinc and the reduction efficiency of lead, additionally limestone be added in subsequent process
In be possible not only to play the effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted, thus reduce
Ensure while energy consumption that gained granular metal has higher degree of metalization, and by the hot pressing that hot pressing form will be used to obtain
Pelletizing supply carries out secondary reduction process to rotary hearth furnace, can significantly improve the utilization rate of reducing agent, and again at dry separation
Reason can realize slag sluicing system.Thus, the present processes is used can to realize the comprehensive of ferrum in zinc leaching residue, silver, zinc and lead
Reclaiming, and the volatility of sulfur reaches more than 80%, the response rate of ferrum reaches more than 90%, and Zinc volatilization rate reaches more than 99%, lead volatility
Rate reaches more than 98%, and silver volatility reaches more than 85%.
With reference to Fig. 2, the method processing zinc leaching residue according to embodiments of the present invention farther includes:
S700: zinc smoke and the flue dust containing zinc oxide, lead oxide and silver are carried out waste heat recovery
According to embodiments of the invention, S300 is obtained zinc smoke and S500 obtains containing zinc oxide, lead oxide
Carry out waste heat recovery with the flue dust of silver, obtain flue dust of lowering the temperature.Thus, by obtained zinc smoke and containing oxidation
The flue dust of zinc, lead oxide and silver carries out waste heat recovery, can be used for generating electricity by this part of waste heat, and the temperature fall of flue dust of lowering the temperature
To about 400 DEG C, thus realize maximally utilizing of resource.
S800: cooling flue dust is carried out cooling process
According to embodiments of the invention, cooling flue dust obtained above is carried out cooling process, can be cooled flue dust.
Concrete, cooling flue dust temperature after surface-cooler obtained above is down to about 250 DEG C.
S900: cooling flue dust is carried out bag collection
According to embodiments of the invention, cooling flue dust obtained above is carried out bag collection, such that it is able to collect dust.
As it has been described above, the method processing zinc leaching residue according to embodiments of the present invention can have selected from following advantage extremely
One of few:
According to embodiments of the present invention process zinc leaching residue method can realize ferrum in zinc leaching residue, silver, zinc, lead comprehensive
Recycling, the response rate that can realize ferrum is more than 90%, and Zinc volatilization rate is more than 99%, and lead volatility rate is more than 98%, the volatilization of silver
The rate technical specification more than 85%.
The method processing zinc leaching residue according to embodiments of the present invention carries out hot pressing by the kiln slag that will obtain in rotary kiln
Block, it is possible to reduce water quenching technology in original technique, saves moisture in kiln slag and dries cost, make full use of kiln slag sensible heat for turning the end
The reduction of stove, saves the energy consumption of whole technique.
Method 1 ton of zinc of more existing employing rotary kiln evaporation PROCESS FOR TREATMENT processing zinc leaching residue according to embodiments of the present invention
Leached mud produces 0.65 ton of kiln slag, and the problem that secondary solid waste amount is big is compared, and the application, by reducing the rotary kiln coal amount of allocating into, turns the end
Stove volatilizees in kiln slag remaining zinc lead sulfur after reclaiming abrasive grit again, and 1 ton of cadmia the most only produces 0.30 ton of tailings, cadmia reduction of discharging
Amount is greatly improved.
According to embodiments of the present invention process zinc leaching residue method by reduce the rotary kiln stage anthracite amount of allocating into,
Semi-coke grain is added, it is ensured that preheating in rotary kiln and the atmosphere of reduction section, the volatility of sulfur can be by original during hot wafering
60% brings up to more than 80%, decreases the generation of zinc sulfide or iron sulfide.
The method processing zinc leaching residue according to embodiments of the present invention uses hot pressing form to reduce in rotary hearth furnace and improves
The utilization rate of carbonaceous reducing agent, decreases the carbon scaling loss caused due to burning.
In another aspect of the invention, what the present invention proposed a kind of method implementing above-mentioned process zinc leaching residue is
System.According to embodiments of the invention, with reference to Fig. 3 and 4, this system includes: drying unit 100, mixing arrangement 200, rotary kiln
300, hot wafering device 400, rotary hearth furnace 500 and dry separation device 600.
According to embodiments of the invention, drying unit 100 has zinc leaching residue entrance 101 and zinc leaching residue drier outlet
102, and be suitable to zinc leaching residue is carried out drying and processing, obtain zinc leaching residue siccative.Thus, it is possible to significantly improve follow-up prereduction
The volatilization efficiency of stage sulfur and zinc and the organic efficiency of lead.Concrete, in gained zinc leaching residue siccative, water content is not higher than
10wt%.
According to embodiments of the invention, mixing arrangement 200 has zinc leaching residue siccative entrance 201, anthracite entrance 202 and
Mixed material outlet 203, zinc leaching residue siccative entrance 201 is connected with zinc leaching residue drier outlet 102, and is suitable to obtain above-mentioned
Zinc leaching residue siccative mix with anthracite, obtain mixed material.Concrete, mixing arrangement can be disk feeder.
According to one embodiment of present invention, zinc leaching residue siccative is not particularly restricted with anthracite mixed proportion, this
Skilled person can select according to actual needs, according to a particular embodiment of the invention, and zinc leaching residue siccative and nothing
Bituminous coal is 100:(20～30 according to mass ratio) mix.Inventor finds, if the anthracite amount of allocating into is too high, it is impossible to ensure back
In rotary kiln, preheating section is oxidizing atmosphere, thus is unfavorable for the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, and
And the too high meeting of the anthracite amount of allocating into causes surplus carbon in the hot kiln slag of follow-up gained too high and increases reducing agent cost, and rotary kiln
In fuel availability low, be not suitable for adding too much anthracite in this stage, and if the anthracite amount of allocating into is too low, do not have
The effect of prereduction.Thus, by being 100:(20～30 with anthracite according to mass ratio by zinc leaching residue siccative) mix,
It is possible not only to save reducing agent cost, and can ensure that in kiln as pre-reduction stage is weak reducing atmosphere, thus reduce sulfur
Change the generation of zinc so that most of zinc in zinc leaching residue and lead volatilize after reducing and carries out in flue with zinc oxide and oxidation
The form of lead is recovered.
According to embodiments of the invention, rotary kiln 300 has mixed material entrance 301, hot kiln slag outlet 302 and contains zinc
Flue dust outlet 303, mixed material entrance 301 is connected with mixed material outlet 203, and is suitable to supply mixed material obtained above
To rotary kiln, carried out pre-reduction treatment, obtained hot kiln slag and zinc smoke.Concrete, by reducing anthracitic allocating into
Amount, it is ensured that in rotary kiln, preheating section is oxidizing atmosphere, thus promote the decomposition of sulfate in zinc leaching residue and sulfur dioxide
Volatilization, guarantee kiln is interior simultaneously is weak reducing atmosphere for pre-reduction stage, thus reduces the generation of zinc sulfide so that zinc leaching residue
In most of zinc and lead reduce after volatilization carry out flue is recovered with the form of zinc oxide and lead oxide, i.e. contained
There is the zinc smoke of zinc oxide and lead oxide.According to a particular embodiment of the invention, the temperature of pre-reduction treatment can be 800～
1150 degrees Celsius.Thus, while improving the volatilization efficiency of pre-reduction stage sulfur and the organic efficiency of zinc and lead further
Effectively prevent the bonding fusing of material and ring formation of rotary kiln, make the hot wafering technique that material caking is less, follow-up.And warp
Crossing detection, the volatility of sulfur reaches more than 80%, and Zinc volatilization rate reaches more than 99%, and lead volatility rate reaches more than 98%, and silver volatility reaches
More than 85%.
According to embodiments of the invention, hot wafering device 400 has hot kiln slag entrance 401, semi-coke entrance 402, Calx
Stone entrance 403 and hot pressing pelletizing outlet 404, hot kiln slag entrance 401 is connected with hot kiln slag outlet 302, and is suitable to above-mentioned
The hot kiln slag obtained carries out hot wafering process with semi-coke and limestone, obtains hot pressing pelletizing.Inventor finds, by turning round
In kiln, the hot kiln slag of gained carries out hot wafering process with semi-coke and limestone, is possible not only to make full use of the sensible heat of hot kiln slag,
And the addition of semi-coke can ensure that in rotary hearth furnace as reducing atmosphere, more of the prior art hot for gained kiln slag is carried out water
Quenching and carry out drying and processing again and compare after process, the application not only eliminates the water quenching technology in original technique, and eliminates water
The drying cost of kiln slag after quenching, and the addition of semi-coke can realize in kiln slag remaining zinc and at a low price iron oxides reduction and
The reduction of silver and volatilization, thus while reducing energy consumption, improve the reduction effect of ferrum, silver, zinc and lead in secondary reduction processing procedure
Rate, additionally limestone be added in subsequent process the effect being possible not only to play flux, and reduction process can be promoted
The agglomeration of middle ferrum granule, thus while reducing energy consumption, ensure that gained granular metal has higher degree of metalization, and
And by the hot pressing pelletizing using hot pressing form to obtain supply is carried out secondary reduction process to rotary hearth furnace, can significantly improve
The utilization rate of reducing agent, and slag sluicing system can be realized through dry separation process again.In this step, concrete, gained in rotary kiln
The hot kiln slag of 800 DEG C carries out hot wafering with semi-coke and limestone after air-cooled being cooled to below 500 DEG C again, such that it is able to effectively
Avoid the scaling loss of semi-coke.
According to one embodiment of present invention, hot kiln slag is limited the most especially with the mixed proportion of semi-coke and limestone
System, those skilled in the art can select according to actual needs, and according to a particular embodiment of the invention, hot kiln slag is with blue
Charcoal and limestone can be 100:(10～20 according to mass ratio): (5～25) mix.Thus, this mixed proportion is used, no
Only can significantly improve the utilization ratio of reducing agent, and can realize remaining zinc in kiln slag and at a low price iron oxides reduction with
And the reduction of silver and volatilization, thus while reducing energy consumption, improve ferrum, silver, zinc and the reduction of lead in secondary reduction processing procedure
Efficiency, and then obtain the granular metal of higher metal rate.
According to embodiments of the invention, rotary hearth furnace 500 has hot pressing pelletizing entrance 501, granular metal outlet 502 and contains
Having the flue dust outlet 503 of zinc oxide, lead oxide and silver, hot pressing pelletizing entrance 501 is connected with hot pressing pelletizing outlet 404, and is suitable to
By hot pressing pelletizing obtained above supply carry out secondary reduction process to rotary hearth furnace, obtain granular metal and containing zinc oxide,
Lead oxide and the flue dust of silver.Inventor finds, by the supply of hot pressing pelletizing is carried out reduction treatment, orchid therein to rotary hearth furnace
Charcoal can realize in kiln slag remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price, obtain granular metal and
Flue dust (wherein silver thing in flue dust is silver oxide, Argentous sulfide. and silver simple substance mutually) containing zinc oxide, lead oxide and silver, thus
Ferrum, silver, zinc and the reduction efficiency of lead, the additionally addition of limestone in secondary reduction processing procedure is improved while reducing energy consumption
In subsequent process, it is possible not only to play the effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted,
Thus ensure that while reducing energy consumption gained granular metal has higher degree of metalization, and by hot pressing form will be used
The hot pressing pelletizing supply obtained carries out secondary reduction process to rotary hearth furnace, can significantly improve the utilization rate of reducing agent, and
Process through dry separation again and can realize slag sluicing system.After testing, the volatility of sulfur reaches more than 80%, and Zinc volatilization rate reaches more than 99%,
Lead volatility rate reaches more than 98%, and silver volatility reaches more than 85%.According to a particular embodiment of the invention, secondary reduction processing procedure
Temperature can be 1250～1400 DEG C, the time can be 15～40 minutes.Processed thus, it is possible to significantly improve secondary reduction
The reduction efficiency of journey.
According to embodiments of the invention, dry separation device 600 has granular metal entrance 601, metallic iron outlet 602 and tailings
Outlet 603, granular metal entrance 601 is connected with granular metal outlet 502, and is suitable to do granular metal obtained above
Choosing processes, and obtains metallic iron and tailings.
Concrete, will can realize dividing of metal iron powder and mine tailing after cooled for gained granular metal, broken, dry type magnetic separation
From.After testing, the response rate of metallic iron reaches more than 90%.
After the system processing zinc leaching residue according to embodiments of the present invention is by mixing zinc leaching residue siccative with anthracite
Supply to rotary kiln, carry out pre-reduction treatment, and by reducing the anthracitic amount of allocating into, it is ensured that in rotary kiln, preheating section is
Oxidizing atmosphere, thus promote the decomposition of sulfate in zinc leaching residue and the volatilization of sulfur dioxide, it is pre-going back in ensureing kiln simultaneously
The former stage is weak reducing atmosphere, thus reduces the generation of zinc sulfide so that most of zinc and lead volatility in zinc leaching residue enter
Row flue is recovered with the form of zinc oxide and lead oxide, secondly by hot for gained in rotary kiln kiln slag and semi-coke and limestone
Carry out hot wafering process, be possible not only to make full use of the sensible heat of hot kiln slag, and in the addition of semi-coke can ensure that rotary hearth furnace
For reducing atmosphere, more of the prior art hot for gained kiln slag is carried out Water Quenching after carry out drying and processing again and compare, this
Application not only eliminates the water quenching technology in original technique, and the drying cost of kiln slag after eliminating shrend, and semi-coke
Addition can realize in kiln slag remaining zinc and the reduction of iron oxides and the reduction of silver and volatilization at a low price, thus is reducing energy consumption
While improve ferrum in secondary reduction processing procedure, silver, zinc and the reduction efficiency of lead, additionally limestone be added in subsequent process
In be possible not only to play the effect of flux, and the agglomeration of ferrum granule in reduction process can be promoted, thus reduce
Ensure while energy consumption that gained granular metal has higher degree of metalization, and by the hot pressing that hot pressing form will be used to obtain
Pelletizing supply carries out secondary reduction process to rotary hearth furnace, can significantly improve the utilization rate of reducing agent, and again at dry separation
Reason can realize slag sluicing system.Thus, the present processes is used can to realize the comprehensive of ferrum in zinc leaching residue, silver, zinc and lead
Reclaiming, and the volatility of sulfur reaches more than 80%, the response rate of ferrum reaches more than 90%, and Zinc volatilization rate reaches more than 99%, lead volatility
Rate reaches more than 98%, and silver volatility reaches more than 85%.
With reference to Fig. 4, the system processing zinc leaching residue according to embodiments of the present invention farther includes: waste heat boiler 700, cold
Radiator cooler 800 and bagroom 900.
According to embodiments of the invention, waste heat boiler 700 has flue dust entrance 701 and cooling flue dust outlet 702, and flue dust enters
Mouth 701 is connected with zinc smoke outlet 303 and the flue dust outlet 503 containing zinc oxide, lead oxide and silver respectively, and is suitable to return
The flue dust containing zinc oxide, lead oxide and silver that rotary kiln obtains zinc smoke and rotary hearth furnace obtains carries out waste heat recovery, obtains
Cooling flue dust.Thus, by obtained zinc smoke and the flue dust containing zinc oxide, lead oxide and silver are carried out waste heat and return
Receive, can be used for generating electricity by this part of waste heat, and the temperature of flue dust of lowering the temperature is down to about 400 DEG C, thus realize resource
Change greatly utilization.
According to embodiments of the invention, chiller 800 has cooling flue dust entrance 801 and cooling flue dust outlet 802, fall
Temperature flue dust entrance 801 is connected with cooling flue dust outlet 702, and is suitable to cooling flue dust obtained above is carried out cooling process, can
To obtain cooling down flue dust.Concrete, chiller can be surface-cooler, and flue dust temperature after surface-cooler of lowering the temperature
It is down to about 250 DEG C.
According to embodiments of the invention, bagroom 900 has cooling flue dust entrance 901, dust outlet 902 and gas
Entrance 903, cooling flue dust entrance 901 is connected with cooling flue dust outlet 802, and is suitable to cooling flue dust obtained above is carried out cloth
Bag gathers dust, such that it is able to collect dust.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, and limit the present invention never in any form.
Embodiment 1
By zinc leaching residue dry to the most aqueous < 10wt%, then allocate into dry slag weight 30% anthracite, given by disk
Supplying after the mixing of material machine and carry out prereduction to rotary kiln, pre-reduction temperature controls, at 800～1100 DEG C, to obtain zinc smoke
With hot kiln slag, in hot kiln slag, < 3wt%, the volatility of sulfur more than Zn content in 65%, and hot kiln slag is sulfur content
6wt%, kiln slag state is the loosest, does not has a harder caking, then by 800 DEG C of hot kiln slags discharging from rotary kiln kilneye through wind
Cold it is cooled to less than 500 DEG C, adds 20% limestone of kiln slag weight, the semi-coke grain of 10% carries out hot wafering, and will obtain
Hot pressing pelletizing is sent into high temperature rotary furnace bottom by conveyer device and is carried out secondary reduction, control temperature in rotary hearth furnace be 1250 DEG C～
1300 DEG C, the recovery time, at 30min, obtains granular metal and containing zinc oxide, lead oxide and the flue dust of silver, after reduction terminates
Obtain content of Pb&Zn in motlten metal agglomerate < 0.1%, silver content < 0.005%, and by obtained motlten metal agglomerate through cold
But, obtaining abrasive grit and tailings after broken, dry type magnetic separation, iron recovery can reach more than 81%.
Embodiment 2
By zinc leaching residue dry to the most aqueous < 10wt%, then allocate into dry slag weight 20% anthracite, given by disk
Supplying after the mixing of material machine and carry out prereduction to rotary kiln, pre-reduction temperature controls, at 900～1150 DEG C, to obtain zinc smoke
With hot kiln slag, in hot kiln slag, < 3wt%, the volatility of sulfur more than Zn content in 70%, and hot kiln slag is sulfur content
7wt%, kiln slag has a small amount of caking, then by the 800 DEG C of hot kiln slags discharged from rotary kiln kilneye through air-cooled be cooled to 500 DEG C with
Under, addition 20% limestone of kiln slag weight, the semi-coke grain of 15% carry out hot wafering, and by the hot pressing pelletizing obtained by carrying
Device is sent into high temperature rotary furnace bottom and is carried out secondary reduction, and in control rotary hearth furnace, temperature is 1350 DEG C～1400 DEG C, the recovery time
At 20min, obtaining granular metal and containing zinc oxide, lead oxide and the flue dust of silver, reduction obtains motlten metal group after terminating
Content of Pb&Zn in block < 0.07%, silver content < 0.003%, and by cooled, broken for obtained motlten metal agglomerate, dry type magnetic
Obtaining abrasive grit and tailings after choosing, iron recovery can reach more than 93%.
Embodiment 3
By zinc leaching residue dry to the most aqueous < 10wt%, then allocate into dry slag weight 20% anthracite, given by disk
Supplying after the mixing of material machine and carry out prereduction to rotary kiln, pre-reduction temperature controls, at 900～1150 DEG C, to obtain zinc smoke
With hot kiln slag, in hot kiln slag, < 3wt%, the volatility of sulfur more than Zn content in 70%, and hot kiln slag is sulfur content
7wt%, kiln slag has a small amount of caking, then by the 800 DEG C of hot kiln slags discharged from rotary kiln kilneye through air-cooled be cooled to 500 DEG C with
Under, addition 10% limestone of kiln slag weight, the semi-coke grain of 5% carry out hot wafering, and by the hot pressing pelletizing obtained by carrying
Device is sent into high temperature rotary furnace bottom and is carried out secondary reduction, and in control rotary hearth furnace, temperature is 1350 DEG C～1400 DEG C, the recovery time
At 20min, obtaining granular metal and containing zinc oxide, lead oxide and the flue dust of silver, reduction obtains motlten metal group after terminating
Content of Pb&Zn in block < 0.3%, silver content < 0.009%, and by cooled, broken for obtained motlten metal agglomerate, dry type magnetic separation
After obtain abrasive grit and tailings, iron recovery can reach more than 93%.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show
Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or spy
Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be in office
One or more embodiments or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the skill of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be tied by art personnel
Close and combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, revises, replaces and modification.
Claims (10)
1. the method processing zinc leaching residue, it is characterised in that including:
(1) zinc leaching residue is carried out drying and processing, in order to obtain zinc leaching residue siccative；
(2) described zinc leaching residue siccative is mixed with anthracite, in order to obtain mixed material；
(3) supply of described mixed material is carried out pre-reduction treatment to rotary kiln, in order to obtain hot kiln slag and zinc smoke；
(4) described hot kiln slag is carried out hot wafering process with semi-coke and limestone, in order to obtain hot pressing pelletizing；
(5) supply of described hot pressing pelletizing is carried out secondary reduction process to rotary hearth furnace, in order to obtain granular metal and containing aerobic
Change zinc, lead oxide and the flue dust of silver；
(6) described granular metal is carried out dry separation process, in order to obtain metallic iron and tailings.
Method the most according to claim 1, it is characterised in that in step (1), described zinc leaching residue is dried in material aqueous
Amount not higher than 10wt%.
Method the most according to claim 1 and 2, it is characterised in that in step (2), by described zinc leaching residue siccative with
Described anthracite is 100:(20～30 according to mass ratio) mix.
Method the most according to claim 3, it is characterised in that in step (3), the temperature of described pre-reduction treatment is
800～1150 degrees Celsius.
Method the most according to claim 1, it is characterised in that in step (4), the temperature of described hot kiln slag is not higher than
500 degrees Celsius.
Method the most according to claim 5, it is characterised in that in step (4), by described hot kiln slag and described semi-coke
It is 100:(10～20 with described limestone according to mass ratio): (5～25) mix.
Method the most according to claim 5, it is characterised in that in step (5), the temperature that described secondary reduction processes is
1250～1400 degrees Celsius, the time is 15～40 minutes.
Method the most according to claim 5, it is characterised in that farther include:
(7) described zinc smoke and the described flue dust containing zinc oxide, lead oxide and silver are carried out waste heat recovery, in order to dropped
Temperature flue dust；
(8) described cooling flue dust is carried out cooling process, in order to cooling flue dust；
(9) described cooling flue dust is carried out bag collection, in order to collect dust.
9. the system of the method implemented according to any one of claim 1-8, it is characterised in that including:
Drying unit, described drying unit has zinc leaching residue entrance and zinc leaching residue drier outlet；
Mixing arrangement, described mixing arrangement has zinc leaching residue siccative entrance, anthracite entrance and mixed material outlet, described zinc
Leached mud siccative entrance is connected with described zinc leaching residue drier outlet；
Rotary kiln, described rotary kiln has mixed material entrance, the outlet of hot kiln slag and zinc smoke outlet, described mixed material
Entrance is connected with the outlet of described mixed material；
Hot wafering device, described hot wafering device has hot kiln slag entrance, semi-coke entrance, limestone entrance and hot pressing pelletizing and goes out
Mouthful, described hot kiln slag entrance is connected with the outlet of described hot kiln slag；
Rotary hearth furnace, described rotary hearth furnace has hot pressing pelletizing entrance, granular metal outlet and contains zinc oxide, lead oxide and silver
Flue dust exports, and described hot pressing pelletizing entrance is connected with the outlet of described hot pressing pelletizing；
Dry separation device, described dry separation device has granular metal entrance, metallic iron outlet and tailings outlet, and described granular metal enters
Mouth is connected with the outlet of described granular metal.
System the most according to claim 9, it is characterised in that farther include:
Waste-heat recovery device, described waste-heat recovery device has flue dust entrance and cooling flue dust outlet, and described flue dust entrance is respectively
It is connected with the outlet of described zinc smoke and the described flue dust outlet containing zinc oxide, lead oxide and silver；
Chiller, described chiller has cooling flue dust entrance and cooling flue dust outlet, described cooling flue dust entrance and institute
State cooling flue dust outlet to be connected；
Bagroom, described bagroom has cooling flue dust entrance, dust outlet and gas outlet, described cooling flue dust
Entrance is connected with the outlet of described cooling flue dust.
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| CN113846234A (en) * | 2021-10-19 | 2021-12-28 | 新疆紫金有色金属有限公司 | Rotary kiln volatilization treatment method for high-silicon zinc leaching residues |
| CN114540628A (en) * | 2022-01-20 | 2022-05-27 | 云南云铜锌业股份有限公司 | Method for treating zinc dipping slag, zinc smelting gypsum slag and blast furnace gas ash |
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| CN107345277A (en) * | 2017-06-16 | 2017-11-14 | 广州湘龙金属加工有限公司 | A kind of ultrafine dust nano active alloy oxidation zinc preparation method |
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| CN113846234B (en) * | 2021-10-19 | 2022-10-11 | 新疆紫金有色金属有限公司 | Rotary kiln volatilization treatment method for high-silicon zinc leaching residues |
| CN114540628A (en) * | 2022-01-20 | 2022-05-27 | 云南云铜锌业股份有限公司 | Method for treating zinc dipping slag, zinc smelting gypsum slag and blast furnace gas ash |
| CN114540628B (en) * | 2022-01-20 | 2023-11-14 | 云南云铜锌业股份有限公司 | Method for treating zinc-impregnated slag, zinc smelting gypsum slag and blast furnace gas ash |
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Effective date of abandoning: 20190507 |