CN107904407A - One kind bismuth technique - Google Patents
One kind bismuth technique Download PDFInfo
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- CN107904407A CN107904407A CN201711241641.6A CN201711241641A CN107904407A CN 107904407 A CN107904407 A CN 107904407A CN 201711241641 A CN201711241641 A CN 201711241641A CN 107904407 A CN107904407 A CN 107904407A
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- bismuth
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- flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
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- Metallurgy (AREA)
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- Environmental & Geological Engineering (AREA)
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- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses one kind bismuth technique, is related to the manufacturing technology field of bismuth, comprises the following steps；Flue dust prepares；Flue dust pre-processes；Agglomeration；Melting；Alloy mold；Slag treatment；Fume treatment；Positive plate manufactures；Electrolysis；Novel residual anode processing；Thick bismuth manufacture；Refined bismuth manufactures.
Description
Technical field
The present invention relates to the manufacturing technology field of bismuth, is specially one kind bismuth technique.
Background technology
Metal of the bismuth for silvery white to pink, matter is crisp easily to be crushed, and the chemical property of bismuth is relatively stablized.Bismuth is in nature
Exist in the form of free metal and mineral, mineral have bismuthine, bismite etc..Bismuth metal is aoxidized by mineral after calcining into three
Two bismuths, then heat-treat and obtain altogether with carbon, high purity bismuth can be made with pyro-refining and electrorefining.Common bismuth process processed is led to
Chang Wei：Pulp, pickling, displacement, concentration, press filtration, dispensing, brickmaking, ball processed, sintering.Common bismuth process processed is with material
Waste, and the processing to exhaust gas is also not thorough enough, can cause air pollution.
The content of the invention
Present invention aims at one kind bismuth technique is provided, to solve the problems mentioned in the above background technology.
One kind bismuth technique, specifically includes following steps：
(1), flue dust prepares：Flue dust used is Copper making flue dust, contains lead, zinc, bismuth, cadmium, indium, arsenic in Copper making flue dust
Deng Multiple components.
(2), flue dust pre-processes：The technique gone out using pulp-water logging pre-processes flue dust, output washing slag and leachate,
Leachate adds iron to replace copper, and displacement mother liquor is concentrated by evaporation recycling zinc after removal of impurities, and liquid, which returns, after concentration leaches.
(3), agglomeration：Agglomeration is carried out to washing slag.
(4), melting：Washing slag after agglomeration is together with flux, reducing agent, according to a certain ratio, is manually directly added with wooden handcart
Enter smelting furnace, lead bismuth alloy, matte, clinker, flue gas are generated by smelting furnace melting.
(5), alloy mold：Lead bismuth alloy and matte are released by putting lead mouth, it is different according to fusing point, first hang out solid ice
Copper, liquid lead bismuth alloy mold.
(6), slag treatment：Clinker is released by slag tap, clinker is clarified by tundish, then flows out water quenching, Water Quenching Slag
Slag bath is directly placed into, cinder field is then transported to by automobile.
(7), fume treatment：Flue gas accepts thick dirt by gravity dust-precipitator, is sent into bagroom by exhaust blower and is removed into one
Dirt, enters back into level-one tubulent contact tower and accepts thin dirt and absorb SO2, two level tubulent contact tower is sent into by second exhaust blower and is further absorbed
SO2, it is up to standard after flue gas emptied by 40 meters of chimneys.
(8), positive plate manufactures：Lead bismuth alloy, the anode scrap of smelting furnace production load in pot, stir, are heated to after fusing
Removing dross is dragged at 500-550 DEG C, then is cast into positive plate, positive plate requirement is smooth, bright and clean, not slag inclusion and debris.
(9), it is electrolysed：Positive plate is shaped, rectifys ear is prepared to be arranged on frame by same pole span in anode, with anode hanger
Foam washing groove is hung to by driving, then send electrolytic cell tankage.
(10), novel residual anode processing：The residual acid of anode scrap washing surface in flushed channel, the then manual removal earth of positive pole, after stripping
Anode scrap is added in refining furnace.
(11), thick bismuth manufacture：The earth of positive pole, sodium carbonate, fine coal stir evenly by a certain percentage, add refining stove heat and melt
Change, slag making, release clinker and thick bismuth, clinker Returning smelting stove.
(12), refined bismuth manufactures：Thick bismuth adds casting iron pan fusing, and blowing air carries out refinement oxide during 700 DEG C of heating, pulls out
Scum silica frost, when being cooled to 400~450 DEG C, reinforcing body alkali, blasts compressed air except tellurium, tin after fusing.Pull scum silica frost zincification desilver out,
By chemical examination, chlorine is led to after silver is qualified and removes lead zinc, adds alkali finally to be refined after lead qualification.
(13), ingot casting：Cooling casting, produces No. 1 refined bismuth.
Preferably, the idiographic flow of the step (3) is：Outsourcing smelting smoke dust is transported to raw material storage, adds water to slurrying tank,
The flue dust in raw material storage, stirring, with leaching tanks are pumped into, by liquid-solid ratio requirement moisturizing in leaching tanks are added by a certain percentage
After be passed through steam heating and leach, leach it is good after press filtration, filtrate first replaces copper, produces copper sponge, displacement mother liquor removal of impurities, after removal of impurities
Liquid concentrates extracting sulfuric acid zinc, and liquid, which returns, after concentration is recycled to leaching, and filter residue send the agglomeration of meltshop workshop.
Preferably, the cleaning solution of tubulent contact tower is alkalescence in step (7), is pumped into tubulent contact tower by circulation, flows out tubulent contact tower
Cleaning solution is clarified by clarifying basin, and supernatant is sent to sewage disposal system, flue dust Returning smelting stove melting, after sewage disposal
Qualifying liquid flows into circulatory pool, into tubulent contact tower cleaning solution process.
Preferably, electrolyte is made of silicofluoric acid and fluosilicic lead plumbate in step (9).
Preferably, in order to ensure the quality of cathode lead in step (9), add in the electrolytic solution suitable gelatine 0.5~
0.8kg/t, and electrolyte is extracted out according to electrolyte situation and is filtered through filter press, cathode send foam washing groove foam washing after going out groove, then send casting
Iron pan heats up 480 DEG C or so, pulls scum silica frost after fusing out, is continuously heating to more than 500 DEG C, after adding solid base in stirring, after
When continuous stirring 0.5 is small, drags for alkaline residue, add NaOH and continue to stir half an hour, big residue is pulled on peace and quiet pot side out, it is qualified after extremely
480 DEG C or so are cast into lead pig and send storehouse to stack.
Preferably, in lead bismuth alloy electrolytic process, under plumbum ion concentration and fluosilicic acid concentration in electrolyte are continuous
Drop, constantly adds lead and silicofluoric acid, additional way is according to operating condition：Silicofluoric acid is added in liquid pool, is added while stirring
Enter yellow lead, Lower tank is added to after dissolving, into electrolyte circulation system.
Preferably, the flue gas produced in the manufacture of thick bismuth is sent into bag type dust collection room through wind turbine, then through more than tubulent contact tower alkaline washing
After dirt and a small amount of pernicious gas composition, emptied through chimney.
Preferably, the flue gas produced in refined bismuth manufacture is cold using water-cooled flue, surface-cooler after expansion chamber settles
But, the flue gas produced after cooling and in the manufacture of thick bismuth gathers dust into bagroom together, is then sent into tubulent contact tower by exhaust blower,
Emptied through tower top chimney.
Beneficial effects of the present invention are：Bismuth is refined using relatively simple directly method, main material is useless after copper metallurgy
Slag, if these smelting smoke dusts return to copper system system, not only reduces stove disposal ability, deteriorates the working of a furnace, and reduce material
Waste, multiple processing has been done to the flue dust of discharge in this technique, to ensure that the exhaust gas being discharged into air will not cause dirt to air
Dye, the soot fraction after processing are also recycled, and improve the utilization rate of product.
Embodiment
Below by the description to embodiment, the shape of for example involved each component of embodiment of the invention, structure
Make, the mutual alignment between each several part and connection relation, the effect of each several part and operation principle, manufacturing process and operate with
Method etc., is described in further detail, to help those skilled in the art to have inventive concept of the invention, technical solution
More complete, accurate and deep understanding.
One kind bismuth technique, specifically includes following steps：
(1), flue dust prepares：Flue dust used is Copper making flue dust, contains lead, zinc, bismuth, cadmium, indium, arsenic in Copper making flue dust
Deng Multiple components.
(2), flue dust pre-processes：The technique gone out using pulp-water logging pre-processes flue dust, output washing slag and leachate,
Leachate adds iron to replace copper, and displacement mother liquor is concentrated by evaporation recycling zinc after removal of impurities, and liquid, which returns, after concentration leaches.
(3), agglomeration：Agglomeration is carried out to washing slag.
(4), melting：Washing slag after agglomeration is together with flux, reducing agent, according to a certain ratio, is manually directly added with wooden handcart
Enter smelting furnace, lead bismuth alloy, matte, clinker, flue gas are generated by smelting furnace melting.
(5), alloy mold：Lead bismuth alloy and matte are released by putting lead mouth, it is different according to fusing point, first hang out solid ice
Copper, liquid lead bismuth alloy mold.
(6), slag treatment：Clinker is released by slag tap, clinker is clarified by tundish, then flows out water quenching, Water Quenching Slag
Slag bath is directly placed into, cinder field is then transported to by automobile.
(7), fume treatment：Flue gas accepts thick dirt by gravity dust-precipitator, is sent into bagroom by exhaust blower and is removed into one
Dirt, enters back into level-one tubulent contact tower and accepts thin dirt and absorb SO2, two level tubulent contact tower is sent into by second exhaust blower and is further absorbed
SO2, it is up to standard after flue gas emptied by 40 meters of chimneys.
(8), positive plate manufactures：Lead bismuth alloy, the anode scrap of smelting furnace production load in pot, stir, are heated to after fusing
Removing dross is dragged at 500-550 DEG C, then is cast into positive plate, positive plate requirement is smooth, bright and clean, not slag inclusion and debris.
(9), it is electrolysed：Positive plate is shaped, rectifys ear is prepared to be arranged on frame by same pole span in anode, with anode hanger
Foam washing groove is hung to by driving, then send electrolytic cell tankage.
(10), novel residual anode processing：The residual acid of anode scrap washing surface in flushed channel, the then manual removal earth of positive pole, after stripping
Anode scrap is added in refining furnace.
(11), thick bismuth manufacture：The earth of positive pole, sodium carbonate, fine coal stir evenly by a certain percentage, add refining stove heat and melt
Change, slag making, release clinker and thick bismuth, clinker Returning smelting stove.
(12), refined bismuth manufactures：Thick bismuth adds casting iron pan fusing, and blowing air carries out refinement oxide during 700 DEG C of heating, pulls out
Scum silica frost, when being cooled to 400~450 DEG C, reinforcing body alkali, blasts compressed air except tellurium, tin after fusing.Pull scum silica frost zincification desilver out,
By chemical examination, chlorine is led to after silver is qualified and removes lead zinc, adds alkali finally to be refined after lead qualification.
(13), ingot casting：Cooling casting, produces No. 1 refined bismuth.
In the present embodiment, the idiographic flow of the step (3) is：Outsourcing smelting smoke dust is transported to raw material storage, adds water to slurry
Change groove, add the flue dust in raw material storage, stirring, with leaching tanks are pumped into, by liquid-solid ratio requirement in leaching tanks by a certain percentage
Steam heating is passed through after moisturizing to leach, leaches good rear press filtration, and filtrate first replaces copper, produces copper sponge, displacement mother liquor removal of impurities, is removed
Liquid concentration extracting sulfuric acid zinc after miscellaneous, liquid, which returns, after concentration is recycled to leaching, and filter residue send the agglomeration of meltshop workshop.
In the present embodiment, the cleaning solution of tubulent contact tower is alkalescence in step (7), is pumped into tubulent contact tower by circulation, outflow is rapid
The cleaning solution of ball tower is clarified by clarifying basin, and supernatant is sent to sewage disposal system, flue dust Returning smelting stove melting, at sewage
Qualifying liquid after reason flows into circulatory pool, into tubulent contact tower cleaning solution process.
In the present embodiment, electrolyte is made of silicofluoric acid and fluosilicic lead plumbate in step (9).
In the present embodiment, suitable gelatine is added in the electrolytic solution in order to ensure the quality of cathode lead in step (9)
0.5~0.8kg/t, and electrolyte is extracted out according to electrolyte situation and is filtered through filter press, cathode send foam washing groove foam washing after going out groove,
Send casting iron pan to heat up 480 DEG C or so again, pull scum silica frost after fusing out, be continuously heating to more than 500 DEG C, solid is added in stirring
After alkali, continue stirring 0.5 it is small when, drag for alkaline residue, add NaOH and continue to stir half an hour, peace and quiet pot side pulls big residue out, closes
Being cast into lead pig to 480 DEG C or so after lattice send storehouse to stack.
In the present embodiment, in lead bismuth alloy electrolytic process, plumbum ion concentration and fluosilicic acid concentration in electrolyte are not
It is disconnected to decline, lead and silicofluoric acid are constantly added according to operating condition, additional way is：Silicofluoric acid, side stirring are added in liquid pool
Side adds yellow lead, Lower tank is added to after dissolving, into electrolyte circulation system.
In the present embodiment, the flue gas produced in thick bismuth manufacture is sent into bag type dust collection room through wind turbine, then through tubulent contact tower alkalescence
More than washing after dirt and a small amount of pernicious gas composition, emptied through chimney.
In the present embodiment, the flue gas produced in refined bismuth manufacture is cooled down after expansion chamber settles using water-cooled flue, surface
Device cools down, and the flue gas produced after cooling and in the manufacture of thick bismuth gathers dust into bagroom together, is then sent into rapid ball by exhaust blower
Tower, empties through tower top chimney.
The present invention is exemplarily described above, it is clear that present invention specific implementation is not subject to the restrictions described above,
As long as the improvement of the various unsubstantialities of inventive concept and technical scheme of the present invention progress is employed, or it is not improved by this
The design of invention and technical solution directly apply to other occasions, within protection scope of the present invention.The guarantor of the present invention
Shield scope should be determined by the scope of protection defined in the claims.
Claims (8)
1. one kind bismuth technique, it is characterised in that specifically include following steps：
(1), flue dust prepares：Flue dust used is Copper making flue dust, and it is a variety of to contain lead, zinc, bismuth, cadmium, indium, arsenic etc. in Copper making flue dust
Component.
(2), flue dust pre-processes：The technique gone out using pulp-water logging pre-processes flue dust, output washing slag and leachate, leachate
Iron is added to replace copper, displacement mother liquor is concentrated by evaporation recycling zinc after removal of impurities, and liquid, which returns, after concentration leaches.
(3), agglomeration：Agglomeration is carried out to washing slag.
(4), melting：Washing slag after agglomeration is together with flux, reducing agent, according to a certain ratio, is manually directly added into wooden handcart molten
Furnace, lead bismuth alloy, matte, clinker, flue gas are generated by smelting furnace melting.
(5), alloy mold：Lead bismuth alloy and matte are released by putting lead mouth, it is different according to fusing point, first hang out solid matte, liquid
State lead bismuth alloy mold.
(6), slag treatment：Clinker is released by slag tap, clinker is clarified by tundish, then flows out water quenching, and Water Quenching Slag is direct
Slag bath is put into, cinder field is then transported to by automobile.
(7), fume treatment：Flue gas accepts thick dirt by gravity dust-precipitator, and bagroom is sent into a dedusting by exhaust blower, then
Thin dirt is accepted into level-one tubulent contact tower and absorbs SO2, two level tubulent contact tower is sent into by second exhaust blower and further absorbs SO2, it is up to standard
Flue gas afterwards is emptied by 40 meters of chimneys.
(8), positive plate manufactures：Lead bismuth alloy, the anode scrap of smelting furnace production load in pot, are stirred after fusing, are heated to 500-550
DEG C when drag for removing dross, then be cast into positive plate, positive plate requires smooth, bright and clean, not slag inclusion and debris.
(9), it is electrolysed：Positive plate is shaped, rectifys ear is prepared to be arranged on frame by same pole span in anode, passes through row with anode hanger
Car is hung to foam washing groove, then send electrolytic cell tankage.
(10), novel residual anode processing：The residual acid of anode scrap washing surface in flushed channel, then the manual removal earth of positive pole, the anode scrap after stripping
It is added in refining furnace.
(11), thick bismuth manufacture：The earth of positive pole, sodium carbonate, fine coal stir evenly by a certain percentage, add refining stove heat fusing, make
Slag, releases clinker and thick bismuth, clinker Returning smelting stove.
(12), refined bismuth manufactures：Thick bismuth adds casting iron pan fusing, and blowing air carries out refinement oxide during 700 DEG C of heating, pulls scum silica frost out,
When being cooled to 400~450 DEG C, reinforcing body alkali, blasts compressed air except tellurium, tin after fusing.Pull scum silica frost zincification desilver, passing through out
Test, chlorine is led to after silver is qualified and removes lead zinc, adds alkali finally to be refined after lead qualification.
(13), ingot casting：Cooling casting, produces No. 1 refined bismuth.
2. one kind bismuth technique according to claim 1, it is characterised in that the idiographic flow of the step (3) is：Outsourcing
Smelting smoke dust is transported to raw material storage, adds water to add the flue dust in raw material storage by a certain percentage, stirring, is soaked with being pumped into slurrying tank
Going out groove, by steam heating leaching is passed through after liquid-solid ratio requirement moisturizing in leaching tanks, leach good rear press filtration, filtrate first replaces copper,
Copper sponge is produced, displacement mother liquor removal of impurities, liquid concentrates extracting sulfuric acid zinc after removal of impurities, and liquid, which returns, after concentration is recycled to leaching, and filter residue send molten
Refine the agglomeration of workshop workshop.
3. one kind bismuth technique according to claim 1, it is characterised in that the cleaning solution of tubulent contact tower is alkali in step (7)
Property, tubulent contact tower is pumped into by circulation, the cleaning solution for flowing out tubulent contact tower is clarified by clarifying basin, and supernatant is sent to sewage disposal system
System, flue dust Returning smelting stove melting, the qualifying liquid after sewage disposal flows into circulatory pool, into tubulent contact tower cleaning solution process.
4. one kind bismuth technique according to claim 1, it is characterised in that electrolyte is by silicofluoric acid and silicon in step (9)
Fluoric acid lead forms.
5. one kind bismuth technique according to claim 1, it is characterised in that in order to ensure the matter of cathode lead in step (9)
Amount, adds suitable 0.5~0.8kg/t of gelatine in the electrolytic solution, and extracts electrolyte out through filter press mistake according to electrolyte situation
Filter, cathode send foam washing groove foam washing after going out groove, then send casting iron pan to heat up 480 DEG C or so, pull scum silica frost after fusing out, are continuously heating to
More than 500 DEG C, after adding solid base in stirring, continue stirring 0.5 it is small when, drag for alkaline residue, add NaOH and continue stirring half
Hour, big residue is pulled on peace and quiet pot side out, and being cast into lead pig to 480 DEG C or so after qualified send storehouse to stack.
6. one kind bismuth technique according to claim 5, it is characterised in that in lead bismuth alloy electrolytic process, electrolyte
In plumbum ion concentration and fluosilicic acid concentration constantly decline, lead and silicofluoric acid are constantly added according to operating condition, additional way is：
Silicofluoric acid is added in liquid pool, yellow lead is added while stirring, Lower tank is added to after dissolving, into electrolyte circulation system.
7. one kind bismuth technique according to claim 1, it is characterised in that the flue gas produced in thick bismuth manufacture is sent through wind turbine
Enter bag type dust collection room, then after dirt more than tubulent contact tower alkaline washing and a small amount of pernicious gas composition, emptied through chimney.
8. one kind bismuth technique according to claim 1, it is characterised in that the flue gas produced in refined bismuth manufacture is through expansion chamber
Cooled down after sedimentation using water-cooled flue, surface-cooler, the flue gas produced after cooling and in the manufacture of thick bismuth is together into bag collection
Device gathers dust, and is then sent into tubulent contact tower by exhaust blower, is emptied through tower top chimney.
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| CN110004298A (en) * | 2019-04-04 | 2019-07-12 | 福建铭祥金属材料有限公司 | A kind of industry dangerous waste Resource comprehensive utilization method |
| CN110607452A (en) * | 2019-09-09 | 2019-12-24 | 攀枝花火凤凰再生资源回收利用有限责任公司 | Comprehensive utilization method of iron ore sintering smoke dust leaching solution |
| CN115354172A (en) * | 2022-08-01 | 2022-11-18 | 河南豫光金铅股份有限公司 | Method for improving direct yield in tellurium removal process in high-tellurium crude bismuth pot refining |
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Application publication date: 20180413 |