CN101565780B - Smelting method of polymetallic lead-zinc sulfide ore - Google Patents
Smelting method of polymetallic lead-zinc sulfide ore Download PDFInfo
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Abstract
The invention discloses a smelting method of a polymetallic lead-zinc sulfide ore, which comprises the steps: carbonation transformation and solid-liquid separation filter are carried out on the polymetallic lead-zinc sulfide ore, solid phase is extracted by an extracting agent and elemental sulfur is recovered, then a carbonation lead-zinc ore containing residual sulfide, a sulfur production agent, a reducing agent and an additive are mixed and smelted in an electric furnace to obtain crude lead; meanwhile, a bag type dust collector collects dusts in smoke dusts generated in the smelting process, the smoke dusts are added into different treating agents according to different metals after being stirred and leached in alkali solution and oxidant solution, and other valuable metals in the smoke dusts are recovered. By transforming the sulfur in the polymetallic lead-zinc sulfide ore into solid sulfur, the invention fundamentally eliminates the influence of gas containing the sulfur to atmospheric evironmental quality, avoids evironmental pollution, recovers various valuable metal elements at the same time, and enhances the comprehensive recovery utilizaiton rate of raw materials.
Description
Technical field
The invention belongs to a kind of method of reducing of metal, particularly relate to a kind of smelting process of polymetallic lead-zinc sulfide ore.
Background technology
Polymetallic lead-zinc sulfide ore contains base metals such as lead, zinc, and normal association has uncommon precious metals such as molybdenum, germanium, indium, vanadium, and gangues such as sulphur, silicon, aluminium; Traditional smelting process is a blast furnace refining pot method; There are shortcomings such as long flow path, energy consumption is big, environmental pollution is big in this method, has occurred direct refining the late nineteen eighties in last century successively to control method, like basic husband's Saite method (flash oven process), oxygen top refining time refining therapy at the bottom of method (TBRC method) and the oxygen; But do not have difference in principle with regard to its oxidation and reduction principle and blast furnace refining pot method; Being oxidation---retailoring, its oxidising process are the sintering processs that adopts, and must under hot conditions, carry out; Not only power consumption comprehensive reutilization rate big, raw material is low, and in oxidising process, can discharge a large amount of sulfurous gass.
In order to eliminate sulfurous gas, to contain the pollution to environment of Pb-Zn dust and lead steam, in recent decades, many metallargists are devoted to study plumbous hydrometallurgy, conclude and get up to have acid the leaching, and alkalescence leaches, and salt leaches and the amine leaching.Representational method mainly contains [what friendly equality, the transformation of lead smelting in China technology geared to the 21st century and development thinking, non-ferrous metal: smelting part, 2000,2-6]: (1) FeCl
3Leaching obtains PbCl
2, PbCl
2Fused salt electrolysis gets plumbous or aqueous electrolysis gets plumbous.But this method exists aqueous chloride solution and chlorine corrosion property strong aspect industriallization; Lead solubleness in chloride system is low, causes equipment size big, increases difficulties such as investment.(2) oxidation of silicofluoric acid medium is leached one and is purified an electrodeposition, and it is fast that it leaches speed of response, and plumbous solubleness in silicofluoric acid solution is bigger, all is its advantage, however because Fe
3+Being reduced to Fe and being easy to carry out than the reaction that Pb is reduced to metallic lead, so need to adopt diaphragm electrolysis, is again its industrialized where the shoe pinches.(3) the lead ore concentrate solid phase transforms the plumbous diaphragm electrolysis output of flotation monochlor(in)ate spongy lead, uses FeCl
3One NaCl solution makes lead be converted into PbCl by PbS
2, use the way of flotation then, sub-elect the sulphur concentrate and the lead chloride that contain other metallic sulfide.The lead chloride diaphragm electrolysis is used P
205Anionic membrane, electrolysis are with graphite or be coated with nail titanium net and do anode, and the titanium plate is done negative electrode, and the spongy lead that electrodeposition produces is fallen on the woven dacron travelling belt of cell bottom, is seen off outside the groove by machinery, and founding becomes product after the densification.But need use methods such as diaphragm electrolysis in the smelting process, there is certain difficulty in operation, and energy consumption is also bigger.
Summary of the invention
One of technical issues that need to address of the present invention are that the sulphur in the polymetallic lead-zinc sulfide ore is changed into solid sulfur, fundamentally eliminate the influence of sulfurous gas to atmosphere quality, reduce environmental pollution;
Another technical problem that the present invention need solve is valuable metal comprehensive reutilization rate and the mixed smelting of end grade polymetallic lead-zinc sulfide ore that improves in the raw material.
In order to address the above problem; One side of the present invention provides a kind of smelting process of polymetallic lead-zinc sulfide ore; It is characterized in that polymetallic lead-zinc sulfide ore through carbonating transform, after solid-liquid separation is filtered, solid phase reclaims elemental sulfur with the extraction agent extraction, the lead carbonate zinc ore that will contain remaining sulfide with make sulphur agent, reductive agent and additive and mix and carry out melting.Wherein make the sulphur agent and be preferably the sulfate cinder that is rich in red stone, reductive agent is preferably fine coal or coke powder, and additive is preferably soda; Extraction agent is preferably from kerosene or tetrafluoroethylene; The lead carbonate zinc ore that contains remaining sulfide with make sulphur agent, reductive agent and additive and mix preferred electrosmelting when carrying out melting.
The method that the present invention provides a kind of polymetallic lead-zinc sulfide ore carbonating to transform on the other hand: it is to be transforming agent with the ammonium carbonate salts that described polymetallic lead-zinc sulfide ore carbonating transforms; In the reaction process of the polymetallic lead-zinc sulfide ore breeze and the ammonium carbonate salts aqueous solution, feed oxygen-containing gas, the reaction after-filtration must contain many metals lead carbonate zinc ore of remaining sulfide.It preferably is transforming agent with the ammonium bicarbonate aqueous solution; In having the steel retort of whisking appliance; The mass ratio of the solid-liquid of breeze and ammonium bicarbonate aqueous solution is 1: 5, the concentration 0.8mol/L of ammonium bicarbonate aqueous solution, 50 ℃ ± 5 ℃ of temperature of reaction; Continuous bubbling air in the reaction process reacts many metals lead carbonate zinc ore that 5～6 hours after-filtration must contain remaining sulfide.
Further aspect of the present invention provides the method for extraction sulphur in the smelting process of polymetallic lead-zinc sulfide ore; The method of said extraction sulphur is for obtaining solid product and kerosene by solid-liquid mass ratio 1: 5 after the polymetallic lead-zinc sulfide ore carbonating is transformed; Pack in the sealed vessel, be heated to 120 ℃, filtered while hot; Filtrating is cooled to room temperature, separates out elementary sulfur.
One aspect of the present invention also provides the slag that the smelting of polymetallic lead-zinc sulfide ore produces and the treatment process of iron sulphur, after slag and the weathering of iron sulphur are sieved, tells slag; With 60～70 ℃ hot water leachings 3 times; The slag that soaks after the filtration is sized mixing, and with 70～80 ℃ of hot washes, filters then; Merge the immersion liquid and the washing water that obtain, handle through carbonating and reclaim molybdenum and regeneration yellow soda ash; To soak slag in drying at room temperature, and then water waters and dries repeatedly, let the color of iron sulphur change reddish yellow gradually into, the back gets the matte slag after extracting sulphur with extraction process.
One aspect of the present invention also provides a kind of many metals zinc sulphide lead ore to smelt the flue dust recovery method that produces; The lead carbonate zinc ore that will contain remaining sulfide with make sulphur agent, reductive agent and additive and mix and carry out the flue dust that melting produces and stir leaching with sodium hydroxide solution; The oxygenant that adds fume amount 6% in the leaching liquid; After solid-liquid separation was filtered, adding concentration by the ge content in the filtrating was 30% tannin, and the reaction after-filtration obtains germanic tannin germanium concentrate more than 2%; Add zinc powder in the alkaline filtrate behind the heavy germanium, the reaction after-filtration obtains spongy lead; Feed dioxide gas in the filtrating, a room temperature reaction 2-3 hour after-filtration gets zinc subcarbonate, and filtrating is converted into sodium hydroxide solution behind lime causticization, returns after it is concentrated and leaches the new flue dust of operation leaching.Preferably resulting flue dust is stirred leaching with sodium hydroxide solution at 95 ℃ ~ 100 ℃, add the oxygenant SODIUMNITRATE of fume amount 6% in the leaching liquid, leaching time 90 minutes; Filtering, is 30% tannin then by the adding of the ge content in filtrating concentration, and germanium is 1/30th at the content of tannin; Stir; Precipitation temperature is 60～70 ℃, 20 minutes stirring reaction time, filters and obtains germanic tannin germanium concentrate more than 2%; The zinc powder that adds granularity-200 in the basic soln behind the heavy germanium, 1.5～2 hours after-filtration of 40 ℃～50 ℃ stirring reactions obtain lead bullion; Feed the 0.6Mpa dioxide gas in the filtrating, a room temperature reaction 2-3 hour after-filtration gets zinc subcarbonate, and surplus liquid is converted into sodium hydroxide solution behind lime causticization, it is concentrated into contain 300g/L, returns and leaches the new flue dust of operation leaching.
Compare with existing many metallic leads zinc ore smelting technology, there is following beneficial effect in the present invention:
1, fundamentally eliminates the influence of sulfurous gas, avoided environmental pollution as far as possible atmosphere quality;
2, the valuable metal recovery utilization rate is high in the raw material, at the bottom of the feed stock for blast furnace grade, has practiced thrift smelting cost.
3, utilize industrial residue such as calcined pyrite (sulfate cinder), both provided cost savings, reclaimed non-ferrous metal and the precious metal in the waste residue simultaneously again.
Description of drawings
Fig. 1 polymetallic lead-zinc sulfide ore or concentrate carbonating transform---and sulphur smelter flowsheet figure is made in reduction
The recycling schema of the flue dust that produces during Fig. 2 polymetallic lead-zinc sulfide ore or concentrate carbonating transform
Embodiment
With the raw material composition is (mass percent): Pb 25-48%, Zn 6-13%, Fe 5.5-22%, S 9-22%, SiO
22-13%, Al
2O
30.6-2.3%; Wherein gold is Ag 180-580g/t with the content of silver; Au 0.8-1.3g/t, breeze granularity-200 purpose polymetallic lead-zinc sulfide ore is an embodiment of the present invention, but content of the present invention is not limited to this specific embodiment; Be out of shape and improve to technical scheme of the present invention, all should drop in protection scope of the present invention.
1, the carbonating of polymetallic lead-zinc sulfide ore transforms
Reaction formula: PbS (Gu)+(NH4)
2CO
3(liquid)+1/2O
2(gas)+H
2O (liquid)=PbCO
3(Gu)+S ° (Gu)+2NH
4OH (liquid)
With the ammonium bicarbonate aqueous solution is transforming agent, and in having the steel retort of whisking appliance, the solid-to-liquid ratio of breeze and ammonium bicarbonate aqueous solution is 1: 5 (mass ratio); The concentration 0.8mol/L of ammonium bicarbonate aqueous solution; 50 ℃ ± 5 ℃ of temperature of reaction, continuous bubbling air reacts after 5～6 hours in reaction process; Solid-liquid separation is filtered, and (staple of filtrating is NH to isolated solid phase part
4OH, otherwise processed).The composition of solid phase part is mainly the gangue in carbonic acid lead ore and a small amount of unconverted lead-zinc sulfide ore and the raw material, has also comprised the sulfide of contained Au, Ag and unreacted Cu, Zn, Mo and the elemental sulfur that is converted to.Lead sulfide carbonating transformation efficiency 75%～85% in the lead-zinc sulfide ore.
2, from solid product, extract sulphur
Adopting kerosene or tetrafluoroethylene is extraction agent.Isolated solid product and kerosene or tetrafluoroethylene among the embodiment 1 are incorporated with in the sealed vessel of reflux exchanger and whisking appliance by solid-to-liquid ratio 1: 5 (weight), adopt chuck to be heated to 120 ℃, the elemental sulfur in the raw material promptly is dissolved in kerosene; Filtered while hot; To carry the sulphur liquid cooling then to room temperature, separate out elementary sulfur, and cross and filter sulphur; Sulfur purity reaches 99%, and the desulfurization filter is more than 96%.The kerosene of extraction elementary sulfur returns collection stream operation, recycles.
3, the molten refining of sulphur is made in the carbonic acid lead ore reduction behind the extraction sulphur
With the carbonic acid lead ore after the desulfurization with make sulphur agent, additive, reductive agent, the mixed ball of flux or the group of pressure.Make the sulphur agent with sulfate cinder, the consumption of sulfate cinder can confirm that sulfate cinder not only should satisfy the requirement that sulphur is made in reduction, also will satisfy the requirement of slag making simultaneously through stoichiometric calculation, and slag contains FeO and is controlled in 22%～32% scope; Additive is a soda, and the amount of soda is 6～10% of an ore deposit amount; Flux is lime powder, and its consumption is 2～4% of an ore deposit amount; Reductive agent is fine coal or coke powder, granularity 0～2mm, and the fixed carbon content requirement is greater than 76%, and consumption is 6～8% of an ore deposit amount; Diameter of phi 10～Φ 25mm of pellet; The agglomerate particle size diameter is 25～40mm then, and the pelletizing or the agglomerate moisture content of going into stove require less than 2%, fall index (＞5mm)＞87%; Dissolving the refining operation is in the electric furnace of 1250KVA, to carry out; WV 82V, working current 8812A dissolves 1050～1150 ℃ of refining temperature).
The product that electric furnace reduction is made the sulphur melting is:
1), lead bullion: Pb, Au, Ag in the lead bullion rich material, the Pb recovery＞97%, the Au recovery＞98%, the Ag recovery＞95%, plumbous content＞98% in the lead bullion, lead bullion can sell.
2), iron sulphur: claim slag matte or sodium matte again.Productive rate is that major ingredient is FeS, NaS, Na into 7～10% of stove ore deposit amount
2SiO
3, iron sulphur is 86% bronze medal (Cu) in the rich material also, 21% zinc (Zn), 90% selenium and tellurium, and 96% above molybdenum (Mo).Iron sulphur can be used as the raw material that extracts copper (Cu), molybdenum (Mo) and reclaim sulphur (S).
3), flue dust: flue dust is the pulverulent material that captures through bagroom, and productive rate is 6～13% of a material quantity, and the lead in raw material part volatilization less gets into flue dust, and 78% zinc and 60% germanium get into flue dust.From flue dust, can reclaim zinc, lead, germanium.
4), slag: the SiO of the overwhelming majority in the raw material
2, Al
2O
3, whole CaO and part FeO get into slag, and slag contains lead content less than 0.5%, and this slag can be sold the cement mill and use.
5), furnace gas: the cigarette furnace gas through behind the pulverulent material of bagroom capture is mainly composition CO
2Gas, CO
2Gas is used as the carbonating of back operation and handles use.
4, the treatment process of iron sulphur
Because iron sulphur contains Na
2S is easy to the weathering that absorbs water, and the iron sulphur after the weathering is sieved, and tells slag; With 60～70 ℃ hot water leaching, Gu liquid/weight ratio is 3: 1, leaching time 50min; Gu soak slag again by liquid/weight ratio 1.5 pulp washings after the filtration, 70～80 ℃ of temperature of washing water, washing 60min after-filtration; Immersion liquid and washing water are merged, and this has just guaranteed that most sodium salts change solution in the iron sulphur, leach liquor also enrichment the molybdenum more than 96% in the iron sulphur.Leached mud has kept copper, the zinc more than 98% more than the FeS and 99% that leaches in the material.This slag can further extract export trade behind the sulphur, and leach liquor is then handled through carbonating and reclaimed molybdenum and regeneration yellow soda ash.
5, from water logging iron sulphur slag, further extract sulphur
Water logging iron sulphur slag is at room temperature dried naturally, and then water waters, dry, several times let the color of iron sulphur change reddish yellow gradually into repeatedly, and FeS is oxidized to red stone (Fe
2O
3) and elementary sulfur.When the transformation efficiency of FeS reaches more than 80%, extract sulphur by the method for front operation kerosene extraction sulphur again.Sulphur is carried twice in the front, and recyclable raw material 99% sulphur is Fe when carrying the remaining thing behind the sulphur
2O
3, this oxide compound (matte slag) contains Cu8 ~ 12%, Zn6 ~ 9%, Pb4 ~ 8%, Fe35 ~ 40%, Ag550 ~ 880g/t.
6, the carbonating of leach liquor in the step 3 and the filtrating in the step 1
(staple is CO to utilize the furnace gas that produces among the embodiment 3
2) respectively two kinds of solvents are carried out the carbonating processing.The carbonating temperature is 40～50 ℃, carbonization pressure 0.6Mpa, and carbonization time 2-3h, iron sulphur leach liquor is separated out NaHCO under these conditions
3, make soda be able to regeneration, the soda consumption of the recyclable whole process 80% of the leach liquor among the embodiment 4.The solution of separating out behind the sodium hydrogencarbonate can adopt conventional method from solution, to reclaim molybdenum.
Filtrating in the step 1 is changed ammonium bicarbonate soln under these conditions again into, and backspace lead-zinc sulfide ore carbonating transforms operation, recycles.Through the NH of the recyclable whole process of above-mentioned processing more than 90%
4HCO
37, reclaim germanium, lead, zinc from flue dust
The concentration 300g/L of sodium hydroxide solution, the solid-to-liquid ratio of flue dust and sodium hydroxide solution is 1: 6,95 ℃ ~ 100 ℃ of extraction temperatures; During the sodium hydroxide solution leaching, add the oxygenant SODIUMNITRATE of flue dust weight 6%, extraction time 90min; Under these conditions in the flue dust leaching yield of zinc greater than 92%; Plumbous leaching yield is greater than 95%, and the leaching yield of germanium is greater than 95%, and leached mud stores through the washing back.
8, from the alkali immersion liquid of embodiment 7, reclaim germanium
Germanium (Ge) cubage of pressing in the solution adds tannin; Tannin and germanium reaction generate tannin germanium, and germanium: the weight ratio of tannin=1: 30 (in ge content), the concentration of tannin are 30%; Temperature of reaction is 60～70 ℃; Stirring reaction time 20min, after-filtration carry out solid-liquid separation and extract germanium, obtain germanic tannin germanium concentrate more than 2%.
9, from the basic soln behind the heavy germanium of step 8, reclaim lead
Plumbous recovery employing zinc dust precipitation, zinc powder particle size-200,40 ℃～50 ℃ of displacement temperature, time swap 1.5～2h, and constantly stir, output spongy lead, after-filtration carry out solid-liquid separation and extract lead, and the plumbous recovery is greater than 99%.Spongy lead is put into the plumbous cover half that dissolves the refining operation through after washing drying, and when utilizing out lead, the sensible heat of molten lead liquid becomes base bullion lead with its impulsive motion.
10, from the solution behind the recovery lead of step 9, reclaim zinc
Feed the 0.6Mpa dioxide gas in the alkalitropism solution, thermotonus 2-3h, the zinc in the solution is promptly with ZnCO
3.Zn (OH)
2Form from solution, separate out, after-filtration carries out solid-liquid separation and extracts zinc subcarbonate, the filtrating of extracting behind the zinc subcarbonate is mainly Na
2CO
3Solution behind lime causticization, is converted into NaOH solution, and its solution concentration to containing NaOH 300g/L concentration, is returned and leached the new flue dust of operation leaching, recycle.
Claims (5)
1. the smelting process of a polymetallic lead-zinc sulfide ore; It is characterized in that in the reaction process of the polymetallic lead-zinc sulfide ore powder and the transforming agent ammonium carbonate salts aqueous solution, feeding oxygen-containing gas; The reaction after-filtration must contain many metals lead carbonate zinc ore of remaining sulfide; Solid-liquid separation is filtered; With solid phase and kerosene or tetrafluoroethylene by the solid-liquid mass ratio encloses container of packing at 1: 5; Be heated to 120 ℃, filtered while hot, filtrating and be cooled to room temperature, separate out elementary sulfur after, the lead carbonate zinc ore that will contain remaining sulfide and the sulfate cinder that is rich in red stone, fixed carbon content greater than 76% fine coal or coke powder, account for the soda of ore deposit amount total amount 6-10% and account for mixed ball of lime powder or the group of the pressure back that ore deposit amount total amount is 2-4% and carry out melting in 1050-1150 ℃; The wherein said consumption that is rich in the red stone sulfate cinder is confirmed through stoichiometric calculation, not only should satisfy the requirement that sulphur is made in reduction, also will satisfy the requirement of slag making simultaneously, and slag contains FeO and is controlled in 22%～32% scope.
2. the smelting process of polymetallic lead-zinc sulfide ore according to claim 1; It is characterized in that with the ammonium bicarbonate aqueous solution being transforming agent, in having the steel retort of whisking appliance, the mass ratio of the solid-liquid of breeze and ammonium bicarbonate aqueous solution is 1: 5; The concentration 0.8mol/L of ammonium bicarbonate aqueous solution; 50 ℃ ± 5 ℃ of temperature of reaction, continuous bubbling air in the reaction process reacts many metals lead carbonate zinc ore that 5～6 hours after-filtration must contain remaining sulfide.
3. the smelting process of polymetallic lead-zinc sulfide ore according to claim 1 and 2; It is characterized in that the lead carbonate zinc ore that contains remaining sulfide mixes slag and the iron sulphur that carries out the melting generation with the sulfate cinder that is rich in red stone, fine coal or coke powder, soda and lime powder, after weathering is sieved, tell slag; With 60～70 ℃ hot water leachings 3 times; The slag that soaks after the filtration is sized mixing, and with 70～80 ℃ of hot washes, filters then; Merge the immersion liquid and the washing water that obtain, handle through carbonating and reclaim molybdenum and regeneration yellow soda ash; To soak slag in drying at room temperature, and then water waters and dries repeatedly, let the color of iron sulphur change reddish yellow gradually into, the back gets the matte slag after extracting sulphur with extraction process.
4. based on the smelting process of the described polymetallic lead-zinc sulfide ore of claim 3; It is characterized in that to contain the flue dust that carries out the melting generation mixing of remaining sulfide and stir leaching with sodium hydroxide solution with the pyrite cinder that is rich in iron oxide, fine coal or coke powder, soda and pulverized limestone; The oxidant that adds fume amount 6% in the leaching liquid; After Separation of Solid and Liquid is filtered; Adding concentration by the Ge content in the filtrating is 30% tannin, and the reaction back is filtered and obtained germanic tannin germanium concentrate more than 2%; Add zinc powder in the alkaline filtrate behind the heavy germanium, the reaction back is filtered and is obtained lead sponge; Feed carbon dioxide in the filtrating, cross after room temperature reaction 2-3 hour and filter basic zinc carbonate, filtrating is converted into sodium hydroxide solution behind lime causticization, returns after it is concentrated and leaches the new flue dust of operation leaching.
5. the smelting process of polymetallic lead-zinc sulfide ore according to claim 4 is characterized in that resulting flue dust stirs leaching with sodium hydroxide solution at 95 ℃～100 ℃, adds the oxygenant SODIUMNITRATE of fume amount 6% in the leaching liquid; Leaching time 90 minutes; Filtering, is 30% tannin then by the adding of the ge content in filtrating concentration, and germanium is 1/30th at the content of tannin; Stir; Precipitation temperature is 60～70 ℃, 20 minutes stirring reaction time, filters and obtains germanic tannin germanium concentrate more than 2%; The zinc powder that adds granularity-200 in the basic soln behind the heavy germanium, 1.5～2 hours after-filtration of 40 ℃～50 ℃ stirring reactions obtain lead bullion; Feed the 0.6Mpa dioxide gas in the filtrating, a room temperature reaction 2-3 hour after-filtration gets zinc subcarbonate, and filtrating is converted into sodium hydroxide solution behind lime causticization, it is concentrated into contain 300g/L, returns and leaches the new flue dust of operation leaching.
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| CN103993164B (en) * | 2014-04-27 | 2015-09-09 | 沙明军 | The method of the many metals of the plumbous zinc of oxysulphied smeltingization separation simultaneously |
| CN104195344B (en) * | 2014-09-01 | 2017-01-18 | 株洲起源科技有限责任公司 | Method for recovering sulfur, lead, zinc and silver from oxygen-rich direct leaching residues of zinc concentrate or lead and zinc mixed ores by virtue of ultrasonic wave intensification |
| CN104229745A (en) * | 2014-09-01 | 2014-12-24 | 株洲起源科技有限责任公司 | Ultrasonic extraction method and process for processing slag containing elemental sulfur |
| CN106637298A (en) * | 2016-11-16 | 2017-05-10 | 昆明冶金研究院 | Electrical lead deposition method of lead-containing multi-metal material |
| JP7050925B2 (en) * | 2017-08-08 | 2022-04-08 | コバルト ブルー ホールディングズ リミテッド | Recovery of metals from pyrite |
| CN110589776B (en) * | 2019-10-28 | 2022-11-08 | 南昌航空大学 | Method for synthesizing magnesium sulfide by mechanical ball milling |
| CN113976600A (en) * | 2021-10-28 | 2022-01-28 | 江苏北矿金属循环利用科技有限公司 | Harmless treatment process for toxic components of high-sulfur slag in zinc smelting |
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