CN110408791A - A method of reduction autovulcanization roasting pretreatment iron vitriol slag - Google Patents
A method of reduction autovulcanization roasting pretreatment iron vitriol slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0066—Preliminary conditioning of the solid carbonaceous reductant
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
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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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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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
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B58/00—Obtaining gallium or indium
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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
- C22B7/04—Working-up slag
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of methods for restoring autovulcanization roasting pretreatment iron vitriol slag, the following steps are included: (1) mixes iron vitriol slag and reducing agent, resulting mixture is subjected to solid-solid and restores sulphur fixing roast, restoring the metal sulfate in iron vitriol slag becomes metal sulfide, obtains reduction roasting product；(2) the resulting reduction roasting product of step (1) is subjected to reduction-sulfurization roasting, iron sulfide and the heavy metallic oxide reaction in reduction roasting product is set to generate iron simple substance and heavy metal sulfide, ferriferous oxide reduction is set to become metallic iron, the agglomeration for realizing Fe and heavy metal sulfide simultaneously, obtains reduction-sulfurization product of roasting.The preprocess method can realize the metallization of the fixation of sulphur, the vulcanization conversion and iron of heavy metal to the greatest extent, and be conducive to valuable constituent and pass through flotation and magnetic separation recovery respectively.
Description
Technical field
Metallurgical technology field of the present invention more particularly to a kind of method for restoring autovulcanization roasting pretreatment iron vitriol slag.
Background technique
Iron vitriol slag is using Jarosite process in the smelting processes such as manganese, zinc, copper, nickel, cobalt except the resulting heavy scum of iron, is certain
Temperature, acidity and have ammonium or alkali metal ion it is existing under the conditions of, the Fe in solution3+The siderotil crystal that ion precipitation is formed,
It is maximum with zinc metallurgical process yield.China took the lead in carrying out jarosite process removing from Liuzhou city, Guangxi province non-ferrous metals smelting works in 1985
Since iron industrial application, there is Shaanxi Shanglou smeltery, Northwest Lead Zinc smeltery and Laibin, Guangxi Province smeltery etc. more than ten successively
Producer carries out zinc abstraction using Jarosite process and removes iron.Iron vitriol slag volume of cargo in storage in China's is more than 30,000,000 tons at present, and per year over 100
Ten thousand tons of speed increases, and quantity is extremely huge.Iron vitriol slag (wet basis) usually contains Fe 25~30%, contains S 8~12%, except this it
Outside also containing valuable metals such as Zn, Pb, Cu, Ni, Cd, Ag, In.Since it contains heavy metal, aqueous 30~50%, it is more unstable
It is fixed, it is not easy to store up, therefore iron vitriol slag is typical hazard solid waste, the requirement of storage slag library is very stringent, and iron vitriol slag stockpiling needs
Environmentally friendly tax is paid by 1000/t, this spending of light is just enough to make many zinc abstraction enterprises hard to carry on.
Currently, a large amount of researcher have done extensive research to iron vitriol slag disposition both at home and abroad.Mainly with desulfurization-reduction-
Based on the pyrogenic attack technique of magnetic separation.The technical thought of traditional thermal process processing iron vitriol slag are as follows: oxidizing roasting desulfurization is first passed through,
Sulphur compound in iron vitriol slag is rapidly decomposed into sulfur dioxide or sulfur trioxide gas, and guarantee sulphur compound not with iron, lead, zinc
Reaction generates sulfide；The metal oxides such as lead, zinc in desulfurization material through reduction volatilization, are recycled in flue gas again；Also
Original object is again through magnetic separation, to obtain metal iron powder and tailing.
Such as Chinese patent literature (CN 107254585A) discloses a kind of side that zinc, indium, iron, gallium are recycled from siderotil
Method, iron vitriol slag and additive is mixed, pelletizing, and reducing agent is added after oxidizing roasting desulfurization and is reduced directly, so that alum slag
In indium, zinc be reduced to metal volatilizing and enriching into flue dust, clinker obtains metallized pellet through cooling, broken, magnetic separation, then will
Metallized pellet fusing, slag-liquid separation obtain rich gallium molten iron.Since alum slag sulfur-bearing is low when the technique desulphurizing roasting, when desulphurizing roasting
The low concentration SO of generation2Gas is just able to satisfy relieving haperacidity requirement after need to using ion liquid enrichment, at high cost；Pelletizing after reduction needs
Then cooling, magnetic separation carries out molten point through high temperature again, process is complicated, and the high cost of energy consumption is big, and in difficulty during reduction volatilization
It is entered in reduced iron in elements such as Cu, Ag, Ni, Co of volatilization, has lost a large amount of valuable metals, valuable metal recovery is insufficient.
The Chinese patent of Publication No. (106544460 A of CN) discloses a kind of method and system for handling iron vitriol slag, should
Method is sent into ring radiation furnace after mixing iron vitriol slag with carbonaceous reducing agent, additive, respectively by baking zone, decomposition
Area, reducing zone, realize the metallization of the drying of iron vitriol slag, desulfurization, the reduction volatilization of zinc lead and iron, and product of roasting is obtained through magnetic separation
Iron ore concentrate, the process flow is short, and energy consumption is lower, but equally exists low concentration SO2The problem of fume treatment difficulty, additionally due to iron
The decomposition of alum is carried out under weakly reducing atmosphere, and the removal efficiency of sulphur only has 70% or so, thus lead when reduction volatilization in resolver
The volatilization effect of zinc is poor.
Generally speaking, existing pyrogenic attack technique has certain application when the constituent contents such as In are very high in iron vitriol slag, but
It is limited desulfurization by actual process to be not thorough, heavy metal sulfide content is high, cannot efficiently separate during magnetic separation, the taste of iron is not
Height, thus the SO of the recycling of iron, the high efficiente callback of other metals and process cannot have been efficiently solved2, secondary tailings and
The problems such as leachate pollutes, because without being widely applied.
There is technology to carry out fine coal reduction roasting-magnetic separation experimental study, magnetic of the output iron-content 58.72% to iron vitriol slag
Iron ore, metallic zinc are then dispersed in concentrate and tailing, and sulphur then disperses in roasting gas, magnetic concentrate and magnetic tailing, this method
Not only the recycling of iron, zinc could not have been solved, but also has produced SO2Tail gas and magnetic tailing secondary pollution, without application prospect.
Liu is superfine to have studied microwave heating sulfating roasting technology, under the conditions of preferably sulfuric acid roasting, water extract technology,
The leaching rate of Fe, Zn, In, Cu, Ag and Cd respectively reach 89.4%, 80.7%, 85.1%, 90.7%, 61.3% and 48.8%,
And Pb is then substantially with PbSO4Form be enriched in leached mud, this method iron is leached simultaneously with other valuable metals, in solution
Iron is separated with other metals to be difficult thoroughly and lacks effective iron resource approach, and application prospect is limited.
Although the processing technique about iron vitriol slag is widely studied, there has been no economically viable processing methods can be real simultaneously
Existing iron and other valuable metal recyclings and secondary pollution is not brought, the iron vitriol slag of enormous amount is almost without being effectively addressed
And all store up, seriously constrain the development of zinc and other several big metal industries.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide it is a kind of can be by valuable constituent maximum journey
Immobilization is spent, and is conducive to the side for the reduction autovulcanization roasting pretreatment iron vitriol slag that valuable constituent is able to recycle by physical separation
Method.
Theoretically, if taking the technical thought opposite with desulfurization-reduction-magnetic separation pyrogenic attack technique, i.e., using reduction
Agent carries out flotation and magnetic separation by the metal autovulcanization in iron vitriol slag, then by the valuable constituent in reducing slag, then both avoids SO2's
Release, but the full doseization for being able to achieve iron vitriol slag utilizes.The main chemical reactions for theoretically including:
1、KFe3(SO4)2(OH)6=1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O
2、Fe2(SO4)3+ 6C=3/2FeS2+1/2Fe+6CO2(g)
3、ZnSO4+ 2C=ZnS+2CO2(g)
4、PbSO4+ 2C=PbS+2CO2(g)
5、Ag2SO4+ 2C=Ag2S+2CO2(g)
6、CuSO4+ 2C=CuS+2CO2(g)
7、ZnO+1/2FeS2+ 1/2C=ZnS+1/2Fe+1/2CO2(g)
8、ZnFe2O4+1/2FeS2+ 2C=ZnS+5/2Fe+2CO2(g)
9、ZnSiO3+1/2FeS2+ 1/2C=ZnS+1/2Fe+SiO2+1/2CO2(g)
10、PbO+1/2FeS2+ 1/2C=PbS+1/2Fe+1/2CO2(g)
11、CuO+1/2FeS2+ 1/2C=CuS+1/2Fe+1/2CO2(g)
12、Fe2O3+ 1.5C=2Fe+1.5CO2(g)
13、AgO+1/4FeS2+ 1/2C=1/2Ag2S+1/4Fe+1/2CO2(g)
14、In2O3+ 1.5C=2In+1.5CO2(g)
However, valuable metal is numerous in iron vitriol slag, the autovulcanization condition of every kind of metal is different and metal sulfate easily divides
Solution is limited at sulfur dioxide and metal oxide, and by technique, therefore real reaction can't be carried out towards above-mentioned ideal response.
Therefore the resource utilization degree of iron vitriol slag is low, it is difficult to obtain high-grade valuable metal mine and iron ore concentrate.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A method of reduction autovulcanization roasting pretreatment iron vitriol slag, comprising the following steps:
(1) iron vitriol slag and reducing agent are mixed, resulting mixture is subjected to solid-solid and restores sulphur fixing roast, makes iron vitriol slag
In metal sulfate reduction become metal sulfide, obtain reduction sulphur fixing roast product；
(2) the resulting reduction roasting product of step (1) is subjected to reduction-sulfurization roasting, makes to restore in sulphur fixing roast product
Iron sulfide and heavy metallic oxide reaction generate iron simple substance and heavy metal sulfide, so that ferriferous oxide is reduced to metallic iron, together
The agglomeration of Shi Shixian Fe and heavy metal sulfide crystal grain obtain reduction-sulfurization product of roasting.
Technical thought of the invention are as follows: first passing through solid-solid reduction sulphur fixing roast technique makes metal sulfate in iron vitriol slag
Reduction becomes metal sulfide, and can prevent metal sulfate from resolving into metal oxide and sulfur dioxide；；Restore the iron generated
Sulfide may participate in the vulcanization reaction of next step as vulcanizing agent；
Key reaction in this step has:
1、KFe3(SO4)2(OH)6=1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O；
2、Fe2(SO4)3+ 6C=3/2FeS2+1/2Fe+6CO2(g)；
3、ZnSO4+ 2C=ZnS+2CO2(g)；
4、PbSO4+ 2C=PbS+2CO2(g)；
5、Ag2SO4+ 2C=Ag2S+2CO2(g)；
6、CuSO4+ 2C=CuS+2CO2(g)；
Generate iron sulfide and reactive metal oxide in reduction roasting product by reduction-sulfurization roasting technique again
Ferriferous oxide is reduced to metallic iron by iron simple substance and metal sulfide, and indium is then reduced into ln or ln2O volatilization, then in flue gas
In be oxidized to ln2O3It is enriched in flue dust, and promotes the life of low-melting compound by technique cooperation and the interaction of additive
At, liquid channel is formed during the reaction, separates iron simple substance and metal sulfide, and promote the agglomeration of crystal grain, from
It and is that flotation, magnetic separation create favorable conditions.
Key reaction in this step has:
7、ZnO+1/2FeS2+ 1/2C=ZnS+1/2Fe+1/2CO2(g)；
8、ZnFe2O4+1/2FeS2+ 2C=ZnS+5/2Fe+2CO2(g)；
9、ZnSiO3+1/2FeS2+ 1/2C=ZnS+1/2Fe+SiO2+1/2CO2(g)；
10、PbO+1/2FeS2+ 1/2C=PbS+1/2Fe+1/2CO2(g)；
11、CuO+1/2FeS2+ 1/2C=CuS+1/2Fe+1/2CO2(g)；
12、Fe2O3+ 1.5C=2Fe+1.5CO2(g)；
13、AgO+1/4FeS2+ 1/2C=1/2Ag2S+1/4Fe+1/2CO2(g)；
14、In2O3+ 1.5C=2In+1.5CO2(g)
It is reacted by above-mentioned step-by-step reduction, the metal in iron vitriol slag can maximumlly be vulcanized to conversion and fixed, SO is avoided2
Release；Zinc, lead in slag etc. are converted into metal sulfide, and silver is converted into sulfide or simple substance, and indium volatilizing and enriching is in flue dust；
Iron is reduced directly to metallic iron, and obtains being easy to the metal sulfide and iron granule using flotation or magnetic separation recovery, thus
After sorted, the concentrate and iron ore concentrate of high-recovery, high-grade heavy metal can be obtained；Other gangue contents exist in iron vitriol slag
After roasting link high-temperature activation, ore dressing tailings can be directly used for production building materials, to can realize that iron vitriol slag full doseization utilizes.
The reduction autovulcanization process of above-mentioned iron vitriol slag, is mainly utilized self-contained metal and sulphur in iron vitriol slag, in carbon
Under reducing condition, autovulcanization is realized, zinc, lead, copper are converted into sulphided state, and silver is converted into sulphided state or metallic state, and iron is converted into gold
Belong to state, in flue dust, reaction is whole to be discharged without oxysulfide indium volatilizing and enriching substantially, without adding solid sulphur reagent, is realized efficient
Self-retaining.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (1), the solid-solid
Reduction sulphur fixing roast carries out under nitrogen protection atmosphere or under oxygen-free atmosphere, and maturing temperature is 400 DEG C~600 DEG C, and the time is
30min~90min.
Reduction roasting is carried out under above-mentioned cryogenic conditions, may make that the ferriferous oxide in iron vitriol slag is reduced to metal, lead,
Zinc, copper, iron sulfate reduction be metal sulfide, silver compound is reduced to metal or metal sulfide.Above-mentioned reaction temperature
Too low, it is too long to will lead to the reaction time, and metal sulfate reduction is insufficient；Reaction temperature is excessively high, and metal sulfate easily occurs to divide
Solution, is unfavorable for the fixation of sulphur.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (2), the reduction
Sulfidation roasting carries out under nitrogen protection atmosphere or under oxygen-free atmosphere, and maturing temperature is 800 DEG C~1100 DEG C, time 60min
~120min.
Sulfidation roasting is carried out under above-mentioned hot conditions, can make to remain in the iron sulfide generated in reducing roasting process and slag
Remaining lead, zinc, Cu oxide reaction, so that the vulcanization of lead, zinc, Cu oxide is converted into sulfide, iron sulfide is converted into metal,
Simultaneously the indium in slag is volatilized；Furthermore this hot environment be conducive to liquid phase generation, be conducive to metal separated with sulfide and crystalline substance
The aggregation growth of grain.If above-mentioned high-temperature roasting temperature is too low, indium volatility is low, and amount of liquid phase is few, is unfavorable for metallic iron crystal grain and gold
Belong to the agglomeration of sulfide crystal grain；If maturing temperature is excessively high, energy consumption is big, product of roasting slag hardness is big, cracking and sorting
Difficulty is big.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (1), the mixing
It further include that the additive for promoting liquid channel to be formed is added in object.
The additive for promoting liquid channel to be formed mainly provides liquid phase medium, on the one hand promotes iron vitriol slag and carbonaceous reducing agent
The progress of solid phase reaction, on the other hand reaction temperature can be reduced by improving reaction efficiency, achieve the purpose that reduce energy consumption.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (1), the reduction
Agent is carbonaceous reducing agent, and the additive for promoting liquid channel to be formed is sodium carbonate or sodium chloride.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (1), the mixing
In object, the mass ratio of the iron vitriol slag, reducing agent and the additive for promoting liquid channel to be formed is 100: 10~20: 5~10.
When the quality of carbonaceous reducing agent is more than the 20% of iron vitriol slag quality, the utilization rate of carbon is low, and remaining carbon is in flotation rank
Section can adsorb a large amount of floating agents, be unfavorable for FLOTATION SEPARATION；When the quality of carbonaceous reducing agent is lower than the 10% of iron vitriol slag quality, In
Carbon dust is gradually consumed in later period reduction-sulfurization roasting process, and reaction system partial pressure of oxygen increases, zinc, lead, silver, iron quilt in fired slags
Oxidation, and will lead to SO2Release is unfavorable for the metallization for vulcanizing conversion, the volatilization of indium, the fixation of sulphur and iron of heavy metal；And
And since reduction-sulfurization roasting effect is poor, vulcanization rate is low, and the amount of liquid phase formed in roasting process is few, heavy metal sulphur in product of roasting
Compound and iron crystal grain are tiny, and flotation, magnetic separation recovery are difficult.
The preferred sodium carbonate of additive for promoting liquid channel to be formed, the quality of sodium carbonate are more than the 10% of iron vanadium slag quality
When, not only increase cost, but also the oxygen gesture of reaction system can be increased, is unfavorable for the vulcanization of heavy metal and the metallization of iron, carbonic acid
When the quality of sodium is lower than the 5% of iron vanadium slag quality, it is unfavorable for generation and the metal sulfide, iron grain growth of liquid phase.
In addition, applicant's using sodium chloride studies have shown that replace sodium carbonate as additive can also promote zinc sulphide,
The generation and growth of vulcanized lead and metallic iron crystal grain, but toxic chlorine can be discharged；It can be generated greatly using sodium sulphate as additive
The hardystonite of amount is unfavorable for the vulcanization of metallic zinc.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that the iron vitriol slag be iron vitriol dreg of yellow sodium,
At least one of Jarosite Residues and argentojarosite slag.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that the carbonaceous reducing agent is stone tar
At least one of powder, coke blacking, active powdered carbon, carbon black powder, graphite powder and charcoal powder.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that in the step (1), the reduction
Further include that gained mixture is subjected to pressure ball before roasting, obtains the mixture that particle of the diameter less than 50mm is constituted.Pressure ball diameter
Mine ball is squeezed and thermally expands and dispersion in kiln when greater than 50mm.
The method of above-mentioned reduction autovulcanization roasting pretreatment iron vitriol slag, it is preferred that further include from the flue gas of step (2)
Recovery indium.
Compared with the prior art, the advantages of the present invention are as follows:
1, technical solution of the present invention can largely existing dangerous waste iron vitriol slag passes through also by existing nonferrous metallurgy industry
Original-autovulcanization roasting will be recycled wherein indium volatilizing and enriching into flue dust, and lead, zinc heavy metal sulfate or oxide are converted into metal
Sulfide, silver compound are converted into metal or metal sulfide, and iron sulfate or ferriferous oxide reduction become metallic iron.Reduced sulphur
The vulcanization rate of zinc and lead is high after changing roasting, and the metal rate of silver and iron is also high, thus for the floating of the valuable metal in iron vitriol slag
It selects method and magnetic method to recycle and creates advantage.Also, the fixed rate of sulphur, up to 95% or more, the sulfenyl sheet in slag is with metal sulphur
Compound form is fixed, rather than is volatized into flue gas, eliminates low concentration SO in conventional pyrogenic process roasting process2Be processed into
Sheet and secondary pollution.
2, technical solution of the present invention process conditions are mild, environmentally protective, easy to operate, at low cost, are conducive to industrialize
Production.
Detailed description of the invention
Fig. 1 is temperature-Gibbs Free Energy Diagram For The Thermodynamical of correlated response during present invention reduction sulphur fixing roast.
Fig. 2 is temperature-Gibbs Free Energy Diagram For The Thermodynamical of correlated response in reduction-sulfurization roasting process of the present invention.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
Embodiment 1:
Using certain iron vitriol dreg of yellow sodium as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 4.07%,
1.96%, 22.47%, 13.52%, 74g/t, 300g/t.By the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
The 15% wooden carbon dust (fixed carbon content is 73%) and 5% sodium carbonate carry out mixing simultaneously pressure ball with batch mixer, obtain diameter and are less than
The mixing sphere of 50mm.
It takes 100kg to be put into rotary kiln above-mentioned mixing sphere, is warming up to 450 DEG C of heat preservation 90min to carry out restoring solid sulphur
Calcination.Key reaction during this has:
1、KFe3(SO4)2(OH)6=1/2Fe2(SO4)3+Fe2O3+1/2K2SO4+3H2O；
2、Fe2(SO4)3+ 6C=3/2FeS2+1/2Fe+6CO2(g)；
3、ZnSO4+ 2C=ZnS+2CO2(g)；
4、PbSO4+ 2C=PbS+2CO2(g)；
5、Ag2SO4+ 2C=Ag2S+2CO2(g)；
6、CuSO4+ 2C=CuS+2CO2(g)；
Fig. 1 is temperature-Gibbs Free Energy Diagram For The Thermodynamical that the present embodiment restores above-mentioned reaction during sulphur fixing roast.
It continues thereafter with and increases temperature to 1000 DEG C, 60min is kept the temperature, to carry out reduction-sulfurization calcination.During this
Key reaction has:
7、ZnO+1/2FeS2+ 1/2C=ZnS+1/2Fe+1/2CO2(g)；
8、ZnFe2O4+1/2FeS2+ 2C=ZnS+5/2Fe+2CO2(g)；
9、ZnSiO3+1/2FeS2+ 1/2C=ZnS+1/2Fe+SiO2+1/2CO2(g)；
10、PbO+1/2FeS2+ 1/2C=PbS+1/2Fe+1/2CO2(g)；
11、CuO+1/2FeS2+ 1/2C=CuS+1/2Fe+1/2CO2(g)；
12、Fe2O3+ 1.5C=2Fe+1.5CO2(g)；
13、AgO+1/4FeS2+ 1/2C=1/2Ag2S+1/4Fe+1/2CO2(g)；
14、In2O3+ 1.5C=2In+1.5CO2(g)
Fig. 2 is temperature-Gibbs Free Energy Diagram For The Thermodynamical of above-mentioned reaction in the present embodiment reduction-sulfurization roasting process.
After heat preservation, cooled to room temperature takes out fired slags, samples and calculate the volatility of indium in iron vitriol slag, sulphur
Fixed rate, zinc, lead, iron, silver vulcanization conversion ratio or degree of metalization.The result shows that indium volatility, the vulcanization of zinc, lead, silver turns
Rate is respectively 95.47%, 92.28%, 86.15%, 33.26%, and the degree of metalization of silver and iron is respectively 63.16% He
84.64%, the fixed rate of sulphur is 97.32%, and rest zinc, lead, silver, iron are respectively with marmatite, elementary lead, silicic acid in fired slags
Silver and ferrous sulfide preservation.
Gained product of roasting is finely ground to -0.074mm through ball mill and accounts for 80%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 41.7%, the rate of recovery 82.3%, argentiferous 835g/t, the rate of recovery 89.7%；Use lime adjustment pH for 10.5 when zinc flotation,
Activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains zinc
Concentrate contains zinc 57.4%, the rate of recovery 84.8%.Flotation tailing obtains iron content 72.6% after one section of low intensity magnetic separation, and the rate of recovery is
84.5% iron ore concentrate.
Lime comparative example 1:
Using certain iron vitriol dreg of yellow sodium as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 4.07%,
1.96%, 22.47%, 13.52%, 74g/t, 300g/t.By the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
The 15% wooden carbon dust (fixed carbon content is 73%) and 5% sodium carbonate carry out mixing simultaneously pressure ball with batch mixer, obtain diameter and are less than
Above-mentioned mixing sphere is taken 100kg to be put into rotary kiln, is warming up to 750 DEG C, constant temperature calcining 120min by the mixing sphere of 50mm,
Subsequent cooled to room temperature takes out fired slags, samples and calculate indium volatility in iron vitriol slag, the fixed rate of sulphur, zinc, lead, iron,
The vulcanization conversion ratio or degree of metalization of silver.The result shows that indium volatility, zinc, lead, silver vulcanization conversion ratio be respectively 45.47%,
63.24%, 73.15%, 33.26%, the metal rate of silver and iron is respectively 63.16% and 64.64%, and the fixed rate of sulphur is
73.68%.
Gained product of roasting is finely ground to -0.074 ㎜ through ball mill and accounts for 80%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 14.3%, the rate of recovery 22.5%, argentiferous 765g/t, the rate of recovery 80.2%；Use lime adjustment pH for 10.5 when zinc flotation,
Activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains zinc
Concentrate contains zinc 23.6%, the rate of recovery 32.3%.Flotation tailing obtains iron content 50.6% after one section of low intensity magnetic separation, and the rate of recovery is
64.5% iron ore concentrate.
Compared to the examples, due to roasting only with one section, a large amount of metal sulfate was decomposed and was released when reduction roasting
SO2 is put, the fixation of sulphur and the reduction-sulfurization of heavy metal are unfavorable for；And since reduction-sulfurization temperature is low, reaction system liquid phase is generated
Amount is insufficient, leads in product of roasting that metal sulfide and iron crystal grain are tiny, is unfavorable for flotation and magnetic separation sorting.
Embodiment 2:
Using certain Jarosite Residues as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 3.25%,
2.36%, 26.36%, 14.52%, 112g/t, 270g/t, by the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
18% coke powder (fixed carbon content be 87%) and 10% sodium carbonate carry out mixing simultaneously pressure ball with batch mixer, obtain diameter and are less than
Above-mentioned mixing sphere is taken 100kg to be put into rotary kiln by the mixing sphere of 50mm, 600 DEG C of heat preservation 60min is warming up to, with subsequent
High-temperature of continuing rising keeps the temperature 60min to 1100 DEG C, and after heat preservation, cooled to room temperature takes out fired slags, samples and calculate
Indium volatility in iron vitriol slag, the fixed rate of sulphur, zinc, lead, iron, silver vulcanization conversion ratio or degree of metalization.The result shows that indium volatilizees
Rate, zinc, lead, silver vulcanization conversion ratio be respectively 96.52%, 95.64%, 78.35% and 27.53%, silver and iron metal rate
Respectively 70.14% and 88.52%, the fixed rate of sulphur is 95.23%, and rest zinc, lead, silver, iron are dodged respectively with iron in fired slags
Zinc ore, elementary lead, silver silicate and ferrous sulfide preservation.
Gained product of roasting is finely ground to -0.074mm through ball mill and accounts for 85%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 44.7%, the rate of recovery 83.2%, argentiferous 1123g/t, the rate of recovery 91.3%；Used when zinc flotation lime adjustment pH for
10.5, activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains
It obtains zinc concentrate and contains zinc 56.8%, the rate of recovery 88.4%.Flotation tailing obtains iron content 81.3% after one section of low intensity magnetic separation, and the rate of recovery is
87.6% iron ore concentrate.
Comparative example 2:
Using certain Jarosite Residues as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 3.25%,
2.36%, 26.36%, 14.52%, 112g/t, 270g/t, by the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
18% coke powder (fixed carbon content is 87%) carries out mixing and pressure ball with batch mixer, obtains the mixing ball that diameter is less than 50mm
Above-mentioned mixing sphere is taken 100kg to be put into rotary kiln by body, is warming up to 600 DEG C of heat preservation 30min, is continued thereafter with and is increased temperature extremely
1000 DEG C, 120min is kept the temperature, after heat preservation, cooled to room temperature takes out fired slags, samples and calculate indium in iron vitriol slag and wave
Hair rate, the fixed rate of sulphur, zinc, lead, iron, silver vulcanization conversion ratio or degree of metalization.The results show that the volatility of indium, zinc, lead,
The vulcanization conversion ratio of silver is respectively 94.48%, 90.28%, 75.07%, 30.86%, and the degree of metalization of silver and iron is respectively
65.35% and 70.26%, the fixed rate of sulphur is 92.41%, and rest zinc, lead, silver, iron are single respectively with marmatite in fired slags
Matter lead, silver silicate and ferrous sulfide preservation.
Gained product of roasting is finely ground to -0.074 ㎜ through ball mill and accounts for 85%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 32.5%, the rate of recovery 63.2%, argentiferous 865g/t, the rate of recovery 76.8%；Use lime adjustment pH for 10.5 when zinc flotation,
Activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains zinc
Concentrate contains zinc 41.3%, the rate of recovery 68.2%.Flotation tailing obtains iron content 64.2% after one section of low intensity magnetic separation, and the rate of recovery is
71.3% iron ore concentrate.
Although the degree of metalization of lead, the vulcanization conversion ratio of zinc and iron is high in comparative example, when due to reduction-sulfurization roasting not
Add carbonic acid sodium additives, reduction-sulfurization roasting process amount of liquid phase is few, sulfide and metal grain can not agglomeration, thus roast
It is tiny to burn metal sulfide grain and metallic particles disseminated grain size in product, flotation and magnetic separation inferior separating effect.
Embodiment 3:
Using Hunan argentojarosite slag as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 8.75%,
4.47%, 20.35%, 15.76%, 656g/t, 425g/t.By the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
74 μm or less 20% graphite powders (fixed carbon content is 93%) and 10% sodium carbonate carry out mixing simultaneously pressure ball with batch mixer, obtain directly
Diameter is less than the mixing sphere of 50mm, takes 100kg to be put into rotary kiln above-mentioned mixing sphere, is warming up to 450 DEG C of heat preservation 90min,
It continues thereafter with and increases temperature to 850 DEG C, keep the temperature 120min, after heat preservation, cooled to room temperature takes out fired slags, sampling
And calculate the volatility of indium in iron vitriol slag, the fixed rate of sulphur, zinc, lead, iron, silver vulcanization conversion ratio or degree of metalization.As a result it shows
Show, the volatility of indium, zinc, lead, silver vulcanization conversion ratio be respectively 82.78%, 96.16%, 86.26% and 74.46%, silver and
The metal rate of iron is respectively 10.52% and 73.32%, and the fixed rate of sulphur is 94.82%, rest zinc, lead, silver, iron in fired slags
Respectively with marmatite, elementary lead, silver silicate and ferrous sulfide preservation.
Gained product of roasting is finely ground to -0.074mm through ball mill and accounts for 85%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 46.7%, the rate of recovery 81.6%, argentiferous 7623g/t, the rate of recovery 93.3%；Used when zinc flotation lime adjustment pH for
10.5, activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains
It obtains zinc concentrate and contains zinc 67.8%, the rate of recovery 86.2%.Flotation tailing obtains iron content 68.3% after one section of low intensity magnetic separation, and the rate of recovery is
82.2% iron ore concentrate.
Comparative example 3:
Using Hunan argentojarosite slag as raw material, the alum slag zinc, lead, iron, sulphur, silver, indium content be respectively 8.75%,
4.47%, 20.35%, 15.76%, 656g/t, 425g/t.By the iron vitriol slag drying it is levigate to 74 μm hereinafter, then by its with
74 μm or less 25% graphite powders (fixed carbon content is 93%) and 10% sodium carbonate carry out mixing simultaneously pressure ball with batch mixer, obtain directly
Diameter is less than the mixing sphere of 50mm, takes 100kg to be put into rotary kiln above-mentioned mixing sphere, is warming up to 700 DEG C of heat preservation 90min,
It continues thereafter with and increases temperature to 1200 DEG C, keep the temperature 120min, after heat preservation, cooled to room temperature takes out fired slags, sampling
And calculate the volatility of indium in iron vitriol slag, the fixed rate of sulphur, zinc, lead, iron, silver vulcanization conversion ratio or degree of metalization.As a result it shows
Show, the volatility of indium, zinc, lead, silver vulcanization conversion ratio be respectively 96.43%, 76.43%, 54.53%, 13.46%, silver and
The metal rate of iron is respectively 80.56% and 93.72%, and the fixed rate of sulphur is 73.72%, due to reduction-sulfurization maturing temperature mistake
Height, carbon proportion are excessive, cause most lead and zinc to be reduced into and are volatized into flue dust for metal.
Gained product of roasting is finely ground to -0.074 ㎜ through ball mill and accounts for 85%, using lead zinc controling differential flotation process for copper recycling lead,
Zinc and silver.The inhibitor for making iron sulfide when lead minerals flotation using vulcanized sodium, makees the inhibitor of zinc sulfide ore using zinc sulfate,
Collecting agent is made using diethyldithiocarbamate+butyl ammonium aerofloat combination medicament, closed circuit flotation process is swept through thick three essence three, obtains lead concentrate
Leaded 28.2%, the rate of recovery 81.6%, argentiferous 11346g/t, the rate of recovery 95.3%；Used when zinc flotation lime adjustment pH for
10.5, activator is made using copper sulphate, lime makees inhibitor, and butyl xanthate makees collecting agent, sweeps closed-circuit test through thick three essence two, obtains
It obtains zinc concentrate and contains zinc 32.8%, the rate of recovery 85.2%.Flotation tailing obtains iron content 84.3% after one section of low intensity magnetic separation, and the rate of recovery is
90.2% iron ore concentrate.
Since carbon matches excessively high, appointing in reduction-sulfurization product of roasting has that a large amount of graphite powders are remaining, and absorption is a large amount of when flotation
Floating agent, while graphite powder can adsorb a large amount of particulate grade particles, floatation process poor selectivity, concentrate grade is low, and medicament disappears
Consumption is big；Additionally due to maturing temperature is excessively high, product of roasting hardness is big, is crushed and ore grinding is difficult.
The above is only the preferred embodiment of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of method for restoring autovulcanization roasting pretreatment iron vitriol slag, which comprises the following steps:
(1) iron vitriol slag and reducing agent are mixed, resulting mixture is subjected to solid-solid and restores sulphur fixing roast, is made in iron vitriol slag
Metal sulfate reduction becomes metal sulfide, obtains reduction sulphur fixing roast product；
(2) the resulting reduction roasting product of step (1) is subjected to reduction-sulfurization roasting, makes to restore the iron sulphur in sulphur fixing roast product
Compound and heavy metallic oxide reaction generate iron simple substance and heavy metal sulfide, so that ferriferous oxide reduction is become metallic iron, simultaneously
The agglomeration for realizing Fe and heavy metal sulfide crystal grain respectively, obtains reduction-sulfurization product of roasting.
2. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 1, which is characterized in that the step
(1) in, solid-solid reduction sulphur fixing roast carries out under nitrogen protection atmosphere or under oxygen-free atmosphere, and maturing temperature is 400 DEG C~
600 DEG C, the time is 30min~90min.
3. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 1, which is characterized in that the step
(2) in, the reduction-sulfurization roasting carries out under nitrogen protection atmosphere or under oxygen-free atmosphere, and maturing temperature is 800 DEG C~1000
DEG C, the time is 60min~120min.
4. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 1, which is characterized in that the step
It (1) further include that the additive for promoting liquid channel to be formed is added in the mixture in.
5. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 4, which is characterized in that the step
(1) in, the reducing agent is carbonaceous reducing agent, and the additive for promoting liquid channel to be formed is sodium carbonate or sodium chloride.
6. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 5, which is characterized in that the step
(1) in, in the mixture, the mass ratio of the iron vitriol slag, reducing agent and the additive for promoting liquid channel to be formed is 100:
10~20: 5~10.
7. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 6, which is characterized in that the siderotil
Slag is at least one of iron vitriol dreg of yellow sodium, Jarosite Residues and argentojarosite slag.
8. the method for reduction autovulcanization roasting pretreatment iron vitriol slag according to claim 6, which is characterized in that the carbonaceous
Reducing agent is at least one of stone tar powder, coke blacking, active powdered carbon, carbon black powder, graphite powder and charcoal powder.
9. the method for described in any item reduction autovulcanization roasting pretreatment iron vitriol slags, feature exist according to claim 1~8
In in the step (1), further including that gained mixture is carried out pressure ball before the reduction roasting, obtain diameter less than 50mm
The mixture that particle is constituted.
10. the method for described in any item reduction autovulcanization roasting pretreatment iron vitriol slags, feature exist according to claim 1~8
In further including the recovery indium from the flue gas of step (2).
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| CN112194171A (en) * | 2020-09-01 | 2021-01-08 | 珠海格力绿色再生资源有限公司 | Novel process for reducing ash content of pyrolysis carbon black and recovering beneficial components |
| CN114317954A (en) * | 2021-12-31 | 2022-04-12 | 上海大学 | Method for cooperatively treating and utilizing stainless steel pickling sludge and blast furnace dust |
| CN115433825A (en) * | 2022-08-16 | 2022-12-06 | 湖南中邦再生资源科技有限公司 | Comprehensive recovery method of iron and sulfur in waste lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112194171A (en) * | 2020-09-01 | 2021-01-08 | 珠海格力绿色再生资源有限公司 | Novel process for reducing ash content of pyrolysis carbon black and recovering beneficial components |
| CN114317954A (en) * | 2021-12-31 | 2022-04-12 | 上海大学 | Method for cooperatively treating and utilizing stainless steel pickling sludge and blast furnace dust |
| CN115433825A (en) * | 2022-08-16 | 2022-12-06 | 湖南中邦再生资源科技有限公司 | Comprehensive recovery method of iron and sulfur in waste lithium battery |
| CN115433825B (en) * | 2022-08-16 | 2023-11-07 | 湖南中邦再生资源科技有限公司 | Comprehensive recovery method of iron and sulfur in waste lithium battery |
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