CN106676221A - Jarosite slag treatment method and system - Google Patents
Jarosite slag treatment method and system Download PDFInfo
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- CN106676221A CN106676221A CN201611111789.3A CN201611111789A CN106676221A CN 106676221 A CN106676221 A CN 106676221A CN 201611111789 A CN201611111789 A CN 201611111789A CN 106676221 A CN106676221 A CN 106676221A
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- iron vitriol
- vitriol slag
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- mother bulb
- mixed material
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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
- C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
- C21B13/105—Rotary hearth-type furnaces
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
-
- 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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
-
- 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
-
- 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
- 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
-
- 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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- 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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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a jarosite slag treatment method and system. The jarosite slag treatment method comprises the steps that jarosite slag and reduction coal are subjected to primary mixing so that a first material mixture can be obtained; the first material mixture is subjected to primary pelletizing treatment so that jarosite slag mother pellets can be obtained; reduction coal, limestone and a binding agent are subjected to secondary mixing so that a second material mixture can be obtained; the jarosite slag mother pellets and the second material mixture are subjected to secondary pelletizing treatment so that the jarosite slag mother pellets can be wrapped by the second material mixture and composite pellets with the jarosite slag mother pellets as cores can be obtained; the composite pellets are sent into an annular furnace for direct reduction treatment so that a reduction product can be obtained; and the reduction product is subjected to ball milling treatment and magnetic separation treatment so that metallic iron powder and tailings can be obtained. By means of the treatment method, volatilization of sulfur in the jarosite slag can be effectively reduced, and desulfurization cost can be lowered.
Description
Technical field
The invention belongs to the energy and field of metallurgy, in particular to the processing method and processing system of iron vitriol slag.
Background technology
Iron vitriol slag belong in Zinc Hydrometallurgy Process produce a kind of leached mud, zinc abstraction adopt technique be generally " roasting-
Leaching-purification-electrodeposition ", using hot acid leaching-ferrovanadium except ferrum process, other 55% for 45% middle phase analysis in zinc hydrometallurgy factory
Using rotary kiln baking process.Iron vitriol slag belongs to " hot acid leaching-ferrovanadium processes (precipitation) except ferrum " precipitation in Zinc Hydrometallurgy Process
A kind of tailings produced in process, i.e., selectively form precipitation, so as to reach ferrum and zinc ferrum element in zinc lixiviating solution
Detached purpose.Its main component is ferrovanadium, and molecular formula can be written as NaFe3(SO4)2(OH)6, total sulphur content be more than 12%, crystallization
Water is up to 10%.This kind of Zinc hydrometallurgy process zinc leaching rate is higher than 98%, and technological equipment investment is little, but the siderotil that technique is produced
Containing more soluble sulphate and heavy metal ion, also dilute scattered noble metal in slag, need construction antiseepage slag field to store up, deposit
In very big Environmental security hidden danger.And because the decomposition temperature of siderotil is higher, the noble metal of preservation cannot also pass through routine
Extract technology is reclaimed using floatation process, can not effectively extract ferrum in slag, zinc and other valuable noble metals.Therefore
Process the elements such as ferrum in iron vitriol slag, lead, zinc, silver, and realize the innoxious of sulfur in slag, generally require using pyrogenic process or wet method
Reclaimed, wet processing has the intractable difficult problem of spent acid waste liquid.Firing method process technological process is short, but due in slag sulfur contain
Amount is high, and pyrogenic attack desulphurization cost is huge, and lead zinc ash byproducts are few, deficiency in economic performance, therefore a large amount of slags are in and store up state.
For this purpose, at present for the handling process of iron vitriol slag need further improvement.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.For this purpose, the present invention
One purpose is the processing method and processing system for proposing iron vitriol slag, can effectively be subtracted using the processing method and processing system
The volatilization of sulfur, reduces desulphurization cost in few ferrovanadium slag.
According to an aspect of the present invention, the present invention proposes a kind of processing method of iron vitriol slag, including：
Iron vitriol slag and reduction coal are carried out into the first mixing, to obtain the first mixed material；
First mixed material is carried out into the first pelletizing process, to obtain iron vitriol slag mother bulb；
Reduction coal, limestone and binding agent are carried out into the second mixing, to obtain the second mixed material；
The iron vitriol slag mother bulb is carried out into the second pelletizing process with second mixed material, to make second mixing
Material is wrapped up the iron vitriol slag mother bulb, obtains the composite pellet with the iron vitriol slag mother bulb as core；
The composite pellet is delivered to and carry out in annular furnace direct-reduction process, to obtain reduzate；And
The reduzate is carried out into ball milling and magnetic separation is processed, to obtain metal iron powder and mine tailing.
Thus, the processing method of the iron vitriol slag of the above embodiment of the present invention, is prepared into ferrum by iron vitriol slag and reduction coal first
Vitriol slag mother bulb, then in the outer layer covers reduction coal and the mixture layer of limestone of iron vitriol slag mother bulb.Secondly will be with iron vitriol slag mother bulb
Composite pellet for core carries out direct-reduction process in annular furnace.Thus the reduction coal and stone of the outer surface of iron vitriol slag mother bulb
The mixture layer of lime stone, can effectively prevent the effusion of iron vitriol slag mother bulb sulphur oxide, and oxysulfide can be with Calx
Stone reaction generates calcium sulfate or sulfuration calcium substance, and sulfur is fixed in metallized pellet.It is possible thereby to efficiently reduce iron vitriol slag
The volatilization of sulfur in mother bulb, reduces flue gas desulfurization cost.
In addition, the processing method of iron vitriol slag according to the above embodiment of the present invention can also have following additional technology special
Levy：
In some embodiments of the invention, the thermal source of the annular furnace adopts gas fired radiant tubes, preferred regenerative gas
Radial canal.Thus the reducing agent in pelletizing integument can occur pyrolysis generation CO gases, and then cause in pelletizing surface and burner hearth
Stronger reducing atmosphere is kept, and then effectively reduces sulfur volatilization (neutral, oxidizing atmosphere is conducive to sulfur to volatilize), increase solid sulfur
Rate.
In some embodiments of the invention, the carbon-to-oxygen ratio of the iron vitriol slag mother bulb is 1.0-1.6.Thus siderotil is conducive to
The reduction of lead, zinc, ferrum in slag mother bulb.
In some embodiments of the invention, by the reduction coal, the limestone and the binding agent according to mass ratio
For 100：40-60：4-6 carries out second mixing.Thus the effusion of iron vitriol slag mother bulb sulphur oxide can effectively be prevented.
In some embodiments of the invention, the particle diameter of the iron vitriol slag mother bulb be 8-12mm, the grain of the composite pellet
Footpath is 10-16mm.
In some embodiments of the invention, the thickness of the second mixed material parcel iron vitriol slag mother bulb is not less than
2mm.It is possible thereby to further increase sulfur-fixing rate.
In some embodiments of the invention, the carbon-to-oxygen ratio of the composite pellet is 2.0-2.6.
In some embodiments of the invention, the temperature that the direct-reduction is processed is 1000-1200 DEG C, and the time is 60-
120min。
According to the second aspect of the invention, the invention allows for a kind of iron vitriol slag described in enforcement right preceding embodiment
The system of processing method, including：
First mixing arrangement, first mixing arrangement has iron vitriol slag entrance, reduction coal entrance and the first mixed material
Outlet；
There is first palletizing device, first palletizing device the first mixed material entrance and iron vitriol slag mother bulb to export, institute
State the first mixed material entrance to be connected with first mixed material outlet；
Second mixing arrangement, second mixing arrangement has reduction coal entrance, limestone entrance, binding agent entrance and
Two mixed materials are exported；
Second palletizing device, second palletizing device has iron vitriol slag mother bulb entrance, the second mixed material entrance and answers
Close pelletizing outlet, the outlet of the iron vitriol slag mother bulb entrance and the iron vitriol slag mother bulb is connected, the second mixed material entrance and
The second mixed material outlet is connected；
Annular furnace, the annular furnace has composite pellet entrance and reduzate outlet, the composite pellet entrance and institute
State composite pellet outlet to be connected；And
Mill ore magnetic selection device, the mill ore magnetic selection device has reduzate entrance, metal iron powder outlet and mine tailing outlet,
The reduzate entrance is connected with reduzate outlet.
Thus, the processing method of the iron vitriol slag of the above embodiment of the present invention, first with the first palletizing device by iron vitriol slag
Iron vitriol slag mother bulb is prepared into reduction coal, the second palletizing device is recycled in the outer layer covers reduction coal and Calx of iron vitriol slag mother bulb
The mixture layer of stone.Secondly composite pellet with iron vitriol slag mother bulb as core is carried out in annular furnace direct-reduction process.By
The reduction coal of the outer surface of this iron vitriol slag mother bulb and the mixture layer of limestone, can effectively prevent sulfur oxidation in iron vitriol slag mother bulb
The effusion of thing, and oxysulfide can generate calcium sulfate or sulfuration calcium substance with limestone reaction, and sulfur is fixed on into metallization
In pelletizing.It is possible thereby to efficiently reduce the volatilization of sulfur in iron vitriol slag mother bulb, flue gas desulfurization cost is reduced.
In some embodiments of the invention, the thermal source in the annular furnace is gas fired radiant tubes.
In some embodiments of the invention, the gas fired radiant tubes is regenerative gas radial canal.
Description of the drawings
Fig. 1 is the flow chart of the processing method of iron vitriol slag according to an embodiment of the invention.
Fig. 2 is the flow chart of the processing method of iron vitriol slag in accordance with another embodiment of the present invention.
Fig. 3 is the structural representation of the processing system of iron vitriol slag according to an embodiment of the invention.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and be not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of processing method of iron vitriol slag, and the method includes：By ferrum
Vitriol slag and reduction coal carry out the first mixing, to obtain the first mixed material；First mixed material is carried out into the first pelletizing
Process, to obtain iron vitriol slag mother bulb；Reduction coal, limestone and binding agent are carried out into the second mixing, to obtain the second mixing
Material；The iron vitriol slag mother bulb is carried out into the second pelletizing process with second mixed material, to make second mixture
Material is wrapped up the iron vitriol slag mother bulb, obtains the composite pellet with the iron vitriol slag mother bulb as core；By the composite balls
Group delivers to and carry out in annular furnace direct-reduction process, to obtain reduzate；And by the reduzate carry out ball milling and
Magnetic separation is processed, to obtain metal iron powder and mine tailing.
Thus, the processing method of the iron vitriol slag of the above embodiment of the present invention, is prepared into ferrum by iron vitriol slag and reduction coal first
Vitriol slag mother bulb, then in the outer layer covers reduction coal and the mixture layer of limestone of iron vitriol slag mother bulb.Secondly will be with iron vitriol slag mother bulb
Composite pellet for core carries out direct-reduction process in annular furnace.Thus the reduction coal and stone of the outer surface of iron vitriol slag mother bulb
The mixture layer of lime stone, can effectively prevent the effusion of iron vitriol slag mother bulb sulphur oxide, and oxysulfide can be with Calx
Stone reaction generates calcium sulfate or sulfuration calcium substance, and sulfur is fixed in metallized pellet.It is possible thereby to efficiently reduce iron vitriol slag
The volatilization of sulfur in mother bulb, reduces desulphurization cost.
According to a particular embodiment of the invention, the process below with reference to Fig. 1-2 to the iron vitriol slag of the above embodiment of the present invention
Method is described in detail：
S100：First mixing
According to a particular embodiment of the invention, iron vitriol slag and reduction coal are carried out into the first mixing, to obtain the first mixing
Material.
According to a particular embodiment of the invention, ferrovanadium slag is hot acid extract technology leached mud, and wherein sulfur content is 13%, lead
Content is 2%, and Zn content is 4%, and iron content is 23%.Specific example of the invention, the granularity of ferrovanadium slag is -325 mesh
Account for more than 95%.
S200：The process of first pelletizing
According to a particular embodiment of the invention, first mixed material is carried out into the first pelletizing process, to obtain ferrum
Vitriol slag mother bulb.
According to a particular embodiment of the invention, the carbon-to-oxygen ratio of iron vitriol slag mother bulb is 1.0-1.6.Inventor's discovery, iron vitriol slag
The too low reduction for being unfavorable for lead, zinc, ferrum of the carbon-to-oxygen ratio of mother bulb.From there through the carbon-to-oxygen ratio of control iron vitriol slag mother bulb, can be effective
Ensure lead, zinc, the reduction of ferrum in iron vitriol slag mother bulb.It is to be understood that carbon-to-oxygen ratio refers to fixed carbon that reduction coal brings into and treats
The atomic ratio of oxygen element contained by iron oxides in reducing material, carbon-to-oxygen ratio is the common saying in direct-reduction field.
According to a particular embodiment of the invention, the particle diameter of iron vitriol slag mother bulb is 8-12mm.Inventor has found, if mother bulb particle diameter
It is too small, it is unfavorable for improve production efficiency, the quality of the excessive contained element sulphur of particle diameter is excessive, needs to entrain into more going back in outer layer
The mixture of raw coal and limestone, is unfavorable for the carrying out of reduction reaction and the fixation of element sulphur.
S300：Second mixing
According to a particular embodiment of the invention, reduction coal, limestone and binding agent are carried out into the second mixing, to obtain
Two mixed materials.Thus it is easy to further process the outer surface parcel reduction coal and Calx in iron vitriol slag mother bulb by the second pelletizing
Stone.Further can effectively reduce the sulfur volatility in iron vitriol slag mother bulb.
According to a particular embodiment of the invention, it is according to mass ratio by reduction coal, the limestone and the binding agent
100：40-60：4-6 carries out second mixing.Specific example of the invention, the granularity of reduction coal can be 100~200
Between mesh, the granularity of limestone can be for below 200 mesh.Reduction coal and limestone are mixed according to aforementioned proportion, can be had
Effect prevents the effusion of iron vitriol slag mother bulb sulphur oxide, and oxysulfide can generate calcium sulfate or sulfuration with limestone reaction
Calcium substance, sulfur is fixed in metallized pellet.It is possible thereby to the sulfur volatility being effectively reduced in iron vitriol slag mother bulb.It is above-mentioned viscous
The adding proportion of knot agent can ensure the intensity of pelletizing shell, prevent pelletizing shell from bursting.
S400：The process of second pelletizing
According to a particular embodiment of the invention, the iron vitriol slag mother bulb is carried out into the second pelletizing with second mixed material
Process, to make second mixed material wrap up the iron vitriol slag mother bulb, obtain with the iron vitriol slag mother bulb as core
The composite pellet of the heart.
According to a particular embodiment of the invention, by the process of above-mentioned second pelletizing, wrap up in the outer surface of iron vitriol slag mother bulb
The mixture of one layer of reduction coal and limestone, and then can effectively prevent the effusion of iron vitriol slag mother bulb sulphur oxide, and sulfur oxygen
Compound can generate calcium sulfate or sulfuration calcium substance with limestone reaction, and sulfur is fixed in metallized pellet.It is possible thereby to have
Effect ground reduces the sulfur volatility in iron vitriol slag mother bulb.
According to a particular embodiment of the invention, the particle diameter of iron vitriol slag mother bulb is 8-12mm, and the particle diameter of composite pellet is 10-
16mm.The thickness of the second mixed material parcel iron vitriol slag mother bulb is not less than 2mm.
According to a particular embodiment of the invention, the carbon-to-oxygen ratio of composite pellet is 2.0-2.6.Inventor's discovery, carbon-to-oxygen ratio mistake
Low, the reducing atmosphere around pelletizing is poor, is unfavorable for the reduction of ferrum lead zinc oxide in pelletizing, and carbon-to-oxygen ratio is too high, and pelletizing is strong
Degree is poor, and cost increases.
S500：Direct-reduction in annular furnace is processed
According to a particular embodiment of the invention, the composite pellet is delivered to and carry out in annular furnace direct-reduction process, with
Just reduzate is obtained.
According to a particular embodiment of the invention, the thermal source of annular furnace adopts gas fired radiant tubes.Gas fired radiant tubes is with heat radiation
Mode provide volatilization, decomposition, reduction needed for heat.Accurate furnace temperature can control using regenerative gas radial canal, and prevent
Only the reducing agent in pelletizing integument can occur pyrolysis generation CO gases, and stronger also Primordial Qi is kept in pelletizing surface and burner hearth
Atmosphere, and then sulfur volatilization is effectively reduced, increase sulfur-fixing rate.According to a particular embodiment of the invention, the preferred heat accumulating type of gas fired radiant tubes
Gas fired radiant tubes.It is possible thereby to further save energy consumption.
According to a particular embodiment of the invention, can be with to the temperature that composite pellet carries out being reduced directly process in annular furnace
For 1000~1200 DEG C.Thus react using the autoreduction of carbonaceous material, lead, zinc oxide in slag are reduced into into lead, zinc list
Matter, is volatized in flue (flue can be separately provided in reducing zone), is oxidized to lead oxide and Zinc Oxide again in flue
In high temperature dust flue dust, through heat exchanger, mix cold wind be reduced to 250 DEG C enter bagroom reclaim zinc oxide dust,
Temperature is too low, it is impossible to realize the reduction of lead zinc, iron oxides.In addition, inventor also has found, if the temperature of direct reduction reactor
It is too high, then it is easy to cause oxysulfide that the decomposition for generating calcium sulfate is reacted with limestone, sulphur oxide gas are escaped, drop on the contrary
Low sulfur-fixing rate.
Further, the time that direct-reduction is processed in annular furnace can be 60~120min.Inventor has found, if also
The former time is too short, and ferrum percent reduction is low, lead, Zinc volatilization rate are relatively low；If the recovery time is long, the scaling loss of carbon is increased, and is unfavorable for protecting
Reducing atmosphere around holding group.
According to a particular embodiment of the invention, the pelletizing behind annular furnace reducing zone is via the drawing mechanism in discharge zone
Discharge out of the furnace, content of Pb＆Zn is less than 0.1% in product metal ball after reduction, and sulfur-fixing rate is more than 90%, sulfur-fixing rate=[(metal
Sulfur percentage composition in pellet weight * metallized pellet)/(sulfur percentage composition in green pellets weight * green pellets)] * 100, green-ball
Group refers to the composite pellet into before annular furnace.Material after reduction can send to slag sluicing system system and obtain iron product and stove
Slag.
S600：Ball milling and magnetic separation are processed
According to a particular embodiment of the invention, above-mentioned reduzate is carried out into ball milling and magnetic separation is processed, to obtain metal
Iron powder and mine tailing.
According to the second aspect of the invention, the invention allows for implementing the processing method of the iron vitriol slag of preceding embodiment
System.According to a particular embodiment of the invention, the processing system of iron vitriol slag is described in detail below with reference to Fig. 3.
According to a particular embodiment of the invention, the system includes：First mixing arrangement 10, the first palletizing device 20, second
Mixing arrangement 30, the second palletizing device 40, annular furnace 50, mill ore magnetic selection device 60.
Wherein, the first mixing arrangement 10 has iron vitriol slag entrance 11, the mixed material of reduction coal entrance 12 and first outlet 13；
First palletizing device 20 has the first mixed material entrance 21 and an iron vitriol slag mother bulb outlet 22, the first mixed material entrance 21 and the
One mixed material outlet 13 is connected；Second mixing arrangement 30 has reduction coal entrance 31, limestone entrance 32, binding agent entrance 33
With the second mixed material outlet 34；Second palletizing device 40 has iron vitriol slag mother bulb entrance 41, the and of the second mixed material entrance 42
Composite pellet outlet 43, iron vitriol slag mother bulb entrance 41 and iron vitriol slag mother bulb export 22 and are connected, the second mixed material entrance 42 and the
Two mixed materials outlet 34 is connected；Annular furnace 50 has composite pellet entrance 51 and reduzate outlet 52, composite pellet entrance
51 are connected with composite pellet outlet 43；And there is mill ore magnetic selection device 60 reduzate entrance 61, metal iron powder to export 62 and
Mine tailing outlet 63, reduzate entrance 61 is connected with reduzate outlet 52.
Thus, the processing method of the iron vitriol slag of the above embodiment of the present invention, first with the first palletizing device by iron vitriol slag
Iron vitriol slag mother bulb is prepared into reduction coal, the second palletizing device is recycled in the outer layer covers reduction coal and Calx of iron vitriol slag mother bulb
The mixture layer of stone.Secondly composite pellet with iron vitriol slag mother bulb as core is carried out in annular furnace direct-reduction process.By
The reduction coal of the outer surface of this iron vitriol slag mother bulb and the mixture layer of limestone, can effectively prevent sulfur oxidation in iron vitriol slag mother bulb
The effusion of thing, and oxysulfide can generate calcium sulfate or sulfuration calcium substance with limestone reaction, and sulfur is fixed on into metallization
In pelletizing.It is possible thereby to efficiently reduce the volatilization of sulfur in iron vitriol slag mother bulb, desulphurization cost is reduced.
Describe the processing system of the iron vitriol slag of the specific embodiment of the invention in detail below with reference to Fig. 3.
First mixing arrangement 10
According to a particular embodiment of the invention, the first mixing arrangement 10 has iron vitriol slag entrance 11, the and of reduction coal entrance 12
First mixed material outlet 13.Iron vitriol slag and reduction coal are carried out the first mixing by this in the first mixing arrangement 10, to obtain
First mixed material.
According to a particular embodiment of the invention, ferrovanadium slag is hot acid extract technology leached mud, and wherein sulfur content is 13%, lead
Content is 2%, and Zn content is 4%, and iron content is 23%.Specific example of the invention, the granularity of ferrovanadium slag is -325 mesh
Account for more than 95%.
First palletizing device 20
According to a particular embodiment of the invention, the first palletizing device 20 has the first mixed material entrance 21 and iron vitriol slag female
Ball outlet 22, the first mixed material entrance 21 is connected with the first mixed material outlet 13.Thus first mixed material is existed
The first pelletizing process is carried out in first palletizing device 20, to obtain iron vitriol slag mother bulb；
According to a particular embodiment of the invention, the carbon-to-oxygen ratio of iron vitriol slag mother bulb is 1.0-1.6.Inventor's discovery, iron vitriol slag
The too low reduction for being unfavorable for lead, zinc, ferrum of the carbon-to-oxygen ratio of mother bulb.From there through the carbon-to-oxygen ratio of control iron vitriol slag mother bulb, can be effective
Ensure lead, zinc, the reduction of ferrum in iron vitriol slag mother bulb.
According to a particular embodiment of the invention, the particle diameter of iron vitriol slag mother bulb is 8-12mm.Inventor has found, if mother bulb particle diameter
It is too small, it is unfavorable for improve production efficiency, if the quality of the excessive contained element sulphur of particle diameter is excessive, needs are entrained into more in outer layer
The mixture of reduction coal and limestone, is unfavorable for the carrying out of reduction reaction and the fixation of element sulphur.
Second mixing arrangement 30
According to a particular embodiment of the invention, the second mixing arrangement 30 has reduction coal entrance 31, limestone entrance 32, glues
Knot agent entrance 33 and the second mixed material outlet 34.Thus by reduction coal, limestone and binding agent in the second mixing arrangement 30
The second mixing is carried out, to obtain the second mixed material.Thus it is easy to further process in iron vitriol slag mother bulb by the second pelletizing
Outer surface parcel reduction coal and limestone.Further can effectively reduce the sulfur volatility in iron vitriol slag mother bulb.
According to a particular embodiment of the invention, it is according to mass ratio by reduction coal, the limestone and the binding agent
100：40-60：4-6 carries out second mixing.Specific example of the invention, the granularity of reduction coal can be 100~200
Between mesh, the granularity of limestone can be for below 200 mesh.Reduction coal and limestone are mixed according to aforementioned proportion, can be had
Effect prevents the effusion of iron vitriol slag mother bulb sulphur oxide, and oxysulfide can generate calcium sulfate or sulfuration with limestone reaction
Calcium substance, sulfur is fixed in metallized pellet.It is possible thereby to the sulfur volatility being effectively reduced in iron vitriol slag mother bulb.It is above-mentioned viscous
The adding proportion of knot agent can ensure the intensity of pelletizing shell, prevent pelletizing shell from bursting.
Second palletizing device 40
According to a particular embodiment of the invention, the second palletizing device 40 has iron vitriol slag mother bulb entrance 41, the second mixture
Material entrance 42 and composite pellet outlet 43, iron vitriol slag mother bulb entrance 41 is connected with iron vitriol slag mother bulb outlet 22, the second mixed material
Entrance 42 is connected with the second mixed material outlet 34.Thus the iron vitriol slag mother bulb is made with second mixed material second
The second pelletizing process is carried out in ball device 40, to make second mixed material wrap up the iron vitriol slag mother bulb, is obtained
To the composite pellet with the iron vitriol slag mother bulb as core.
According to a particular embodiment of the invention, by the process of above-mentioned second pelletizing, wrap up in the outer surface of iron vitriol slag mother bulb
The mixture of one layer of reduction coal and limestone, and then can effectively prevent the effusion of iron vitriol slag mother bulb sulphur oxide, and sulfur oxygen
Compound can generate calcium sulfate or sulfuration calcium substance with limestone reaction, and sulfur is fixed in metallized pellet.It is possible thereby to have
Effect ground reduces the sulfur volatility in iron vitriol slag mother bulb.
According to a particular embodiment of the invention, the particle diameter of iron vitriol slag mother bulb is 8-12mm, and the particle diameter of composite pellet is 10-
16mm.The thickness of the second mixed material parcel iron vitriol slag mother bulb is not less than 2mm.
According to a particular embodiment of the invention, the carbon-to-oxygen ratio of composite pellet is 2.0-2.6.Inventor's discovery, carbon-to-oxygen ratio mistake
Low, the reducing atmosphere around pelletizing is poor, is unfavorable for the reduction of ferrum lead zinc oxide in pelletizing, and carbon-to-oxygen ratio is too high, and pelletizing is strong
Degree is poor, and cost increases.
Annular furnace 50
According to a particular embodiment of the invention, annular furnace 50 has composite pellet entrance 51 and reduzate outlet 52, multiple
Close pelletizing entrance 51 to be connected with composite pellet outlet 43.Thus the composite pellet is delivered in annular furnace to enter in annular furnace 50
Row direct-reduction is processed, to obtain reduzate.
According to a particular embodiment of the invention, the thermal source of annular furnace is gas fired radiant tubes.Gas fired radiant tubes is with thermal-radiating
Mode provides the heat needed for volatilization, decomposition, reduction.Accurate furnace temperature can control using regenerative gas radial canal, and prevent
Reducing agent pyrolysis in pelletizing integument produces CO gases, the stronger reducing atmosphere of holding in pelletizing surface and burner hearth, and then effectively
Sulfur volatilization is reduced, increases sulfur-fixing rate.According to a particular embodiment of the invention, the preferred regenerative gas radial canal of gas fired radiant tubes.
It is possible thereby to further save energy consumption.
According to a particular embodiment of the invention, can be with to the temperature that composite pellet carries out being reduced directly process in annular furnace
For 1000~1200 DEG C.Thus react using the autoreduction of carbonaceous material, lead, zinc oxide in slag are reduced into into lead, zinc list
Matter, is volatized in flue (flue can be separately provided in reducing zone), is oxidized to lead oxide and Zinc Oxide again in flue
In high temperature dust flue dust, through heat exchanger, mix cold wind be reduced to 250 DEG C enter bagroom reclaim zinc oxide dust,
Temperature is too low, it is impossible to realize the reduction of lead zinc, iron oxides.In addition, inventor also has found, if the temperature of direct reduction reactor
It is too high, then it is easy to cause oxysulfide that the decomposition for generating calcium sulfate is reacted with limestone, sulphur oxide gas are escaped, drop on the contrary
Low sulfur-fixing rate.
Further, the time that direct-reduction is processed in annular furnace can be 60~120min.Inventor has found, if also
The former time is too short, and ferrum percent reduction is low, lead, Zinc volatilization rate are relatively low；If the recovery time is long, the scaling loss of carbon is increased, and is unfavorable for protecting
Reducing atmosphere around holding group.
According to a particular embodiment of the invention, the pelletizing behind annular furnace reducing zone is via the drawing mechanism in discharge zone
Discharge out of the furnace, content of Pb＆Zn is less than 0.1% in product metal ball after reduction, and sulfur-fixing rate is more than 90%, sulfur-fixing rate=[(metal
Sulfur percentage composition in pellet weight * metallized pellet)/(sulfur percentage composition in green pellets weight * green pellets)] * 100, reduction
Material afterwards can send to slag sluicing system system and obtain iron product and slag.
Mill ore magnetic selection device 60
According to a particular embodiment of the invention, mill ore magnetic selection device 60 is exported with reduzate entrance 61, metal iron powder
62 and mine tailing outlet 63, reduzate entrance 61 and reduzate export 52 and are connected.Thus by the reduzate in ore grinding magnetic
Ball milling is carried out in screening device 60 and magnetic separation is processed, to obtain metal iron powder and mine tailing.
Embodiment 1
(1) iron vitriol slag (S contents are 13%, Zn content 4%, lead content 2%) is mixed, mixed proportion with reduction coal
For 100:15, carbon-to-oxygen ratio is 1.2, and the first mixed material is carried out into pelletizing, obtains iron vitriol slag mother bulb, the pelletizing grade 8~
In the range of 12mm, underproof pelletizing returns after screening damp mill, reenters the charging zone of the first pelletizing operation.Will reduction
Coal, limestone, binding agent are according to 100：40：5 are mixed, with iron vitriol slag mother bulb as mother bulb after mixing, into the second pelletizing work
Sequence, by the second mixed material iron vitriol slag mother bulb surface is uniformly wrapped in, and obtains composite pellet, and the granularity of composite pellet is 10~
16mm, carbon-to-oxygen ratio is 2.0~2.2.
(2) composite pellet is uniformly distributed in radial canal annular furnace and is reduced directly, respectively fed in annular furnace
Area, reducing zone and discharge zone, the temperature in reducing zone is 1100 DEG C, and the recovery time is 90min, and lead, zinc sulfate further divide
Solve as lead oxide, Zinc Oxide, oxide is reduced to simple substance zinc, elementary lead, is oxidized to lead oxide and oxygen again in flue
Change zinc, ash-laden gas through heat exchanger, mix cold wind be reduced to 250 DEG C enter bagroom reclaim zinc oxide dust.
(3) reduction terminates rear pelletizing Jing drawing mechanisms and discharges out of the furnace, and Pb, Zn content is less than 0.08% in reducing material, Gu sulfur
Rate is 85~90%.
(4) metallized pellet obtains metal iron powder and mine tailing Jing after mill ore magnetic selection, sulfur content in metal iron powder<0.1%.
Embodiment 2
(1) iron vitriol slag (S contents are 13%, Zn content 4%, lead content 2%) is mixed, mixed proportion with reduction coal
For 100:15, carbon-to-oxygen ratio is 1.4, and the first mixed material is carried out into pelletizing, obtains iron vitriol slag mother bulb, the pelletizing grade 8~
In the range of 12mm, underproof pelletizing returns after screening damp mill, reenters the charging zone of the first pelletizing operation.Will reduction
Coal, limestone, binding agent are according to 100：50：5 are mixed, with iron vitriol slag mother bulb as mother bulb after mixing, into the second pelletizing work
Sequence, by the second mixed material iron vitriol slag mother bulb surface is uniformly wrapped in, and obtains composite pellet, and the granularity of composite pellet is 10~
16mm, carbon-to-oxygen ratio is 2.0~2.2.
(2) composite pellet is uniformly distributed in radial canal annular furnace and is reduced directly, respectively fed in annular furnace
Area, reducing zone and discharge zone, the temperature in reducing zone is 1100 DEG C, and the recovery time is 90min, and lead, zinc sulfate further divide
Solve as lead oxide, Zinc Oxide, oxide is reduced to simple substance zinc, elementary lead, is oxidized to lead oxide and oxygen again in flue
Change zinc, ash-laden gas through heat exchanger, mix cold wind be reduced to 250 DEG C enter bagroom reclaim zinc oxide dust.
(3) reduction terminates rear pelletizing Jing drawing mechanisms and discharges out of the furnace, and Pb, Zn content is less than 0.05% in reducing material, Gu sulfur
Rate is 88~92%.
(4) metallized pellet obtains metal iron powder and mine tailing Jing after mill ore magnetic selection, sulfur content in metal iron powder<0.1%.
Embodiment 3
(1) iron vitriol slag (S contents are 13%, Zn content 4%, lead content 2%) is mixed, mixed proportion with reduction coal
For 100:18, carbon-to-oxygen ratio is 1.6, and the first mixed material is carried out into pelletizing, obtains iron vitriol slag mother bulb, the pelletizing grade 8~
In the range of 12mm, underproof pelletizing returns after screening damp mill, reenters the charging zone of the first pelletizing operation.Will reduction
Coal, limestone, binding agent are according to 100：60：5 are mixed, with iron vitriol slag mother bulb as mother bulb after mixing, into the second pelletizing work
Sequence, by the second mixed material iron vitriol slag mother bulb surface is uniformly wrapped in, and obtains composite pellet, and the granularity of composite pellet is 10~
16mm, carbon-to-oxygen ratio is 2.2~2.4.
(2) composite pellet is uniformly distributed in radial canal annular furnace and is reduced directly, respectively fed in annular furnace
Area, reducing zone and discharge zone, the temperature in reducing zone is 1150 DEG C, and the recovery time is 60min, and lead, zinc sulfate further divide
Solve as lead oxide, Zinc Oxide, oxide is reduced to simple substance zinc, elementary lead, is oxidized to lead oxide and oxygen again in flue
Change zinc, ash-laden gas through heat exchanger, mix cold wind be reduced to 250 DEG C enter bagroom reclaim zinc oxide dust.
(3) reduction terminates rear pelletizing Jing drawing mechanisms and discharges out of the furnace, and Pb, Zn content is less than 0.03% in pelletizing after reduction, Gu
Sulfur rate is 92~94%.
(4) metallized pellet obtains metal iron powder and mine tailing Jing after mill ore magnetic selection, sulfur content in metal iron powder<0.1%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be arbitrary
Combine in an appropriate manner in individual or multiple embodiments or example.Additionally, in the case of not conflicting, the technology of this area
Personnel can be combined the feature of the different embodiments or example described in this specification and different embodiments or example
And combination.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of processing method of iron vitriol slag, it is characterised in that include：
Iron vitriol slag and reduction coal are carried out into the first mixing, to obtain the first mixed material；
First mixed material is carried out into the first pelletizing process, to obtain iron vitriol slag mother bulb；
Reduction coal, limestone and binding agent are carried out into the second mixing, to obtain the second mixed material；
The iron vitriol slag mother bulb is carried out into the second pelletizing process with second mixed material, to make second mixed material
The iron vitriol slag mother bulb is wrapped up, the composite pellet with the iron vitriol slag mother bulb as core is obtained；
The composite pellet is delivered to and carry out in annular furnace direct-reduction process, to obtain reduzate；And
The reduzate is carried out into ball milling and magnetic separation is processed, to obtain metal iron powder and mine tailing.
2. the processing method of iron vitriol slag according to claim 1, it is characterised in that the thermal source of the annular furnace adopts combustion gas
Radial canal, preferred regenerative gas radial canal.
3. the processing method of iron vitriol slag according to claim 1, it is characterised in that the carbon-to-oxygen ratio of the iron vitriol slag mother bulb is
1.0-1.6。
4. the processing method of iron vitriol slag according to claim 1, it is characterised in that by the reduction coal, the limestone
With the binding agent according to mass ratio be 100：40-60：4-6 carries out second mixing.
5. the processing method of iron vitriol slag according to claim 1, it is characterised in that the particle diameter of the iron vitriol slag mother bulb is 8-
12mm, the particle diameter of the composite pellet is 10-16mm,
Optionally, the thickness of the second mixed material parcel iron vitriol slag mother bulb is not less than 2mm.
6. the processing method of iron vitriol slag according to claim 1, it is characterised in that the carbon-to-oxygen ratio of the composite pellet is
2.0-2.6。
7. the processing method of iron vitriol slag according to claim 1, it is characterised in that the temperature that the direct-reduction is processed is
1000-1200 DEG C, the time is 60-120min.
8. it is a kind of implement any one of claim 1-7 described in iron vitriol slag processing method system, it is characterised in that include：
First mixing arrangement, first mixing arrangement has the outlet of iron vitriol slag entrance, reduction coal entrance and the first mixed material；
There is first palletizing device, first palletizing device the first mixed material entrance and iron vitriol slag mother bulb to export, and described the
One mixed material entrance is connected with first mixed material outlet；
Second mixing arrangement, second mixing arrangement has reduction coal entrance, limestone entrance, binding agent entrance and second mixed
Close material outlet；
Second palletizing device, second palletizing device has iron vitriol slag mother bulb entrance, the second mixed material entrance and composite balls
Group's outlet, the iron vitriol slag mother bulb entrance and iron vitriol slag mother bulb outlet is connected, the second mixed material entrance with it is described
The outlet of second mixed material is connected；
Annular furnace, the annular furnace has composite pellet entrance and reduzate outlet, and the composite pellet entrance is multiple with described
Close pelletizing outlet to be connected；And
Mill ore magnetic selection device, the mill ore magnetic selection device has reduzate entrance, metal iron powder outlet and mine tailing outlet, described
Reduzate entrance is connected with reduzate outlet.
9. system according to claim 8, it is characterised in that the thermal source in the annular furnace is gas fired radiant tubes.
10. system according to claim 9, it is characterised in that the gas fired radiant tubes is regenerative gas radial canal.
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| CN201611111789.3A CN106676221A (en) | 2016-12-06 | 2016-12-06 | Jarosite slag treatment method and system |
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| CN107267753A (en) * | 2017-05-22 | 2017-10-20 | 中南大学 | A kind of additive and pelletizing process that pelletizing is reclaimed for iron vitriol slag |
| CN107299218A (en) * | 2017-05-22 | 2017-10-27 | 中南大学 | A kind of iron vitriol slag desulfurization pelletizing, preparation and its application |
| CN113774237A (en) * | 2021-09-15 | 2021-12-10 | 中冶赛迪工程技术股份有限公司 | Method for preparing vanadium-rich liquid by using vanadium-rich slag |
| CN115247232A (en) * | 2022-03-02 | 2022-10-28 | 西南科技大学 | Method for settling and separating chalcoalumite slag calcification product |
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| CN115247232A (en) * | 2022-03-02 | 2022-10-28 | 西南科技大学 | Method for settling and separating chalcoalumite slag calcification product |
| CN115247232B (en) * | 2022-03-02 | 2024-04-09 | 广州大鱼创福科技有限公司 | Settling separation method for chalcanthite slag calcified products |
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