CN107815536A - Handle the method and system of stanniferous franklinite - Google Patents
Handle the method and system of stanniferous franklinite Download PDFInfo
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- CN107815536A CN107815536A CN201711209047.9A CN201711209047A CN107815536A CN 107815536 A CN107815536 A CN 107815536A CN 201711209047 A CN201711209047 A CN 201711209047A CN 107815536 A CN107815536 A CN 107815536A
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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
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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
- C22B19/02—Preliminary treatment of ores; Preliminary refining of zinc oxide
-
- 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
-
- 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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry processes
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
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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
Abstract
The invention discloses the method and system for handling stanniferous franklinite, wherein, method includes：First reduction roasting processing is carried out to stanniferous franklinite, to obtain detin product of roasting and stanniferous flue dust；Oxidizing roasting processing is carried out to detin product of roasting, to obtain desulphurizing roasting product and to reclaim sulfur-containing smoke gas；Desulphurizing roasting product is mixed with carbonaceous material and carries out the second reduction roasting processing, to obtain reduction roasting product and to reclaim zinc oxide dust；Slag sluicing system processing is carried out to reduction roasting product, to obtain metallic iron and tailings；Leaching process is carried out to stanniferous flue dust, to obtain containing zinc lixiviating solution and tin-oxide；Tin-oxide is uniformly mixed with carbonaceous material and additive and carries out melting processing, to obtain thick tin product；And electrorefining processing is carried out to thick tin product, to obtain metallic tin.It can be realized using this method and tin, zinc and ferro element in stanniferous franklinite are separately recovered.
Description
Technical field
The invention belongs to field of metallurgy, and specifically, the present invention relates to the method and system for handling stanniferous franklinite.
Background technology
Tin-zinc containing Complex Iron Ore is associated with a large amount of valuable metal elements, has very high value of exploiting and utilizing, is current weight
One of iron ore deposit wanted.But because the symbiosis of the ore deposit associated metal element is extremely complex, and disseminated grain size is thin, tin,
Zinc separates difficulty with iron, so as to which the iron ore concentrate for causing to select can not meet wanting for blast furnace ironmaking due to Sn, Zn content overproof
Ask, thus do not obtain large-scale exploitation so far industrially and utilize.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is to propose the method and system for handling stanniferous franklinite, using the side of the stanniferous franklinite of processing proposed by the present invention
Method can realize being separately recovered for tin, zinc and ferro element.
According to an aspect of the present invention, the present invention proposes a kind of method for handling stanniferous franklinite, including：
(1) the first reduction roasting processing is carried out to stanniferous franklinite, to obtain detin product of roasting and stanniferous flue dust；
(2) oxidizing roasting processing is carried out to the detin product of roasting, to obtain desulphurizing roasting product and to reclaim sulfur-bearing
Flue gas；
(3) the desulphurizing roasting product is mixed with carbonaceous material and carries out the second reduction roasting processing, to be gone back
Former product of roasting simultaneously reclaims zinc oxide dust；
(4) slag sluicing system processing is carried out to the reduction roasting product, to obtain metallic iron and tailings；
(5) leaching process is carried out to the stanniferous flue dust, to obtain containing zinc lixiviating solution and tin-oxide；
(6) tin-oxide, carbonaceous material and additive are uniformly mixed and carries out melting processing, to obtain thick tin
Product；And
(7) electrorefining processing is carried out to the thick tin product, to obtain metallic tin.
Inventor has found that the zinc in stanniferous franklinite mainly exists in the form of ZnS, and ZnS is basic in reducing atmosphere
It is stabilized, therefore reduction phase is stayed in iron ore mostly in the early stage, a small amount of Zn can be reduced volatilization；But stanniferous franklinite
In tinbase sheet with cassiterite (SnO2) form exist, under conditions of less than 1200 degrees Celsius, Sn and SnO2It can not volatilize, only
There is the Main Morphology that gaseous SnO is only tin volatilization.By carrying out the first reduction roasting to stanniferous franklinite first in the present invention
Processing, can make the SnO in tin-zinc containing iron ore2Generation reduction reaction generates SnO, and then realizes the volatilization removing of tin, then distinguishes
Handle the first reduction roasting obtained detin product of roasting and stanniferous flue dust is handled, on the one hand, can be by detin
Product of roasting carries out oxidizing roasting processing, ZnS is oxidized to ZnO, and element sulphur then volatilizees in a gaseous form, then to desulphurizing roasting
Product carries out the second reduction roasting processing, ZnO is reduced to Zn, and Zn volatilizees effusion at high temperature, is obtained by fume recovery
ZnO dust, zinc-iron separation and the recovery of zinc are realized, slag sluicing system processing then is carried out to reduction roasting product, can be final
To metallic iron；On the other hand, handled by carrying out leaching process, melting processing and electrorefining to stanniferous flue dust successively, may be used also
To finally give the metallic tin of high-quality.Thus, by using the above embodiment of the present invention the stanniferous franklinite of processing method,
Being separately recovered for tin in stanniferous franklinite, zinc and ferro element can be realized.
In addition, the method for the stanniferous franklinite of processing according to the above embodiment of the present invention can also have skill additional as follows
Art feature：
In some embodiments of the invention, in step (1), the first reduction roasting processing is in carbonomonoxide concentration
For what is carried out in 20-40 volumes % reducing atmosphere, the temperature of the first reduction roasting processing is 950-1100 degrees Celsius, roasting
The burning time is 15-30 minutes.Thus, it is possible to so that SnO2SnO is reduced to, and then realizes the separation of tin and zinc and iron.
In some embodiments of the invention, in step (2), it in oxygen concentration is 20-30 that oxidizing roasting processing, which is,
Carried out in volume % oxidizing atmosphere, the temperature of the oxidizing roasting processing is 600-800 degrees Celsius, roasting time 15-
30 minutes.Thus, it not only can further improve the efficiency of oxidizing roasting processing and obtain SO2Gas and desulfurization iron ore, realize
The separation of zinc and iron, it can also further improve the rate of recovery of zinc.
In some embodiments of the invention, in the carbonaceous material in the molal quantity of carbon and the stanniferous franklinite zinc and
The ratio of the total mole number of iron is (1.2-1.5)：1.Thus, the ZnO and ferriferous oxide in desulphurizing roasting product can not only be made
It is reduced sufficiently, and then realizes the separation of zinc and iron, and further improve the rate of recovery of zinc and iron, moreover it is possible to improves the utilization of raw material
Rate.
In some embodiments of the invention, in step (3), second reduction roasting processing inert atmosphere or it is weak also
Carried out under the conditions of Primordial Qi atmosphere, the temperature of the second reduction roasting processing is 1150-1250 degrees Celsius, roasting time 20-40
Minute, it is preferable that the second reduction roasting processing is in N2, the inert gas atmosphere such as Ar or CO volumetric concentrations be 1500-
Carried out under 3000ppm weak reducing atmosphere.Thus, it is possible to make ZnO in desulphurizing roasting product and ferriferous oxide by fully also
Original, and then further improve the rate of recovery of zinc and iron.
In some embodiments of the invention, in step (5), using sulfuric acid solution and/or NH3-NH4C1 solution is to described
Stanniferous flue dust carries out leaching process.Thus, it is possible to effectively remove the zinc in stanniferous flue dust, and then obtain pure tin-oxide.
In some embodiments of the invention, the solid mass ratio of the liquid of the leaching process is (4-5)：1.Thus, it is possible to enter
One step improves the efficiency of leaching process.
In some embodiments of the invention, in step (6), the tin-oxide, the carbonaceous material and the addition
The mass ratio of agent is 100：(15-30)：(5-15).Thus, it is possible to further improve the effect that melting processing is carried out to tin-oxide
Rate, and significantly improve the rate of recovery of tin.
In some embodiments of the invention, in step (6), the melting processing is the temperature at 1280-1400 degrees Celsius
Degree is lower to carry out 1.5-2 hour completions.Thus, it is possible to tin-oxide is reduced sufficiently in melting processing procedure, Jin Erjin
One step improves the rate of recovery of tin.
According to the second aspect of the invention, the invention also provides a kind of method for implementing the above-mentioned stanniferous franklinite of processing
System, including：
First reduction roasting device, first reduction roasting device have stanniferous franklinite entrance, detin product of roasting
Outlet and the outlet of stanniferous flue dust；
Oxidizing roasting device, the oxidizing roasting device have detin product of roasting entrance, desulphurizing roasting product exit and
Sulfur-containing smoke gas exports, and the detin product of roasting of the detin product of roasting entrance and first reduction roasting device exports phase
Even；
Second reduction roasting device, second reduction roasting device have desulphurizing roasting product inlet, the first carbon containing thing
Matter entrance, reduction roasting product exit and zinc oxide dust outlet, the desulphurizing roasting product inlet fill with the oxidizing roasting
The desulphurizing roasting product exit put is connected；
There is reduction roasting product inlet, metallic iron outlet and tailings to go out for slag sluicing system device, the slag sluicing system device
Mouthful, the reduction roasting product inlet is connected with the reduction roasting product exit of second reduction roasting device；
Leaching device, the leaching device have stanniferous flue dust entrance, leach stoste entrance, containing zinc lixiviating solution outlet and tin
Oxidate outlet, the stanniferous flue dust entrance are connected with the stanniferous flue dust outlet of first reduction roasting device；
Smelting apparatus, the smelting apparatus have tin-oxide entrance, the second carbonaceous material entrance, additive entrance and thick
Tin product exit, the tin-oxide entrance are connected with the tin-oxide outlet of the leaching device；
Purifier, the purifier have thick tin product inlet, electrolytic solution entrance, metallic tin outlet and electrolysis useless
Liquid exports, and the thick tin product inlet is connected with the thick tin product exit of the smelting apparatus.
The system of the stanniferous franklinite of processing according to the above embodiment of the present invention, can be filled first with the first reduction roasting
Put and the first reduction roasting processing is carried out to stanniferous franklinite, obtain detin product of roasting and stanniferous flue dust, then on the one hand utilize
Oxidizing roasting device carries out oxidizing roasting processing desulfurization to detin product of roasting, then by desulfurization in the second reduction roasting device
Product of roasting mixes with carbonaceous material and carries out the second reduction roasting processing, obtains reduction roasting product and reclaims oxide powder and zinc
Dirt, the separation of zinc-iron and the recovery of zinc are realized, then reduction roasting product is carried out at slag sluicing system in slag sluicing system device
Reason, obtains metallic iron；On the other hand leaching process is carried out to stanniferous flue dust using leaching device, obtains containing zinc lixiviating solution and pure
Tin-oxide, then tin-oxide, carbonaceous material and additive are uniformly mixed in smelting apparatus and carry out melting processing,
Thick tin product is obtained, refining treatment finally is carried out to thick tin product using purifier, metallic tin can be finally given.Thus,
By using the system of the stanniferous franklinite of processing of the above embodiment of the present invention, it is possible to achieve tin, zinc and iron in stanniferous franklinite
Element is separately recovered.
Brief description of the drawings
Fig. 1 is the flow chart of the method for the stanniferous franklinite of processing according to an embodiment of the invention.
Fig. 2 is the structural representation of the system of the stanniferous franklinite of processing according to an embodiment of the invention.
Fig. 3 is the structural representation according to the system of the stanniferous franklinite of processing of another embodiment of the invention.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
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 is not considered as limiting the invention.
According to an aspect of the present invention, the present invention proposes a kind of method for handling stanniferous franklinite, as shown in figure 1,
Including：
(1) the first reduction roasting processing is carried out to stanniferous franklinite, to obtain detin product of roasting and stanniferous flue dust；
(2) oxidizing roasting processing is carried out to detin product of roasting, to obtain desulphurizing roasting product and to reclaim sulfur-containing smoke gas；(3) will be de-
Sulphur product of roasting mixes with carbonaceous material and carries out the second reduction roasting processing, to obtain reduction roasting product and to reclaim oxidation
Zinc powder dirt；(4) slag sluicing system processing is carried out to reduction roasting product, to obtain metallic iron and tailings；(5) stanniferous flue dust is entered
Row leaching process, to obtain containing zinc lixiviating solution and tin-oxide；(6) tin-oxide, carbonaceous material and additive are uniformly mixed
Merge and carry out melting processing, to obtain thick tin product；And (7) carry out electrorefining processing to thick tin product, to obtain
Metallic tin.
Inventor has found that the zinc in stanniferous franklinite mainly exists in the form of ZnS, and ZnS is basic in reducing atmosphere
It is stabilized, therefore reduction phase is stayed in iron ore mostly in the early stage, a small amount of Zn can be reduced volatilization；But stanniferous franklinite
In tinbase sheet with cassiterite (SnO2) form exist, under conditions of less than 1200 degrees Celsius, Sn and SnO2It can not volatilize, only
There is the Main Morphology that gaseous SnO is only tin volatilization.By carrying out the first reduction roasting to stanniferous franklinite first in the present invention
Processing, can make the SnO in tin-zinc containing iron ore2Generation reduction reaction generates SnO, and then realizes the volatilization removing of tin, then distinguishes
Handle the first reduction roasting obtained detin product of roasting and stanniferous flue dust is handled, on the one hand, can be by detin
Product of roasting carries out oxidizing roasting processing, ZnS is oxidized to ZnO, and element sulphur then volatilizees in a gaseous form, then to desulphurizing roasting
Product carries out the second reduction roasting processing, ZnO is reduced to Zn, and Zn volatilizees effusion at high temperature, is obtained by fume recovery
ZnO dust, zinc-iron separation and the recovery of zinc are realized, slag sluicing system processing then is carried out to reduction roasting product, can be final
To metallic iron；On the other hand, handled by carrying out leaching process, melting processing and electrorefining to stanniferous flue dust successively, may be used also
To finally give the metallic tin of high-quality.Thus, by using the above embodiment of the present invention the stanniferous franklinite of processing method,
Being separately recovered for tin in stanniferous franklinite, zinc and ferro element can be realized.
It is described in detail below with reference to the method for processing stanniferous franklinites of the Fig. 1 to the above embodiment of the present invention.
According to a particular embodiment of the invention, in step (1), the first reduction roasting processing can be in carbonomonoxide concentration
Carried out in 20-40 volumes % reducing atmosphere.Inventor's discovery, SnO2Reduction reaction mainly by being reduced with CO
React SnO2+ CO=SnO ↑+CO2Complete, when temperature is 950 degrees Celsius, the CO equilibrium concentration scopes that SnO is stabilized are
13-17.5%, and in actual reduction process, the CO that the CO concentration inside reduction roasting device is far below in reducing atmosphere is dense
Degree, by controlling CO concentration in reducing atmosphere it is 20-40 volume % in the present invention, the reduction that not only can further improve tin is waved
Efficiency is sent out, realizes the separation of tin and zinc and iron, moreover it is possible to further improves the rate of recovery of tin.
According to a particular embodiment of the invention, the temperature of the first reduction roasting processing can be 950-1100 degrees Celsius, roasting
It can be 15-30 minutes to burn the time.Inventor has found, if the temperature of the first reduction roasting processing is too low, SnO2Reduction generation
SnO can not be stabilized, and influence the volatilization effect of tin；And if the temperature of reduction roasting processing is too high, occurred that reduction was existing
As SnO2Gradually it is reduced into the metal Sn that can not be volatilized.Thus, SnO volatilization is not only influenceed, can also reduce the removing effect of tin
Fruit and the rate of recovery.If in addition, the first reduction roasting processing time it is too short, SnO2It can not be completely reduced and volatilize, and
If the overlong time of the first reduction roasting processing, can not further improve the removal effect and the rate of recovery of tin, can also cause energy
Source wastes.Thus, it is 950-1100 degrees Celsius by controlling the temperature that the first reduction roasting is handled in the present invention, roasting time is
15-30 minutes, the efficiency of the first reduction roasting processing not only can be further improved, the SnO in stanniferous franklinite can also be made2
It is reduced sufficiently as SnO and volatilizees, and then realize the separation of tin and zinc and iron, and further improves the rate of recovery of tin.
According to a particular embodiment of the invention, in step (2), oxidizing roasting processing can be 20-30 bodies in oxygen concentration
Carried out in product % oxidizing atmosphere, the temperature of oxidizing roasting processing can be 600-800 degrees Celsius, and roasting time can be 15-
30 minutes.Inventor has found, by carrying out oxidizing roasting processing to detin iron ore, can make in tin-zinc containing iron ore mainly with ZnS
Zinc is oxidized to zinc oxide and sulfur dioxide existing for form, reaches the purpose of desulfurization, and ZnS is heated to 480 and taken the photograph in atmosphere
Family name's degree i.e. slowly oxidation, reaction is as follows：2ZnS+3O2=2ZnO+2SO2, reaction is just fierce when more than 600 degrees Celsius is carried out, but
If being that the reaction time is too short, the ZnS in detin iron ore can not be substantially oxidized, can not be further if the reaction time is long
The rate of recovery of zinc is improved, can also cause energy waste；Meanwhile if the concentration of oxygen is too low in oxidizing roasting processing procedure, ZnS without
Method fully reacts generation ZnO, causes the zinc in follow-up second reduction roasting processing procedure not volatilize fully, influences the recovery of zinc
Rate.Thus, oxygen concentration is 20-30 volume % in oxidizing atmosphere when being handled in the present invention by controlling oxidizing roasting, oxidation roasting
The temperature for burning processing is 600-800 degrees Celsius, and roasting time is 15-30 minutes, further can not only be improved at oxidizing roasting
The efficiency of reason simultaneously obtains SO2Gas and desulfurization iron ore, realize the separation of zinc and iron, can also further improve the rate of recovery of zinc.
According to a particular embodiment of the invention, sulfur-containing smoke gas can be reclaimed and be used for relieving haperacidity, thus, can not only be avoided pair
Environment pollutes, and can also further improve the comprehensive utilization ratio of stanniferous franklinite.
According to a particular embodiment of the invention, the molal quantity of carbon and zinc in stanniferous franklinite and iron always rub in carbonaceous material
Your ratio of number can be (1.2-1.5)：1.Inventor has found, in carbonaceous material the molal quantity of carbon and zinc in stanniferous franklinite and
When the ratio of the total mole number of iron is too small, i.e. the addition of carbonaceous material is very few, ZnO and ferriferous oxide in desulphurizing roasting product
Can not be reduced sufficiently, influence the rate of recovery of zinc and iron, and if in carbonaceous material in the molal quantity of carbon and stanniferous franklinite zinc and
The ratio of the total mole number of iron is excessive, then excessively can remain in material, can not only influence the aggregation of iron granule, can also make
Into material waste.Therefore, by controlling the total of the molal quantity of carbon and zinc in stanniferous franklinite and iron in carbonaceous material in the present invention
The ratio of molal quantity is (1.2-1.5)：1, the ZnO in desulphurizing roasting product and ferriferous oxide can not only be reduced sufficiently,
And then the separation of zinc and iron is realized, and further improve the rate of recovery of zinc and iron, moreover it is possible to improve the utilization rate of raw material.
According to a particular embodiment of the invention, in step (3), the second reduction roasting processing is in inert atmosphere or weak also Primordial Qi
Carried out under the conditions of atmosphere, the temperature of the second reduction roasting processing is 1150-1250 degrees Celsius, and roasting time is 20-40 minutes.This hair
The condition of processing is handled in bright by using above-mentioned second reduction roasting, not only it is possible to prevente effectively from the burning of carbonaceous material, makes
The carbonaceous material reduction as much as possible for ferriferous oxide and zinc oxide, moreover it is possible to make ferriferous oxide and zinc oxide above-mentioned
It is reduced sufficiently under the conditions of reduction roasting as simple substance, while metallic zinc is fully volatilized under above-mentioned sintering temperature, thus, it is possible to enter
One step improves the rate of recovery of zinc and iron.
According to a particular embodiment of the invention, in step (3), the second reduction roasting processing can be preferably in N2, Ar etc. it is lazy
Property gas atmosphere or CO volumetric concentrations be 1500-3000ppm weak reducing atmosphere under carry out.By above-mentioned in the present invention
The second reduction roasting processing is carried out under atmosphere, further carbonaceous material can be made to be used as reducing agent, and then can be further
Improve the efficiency and the rate of recovery of zinc and iron of the second reduction roasting processing.
According to a particular embodiment of the invention, inventor has found, a small amount of zinc in stanniferous franklinite is in the first reduction roasting
Volatilization can be reduced in processing procedure, makes to contain a small amount of zinc in the stanniferous flue dust of recovery.By to stanniferous flue dust in the present invention
Leaching process is carried out, can effectively remove the zinc in stanniferous flue dust, and then obtain pure tin-oxide.
According to a particular embodiment of the invention, in step (5), sulfuric acid solution and/or NH can be used3-NH4C1 solution pair
Stanniferous flue dust carries out leaching process, the zinc oxide in stanniferous flue dust is generated soluble ZnSO4Or [Zn (NH3)4]2+From
Son, so as to remove a small amount of zinc in stanniferous flue dust, and then obtain pure tin-oxide.
According to a particular embodiment of the invention, the solid mass ratio of the liquid of leaching process can be (4-5)：1.Pass through in the present invention
The solid mass ratio of liquid for controlling leaching process is (4-5)：1, the zinc in stanniferous flue dust can not only fully leached, moreover it is possible to enter one
Step improves the efficiency of leaching process.
According to a particular embodiment of the invention, in step (6), additive can be lime stone, quartz sand etc..In the present invention
By adding above-mentioned additive during molten office reason, the mobility of slag can be improved, thus, it is possible to further improve to tin
Oxide carries out the efficiency of melting processing.
According to a particular embodiment of the invention, in step (6), the mass ratio of tin-oxide, carbonaceous material and additive can
Think 100：(15-30)：(5-15).Inventor's discovery, when the addition of carbonaceous material is very few, in melting processing procedure not
Tin-oxide can be made fully to reduce, and then influence the rate of recovery of tin, and when the addition of carbonaceous material is excessive, one can not be entered
Step improves the rate of recovery of tin, can also cause wastage of material；And when the addition of additive is very few, it can not fully reduce tin oxidation
Thing, when the addition of additive is excessive, have it is excessive remain in after reduction in material, cause material waste.Thus, in the present invention
It is 100 by controlling the mass ratio of tin-oxide, carbonaceous material and additive：(15-30)：(5-15), not only can be further
The efficiency that melting processing is carried out to tin-oxide is improved, tin-oxide can also be reduced sufficiently, and significantly improves returning for tin
The grade of yield and thick tin product.
According to a particular embodiment of the invention, in step (6), melting processing can be in 1280-1400 degrees Celsius of temperature
Lower progress 1.5-2 hour completions.Thus, it is possible to tin-oxide is reduced sufficiently in melting processing procedure, and then further
Improve the rate of recovery of tin.
According to a particular embodiment of the invention, by using the side for handling stanniferous franklinite of the above embodiment of the present invention
Method, the content of tin reaches more than 98% in the thick tin that can make to be prepared.
According to a particular embodiment of the invention, in step (7), acidic electrolysis bath can be used to carry out electrorefining to thick tin
Processing, the current density of electrorefining processing can be 100-150A/m2, tank voltage can be 0.2-0.4V.Lead in the present invention
Cross and control above-mentioned electrorefining to handle, can make the tin metal in thick tin in anodic solution into electrolyte, while Sn2+Ion exists
Cathodic reduction generates metal, and then tin is separated with impurity, obtains the metallic tin of high purity more than 99.5%.
According to the second aspect of the invention, the invention also provides a kind of method for implementing the above-mentioned stanniferous franklinite of processing
System, as shown in Fig. 2 including：First reduction roasting device 100, oxidizing roasting device 200, the second reduction roasting device
300th, slag sluicing system device 400, leaching device 500, smelting apparatus 600 and purifier 700.
Wherein, the first reduction roasting device 100 has stanniferous franklinite entrance 110, detin product of roasting outlet 120 and contained
Tin flue dust outlet 130；Oxidizing roasting device 200 has detin product of roasting entrance 210, desulphurizing roasting product exit 220 and contained
Sulphur exhanst gas outlet 230, detin product of roasting entrance 210 are connected with detin product of roasting outlet 120；Second reduction roasting device
300 have desulphurizing roasting product inlet 310, the first carbonaceous material entrance 320, reduction roasting product exit 330 and oxide powder and zinc
Dirt outlet 340, desulphurizing roasting product inlet 310 is connected with desulphurizing roasting product exit 220；Slag sluicing system device 400 has also
Former product of roasting entrance 410, metallic iron outlet 420 and tailings outlet 430, reduction roasting product inlet 410 produces with reduction roasting
Thing outlet 330 is connected；Leaching device 500 has stanniferous flue dust entrance 510, leaches stoste entrance 520, exported containing zinc lixiviating solution
530 and tin-oxide outlet 540, stanniferous flue dust entrance 510 and stanniferous flue dust export 130 and be connected；Smelting apparatus 600 has tin oxygen
Compound entrance 610, the second carbonaceous material entrance 620, additive entrance 630 and thick tin product exit 640, tin-oxide entrance
610 are connected with tin-oxide outlet 540；Purifier 700 has thick tin product inlet 710, electrolytic solution entrance 720, metal
Tin outlet 730 and electrolysis waste solution outlet 740, thick tin product inlet 710 is connected with thick tin product exit 640.
The system of the stanniferous franklinite of processing according to the above embodiment of the present invention, can be filled first with the first reduction roasting
Put 100 pairs of stanniferous franklinites and carry out the first reduction roasting processing, obtain detin product of roasting and stanniferous flue dust, it is then on the one hand sharp
Oxidizing roasting processing desulfurization is carried out to detin product of roasting with oxidizing roasting device 200, then in the second reduction roasting device 300
It is middle that desulphurizing roasting product is mixed with carbonaceous material and carries out the second reduction roasting processing, obtain reduction roasting product and reclaim oxygen
Change zinc powder dirt, realize the separation of zinc-iron and the recovery of zinc, slag then is carried out to reduction roasting product in slag sluicing system device 400
Iron separating treatment, obtains metallic iron；On the other hand leaching process is carried out to stanniferous flue dust using leaching device 500, obtains containing zinc
Leachate and pure tin-oxide, then uniformly mix tin-oxide, carbonaceous material and additive in smelting apparatus 600
And melting processing is carried out, and thick tin product is obtained, refining treatment finally is carried out to thick tin product using purifier 700, can be most
Metallic tin is obtained eventually.Thus, by using the system for handling stanniferous franklinite of the above embodiment of the present invention, it is possible to achieve stanniferous
Tin in franklinite, zinc and ferro element are separately recovered.
It is described in detail below with reference to the system of the stanniferous franklinite of processing of Fig. 2-3 pairs of the above embodiment of the present invention.
First reduction roasting device 100
According to an embodiment of the invention, there is the first reduction roasting device 100 stanniferous franklinite entrance 110, detin to be calcined
Product exit 120 and stanniferous flue dust outlet 130, and suitable for carrying out the first reduction roasting processing to stanniferous franklinite, to obtain
Detin product of roasting and stanniferous flue dust.
According to a particular embodiment of the invention, the first reduction roasting processing can be 20-40 bodies in carbonomonoxide concentration
Carried out in product % reducing atmosphere.Inventor's discovery, SnO2Reduction reaction mainly by carrying out reduction reaction SnO with CO2
+ CO=SnO ↑+CO2Complete, when temperature is 950 degrees Celsius, the CO equilibrium concentrations scope that SnO is stabilized is 13-
17.5%, and in actual reduction process, the CO concentration inside reduction roasting device is far below the CO concentration in reducing atmosphere, this
By controlling CO concentration in reducing atmosphere it is 20-40 volume % in invention, not only can further improves the reduction volatilization effect of tin
Rate, realize the separation of tin and zinc and iron, moreover it is possible to further improve the rate of recovery of tin.
According to a particular embodiment of the invention, the temperature of the first reduction roasting processing can be 950-1100 degrees Celsius, roasting
It can be 15-30 minutes to burn the time.Inventor has found, if the temperature of the first reduction roasting processing is too low, SnO2Reduction generation
SnO can not be stabilized, and influence the volatilization effect of tin；And if the temperature of reduction roasting processing is too high, occurred that reduction was existing
As SnO2Gradually it is reduced into and is unable to volatilized metal Sn, thus, not only influences SnO volatilization, can also reduce the removal effect of tin
And the rate of recovery.If in addition, the first reduction roasting processing time it is too short, SnO2It can not be completely reduced and volatilize, and if
The overlong time of first reduction roasting processing, can not further improve the removal effect and the rate of recovery of tin, can also cause the energy
Waste.Thus, it is 950-1100 degrees Celsius by controlling the temperature that the first reduction roasting is handled in the present invention, roasting time is
15-30 minutes, the efficiency of the first reduction roasting processing not only can be further improved, the SnO in stanniferous franklinite can also be made2
It is reduced sufficiently as SnO and volatilizees, and then realize the separation of tin and zinc and iron, and further improves the rate of recovery of tin.
According to an embodiment of the invention, as shown in figure 3, the system for handling stanniferous franklinite can further include it is broken
Device 800, breaker 800 are connected with the stanniferous franklinite entrance 110 of the first reduction roasting device 100, and suitable for carrying out
Break process is carried out to stanniferous franklinite before first reduction roasting processing, it is possible thereby to further improve at the first reduction roasting
The efficiency of reason.
According to a particular embodiment of the invention, the first reduction roasting device 100 can be rotary hearth furnace, rotary kiln etc., thus,
The efficiency of the first reduction roasting processing can further be improved.
According to a particular embodiment of the invention, stanniferous flue dust can be reclaimed using bag collection device, thus, can
So that the tin in Iron Ore Containing Tin is effectively reclaimed.
Oxidizing roasting device 200
According to an embodiment of the invention, there is oxidizing roasting device 200 detin product of roasting entrance 210, desulphurizing roasting to produce
Thing outlet 220 and sulfur-containing smoke gas outlet 230, detin product of roasting entrance 210 are connected with detin product of roasting outlet 120, and suitable
In carrying out oxidizing roasting processing to detin product of roasting, to obtain desulphurizing roasting product and to reclaim sulfur-containing smoke gas.
According to a particular embodiment of the invention, oxidizing roasting processing can be in the oxidation that oxygen concentration is 20-30 volumes %
Carried out in atmosphere, the temperature of oxidizing roasting processing can be 600-800 degrees Celsius, and roasting time can be 15-30 minutes.Invention
People has found, by carrying out oxidizing roasting processing to detin iron ore, can make in tin-zinc containing iron ore mainly in the form of ZnS existing for zinc
Zinc oxide and sulfur dioxide are oxidized to, reaches the purpose of desulfurization, and ZnS is heated to 480 degrees Celsius of i.e. slow oxygen in atmosphere
Change, reaction is as follows：2ZnS+3O2=2ZnO+2SO2, reaction is just fierce when more than 600 degrees Celsius is carried out, if but the reaction time
Too short, then the ZnS in detin iron ore can not be substantially oxidized, if the reaction time is long, can not further improve the recovery of zinc
Rate, it can also cause energy waste；Meanwhile if the concentration of oxygen is too low in oxidizing roasting processing procedure, ZnS can not fully react raw
Into ZnO, cause the zinc in follow-up second reduction roasting processing procedure not volatilize fully, influence the rate of recovery of zinc.Thus, this hair
Oxygen concentration is 20-30 volume % in oxidizing atmosphere when being handled in bright by controlling oxidizing roasting, the temperature of oxidizing roasting processing
For 600-800 degrees Celsius, roasting time is 15-30 minutes, not only can further improve the efficiency of oxidizing roasting processing and obtain
Obtain SO2Gas and desulfurization iron ore, realize the separation of zinc and iron, can also further improve the rate of recovery of zinc.
According to a particular embodiment of the invention, sulfur-containing smoke gas can be reclaimed and be used for relieving haperacidity, thus, can not only be avoided pair
Environment pollutes, and can also further improve the comprehensive utilization ratio of stanniferous franklinite.
According to a particular embodiment of the invention, oxidizing roasting device 200 can be tunnel cave, rotary kiln, revolving bed, turn bottom
Stove etc., thus, it is possible to further improve the efficiency of oxidizing roasting processing.
Second reduction roasting device 300
According to an embodiment of the invention, there is the second reduction roasting device 300 desulphurizing roasting product inlet 310, first to contain
Carbonizable substance entrance 320, reduction roasting product exit 330 and zinc oxide dust outlet 340, desulphurizing roasting product inlet 310 is with taking off
Sulphur product of roasting outlet 220 is connected, and suitable for mixing and carrying out at the second reduction roasting desulphurizing roasting product with carbonaceous material
Reason, to obtain reduction roasting product and to reclaim zinc oxide dust.
According to a particular embodiment of the invention, the molal quantity of carbon and zinc in stanniferous franklinite and iron always rub in carbonaceous material
Your ratio of number can be (1.2-1.5)：1.Inventor has found, in carbonaceous material the molal quantity of carbon and zinc in stanniferous franklinite and
When the ratio of the total mole number of iron is too small, i.e. the addition of carbonaceous material is very few, and the ZnO in desulphurizing roasting product can not be abundant
Reduction, the rate of recovery of zinc is influenceed, and if the molal quantity of carbon and the total mole number of zinc and iron in stanniferous franklinite in carbonaceous material
Ratio is excessive, can not only be influenceed during the second reduction roasting processing the aggregation of iron granule, can also cause material waste.
Therefore, by controlling the ratio of the total mole number of zinc and iron in the molal quantity of carbon and stanniferous franklinite in carbonaceous material in the present invention
For (1.2-1.5)：1, the ZnO in desulphurizing roasting product and ferriferous oxide can not only be reduced sufficiently, and then realize zinc and
The separation of iron, and further improve the rate of recovery of zinc and iron, moreover it is possible to improve the utilization rate of raw material.
According to a particular embodiment of the invention, the second reduction roasting processing is entered under the conditions of inert atmosphere or weakly reducing atmosphere
OK, the temperature of the second reduction roasting processing is 1150-1250 degrees Celsius, and roasting time is 20-40 minutes.By adopting in the present invention
The condition handled with above-mentioned second reduction roasting processing, not only it is possible to prevente effectively from the burning of carbonaceous material, uses up carbonaceous material
The reduction for being used for ferriferous oxide and zinc oxide more than possible, moreover it is possible to make ferriferous oxide and zinc oxide in above-mentioned reduction roasting bar
It is reduced sufficiently under part as simple substance, while metallic zinc is fully volatilized under above-mentioned sintering temperature, thus, it is possible to further improve zinc
With the rate of recovery of iron.
According to a particular embodiment of the invention, the second reduction roasting processing can be preferably in N2, the inert gas atmosphere such as Ar
Or carried out under the weak reducing atmosphere that CO volumetric concentrations fraction is 1500-3000ppm.By under above-mentioned atmosphere in the present invention
The second reduction roasting processing is carried out, further carbonaceous material can be made to be used as reducing agent, and then can further improve
The efficiency and the rate of recovery of zinc and iron of two reduction roastings processing.
According to a particular embodiment of the invention, the second reduction roasting device 300 can be rotary hearth furnace, Muffle furnace, rotary kiln
Deng thus, it is possible to further improve the efficiency of the second reduction roasting processing.
Slag sluicing system device 400
According to an embodiment of the invention, there is slag sluicing system device 400 reduction roasting product inlet 410, metallic iron to export
420 and tailings outlet 430, reduction roasting product inlet 410 is connected with reduction roasting product exit 330, and suitable for reduce roasting
Burn product and carry out slag sluicing system processing, to obtain metallic iron and tailings.
According to an embodiment of the invention, slag sluicing system device 400 can be ore grinding-concentration equipment or molten separating device.Thus,
Efficiently separating for slag iron can be realized.
Leaching device 500
According to an embodiment of the invention, leaching device 500 has stanniferous flue dust entrance 510, leaches stoste entrance 520, contains
Zinc lixiviating solution outlet 530 and tin-oxide outlet 540, stanniferous flue dust entrance 510 is connected with stanniferous flue dust outlet 130, and is suitable to
Leaching process is carried out to stanniferous flue dust, to obtain containing zinc lixiviating solution and tin-oxide.
According to a particular embodiment of the invention, inventor has found, a small amount of zinc in stanniferous franklinite is in the first reduction roasting
Volatilization can be reduced in processing procedure, makes to contain a small amount of zinc in the stanniferous flue dust of recovery.By to stanniferous flue dust in the present invention
Leaching process is carried out, can effectively remove the zinc in stanniferous flue dust, and then obtain pure tin-oxide.
According to a particular embodiment of the invention, sulfuric acid solution and/or NH can be used3-NH4C1 solution enters to stanniferous flue dust
Row leaching process, the zinc oxide in stanniferous flue dust is set to generate soluble ZnSO4Or [Zn (NH3)4]2+Ion, so as to
A small amount of zinc in stanniferous flue dust is removed, and then obtains pure tin-oxide.
According to a particular embodiment of the invention, the solid mass ratio of the liquid of leaching process can be (4-5)：1.Pass through in the present invention
The solid mass ratio of liquid for controlling leaching process is (4-5)：1, the zinc in stanniferous flue dust can not only fully leached, moreover it is possible to enter one
Step improves the efficiency of leaching process.
Smelting apparatus 600
According to an embodiment of the invention, smelting apparatus 600 has tin-oxide entrance 610, the second carbonaceous material entrance
620th, additive entrance 630 and thick tin product exit 640, tin-oxide entrance 610 are connected with tin-oxide outlet 540, and suitable
In uniformly being mixed tin-oxide with carbonaceous material and additive and carrying out melting processing, to obtain thick tin product.
According to a particular embodiment of the invention, additive can be lime stone, quartz sand etc..By melting office in the present invention
Above-mentioned additive is added during reason, the mobility of slag can be improved, tin-oxide is carried out thus, it is possible to further improve
The efficiency of melting processing.
According to a particular embodiment of the invention, the mass ratio of tin-oxide, carbonaceous material and additive can be 100：
(15-30)：(5-15).Inventor is had found, when the addition of carbonaceous material is very few, tin oxygen can not be made in melting processing procedure
Compound fully reduces, and then influences the rate of recovery of tin, and when the addition of carbonaceous material is excessive, it can not further improve tin
The rate of recovery, can also cause wastage of material；And when the addition of additive is very few, tin-oxide can not be fully reduced, when adding
When adding the addition of agent excessive, have it is excessive remain in after reduction in material, cause material waste.Thus, control is passed through in the present invention
The mass ratio of tin-oxide processed, carbonaceous material and additive is 100：(15-30)：(5-15), not only can further be improved pair
Tin-oxide carries out the efficiency of melting processing, can also be reduced sufficiently tin-oxide, and significantly improve the rate of recovery of tin with
And the grade of thick tin product.
According to a particular embodiment of the invention, melting processing can carry out 1.5-2 at a temperature of 1280-1400 degrees Celsius
Hour completes.Thus, it is possible to make tin-oxide be reduced sufficiently in melting processing procedure, and then further improve the recovery of tin
Rate.
According to a particular embodiment of the invention, it is by using the processing stanniferous franklinite of the above embodiment of the present invention
Unite, the content of tin reaches more than 98% in the thick tin that can make to be prepared.
According to a particular embodiment of the invention, smelting apparatus 600 can be mineral hot furnace, electric furnace etc., thus, it is possible to further
Improve the efficiency of melting processing.
Purifier 700
According to an embodiment of the invention, purifier 700 has thick tin product inlet 710, electrolytic solution entrance 720, gold
Belonging to tin outlet 730 and electrolysis waste solution outlet 740, thick tin product inlet 710 is connected with thick tin product exit 640, and suitable for thick
Tin product carries out electrorefining processing, to obtain metallic tin.
According to a particular embodiment of the invention, acidic electrolysis bath can be used to carry out electrorefining processing, electrolysis to thick tin
The current density of refining treatment can be 100-150A/m2, tank voltage can be 0.2-0.4V.It is above-mentioned by controlling in the present invention
Electrorefining processing, can make the tin metal in thick tin in anodic solution into electrolyte, while Sn2+Ion is given birth in cathodic reduction
Into metal, and then tin is separated with impurity, obtain the metallic tin of high purity more than 99.5%.
Embodiment 1
TFe contents are that 63.51%, FeO contents are that 26.54%, Sn is content 0.25% in tin-zinc containing iron ore concentrate, Zn contents
It is 0.18% for 0.21%, S contents.
(1) first reduction roasting processing, sintering temperature are carried out to stanniferous franklinite under the atmosphere of CO volumetric concentrations 20%
For 950 DEG C, roasting time 30min, tin and a small amount of zinc in iron ore are reduced volatilization, obtain detin product of roasting and stanniferous cigarette
Dirt；
(2) detin product of roasting is subjected to oxidizing roasting processing in air atmosphere, obtains desulphurizing roasting product, wherein roasting
It is 600 DEG C, roasting time 30min to burn temperature, and element sulphur volatilizees in a gaseous form in the process, by off-gas recovery,
For relieving haperacidity；
(3) it is 100 according to mass ratio by desulphurizing roasting product and the anthracite of fixed carbon content 82.66%：30 (anthracites
The ratio of the molal quantity of middle carbon and the total mole number of zinc and iron in stanniferous franklinite is about after 1.2) carrying out mixed-forming, in N2It is lazy
Property gas under carry out the second reduction roasting processing, obtain reduction roasting product, wherein, sintering temperature be 1150 DEG C, roasting time
For 40min, and zinc oxide reduction and volatilize in the process, recovered flue gas can obtain the oxide powder and zinc that Zn grades are 56.87%
Dirt；
(4) slag sluicing system processing is carried out to reduction roasting product using mill ore magnetic selection technique, obtains metal iron powder and tailings,
Wherein the Iron grade of metal iron powder is 90.05%, and the rate of recovery of iron is 88.79%；
(5) leaching process is carried out to stanniferous flue dust using the sulfuric acid solution of concentration 20%, obtained containing zinc lixiviating solution and pure
Tin-oxide, wherein, the liquid-solid ratio of sulfuric acid solution and stanniferous flue dust is 4:1, acidleach temperature is 55 DEG C, and the time is 1.2 hours；
(6) by tin-oxide, coke, quartz sand and lime stone according to 100:15:2:3 mass ratio uniformly mixing and
Melting handles 2h at 1280 DEG C, obtains the thick tin product that tin purity is 98.24%；
(7) electrorefining is carried out to thick tin product in acidic electrolysis bath, controls certain current density (100-150A/
m2) and tank voltage (0.2-0.4V), obtain the metallic tin that purity is 99.59%.
Embodiment 2
TFe contents are that 65.23%, FeO contents are that 26.54%, Sn contents are 0.36%, Zn contents in tin-zinc containing iron ore concentrate
It is 0.23% for 0.27%, S contents.
(1) first reduction roasting processing, sintering temperature are carried out to stanniferous franklinite under the atmosphere of CO volumetric concentrations 30%
For 1050 DEG C, roasting time 23min, tin and a small amount of zinc in iron ore are reduced volatilization, obtain detin product of roasting and stanniferous
Flue dust；
(2) detin product of roasting is subjected to oxidizing roasting processing in the case where oxygen concentration is 25 volume % atmosphere, taken off
Sulphur product of roasting, wherein sintering temperature are 700 DEG C, roasting time 22min, and element sulphur is waved in a gaseous form in the process
Hair, by off-gas recovery, for relieving haperacidity；
(3) it is 100 according to mass ratio by desulphurizing roasting product and the anthracite of fixed carbon content 75.67%：37 (anthracites
The ratio of the molal quantity of middle carbon and the total mole number of zinc and iron in stanniferous franklinite is about after 1.35) carrying out mixed-forming, in CO
Volumetric concentration is to carry out the second reduction roasting processing under 1500ppm atmosphere, obtains reduction roasting product, wherein, sintering temperature
For 1200 DEG C, roasting time 30min, and zinc oxide reduction and volatilize in the process, recovered flue gas can obtain Zn grades and be
55.62% zinc oxide dust；
(4) slag sluicing system processing is carried out to reduction roasting product using molten division technique, obtains metal iron block and tailings, wherein
The Iron grade of metal iron powder is 95.42%, and the rate of recovery of iron is 93.77%；
(5) NH of concentration 30% is used3+NH4Cl composite solutions carry out leaching process to stanniferous flue dust, obtain leaching containing zinc
Liquid and pure tin-oxide, wherein, NH3+NH4The liquid-solid ratio of Cl composite solutions and stanniferous flue dust is 5:1, leaching process temperature
For 60 DEG C, the time is 1.0 hours；
(6) by tin-oxide and reduction coal, quartz sand and lime stone according to 100:20:5:7 mass ratio uniformly mixes simultaneously
Melting handles 1.75h at 1340 DEG C, obtains the thick tin product that tin purity is 98.31%；
(7) electrorefining is carried out to thick tin product in acidic electrolysis bath, controls certain current density (100-150A/
m2) and tank voltage (0.2-0.4V), obtain the metallic tin that purity is 99.60%.
Embodiment 3
TFe contents are that 65.70%, Sn contents are that 0.28%, Zn contents are that 0.17%, S contents are in tin-zinc containing iron ore concentrate
0.09%.
(1) first reduction roasting processing, sintering temperature are carried out to stanniferous franklinite under the atmosphere of CO volumetric concentrations 40%
For 1100 DEG C, roasting time 15min, tin and a small amount of zinc in iron ore are reduced volatilization, obtain detin product of roasting and stanniferous
Flue dust；
(2) detin product of roasting is subjected to oxidizing roasting processing in the case where oxygen concentration is 30 volume % atmosphere, taken off
Sulphur product of roasting, wherein sintering temperature are 800 DEG C, roasting time 15min, and element sulphur is waved in a gaseous form in the process
Hair, by off-gas recovery, for relieving haperacidity；
(3) it is 100 according to mass ratio by desulphurizing roasting product and the anthracite of fixed carbon content 79.05%：40 (anthracites
The ratio of the molal quantity of middle carbon and the total mole number of zinc and iron in stanniferous franklinite is about after 1.5) carrying out mixed-forming, in CO bodies
Product concentration is to carry out the second reduction roasting processing under 3000ppm atmosphere, obtains reduction roasting product, wherein, sintering temperature is
1250 DEG C, roasting time 20min, and zinc oxide reduction and volatilize in the process, recovered flue gas can obtain Zn grades and be
50.34% zinc oxide dust；
(4) slag sluicing system processing is carried out to reduction roasting product using molten division technique, obtains metal iron block and tailings, wherein
The Iron grade of metal iron powder is 94.97%, and the rate of recovery of iron is 95.06%；
(5) leaching process is carried out to stanniferous flue dust using the sulfuric acid solution of concentration 30%, obtained containing zinc lixiviating solution and pure
Tin-oxide, wherein, the liquid-solid ratio of sulfuric acid solution and stanniferous flue dust is 4.5:1, leaching process temperature is 50 DEG C, and the time is
1.5 hour；
(6) by tin-oxide and biomass carbon, quartz sand and lime stone according to 100:30:7:8 mass ratio uniformly mixes
And melting handles 1.5h at 1400 DEG C, the thick tin product that tin purity is 98.67% is obtained；
(7) electrorefining is carried out to thick tin product in acidic electrolysis bath, controls certain current density (100-150A/
m2) and tank voltage (0.2-0.4V), obtain the metallic tin that purity is 99.69%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be any
Combined in an appropriate manner in individual or multiple embodiments or example.In addition, in the case of not conflicting, the technology of this area
Different embodiments or example and the feature of different embodiments or example described in this specification can be combined by personnel
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, changed, replacing and modification.
Claims (10)
- A kind of 1. method for handling stanniferous franklinite, it is characterised in that including：(1) the first reduction roasting processing is carried out to stanniferous franklinite, to obtain detin product of roasting and stanniferous flue dust；(2) oxidizing roasting processing is carried out to the detin product of roasting, to obtain desulphurizing roasting product and to reclaim sulfur-containing smoke gas；(3) the desulphurizing roasting product is mixed with carbonaceous material and carries out the second reduction roasting processing, to obtain reduction roasting Burn product and reclaim zinc oxide dust；(4) slag sluicing system processing is carried out to the reduction roasting product, to obtain metallic iron and tailings；(5) leaching process is carried out to the stanniferous flue dust, to obtain containing zinc lixiviating solution and tin-oxide；(6) tin-oxide, carbonaceous material and additive are uniformly mixed and carries out melting processing, to obtain thick tin production Thing；And(7) electrorefining processing is carried out to the thick tin product, to obtain metallic tin.
- 2. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that in step (1), described first also Former calcination process is carried out in the reducing atmosphere that carbonomonoxide concentration is 20-40 volumes %, at first reduction roasting The temperature of reason is 950-1100 degrees Celsius, and roasting time is 15-30 minutes.
- 3. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that in step (2), the oxidation roasting Burning processing is what is carried out in the oxidizing atmosphere that oxygen concentration is 20-30 volumes %, and the temperature of the oxidizing roasting processing is 600-800 degrees Celsius, roasting time is 15-30 minutes.
- 4. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that carbon rubs in the carbonaceous material Your ratio of number and the total mole number of zinc and iron in the stanniferous franklinite is (1.2-1.5)：1.
- 5. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that in step (3), described second also Former calcination process is carried out under the conditions of inert atmosphere or weakly reducing atmosphere, and the temperature of the second reduction roasting processing is 1150- 1250 degrees Celsius, roasting time is 20-40 minutes,Preferably, the second reduction roasting processing is in N2, the inert gas atmosphere such as Ar or CO volumetric concentrations fraction be 1500- Carried out under 3000ppm weak reducing atmosphere.
- 6. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that molten using sulfuric acid in step (5) Liquid and/or NH3-NH4C1 solution carries out leaching process to the stanniferous flue dust.
- 7. the method for the stanniferous franklinite of processing according to claim 6, it is characterised in that the liquid stereoplasm of the leaching process It is (4-5) to measure ratio：1.
- 8. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that in step (6), the tin oxidation The mass ratio of thing, the carbonaceous material and the additive is 100：(15-30)：(5-15).
- 9. the method for the stanniferous franklinite of processing according to claim 1, it is characterised in that in step (6), at the melting Reason is the progress 1.5-2 hour completions at a temperature of 1280-1400 degrees Celsius.
- A kind of 10. system for the method for implementing any one of the claim 1-9 stanniferous franklinites of processing, it is characterised in that bag Include：First reduction roasting device, first reduction roasting device have stanniferous franklinite entrance, the outlet of detin product of roasting Exported with stanniferous flue dust；Oxidizing roasting device, the oxidizing roasting device have detin product of roasting entrance, desulphurizing roasting product exit and sulfur-bearing Exhanst gas outlet, the detin product of roasting entrance are connected with detin product of roasting outlet；There is desulphurizing roasting product inlet, the first carbonaceous material to enter for second reduction roasting device, second reduction roasting device Mouth, reduction roasting product exit and zinc oxide dust outlet, the desulphurizing roasting product inlet go out with the desulphurizing roasting product Mouth is connected；Slag sluicing system device, the slag sluicing system device have reduction roasting product inlet, metallic iron outlet and tailings outlet, institute Reduction roasting product inlet is stated with the reduction roasting product exit to be connected；Leaching device, the leaching device have stanniferous flue dust entrance, leach stoste entrance, containing zinc lixiviating solution outlet and tin oxidation Thing exports, and the stanniferous flue dust entrance is connected with the stanniferous flue dust outlet；Smelting apparatus, the smelting apparatus have tin-oxide entrance, the second carbonaceous material entrance, additive entrance and the production of thick tin Thing exports, and the tin-oxide entrance is connected with tin-oxide outlet；There is thick tin product inlet, electrolytic solution entrance, metallic tin outlet and electrolysis waste solution to go out for purifier, the purifier Mouthful, the thick tin product inlet is connected with the thick tin product exit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711209047.9A CN107815536A (en) | 2017-11-27 | 2017-11-27 | Handle the method and system of stanniferous franklinite |
Applications Claiming Priority (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066898A (en) * | 2019-05-24 | 2019-07-30 | 关宇 | A kind of process of blast furnace separation solid waste containing zinc |
| CN115418497A (en) * | 2022-09-30 | 2022-12-02 | 昆明理工大学 | Method for co-processing associated multi-metal low-tin resource by using aluminum electrolysis waste cathode carbon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066898A (en) * | 2019-05-24 | 2019-07-30 | 关宇 | A kind of process of blast furnace separation solid waste containing zinc |
| CN115418497A (en) * | 2022-09-30 | 2022-12-02 | 昆明理工大学 | Method for co-processing associated multi-metal low-tin resource by using aluminum electrolysis waste cathode carbon |
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