CN107964587A - The system and method for handling the slag containing arsenical copper - Google Patents

The system and method for handling the slag containing arsenical copper Download PDF

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Publication number
CN107964587A
CN107964587A CN201711458414.9A CN201711458414A CN107964587A CN 107964587 A CN107964587 A CN 107964587A CN 201711458414 A CN201711458414 A CN 201711458414A CN 107964587 A CN107964587 A CN 107964587A
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China
Prior art keywords
entrance
zinc
dearsenification
arsenic
outlet
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CN201711458414.9A
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Chinese (zh)
Inventor
宋文臣
王静静
李红科
曹志成
汪勤亚
吴道洪
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Priority to CN201711458414.9A priority Critical patent/CN107964587A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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
    • 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 a kind of system and method for handling copper ashes, which includes：Dearsenification calciner, the dearsenification calciner have the entrance of slag containing arsenical copper, oxygen intake, the outlet of low arsenic fired slags and arsenical fume outlet；Mixed-forming device, the mixed-forming device have low arsenic fired slags entrance, reduction coal entrance, binding agent entrance and the outlet of mixing pelletizing；Direct reduction unit, the direct reduction unit have mixing pelletizing entrance, metallized pellet outlet and zinc-containing dust outlet；Separator, the separator have metallized pellet entrance, the outlet of low arsenic iron product and tailings outlet；Wet method dearsenication device, the wet method dearsenication device have zinc-containing dust entrance, sour entrance, hydrogen peroxide entrance, thick zinc sulphide products export and arsenious waste solution outlet.The system is roasted with being reduced directly the dearsenicating technology twice being combined using dearsenification, has obtained the low arsenic iron product that arsenic content is not higher than 0.03wt%, comprehensive energy consumption and cost reduction more than 5%.

Description

The system and method for handling the slag containing arsenical copper
Technical field
The invention belongs to metallurgical field of solid waste disposal, specifically, system and side the present invention relates to processing slag containing arsenical copper Method.
Background technology
Copper ashes is the tailings produced during copper metallurgy, and 2.2 tons of copper ashes, China's copper metallurgy can be produced while smelting 1 ton of refined copper Clinker yield is big, produces 1500000 tons or so per year.The bulk deposition of copper ashes can bring serious water pollution and soil pollution, thus The comprehensive utilization for strengthening copper ashes is extremely important.The main component of copper ashes is ferriferous oxide and silica, and main thing is mutually iron olive Olive stone and a small amount of magnetic iron ore.
The valuable metal iron, zinc and the lead that extract in copper ashes, the side of use are concentrated mainly on to the research on utilization of copper ashes at present Method has the technological means such as beneficiating method, pyrometallurgical smelting, hydrometallurgy, wherein, rotary hearth furnace direct-reduction is current most promising place The pyrometallurgical smelting method of copper ashes is managed, copper ashes can be recycled into iron, zinc and lead therein by direct-reduction, but this technique is also deposited In the common fault of pyrometallurgical smelting high energy consumption, Chinese patent CN101591718A discloses reduction treatment temperature of the copper ashes in rotary hearth furnace For 1100~1350 DEG C, it is seen then that the temperature of copper ashes rotary hearth furnace direct-reduction is at least more than 1100 DEG C.
Arsenic is the harmful element of steel, and arsenic easily in the grain boundaries segregation of steel, can cause component macrosegregation, destroy metallic matrix Continuity, influence the brittleness of steel.And arsenic can reduce elongation percentage, the contraction percentage of area and the impact flexibility of steel, and make the weldering of steel Connect degradation.By taking carbon steel as an example, arsenic content is generally required to be less than 0.045wt%.Arsenic in slag containing arsenical copper passes through directly also Original place reason can be also entered in final iron product, make arsenic content in iron exceeded (arsenic content is up to 0.30wt%), product market plane It is narrow to be difficult to be utilized.In addition, partial oxidation arsenic can be volatized into zinc-containing dust, the recycling of zinc is influenced.
Thus, it is badly in need of finding a kind of new technology for cleaning metallurgy slag containing arsenical copper.
The content of the invention
It is contemplated that solve at least some of the technical problems in related technologies.For this reason, the present invention One purpose is to propose a kind of system and method for handling the slag containing arsenical copper.The system is roasted using dearsenification and mutually tied with direct-reduction The dearsenicating technology twice closed, has obtained the low arsenic iron product that arsenic content is not higher than 0.03wt%, comprehensive energy consumption and cost reduction 5% More than.
In one aspect of the invention, the present invention proposes a kind of system for handling the slag containing arsenical copper, real according to the present invention Example is applied, which includes：
Dearsenification calciner, the dearsenification calciner have the entrance of slag containing arsenical copper, oxygen intake, the outlet of low arsenic fired slags Exported with arsenical fume；
Mixed-forming device, the mixed-forming device have low arsenic fired slags entrance, reduction coal entrance, binding agent entrance With the outlet of mixing pelletizing, the low arsenic fired slags entrance is connected with the low arsenic fired slags outlet；
Direct reduction unit, the direct reduction unit have mixing pelletizing entrance, metallized pellet outlet and zincilate Dirt exports, and the mixing pelletizing entrance is connected with the mixing pelletizing outlet；
Separator, the separator has metallized pellet entrance, the outlet of low arsenic iron product and tailings outlet, described Metallized pellet entrance is connected with metallized pellet outlet；
Wet method dearsenication device, the wet method dearsenication device have zinc-containing dust entrance, sour entrance, hydrogen peroxide entrance, sulphur Change sodium entrance, thick zinc sulphide products export and arsenious waste solution outlet, the zinc-containing dust entrance and export phase with the zinc-containing dust Even.
The system of processing slag containing arsenical copper according to embodiments of the present invention, is supplied to dearsenification calciner by that will contain arsenical copper slag In, the arsenones in slag containing arsenical copper under the action of oxygen are oxidized to arsenic trioxide, and arsenic trioxide is at high temperature with gaseous Form is discharged into flue gas, is handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process, iron olive Stone is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and the iron under the state is easily reduced, because This need not add the additives such as lime stone in Direct Reduction, and 1300 degrees Celsius of high temperature is up to without the prior art, Comprehensive energy consumption and cost reduction more than 5%.Arsenic in the low arsenic fired slags that dearsenification roasts is mainly with the shape of high price arsenate Formula exists, and high price arsenate generates arsenic trioxide in reduction process and enters zinc-containing dust, is achieved in second of dearsenification processing. Again through separating treatment after the processing of dearsenification twice, arsenic content is not higher than 0.03wt% in obtained low arsenic iron product.Zinc-containing dust After wet method dearsenication, thick vulcanization zinc product and arsenious waste solution are can obtain, thus, improves the added value of zinc product.
In addition, the system of processing slag containing arsenical copper according to the above embodiment of the present invention can also have technology additional as follows Feature：
In some embodiments of the invention, the dearsenification calciner is multihearth roaster or rotary kiln.Thus, favorably In a dearsenification efficiency for improving the slag containing arsenical copper.
In some embodiments of the invention, the mixed-forming device fills for the linkage of batch mixer and disc balling machine Put.Thus, be conducive to improve the mixed-forming efficiency of low arsenic fired slags, and for direct reduction unit provide it is satisfactory enter stove Raw material.
In another aspect of the invention, the present invention is proposed at a kind of system implementation using above-mentioned processing slag containing arsenical copper The method for managing the slag containing arsenical copper, according to an embodiment of the invention, this method includes：
(1) arsenical copper slag will be contained to supply into the dearsenification calciner, taken off under the action of oxygen and neutral gas Arsenic calcination process, to obtain low arsenic fired slags and arsenical fume；
(2) low arsenic fired slags, reduction coal and the binding agent are supplied into the mixed-forming device and is mixed into Type processing, to obtain mixing pelletizing；
(3) the mixing pelletizing is supplied and direct-reduction processing is carried out into the direct reduction unit, to obtain gold Belong to pellet and zinc-containing dust；
(4) metallized pellet is supplied and separating treatment is carried out into the separator, to obtain low arsenic iron production Product and tailings；
(5) zinc-containing dust, acid, hydrogen peroxide and vulcanized sodium are supplied and desulfurization is carried out into the wet desulphurization device Processing, to obtain slightly vulcanizing zinc product and arsenious waste solution.
The method of processing slag containing arsenical copper according to embodiments of the present invention, is supplied to dearsenification calciner by that will contain arsenical copper slag In, the arsenones in slag containing arsenical copper under the action of oxygen are oxidized to arsenic trioxide, and arsenic trioxide is at high temperature with gaseous Form is discharged into flue gas, is handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process, iron olive Stone is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and the iron under the state is easily reduced, because This need not add the additives such as lime stone in Direct Reduction, and 1300 degrees Celsius of high temperature is up to without the prior art, Comprehensive energy consumption and cost reduction more than 5%.Arsenic in the low arsenic fired slags that dearsenification roasts is mainly with the shape of high price arsenate Formula exists, and high price arsenate generates arsenic trioxide in reduction process and enters zinc-containing dust, is achieved in second of dearsenification processing. Again through separating treatment after the processing of dearsenification twice, arsenic content is not higher than 0.03wt% in obtained low arsenic iron product.Zinc-containing dust After wet method dearsenication, thick vulcanization zinc product and arsenious waste solution are can obtain, thus, improves the added value of zinc product.
In addition, the method for processing slag containing arsenical copper according to the above embodiment of the present invention can also have technology additional as follows Feature：
In some embodiments of the invention, in step (1), Fe contents are 35~45wt% in the slag containing arsenical copper, SiO2Content is 30~35wt%, and As contents are 0.1~0.3wt%.Thus, be conducive to improve the economy of this technique.
In some embodiments of the invention, in step (1), the volumetric concentration of the oxygen is 0.5-3vt%.By This, can be avoided for arsenic being oxidized to the diarsenic pentoxide for being difficult to remove after slagging.
In some embodiments of the invention, in step (1), the temperature of the dearsenification calcination process is taken the photograph for 700-900 Family name's degree, time 10-90min.Thus, it can be achieved that a dearsenification of the slag containing arsenical copper and the oxygenolysis of fayalite.
In some embodiments of the invention, it is the low arsenic fired slags and the reduction coal, described viscous in step (2) The mass ratio for tying agent is 100：(15-20)：(1-5).Thus, be conducive to improve the separating by extraction of low arsenic fired slags.
In some embodiments of the invention, in step (3), the temperature of the direct-reduction processing is taken the photograph for 800-1100 Family name's degree, time 30-90min.Thus, it can further improve the metallization of the separating by extraction and metallized pellet of low arsenic fired slags Rate.
In some embodiments of the invention, in step (5), the zinc-containing dust and sour, the described hydrogen peroxide Mass ratio be 100：(100-300)：(10-30).Thus, be conducive to improve the separating by extraction of zinc-containing dust, improve thick vulcanization The grade of zinc product.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment Substantially and it is readily appreciated that, wherein：
Fig. 1 is the system structure diagram of processing slag containing arsenical copper according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram of processing slag containing arsenical copper according to an embodiment of the invention.
Embodiment
The embodiment of the present invention is 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 has the function of same or like element.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.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " connected ", " connection ", " fixation " etc. Term should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or integrally；Can be that machinery connects Connect or be electrically connected；It can be directly connected, can also be indirectly connected by intermediary, can be in two elements The connection in portion or the interaction relationship of two elements, unless otherwise restricted clearly.For those of ordinary skill in the art For, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.
In one aspect of the invention, the present invention proposes a kind of system for handling the slag containing arsenical copper, real according to the present invention Example is applied, with reference to figure 1, which includes：Dearsenification calciner 100, mixed-forming device 200, direct reduction unit 300, separation Device 400 and wet method dearsenication device 500.
According to an embodiment of the invention, dearsenification calciner 100 has the entrance of slag containing arsenical copper 101, oxygen intake 102, low Arsenic fired slags outlet 103 and arsenical fume outlet 104, and carried out suitable for arsenical copper slag will be contained under the action of oxygen and neutral gas Dearsenification calcination process, to obtain low arsenic fired slags and arsenical fume.Specifically, the granularity of the slag containing arsenical copper can be 0.074~ 0.15mm, and granularity is thinner, the gas permeability of material is poorer, so as to influence the ease of the arsenic trioxide obtained by the dearsenification of slag containing arsenical copper Go out；And granularity is thicker, the specific surface area of the raw material of slag containing arsenical copper is small, kinetically can seriously reduce dearsenification roasting speed.Invention People has found that the arsenones in slag containing arsenical copper under the action of oxygen are oxidable at high temperature may be used into arsenic trioxide, arsenic trioxide Enter flue gas in the form of a vapor to discharge, handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process In, fayalite is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and di-iron trioxide accounts for 60~90wt%, ferroso-ferric oxide account for 10~40wt%.As contents are 0.05~0.15wt% in the low arsenic fired slags of gained, i.e., The arsenic-removing rate of dearsenification is up to 50%.Remaining arsenic exists in the form of arsenate in low-temperature bake slag.The correlated response being related to Chemical formula have：
AsmSn+(0.75m+n)O2=0.5mAs2O3↑+nSO2↑
2FeO·SiO2+0.5O2=Fe2O3+SiO2
2FeO·SiO2+O2=2/3Fe3O4+SiO2
Arsenic is not oxidized to by diarsenic pentoxide by control in dearsenification roasting process, because diarsenic pentoxide can be with copper The stable arsenate of some basic anhydride reaction generations in slag, so as to cannot be removed, the chemical formula for the correlated response being related to Have：
FeO+As2O5=FeOAs2O5
CaO+As2O5=CaOAs2O5
According to one embodiment of present invention, dearsenification calciner can be multihearth roaster or rotary kiln.Thus, favorably Efficiency is roasted in the dearsenification for improving the slag containing arsenical copper.
According to still a further embodiment, TFe contents are 35~45wt%, SiO in slag containing arsenical copper2Content for 30~ 35wt%, As content are 0.1~0.3wt%.Thus, it can be realized by the technique of the application and the efficient of arsenic in slag containing arsenical copper is taken off Remove and the high efficiente callback of iron utilizes, and the content for working as silica, arsenic and iron is within the above range, is remarkably improved this technique Economy.
According to still another embodiment of the invention, the volumetric concentration of oxygen can be 0.5-3vt%.Specifically, oxygen Concentration is 0.5-3vt%, remaining is neutral gas, such as nitrogen or inert gas.Inventor's discovery, the oxidation of the dearsenification of slag containing arsenical copper Atmosphere is too strong, and arsenones can be caused to be oxidized to diarsenic pentoxide, and is difficult to remove after diarsenic pentoxide slagging.Thus, use Weak oxide atmosphere described herein may be such that the arsenones in slag containing arsenical copper are oxidized to arsenic trioxide, and arsenic trioxide is in height Exist under temperature with gaseous state, and dearsenification calciner is discharged with arsenical fume, thus, it can be achieved that a dearsenification of the slag containing arsenical copper.
According to still another embodiment of the invention, the temperature of dearsenification calcination process can be 700-900 degrees Celsius, and the time can Think 10-90min.Inventor has found that the temperature of dearsenification calcination process is excessive or roasting time is long, and part three can be caused to aoxidize Two arsenic are oxidized to diarsenic pentoxide, and easily with copper ashes neutral and alkali oxide salt-forming reaction occurs for diarsenic pentoxide, obtain being not easy by The stabilization arsenate of removing；The temperature of dearsenification calcination process is too low or roasting time is too short, can all cause dearsenification reaction to carry out It is insufficient, the removal efficiency of arsenic can be made low.
According to an embodiment of the invention, mixed-forming device 200 has low arsenic fired slags entrance 201, reduction coal entrance 202nd, binding agent entrance 203 and mixing pelletizing outlet 204, low arsenic fired slags entrance 201 is connected with low arsenic fired slags outlet 103, And suitable for low arsenic fired slags, reduction coal and binding agent are carried out mixed-forming processing, to obtain mixing pelletizing.It is specifically, viscous It can be at least one of bentonite, starch solution, molasses or pitch to tie agent.Because the iron in low arsenic fired slags is with four oxidations three The admixture of iron and di-iron trioxide exists, and di-iron trioxide accounts for 60~90wt%, and ferroso-ferric oxide accounts for 10~40wt%, Thus, the reduction that ferriferous oxide can be achieved in the additives such as lime stone need not be added in Direct Reduction.
According to one embodiment of present invention, mixed-forming device can be the linkage dress of batch mixer and disc balling machine Put.Thus, it can be achieved that the batch mixing of low arsenic fired slags and reduction coal and binding agent, and provide for follow-up direct reduction unit meet into The raw material of stove requirement.
According to still a further embodiment, the mass ratio of low arsenic fired slags and reduction coal, binding agent can be 100： (15-20)：(1-5).Inventor has found, if the addition of reduction coal is very few, the ferriferous oxide reduction in low arsenic fired slags is not Fully, and if the addition of reduction coal is excessive, the reducing atmosphere in follow-up direct reduction unit is too strong, and in low arsenic fired slags Arsenate arsenic trioxide can be just reduced into only in weakly reducing atmosphere, arsenate can be direct when under strongly reducing atmosphere Elemental arsenic is reduced to, arsenic simple substance easily combines to form stable FeAs with iron and can not remove, so as to reduce subsequent metallisation ball The grade of group.Thus, the secondary dearsenification processing of the low arsenic fired slags i.e. effect of direct-reduction processing and the addition of reduction coal are close Cut phase is closed, and only could realize conversion of the arsenate to arsenic trioxide under the weakly reducing atmosphere that appropriate reduction coal provides, into And realize the secondary removing of arsenic.
According to an embodiment of the invention, direct reduction unit 300 has mixing pelletizing entrance 301, metallized pellet outlet 302 and zinc-containing dust outlet 303, mixing pelletizing entrance 301 be connected with mixing pelletizing outlet 204, and suitable for will mix pelletizing into Row direct-reduction is handled, to obtain metallized pellet and zinc-containing dust.Inventor has found, in direct reduction unit, mixing Reduction coal in pelletizing provides weakly reducing atmosphere, and arsenate is decomposed under the atmosphere, arsenic trioxide is obtained, in high temperature Under, arsenic trioxide is discharged in the form of a vapor, realizes secondary dearsenification.Meanwhile mix the di-iron trioxide in pelletizing, four oxidations With carbon reduction reaction occurs for three-iron and zinc oxide, obtains fe and zinc, zinc is discharged in a gaseous form at high temperature.Because mixing ball Iron di-iron trioxide in group accounts for 60~90wt%, and ferroso-ferric oxide accounts for 10~40wt%, thus, is only needed in direct reduction unit The reduction that iron can be achieved in relatively low temperature is provided, obtains iron simple substance.1300 degrees Celsius of high temperature is up to compared with the prior art, Comprehensive energy consumption and cost reduction more than 5%.The degree of metalization of obtained metallized pellet is 80~95%, ZnO in zinc-containing dust Content is 60~75wt%, As2O3Content is 3~4wt%.Specifically, direct reduction unit can be rotary hearth furnace or rotary kiln. The related chemistry reaction equation being related to has：
Me3(AsO4)2=Me3(AsO3)2+O2↑
Me3(AsO3)2=3MeO+As2O3↑
2Fe2O3+ 3C=4Fe+3CO ↑
2Fe3O4+ 8C=6Fe+8CO ↑
ZnO+C=Zn ↑+CO ↑
According to one embodiment of present invention, the temperature for being reduced directly processing can be 800-1100 degrees Celsius, and the time can Think 30-90min.Inventor has found that, because the iron di-iron trioxide in mixing pelletizing accounts for 60~90wt%, ferroso-ferric oxide accounts for 10 ~40wt%, thus, need to only provide the reduction that iron can be achieved in relatively low temperature, obtain iron simple substance in direct reduction unit.Phase Than the high temperature that 1300 degrees Celsius are up in the prior art, comprehensive energy consumption and cost reduction more than 5%.
According to an embodiment of the invention, separator 400 has metallized pellet entrance 401, low arsenic iron product outlet 402 With tailings outlet 403, metallized pellet entrance 401 is connected with metallized pellet outlet 302, and suitable for metallized pellet is carried out Separating treatment, to obtain low arsenic iron product and tailings.Specifically, the linkage that separator can be ball mill-magnetic separator fills Put, separating device is melted in combustion gas or electric smelting separating device.Thus, it can be achieved that the separation of low arsenic iron product and tailings, it is not low to obtain Fe contents In 90wt%, low arsenic iron powder of the As contents not higher than 0.03wt% or low arsenic molten iron.
According to an embodiment of the invention, wet method dearsenication device 500 has zinc-containing dust entrance 501, sour entrance 502, peroxide Change hydrogen entrance 503, vulcanized sodium entrance 504, thick zinc sulphide products export 505 and arsenious waste solution outlet 506, zinc-containing dust entrance 501 are connected with zinc-containing dust outlet 303, and suitable for zinc-containing dust, acid, hydrogen peroxide and vulcanized sodium are carried out desulfurization process, with Just obtain slightly vulcanizing zinc product and arsenious waste solution.Specifically, zinc-containing dust is mixed with acid, the zinc oxide in zinc-containing dust is molten Solution, arsenic trioxide are dissolved in water generation trivalent arsenic acid, add after hydrogen peroxide, trivalent arsenic acid is oxidized to pentavalent arsenic acid, so PH value of solution=4.5-5.0 is adjusted afterwards, adds vulcanized sodium, and zinc ion can react generation zinc sulphide precipitation with vulcanized sodium, finally obtain Thick vulcanization zinc product and the arsenious waste solution containing trivalent arsenic acid and pentavalent arsenic acid, the arsenical fume obtained by dearsenification calciner can lead to Enter in arsenious waste solution and focus on.Hereby it is achieved that zinc-containing dust dearsenification, the added value of zinc product, and the wet method are improved Dearsenification device can be the leaching tanks with agitating function and acidproof material.The related chemistry reaction equation being related to has：
ZnO+2H+=Zn2++H2O
As2O3+3H2O=2H3AsO3
H3AsO3+H2O2=H3AsO4+H2O
Zn2++Na2S=2Na++ZnS↓
According to one embodiment of present invention, the mass ratio of zinc-containing dust and acid, hydrogen peroxide, vulcanized sodium can be 100： (100-300)：(10-30)：(60-70).Inventor has found, if acid is excessive with the addition of hydrogen peroxide, vulcanized sodium, causes The waste of acid and hydrogen peroxide, and the purity of final products can be influenced, and if acid and hydrogen peroxide, the addition mistake of vulcanized sodium Few, then the arsenic-removing rate of zinc-containing dust declines, and the added value of gained zinc product reduces, and is unfavorable for improving the economy of this technique.
The system of processing slag containing arsenical copper according to embodiments of the present invention, is supplied to dearsenification calciner by that will contain arsenical copper slag In, the arsenones in slag containing arsenical copper under the action of oxygen are oxidized to arsenic trioxide, and arsenic trioxide is at high temperature with gaseous Form is discharged into flue gas, is handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process, iron olive Stone is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and the iron under the state is easily reduced, because This need not add the additives such as lime stone in Direct Reduction, and 1300 degrees Celsius of high temperature is up to without the prior art, Comprehensive energy consumption and cost reduction more than 5%.Arsenic in the low arsenic fired slags that dearsenification roasts is mainly with the shape of high price arsenate Formula exists, and high price arsenate generates arsenic trioxide in reduction process and enters zinc-containing dust, is achieved in second of dearsenification processing. Again through separating treatment after the processing of dearsenification twice, arsenic content is not higher than 0.03wt% in obtained low arsenic iron product.Zinc-containing dust After wet method dearsenication, thick vulcanization zinc product and arsenious waste solution are can obtain, thus, improves the added value of zinc product.
In another aspect of the invention, the present invention is proposed at a kind of system implementation using above-mentioned processing slag containing arsenical copper The method for managing the slag containing arsenical copper, according to an embodiment of the invention, with reference to figure 2, this method includes：
S100：Arsenical copper slag will be contained to supply into dearsenification calciner, dearsenification is carried out under the action of oxygen and neutral gas Calcination process
In the step, arsenical copper slag will be contained and supplied into dearsenification calciner, carried out under the action of oxygen and neutral gas Dearsenification calcination process, to obtain low arsenic fired slags and arsenical fume.Specifically, the granularity of the slag containing arsenical copper can be 0.074~ 0.15mm, and granularity is thinner, the gas permeability of material is poorer, so as to influence the ease of the arsenic trioxide obtained by the dearsenification of slag containing arsenical copper Go out；And granularity is thicker, the specific surface area of the raw material of slag containing arsenical copper is small, kinetically can seriously reduce dearsenification roasting speed.Invention People has found that the arsenones in slag containing arsenical copper under the action of oxygen are oxidable at high temperature may be used into arsenic trioxide, arsenic trioxide Enter flue gas in the form of a vapor to discharge, handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process In, fayalite is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and di-iron trioxide accounts for 60~90wt%, ferroso-ferric oxide account for 10~40wt%.As contents are 0.05~0.15wt% in the low arsenic fired slags of gained, i.e., The arsenic-removing rate of dearsenification is up to 50%.Remaining arsenic exists in the form of arsenate in low-temperature bake slag.The correlated response being related to Chemical formula have：
AsmSn+(0.75m+n)O2=0.5mAs2O3↑+nSO2↑
2FeO·SiO2+0.5O2=Fe2O3+SiO2
2FeO·SiO2+O2=2/3Fe3O4+SiO2
Arsenic is not oxidized to by diarsenic pentoxide by control in dearsenification roasting process, because diarsenic pentoxide can be with copper The stable arsenate of some basic anhydride reaction generations in slag, so as to cannot be removed, the chemical formula for the correlated response being related to Have：
FeO+As2O5=FeOAs2O5
CaO+As2O5=CaOAs2O5
According to one embodiment of present invention, Fe contents are 35~45wt%, SiO in slag containing arsenical copper2Content for 30~ 35wt%, As content are 0.1~0.3wt%.Thus, it can be realized by the technique of the application and the efficient of arsenic in slag containing arsenical copper is taken off Remove and the high efficiente callback of iron utilizes, and the content for working as silica, arsenic and iron is within the above range, is remarkably improved this technique Economy.
According to still a further embodiment, the volumetric concentration of oxygen can be 0.5-3vt%.Specifically, oxygen Concentration is 0.5-3vt%, remaining is neutral gas, such as nitrogen or inert gas.Inventor's discovery, the oxidation of the dearsenification of slag containing arsenical copper Atmosphere is too strong, and arsenones can be caused to be oxidized to diarsenic pentoxide, and is difficult to remove after diarsenic pentoxide slagging.Thus, use Weak oxide atmosphere described herein may be such that the arsenones in slag containing arsenical copper are oxidized to arsenic trioxide, and arsenic trioxide is in height Exist under temperature with gaseous state, and dearsenification calciner is discharged with arsenical fume, thus, it can be achieved that a dearsenification of the slag containing arsenical copper.
According to still another embodiment of the invention, the temperature of dearsenification calcination process can be 700-900 degrees Celsius, and the time can Think 10-90min.Inventor has found that the temperature of dearsenification calcination process is excessive or roasting time is long, and part three can be caused to aoxidize Two arsenic are oxidized to diarsenic pentoxide, and easily with copper ashes neutral and alkali oxide salt-forming reaction occurs for diarsenic pentoxide, obtain being not easy by The temperature arsenate of removing；The temperature of dearsenification calcination process is too low or roasting time is too short, can all cause dearsenification reaction to carry out It is insufficient, the removal efficiency of arsenic can be made low.
S200：Low arsenic fired slags, reduction coal and binding agent are supplied into mixed-forming device and carry out mixed-forming processing
In the step, low arsenic fired slags, reduction coal and binding agent are supplied mixed-forming is carried out into mixed-forming device Processing, to obtain mixing pelletizing.Specifically, binding agent can be at least one in bentonite, starch solution, molasses or pitch Kind.Because the iron in low arsenic fired slags is with the presence of the admixture of ferroso-ferric oxide and di-iron trioxide, and di-iron trioxide accounts for 60 ~90wt%, ferroso-ferric oxide account for 10~40wt%, thus, the additives such as lime stone need not be added i.e. in Direct Reduction The reduction of ferriferous oxide can be achieved.
According to one embodiment of present invention, the mass ratio of low arsenic fired slags and reduction coal, binding agent can be 100： (15-20)：(1-5).Inventor has found, if the addition of reduction coal is very few, the ferriferous oxide reduction in low arsenic fired slags is not Fully, and if the addition of reduction coal is excessive, the reducing atmosphere in follow-up direct reduction unit is too strong, and in low arsenic fired slags Arsenate arsenic trioxide can be just reduced into only in weakly reducing atmosphere, arsenate can be direct when under strongly reducing atmosphere Elemental arsenic is reduced to, arsenic simple substance easily combines to form stable FeAs with iron and can not remove, so as to reduce subsequent metallisation ball The grade of group.Thus, the secondary dearsenification processing of the low arsenic fired slags i.e. effect of direct-reduction processing and the addition of reduction coal are close Cut phase is closed, and only could realize conversion of the arsenate to arsenic trioxide under the weakly reducing atmosphere that appropriate reduction coal provides, into And realize the secondary removing of arsenic.
S300：Mixing pelletizing is supplied into direct reduction unit and carries out direct-reduction processing
In the step, mixing pelletizing is supplied into direct reduction unit and carries out direct-reduction processing, to obtain metal Pellet and zinc-containing dust.Inventor has found, in direct reduction unit, mixes the reduction coal in pelletizing and provides weak also Primordial Qi Atmosphere, arsenate are decomposed under the atmosphere, obtain arsenic trioxide, and at high temperature, arsenic trioxide is arranged in the form of a vapor Go out, realize secondary dearsenification.Meanwhile mix di-iron trioxide, ferroso-ferric oxide and zinc oxide in pelletizing and carbon generation reduction instead Should, fe and zinc are obtained, zinc is discharged in a gaseous form at high temperature.Because the iron di-iron trioxide in mixing pelletizing accounts for 60~ 90wt%, ferroso-ferric oxide account for 10~40wt%, and thus, in direct reduction unit need to only provide relatively low temperature can be achieved iron Reduction, obtain iron simple substance.Be up to compared with the prior art 1300 degrees Celsius of high temperature, comprehensive energy consumption and cost reduction 5% with On.The degree of metalization of obtained metallized pellet is 80~95%, and ZnO content is 60~75wt%, As in zinc-containing dust2O3Contain Measure as 3~4wt%.Specifically, direct reduction unit can be rotary hearth furnace or rotary kiln.The related chemistry reaction equation being related to has：
Me3(AsO4)2=Me3(AsO3)2+O2↑
Me3(AsO3)2=3MeO+As2O3↑
2Fe2O3+ 3C=4Fe+3CO ↑
2Fe3O4+ 8C=6Fe+8CO ↑
ZnO+C=Zn ↑+CO ↑
According to one embodiment of present invention, the temperature for being reduced directly processing can be 800-1100 degrees Celsius, and the time can Think 30-90min.Inventor has found that, because the iron di-iron trioxide in mixing pelletizing accounts for 60~90wt%, ferroso-ferric oxide accounts for 10 ~40wt%, thus, need to only provide the reduction that iron can be achieved in relatively low temperature, obtain iron simple substance in direct reduction unit.Phase Than the high temperature that 1300 degrees Celsius are up in the prior art, comprehensive energy consumption and cost reduction more than 5%.
S400：Metallized pellet is supplied into separator and carries out separating treatment
In the step, metallized pellet is supplied into separator and carries out separating treatment, to obtain low arsenic iron product And tailings.Specifically, separator, which can be the linkage of ball mill-magnetic separator, combustion gas, melts separating device or electric smelting separating device. Thus, it can be achieved that the separation of low arsenic iron product and tailings, obtains Fe contents and be not less than 90wt%, As contents are not higher than 0.03wt% Low arsenic iron powder or low arsenic molten iron.
S500：Zinc-containing dust, acid, hydrogen peroxide and vulcanized sodium are supplied into wet desulphurization device and carry out desulfurization process
In the step, zinc-containing dust, acid, hydrogen peroxide and vulcanized sodium are supplied into wet desulphurization device and carried out at desulfurization Reason, to obtain slightly vulcanizing zinc product and arsenious waste solution.Specifically, zinc-containing dust is mixed with acid, the oxidation in zinc-containing dust Zinc dissolves, and arsenic trioxide is dissolved in water generation trivalent arsenic acid, adds after hydrogen peroxide, trivalent arsenic acid is oxidized to pentavalent arsenic Acid, then adjusts pH value of solution=4.5-5.0, adds vulcanized sodium, and zinc ion can react generation zinc sulphide precipitation with vulcanized sodium, finally Obtain slightly vulcanizing zinc product and the arsenious waste solution containing trivalent arsenic acid and pentavalent arsenic acid, the arsenical fume obtained by S100, which can be passed through, to be contained Focused in arsenic waste solution.Hereby it is achieved that zinc-containing dust dearsenification, the added value of zinc product is improved.The related chemistry being related to Reaction equation has：
ZnO+2H+=Zn2++H2O
As2O3+3H2O=2H3AsO3
H3AsO3+H2O2=H3AsO4+H2O
Zn2++Na2S=2Na++ZnS↓
According to one embodiment of present invention, the mass ratio of zinc-containing dust and acid, hydrogen peroxide, vulcanized sodium can be 100： (100-300)：(10-30)：(60-70).Inventor has found, if acid is excessive with the addition of hydrogen peroxide, vulcanized sodium, causes The waste of acid and hydrogen peroxide, and the purity of final products can be influenced, and if acid and hydrogen peroxide, the addition mistake of vulcanized sodium Few, then the arsenic-removing rate of zinc-containing dust declines, and the added value of gained zinc product reduces, and is unfavorable for improving the economy of this technique.
The method of processing slag containing arsenical copper according to embodiments of the present invention, is supplied to dearsenification calciner by that will contain arsenical copper slag In, the arsenones in slag containing arsenical copper under the action of oxygen are oxidized to arsenic trioxide, and arsenic trioxide is at high temperature with gaseous Form is discharged into flue gas, is handled so as to fulfill the first time dearsenification of the slag containing arsenical copper.At the same time in dearsenification roasting process, iron olive Stone is mutually destroyed, and iron is oxidized to the admixture of ferroso-ferric oxide and di-iron trioxide, and the iron under the state is easily reduced, because This need not add the additives such as lime stone in Direct Reduction, and 1300 degrees Celsius of high temperature is up to without the prior art, Comprehensive energy consumption and cost reduction more than 5%.Arsenic in the low arsenic fired slags that dearsenification roasts is mainly with the shape of high price arsenate Formula exists, and high price arsenate generates arsenic trioxide in reduction process and enters zinc-containing dust, is achieved in second of dearsenification processing. Again through separating treatment after the processing of dearsenification twice, arsenic content is not higher than 0.03wt% in obtained low arsenic iron product.Zinc-containing dust After wet method dearsenication, thick vulcanization zinc product and arsenious waste solution are can obtain, thus, improves the added value of zinc product.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only to describe Property, without limiting the invention in any way.
Embodiment 1
By slag containing arsenical copper (TFe the contents 45wt%, SiO of 0.074~0.15mm of granularity2Content 30wt%, As content Dearsenification calcination process 0.3wt%) is carried out, actual conditions is：Any additive is not added with, oxygen volumetric concentration 3%, remaining is nitrogen Gas, 700 DEG C of calcination temperature, roasting time 90min.Dearsenification fired slags and arsenical fume, dearsenification fired slags are obtained after reaction Middle As contents are 0.15wt%, and iron mainly exists in the form of di-iron trioxide and ferroso-ferric oxide, and ratio is that di-iron trioxide accounts for 90wt%, ferroso-ferric oxide account for 10wt%.Then by dearsenification fired slags, reduction coal and bentonite in mass ratio 100：20：5 carry out Mixed-forming processing, obtains mixing pelletizing, and mixing pelletizing is carried out direct-reduction processing, reduction temperature 1100 in rotary hearth furnace DEG C, time 30min, collects to obtain zinc-containing dust after reduction reaction, wherein ZnO content is from rotary hearth furnace dust arrester installation 75wt%, As2O3Content is 4wt%；Metallized pellet is discharged from rotary hearth furnace, pelletizing degree of metalization is 95%, by metallized pellet Mill ore magnetic selection processing is carried out, obtains low arsenic iron powder and tailings, Fe contents are 92wt% in low arsenic iron powder, and As contents are 0.028%. Then zinc-containing dust is subjected to dearsenification processing, is specially：Zinc-containing dust is subjected to dissolving with hydrochloric acid first, then adds H2O2Solution By H3AsO3It is oxidized to H3AsO4, pH=4.5 is then adjusted, the vulcanized sodium of zinc-containing dust weight 70% is added, makes zinc with ZnS shapes Formula precipitates, and thick vulcanization zinc product and arsenious waste solution are finally obtained after separation of solid and liquid.Arsenical fume obtained by dearsenification calcination process leads to Enter and be uniformly processed into arsenious waste solution.
Embodiment 2
By slag containing arsenical copper (TFe the contents 35wt%, SiO of 0.074~0.15mm of granularity2Content 35wt%, As content Dearsenification calcination process 0.1wt%) is carried out, actual conditions is：Any additive is not added with, oxygen volumetric concentration 0.5%, remaining is argon Gas, 900 DEG C of calcination temperature, roasting time 10min.Dearsenification fired slags and arsenical fume, dearsenification fired slags are obtained after reaction Middle As contents are 0.05wt%, and iron mainly exists in the form of di-iron trioxide and ferroso-ferric oxide, and ratio is that di-iron trioxide accounts for 60wt%, ferroso-ferric oxide account for 40wt%.Then by dearsenification fired slags, reduction coal and bentonite in mass ratio 100：15：1 carries out Mixed-forming processing, obtains mixing pelletizing, and mixing pelletizing carried out direct-reduction processing in rotary hearth furnace, 800 DEG C of reduction temperature, Time 90min, collects to obtain zinc-containing dust after reduction reaction from rotary hearth furnace dust arrester installation, and wherein ZnO content is 60wt%, As2O3Content is 3wt%；Metallized pellet is discharged from rotary hearth furnace, pelletizing degree of metalization is 80%, by metallized pellet 1600 Molten office reason is carried out under degree Celsius, obtains low arsenic molten iron and tailings, Fe contents are 98wt% in low arsenic molten iron, and As contents are 0.009%.Then zinc-containing dust is subjected to dearsenification processing, is specially：Zinc-containing dust is subjected to dissolving with hydrochloric acid first, is then added H2O2Solution is by H3AsO3It is oxidized to H3AsO4, pH=4.6 is then adjusted, the vulcanized sodium of zinc-containing dust weight 60% is added, makes zinc Precipitated in the form of ZnS, thick vulcanization zinc product and arsenious waste solution are finally obtained after separation of solid and liquid.Contain arsenic obtained by dearsenification calcination process Flue gas is passed into arsenious waste solution and is uniformly processed.
Embodiment 3
By slag containing arsenical copper (TFe the contents 40wt%, SiO of 0.074~0.15mm of granularity2Content 32wt%, As content Dearsenification calcination process 0.15wt%) is carried out, actual conditions is：Any additive is not added with, oxygen volumetric concentration 1%, remaining is helium Gas, 800 DEG C of calcination temperature, roasting time 45min.Dearsenification fired slags and arsenical fume, dearsenification fired slags are obtained after reaction Middle As contents are 0.08wt%, and iron mainly exists in the form of di-iron trioxide and ferroso-ferric oxide, and ratio is that di-iron trioxide accounts for 75wt%, ferroso-ferric oxide account for 25wt%.Then by dearsenification fired slags, reduction coal and bentonite in mass ratio 100：18：3 carry out Mixed-forming processing, obtains mixing pelletizing, and mixing pelletizing carried out direct-reduction processing in rotary hearth furnace, 900 DEG C of reduction temperature, Time 60min, collects to obtain zinc-containing dust after reduction reaction from rotary hearth furnace dust arrester installation, and wherein ZnO content is 70wt%, As2O3Content is 3.5wt%；Metallized pellet is discharged from rotary hearth furnace, pelletizing degree of metalization is 90%, and metallized pellet is carried out Mill ore magnetic selection processing, obtains low arsenic iron powder and tailings, and Fe contents are 93wt% in low arsenic iron powder, and As contents are 0.012%.Then Zinc-containing dust is subjected to dearsenification processing, is specially：Zinc-containing dust is subjected to dissolving with hydrochloric acid first, then adds H2O2Solution will H3AsO3It is oxidized to H3AsO4, pH=4.8 is then adjusted, the vulcanized sodium of zinc-containing dust weight 65% is added, makes zinc in the form of ZnS Precipitate, thick vulcanization zinc product and arsenious waste solution are finally obtained after separation of solid and liquid.Arsenical fume obtained by dearsenification calcination process is passed through It is uniformly processed into arsenious waste solution.
Embodiment 4
By slag containing arsenical copper (TFe the contents 42wt%, SiO of 0.074~0.15mm of granularity2Content 32wt%, As content Dearsenification calcination process 0.25wt%) is carried out, actual conditions is：Any additive is not added with, oxygen volumetric concentration 2%, remaining is nitrogen Gas, 850 DEG C of calcination temperature, roasting time 70min.Dearsenification fired slags and arsenical fume, dearsenification fired slags are obtained after reaction Middle As contents are 0.13wt%, and iron mainly exists in the form of di-iron trioxide and ferroso-ferric oxide, and ratio is that di-iron trioxide accounts for 85wt%, ferroso-ferric oxide account for 15wt%.Then by dearsenification fired slags, reduction coal and bentonite in mass ratio 100：15：4 carry out Mixed-forming processing, obtains mixing pelletizing, and mixing pelletizing is carried out direct-reduction processing, reduction temperature 1000 in rotary hearth furnace DEG C, time 45min, collects to obtain zinc-containing dust after reduction reaction, wherein ZnO content is from rotary hearth furnace dust arrester installation 72wt%, As2O3Content is 3.2wt%；Metallized pellet is discharged from rotary hearth furnace, pelletizing degree of metalization is 88%, by the ball that metallizes Group carries out molten office reason under 1550 degrees Celsius, obtains low arsenic molten iron and tailings, Fe contents are 97.5wt%, As in low arsenic molten iron Content is 0.022%.Then zinc-containing dust is subjected to dearsenification processing, is specially：Zinc-containing dust is subjected to dissolving with hydrochloric acid first, so After add H2O2Solution is by H3AsO3It is oxidized to H3AsO4, pH=4.8 is then adjusted, adds the vulcanization of zinc-containing dust weight 66% Sodium, makes zinc be precipitated in the form of ZnS, and thick vulcanization zinc product and arsenious waste solution are finally obtained after separation of solid and liquid.Dearsenification calcination process institute The arsenical fume obtained, which is passed into arsenious waste solution, to be uniformly processed.
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 of the present invention or example.In the present specification, schematic expression of the above terms is not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office Combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this area Art personnel can be tied the different embodiments or example described in this specification and different embodiments or exemplary feature Close and combine.
Although the embodiment of the present invention has 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, those 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 1. system for handling the slag containing arsenical copper, it is characterised in that including：
    Dearsenification calciner, the dearsenification calciner have the entrance of slag containing arsenical copper, oxygen intake, the outlet of low arsenic fired slags and contain Arsenic exhanst gas outlet；
    Mixed-forming device, the mixed-forming device have low arsenic fired slags entrance, reduction coal entrance, binding agent entrance and mix Pelletizing outlet is closed, the low arsenic fired slags entrance is connected with the low arsenic fired slags outlet；
    There is mixing pelletizing entrance, metallized pellet outlet and zinc-containing dust to go out for direct reduction unit, the direct reduction unit Mouthful, the mixing pelletizing entrance is connected with the mixing pelletizing outlet；
    Separator, the separator have metallized pellet entrance, the outlet of low arsenic iron product and tailings outlet, the metal Pellet entrance is connected with metallized pellet outlet；
    Wet method dearsenication device, the wet method dearsenication device have zinc-containing dust entrance, sour entrance, hydrogen peroxide entrance, vulcanized sodium Entrance, thick zinc sulphide products export and arsenious waste solution outlet, the zinc-containing dust entrance are connected with zinc-containing dust outlet.
  2. 2. system according to claim 1, it is characterised in that the dearsenification calciner is multihearth roaster or revolution Kiln.
  3. 3. system according to claim 1 or 2, it is characterised in that the mixed-forming device is made for batch mixer and disk The linkage of ball machine.
  4. 4. a kind of method that system using any one of claim 1-3 implements processing slag containing arsenical copper, it is characterised in that Including：
    (1) arsenical copper slag will be contained to supply into the dearsenification calciner, dearsenification roasting is carried out under the action of oxygen and neutral gas Burning processing, to obtain low arsenic fired slags and arsenical fume；
    (2) low arsenic fired slags, reduction coal and the binding agent are supplied into the mixed-forming device and carried out at mixed-forming Reason, to obtain mixing pelletizing；
    (3) the mixing pelletizing is supplied and direct-reduction processing is carried out into the direct reduction unit, to be metallized Pelletizing and zinc-containing dust；
    (4) metallized pellet is supplied and separating treatment is carried out into the separator, so as to obtain low arsenic iron product and Tailings；
    (5) zinc-containing dust, acid, hydrogen peroxide and vulcanized sodium are supplied into the wet desulphurization device and carried out at desulfurization Reason, to obtain slightly vulcanizing zinc product and arsenious waste solution.
  5. 5. according to the method described in claim 4, it is characterized in that, in step (1), TFe contents are in the slag containing arsenical copper 35~45wt%, SiO2Content is 30~35wt%, and As contents are 0.1~0.3wt%.
  6. 6. according to the method described in claim 5, it is characterized in that, in step (1), the volumetric concentration of the oxygen is 0.5- 3vt%.
  7. 7. according to the method described in claim 6, it is characterized in that, in step (1), the temperature of the dearsenification calcination process is 700-900 degrees Celsius, time 10-90min.
  8. 8. according to the method described in claim 4, it is characterized in that, in step (2), the low arsenic fired slags and the reduction Coal, the mass ratio of the binding agent are 100：(15-20)：(1-5).
  9. 9. according to the method described in claim 4, it is characterized in that, in step (3), the temperature of the direct-reduction processing is 800-1100 degrees Celsius, time 30-90min.
  10. 10. according to the method described in claim 4, it is characterized in that, in step (5), the zinc-containing dust and the acid, institute The mass ratio for stating hydrogen peroxide is 100：(100-300)：(10-30).
CN201711458414.9A 2017-12-28 2017-12-28 The system and method for handling the slag containing arsenical copper Pending CN107964587A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109055720A (en) * 2018-09-06 2018-12-21 钢研晟华科技股份有限公司 A method of iron powder is prepared based on the modified copper ashes with cryogenic vulcanization reduction of alkaline process
CN115011803A (en) * 2021-12-23 2022-09-06 昆明理工大学 Reduction conversion roasting dearsenification method for high-arsenic germanium-containing neutralization slag

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109055720A (en) * 2018-09-06 2018-12-21 钢研晟华科技股份有限公司 A method of iron powder is prepared based on the modified copper ashes with cryogenic vulcanization reduction of alkaline process
CN115011803A (en) * 2021-12-23 2022-09-06 昆明理工大学 Reduction conversion roasting dearsenification method for high-arsenic germanium-containing neutralization slag

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