CN108103306A - The system and method for handling copper ashes - Google Patents
The system and method for handling copper ashes Download PDFInfo
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- CN108103306A CN108103306A CN201711459937.5A CN201711459937A CN108103306A CN 108103306 A CN108103306 A CN 108103306A CN 201711459937 A CN201711459937 A CN 201711459937A CN 108103306 A CN108103306 A CN 108103306A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of system and method for handling copper ashes, which includes：Alkali oxide bath unit, alkali oxide bath unit have copper ashes entrance, oxygen intake, alkali liquor inlet, the outlet of siliceous leachate and rich scum outlet；Mixed-forming device, mixed-forming device have rich scum entrance, reduction coal entrance, binding agent entrance and the outlet of mixing pelletizing, and rich scum entrance is connected with rich scum outlet；Direct reduction unit, direct reduction unit have mixing pelletizing entrance, metallized pellet outlet and zinc-containing dust outlet, and mixing pelletizing entrance is connected with the outlet of mixing pelletizing；Separator, separator have metallized pellet entrance, the outlet of low arsenic iron product and tailings outlet, and metallized pellet entrance is connected with metallized pellet outlet.The system can realize that silicon, the comprehensive reutilization of iron and zinc in copper ashes, and compared with the prior art the energy consumption of direct-reduction reduces by more than 20%, and iron content is not higher than 0.03wt% not less than 96wt%, arsenic content in the low arsenic iron product of gained.
Description
Technical field
The invention belongs to metallurgical field of solid waste disposal, and specifically, the present invention relates to the system and method for processing copper ashes.
Background technology
Copper ashes is the tailings of generation during copper metallurgy, and 2.2 tons of copper ashes, China's copper metallurgy can be generated 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.Copper ashes main component is ferriferous oxide and silica, and main object is mutually iron olive
Stone and a small amount of magnetic iron ore.
Valuable metal iron, zinc and the lead being concentrated mainly at present to the research on utilization of copper ashes in extraction copper ashes, the side of use
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 therein, zinc and lead 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 at 1100 DEG C or more.
Arsenic is the harmful element of steel, and arsenic easily in the grain boundaries segregation of steel, can cause ingredient macrosegregation, destroy metallic matrix
Continuity.Arsenic excessively can also influence the brittleness of steel in steel, and elongation percentage, the contraction percentage of area and the impact flexibility of steel reduce, and make
The welding performance of steel is deteriorated, and by taking carbon steel as an example, arsenic content is generally required to be less than 0.045wt%.Arsenic in copper ashes passes through direct
Reduction treatment can be also entered in final iron product, make arsenic content in iron exceeded (arsenic content is up to 0.30wt%), product market
Face is narrow to be difficult to be utilized.
It is badly in need of finding a kind of new technology for cleaning metallurgy copper ashes as a result,.
The content of the invention
It is contemplated that it solves at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose a kind of system and method for handling copper ashes.The system can realize in copper ashes silicon, iron and zinc it is comprehensive
It closes and recycles, and compared with the prior art, the energy consumption of direct-reduction reduces by more than 20%, and iron contains in the low arsenic iron product of gained
Amount is not higher than 0.03wt% not less than 96wt%, arsenic content.
In one aspect of the invention, the present invention proposes a kind of system for handling copper ashes, according to an embodiment of the invention,
The system includes：
Alkali oxide bath unit, the alkali oxide bath unit have copper ashes entrance, oxygen intake, alkali liquor inlet, siliceous leaching
Liquid exports and rich scum exports；
Mixed-forming device, the mixed-forming device have rich scum entrance, reduction coal entrance, binding agent entrance and mix
Pelletizing outlet is closed, the richness scum entrance is connected with the rich scum 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.
The system of processing copper ashes according to embodiments of the present invention, the main object in copper ashes is mutually fayalite, by by copper
Slag, which is sent into alkali oxide bath unit, to be decomposed with oxygen and lye effect, fayalite by destroying, and silica therein can be with
Alkaline reaction generates silicate, and the ferrous oxide that the ferroso-ferric oxide in copper ashes is decomposited with fayalite can be oxidized by oxygen
For di-iron trioxide, the zinc oxide in di-iron trioxide and copper ashes is easily reduced, so only being needed in follow-up Direct Reduction
The recycling of iron and zinc can be realized in 800-1000 degrees Celsius of temperature conditionss, and compared with tradition is reduced directly technique, energy consumption reduces
More than 20%, and Zn content is 60-75wt% in the zinc-containing dust of gained；Meanwhile the arsenic in copper ashes can be anti-with oxygen and lye
Water-soluble arsenate should be generated and enter liquid phase, so as to fulfill the separation of arsenic and iron phase so that the low arsenic iron product subsequently obtained
Arsenic content is not higher than 0.03wt%, compared with the iron product that existing copper ashes carries the gained of iron, the low arsenic iron product obtained by the application
Higher is worth, it is wider using face.
In addition, the system of processing copper ashes according to the above embodiment of the present invention can also have following additional technology spy
Sign：
In some embodiments of the invention, the system of above-mentioned processing copper ashes further comprises：Acid precipitation device, it is described
Acid precipitation device has siliceous leachate entrance, sour entrance and an outlet of silicic acid gel precipitation, the siliceous leachate entrance with
The siliceous leachate outlet is connected.Thus, it can be achieved that in copper ashes silicon recycling.
In some embodiments of the invention, there is mixing component in the acid precipitation device.Be conducive to improve as a result,
The acid precipitation efficiency of siliceous leachate.
In some embodiments of the invention, the separator is ball mill-magnetic separator linkage.It is favourable as a result,
In the separative efficiency for improving metallized pellet.
In another aspect of the invention, the present invention proposes a kind of system using above-mentioned processing copper ashes and implements processing copper
The method of slag, according to an embodiment of the invention, this method includes：
(1) copper ashes and lye are supplied into the alkali oxide bath unit, is carried out under the action of oxygen at alkali oxide leaching
It manages, siliceous leachate and rich scum is obtained after separation of solid and liquid；
(2) the rich scum, reduction coal and 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 reduction treatment 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, to obtain low arsenic iron production
Product and tailings.
The method of processing copper ashes according to embodiments of the present invention, the main object in copper ashes is mutually fayalite, by by copper
Slag, which is sent into alkali oxide bath unit, to be decomposed with oxygen and lye effect, fayalite by destroying, and silica therein can be with
Alkaline reaction generates silicate, and the ferrous oxide that the ferroso-ferric oxide in copper ashes is decomposited with fayalite can be oxidized by oxygen
For di-iron trioxide, the zinc oxide in di-iron trioxide and copper ashes is easily reduced, so only being needed in follow-up Direct Reduction
The recycling of iron and zinc can be realized in 800-1000 degrees Celsius of temperature conditionss, and compared with tradition is reduced directly technique, energy consumption reduces
More than 20%, and Zn content is 60-75wt% in the zinc-containing dust of gained；Meanwhile the arsenic in copper ashes can be anti-with oxygen and lye
Water-soluble arsenate should be generated and enter liquid phase, so as to fulfill the separation of arsenic and iron phase so that the low arsenic iron product subsequently obtained
Arsenic content is not higher than 0.03wt%, compared with the iron product that existing copper ashes carries the gained of iron, the low arsenic iron product obtained by the application
Higher is worth, it is wider using face.
In addition, the method for processing copper ashes according to the above embodiment of the present invention can also have following additional technology spy
Sign：
In some embodiments of the invention, the method for above-mentioned processing copper ashes further comprises：(5) by the siliceous leaching
Liquid and acid supply carry out acid precipitation processing into the acid precipitation device, to obtain silicic acid gel precipitation.It is favourable as a result,
The recycling of silicon in realizing to copper ashes.
In some embodiments of the invention, in step (1), TFe contents are 35~45wt%, SiO in the copper ashes2
Content is 30~35wt%, and As contents are 0.1~0.3wt%.
In some embodiments of the invention, in step (1), the mass ratio of the copper ashes and the lye is 1：(4-
8).Be conducive to improve the alkali leaching efficiency of copper ashes as a result,.
In some embodiments of the invention, in step (2), the richness scum and the reduction coal, the binding agent
Mass ratio be 100：(25-35)：(1-5).Be conducive to improve the reduction efficiency of rich scum as a result,.
In some embodiments of the invention, in step (3), the temperature of the reduction treatment is Celsius for 800-1000
Degree, time 30-50min.The high metallized pellet of degree of metalization can be obtained while energy consumption is saved as a result,.
In some embodiments of the invention, in step (5), the concentration of the acid is 1-2mol/L.Be conducive to as a result,
Improve the organic efficiency and grade of silicon.
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
It obtains substantially or is recognized by the practice of the present invention.
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 copper ashes according to an embodiment of the invention；
Fig. 2 is the system structure diagram of the processing copper ashes of further embodiment according to the present invention；
Fig. 3 is the method flow schematic diagram of processing copper ashes according to an embodiment of the invention；
Fig. 4 is the method flow schematic diagram of the processing copper ashes of further embodiment according to the present invention.
Specific 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 being fixedly connected or being detachably connected or integral；Can be that machinery connects
It connects or is 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 copper ashes, according to an embodiment of the invention,
With reference to figure 1, which includes：Alkali oxide bath unit 100, mixed-forming device 200, direct reduction unit 300 and separator
400。
According to an embodiment of the invention, there is alkali oxide bath unit 100 copper ashes entrance 101, oxygen intake 102, lye to enter
Mouth 103, siliceous leachate outlet 104 and rich scum outlet 105, and suitable for copper ashes and lye are carried out oxygen under the action of oxygen
Choline leaching is handled, and siliceous leachate and rich scum are obtained after separation of solid and liquid.Specifically, lye can be sodium hydroxide or hydroxide
Potassium, concentration 40-80wt%, excessive concentration can cause lye to volatilize, and cause the loss of raw material.Under normal pressure, by copper ashes with
Lye mixing is leached, and maintaining extraction temperature, temperature is excessively high lye to be caused to volatilize, and cause original in 100-200 degree Celsius ranges
The loss of material, while oxygen is passed through, the flow of oxygen can be 0.5~2L/min, when leaching 1-6 is small, complete the oxygen of copper ashes
Choline leaching is handled.Inventor has found that the main object in copper ashes is mutually fayalite, by sending copper ashes into alkali oxide bath unit
It being acted on oxygen and lye, for fayalite by decomposition is destroyed, silica therein can generate silicate with alkaline reaction, and
Ferroso-ferric oxide in copper ashes and the ferrous oxide that fayalite decomposites can be oxidized by oxygen as di-iron trioxide, meanwhile, copper
Arsenic in slag can enter liquid phase with oxygen and the water-soluble arsenate of alkaline reaction generation, so as to fulfill the separation of arsenic and iron phase.Copper
The granularity of slag can be not more than 0.074m, and granularity is thinner, be soaked in the alkali oxide for being kinetically more conducive to copper ashes.Alkali oxide soaks
In obtained rich scum, all iron content 57-68wt%.Specifically, alkali oxide bath unit can be with stirring, heating function
Alkaline-resisting material reactive tank, can accelerate as a result, copper ashes alkali oxide soak efficiency, improve the production efficiency of technique, while can improve
The service life of alkali oxide bath unit reduces production cost.Lye is by taking sodium hydroxide as an example, the master involved in the dipped journey of alkali oxide
The reaction equation is wanted to be：
2FeO·SiO2=2FeO+SiO2
2NaOH+SiO2=Na2SiO3+H2O
4FeO+O2=2Fe2O3
4Fe3O4+O2=6Fe2O3
6NaOH+As2O3+O2=2Na3AsO4+3H2O
12NaOH+2As2S3+11O2=4Na3AsO4+6H2O+6SO2
According to one embodiment of present invention, TFe contents are 35~45wt%, SiO in copper ashes2Content for 30~
35wt%, As content are 0.1~0.3wt%.The height to silicon, arsenic and iron in copper ashes can be realized by the technique of the application as a result,
Effect recycles, and the content for working as silica, arsenic and iron is within the above range, is remarkably improved the economy of this technique.
According to still a further embodiment, the mass ratio of copper ashes and lye can be 1：(4-8).Inventor's discovery,
If the mass ratio of copper ashes and lye is excessively high, i.e., lye is insufficient, then the fayalite structure in copper ashes can not be sufficiently destroyed, from
And the content of the silicon and arsenic released from copper ashes is caused to reduce so that the impurity contents such as silicon raise in rich scum, influence final
The grade of the low arsenic iron product of gained；And if the mass ratio of copper ashes and lye is too low, i.e. lye is excessive, then is obtaining identical grade
The cost of raw material improves in the case of low arsenic iron product, is unfavorable for improving the economy and production efficiency of entire technique.
According to an embodiment of the invention, mixed-forming device 200 has rich scum entrance 201, reduction coal entrance 202, glues
Tie agent entrance 203 and mixing pelletizing outlet 204, rich scum entrance 201 exports 105 with rich scum and is connected, and be suitable for by rich scum,
Reduction coal and binding agent carry out mixed-forming processing, to obtain mixing pelletizing.Inventor has found, because the iron in rich scum is with three
The form for aoxidizing two iron exists, and zinc exists in the form of zinc oxide, and iron oxide and zinc oxide are easily reduced, therefore follow-up
During direct-reduction the reduction that rich scum can be realized in reduction coal need to be only added in without in addition addition additive.Specifically,
Mixed-forming device can be the linkage of batch mixer and disc balling machine.
According to one embodiment of present invention, the mass ratio of rich scum and reduction coal, binding agent can be 100：(25-
35)：(1-5).Inventor has found that reduction coal dosage is very few, can cause the elements such as the iron in rich scum, zinc that cannot fully be reduced
Recycling；Reduction coal dosage is excessive, can not improve the rate of recovery of the elements such as iron, zinc, can also introduce excessive impurity, reduce iron,
The recycling grade of the elements such as zinc, in addition, also resulting in the waste of reduction coal raw material.
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 be suitable for mixing pelletizing into
Row reduction treatment, to obtain metallized pellet and zinc-containing dust.Inventor has found, because the iron in rich scum is with di-iron trioxide
Form exist, zinc exists in the form of zinc oxide, and iron oxide and zinc oxide are all easily reduced, in the effect of reduction coal
Under, direct reduction unit need to only provide the reduction that iron and zinc can be realized in relatively low temperature, the metal of the metallized pellet of gained
Rate reaches 80-95%, and Zn content is 60-75wt% in zinc-containing dust.Meanwhile because the impurity such as silicon, the arsenic in rich scum are removed,
So single can add in more oxidized alkali leachings treated rich scum in constant direct reduction unit, significantly improve entire
The production efficiency of technique.Specifically, direct reduction unit can be rotary hearth furnace or rotary kiln.The related chemistry reaction equation master being related to
Have：
2Fe2O3+ 3C=4Fe+3CO
ZnO+C=Zn+CO
According to one embodiment of present invention, the temperature of reduction treatment can be 800-1000 degrees Celsius, preferably 950-
1000 degrees Celsius, the time can be 30-50min.Inventor has found, because the iron in rich scum is deposited in the form of di-iron trioxide
Zinc exists in the form of zinc oxide, and iron oxide and zinc oxide are all easily reduced, so existing with traditional direct-reduction
It being compared under conditions of 1100-1350 degrees Celsius, the reduction of zinc-iron only can be realized in the application under 800-1000 degrees Celsius,
Energy consumption reduces by more than 20%.
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.Inventor's discovery, the oxidized alkali leaching silicon of copper ashes, arsenic and other theobromines
After solubility impurity and direct-reduction remove zinc, the low arsenic that iron content is not higher than 0.03wt% not less than 96wt%, arsenic content can obtain
Iron product.
According to one embodiment of present invention, separator 400 can be that ball mill-magnetic separator linkage or combustion gas are melted
Separating device, electric smelting separating device.Thus, it can be achieved that low arsenic iron product and tailings efficiently separate.
The system of processing copper ashes according to embodiments of the present invention, the main object in copper ashes is mutually fayalite, by by copper
Slag, which is sent into alkali oxide bath unit, to be decomposed with oxygen and lye effect, fayalite by destroying, and silica therein can be with
Alkaline reaction generates silicate, and the ferrous oxide that the ferroso-ferric oxide in copper ashes is decomposited with fayalite can be oxidized by oxygen
For di-iron trioxide, the zinc oxide in di-iron trioxide and copper ashes is easily reduced, so only being needed in follow-up Direct Reduction
The recycling of iron and zinc can be realized in 800-1000 degrees Celsius of temperature conditionss, and compared with tradition is reduced directly technique, energy consumption reduces
More than 20%, and Zn content is 60-75wt% in the zinc-containing dust of gained；Meanwhile the arsenic in copper ashes can be anti-with oxygen and lye
Water-soluble arsenate should be generated and enter liquid phase, so as to fulfill the separation of arsenic and iron phase so that the low arsenic iron product subsequently obtained
Arsenic content is not higher than 0.03wt%, compared with the iron product that existing copper ashes carries the gained of iron, the low arsenic iron product obtained by the application
Higher is worth, it is wider using face.
According to an embodiment of the invention, with reference to figure 2, the system of above-mentioned processing copper ashes further comprises：Acid precipitation fills
500。
According to an embodiment of the invention, acid precipitation device 500 has siliceous leachate entrance 501, sour entrance 502 and silicon
Acid gel precipitation outlet 503, siliceous leachate entrance 501 is connected with siliceous leachate outlet 104, and is suitable for siliceous leachate
Acid precipitation processing is carried out with acid, to obtain silicic acid gel precipitation.Specifically, acid precipitation processing acid can be hydrochloric acid,
Sulfuric acid or nitric acid when adding in acid into siliceous leachate, control the pH of solution to make the silicon in siliceous leachate between 8-9
Hydrochlorate is acidified generation silicic acid gel precipitation.
According to one embodiment of present invention, there can be mixing component in acid precipitation device.Specifically, acid precipitation
Device can be the reactive tank with mixing component and alkaline-resisting material.Be conducive to improve the acid precipitation of siliceous leachate as a result,
Efficiency improves the production efficiency of technique, while can improve the service life of acid precipitation device, improves the economy of technique.
According to still a further embodiment, sour concentration can be 1-2mol/L.Inventor's discovery, acid concentration mistake
Low, the slower of progress is reacted in the formation of silicic acid gel；Acid concentration is excessively high, can not accelerate the formation reaction of silicic acid gel, instead
It can cause the waste of sour chemical reagent.
In another aspect of the invention, the present invention proposes a kind of system using above-mentioned processing copper ashes and implements processing copper
The method of slag, according to an embodiment of the invention, with reference to figure 3, this method includes：
S100：Copper ashes and lye are supplied into alkali oxide bath unit, alkali oxide leaching processing is carried out under the action of oxygen
In the step, copper ashes and lye are supplied into alkali oxide bath unit, alkali oxide leaching is carried out under the action of oxygen
It handles, siliceous leachate and rich scum is obtained after separation of solid and liquid.Specifically, lye can be sodium hydroxide or potassium hydroxide, it is dense
It spends for 40-80wt%, excessive concentration can cause lye to volatilize, cause the loss of raw material.Under normal pressure, copper ashes and lye are mixed
It closes and leaches, maintaining extraction temperature, temperature is excessively high lye to be caused to volatilize, and cause raw material in 100-200 degree Celsius ranges
Loss, while oxygen is passed through, the flow of oxygen can be 0.5~2L/min, when leaching 1-6 is small, complete the alkali oxide leaching of copper ashes
Processing.Inventor has found that the main object in copper ashes is mutually fayalite, by sending copper ashes into alkali oxide bath unit and oxygen
It being acted on lye, for fayalite by decomposition is destroyed, silica therein can generate silicate with alkaline reaction, and in copper ashes
The ferrous oxide that decomposites of ferroso-ferric oxide and fayalite can be oxidized by oxygen as di-iron trioxide, meanwhile, in copper ashes
Arsenic can enter liquid phase with oxygen and the water-soluble arsenate of alkaline reaction generation, so as to fulfill the separation of arsenic and iron phase.The grain of copper ashes
Degree can be not more than 0.074m, and granularity is thinner, be soaked in the alkali oxide for being kinetically more conducive to copper ashes.What alkali oxide soaked
In rich scum, all iron content 57-68wt%.Specifically, alkali oxide bath unit can be with stirring, heating function and alkaline-resisting
The reactive tank of material can accelerate the alkali oxide of copper ashes to soak efficiency, improve the production efficiency of technique, while can improve oxidation as a result,
The service life of alkali bath unit reduces production cost.Lye is main anti-involved in the dipped journey of alkali oxide by taking sodium hydroxide as an example
The equation is answered to be：
2FeO·SiO2=2FeO+SiO2
2NaOH+SiO2=Na2SiO3+H2O
4FeO+O2=2Fe2O3
4Fe3O4+O2=6Fe2O3
6NaOH+As2O3+O2=2Na3AsO4+3H2O
12NaOH+2As2S3+11O2=4Na3AsO4+6H2O+6SO2
According to one embodiment of present invention, TFe contents are 35~45wt%, SiO in copper ashes2Content for 30~
35wt%, As content are 0.1~0.3wt%.The height to silicon, arsenic and iron in copper ashes can be realized by the technique of the application as a result,
Effect recycles, and the content for working as silica, arsenic and iron is within the above range, is remarkably improved the economy of this technique.
According to still a further embodiment, the mass ratio of copper ashes and lye can be 1：(4-8).Inventor's discovery,
If the mass ratio of copper ashes and lye is excessively high, i.e., lye is insufficient, then the fayalite structure in copper ashes can not be sufficiently destroyed, from
And the content of the silicon and arsenic released from copper ashes is caused to reduce so that the impurity contents such as silicon raise in rich scum, influence final
The grade of the low arsenic iron product of gained；And if the mass ratio of copper ashes and lye is too low, i.e. lye is excessive, then is obtaining identical grade
The cost of raw material improves in the case of low arsenic iron product, is unfavorable for improving the economy and production efficiency of entire technique.
S200：Rich scum, reduction coal and binding agent are supplied into mixed-forming device and carry out mixed-forming processing
In the steps, rich scum, reduction coal and binding agent are supplied into mixed-forming device and carry out mixed-forming processing,
To obtain mixing pelletizing.Inventor has found that, because the iron in rich scum exists in the form of di-iron trioxide, zinc is with zinc oxide
Form exists, and iron oxide and zinc oxide are easily reduced, therefore without in addition adding during follow-up direct-reduction
Add agent that need to only add in the reduction that rich scum can be realized in reduction coal.Specifically, mixed-forming device can be batch mixer and disk
The linkage of pelletizer.
According to one embodiment of present invention, the mass ratio of rich scum and reduction coal, binding agent can be 100：(25-
35)：(1-5).Inventor has found that reduction coal dosage is very few, can cause the elements such as the iron in rich scum, zinc that cannot fully be reduced
Recycling；Reduction coal dosage is excessive, can not improve the rate of recovery of the elements such as iron, zinc, can also introduce excessive impurity, reduce iron,
The recycling grade of the elements such as zinc, in addition, also resulting in the waste of reduction coal raw material.
S300：Mixing pelletizing is supplied into direct reduction unit and carries out reduction treatment
In the step, mixing pelletizing is supplied into direct reduction unit and carries out reduction treatment, to obtain metallization ball
Group and zinc-containing dust.Inventor has found that, because the iron in rich scum exists in the form of di-iron trioxide, zinc is in the form of zinc oxide
In the presence of, and iron oxide and zinc oxide are all easily reduced, under the action of reduction coal, direct reduction unit need to only provide relatively low
Temperature can be realized the reduction of iron and zinc, and the degree of metalization of the metallized pellet of gained is up to 80-95%, Zn content in zinc-containing dust
For 60-75wt%.Meanwhile because the impurity such as silicon, the arsenic in rich scum are removed, so the single in constant direct reduction unit
More oxidized alkali leachings can be added in treated rich scum, significantly improve the production efficiency of entire technique.Specifically, direct-reduction
Device can be rotary hearth furnace or rotary kiln.The related chemistry reaction equation being related to mainly has：
2Fe2O3+ 3C=4Fe+3CO
ZnO+C=Zn+CO
According to one embodiment of present invention, the temperature of reduction treatment can be 800-1000 degrees Celsius, preferably 950-
1000 degrees Celsius, the time can be 30-50min.Inventor has found, because the iron in rich scum is deposited in the form of di-iron trioxide
Zinc exists in the form of zinc oxide, and iron oxide and zinc oxide are all easily reduced, so existing with traditional direct-reduction
It being compared under conditions of 1100-1350 degrees Celsius, the reduction of zinc-iron only can be realized in the application under 800-1000 degrees Celsius,
Energy consumption reduces by more than 20%.
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.It, can after inventor's discovery, the oxidized alkali leaching silicon of copper ashes, arsenic and other alkali soluble impurity and direct-reduction remove zinc
Obtain the low arsenic iron product that iron content is not higher than 0.03wt% not less than 96wt%, arsenic content.It should be noted that separating treatment
Can be that mill ore magnetic selection handles or melt office reason.
The method of processing copper ashes according to embodiments of the present invention, the main object in copper ashes is mutually fayalite, by by copper
Slag, which is sent into alkali oxide bath unit, to be decomposed with oxygen and lye effect, fayalite by destroying, and silica therein can be with
Alkaline reaction generates silicate, and the ferrous oxide that the ferroso-ferric oxide in copper ashes is decomposited with fayalite can be oxidized by oxygen
For di-iron trioxide, the zinc oxide in di-iron trioxide and copper ashes is easily reduced, so only being needed in follow-up Direct Reduction
The recycling of iron and zinc can be realized in 800-1000 degrees Celsius of temperature conditionss, and compared with tradition is reduced directly technique, energy consumption reduces
More than 20%, and Zn content is 60-75wt% in the zinc-containing dust of gained；Meanwhile the arsenic in copper ashes can be anti-with oxygen and lye
Water-soluble arsenate should be generated and enter liquid phase, so as to fulfill the separation of arsenic and iron phase so that the low arsenic iron product subsequently obtained
Arsenic content is not higher than 0.03wt%, compared with the iron product that existing copper ashes carries the gained of iron, the low arsenic iron product obtained by the application
Higher is worth, it is wider using face.
According to an embodiment of the invention, with reference to figure 4, the method for above-mentioned processing copper ashes further comprises：
S500：Siliceous leachate and acid supply are subjected to acid precipitation processing into acid precipitation device
In the step, siliceous leachate and acid supply are subjected to acid precipitation processing into acid precipitation device, so as to
It is precipitated to silicic acid gel.Specifically, the acid of acid precipitation processing can be hydrochloric acid, sulfuric acid or nitric acid, into siliceous leachate
When adding in acid, the pH of solution is controlled between 8-9, and the silicate in siliceous leachate is made to be acidified generation silicic acid gel precipitation.
According to one embodiment of present invention, sour concentration can be 1-2mol/L.Inventor has found that acid concentration is too low,
The formation reaction of silicic acid gel carries out slower；Acid concentration is excessively high, can not accelerate the formation reaction of silicic acid gel, can make instead
Into the waste of sour chemical reagent.
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
Granularity is less than to copper ashes (TFe the contents 35wt%, SiO of 0.074mm2Content 35wt%, As content 0.3wt%) into
The leaching of row alkali oxide is handled, and actual conditions is：NaOH mass concentrations are 40wt%, and NaOH is 8 with copper ashes mass ratio：1, extraction temperature
For 100 DEG C, when extraction time 6 is small, oxygen flow 2L/min, pressure is normal pressure.After reaction, infusion solution is filtered,
Siliceous leachate and rich scum are obtained after separation of solid and liquid, the XRD analysis of rich scum are the result shows that main object is mutually Fe2O3, chemistry point
Full iron TFe contents are 57wt% in the rich scum of analysis.The hydrochloric acid that 1mol/L is added in into siliceous leachate is acidified, and adjusting pH value of solution=
9, obtain silicic acid gel precipitation.By rich scum, reduction coal and bentonite in mass ratio 100：25：5 carry out mixed-forming processing, obtain
To mixing pelletizing, mixing pelletizing is subjected to direct-reduction processing in rotary hearth furnace, 1000 DEG C, recovery time 30min of reduction temperature,
Collect to obtain zinc-containing dust from rotary hearth furnace dust arrester installation after reduction reaction, wherein Zn content is 65wt%；It is arranged from rotary hearth furnace
Go out metallized pellet, pelletizing degree of metalization is 95%, and metallized pellet is carried out mill ore magnetic selection processing, obtains low arsenic iron powder and tail
Slag, Fe contents are 97wt% in low arsenic iron powder, and As contents are 0.029wt%.
Embodiment 2
Granularity is less than to copper ashes (TFe the contents 45wt%, SiO of 0.074mm2Content 30wt%, As content 0.1wt%) into
The leaching of row alkali oxide is handled, and actual conditions is：NaOH mass concentrations are 80wt%, and NaOH is 4 with copper ashes mass ratio：1, extraction temperature
For 200 DEG C, when extraction time 1 is small, oxygen flow 0.5L/min, pressure is normal pressure.After reaction, by infusion solution mistake
It filters, siliceous leachate and rich scum is obtained after separation of solid and liquid, the XRD analysis of rich scum are the result shows that main object is mutually Fe2O3, change
Full iron TFe contents are 68wt% in the rich scum of credit analysis.The hydrochloric acid acidifying of 2mol/L is added in into siliceous leachate, adjusts solution
PH=8 obtains silicic acid gel precipitation.By rich scum, reduction coal and bentonite in mass ratio 100：35：3 carry out at mixed-forming
Reason obtains mixing pelletizing, and mixing pelletizing is carried out direct-reduction processing, 800 DEG C of reduction temperature, recovery time in rotary hearth furnace
50min collects from rotary hearth furnace dust arrester installation after reduction reaction to obtain zinc-containing dust, and wherein Zn content is 75wt%；From turn
Bottom fire grate goes out metallized pellet, and pelletizing degree of metalization is 80%, and metallized pellet is carried out to molten office reason under 1600 degrees Celsius,
Low arsenic molten iron and tailings are obtained, Fe contents are 98wt% in low arsenic molten iron, and As contents are 0.008wt%.
Embodiment 3
Granularity is less than to copper ashes (TFe the contents 40wt%, SiO of 0.074mm2Content 32wt%, As content 0.15wt%)
Alkali oxide leaching processing is carried out, actual conditions is：NaOH mass concentrations are 60wt%, and NaOH is 6 with copper ashes mass ratio：1, leach temperature
It spends for 150 DEG C, when extraction time 3.5 is small, oxygen flow 1L/min, pressure is normal pressure.After reaction, by infusion solution mistake
It filters, siliceous leachate and rich scum is obtained after separation of solid and liquid, the XRD analysis of rich scum are the result shows that main object is mutually Fe2O3, change
Full iron TFe contents are 62wt% in the rich scum of credit analysis.The hydrochloric acid acidifying of 1mol/L is added in into siliceous leachate, adjusts solution
PH=8.5 obtains silicic acid gel precipitation.By rich scum, reduction coal and bentonite in mass ratio 100：30：2 carry out mixed-forming
Processing obtains mixing pelletizing, and mixing pelletizing is carried out direct-reduction processing, 900 DEG C of reduction temperature, recovery time in rotary hearth furnace
40min collects from rotary hearth furnace dust arrester installation after reduction reaction to obtain zinc-containing dust, and wherein Zn content is 65wt%；From turn
Bottom fire grate goes out metallized pellet, and pelletizing degree of metalization is 88%, and metallized pellet is carried out mill ore magnetic selection processing, obtains low arsenic iron
Powder and tailings, Fe contents are 97.5wt% in low arsenic iron powder, and As contents are 0.012wt%.
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
It is combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the different embodiments described in this specification or example and different embodiments or exemplary feature
It closes and combines.
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 system for handling copper ashes, which is characterized in that including：
There is copper ashes entrance, oxygen intake, alkali liquor inlet, siliceous leachate to go out for alkali oxide bath unit, the alkali oxide bath unit
Mouth and rich scum export；
Mixed-forming device, the mixed-forming device have rich scum entrance, reduction coal entrance, binding agent entrance and mixing ball
Group outlet, the richness scum entrance are connected with the rich scum 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.
2. system according to claim 1, which is characterized in that further comprise：
Acid precipitation device, the acid precipitation device have siliceous leachate entrance, sour entrance and the outlet of silicic acid gel precipitation,
The siliceous leachate entrance is connected with the siliceous leachate outlet.
3. system according to claim 1 or 2, which is characterized in that there is mixing component in the acid precipitation device；
Optional, the separator is ball mill-magnetic separator linkage.
4. a kind of method that system using any one of claim 1-3 implements processing copper ashes, which is characterized in that bag
It includes：
(1) copper ashes and lye are supplied into the alkali oxide bath unit, alkali oxide leaching processing is carried out under the action of oxygen, Gu
Siliceous leachate and rich scum are obtained after liquid separation；
(2) the rich scum, reduction coal and binding agent are supplied into the mixed-forming device and carries out mixed-forming processing, with
Just mixing pelletizing is obtained；
(3) the mixing pelletizing is supplied and reduction treatment is carried out into the direct reduction unit, to obtain metallized pellet
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. according to the method described in claim 4, it is characterized in that, further comprise：
(5) the siliceous leachate and acid supply are subjected to acid precipitation processing into the acid precipitation device, to obtain
Silicic acid gel precipitates.
6. method according to claim 4 or 5, which is characterized in that in step (1), TFe contents are 35 in the copper ashes
~45wt%, SiO2Content is 30~35wt%, and As contents are 0.1~0.3wt%.
7. according to the method described in claim 6, it is characterized in that, in step (1), the quality of the copper ashes and the lye
Than for 1：(4-8).
8. according to the method described in claim 4, it is characterized in that, in step (2), the richness scum and the reduction coal,
The mass ratio of the binding agent is 100：(25-35)：(1-5).
9. according to the method described in claim 4, it is characterized in that, in step (3), the temperature of the reduction treatment is 800-
1000 degrees Celsius, time 30-50min.
10. according to the method described in claim 5, it is characterized in that, in step (5), the concentration of the acid is 1-2mol/L.
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| CN110643830A (en) * | 2019-10-17 | 2020-01-03 | 宝武集团环境资源科技有限公司 | Method for producing zinc oxide and ferrosilicon alloy by using copper slag |
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| CN110643830A (en) * | 2019-10-17 | 2020-01-03 | 宝武集团环境资源科技有限公司 | Method for producing zinc oxide and ferrosilicon alloy by using copper slag |
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