CN107674982A - The system and method for wet method pyrogenic process Combined Treatment arsenic-containing smoke dust - Google Patents

Abstract

The invention discloses a kind of system and method for wet method pyrogenic process Combined Treatment arsenic-containing smoke dust, the system includes：Oxygen-free acid bath unit, there is arsenic-containing smoke dust entrance, acid solution entrance, the outlet of leached mud containing arsenic and leachate outlet；Mixing device, there is the entrance of leached mud containing arsenic, additive entrance, reducing agent entrance, ferrous material entrance, binding agent entrance and mixed material outlet；Shaped device, there is mixed material entrance and the outlet of shaping pelletizing；Drying unit, there is shaping pelletizing entrance and dry pelletizing outlet；Rotary hearth furnace, including：Rotatable stove bottom；Annular furnace, along furnace bottom rotation direction, it is divided into cloth area, preheating zone in the burner hearth that goes in ring successively by barricade, mends wind anallobar, middle warm area, high-temperature region and discharge zone；First flue；Second flue；Drawing mechanism；Mend wind supercharging burner；Fuel burner nozzle；Dry pelletizing entrance；Exhanst gas outlet containing arsenic trioxide；Leaded zinc exhanst gas outlet and the outlet of hot product of roasting.

Description

The system and method for wet method pyrogenic process Combined Treatment arsenic-containing smoke dust

Technical field

The invention belongs to metallurgical technology field, and specifically, the present invention relates to wet method pyrogenic process Combined Treatment arsenic-containing smoke dust System and method.

Background technology

Flue dust caused by colored metallurgical industrial is in the landfills such as copper, lead, zinc, cobalt, tin containing arsenic ore Smelting, roasting or waste residue fuming removal process.Wherein, a variety of valuable metals such as Cu, Pb, Zn, chemical composition are contained in copper fumes Complexity, and if copper fumes directly return to copper metallurgy industry, can not only greatly increase the impurity content of feed stock for blast furnace, deteriorate stove Condition, the disposal ability of stove is reduced, and the circulative accumulation of the impurity such as As, Bi, Zn will directly affect electrolytic copper quality.In addition, As Also by the service life for influenceing relieving haperacidity catalyst and then reduce SO₂Conversion ratio and sulfuric acid product quality.Therefore, by copper fumes from copper Open circuit processing, comprehensively recovering valuable metal are very necessary in smelting system.

At present, domestic smelting enterprise is handled smelting smoke dust using " wet method+pyrogenic process " process integration more, i.e., first used Water or dilute sulfuric acid leach the valuable elements such as Cu, Zn in cigarette ash, then are reclaimed respectively；Leached mud (main leaded) is used as dispensing Return to the metal such as smelting system, pyrogenic process recovery Pb.Technological process is：The acidleach one of flue dust one is sunk the evaporative crystallization of one iron removaling arsenic of copper one and sunk The white vitriol of zinc one, obtained leached mud send pyrogenic process process to reclaim lead, and copper sponge send copper system to unite, and iron arsenic slag muck is deposited, seven water sulphur Sold outside sour zinc.But the technique there is also some problems：During wet-treating, the leaching rate of arsenic is not high for lead, Copper making flue dust, Only 20%-30%, remaining most of arsenic are residued in leached mud, return to pyrogenic process process again by feed proportioning system, circulation can make Obtain arsenic content in flue dust and be up to 40%-45%, endanger normal production；It is not easy to be immersed because the copper of a part of form is insoluble in acid Go out, residue in leached mud so that copper recovery is down to 60%-65%.

Therefore, the technology of existing processing flue dust is further improved.

The content of the invention

It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention One purpose is to propose a kind of system and method with wet method pyrogenic process Combined Treatment arsenic-containing smoke dust.Can be real using the system The high efficiente callback of the valuable metal such as arsenic, zinc, lead and copper in existing arsenic-containing smoke dust, so as to realize the recycling of arsenic-containing smoke dust.

In terms of one of the present invention, the present invention proposes a kind of system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust, According to an embodiment of the invention, the system includes：

Oxygen-free acid bath unit, the oxygen-free acid bath unit have arsenic-containing smoke dust entrance, acid solution entrance, the outlet of leached mud containing arsenic Exported with leachate；

Mixing device, the mixing device have the entrance of leached mud containing arsenic, additive entrance, reducing agent entrance, chalybeate Expect entrance, binding agent entrance and mixed material outlet, the entrance of leached mud containing arsenic is connected with the leached mud containing arsenic outlet；

Shaped device, the shaped device have mixed material entrance and the outlet of shaping pelletizing, the mixed material entrance It is connected with mixed material outlet；

Drying unit, the drying unit, which has shaping pelletizing entrance and dries pelletizing, to be exported, the shaping pelletizing entrance It is connected with the shaping pelletizing outlet；

Rotary hearth furnace, the rotary hearth furnace include：

Rotatable stove bottom；

Annular furnace, it is divided into cloth area, pre- successively by barricade along the furnace bottom rotation direction, in the belt burner hearth Hot-zone, mend wind anallobar, middle warm area, high-temperature region and discharge zone；

First flue, first flue are arranged in the preheating zone；

Second flue, second flue are arranged in the middle warm area；

Drawing mechanism, the drawing mechanism are arranged in the discharge zone；

Wind supercharging burner is mended, the benefit wind supercharging burner is arranged in the benefit wind anallobar；

Fuel burner nozzle, the fuel burner nozzle are arranged in the preheating zone, the middle warm area and the high-temperature region；

Dry pelletizing entrance, the dry pelletizing entrance is arranged in the cloth area, and the dry pelletizing entrance with The dry pelletizing outlet is connected；

Exhanst gas outlet containing arsenic trioxide, the exhanst gas outlet containing arsenic trioxide be arranged in the preheating zone and with it is described First flue is connected；

Leaded zinc exhanst gas outlet, the leaded zinc exhanst gas outlet be arranged in the middle warm area and with the second flue phase Even；

Hot product of roasting outlet, the hot product of roasting outlet are arranged in the discharge zone.

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention by using anaerobic acidleach side Method handles arsenic-containing smoke dust, arsenic oxide can be avoided to be dissolved in acid solution, and by other dissolving metals, on the one hand subtract in few leachate Arsenic content, be advantageous to subsequently extract high-value product from leachate, on the other hand can make more arsenic enter containing arsenic leach In slag, then gained leached mud containing arsenic is supplied into rotary hearth furnace, by controlling the temperature in each subregion of rotary hearth furnace, preheated Area reclaims flue gas containing arsenic trioxide, contain Pb-Zn dust in middle warm area and high-temperature region recovery, and copper reduction hot be calcined of entering is produced In thing, so as to realize the high efficiente callback of the valuable metals such as arsenic in arsenic-containing smoke dust, zinc, lead and copper, so as to realize arsenic-containing smoke dust Recycling.Thus, whole scheme solves that arsenic leaching rate in existing " wet method+pyrogenic process " technique is low, lead is in smelting system Constantly circulate and cause the problems such as smelting system closed cycle harm is big, copper recovery is low, be truly realized arsenic and valuable metal Efficiently separate.

In addition, the system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to the above embodiment of the present invention can also have such as Additional technical characteristic down：

In some embodiments of the invention, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： There is hot product of roasting entrance and water quenching material to export for granulating unit, granulating unit, the hot product of roasting entrance with it is described Hot product of roasting outlet is connected；Wet mill unit, the wet mill unit have water quenching material entrance and slurry outlet, the water quenching material Entrance is connected with water quenching material outlet；Concentration equipment, the concentration equipment have ore pulp entrance, metal iron powder outlet and magnetic separation Mine tailing exports, and the ore pulp entrance is connected with the slurry outlet；There is magnetic tailing to enter for gravity concentration apparatus, the gravity concentration apparatus Mouth, the outlet of slag containing arsenic and copper concentrate outlet, the magnetic tailing entrance are connected with magnetic tailing outlet.Thus, can be achieved The high efficiente callback of copper resource.

In some embodiments of the invention, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： There is leachate entrance, metal iron powder entrance, copper sponge outlet and copper displaced liquid to go out for copper displacement apparatus, the copper displacement apparatus Mouthful, the leachate entrance is connected with leachate outlet, and the metal iron powder entrance is connected with metal iron powder outlet； Arsenic removing apparatus, the arsenic removing apparatus have copper displaced liquid entrance, oxidant inlet, ferric sulfate entrance, the outlet of iron arsenic slag and removed Liquid exports after arsenic, and the copper displaced liquid entrance is connected with copper displaced liquid outlet；Deironing apparatus, the deironing apparatus tool Liquid exports after having liquid entrance after arsenic removal, ammonium sulfate entrance, iron vitriol slag outlet and iron removaling, liquid entrance and the arsenic removal after the arsenic removal Liquid outlet afterwards is connected；Concentration and crystallization device, the concentration and crystallization device have liquid entrance, the outlet of thick zinc sulfate and mother liquor after iron removaling Export, liquid entrance is connected with liquid outlet after the iron removaling after the iron removaling, and the mother liquor outlet is connected with the acid solution entrance.By This, can be achieved the high efficiente callback of the valuable metal such as copper, iron, zinc in leachate.

In some embodiments of the invention, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： Bag collection device, flue gas goes out after the bag collection device has leaded zinc smoke inlet, leaded zinc dust outlet and dedusting Mouthful, the leaded zinc smoke inlet is connected with the leaded zinc exhanst gas outlet；Acidleach device, the acidleach device have leaded zinc Liquid exports after dust inlet, sulfuric acid entrance, lead sulfate outlet and acidleach, the leaded zinc dust inlet and the leaded zinc powder dirt Outlet is connected, and liquid is exported and is connected with liquid entrance after the iron removaling after the acidleach.Thus, the high efficiente callback of lead can be achieved.

In some embodiments of the invention, the cloth area, the preheating zone, the benefit wind anallobar, the medium temperature Area, the high-temperature region and the discharge zone are respectively 15~22 relative to the angle of the central angle corresponding to the belt burner hearth center of circle Spend, 80~140 degree, 0.5~10 degree, 40~80 degree, 100~160 degree and 15~30 degree.Thus, it is possible to realize copper, arsenic and lead zinc Effective recovery.

In another aspect of the invention, the present invention proposes a kind of using above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust System implement wet method pyrogenic process Combined Treatment arsenic-containing smoke dust method, according to an embodiment of the invention, this method includes：

(1) arsenic-containing smoke dust and acid solution are supplied into the oxygen-free acid bath unit, acid is carried out under conditions of starvation Leaching reaction, to obtain leached mud containing arsenic and leachate；

(2) leached mud containing arsenic, additive, reducing agent, ferrous material and binding agent are supplied to the mixing device Middle carry out mixed processing, to obtain mixed material；

(3) mixed material is supplied and forming processes is carried out into the shaped device, to obtain being molded pelletizing；

(4) the shaping pelletizing is supplied into the drying unit and processing is dried, to obtain drying pelletizing；

(5) the dry pelletizing is supplied to the cloth area of the rotary hearth furnace, and with the furnace bottom rotation according to It is secondary to pass through the preheating zone, benefit wind anallobar, the middle warm area, the high-temperature region and the discharge zone, to be contained Arsenic trioxide flue gas, leaded zinc flue gas and hot product of roasting.

The method of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention by using anaerobic acidleach side Method handles arsenic-containing smoke dust, arsenic oxide can be avoided to be dissolved in acid solution, and by other dissolving metals, on the one hand subtract in few leachate Arsenic content, be advantageous to subsequently extract high-value product from leachate, on the other hand can make more arsenic enter containing arsenic leach In slag, then gained leached mud containing arsenic is supplied into rotary hearth furnace, by controlling the temperature in each subregion of rotary hearth furnace, preheated Area reclaims flue gas containing arsenic trioxide, contain Pb-Zn dust in middle warm area and high-temperature region recovery, and copper reduction hot be calcined of entering is produced In thing, so as to realize the high efficiente callback of the valuable metals such as arsenic in arsenic-containing smoke dust, zinc, lead and copper, so as to realize arsenic-containing smoke dust Recycling.Thus, whole scheme solves that arsenic leaching rate in existing " wet method+pyrogenic process " technique is low, lead is in smelting system Constantly circulate and cause the problems such as smelting system closed cycle harm is big, copper recovery is low, be truly realized arsenic and valuable metal Efficiently separate.

In addition, the method for wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to the above embodiment of the present invention can also have such as Additional technical characteristic down：

In some embodiments of the invention, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： (6) the hot product of roasting is supplied and Water Quenching is carried out into the granulating unit, to obtain water quenching material；(7) by institute State water quenching material and supply and wet ground is carried out into the wet mill unit, to obtain ore pulp；(8) ore pulp is supplied to described Magnetic separation processing is carried out in concentration equipment, to obtain metal iron powder and magnetic tailing；(9) magnetic tailing is supplied to described Re-selection process is carried out in gravity concentration apparatus, to obtain slag containing arsenic and copper concentrate.Thus, the high efficiente callback of copper resource can be achieved.

In some embodiments of the invention, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： (10) leachate and the metal iron powder are supplied into the copper displacement apparatus and copper displacement reaction occurs, to obtain sea Continuous copper and copper displaced liquid；(11) the copper displaced liquid, oxidant and sulfuric acid iron supply are carried out into the arsenic removing apparatus Arsenic removal is reacted, to obtain liquid after iron arsenic slag and arsenic removal；(12) liquid after the arsenic removal and ammonium sulfate are supplied to the iron removaling and filled Middle progress iron removaling reaction is put, to obtain liquid after iron vitriol slag and iron removaling；(13) liquid after the iron removaling is supplied to the concentration and tied Condensing crystallizing is carried out in brilliant device, to obtain thick zinc sulfate and mother liquor, and the mother liquor is back to the nothing of step (1) Used in oxygen acidleach device as acid solution.Thus, the high efficiente callback of the valuable metal such as copper, iron, zinc in leachate can be achieved.

In some embodiments of the invention, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust further comprises： (14) the leaded zinc flue gas is supplied and carries out processing of gathering dust into the bag collection device, so as to obtain leaded zinc powder dirt and Flue gas after dedusting；(15) the leaded zinc powder dirt and sulfuric acid are supplied into the acidleach device and carries out acidleach processing, so as to Liquid after to lead sulfate and acidleach, and liquid after the acidleach supplied into the concentration and crystallization device in step (13) carry out it is dense Contracting crystallization treatment.Thus, the high efficiente callback of lead can be achieved.

In some embodiments of the invention, in step (2), the leached mud containing arsenic and the additive, it is described also The mixing quality ratio of former agent, the ferrous material and the binding agent is 100：(5-20)：(10-50)：(10-30)：(0.5- 10).Thus, be advantageous to improve the grade and arsenic, lead, the rate of recovery of zinc of gained copper concentrate.

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 wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to an embodiment of the invention；

Fig. 2 is the rotary hearth furnace top view of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to an embodiment of the invention；

Fig. 3 is illustrated according to the system architecture of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of further embodiment of the present invention Figure；

Fig. 4 is illustrated according to the system architecture of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of another embodiment of the invention Figure；

Fig. 5 is illustrated according to the system architecture of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of another embodiment of the invention Figure；

Fig. 6 is the method flow schematic diagram of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to an embodiment of the invention；

Fig. 7 is illustrated according to the method flow of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of further embodiment of the present invention Figure；

Fig. 8 is illustrated according to the method flow of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of another embodiment of the invention Figure；

Fig. 9 is illustrated according to the method flow of the wet method pyrogenic process Combined Treatment arsenic-containing smoke dust of another embodiment of the invention Figure.

Embodiment

Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.

In the description of the invention, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ", " thickness ", " on ", " under ", "front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom ", " interior ", " outer ", " up time The orientation or position relationship of the instruction such as pin ", " counterclockwise ", " axial direction ", " radial direction ", " circumference " be based on orientation shown in the drawings or Position relationship, it is for only for ease of and describes the present invention and simplify description, rather than indicates or imply that signified device or element must There must be specific orientation, with specific azimuth configuration and operation, therefore be not considered as limiting the invention.

In addition, term " first ", " second " are only used for describing purpose, and it is not intended that instruction or hint relative importance Or the implicit quantity for indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can be expressed or Implicitly include at least one this feature.In the description of the invention, " multiple " are meant that at least two, such as two, three It is individual etc., unless otherwise specifically defined.

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 electrically connect；Can be joined directly together, can also be indirectly connected by intermediary, can be in two elements The connection in portion or the interaction relationship of two elements, limited unless otherwise clear and definite.For one 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 terms of one of the present invention, the present invention proposes a kind of system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust, According to an embodiment of the invention, include with reference to figure 1, the system：Oxygen-free acid bath unit 100, mixing device 200, shaped device 300th, drying unit 400 and rotary hearth furnace 500.

According to an embodiment of the invention, oxygen-free acid bath unit 100 has arsenic-containing smoke dust entrance 101, acid solution entrance 102, contained Arsenic leached mud outlet 103 and leachate outlet 104, and suitable for arsenic-containing smoke dust and acid solution to be carried out to acid under conditions of starvation Leaching reaction, to obtain leached mud containing arsenic and leachate.In this programme, anaerobic acid leaching process can in advance by arsenic-containing smoke dust compared with Diffluent part valuable metal is dissolved into acid solution, subsequently using wet processing extract, and less soluble part allow its after It is continuous to stay in leached mud containing arsenic, subsequently extracted using thermal process.The process integration of wet method+pyrogenic process is used in the application, with reference to The advantages of the advantages of wet method low energy consumption and pyrogenic process reaction rate are fast, the rate of recovery is high, effectively overcomes that wet-leaching rate is low to be lacked Point so that the leaching rate of wet processing obtains fast lifting, and the cycle of whole technique greatly shortens.Specifically, in anaerobic Under the conditions of using dilute sulfuric acid make solvent dissolving arsenic-containing smoke dust, starvation can reduce arsenic and be dissolved into solution during leaching, It is allowed to more enter in leached mud containing arsenic, the arsenic leached on a small quantity in leachate is with Soluble Arsenic hydrochlorate such as natrium arsenicum, arsenic The forms such as sour potassium are present, and most zinc, copper etc. are dissolved in acid solution in arsenic-containing smoke dust.After the completion of Leach reaction, using press filtration Machine carries out separation of solid and liquid, obtains leached mud containing arsenic and leachate.Because the occurrence status of each valuable metal in arsenic-containing smoke dust are more multiple Miscellaneous, same metal has preservation in more diffluent compound, also has preservation in less soluble compound, and compared with indissoluble solution Part have a strong impact on the overall recovery of the metal.In the prior art it is general using strengthen acid, heating, the harsh conditions such as pressurize come The leaching rate of the less soluble metal in the part is improved, foreign ion arsenic, lead etc. can also can be dissolved simultaneously more under these conditions It is more, bring serious puzzlement for the removal of impurities of subsequent technique product.And inventor is had been surprisingly found that by many experiments, by using this hair Bright above-mentioned anaerobic acid leaching process can effectively avoid above mentioned problem so that and arsenic, lead etc. are more entered in leached mud containing arsenic, and Other valuable metals are dissolved into leachate, thus, significantly improve the economy of this technique.

According to one embodiment of present invention, arsenic content is not less than 3wt% in arsenic-containing smoke dust, and copper content is not less than 3wt%, And copper more than 50% dissolves in dilute sulfuric acid, the total content of lead and zinc is not less than 2wt%.Specifically, the cigarette containing arsenic used in this technique Dirt is the smelting smoke dust of the industries such as lead, copper and zinc.This technique is mainly for high-arsenic dust, to reduce arsenic in the products such as lead, zinc Enrichment, if valuable metal recovery value it is not high, the economy of the technique can be influenceed.Thus, using the cigarette containing arsenic of the present invention Dirt is advantageous to improve the economy of technique.

According to still a further embodiment, acid solution and the liquid-solid ratio of arsenic-containing smoke dust can be (2-4)：1.Invention human hair It is existing, if acid solution and the liquid-solid ratio of arsenic-containing smoke dust are high, extraction time can be shortened, but obtain in leachate, the valuable ion such as copper and zinc Concentration cross dilution, subsequent extracted difficulty is big；And if liquid-solid ratio is low, required extraction time length, but leachate is few, and concentration is high, just Concentrate and purify in follow-up leachate.

According to still another embodiment of the invention, the temperature of anaerobic leaching can be 15-50 degrees Celsius, and the time can be 20-60min.Inventor has found that, if the temperature of anaerobic leaching is high, Leach reaction is fast, and required time is short, and treating capacity is high, but energy consumption Height, arsenic impurities are soluble to enter solution；And if the temperature of anaerobic leaching is low, required extraction time is grown, and treating capacity is low.If leach Between it is too short, reaction it is incomplete, copper, zinc are less into solution；If extraction time is long, process cycle is grown, and treating capacity is low.

According to an embodiment of the invention, mixing device 200 has the entrance of leached mud containing arsenic 201, additive entrance 202, gone back Former agent entrance 203, ferrous material entrance 204, binding agent entrance 205 and mixed material outlet 206, the entrance of leached mud containing arsenic 201 It is connected with the outlet of leached mud containing arsenic 103, and carried out suitable for arsenic leached mud, additive, reducing agent, ferrous material and binding agent will be contained Mixed processing, to obtain mixed material.Thus, leached mud containing arsenic and additive, reducing agent, ferrous material and bonding are advantageous to Agent is well mixed, so as to realize follow-up rotary hearth furnace include arsenic leached mud roasting it is abundant.

According to one embodiment of present invention, leached mud containing arsenic and additive, reducing agent, ferrous material and binding agent is mixed It is 100 to close mass ratio：(5-20)：(10-30)：(10-50)：(0.5-10).Inventor has found, when reducing agent dosage is less, Lead, zinc and copper reduction are incomplete, residue in slag and are not recovered, and cause overall recovery to decline；And when reducing agent dosage is more, Reducing agent is caused to waste.It is weaker to the fixation of arsenic in middle warm area and high-temperature region additive when additive amount is less, arsenic It is volatile to enter in leaded zinc flue gas, influence the quality of lead zinc dusting product；When additive amount is more, quantity of slag increase, energy Consumption increase, and cause the waste of additive.When ferrous material is less, mixed material reduction temperature is low, influences lead, zinc, copper etc. The overall recovery of valuable metal；When ferrous material is excessive, copper powder copper grade is influenceed.When consumption of binder is less, ball Group's intensity difference, easy fragmentation, influences the reduction effect of pelletizing, finally influences the overall recovery of the valuable metals such as copper, lead, zinc；When viscous When knot agent dosage is more, the waste of binding agent is caused, increases process costs.

According to still a further embodiment, additive can be lime stone, marble, dolomite, calcite, aragonite At least one of with chalk, wherein, preferably calcite and dolomite.Inventor has found that such additive is when temperature is relatively low (less than 700 degrees Celsius) are that preheating zone is not reacted with arsenic substantially, do not interfere with the volatilization of arsenic oxide, and it is when temperature is higher (reaching 1000 degrees Celsius) i.e. middle warm area and high-temperature region, decomposable asymmetric choice net go out calcium oxide, and copper, lead, zinc etc. can be promoted to be reduced to simple substance, by This, be advantageous to subsequent copper, lead and zinc is separately recovered utilization.

According to still another embodiment of the invention, reducing agent can be bituminous coal, coking coal, graphite, coal slime, anthracite, semi-coke, At least one of coke and lignite.Specifically, reducing agent is mainly carbonaceous material, the work of reduction valuable metal is primarily served With preferably content of ashes is less than 25wt%.Thus, can be abundant by the lead in arsenic-containing smoke dust, zinc and copper reduction, improve respective time Yield.

According to still another embodiment of the invention, ferrous material can be bloodstone, limonite, magnetic iron ore, pyrite, water chestnut At least one of iron ore, iron scale, ilmenite, vanadium titano-magnetite, copper smelting slag, sulfate slag and nickel fibers slag.Inventor It was found that supplying ferrous material can improve the sintering temperature of mixed material, so as to improve the volatility of lead, and chalybeate is mixed into The metal iron powder that material is handled through sequential reduction, fine grinding and magnetic separation obtain can be as the reducing agent of copper replacement process, so as to drop The economy of whole system is improved while low-reductant cost.

According to still another embodiment of the invention, the granularity of ferrous material can account for more than 50% more than 0.15mm.Hair A person of good sense has found, the supplying of coarse grain ferrous material, is on the one hand advantageous to mixed material shaping, on the other hand, is advantageous to improve mixing Material sintering temperature, and improve the volatility of lead.

According to still another embodiment of the invention, binding agent can be organic liquid binding agent, starch, sodium humate, carboxylic At least one of sodium carboxymethylcellulose pyce, pitch, pectin, bentonite, clay, kaolin and red mud.Thus, it is possible to ensure gained Shaping pelletizing has higher intensity, so as to suitable for the reduction roasting in rotary hearth furnace.

According to an embodiment of the invention, shaped device 300 has mixed material entrance 301 and shaping pelletizing outlet 302, mixes Material inlet 301 is closed with mixed material outlet 206 to be connected, and suitable for mixed material is carried out into forming processes, to be molded Pelletizing.Thus, it can further increase the contact area of each composition in mixed material, arsenic leaching is included so as to improve follow-up rotary hearth furnace The reaction rate of slag and reducing agent, ferrous material and additive, save rotary hearth furnace energy consumption.It should be noted that art technology Personnel can select according to the particle size and shape being actually needed to being molded pelletizing, such as can be molded pelletizing and can be Flat, pillow shape or spherical.

According to an embodiment of the invention, drying unit 400, which has shaping pelletizing entrance 401 and dries pelletizing, exports 402, into Type pelletizing entrance 401 is connected with shaping pelletizing outlet 302, and suitable for shaping pelletizing is dried into processing, to obtain drying Pelletizing.Specifically, the moisture content for drying pelletizing is less than 0.5wt%, by the way that shaping pelletizing is dried, pelletizing can be avoided in rotary hearth furnace Burst in roasting process, ensure roasting effect.

According to an embodiment of the invention, include with reference to figure 1 and Fig. 2, rotary hearth furnace 500：Rotatable stove bottom 51, annular furnace 52nd, barricade 53, the first flue 54, the second flue 55, drawing mechanism 56, benefit wind supercharging burner 57, burning burner 58, dry pelletizing Entrance 501, exhanst gas outlet containing arsenic trioxide 502, leaded zinc exhanst gas outlet 503 and hot product of roasting outlet 504.

According to one embodiment of present invention, along the rotation direction of furnace bottom 51, divided successively by barricade 53 in the burner hearth 52 that goes in ring Be divided into cloth area 510, preheating zone 520, mend wind anallobar 530, middle warm area 540, high-temperature region 550 and discharge zone 560, thus with The drying pelletizing that the rotation of ring-shaped furnace bottom to step into cloth area is successively by preheating zone, benefit wind anallobar, middle warm area, high-temperature region And discharge zone；And in rotary hearth furnace, using barricade by belt burner hearth be divided into successively cloth area, preheating zone, mend wind anallobar, Middle warm area, high-temperature region and discharge zone, the temperature in each region on the one hand can be kept, on the one hand can avoid the dust in cloth area and go out Expect that the flue dust in area enters roasting region, while the flue gas containing arsenic trioxide of preheating zone and the leaded zinc flue gas of middle warm area can be ensured Not mutual crossfire, so as to ensure both qualities.

According to still a further embodiment, the first flue 54 is arranged in preheating zone 520.Specifically, in preheating zone, Dry the part arsenic trioxide in pelletizing and be volatized into flue gas, while part arsenic and five oxidations two have been acted in reducing agent Arsenic, it is reduced into arsenic trioxide and is volatized into flue gas, rotary hearth furnace, the clearance of arsenic trioxide is pulled out out by the first flue Not less than 90%, the remaining arsenic for being difficult to reduction abjection and lead, zinc mend wind anallobar as pelletizing enters in this region；And the One flue can be arranged in the side wall of preheating zone.

According to still another embodiment of the invention, the second flue 55 is arranged in middle warm area 540.Specifically, middle warm area with In high-temperature region, with the rise of temperature, additive starts to react with the arsenic that residue is difficult to remove, and generation chemical property is stable Ca₃(AsO₄)₂, when temperature, which further raises, reaches 1100 degrees Celsius, FeAsO₄The poor arsenate of equistability also can be with The higher Ca of additive reaction generation stability₃(AsO₄)₂, residue in slag, realize the harmless treatment to arsenical, Simultaneously in the presence of additive, lead, zinc compound in pelletizing are reduced, and are formed lead zinc volatile matter and are entered in flue gas, by the Two flues are pulled out out rotary hearth furnace, realize and are efficiently separated with other materials in pelletizing, and copper is with sulfate, oxidation in flue dust The diversified forms such as thing, arsenate, sulfide, metal are present, various forms of in roasting (when temperature reaches 1000 degrees Celsius) Copper can be reduced into copper simple substance in the effect of additive and reducing agent；And the second flue can be arranged in the side wall of middle warm area On.

According to still another embodiment of the invention, drawing mechanism 56 is arranged in discharge zone 560, so as to be advantageous to obtain Hot product of roasting smoothly discharges rotary hearth furnace.

According to still another embodiment of the invention, mend wind supercharging burner 57 and be arranged in benefit wind anallobar 530.Specifically, mend Wind anallobar each blows back the flue gas containing arsenic trioxide of preheating zone and the leaded zinc flue gas in high temperature area, separates, keeps away Exempt from flue gas mutually to pollute, while it is oxidizing atmosphere to mend wind anallobar, the arsenic that residue is difficult to reduction abjection is aoxidized, again solid It is scheduled in pelletizing.

According to still another embodiment of the invention, fuel burner nozzle 58 is arranged in preheating zone 520, middle warm area 540 and high-temperature region 550, so as to spray into air and fuel gas into burner hearth simultaneously by fuel burner nozzle, burning produces flame, so as to heat roasting Burn material.

According to still another embodiment of the invention, dry pelletizing entrance 501 and be arranged in cloth area 510, and dry pelletizing Entrance 501 is connected with drying pelletizing outlet 402, and suitable for the drying pelletizing that drying device obtains is supplied to rotary hearth furnace cloth Area.

According to still another embodiment of the invention, exhanst gas outlet containing arsenic trioxide 502 is arranged in preheating zone 520 and with One flue 54 is connected, and suitable for the flue gas containing arsenic trioxide collected through the first flue is discharged into rotary hearth furnace.

According to still another embodiment of the invention, leaded zinc exhanst gas outlet 503 be arranged in middle warm area 540 and with the second flue 55 are connected, and suitable for the leaded zinc flue gas collected through the second flue is discharged into rotary hearth furnace.

According to still another embodiment of the invention, hot product of roasting outlet 504 is arranged in discharge zone 560, and suitable for inciting somebody to action Obtained hot product of roasting discharge rotary hearth furnace.

According to still another embodiment of the invention, cloth area fabric thickness is 10-50mm.Inventor has found, if bed of material mistake Thickness, the heat transfer between the bed of material can be influenceed so that bottom pelletizing slow temperature of being heated is low, causes pellet roasting incomplete, influences to roast Burn effect.

According to still another embodiment of the invention, cloth area, preheating zone, benefit wind anallobar, middle warm area, high-temperature region and discharging Area relative to the angle of the central angle corresponding to the belt burner hearth center of circle is respectively 15~22 degree, 80~140 degree, 0.5~10 degree, 40 ~80 degree, 100~160 degree and 15~30 degree.Inventor has found that if cloth area angle too small, locus is narrow, is unfavorable for putting Put distributing device and carry out uniform distribution；Space waste is caused if cloth area angle is excessive.If preheating zone angle too small, material stop Time is short, and arsenic volatilization is incomplete, and the arsenic rate of recovery is low；If preheating zone angle is excessive, arsenic has volatilized completely, causes what is spatially and thermally measured Waste.If mending wind anallobar angle too small, the operation for separating the gas for mending wind anallobar both sides is difficult to control；If mend wind supercharging Area's angle is excessive, causes the waste spatially and thermally measured.Middle warm area is mainly used in the gold such as roasting reduction lead, zinc, copper with high-temperature region Category, if high-temperature region angle too small, material reduction is incomplete, and the metal recovery rate such as copper-lead zinc is low；If high-temperature region angle is excessive Cause space waste.If middle warm area angle too small, the material heating-up time is too short, and heating rate is limited, can not be connected high-temperature region Domain, cause high-temperature area temperature low, material reduction is insufficient.The size of discharge zone angle determines whether discharging facilitates, if discharging Area's angle crosses the waste that conference causes spatially and thermally to measure.

According to still another embodiment of the invention, the temperature of preheating zone can be 350~700 degrees Celsius, the temperature of middle warm area Degree can be 700~1200 degrees Celsius, and the temperature of high-temperature region can be 1200-1350 degrees Celsius.Inventor has found, if preheating zone Temperature it is too high, then lead zinc easily forms volatile matter and enters smoke pollution arsenic trioxide dust；If the temperature of preheating zone is too low Arsenic volatilization is incomplete, and the rate of recovery is low.If the temperature of middle warm area and high-temperature region is too low, material reduction is incomplete, copper-lead zinc-iron The rate of recovery is low；If the temperature of middle warm area and high-temperature region is too high, pellets are serious, corrode furnace bottom, and can cause energy dissipation.

According to still another embodiment of the invention, the air pressure of preheating zone is -5~50Pa, and the air pressure for mending wind anallobar is 200-2000Pa, the air pressure of middle warm area is -5~50Pa.Inventor has found that the air pressure ratio of preheating zone and middle warm area mends wind anallobar It is low, flue gas can be facilitated to exclude rotary hearth furnace, avoid excessive, run helter-skelter to other regions.And if the air pressure for mending wind anallobar is too low, by nothing Method completely cuts off the flue gas of preheating zone and middle warm area so that the flue gas in two regions mutually pollutes, and influences the quality of respective dust；If mend The air pressure of wind anallobar is too high, easily blows pelletizing, rolls into furnace bottom water sealed tank.

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention by using anaerobic acidleach side Method handles arsenic-containing smoke dust, arsenic oxide can be avoided to be dissolved in acid solution, and by other dissolving metals, on the one hand subtract in few leachate Arsenic content, be advantageous to subsequently extract high-value product from leachate, on the other hand can make more arsenic enter containing arsenic leach In slag, then gained leached mud containing arsenic is supplied into rotary hearth furnace, by controlling the temperature in each subregion of rotary hearth furnace, preheated Area reclaims flue gas containing arsenic trioxide, contain Pb-Zn dust in middle warm area and high-temperature region recovery, and copper reduction hot be calcined of entering is produced In thing, so as to realize the high efficiente callback of the valuable metals such as arsenic in arsenic-containing smoke dust, zinc, lead and copper, so as to realize arsenic-containing smoke dust Recycling..Thus, whole scheme solves that arsenic leaching rate in existing " wet method+pyrogenic process " technique is low, lead is in smelting system Constantly circulate and cause the problems such as smelting system closed cycle harm is big, copper recovery is low, be truly realized arsenic and valuable metal Efficiently separate.

According to an embodiment of the invention, further wrapped with reference to figure 3, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：Granulating unit 600, wet mill unit 700, concentration equipment 800 and gravity concentration apparatus 900.

According to an embodiment of the invention, granulating unit 600 expects outlet after having hot product of roasting entrance 601 and water quenching 602, hot product of roasting entrance 601 is connected with hot product of roasting outlet 504, and suitable for hot product of roasting is carried out into water quenching Processing, to expect after obtaining water quenching.Inventor has found, by the way that the hot product of roasting of high temperature is directly carried out into water quenching, may be such that Hot product of roasting internal stress drastically raises, and so as to reach the effect of broken hot product of roasting, reduces the energy consumption of follow-up ore grinding, The temperature expected simultaneously after water quenching after water quenching is decreased obviously, and is advantageous to protect subsequent handling equipment.

According to an embodiment of the invention, ore grinding device 700 expects entrance 701 and slurry outlet 702 after having water quenching, after water quenching Material entrance 701 is connected with material outlet 602 after water quenching, and suitable for material after water quenching is carried out into wet ground, to obtain ore pulp.

According to one embodiment of present invention, the concentration of ore pulp is 67-85wt%.Inventor has found that ore pulp is in this concentration In the range of be advantageous to improve grinding efficiency, if the excessive concentration of ore pulp, be unfavorable for ore pulp discharging.

According to still a further embodiment, the granularity of particle is the accounting more than 85% less than 0.037mm in ore pulp. Thus, it is advantageously implemented and selects metal iron powder subsequently through magnetic separation process.

According to an embodiment of the invention, concentration equipment 800 has ore pulp entrance 801, metal iron powder outlet 802 and magnetic separation tail Ore deposit outlet 803, ore pulp entrance 801 is connected with slurry outlet 702, and suitable for ore pulp is carried out into magnetic separation processing, to obtain metal Iron powder and magnetic tailing.It should be noted that the related process parameters of magnetic separation are not particularly limited, those skilled in the art It can be selected according to needs of production.Ore pulp can obtain the metal iron powder that grade is more than 90% after magnetic separation, drying.

According to an embodiment of the invention, gravity concentration apparatus 900 has magnetic tailing entrance 901, the outlet of slag containing arsenic 902 and copper essence Ore deposit outlet 903, magnetic tailing entrance 901 are connected with magnetic tailing outlet 803, and suitable for magnetic tailing is carried out into re-selection process, To obtain slag containing arsenic and copper concentrate.Inventor has found, though copper in flue dust with sulfate, oxide, arsenate, sulfide, The diversified forms such as metal are present, but in roasting, various forms of copper can be reduced into the effect of additive and reducing agent Copper simple substance, and because copper simple substance proportion is larger, can be efficiently separated by gravity treatment with other impurities, copper grade is obtained more than 85% Copper concentrate.It should be noted that the uninterrupted that current are rinsed during gravity treatment has no particular limits with pulp density, this area Technical staff can be adjusted according to practical condition and processing requirement.

According to one embodiment of present invention, gravity concentration apparatus can be shaking table, chute, spiral concentrator or centrifugal separation Machine.Thus, be advantageous to improve the reselection efficiency of gravity concentrate.

According to an embodiment of the invention, further wrapped with reference to figure 4, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：Copper displacement apparatus 1000, arsenic removing apparatus 1100, deironing apparatus 1200 and concentration and crystallization device 1300.

According to an embodiment of the invention, copper displacement apparatus 1000 have leachate entrance 1001, metal iron powder entrance 1002, Copper sponge outlet 1003 and copper displaced liquid outlet 1004, leachate entrance 1001 are connected with leachate outlet 104, metal iron powder Entrance 1002 is connected with metal iron powder outlet 802, and suitable for leachate and metal iron powder into copper displacement reaction occur, to obtain Copper sponge and copper displaced liquid.Inventor find, metal iron powder exist grain graininess it is tiny (be less than 0.037mm accountings 65% with On), the features such as grain shape is irregular, specific surface area is big and reactivity is high, can use it for participating in copper displacement reaction, will soak The copper gone out in liquid cements out, and has the advantages that reaction rate is fast.Specifically, conditions of replacement reaction is preferably to add sulfuric acid adjustment The amount that copper displacement carries out preferably, adding metal iron powder under conditions of pH is 2-4 can be theoretical amount needed for displacement reaction More than 1.1 times.It should be noted that those skilled in the art can be according to the content feelings of copper ion in actual conditions, leachate Condition and processing requirement are adjusted to displacement conditional parameter.And solid-liquid point is carried out using filter press after the completion of copper displacement reaction From, obtain cupric more than 90% copper sponge and copper displaced liquid.

According to one embodiment of present invention, the temperature of copper displacement can be 50-70 degrees Celsius, and the time can be 30- 60min.Inventor has found that the temperature of copper displacement is high, and displacement reaction is fast, but iron loss is big；Temperature is low, then reaction is slow, required leaching Go out time length, replacement result is poor.If extraction time is too short, react not completely, copper sponge ferrous contaminants are high, poor quality；If leaching Go out overlong time, then process cycle is grown, and treating capacity is low.

According to an embodiment of the invention, arsenic removing apparatus 1100 have copper displaced liquid entrance 1101, oxidant inlet 1102, Liquid outlet 1105 after ferric sulfate entrance 1103, iron arsenic slag outlet 1104 and arsenic removal, after copper displaced liquid entrance 1101 is replaced with copper Liquid outlet 1004 be connected, and suitable for by copper displaced liquid, oxidant and ferric sulfate carry out arsenic removal reaction, so as to obtain iron arsenic slag and Liquid after arsenic removal.Inventor's discovery, can be by the low price arsenic in copper displaced liquid and Asia by adding oxidant into copper displaced liquid Ferrous ions oxidation is into high price, and under the conditions of suitable pH, i.e. when pH is 2-4, high price iron can form precipitated ferric arsenate with high price arsenic Separate out, obtained after separation of solid and liquid containing liquid after the lower arsenic removal of arsenic.Hereby it is achieved that the arsenic removal to copper displaced liquid.Key reaction It is as follows：Fe³⁺+AsO₄ ^3-=FeAsO₄↓.It should be noted that can be according to arsenic ion in solution and iron ion during arsenic removal Content, add ferric sulfate, with ensure iron in solution/arsenic mol ratio be more than 1.2.

According to one embodiment of present invention, oxidant is mainly that oxygen coordinates manganese dioxide, ozone or H₂O₂.Thus, may be used Significantly improve the effect of removing arsenic of copper displaced liquid.

According to still a further embodiment, the temperature of arsenic removal processing can be 70-90 degrees Celsius.Inventor's discovery, The temperature of arsenic removal processing is high, and arsenic removal reaction is fast, but energy consumption is big；And temperature is low, then reaction is slow, and effect of removing arsenic is poor.

According to an embodiment of the invention, deironing apparatus 1200 has liquid entrance 1201, ammonium sulfate entrance 1202, iron after arsenic removal Liquid outlet 1204 behind alum slag outlet 1203 and iron removaling, liquid entrance 1201 is connected with liquid outlet 1105 after arsenic removal after arsenic removal, and is suitable to Liquid after arsenic removal and ammonium sulfate are subjected to iron removaling reaction, to obtain liquid after iron vitriol slag and iron removaling.Inventor has found, to reduce solution Influence of the middle iron ion to subsequent sulphuric acid zinc product, when the circulative accumulation content of iron in liquid after arsenic removal is more than 8g/L, it is necessary to right Liquid carries out iron removaling processing after arsenic removal.Specifically, ammonium sulfate can be added into liquid after arsenic removal carries out iron removaling, it is left for 2 in the pH of iron removaling When right, temperature is in the solution of 90 degrees centigrades, ferric ion after arsenic removal in liquid can with ammonium ion and sulfate radical from Son reaction, generation are easy to the ammonium jarosite crystalline particle of precipitation filtering, while produce sulfuric acid, obtained after separation of solid and liquid iron vitriol slag and Liquid after iron removaling.Thus, by carrying out iron removaling to liquid after arsenic removal from ammonium sulfate, you can realize that iron removaling again will not be to subsequent sulphuric acid zinc Product brings impurity into.

According to an embodiment of the invention, concentration and crystallization device 1300 has liquid entrance 1301, the outlet of thick zinc sulfate after iron removaling 1302 and mother liquor outlet 1303, liquid entrance 1301 is connected with liquid outlet 1204 after iron removaling after iron removaling, mother liquor outlet 1303 and acid solution Entrance 102 is connected, and suitable for liquid after iron removaling is carried out into condensing crystallizing, to obtain thick zinc sulfate and mother liquor, and mother liquor is returned Used into oxygen-free acid bath unit as acid solution.Inventor has found that Zn content is very high in liquid after iron removaling, is concentrated by heating evaporation It is more than 1.5g/cm to gravity³When to be put into cooling in crystallizing pond crystallizable, it is filtered to can obtain thick zinc sulfate crystal and mother Liquid.10-30g/L containing zinc in mother liquor, while contain substantial amounts of sulfuric acid in mother liquor, mother liquor can be returned and make acid in oxygen-free acid bath unit Liquid uses, and makes full use of the sulfuric acid in mother liquor, and reclaims remnants zinc.

According to an embodiment of the invention, further wrapped with reference to figure 5, the system of above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：Bag collection device 1400 and acidleach device 1500.

According to an embodiment of the invention, bag collection device 1400 has leaded zinc smoke inlet 1401, leaded zinc powder dirt Exhanst gas outlet 1403 behind outlet 1402 and dedusting, leaded zinc smoke inlet 1401 is connected with leaded zinc exhanst gas outlet 503, and is suitable to Leaded zinc flue gas is subjected to processing of gathering dust, to obtain flue gas after leaded zinc powder dirt and dedusting.Specifically, the master of leaded zinc powder dirt The oxide or sulfate that composition is lead are wanted, is secondly the oxide or sulfate of zinc, product purity is higher, remaining impurity content Less than 2wt%.Hereby it is achieved that the high efficiente callback of lead, zinc.

According to an embodiment of the invention, acidleach device 1500 has leaded zinc dust inlet 1501, sulfuric acid entrance 1502, sulphur Liquid outlet 1504 behind lead plumbate outlet 1503 and acidleach, leaded zinc dust inlet 1501 is connected with leaded zinc dust outlet 1402, acid Liquid outlet 1504 is connected with liquid entrance 1301 after iron removaling after leaching, and suitable for sulfuric acid and leaded zinc powder dirt are carried out into acidleach processing, with Just liquid after lead sulfate and acidleach is obtained.Inventor has found that acidleach makees solvent using sulfuric acid, and zinc can be enriched in the form of zinc sulfate In solution, lead can be enriched in precipitation in the form of lead sulfate, and (zinc sulfate is molten for liquid after can respectively obtaining acidleach after separation of solid and liquid Liquid) and lead sulfate.Wherein, PbSO in lead sulfate product₄Content is more than 93%, and because leaded zinc powder dirt degree of purity is higher, institute So that using after vitriol lixiviation, the operation leaching rate of zinc may be up to more than 99%, and Zn content is more than 60g/L in liquid after acidleach.

According to one embodiment of present invention, the liquid-solid ratio of sulfuric acid and leaded zinc powder dirt is not particularly restricted, this area Technical staff can be selected according to being actually needed, according to the specific embodiment of the present invention, sulfuric acid and lead zinc powder dirt Liquid-solid ratio can be (1.5-5)：1.Inventor has found that the liquid-solid ratio of sulfuric acid and leaded zinc powder dirt is high, leaches soon, but gained sulphur Sour zinc solution is diluter, is unfavorable for subsequent concentration crystallization；And required extraction time is longer if liquid-solid ratio is low.

According to still a further embodiment, the temperature of acidleach processing can be 10-35 degrees Celsius, and the time can be 20-60min.Inventor has found that the temperature of acidleach processing is high, then reaction is fast, and it is short but rotten to equipment to leach the required time Erosion is big；Temperature is low then to leach slow, length the time required to leaching.Extraction time is too short then to be leached not exclusively, influences the rate of recovery and sulfuric acid Lead product quality；Overlong time, then leach and completed, influence treating capacity.

According to an embodiment of the invention, the system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust proposed by the present invention at least has What follows one of advantage：

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention, handle and contain by using rotary hearth furnace Arsenic flue dust, lead product can be directly obtained, influence the treating capacity of smelting system without leached mud is returned into smelting system；

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention, overcomes old " wet method+pyrogenic process " Arsenic leaching rate is low in process integration, the shortcomings that need to constantly being circulated in smelting system, and be truly realized arsenic and valuable metal has Effect separation, and open circuit harmless treatment has been carried out to arsenic；

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention, using anaerobic diluted acid leaching method, Avoid arsenic oxide from dissolving in the solution, on the one hand reduce the arsenic content in leachate, be advantageous to leachate extraction high value Product, more arsenic is entered in leached mud containing arsenic, be advantageous to reclaim arsenic product by rotary hearth furnace process；

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention, by by wet method and thermal process Ingenious combination, obtain a variety of high-value products, and during acidleach after liquid can return to utilization, improve the profit of liquid after acidleach With value；

The system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention, because of the resultant metal obtained by pyrogenic process Iron powder, granularity is tiny, irregular, reactivity is strong, can be directly as the replenishers that copper is replaced in wet processing, and effect is good It is good, i.e., make reactant by using technique self-production material, reduce the cost of whole technique.

In another aspect of the invention, the present invention proposes a kind of using above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust System implement wet method pyrogenic process Combined Treatment arsenic-containing smoke dust method, according to an embodiment of the invention, with reference to figure 6, this method bag Include：

S100：Arsenic-containing smoke dust and acid solution are supplied into oxygen-free acid bath unit, acidleach is carried out under conditions of starvation Reaction

In the step, arsenic-containing smoke dust and acid solution are supplied into oxygen-free acid bath unit, carried out under conditions of starvation Acid-leaching reaction, to obtain leached mud containing arsenic and leachate.In this programme, anaerobic acid leaching process can be in advance by arsenic-containing smoke dust More diffluent part valuable metal is dissolved into leachate, is subsequently extracted using wet processing, and less soluble part allows It continues to stay in leached mud containing arsenic, is subsequently extracted using thermal process.The process integration of wet method+pyrogenic process is used in the application, The advantages of the advantages of combining wet method low energy consumption and pyrogenic process reaction rate are fast, the rate of recovery is high, it is low effectively to overcome wet-leaching rate The shortcomings that so that the leaching rate of wet processing obtains fast lifting, and the cycle of whole technique greatly shortens.Specifically, in nothing Solvent dissolving arsenic-containing smoke dust is made using dilute sulfuric acid under conditions of oxygen, starvation can reduce arsenic and be dissolved into solution during leaching In, be allowed to more enter in leached mud containing arsenic, the arsenic leached on a small quantity in leachate with Soluble Arsenic hydrochlorate such as natrium arsenicum, The forms such as Macquer's salt are present, and most zinc-copper etc. is dissolved in acid solution in arsenic-containing smoke dust.After the completion of Leach reaction, using press filtration Machine carries out separation of solid and liquid, obtains leached mud containing arsenic and leachate.Because the occurrence status of each valuable metal in arsenic-containing smoke dust are more multiple Miscellaneous, same metal has preservation in more diffluent compound, also has preservation in less soluble compound, and compared with indissoluble solution Part have a strong impact on the overall recovery of the metal.In the prior art it is general using strengthen acid, heating, the harsh conditions such as pressurize come The leaching rate of the less soluble metal in the part is improved, foreign ion arsenic, lead etc. can also can be dissolved simultaneously more under these conditions It is more, bring serious puzzlement for the removal of impurities of subsequent technique product.And inventor is had been surprisingly found that by many experiments, by using this hair Bright above-mentioned anaerobic acid leaching process can effectively avoid above mentioned problem so that and arsenic, lead etc. are more entered in leached mud containing arsenic, and Other valuable metals are dissolved into leachate, thus, significantly improve the economy of this technique.

According to one embodiment of present invention, arsenic content is not less than 3wt% in arsenic-containing smoke dust, and copper content is not less than 3wt%, And copper more than 50% dissolves in dilute sulfuric acid, the total content of lead and zinc is not less than 2wt%.Specifically, the cigarette containing arsenic used in this technique Dirt is the smelting smoke dust of the industries such as lead, copper and zinc.This technique is mainly for high-arsenic dust, to reduce arsenic in the products such as lead, zinc Enrichment, if valuable metal recovery value it is not high, the economy of the technique can be influenceed.Thus, using the cigarette containing arsenic of the present invention Dirt is advantageous to improve the economy of technique.

According to still a further embodiment, acid solution and the liquid-solid ratio of arsenic-containing smoke dust can be (2-4)：1.Invention human hair It is existing, if acid solution and the liquid-solid ratio of arsenic-containing smoke dust are high, extraction time can be shortened, but obtain in leachate, the valuable ion such as copper and zinc Concentration cross dilution, subsequent extracted difficulty is big；And if liquid-solid ratio is low, required extraction time length, but leachate is few, and concentration is high, just Concentrate and purify in follow-up leachate.

According to still another embodiment of the invention, the temperature of anaerobic leaching can be 15-50 degrees Celsius, and the time can be 20-60min.Inventor has found that, if the temperature of anaerobic leaching is high, Leach reaction is fast, and required time is short, and treating capacity is high, but energy consumption Height, arsenic impurities are soluble to enter solution；And if the temperature of anaerobic leaching is low, required extraction time is grown, and treating capacity is low.If leach Between it is too short, reaction it is incomplete, copper, zinc are less into solution；If extraction time is long, process cycle is grown, and treating capacity is low.

S200：Arsenic leached mud, additive, reducing agent, ferrous material and binding agent will be contained supply into mixing device and carry out Mixed processing

In the step, arsenic leached mud, additive, reducing agent, ferrous material and binding agent will be contained and supplied into mixing device Mixed processing is carried out, to obtain mixed material.Thus, be advantageous to leached mud containing arsenic and additive, reducing agent, ferrous material and Binding agent is well mixed, so as to realize follow-up rotary hearth furnace include arsenic leached mud roasting it is abundant.

According to one embodiment of present invention, leached mud containing arsenic and additive, reducing agent, ferrous material and binding agent is mixed It is 100 to close mass ratio：(5-20)：(10-30)：(10-50)：(0.5-10).Inventor has found, when reducing agent dosage is less, Lead, zinc and copper reduction are incomplete, residue in slag and are not recovered, and cause overall recovery to decline；And when reducing agent dosage is more, Reducing agent is caused to waste.It is weaker to the fixation of arsenic in middle warm area and high-temperature region additive when additive amount is less, arsenic It is volatile to enter in leaded zinc flue gas, influence the quality of lead zinc dusting product；When additive amount is more, quantity of slag increase, energy Consumption increase, and cause the waste of additive.When ferrous material is less, mixed material reduction temperature is low, influences lead, zinc, copper etc. The overall recovery of valuable metal；When ferrous material is excessive, copper powder copper grade is influenceed.When consumption of binder is less, ball Group's intensity difference, easy fragmentation, influences the reduction effect of pelletizing, finally influences the overall recovery of the valuable metals such as copper, lead, zinc；When viscous When knot agent dosage is more, the waste of binding agent is caused, increases process costs.

According to still a further embodiment, additive can be lime stone, marble, dolomite, calcite, aragonite At least one of with chalk, wherein, preferably calcite and dolomite.Inventor has found that such additive is when temperature is relatively low (less than 700 degrees Celsius) are that preheating zone is not reacted with arsenic substantially, do not interfere with the volatilization of arsenic oxide, and it is when temperature is higher (reaching 1000 degrees Celsius) i.e. middle warm area and high-temperature region, decomposable asymmetric choice net go out calcium oxide, and copper, lead, zinc etc. can be promoted to be reduced to simple substance, by This, be advantageous to subsequent copper, lead and zinc is separately recovered utilization.

According to still another embodiment of the invention, reducing agent can be bituminous coal, coking coal, graphite, coal slime, anthracite, semi-coke, At least one of coke and lignite.Specifically, reducing agent is mainly carbonaceous material, the work of reduction valuable metal is primarily served With preferably content of ashes is less than 25wt%.Thus, can be abundant by the lead in arsenic-containing smoke dust, zinc and copper reduction, improve respective time Yield.

According to still another embodiment of the invention, ferrous material can be bloodstone, limonite, magnetic iron ore, pyrite, water chestnut At least one of iron ore, iron scale, ilmenite, vanadium titano-magnetite, copper smelting slag, sulfate slag and nickel fibers slag.Inventor It was found that supplying ferrous material can improve the sintering temperature of mixed material, so as to improve the volatility of lead, and chalybeate is mixed into The metal iron powder that material is handled through sequential reduction, fine grinding and magnetic separation obtain can be as the reducing agent of copper replacement process, so as to drop The economy of whole system is improved while low-reductant cost.

According to still another embodiment of the invention, the granularity of ferrous material can account for more than 50% more than 0.15mm.Hair A person of good sense has found, the supplying of coarse grain ferrous material, is on the one hand advantageous to mixed material shaping, on the other hand, is advantageous to improve mixing Material sintering temperature, and improve the volatility of lead.

According to still another embodiment of the invention, binding agent can be organic liquid binding agent, starch, sodium humate, carboxylic At least one of sodium carboxymethylcellulose pyce, pitch, pectin, bentonite, clay, kaolin and red mud.Thus, it is possible to ensure gained Shaping pelletizing has higher intensity, so as to suitable for the reduction roasting in rotary hearth furnace.

S300：Mixed material is supplied into shaped device and carries out forming processes

In the step, mixed material is supplied into shaped device and carries out forming processes, to obtain being molded pelletizing.By This, can further increase the contact area of each composition in mixed material, and arsenic leached mud is included with going back so as to improve follow-up rotary hearth furnace The reaction rate of former agent, ferrous material and additive, save rotary hearth furnace energy consumption.It should be noted that those skilled in the art can To be selected according to the particle size and shape that are actually needed to being molded pelletizing, such as it can be flat that can be molded pelletizing Shape, pillow shape or spherical.

S400：Shaping pelletizing is supplied processing is dried into drying unit

In the step, shaping pelletizing is supplied processing is dried into drying unit, to obtain drying pelletizing.Specifically , the moisture content for drying pelletizing is less than 0.5wt%, by the way that shaping pelletizing is dried, can avoid pelletizing in rotary hearth furnace roasting process It is middle to burst, ensure roasting effect.

S500：Pelletizing will be dried to supply to the cloth area of rotary hearth furnace, and as the rotation of furnace bottom is successively by preheating zone, benefit Wind anallobar, middle warm area, high-temperature region and discharge zone

In the step, pelletizing will be dried and supplied to the cloth area of rotary hearth furnace, and as the rotation of furnace bottom is successively by preheating Area, wind anallobar, middle warm area, high-temperature region and discharge zone are mended, to obtain flue gas containing arsenic trioxide, leaded zinc flue gas and hot Product of roasting.Specifically, dry pelletizing enters rotary hearth furnace by cloth area, in preheating zone, the part three dried in pelletizing aoxidizes Two arsenic are volatized into flue gas, while have acted on part arsenic and diarsenic pentoxide in reducing agent, are reduced into arsenic trioxide simultaneously Flue gas is volatized into, rotary hearth furnace is pulled out out by the first flue, the clearance of arsenic trioxide is not less than 90%, in this region Residue is difficult to the arsenic of reduction abjection and lead, zinc mend wind anallobar as pelletizing enters, and mends wind anallobar and preheating zone is contained into three oxygen Change two arsenic flue gases and the leaded zinc flue gas in high temperature area is each blown back, separate, avoid flue gas from mutually polluting, while mend wind increasing Nip is oxidizing atmosphere, and the arsenic that residue is difficult to reduction abjection is aoxidized, and is retightened in pelletizing；In middle warm area and high temperature Qu Zhong, with the rise of temperature, additive starts to react with arsenic, the stable Ca of generation chemical property₃(AsO₄)₂, residue in In slag, the harmless treatment to arsenical is realized, while in the presence of additive, lead, zinc compound are reduced, and are formed Lead zinc volatile matter enters in flue gas, is pulled out out rotary hearth furnace by the second flue, realizes and effectively divide with other materials in pelletizing From；Copper exists with diversified forms such as sulfate, oxide, arsenate, sulfide, metals in flue dust, in roasting, multi-form Copper can be reduced into copper simple substance in the effect of additive and reducing agent.Thus, effectively dividing for copper, arsenic and lead zinc can be achieved From.

According to one embodiment of present invention, cloth area fabric thickness is 10-50mm.Inventor has found, if the bed of material is blocked up, The heat transfer between the bed of material can be influenceed so that bottom pelletizing slow temperature of being heated is low, causes pellet roasting incomplete, influences roasting effect Fruit.

According to still a further embodiment, the temperature of preheating zone can be 350~700 degrees Celsius, the temperature of middle warm area Degree can be 700~1200 degrees Celsius, and the temperature of high-temperature region can be 1200-1350 degrees Celsius.Inventor has found, if preheating zone Temperature it is too high, then lead zinc easily forms volatile matter and enters smoke pollution arsenic trioxide dust；If the temperature of preheating zone is too low Arsenic volatilization is incomplete, and the rate of recovery is low.If the temperature of middle warm area and high-temperature region is too low, material reduction is incomplete, copper-lead zinc-iron The rate of recovery is low；If the temperature of middle warm area and high-temperature region is too high, pellets are serious, corrode furnace bottom, and can cause energy dissipation.

According to still another embodiment of the invention, the air pressure of preheating zone is -5~50Pa, and the air pressure for mending wind anallobar is 200-2000Pa, the air pressure of middle warm area is -5~50Pa.Inventor has found that the air pressure ratio of preheating zone and middle warm area mends wind anallobar It is low, flue gas can be facilitated to exclude rotary hearth furnace, avoid excessive, run helter-skelter to other regions.And if the air pressure for mending wind anallobar is too low, by nothing Method completely cuts off the flue gas of preheating zone and middle warm area so that the flue gas in two regions mutually pollutes, and influences the quality of respective dust；If mend The air pressure of wind anallobar is too high, easily blows pelletizing, rolls into furnace bottom water sealed tank.

The method of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust according to embodiments of the present invention by using anaerobic acidleach side Method handles arsenic-containing smoke dust, arsenic oxide can be avoided to be dissolved in acid solution, and by other dissolving metals, on the one hand subtract in few leachate Arsenic content, be advantageous to subsequently extract high-value product from leachate, on the other hand can make more arsenic enter containing arsenic leach In slag, then gained leached mud containing arsenic is supplied into rotary hearth furnace, by controlling the temperature in each subregion of rotary hearth furnace, preheated Area reclaims flue gas containing arsenic trioxide, contain Pb-Zn dust in middle warm area and high-temperature region recovery, and copper reduction hot be calcined of entering is produced In thing, so as to realize the high efficiente callback of the valuable metals such as arsenic in arsenic-containing smoke dust, zinc, lead and copper, so as to realize arsenic-containing smoke dust Recycling..Thus, whole scheme solves that arsenic leaching rate in existing " wet method+pyrogenic process " technique is low, lead is in smelting system Constantly circulate and cause the problems such as smelting system closed cycle harm is big, copper recovery is low, be truly realized arsenic and valuable metal Efficiently separate.

According to an embodiment of the invention, further wrapped with reference to figure 7, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：

S600：Hot product of roasting is supplied into granulating unit and carries out Water Quenching

In the step, hot product of roasting is supplied into granulating unit and carries out Water Quenching, to obtain water quenching material.Hair A person of good sense has found, by the way that the hot product of roasting of high temperature is directly carried out into water quenching, may be such that hot product of roasting internal stress drastically rises Height, so as to reach the effect of broken hot product of roasting, the energy consumption of follow-up ore grinding is reduced, while the temperature expected after water quenching after water quenching Degree is decreased obviously, and is advantageous to protect subsequent handling equipment.

S700：Water quenching material is supplied into wet mill unit and carries out wet ground

In the step, water quenching material is supplied into wet mill unit and carries out wet ground, to obtain ore pulp.

According to one embodiment of present invention, the concentration of ore pulp is 67-85wt%.Inventor has found that ore pulp is in this concentration In the range of be advantageous to improve grinding efficiency, if the excessive concentration of ore pulp, be unfavorable for ore pulp discharging.

According to still a further embodiment, the granularity of particle is the accounting more than 85% less than 0.037mm in ore pulp. Thus, it is advantageously implemented and selects metal iron powder subsequently through magnetic separation process.

S800：Ore pulp is supplied into concentration equipment and carries out magnetic separation processing

In the step, ore pulp is supplied into concentration equipment and carries out magnetic separation processing, to obtain metal iron powder and magnetic separation tail Ore deposit.It should be noted that the related process parameters of magnetic separation are not particularly limited, those skilled in the art can be according to reality Production needs are selected.Ore pulp can obtain the metal iron powder that grade is more than 90% after magnetic separation, drying.

S900：Magnetic tailing is supplied into gravity concentration apparatus and carries out re-selection process

In the step, magnetic tailing is supplied into gravity concentration apparatus and carries out re-selection process, to obtain slag containing arsenic and copper essence Ore deposit.Inventor has found, though the copper in flue dust exists with diversified forms such as sulfate, oxide, arsenate, sulfide, metals, In roasting, various forms of copper can be reduced into copper simple substance in the effect of additive and reducing agent, and due to copper simple substance ratio Weight is larger, can be efficiently separated by gravity treatment with other impurities, obtains the copper concentrate that copper grade is more than 85%.Need what is illustrated It is that the uninterrupted that current are rinsed during gravity treatment has no particular limits with pulp density, and those skilled in the art can be according to reality The border condition of production and processing requirement are adjusted.

According to one embodiment of present invention, gravity concentration apparatus can be shaking table, chute, spiral concentrator or centrifugal separation Machine.Thus, be advantageous to improve the reselection efficiency of gravity concentrate.

According to an embodiment of the invention, further wrapped with reference to figure 8, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：

S1000：Leachate and metal iron powder are supplied into copper displacement apparatus copper displacement reaction occurs

In the step, leachate and metal iron powder are supplied into copper displacement apparatus copper displacement reaction occurs, to obtain Copper sponge and copper displaced liquid.Inventor find, metal iron powder exist grain graininess it is tiny (be less than 0.037mm accountings 65% with On), the features such as grain shape is irregular, specific surface area is big and reactivity is high, can use it for participating in copper displacement reaction, will soak The copper gone out in liquid cements out, and has the advantages that reaction rate is fast.Specifically, conditions of replacement reaction is preferably to add sulfuric acid adjustment The amount that copper displacement carries out preferably, adding metal iron powder under conditions of pH is 2-4 can be theoretical amount needed for displacement reaction More than 1.1 times.It should be noted that those skilled in the art can be according to the content feelings of copper ion in actual conditions, leachate Condition and processing requirement are adjusted to displacement conditional parameter.And solid-liquid point is carried out using filter press after the completion of copper displacement reaction From, obtain cupric more than 90% copper sponge and copper displaced liquid.

According to one embodiment of present invention, the temperature of copper displacement can be 50-70 degrees Celsius, and the time can be 30- 60min.Inventor has found that the temperature of copper displacement is high, and displacement reaction is fast, but iron loss is big；Temperature is low, then reaction is slow, required leaching Go out time length, replacement result is poor.If extraction time is too short, react not completely, copper sponge ferrous contaminants are high, poor quality；If leaching Go out overlong time, then process cycle is grown, and treating capacity is low.

S1100：Copper displaced liquid, oxidant and sulfuric acid iron supply are subjected to arsenic removal reaction into arsenic removing apparatus

In the step, copper displaced liquid, oxidant and sulfuric acid iron supply are subjected to arsenic removal reaction into arsenic removing apparatus, so as to Obtain liquid after iron arsenic slag and arsenic removal.Inventor's discovery, can be by copper displaced liquid by adding oxidant into copper displaced liquid Low price arsenic and ferrous ions into high price, under the conditions of suitable pH, i.e. when pH be 2-4, high price iron and high price arsenic can shapes Separate out into precipitated ferric arsenate, obtained after separation of solid and liquid containing liquid after the lower arsenic removal of arsenic.Hereby it is achieved that copper displaced liquid is removed Arsenic.Key reaction is as follows：Fe³⁺+AsO₄ ^3-=FeAsO₄↓.It should be noted that can be according to arsenic in solution during arsenic removal The content of ion and iron ion, adds ferric sulfate, to ensure that iron in solution/arsenic mol ratio is more than 1.2.

According to one embodiment of present invention, oxidant is mainly that oxygen coordinates manganese dioxide, ozone or H₂O₂.Thus, may be used Significantly improve the effect of removing arsenic of copper displaced liquid.

According to still a further embodiment, the temperature of arsenic removal processing can be 70-90 degrees Celsius.Inventor's discovery, The temperature of arsenic removal processing is high, and arsenic removal reaction is fast, but energy consumption is big；And temperature is low, then reaction is slow, and effect of removing arsenic is poor.

S1200：Liquid after arsenic removal and ammonium sulfate are supplied into deironing apparatus and carry out iron removaling reaction

In the step, liquid after arsenic removal and ammonium sulfate are supplied into deironing apparatus and carry out iron removaling reaction, to obtain siderotil Liquid after slag and iron removaling.Inventor has found, to reduce influence of the iron ion to subsequent sulphuric acid zinc product in solution, after arsenic removal in liquid , it is necessary to carry out iron removaling processing to liquid after arsenic removal when the circulative accumulation content of iron is more than 8g/L.Specifically, it can add into liquid after arsenic removal Enter ammonium sulfate and carry out iron removaling, when in the solution that the pH of iron removaling is 2 or so, temperature is 90 degrees centigrades, after arsenic removal in liquid Ferric ion can react with ammonium ion and sulfate ion, and generation is easy to the ammonium jarosite crystalline particle of precipitation filtering, together When produce sulfuric acid, liquid after iron vitriol slag and iron removaling is obtained after separation of solid and liquid.Thus, by being removed from ammonium sulfate to liquid after arsenic removal Iron, you can realize that iron removaling will not bring impurity into subsequent sulphuric acid zinc product again.

S1300：Liquid after iron removaling is supplied into concentration and crystallization device and carries out condensing crystallizing

In the step, liquid after iron removaling is supplied into concentration and crystallization device and carries out condensing crystallizing, to obtain thick zinc sulfate And mother liquor, and mother liquor is back in S100 oxygen-free acid bath unit and used as acid solution.Inventor has found, zinc in liquid after iron removaling Content is very high, and being concentrated into gravity by heating evaporation is more than 1.5g/cm³When to be put into cooling in crystallizing pond crystallizable, pass through Filter can obtain thick zinc sulfate crystal and mother liquor.10-30g/L containing zinc in mother liquor, while contain substantial amounts of sulfuric acid in mother liquor, can be by mother Liquid, which is returned in oxygen-free acid bath unit, makees acid solution use, makes full use of the sulfuric acid in mother liquor, and reclaim remnants zinc.

According to an embodiment of the invention, further wrapped with reference to figure 9, the method for above-mentioned wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Include：

S1400：Leaded zinc flue gas is supplied processing of gathering dust is carried out into bag collection device

In the step, leaded zinc flue gas is supplied processing of gathering dust is carried out into bag collection device, to obtain leaded zinc Flue gas after dust and dedusting.Specifically, the main component of leaded zinc powder dirt is the oxide or sulfate of lead, secondly it is the oxygen of zinc Compound or sulfate, product purity is higher, and remaining impurity content is less than 2wt%.Hereby it is achieved that the high efficiente callback of lead, zinc.

S1500：Leaded zinc powder dirt and sulfuric acid are supplied into acidleach device and carry out acidleach processing

In the step, leaded zinc powder dirt and sulfuric acid are supplied into acidleach device and carry out acidleach processing, to obtain sulfuric acid Liquid after lead and acidleach, and liquid after acidleach is supplied in the concentration and crystallization device into S1300 and carries out condensing crystallizing processing.Inventor It was found that acidleach makees solvent using sulfuric acid, zinc can be enriched in solution in the form of zinc sulfate, and lead can be enriched with the form of lead sulfate Liquid (solution of zinc sulfate) and lead sulfate after acidleach can be respectively obtained in precipitation, after separation of solid and liquid.Wherein, in lead sulfate product PbSO₄Content is more than 93%, and because leaded zinc powder dirt degree of purity is higher, so after using vitriol lixiviation, the operation of zinc is leached Rate may be up to more than 99%, and Zn content is more than 60g/L in liquid after acidleach.

According to one embodiment of present invention, the liquid-solid ratio of sulfuric acid and leaded zinc powder dirt is not particularly restricted, this area Technical staff can be selected according to being actually needed, according to the specific embodiment of the present invention, sulfuric acid and lead zinc powder dirt Liquid-solid ratio can be (1.5-5)：1.Inventor has found that the liquid-solid ratio of sulfuric acid and leaded zinc powder dirt is high, leaches soon, but gained sulphur Sour zinc solution is diluter, is unfavorable for subsequent concentration crystallization；And required extraction time is longer if liquid-solid ratio is low.

According to still a further embodiment, the temperature of acidleach processing can be 10-35 degrees Celsius, and the time can be 20-60min.Inventor has found that the temperature of acidleach processing is high, then reaction is fast, and it is short but rotten to equipment to leach the required time Erosion is big；Temperature is low then to leach slow, length the time required to leaching.Extraction time is too short then to be leached not exclusively, influences the rate of recovery and sulfuric acid Lead product quality；Overlong time, then leach and completed, influence treating capacity.

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

Certain flue dust (cupric 3.67wt%, leaded 5.41wt%, 9.98wt% containing zinc, containing arsenic 4.13wt%) slurrying is soaked Go out, leaching condition is：Dilute sulfuric acid anaerobic leaching, liquid-solid ratio 2：1.Extraction temperature is 30-35 degrees Celsius, leaches 30min.Solid-liquid Arsenic leached mud (cupric 2.14wt%, leaded 9.01wt%, 2.5wt% containing zinc, containing arsenic 4.82wt%) and leachate must be contained by separating (cupric 11.93g/L, leaded 0.01g/L, 42.4g/L containing zinc, containing arsenic 6.19g/L).

After the drying of leached mud containing arsenic, 8% dolomite, 30% limonite (granularity 1mm or so), 25% are incorporated by weight proportion Anthracite (containing fixed carbon 74%) and a small amount of binding agent.Pelletizing is prepared after mixing, pelletizing is dried to moisture content and is less than 0.5wt%. It is sent into rotary hearth furnace and is calcined afterwards.Rotary hearth furnace roasting system is as shown in table 1.

Arsenic trioxide 90.79wt% arsenic trioxide dust must be contained by being collected from the first flue of rotary hearth furnace, from turning bottom The flue of stove second collects to obtain leaded zinc powder dirt, leaded 50.79wt%, 17.76wt% containing zinc.Leaded zinc powder dirt presses liquid using sulfuric acid Admittedly than 3：1 is leached, and is obtained containing liquid and the leaded lead sulfate solid more than 66wt% after acidleach of the zinc more than 80g/L.

The hot product of roasting discharge laggard water-filling of rotary hearth furnace is quenched and wet grinding.Pulp density is 75wt% during ore grinding, is obtained To the ore pulp that granularity is below 0.037mm accountings more than 85%, ore pulp uses the magnetic separation under 80A/m magnetic field intensity, obtains magnetic Concentrate selection and magnetic tailing, after the filtering of magnetic separation magnetic concentrate, drying, finally give the metal iron powder that iron content is more than 93wt%.Magnetic Select mine tailing to carry out gravity treatment using shaking table, obtain gravity concentrate and gravity tailings slag containing arsenic, gravity concentrate is filtered, after drying, most Cupric 85.11wt% copper concentrate is obtained eventually.

Metal iron powder displacement copper is added in leachate, it is 2 or so to control pH, replaces 30min under 70 degrees Celsius, is contained Copper 91.01wt% copper sponge, cupric 0.9g/L, iron content 18.49g/L, 6.43g/L containing arsenic, containing zinc in copper displaced liquid 41.12g/L.Copper displaced liquid is 2 or so in pH, and oxidant hydrogen peroxide is added under conditions of the degrees centigrade of temperature 80 and is coordinated It is passed through oxygen, the arsenic ion in cement copper displaced liquid, separation of solid and liquid obtains liquid after iron arsenic slag and arsenic removal, contains arsenic after arsenic removal in liquid 0.05g/L, iron content 8.46g/L, 40.05g/L containing zinc.Liquid is 2 or so in pH after arsenic removal, under conditions of the degrees centigrade of temperature 90 Ammonium sulfate is added, precipitates the iron ion in liquid after arsenic removal, separation of solid and liquid obtains liquid after iron vitriol slag and iron removaling, contains zinc in liquid after iron removaling 41.77g/L iron content 0.06g/L.Finally liquid heating evaporation after liquid after iron removaling and acidleach is concentrated, gravity is concentrated into and is more than 1.5g/cm³, it is put into crystallisation by cooling in crystallizing pond, crystallization and filtration obtains thick zinc sulfate crystal and mother liquor, 15- containing zinc in mother liquor 20g/L, mother liquor is returned into arsenic-containing smoke dust anaerobic acid leaching process and recycled.

In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification Close and combine.

Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changed, replacing and modification.

Claims (10)

1. A kind of 1. system of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust, it is characterised in that including：

   Oxygen-free acid bath unit, the oxygen-free acid bath unit have arsenic-containing smoke dust entrance, acid solution entrance, the outlet of leached mud containing arsenic and leaching Eluate outlet；

   There is the entrance of leached mud containing arsenic, additive entrance, reducing agent entrance, ferrous material to enter for mixing device, the mixing device Mouth, binding agent entrance and mixed material outlet, the entrance of leached mud containing arsenic are connected with the leached mud containing arsenic outlet；

   Shaped device, the shaped device have mixed material entrance and the outlet of shaping pelletizing, the mixed material entrance and institute Mixed material outlet is stated to be connected；

   Drying unit, the drying unit, which has shaping pelletizing entrance and dries pelletizing, to be exported, the shaping pelletizing entrance and institute The outlet of shaping pelletizing is stated to be connected；

   Rotary hearth furnace, the rotary hearth furnace include：

   Rotatable stove bottom；

   Annular furnace, along the furnace bottom rotation direction, it is divided into cloth area, preheating in the belt burner hearth successively by barricade Area, mend wind anallobar, middle warm area, high-temperature region and discharge zone；

   First flue, first flue are arranged in the preheating zone；

   Second flue, second flue are arranged in the middle warm area；

   Drawing mechanism, the drawing mechanism are arranged in the discharge zone；

   Wind supercharging burner is mended, the benefit wind supercharging burner is arranged in the benefit wind anallobar；

   Fuel burner nozzle, the fuel burner nozzle are arranged in the preheating zone, the middle warm area and the high-temperature region；

   Dry pelletizing entrance, the dry pelletizing entrance is arranged in the cloth area, and the dry pelletizing entrance with it is described Pelletizing outlet is dried to be connected；

   Exhanst gas outlet containing arsenic trioxide, the exhanst gas outlet containing arsenic trioxide are arranged in the preheating zone and with described first Flue is connected；

   Leaded zinc exhanst gas outlet, the leaded zinc exhanst gas outlet are arranged in the middle warm area and are connected with second flue；

   Hot product of roasting outlet, the hot product of roasting outlet are arranged in the discharge zone.
2. 2. system according to claim 1, it is characterised in that further comprise：

   There is hot product of roasting entrance and water quenching material to export for granulating unit, granulating unit, the hot product of roasting entrance with The hot product of roasting outlet is connected；

   Wet mill unit, the wet mill unit have water quenching material entrance and slurry outlet, the water quenching material entrance and the water quenching material Outlet is connected；

   Concentration equipment, the concentration equipment have ore pulp entrance, metal iron powder outlet and magnetic tailing outlet, the ore pulp entrance It is connected with the slurry outlet；

   Gravity concentration apparatus, the gravity concentration apparatus have magnetic tailing entrance, the outlet of slag containing arsenic and copper concentrate outlet, the magnetic tailing Entrance is connected with magnetic tailing outlet.
3. 3. system according to claim 2, it is characterised in that further comprise：

   Copper displacement apparatus, after the copper displacement apparatus has leachate entrance, metal iron powder entrance, copper sponge outlet and copper displacement Liquid exports, and the leachate entrance is connected with leachate outlet, and the metal iron powder entrance exports with the metal iron powder It is connected；

   Arsenic removing apparatus, the arsenic removing apparatus have copper displaced liquid entrance, oxidant inlet, ferric sulfate entrance, the outlet of iron arsenic slag Exported with liquid after arsenic removal, the copper displaced liquid entrance is connected with copper displaced liquid outlet；

   Deironing apparatus, liquid goes out after the deironing apparatus has liquid entrance after arsenic removal, ammonium sulfate entrance, iron vitriol slag outlet and iron removaling Mouthful, liquid entrance is connected with liquid outlet after the arsenic removal after the arsenic removal；

   Concentration and crystallization device, the concentration and crystallization device has liquid entrance, the outlet of thick zinc sulfate and mother liquor outlet after iron removaling, described Liquid entrance is connected with liquid outlet after the iron removaling after iron removaling, and the mother liquor outlet is connected with the acid solution entrance.
4. 4. system according to claim 3, it is characterised in that further comprise：

   Bag collection device, the bag collection device have cigarette after leaded zinc smoke inlet, leaded zinc dust outlet and dedusting Gas exports, and the leaded zinc smoke inlet is connected with the leaded zinc exhanst gas outlet；

   Acidleach device, the acidleach device have leaded zinc dust inlet, sulfuric acid entrance, lead sulfate outlet and acidleach after liquid go out Mouthful, the leaded zinc dust inlet is connected with the leaded zinc dust outlet, liquid outlet and liquid after the iron removaling after the acidleach Entrance is connected.
5. 5. system according to claim 1, it is characterised in that the cloth area, the preheating zone, the benefit wind supercharging Area, the middle warm area, the high-temperature region and the discharge zone are divided relative to the angle of the central angle corresponding to the belt burner hearth center of circle Wei not be 15~22 degree, 80~140 degree, 0.5~10 degree, 40~80 degree, 100~160 degree and 15~30 degree.
6. 6. a kind of system using any one of claim 1-5 implements the side of wet method pyrogenic process Combined Treatment arsenic-containing smoke dust Method, it is characterised in that including：

   (1) arsenic-containing smoke dust and acid solution are supplied into the oxygen-free acid bath unit, it is anti-that acidleach is carried out under conditions of starvation Should, to obtain leached mud containing arsenic and leachate；

   (2) leached mud containing arsenic, additive, reducing agent, ferrous material and binding agent are supplied into the mixing device Row mixed processing, to obtain mixed material；

   (3) mixed material is supplied and forming processes is carried out into the shaped device, to obtain being molded pelletizing；

   (4) the shaping pelletizing is supplied into the drying unit and processing is dried, to obtain drying pelletizing；

   (5) the dry pelletizing is supplied to the cloth area of the rotary hearth furnace, and passed through successively with the rotation of the furnace bottom The preheating zone, benefit wind anallobar, the middle warm area, the high-temperature region and the discharge zone are crossed, to obtain containing three oxygen Change two arsenic flue gases, leaded zinc flue gas and hot product of roasting.
7. 7. according to the method for claim 6, it is characterised in that further comprise：

   (6) the hot product of roasting is supplied and Water Quenching is carried out into the granulating unit, to obtain water quenching material；

   (7) the water quenching material is supplied and wet ground is carried out into the wet mill unit, to obtain ore pulp；

   (8) ore pulp is supplied into the concentration equipment and carries out magnetic separation processing, to obtain metal iron powder and magnetic tailing；

   (9) magnetic tailing is supplied and re-selection process is carried out into the gravity concentration apparatus, to obtain slag containing arsenic and copper concentrate.
8. 8. according to the method for claim 7, it is characterised in that further comprise：

   (10) leachate and the metal iron powder are supplied into the copper displacement apparatus and copper displacement reaction occurs, so as to To copper sponge and copper displaced liquid；

   (11) the copper displaced liquid, oxidant and sulfuric acid iron supply are subjected to arsenic removal reaction into the arsenic removing apparatus, so as to Obtain liquid after iron arsenic slag and arsenic removal；

   (12) liquid after the arsenic removal and ammonium sulfate are supplied into the deironing apparatus and carries out iron removaling reaction, to obtain iron vitriol slag With liquid after iron removaling；

   (13) liquid after the iron removaling is supplied and condensing crystallizing is carried out into the concentration and crystallization device, so as to obtain thick zinc sulfate and Mother liquor, and the mother liquor is back in the oxygen-free acid bath unit of step (1) and used as acid solution.
9. 9. according to the method for claim 8, it is characterised in that further comprise：

   (14) the leaded zinc flue gas is supplied and carries out processing of gathering dust into the bag collection device, to obtain leaded zinc powder Flue gas after dirt and dedusting；

   (15) the leaded zinc powder dirt and sulfuric acid are supplied into the acidleach device and carries out acidleach processing, to obtain lead sulfate With liquid after acidleach, and by liquid after the acidleach supply into the concentration and crystallization device in step (13) carry out condensing crystallizing at Reason.
10. 10. according to the method for claim 6, it is characterised in that in step (2), the leached mud containing arsenic adds with described The mixing quality ratio for adding agent, the reducing agent, the ferrous material and the binding agent is 100：(5-20)：(10-50)：(10- 30)：(0.5-10).