CN106834690B - A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves - Google Patents

A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves Download PDF

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CN106834690B
CN106834690B CN201611240137.XA CN201611240137A CN106834690B CN 106834690 B CN106834690 B CN 106834690B CN 201611240137 A CN201611240137 A CN 201611240137A CN 106834690 B CN106834690 B CN 106834690B
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lead
melting
stage
ausmelt
slag
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CN106834690A (en
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马雁鸿
陈鹏
朱海成
孟庆宇
刘启忠
罗恒
石磊
张志国
夏忠和
徐学鸥
刘黎波
罗志丹
邓伟
梁艳辉
伍贺东
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Hulun Buir Chi Hong Mining Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

A kind of method for handling valuable metal by Ausmelt stoves the invention discloses oxygen leaching slag, it is characterised in that it includes the following steps：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melting.The present invention is using oxygen leaching slag as a kind of raw material, proportionally dispensing is put into pyrometallurgical smelting is carried out in Ausmelt stoves with lead fume dirt and lead concentrate, while output lead bullion, recycle valuable element in oxygen leaching slag, wherein S elements enter acid making system relieving haperacidity, Ag enter lead bullion after be electrolysed after enter lead anode slurry in, more than 98% Fe enters grey slag, the Fe in oxygen leaching slag is efficiently separated and is recycled with Ag.This technique not only can normally produce output lead bullion, while recycle valuable metal Fe and Ag etc., three-waste free discharge in whole production process in oxygen leaching slag, prevent the generation of production environment accident.

Description

A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves
Technical field：
The present invention relates to a kind of oxygen leaching Slag treatment method, more particularly to a kind of oxygen leaching slag to pass through Ausmelt stoves The method for handling valuable metal.
Background technology：
With the expansion of zinc metallurgy production scale of enterprise, the volume of cargo in storage of oxygen leaching slag is also more and more, according to statistics, state at present About 800~9,000,000 t of oxygen leaching slag of interior major smeltery's stockpiling, the processing to oxygen leaching slag are extremely urgent.
The oxygen leaching residues processing technique obtained at present in zinc hydrometallurgy mainly has two kinds：One kind is pyrogenic attack technique, That is rotary kiln evaporation method (also known as waelz process), which is that (dry zinc leaching residue is contained H2O：12%~18%) it is equipped with 45% ~55% coke powder adds rotary kiln, and slag reduction volatilization is realized under 1100~1300 DEG C of high temperature, is then recycled with ZnO powder, together When in flue dust the valuable metal such as recyclable Pb, Cd, In, Ge, Ga.Another kind is wet processing process, i.e. hot acid lixiviation process；And According to the difference of hot acid leachate method for removing iron, and there are jarosite process, goethite process and hematite process etc..But above-mentioned oxygen Treatment technology of leached residue is pressed there are larger defect, specifically, rotary kiln evaporation method：Fe and Ag cannot be efficiently separated in slag And recycling, technological process is longer, and maintenance of equipment amount is big, and investment is high, and working environment is poor, and high energy consumption is, it is necessary to a large amount of coal-fired or smeltings It is golden burnt, and ZnO powder enters leaching stream Cheng Qian and need to consider to deviate from fluorine chlorine；Hot acid lixiviation process：There is plurality of heavy metal after processing in slag Ion, easily causes environmental pollution and metal waste.This two kinds of techniques can not achieve oxygen leaching metal in the dreg comprehensive utilization and Recycling, and waste residue, exhaust gas are produced in production process, environmental pollution is not only caused, and cause a large amount of valuable metals to be lost in.
The content of the invention：
It is valuable by the processing of Ausmelt stoves it is an object of the invention to provide a kind of oxygen leaching slag to solve the above problems The method of metal.
The purpose of the present invention is implemented by following technical solution, and a kind of oxygen leaching slag handles valuable gold by Ausmelt stoves The method of category, it is characterised in that it includes the following steps：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melt Refining, specifically：
Step (1) Ausmelt stove meltings, including such as the next stage：1) the oxidizing semlting stage；2) reduction melting I-stage；3) also The former melting II stages, wherein：
1) the oxidizing semlting stage：Oxygen leaching slag, lead concentrate and lead fume dirt are subjected to batch mixing, obtain leaded more than 25wt% Lead-containing material, then will be continuously added to Ausmelt stoves after 25~30t/h of lead-containing material and lime stone, quartz sand mixing granulation It is interior, 1050~1350Nm of oxygen is sprayed into the Ausmelt stoves3/ h, 11000~15000Nm of air3/ h, fine coal 0.9~ 1.45t/h, keeps oxygen-rich concentration：29~31v%, controls 1050~1150 DEG C of bath temperature, oxidizing semlting is carried out, when entering stove thing When doses reaches specified inventory and 35~42wt% of lead-in-dreg, 1) the oxidizing semlting stage completes；
2) reduction melting I-stage：The lead essence is added in the Ausmelt stoves for completing 1) the oxidizing semlting stage Ore deposit and lump coal, wherein, the input amount of the lead concentrate for 1) the oxidizing semlting stage enter lead-containing material amount described in stove 3~ 10wt%, the input amount of the lump coal enter 0.5~1wt% of lead-containing material amount described in stove, institute for 1) the oxidizing semlting stage The input amount for stating lead concentrate and the lump coal is adjusted according to the actual lead-in-dreg amount for entering 2) the reduction melting I-stage； 15000~19500Nm of air is sprayed into the Ausmelt stoves3/ h, 1.5~2.2t/h of fine coal, control bath temperature 1130~ 1230 DEG C, reduction melting is carried out, as 13~18wt% of lead-in-dreg, 2) the reduction melting I-stage is completed；The reduction phase with Based on the reduction of concentrate of lead sulfide ore cross reaction, supplemented by carbon reduction.
3) the reduction melting II stages：Described piece is added in the Ausmelt stoves for completing 2) the reduction melting I-stage Coal, the addition of the lump coal enter lead-containing material amount described in stove and 2) the reduction melting I ranks for 1) the oxidizing semlting stage Section enters 0.3~0.8wt% of lead concentrate amount summation described in stove, and 7000~15000Nm of air is sprayed into the Ausmelt stoves3/ H, 1.4~2.25t/h of fine coal, controls 1150~1250 DEG C of bath temperature, continues reduction melting, work as lead-in-dreg<5wt% When, 3) the reduction melting II stages complete, and obtain lead bullion and grey slag；
Step (2) refining of lead bullion：The lead bullion interval that the step (1) Ausmelt stoves melting is produced is discharged into Lead pan inside holding is kept the temperature, the lead copper matte on the insulation lead pan surface is salvaged, is sold outside lead copper matte, lead liquid manufacture cathode sheets and anode Plate, then loads electrolytic cell and is electrolysed, finally obtain the lead electrode of qualification, ingot casting is carried out after lead electrode is put into lead pan fusing Output lead pig, silver are all introduced into lead anode slurry；Lead fume dirt returns to Ausmelt stoves as one of Ausmelt stove melting raw materials and returns Receive lead；
Step (3) grey slag melting, sinks lead heel row by the grey slag that the step (1) Ausmelt stoves melting produces Enter blast furnace fuming, 8800~14500Nm of air is blown into the grey slag by nozzle30.3~1.35t/ of/h and fine coal H, 1000~1500Nm of air is blown into the fuming furnace by fuming furnace top tertiary air orifice3/ h, controls molten bath temperature 1150~1250 DEG C of degree, flue dust through waste heat recovery, gather dust, emptied after desulfurization, gather dust for zinc abstraction；Finally obtain scum.
Further, the addition of the lime stone and the quartz sand according to enter in stove material Fe contents, CaO content And SiO2Content calculation and obtain；M [Fe] in slag in control fusion process:m(SiO2)=1.20~1.22, CaO=5~6wt%.
Further, the lump coal：20~35mm of granularity, fixed carbon >=65wt%, ash content≤20wt%, sulfur-bearing≤ 1wt%.
Further, the fine coal：Fixed carbon >=60wt%, ash content≤20wt%, the mesh of granularity -160 ＞ 80%, moisture≤ 1wt%.
Advantages of the present invention：The present invention be using oxygen leaching slag as a kind of raw material, with lead fume dirt and lead concentrate according to than Example dispensing is put into pyrometallurgical smelting is carried out in Ausmelt stoves, while output lead bullion, recycles valuable element in oxygen leaching slag, Wherein S elements enter acid making system relieving haperacidity, Ag enters after lead bullion be electrolysed after enter in lead anode slurry, more than 98% Fe into Enter grey slag, the Fe in oxygen leaching slag is efficiently separated and is recycled with Ag.It is thick that this technique not only can normally produce output Lead, while valuable metal Fe and Ag etc. in oxygen leaching slag are recycled, three-waste free discharge in whole production process, prevents production environment Accident occurs.
Brief description of the drawings：
Fig. 1 is the process flow chart of the present invention.
Embodiment：
Embodiment 1：
A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves, it is characterised in that it includes step as follows Suddenly：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melting, specifically：
Step (1) Ausmelt stove meltings, including such as the next stage：1) the oxidizing semlting stage；2) reduction melting I-stage；3) also The former melting II stages, wherein：
1) the oxidizing semlting stage：Oxygen leaching slag, lead concentrate and lead fume dirt are subjected to batch mixing, obtain leaded more than 25wt% Lead-containing material, will be then continuously added to after lead-containing material 25t/h and lime stone, quartz sand mixing granulation in Ausmelt stoves, to Oxygen 1050Nm is sprayed into Ausmelt stoves3/ h, air 11000Nm3/ h, fine coal 0.9t/h, keep oxygen-rich concentration：29~31v%, Control 1050~1150 DEG C of bath temperature, carry out oxidizing semlting, when enter stove inventory reach specified inventory and lead-in-dreg 35~ During 42wt%, 1) completion of oxidizing semlting stage；
2) reduction melting I-stage：Complete 1) to add lead concentrate and lump coal in the Ausmelt stoves in oxidizing semlting stage, its In, the input amount of lead concentrate enters 3~10wt% of stove lead-containing material amount for 1) the oxidizing semlting stage, and the input amount of lump coal is 1) oxygen Change smelt stage and enter 0.5~1wt% of stove lead-containing material amount, the input amount of lead concentrate and lump coal is according into 2) reduction melting I The actual lead-in-dreg amount in stage is adjusted；Air 15000Nm is sprayed into Ausmelt stoves3/ h, fine coal 1.5t/h, control are molten 1130 DEG C of pond temperature, carries out reduction melting, as 13~18wt% of lead-in-dreg, 2) completion of reduction melting I-stage；
3) the reduction melting II stages：Complete 2) to add lump coal in the Ausmelt stoves of reduction melting I-stage, lump coal adds Enter amount for 1) the oxidizing semlting stage enters stove lead-containing material amount and 2) reduction melting I-stage enters the 0.3wt% of stove lead concentrate amount summation, Air 7000Nm is sprayed into Ausmelt stoves3/ h, fine coal 1.4t/h, control 1150 DEG C of bath temperature, and it is molten to continue reduction Refining, works as lead-in-dreg<During 5wt%, 3) the reduction melting II stages complete, and obtain lead bullion and grey slag；
Step (2) refining of lead bullion：The lead bullion interval that step (1) Ausmelt stoves melting is produced is discharged into insulation lead pan Inside holding, the lead copper matte for keeping the temperature lead pan surface is salvaged, is sold outside lead copper matte, and lead liquid manufacture cathode sheets and positive plate, then load Electrolytic cell is electrolysed, and finally obtains the lead electrode of qualification, and lead electrode is put into after lead pan fusing and carries out ingot casting output lead pig, silver It is all introduced into lead anode slurry；Lead fume dirt returns to Ausmelt stoves recycling lead as one of Ausmelt stove melting raw materials；
Step (3) grey slag melting, the grey slag that step (1) Ausmelt stoves melting produces is sunk and is discharged into fuming furnace after lead Fuming, air 8800Nm is blown into by nozzle into grey slag3/ h and fine coal 0.3t/h, by fuming furnace top tertiary air orifice to Air 1000Nm is blown into fuming furnace3/ h, control 1150~1250 DEG C of bath temperature, flue dust through waste heat recovery, gather dust, after desulfurization Emptying, gathers dust for zinc abstraction；Finally obtain scum.
The addition of lime stone and quartz sand is according to Fe contents, CaO content and the SiO entered in stove material2Content calculation and ；M [Fe] in slag in control fusion process:m(SiO2)=1.20~1.22, CaO=5~6wt%.
Lump coal：20~35mm of granularity, fixed carbon >=65wt%, ash content≤20wt%, sulfur-bearing≤1wt%.
Fine coal：Fixed carbon >=60wt%, ash content≤20wt%, the mesh of granularity -160 ＞ 80%, moisture≤1wt%.
Embodiment 2：
A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves, it is characterised in that it includes step as follows Suddenly：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melting, specifically：
Step (1) Ausmelt stove meltings, including such as the next stage：1) the oxidizing semlting stage；2) reduction melting I-stage；3) also The former melting II stages, wherein：
1) the oxidizing semlting stage：Oxygen leaching slag, lead concentrate and lead fume dirt are subjected to batch mixing, obtain leaded more than 25wt% Lead-containing material, will be then continuously added to after lead-containing material 27t/h and lime stone, quartz sand mixing granulation in Ausmelt stoves, to Oxygen 1200Nm is sprayed into Ausmelt stoves3/ h, air 13000Nm3/ h, fine coal 1.2t/h, keep oxygen-rich concentration：29~31v%, Control 1050~1150 DEG C of bath temperature, carry out oxidizing semlting, when enter stove inventory reach specified inventory and lead-in-dreg 35~ During 42wt%, 1) completion of oxidizing semlting stage；
2) reduction melting I-stage：Complete 1) to add lead concentrate and lump coal in the Ausmelt stoves in oxidizing semlting stage, its In, the input amount of lead concentrate enters 3~10wt% of stove lead-containing material amount for 1) the oxidizing semlting stage, and the input amount of lump coal is 1) oxygen Change smelt stage and enter 0.5~1wt% of stove lead-containing material amount, the input amount of lead concentrate and lump coal is according into 2) reduction melting I The actual lead-in-dreg amount in stage is adjusted；Air 17000Nm is sprayed into Ausmelt stoves3/ h, fine coal 1.8t/h, control are molten 1130~1230 DEG C of pond temperature, carries out reduction melting, as 13~18wt% of lead-in-dreg, 2) completion of reduction melting I-stage；
3) the reduction melting II stages：Complete 2) to add lump coal in the Ausmelt stoves of reduction melting I-stage, lump coal adds Enter amount for 1) the oxidizing semlting stage enters stove lead-containing material amount and 2) reduction melting I-stage enters the 0.6wt% of stove lead concentrate amount summation, Air 11000Nm is sprayed into Ausmelt stoves3/ h, fine coal 1.8t/h, control 1150~1250 DEG C of bath temperature, continue Reduction melting, works as lead-in-dreg<During 5wt%, 3) the reduction melting II stages complete, and obtain lead bullion and grey slag.
Step (2) refining of lead bullion：The lead bullion interval that step (1) Ausmelt stoves melting is produced is discharged into insulation lead pan Inside holding, the lead copper matte for keeping the temperature lead pan surface is salvaged, is sold outside lead copper matte, and lead liquid manufacture cathode sheets and positive plate, then load Electrolytic cell is electrolysed, and finally obtains the lead electrode of qualification, and lead electrode is put into after lead pan fusing and carries out ingot casting output lead pig, silver It is all introduced into lead anode slurry；Lead fume dirt returns to Ausmelt stoves recycling lead as one of Ausmelt stove melting raw materials.
Step (3) grey slag melting, the grey slag that step (1) Ausmelt stoves melting produces is sunk and is discharged into fuming furnace after lead Fuming, air 1200Nm is blown into by nozzle into grey slag3/ h and fine coal 0.6t/h, by fuming furnace top tertiary air orifice to Air 1200Nm is blown into fuming furnace3/ h, control 1150~1250 DEG C of bath temperature, flue dust through waste heat recovery, gather dust, after desulfurization Emptying, gathers dust for zinc abstraction；Finally obtain scum.
The addition of lime stone and quartz sand is according to Fe contents, CaO content and the SiO entered in stove material2Content calculation and ；M [Fe] in slag in control fusion process:m(SiO2)=1.20~1.22, CaO=5~6wt%.
Lump coal：20~35mm of granularity, fixed carbon >=65wt%, ash content≤20wt%, sulfur-bearing≤1wt%.
Fine coal：Fixed carbon >=60wt%, ash content≤20wt%, the mesh of granularity -160 ＞ 80%, moisture≤1wt%.
Embodiment 3：
A kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves, it is characterised in that it includes step as follows Suddenly：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melting, specifically：
Step (1) Ausmelt stove meltings, including such as the next stage：1) the oxidizing semlting stage；2) reduction melting I-stage；3) also The former melting II stages, wherein：
1) the oxidizing semlting stage：Oxygen leaching slag, lead concentrate and lead fume dirt are subjected to batch mixing, obtain leaded more than 25wt% Lead-containing material, will be then continuously added to after lead-containing material 30t/h and lime stone, quartz sand mixing granulation in Ausmelt stoves, to Oxygen 1350Nm is sprayed into Ausmelt stoves3/ h, air 15000Nm3/ h, fine coal 1.45t/h, keep oxygen-rich concentration：29~ 31v%, controls 1050~1150 DEG C of bath temperature, carries out oxidizing semlting, stove inventory reaches specified inventory and slag contains when entering During 35~42wt% of lead, 1) completion of oxidizing semlting stage；
2) reduction melting I-stage：Complete 1) to add lead concentrate and lump coal in the Ausmelt stoves in oxidizing semlting stage, its In, the input amount of lead concentrate enters 3~10wt% of stove lead-containing material amount for 1) the oxidizing semlting stage, and the input amount of lump coal is 1) oxygen Change smelt stage and enter 0.5~1wt% of stove lead-containing material amount, the input amount of lead concentrate and lump coal is according into 2) reduction melting I The actual lead-in-dreg amount in stage is adjusted；Air 19500Nm is sprayed into Ausmelt stoves3/ h, fine coal 2.2t/h, control are molten 1130~1230 DEG C of pond temperature, carries out reduction melting, as 13~18wt% of lead-in-dreg, 2) completion of reduction melting I-stage；
3) the reduction melting II stages：Complete 2) to add lump coal in the Ausmelt stoves of reduction melting I-stage, lump coal adds Enter amount for 1) the oxidizing semlting stage enters stove lead-containing material amount and 2) reduction melting I-stage enters the 0.8wt% of stove lead concentrate amount summation, Air 15000Nm is sprayed into Ausmelt stoves3/ h, fine coal 2.25t/h, control 1150~1250 DEG C of bath temperature, continue Reduction melting, works as lead-in-dreg<During 5wt%, 3) the reduction melting II stages complete, and obtain lead bullion and grey slag；
Step (2) refining of lead bullion：The lead bullion interval that step (1) Ausmelt stoves melting is produced is discharged into insulation lead pan Inside holding, the lead copper matte for keeping the temperature lead pan surface is salvaged, is sold outside lead copper matte, and lead liquid manufacture cathode sheets and positive plate, then load Electrolytic cell is electrolysed, and finally obtains the lead electrode of qualification, and lead electrode is put into after lead pan fusing and carries out ingot casting output lead pig, silver It is all introduced into lead anode slurry；Lead fume dirt returns to Ausmelt stoves recycling lead as one of Ausmelt stove melting raw materials；
Step (3) grey slag melting, the grey slag that step (1) Ausmelt stoves melting produces is sunk and is discharged into fuming furnace after lead Fuming, air 14500Nm is blown into by nozzle into grey slag3/ h and fine coal 1.35t/h, passes through fuming furnace top tertiary air orifice Air 1500Nm is blown into fuming furnace3/ h, control 1150~1250 DEG C of bath temperature, flue dust through waste heat recovery, gather dust, desulfurization After empty, gather dust for zinc abstraction；Finally obtain scum.
The addition of lime stone and quartz sand is according to Fe contents, CaO content and the SiO entered in stove material2Content calculation and ；M [Fe] in slag in control fusion process:m(SiO2)=1.20~1.22, CaO=5~6wt%.
Lump coal：20~35mm of granularity, fixed carbon >=65wt%, ash content≤20wt%, sulfur-bearing≤1wt%.
Fine coal：Fixed carbon >=60wt%, ash content≤20wt%, the mesh of granularity -160 ＞ 80%, moisture≤1wt%.
In fusion process, lead-in-dreg amount can be inserted into by adjusting oxygen gesture (oxygen-rich concentration) and/or spray gun pool depth into Row regulation and control, when lead-in-dreg amount is high, oxygen-rich concentration is lowered according to bias, reduces oxygen gesture to reduce lead-in-dreg amount in proportion；Together When/or increase spray gun insertion pool depth, increase spray gun side pressure；Conversely, raised in proportion according to bias oxygen-rich concentration and/or Spray gun insertion pool depth is reduced, gun insertion depth is generally 250~500mm.
In the oxidizing semlting stage, can also regulate and control lead-in-dreg amount by adjusting material feed speed, when lead-in-dreg is less than expection During 5~10wt% of value, material feed speed is reduced；When lead-in-dreg is higher than 5~10wt% of desired value, material feed speed is improved.
It is mutually as follows in the reaction of oxidation panel in relation to various sulphur things in oxygen leaching slag：
A, sulfuric acid type double salt
Sulfuric acid type double salt is heated first to be decomposed into corresponding sulfate, vapor, as temperature further raises, sulfate Continue to decompose, reaction equation is such as shown in [1]：
Wherein Me=Fe, Pb, Zn etc..
Sulfuric acid type double salt is decomposed into the endothermic reaction, and therefore, substantial amounts of sulfuric acid type double salt endothermic decomposition is led in oxygen leaching slag Furnace temperature is caused to reduce, it is necessary to supplement a large amount of fine coal.
B, sulfide
MeS+3/2O2=MeO+SO2 [2]
Wherein Me=Fe, Zn, Cu, Pb etc..
C, elementary sulfur
Elementary sulfur is acted on oxygen, is generated SO2 gases, is also served as flue gas and enter smoke processing system, reaction equation such as [3] institute Show；
Due to S in oxygen leaching slag0Presence may also occur that PbO and S0Reaction, directly generate thick Pb, SO2, instead Shown in Ying Shiru [4].
S0+O2=SO2 [3]
PbO+1/2S0=Pb+1/2SO2 [4]
D, valuable metal Ag is settled during melting reaction with lead bullion in oxygen leaching slag, is enriched in lead bullion.
Lead fume dirt is as follows in each stage melting reaction mechanism of Ausmelt stoves：
Oxidation panel
Flue dust main component is PbSO4, PbO, into molten bath after PbSO4, PbS and O2Reaction generation PbO, SO2, reaction equation As shown in [5]；Meanwhile PbSO can also occur4Directly PbO, SO are generated by pyrolysis2And O2, reaction equation is such as shown in [6].
PbSO4+PbS+O2=2PbO+2SO2 [5]
PbSO4=PbO+SO2+1/2O2 [6]
By the above process, (leaded about 40%) and concentration are 3%~9% or so for final output lead bullion, lead-rich slag SO2Flue gas.
1 section of reduction
Then enter reduction I-stage operation when smelt stage inlet amount and lead-in-dreg reach requirement, be divided into cross reaction Reduction and carbonizing reduction：
Cross reaction reduces
The PbS concentrate of addition and PbO reactions generation Pb and SO in clinker2, reaction equation is such as shown in [7]：
PbS+2PbO=3Pb+SO2 [7]
Carbonizing reduction
Under reducing atmosphere, CO and PbO in clinker first reacts generation Pb and CO2, react the CO of generation2With carbon content in coal into The gasification reaction (i.e. cloth Dorr reacts) of row carbon regenerates CO, and CO then continues to participate in the reduction of PbO in clinker, and reaction equation is such as [8] and shown in [9]：
PbO+CO=Pb+CO2 [8]
C+CO2=2CO [9]
Reduction I-stage must control appropriate PbS concentrate additions, on the one hand further increase PbS by cross reaction Concentrate treating capacity and the more lead bullion of output, on the other hand cannot add excessive PbS concentrate, be likely to occur in molten bath no enough PbO consumes the situation of PbS, forms lead copper matte.
Reduce the II stages
Then enter reductase 12 section operation when lead-in-dreg reaches requirement, which only has carbonizing reduction, reaction equation such as [8] and [9] shown in.
In reduction phase reduction reaction mainly occurs for iron, and reaction is as shown in [10] and [11]：
2FexOy+yC=2xFe+yCO2 [10]
FexOy+yCO=xFe+yCO2 [11]
Iron is entered in grey slag with simple substance form.

Claims (4)

1. a kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves, it is characterised in that it includes step as follows Suddenly：(1) Ausmelt stoves melting, (2) refining of lead bullion, (3) grey slag melting, specifically：
Step (1) Ausmelt stove meltings, including such as the next stage：1) the oxidizing semlting stage；2) reduction melting I-stage；3) reduction is molten The II stages are refined, wherein：
1) the oxidizing semlting stage：Oxygen leaching slag, lead concentrate and lead fume dirt are subjected to batch mixing, obtain containing for leaded more than 25wt% Lead materials, then will be continuously added to Ausmelt stoves after the 25~30t/h of lead-containing material and lime stone, quartz sand mixing granulation It is interior, 1050~1350Nm of oxygen is sprayed into the Ausmelt stoves3/ h, 11000~15000Nm of air3/ h, fine coal 0.9~ 1.45t/h, keeps oxygen-rich concentration：29~31v%, controls 1050~1150 DEG C of bath temperature, oxidizing semlting is carried out, when entering stove thing When doses reaches specified inventory and 35~42wt% of lead-in-dreg, 1) the oxidizing semlting stage completes；
2) reduction melting I-stage：Added in the Ausmelt stoves for completing 1) oxidizing semlting stage the lead concentrate and Lump coal, wherein, the input amount of the lead concentrate for 1) the oxidizing semlting stage enter lead-containing material amount described in stove 3~ 10wt%, the input amount of the lump coal enter 0.5~1wt% of lead-containing material amount described in stove for 1) the oxidizing semlting stage；To 15000~19500Nm of air is sprayed into the Ausmelt stoves3/ h, 1.5~2.2t/h of fine coal, control bath temperature 1130~ 1230 DEG C, reduction melting is carried out, as 13~18wt% of lead-in-dreg, 2) the reduction melting I-stage is completed；
3) the reduction melting II stages：The lump coal is added in the Ausmelt stoves for completing 2) the reduction melting I-stage, The addition of the lump coal enters lead-containing material amount described in stove for 1) the oxidizing semlting stage and 2) the reduction melting I-stage enters 0.3~0.8wt% of lead concentrate amount summation described in stove, 7000~15000Nm of air is sprayed into the Ausmelt stoves3/ h, powder 1.4~2.25t/h of coal, controls 1150~1250 DEG C of bath temperature, continues reduction melting, work as lead-in-dreg<During 5wt%, institute State 3) the reduction melting II stages to complete, obtain lead bullion and grey slag；
Step (2) refining of lead bullion：The lead bullion interval that the step (1) Ausmelt stoves melting is produced is discharged into insulation Lead pan inside holding, the lead copper matte on the insulation lead pan surface is salvaged, remaining lead liquid manufacture cathode sheets and positive plate, then electric Solution refining obtains the lead electrode of qualification and containing silver anode slime；The lead fume dirt that step (2) refining of lead bullion produces is as Ausmelt One of stove melting raw material returns to Ausmelt stoves recycling lead；
Step (3) grey slag melting, the grey slag that the step (1) Ausmelt stoves melting produces is sunk and is discharged into cigarette after lead Change stove fuming, 8800~14500Nm of air is blown into the grey slag by nozzle30.3~1.35t/h of/h and fine coal, leads to Cross fuming furnace top tertiary air orifice and 1000~1500Nm of air is blown into the fuming furnace3/ h, controls bath temperature 1150~1250 DEG C, flue dust through waste heat recovery, gather dust, emptied after desulfurization, gather dust for zinc abstraction；Finally obtain scum.
2. a kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves according to claim 1, its feature exist In the addition of the lime stone and the quartz sand is according to Fe contents, CaO content and the SiO entered in stove material2Content calculation And obtain；M [Fe] in slag in control fusion process:m(SiO2)=1.20~1.22, CaO=5~6wt%.
3. a kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves according to claim 1, its feature exist In the lump coal：20~35mm of granularity, fixed carbon >=65wt%, ash content≤20wt%, sulfur-bearing≤1wt%.
4. a kind of method that oxygen leaching slag handles valuable metal by Ausmelt stoves according to claim 1, its feature exist In the fine coal：Fixed carbon >=60wt%, ash content≤20wt%, the mesh of granularity -160 ＞ 80%, moisture≤1wt%.
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CN114438323B (en) * 2022-01-25 2023-09-12 呼伦贝尔驰宏矿业有限公司 Environment-friendly harmless treatment method for iron slag, cobalt slag, lead slag and sulfur tailings

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CN101705366A (en) * 2009-11-23 2010-05-12 长沙有色冶金设计研究院 Direct lead smelting method for processing zinc smelting slag by matching
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