CN102517439A - Method for selectively roasting and separating tin, zinc and arsenic in compound iron ore containing tin, zinc and arsenic - Google Patents
Method for selectively roasting and separating tin, zinc and arsenic in compound iron ore containing tin, zinc and arsenic Download PDFInfo
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Abstract
The invention discloses a method for selectively roasting and separating tin, zinc and arsenic in compound iron ore containing tin, zinc and arsenic. The method comprises the following steps of: burdening iron concentrate containing tin, zinc and arsenic with a bonding agent, mixing uniformly, performing damp milling and pelletizing; drying and dehydrating green balls; removing arsenic by performing low-temperature roasting in a first weak reduction atmosphere; removing sulfur by roasting in an oxidizing atmosphere; and removing tin and zinc by performing high-temperature roasting in a second weak reduction atmosphere to obtain pre-reduced pellet ore. The obtained pre-reduced pellet ore can be used for producing metalized pellets (DRI (Direct Reduced Iron)), and can be taken as a blast furnace iron-making furnace material. Due to the adoption of the method, concentrated treatment and recovery of toxic and harmful elements, i.e., arsenic and sulfur are realized; and the oxides of tin, zinc and arsenic can be separated and recovered segmentally from flue gas, so that the environment is protected. Large-scale processing and efficient utilization of compound iron ore containing tin, zinc and arsenic can be realized.
Description
Technical field
The invention belongs to and extract metallurgical and mineral manufacture field, relate to a kind of method of from stanniferous zinc arsenic complex iron ore, separating tin, zinc, arsenic, also relate to a kind of method of utilizing the selectivity roasting technology to separate tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore especially.
Background technology
Though China's iron ore deposit reserves are big, lean ore is many, rich ore is few, and complicated ore hard to manage is many.Stanniferous zinc arsenic complex iron ore is the iron ore deposit typical hard to manage of one of them, mainly contains the industrial mineral of magnetite, cassiterite, zink sulphide, mispickel etc.Process mineralogy research shows, the main carrier mineral of iron in ore is magnetite (accounts for TFe 96.45%), and is monomer output (accounting for 93.4%) more, and all the other are on a small quantity with other form and metallic sulfide, cassiterite and gangue adhesion or parcel; Independently containing tin mineral in the ore is cassiterite; Particulate or coarse grain polymer embedding cloth were in fluorite or silicate during major part was; Only minority and magnetite, zink sulphide and arsenopyrite explanation embedding cloth are in gangue mineral; In the crack of magnetite, often be filled with cassiterite monomer or polymer, also often visible particulate cassiterite inclusion in magnetite, zink sulphide and arsenopyrite; Mainly there be (distributive law of zinc in zink sulphide and marmatite reaches 89%) in zinc in the ore with the sulphide ores form, and zink sulphide is how granular or constitute intergrowth with irregular with magnetite and other mineral with monomer; To deposit mineral be mispickel in the main tax of arsenic in the ore, is smaltite and symplesite etc. on a small quantity, and normal and magnetite of most of mispickel or zink sulphide are inlayed the formation intergrowth, and the mispickel proportion is higher than 50% mostly in the intergrowth.In addition, also see microfine mispickel inclusion in magnetite inside.
Since mineral such as cassiterite, zink sulphide, mispickel many with microfine inclusion embedding cloth in magnetite; Employing comprises magnetic separation, flotation and flotation-when the magnetic separation combined process flow is handled; Remaining Sn, Zn, As quality percentage composition still reach 0.13%～0.28%, 0.11%～0.23%, 0.13%～0.29% respectively in the iron ore concentrate that is obtained, and can't satisfy the basic demand (Sn＜0.08%, Zn＜0.1%, As＜0.1%) of blast-furnace smelting to tin, zinc, arsenic quality percentage composition in the furnace charge at all.
Thermal process is a main method of handling stanniferous, zinc, arsenic material.Be seen in reported method and mainly contain sulfiding volatilization, chloridizing volatilization, retailoring, reduction sintering and reduction volatilization etc.
The sulfiding volatilization method is to utilize SnS and the difference of other component sulfide on volatility to come Separation and Recovery tin; This method is to handle the otherwise effective technique of medium tin ore, poor tin concentrate or tin metallurgy lean slag at present in the world; The evaporation rate of tin is high, can realize preferably that Sn, Fe separate.Such as, adopt fuming furnace sulfiding volatilization method to handle medium tin ore, the Sn evaporation rate all can reach more than 98%, and containing Sn in the waste can reduce to below 0.07%, but this method vulcanizes temperature required height (1180～1300 ℃) and causes energy consumption big, and SO in the flue gas
2Gas need be anticipated and could be discharged, otherwise causes environmental pollution easily.
Chloride volatility process is applicable to the poor tin material of low-grade, the high impurity (especially arsenic, iron level height) that the common tin smelting system can't be handled, and is the efficient processing means that comprehensively reclaim the multi-metal complex ore deposit.But because chlorine or hydrogenchloride are big to industrial equipments corrodibility, and be prone to cause problem such as environmental pollution, thereby greatly limited the widespread use of this method.
Reducing smelting process is under strongly reducing atmosphere, makes the cassiterite in the tin concentrate be reduced into metallic tin gaseous volatilization entering flue gas system through twice melting, and iron separates with tin with the gangue content slag making simultaneously.The major advantage of this method is that, furnace atmosphere strong to adaptability to raw material is prone to control, operation of equipment is convenient, but outstanding technical problem is exactly the unusual difficulty of effective separation that realizes Fe, Sn.
Though the reduction sintering process can obtain remaining Sn content less than 0.08% agglomerate, there are problems such as the coke powder consumption is big, energy consumption height in this method.In addition, the stable control to the sintering process reducing atmosphere is key problem in technology in the industrial implementation.
The reduction volatilization method is to utilize the characteristics that vapour pressure is high, volatility is good of SnO under the high temperature, metallic zinc and arsenic, the iron ore concentrate through magnetic separation is carried out reducing roasting SnO, zinc and arsenic volatilization entering flue gas system are handled.The reduction volatilization method mainly contains two kinds of direct-reduction process and weak reduction methods.Direct-reduction process can reach more than 90% the decreasing ratio of tin, zinc and arsenic, and the ferrous metal rate reaches as high as 94%, but has problems such as roasting time length (180min), energy consumption is high, production efficiency is low, cost is high, and tin and zinc arsenic recovery difficult are big.With respect to direct reducing roasting; Weak reducing roasting technology reducing roasting temperature is low, the time is short, energy consumption is low; Tin, zinc and arsenic removal effect are good, but this method do not focus on and reclaim poisonous and harmful element arsenic, sulphur, and the difficulty that from rotary kiln exhaust gas, reclaims tin, zinc, arsenic is big.
Therefore,, only be to join the ore deposit at present with other common iron ore for the utilization of tin zinc arsenic complex iron ore, behind the sintering again through blast furnace ironmaking.But the comprehensive recovery problem of wherein poisonous element arsenic and sulphur, especially valuable element tin and zinc still is not well solved.Under current resource supply and demand intense situation, be badly in need of the treatment process of a kind of technical feasibility, economical rationality, to realize large-scale development and efficient utilization to tin zinc arsenic complex iron ore.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, and provide that tin in a kind of stanniferous zinc arsenic complex iron ore, zinc, arsenic separation efficiency are high, the poisonous and harmful element pozzuolite focuses on, the multiple metallic element step reclaims, environment is not produced the method that the selectivity roasting of harm separates tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore.
Selectivity roasting of the present invention separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore; Be with the stanniferous zinc arsenic iron ore concentrate of certain particle size and binder formulation, mixing; Make ball behind the profit mill; Green-ball successively through high-temperature roasting detin in the first weakly reducing atmosphere low-temperature bake dearsenification, oxidizing atmosphere desulfurization with roasting technique, second weakly reducing atmosphere, zinc, obtains prereduction pellet after drying.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and the granularity of the compound iron ore concentrate of said stanniferous zinc arsenic is that the shared mass percent of-200 order grades is more than or equal to 80%.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and said sticker is the coal sodium humate, and the addition of said coal sodium humate accounts for 0.5%～1.0% of iron ore concentrate mass percent; When mill profit, add the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate and coal sodium humate total amount and be 5%～8% water, the profit time consuming is 4min～7min.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and the volumetric concentration of CO is 5%～15% in said first weakly reducing atmosphere, and low-temperature bake dearsenification temperature is 350 ℃～500 ℃, and roasting time is 3min～5min; O in the oxidizing atmosphere of said desulfurization with roasting technique
2Volumetric concentration be 15%～19%, control desulfurization with roasting technique temperature be 600 ℃～850 ℃, roasting time is 4min～6min; The volumetric concentration of CO is 40%～50% in said second weakly reducing atmosphere, and the temperature of control roasting detin, zinc is 925 ℃～1000 ℃, and roasting time is 30min～35min.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, from low-temperature bake dearsenification flue gas, reclaims arsenic compound, reclaims tin, zn cpds in the flue gas of therefrom high-temperature roasting detin, zinc.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and the quality percentage composition of remaining tin, zinc, arsenic is smaller or equal to 0.075% in the said finished product prereduction pellet.
Selectivity roasting of the present invention separates in the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and said finished product prereduction pellet is as preparation dri (DRI) or blast furnace ironmaking raw material.
Know-why of the present invention is:
The weakly reducing atmosphere low-temperature bake makes the arsenopyrite reduction decomposition remove arsenic, i.e. 2FeAsS → 2FeS+As
2 (g)
The purpose of oxidizing atmosphere roasting is to be zinc oxide and Fe with ZnS and FeS selective oxidation
2O
3Remove sulphur simultaneously, i.e. 2ZnS+3O
2→ 2ZnO
(s)+ 2SO
2, 4FeS+7O
2→ 2Fe
2O
3+ 4SO
2For follow-up reduction ZnO becomes Zn
(g)And dezincify creates conditions.
The main purpose of high-temperature roasting is reduction cassiterite and zinc oxide, i.e. SnO in the weakly reducing atmosphere
2+ CO → SnO
(g)+ CO
2And ZnO+CO → Zn
(g)+ CO
2, tin and zinc remove with SnO, Zn (g) volatilization respectively.This process is with the reduction of ferriferous oxide, i.e. Fe
2O
3/ Fe
3O
4+ CO → FeO+CO
2
Innovation part of the present invention is:
Fundamental characteristics from stanniferous zinc arsenic complex iron ore; Through regulation and control maturing temperature and atmosphere; Both are mated each other; Having solved poisonous and harmful element arsenic, sulphur needs the prefecture to handle, and overcomes the technical barrier that valuable metal tin, zinc and iron step separate and reclaim simultaneously, and realization valuable metal tin, zinc separates with the iron step and reclaim.
Use technology provided by the present invention, can realize that the step of iron, tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore separates and recovery, separation efficiency is high, and environment is not produced harm.
Description of drawings
The selectivity roasting that accompanying drawing 1 adopts for the present invention separates the schematic flow sheet of tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore.
Embodiment
Tin, zinc, arsenic are illustrated in 1 pair of selectivity roasting separation of contrast accompanying drawing stanniferous zinc arsenic complex iron ore below.
Wherein: compound iron ore concentrate main chemical compositions of stanniferous zinc arsenic and content are: TFe:65.7%, Sn:0.26%, Zn:0.14%, As:0.29%.
Embodiment 1: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 0.5% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 5.0% water moistens mill, the profit time consuming is 4min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 15%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.032%, 0.03% in the gained pre-reduced pellet.
Embodiment 2: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 15%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.068%, 0.031%, 0.032% in the gained pre-reduced pellet.
Embodiment 3: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 8.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 15%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.030%, 0.031% in the gained pre-reduced pellet.
Embodiment 4: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 350 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 17%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.07%, 0.032%, 0.052% in the gained pre-reduced pellet.
Embodiment 5: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 450 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 17%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.071%, 0.030%, 0.041% in the gained pre-reduced pellet.
Embodiment 6: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 5% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 17%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.068%, 0.031%, 0.034% in the gained pre-reduced pellet.
Embodiment 7: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 15% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 17%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.035%, 0.054% in the gained pre-reduced pellet.
Embodiment 8: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 600 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.067%, 0.065%, 0.03% in the gained pre-reduced pellet.
Embodiment 9: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 800 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.067%, 0.056%, 0.036% in the gained pre-reduced pellet.
Embodiment 10: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 35min, and the volumetric concentration of CO is 40% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.072%, 0.035%, 0.036% in the gained pre-reduced pellet.
Embodiment 11: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 925 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.75%, 0.032%, 0.033% in the gained pre-reduced pellet.
Embodiment 12: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 950 ℃, and roasting time is 35min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.074%, 0.030%, 0.03% in the gained pre-reduced pellet.
Embodiment 13: in the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate is 1.0% ratio, add coal sodium humate sticker and prepare burden, mixing, compound; Add in compound that to account for mixture quality per-cent be that 7.0% water moistens mill, the profit time consuming is 7min, obtains moistening abrasive material; The profit abrasive material is used to make ball, makes the green-ball that diameter is 10mm～16mm; Green-ball carries out high-temperature roasting detin zinc in drying and dehydrating, the dearsenification of weakly reducing atmosphere low-temperature bake, oxidizing atmosphere desulfurization with roasting technique, the weakly reducing atmosphere; Drying system, drying temperature are 300 ℃, and be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature are 500 ℃, and roasting time is 5min, and the volumetric concentration of CO is 12% in the flue gas; Oxidizing atmosphere roasting system, maturing temperature are that 725 ℃, roasting time are that the volumetric concentration of oxygen in 6min, the oxidizing atmosphere is 19%; High-temperature roasting system in the weakly reducing atmosphere, maturing temperature are 1000 ℃, and roasting time is 30min, and the volumetric concentration of CO is 50% in the atmosphere; The quality percentage composition of remaining tin, zinc, arsenic is respectively 0.07%, 0.031%, 0.032% in the gained pre-reduced pellet.
Claims (7)
1. the selectivity roasting separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore; It is characterized in that: at first with stanniferous zinc arsenic iron ore concentrate and binder formulation, mixing; Make ball behind the profit mill; Green-ball successively through high-temperature roasting detin in the first weakly reducing atmosphere low-temperature bake dearsenification, oxidizing atmosphere desulfurization with roasting technique, second weakly reducing atmosphere, zinc, obtains prereduction pellet after drying.
2. selectivity roasting according to claim 1 separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, it is characterized in that: the granularity of the compound iron ore concentrate of said stanniferous zinc arsenic is that the shared mass percent of-200 order grades is more than or equal to 80%.
3. selectivity roasting according to claim 2 separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore; It is characterized in that: said sticker is the coal sodium humate, and the addition of said coal sodium humate accounts for 0.5%～1.0% of iron ore concentrate mass percent; When mill profit, add the mass percent that accounts for stanniferous zinc arsenic iron ore concentrate and coal sodium humate total amount and be 5%～8% water, the profit time consuming is 4min～7min.
4. selectivity roasting according to claim 3 separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore; It is characterized in that: the volumetric concentration of CO is 5%～15% in said first weakly reducing atmosphere; Low-temperature bake dearsenification temperature is 350 ℃～500 ℃, and roasting time is 3min～5min; The volumetric concentration of O2 is 15%～19% in the oxidizing atmosphere of said desulfurization with roasting technique, and the temperature of control desulfurization with roasting technique is 600 ℃～850 ℃, and roasting time is 4min～6min; The volumetric concentration of CO is 40%～50% in said second weakly reducing atmosphere, and the temperature of control roasting detin, zinc is 925 ℃～1000 ℃, and roasting time is 30min～35min.
5. selectivity roasting according to claim 4 separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore; It is characterized in that: from low-temperature bake dearsenification flue gas, reclaim arsenic compound, reclaim tin, zn cpds in the flue gas of therefrom high-temperature roasting detin, zinc.
6. selectivity roasting according to claim 5 separates the method for tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore, and it is characterized in that: the quality percentage composition of remaining tin, zinc, arsenic is smaller or equal to 0.075% in the said finished product prereduction pellet.
7. the method that any described selectivity roasting separates tin, zinc, arsenic in the stanniferous zinc arsenic complex iron ore according to claim 1-6, it is characterized in that: said finished product prereduction pellet is as preparation dri or blast furnace ironmaking raw material.
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| CN102965522A (en) * | 2012-11-13 | 2013-03-13 | 中南大学 | Method for separating and recovering tin from tin-containing mill tailings |
| CN103103340A (en) * | 2013-01-18 | 2013-05-15 | 昆明理工大学 | Method for treating high iron low tin ore by sulfiding volatilizing-magnetizing roasting method |
| CN103555931A (en) * | 2013-11-15 | 2014-02-05 | 湖南省环境保护科学研究院 | Method for comprehensive utilization of removed arsenium of high-arsenium-sulfur-iron watercourse tailings |
| CN104152718A (en) * | 2014-07-21 | 2014-11-19 | 中南大学 | Method for synchronously separating tin and iron from tin-containing iron tailings |
| CN105543488A (en) * | 2015-12-31 | 2016-05-04 | 耒阳市焱鑫有色金属有限公司 | Sublimation arsenic-removal method for high-arsenic materials |
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| CN110205483A (en) * | 2019-06-13 | 2019-09-06 | 云南锡业股份有限公司铜业分公司 | A kind of reduction roasting handles the system and technique of low-grade tin raw material |
| CN114836617A (en) * | 2022-04-20 | 2022-08-02 | 柳州华锡有色设计研究院有限责任公司 | Method for efficiently smelting high-sulfur high-arsenic tin concentrate |
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| CN110042255A (en) * | 2019-04-29 | 2019-07-23 | 中南大学 | A kind of method that multistage control atmosphere baking separation recycles valuable metal in Copper making cigarette ash |
| CN110042255B (en) * | 2019-04-29 | 2020-03-13 | 中南大学 | Method for recovering valuable metals in copper smelting soot through multistage controlled atmosphere roasting separation |
| CN110205483A (en) * | 2019-06-13 | 2019-09-06 | 云南锡业股份有限公司铜业分公司 | A kind of reduction roasting handles the system and technique of low-grade tin raw material |
| CN114836617A (en) * | 2022-04-20 | 2022-08-02 | 柳州华锡有色设计研究院有限责任公司 | Method for efficiently smelting high-sulfur high-arsenic tin concentrate |
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