CN102517439B - 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 from stannum-zinc-arsenic-contained complex iron ore the method for Separation of Tin, zinc, arsenic, also relate to especially a kind of method of utilizing tin, zinc, arsenic in selectivity roasting technology separation stannum-zinc-arsenic-contained complex iron ore.
Background technology
Although China's iron ore deposit reserves are large, lean ore is many, rich ore is few, and it is many that complicated difficult is processed ore.Stannum-zinc-arsenic-contained complex iron ore is the difficult iron ore deposit of the typical case of one of them, mainly contains the industrial mineral of magnetite, cassiterite, zink sulphide, mispickel etc.Process mineralogy research shows, the main carriers mineral of iron in ore are magnetite (account for TFe 96.45%), and are 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; In ore, containing tin mineral, be independently cassiterite, major part is middle particulate or coarse grain polymer embedding cloth in fluorite or silicate, only minority and magnetite, zink sulphide and arsenopyrite explanation embedding cloth are in gangue mineral, often be filled with cassiterite monomer or polymer in the crack of magnetite, also frequent visible Fine 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 ore with the sulphide ores form, and zink sulphide is granular or form intergrowth with irregular and magnetite and other mineral mainly with monomer; In ore, to deposit mineral be mispickel in the main tax of arsenic, is smaltite and symplesite etc. on a small quantity, and the normal and magnetite of most of mispickel or zink sulphide are inlayed the formation intergrowth, and in intergrowth, the mispickel proportion is mostly higher than 50%.In addition, also see microfine mispickel inclusion in magnetite inside.
Due to the mineral such as cassiterite, zink sulphide, mispickel mainly with microfine inclusion embedding cloth in magnetite, employing comprises when magnetic separation, flotation and flotation-magnetic separation combined process flow is processed, in the iron ore concentrate obtained, remaining Sn, Zn, As quality percentage composition still reach respectively 0.13%～0.28%, 0.11%～0.23%, 0.13%～0.29%, can't meet the basic demand (Sn<0.08%, Zn<0.1%, As<0.1%) of blast-furnace smelting to tin, zinc, arsenic quality percentage composition in furnace charge at all.
Thermal process is the main method of processing stanniferous, zinc, arsenic material.The method that is seen in report mainly contains 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 carry out Separation and Recovery tin, this method is to process in the world at present medium tin ore, lean tin concentrate or the most effective technology of tin metallurgy lean slag, the evaporation rate of tin is high, can realize preferably that Sn, Fe separate.Such as, adopt fuming furnace sulfiding volatilization method to process medium tin ore, the Sn evaporation rate all can reach more than 98%, in waste, containing Sn, can be down to below 0.07%, but this method vulcanizes temperature required height (1180～1300 ℃) and causes energy consumption large, and SO in flue gas
2gas need be anticipated and could be discharged, otherwise easily causes environmental pollution.
Chloride volatility process is applicable to the lean tin material of low-grade, the high impurity that the common tin smelting system can't process (especially arsenic, iron level high), is the efficient processing means that comprehensively reclaim the multi-metal complex ore deposit.But due to chlorine or hydrogenchloride large to industrial equipments corrodibility, and easily cause the problems such as environmental pollution, thereby greatly limited the widespread use of this method.
Reducing smelting process is under strongly reducing atmosphere, by twice melting, makes cassiterite in the tin concentrate be reduced into the metallic tin gaseous volatilization and enters flue gas system, and iron separates with tin with the gangue content slag making simultaneously.The major advantage of this method be strong to adaptability to raw material, furnace atmosphere is easily controlled, operation of equipment is convenient, but outstanding technical problem is exactly to realize that effective separation of Fe, Sn is very difficult.
Although the reduction sintering process can obtain the agglomerate that remaining Sn content is less than 0.08%, there are the problems such as the coke powder consumption is large, energy consumption is high in the method.In addition, in industrial implementation, the stable control to the sintering process reducing atmosphere is key problem in technology.
The reduction volatilization method be utilize the vapour pressure of SnO under high temperature, metallic zinc and arsenic high, characteristics that volatility is good, the iron ore concentrate through magnetic separation is carried out to reducing roasting and makes SnO, zinc and arsenic volatilization enter flue gas system to process.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 the problems such as roasting time is grown (180min), energy consumption is high, production efficiency is low, cost is high, and tin and zinc arsenic recovery difficult are large.With respect to the direct-reduction 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 the method do not focused on and reclaim poisonous and harmful element arsenic, sulphur, and the difficulty that reclaims tin, zinc, arsenic from rotary kiln exhaust gas is large.
Therefore, at present, for the utilization of tin zinc arsenic complex iron ore, with other common iron ore, joined ore deposit, after sintering again through blast furnace ironmaking.But the comprehensive recovery problem of poisonous element arsenic and sulphur wherein, especially valuable element tin and zinc, still be 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 the to tin zinc arsenic complex iron ore.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, and tin in a kind of stannum-zinc-arsenic-contained complex iron ore, zinc are provided, the arsenic separation efficiency is high, the poisonous and harmful element pozzuolite focuses on, the multiple metallic element step reclaims, environment is not produced to the method for tin, zinc, arsenic in the selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of harm.
The method of tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, be by the tin-zinc containing arsenic iron ore concentrate of certain particle size and binder formulation, mix, pelletizing after the profit mill, green-ball, after drying successively through high-temperature roasting detin in the first weakly reducing atmosphere low-temperature bake dearsenification, oxidizing atmosphere desulfurization with roasting technique, the second weakly reducing atmosphere, zinc, obtains prereduction pellet.
In selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, in the method for tin, zinc, arsenic, the granularity of described tin-zinc containing arsenic compound iron concentrate is more than or equal to 80% for the shared mass percent of-200 order grade.
In selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, in the method for tin, zinc, arsenic, described binding agent is the coal sodium humate, and the addition of described coal sodium humate accounts for 0.5%～1.0% of Iron Concentrate Quality percentage ratio; When mill profit, the water that to add the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate and coal sodium humate total amount be 5%～8%, the profit time consuming is 4min～7min.
In selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, in the method for tin, zinc, arsenic, in described the first weakly reducing atmosphere, the volumetric concentration of CO is 5%～15%, and low-temperature bake dearsenification temperature is 350 ℃～500 ℃, and roasting time is 3min～5min; O in the oxidizing atmosphere of described desulfurization with roasting technique
2volumetric concentration be 15%～19%, the temperature of controlling desulfurization with roasting technique is 600 ℃～850 ℃, roasting time is 4min～6min; In described the second weakly reducing atmosphere, the volumetric concentration of CO is 40%～50%, and the temperature of controlling roasting detin, zinc is 925 ℃～1000 ℃, and roasting time is 30min～35min.
In the method for tin, zinc, arsenic, from low-temperature bake dearsenification flue gas, reclaim arsenic compound in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, reclaim tin, zn cpds in the flue gas of therefrom high-temperature roasting detin, zinc.
In selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, in the method for tin, zinc, arsenic, in described finished product prereduction pellet, the quality percentage composition of remaining tin, zinc, arsenic is less than or equal to 0.075%.
In selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention, in the method for tin, zinc, arsenic, described finished product prereduction pellet is as preparing direct-reduced iron (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 that ZnS and FeS are oxidized to respectively to zinc oxide and Fe
2o
3remove sulphur, i.e. 2ZnS+3O simultaneously
2→ 2ZnO
(s)+ 2SO
2, 4FeS+7O
2→ 2Fe
2o
3+ 4SO
2.For follow-up reduction ZnO becomes Zn
(g)and dezincify creates conditions.
In weakly reducing atmosphere, the main purpose of high-temperature roasting is reduction cassiterite and zinc oxide, i.e. SnO
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 of the present invention is:
Fundamental characteristics from stannum-zinc-arsenic-contained complex iron ore, by regulation and control maturing temperature and atmosphere, both are mated mutually, having solved poisonous and harmful element arsenic, sulphur needs prefecture to process, overcome valuable metal tin, zinc and the technical barrier that the iron step separates and reclaims simultaneously, realize that valuable metal tin, zinc and iron step separate and reclaim.
Apply technology provided by the present invention, can realize that the step of iron in stannum-zinc-arsenic-contained complex iron ore, tin, zinc, arsenic separates and reclaims, separation efficiency is high, and environment is not produced to harm.
The accompanying drawing explanation
Accompanying drawing 1 is the schematic flow sheet of tin, zinc, arsenic in the selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of the present invention's employing.
Embodiment
Below in 1 pair of selectivity baking separation stannum-zinc-arsenic-contained complex iron ore of contrast accompanying drawing, tin, zinc, arsenic are illustrated.
Wherein: tin-zinc containing arsenic compound iron concentrate main chemical compositions and content are: TFe:65.7%, Sn:0.26%, Zn:0.14%, As:0.29%.
Embodiment 1: the ratio that is 0.5% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 5.0% and moisten mill to adding in compound, it is 4min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 15%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.032%, 0.03%.
Embodiment 2: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 15%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.068%, 0.031%, 0.032%.
Embodiment 3: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 8.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 15%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.030%, 0.031%.
Embodiment 4: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 350 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 17%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.07%, 0.032%, 0.052%.
Embodiment 5: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 450 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 17%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.071%, 0.030%, 0.041%.
Embodiment 6: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 5%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 17%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.068%, 0.031%, 0.034%.
Embodiment 7: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 15%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 17%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.069%, 0.035%, 0.054%.
Embodiment 8: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 600 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.067%, 0.065%, 0.03%.
Embodiment 9: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 800 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.067%, 0.056%, 0.036%.
Embodiment 10: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 40%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.072%, 0.035%, 0.036%.
Embodiment 11: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 925 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.75%, 0.032%, 0.033%.
Embodiment 12: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 950 ℃, and roasting time is 35min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.074%, 0.030%, 0.03%.
Embodiment 13: the ratio that is 1.0% in the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate, and add coal sodium humate binding agent and prepared burden, mix, obtain compound; Account for the water that mixture quality per-cent is 7.0% and moisten mill to adding in compound, it is 7min that profit is consumed time, and obtains moistening abrasive material; The profit abrasive material, for pelletizing, 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, weakly reducing atmosphere; Drying system, drying temperature is 300 ℃, be 6min time of drying; Weakly reducing atmosphere low-temperature bake system, maturing temperature is 500 ℃, and roasting time is 5min, and in flue gas, the volumetric concentration of CO is 12%; Oxidizing atmosphere roasting system, maturing temperature is that the volumetric concentration that 725 ℃, roasting time are oxygen in 6min, oxidizing atmosphere is 19%; High-temperature roasting system in weakly reducing atmosphere, maturing temperature is 1000 ℃, and roasting time is 30min, and in atmosphere, the volumetric concentration of CO is 50%; In the gained pre-reduced pellet, the quality percentage composition of remaining tin, zinc, arsenic is respectively 0.07%, 0.031%, 0.032%.
Claims (6)
1. the method for tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore, it is characterized in that: at first by tin-zinc containing arsenic iron ore concentrate and binder formulation, mix, pelletizing after the profit mill, green-ball, after drying successively through high-temperature roasting detin in the first weakly reducing atmosphere low-temperature bake dearsenification, oxidizing atmosphere desulfurization with roasting technique, the second weakly reducing atmosphere, zinc, obtains prereduction pellet; In described the first weakly reducing atmosphere, the volumetric concentration of CO is 5%～15%, and low-temperature bake dearsenification temperature is 350 ℃～500 ℃, and roasting time is 3min～5min; O in the oxidizing atmosphere of described desulfurization with roasting technique
2volumetric concentration be 15%～19%, the temperature of controlling desulfurization with roasting technique is 600 ℃～850 ℃, roasting time is 4min～6min; In described the second weakly reducing atmosphere, the volumetric concentration of CO is 40%～50%, and the temperature of controlling roasting detin, zinc is 925 ℃～1000 ℃, and roasting time is 30min～35min.
2. the method for tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore according to claim 1, it is characterized in that: the granularity of described tin-zinc containing arsenic compound iron concentrate is more than or equal to 80% for the shared mass percent of-200 order grade.
3. the method for tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore according to claim 2, it is characterized in that: described binding agent is the coal sodium humate, and the addition of described coal sodium humate accounts for 0.5%～1.0% of Iron Concentrate Quality percentage ratio; When mill profit, the water that to add the mass percent that accounts for tin-zinc containing arsenic iron ore concentrate and coal sodium humate total amount be 5%～8%, the profit time consuming is 4min～7min.
4. the method for tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore according to claim 3, it is characterized in that: reclaim arsenic compound from low-temperature bake dearsenification flue gas, reclaim tin, zn cpds in the flue gas of therefrom high-temperature roasting detin, zinc.
5. the method for tin, zinc, arsenic in selectivity baking separation stannum-zinc-arsenic-contained complex iron ore according to claim 4, it is characterized in that: in described prereduction pellet, the quality percentage composition of remaining tin, zinc, arsenic is less than or equal to 0.075%.
6. according to the method for tin, zinc, arsenic in the described selectivity baking separation of claim 1-5 any one stannum-zinc-arsenic-contained complex iron ore, it is characterized in that: described prereduction pellet is as preparing direct-reduced iron or blast furnace ironmaking raw material.
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| CN102965522B (en) * | 2012-11-13 | 2014-06-04 | 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 |
| CN104152718B (en) * | 2014-07-21 | 2015-10-21 | 中南大学 | A kind of method of stanniferous iron tailings separated in synchronization tin and iron |
| CN105543488B (en) * | 2015-12-31 | 2017-07-21 | 耒阳市焱鑫有色金属有限公司 | A kind of method of dearsenification from high-arsenic material to reclaim wherein valuable metal |
| CN108126970A (en) * | 2017-12-29 | 2018-06-08 | 永仁共创锌业有限公司 | Industrial integrated conduct method containing Zn scrap returns |
| 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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| GB396058A (en) * | 1931-02-09 | 1933-07-26 | Ver Stahlwerke Ag | Process for eliminating arsenic and antimony from iron ores and manganese ores |
| JPS522806A (en) * | 1975-06-26 | 1977-01-10 | Kawasaki Steel Corp | Process for treatment of ironmaking dust containing zinc |
| JPH0589802A (en) * | 1991-09-25 | 1993-04-09 | Matsushita Electric Ind Co Ltd | Fixing seat mounting device linear cathode of thin type image display tube |
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| CN1924032A (en) * | 2005-09-01 | 2007-03-07 | 中南大学 | Method of producing acidic pellet ore for blast furnace from tin-zinc magnetic concentrate |
| CN1924037A (en) * | 2005-09-01 | 2007-03-07 | 中南大学 | Method of comprehensive utilizing tin-zinc containing magnetic concentrate |
| CN100404707C (en) * | 2006-08-03 | 2008-07-23 | 山东国大黄金股份有限公司 | Method of extracting gold and silver from arsenic containing aurin ore |
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