CN105603178B - A kind of method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin - Google Patents
A kind of method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin Download PDFInfo
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- CN105603178B CN105603178B CN201610143174.2A CN201610143174A CN105603178B CN 105603178 B CN105603178 B CN 105603178B CN 201610143174 A CN201610143174 A CN 201610143174A CN 105603178 B CN105603178 B CN 105603178B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C35/00—Master alloys for iron or steel
- C22C35/005—Master alloys for iron or steel based on iron, e.g. ferro-alloys
Abstract
The invention discloses a kind of method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, this method be Iron Ore Containing Tin is crushed, it is levigate after, with the compound additive mixing agglomeration being made of calcium carbonate, sodium carbonate, sodium sulphate, borax and sodium humate；Gained agglomerate after drying, carries out high temperature reduction roasting；For reduction roasting product successively after supercooling, crushing and is levigate, magnetic separation separation, obtains thick tin iron alloy powder；This method has the characteristics that low to ingredient requirement, tin iron comprehensive recovery is high, flow is simple, energy consumption is low, environmental-friendly, and obtained thick tin iron alloy powder can be directly as the raw material for smelting tin-containing free cutting steel and Sn-containing alloy cast iron.
Description
Technical field
The present invention relates to a kind of method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, belong to field of steel metallurgy.
Background technology
Automatic steel is by adding suitable chemical element (such as sulphur, phosphorus, lead, calcium, selenium, tellurium that can improve machinability
Deng), favourable non-metallic inclusion is formed in steel, the addition also having can dissolve in solid solution (such as ferrite) to improve its cutting
The steel alloy of property.Such steel can carry out machining with higher cutting speed and larger cutting depth.Its major advantage
It is that the resistance to cutting for making steel reduces, while the characteristic of Cutting free element in itself plays lubrication cutting tool with the compound formed
Effect, easy chip breaking, alleviates abrasion, so as to reduce the surface roughness of workpiece, improves cutter life and production efficiency.Easily
Cutting Steel is mainly used for auto industry, precision instruments industries and appliance industry.At present, lead system and resulfurizing series free cutting steel product
Utilization it is the most extensive, but lead smelt and leaded waste steel recycling fusion process in pollute the environment, make its application limited
System, some American-European countries have stopped recycling leaded auto parts and components.Tin and lead are all IVA races element, and physico-chemical property is similar, and
Tin price compared with selenium, tellurium is relatively low, in recent years the excessively inside and outside research work for having started tin-containing free cutting steel.It is generally acknowledged that containing
In tin automatic steel, control tin element content is no more than 0.05%, can reach good Cutting free index, while do not influence steel
The mechanical strength of material.In Cast Iron Production technique, there are numerous studies to show, when Theil indices are in 0.1-0.2%, tin element is to carrying
The corrosion resistance of high cast iron has obvious effect, and main cause is the formation that tin promotes cast iron medium pearlite, improves pearlite more
Divergence, meanwhile, micro tin element helps to improve the tensile strength and Brinell hardness of cast iron.Production tin-containing free cutting steel at present
And the main method of tin-containing iron is that quantitative tin is added in molten iron, and the tin added in molten iron must be high-purity
Refined tin (purity more than 99.9%).
A kind of typical difficult iron ore deposit in Iron Ore Containing Tin stone China, gross reserves is more than 500,000,000 tons, existing ore-dressing technique
Method (including magnetic separation, gravity treatment, flotation etc.) is difficult to realize the separation and recovery of tin and iron, is primarily due to tin mineral (mainly tin
Stone) and symbiosis thin with iron mineral (magnetic iron ore, bloodstone etc.) disseminated grain size, association relationship be complicated.Cassiterite is crisp at the same time, repeatedly
Crushing, argillization occurred during mill-ore-dressing practice, reduce further the recycling of tin, at present total recycling of ore-dressing practice tin
Rate is generally below 30%.Since iron phase is relatively low for the economic value of tin, in cassiterite ore dressing process, generally by red, limonite
The iron ore of type is as impurity element without considering recycling；And to the Iron Ore Containing Tin of magnetic iron ore type only with magnetic separation recovery part iron,
Theil indices in such iron ore are generally between 0.1-0.5%, it is difficult to which reaching the requirement of blast furnace process, (Sn contents are less than
0.08%).
The group of the Iron Ore Containing Tin of thermal process processing at present wants method to include sulfiding volatilization, chloridizing volatilization and reduction volatilization method.
Its primary raw material is to utilize SnS, SnCl2, SnO vaporization at high temperature characteristic, by stanniferous material and vulcanizing agent, chlorinating agent and also
Former agent carries out high-temperature roasting after mixing, fuming volatility process can be very good to realize the separation of tin ferro element, but vulcanize, chlorination
The SO that journey produces2, HCl, Cl2Environment, etching apparatus, high-temperature roasting high energy consumption, production cost height are seriously polluted Deng pernicious gas.
In conclusion the technique of existing comprehensive utilization Iron Ore Containing Tin resource is low, of high cost, seriously polluted etc. there are the rate of recovery
Problem, is badly in need of developing a kind of method of high-efficiency environment friendly comprehensive utilization Iron Ore Containing Tin resource.
The content of the invention
For the prior art to the treatment process of Iron Ore Containing Tin resource there are the defects of, to realize the height of Iron Ore Containing Tin resource
Effect, environmental protection utilization, the purpose of the invention is to provide one kind make full use of in Iron Ore Containing Tin the embedding cloth of tin-iron mine thing it is close,
Difficult characteristic is separated, using Iron Ore Containing Tin as raw material, the method that directly prepares the thick alloyed powder of tin iron, this method can obtain conduct
The thick alloyed powder of tin iron of the raw material of tin-containing free cutting steel and tin-containing iron is smelted, adequately achieves the synchronization of tin and iron valuable element
High efficiente callback.
In order to realize above-mentioned technical purpose, the present invention provides a kind of side that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin
Method, this method be Iron Ore Containing Tin is crushed, it is levigate after, with compound additive mixing agglomeration；Gained agglomerate after drying, in 900
Reduction roasting is carried out at a temperature of~1050 DEG C；Successively after supercooling, crushing and is levigate, magnetic separation separation, obtains reduction roasting product
To thick tin iron alloy powder；The compound additive is by calcium carbonate, sodium carbonate, sodium sulphate, borax and sodium humate in mass ratio 5
~10:8~12:3~5:1~2:1~2 composition.
In the prior art, due in Iron Ore Containing Tin the embedding cloth of tin-iron mine thing itself it is close, separation is difficult, conventional ore dressing-smelting
Refining process is difficult to synchronous high-efficiency and recycles tin and iron, and tin and iron recovery are low, and loss late is big.Technical scheme is abundant
Using the synchronous reduction act of tin and iron mineral in reduction process, and have between metallic tin and metallic iron compared with strong affinity
Property, with the addition of a kind of special compound additive in Iron Ore Containing Tin roasting process, on the one hand which can promote
Assemble, grow up into the synchronous reduction of tin and ferriferous oxide, and crystal grain, form thick tin ferroalloy, on the other hand can suppress also
Tin forms tin volatilization loss caused by SnO during original.The tin ferroalloy of formation can utilize the ferromagnetism feature of metallic iron, lead to
Ore grinding-magnetic separation is crossed to separate with gangue mineral, it is final to obtain the few tin ferroalloy of impurity, can be stanniferous easily directly as electric furnace smelting
The quality raw materials of Cutting Steel, Sn-containing alloy cast iron.
Preferable scheme, calcium carbonate, sodium carbonate, sodium sulphate, the quality of borax and sodium humate are respectively Iron Ore Containing Tin matter
5~10%, 8~12%, 3~5%, 1~2% and the 1~2% of amount.
Preferable scheme, the magnetic field intensity that magnetic separation separation uses is 500~1500Gs.
Preferable scheme, reduction roasting is using coal and/or natural gas as reducing agent.The dosage of reducing agent generally required
Amount is to ensure reduction process as strong reducing property atmosphere.
Preferable scheme, reduction roasting time are 60~120min.
Preferable scheme, the Iron Ore Containing Tin is after broken and levigate, granularity satisfaction -0.074mm grade quality percentages
More than 80% is accounted for than content.
Preferable scheme, Iron Ore Containing Tin are at least one of tin-iron mine raw ore, tin iron tailings, high ferro tin metallurgical slag.
Preferable scheme, the reduction roasting product is after broken and levigate, granularity satisfaction -0.074mm grade quality
Degree accounts for more than 80%.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1) technical scheme, can be from tin-iron mine raw ore, tin-iron mine ore dressing from the limitation of Iron Ore Containing Tin raw material
The low-grade Iron Ore Containing Tin raw materials such as tailing, high ferro tin metallurgical slag directly prepare the original for meeting tin-containing free cutting steel and tin-containing iron
Expect the desired thick alloy of high-grade tin iron.And in these low-grade Iron Ore Containing Tin raw materials, the embedding cloth of tin-iron mine thing is close, and separation is tired
Difficulty, is difficult to synchronous high-efficiency using traditional ore dressing-smelting process and recycles tin and iron, and tin and iron recovery are low, loss late
Greatly.
2) technical scheme employs a kind of special compound additive, and compound additive is in Iron Ore Containing Tin raw material
On the one hand the synchronous reduction of tin and ferriferous oxide can be promoted in reducing roasting process, and promote crystal grain aggregation, grow up, generated
Tin ferroalloy, another aspect compound additive can suppress tin volatilization loss caused by forming SnO in reduction process, in addition, multiple
Reduction roasting temperature can be reduced by closing additive, and reduction system is solid state reduction, and system does not have slag phase to be formed, and will not cause tin iron
Loss, at the same it is low for equipment requirements, and energy consumption is low.Be conducive to the comprehensive high-efficiency recycling (up to more than 90%) of tin and iron.It is and traditional
The middle tailing that can generally be produced in ore dressing-smelting process, metallurgical slag etc., inevitably result in the loss of tin and iron；With tin
Exemplified by ore dressing and smelting process, the tin rate of recovery of general beneficiation flowsheet is not higher than 30%, and the rate of recovery that tin is smelted generally exists
80% or so, the tin rate of recovery is only 25% or so in main-process stream.
3) technical solution of the present patent application reduces tin and the synchronous of ferriferous oxide by reduction roasting, forms tin iron and closes
Jin Hou, then separated by magnetic separation, tin iron recovery is high, and impurity is few.
4) technical scheme is easy to operate, cost is low, environmentally friendly, is conducive to industrialized production.
Embodiment
Following embodiments are intended to further illustrate present invention, rather than the protection model of limitation the claims in the present invention
Enclose.
A kind of technique that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin of the present invention is illustrated below.
Embodiment 1：
TFe grades 32.11%, the Iron Ore Containing Tin of Sn contents 0.18%, 80% is accounted for by broken, ore grinding to -0.074mm；
Additive calcium carbonate, sodium carbonate, sulfuric acid are separately added into according to the 10% of Iron Ore Containing Tin mass fraction, 10%, 3%, 1%, 2%
Sodium, borax, sodium humate, in disc balling machine pelletizing after mixing；With excessive lignite as reducing agent, reduction outside dry pelletizing
1050 DEG C of temperature, recovery time 60min；Ore grinding extremely -0.074mm accounts for 85% after the cooling of reduction roasting product, in the magnetic of 1000Gs
Intensity is selected to carry out magnetic separation.Obtain Iron grade 90.11% in the thick alloyed powder of tin iron, iron recovery 92.19%；Tin grade 0.52%,
The tin rate of recovery 92.10%.
Embodiment 2：
TFe grades 32.11%, the Iron Ore Containing Tin of Sn contents 0.18%, 85% is accounted for by broken, ore grinding to -0.074mm；
According to the 6% of Iron Ore Containing Tin mass fraction, 12%, 5%, 2%, 1% be separately added into additive calcium carbonate, sodium carbonate, sodium sulphate,
Borax, sodium humate, in disc balling machine pelletizing after mixing；With excessive bituminous coal as reducing agent, reduction temperature outside dry pelletizing
900 DEG C of degree, recovery time 120min；Ore grinding extremely -0.074mm accounts for 87% after the cooling of reduction roasting product, strong in the magnetic separation of 800Gs
Degree carries out magnetic separation.Obtain Iron grade 89.23% in the thick alloyed powder of tin iron, iron recovery 93.19%；Tin grade 0.50%, tin return
Yield 90.31%.
Embodiment 3：
TFe grades 32.11%, the Iron Ore Containing Tin of Sn contents 0.18%, 83% is accounted for by broken, ore grinding to -0.074mm；
Additive calcium carbonate, sodium carbonate, sulfuric acid are separately added into according to the 5% of Iron Ore Containing Tin mass fraction, 8%, 3%, 1.5%, 1.6%
Sodium, borax, sodium humate, briquetting is carried out after mixing；With excessive lignite as reducing agent, reduction temperature 1000 outside dry agglomerate
DEG C, recovery time 100min；Ore grinding accounts for 81% to -0.074mm after the cooling of reduction roasting product, 1500Gs magnetic separation strength into
Row magnetic separation.Obtain Iron grade 88.81% in the thick alloyed powder of tin iron, iron recovery 94.00%；Tin grade 0.50%, the tin rate of recovery
91.67%.
Embodiment 4：
TFe grades 56.31%, the tin-iron mine of Sn contents 0.41%, 83% is accounted for by broken, ore grinding to -0.074mm；Press
5%, 12%, 4.5%, 1.2%, 1.6% according to Iron Ore Containing Tin mass fraction is separately added into additive calcium carbonate, sodium carbonate, sulphur
Sour sodium, borax, sodium humate, in disc balling machine pelletizing after mixing；Gone back outside dry pelletizing with excessive lignite as reducing agent
Former 1000 DEG C of temperature, recovery time 85min；Ore grinding extremely -0.074mm accounts for 82% after the cooling of reduction roasting product, 1000Gs's
Magnetic separation strength carries out magnetic separation.Obtain Iron grade 90.09% in the thick alloyed powder of tin iron, iron recovery 92.78%；Tin grade
0.66%, the tin rate of recovery 93.19%.
Embodiment 5：
TFe grades 56.31%, the tin-iron mine of Sn contents 0.41%, 88% is accounted for by broken, ore grinding to -0.074mm；Press
5%, 10.5%, 3.5%, 1.4%, 1.6% according to Iron Ore Containing Tin mass fraction be separately added into additive calcium carbonate, sodium carbonate,
Sodium sulphate, borax, sodium humate, in disc balling machine pelletizing after mixing；With excessive lignite as reducing agent outside dry pelletizing,
1025 DEG C of reduction temperature, recovery time 90min；Ore grinding extremely -0.074mm accounts for 82% after the cooling of reduction roasting product, in 1500Gs
Magnetic separation strength carry out magnetic separation.Obtain Iron grade 91.81% in the thick alloyed powder of tin iron, iron recovery 89.12%；Tin grade
0.68%, the tin rate of recovery 90.43%.
Embodiment 6：
TFe grades 26.30%, stanniferous, the iron tailings of Sn contents 0.10%, the relatively thin -0.074mm of tailing granularity account for 91%；
According to the 10% of Iron Ore Containing Tin mass fraction, 10.5%, 3.2%, 1%, 1.8% be separately added into additive calcium carbonate, sodium carbonate,
Sodium sulphate, borax, sodium humate, in disc balling machine pelletizing after mixing；Dry pelletizing is in rotary kiln using natural gas as reduction
Agent, 1050 DEG C of reduction temperature, recovery time 75min；Ore grinding extremely -0.074mm accounts for 83% after the cooling of reduction roasting product,
The magnetic separation strength of 1200Gs carries out magnetic separation.Obtain Iron grade 91.01% in the thick alloyed powder of tin iron, iron recovery 92.91%；Tin product
Position 0.33%, the tin rate of recovery 89.12%.
Embodiment 7：
TFe grades 46.17%, stanniferous, the iron tailings of Sn contents 0.17%, the relatively thin -0.074mm of tailing granularity account for 82%；
Additive calcium carbonate, sodium carbonate, sulphur are separately added into according to the 5.5% of Iron Ore Containing Tin mass fraction, 12%, 4.5%, 2%, 2%
Sour sodium, borax, sodium humate, in disc balling machine pelletizing after mixing；Pelletizing is dried in rotary kiln using natural gas as reducing agent,
950 DEG C of reduction temperature, recovery time 70min；Ore grinding extremely -0.074mm accounts for 83% after the cooling of reduction roasting product, 1300Gs's
Magnetic separation strength carries out magnetic separation.Obtain Iron grade 89.36% in the thick alloyed powder of tin iron, iron recovery 91.21%；Tin grade
0.34%, the tin rate of recovery 95.31%.
Comparative example 1：(unused additive)
TFe grades 46.17%, stanniferous, the iron tailings of Sn contents 0.17%, the relatively thin -0.074mm of tailing granularity account for 82%；
By its pelletizing, it is dry after again in rotary kiln using natural gas as reducing agent, 950 DEG C of reduction temperature, recovery time 70min；Reduction
Ore grinding accounts for 83% to -0.074mm after product of roasting cooling, and magnetic separation is carried out in the magnetic separation strength of 1300Gs.Obtain the thick alloy of tin iron
Iron grade 78.16% in powder, iron recovery 31.01%；Tin grade 0.13%, the tin rate of recovery 25.55%.
Comparative example 2~8：
Other experimental conditions only change additive composition (mass percent for accounting for tin iron material), obtain tin with embodiment 7
The indices of the thick alloyed powder of iron see the table below shown.
By data in table as it can be seen that a kind of method that the thick alloyed powder of stanniferous iron is prepared by Iron Ore Containing Tin of the present invention, additive
The use of, composition and dosage is one of crucial governing factor, from embodiment 7 and comparative example 1~8 it can be seen that, if using adding
Add agent, the composition of additive, have a significant impact with the separation and recovery for comparing the thick alloyed powder of tin iron, composition of each additive in optimization
With can just be functioned optimally under conditions of mixture ratios.
Claims (6)
- A kind of 1. method that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, it is characterised in that：Iron Ore Containing Tin is crushed, it is levigate after, With compound additive mixing agglomeration；Gained agglomerate after drying, carries out reduction roasting at a temperature of 900~1050 DEG C；Reduction roasting Product is burnt successively after supercooling, crushing and is levigate, and magnetic separation separation, obtains thick tin iron alloy powder；The compound additive by Calcium carbonate, sodium carbonate, sodium sulphate, borax and sodium humate in mass ratio 5~10:8~12:3~5:1~2:1~2 composition；Calcium carbonate, sodium carbonate, sodium sulphate, the quality of borax and sodium humate be respectively the 5~10% of Iron Ore Containing Tin quality, 8~ 12%th, 3~5%, 1~2% and 1~2%；The Iron Ore Containing Tin is at least one of tin-iron mine raw ore, tin-iron mine milltailings, high ferro tin metallurgical slag.
- 2. the method according to claim 1 that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, it is characterised in that：The magnetic The magnetic field intensity that choosing separation uses is 500~1500Gs.
- 3. the method according to claim 1 that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, it is characterised in that：Described goes back Original roasting is using coal and/or natural gas as reducing agent.
- 4. the method according to claim 1 that the thick alloyed powder of tin iron is prepared by Iron Ore Containing Tin, it is characterised in that：Described goes back Former roasting time is 60~120min.
- 5. preparing the method for the thick alloyed powder of tin iron by Iron Ore Containing Tin according to Claims 1 to 4 any one of them, its feature exists In：For the Iron Ore Containing Tin after broken and levigate, granularity satisfaction -0.074mm grade mass percentage contents account for more than 80%.
- 6. preparing the method for the thick alloyed powder of tin iron by Iron Ore Containing Tin according to Claims 1 to 4 any one of them, its feature exists In：For the reduction roasting product after broken and levigate, granularity satisfaction -0.074mm grade mass percentage contents account for 80% More than.
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| CN106222401A (en) * | 2016-09-21 | 2016-12-14 | 内蒙古包钢钢联股份有限公司 | The preparation method of pellet |
| CN107034354B (en) * | 2017-04-28 | 2019-01-22 | 中南大学 | Additive and tin iron tailings calcification baking Separation of Tin iron method for strong permanent magnet mine type tin iron tailings calcification baking |
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