CN104060104B - Bottom blowing tin-making process - Google Patents
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- CN104060104B CN104060104B CN201410295214.6A CN201410295214A CN104060104B CN 104060104 B CN104060104 B CN 104060104B CN 201410295214 A CN201410295214 A CN 201410295214A CN 104060104 B CN104060104 B CN 104060104B
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Abstract
The present invention relates to a kind of bottom blowing tin-making process.Described bottom blowing tin-making process comprises the following steps: stanniferous material and flux are joined in the molten bath of described furnace chamber; Described Bottom Blowing Ejection Gun is utilized in described furnace chamber, to be blown into oxygen-containing gas and fuel from the bottom of described furnace chamber, to carry out melting to stanniferous material and to produce thick tin and hardhead; Reductive agent is joined in described furnace chamber, to utilize reductive agent reduce to described hardhead and obtain slag; Discharge thick tin with from described thick tin discharge outlet, discharge slag from described slag-drip opening.Have according to the bottom blowing tin-making process of the embodiment of the present invention that technique is simple, energy consumption is low, the feature of environmental protection is high, level of automation advantages of higher.
Description
Technical field
The present invention relates to technical field of non-ferrous metallurgy, especially relate to bottom blowing tin-making process.
Background technology
The technology of tin metallurgy has Tin concentrate reverberatory smelting technique, electrosmelting technique, Ausmelt melting technology, blast furnace smelting process, rotary furnace smelting technique, Kaldo Furnace tin-making process.Rotary furnace smelting technique system interruption smelting technology is because of investment, management and maintenance cost is high, exhaust gas volumn large, and fluctuation also greatly, and direct yield is low to be eliminated already.Kaldo Furnace is complicated for tiltedly blowing rotating furnace type device structure, and maintenance cost is high, and the stove longevity is short, and refractory consumption rate is large.Reverberatory furnace, due to shortcomings such as the low production efficiency of its ability are low, thermo-efficiency is low, fuel consumption is large, labour intensity is large, is reinforced just rapidly melting method and replaces.The shortcoming power consumption of electric furnace tin-smelting is too high, is only suitable for processing low iron material and the abundant area of electric power; Blast furnace smelting process requirement material needs to granulate or briquetting, and the shortcomings such as consume expensive metallurgical coke, furnace atmosphere is restive, the evaporation rate height of tin, do not re-use.Ausmelt melting belongs to strengthening molten pool melting technology, segmentation operation, and slag is stanniferous is down to lower level, but investment is large, and maintenance cost is high, and complicated operation.
Summary of the invention
The present invention is intended to solve one of technical problem in above-mentioned tin-making process correlation technique at least to a certain extent.For this reason, one object of the present invention is to propose a kind ofly have that technique is simple, energy consumption is low, the feature of environmental protection is high, the bottom blowing tin-making process of level of automation advantages of higher.
According to the embodiment of the present invention, a kind of bottom blowing tin-making process utilizing bottom blowing tin metallurgy device to implement is proposed, described bottom blowing tin metallurgy device comprises: body of heater, in described body of heater, there is furnace chamber, described body of heater have charging opening for adding material in described furnace chamber, for discharge slag slag-drip opening, for discharge thick tin thick tin discharge outlet, for discharging the smoke outlet of flue gas and being located at the spray gun jack of bottom of described body of heater; And Bottom Blowing Ejection Gun, described Bottom Blowing Ejection Gun is inserted in described spray gun jack, for being blown into oxygen-containing gas and fuel in described furnace chamber;
Described bottom blowing tin-making process comprises the following steps: stanniferous material and flux are joined in the molten bath of described furnace chamber; Described Bottom Blowing Ejection Gun is utilized in described furnace chamber, to be blown into oxygen-containing gas and fuel from the bottom of described furnace chamber, to carry out melting to stanniferous material and to produce thick tin and hardhead; Reductive agent is joined in described furnace chamber, to utilize reductive agent reduce to described hardhead and obtain slag; Discharge thick tin with from described thick tin discharge outlet, discharge slag from described slag-drip opening.
Have according to the bottom blowing tin-making process of the embodiment of the present invention that technique is simple, energy consumption is low, the feature of environmental protection is high, level of automation advantages of higher.
According to one embodiment of present invention, described oxygen-containing gas and described fuel are continuously blown in described furnace chamber.
According to one embodiment of present invention, described stanniferous material is joined in described furnace chamber discontinuously, and described thick tin and described slag are discharged discontinuously.
According to one embodiment of present invention, described bottom blowing tin-making process comprises further:
Utilize the heat that waste heat boiler reclaims the heat in the flue gas of melting generation and reduces in the flue gas of generation; With
The stanniferous flue dust utilizing dust-precipitator to reclaim the stanniferous flue dust in the flue gas of melting generation and reduce in the flue gas of generation, turns back in described furnace chamber after granulating.
According to one embodiment of present invention, the volumetric concentration of the oxygen of described oxygen-containing gas is 24%-60%.
According to one embodiment of present invention, described fuel is selected from least one in fine coal, Sweet natural gas, coke-oven gas and producer gas.
According to one embodiment of present invention, described reductive agent is beans.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 is the schematic diagram of the bottom blowing tin metallurgy device according to the embodiment of the present invention;
Fig. 2 is the transverse sectional view of the bottom blowing tin metallurgy device according to the embodiment of the present invention;
Fig. 3 is the transverse sectional view of the bottom blowing tin metallurgy device according to the embodiment of the present invention;
Fig. 4 is the schematic diagram of the projection of bottom blowing tin metallurgy device on perpendicular according to the embodiment of the present invention;
Fig. 5 is the schema of the bottom blowing tin-making process according to the embodiment of the present invention.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.
In metallurgical technology field, the difference of top blast and side-blown is not only the change of Burners Positions, and what the two reacted is diverse smelting equipment and technique.Such as, in steelmaking technical field, initial is all bottom blowing steel-making, but the top blast developed afterwards steel-making is initiative invention, diverse technology with bottom blowing, this is not simply spray gun is become top blast from bottom blowing, but embodies diverse ways and condition, is the diverse two class type of furnace and techniques.
In metallurgical technology field, adopt top blast technology still to adopt side-blown technology, the dynamic conditions of melt in stove, Melt Stirring state and reaction mechanism (reaction sequence) can be caused different.
More specifically, existing tin smelting technology is all the process based on oxidizing semlting, retailoring.But, specifically adopt any equipment to realize oxidizing semlting in practice, retailoring be problem most crucial in through engineering approaches application.The different choice of equipment is determined to the different technologies route (established technology) realizing oxidizing semlting, retailoring process, technological line will determine the advance of industrialized reliability, exploitativeness and technical indicator.The selection (i.e. the installation site of spray gun) of position of jetting is then one of problem basic, the most most crucial in equipment choice, equipment de-sign.When have selected side-blown or top blast, its smelting equipment (type of furnace) structure formation, spray gun structure, layout are diverse.
No matter to those skilled in the art, there is any technical problem in a kind of smelting device of basic forming, and no matter which kind of carries out to it and improve, this improvement all can not change the selection of its winding-up position.Therefore, to those skilled in the art, the change of Burners Positions is not conventional, an apparent selection.
And each metallic element has unique physical properties and chemical property.Therefore, smelt a kind of device of metal and technique without performing creative labour (change), can not be used for smelting another kind of metal.Such as, device and the technique of smelting tin are different from the device and technique of smelting lead completely.That is, without performing creative labour (change), cannot utilize and smelt plumbous device and technique smelting tin.
Below with reference to Fig. 1-Fig. 4, the bottom blowing tin metallurgy device 10 according to the embodiment of the present invention is described.As Figure 1-Figure 4, body of heater 101 and Bottom Blowing Ejection Gun 102 is comprised according to the bottom blowing tin metallurgy device 10 of the embodiment of the present invention.
There is in body of heater 101 furnace chamber 1011, body of heater 101 have charging opening for adding material in furnace chamber 1011, for discharge slag slag-drip opening 1013, for discharge thick tin thick tin discharge outlet 1014, for discharging the smoke outlet 1015 of flue gas and being located at the spray gun jack 1016 of bottom of body of heater 101.Bottom Blowing Ejection Gun 102 is inserted in spray gun jack, and Bottom Blowing Ejection Gun 102 for being blown into oxygen-containing gas and fuel in furnace chamber 1011.
The bottom blowing tin-making process utilizing and implement according to the bottom blowing tin metallurgy device 10 of the embodiment of the present invention is described below with reference to Fig. 5.As shown in Figure 5, comprise the following steps according to the bottom blowing tin-making process of the embodiment of the present invention:
Stanniferous material is joined in the molten bath of furnace chamber 1011;
Bottom Blowing Ejection Gun 102 is utilized in furnace chamber 1011, to be blown into oxygen-containing gas and fuel from the bottom of furnace chamber 1011, to carry out melting to stanniferous material and to produce thick tin and hardhead;
Reductive agent is joined in furnace chamber 1011, to utilize described reductive agent reduce to described hardhead and obtain slag; With
Discharge thick tin from thick tin discharge outlet 1014, discharge slag from slag-drip opening 1013.
In furnace chamber 1011, oxygen-containing gas and fuel is blown into from the bottom of furnace chamber 1011 to blow to stanniferous material by utilizing Bottom Blowing Ejection Gun 102 according to the bottom blowing tin metallurgy device 10 of the embodiment of the present invention, thus can realize melting and reduction in single bottom blowing tin metallurgy device 10, namely in single closed bottom blowing tin metallurgy device 10, blowing tin is realized, therefore good seal performance, the feature of environmental protection is high.Not only can utilize the heat content of hardhead thus fully, only need to consume less fuel when reducing hardhead and carry out additional heat, and greatly can shorten the flow process of blowing tin, simplify blowing process of tin.
Therefore, according to the bottom blowing tin metallurgy device 10 of the embodiment of the present invention, there is the advantages such as energy consumption is low, good seal performance, the feature of environmental protection are high, structure is simple, easy to operate.
Have according to the bottom blowing tin-making process of the embodiment of the present invention that technique is simple, energy consumption is low, the feature of environmental protection is high, level of automation advantages of higher.
As shown in Figure 1, in some embodiments of the invention, charging opening can comprise the first charging opening 10121 for adding stanniferous material (such as Tin concentrate) in furnace chamber 1011, for adding the second charging opening 10122 of stanniferous flue dust and the 3rd charging opening 10123 for adding reductive agent in furnace chamber 1011 in furnace chamber 1011.The structure of bottom blowing tin metallurgy device 10 can be made thus more reasonable.
Advantageously, as shown in Figure 1, body of heater 101 is rotating cylindrical horizontal reactor.By rotating furnace 101, can change and keep in repair Bottom Blowing Ejection Gun 102 easily, and the melt in the time of needing repairing emptying furnace chamber 1011.Thick tin discharge outlet 1014 can be located at the first end of cylindrical horizontal reactor, and smoke outlet 1015 can be close to the first end of cylindrical horizontal reactor, and slag-drip opening 1013 can be located at the second end of cylindrical horizontal reactor.
As shown in Figure 1, bottom blowing tin metallurgy device 10 may further include bracket 103, backing ring 104, gear ring 105 and drive unit 106.Backing ring 104 to be set on body of heater 101 and to be rotatably supported on bracket 103.Gear ring 105 is set on the outside surface of body of heater 101.Drive unit 106 is connected with gear ring 105, to drive body of heater 101 to rotate by driving gear ring 105 to rotate.
Drive unit 106 such as can comprise motor, the speed reduction unit be connected with motor, and the output shaft of speed reduction unit can install gear, and gear engages with gear ring 105 to drive gear ring 105 to rotate.Body of heater 101, under the drive of gear ring 105, bracket 103 rotates, and because body of heater 101 can rotate, is convenient to change Bottom Blowing Ejection Gun 102 and other operations.
Stanniferous material can be joined in furnace chamber 1011 discontinuously, and thick tin and slag can be discharged discontinuously.Oxygen-containing gas and fuel can be continuously blown in furnace chamber 1011.Fuel can be selected from least one in fine coal, Sweet natural gas, coke-oven gas and producer gas.
Flux can also be added in furnace chamber 1011.Described flux can be the mixture of Wingdale, quartzite, quartzite and lime.Also flux can not be added according to raw material condition.
The volumetric concentration of the oxygen of oxygen-containing gas can be 24%-60%.That is, the oxygen level of oxygen-containing gas is 24v%-60v%, and therefore, oxygen-containing gas is industrial oxygen or oxygen-rich air.
Described reductive agent can be beans.Those skilled in the art generally believe: utilize metallurgical coke can effectively reduce to hardhead as reductive agent.Contriver finds after performing creative labour through deep research: carry out compared with reduction with utilizing metallurgical coke to hardhead, beans is utilized to reduce to hardhead, the Theil indices (Theil indices in slag is less than or equal to 3wt%) in slag can be reduced further, thus direct yield and the rate of recovery of tin can be improved further.Therefore, by utilizing beans as reductive agent, overcome technology prejudice, and can reduce costs.
In examples more of the present invention, bottom blowing tin metallurgy device 10 can also comprise waste heat boiler, described waste heat boiler can be connected with smoke outlet 1015, to utilize the heat in described waste heat boiler recovered flue gas, namely utilize the heat that described waste heat boiler reclaims the heat in the flue gas of melting generation and reduces in the flue gas of generation.
Bottom blowing tin metallurgy device 10 can also comprise dust-precipitator (such as bagroom), described dust-precipitator can be connected with described waste heat boiler, to utilize the stanniferous flue dust in described dust-precipitator recovered flue gas, namely utilize the stanniferous flue dust that described dust-precipitator reclaims the stanniferous flue dust in the flue gas of melting generation and reduces in the flue gas of generation, turn back in furnace chamber 1011 after then stanniferous flue dust being granulated.
Stanniferous flue dust can join in furnace chamber 1011 by independent charging opening (such as the second charging opening 10122), also can join in furnace chamber 1011 together with stanniferous material.When starting to start bottom blowing tin metallurgy device 10, owing to not producing stanniferous flue dust, therefore stanniferous material and flux can be joined in furnace chamber 1011.After stanniferous flue dust to be generated, stanniferous flue dust, stanniferous material and flux can be joined in furnace chamber 1011.
Bottom blowing tin metallurgy device 10 may further include water cooler, and described water cooler can be connected with described waste heat boiler and described dust-precipitator can be connected with described water cooler.
As shown in Figure 1, in one embodiment of the invention, described spray gun jack can be multiple and Bottom Blowing Ejection Gun 102 can be multiple, multiple described spray gun jacks can be formed in the bottom of body of heater 101 at interval, multiple Bottom Blowing Ejection Gun 102 can be inserted in multiple described spray gun jack correspondingly, and namely a Bottom Blowing Ejection Gun 102 can be inserted in a described spray gun jack.Oxygen-containing gas and fuel can be blown in furnace chamber 1011 more equably thus.
It is to be appreciated that term " bottom " here should make broad understanding, comprise any suitable position of below the horizontal center line X of body of heater 101.Bottom Blowing Ejection Gun 102 can be located at below the horizontal center line X of body of heater 101.Preferably, Bottom Blowing Ejection Gun 102 immediately below body of heater 101, will be able to be described in more detail below.
As shown in figs 2-4, the angle α between Bottom Blowing Ejection Gun 102 and direction straight up can spend to+120 scopes spent-120, and namely-120 degree≤α≤+ 120 are spent.In other words, the angle between the emission direction of Bottom Blowing Ejection Gun 102 and direction is straight up spent to+120 scopes spent-120.As shown in figs 2-4, from the blowing direction of Bottom Blowing Ejection Gun 102 in the counterclockwise direction to the angle α in direction straight up be just, from the blowing direction of Bottom Blowing Ejection Gun 102 along clockwise direction to the angle α in direction be straight up negative.
More specifically, the angle α between Bottom Blowing Ejection Gun 102 and direction straight up can spend to+60 scopes spent-60, and namely-60 degree≤α≤+ 60 are spent.Advantageously, the angle between Bottom Blowing Ejection Gun 102 and direction is straight up spent to+30 scopes spent-30, and namely-30 degree≤α≤+ 30 are spent.Preferably, the angle between Bottom Blowing Ejection Gun 102 and direction is straight up spent to+20 scopes spent-20, and namely-20 degree≤α≤+ 20 are spent.Blowing effect can be improved thus.
In optional embodiment of the present invention, Bottom Blowing Ejection Gun 102 and be orthogonal to body of heater 101 axis direction (vertical direction namely in Fig. 1) between angle β spend in+30 scopes spent-30.More preferably, angle β is 0 degree, and namely Bottom Blowing Ejection Gun 102 is vertically directed.Wherein, vertical direction is as shown in the arrow A in Fig. 1.
In order to improve the life-span of Bottom Blowing Ejection Gun 102, between the periphery of Bottom Blowing Ejection Gun 102 and body of heater 101, be provided with gas permeable brick or the first watercooling jacket.Gas permeable brick can cool Bottom Blowing Ejection Gun 102 and can improve the mobility of the melt in furnace chamber 1011, improves blowing effect.
Optionally, nitrogen can be sprayed by gas permeable brick in furnace chamber 1011, then can cool Bottom Blowing Ejection Gun 102 better and stir the melt in furnace chamber 1011 better.When arranging watercooling jacket, watercooling jacket leads to water coolant, cools Bottom Blowing Ejection Gun 102.
Preferably, the slag blanket region of furnace chamber 1011 is provided with the second watercooling jacket.The work-ing life of body of heater 101 can be extended thus further.Preferably, the first and second watercooling jackets are copper water jacket.Compared to traditional molten steel cover, copper water jacket has the advantage such as good cooling results, long service life.
Be according to the bottom blowing tin metallurgy device 10 of the embodiment of the present invention and the technical superiority of bottom blowing tin-making process:
1, energy consumption is low: inside a stove, achieve the fusion process from tin material to thick tin, fusion process adopts industrial oxygen (carrier of oxygen volume concentrations 30%-100%), exhaust gas volumn is few, dust rate is low, adopt broken coal (beans) as reductive agent, do not need relatively costly metallurgical coke, the waste heat simultaneously in recovered flue gas.
2, environmental protection is good: Tin concentrate fusion process carries out in an airtight body of heater 101, avoid flue gas to escape, directly stove is entered after Tin concentrate or other tin raw material coordinate granulation, material preparation process is simple, in production process, the tin flue dust of output all seals and carries and return batching, effectively prevent the disperse of tin dirt; The flue gas of melting output, through waste heat recovery with after gathering dust, send desulphurization system.The thick tin of bottom convertor output is discharged from tin discharge outlet, and the slag of output is discharged from slag notch, establishes ventilating chamber simultaneously, prevent the diffusion of tin steam at tin discharge outlet and slag notch.Substantially the problem of tin flue gas during smelting, tin dust pollution is solved.
3, the rate of recovery is high: in bottom blowing tin metallurgy stove, and fusion process adopts industrial oxygen, uses broken coal to significantly reduce exhaust gas volumn and dust rate, the Theil indices reduced in slag as reductive agent, improves direct yield and the rate of recovery of tin.
4, bottom blowing sn smelting method is in all tin metallurgy methods, comprises material preparation system, the technique that flow process is the shortest, and process unit is simple, reduced investment.
In describing the invention, it will be appreciated that, term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ", " thickness ", " on ", D score, " front ", " afterwards ", " left side ", " right side ", " vertically ", " level ", " top ", " end " " interior ", " outward ", " clockwise ", " counterclockwise ", " axis ", " radial direction ", orientation or the position relationship of the instruction such as " circumference " are based on orientation shown in the drawings or position relationship, only the present invention for convenience of description and simplified characterization, instead of indicate or imply that the device of indication or element must have specific orientation, with specific azimuth configuration and operation, therefore limitation of the present invention can not be interpreted as.
In addition, term " first ", " second " only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technical characteristic.Thus, be limited with " first ", the feature of " second " can express or impliedly comprise at least one this feature.In describing the invention, the implication of " multiple " is at least two, such as two, three etc., unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, the term such as term " installation ", " being connected ", " connection ", " fixing " should be interpreted broadly, and such as, can be fixedly connected with, also can be removably connect, or integral; Can be mechanical connection, also can be electrical connection; Can be directly be connected, also indirectly can be connected by intermediary, can be the connection of two element internals or the interaction relationship of two elements, unless otherwise clear and definite restriction.For the ordinary skill in the art, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score can be that the first and second features directly contact, or the first and second features are by intermediary indirect contact.And, fisrt feature second feature " on ", " top " and " above " but fisrt feature directly over second feature or oblique upper, or only represent that fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " below " and " below " can be fisrt feature immediately below second feature or tiltedly below, or only represent that fisrt feature level height is less than second feature.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not must for be identical embodiment or example.And the specific features of description, structure, material or feature can combine in one or more embodiment in office or example in an appropriate manner.In addition, when not conflicting, the feature of the different embodiment described in this specification sheets or example and different embodiment or example can carry out combining and combining by those skilled in the art.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (4)
1. the bottom blowing tin-making process utilizing bottom blowing tin metallurgy device to implement, is characterized in that,
Described bottom blowing tin metallurgy device comprises:
Body of heater, in described body of heater, there is furnace chamber, described body of heater have charging opening for adding material in described furnace chamber, for discharge slag slag-drip opening, for discharge thick tin thick tin discharge outlet, for discharging the smoke outlet of flue gas and multiple spray gun jack being located at the bottom of described body of heater; With
Multiple Bottom Blowing Ejection Gun, multiple described Bottom Blowing Ejection Gun is inserted in multiple described spray gun jack correspondingly, for being blown into oxygen-containing gas and fuel in described furnace chamber;
Described bottom blowing tin-making process comprises the following steps:
Stanniferous material and flux are joined in the molten bath of described furnace chamber, described stanniferous material is joined in described furnace chamber discontinuously;
Multiple described Bottom Blowing Ejection Gun is utilized in described furnace chamber, to be blown into oxygen-containing gas and fuel from the bottom of described furnace chamber, to carry out melting to stanniferous material and to produce thick tin and hardhead, described oxygen-containing gas and described fuel are continuously blown in described furnace chamber, and the volumetric concentration of the oxygen of described oxygen-containing gas is 24%-60%;
Reductive agent is joined in described furnace chamber, to utilize reductive agent reduce to described hardhead and obtain slag; With
Discharge thick tin from described thick tin discharge outlet, discharge slag from described slag-drip opening, described thick tin and described slag are discharged discontinuously.
2. bottom blowing tin-making process according to claim 1, is characterized in that, comprise further:
Utilize the heat that waste heat boiler reclaims the heat in the flue gas of melting generation and reduces in the flue gas of generation; With
The stanniferous flue dust utilizing dust-precipitator to reclaim the stanniferous flue dust in the flue gas of melting generation and reduce in the flue gas of generation, turns back in described furnace chamber after granulating.
3. bottom blowing tin-making process according to claim 1 and 2, is characterized in that, described fuel is selected from least one in fine coal, Sweet natural gas, coke-oven gas and producer gas.
4. bottom blowing tin-making process according to claim 1 and 2, is characterized in that, described reductive agent is beans.
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| CN106636659A (en) * | 2016-10-17 | 2017-05-10 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for smelting tin from tin smelting powder residue |
| CN107201449B (en) * | 2017-06-08 | 2018-06-08 | 安徽省金鸿再生资源科技有限公司 | A kind of method of the recycling of waste residue containing slicker solder tin |
| CN108251660A (en) * | 2018-02-02 | 2018-07-06 | 赣州市赤鼎再生资源有限公司 | A kind of method of stanniferous abandoned mine material recycling tin |
| CN111961840B (en) * | 2020-09-01 | 2021-11-23 | 云南锡业股份有限公司锡业分公司 | Roasting treatment process of high-As high-S tin concentrate in fluidized bed roaster |
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| CN104060104A (en) | 2014-09-24 |
| CN104152715B (en) | 2016-08-24 |
| CN104152715A (en) | 2014-11-19 |
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