CN100352956C - Side-blown submerged smelting bath smelting process - Google Patents
Side-blown submerged smelting bath smelting process Download PDFInfo
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- CN100352956C CN100352956C CNB2006100109476A CN200610010947A CN100352956C CN 100352956 C CN100352956 C CN 100352956C CN B2006100109476 A CNB2006100109476 A CN B2006100109476A CN 200610010947 A CN200610010947 A CN 200610010947A CN 100352956 C CN100352956 C CN 100352956C
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Abstract
The present invention relates to a smelting method for a side blowing submerged smelting bath. Raw materials and fluxing agents are proportioned according to the silicate degree (0.75 to 1.35) of furnace slag, wherein the raw materials contain tin containing materials of which the grain size is less than 30mm and the tin containing weight percent is 2 to 74 percent, and the fluxing agents contain quartz stone of which the weight percent containing SiO2 is more than or is equal to 86 percent, limestone of which the weight percent containing CaO is more than 50 percent, iron ore of which the weight percent containing Fe is more than 48 percent, and iron ore of which the grain size of the fluxing agents is less than 20 percent; the raw materials and the fluxing agents are added in a material mixing device and are evenly mixed to be added to a smelting furnace of a side blowing submerged smelting bath, and the two-step reduction smelting is carried out. Crude tin and furnace slag are obtained. The furnace slag is smelted through sulfiding volatilization, and waste slag containing less than 0.2 percent of Sn and tin smoke containing less than 45 percent of Sn are obtained after the depletion smelting of tin furnace slag is carried out. The method is smelting technology which integrates crude tin smelting with tin furnace slag depletion. The melting technology is integrally formed through the characteristics of reduction smelting technology and smoke volatilizing technology. The present invention has the characteristics of equipment investment saving, short technological process, low production cost, convenient control by a computer, etc.
Description
(1) technical field: the present invention relates to a kind of pyrometallurgical smelting process of non-ferrous metal, belong to the nonferrous smelting technical field.
(2) background technology: in the slightly refining process of pyrogenic process of tin, the melting method that uses has two classes at present: a class is with the retailoring of tin concentrate, the fusion process of thick tin metal of output and stanniferous slag, the common name reducing smelting process, the Australia Si Maite smelting process that traditional reverberatory furnace reducing smelting process, electric furnace smelting process and modern metallurgical intensified smelting technology are arranged of widespread usage etc.; Another kind of is to handle stanniferous materials such as low-grade tin slag or chats, the smelting process of output stanniferous flue dust and waste, widespread usage be fuming furnace sulfiding volatilization method.
When the reverberatory furnace reducing smelting process is handled the tin concentrate, be that flame passes through from the furnace charge surface, reaches the purpose of melting materials capable by the radiative transfer mode with in the static siege that places reverberatory furnace of material.Reverberatory furnace has become the major equipment of tin metallurgy at present, and it produces the tin amount and accounts for 60～70% of Gross World Product.The major advantage of tin concentrate reverberatory furnace reducing smelting process: the one, strong to the adaptability of raw material, promptly granularity and the moisture to concentrate does not have particular requirement; The 2nd, fuel there is not particular requirement; The 3rd, less investment, simple to operate; The 4th, material remains static in the fusion process, so the dust rate of reverberatory furnace only is 12～14%.But as retailoring technology, the shortcoming of reverberatory furnace reducing smelting process also is conspicuous: the one, because the radiative transfer mode, so its thermo-efficiency only is 20～30%, thereby the fuel consumption height; The 2nd, mechanization degree is low, and labour intensity is big; The 3rd, the flue gas uncontrollable discharge is serious, and is big for environment pollution; The 4th, floor space is big, and refractory consumption rate is big; The 5th, processing power is low, only is 1～1.4t/m
2D.
Electric furnace smelting process mainly is to use arc resistance furnace, electric current is that the electrode by direct insertion slag infeeds the molten bath, rely on electrode and slag contact position to produce electric arc, and electric current is by furnace charge and slag heating carrying out retailoring, 10% of the tin ultimate production produced by electric furnace smelting process in the world at present.Electric furnace smelting process has following characteristics: the one, under the effect of virtual resistance, electric energy directly changes heat energy in the molten bath, the thermo-efficiency height, thereby obtain higher and concentrated furnace temperature easily, the concentrate many to refractory metals such as melting tungstenic, tantalum and niobiums have more advantage; The 2nd, electrosmelting seals substantially, can keep higher carbon monoxide concentration in the stove, and reducing atmosphere is strong, therefore general the low iron material of suitable treatment; The 3rd, the exhaust gas volumn that produces during the identical furnace charge of melting only for 1/16～1/18 of reverberatory furnace, has reduced metal loss, has simplified dust collecting system; The 4th, slag stanniferous lower (3% ±), the direct yield height of tin.But, influenced being extensive use of in large-scale tin-smelting plant owing to reasons such as power consumption height.
The essence of Australia Si Maite (Ausmelt) smelting process is: with the concentric spray gun of a root multi-layer, among the melt in the top insertion burner hearth, air and fuel spray into melt from the spray gun end, in stove, cause a weld pool surface that seethes, furnace charge is directly added by the top feeding mouth among the molten bath, by adjusting the coal-air ratio example of supplying with spray gun, controls smelting temperature and reducing atmosphere in the stove, reach the purpose of the thick tin of melting, so it is referred to as " top-blown submergence spray gun " smelting technique.Yunnan Tin Industrial Corp. in 2000 introduces Australia Si Maite stove smelting technique and has built up 60000 tons of tin concentrate of processing, the Production Flow Chart of producing 25000 tons of refined tins.Its Australia Si Maite stove overall dimensions are Φ 4200*9500mm, size of burner hearth Φ 3400*9000mm, molten bath area 9m
2The advantage of Australia Si Maite smelting process: the one, the furnace charge form there is not particular requirement, furnace charge preparation work is simple; The 2nd, total system is in air-tight state, is convenient to the processing to flue gas, and environmental pollution is little; The 3rd, spray gun directly inserts the melt internal heating, so thermo-efficiency is up to 40～60%; The 4th, smelting intensity is big, and processing power can reach 18～20t/m
2D.But the defective of Australia Si Maite smelting process is also very outstanding: the one, and facility investment is big, and Australia's Si Maite furnace project of Yunnan Tin Industrial Corp. is invested nearly 200,000,000 yuan, and medium-sized and small enterprises are difficult to carry out; The 2nd, spray gun is wanted VTOL (vertical take off and landing), so power house is up to 56m, and capital construction investment is big; The 3rd, because melt is in the intensive whipped state, the refractory corrosion of body of heater is serious, and will change half a year, influence cost and operating rate; The 4th, because spray gun is that cooling intensity is limited by the sleeve air cooling,, easily to be corroded by high-temperature fusant so spray gun inserts the part of melt, the spray gun maintenance is frequent, will repair once in 8～12 hours; The 5th, owing to the mode that adopts from the furnace roof charging, the feeding platform absolute altitude reaches 20m, and energy consumption increases; The 6th, furnace charge drop in stove reaches 9m, and furnace charge and flue gas are antikinesises, and a lot of particulate furnace charges are also failed to arrive the molten bath and just brought into dust collecting system by flue gas, thus dust rate up to more than 25%, thereby reduced direct recovery rate.The 7th, because the blower pressure selected for use is up to 0.24MPa, and spray gun will often propose stove and overhaul outward, thereby noise of equipment reaches more than 90 decibels.
Because tin is smelted, by the tin slag of above melting method output, stanniferous 3～25% does not reach the degree that can abandon, therefore must carry out dilution to the tin slag, with further recovery tin wherein.At present the method for depleted tin slag has two kinds, and a kind of is the secondary reduction smelting process that adopts reverberatory furnace or blast furnace, promptly adds more reductive agent in the tin slag, makes the tin reductive simultaneously, and iron also reduces, output ferro-tin alloy and reclaim tin.But the waste stanniferous of this method generally all reaches 2～5%, and effect is not very good; Another kind is low-grade tin slag (Sn10% ±) to be carried out fuming furnace sulfiding volatilization method handle, and waste contains Sn＜0.2%.Second stage of the thick refining of tin that Here it is, i.e. the dilution stage of tin slag.
Fuming furnace sulfiding volatilization method just put forward as far back as 1930's, it is the volatile characteristics of sulfide of utilizing non-ferrous metal such as tin, lead in the material, in the time of 1150～1280 ℃, under the condition that adds vulcanizing agent, non-ferrous metals such as tin are enriched in the flue dust with the form volatilization of sulfide.Yunnan Tin Industrial Corp. adopted fuming furnace sulfiding volatilization method to handle the success of tin slag in 1963, adopted fuming furnace sulfiding volatilization method to handle the medium tin ore success again in 1972.So just broken through the traditional ore dressing and the limitation of metallurgical technology, solved the contradiction of ore dressing and smelting concentrate grade, the rate of recovery, made the smelting total yield that selects of Yunnan Tin Industrial Corp.'s tin improve 10%.Fuming furnace sulfiding volatilization method has become effective technology of handling multiple stanniferous material, as medium tin ore, stanniferous slag, flue dust and hardhead etc., handle as long as stanniferous can carry out fuming furnace sulfiding volatilization method at the material more than 2%, and final waste contains Sn＜0.2%.
In sum, what retailoring such as reverberatory smelting method and Australia Si Maite smelting process were handled is the tin concentrate, output be thick tin metal and stanniferous slag; Fuming furnace sulfiding volatilization method is handled is low-tin material such as stanniferous slag, output be tin flue dust and waste, the tin flue dust returns reducing and smelting furnace and makes raw material.The function and the mission of these two kinds of melting technologies have nothing in common with each other, and be interdependent each other, indispensable, all is essential melting technology and the equipment that is equipped with in the slightly refining process of tin.Reducing smelting process such as reverberatory furnace and fuming furnace sulfiding volatilization method can only be finished the function of half separately, so the thick sweetening process long flow path of existing tin, facility investment is big, the smelting cost height, and intermediates overstock many, and current assets takies greatly.
(3) summary of the invention:
1, goal of the invention:
The invention provides a kind of side-blown submerged smelting bath smelting process, be a melting technology that integrates thick tin of melting and depleted tin slag, promptly in same metallurgical equipment, can the thick tin metal of retailoring output, can carry out sulfiding volatilization again is the depleted tin slag process, the tin slag can be reached abandon.By the bath smelting feature is carried out integrated integration with fuming volatilization feature, integrated integration is carried out in these two kinds of melting technology process control, this melting technology that research and design goes out, the function that replaces above-mentioned two kinds of smelting processes is to realize low equipment investment, targets such as technical process is short, production cost is low, convenient computer control.
2, summary of the invention:
The present invention is to be that disclosed name is called in " side-blown submerged bath smelting furnace " (hereinafter to be referred as side-blown converter) substep and finishes in 200520100035.9 at the applicant's application number.
(1) the composition structure of side-blown converter:
As shown in Figure 1, comprise opening for feed 1, melt cinder opening for feed 2, spray gun 3, put metal mouth 4, chute 5, movable external crucible 6, slag notch 7, slag chute 8, furnace water jacket 9, funnel uptake 10, furnace bottom refractory brick 11, furnace bottom water jacket 12 and screw block supporting 13.Furnace shell is all assembled by water jacket, opening for feed is positioned on the stove end water jacket, from bath surface height 1.2～1.6m, its diameter 80～120mm, become 30～50 degree angles with vertical line, spray gun is installed in along on the orlop water jacket of stove length direction, the two sides symmetry is installed, from furnace bottom height 300～600mm, gun slot tilts to furnace bottom, and following oblique angle β is 0～6 degree, the spray gun internal diameter is 20～40mm, spacing 180～280mm between the spray gun, it is equal with furnace bottom to put the metal mouth, to guarantee to enter before the sulfiding volatilization operation, can all emit the metal in the stove, slag notch is positioned at the opposite of putting the metal mouth, and apart from the high 200～500mm of furnace bottom, funnel uptake is arranged on the molten bath longitudinal cenlerline by slag notch on one side, put the metal mouth, chute, movable external crucible and slag notch, slag chute and molten bath are in together on the cross central line, the furnace bottom water jacket lies in a horizontal plane in the screw block supporting, the weight of bearing body of heater, hearth area 1～14m
2, processing power is 15～21t/m
2D.
(2), processing condition:
1) raw material: various stanniferous materials comprise the stanniferous material of granularity＜30mm, stanniferous weight percent 2～74%;
2) flux: comprise containing SiO
2The quartzite of weight percent 〉=86%, granularity＜20mm contains the Wingdale of CaO weight percent＞50%, granularity＜20mm, contains the iron ore of Fe weight percent＞48%, granularity＜20mm;
3) batching: slag silicate degree 0.75～1.35 is determined ratio of components;
4) blast: 0.03～0.08MPa;
5) air quantity: 30～40Nm
3/ m
2Min;
6) fine coal consumption: 4.66～8.2Kg/m
2Min;
7) smelting temperature: 1100～1350 ℃;
8) melt bed depth: 600mm～1400mm;
9) gun slot diameter: 20～40mm;
10) excess air coefficient: 0.7～0.95;
11) the siege ability of side-blown converter: 15～21t/m
2D;
12) melting cycle of every stove: 3～6h;
13) the melting inventory of every stove: 3～6t/ (m
2Heat);
(3) material preparation and blow-on:
With various stanniferous materials, comprise various stanniferous materials and the flux of stanniferous 2～74%, granularity＜30mm, comprise containing SiO
2〉=86%, the quartzite of granularity＜20mm contains the Wingdale of CaO＞50%, granularity＜20mm and contains the iron ore of Fe＞48%, granularity＜20mm, press slag silicate degree 0.75～1.35 and determines ratio of components, adds even batch mixing in the blending device.Because " side-blown submerged smelting bath smelting process " is a molten bath intensified smelting process, so the melt that must have 100～200mm degree of depth before fusion process begins in the regular furnace run, is to go up the waste that one-period stays.First blow-on then should add dried slag or high scruff, drops into timber, coke or heavy oil in stove, makes it fusing in the heating of material surface, when having formed the melt of 100～200mm degree of depth, sprays into fine coal, promptly enters the normal smelting stage.
(4) melting operation divided for three steps carried out in side-blown converter:
The first step, weak retailoring process: the material that mixes is evenly added in the side-blown converter continuously, and add-on can in time melt with material, and not accumulating raw material is principle, and promptly feeding rate and melting rate adapt.Control blast 0.03～0.08MPa, air quantity 30～35Nm
3/ m
2Min, fine coal consumption 4.66～6.9kg/m
2Min, smelting temperature 1100-1200 ℃; Furnace charge constantly melts, and reduction reaction generates metallic tin and gathers at furnace bottom, forms the metallic tin liquid layer.When melt bed depth during, stop charging to 600mm～1400mm.Afterwards, per 40～60 minutes put tin once, treat that furnace bottom metal tin liquor has been put after, promptly finished weak retailoring process, this process is actually furnace charge fusing of margin limit reductive process, the thick tin of output iron content weight percent＜1% and the slag of stanniferous weight percent 10～25%.
The main chemical reactions of weak retailoring process is:
SnO
2+C＝Sn+CO
2
SnO
2+2CO＝Sn+2CO
2
In second step, strong retailoring process: be that slag to stanniferous 10～25% carries out strong retailoring, this process is to strengthen the fine coal amount of feeding, and strengthens retailoring atmosphere, makes that SnO further reduces in the slag.Control blast 0.06～0.08MPa, air quantity 35～38Nm
3/ m
2Min, fine coal consumption 5.2～8.2kg/m
2Min, smelting temperature 1200-1300 ℃.The strong retailoring activity duration is 20～40 minutes, opens to put Xi Kou and emit the metal tin liquor, promptly finishes strong retailoring process, this process output iron content weight percent＞5% the thick tin and the slag of stanniferous weight percent 3～8%.The main chemical reactions of strong reducing and smelting process is:
SnO
2+2CO＝Sn+2CO
2
The present invention can reach means such as repeatedly emitting metal by adjusting air excess amount, fine coal adding speed, reaches the purpose of control molecular balance and speed, thereby has reduced the content of tin in the slag.
In the 3rd step, the sulfiding volatilization process: being that slag to stanniferous amount 3～8% carries out sulfiding volatilization and handles, is the dilution process of tin slag.Control blast 0.06～0.08MPa, air quantity 36～40Nm
3/ m
2Min, fine coal consumption 6.2～8.2kg/m
2Min, smelting temperature 1250-1340 ℃, every stove adds pyrite and make vulcanizing agent to scruff, and the vulcanizing agent add-on is Sn=0.54～0.6 in the S/ slag in the pyrite, and SnO and Sn in the slag are volatilized with the SnS form.The SnS instability, very fast oxidation by air again, in dust-precipitator with SnO
2The form output.Watch flue gas to become limpid when transparent from vision slit, get final product sampling analysis, when slag contains Sn weight percent＜0.2%, become waste, then be the terminal point of sulfiding volatilization.The tin flue dust contains Sn weight percent＞45% and returns reducing and smelting furnace and make raw material, abandons after the waste shrend, the waste melt of 100～200mm degree of depth is stayed in the molten bath, as the bed material in next campaign.
The main chemical reactions of sulfiding volatilization process is:
3SnO
2+4FeS＝4FeO+3SnS+SO
2
SnO+SO
2+3CO＝SnS+3CO
2
SnS+2O
2＝SnO
2+SO
2
Above-mentioned three smelting processes are melting cycle of the present invention, and each cycle needs 3～6 hours.
3, the present invention compares with the thick sweetening process flow process of known tin, has the following advantages and positively effect:
1), the present invention collects the thick tin of melting and two kinds of pyrometallurgical smelting processes of depleted tin slag in same body of heater, simplified thick tin smelter process flow; Productive expense such as fuel consumption, the number of working processes significantly reduces, and tin is smelted production cost can reduce by 20～40%; With two cover smelting furnace system simplifications is a cover smelting furnace system, has saved facility investment.
2), the smelting intensity height, processing power can reach 15t/m
2More than the d, exceed 10～12 times than the processing power of reverberatory smelting method, suitable with the processing power of Australia Si Maite smelting process; Under the situation of same treatment amount, to compare with reverberatory smelting method and other smelting process, occupation area of equipment is little.
3), side-blown spray gun is evenly distributed, and just has a top-blown spray gun to compare with the molten bath of Australia Si Maite smelting process, smelting temperature and atmosphere in the stove more easy to control; Its side-blown spray gun is that the water jacket that passes the furnace side enters the molten bath; because the protection of water coolant is arranged; so the part dross protection automatically of spray gun contact melt, it can not corroded by high-temperature fusant as the spray gun of Australia Si Maite smelting process, thereby has exempted the maintenance of spray gun.
4), adopt the furnace side charging, the absolute altitude of feeding platform has only 5～6m, thereby has reduced energy consumption; Reduced the antikinesis of material and flue gas, so its dust rate has reduced by 6～8% than Australia's Si Maite smelting process.
5), side-blown spray gun is to be fixed on the furnace water jacket, thereby installs simple and directly, easy to operate, the highest the need 12～14m in workshop just can satisfy processing requirement, thereby reduced construction costs; Body of heater is made up of watercooling jacket or steam jacket, and the water jacket inwall is welded with the dross fourth, behind the material melting, and the automatic dross 20～40mm of wall energy in the water jacket, the thermal conductivity of this solid-state shell is about 0.06W/cm
2K is equivalent to pure Al
2O
3Thermal conductivity, it has not only protected the water jacket steel plate not to be subjected to the corrosion of high-temperature slag, has also reduced thermosteresis, has strengthened hot running balance in the stove, so " side-blown submerged smelting bath smelting process " do not consume valuable refractory materials.
6), the blast selected for use is 0.03～0.08MPa, and spray gun is to be fixed on the water jacket of furnace side, the spray gun outlet is submerged among the melt during melting, so the noise of production scene is less than 70 decibels.
7), furnace binding is simple, easy to operate, so its computer controlled automatic is more more terse than Australia Si Maite smelting process.Operating machine degree height can reduce operator significantly, raises labour productivity.
In sum, on thick tin melting link, both bring into play the high characteristics of Australia Si Maite smelting process smelting intensity, overcome the defective of Australia Si Maite smelting process again; On the link of depleted tin slag, " side-blown submerged smelting bath smelting process " inherited the advantage of fuming furnace sulfiding volatilization method again, and these two kinds complete dissimilar equipment and smelting technology are organically combined together.
(4) description of drawings: Fig. 1 is that the body of heater of " side-blown submerged bath smelting furnace " is formed structural representation.
Among the figure: 1 opening for feed, 2 melt cinder imports, 3 side-blown spray guns, 4 are put Xi Kou, 5 tin chutes, 6 portable external crucibles, 7 slag notch, 8 slag chutes, 9 furnace water jackets, 10 funnel uptakes, 11 furnace bottom refractory brick, 12 furnace bottom water jackets, the supporting of 13 screw block.
(5) embodiment
Embodiment one: carry out in vertical rectangular side blown converter.
1. vertical rectangular side blown converter design variable: hearth area 4.0m
2, the high 7.2m of stove, processing power 17t/m
2D, gun slot diameter 32mm, 16 of spray gun quantity, the oblique angle is 0 ° under the spray gun, spray gun width between centers 280mm, spray gun burning capacity 1118～1968kg/h, fuel is fine coal.
2. material preparation and blow-on:
To contain Sn42% tin concentrate and tin material, contain SiO
288% quartz sand, contain CaO53% Wingdale and returning charge flue dust, press slag silicate degree 0.95～1.25 and determine ratio of components, add in the blending device evenly batch mixing.Add 1.8 tons of dried slags, drop into timber in stove, insert interim spray bar from slag notch, the heavy oil amount is 100～226kg/h, igniting back control blast 0.04～0.06Mpa, air quantity 2600～3000Nm
3/ h makes it fusing in the heating of material surface, when having formed the melt of the 200mm degree of depth, removes interim spray bar, sprays into fine coal, promptly enters the normal smelting stage;
3. melting operation divided for three steps carried out:
The first step, weak retailoring process: the material that mixes is added in the vertical rectangular side blown converter continuously control blast 0.03～0.06MPa, air quantity 7200～8400Nm
3/ h, fine coal consumption 1120～1656kg/h, 1140～1180 ℃ of smelting temperatures, furnace charge constantly melts, and reduction reaction generates metallic tin and gathers at furnace bottom, forms the metallic tin liquid layer.When molten bath bed depth during, stop charging to 1200mm.Put tin once every 40 minutes afterwards, after 2 hours, furnace bottom metal tin liquor has been put, promptly finish weak retailoring process.The slag of output stanniferous weight percent 10～15% and the thick tin of iron content weight percent＜1%, this thick tin is best in quality, can directly enter rectification systems and produce refined tin.
Second step, strong retailoring process: be that slag to stanniferous 10～15% carries out strong retailoring, control blast 0.06～0.08MPa, air quantity 8400～9120Nm
3/ h, fine coal consumption 1288～1968kg/h, 1240～1270 ℃ of smelting temperatures, the strong retailoring activity duration is 20～40 minutes, furnace bottom metal tin liquor has been put, promptly finish strong retailoring process, this process output iron content weight percent＞5% the thick tin and the slag of stanniferous weight percent 3～7%.
The 3rd step, sulfiding volatilization process: be that slag to stanniferous 3～7% carries out the sulfiding volatilization melting, control blast 0.06～0.08MPa, air quantity 8640～9600Nm
3/ h, fine coal consumption 1488～1968kg/h, 1300～1340 ℃ of smelting temperatures, every stove adds the pyrite that contains S＞30% and make vulcanizing agent to slag, the pyrite add-on is controlled by weight S/Sn=0.6, makes SnO in the slag and Sn with the volatilization of SnS form, in dust-precipitator with SnO
2Form output, sulfiding volatilization process continue 40～60 minutes, watch flue gas to become limpid when transparent from vision slit, get final product sampling analysis, when sample contains Sn weight percent＜0.2%, become waste, then are the terminal point of sulfiding volatilization.The tin flue dust contains Sn weight percent＞45% and returns reducing and smelting furnace and make raw material, abandons after the waste shrend.The waste melt of the 200mm degree of depth is stayed in the molten bath, as the bed material in next campaign.
4. the key technical indexes:
Fuel combustion heat utilization efficiency 〉=60%;
Tin recovery rate 〉=70%;
Tin is gone into dust rate≤12%;
Waste tin grade≤0.2%;
Embodiment two
1. vertical rectangular side blown converter design variable: hearth area 2.2m
2, the high 6.2m of stove, siege ability 18t/m
2D, gun slot diameter 40mm, 8 of spray gun quantity, the oblique angle is 4 ° under the spray gun, and spray gun width between centers 280mm, spray gun burning capacity are 558～991kg/h, and fuel is fine coal.
2. material preparation and blow-on:
To contain Sn72% the tin concentrate, contain SiO
288% quartz, contain the CaO53% Wingdale, contain materials such as the iron ore of Fe48% and returning charge flue dust, press slag silicate degree 0.75～0.9 and determine ratio of components, add in the blending device evenly batch mixing, left the melt of the 200mm degree of depth in the stove.
3. melting operation divided for three steps carried out:
The first step, weak retailoring process: control blast 0.03～0.08MPa, air quantity 3960～4620Nm
3/ h, fine coal consumption 615～910kg/h, 1140～1180 ℃ of smelting temperatures when molten bath bed depth during to 1400mm, stop charging.Put tin once every 40 minutes afterwards, after 2 hours, furnace bottom metal tin liquor has been put.
The slag stanniferous amount that weak retailoring process is produced is 20～25%, and thick tin iron content＜1% is best in quality, can directly enter rectification systems.
Second step, strong retailoring process: be that slag to stanniferous 20～25% carries out strong retailoring, control blast 0.06～0.08MPa, air quantity 4620～5016Nm
3/ h, coal amount 686～1082kg/h, 1240～1270 ℃ of smelting temperatures, the strong retailoring activity duration is 20～40 minutes, the thick tin of this process output iron content＞5% and the slag of stanniferous 5～8%.
The 3rd step, sulfiding volatilization process: be that slag to stanniferous 5～8% carries out sulfiding volatilization, control blast 0.06～0.08MPa, air quantity 4752～5280Nm
3/ h, fine coal consumption 818～1082kg/h, smelting temperature 1260-1340 ℃, every stove adds the pyrite that contains S＞30% and makes vulcanizing agent, the pyrite add-on is controlled by weight S/Sn=0.55, the sulfiding volatilization process continues 40～60 minutes, and output contains Sn＜0.2% waste and contains the tin flue dust of Sn＞45%.Abandon after the waste shrend, the waste melt of the 200mm degree of depth is stayed in the molten bath, as the bed material in next campaign.
4. the key technical indexes:
Fuel combustion heat utilization efficiency 〉=60%;
Tin recovery rate 〉=80%;
Tin is gone into dust rate≤12%;
Waste tin grade≤0.2%;
Embodiment three
1. vertical rectangular side blown converter design variable:
Hearth area 14.0m
2, the high 9.2m of stove, siege ability 18t/m
2D, gun slot diameter 32mm, 56 of spray gun quantity, the oblique angle is 2 ° under the spray gun, and spray gun width between centers 280mm, spray gun burning capacity are 3914～6888kg/h, and fuel is fine coal.
2. material preparation and blow-on:
(1) will contain in three kinds of medium tin ore, stanniferous 10～15% tin flue dust, stanniferous 10～15% all kinds of scruffs of Sn10～15% one or more, contain SiO
288% quartz contains the Wingdale of CaO53% and contains the iron ore of Fe48%, press slag silicate degree 0.75～0.9 and determines ratio of components, is uniformly mixed into material in the adding blending device.
(2) will contain Sn45～60% tin flue dust, contain Sn25～35% fuming furnace quick ash, making granularity＜30mm pellet stores up standby, with stanniferous 15～25% all kinds of scruffs also be broken into the classification of granularity＜30mm store up standby, and strong retailoring process produce in the four kinds of raw materials of ferro-tin alloy that contain Sn＞55% one or more and contain SiO
288% quartz contains the Wingdale of CaO53%, press slag silicate degree 0.75～1.25 batching after, add in the blending device and be uniformly mixed into material.。
(3) will contain the medium tin ore of Sn3～5%, stanniferous 5～10% stanniferous flue dust, one or more in stanniferous 2～5% all kinds of scruffs with contain SiO
288% quartz contains the Wingdale of CaO53% and contains the iron ore of Fe48%, press slag silicate degree 0.75～0.9 batching, is uniformly mixed into material in the adding blending device.
3. melting operation divided for three steps carried out:
The first step, weak retailoring process: the material (1) or (2) that mix are added in the vertical rectangle stove of side-blown submerged bath smelting continuously control blast 0.03～0.06MPa, fine coal consumption 26000～29400Nm
3/ h, coal amount 4000～5796kg/h, 1140～1180 ℃ of smelting temperatures when melt bed depth during to 1200mm, stop charging.Put tin once every 30-40 minute afterwards, after 2 hours, furnace bottom metal tin liquor has been put, promptly finish weak retailoring process, the thick tin of output iron content＜1% and the slag of stanniferous 5～7%.
Second step, strong retailoring process: be that slag to stanniferous 5～7% carries out strong retailoring, control blast 0.06～0.08MPa, air quantity 29400～32000Nm
3/ h, fine coal consumption 4368～6888kg/h, 1240～1270 ℃ of smelting temperatures, the strong retailoring activity duration is 20～40 minutes.The thick tin of this process output stanniferous＞55% and the slag of stanniferous 3～5%.
The 3rd step, sulfiding volatilization process: be that slag to stanniferous 3～5% carries out the sulfiding volatilization melting, control blast 0.06～0.08MPa, air quantity 30240～33600Nm
3/ h, fine coal consumption 5208～6888kg/h, 1300～1340 ℃ of smelting temperatures, add the material (3) that mixes in the stove continuously, when melt bed depth during to 1400mm, stop charging, after treating that material all melts in the stove, every stove adds in the pyritic cinders that contains S＞30% makes vulcanizing agent, the pyrite add-on is controlled by weight S/Sn=0.6, and the sulfiding volatilization process continues 40～60 minutes, obtains waste and the tin flue dust that contains Sn＞45%, tin flue dust Returning smelting stove is made raw material, abandons after the waste shrend.The waste melt of the 200mm degree of depth is stayed in the molten bath, as the bed material in next campaign.
4. the key technical indexes:
Fuel combustion heat utilization efficiency 〉=60%;
Tin recovery rate 〉=60%;
Tin is gone into dust rate≤36%;
Waste tin grade≤0.2%;
Claims (8)
1, a kind of side-blown submerged smelting bath smelting process, it is characterized in that: it is finished according to the following steps,
1), will contain tin raw material and flux by slag silicate degree 0.75～1.35 batching, add in the blending device and be uniformly mixed into material;
2), melting operation divided for three steps carried out in side-blown converter, the first step evenly adds side-blown converter continuously with the material that mixes and has formed in the molten bath of melt of 100～200mm degree of depth and carry out weak retailoring, control blast 0.03～0.08MPa, air quantity 30～35Nm
3/ m
2Min, fine coal consumption 4.66～6.9kg/m
2Min, smelting temperature 1100-1200 ℃; Furnace charge constantly melts, reduction reaction generates metallic tin and gathers at furnace bottom, form the metallic tin liquid layer, when melt bed depth during, stop charging, afterwards to 600mm～1400mm, per 40～60 minutes put tin once, after treating that furnace bottom metal tin liquor has been put, promptly finished weak retailoring process, the thick tin of output iron content weight percent＜1% and the slag of stanniferous weight percent 10～25%;
3), second step, be that the slag to stanniferous 10～25% carries out strong retailoring, control blast 0.06～0.08MPa, air quantity 35～38Nm
3/ m
2Min, fine coal consumption 5.2～8.2kg/m
2Min, smelting temperature 1200-1300 ℃, the melting operation time is 20～40 minutes, the thick tin of output iron content weight percent＞5% and the slag of stanniferous weight percent 3～8%;
4), the 3rd step is for the sulfiding volatilization process, is that slag to stanniferous amount 3～8% carries out sulfiding volatilization and handles control blast 0.06～0.08MPa, air quantity 36～40Nm
3/ m
2Min, fine coal consumption 6.2～8.2kg/m
2Min, smelting temperature 1250-1340 ℃, every stove adds pyrite and make vulcanizing agent to scruff, the vulcanizing agent add-on is pressed in the pyrite Sn=0.54 in the S/ slag～0.6 and is calculated, and when slag contains Sn weight percent＜0.2%, becomes waste, then for the terminal point of sulfiding volatilization, output contains the tin flue dust of Sn weight percent＞45% and contains the waste of Sn weight percent＜0.2%, finishes a melting cycle, always takes time 3～6 hours.
2, side-blown submerged smelting bath smelting process according to claim 1 is characterized in that: describedly contain the material that tin raw material is granularity＜30mm, stanniferous weight percent 2～74%, comprise the tin concentrate, medium tin ore, tin flue dust, all kinds of scruffs and fuming furnace quick ash.
3, side-blown submerged smelting bath smelting process according to claim 1 and 2 is characterized in that: described flux is for containing SiO
2The quartzite of weight percent 〉=86%, granularity＜20mm contains the Wingdale of CaO weight percent＞50%, granularity＜20mm, contains the iron ore of Fe weight percent＞48%, granularity＜20mm.
4, side-blown submerged smelting bath smelting process according to claim 1, it is characterized in that: the melt that has formed 100～200mm degree of depth in the described side-blown converter molten bath is to add dried slag or high scruff when going up waste that one-period stays or first blow-on, in stove, drop into timber, coke or heavy oil, make it fusing in the heating of material surface, formed the melt of 100～200mm degree of depth.
5, side-blown submerged smelting bath smelting process according to claim 1 is characterized in that: described vulcanizing agent is the pyrite that contains S＞30%.
6, side-blown submerged smelting bath smelting process according to claim 1 is characterized in that: described raw material is to contain the tin concentrate of Sn42% and tin material, described flux for containing SiO
288% quartz sand, containing CaO53% Wingdale and returning charge flue dust, is 0.95～1.25 to determine batching by the slag silicate degree, adds vertical rectangular side blown converter and carries out three step meltings, and vertical rectangular side blown converter design variable is hearth area 4.0m
2, the high 7.2m of stove, processing power 17t/m
2D, gun slot diameter 32mm, 16 of spray gun quantity, 0 ° at spray gun inclination angle, spray gun width between centers 280mm, spray gun burning capacity 1118～1968kg/h, the first step, control blast, air quantity and fine coal consumption, 1140～1180 ℃ of smelting temperatures when molten bath bed depth during to 1200mm, stop charging, put tin once every 40 minutes afterwards, the slag of output stanniferous weight percent 10～15% and the thick tin of iron content weight percent＜1% after 2 hours, furnace bottom metal tin liquor have been put; Second step was that the slag to stanniferous 10～15% carries out strong retailoring, control blast, air quantity, fine coal consumption, 1240～1270 ℃ of smelting temperatures, the thick tin of output iron content weight percent＞5% and the slag of stanniferous weight percent 3～7%; The 3rd step, sulfiding volatilization process: be that slag to stanniferous 3～7% carries out the sulfiding volatilization melting, the control blast, air quantity, fine coal consumption, 1300～1340 ℃ of smelting temperatures, every stove adds the pyrite that contains S＞30% and make vulcanizing agent to slag, the pyrite add-on is controlled by weight S/Sn=0.6, when sample contains Sn weight percent＜0.2%, then is the terminal point of sulfiding volatilization.
7, side-blown submerged smelting bath smelting process according to claim 1 is characterized in that: described raw material is that the tin concentrate that contains Sn72%, described flux are for containing SiO
288% quartz sand, contain the CaO53% Wingdale, contain iron ore and the returning charge flue dust of Fe48%, press slag silicate degree 0.75～0.9 and determine ratio of components, add vertical rectangular side blown converter and carry out three step meltings, vertical rectangular side blown converter design variable is hearth area 2.2m
2, the high 6.2m of stove, processing power 18t/m
2D, gun slot diameter 40mm, 8 of spray gun quantity, the oblique angle is 4 ° under the spray gun, and spray gun width between centers 280mm, spray gun burning capacity are 615～991kg/h, fuel is fine coal, the first step, control blast, air quantity, coal amount, 1140～1180 ℃ of smelting temperatures when molten bath bed depth during to 1400mm, stop charging.Put tin once every 40 minutes afterwards, after 2 hours, furnace bottom metal tin liquor has been put, output stanniferous amount is 20～25% slag and the thick tin of iron content＜1%; Second step was that the slag to stanniferous 20～25% carries out strong retailoring, control blast, air quantity, coal amount, 1240～1270 ℃ of smelting temperatures, the thick tin of output iron content＞5% and the slag of stanniferous 5～8%; The 3rd step, be that slag to stanniferous 5～8% carries out sulfiding volatilization, the control blast, air quantity, coal amount, smelting temperature 1260-1340 ℃, every stove adds the pyrite that contains S＞30% and makes vulcanizing agent, the pyrite add-on is controlled by weight S/Sn=0.55, and the sulfiding volatilization process continues 40～60 minutes.
8, side-blown submerged smelting bath smelting process according to claim 1 is characterized in that described raw material and the slag silicate degree proportioning that cooperates with it are:
1), contain in three kinds of medium tin ore, stanniferous 10～15% tin flue dust, stanniferous 10～15% all kinds of scruffs of Sn10～15% one or more, contain SiO
288% quartz contains the Wingdale of CaO53% and contains the iron ore of Fe48%, and press slag silicate degree 0.75～0.9 and determine to prepare burden, or
2), contain Sn45～60% tin flue dust, contain Sn25～35% fuming furnace quick ash, make granularity＜30mm pellet, stanniferous 15～25% all kinds of scruffs also are broken into the pellet of granularity＜30mm, and strong retailoring process produce in the four kinds of raw materials of ferro-tin alloy that contain Sn＞55% one or more and contain SiO
288% quartz contains the Wingdale of CaO53%, presses slag silicate degree 0.75～1.25 batching, or
3), contain the medium tin ore of Sn3～5%, one or more in stanniferous 5～10% stanniferous flue dust, three kinds of stanniferous 2～5% all kinds of scruffs with contain SiO
288% quartz contains the Wingdale of CaO53% and contains the iron ore of Fe48%, press slag silicate degree 0.75～0.9 and prepares burden.
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| WO2015196889A1 (en) * | 2014-06-25 | 2015-12-30 | 中国恩菲工程技术有限公司 | Side-blast tin smelting apparatus |
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| CN113388744A (en) * | 2020-03-11 | 2021-09-14 | 云南乘风有色金属股份有限公司 | Process for reducing and smelting tin in tin-containing material by direct-current ore-smelting electric furnace |
| CN111607710B (en) * | 2020-06-23 | 2023-05-09 | 云南锡业股份有限公司锡业分公司 | Equipment and method for non-melting fuming volatile tin |
| CN111910087A (en) * | 2020-09-07 | 2020-11-10 | 云南锡业股份有限公司锡业分公司 | Smelting furnace and smelting method for continuously fuming low-grade tin material |
| CN114438331B (en) * | 2022-01-25 | 2023-09-22 | 莱阳市裕铭环保科技有限公司 | Co-treatment method for metal-containing hazardous waste and cyanide tailings |
| CN115896466B (en) * | 2023-01-05 | 2023-05-09 | 昆明理工大学 | Method for treating complex nonferrous metal secondary material |
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