CN103173637A - Antimony sulfide concentrate oxygen-enriched melting tank melting method and side-blown furnace - Google Patents
Antimony sulfide concentrate oxygen-enriched melting tank melting method and side-blown furnace Download PDFInfo
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- CN103173637A CN103173637A CN2013100703981A CN201310070398A CN103173637A CN 103173637 A CN103173637 A CN 103173637A CN 2013100703981 A CN2013100703981 A CN 2013100703981A CN 201310070398 A CN201310070398 A CN 201310070398A CN 103173637 A CN103173637 A CN 103173637A
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Abstract
The invention discloses an antimony sulfide concentrate oxygen-enriched melting tank melting method and a side-blown furnace. For solving problems of high pollution and high energy consumption of existing blast furnace volatilization melting technologies, and the impossibility of practical industrialization of existing oxygen-enriched melting tank melting technologies, the melting tank melting method provided by the invention comprises the steps that: (1) raw materials such as antimony concentrate are prepared and blended; (2) the blended material is subjected to humidified granulation; (3) prepared pellets are placed into the side-blown furnace; metal antimony, antimony sulfonium, and furnace slag produced by reaction are clarified and stratified into three layers in the melting tank, wherein the bottom layer is a metal antimony layer, the intermediate layer is an antimony sulfonium layer, and the upper layer is a furnace slag layer; and (4) metal antimony, antimony sulfonium, and furnace slag are discharged in a stratified manner. With the method provided by the invention, oxygen-enriched melting is adopted, antimony sulfide concentrate self-heat melting is realized, metal antimony yield is greatly increased, and antimony white quality is good.
Description
Technical field
The present invention relates to a kind of method and apparatus of antimony sulfide bath smelting, particularly a kind of stibnite concentrate oxygen enriched molten bath melting method and side-blown converter.
Background technology
Tradition antimony is smelted and usually to be adopted blast furnace volatile smelting technology, forms needle antimony oxygen in flue dust by the antimony in stibnite concentrate is evaporate into the form of weisspiessglanz, and this process need is allocated a large amount of coke into as reductive agent and thermal source, and output contains low concentration SO in a large number simultaneously
2Flue gas, the high and low concentration SO of energy consumption
2Seriously polluted.
In order to overcome the above problems, large quantity research has been incorporated into the oxygen-enriched air smelting technology in the antimony smelting, Chinese patent CN10942575 adopts at the lead bronze smelting industry and uses very ripe oxygen-enriched bottom-blowing stove as the melting instrument, white antimony is carried out oxygen-enriched air smelting, and this technology has solved antimony and has smelted the energy consumption height and produce low concentration SO
2Problem, but because oxygen blasts bottom bottom convertor, at first oxygen contact with the metallic antimony that generates and make it to occur oxidizing reaction, relies on the weisspiessglanz that oxidation generates to transmit oxygen to the top antimony sulfide, and then with the antimony sulfide oxidation, this process causes the metallic antimony growing amount greatly to reduce; In addition, because antimony sulfide is easy to volatilization, the antimony sulfide that enters into the high temperature molten bath is volatilized soon and is entered flue dust, and when transmitting oxygen by weisspiessglanz, the reaction times is longer, has extended the antimony volatilization time, cause the antimony sulfide volatile quantity to increase, the antimony sulfide volatilization process belongs to thermo-negative reaction, and this just tends to cause fusion process can't realize self-heating, does not all utilize the antimony sulfide oxidation reaction heat; The antimony sulfide that enters into flue is very easy in the flue surface adhesion, makes fusion process be difficult to carry out smoothly; In addition, oxygen, easily is blown into material in flue dust toward blowing up from the bottom, and dust rate tends to reach more than 20%, has a strong impact on the stibium trioxide quality.
Patent CN101768672 also provides a kind of antimony smelting method with the oxygen-enriched top blowing antimony regulus, the method is placed in a tubbiness stove with material, the oxygen rifle of coming in and going out from the top carries out oxygen-enriched air converting to it, but because the oxygen rifle need to all be inserted in melt, life-span of oxygen lance can't guarantee; In addition, high velocity air stirs very large to melt, and slag and metal can't layerings, can blowing after the rear standing demix that stove need to be stopped, and make fusion process to carry out continuously.
Due to above various reasons, above oxygen enriched molten bath smelting technique does not all obtain industrial utilization, and existing antimony is smelted and still adopted original blast furnace volatile smelting technology, needs a kind of practical oxygen-enriched air smelting technology of exploitation badly it is transformed.
Summary of the invention
High pollution, high energy consumption and the existing oxygen enriched molten bath smelting technique that exists for existing blast furnace volatile smelting technology be the deficiency of industrialization conscientiously, the present invention aims to provide a kind of stibnite concentrate oxygen enriched molten bath melting method and side-blown converter, this fused bath smelting method adopts oxygen-enriched air smelting, can realize the pyritic smelting of stibnite concentrate, and the metallic antimony productive rate increases greatly, and the stibium trioxide quality is good.
To achieve these goals, the technical solution adopted in the present invention is:
A kind of stibnite concentrate oxygen-enriched side-blowing furnace, its constructional feature be, comprises the laying fireproof bricks cupola well that is positioned at the side-blown bottom of furnace body, is positioned at the copper water jacket at body of heater middle part and the molten steel cover that is positioned at upper of furnace body; Described copper water jacket and/or molten steel put and are provided with charging opening, and described molten steel puts and has smoke outlet, are provided with main air port in described copper water jacket bottom, and this copper water jacket top is provided with overfiren air port, puts at described molten steel and is provided with tertiary air orifice; Be provided with successively from top to bottom slag escape orifice, antimony sulfonium escape orifice and metal escape orifice at the cupola well sidewall; Described slag escape orifice is arranged on below main air port.
Further, the present invention also provides a kind of stibnite concentrate oxygen enriched molten bath melting method, comprises the steps:
1) processing of first antimony concentrate, Wingdale, quartz sand and iron ore being got the raw materials ready separately, the above-mentioned material that then will get ready is prepared burden, in the compound after preparing:
Sb quality percentage composition is 15% ~ 40%, and the quality percentage composition of silicon, iron, calcium and mutual ratio are SiO
2: FeO:CaO=(8% ~ 30%): (7% ~ 41%): (3% ~ 25%), sulphur quality percentage composition〉14%;
2) compound for preparing in step 1) is carried out humidification and granulate, the quality percentage composition that pelletization is controlled water in material is 7% ~ 15%, and the spherolite particle diameter of making is 3mm ~ 25mm;
3) with step 2) spherolite of preparation adds in side-blown converter as above, and the spherolite charging drops in the side-blown converter molten bath, the oxygen-rich air oxidation of the side-blown converter that is blasted; Smelting temperature is 950 ℃ ~ 1400 ℃, and metallic antimony, antimony sulfonium and the slag that reaction generates all clarified in the molten bath and be divided into three layers, and the lowest layer is metallic antimony, and the middle layer is antimony sulfonium layer, and the superiors are slag layer;
4) metallic antimony, antimony sulfonium and slag are emitted in layering.
Further, the degree of depth of described metallic antimony is 300mm ~ 600mm; This moment, described antimony sulfonium layer thickness was 150mm ~ 300mm, and described slag layer thickness is 500mm ~ 1500mm.
In step 3), pass into secondary air in from overfiren air port to side-blown converter, pass into tertiary air, O in described secondary air and tertiary air in from tertiary air orifice to side-blown converter
2Volumetric concentration be 30% ~ 90%, all the other are N
2, pressure is 0.1 ~ 0.4MPa, O in secondary air
2Flow and inlet amount satisfy (20Nm
3~ 120Nm
3)/(t concentrate), O in tertiary air
2Flow and inlet amount satisfy (5Nm
3~ 80Nm
3)/(t concentrate);
In step 1), when antimony concentrate, Wingdale, quartz sand and iron ore were got the raw materials ready processing, the particle diameter of each composition was in 20mm.
In step 3), O in oxygen-rich air
2Volumetric concentration is 30% ~ 90%, and all the other are N
2, oxygen-rich air pressure is 0.2MPa ~ 1.6MPa, O in oxygen-rich air
2Flow and spherolite charging the relationship between quantities are: (180Nm
3~ 420Nm
3)/(t concentrate).
nationality is by aforesaid method, the present invention is first with stibnite concentrate and Wingdale, quartz sand and iron ore etc. are prepared burden, compound after preparing is joined in side-blown converter, blast oxygen enrichment and carry out melting, the fusion process oxygen enrichment directly blasts slag blanket, oxygen and the antimony sulfide direct reaction that falls into slag blanket, greatly accelerated speed of response, the metallic antimony that reaction generates is because density sinks to greatly the bottommost in molten bath, finally emitted by siphon port, the antimony sulfonium that reaction process generates is in the middle of slag blanket and metallic antimony layer, emitted by antimony sulfonium mouth, slag blanket floats on the molten bath topmost, the following smelting slag in air port stirs little, metallic antimony wherein and antimony sulfonium have all obtained precipitate and separate, it can be emitted from the slag escape orifice equally, for volatilization being entered into antimony sulfide Quick Oxidation in stove of gas phase, be provided with overfiren air port on the molten bath, from wherein blasting oxygen rich gas, as far as possible stay stove in to guarantee antimony sulfide oxidation institute liberated heat the antimony sulfide oxidation, be provided with tertiary air orifice pressing close to the smoke outlet place, can guarantee the antimony sulfide of volatilizing fully oxidation again before entering flue, make antimony enter into flue with the weisspiessglanz form fully, can effectively prevent from vulcanizing the bonding on flue.
1, the processing of first antimony concentrate, Wingdale, quartz sand and iron ore being got the raw materials ready separately, control all material particular diameters below 20mm, the above-mentioned material of getting ready is prepared burden, in compound after preparing, Sb quality percentage composition is 15 ~ 40%, and wherein silicon, iron, calcareous amount percentage composition satisfy SiO
2: FeO:CaO is (8 ~ 30%): (7 ~ 41%): (3 ~ 25%), sulphur quality percentage composition is controlled at〉14%;
2, above-mentioned material is carried out humidification in disk or drum pelletizer and granulate, pelletization is controlled material moisture quality percentage composition 7 ~ 15%, and the qualified spherolite particle diameter of making is controlled between 3mm ~ 25mm;
3, with the spherolite that makes by quantitatively joining in stove in two opening for feeds as shown in Fig. 13, charging drops in the molten bath, by the oxygen-rich air oxidation that is blasted by blast orifice 2 shown in Figure 1, O in oxygen-rich air
2Concentration is controlled between 30% ~ 90%, and all the other are N
2, the oxygen-rich air pressure-controlling is at 0.2 ~ 1.6MPa, O in oxygen-rich air
2Flow and inlet amount satisfy (180Nm
3~ 420Nm
3)/(t concentrate);
4, control smelting temperature between 950 ~ 1400 ℃, the metallic antimony that reaction generates, antimony sulfonium and slag are all clarified layering in molten bath 1, the molten bath is divided into three layers, the lowest layer is metallic antimony, its severity control is at 300 ~ 600mm, metallic antimony is by putting antimony mouth 9 continuously or being interrupted and emitting, the metallic antimony upper strata is antimony sulfonium layer, antimony sulfonium controlling depth is between 150 ~ 300mm, be interrupted or emit continuously by antimony sulfonium escape orifice 8, slag layer is on antimony sulfonium layer top, slag layer is divided into again the above and following two portions in air port in air port, whole slag layer is controlled at 500 ~ 1500mm, the following severity control in air port is more than 400mm, slag escape orifice 7 is arranged on below the air port, to guarantee that slag blanket can very high clarification.
5, secondary air and tertiary air are passed into by overfiren air port 6 and tertiary air orifice 5 respectively, O in secondary air and tertiary air
2Concentration is controlled between 30% ~ 90%, and all the other are N
2, pressure-controlling is at 0.1 ~ 0.4MPa, O in secondary air
2Flow and inlet amount satisfy (20Nm
3~ 120Nm
3)/(t concentrate), O in tertiary air
2Flow and inlet amount satisfy (5Nm
3~ 80Nm
3)/(t concentrate);
6, the present invention's melting equipment used side-blown converter as depicted in figs. 1 and 2.In figure, 1 is the molten bath district, and the molten bath district strengthens by the metal escape orifice 9 places cupola well degree of depth, can make this place's metal level degree of depth darker, can reduce the content of emitting antimony sulfonium and slag in metal; Main air port 2 respectively arranges 3 ~ 8 according to smelting scale both sides; Charging opening 3 arranges two, when treatment scale hour can only arrange one; Smoke outlet 4 high-temperature flue gas are got rid of from here; Tertiary air orifice 5 and overfiren air port 6 can be respectively respectively arrange 3 ~ 8 in stove both sides according to treatment scale; Slag escape orifice 7, antimony sulfonium escape orifice 8 and metal escape orifice 9 set gradually from top to bottom, and particular location and size are decided according to each melt layer height and amount.Whole stove is comprised of laying fireproof bricks cupola well, middle part copper water jacket and upper steel water jacket.
Compared with prior art, the invention has the beneficial effects as follows:
1, can realize the pyritic smelting of stibnite concentrate, not need to add any fuel, and then antimony can be smelted comprehensive energy consumption and drop to 800kg mark coal/below ton;
2, the metallic antimony productive rate accounts for 10% ~ 25% of full antimony amount, compares traditional antimony regulus mode, and the metallic antimony productive rate increases greatly;
3, SO in the melting flue gas
2The quality percentage composition can satisfy direct relieving haperacidity requirement more than 6%;
4, in dust collecting system, stibium trioxide contains antimony more than 78%, and the stibium trioxide quality is good, but Direct Reductive Melting obtains star metal.
Description of drawings
Fig. 1 is the front view of side-blown converter of the present invention;
Fig. 2 is the side-view of side-blown converter of the present invention.
In the drawings
1-molten bath district; The 2-main air port; The 3-charging opening; The 4-smoke outlet;
The 5-tertiary air orifice; The 6-overfiren air port; 7-slag escape orifice; 8-antimony sulfonium escape orifice;
9-metal escape orifice; The 10-cupola well; The 11-copper water jacket; 12-molten steel cover.
Embodiment
Embodiment 1
The design cupola well is of a size of 1600 * 2500mm, hearth area is 4m
2Side-blown converter, the stove both sides respectively arrange 3 main air ports, by slag escape orifice, antimony sulfonium escape orifice and put metallic antimony mouth Position Design guarantee the slag blanket degree of depth in 1200mm, antimony sulfonium layer depth in 200mm, metallic antimony layer depth at 500mm, stove both sides, 1500mm place respectively arrange 3 overfiren air ports on melt liquid level, stove both sides, 1000mm place, overfiren air port top respectively arrange 2 tertiary air orifices, one of φ 300mm charging opening is set, and smoke outlet is of a size of 400 * 400mm.
Test in above-mentioned side-blown converter.
Get the raw materials ready:
Antimony concentrate and the Wingdale, quartz sand and the iron ore that are crushed to below 20mm are prepared burden, in compound after preparing, Sb quality percentage composition is 25%, wherein silicon, iron, calcareous amount percentage composition are respectively 26%, 18%, 9%, and sulphur quality percentage composition is 19%; Above-mentioned material is added water to material moisture in drum pelletizer be 8%, makes particle diameter standby at the spherolite of 5mm ~ 18mm.
Melting:
The feed rate of above-mentioned spherolite material with 10t/h joined in above-mentioned side-blown converter, and smelting temperature is controlled between 1050 ~ 1300 ℃, O in the oxygen-rich air that main air port blasts
2Concentration is 50%, and all the other are N
2, oxygen-rich air pressure is 0.8MPa, the oxygen-rich air flow is 4500Nm
3/ h; O in secondary air and tertiary air
2Concentration is all 50%, and all the other are N
2, pressure-controlling is at 0.2MPa, and secondary air flow is 800Nm
3/ h, tertiary air flow are 500Nm
3/ h.Can realize pyritic smelting under these conditions, the productive rate of metallic antimony is 18%, SO in flue gas
2Concentration reaches 8.3%, and in dust collecting system, stibium trioxide contains antimony 81%.
Smelting furnace is identical with embodiment 1.
Get the raw materials ready:
Antimony concentrate and the Wingdale, quartz sand and the iron ore that are crushed to below 20mm are prepared burden, in compound after preparing, Sb quality percentage composition is 33%, wherein silicon, iron, calcareous amount percentage composition are respectively 20%, 12%, 10%, and sulphur quality percentage composition is 16%; Above-mentioned material is added water to material moisture in drum pelletizer be 10%, makes particle diameter standby at the spherolite of 5mm ~ 22mm.
Melting:
The feed rate of above-mentioned spherolite material with 10t/h joined in above-mentioned side-blown converter, and smelting temperature is controlled between 1000 ~ 1200 ℃, O in the oxygen-rich air that main air port blasts
2Concentration is 80%, and all the other are N
2, oxygen-rich air pressure is 1.2MPa, the oxygen-rich air flow is 2800Nm
3/ h; O in secondary air and tertiary air
2Concentration is all 80%, and all the other are N
2, pressure-controlling is at 0.2MPa, and secondary air flow is 300Nm
3/ h, tertiary air flow are 200Nm
3/ h.Can realize pyritic smelting under these conditions, the productive rate of metallic antimony is 11%, SO in flue gas
2Concentration reaches 13%, and in dust collecting system, stibium trioxide contains antimony 79.4%.
The content that above-described embodiment is illustrated should be understood to these embodiment and only is used for being illustrated more clearly in the present invention, limit the scope of the invention and be not used in, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
Claims (5)
1. a stibnite concentrate oxygen-enriched side-blowing furnace, is characterized in that, comprises the laying fireproof bricks cupola well (10) that is positioned at the side-blown bottom of furnace body, the copper water jacket (11) that is positioned at body of heater middle part and the molten steel cover (12) that is positioned at upper of furnace body; Described copper water jacket (11) and/or molten steel cover (12) are provided with charging opening (3), have smoke outlet (4) on described molten steel cover (12), be provided with main air port (2) in described copper water jacket (11) bottom, this copper water jacket (11) top is provided with overfiren air port (6), is provided with tertiary air orifice (5) on described molten steel cover (12); Be provided with successively from top to bottom slag escape orifice (7), antimony sulfonium escape orifice (8) and metal escape orifice (9) at cupola well (10) sidewall; Described slag escape orifice (7) is arranged on below main air port (2).
2. a stibnite concentrate oxygen enriched molten bath melting method, is characterized in that, comprises the steps:
1) processing of first antimony concentrate, Wingdale, quartz sand and iron ore being got the raw materials ready separately, the above-mentioned material that then will get ready is prepared burden, in the compound after preparing:
Sb quality percentage composition is 15% ~ 40%, and the quality percentage composition of silicon, iron, calcium and mutual ratio are SiO
2: FeO:CaO=(8% ~ 30%): (7% ~ 41%): (3% ~ 25%), sulphur quality percentage composition〉14%;
2) compound for preparing in step 1) is carried out humidification and granulate, the quality percentage composition that pelletization is controlled water in material is 7% ~ 15%, and the spherolite particle diameter of making is 3mm ~ 25mm;
3) with step 2) spherolite of preparation adds in side-blown converter as claimed in claim 1, and the spherolite charging drops in the side-blown converter molten bath, the oxygen-rich air oxidation of the side-blown converter that is blasted; Smelting temperature is 950 ℃ ~ 1400 ℃, and metallic antimony, antimony sulfonium and the slag that reaction generates all clarified in the molten bath and be divided into three layers, and the lowest layer is metallic antimony, and the middle layer is antimony sulfonium layer, and the superiors are slag layer;
4) metallic antimony, antimony sulfonium and slag are emitted in layering.
3. stibnite concentrate oxygen enriched molten bath melting method according to claim 2, is characterized in that, the degree of depth of described metallic antimony is 300mm ~ 600mm.
4. stibnite concentrate oxygen enriched molten bath melting method according to claim 2, it is characterized in that, in step 3), pass into secondary air from overfiren air port (6) in side-blown converter, pass into tertiary air from tertiary air orifice (5) in side-blown converter, O in described secondary air and tertiary air
2Volumetric concentration be 30% ~ 90%, all the other are N
2, pressure is 0.1 ~ 0.4MPa, O in secondary air
2Flow and inlet amount satisfy (20Nm
3~ 120Nm
3)/(t concentrate), O in tertiary air
2Flow and inlet amount satisfy (5Nm
3~ 80Nm
3)/(t concentrate);
Stibnite concentrate oxygen enriched molten bath melting method according to claim 2 is characterized in that, in step 1), when antimony concentrate, Wingdale, quartz sand and iron ore were got the raw materials ready processing, the particle diameter of each composition was in 20mm.
5. stibnite concentrate oxygen enriched molten bath melting method according to claim 2, is characterized in that, in step 3), and O in oxygen-rich air
2Volumetric concentration is 30% ~ 90%, and all the other are N
2, oxygen-rich air pressure is 0.2MPa ~ 1.6MPa, O in oxygen-rich air
2Flow and spherolite charging the relationship between quantities are: (180Nm
3~ 420Nm
3)/(t concentrate).
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