CN103757165A - Comprehensive valuable component utilization method of blast-furnace smelting of high iron bauxite - Google Patents

Comprehensive valuable component utilization method of blast-furnace smelting of high iron bauxite Download PDF

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CN103757165A
CN103757165A CN201410048304.5A CN201410048304A CN103757165A CN 103757165 A CN103757165 A CN 103757165A CN 201410048304 A CN201410048304 A CN 201410048304A CN 103757165 A CN103757165 A CN 103757165A
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iron
bauxite
iron bauxite
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CN103757165B (en
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柳政根
储满生
唐珏
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Northeastern University China
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Abstract

A comprehensive valuable component utilization method of blast-furnace smelting of high iron bauxite is characterized by comprising the steps of preparing sintered high iron bauxite and a high iron bauxite hot briquette respectively with the high iron bauxite, intensively mixing the sintered high iron bauxite and the high iron bauxite hot briquette to form an iron-bearing furnace burden, loading the iron-bearing furnace burden and coke from the top of a blast furnace sequentially and alternately for blast-furnace smelting, controlling the temperature of molten iron to be 1450-1550 DEG C and slag temperature to be 1550-1650 DEG C, loading the vanadium-bearing molten iron with the temperature not less than 1260 DEG C into a converter for vanadium blowing smelting to obtain vanadium slag and molten steel, controlling the cooling speed of slag of the blast furnace not to exceed 6 DEG C/min, and obtaining products such as cement, gallium concentrate and aluminum oxide through treatment such as secondary leaching, desilication, carbonation decomposition and roasting after the slag is cooled to the room temperature, wherein the time of the furnace burden from the top of the furnace to generating of the molten iron and the calcium aluminate slag is approximately 8-10h. The method can treat the high iron bauxite of any grade, achieves high yields of iron, aluminum, vanadium and gallium at the same time, and contributes to large-scale exploitation and utilization of a high iron bauxite resource high in reserve volume.

Description

A kind of high-iron bauxite blast-furnace smelting has valency constituent element method of comprehensive utilization
Technical field
The invention belongs to Metallurgical resources comprehensive utilization technique field, being specifically related to a kind of high-iron bauxite blast-furnace smelting has valency constituent element method of comprehensive utilization.
Background technology
In recent years, economic fast development has promoted growing continuously and fast of China's Iron And Steel Industry, and iron ore resource disparities between supply and demand become increasingly conspicuous.And China's iron ore rich ore is few, lean ore is many, the iron ore deposit of high-quality and easy choosing is fewer and feweri, domestic Iron And Steel Industry is had to more dependence on import iron ore to meet the demand of large-scale industrial production, to 2012, China surpasses 60% to the dependency degree of imported iron ore stone, adds iron ore price continuous rise year after year, and the safety of Zhe Gei China Iron And Steel Industry and even whole national economy is brought major hidden danger.Therefore, in the urgent need to relying on technical progress to develop to greatest extent low-grade complex difficulty, select iron-stone resource.Meanwhile, the import volume of China's bauxite resource mineral products is also increasing year by year in recent years, the import volume of bauxite in 2012 has reached 3,961 ten thousand tons, account for the over half of China's bauxite industrial consumption amount, according to relevant estimation, bauxite resource may become China's Mineral resources next under one's control.
The areas such as Zhangpu, Fujian, Penglai, Hainan Province, Taiwan great Tun Shan and Guigang, Guangxi in China exist a kind of high-iron bauxite, are the mutual embedding cloth of a kind of iron aluminium mineral, unmanageable complicated iron aluminium mineral intergrowth, are a kind of important iron ore of China and bauxite resource.According to the data analysis of geology department, its national prospective reserves surpasses 1,500,000,000 tons, and only the domestic reserves in Guangxi are just over 2.0 hundred million tons.The domestic high-iron bauxite in Guangxi of take is example, and this high-iron bauxite is distributed widely in Central Guangxi Nanning to Yulin one Dai Shiyuge counties and cities, and relatively concentrates on Guigang, Binyang, Heng County and neighbouring area, and mineralising area is large, and ore body distributes in groups, and reserves are very abundant.Ore body is comprised of red clay and bauxite, and mine-containing amount is generally 550~1500kg/m 3, orebody thickness 1.2~6.8m, buries shallowly, and topsoil is generally 0.5~1.5m, and most ores can be realized strip mining transformation.
Ore chemistry composition analysis shows, this high-iron bauxite A1 2o 3content is 22%~37%, average content 27%; Fe 2o 3content is 35%~48%, average content 40%; SiO 2content 4%~13%, average content 9%, is the mineral wealth of utility value.From its composition, can find out that this bauxite belongs to high ferro high-silicon type bauxite, wherein Fe 2o 3and Al 2o 3content all do not reach industrial grade requirement separately, can not by traditional method, produce Al merely 2o 3or metallic iron product.Meanwhile, the useful component gallium of association, vanadium etc. in high-iron bauxite, wherein gallium content 0.068%~0.081%, V 2o 5content 0.10%~0.16% is all the resources that have utility value.Therefore the utilization of high-iron bauxite should be conceived to the high-efficiency comprehensive utilization that it has valency constituent element.
Comprehensive utilizating research for high-iron bauxite has carried out for many years both at home and abroad.Essence according to its iron aluminium separation can be divided into: aluminium method after iron processes, first iron after iron aluminium separating method, first aluminium.
Iron aluminium separating method is due to Iron In Iron-rich Containing Bauxite aluminium embedding cloth gummed, symbiosis closely, thereby it is separated to be difficult to realize iron aluminium by General Physics beneficiation method; After first aluminium, iron processes is also called and first soaks rear smelting method, and the aluminium stone first being easy in ore being leached leaches, richer iron red mud is smelted, but the method Al not only 2o 3leaching yield is low, and alkaline consumption is high, has brought certain difficulty adding with the residual blast furnace ironmaking to iron ore of alkali simultaneously, and after first aluminium, iron not can solve the exploitation problem of high-iron bauxite.
After first iron, aluminium method mainly refers to pyrogenic process separation of iron and aluminium, wherein, is typically the most sintering-blast-furnace smelting flow process of Lee Yin Tai of Northeastern University professor and other unit cooperative development.It can realize more than 90% recovery rate of iron aluminium, and likely realize large-scale industrial production, but its main drawback is high-iron bauxite sintering difficulty, high-iron bauxite agglomerate reductibility is poor simultaneously, and this blast furnace smelting process seriously relies on coke (coke ratio is not less than 1.3 tons).Therefore, up to the present, these high-iron bauxite research and utilization techniques are showed no industrial applications and enforcement.So this composite factor that contains the valuable metals such as iron, aluminium of high-iron bauxite still fails to obtain effective exploitation utilization at present.
In recent years, not only sharply the increasing of China's iron ore and bauxite import volume, and also price goes up year by year, eaten up most of profit of metallurgy industry.How effective exploitation utilizes high-iron bauxite resource, alleviates the worsening shortages situation of China's iron ore deposit and bauxite resource, has become an important topic.Therefore, develop a kind of new high-iron bauxite composite technology and all there is important strategic importance for China's Iron And Steel Industry and aluminium industry.
Summary of the invention
For traditional high-iron bauxite, after sintering, utilize that blast furnace is smelted existing sintering difficulty, agglomerate reductibility is poor simultaneously, smelting technology seriously relies on the problems such as coke (coke ratio is not less than 1.3 tons), the present invention proposes a kind of method that high-iron bauxite blast-furnace smelting has the comprehensive utilization of valency constituent element.
The method that the present invention realizes specifically comprises the following steps:
1. high-iron bauxite, flux, coke powder are pressed to the ratio of the mass fraction calculating with specific ingredients principle, in the ratio of mass fraction, calculate high-iron bauxite: flux: the ratio of coke powder=60~65:25~35:6~12 is carried out accurate dosing mixing granulation, the granularity of the high-iron bauxite that used here for 3-5mm, the flux granularity granularity that is-0.5mm, coke powder be-3.0mm; Recycling sinter machine carries out down draft sintering, and then through broken, screening, the high-iron bauxite agglomerate that granularity is 10-25mm is used as entering stove agglomerate, and the high-iron bauxite agglomerate that granularity is less than 10mm is used as sinter return fine; In batching, the flux of use is lime, i.e. industrial production calcium oxide used, and its effective flux is not less than 70%, and specific ingredients principle is that the CaO based in agglomerate is divided into two parts and uses, i.e. partial CaO and SiO 2in conjunction with generating 2CaOSiO 2(CaO and SiO 2the ratio of amount be 2.0), another part CaO and Al 2o 3in conjunction with, mainly generate CaOAl 2o 3(CaO and Al 2o 3the ratio of amount be 1.5~1.9 (more specifically, 1.5~1.7), for example 12CaO7Al 2o 3), sinter basicity (is total CaO and SiO 2mass ratio) be controlled between 3.8~4.2; The high-iron bauxite agglomerate reduction degradation index RDI of preparation + 3.15be not less than 60%.
High-iron bauxite is broken 2., and calculate high-iron bauxite in the ratio of mass fraction: pulverized bituminous coal: the ratio of flux=100:20~25:10~15 is prepared burden, then through mixing, the technological process such as heating, briquetting, thermal treatment, make high-iron bauxite hot wafering, wherein, the high-iron bauxite granularity after pulverizing is not more than 0.15mm; The granularity of pulverized bituminous coal is not more than 0.15mm, and fixed carbon content is not less than 50%, and volatile content is 20%~35%, and sulphur content is not higher than 0.3%, and plastometer indice is not less than 8; The granularity of flux lime is not more than 0.15mm, and effectively flux is not less than 70%; Ultimate compression strength before the high-iron bauxite hot wafering thermal treatment of preparation is not less than 1000N/, after heat treatment ultimate compression strength is not less than 2000N/, and granularity is 20~40mm, and reduction swellability index is not more than 15%, joining carbon ratio (FC/O) is 0.8~1.2, CaO and SiO 2the dual alkalinity forming is not more than 1.20.
3. high-iron bauxite agglomerate and high-iron bauxite hot wafering are thoroughly mixed to form to iron-containing charge, again iron-containing charge, coke are alternately packed into from blast furnace roof successively, from Blast Furnace Injection 50~100 ㎏/tHM coal dust, use temperature is the oxygen-enriched hot air that 1000~1300 ℃, oxygen enrichment percentage are 1.0%~3.0%, furnace roof packs the coke of 800~920 ㎏/tHM into, carries out blast-furnace smelting.Furnace charge is approximately 8~10 hours from furnace roof to the time that generates molten iron and calcium aluminate slag; Controlling molten iron temperature is 1450~1550 ℃, and slag temperature is 1550~1650 ℃; Hot metal composition is: Fe content is that 94.534%~95.443%, Si content is that 0.24%~0.56%, C content is that 3.86%~4.27%, V content is 0.20%~0.25%, other composition trace; Slag chemical composition is: CaO47%~53%, SiO 211%~15%, Al 2o 327%~33%, MgO2%~4%, all the other compositions are other, slag dual alkalinity is 3.8~4.2; In iron-containing charge, the proportioning of high-iron bauxite hot wafering is 10%~40% of iron-containing charge total mass by mass percent;
4. the vanadium-bearing hot metal that temperature is not less than to 1260 ℃ packs converter into, carries out converter and blows vanadium smelting, obtains vanadium slag and molten steel.
5. the speed of cooling of controlling blast furnace calcium aluminate slag is no more than 6 ℃/min, after its cool to room temperature, through processing such as secondary leaching, desiliconization, carbonating decomposition, calcinings, can obtain the products such as cement, gallium concentrate, aluminium sesquioxide.
The advantage of this invention is: adopt high-iron bauxite hot wafering can process the high-iron bauxite of any grade, hot wafering adopts bituminous coal as reductive agent and binding agent simultaneously, hot pressing temperature is 500 ℃ of left and right, far below 1300 ℃ of sintering, and high-iron bauxite hot wafering rate of reduction is far above high-iron bauxite agglomerate.The present invention, in conjunction with the advantage of high-iron bauxite agglomerate, high-iron bauxite hot wafering and blast-furnace smelting, has solved the problem that traditional high-iron bauxite sintering-blast-furnace smelting exists effectively, and the recovery rate of iron, aluminium, vanadium, gallium is high simultaneously.Therefore, the present invention has that recovery rate is high, production intensity is high, less energy consumption, comprehensive utilization of resources, saving coke resource, production cost are low, the features such as industrial scale is large, contribute to China to large-scale develop and utilize the abundant high-iron bauxite resource of reserves, have broad application prospects.
Embodiment
Below in conjunction with specific embodiment, further describe the present invention, advantage and disadvantage of the present invention can be more clear in description, but these embodiment are only exemplary in nature, scope of the present invention are not formed to any restriction.
Embodiment 1
Certain high-iron bauxite TFe content is 34.68%, Al 2o 3content be 23.85%, its chemical composition is listed in table 1.
The main chemical compositions of table 1 high-iron bauxite
The ratio that high-iron bauxite, flux and coke powder are calculated in specific ingredients principle (63.17:28.83:8) is accurately joined ore deposit granulation, sintering, fragmentation, screening, obtain high-iron bauxite agglomerate, wherein, CaO in agglomerate is divided into the principle that two parts are used, i.e. partial CaO and SiO 2in conjunction with generating 2CaOSiO 2(CaO and SiO 2the ratio of amount of substance be 2.0), another part CaO and Al 2o 3in conjunction with, generate 12CaO7Al 2o 3, sinter basicity is 4.0; Its main chemical compositions is listed in table 2.
The main chemical compositions (quality %) of table 2 high-iron bauxite agglomerate
This high-iron bauxite, flux and pulverized bituminous coal, by joining carbon ratio n (FC)/n (O)=1.0 (be bituminous coal fixed carbon amount with high-iron bauxite ferriferous oxide in the ratio of amount of substance of oxygen), ω (CaO)/ω (SiO 2)=1.0, then fully mix, the step such as heating, briquetting, thermal treatment, obtain high-iron bauxite hot wafering, and its main chemical compositions is listed in table 3.
The main chemical compositions (quality %) of table 3 high-iron bauxite hot wafering
High-iron bauxite hot wafering in high-iron bauxite agglomerate in table 2, table 3, coke, coal dust etc. are carried out to blast-furnace smelting, and be 10 hours tap to tap time, obtains pig iron containing vanadium and calcium aluminate slag.Wherein in iron-containing charge, the ratio of high-iron bauxite hot wafering is 10%, and hot blast temperature is 1150 ℃, and oxygen enrichment percentage is 1%.Its material balance and energy balance are listed in respectively table 4, table 5.
Blast-furnace smelting material balance when table 4 high-iron bauxite hot wafering is 10%
Blast-furnace smelting energy balance when table 5 high-iron bauxite hot wafering is 10%
When high-iron bauxite hot wafering accounts for iron-containing charge mass ratio and is 10%, the vanadium-bearing hot metal that blast-furnace smelting obtains and calcium aluminate slag composition are respectively as shown in table 6, table 7.
Blast-furnace smelting vanadium-bearing hot metal main chemical compositions when table 6 high-iron bauxite hot wafering is 10%
The main chemical compositions of blast-furnace smelting calcium aluminate slag when table 7 high-iron bauxite hot wafering is 10%
Vanadium smelting is blown in the further converter of vanadium-bearing hot metal can obtain approximately 15 ㎏ vanadium slags (containing the V of vanadium 20% 2o 5) and 1100 ㎏ steel ingots; Calcium aluminate slag is cooling by controlling, and the processing such as secondary leaching, desiliconization, manufacture of cement, carbonating decomposition, calcining can obtain the products such as approximately 60 ㎏ cement, 0.5 ㎏ gallium concentrate, 800 ㎏ aluminium sesquioxides.Therefore, the ton iron energy consumption of this technique is 936 ㎏ coke, and 100 ㎏ coal dusts have obtained the said products simultaneously.
Embodiment 2
The crude fuel conditions such as the high-iron bauxite agglomerate in employing embodiment 1, high-iron bauxite hot wafering, coke, coal dust, the ratio of high-iron bauxite hot wafering is brought up to 20% by 10%, hot blast temperature is 1150 ℃, oxygen enrichment percentage is 1%, approximately shorten to 9.2 hours tap to tap time, and its material balance and energy balance are respectively as shown in table 8, table 9.
Blast-furnace smelting material balance when table 8 high-iron bauxite hot wafering is 20%
Blast-furnace smelting energy balance when table 9 high-iron bauxite hot wafering is 20%
Vanadium smelting is blown in the further converter of vanadium-bearing hot metal can obtain approximately 14.5 ㎏ vanadium slags (containing the V of vanadium 20% 2o 5) and 1100 ㎏ steel ingots; Calcium aluminate slag is cooling by controlling, and the processing such as secondary leaching, desiliconization, manufacture of cement, carbonating decomposition, calcining can obtain the products such as approximately 56 ㎏ cement, 0.45 ㎏ gallium concentrate, 820 ㎏ aluminium sesquioxides.Therefore, the ton iron energy consumption of this technique is 904.80 ㎏ coke, and 100 ㎏ coal dusts, significantly reduce coke ratio approximately 30 ㎏ than embodiment 1.
Embodiment 3
The crude fuel conditions such as the high-iron bauxite agglomerate in employing embodiment 1, high-iron bauxite hot wafering, coke, coal dust, the ratio of high-iron bauxite hot wafering is brought up to 30% by 10%, hot blast temperature is 1150 ℃, oxygen enrichment percentage is 1%, approximately reduce to 8.5 hours tap to tap time, and its material balance and energy balance are respectively as shown in table 10, table 11.
Blast-furnace smelting material balance when table 10 high-iron bauxite hot wafering is 30%
Blast-furnace smelting energy balance when table 11 high-iron bauxite hot wafering is 30%
Vanadium smelting is blown in the further converter of vanadium-bearing hot metal can obtain approximately 14.0 ㎏ vanadium slags (containing the V of vanadium 20% 2o 5) and steel ingot; Calcium aluminate slag is cooling by controlling, and the processing such as secondary leaching, desiliconization, carbonating decomposition, calcining can obtain the products such as approximately 54 ㎏ cement, 0.42 ㎏ gallium concentrate, 840 ㎏ aluminium sesquioxides.Therefore, the ton iron energy consumption of this technique is 878.80 ㎏ coke, and 100 ㎏ coal dusts, significantly reduce coke ratio approximately 25 ㎏ than embodiment 2.
To sum up described in 3 embodiment, with technique of the present invention, successfully solved the problem that high-iron bauxite sintering-blast furnace smelting process exists, high-iron bauxite agglomerate and coke energy consumption have significantly been reduced, energy consumption significantly reduces simultaneously, accelerated smelting speed, increase output, saved a large amount of production costs.

Claims (3)

1. high-iron bauxite blast-furnace smelting has a valency constituent element method of comprehensive utilization, it is characterized in that realized method specifically comprises the following steps:
(1) coke powder that be 3-5mm high-iron bauxite, granularity by granularity is-3.0mm for the flux of-0.5mm, granularity carries out accurate dosing mixing granulation in the ratio of ratio 60~65:25~35:6~12 of the mass fraction calculating with specific ingredients principle, recycling sinter machine carries out down draft sintering, then through broken, screening, the high-iron bauxite agglomerate that granularity is 10-25mm is used as entering stove agglomerate; In batching, effective flux of flux is not less than 70%, the CaO that agglomerate is total and SiO 2mass ratio be controlled between 3.8~4.2; The high-iron bauxite agglomerate reduction degradation index RDI of preparation + 3.15be not less than 60%;
(2) high-iron bauxite is broken, and in the ratio high-iron bauxite of mass fraction: pulverized bituminous coal: the ratio of flux=100:20~25:10~15 is prepared burden, then through mixing, the technological process such as heating, briquetting, thermal treatment, make high-iron bauxite hot wafering, wherein, the high-iron bauxite granularity after pulverizing is not more than 0.15mm; The granularity of pulverized bituminous coal is not more than 0.15mm, and fixed carbon content is not less than 50%, and volatile content is 20%~35%, and sulphur content is not higher than 0.3%, and plastometer indice is not less than 8; Flux granularity is not more than 0.15mm, and effectively flux is not less than 70%; Ultimate compression strength before the high-iron bauxite hot wafering thermal treatment of preparation is not less than 1000N/, after heat treatment ultimate compression strength is not less than 2000N/, and granularity is 20~40mm, and reduction swellability index is not more than 15%, joining carbon ratio (FC/O) is 0.8~1.2, CaO and SiO 2the dual alkalinity forming is not more than 1.20;
(3) high-iron bauxite agglomerate and high-iron bauxite hot wafering are fully mixed into iron-containing charge, again iron-containing charge, coke are alternately packed into from blast furnace roof successively, from Blast Furnace Injection 50~100kg/tHM coal dust, use temperature is the oxygen-enriched hot air that 1000~1300 ℃, oxygen enrichment percentage are 1.0%~3.0%, furnace roof packs the coke of 800~920kg/tHM into, carry out blast-furnace smelting, furnace charge is approximately 8~10 hours from furnace roof to the time that generates molten iron and calcium aluminate slag; Controlling molten iron temperature is 1450~1550 ℃, and slag temperature is 1550~1650 ℃; Hot metal composition is: Fe content is that 94.534%~95.443%, Si content is that 0.24%~0.56%, C content is that 3.86%~4.27%, V content is 0.20%~0.25%, other composition trace; Slag chemical composition is: CaO47%~53%, SiO 211%~15%, Al 2o 327%~33%, MgO2%~4%, all the other compositions are other, slag dual alkalinity is 3.8~4.2; In iron-containing charge, the proportioning of high-iron bauxite hot wafering is 10%~40% of iron-containing charge total mass by mass percent;
(4) temperature is not less than to the vanadium-bearing hot metal of 1260 ℃ and packs converter into, carry out converter and blow vanadium smelting, obtain vanadium slag and molten steel;
(5) speed of cooling of control blast furnace calcium aluminate slag is no more than 6 ℃/min, after its cool to room temperature, through processing such as secondary leaching, desiliconization, carbonating decomposition, calcinings, can obtain the products such as cement, gallium concentrate, aluminium sesquioxide.
2. high-iron bauxite blast-furnace smelting has a valency constituent element method of comprehensive utilization, it is characterized in that the flux using in method is commercial lime.
3. high-iron bauxite blast-furnace smelting has a valency constituent element method of comprehensive utilization, it is characterized in that the specific ingredients principle described in method refers to that the CaO based in agglomerate is divided into two part uses, i.e. partial CaO and SiO 2in conjunction with generating 2CaOSiO 2(CaO and SiO 2the ratio of amount be 2.0), another part CaO and Al 2o 3in conjunction with, generate CaOAl 2o 3, wherein CaO and Al 2o 3the ratio of amount be 1.5~1.9.
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