CN101914639A - Method for recycling iron on line from iron-containing industrial slag and preparing glass ceramics frit - Google Patents

Method for recycling iron on line from iron-containing industrial slag and preparing glass ceramics frit Download PDF

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Publication number
CN101914639A
CN101914639A CN2010102759564A CN201010275956A CN101914639A CN 101914639 A CN101914639 A CN 101914639A CN 2010102759564 A CN2010102759564 A CN 2010102759564A CN 201010275956 A CN201010275956 A CN 201010275956A CN 101914639 A CN101914639 A CN 101914639A
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slag
iron
frit
agent
prepare
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李宇
刘晓明
张玲玲
苍大强
杨志杰
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

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Abstract

The invention relates to a method for recycling iron on line from iron-containing industrial slag and preparing a glass ceramics frit, belonging to the technical field of resource comprehensive utilization and material preparation and mainly comprising a two-step method process of iron-containing industrial slag online rough adjustment and modification for reducing iron and fine adjustment and modification for preparing the frit. The method comprises the steps of: discharging high-temperature iron-containing slag into a high-temperature furnace device, and simultaneously adding a reducing agent and a modifying agent to ensure that slag components are adjusted to reach the optimal component point in which iron oxide is reduced; after fully reacted, separating reduced molten iron from the slag, and recycling to obtain high-temperature molten iron; further adding a modifying agent and an adjusting agent into the slag remained after the separation to ensure that the slag components are adjusted to achieve the quality requirement of slag glass ceramics on the frit; and water-hardening, drying and grading the qualified slag to prepare the glass ceramics frit. The invention realizes multiple purposes that the heat of the slag is directly utilized and metal iron is recycled to prepare a high addition value product as well as solid wastes are massively utilized, and the like.

Description

A kind of recycling iron on line from iron-containing industrial slag and prepare the method for glass ceramics frit
Technical field
The invention belongs to the technical field of comprehensive utilization of resources and material preparation, especially in metallurgical cinder high value added utilization and devitrified glass preparation field.
Background technology
As everyone knows, the a large amount of high temperature iron content slag of discharging in the industry production such as China's metallurgy, the bessemer furnace slag, electric furnace slag, stainless steel slag, the nickel slag that comprise molten state, and ferruginous molten state ferroalloy slag, refining slag, liquid slag from power plant, desulfurization slag, phosphorus slag etc.
These high-temperature slags generally adopt the method for utilizing again after the direct cooling at present, and there is the difficult problem of the high value added utilization of sensible heat utilization, the plain resources effective recovery of iron, slag in this method, and fails to solve always.Cooled solid slag can only reclaim 15% iron through the traditional method of graded crushing magnetic separation, and second half iron is present in non magnetic or part weak magnetism oxide compound in and can't separate.Simultaneously, high-temperature slag deslagging temperature〉1400 ℃, have heat quality height, quantity big (sensible heat〉60kgce/t).Yet prior art fails to realize the utilization of slag heat, and a large amount of sensible heats are directly cooled waste in air.Cooled slag is mostly as low value-added utilization such as cement mixture, roadbed material or can not effectively utilize and store up in a large number.
Devitrified glass is called glass-ceramic again, is the parent glass with specific composition, and a class that makes by the control crystallization in heat-processed contains the polycrystalline solid material that a large amount of crystallites reach glassy phase mutually.
On technology, the preparation process of devitrified glass has 1500 ℃ of left and right sides high-temperature fusion of raw material and 700 ~ 1000 ℃ of heat treated two heat-processedes of parent glass, and first high-temperature fusion process and slag melt temperature are approaching.
On forming, CaO-Al 2O 3-SiO 2Microcrystalline glass in series is one of them important class.The major ingredient of this class devitrified glass is SiO 2, Al 2O 3, CaO and MgO, approaching with the composition of slag.
Therefore, appropriately adjust iron and steel slag component and temperature under the high temperature fused state, just steel slag directly can be utilized as the high-temperature fusion raw material of devitrified glass, thereby avoided traditional devitrified glass raw material high energy consumption melting process.
To CaO-Al 2O 3-SiO 2Be the existing very long history of research of cinder microcrystalline glass.Last century the fifties end, cinder microcrystalline glass is succeeded in developing in USSR (Union of Soviet Socialist Republics), subsequently, is the CaO-Al of representative with the cinder microcrystalline glass 2O 3-SiO 2The microcrystalline glass in series fast development, and realized industrialization production.Because CaO-Al 2O 3-SiO 2Microcrystalline glass in series has the advantages that bending resistance, resistance to compression and shock resistance are good, chemical stability good, wear resistance is strong, has been widely used as high-grade construction decoration material and has substituted natural granite and high-grade wall floor tile; Be applied to fields such as metallurgy, chemical industry, machinery, building materials, the energy simultaneously as wear-resisting, corrosion resistant material.
Both at home and abroad the investigator is (as license number: CN101125735 B; Application number: 200710054035.3; Application number: 200710010130.3; Application number: 200410073239.8) to CaO-Al 2O 3-SiO 2The research of microcrystalline glass in series is mainly enlarging raw material sources, is improving the solid waste volume, is exploring devitrified glass and form mechanism, reduction and reclaim and carry out extensive work aspect the molten iron in the slag.Yet, more than study the tradition that all adopts cold slag remelting to prepare devitrified glass and utilize technology.At present, the CaO-Al on the market 2O 3-SiO 2Microcrystalline glass in series adopts this traditional technology to utilize waste residue not have clear superiority still based on natural mineral raw.Its key issue is how to reduce this process energy consumption and guarantees quality product.
Recently, many investigators attempt directly high-temperature slag being prepared into devitrified glass, as patent " slag microcrystalline glass directly made by industry furnace molten cinder " (application number: 91102237.6), " a kind of method of utilizing thermal power plant's liquid sludge-removing furnace to prepare sintered glass-ceramics " (application number: 200810018384.4), " comprehensive utilization yellow phosphorus slag and tail gas are produced the method for devitrified glass " (application number: 200710077733.5).But all adopt single stage method in these patents, promptly directly hot industry waste residue upgrading is become to satisfy the qualified slag of devitrified glass ingredient requirement, do not have the content of iron recovery and coarse adjustment upgrading.
Summary of the invention
One of purpose of the present invention: propose to utilize simultaneously the high value added utilization method of iron-contained industrial slag heat, iron, slag, guaranteed not only obvious social benefit of the present invention, technical feasibility, and have good economic benefit equally.By the slag alternative materials of directly utilizing industry to discharge, avoid the energy consumption of fusion industrial residue again, than traditional technology energy efficient 120kgce/T, reduce discharging CO 2300kg/T; Directly reclaim iron and will obtain high temperature liquid iron, be worth about 2200 yuan/ton; The preparation glass ceramics frit is worth about 6000 yuan/ton.
Two of purpose of the present invention: the two-step approach process modifying process of setting up online " coarse adjustment upgrading reduced iron "+" the fine tuning upgrading prepares frit ", solve the slag metallic reducing and reclaim the contradiction of controlling with quality of materials, that is: show the optimum alkalinity 0.8 ~ 1.25 of the iron-contained industrial slag basicity being adjusted to reducing iron oxides, this process is a reducing atmosphere; Slag basicity after then slag iron being separated is adjusted to the basicity 0.25 ~ 0.90 of common cinder microcrystalline glass, and this process is an air atmosphere.
Three of purpose of the present invention: a kind of method of utilizing industrial solid castoff in a large number is provided, the technology of i.e. " coarse adjustment "+" fine tuning " makes, in the technology of " coarse adjustment upgrading reduced iron ", can be used as modification agent and add a large amount of solid waste, allow the fluctuation in the modification agent composition certain limit; Slag composition is carried out meticulous adjustment by modification agent and adjustment agent again in " fine tuning upgrading " process, guarantee that the slag composition meets the demands.
Four of purpose of the present invention: propose devitrified glass feedstock production (high-temperature fusion) and prepare the technology that (thermal treatment) separates with the devitrified glass finished product, that is: do not prepare devitrified glass at the scene of discharge slags such as metallurgy, but preparation devitrified glass raw material---frit, then frit is transported to other place and further become devitrified glass, perhaps directly as commercial articles vending through prepared such as Overheating Treatment.Adopt the advantage of this technology to be that slag utilizes technology succinct more, flexibly, and its required space can save greatly, can satisfy the reality at existing industrial production scene.
A kind of recycling iron on line from iron-containing industrial slag and prepare the method for glass ceramics frit is characterized in that comprising the two-step process of iron-contained industrial slag online " coarse adjustment upgrading reduced iron " and " the fine tuning upgrading prepares frit ", and is specific as follows
The first step:
A) high temperature iron content slag is entered high temperature kiln equipment, add reductive agent and modification agent simultaneously, make the adjustment of slag component reach wherein ferriferous oxide reductive optimal components point, and with slag, reductive agent, modification agent stirring and evenly mixing, the ferriferous oxide reduction reaction is fully carried out;
B) molten iron after will reducing separates with slag, reclaims to obtain high temperature liquid iron;
Second step:
C) further add modification agent and adjustment agent in the slag of remainder after separation, making the adjustment of slag component reach cinder microcrystalline glass is the specification of quality of frit to frit;
D) with qualified slag water quenching, drying, classification, prepare glass ceramics frit.
Wherein high temperature iron content slag comprises bessemer furnace slag, electric furnace slag, stainless steel slag, the nickel slag of molten state, and ferruginous high-temperature fusion attitude ferroalloy slag, refining slag, liquid slag from power plant, desulfurization slag, phosphorus slag.
Wherein reductive agent refers to one or more materials in coal dust, Graphite Powder 99, carbonization rice husk, sawdust, stalk, coke powder, coal gangue, resinous shale, silicon carbide, the hydrogen; Modification agent refers to one or more materials in all kinds of flyash, mine tailing, tailings, lean ore, coal gangue, volcanic ash, silicon ash, cullet, quartz sand, sandstone, feldspar, rhombspar, calcite, bauxite, borax, alabaster, soda ash, saltcake, nitre, magnesite, mud, red mud, boron mud, the building waste; The adjustment agent refers to one or more materials in the required tinting material of devitrified glass, the nucleus agent.
Wherein ferriferous oxide reductive optimal components point is meant i.e. (CaO+MgO) and (SiO 2+ Al 2O 3) ratio be that basicity is that 0.80 ~ 1.25 o'clock slag is formed.
Wherein make the adjustment of slag component reach cinder microcrystalline glass the specification of quality of frit is meant that slag predominant quantity per-cent consists of: 30 ~ 65 SiO 2, 2 ~ 15 Al 2O 3, 10 ~ 45 CaO, 0 ~ 20 MgO, 0 ~ 10 Fe 2O 3, 0 ~ 10 R 2O, 1 ~ 10 adjustment agent, R is a monovalent metallic ion; Prepare qualified frit and can nearby or be transported to and further be processed into devitrified glass outside the factory, or directly as commercial articles vending.
The present invention utilizes slag to prepare the different of devitrified glass patent with other and is: 1. the present invention is directed to ferruginous industrial slag; 2. the present invention proposes is not only the online modifying process that utilizes slag heat, and is the two-step process by " coarse adjustment upgrading reduced iron "+" the fine tuning upgrading prepares frit "; 3. the present invention does not directly prepare devitrified glass, but raw material---the frit of preparation devitrified glass; What 4. the present invention was prepared is high temperature liquid iron, two kinds of high value added products of glass ceramics frit; What significantly save is energy consumption cost and the raw materials cost that utilizes slag heat and utilize solid waste.
Description of drawings
Fig. 1 is the synoptic diagram of a kind of recycling iron on line from iron-containing industrial slag and preparation glass ceramics frit method.
Embodiment
Embodiment 1
The bessemer furnace slag that discharge certain Steel Plant stokehold consists of 12.92% SiO 2, 0.79% Al 2O 3, 29.18% CaO, 3.58% MgO, 42.29% TFe, 26.35% MFe, 13.25% FeO, 8.03% Fe 2O 3, 2.46% MnO, 1.80% P 2O 5, 0.15% R 2O(R is a monovalent metallic ion).With this slag fusion again, form the iron-contained industrial slag.
According to technology shown in Figure 1, in the coarse adjustment upgrading, will be equivalent to the modification agent of slag weight 34% flyash, 5% quartz sand, 10% waste resistant material composition, the reductive agent that is equivalent to slag weight 13% coal dust composition adds in the high-temperature slag, and stir, make slag basicity reach 1.1; Behind insulation 20min under 1550 ℃, pour slag into the fine tuning reaction package, remaining molten iron obtains to reclaim.The rate of recovery of iron reaches 95% in the slag.
In the fine tuning upgrading, reach the requirement of cinder microcrystalline glass for making slag composition, will be equivalent to the modification agent of slag weight 35%, the adjustment agent that is equivalent to slag weight 10.0% adds in the slag after slag iron separates, stirs; Behind insulation 20min under 1550 ℃, pour slag in pond shrend; With after shrend frit drying, the classification, obtain the qualified frit of 0.5 ~ 6mm then.
Embodiment 2
The bessemer furnace slag chemical constitution that certain Steel Plant discharges is 20.23% SiO 2, the Al of 1.36 % 2O 3, 38.58% CaO, 4.63% MgO, 26.8% Fe 2O 3, 3.46% MnO, 2.9% P 2O 5, the TiO of 0.96 % 2, the TiO of 0.5 % 2With this slag fusion again, form the iron-contained industrial slag.
According to technology shown in Figure 1, in the coarse adjustment upgrading, will be equivalent to the modification agent of slag weight 36% flyash, 15% CHARACTERISTICS OF TAILINGS SAND, 5% bof sludge composition, the reductive agent that is equivalent to slag weight 15% coal dust composition adds in the high-temperature slag, and stir, make slag basicity reach 1.05; Behind insulation 20min under 1550 ℃, pour slag into the fine tuning reaction package, remaining molten iron obtains to reclaim.The rate of recovery of iron reaches 96% in the slag.
In the fine tuning upgrading, reach the requirement of cinder microcrystalline glass for making slag composition, will be equivalent to the modification agent of slag weight 30%, the adjustment agent that is equivalent to slag weight 8.0% adds in the slag after slag iron separates, stirs; Behind insulation 20min under 1550 ℃, pour slag in pond shrend; With after shrend frit drying, the classification, obtain the qualified frit of 0.5 ~ 6mm then.
Frit further is prepared into devitrified glass, and final devitrified glass performance is bending strength 91.3MPa, microhardness 7.76GPa, density 3.07g/cm 3

Claims (5)

1. a recycling iron on line from iron-containing industrial slag and prepare the method for glass ceramics frit is characterized in that comprising the two-step process of iron-contained industrial slag online " coarse adjustment upgrading reduced iron " and " the fine tuning upgrading prepares frit ", and is specific as follows
The first step:
A) high temperature iron content slag is entered high temperature kiln equipment, add reductive agent and modification agent simultaneously, make the adjustment of slag component reach wherein ferriferous oxide reductive optimal components point, and with slag, reductive agent, modification agent stirring and evenly mixing, the ferriferous oxide reduction reaction is fully carried out;
B) molten iron after will reducing separates with slag, reclaims to obtain high temperature liquid iron;
Second step:
C) further add modification agent and adjustment agent in the slag of remainder after separation, making the adjustment of slag component reach cinder microcrystalline glass is the specification of quality of frit to frit;
D) with qualified slag water quenching, drying, classification, prepare glass ceramics frit.
2. a kind of recycling iron on line from iron-containing industrial slag as claimed in claim 1 and prepare the method for glass ceramics frit, it is characterized in that high temperature iron content slag wherein comprises bessemer furnace slag, electric furnace slag, stainless steel slag, the nickel slag of molten state, and ferruginous high-temperature fusion attitude ferroalloy slag, refining slag, liquid slag from power plant, desulfurization slag, phosphorus slag.
3. a kind of recycling iron on line from iron-containing industrial slag as claimed in claim 1 and prepare the method for glass ceramics frit is characterized in that reductive agent wherein refers to one or more materials in coal dust, Graphite Powder 99, carbonization rice husk, sawdust, stalk, coke powder, coal gangue, resinous shale, silicon carbide, the hydrogen; Modification agent refers to one or more materials in all kinds of flyash, mine tailing, tailings, lean ore, coal gangue, volcanic ash, silicon ash, cullet, quartz sand, sandstone, feldspar, rhombspar, calcite, bauxite, borax, alabaster, soda ash, saltcake, nitre, magnesite, mud, red mud, boron mud, the building waste; The adjustment agent refers to one or more materials in the required tinting material of devitrified glass, the nucleus agent.
4. a kind of recycling iron on line from iron-containing industrial slag as claimed in claim 1 and prepare the method for glass ceramics frit is characterized in that wherein ferriferous oxide reductive optimal components point is meant i.e. (CaO+MgO) and (SiO 2+ Al 2O 3) ratio be that basicity is that 0.80 ~ 1.25 o'clock slag is formed.
5. a kind of recycling iron on line from iron-containing industrial slag as claimed in claim 1 and prepare the method for glass ceramics frit is characterized in that wherein making the adjustment of slag component to reach cinder microcrystalline glass the specification of quality of frit is meant that slag predominant quantity per-cent consists of: 30 ~ 65 SiO 2, 2 ~ 15 Al 2O 3, 10 ~ 45 CaO, 0 ~ 20 MgO, 0 ~ 10 Fe 2O 3, 0 ~ 10 R 2O, 1 ~ 10 adjustment agent, R is a monovalent metallic ion; Prepare qualified frit and can nearby or be transported to and further be processed into devitrified glass outside the factory, or directly as commercial articles vending.
CN2010102759564A 2010-09-08 2010-09-08 Method for recycling iron on line from iron-containing industrial slag and preparing glass ceramics frit Pending CN101914639A (en)

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