CN108642231B - Converter slag modifier and method for preparing low-alkalinity slag system by using same - Google Patents

Converter slag modifier and method for preparing low-alkalinity slag system by using same Download PDF

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CN108642231B
CN108642231B CN201810462306.7A CN201810462306A CN108642231B CN 108642231 B CN108642231 B CN 108642231B CN 201810462306 A CN201810462306 A CN 201810462306A CN 108642231 B CN108642231 B CN 108642231B
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mass
slag
less
modifier
converter slag
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CN108642231A (en
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唐复平
王亮
廖相巍
韩子文
李金莲
任伟
张伟
张立国
王再义
童晓宇
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Angang Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/36—Processes yielding slags of special composition
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/36—Processes yielding slags of special composition
    • C21C2005/363—Slag cements

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)

Abstract

The present invention providesA converter slag modifier and a method for preparing a low-alkalinity slag system by using the same are disclosed, wherein the modifier comprises the following components in percentage by weight: the sum of the blast furnace dust and the iron tailings is 90-100%, the mass ratio of the blast furnace dust/the iron tailings is 0.7-6.0, and the mass percentage of the waste aluminum carbon bricks is 0-10%. The method for preparing the low-alkalinity slag system by using the converter slag modifier fully and uniformly mixes the modifier with the converter slag according to the mass ratio of 0.5-1.3, and the mixed mixture meets the following requirements: mc＞0.27×MFe2O3+0.2×MFeO；MCaO＜2.8×MSiO2+0.941×MAl2O3+1.4×MMgO(ii) a Roasting the mixture in non-oxidizing atmosphere at 1450 deg.c for 20 min to obtain slag system with basicity of 0.5-1.3. The invention solves the problem of recycling converter slag, reduces the waste discharge and obtains the low-alkalinity slag system of high value-added products.

Description

Converter slag modifier and method for preparing low-alkalinity slag system by using same
Technical Field
The invention belongs to the field of recycling of solid waste resources in the converter steelmaking process, and particularly relates to a converter slag modifier and a method for preparing a low-alkalinity slag system by using the same.
Background
Converter slag is an industrial solid waste generated in the process of converter steelmaking. 0.1 to 0.13 ton of steel slag is produced as a byproduct in each 1 ton of steel produced at the temperature of 1350 to 1450 ℃. The iron-containing slag-free smelting furnace further contains 10-30% of total iron (TFe) and a large amount of beneficial elements such as calcium, magnesium and silicon, so that the recycling of converter slag resources is increased, and the iron-containing slag-free smelting furnace becomes a main means for reducing the smelting cost of a steel mill and realizing zero emission of wastes. At present, the main treatment method for converter slag is to crush, screen and magnetically separate cold converter slag, extract metal oxides in the cold converter slag and then utilize the extracted metal oxides, and the treated converter slag is usually used for foundation backfill, road paving, cement raw materials, water purifying agents, steel slag fertilizers and the like. The two products obtained by the treatment method are the iron oxide and the high-alkalinity slag system respectively, and the added value of the products is lower.
A method for reducing converter slag and recycling slag by using coal gas (CN 105624359A) discloses a method for reducing converter slag and recycling slag by using coal gas, which comprises the following steps: the converter smelting process is divided into two flows of converter steelmaking and converter slag heat treatment, wherein in the converter steelmaking flow, impurity elements in molten iron enter the converter slag in the form of oxides through oxidation reaction to form thermal state converter slag with high phosphorus content; pouring the converter slag into a processing slag filling unit, entering the heat treatment process of the converter slag, transferring the slag filling unit containing the converter slag to a converter slag processing station, carrying out thermal state reduction by taking coal gas as a reduction medium in the converter slag processing station, wherein the reduction ratio of FeO is more than 80%, the reduction ratio of P2O5 is more than 80%, carrying out waste heat recovery and gaseous phosphorus recovery of the converter slag in the thermal state reduction process, and returning the converter slag after the treatment as pre-molten slag and iron-containing cooling materials to the converter for reuse. The binary alkalinity of the slag system obtained by the method is generally higher, free calcium oxide exists in the slag, and the slag system cannot be applied to the industries of road paving, cement preparation and the like.
A steel slag processing method and a device thereof (CN 103757152B) disclose a steel slag processing method which comprises the steps of feeding silicon-aluminum acidic oxide and steel slag, wherein the molar ratio of the total silicon-aluminum acidic oxide to the basic oxide in the mixture is 1: 2.5-2.9; the temperature of the rotary kiln is 1350-; granulating the product into granules, performing water quenching and cooling, then falling into water, and performing dehydration treatment; and (4) carrying out magnetic separation on the dehydrated particles, and separating the steel particles from the silicate particles. In the method, the reducing agent is a mixture of carbon monoxide and coal powder, so that the cost of the raw materials is high. And the combustion process of the pulverized coal of the rotary kiln necessarily introduces oxygen in the air, and compared with a reducing agent, the process is complex and the reduction efficiency is low.
A method disclosed in "a method for recovering iron and phosphorus from steelmaking slag" (CN 102264919 a) includes the steps of recovering phosphorus and iron from the steelmaking slag at low cost, and effectively utilizing the recovered phosphorus and iron as resources, respectively: a first step of reducing phosphorus-containing steel-making slag such as dephosphorization slag with a reducing agent such as carbon, Si, Al, etc., and reducing and recovering iron oxide and phosphorus oxide in the slag as phosphorus-containing molten iron; a second step of using the steel-making slag from which the iron oxides and phosphorus oxides have been removed as a CaO source in the sintering step, and recycling the obtained sintered ore to the blast furnace; a third step of concentrating phosphorus in a CaO flux by dephosphorizing the molten iron containing phosphorus recovered by the reduction treatment until the phosphorus concentration in the molten iron containing phosphorus becomes 0.1 mass% or less; and a fourth step of mixing the phosphorus-containing molten iron having a phosphorus concentration of 0.1 mass% or less as an iron source into the blast furnace molten iron. The slag obtained by the method has high CaO content in percentage by mass, so that only a small amount of CaO in a sintering process can be replaced, the slag with gelling property cannot be obtained, the added value of the product is low, and the recycling value of the slag is limited.
Recovery of Fe and P from CaO-SiO by Taeyoung Kim et al2-FetO-P2O5The Slag byMicrowave Treatment article introduces a laboratory study of the reduction Treatment of converter Slag by graphite carbon heated by microwave. Wherein the equilibrium constant of carbon is 1.69, the reduction rate of iron reaches 0.97 after heating for 15 minutes, and the reduction rate of phosphorus is 0.89. The Liuchun Wei et al, the theory of Valorization of BOF Steel Slag by Reduction and Phase Modification, Metarecovery and Slag Valorization, introduced the laboratory study of carbothermic Reduction of iron and phosphorus oxides in Slag and the adjustment of alkalinity by adding alumina and silica to prepare different Slag products. The reaction is reduced for 1 hour at 1600 ℃, the removal rate of iron oxide is more than 0.9, and the removal mechanism of iron-phosphorus oxide is introduced. The reducing agents used in both articles are graphitic carbon, which is difficult to achieve economically in large-scale industrializationIt is beneficial to.
The invention provides a converter slag modifier prepared from blast furnace dust and mine difficultly-treated tailings, wherein the raw materials of the modifier are all wastes, and the products obtained by treating the converter slag are iron and low-alkalinity slag systems which are all high value-added products.
Based on the above background information, the present invention provides a converter slag modifier and a method for preparing low alkalinity slag system.
Disclosure of Invention
The invention aims to overcome the problems and the defects and provide a converter slag modifier and a method for preparing a low-alkalinity slag system by using the converter slag modifier.
The purpose of the invention is realized as follows:
a converter slag modifier comprises blast furnace fly ash, iron tailings and waste aluminum carbon bricks; the modifier comprises the following components in percentage by weight: the sum of the blast furnace dust and the iron tailings is 90-100%, the mass ratio of the blast furnace dust/the iron tailings is 0.7-6.0, and the mass percentage of the waste aluminum carbon bricks is 0-10%.
Further, the water content of the blast furnace dust is lower than 2% by mass, the grain size is smaller than 100 meshes and accounts for more than 90% by mass, and the mass ratio of carbon to total iron is not lower than 0.7.
Further, the iron tailings contain less than 1% of water by mass, the grain size is smaller than 100 meshes and accounts for more than 90% of the iron tailings by mass, and the mass ratio of silicon oxide to total iron is not less than 5.0.
Furthermore, the water content of the waste aluminum-carbon brick is less than 2% by mass, the grain size is less than 100 meshes and accounts for more than 90% by mass, and the MgO content is less than 5% by mass.
The second technical scheme provided by the invention is a method for preparing a low-alkalinity slag system by using the converter slag modifier, wherein the modifier and the converter slag are fully and uniformly mixed according to the mass ratio of 0.5-1.3, and the mixed mixture meets the following formula:
Mc＞0.27×MFe2O3+0.2×MFeO
MCaO＜2.8×MSiO2+0.941×MAl2O3+1.4×MMgO
wherein: mcMass of carbon in the mixture, MFe2O3Fe in mix2O3Mass, MFeOQuality of FeO in the mixture, MCaOQuality of calcium oxide in the mixture, MSiO2Quality of silica in the mixture, MAl2O3Quality of alumina in the mixture, MMgO-the mass of magnesium oxide in the mix;
and then roasting the mixture under the condition of non-oxidizing atmosphere at the temperature of not less than 1450 ℃ for not less than 20 minutes to obtain a low-alkalinity slag system with alkalinity R2 of 0.5-1.3.
The invention has the beneficial effects that: the modifier raw materials, namely blast furnace dust, iron tailings and waste aluminum carbon bricks, are waste materials, so that the waste discharge is reduced while the recycling of converter slag is realized. The obtained product is iron and can be used for preparing low-alkalinity slag systems of high value-added products such as cement, geopolymer and the like.
Detailed Description
The present invention is further illustrated by the following examples.
A converter slag modifier comprises blast furnace fly ash, iron tailings and waste aluminum carbon bricks; the modifier comprises the following components in percentage by weight: the sum of the blast furnace dust and the iron tailings is 90-100%, the mass ratio of the blast furnace dust/the iron tailings is 0.7-6.0, and the mass percentage of the waste aluminum carbon bricks is 0-10%.
The blast furnace dust removal ash contains less than 2% of water by mass, the grain size is less than 100 meshes and accounts for more than 90% of the mass, and the mass ratio of carbon to total iron is not less than 0.7.
The iron tailings contain less than 1% of water by mass, the grain size is smaller than 100 meshes and accounts for more than 90% of the iron tailings by mass, and the mass ratio of silicon oxide to total iron is not less than 5.0.
The waste aluminum-carbon brick contains less than 2% of water by mass, the grain size of less than 100 meshes accounts for more than 90% of the mass, and the MgO by mass is less than 5%.
The method for preparing the low-alkalinity slag system by using the converter slag modifier comprises the following steps of fully and uniformly mixing the modifier with converter slag according to the mass ratio of 0.5-1.3, wherein the mixed mixture meets the following formula:
Mc＞0.27×MFe2O3+0.2×MFeO
MCaO＜2.8×MSiO2+0.941×MAl2O3+1.4×MMgO
wherein: mcMass of carbon in the mixture, MFe2O3Fe in mix2O3Mass, MFeOQuality of FeO in the mixture, MCaOQuality of calcium oxide in the mixture, MSiO2Quality of silica in the mixture, MAl2O3Quality of alumina in the mixture, MMgO-the mass of magnesium oxide in the mix;
and then roasting the mixture under the condition of non-oxidizing atmosphere at the temperature of not less than 1450 ℃ for not less than 20 minutes to obtain a low-alkalinity slag system with alkalinity R2 of 0.5-1.3.
The chemical composition analysis of the raw materials of the modifier in the embodiment of the invention is shown in table 1, the component design of the modifier in the embodiment of the invention is shown in table 2, the chemical composition analysis of the converter slag in the embodiment of the invention is shown in table 3, the mixed ingredients of the modifier and the converter slag in the embodiment of the invention are shown in table 4, and the experimental evaluation results of the low-alkalinity slag system prepared in the embodiment of the invention are shown in table 5.
TABLE 1 raw material chemical composition analysis (wt%) of modifiers of inventive examples
Figure BDA0001661158360000071
Table 2 composition of modifier for inventive examples table (wt/%)
Figure BDA0001661158360000072
Tables 1 to 3 chemical composition (wt%) of converter slag of examples of the present invention
Converter slag FeO Fe2O3 SiO2 CaO MgO Al2O3
1 0.72 23.14 12.89 38.38 10.76 9.18
2 0.66 22.56 13.22 39.1 9.86 9.57
3 0.66 22.56 13.22 39.1 9.86 9.57
4 0.72 23.14 12.89 38.38 10.76 9.18
Table 4 blending table of modifier and converter slag according to the embodiment of the present invention
Figure BDA0001661158360000081
TABLE 5 Experimental evaluation results of low alkalinity slag system prepared by the embodiment of the invention
Figure BDA0001661158360000082
In order to express the present invention, the above embodiments are properly and fully described by way of examples, and the above embodiments are only used for illustrating the present invention and not for limiting the present invention, and those skilled in the relevant art can make various changes and modifications without departing from the spirit and scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. made by the persons skilled in the relevant art should be included in the protection scope of the present invention, and the protection scope of the present invention should be defined by the claims.

Claims (5)

1. A converter slag modifier is characterized by comprising blast furnace fly ash, iron tailings and waste aluminum carbon bricks; the modifier comprises the following components in percentage by weight: the sum of the blast furnace dust removal ash and the iron tailings is 90-97.8%, the mass ratio of the blast furnace dust removal ash to the iron tailings is = 0.7-1.2, the mass percentage of the waste aluminum carbon bricks is 2.2-10%, and the mass ratio of the blast furnace dust removal ash carbon to the total iron is not lower than 0.7.
2. The converter slag modifier according to claim 1, wherein the water content of the blast furnace dust is less than 2% by mass, and the particle size fraction of the blast furnace dust is less than 100 meshes and accounts for more than 90% by mass.
3. The converter slag modifier according to claim 1, wherein the iron tailings contain less than 1% of water by mass, have a grain size of less than 100 meshes and account for more than 90% of the iron tailings by mass, and the mass ratio of silicon oxide to total iron is not less than 5.0.
4. The converter slag modifier according to claim 1, wherein the waste aluminum carbon brick contains less than 2% of water by mass, has a particle size of less than 100 meshes and accounts for more than 90% of the mass, and contains less than 5% of MgO by mass.
5. The method for preparing the low-alkalinity slag system by using the converter slag modifier of claims 1-4 is characterized in that the modifier and the converter slag are fully and uniformly mixed according to the mass ratio of 0.5-1.3, and the mixed mixture meets the following formula:
Mc＞0.27×MFe2O3+0.2×MFeO
MCaO＜2.8×MSiO2+0.941×MAl2O3+1.4×MMgO
wherein: mcMass of carbon in the mixture, MFe2O3Fe in mix2O3Mass, MFeOQuality of FeO in the mixture, MCaOQuality of calcium oxide in the mix，MSiO2Quality of silica in the mixture, MAl2O3Quality of alumina in the mixture, MMgO-the mass of magnesium oxide in the mix;
and then roasting the mixture under the condition of non-oxidizing atmosphere at the temperature of not less than 1450 ℃ for not less than 20 minutes to obtain a low-alkalinity slag system with alkalinity R2 of 0.5-1.3.
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CN104805250A (en) * 2015-04-21 2015-07-29 北京科技大学 High-temperature slag continuous modification processing method
CN106591575A (en) * 2017-03-11 2017-04-26 重庆臻焱节能环保科技有限公司 Low-energy-consumption cold-pressing pellet and preparation method thereof
CN106755981A (en) * 2016-11-25 2017-05-31 江苏省沙钢钢铁研究院有限公司 A kind of method that utilization iron ore mine produces metallized pellet

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Publication number Priority date Publication date Assignee Title
CN101413043A (en) * 2008-12-05 2009-04-22 攀枝花钢城集团有限公司 Steel-smelting regulator and preparation thereof
CN104131130A (en) * 2014-07-17 2014-11-05 攀钢集团西昌钢钒有限公司 Converter final-slag modifier and use thereof
CN104805250A (en) * 2015-04-21 2015-07-29 北京科技大学 High-temperature slag continuous modification processing method
CN106755981A (en) * 2016-11-25 2017-05-31 江苏省沙钢钢铁研究院有限公司 A kind of method that utilization iron ore mine produces metallized pellet
CN106591575A (en) * 2017-03-11 2017-04-26 重庆臻焱节能环保科技有限公司 Low-energy-consumption cold-pressing pellet and preparation method thereof

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