CN105200172A - Synergistic processing method of stacked EAF stainless steel slag and LF refining slag - Google Patents
Synergistic processing method of stacked EAF stainless steel slag and LF refining slag Download PDFInfo
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- CN105200172A CN105200172A CN201510565156.9A CN201510565156A CN105200172A CN 105200172 A CN105200172 A CN 105200172A CN 201510565156 A CN201510565156 A CN 201510565156A CN 105200172 A CN105200172 A CN 105200172A
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Abstract
The invention discloses a synergistic processing method of stacked EAF stainless steel slag and LF refining slag. The method comprises the following steps: uniformly mixing the stacked EAF stainless steel slag, the LF refining slag and coke powder and/or pulverized coal to form mixed slag, and then heating, cooling and post-processing the mixed slag to obtain the processed refined slag. Under the high temperature effect, carbon in the coke powder or pulverized coal is used for reducing Cr<6+> in the EAF stainless steel slag to Cr<3+>; by sufficiently utilizing the characteristic that the high content of Al2O3 in the LF refining slag facilitates the generation of spinel, the reduced Cr2O3 enters the spinel to be cured and sealed, the leaching concentration of Cr<6+> in the refining slag is several micrograms per liter and is far less than a standard limit value of the national standard dangerous waste identification standard leaching toxicity identification (GB5085.3-2007), the harmless treatment of the stacked EAF stainless steel slag is effectively realized, and the harmless treatment of the EAF stainless steel slag and synergistic treatment on the cold-state LF refining slag can be realized; the process is simple, the waste is treated by virtue of waste, and the harmless treatment cost is saved; the method has characteristics of energy conservation, environmental protection and good treatment effect.
Description
Technical field
The present invention relates to a kind for the treatment of process of slag, especially a kind of cooperative processing method storing up EAF stainless steel slag and LF refining slag.
Background technology
2014, Chinese stainless steel crude steel output was 2169.2 ten thousand tons, increases by 14.27% on a year-on-year basis.Produce 1 ton containing chromium refuse (mainly comprising stainless steel slag, acid-washing stainless steel mud etc.) by every 3 tons of stainless steels, exceed 7,000,000 tons containing chromium refuse year generation.At present, stainless steel main production equipments is electric furnace (ElectricArcFurnace, EAF) and argon oxygen decarburizing furnace (ArgonOxygenDecarburization, AOD), and therefore stainless steel slag mainly comprises EAF slag and AOD slag.Stainless steel slag principal element is Ca, Si, Mg, Al, Fe etc., but due to the heavy metal content such as Cr in stainless steel slag higher, its recycling must consider its pulverability, stability and leaching.Pulverability is mainly by oblique crystal β-C
2s is to octahedra γ-C
2s without about there being the volumetric expansion of 12% to cause in hot phase transition process; Stability by f-CaO and f-MgO hydrolytic process 97.8% and 148% volumetric expansion cause; Leaching refers to that stainless steel slag is stacked or tailings is used as after material of construction under the leaching liquor effects such as rainwater, and the toxic heavy metals such as Cr enter the ability of water body.Due to heavy metal leachings such as chromium, the comprehensive Utilization Ways of stainless steel slag is restricted, and on a small quantity for steel slag cement and material of construction preparation, and more stainless steel slags can only to store up process.
Because the melting later stage is reducing atmosphere, hypoxemia gesture controls the oxidation of metal and metalloid, therefore the Cr in EAF stainless steel slag mainly exists with metallic state and+3 valency forms, metallic state chromium usually and Ni, Fe form alloy, reclaimed by fine grinding and magnetic separation, and trivalent chromium is mainly present in Ca-Mg-Al silicate and spinels mineral.A lot of scholar thinks, not only the Cr in stainless steel slag when high temperature
3+cr can be oxidized to
6+, under normal temperature state, this reaction also possesses thermodynamical reaction condition, and after especially material absorbs moisture, CaO hydrolysis will generate the more Ca in oxygen center (OH)
2, make the Cr that oxytropism is stronger
3+more easily be oxidized to Cr
6+, thus increase the leaching toxicity of chromium in EAF stainless steel slag.Due to the impact by kinetic factor, EAF stainless steel slag stores up Cr after 1 year
3+oxidation ratio about 10%, greatly strengthen the leaching toxicity of EAF stainless steel slag.Therefore, rationally disposal is stored up for some time and is contained a certain amount of Cr
6+eAF stainless steel slag of storing up be disposal of waste gas, water and industrial residue field worker's issues that need special attention.At present, store up the harmless treatment of EAF stainless steel slag and mainly contain three classes:
(1) high temperature reduction method: pyrocarbon reduction is with coke, powdered carbon, wood chip, coal gangue and eutrophication algae slag etc. as reductive agent, and the excessive C that utilization wherein contains and stainless steel slag carry out high-temperature fusion reaction, by Cr in slag
6+be reduced to Cr
3+, finally exist with vitreous state or spinel, can be used as Product recycling and use.Except solid state reduction agent, the gases such as hydrogen, methane, carbon monoxide also can be adopted as reductive agent to Cr
3+reduce.It is not thorough often to there is reduction in solid phase high temperature reduction, and it is inflammable gas that gas phase high temperature reduction exists again reductive agent, technique relative complex, otherwise easily causes new pollution.
(2) wet reducing method: stainless steel slag mixes with acid or basic solution, and adds in solution containing the reducing substances such as ferrous sulfate, alkali metalsulphide, by Cr
6+be reduced to Cr
3+, and in basic solution Precipitation Cr (OH)
3with recycling use.Different according to reaction conditions, acidic reduction method, alkaline reduction method and organophosphorus waste liquid reduction method can be divided into.These methods need consumption acids alkaline solution, and produce new sewage need process.
(3) cement solidification method: by a certain amount of stainless steel ground-slag with addition of a certain amount of FeSO
4, FeCl
2deng adding cement clinker after additive, the mixing that adds water, stirring, shaping and solidify, along with aquation and the setting and harden process of cement, Cr is sealed in not stripping in hardening of cement body, reaches stable and innoxious object.Its shortcoming to be after cement solidification, due to the volumetric expansion of chromium slag, to cause cement and concrete stability.
LF refining has the metallurgical characteristics such as equipment is simple, investment cost is low, flexible operation, refining effect are good, is developed rapidly, become indispensable one critical process in modernization Iron and Steel Production short route as the effective means promoting steel metallurgical quality.In LF refining process, the feature of refining slag high alkalinity, low oxidative and high sulfur capacity is mainly utilized to carry out refining to molten steel, to realize steel liquid deoxidation, desulfurization, the metallurgical functions such as the form of the inclusion in absorption steel, control inclusion, improve molten steel cleanness.But, also produce a large amount of refining slag after refining, account for about 3% of output of steel.Produce 8.23 hundred million tons of steel per year according to 2014,1/2 calculates, then every year by generation 1,235 ten thousand tons of LF refining slags through LF refining.The direct discharge of a large amount of LF refining slag, by the waste of the severe contamination and resource that cause environment, does not meet green, ecological metallurgical demand for development.
At present, LF refining slag is recycled and is mainly contained hot Returning utilization and cold conditions process two kinds of techniques.Hot refining slag is mainly returned electric furnace or converter procedure by hot Returning utilization, lime desulfurization, dephosphorization is replaced to reduce the lime consumption of steel making working procedure, the heat of residue effectively recycled simultaneously, reduce steel making working procedure energy consumption, reduce pollution to environment; But due to the enrichment of sulphur, phosphorus content in slag, the number of times of hot refining slag cycling and reutilization is restricted.Cold conditions process returns blast furnace ironmaking or converter steelmaking by after cold conditions refining slag and the mixing of materials such as ferrous material, binding agent, coldmoulding; But this kind of method can only utilize the flux effect of refining slag, and processing rate is restricted.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of effectively, the cooperative processing method storing up EAF stainless steel slag and LF refining slag of environmental protection.
For solving the problems of the technologies described above, the technical solution used in the present invention is: it will store up EAF stainless steel slag, LF refining slag, be mixed into coke powder and/or coal dust and mix slag, then mix slag after heating, cooling, aftertreatment, obtain the refining slag after processing.
In mixing slag of the present invention, the mass percentage of each material is: store up EAF stainless steel slag 3% ~ 10%, LF refining slag 88% ~ 96%, coke powder and/or coal dust 1% ~ 2%.
The present invention adopts microwave to heat.Described microwave power is 150W ~ 900W, and heat-up time is 30 ~ 90min.
The beneficial effect adopting technique scheme to produce is: the present invention utilizes the carbon in coke powder or coal dust to make to store up Cr in EAF stainless steel slag under high temperature action
6+be reduced to Cr
3+; Make full use of LF refining slag height Al
2o
3content is conducive to the feature that spinel generates, and makes the Cr of reduction
2o
3enter spinel be cured and seal up for safekeeping, the refining slag Cr after process
6+leaching concentration is a few microgram liters, far below the standard limited value in country " Hazardous wastes judging standard leaching characteristic identification " (GB5085.3-2007), have effectively achieved the harmless treatment of storing up EAF stainless steel slag, realize storing up the innoxious of EAF stainless steel slag and cold conditions LF refining slag associated treatment.Therefore, present invention process is simple, and the treatment of wastes with processes of wastes against one another, has saved harmless treatment cost; There is energy-conserving and environment-protective, feature that treatment effect is good.
When the present invention adopts microwave heating, make full use of the features such as microwave method heating is fast, hear rate is little, homogeneous heating, effectively can promote treatment effect, reduce process energy consumption.
Embodiment
Originally the cooperative processing method storing up EAF stainless steel slag and LF refining slag adopts following processing step: will store up EAF stainless steel slag, LF refining slag, coke powder and/or coal dust and be placed in respectively in loft drier be cooled to normal temperature after dry 3 ~ 6h at 100 ~ 120 DEG C; According to the percent mass proportioning of storing up EAF stainless steel slag 3% ~ 10%, LF refining slag 88% ~ 96%, coke powder and/or coal dust 1% ~ 2%, mixing of materials is evenly become to mix slag.Mix slag and load ceramic crucible, then ceramic crucible is put into microwave oven, with slag wool insulation around crucible, heat 30 ~ 90min under 150W ~ 900W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature.Cooled mixing slag adopts the method for conventional steel Slag treatment to carry out aftertreatment, can obtain innoxious, after process refining slag.
Below in conjunction with specific embodiment, the present invention is further detailed explanation, the material component in following embodiment and reaction process as described below.
(1) store up EAF stainless steel slag described in and derive from EAF explained hereafter stainless iron and steel enterprise stockyard, its main chemical compositions and content as shown in table 1.
Table 1: main chemical compositions and the content (quality %) of storing up EAF stainless steel slag
(2) main chemical compositions of described LF refining slag and content as shown in table 2.
The chemical composition of table 2:LF refining slag and content (quality %)
(3) carbon in described coke powder and fine coal can make to store up EAF stainless steel slag and store up the Cr that process oxidation generates
6+be reduced to Cr
3+, the principal reaction in microwave heating process is shown in that formula (1) is to formula (3):
2C+O
2→2CO（1）
3CO+2CrO
3→Cr
2O
3+3CO
2（2）
CO
2+C→2CO（3）。
Embodiment 1: gather and store up the EAF stainless steel slag of more than a year, this stores up the main chemical compositions of EAF stainless steel slag and content is: CaO40%, MgO8%, SiO
220%, Al
2o
35%, FeO8%, MnO2%, Cr
2o
32%, above-mentioned content is weight proportion.Gather cold conditions LF refining slag, the main chemical compositions of this LF refining slag and content are: CaO30%, MgO7%, SiO
26%, Al
2o
310%, FeO0.3%, Fe0.3%, above-mentioned content is weight proportion.Store up EAF stainless steel slag, LF refining slag and coke powder to be placed in respectively in loft drier to be cooled to normal temperature after dry 6h at 100 DEG C, according to storing up EAF stainless steel slag: LF refining slag: the mass ratio of coke powder=3:96:1, after mixing of materials is even, load ceramic crucible, then ceramic crucible is put into microwave oven, be incubated with slag wool around crucible, heat 90min under 150W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature, cooled mixing slag adopts the method for conventional steel Slag treatment to carry out aftertreatment, can obtain the refining slag after processing.Cr in refining slag after adopting GB5085.3-2007 to measure process
6+leaching concentration, result shows: Cr
6+leaching concentration < 5 μ g/L.
Embodiment 2: gather and store up the EAF stainless steel slag of more than a year, this stores up the main chemical compositions of EAF stainless steel slag and content is: CaO50%, MgO10%, SiO
230%, Al
2o
310%, FeO22%, MnO3%, Cr
2o
310%, above-mentioned content is weight proportion.Gather cold conditions LF refining slag, the main chemical compositions of this LF refining slag and content are: CaO70%, MgO16%, SiO
230%, Al
2o
345%, FeO2.5%, Fe2.5%, above-mentioned content is weight proportion.Store up EAF stainless steel slag, LF refining slag and coal dust to be placed in respectively in loft drier to be cooled to normal temperature after dry 5.5h at 105 DEG C, according to storing up EAF stainless steel slag: LF refining slag: the mass ratio of coal dust=5:94:1, after mixing of materials is even, load ceramic crucible, then ceramic crucible is put into microwave oven, be incubated with slag wool around crucible, heat 70min under 300W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature, the mixing slag of cooling adopts the method for conventional steel Slag treatment to carry out aftertreatment, can obtain the refining slag after processing.Cr in refining slag after adopting GB5085.3-2007 to measure process
6+leaching concentration, result shows: Cr
6+leaching concentration < 5 μ g/L.
Embodiment 3: gather and store up the EAF stainless steel slag of more than a year, this stores up the main chemical compositions of EAF stainless steel slag and content is: CaO45%, MgO9%, SiO
225%, Al
2o
37.5%, FeO15%, MnO2.5%, Cr
2o
36%, above-mentioned content is weight proportion.Gather cold conditions LF refining slag, the main chemical compositions of this LF refining slag and content are: CaO50%, MgO12%, SiO
218%, Al
2o
323%, FeO1.4%, Fe1.4%, above-mentioned content is weight proportion.Store up EAF stainless steel slag, LF refining slag and coke powder to be placed in respectively in loft drier to be cooled to normal temperature after dry 4.5h at 110 DEG C, according to storing up EAF stainless steel slag: LF refining slag: the mass ratio of coke powder=7:91:2, after mixing of materials is even, load ceramic crucible, then ceramic crucible is put into microwave oven, be incubated with slag wool around crucible, heat 50min under 450W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature, the mixing slag of cooling adopts the method for conventional steel Slag treatment to carry out aftertreatment, can obtain the refining slag after processing.Cr in refining slag after adopting GB5085.3-2007 to measure process
6+leaching concentration, result shows: Cr
6+leaching concentration < 5 μ g/L.
Embodiment 4: gather and store up the EAF stainless steel slag of more than a year, this stores up the main chemical compositions of EAF stainless steel slag and content is: CaO43%, MgO8.7%, SiO
227%, Al
2o
37.5%, FeO15.8%, MnO2.8%, Cr
2o
37.5%, above-mentioned content is weight proportion.Gather cold conditions LF refining slag, the main chemical compositions of this LF refining slag and content are: CaO46%, MgO11%, SiO
216%, Al
2o
321%, FeO0.9%, Fe0.8%, above-mentioned content is weight proportion.Store up EAF stainless steel slag, LF refining slag and coal dust to be placed in respectively in loft drier to be cooled to normal temperature after dry 3h at 115 DEG C, according to EAF stainless steel slag: LF refining slag: the mass ratio of coal dust=8:90:2, after mixing of materials is even, load ceramic crucible, then ceramic crucible is put into microwave oven, be incubated with slag wool around crucible, heat 40min under 900W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature, the mixing slag of cooling adopts the method for conventional steel Slag treatment to carry out aftertreatment, can obtain the refining slag after processing.Cr in refining slag after adopting GB5085.3-2007 to measure process
6+leaching concentration, result shows: Cr
6+leaching concentration < 5 μ g/L.
Embodiment 5: gather and store up the EAF stainless steel slag of more than a year, this stores up the main chemical compositions of EAF stainless steel slag and content is: CaO47%, MgO9.2%, SiO
223%, Al
2o
36.3%, FeO12.9%, MnO2.12%, Cr
2o
33.8%, above-mentioned content is weight proportion.Gather cold conditions LF refining slag, the main chemical compositions of this LF refining slag and content are: CaO54%, MgO13%, SiO
220%, Al
2o
325%, FeO1.5%, Fe1.6%, above-mentioned content is weight proportion.Store up EAF stainless steel slag, LF refining slag, coke powder and coal dust (weight ratio 1:1) are placed in respectively in loft drier and are cooled to normal temperature after dry 3.5h at 120 DEG C, according to EAF stainless steel slag: LF refining slag: the mass ratio of coke powder and coal dust=10:88:2, after mixing of materials is even, load ceramic crucible, then ceramic crucible is put into microwave oven, be incubated with slag wool around crucible, heat 30min under 600W microwave power after, close microwave oven, open fire door taking-up material and be cooled to normal temperature, the mixing slag of cooling adopts the method for conventional steel Slag treatment to carry out aftertreatment, the refining slag after processing can be obtained.Cr in refining slag after adopting GB5085.3-2007 to measure process
6+leaching concentration, result shows: Cr
6+leaching concentration < 5 μ g/L.
Claims (4)
1. store up the cooperative processing method of EAF stainless steel slag and LF refining slag for one kind, it is characterized in that: it will store up EAF stainless steel slag, LF refining slag, be mixed into coke powder and/or coal dust and mix slag, then mix slag after heating, cooling, aftertreatment, obtain the refining slag after processing.
2. the cooperative processing method storing up EAF stainless steel slag and LF refining slag according to claim 1, it is characterized in that, in described mixing slag, the mass percentage of each material is: store up EAF stainless steel slag 3% ~ 10%, LF refining slag 88% ~ 96%, coke powder and/or coal dust 1% ~ 2%.
3. the cooperative processing method storing up EAF stainless steel slag and LF refining slag according to claim 1 and 2, is characterized in that: adopt microwave to heat.
4. the cooperative processing method storing up EAF stainless steel slag and LF refining slag according to claim 3, is characterized in that: described microwave power is 150W ~ 900W, and heat-up time is 30 ~ 90min.
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2015
- 2015-09-08 CN CN201510565156.9A patent/CN105200172B/en not_active Expired - Fee Related
Patent Citations (9)
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| JP2002053351A (en) * | 2000-08-07 | 2002-02-19 | Sumitomo Metal Ind Ltd | Pollution-free stainless steel slag and method for manufacturing the same |
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