CN105039617B - Store up the processing method of EAF stainless steel slags - Google Patents
Store up the processing method of EAF stainless steel slags Download PDFInfo
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- CN105039617B CN105039617B CN201510565139.5A CN201510565139A CN105039617B CN 105039617 B CN105039617 B CN 105039617B CN 201510565139 A CN201510565139 A CN 201510565139A CN 105039617 B CN105039617 B CN 105039617B
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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
- 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 discloses a kind of processing method for storing up EAF stainless steel slags, it will store up EAF stainless steel slags and be mixed with LF refining slag, and refining forms refining finishing slag under reducing atmosphere, and refining finishing slag is post-treated, you can the refining slag after being handled.This method takes full advantage of the high temperature and reducing atmosphere of LF refining, makes Cr in the EAF stainless steel slags stored up6+It is reduced to Cr3+.This method makes full use of the high Al of LF refining slag2O3Content is conducive to the characteristics of spinelle is generated, and promotes to store up Cr in EAF stainless steel slags by LF refining high-temperature reductibility atmosphere6+It is reduced to Cr3+, make a small amount of Cr into refining slag2O3It is cured and seals up for safekeeping into spinelle, the refining slag Cr after processing6+A few microgram liters of leaching concentration, far below country《Hazardous waste judging standard leaching characteristic identification》（GB5085.3‑2007）In standard limited value, realize the harmless treatment for storing up EAF stainless steel slags.This method technique is simple, easy to operate, further saves harmless treatment cost.
Description
Technical field
The present invention relates to a kind of processing method of slag, especially a kind of processing method for storing up EAF stainless steel slags.
Background technology
2014, Chinese stainless steel crude steel yield was 2169.2 ten thousand tons, increases by 14.27% on a year-on-year basis.Produced by every 3 tons of stainless steels
Raw 1 ton of waste containing chromium（Mainly include stainless steel slag, acid-washing stainless steel sludge etc.）Meter, waste containing chromium year yield has exceeded 700
Ten thousand tons.At present, stainless steel main production equipments are electric furnace（Electric Arc Furnace, EAF）And argon oxygen decarburizing furnace
（Argon Oxygen Decarburization, AOD）, therefore stainless steel slag mainly includes EAF slags and AOD slags.Stainless steel slag
Essential element is Ca, Si, Mg, Al, Fe etc., but due in stainless steel slag the content of beary metal such as Cr it is higher, its recycling must
Its pulverability, stability and leaching must be considered.Pulverability is mainly by monoclinic crystal β-C2S is to octahedra γ-C2S nothing
The volumetric expansion that 12% is there are about in hot phase transition process is caused；Stability is 97.8% and 148% in f-CaO and f-MgO hydrolytic processes
Volumetric expansion causes；Leaching refers to that stainless steel slag is stacked or tailings is used as after construction material under the effect of the leaching liquors such as rainwater,
The toxic heavy metals such as Cr enter the ability of water body.Due to the heavy metal leaching such as chromium, the comprehensive Utilization Ways system of stainless steel slag
About, slag cement and construction material are used on a small quantity prepare, and more stainless steel slags can only be to store up processing.
Because the melting later stage is reducing atmosphere, hypoxemia gesture controls the oxidation of metal and metalloid, therefore EAF stainless steels
Cr in slag is main with metallic state and the presence of+trivalent form, and metallic state chromium generally forms alloy with Ni, Fe, passes through fine grinding and magnetic separation
Reclaimed, and trivalent chromium is primarily present in Ca-Mg-Al silicate and spinels mineral.Many scholars think, not only in height
Cr in stainless steel slag when warm3+Cr can be oxidized to6+, the reaction also possesses thermodynamical reaction condition under normal temperature state；Especially
Material is absorbed after moisture, and CaO hydrolysis will the generation more Ca in oxygen center (OH)2So that the stronger Cr of oxytropism3+Easily by oxygen
Turn to Cr6+, so as to increase the leaching toxicity of chromium in EAF stainless steel slags.Due to being influenceed by kinetic factor, EAF stainless steel slags
Store up Cr after 1 year3+Oxygenation efficiency 10% or so, greatly strengthen the leaching toxicity of EAF stainless steel slags.Therefore, heap is rationally disposed
Deposit a period of time and contain a certain amount of Cr6+EAF stainless steel slags, that is, store up EAF stainless steel slags, be disposal of waste gas, water and industrial residue field work
Person's issues that need special attention.At present, the harmless treatment of EAF stainless steel slags mainly has three classes：
（1）High temperature reduction method：Pyrocarbon reduction with coke, powdered carbon, wood chip, gangue and eutrophication algae slag etc. as
Reducing agent, carries out high-temperature fusion reaction, by Cr in slag using the excessive C and stainless steel slag wherein contained6+It is reduced to Cr3+, finally
Exist with glassy state or spinelle, can be used as Product recycling., also can be using hydrogen, methane, an oxidation except solid state reduction agent
The gases such as carbon are as reducing agent to Cr3+Reduced.Solid phase high temperature reduction is not often thorough in the presence of reducing, and gas phase high temperature reduction is again
There is reducing agent for fuel gas, technique is relative complex, otherwise easily causes new pollution.
（2）Wet reducing method：Stainless steel slag is mixed with acid or alkaline solution, and is added into solution containing sulfuric acid Asia
The reducing substanceses such as iron, alkali metal sulphide, by Cr6+It is reduced to Cr3+, and Precipitation Cr (OH) in alkaline solution3To return
Receive and recycle.It is different according to reaction condition, acidic reduction method, alkaline reduction method and organic phosphorus waste liquid reducing process can be divided into.This
A little methods need to consume acid-base solution, and produce new sewage and need processing.
（3）Cement solidification method：By a certain amount of stainless steel ground-slag with addition of a certain amount of FeSO4、FeCl2Deng adding water after additive
Mud clinker, Cr, with the aquation and condensation hardening process of cement, is sealed in cement hard by the mixing that adds water, stirring, shaping and solidification
Change in vivo without dissolution, reach stable and innoxious purpose.Its shortcoming is after cement solidification due to chromium slag volumetric expansion,
Cause the stability of cement and concrete.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of innoxious processing method for storing up EAF stainless steel slags.
In order to solve the above technical problems, the technical solution used in the present invention is：It will store up EAF stainless steel slags and LF essences
Slag mixing is refined, refining forms refining finishing slag under reducing atmosphere, and refining finishing slag is post-treated, you can the refining after being handled
Slag.
The consumption of the present invention for storing up EAF stainless steel slags be LF refining slag and store up EAF stainless steel slag gross weights 3%~
10%。
Refining temperature of the present invention is 1500 DEG C~1600 DEG C, and the time is 25~50min.
EAF stainless steel slags of the present invention of storing up are mixed after drying, magnetic separation with LF refining slag.It is described that to store up EAF stainless
Slag dries 3~6h at 100~120 DEG C.
It is using the beneficial effect produced by above-mentioned technical proposal：（1）The present invention takes full advantage of the high temperature of LF refining
And reducing atmosphere, make Cr in the EAF stainless steel slags stored up6+It is reduced to Cr3+。
（2）The present invention makes full use of the high Al of LF refining slag2O3Content is conducive to the characteristics of spinelle is generated, and passes through LF refining
High-temperature reductibility atmosphere promotes to store up Cr in EAF stainless steel slags6+It is reduced to Cr3+, make a small amount of Cr into refining slag2O3Into point
Spar is cured and sealed up for safekeeping, the refining slag Cr after processing6+A few microgram liters of leaching concentration, far below country《Hazardous waste differentiates mark
Quasi- leaching characteristic identification》（GB5085.3-2007）In standard limited value, realize the innoxious place for storing up EAF stainless steel slags
Reason.
（3）Present invention process is simple, easy to operate, further saves harmless treatment cost.
Embodiment
Originally the processing method for storing up EAF stainless steel slags uses following processing steps：EAF stainless steel slags will be stored up and be placed in drying
In being cooled to normal temperature after dry 3~6h at 100~120 DEG C in case, magnetic separation is extracted uses papery or polybag to enter after magnetisable material
Row packaging, is transported to refining plant stand-by.According to storing up EAF stainless steel slags consumption for LF refining slag and to store up EAF stainless steel slags total
3%~10% proportioning of weight, mixing slag is mixed into by packed EAF stainless steel slags and LF refining slag.The mixing slag adds LF
Refining furnace, is refined under reducing atmosphere, and refining temperature is 1500 DEG C~1600 DEG C, refining time is 25~50min, essence
During refining, mixing slag high temperature fully melts, reduce after, form refining finishing slag.After the completion of LF refining, refining finishing slag is transported through slag ladle
Slag treatment workshop is delivered to, is post-processed using the processing method of conventional slag, the refining slag after being handled.
In treatment method：（1）It is described to store up the iron and steel enterprise that EAF stainless steel slags derive from EAF technique productions stainless steels
Stockyard, its main chemical compositions and content are as shown in table 1.
Table 1：Store up the main chemical compositions and content of EAF stainless steel slags（Weight %）
2）The main chemical compositions of the LF refining slag are as shown in table 2.
Table 2：The main chemical compositions and content of LF refining slag（Weight %）
（3）In refining process, strong reductant Al addition can make the Cr for storing up process oxidation generation6+It is reduced to Cr3+,
Even partial reduction enters molten steel into crome metal.The reduction reaction process of chromium is shown in formula in refining process（1）And formula（2）：
2Al+2CrO3→Cr2O3+Al2O3（1）
2Al+Cr2O3→2Cr+Al2O3（2）.
With reference to specific embodiment, the present invention is further detailed explanation.
Embodiment 1：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 40%、MgO 8%、SiO2 20%、Al2O3 5%、FeO 8%、MnO 2%、Cr2O32%, above-mentioned content is attached most importance to
Measure content.Above-mentioned EAF stainless steel slags of storing up are placed in drying box in being cooled to normal temperature after dry 6h at 105 DEG C, and magnetic is extracted in magnetic separation
Property material after tailings packed using papery or polybag, be transported to refining plant stand-by.According to LF refining slag:Store up EAF
Stainless steel slag=97:3 mass ratio mixing, adds LF refining furnace by mixing slag, 1500 DEG C, 50min is passed through under reducing atmosphere
Refining finishing slag is formed after refining.After the completion of LF refining, refining finishing slag be transported to Slag treatment workshop through slag ladle, using with conventional slag
The consistent method of processing is post-processed, the refining slag after being handled.Refining after being handled using GB5085.3-2007 measure
Cr in slag6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5, less than concentration limit.
Embodiment 2：The EAF stainless steel slags of more than 1 year are stored up in collection, and this is stored up the main component of EAF stainless steel slags and contained
Measure and be：CaO 50%、MgO 10%、SiO2 30%、Al2O3 10%、FeO 22%、MnO 3%、Cr2O310%, above-mentioned content is attached most importance to
Measure content.Above-mentioned EAF stainless steel slags of storing up are placed in drying box in being cooled to normal temperature after dry 5h at 105 DEG C, and magnetic is extracted in magnetic separation
Property material after tailings packed using papery or polybag, be transported to refining plant stand-by.According to LF refining slag:Store up EAF
Stainless steel slag=95:5 mass ratio mixing, adds LF refining furnace by mixing slag, 1540 DEG C, 40min is passed through under reducing atmosphere
Refining finishing slag is formed after refining.After the completion of LF refining, refining finishing slag be transported to Slag treatment workshop through slag ladle, using with conventional slag
The consistent method of processing is post-processed, the refining slag after being handled.Refining after being handled using GB5085.3-2007 measure
Cr in slag6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5, less than concentration limit.
Embodiment 3：The EAF stainless steel slags of more than 1 year are stored up in collection, and this is stored up the main component of EAF stainless steel slags and contained
Measure and be：CaO 45%、MgO 9%、SiO2 26%、Al2O3 7.5%、FeO 15%、MnO 2.5%、Cr2O36%, above-mentioned content is
Weight content.Above-mentioned EAF stainless steel slags of storing up are placed in drying box in being cooled to normal temperature after dry 5.5h at 100 DEG C, and magnetic separation is carried
The tailings after magnetisable material is taken to be packed using papery or polybag, it is stand-by to be transported to refining plant, according to LF refining slag:Store up
EAF stainless steel slag=93:7 mass ratio mixing, mixing slag is added into LF refining furnace, under reducing atmosphere by 1560 DEG C,
Refining finishing slag is formed after 35min refinings.After the completion of LF refining, refining finishing slag be transported to Slag treatment workshop through slag ladle, using with it is normal
The consistent method of rule slag processing is post-processed, the refining slag after being handled.After being handled using GB5085.3-2007 measure
Refining slag in Cr6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5, less than concentration limit.
Embodiment 4：The EAF stainless steel slags of more than 1 year are stored up in collection, and this is stored up the main component of EAF stainless steel slags and contained
Measure and be：CaO 43%、MgO 8.5%、SiO2 28%、Al2O3 8.6%、FeO 17.2%、MnO 2.2%、Cr2O35.2%, it is above-mentioned to contain
Amount is weight content.It is above-mentioned store up EAF stainless steel slags and be placed in drying box be cooled to normal temperature, magnetic after 3h is dried at 110 DEG C
Choosing is extracted the tailings after magnetisable material and packed using papery or polybag, is transported to refining plant stand-by.According to LF refining slag:
Store up EAF stainless steel slag=92.5:7.5 mass ratio mixing, adds LF refining furnace by mixing slag, passes through under reducing atmosphere
1600 DEG C, 30min refining after formed refining finishing slag.After the completion of LF refining, refining finishing slag is transported to Slag treatment workshop through slag ladle, adopts
Post-processed with the method consistent with conventional slag processing, the refining slag after being handled.Determined using GB5085.3-2007
Cr in refining slag after processing6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5, less than concentration limit.
Embodiment 5：The EAF stainless steel slags of more than 1 year are stored up in collection, and this is stored up the main component of EAF stainless steel slags and contained
Measure and be：CaO 47%、MgO 9.2%、SiO2 22%、Al2O3 6.5%、FeO 12.6%、MnO 2.85%、Cr2O38%, above-mentioned content
It is weight content.It is above-mentioned store up EAF stainless steel slags and be placed in drying box be cooled to normal temperature, magnetic separation after 4h is dried at 120 DEG C
Extract the tailings after magnetisable material to be packed using papery or polybag, be transported to refining plant stand-by.According to LF refining slag:Heap
Deposit EAF stainless steel slag=90:10 mass ratio mixing, adds LF refining furnace by mixing slag, 1580 is passed through under reducing atmosphere
DEG C, 25min refining after formed refining finishing slag.After the completion of LF refining, refining finishing slag be transported to Slag treatment workshop through slag ladle, using with
The consistent method of conventional slag processing is post-processed, the refining slag after being handled.Handled using GB5085.3-2007 measure
Cr in refining slag afterwards6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5, less than concentration limit.
Claims (4)
1. a kind of processing method for storing up EAF stainless steel slags, it is characterised in that：It will store up EAF stainless steel slags and LF refining slag
Mixing, is added in LF refining furnace, is refined under reducing atmosphere, and refining finishing slag is formed after the completion of LF refining, finishing slag is refined
It is post-treated, you can the refining slag after being handled, the main chemical compositions and percentage by weight for storing up EAF stainless steel slags
Content is：CaO 40-50、MgO 8-10、SiO2 20-30、Al2O3 5-10、FeO 8-22、MnO 2-3、Cr2O32-10；Institute
The main chemical compositions and weight percent content for stating LF refining slag are：CaO 40-60、MgO 5-10、SiO2 5、Al2O3 15-
35th, FeO 0.3-0.6, MnO ＜ 0.5, CaF2＜ 6, the consumption for storing up EAF stainless steel slags is LF refining slag and stores up EAF
The 3%~10% of stainless steel slag gross weight.
2. the processing method according to claim 1 for storing up EAF stainless steel slags, it is characterised in that：The refining temperature is
1500 DEG C~1600 DEG C, the time is 25~50min.
3. the processing method according to claim 1 or 2 for storing up EAF stainless steel slags, it is characterised in that：It is described to store up EAF
Stainless steel slag is mixed after drying, magnetic separation with LF refining slag.
4. the processing method according to claim 3 for storing up EAF stainless steel slags, it is characterised in that：It is described that to store up EAF stainless
Slag dries 3~6h at 100~120 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510565139.5A CN105039617B (en) | 2015-09-08 | 2015-09-08 | Store up the processing method of EAF stainless steel slags |
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| CN201510565139.5A CN105039617B (en) | 2015-09-08 | 2015-09-08 | Store up the processing method of EAF stainless steel slags |
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| Publication Number | Publication Date |
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| CN105039617A CN105039617A (en) | 2015-11-11 |
| CN105039617B true CN105039617B (en) | 2017-09-01 |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5289272A (en) * | 1976-01-20 | 1977-07-26 | Shizuo Suzuki | Method of treating industrial waste |
| TW477818B (en) * | 1997-03-27 | 2002-03-01 | Kawasaki Steel Co | Method for processing chromium oxide-containing substances in large quantities, method for utilizing the processed substances, and products comprising the processed substances |
| JP2000319047A (en) * | 1999-03-10 | 2000-11-21 | Kawasaki Steel Corp | Reforming treatment of stainless steel refining slag |
| CN104862490B (en) * | 2015-05-28 | 2017-10-17 | 中冶南方工程技术有限公司 | Stainless steel slag recovery and reusing and recycling method and its device |
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