CN108342585A - A kind of method of comprehensive utilization of magnesium-smelting reduction slag - Google Patents

A kind of method of comprehensive utilization of magnesium-smelting reduction slag Download PDF

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CN108342585A
CN108342585A CN201810203208.1A CN201810203208A CN108342585A CN 108342585 A CN108342585 A CN 108342585A CN 201810203208 A CN201810203208 A CN 201810203208A CN 108342585 A CN108342585 A CN 108342585A
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magnesium
smelting reduction
silcaz
reduction slag
comprehensive utilization
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CN108342585B (en
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王耀武
马占山
彭建平
狄跃忠
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Northeastern University China
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20Obtaining alkaline earth metals or magnesium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06Alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04Refining by applying a vacuum
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

A kind of method of comprehensive utilization of magnesium-smelting reduction slag, includes the following steps:(1) powdered magnesium-smelting reduction slag, Cab-O-sil, carbonaceous reductant and binder are mixed;(2) it is dried after pelletizing is made;(3) electric arc furnaces is used to carry out melting, the Silcaz for forming liquid after melting is deposited on electric arc furnace bottom;(4) it after the Silcaz of liquid being discharged, pours into pig moulding machine and pours into Silcaz block;Silcaz block is directly as finished product or carries out step (5);(5) broken be put into of Silcaz block is evaporated in vacuo in tank, is evaporated in vacuo, calcium is distilled off, and surplus material is Antaciron.The technique of the present invention can realize the comprehensive utilization of reducing slag, be a kind for the treatment of process of green.

Description

A kind of method of comprehensive utilization of magnesium-smelting reduction slag
Technical field
The invention belongs to metallurgical technology field, more particularly to a kind of method of comprehensive utilization of magnesium-smelting reduction slag.
Background technology
85% or more magnesium metal is produced using ferrosilicon process in the world at present, now worldwide, the silicon of application Hot method is mainly Pidgeon process and interior electrical resistance heating.Either still interior electrical resistance heating, reducing agent used are Pidgeon process Ferrosilicon, raw material are dolomite, and the two differs only in mode of heating difference.Using the magnesium-smelting silicothermic process that ferrosilicon is reducing agent Technology, 10 tons or more of dolomite and one ton or more of ferrosilicon will be consumed by often producing one ton of magnesium, while generate 5 tons or more of refining magnesium Reducing slag.
The main ingredient of magnesium-smelting reduction slag is calcium orthosilicate, is in addition to this also had neither part nor lot in containing 4~7% MgO and part The ferrosilicon of reduction reaction and some other impurity.In magnesium-smelting reduction slag in the form of ferrosilicon existing for silicon be about 3-5%, iron about exists 5% or so;Magnesium-smelting reduction slag contains calcium oxide about 50~60%, and silica about 28~35% (contains unreacted silicon);Magnesium smelting reducing Slag is mainly used for making cement raw material or for producing various bricks, but due to higher containing magnesium amount is aoxidized in reducing slag, cement plant addition Measure limited, and brickmaking profit is relatively low, and dosage is also limited, therefore most magnesium-smelting reduction slag is simply discarded or fills, This can undoubtedly cause environmental problem;Therefore, the process problem of magnesium-smelting reduction slag, which has become, restricts Smelting magnesium industry value chain A main problem.
Invention content
The above problem existing for the magnesium-smelting reduction slag treatment technology formed for existing ferrosilicon process production magnesium metal, the present invention A kind of method of comprehensive utilization of magnesium-smelting reduction slag is provided, this method is using magnesium-smelting reduction slag as raw material, using carbonaceous material as reducing agent, It first carries out melting and produces Silcaz, Silcaz is used to return to reduction magnesium process as magnesium smelting reducing agent, or carries out true Sky distillation obtains calcium metal and Antaciron, and Antaciron is used to return to refining magnesium process as reducing agent, is not generating secondary dirt While dye, reducing slag waste material is efficiently utilized.
The method of the present invention includes the following steps:
1, powdered magnesium-smelting reduction slag, Cab-O-sil, carbonaceous reductant and binder are uniformly mixed, mixture is made Material;Wherein the dosage of Cab-O-sil is 0.4~2.0 times of magnesium-smelting reduction slag quality;The dosage of carbonaceous reductant presses fixation therein Carbon and calcium oxide, silica and the complete Response calculation of magnesia, based on reaction equation be:
CaO+C=CO+Ca (1),
SiO2+ C=Si+CO (2)
With MgO+C=Mg+CO (3);
The dosage of binder is the 90~100% of carbonaceous reductant gross mass;
2, pelletizing is made in mixed material, then dried;
3, the pelletizing after drying is subjected to melting using electric arc furnaces, the Silcaz that liquid is formed after melting is deposited on electricity Arc furnace bottom;
4, it after the Silcaz of liquid being discharged, pours into pig moulding machine and pours into Silcaz block;The silico-calcium of acquisition Iron alloy block is directly as finished product or carries out step 5;
5, Silcaz block is broken into granularity≤10cm fragments, be put into vacuum distillation tank in, vacuum degree be 0.1~ It is heated to 900~1250 DEG C under conditions of 50Pa to be evaporated in vacuo, the time is 2~12h;Vacuum is kept in vacuum distillation process Degree is 0.1~50Pa;After the completion of vacuum distillation, calcium is distilled off and becomes solid metallic calcium in condensation, and surplus material is silicon Ferroalloy.
The ingredient of above-mentioned magnesium-smelting reduction slag contains MgO 4~7%, SiO by mass percentage225~32%, CaO 60~ 66%, Fe2O33~5%.
In the above method, scrap iron is added in step 3 before melting into electric arc furnaces, control the Silcaz finally obtained In, the mass percent of calcium is 29~50%, and the mass percent of silicon is 40~70%, and the mass percent of iron is 1~15%.
Grain size≤0.15mm of above-mentioned Cab-O-sil, grain size≤0.15mm of the carbonaceous reductant.
Above-mentioned carbonaceous reductant select coal, coke, semi-coke, forge after without coal-fired, petroleum coke and/or metallurgical coke.
Above-mentioned binder selects sulfite cellulose binder, bentonite, waterglass or other organic binders.
Briquetting pressure is 50~150MPa, the temperature 50~250 when drying when pelletizing being made in the above method, in step 2 DEG C, 2~8h of drying time.
In the above method, the Silcaz of liquid is discharged every 2~10h when melting in step 3.
In the above method, in step 3 when melting, part CaO, SiO in raw material2After metal being reduced into MgO, due to Vapour pressure is higher to be evaporated, and is reoxidized as corresponding oxide, and deposited in dust arrester installation, and oxidation is formed The mixture of object;It is reused as magnesium-smelting reduction slag in the hopcalite return to step 1.
In the above method, Silcaz block is as magnesium smelting reducing agent for restoring refining magnesium process.
In the above method, Antaciron is as magnesium smelting reducing agent for restoring refining magnesium process.
In the method fusion process of the present invention in addition to generating portion gas, solid slag is not generated;It is all valuable in raw material Ingredient enters in alloy;Calcium in Silcaz is distilled off condensation, and ferrosilicon stays in thermal region, to realize calcium With the separation of ferrosilicon;The calcium of acquisition is sold after remelting refining ingot casting as metal calcium product, and remaining ferrosilicon is as refining magnesium Reducing agent returns to refining magnesium process;The vacuum distillation tank of use is divided into heating zone and condensing zone, and heating zone is located in heating furnace and adds Heat, condensing zone are located at the outside of heating furnace, and heating furnace is resistance furnace or gas burner, and reductive jar can take out out of reduction furnace, with Convenient for fast cooling.
Process smelting silicothermic process magnesium reduction slag through the invention can realize the comprehensive utilization of reducing slag, refine after processing Oxide in magnesium reduction slag is changed into Silcaz, and Silcaz can be used as reducing agent and return to refining magnesium process, can also Silcaz is further distilled and obtains calcium and two kinds of products of ferrosilicon, and calcium is sold as product, Antaciron is as reduction Agent returns to refining magnesium process.No matter which kind of method, any waste water in processing procedure, the secondary pollutions such as waste residue are a kind of places of green Science and engineering skill, while can get certain economic benefit.
Description of the drawings
Fig. 1 is the method for comprehensive utilization process flow chart of the magnesium-smelting reduction slag of the embodiment of the present invention 1;
Fig. 2 is the method for comprehensive utilization process flow chart of the magnesium-smelting reduction slag of the embodiment of the present invention 2;
Fig. 3 is the X-ray diffraction material phase analysis XRD diagram for the Silcaz that the embodiment of the present invention 1 obtains.
Specific implementation mode
The vacuum distillation tank used in the embodiment of the present invention is equipped with heating zone and condensing zone, and heating zone is placed in heating furnace, Condensing zone is located at outside heating furnace;The heating furnace is resistance furnace or gas burner.
The ingredient of the magnesium-smelting reduction slag used in the embodiment of the present invention contains MgO 4~7%, SiO by mass percentage2 25 ~32%, CaO 60~66%, Fe2O33~5%.
Antaciron by mass percentage siliceous 65~80%, iron 35~20% in the embodiment of the present invention.
Cab-O-sil, carbonaceous reductant and the binder used in the embodiment of the present invention is commercial products.
The scrap iron used in the embodiment of the present invention is commercial products, main component Fe, FeO and Fe3O4, wherein iron content It should be greater than 98%.
The model X Pert Pro MPDDY2094 of X-ray diffraction equipment in the embodiment of the present invention.
The equipment that pelletizing uses is made in the embodiment of the present invention as briquetting machine.
The Silcaz discharge of state is to go out the discharge of alloy mouth by electric arc furnace bottom in liquid embodiment of the present invention.
Temperature is subject to whole material melts when melting in the embodiment of the present invention.
Magnesium step is refined in vacuum-thermal reduction in the embodiment of the present invention:Magnesium-Crystalline Magnesium-refining-ingot casting is refined in vacuum reduction, obtains Obtain magnesium ingot.
The small agglomerate size produced with production of magnesium by pidgeonprocess process of agglomerate size produced in the embodiment of the present invention is identical.
The briquetting machine used in the embodiment of the present invention is industrial production of magnesium by pidgeonprocess briquetting machine.
Embodiment 1
Powdered magnesium-smelting reduction slag, Cab-O-sil, carbonaceous reductant and binder are uniformly mixed, mixed material is made; Wherein the dosage of Cab-O-sil is 0.4 times of magnesium-smelting reduction slag quality;The dosage of carbonaceous reductant is by fixed carbon therein and oxidation Calcium, silica and the complete Response calculation of magnesia;The dosage of binder is the 90% of carbonaceous reductant gross mass;The grain of Cab-O-sil Diameter≤0.15mm, carbonaceous reductant are coal, grain size≤0.15mm;Binder is sulfite cellulose binder;
Pelletizing is made in mixed material, is then dried;Briquetting pressure is 50MPa, the temperature 50 when drying when pelletizing is made DEG C, drying time 8h;
Pelletizing after drying is subjected to melting using electric arc furnaces, the Silcaz that liquid is formed after melting is deposited on electric arc Furnace bottom;Scrap iron is added before melting into electric arc furnaces, is controlled in the Silcaz finally obtained, the mass percent of calcium is 45%, the mass percent of silicon is 40%, and the mass percent of iron is 15%;The Silcaz of liquid is discharged every 10h;It is former Part CaO, SiO in material2After being reduced into metal with MgO, evaporates, be reoxidized as phase since vapour pressure is higher The oxide answered, and deposited in dust arrester installation, form hopcalite;The hopcalite is as refining magnesium Reducing slag is reused;
After the Silcaz of liquid is discharged, pours into pig moulding machine and pour into Silcaz block;The silico-calcium iron of acquisition The results are shown in Figure 3 for the X-ray diffraction material phase analysis of alloy block, as magnesium smelting reducing agent for restoring refining magnesium process, by true Sky reduction refining magnesium-Crystalline Magnesium-refining-ingot casting obtains magnesium ingot, and the magnesium-smelting reduction slag that wherein vacuum reduction refining magnesium generates is as synthesis Using the raw material of method, flow is as shown in Figure 1.
Embodiment 2
Powdered magnesium-smelting reduction slag, Cab-O-sil, carbonaceous reductant and binder are uniformly mixed, mixed material is made; Wherein the dosage of Cab-O-sil is 0.6 times of magnesium-smelting reduction slag quality;The dosage of carbonaceous reductant is by fixed carbon therein and oxidation Calcium, silica and the complete Response calculation of magnesia;The dosage of binder is the 90% of carbonaceous reductant gross mass;The grain of Cab-O-sil Diameter≤0.15mm, carbonaceous reductant are coke, grain size≤0.15mm;Binder is sulfite cellulose binder;
Pelletizing is made in mixed material, is then dried;Briquetting pressure is 50MPa, the temperature 100 when drying when pelletizing is made DEG C, drying time 6h;
Pelletizing after drying is subjected to melting using electric arc furnaces, the Silcaz that liquid is formed after melting is deposited on electric arc Furnace bottom;Scrap iron is added before melting into electric arc furnaces, is controlled in the Silcaz finally obtained, the mass percent of calcium is 26%, the mass percent of silicon is 62%, and the mass percent of iron is 12%;The Silcaz of liquid is discharged every 8h;It is former Part CaO, SiO in material2After being reduced into metal with MgO, evaporates, be reoxidized as phase since vapour pressure is higher The oxide answered, and deposited in dust arrester installation, form hopcalite;The hopcalite is as refining magnesium Reducing slag is reused;
After the Silcaz of liquid is discharged, pours into pig moulding machine and pour into Silcaz block;
Silcaz block is broken into granularity≤10cm fragments, is put into vacuum distillation tank, is 0.1Pa's in vacuum degree Under the conditions of be heated to 900 DEG C and be evaporated in vacuo, time 12h;It is 0.1Pa that vacuum degree is kept in vacuum distillation process;Vacuum After the completion of distillation, calcium is distilled off and becomes solid metallic calcium in condensation, and surplus material is Antaciron, as magnesium smelting reducing Agent refines magnesium-Crystalline Magnesium-refining-ingot casting for restoring refining magnesium process, by vacuum reduction, obtains magnesium ingot, and wherein vacuum reduction is refined Raw material of the magnesium-smelting reduction slag that magnesium generates as method of comprehensive utilization, flow are as shown in Figure 2.
Embodiment 3
With embodiment 1, difference is method:
(1) dosage of Cab-O-sil is 0.8 times of magnesium-smelting reduction slag quality;The dosage of binder is carbonaceous reductant gross mass 95%;Carbonaceous reductant is semi-coke;Binder is bentonite;
(2) briquetting pressure is 100MPa, 150 DEG C of temperature when drying, drying time 5h;
(3) scrap iron is added before melting into electric arc furnaces, is controlled in the Silcaz finally obtained, the mass percent of calcium It is 50%, the mass percent of silicon is 40%, and the mass percent of iron is 10%;The Silcaz of liquid is discharged every 6h.
Embodiment 4
With embodiment 1, difference is method:
(1) dosage of Cab-O-sil is 1.0 times of magnesium-smelting reduction slag quality;The dosage of binder is carbonaceous reductant gross mass 95%;Carbonaceous reductant is after forging without fire coal;Binder is waterglass;
(2) briquetting pressure is 100MPa, 200 DEG C of temperature when drying, drying time 4h;
(3) scrap iron is added before melting into electric arc furnaces, is controlled in the Silcaz finally obtained, the mass percent of calcium It is 33%, the mass percent of silicon is 59%, and the mass percent of iron is 8%;The Silcaz of liquid is discharged every 5h.
Embodiment 5
With embodiment 2, difference is method:
(1) dosage of Cab-O-sil is 1.5 times of magnesium-smelting reduction slag quality;The dosage of binder is carbonaceous reductant gross mass 100%;Carbonaceous reductant is petroleum coke;Binder is bentonite;
(2) briquetting pressure is 150MPa, 220 DEG C of temperature when drying, drying time 3h;
(3) scrap iron not to be added when melting, is controlled in the Silcaz finally obtained, the mass percent of calcium is 22%, The mass percent of silicon is 75%, and the mass percent of iron is 3%;The Silcaz of liquid is discharged every 3h;
(4) vacuum degree being evaporated in vacuo is 5Pa, 1000 DEG C of temperature, time 6h;Holding vacuum degree is in vacuum distillation process 5Pa。
Embodiment 6
With embodiment 2, difference is method:
(1) dosage of Cab-O-sil is 2.0 times of magnesium-smelting reduction slag quality;The dosage of binder is carbonaceous reductant gross mass 100%;Carbonaceous reductant is metallurgical coke;Binder is waterglass;
(2) briquetting pressure is 150MPa, 250 DEG C of temperature when drying, drying time 2h;
(3) scrap iron not to be added when melting, is controlled in the Silcaz finally obtained, the mass percent of calcium is 19%, The mass percent of silicon is 80%, and the mass percent of iron is 1%;The Silcaz of liquid is discharged every 2h;
(4) vacuum degree being evaporated in vacuo is 50Pa, 1250 DEG C of temperature, time 2h;Vacuum degree is kept in vacuum distillation process For 50Pa.

Claims (9)

1. a kind of method of comprehensive utilization of magnesium-smelting reduction slag, it is characterised in that include the following steps:
(1) powdered magnesium-smelting reduction slag, Cab-O-sil, carbonaceous reductant and binder are uniformly mixed, mixed material is made;Its The dosage of middle Cab-O-sil is 0.4~2.0 times of magnesium-smelting reduction slag quality;The dosage of carbonaceous reductant presses fixed carbon therein and oxygen Change calcium, silica and the complete Response calculation of magnesia, based on reaction equation be:
CaO+C=CO+Ca (1),
SiO2+ C=Si+CO (2)
With MgO+C=Mg+CO (3);
The dosage of binder is the 90~100% of carbonaceous reductant gross mass;
(2) pelletizing is made in mixed material, then dried;
(3) pelletizing after drying is subjected to melting using electric arc furnaces, the Silcaz that liquid is formed after melting is deposited on electric arc Furnace bottom;
(4) it after the Silcaz of liquid being discharged, pours into pig moulding machine and pours into Silcaz block;The silico-calcium iron of acquisition closes Gold bullion is directly as finished product or carries out step (5);
(5) Silcaz block is broken into granularity≤10cm fragments, be put into vacuum distillation tank in, vacuum degree be 0.1~ It is heated to 900~1250 DEG C under conditions of 50Pa to be evaporated in vacuo, the time is 2~12h;Vacuum is kept in vacuum distillation process Degree is 0.1~50Pa;After the completion of vacuum distillation, calcium is distilled off and becomes solid metallic calcium in condensation, and surplus material is silicon Ferroalloy.
2. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that the refining magnesium is also The ingredient of former slag contains MgO 4~7%, SiO by mass percentage225~32%, CaO 60~66%, Fe2O33~5%.
3. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that melting in step (3) Scrap iron is added in forward direction electric arc furnaces, is controlled in the Silcaz finally obtained, and the mass percent of calcium is 29~50%, silicon Mass percent is 40~70%, and the mass percent of iron is 1~15%.
4. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that the Cab-O-sil Grain size≤0.15mm, grain size≤0.15mm of the carbonaceous reductant.
5. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that the carbonaceous is also Former agent select coal, coke, semi-coke, forge after without coal-fired, petroleum coke and/or metallurgical coke.
6. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that the binder Select sulfite cellulose binder, bentonite or waterglass.
7. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that step is made in (2) Briquetting pressure is 50~150MPa, 50~250 DEG C of temperature when drying, 2~8h of drying time when pelletizing.
8. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that melting in step (3) When every 2~10h be discharged liquid Silcaz.
9. a kind of method of comprehensive utilization of magnesium-smelting reduction slag according to claim 1, it is characterised in that melting in step (3) When, part CaO, SiO in raw material2After being reduced into metal with MgO, evaporates, be reoxidized since vapour pressure is higher It as corresponding oxide, and is deposited in dust arrester installation, forms hopcalite;The hopcalite returns It returns in step 1 and is reused as magnesium-smelting reduction slag.
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CN104245974A (en) * 2012-04-27 2014-12-24 姜远燮 Method for preparing ferro-silicon and magnesium using ferro-nickel slag, preparation apparatus used therefor, and smelting reduction furnace
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CN106467936A (en) * 2016-09-08 2017-03-01 江苏省冶金设计院有限公司 A kind of preparation method of Silcaz
CN107090547A (en) * 2017-05-17 2017-08-25 西安建筑科技大学 It is a kind of to reduce the method that magnesium process prepares AL-Si-Fe alloy and reduces magnesium in Pidgeon process

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