CN106467935A - A kind of copper ashes and the Application way of carbide slag - Google Patents

A kind of copper ashes and the Application way of carbide slag Download PDF

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Publication number
CN106467935A
CN106467935A CN201610809817.2A CN201610809817A CN106467935A CN 106467935 A CN106467935 A CN 106467935A CN 201610809817 A CN201610809817 A CN 201610809817A CN 106467935 A CN106467935 A CN 106467935A
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CN
China
Prior art keywords
silicon
carbide slag
copper ashes
carbide
application way
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Pending
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CN201610809817.2A
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Chinese (zh)
Inventor
闫方兴
任中山
徐刚
曹志成
吴道洪
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Jiangsu Province Metallurgical Design Institute Co Ltd
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Priority to CN201610809817.2A priority Critical patent/CN106467935A/en
Publication of CN106467935A publication Critical patent/CN106467935A/en
Pending legal-status Critical Current

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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
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/2406Binding; Briquetting ; Granulating pelletizing
    • 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
    • C22B1/243Binding; Briquetting ; Granulating with binders inorganic
    • 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

Abstract

The invention discloses the Application way of a kind of copper ashes and carbide slag, comprise the following steps:(1) copper ashes, Silicon stone, carbonaceous reducing agent and binding agent mixing aftershaping are obtained wet bulb group, dry and obtain dry bulb group;(2) dry bulb group is distributed into melting in electric furnace, obtains the high silicon ferrosilicon of molten state;(3) the high silicon ferrosilicon of molten state is gone in another electric furnace, add carbide solid impurity particle and carry out melting, standing slagging-off, obtain Silcaz.The present invention makes full use of the valuable components such as the silicon dioxide in calcium oxide and copper ashes in carbide slag, produce the ferroalloy of high added value, not only achieve the comprehensive utilization of solid waste valuable constituent, and reduce production cost, turn waste into wealth, it is to avoid environmental pollution.

Description

A kind of copper ashes and the Application way of carbide slag
Technical field
The present invention relates to a kind of preparation method of Silcaz, the more particularly, to Application way of scum and carbide slag, belong to Utilization field in copper ashes and carbide slag.
Background technology
Silcaz has important function in smelting iron and steel and use, is that a kind of smelting high-quality steel is comparatively ideal compound Deoxidizer and desulfurizing agent.In addition, calcium-silicon can also make the heating agent of pneumatic steelmaking and the agent of mainly dusting of ladle refining, casting Additive in inovulant in ferrum production and spheroidal graphite cast-iron production.
In existing smelting process, the preparation method of Silcaz has one-step method and two step method, and raw material is Silicon stone, stone Ash, carbonaceous reducing agent etc..One-step method is to reduce Silicon stone and Calx with carbon in same electric furnace simultaneously and obtain calcium-silicon, point For mixing charging method and layering charging method.Two step method produces two kinds, and one kind is first to use Calx and coke raw in an electric furnace Produce carbide, then produce calcium-silicon with carbide and Silicon stone, coke in another electric furnace;Another kind is in an electric furnace Produce high silicon ferrosilicon, then add Calx with high silicon ferrosilicon and produce calcium-silicon, i.e. silicothermic process in another electric furnace.
The patent of Publication No. CN104099487A provides a kind of preparation method of calcium-silicon, specially:A, in anti- Answer the metallic addition adding molten condition in stove;B, furnace charge is added in reacting furnace, remelting, mixed at 1400~1550 DEG C Close, obtain furnace charge fused solution;Described furnace charge is made up of Calx, ferrosilicon and flux, by weight, Calx:Flux=1:0.2~ 0.5, described flux is aluminium oxide;C, furnace charge fused solution is cast, cooling, obtain final product calcium-silicon.In the invention, a side Face, using mixing charging method, CaO and SiO2Easily generate the silicate of low melting point, and make silicon and the reduction of calcium become difficult;Another Aspect, makees raw material using convenient source Calx, ferrosilicon and a large amount of metallic addition, cost of material is higher.
Copper ashes is the industrial solid castoff of generation during Copper making, and China is annual to produce about 10,000,000 t copper smelting slags. Copper ashes main component is ferrous oxide and silicon dioxide, is the raw material of smelting duriron.At present, carbide slag yield in the world's is about 20000000 t/a, wherein fine ore (particle diameter is less than 8mm) account for 80%, and the fine ore price of carbide slag is less than lump ore, such as will be this kind of Resource is applied to smelt Silcaz, can not only realize the comprehensive utilization of solid waste valuable constituent, and can drop Low production cost, turn waste into wealth, it is to avoid environmental pollution.
Therefore, the resources such as copper ashes, carbide slag ore deposit are used for smelting Silcaz and there is great economic benefit and society Benefit.
Content of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, provides the profit of a kind of scum and carbide slag With method, the method not only make full use of the valuable components such as the silicon dioxide in calcium oxide and copper ashes in carbide slag it is achieved that Copper ashes and the effectively utilizes of carbide slag, produce the ferroalloy of high added value, reduce production cost moreover it is possible to turn waste into wealth, keep away Exempt from environmental pollution.
For solving above-mentioned technical problem, the technical scheme that the present invention takes is:
The invention provides the Application way of a kind of copper ashes and carbide slag, comprise the following steps:
(1) copper ashes, Silicon stone, carbonaceous reducing agent and binding agent mixing aftershaping are obtained wet bulb group, dry and obtain dry bulb group;
(2) dry bulb group is added to melting in electric furnace, obtains the high silicon ferrosilicon of molten state;
(3) the high silicon ferrosilicon of molten state is gone in another electric furnace, add carbide solid impurity particle and carry out melting, standing is removed Slag, obtains Silcaz.
It is primary raw material that the present invention utilizes copper ashes and carbide slag, is equipped with carbonaceous reducing agent, by Reasonable adjustment ratio Lai excellent The production of SiClx Ca-Fe alloy, finally determines copper ashes, Silicon stone, carbonaceous reducing agent and binding agent in step (1) according to 100: (80-120):(100-120):(3-15) mass ratio is mixed.
Wherein, in step (1), copper ashes and carbonaceous reducing agent are carried out break process, Silicon stone is carried out levigate process;Will Product after above-mentioned process obtains wet bulb group with binding agent mixing aftershaping;Copper ashes after broken and the granule of carbonaceous reducing agent Task-size Controlling is in below 0.1mm;Silica granule granularity after levigate controls more than 80% in 0.074mm particles below.
Described copper ashes is the tailings of Copper making it is preferred that iron content 30-40wt%, silicone content 30-50wt% in copper ashes; SiO in Silicon stone2Content is more than 95%;Described carbonaceous reducing agent is any in metallurgical coke, semi-coke, petroleum coke, coal or semicoke One or more are according to the mixture of arbitrary proportion composition;Described binding agent is carbide slag slurry, preferably carbide slag slurry Middle Ca (OH)2Concentration be 10-30wt%.
In order to cost-effective, more reasonably there is valence group using silicon dioxide in the calcium oxide and copper ashes in carbide slag etc. Point, effectively prepare Silcaz, rational optimization has been carried out to following condition, has finally given:
The material block granularity of the group of wet bulb described in step (1) is 8-24mm;Described dry bulb ball moisture control 0.5% with Under.
Electro-smelting temperature described in step (2) is 1600 DEG C~2000 DEG C;
In step (3), the addition of carbide solid impurity particle is the 150%~200% of high silicon ferrosilicon quality;Described melting temperature Spend for 1800 DEG C~2200 DEG C;Described carbide solid impurity particle is carbide slag calcined dehydration to be carried out break process obtain carbide slag Grain, its granularity is preferably 15-40mm;It is furthermore preferred that described carbide slag calcined dehydration is in 600~800 DEG C of calcining carbide slags extremely Below moisture 0.5%.
Wherein, described carbide slag is remaining tailings after carbide legal system acetylene;Preferably, calcium hydroxide in carbide slag More than content 80wt%.
It is primary raw material that the present invention adopts copper ashes, Silicon stone, carbide slag, is equipped with carbonaceous reducing agent and smelts Silcaz, leads to Cross Reasonable adjustment ratio and addition sequence produces the Silcaz of high added value.Copper ashes is the side-product of Copper making, main one-tenth Dividing is FeO and SiO2, carbide slag main component is CaO, exactly the primary raw material of smelting Si-Ca alloy.Silicon is produced using two step method Calcium alloy, the first step, the pelletizing that copper ashes, Silicon stone, reducing agent are made adds reduction in the mineral hot furnace of more than 1600 DEG C of temperature molten It is smelt high silicon ferrosilicon;Second step, high silicon ferrosilicon reacts generation silico-calcium conjunction with the CaO in carbide solid impurity particle in another electric furnace Gold.First step electro-smelting effectively removes the impurity in copper ashes, improves ferrosilicon purity, reduces the quantity of slag and the electricity of second step melting Consumption.The present invention makes full use of the SiO in copper ashes2And the CaO in carbide slag, not only achieve solid waste valuable constituent Comprehensive reutilization, and reduce production cost, turn waste into wealth, it is to avoid environmental pollution.
The invention also discloses the Silcaz being prepared using said method.
Technical solution of the present invention compared with prior art, has the advantages that:
1st, the present invention makes full use of the valuable components such as the silicon dioxide in the calcium oxide and copper ashes in carbide slag, not only realizes The comprehensive utilization of solid waste valuable constituent, and reduce production cost, turn waste into wealth, it is to avoid environmental pollution.
2nd, the present invention adopts two step method, and first step electro-smelting effectively removes the impurity in copper ashes, improves ferrosilicon purity, subtracts The quantity of slag of few second step melting and power consumption.
3rd, the present invention makees binding agent using carbide slag slurry, reduces agglomeration cost.
4th, the present invention is sent using carbide solid impurity particle and ferrosilicon melt heat, reduces the power consumption of second step electro-smelting.
Specific embodiment
To further describe the present invention with reference to specific embodiment, advantages of the present invention and feature will be with description and Apparent.But these embodiments are only exemplary, any restriction is not constituted to the scope of the present invention.People in the art Member it should be understood that lower without departing from the spirit and scope of the present invention can modifying to the details of the present invention and form or Replace, but these modifications and replacement each fall within protection scope of the present invention.
Embodiment 1
(1) copper ashes, coal are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below more than 80%, presses According to copper ashes:Silicon stone:Coal:Carbide slag slurry=32:32:32:4 quality compares mix homogeneously;Finish mix for a compound piece granularity is The wet bulb group of 10mm, dries, and dry bulb rolls into a ball water content 0.2%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 15wt%;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.2% at 600 DEG C, be broken into the carbide slag of 15mm Granule;
(3) dry bulb group is put into melting in electric furnace, 1700 DEG C of furnace temperature, tap a blast furnace and obtain the high silicon ferrosilicon of molten state;
(4) the high silicon ferrosilicon heat of molten state is delivered in another electric furnace, add the carbide slag of high silicon ferrosilicon quality 160% Granule carries out melting, 1900 DEG C of temperature, and after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 24%, silicone content 44%, ferrum Content 30%, remaining is impurity.
Embodiment 2
(1) copper ashes, semicoke are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below more than 80%, According to copper ashes:Silicon stone:Semicoke:Carbide slag slurry=30:34:33:3 quality compares mix homogeneously;Compound is made wet bulb group, Dry, dry bulb rolls into a ball water content 0.3%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 25wt%;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.3% at 750 DEG C, be broken into the carbide slag of 20mm Granule;
(3) dry bulb is put into melting in electric furnace, 1780 DEG C of mineral hot furnace temperature, tap a blast furnace and obtain the high silicon ferrosilicon of molten state;
(4) the high silicon ferrosilicon heat of molten state is delivered in another electric furnace, add the carbide slag of high silicon ferrosilicon quality 180% Granule carries out melting, 2000 DEG C of temperature, and after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 27%, silicone content 48%, ferrum Content 23%, remaining is impurity.
Embodiment 3
(1) copper ashes, coke powder are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below more than 80%, According to copper ashes:Silicon stone:Coke powder:Carbide serosity=30:36:32:2 quality compares mix homogeneously;Compound is made wet bulb group, dries Dry, dry bulb rolls into a ball water content 0.1%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 5wt%;Described coke powder be metallurgical coke, semi-coke, petroleum coke, Coal, the mixture of semicoke;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.1% at 800 DEG C, be broken into the carbide slag of 20mm Granule;
(3) dry bulb is put into melting in electric furnace, 1830 DEG C of mineral hot furnace temperature, tap a blast furnace and obtain high silicon ferrosilicon;
(4) high silicon ferrosilicon liquid heat is delivered in another electric furnace, add the carbide solid impurity particle of high silicon ferrosilicon quality 180% to enter Row melting, 2100 DEG C of temperature, after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 28%, silicone content 50%, ferrum Content 21%, remaining is impurity.
Embodiment 4
(1) copper ashes, metallurgical coke are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below 80% with On, according to copper ashes:Silicon stone:Metallurgical coke:Carbide slag slurry=100:80:100:3 quality compares mix homogeneously;Compound is made Material block granularity is the wet bulb group of 8mm, dries, and dry bulb rolls into a ball water content 0.4%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 10wt%;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.4% at 600 DEG C, be broken into the carbide slag of 15mm Granule;
(3) dry bulb is put into melting in electric furnace, 1600 DEG C of furnace temperature, tap a blast furnace and obtain the high silicon ferrosilicon of molten state;
(4) the high silicon ferrosilicon heat of molten state is delivered in another electric furnace, add the carbide slag of high silicon ferrosilicon quality 150% Granule carries out melting, 1800 DEG C of temperature, and after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 23%, silicone content 46%, ferrum Content 27%, remaining is impurity.
Embodiment 5
(1) copper ashes, semi-coke are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below more than 80%, According to copper ashes:Silicon stone:Semi-coke:Carbide slag slurry=20:24:24:3 quality compares mix homogeneously;By finish mix for compound piece of grain Spend the wet bulb group for 24mm, dry, dry bulb rolls into a ball water content 0.1%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 30wt%;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.1% at 800 DEG C, be broken into the carbide slag of 40mm Granule;
(3) dry bulb is put into melting in electric furnace, 2000 DEG C of furnace temperature, tap a blast furnace and obtain the high silicon ferrosilicon of molten state;
(4) the high silicon ferrosilicon heat of molten state is delivered in another electric furnace, add the carbide slag of high silicon ferrosilicon quality 200% Granule carries out melting, 2200 DEG C of temperature, and after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 30%, silicone content 49%, ferrum Content 17%, remaining is impurity.
Embodiment 6
(1) copper ashes, petroleum coke are crushed to below 0.1mm, Silicon stone is levigate to 0.074mm particles below 80% with On, according to copper ashes:Silicon stone:Petroleum coke:Carbide slag slurry=10:10:11:1 quality compares mix homogeneously;Compound is finish mix Block granularity is the wet bulb group of 16mm, dries, and dry bulb rolls into a ball water content 0.3%;
Wherein, Ca (OH) in carbide slag slurry2Concentration be 20wt%;
(2) carbide slag is carried out being dehydrated pretreatment, be fired to water content 0.3% at 700 DEG C, be broken into the carbide slag of 30mm Granule;
(3) dry bulb is put into melting in electric furnace, 1800 DEG C of furnace temperature, tap a blast furnace and obtain the high silicon ferrosilicon of molten state;
(4) the high silicon ferrosilicon heat of molten state is delivered in another electric furnace, add the carbide slag of high silicon ferrosilicon quality 175% Granule carries out melting, 2000 DEG C of temperature, and after the completion of melting, standing slagging-off obtains Silcaz.
The main component percentage by weight of Silcaz that the present invention produces is:Calcium content 26%, silicone content 45%, ferrum Content 25%, remaining is impurity.

Claims (10)

1. the Application way of a kind of copper ashes and carbide slag is it is characterised in that comprise the following steps:
(1) copper ashes, Silicon stone, carbonaceous reducing agent and binding agent mixing aftershaping are obtained wet bulb group, dry and obtain dry bulb group;
(2) dry bulb group is distributed into melting in electric furnace, obtains the high silicon ferrosilicon of molten state;
(3) the high silicon ferrosilicon of molten state is gone in another electric furnace, adds carbide solid impurity particle and carry out melting, standing removes the gred, Obtain Silcaz.
2. according to the Application way described in claim 1 it is characterised in that:Copper ashes and carbonaceous reducing agent are entered in (1) by step Row break process, Silicon stone is carried out levigate process;Product after above-mentioned process is obtained wet bulb group with binding agent mixing aftershaping; The grain graininess of the copper ashes after broken and carbonaceous reducing agent controls in below 0.1mm;Silica granule granularity after levigate exists 0.074mm particles below controls more than 80%.
3. according to the Application way described in claim 1 or 2 it is characterised in that:By copper ashes, Silicon stone, carbonaceous reduction in step (1) Agent and binding agent are according to 100:(80-120):(100-120):(3-15) mass ratio is mixed.
4. according to the Application way described in claim 1 or 3 it is characterised in that:Described copper ashes is the tailings of Copper making;In Silicon stone SiO2Content is more than 95%;Described carbonaceous reducing agent is metallurgical coke, semi-coke, petroleum coke, in coal or semicoke any one or More than one are according to the mixture of arbitrary proportion composition;Described binding agent is carbide slag slurry, preferably Ca in carbide slag slurry (OH)2Concentration be 10-30wt%.
5. according to the Application way described in claim 1 it is characterised in that:Described in step (3), carbide solid impurity particle is by carbide Slag calcined dehydration carries out break process and obtains carbide solid impurity particle, and its granularity is preferably 15-40mm;It is furthermore preferred that described carbide slag Calcined dehydration is to moisture below 0.5% in 600~800 DEG C of calcining carbide slags.
6. according to the Application way described in claim 1 it is characterised in that:Described carbide slag is remaining after carbide legal system acetylene Tailings.
7. according to the Application way described in claim 1 it is characterised in that:The material block granularity of described wet bulb group is 8-24mm;Institute State dry bulb group moisture to control below 0.5%.
8. according to the Application way described in claim 1 it is characterised in that:Electro-smelting temperature described in step (2) is 1600 DEG C~2000 DEG C;Smelting temperature described in step (3) is 1800 DEG C~2200 DEG C.
9. according to the Application way described in claim 1 it is characterised in that:In step (3), the addition of carbide solid impurity particle is height The 150%~200% of silicon ferrosilicon quality.
10. the Silcaz that any one Application way described in claim 1-9 obtains.
CN201610809817.2A 2016-09-08 2016-09-08 A kind of copper ashes and the Application way of carbide slag Pending CN106467935A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN110643823A (en) * 2019-11-07 2020-01-03 郑州大学 Method for pyrogenically recovering valuable metals from oil-contaminated cylinder liner honing waste
CN110669945A (en) * 2019-10-17 2020-01-10 宝武集团环境资源科技有限公司 Method for treating copper slag by using direct reduction of rotary hearth furnace and smelting reduction of ore-smelting electric furnace
CN111363921A (en) * 2020-04-09 2020-07-03 石嘴山市宝马兴庆特种合金有限公司 Preparation method of silicon-barium-calcium series multi-element alloy

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669945A (en) * 2019-10-17 2020-01-10 宝武集团环境资源科技有限公司 Method for treating copper slag by using direct reduction of rotary hearth furnace and smelting reduction of ore-smelting electric furnace
CN110643823A (en) * 2019-11-07 2020-01-03 郑州大学 Method for pyrogenically recovering valuable metals from oil-contaminated cylinder liner honing waste
CN110643823B (en) * 2019-11-07 2021-05-14 郑州大学 Method for pyrogenically recovering valuable metals from oil-contaminated cylinder liner honing waste
CN111363921A (en) * 2020-04-09 2020-07-03 石嘴山市宝马兴庆特种合金有限公司 Preparation method of silicon-barium-calcium series multi-element alloy

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Application publication date: 20170301