CN110016563B - High-value utilization method of high-temperature carbon reduction black tungsten slag - Google Patents

High-value utilization method of high-temperature carbon reduction black tungsten slag Download PDF

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Publication number
CN110016563B
CN110016563B CN201910331091.XA CN201910331091A CN110016563B CN 110016563 B CN110016563 B CN 110016563B CN 201910331091 A CN201910331091 A CN 201910331091A CN 110016563 B CN110016563 B CN 110016563B
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slag
alloy
under
temperature
sio
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CN201910331091.XA
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CN110016563A (en
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王旭
赵宝军
焦芸芬
郭超
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江西理工大学
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002Use of waste materials, e.g. slags
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00Hydraulic cements
    • C04B7/14Cements containing slag
    • C04B7/147Metallurgical 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
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/06Obtaining bismuth
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/10Obtaining titanium, zirconium or hafnium
    • C22B34/12Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry 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
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/24Obtaining niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/30Obtaining chromium, molybdenum or tungsten
    • C22B34/36Obtaining tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • 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
    • 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
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/10Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The invention relates to a black tungsten slag treatment technology, in particular to a high-value utilization method of high-temperature carbon reduction black tungsten slag. The invention comprises the following steps: (1) proportioning raw materials; (2) pressing and molding-presintering; (3) high-temperature carbon reduction; (4) and (5) collecting a product. The invention adopts a high-temperature carbon reduction method to carry out resource utilization on the alkali-boiled wolframite slag, the alloy of the product is W-Fe-Mn- (Nb, Ti and Bi), and the slag system is CaO-SiO2-Al2O3,The method well solves the problems of energy consumption and cost in the treatment of the black tungsten slag, and is environment-friendly. The tungsten slag is reduced at high temperature with low energy consumption through high-temperature carbon reduction treatment, valuable metals are efficiently separated to prepare intermediate alloy, and secondary slag is used as a raw material for preparing glass and cement, so that the tungsten slag is subjected to high-value utilization and harmless treatment.

Description

High-value utilization method of high-temperature carbon reduction black tungsten slag

Technical Field

The invention relates to a black tungsten slag treatment technology, in particular to a high-value utilization method of high-temperature carbon reduction black tungsten slag.

Background

China is that the total storage of tungsten ore resources accounts for 56% of the world, the yield is also in the first place in the world, and the percentage of the total yield in 2017 is 83% of the total world. At present, in the process of producing APT by tungsten metallurgy in China, the mainstream process is alkali leaching-purification-ammonium salt transformation. Insoluble substances in the alkaline leaching process are called tungsten slag and comprise the following components: black tungsten slag (black tungsten concentrate leaching slag), white tungsten slag (white tungsten concentrate leaching slag), and black and white tungsten mixed slag (black and white tungsten mixed concentrate leaching slag). At present, the quantity of the tungsten slag is increased by nearly 8 ten thousand tons every year in China, the tungsten slag contains valuable elements such as tungsten, manganese, iron, niobium, titanium, yttrium, zirconium, bismuth, tin and the like, and the tungsten, iron, manganese and other metals have potential extraction values. Therefore, the method has important significance for high-value utilization of valuable metal resources in the tungsten production and tungsten slag treatment major countries.

Disclosure of Invention

The invention aims to provide a high-value utilization method of high-temperature carbon reduction black tungsten slag, which is used for extracting main valuable metals in the black tungsten slag by one step of high-temperature carbon reduction.

The technical scheme of the invention is as follows: a high-value utilization method of high-temperature carbon reduction black tungsten slag comprises the following steps:

(1) proportioning raw materials:

dehydrated black tungsten slag, graphite and anhydrous sodium silicate (Na)2SiO3) Is prepared from the following raw materials in percentage by mass: 80-85% of dehydrated black tungsten slag, 10-13% of graphite and anhydrous Na2SiO32-10% of the total;

(2) press molding-presintering:

fully mixing the raw materials in the step (1), and pressing and forming under the condition that the pressure is 5-10 MPa; activating and presintering for 1h under the protection of nitrogen at the temperature of 600-800 ℃;

(3) high-temperature carbon reduction:

reducing the pre-sintered product in the step (2) for 2-3 h at 1300-1500 ℃ under the protection of nitrogen;

(4) and (3) collecting a product:

and (4) separating the liquid alloy reduced in the step (3) from secondary slag (prior art), wherein the alloy is cast into ingots, and the secondary slag is collected in an air cooling mode (prior art).

The main control conditions and bases are as follows:

1. ensuring the conditions of full activation of raw material components and increasing the reaction surface: pressing and forming under the pressure of 5 MPa-10 MPa; activating and presintering for 1h under the protection of nitrogen at the temperature of 600-800 ℃;

2. ensuring the conditions of full reduction of the molding-presintering product and effective separation of slag and gold: reducing for 2-3 h at 1300-1500 ℃ under the protection of nitrogen;

the invention adopts a high-temperature carbon reduction method to carry out resource utilization on the alkali-boiled wolframium residue, the product alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the residueMainly comprising CaO-SiO2-Al2O3The method well solves the problems of energy consumption and cost in the treatment of the black tungsten slag, and is environment-friendly. The tungsten slag is reduced at high temperature with low energy consumption through high-temperature carbon reduction treatment, valuable metals are efficiently separated to prepare intermediate alloy, and secondary slag is used as a raw material for preparing glass and cement, so that the tungsten slag is subjected to high-value utilization and harmless treatment.

Detailed Description

Example 1: dehydrated black tungsten slag (81 percent by mass), graphite (11 percent by mass) and anhydrous Na2SiO3(8 percent by mass) are fully mixed, pressed and formed under the condition of 7Mpa, and activated and presintered for 1h under the protection of nitrogen and at the temperature of 650 ℃; reducing for 2.5h under the nitrogen protection condition at the temperature of 1350 ℃; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Example 2: dehydrated black tungsten slag (82% by mass), graphite (11.5% by mass) and anhydrous Na2SiO3(6.5 percent by mass) are fully mixed, pressed and formed under the condition of 8Mpa, and activated and presintered for 1h under the protection of nitrogen and at the temperature of 700 ℃; reducing for 3h under the nitrogen protection condition at the temperature of 1400 ℃; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Example 3: dehydrated black tungsten slag (83 percent by mass), graphite (12 percent by mass) and anhydrous Na2SiO3(5 percent by mass) fully mixing, pressing and molding under the condition of 9Mpa, and activating and presintering for 1h under the conditions of nitrogen protection and 750 ℃; reducing for 3h at 1450 ℃ under the nitrogen protection condition; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Example 4: dehydrated black tungsten slag (84 percent by mass), graphite (12.5 percent by mass) and anhydrous Na2SiO3(3.5 percent by mass) are fully mixed, pressed and molded under the condition of 6Mpa, and activated and presintered for 1h under the protection of nitrogen and at the temperature of 750 ℃; reducing for 2.5h at 1450 ℃ under the nitrogen protection condition; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Example 5: dehydrated black tungsten slag (85 percent by mass), graphite (13 percent by mass) and anhydrous Na2SiO3(2 percent by mass) fully mixing, pressing and molding under the condition of 10Mpa, and activating and presintering for 1h under the conditions of nitrogen protection and 800 ℃; reducing for 3h under the nitrogen protection condition at the temperature of 1500 ℃; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Example 6: dehydrated black tungsten slag (80 percent by mass), graphite (10 percent by mass) and anhydrous Na2SiO3(10 percent by mass) fully mixing, pressing and molding under the condition of 5Mpa, and activating and presintering for 1h under the conditions of nitrogen protection and 600 ℃; reducing for 2h under the nitrogen protection condition at the temperature of 1300 ℃; and separating the liquid alloy and the secondary slag after reduction, casting the alloy ingot, and collecting the secondary slag through air cooling. The alloy is mainly W-Fe-Mn- (Nb, Ti and Bi), and the slag system is mainly CaO-SiO2-Al2O3

Claims (2)

1. A high-value utilization method of high-temperature carbon reduction black tungsten slag is characterized by comprising the following steps:
(1) proportioning raw materials:
the method is characterized in that dehydrated black tungsten slag, graphite and anhydrous sodium silicate are used as raw materials, and the raw materials comprise the following components in percentage by mass: 80-85% of dehydrated black tungsten slag, 10-13% of graphite and anhydrous Na2SiO32-10% of the total;
(2) press molding-presintering:
fully mixing the raw materials in the step (1), and pressing and forming under the condition that the pressure is 5-10 MPa; activating and presintering for 1h under the protection of nitrogen at the temperature of 600-800 ℃;
(3) high-temperature carbon reduction:
reducing the pre-sintered product in the step (2) for 2-3 h at 1300-1500 ℃ under the protection of nitrogen;
(4) and (3) collecting a product:
separating the liquid alloy and the secondary slag after reduction in the step (3), wherein the alloy is cast into ingots, and the alloy is W-Fe-Mn- (Nb, Ti and Bi); collecting the secondary slag by air cooling, wherein the slag system is CaO-SiO2-Al2O3
2. The method for high-value utilization of high-temperature carbon reduced black tungsten slag as claimed in claim 1, wherein the method comprises the following steps: the dehydrated black tungsten slag, the graphite and the anhydrous Na with the mass percentage of 81 percent, 11 percent and 8 percent respectively2SiO3Fully mixing, pressing and molding under the condition of 7Mpa, and activating and presintering for 1h under the protection of nitrogen and at the temperature of 650 ℃; reducing for 2.5h under the nitrogen protection condition at the temperature of 1350 ℃; separating liquid alloy and secondary slag after reduction, and carrying out alloy ingot casting, wherein the alloy is W-Fe-Mn- (Nb, Ti and Bi); collecting the secondary slag by air cooling, wherein the slag system is CaO-SiO2-Al2O3
CN201910331091.XA 2019-04-24 2019-04-24 High-value utilization method of high-temperature carbon reduction black tungsten slag CN110016563B (en)

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CN110656273A (en) * 2019-09-29 2020-01-07 中色(宁夏)东方集团有限公司 Method for preparing ferrotungsten alloy by carbon reduction

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2020175C1 (en) * 1992-03-19 1994-09-30 Алексей Федорович Вишкарев Process for recovering tungsten, scandium, iron and manganese from tungsten-containing raw material
CN103305707A (en) * 2013-06-25 2013-09-18 湖南柿竹园有色金属有限责任公司 Method for smelting bismuth-molybdenum or bismuth-tungsten concentrates
CN103614545A (en) * 2013-11-22 2014-03-05 中南大学 Method for treating low-grade tungsten concentrate and tungsten slag
CN107164644A (en) * 2017-06-01 2017-09-15 青岛聚鑫园工贸有限公司 A kind of method that efficient process tungsten waste produces coarse tungsten powder
CN108384960A (en) * 2018-03-30 2018-08-10 中南大学 A kind of method of synchronous extraction tungsten slag and tungsten, aluminium, sodium and iron in red mud
CN108796226A (en) * 2018-07-04 2018-11-13 赣州有色冶金研究所 A method of it recycling alkali and soaks tungsten slag

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2020175C1 (en) * 1992-03-19 1994-09-30 Алексей Федорович Вишкарев Process for recovering tungsten, scandium, iron and manganese from tungsten-containing raw material
CN103305707A (en) * 2013-06-25 2013-09-18 湖南柿竹园有色金属有限责任公司 Method for smelting bismuth-molybdenum or bismuth-tungsten concentrates
CN103614545A (en) * 2013-11-22 2014-03-05 中南大学 Method for treating low-grade tungsten concentrate and tungsten slag
CN107164644A (en) * 2017-06-01 2017-09-15 青岛聚鑫园工贸有限公司 A kind of method that efficient process tungsten waste produces coarse tungsten powder
CN108384960A (en) * 2018-03-30 2018-08-10 中南大学 A kind of method of synchronous extraction tungsten slag and tungsten, aluminium, sodium and iron in red mud
CN108796226A (en) * 2018-07-04 2018-11-13 赣州有色冶金研究所 A method of it recycling alkali and soaks tungsten slag

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