CN117778724A - Method for recycling valuable metals in waste tungsten slag - Google Patents
Method for recycling valuable metals in waste tungsten slag Download PDFInfo
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- CN117778724A CN117778724A CN202311837452.0A CN202311837452A CN117778724A CN 117778724 A CN117778724 A CN 117778724A CN 202311837452 A CN202311837452 A CN 202311837452A CN 117778724 A CN117778724 A CN 117778724A
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- 239000002893 slag Substances 0.000 title claims abstract description 135
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 86
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010937 tungsten Substances 0.000 title claims abstract description 83
- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 66
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 150000002739 metals Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 101
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 66
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 238000003723 Smelting Methods 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000011863 silicon-based powder Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002817 coal dust Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 38
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910021332 silicide Inorganic materials 0.000 abstract description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010955 niobium Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recycling valuable metals in waste tungsten slag, and relates to the technical field of solid waste recycling. According to the invention, on the basis of reduction smelting of waste tungsten slag, the composite reducing agent containing the carbonaceous reducing agent and the siliceous reducing agent is adopted, so that the melting point and viscosity of a slag system can be reduced, and the energy consumption is reduced; and the method can promote the formation of high-density silicide of the valuable metal, accelerate the sedimentation of alloy liquid, reduce the residue of the valuable metal in the slag phase and improve the recovery rate of the valuable metal element.
Description
Technical Field
The invention relates to the technical field of solid waste recovery, in particular to a method for recovering valuable metals in waste tungsten slag.
Background
At present, the processes for recovering valuable metals such as tungsten, tantalum, niobium, cobalt, nickel and the like from metallurgical solid wastes are mainly divided into a wet process and a fire process, and the two processes have respective defects, and are specifically as follows:
(1) The wet process mainly utilizes high-concentration acid solution to leach metal elements in slag, and the metal elements are recovered through purification and separation processes after leaching. The process has the defects of high acid consumption, low metal leaching rate, complex process route and large environmental pollution.
(2) The pyrometallurgical process generally employs reduction smelting, which recovers metal oxides in the slag by adding a carbonaceous reductant at high temperature and forming an alloy phase. In the carbothermic reduction process of tungsten slag, valuable metal elements such as tungsten, tantalum, niobium and the like are reduced and carbonized to form high-melting-point carbide, so that the viscosity of a slag system is increased, the aggregation and sedimentation of the carbide are not facilitated, and the slag-metal separation is difficult. Therefore, the carbothermic reduction process of tungsten slag generally needs higher smelting temperature, and has the defects of high energy consumption, difficulty in breaking and separating the generated alloy phase, high loss of alloy inclusion in slag and the like.
Therefore, development of a process with low energy consumption and high recovery rate of valuable metals is needed at present, and the aim of efficiently recovering the valuable metal elements in tungsten slag can be achieved.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for recycling valuable metals in waste tungsten slag, which aims to reduce energy consumption and improve the recycling rate of valuable metal elements.
The invention is realized in the following way:
in a first aspect, the invention provides a method for recovering valuable metals from waste tungsten slag, comprising: mixing the waste tungsten slag with a slag former and a composite reducing agent, and then carrying out reduction smelting;
wherein the composite reducing agent comprises a carbonaceous reducing agent and a siliceous reducing agent, and the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent is 1: (4-10), the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.05-0.20).
In an alternative embodiment, the mass ratio of carbonaceous reducing agent to siliceous reducing agent is 1: (6-8);
preferably, the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.08-0.15).
In an alternative embodiment, the carbonaceous reducing agent is selected from at least one of graphite, coke, coal fines, charcoal, activated carbon, and carbon black.
In an alternative embodiment, the siliceous reducing agent is selected from at least one of the group consisting of metallic silicon powder, silicon chunks, and silicon wafers.
In an alternative embodiment, the slag former is selected from Na 2 CO 3 And at least one of CaO;
preferably, the mass ratio of the waste tungsten slag to the slag former is 1: (0.1-0.5).
In an alternative embodiment, the process of reduction smelting includes: mixing the waste tungsten slag with a slag former and a composite reducing agent, and performing cold isostatic pressing to obtain a blank; heating the blank to 1350-1700 ℃ in inert atmosphere, and carrying out melt heat preservation;
preferably, the smelting temperature is controlled to be 1400-1700 ℃;
preferably, the blank is placed in a magnesia crucible for smelting;
preferably, the heat preservation time of the melt is 1-3 h;
preferably, the temperature rising rate of the blank body is controlled to be 5-15 ℃ per minute.
In an alternative embodiment, after the melt is insulated, slag is extracted to obtain a stable melt, and then the temperature is reduced to room temperature to obtain an alloy ingot.
In an alternative embodiment, the melt obtained after slag pulling is cooled to 800-1200 ℃ at a rate of 2-5 ℃/min, and then cooled to room temperature at a rate of 5-10 ℃/min.
In an alternative embodiment, the waste tungsten slag comprises, in mass percent: w1-10%, co 1-30%, ta 0.5-5%, nb 0.5-5%, siO 2 5％～30％、TiO 2 5-30% and 5-20% of Fe.
In an alternative embodiment, the waste tungsten slag is processed into dry powder and then mixed with the slag former and the composite reducing agent; the particle size of the dry powder is controlled to be 1-10 mu m.
The invention has the following beneficial effects: according to the invention, on the basis of reduction smelting of waste tungsten slag, the composite reducing agent containing the carbonaceous reducing agent and the siliceous reducing agent is adopted, so that the melting point and viscosity of a slag system can be reduced, and the energy consumption is reduced; and the method can promote the formation of high-density silicide of the valuable metal, accelerate the sedimentation of alloy liquid, reduce the residue of the valuable metal in the slag phase and improve the recovery rate of the valuable metal element.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a method for recycling valuable metals in waste tungsten slag, which comprises the following specific steps of:
s1, pretreatment
The waste tungsten slag is firstly processed into dry powder for standby.
The waste tungsten slag comprises the following components in percentage by mass: w1%～10％、Co 1％～30％、Ta 0.5％～5％、Nb 0.5％～5％、SiO 2 5％～30％、TiO 2 5-30% of Fe 5-20%, and the sum of the mass contents of the components is 100%. The waste tungsten slag contains W, co, ta, nb and other valuable metals, and the content of each component is suitable for the recovery method provided by the embodiment of the invention in the wider range, so that the recovery rate of W, co, ta, nb and other valuable metals can be effectively improved.
Specifically, the mass fraction of the W element may be 1%, 3%, 5%, 8%, 10%, or the like; the mass fraction of Co element can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, etc.; the mass fraction of the Ta element can be 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, etc.; the mass fraction of Nb element may be 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, etc.; siO (SiO) 2 May be 5%, 10%, 15%, 20%, 25%, 30%, etc.; tiO (titanium dioxide) 2 May be 5%, 10%, 15%, 20%, 25%, 30%, etc.; the mass fraction of Fe element may be 5%, 8%, 10%, 13%, 15%, 18%, 20%, etc.
In some embodiments, the particle size of the processed dry powder is 1 μm to 10 μm, and entering the subsequent process with smaller particle sizes can improve the sufficiency of the reaction, resulting in a more uniform product.
Specifically, the particle size of the processed dry powder may be 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, or the like.
S2, press molding
And mixing the waste tungsten slag, a slag former and a composite reducing agent, performing cold isostatic pressing, and pressing to obtain a blank. The operation parameters of the cold isostatic pressing are not limited, the pressure can be controlled to be 180MPa-200MPa, the temperature is 10-30 ℃, and the operation time is 2-8 min.
In some embodiments, the slag former is selected from Na 2 CO 3 And CaO, which can be any one or more of the above; the mass ratio of the waste tungsten slag to the slag forming agent is 1: (0.1 to 0.5), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, etc.
In some embodiments, the carbonaceous reducing agent is selected from at least one of graphite, coke, coal fines, charcoal, activated carbon, and carbon black, and may be any one or more of the above; the siliceous reducing agent is at least one selected from metal silicon powder, silicon blocks and silicon wafers, and can be any one or more of the above carbonaceous reducing agents or siliceous reducing agents which are all commercially available raw materials. Si in the metal silicon powder is more than or equal to 95 percent, and the metal silicon powder can be selected from high-purity silicon cutting waste.
Further, the composite reducing agent comprises a carbonaceous reducing agent and a siliceous reducing agent, and the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent is 1: (4-10), the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.05-0.20). The recovery rate of valuable metal elements is improved to a greater extent by adding the carbonaceous reducing agent and the siliceous reducing agent and controlling the dosage ratio of the carbonaceous reducing agent and the siliceous reducing agent and the total dosage of the composite reducing agent, and the melting point and the viscosity of a slag system are reduced, so that the aim of reducing the process energy consumption is fulfilled.
Specifically, the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent may be 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., and the mass ratio of the waste tungsten slag to the composite reducing agent may be 1:0.05, 1:0.08, 1:0.10, 1:0.12, 1:0.15, 1:0.18, 1:0.20, etc.
In a preferred embodiment, the mass ratio of carbonaceous reducing agent to siliceous reducing agent is 1: (6-8); the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.08-0.15). The recovery rate of valuable metals can be further improved by further controlling the ratio of the amounts of carbonaceous reducing agent and siliceous reducing agent and the total amount of the composite reducing agent.
S3, smelting
Heating the blank to 1350-1700 deg.c, preferably 1400-1700 deg.c, in inert atmosphere, maintaining the temperature of the melt, reducing the valuable metal to produce alloy phase through reduction smelting, and recovering the valuable metal.
Specifically, the kind of inert atmosphere is not limited, and may be nitrogen, argon, or the like; the smelting temperature can be 1300 ℃, 1350 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃ and the like.
In some embodiments, the melt hold time may be 1h to 3h, such as may be 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, etc. The heating rate of controlling the heating of the blank to the smelting temperature can be 5 ℃/min-15 ℃/min, such as 5 ℃/min, 10 ℃/min, 15 ℃/min and the like.
In the actual operation process, the blank is placed in a magnesium oxide crucible for smelting, the crucible is corroded into slag in the smelting process, the dissolution of magnesium oxide can reduce the viscosity of slag, and alloy liquid drops are prevented from adhering to the crucible wall. After the melt is insulated, slag can be pulled out to obtain a stable melt, and then the temperature is reduced to room temperature to obtain an alloy ingot casting product, wherein the slag pulling operation can be performed by adopting a general slag pulling machine according to the prior art.
In some embodiments, the cooling may be performed in a staged cooling manner, first at a slower rate, and then at a faster rate, to prevent the cooling rate from excessively fast resulting in melt quenching, affecting product morphology. The obtained melt after slag pulling can be cooled to 800-1200 ℃ at the speed of 2-5 ℃/min and then cooled to room temperature at the speed of 5-10 ℃/min.
Specifically, during the first stage cooling, the cooling rate can be controlled to be 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min and the like, and the cooling rate can be controlled to be 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ and the like. In the second stage of cooling, the cooling rate can be controlled to be 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, etc., and the temperature is reduced to the room temperature such as 25 ℃.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a method for recycling valuable metals in waste tungsten slag, which comprises the following specific steps:
(1) Pretreatment of
The waste tungsten slag is crushed and dried to obtain waste tungsten slag powder with the grain diameter of about 1 mu m to 5 mu m.
In the waste tungsten slag powder, the mass content of W is 8%, the mass content of Co is 15%, the mass content of Ta is 4%, the mass content of Nb is 2%, and SiO is contained 2 28% by mass of TiO 2 The mass content of (2) is 20% and the mass content of Fe is 10%.
(2) Compression molding
Taking 5Kg of dry waste tungsten slag powder and slag former (Na 2 CO 3 ) And a composite reducing agent (i.e., graphite powder having a particle diameter of 30 μm and metal silicon powder having a particle diameter of 1 μm, the mass ratio of graphite powder to metal silicon powder being 1: 8) After mixing, cold isostatic pressing (with the pressure of 190MPa and the temperature of 20 ℃ C. For 5 min) is carried out to obtain a blank. The mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.25:0.1.
(3) Smelting
Placing the blank body obtained in the step (2) into a magnesium oxide crucible, heating the blank body to 1500 ℃ at 10 ℃/min under the inert atmosphere (nitrogen, the same applies below), preserving heat for 2.5h, and pulling slag to obtain a stable melt.
And cooling the stable melt to 1000 ℃ at 3 ℃/min, and then cooling to room temperature at 7.5 ℃/min to obtain the alloy cast ingot enriched with valuable metals.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 35%, the Co content is 40%, the Ta content is 9%, the Nb content is 5%, and the alloy mass recovery rate in the waste tungsten slag reaches 98%.
Example 2
The embodiment provides a method for recycling valuable metals in waste tungsten slag, which comprises the following specific steps:
(1) Pretreatment of
The waste tungsten slag is crushed and dried to obtain waste tungsten slag powder with the grain diameter of about 1 mu m to 5 mu m.
In the waste tungsten slag powder, the mass content of W is 4%, the mass content of Co is 24%, the mass content of Ta is 2%, the mass content of Nb is 1.5%, and SiO is contained 2 The mass content of (2%) is TiO 2 The mass content of (2) was 17% and the mass content of Fe was 12%.
(2) Compression molding
Mixing 5Kg of dry waste tungsten slag powder, a slag former and a composite reducing agent (namely, carbonaceous reducing agent graphite powder with the particle size of 30 mu m and siliceous reducing agent metal silicon powder with the particle size of 1 mu m, wherein the mass ratio of the graphite powder to the metal silicon powder is 1:7), and performing cold isostatic pressing (the pressure is 200MPa, the temperature is 20 ℃ C., and the time is 4 min) to obtain a blank body. The mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.4:0.08.
(3) Smelting
Placing the blank body in a magnesium oxide crucible, heating the blank body to 1600 ℃ at 15 ℃/min under inert atmosphere, preserving heat for 2 hours, and pulling slag to obtain a stable melt.
And cooling the stable melt to 800 ℃ at 5 ℃/min, and then cooling to room temperature at 10 ℃/min to obtain the alloy cast ingot enriched with valuable metals.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 35%, the Co content is 37%, the Ta content is 8%, the Nb content is 4%, and the alloy mass recovery rate in the waste tungsten slag reaches 96%.
Example 3
The embodiment provides a method for recycling valuable metals in waste tungsten slag, which comprises the following specific steps:
(1) Pretreatment of
The waste tungsten slag is crushed and dried to obtain waste tungsten slag powder with the grain diameter of about 5 mu m to 10 mu m.
In the waste tungsten slag powder, the mass content of W is 6%, the mass content of Co is 10%, the mass content of Ta is 1.5%, the mass content of Nb is 3%, and SiO 2 The mass content of (C) is 18%, tiO 2 24% by mass and 11% by mass of Fe.
(2) Compression molding
Taking 5Kg of dry waste tungsten slag powder and slag former (Na 2 CO 3 ) And a composite reducing agent (i.e., graphite powder having a particle diameter of 30 μm and metal silicon powder having a particle diameter of 1 μm, the mass ratio of graphite powder to metal silicon powder being 1: 6) After mixing, cold isostatic pressing (pressure 200MPa, temperature 25 ℃ C., time 6 min) is carried out to obtain a blank. The mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.12.
(3) Smelting
Placing the blank body in a magnesium oxide crucible, heating the blank body to 1400 ℃ at a speed of 5 ℃/min under an inert atmosphere, preserving heat for 2 hours, and pulling slag to obtain a stable melt;
and cooling the stable melt to 800 ℃ at 5 ℃/min, and then cooling to room temperature at 10 ℃/min to obtain the alloy cast ingot enriched with valuable metals.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 32%, the Co content is 33%, the Ta content is 9%, the Nb content is 6%, and the alloy mass recovery rate in the waste tungsten slag reaches 93%.
Example 4
The only difference from example 1 is that: and (3) heating the blank body to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 1h, and pulling out slag to obtain a stable melt. That is, example 4 and example 1 differ only in the incubation time.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 28%, the Co content is 29%, the Ta content is 2%, the Nb content is 1%, and the alloy mass recovery rate in the waste tungsten slag reaches 83%.
Example 5
This embodiment differs from embodiment 1 only in that: and (3) heating the blank in the step (3) to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 1.5h, and pulling slag to obtain a stable melt. That is, example 5 and example 1 differ only in the incubation time.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 31%, the Co content is 33%, the Ta content is 3%, the Nb content is 2%, and the alloy mass recovery rate in the waste tungsten slag reaches 88%.
Example 6
This embodiment differs from embodiment 1 only in that: and (3) heating the blank body to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 2 hours, and pulling slag to obtain a stable melt. That is, example 6 and example 1 differ only in the incubation time.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 32%, the Co content is 35%, the Ta content is 6%, the Nb content is 3%, and the alloy mass recovery rate in the waste tungsten slag reaches 91%.
It is noted that, as can be seen from comparative examples 1 and examples 4 to 6, the recovery rate can reach more than 80% when the heat preservation time is 1 to 3 hours; the heat preservation time is 2-3 h, and the recovery rate can reach more than 90%.
Example 7
This embodiment differs from embodiment 2 only in that: in the step (2), the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent in the composite reducing agent is 1:4.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 30%, the Co content is 30%, the Ta content is 4%, the Nb content is 2%, and the alloy mass recovery rate in the waste tungsten slag reaches 84%.
Example 8
This embodiment differs from embodiment 2 in that: in the step (2), the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent in the composite reducing agent is 1:5.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 31%, the Co content is 32%, the Ta content is 5%, the Nb content is 3%, and the alloy mass recovery rate in the waste tungsten slag reaches 86%.
Example 9
This embodiment differs from embodiment 2 in that: in the step (2), the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent in the composite reducing agent is 1:10.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 28%, the Co content is 29%, the Ta content is 2%, the Nb content is 2%, and the alloy mass recovery rate in the waste tungsten slag reaches 81%.
It is noted that comparative example 2 and examples 7 to 9 show that the mass ratio of carbonaceous reducing agent to siliceous reducing agent is controlled to be 1: (4-10) has better effect and can reach the recovery rate of more than 80 percent; the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent is 1: (6-8) the best effect, can reach the recovery rate of more than 90%.
Example 10
This embodiment differs from embodiment 3 in that: in the step (2), the mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.05.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 26%, the Co content is 27%, the Ta content is 4%, the Nb content is 3%, and the alloy mass recovery rate in the waste tungsten slag reaches 80%.
Example 11
This embodiment differs from embodiment 3 in that: in the step (2), the mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.15.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 31%, the Co content is 31%, the Ta content is 7%, the Nb content is 5%, and the alloy mass recovery rate in the waste tungsten slag reaches 90%.
Example 12
This embodiment differs from embodiment 3 in that: in the step (2), the mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.18.
and (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 25%, the Co content is 26%, the Ta content is 6%, the Nb content is 5%, and the alloy mass recovery rate in the waste tungsten slag reaches 82%.
As can be seen from comparative example 3 and examples 10 to 12, the mass ratio of the waste tungsten slag powder, the slag former and the composite reducing agent was controlled to be 1: (0.1-0.5): (0.05-0.2) has better effect, and the recovery rate can reach more than 80 percent; the control is as follows: (0.1-0.5): (0.08-0.15) has the best effect, and the recovery rate is more than 90 percent.
Example 13
This embodiment differs from embodiment 1 in that: the smelting temperature was changed from 1500 ℃ to 1350 ℃.
And (3) product testing: and analyzing the obtained alloy cast ingot enriched with valuable metals, wherein the alloy layer is tested by ICP-AES, the W content is 29%, the Co content is 28%, the Ta content is 1%, the Nb content is 1%, and the alloy mass recovery rate in the waste tungsten slag reaches 83%.
Comparative example 1
This comparative example differs from example 1 only in that: and (3) heating the blank in the step (3) to 1500 ℃ at a speed of 10 ℃/min, preserving heat for 0.5h, and pulling slag to obtain a stable melt. Comparative example 1 differs from example 1 only in the incubation time.
And (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 12%, the Co content is 16%, the Ta content is 0.1%, the Nb content is 0.1%, and the alloy mass recovery rate in the waste tungsten slag reaches 48%.
It can be seen that too short a soak time can result in a significant decrease in alloy recovery.
Comparative example 2
The difference between this comparative example and example 1 is that: and (3) heating the blank body to 1300 ℃ at a speed of 10 ℃/min, preserving heat for 2.5h, and pulling slag to obtain a stable melt. Comparative example 2 differs from example 1 only in the smelting temperature.
And (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 16%, the Co content is 20%, the Ta content is 3%, the Nb content is 2%, and the alloy mass recovery rate in the waste tungsten slag reaches 62%.
Comparative example 3
The difference between this comparative example and example 2 is that: in the step (2), the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent in the composite reducing agent is 1:2.
and (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 17%, the Co content is 19%, the Ta content is 0.2%, the Nb content is 0.5%, and the alloy mass recovery rate in the waste tungsten slag reaches 58%.
Comparative example 4
This comparative example differs from example 2 only in that: in the step (2), the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent in the composite reducing agent is 1:15.
and (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 15%, the Co content is 17%, the Ta content is 0.2%, the Nb content is 0.1%, and the alloy mass recovery rate in the waste tungsten slag reaches 52%.
It should be noted that comparative example 2 and comparative examples 3 to 4 show that the mass ratio of carbonaceous reducing agent to siliceous reducing agent does not satisfy 1: (4-10), the recovery rate of the alloy element is significantly reduced.
Comparative example 5
This comparative example differs from example 2 only in that: the siliceous reducing agent of example 2 was replaced with an equivalent amount of carbonaceous reducing agent.
And (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 9%, the Co content is 10%, the Ta content is 0%, the Nb content is 0.1%, and the alloy mass recovery rate in the waste tungsten slag reaches 37%.
Comparative example 6
This comparative example differs from example 3 only in that: in the step (2), the mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.03.
and (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 23%, the Co content is 23%, the Ta content is 1%, the Nb content is 1%, and the alloy mass recovery rate in the waste tungsten slag reaches 70%.
Comparative example 7
This comparative example differs from example 3 only in that: in the step (2), the mass ratio of the waste tungsten slag powder to the slag former to the composite reducing agent is 1:0.3:0.3.
and (3) product testing: ICP-AES analysis is carried out on the alloy cast ingot enriched with valuable metals, wherein the W content is 16%, the Co content is 12%, the Ta content is 2%, the Nb content is 2%, and the alloy mass recovery rate in the waste tungsten slag reaches 53%.
As can be seen from comparative example 3 and comparative examples 5 to 7, the mass ratio of the waste tungsten slag to the siliceous reducing agent does not conform to 1: (0.05-0.2), the recovery rate of the alloy element is significantly reduced.
In conclusion, on the basis of tungsten slag reduction smelting, the composite reducing agent containing the carbonaceous reducing agent and the siliceous reducing agent is adopted, so that valuable metal residues in a slag phase can be effectively reduced, the slag-gold separation effect is good, and the recovery rate of W, co, ta, nb can be remarkably improved. In addition, the method provided by the invention can also reduce the melting point and viscosity of the slag system, thereby reducing the energy consumption and having very good market application prospect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recovering valuable metals from waste tungsten slag, which is characterized by comprising the following steps: mixing the waste tungsten slag with a slag former and a composite reducing agent, and then carrying out reduction smelting;
wherein the composite reducing agent comprises a carbonaceous reducing agent and a siliceous reducing agent, and the mass ratio of the carbonaceous reducing agent to the siliceous reducing agent is 1: (4-10), wherein the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.05-0.20).
2. The method according to claim 1, wherein the mass ratio of the carbonaceous reducing agent and the siliceous reducing agent is 1: (6-8);
preferably, the mass ratio of the waste tungsten slag to the composite reducing agent is 1: (0.08-0.15).
3. The method according to claim 1 or 2, wherein the carbonaceous reducing agent is selected from at least one of graphite, coke, coal dust, charcoal, activated carbon, and carbon black.
4. A method according to claim 1 or claim 2, wherein the siliceous reducing agent is selected from at least one of metal silicon powder, silicon nuggets and silicon wafers.
5. The method of claim 1, wherein the slag former is selected from Na 2 CO 3 And at least one of CaO;
preferably, the mass ratio of the waste tungsten slag to the slag former is 1: (0.1-0.5).
6. The method according to claim 1, characterized in that the process of reduction smelting comprises: mixing the waste tungsten slag with the slag former and the composite reducing agent, and performing cold isostatic pressing to obtain a blank; heating the blank to 1350-1700 ℃ in inert atmosphere, and carrying out melt heat preservation;
preferably, the smelting temperature is controlled to be 1400-1700 ℃;
preferably, the blank is placed in a magnesia crucible for smelting;
preferably, the heat preservation time of the melt is 1-3 h; more preferably 2 to 3 hours;
preferably, the temperature rising rate of the blank body is controlled to be 5-15 ℃ per minute.
7. The method of claim 6, wherein the stable melt is obtained by slag withdrawal after heat preservation of the melt, and then the alloy ingot is obtained by cooling to room temperature.
8. The method according to claim 7, wherein the melt obtained after slag extraction is cooled to 800-1200 ℃ at a rate of 2-5 ℃/min and then cooled to room temperature at a rate of 5-10 ℃/min.
9. The method according to claim 1, wherein the waste tungsten slag comprises, in mass percent: w1-10%, co 1-30%, ta 0.5-5%, nb 0.5-5%, siO 2 5％～30％、TiO 2 5-30% and 5-20% of Fe.
10. The method of claim 9, wherein the waste tungsten slag is mixed with the slag former and the composite reductant after being processed into a dry powder; the particle size of the dry powder is controlled to be 1-10 mu m.
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