CN117965911A - Secondary recovery method for tungsten-containing waste after recovery treatment - Google Patents
Secondary recovery method for tungsten-containing waste after recovery treatment Download PDFInfo
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- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 128
- 239000010937 tungsten Substances 0.000 title claims abstract description 128
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000011084 recovery Methods 0.000 title claims abstract description 104
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000007670 refining Methods 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 238000004064 recycling Methods 0.000 claims abstract description 24
- 150000002739 metals Chemical class 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052786 argon Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910000905 alloy phase Inorganic materials 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000601 superalloy Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 238000009694 cold isostatic pressing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1295—Refining, melting, remelting, working up of titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working 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
- C22B7/001—Dry processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling the tungsten-containing waste after recycling treatment, which has stronger applicability, low cost and high efficiency, and realizes the high-efficiency secondary recycling of valuable elements in the tungsten recycling waste residue. The method comprises the following steps: s1, crushing and grinding tungsten-containing recovery waste into powder; s2, preparing a refining recovery agent, adding the refining recovery agent according to a specific proportion, uniformly mixing and compressing the refining recovery agent into a refining blank; s3, two-stage high-temperature refining under the protection of argon and cooling; s4, mechanically separating to obtain valuable metal recovery materials. The method has wide applicability and simple process steps, is applicable to tungsten waste leaching residues after the recovery treatment of tungsten-containing waste by adopting a hydrometallurgy process, is not limited to the types of tungsten-containing waste recovered at one time, and has high recovery rate, and the total recovery rate of valuable metals can reach more than 80 percent.
Description
Technical Field
The invention belongs to the technical field of tungsten waste resource recovery, and particularly relates to a secondary recovery method after tungsten-containing waste recovery treatment.
Background
Tungsten is a strategic metal, and has wide application in the modern industry and the high-tech field due to its excellent performance, and is mainly used for preparing hard alloy, alloy steel, heat-resistant and wear-resistant alloy, etc. China is the largest tungsten product producing country in the world, has a complete industrial chain from tungsten smelting to processing, and has abundant tungsten resources, but in recent years, the exploitation and smelting of tungsten cause great damage to the environment, the reserves and the grade of tungsten are reduced, and the recycling of the existing waste tungsten products is urgently needed. About 35% of tungsten supply worldwide comes from recycling of waste tungsten products, secondary tungsten resources in developed countries occupy the main market, the regeneration rate of some countries reaches 80%, tungsten yield in China is more than 80% worldwide, tungsten concentrate is mainly used as raw materials, the tungsten recovery rate is far lower than the level of developed countries, and recycling of waste tungsten products becomes an important direction for realizing sustainable development of tungsten material industry in China under the condition of increasingly serious resource and environment problems.
The tungsten-containing waste materials commonly used in industry mainly comprise tungsten carbide hard alloy, waste pure tungsten products, waste tungsten steel, tungsten materials, tungsten tailings, tungsten slag, waste tungsten compounds and the like. Currently, the main recovery method of waste tungsten products is still hydrometallurgical, including zinc smelting, saltpeter smelting and roasting alkaline leaching. The zinc melting method is based on forming low-melting-point alloy by zinc and binding phase metals such as cobalt, nickel and the like in the hard alloy, so that the binding metal is separated from the hard alloy, and zinc cannot react with various refractory metal carbides, thereby achieving the aim of recovering tungsten; in the nitrate smelting method, nitrate is used as an oxidant, tungsten carbide in tungsten waste is converted into sodium tungstate at a high temperature, and other impurity elements are oxidized into metal oxides which are insoluble in water, so that the purpose of recovering tungsten is achieved; the roasting alkaline leaching method is that tungsten waste is converted into tungsten oxide through oxidation roasting, and sodium tungstate is generated through alkaline leaching reaction of the tungsten oxide, so that the purpose of recovering tungsten is achieved.
Hydrometallurgical processes are the primary recovery method for the treatment of most tungsten waste, the primary route of which is to oxidize the waste tungsten product in air and then leach it in alkaline and acidic conditions to recover tungsten, cobalt, etc., however, there is a large amount of tungsten leaching residue which contains a large amount of harmless oxides such as SiO 2、TiO2, and a small amount of valuable oxides such as tungsten, cobalt, tantalum, nickel, etc. The generated tungsten leaching residues are classified as dangerous solid waste, landfill treatment cannot be carried out, and the increase of recycling requirements of waste tungsten products causes accumulation of a large amount of tungsten leaching residues, if the tungsten leaching residues can be effectively recycled for the second time, valuable elements in the tungsten leaching residues are extracted, and the tungsten leaching residues continue to be used as raw materials in the tungsten raw material industry, so that the tungsten leaching residues have remarkable economic benefit and environmental protection value.
The methods of liquid-liquid extraction, pressure leaching, alkaline melting and the like are commonly used methods for recycling secondary resources of leaching residues after tungsten waste treatment, however, due to the existence of a large amount of oxides, the applicability of the methods to tungsten residues is obviously limited. The method for recycling the tungsten-containing waste material after recycling treatment has stronger applicability, low cost and high efficiency, realizes the high-efficiency secondary recycling of valuable elements in the tungsten recycling waste residue, and has obvious economic significance and environmental protection value.
Disclosure of Invention
The invention aims to solve the technical problem of developing a method for recycling the tungsten-containing waste after recycling treatment, which has stronger applicability, low cost and high efficiency, and realizes the high-efficiency secondary recycling of valuable elements in the tungsten recycling waste residue.
Specifically, the invention provides a secondary recovery method after recovery treatment of tungsten-containing waste, which comprises the following steps:
S1, crushing and grinding tungsten-containing recovery waste into powder to obtain tungsten waste recovery powder, wherein the tungsten-containing recovery waste is tungsten leaching waste residue obtained in the hydrometallurgical recovery process of the tungsten-containing waste, and the tungsten-containing waste comprises at least one of a tungsten carbide cutter, a tungsten-based alloy, a tungsten-containing hard alloy, a tungsten-containing superalloy, waste tungsten mud and a waste tungsten rod;
S2, adding a refining recovery agent into the ground tungsten waste recovery powder according to a specific proportion, uniformly mixing, and compressing the mixed material to prepare a refining blank;
s3, refining the refining blank at high temperature under the protection of argon, and cooling to obtain refined slag and refined alloy phase;
S4, mechanically separating the refined slag from the refined alloy phase, wherein the obtained refined alloy phase is valuable metal recovery materials.
Preferably, in the step S1, the particle size of the tungsten waste recovery powder is 40 to 200 mesh.
After the recovered materials are crushed, chemical reaction is easier to fully perform in the refining process, the refining recovery time can be shortened, the refining effect is improved, but the particle size of the powder is too small, so that the grinding cost is increased, meanwhile, the specific surface area of the material powder is remarkably increased, the material powder is easier to burn out, and under the action of the surface tension of particles, the material is easy to overflow along with refined scum in the refining process, so that the material loss is caused; the particle size is too coarse, and the density of the compressed blank is low, so that the chemical reaction degree in the refining process is reduced, and the refining reaction time is increased. The powder particle size of 40-200 meshes has the best comprehensive effect.
Preferably, in the step S2, the specific proportion is that, in weight percentage, the tungsten waste recovery powder: refining recovery agent = 2-4: 1.
The target phases of valuable metals contained in the tungsten waste recovery powder exist in an oxidized form, such as WO 3、CoO、Ta2O5 and Nb 2O5, and a large amount of SiO 2 and TiO 2 are also added, if the refining is directly carried out, a large amount of oxides such as SiO 2, tiO 2 and the like remained in the tungsten leaching waste residue cannot form a uniform slag phase, namely the refining and purifying purposes cannot be achieved.
The material ratio of the tungsten waste recovery powder to the refining recovery agent is a key factor for ensuring the refining recovery effect, if the addition amount of the refining recovery agent is low, the chemical reaction with the tungsten waste recovery powder cannot be fully completed, the refining recovery yield is obviously reduced, excessive addition of the refining recovery agent does not cause material waste, the excessive material also easily pollutes the refined target melt, and the refining recovery effect is reduced. The material ratio of the tungsten waste recovery powder to the refining recovery agent is based on factors such as the types and the contents of elements in the tungsten waste recovery powder, the existence mode and the like, and can be obtained through phase diagram theoretical calculation and systematic experiments.
Preferably, in the step S2, the refining recovery agent is a mixture of Na 2O、SiO2 and NaF, and Na 2O：SiO2 is calculated according to weight percentage: naf=4-5:2-3:1-2.
Na 2 O can change the forming temperature of the liquid phase of the slag, and can react with the original oxides such as SiO 2, tiO 2 and the like in the tungsten waste leaching slag to generate silicate. However, simply adding Na 2 O can cause the reduction of melt viscosity, and the phase transformation of valuable metals in the tungsten waste leaching residue cannot be completely realized, according to the types and the forms of the valuable metals in the waste leaching residue and the accurate calculation of a phase diagram theory, siO 2 and Na 2 O are matched, reasonable material proportion is designed, and oxides of the valuable metals such as tungsten, tantalum, niobium, cobalt and the like scattered in different areas of the tungsten waste leaching residue can be effectively reduced. WO 3、Ta2O5 and Nb 2O5 are reduced to carbides (WC, taC and NbC), coO is reduced and then reacts with SiO 2 to form silicide, which realizes phase transformation of valuable metals in the spent tungsten leaching slag and separation of alloy phase from slag phase. On the basis of a proper Na 2O-SiO2 system, naF is further increased, so that not only can the liquid phase formation temperature be reduced, but also the quality of a liquid slag phase can be increased, and fluoride ions in NaF can react with a large silicate network, so that the slag structure is depolymerized, the solution viscosity is reduced, the mass transfer process in slag is accelerated, and a more uniform alloy phase can be obtained.
Preferably, in the step S2, the compressing is cold isostatic pressing, and the blank is one or more of cylindrical, square and conical.
After powder materials are compressed through cold isostatic pressing, compact blanks can effectively prevent liquid phase from splashing in the refining melting process, material loss and operation risks are reduced, different blank shapes can adapt to the volumes of reaction furnaces of different specifications, and the blanks are heated more uniformly and efficiently.
Preferably, in the step S3, the high-temperature refining is two-stage temperature control refining, the two-stage temperature control refining is to control the temperature rising rate to be 2-10 ℃/min, keep the temperature at 1200-1400 ℃ for 1-2 h, raise the temperature to 1500-1700 ℃ at the temperature rising rate of 4-5 ℃/min, refine the temperature keeping time to be 1-3 h, and then cool the temperature to the room temperature at the speed of 5-10 ℃/min.
The refining temperature is closely related to the phase reaction between the refining recovery agent and valuable elements in the tungsten waste leaching slag, and is also related to a melt viscosity system, the alloy phase conversion temperature formed between the refining recovery agent and the valuable elements in the leaching slag is directly related to the type and the proportion of the refining recovery agent, the melt viscosity is closely related to the mass transfer of the refining process, the temperature rising rate, the refining temperature, the heat preservation time and the cooling rate are a whole set of complete temperature control measures, and the refining recovery effect can be ensured through the cooperation of two-stage temperature control refining and the designed refining recovery agent.
Preferably, in the step S4, the valuable metal recovery material is a carbide alloy phase and a silicide alloy phase of valuable metals.
Preferably, in the step S4, the valuable metal recovery material includes, but is not limited to, tungsten, tantalum, niobium, titanium, cobalt.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method has wide applicability and simple process steps, is applicable to tungsten waste leaching residues after the recovery treatment of tungsten-containing waste by adopting a hydrometallurgy process, is basically not limited to the types of tungsten-containing waste subjected to primary recovery treatment, effectively widens the applicability of raw materials for secondary recovery of tungsten-containing waste, and reduces the cost of raw materials.
(2) A ternary Na 2O-SiO2 -NaF refining recovery agent system is developed, a two-stage temperature control refining method matched with the ternary Na 2O-SiO2 -NaF refining recovery agent system is provided, a small amount of valuable metal elements scattered in different positions of tungsten waste leaching residues in an oxide form can be converted and enriched on formed metal carbide and silicide, and the metal carbide and silicide can be continuously used as raw materials of tungsten raw material industry.
(2) The recovery rate is high, the total recovery rate of valuable metals can reach 80 percent by the method, wherein the recovery rate of tungsten element reaches 95 percent, the recovery rate of tantalum element reaches 60 percent, the recovery rate of niobium element reaches 82 percent and the recovery rate of cobalt element reaches 65 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. Unless otherwise indicated, all chemical reagents used in the examples were conventional commercial reagents, and the technical means used in the examples were conventional means well known to those skilled in the art.
Example 1
Calculated in weight percent, according to Na 2O：SiO2: naf=4:2:1 ratio configured as a refinery recovery agent; weighing 1kg of tungsten-containing recovered waste, and crushing and grinding the tungsten-containing recovered waste into 40-mesh powder by a grinder; calculated according to weight percentage, the powder is recovered according to tungsten waste: refining recovery agent = 2:1, weighing the prepared refining reclaiming agent, and uniformly mixing the refining reclaiming agent with the ground tungsten waste reclaimed powder; placing the mixed material into a compression mold for multiple times in batches, and compressing the mixed material into cylindrical blanks by utilizing a cold isostatic pressing device; placing the blank into a graphite crucible, placing the crucible into an induction resistance heating furnace, and introducing argon for protection; setting the heating rate of a heating furnace to be 4 ℃/min, heating to 1200 ℃, preserving heat for 2h for refining, heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h for refining, and cooling along with the furnace at the cooling rate of 5 ℃/min; taking the refined material out of the crucible, and mechanically separating the upper refined slag from the lower alloy phase to obtain the secondary recovered material enriched with valuable metals.
And (3) measuring the element content in the alloy phase obtained after the neutralization and refining of the tungsten-containing recovered waste by adopting an inductively coupled plasma-atomic emission spectrometry, and calculating the total recovery rate of valuable metals and the recovery rate of each main metal element.
The total recovery of valuable metals was calculated to be 80.2%, with a tungsten recovery of 95.4%, a tantalum recovery of 63.3%, a niobium recovery of 82.8% and a cobalt recovery of 65.7%.
Example 2
Calculated in weight percent, according to Na 2O：SiO2: naf=5:3:1 ratio configured as a refinery recovery agent; weighing 1kg of tungsten-containing recovered waste, and crushing and grinding the tungsten-containing recovered waste into 100-mesh powder by a grinder; calculated according to weight percentage, the powder is recovered according to tungsten waste: refining recovery agent = 3:1, weighing the prepared refining reclaiming agent, and uniformly mixing the refining reclaiming agent with the ground tungsten waste reclaimed powder; placing the mixed material into a compression mold for multiple times in batches, and compressing the mixed material into square blanks by utilizing a cold isostatic pressing device; placing the blank into a graphite crucible, placing the crucible into an induction resistance heating furnace, and introducing argon for protection; setting the heating rate of a heating furnace to be 5 ℃/min, heating to 1300 ℃, preserving heat for 1.5h for refining, heating to 1650 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h for refining, and cooling along with the furnace at the cooling rate of 8 ℃/min; taking the refined material out of the crucible, and mechanically separating the upper refined slag from the lower alloy phase to obtain the secondary recovered material enriched with valuable metals.
And (3) measuring the element content in the alloy phase obtained after the neutralization and refining of the tungsten-containing recovered waste by adopting an inductively coupled plasma-atomic emission spectrometry, and calculating the total recovery rate of valuable metals and the recovery rate of each main metal element.
The total recovery of valuable metals was 83.8%, with a tungsten recovery of 96.6%, a tantalum recovery of 65.2%, a niobium recovery of 84.5% and a cobalt recovery of 66.7%.
Example 3
Calculated in weight percent, according to Na 2O：SiO2: naf=5:3:2 ratio, configured as a refinery recovery agent; weighing 1kg of tungsten-containing recovered waste, and crushing and grinding the tungsten-containing recovered waste into 200-mesh powder by a grinder; calculated according to weight percentage, the powder is recovered according to tungsten waste: refining recovery agent = 4:1, weighing the prepared refining reclaiming agent, and uniformly mixing the refining reclaiming agent with the ground tungsten waste reclaimed powder; placing the mixed material into a compression mold for multiple times in batches, and compressing the mixed material into conical blanks by utilizing a cold isostatic pressing device; placing the blank into a graphite crucible, placing the crucible into an induction resistance heating furnace, and introducing argon for protection; setting the heating rate of a heating furnace to be 7 ℃/min, heating to 1400 ℃, preserving heat for 1h for refining, heating to 1700 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h for refining, and cooling along with the furnace at the cooling rate of 110 ℃/min; taking the refined material out of the crucible, and mechanically separating the upper refined slag from the lower alloy phase to obtain the secondary recovered material enriched with valuable metals.
And (3) measuring the element content in the alloy phase obtained after the neutralization and refining of the tungsten-containing recovered waste by adopting an inductively coupled plasma-atomic emission spectrometry, and calculating the total recovery rate of valuable metals and the recovery rate of each main metal element.
The total recovery of valuable metals was calculated to be 81.4%, with a tungsten recovery of 95.8%, a tantalum recovery of 60.6%, a niobium recovery of 82.4% and a cobalt recovery of 67.2%.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. The secondary recovery method after the recovery treatment of the tungsten-containing waste is characterized by comprising the following steps of:
S1, crushing and grinding tungsten-containing recovery waste into powder to obtain tungsten waste recovery powder, wherein the tungsten-containing recovery waste is tungsten leaching waste residue obtained in the hydrometallurgical recovery process of the tungsten-containing waste, and the tungsten-containing waste comprises at least one of a tungsten carbide cutter, a tungsten-based alloy, a tungsten-containing hard alloy, a tungsten-containing superalloy, waste tungsten mud and a waste tungsten rod;
S2, adding a refining recovery agent into the ground tungsten waste recovery powder according to a specific proportion, uniformly mixing, and compressing the mixed material to prepare a refining blank;
s3, refining the refining blank at high temperature under the protection of argon, and cooling to obtain refined slag and refined alloy phase;
S4, mechanically separating the refined slag from the refined alloy phase, wherein the obtained refined alloy phase is valuable metal recovery materials.
2. The post-recovery method according to claim 1, wherein in step S1, the particle size of the tungsten-containing waste recovery powder is 40 to 200 mesh.
3. The post-recovery method according to claim 1, wherein in step S2, the specific proportion is, in weight percent, tungsten waste recovery powder: refining recovery agent = 2-4: 1.
4. The post-tungsten-containing waste recycling method according to claim 1, wherein in the step S2, the refining recycling agent is a mixture of Na 2O、SiO2 and NaF, and the weight percentage of Na 2O：SiO2 is as follows:
NaF＝4～5:2～3:1～2。
5. The post-tungsten-containing waste recycling method according to claim 1, wherein in the step S2, the compression is cold isostatic compression, and the billet is one or more of cylindrical, square and conical.
6. The post-recovery method according to claim 1, wherein in step S3, the high-temperature refining is a two-stage temperature-controlled refining, the two-stage temperature-controlled refining is performed at a controlled temperature-rising rate of 2 to 10 ℃/min, the temperature is maintained at 1200 to 1400 ℃ for 1 to 2 hours, the temperature is raised to 1500 to 1700 ℃ at a temperature-rising rate of 4 to 5 ℃/min, the refining temperature-maintaining time is 1 to 3 hours, and the temperature is cooled to room temperature at a rate of 5 to 10 ℃/min.
7. The post-tungsten-containing waste recycling method according to claim 1, wherein in step S4, the valuable metal recycling material is a carbide alloy phase of valuable metals.
8. The post-tungsten-containing waste recycling method according to claim 7, wherein in step S4, the valuable metal recycling materials include, but are not limited to, tungsten, tantalum, niobium, titanium, cobalt.
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| CN114317989A (en) * | 2021-12-28 | 2022-04-12 | 厦门大学 | Method for recovering valuable metals in waste tungsten slag |
| CN114875252A (en) * | 2022-05-13 | 2022-08-09 | 中南大学 | Method for recovering tungsten-containing waste |
| CN115927842A (en) * | 2022-12-23 | 2023-04-07 | 厦门钨业股份有限公司 | Method for recovering valuable metals in waste tungsten slag |
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| CN114317989A (en) * | 2021-12-28 | 2022-04-12 | 厦门大学 | Method for recovering valuable metals in waste tungsten slag |
| CN114875252A (en) * | 2022-05-13 | 2022-08-09 | 中南大学 | Method for recovering tungsten-containing waste |
| CN115927842A (en) * | 2022-12-23 | 2023-04-07 | 厦门钨业股份有限公司 | Method for recovering valuable metals in waste tungsten slag |
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