CN113666374A - Method for recovering carbide from waste Ti (C, N) -based metal ceramic - Google Patents
Method for recovering carbide from waste Ti (C, N) -based metal ceramic Download PDFInfo
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- CN113666374A CN113666374A CN202110966296.2A CN202110966296A CN113666374A CN 113666374 A CN113666374 A CN 113666374A CN 202110966296 A CN202110966296 A CN 202110966296A CN 113666374 A CN113666374 A CN 113666374A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 63
- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011195 cermet Substances 0.000 claims abstract description 33
- 238000001238 wet grinding Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 150000001247 metal acetylides Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 229910003470 tongbaite Inorganic materials 0.000 claims description 6
- 238000002386 leaching Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 34
- 238000000498 ball milling Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 150000007522 mineralic acids Chemical class 0.000 description 9
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
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- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
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- B22F2998/10—Processes characterised by the sequence of their steps
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Abstract
The invention discloses a method for recovering carbide from waste Ti (C, N) -based metal ceramic, belonging to the field of manufacturing of metal ceramic composite materials. Specifically disclosed is: crushing Ti (C, N) -based cermet, dissolving the cermet in hydrochloric acid and nitric acid in sequence, and washing, wet-grinding and drying solid obtained by solid-liquid separation to realize recovery of carbide; after being dissolved by hydrochloric acid and nitric acid, the method also comprises the step of dissolving by a mixed solution of nitric acid and hydrofluoric acid. The invention is based on waste Ti (C, N) -based metalThe specific carbide is extracted by selecting hydrochloric acid, nitric acid and mixed solution of nitric acid and hydrofluoric acid according to different components in the ceramic, and the implementation steps can be flexibly selected so as to obtain Mo2C. One or more of WC, TaC, and NbC. The invention does not need to carry out complex process flows such as roasting, leaching, crystallization and the like, and the recovered carbide can be directly used for preparing Ti (C, N) -based metal ceramic.
Description
Technical Field
The invention relates to the field of manufacturing of metal ceramic composite materials, in particular to a method for recovering carbides from waste Ti (C, N) -based metal ceramics.
Background
Titanium carbonitride-based cermets, which are a type of titanium-based cemented carbide, are used for manufacturing sintered bodies of cutting tools and wear-resistant parts because of their higher red hardness, better oxidation resistance and stronger wear resistance than tungsten-cobalt cemented carbide, and are often used in semi-finishing and finishing because of their excellent surface finish quality.
However, with the application of a large amount of titanium carbonitride-based cermets, the amount of waste titanium carbonitride-based cermets is increasing, and although the raw materials do not contain noble metals, the price is still high, and the waste titanium carbonitride-based cermets are easy to collect, so that the research and development of a technology for recovering the raw materials from the waste titanium carbonitride-based cermets have great significance in saving resources, protecting the environment and recycling the raw materials.
The titanium carbonitride-based cermet has an extremely high strength and cannot be directly recycled for remanufacturing, and in the titanium carbonitride-based cermet, carbide is one of the main components thereof, and has a large amount of Mo removed2The outside of the C is reacted with a specific inorganic acid solution, and the like, and becomes the most worthy raw material recovered from the waste Ti (C, N) -based metal ceramic. However, the method of dissolving, roasting, leaching, crystallizing, precipitating and the like by using inorganic acid to separate metal components such as W, Mo, Ti, Co, Ni and the like from the waste Ti (C, N) -based cermet not only has complex process flow, but also can prepare raw materials WC, Mo and the like for producing the Ti (C, N) -based cermet by carbonizing the extracted metal elements2C and the like.
At present, no systematic process method exists for directly recovering carbides from waste Ti (C, N) -based metal ceramics.
Disclosure of Invention
The invention aims to provide a method for recovering carbides from waste Ti (C, N) -based metal ceramics, which aims to solve the problems in the prior art and separate and extract specific carbides in the Ti (C, N) -based metal ceramics, thereby realizing the recovery and reutilization of specific carbides in the Ti (C, N) -based metal ceramics and greatly saving resources.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for recovering carbide from Ti (C, N) -based cermet, which comprises the following steps:
crushing the Ti (C, N) -based cermet, dissolving the Ti (C, N) -based cermet by hydrochloric acid and nitric acid in sequence, and washing, wet-grinding and drying a solid obtained by solid-liquid separation to realize recovery of the carbide;
the Ti (C, N) -based cermet includes a first ceramic phase, a second ceramic phase, and a metal phase; the first ceramic phase is titanium carbonitride, and the second ceramic phase is carbide of IV, V and VI subgroup elements; the metal phase is cobalt and/or nickel.
Preferably, the volume fraction of the hydrochloric acid is 20-30%, and the volume fraction of the nitric acid is 30-40%.
Preferably, the mass fraction of the first ceramic phase is 20-60%, the mass fraction of the metal phase is 10-20%, and the balance is the second ceramic phase.
Preferably, the carbide of the IV, V and VI subgroup elements is Mo2C. One or more of WC, TaC and NbC, and the recovery method comprises the following steps:
and crushing the Ti (C, N) -based metal ceramic, dissolving the crushed Ti (C, N) -based metal ceramic by using a mixed solution of hydrochloric acid, nitric acid and hydrofluoric acid in sequence, and washing, wet-grinding and drying a solid obtained by solid-liquid separation to realize recovery of the carbide.
More preferably, the carbide of the IV, V, VI subgroup element also comprises VC and/or Cr3C2。
Preferably, the volume fraction of the mixed solution of nitric acid and hydrofluoric acid is 20-30%, and the molar ratio of nitric acid to hydrofluoric acid in the mixed solution of nitric acid and hydrofluoric acid is 4-5: 1.
Preferably, the carbide of the IV, V, VI subgroup elements also comprises VC and/or Cr3C2。
Preferably, deionized water or ethanol is adopted as a wet grinding solvent in the wet grinding, the mass of the solvent/the mass of raw materials is 2: 1-3: 1, hard alloy balls or steel balls are used as grinding media, the mass of the grinding media/the mass of the raw materials is 5: 1-7: 1, the ball milling time is 20-30 h, and the temperature of ball milling slurry is 5-25 ℃; the drying is selected from spray drying, oven drying, rotary evaporation drying or freeze drying.
The acid used in the invention is inorganic acid, and the following steps are added and reduced according to the specific components of the waste Ti (C, N) -based cermet when in dissolution: putting the waste Ti (C, N) -based cermet into a polyacrylic acid hydrolysis tank, firstly adding hydrochloric acid to completely soak the cermet for 1-2 h, filtering and precipitating, and carrying out solid-liquid separation (for removing Ti (C, N) and Cr in the cermet3C2And cobalt), adding nitric acid (for removing VC and nickel), nitric acid + hydrofluoric acid mixed solution (for removing TaC, NbC and WC) in turn by the same method, and dissolving with inorganic acid; and washing and re-washing the metal ceramic for 2-5 times by using deionized water.
The invention also provides application of the method in recovery of waste Ti (C, N) -based metal ceramics.
The principle of the inorganic acid pickling is as follows: due to Ti and Cr in Ti (C, N)3C2The Cr and the cobalt in the alloy can react with hydrochloric acid with the concentration of more than 20 percent at normal temperature:
2Ti+6HCl＝2TiCl3+3H2↑
Co+2HCl＝CoCl2+H2↑
2Cr+6HCl＝2CrCl3+3H2↑
after reaction, the product is dissolved in hydrochloric acid and removed by solid-liquid separation.
Similarly, both VC and nickel can react with nitric acid at normal temperature and are finally dissolved in nitric acid, but the reaction product of VC and nitric acid is too complex, and the reaction equation of nickel and nitric acid is only given as follows:
Ni+6HNO3→Ni(NO3)3+3NO2+3H2↑
ta, Nb and W in TaC, NbC and WC can be dissolved in the mixed solution of nitric acid and hydrofluoric acid at normal temperature:
3Ta+5HNO3+21HF→3H2[TaF7]+5NO↑+10H2O
3Nb+5HNO3+21HF→3H2[NbF7]+5NO↑+10H2O
W+2HNO3+6HF→WF6(g)+2NO(g)+4H2O
the inorganic acid dissolution sequence is as follows:
(1) hydrochloric acid; (2) nitric acid; (3) nitric acid + hydrofluoric acid mixed solution.
The sequence can reduce the influence of Cl to the maximum extent, and besides washing, hydrofluoric acid and nitric acid can be removed in a subsequent Ti (C, N) -based metal ceramic preparation process in a lighting or sintering mode.
The technical principle of the invention is as follows:
mo removal of existing Ti (C, N) -based metal ceramic raw materials2Besides C, the carbon can be dissolved in various inorganic acids, so that the possibility of filtering, precipitating and extracting different carbides is provided.
On one hand, the extraction of metal components in the waste Ti (C, N) -based metal ceramic causes the process to be too complex and the cost to be too high, and on the other hand, the extracted metal components can not be directly used for preparing the Ti (C, N) -based metal ceramic. In the technical scheme of the invention, in order to realize the technical purpose, the waste Ti (C, N) -based metal ceramic washed by deionized water is crushed into fragments by a hydraulic crushing hammer, and then hydrochloric acid, nitric acid and a mixed solution of nitric acid and hydrofluoric acid are selected according to different components in the recovered waste Ti (C, N) -based metal ceramic to extract specific carbides.
When the concentration of the selected inorganic acid is lower than the content limited by the invention, the concentration is too low to react with the corresponding carbide or too slow to react; above the content defined in the present invention, the acid concentration is too high to cause ionization, so that the acid cannot be dissolved after reacting with the corresponding carbide. In the ball milling process, the extracted carbide can be ground, the residual acid radical ions are uniformly distributed in the ball milling solvent, and the residual acid radical ions are evaporated along with the ball milling solvent in the subsequent drying process.
In order to realize the quality stability of the recovered carbide powder, the following condition (1) needs to be satisfied to control the average grain diameter of the recovered carbide powder to be 0.6-5 μm; (2) the quality of the ball milling medium/raw material, the ball milling time and the temperature of the ball milling slurry are controlled, and the ball milling time is not excessively prolonged to generate ultrafine particles on the premise of full ball milling.
The invention discloses the following technical effects:
the carbide recovered by the method can be directly used for preparing Ti (C, N) -based metal ceramics, even if the recovered carbide is a mixture of more than one kind, the mass ratio of various carbides is consistent with that of the original waste Ti (C, N) -based metal ceramics, and the method can also be used for preparing the original formula Ti (C, N) -based metal ceramics again without carrying out chemical treatment again.
The invention does not need to carry out complex process flows such as roasting, leaching, crystallization and the like, and can flexibly adjust the implementation steps according to the components of the raw materials contained in the recovered waste Ti (C, N) -based metal ceramic. The extracted raw material has stable grain diameter (the average grain diameter can reach 0.6-5 mu m) and high purity of 90-95 percent after being ball-milled and dried by a wet method, and other metal impurities can not be introduced in the processes of inorganic acid pickling and deionized water washing. The basic reaction principle of the invention also provides a theoretical basis for the application of recovering other waste metal ceramic raw materials.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1 Mo recovery2C
(1) The recycled waste Ti (C, N) -based metal ceramic comprises the following components: 40% of titanium carbonitride, 15% of cobalt and the balance of WC and Mo2C；
(2) Preparing raw materials according to volume fraction: 35% of nitric acid, 25% of hydrochloric acid and a mixed solution (M) of nitric acid and hydrofluoric acidHNO3:MHF＝4.5:1)25％；
(3) Washing the recovered waste Ti (C, N) -based metal ceramic by using deionized water, crushing the waste Ti (C, N) -based metal ceramic into fragments by using a hydraulic breaking hammer, putting the waste Ti (C, N) -based metal ceramic into a polyacrylic acid hydrolysis tank, adding hydrochloric acid to completely soak the metal ceramic for 1.5h, filtering and precipitating, and carrying out solid-liquid separation; and sequentially putting the mixture into a mixed solution of nitric acid, nitric acid and hydrofluoric acid for soaking for 1.5h, filtering and precipitating, and washing with deionized water after solid-liquid separation.
(4) Weighing powder raw materials, uniformly mixing, placing in a ball mill, carrying out wet milling and drying to obtain Mo2And C, powder lot. The detection proves that the purity of the powder is 93% and average particle size was 2.6. mu.m.
Wherein the wet milling conditions are as follows: ethanol is used as a wet grinding solvent, the mass of the solvent/the mass of raw materials is 2:1, hard alloy balls are used as grinding media, the mass of the grinding media/the mass of the raw materials is 5:1, the ball milling time is 20 hours, and the temperature of ball milling slurry is 5 ℃; the drying is spray drying.
Example 2 recovery of WC and NbC
(1) The recycled waste Ti (C, N) -based metal ceramic comprises the following components: 55% of titanium carbonitride, 8% of nickel, 7% of cobalt and the balance of WC, NbC and Cr3C2；
(2) Preparing raw materials according to volume fraction: 32% of nitric acid and 24% of hydrochloric acid;
(3) washing the recovered waste Ti (C, N) -based cermet with deionized water, crushing the washed waste Ti (C, N) -based cermet into fragments by using a hydraulic breaking hammer, putting the waste Ti (C, N) -based cermet into a polyacrylic acid hydrolysis tank, adding hydrochloric acid to completely soak the cermet for 2 hours, filtering, precipitating and carrying out solid-liquid separation; then adding nitric acid, soaking for 2h, filtering and precipitating, and washing with deionized water after solid-liquid separation.
(4) Weighing powder raw materials, uniformly mixing, placing in a ball mill, carrying out wet milling, and drying to obtain WC and NbC mixed powder. The purity of the WC and NbC mixed powder is 91 percent and the average grain diameter is 1.81 mu m.
Wherein the wet milling conditions are as follows: ethanol is used as a wet grinding solvent, the mass of the solvent/the mass of raw materials is 3:1, hard alloy balls are used as grinding media, the mass of the grinding media/the mass of the raw materials is 7:1, the ball milling time is 24 hours, and the temperature of ball milling slurry is 15 ℃; the drying is spray drying.
Example 3 recovery of TaC
(1) The recycled waste Ti (C, N) -based metal ceramic comprises the following components: 55% of titanium carbonitride, 8% of nickel, 7% of cobalt and the balance of TaC, VC and Cr3C2；
(2) Preparing raw materials according to volume fraction: 30% of nitric acid and 20% of hydrochloric acid;
(3) washing the recovered waste Ti (C, N) -based cermet with deionized water, crushing the washed waste Ti (C, N) -based cermet into fragments by using a hydraulic breaking hammer, putting the waste Ti (C, N) -based cermet into a polyacrylic acid hydrolysis tank, adding hydrochloric acid to completely soak the cermet for 1 hour, filtering, precipitating and carrying out solid-liquid separation; then adding nitric acid, soaking for 1h, filtering and precipitating, and washing with deionized water after solid-liquid separation.
(4) Weighing powder raw materials, uniformly mixing, placing in a ball mill, carrying out wet milling, and drying to obtain TaC powder. The detection proves that the purity of the powder is 94 percent, and the average particle size is 1.46 mu m.
Wherein the wet milling conditions are as follows: ethanol is used as a wet grinding solvent, the mass of the solvent/the mass of raw materials is 3:1, hard alloy balls are used as grinding media, the mass of the grinding media/the mass of the raw materials is 5:1, the ball milling time is 30 hours, and the temperature of ball milling slurry is 20 ℃; the drying is spray drying.
Example 4 recovery of WC and Mo2C
(1) The recycled waste Ti (C, N) -based metal ceramic comprises the following components: titanium carbonitride 50%, nickel 9%, cobalt 8%, balance WC, Mo2C；
(2) Preparing raw materials according to volume fraction: 40% of nitric acid and 30% of hydrochloric acid;
(3) washing the recovered waste Ti (C, N) -based cermet with deionized water, crushing the washed waste Ti (C, N) -based cermet into fragments by using a hydraulic breaking hammer, putting the waste Ti (C, N) -based cermet into a polyacrylic acid hydrolysis tank, adding hydrochloric acid to completely soak the cermet for 1.8h, filtering, precipitating and carrying out solid-liquid separation; then adding nitric acid, soaking for 1.8h, filtering and precipitating, and washing with deionized water after solid-liquid separation.
(4) Weighing powder raw materials, uniformly mixing, placing in a ball mill, wet-milling and drying to obtain WC and Mo2C, mixing the powder. Detected, WC and Mo2The purity of the powder mixture C was 92%, and the average particle diameter was 1.64. mu.m.
Wherein the wet milling conditions are as follows: ethanol is used as a wet grinding solvent, the mass of the solvent/the mass of raw materials is 2:1, hard alloy balls are used as grinding media, the mass of the grinding media/the mass of the raw materials is 7:1, the ball milling time is 28 hours, and the temperature of ball milling slurry is 25 ℃; the drying is spray drying.
Example 5 TaC recovered from example 3 was used in the preparation of a reformulated Ti (C, N) -based cermet
The preparation of Ti (C, N) -based cermet with the original formula is carried out by using commercially available TaC powder and recovered TaC powder according to the same process method, and the mechanical properties are compared. The mechanical property test sample adopts a standard B style, and the standards are GBT3851-2015, GBT7997-2014 and JBT 12616-2016.
(1) Weighing the following raw materials in percentage by mass: 55% of titanium carbonitride, 8% of nickel, 7% of cobalt and the balance of TaC, VC and Cr3C2(ii) a The average grain diameter of the raw material powder is 0.6-5 mu m;
(2) weighing powder raw materials, uniformly mixing, placing the powder raw materials in a ball mill, carrying out wet grinding, drying, and pressing into a blank by a press;
wherein the wet milling conditions are as follows: ethanol is used as a wet grinding solvent, the mass of the solvent/raw material is 2:1, hard alloy balls are used as grinding media, the mass of the grinding media/raw material is 5:1, the ball milling time is 24 hours, and the temperature of ball milling slurry is 20 ℃; the drying is spray drying;
and (4) performing unidirectional die pressing, wherein the pressing pressure is 150 MPa.
(3) Placing the obtained blank in a sintering furnace, heating from room temperature to 500 ℃, keeping the temperature for 2h (the heating rate is 8 ℃/min), continuing heating to 1500 ℃ (the heating rate is 10 ℃/min), and keeping the temperature for 2 h; keeping the vacuum degree of a sintering environment to be lower than 100Pa in the high-temperature sintering process; and cooling the sintered product to room temperature along with the furnace to obtain the titanium carbonitride base cermet.
Mechanical property verification is carried out on the Ti (C, N) -based metal ceramic (A) prepared by the original formula from the commercial TaC powder and the Ti (C, N) -based metal ceramic (B) prepared by the original formula from the recycled TaC powder, and the property data are shown in Table 1.
TABLE 1
| Hardness HV30 | Bending strength, MPa | Fracture toughness, MPa m1/2 | |
| A | 1632 | 1564 | 10.2 |
| B | 1624 | 1512 | 10.3 |
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. A method for recovering carbides from a Ti (C, N) -based cermet, comprising the steps of:
crushing the Ti (C, N) -based cermet, dissolving the Ti (C, N) -based cermet by hydrochloric acid and nitric acid in sequence, and washing, wet-grinding and drying a solid obtained by solid-liquid separation to realize recovery of the carbide;
the Ti (C, N) -based cermet includes a first ceramic phase, a second ceramic phase, and a metal phase; the first ceramic phase is titanium carbonitride, and the second ceramic phase is carbide of elements in IV, V and VI subgroups; the metal phase is cobalt and/or nickel.
2. The method according to claim 1, wherein the volume fraction of the hydrochloric acid is 20-30% and the volume fraction of the nitric acid is 30-40%.
3. The method of claim 1, wherein the first ceramic phase is 20 to 60% by mass, the metal phase is 10 to 20% by mass, and the balance is the second ceramic phase.
4. The method of claim 1, wherein the carbide of an element of sub-groups IV, V, and VI is Mo2C. One or more of WC, TaC, and NbC.
5. The method according to claim 4, wherein the carbides of elements of sub-groups IV, V, VI further comprise VC and/or Cr3C2。
6. The method according to claim 4, characterized in that it comprises the following steps: and crushing the Ti (C, N) -based metal ceramic, dissolving the crushed Ti (C, N) -based metal ceramic by using a mixed solution of hydrochloric acid, nitric acid and hydrofluoric acid in sequence, and washing, wet-grinding and drying a solid obtained by solid-liquid separation to realize recovery of the carbide.
7. The method according to claim 4, wherein the volume fraction of the mixed solution of nitric acid and hydrofluoric acid is 20-30%, and the molar ratio of nitric acid to hydrofluoric acid in the mixed solution of nitric acid and hydrofluoric acid is 4-5: 1.
8. The method according to claim 1, wherein the temperature of the slurry in the wet grinding process is 5-25 ℃, and the wet grinding time is 20-30 h.
9. Use of the process according to any one of claims 1 to 8 in the recovery of spent Ti (C, N) -based cermets.
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| GB2404096.6A GB2625232A (en) | 2021-08-23 | 2021-09-08 | Method for recovering carbide from waste TI(C,N)-based metal ceramic |
| PCT/CN2021/117065 WO2023024162A1 (en) | 2021-08-23 | 2021-09-08 | Method for recovering carbide from waste ti(c,n)-based metal ceramic |
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