WO2023024162A1 - 一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法 - Google Patents

一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法 Download PDF

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WO2023024162A1
WO2023024162A1 PCT/CN2021/117065 CN2021117065W WO2023024162A1 WO 2023024162 A1 WO2023024162 A1 WO 2023024162A1 CN 2021117065 W CN2021117065 W CN 2021117065W WO 2023024162 A1 WO2023024162 A1 WO 2023024162A1
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nitric acid
acid
waste
carbide
carbides
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French (fr)
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李宇涵
王诗阳
王博
南勋
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嘉兴鸷锐新材料科技有限公司
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Publication of WO2023024162A1 publication Critical patent/WO2023024162A1/zh

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22C29/06—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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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

Definitions

  • the invention relates to the field of manufacturing cermet composite materials, in particular to a method for recovering carbides from waste Ti(C,N)-based cermets.
  • Titanium carbonitride-based cermets as a type of titanium-based cemented carbide, are used in the manufacture of cutting materials because they have higher red hardness, better oxidation resistance and stronger wear resistance than tungsten-cobalt cemented carbide.
  • Titanium carbonitride-based cermets have extremely high strength and cannot be directly recycled for remanufacturing.
  • carbide is one of the main components, which has a large amount and the ability to remove Mo 2 C can react with a specific inorganic acid solution and become the most worthy raw material to recover from waste Ti(C,N)-based cermets.
  • using inorganic acid dissolution, roasting, leaching, crystallization, precipitation and other methods to separate W, Mo, Ti, Co, Ni and other metal components from waste Ti(C,N)-based cermets is not only complicated in process, but also extracts The metal elements need to be carbonized to prepare the raw materials WC, Mo 2 C, etc. for the production of Ti(C,N)-based cermets.
  • the purpose of the present invention is to provide a method for reclaiming carbides from waste Ti(C,N)-based cermets, to solve the problems in the prior art mentioned above, to reduce specific carbides in Ti(C,N)-based cermets
  • the material is separated and extracted, so as to realize the recovery and reuse of specific types of carbides in Ti(C,N)-based cermets, which greatly saves resources.
  • the present invention provides the following scheme:
  • the invention provides a method for reclaiming carbides from Ti(C,N)-based cermets, comprising the following steps:
  • 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 subgroup IV, V, VI Carbides of elements; the metallic phase is cobalt and/or nickel.
  • the volume fraction of the hydrochloric acid is 20%-30%, and the volume fraction of the nitric acid is 30%-40%.
  • the first ceramic phase is 20%-60%
  • the metal phase is 10-20%
  • the rest is the second ceramic phase.
  • the carbides of subgroup IV, V and VI elements are one or more of Mo 2 C, WC, TaC and NbC, and the recovery method includes the following steps:
  • the Ti(C,N)-based cermet is crushed, dissolved in a mixed solution of hydrochloric acid, nitric acid, nitric acid and hydrofluoric acid in sequence, and the solid obtained by solid-liquid separation is washed, wet-milled, and dried to achieve the carbide Recycle.
  • the carbides of subgroup IV, V and VI elements also include VC and/or Cr 3 C 2 .
  • the volume fraction of the mixed solution of nitric acid and hydrofluoric acid is 20%-30%, and the molar ratio of nitric acid and hydrofluoric acid in the mixed solution of nitric acid and hydrofluoric acid is 4-5:1.
  • the carbides of subgroup IV, V and VI elements also include VC and/or Cr 3 C 2 .
  • the acid used in the present invention is an inorganic acid.
  • the following steps should be increased or decreased according to the specific components of the waste Ti(C,N)-based cermet: put the waste Ti(C,N)-based cermet into the polyacrylic acid solution tank, and first add Soak the cermet in hydrochloric acid for 1h ⁇ 2h, filter the precipitate, separate solid and liquid (for removing Ti(C,N), Cr 3 C 2 and cobalt), add nitric acid in the same way (for removing VC and Nickel), nitric acid + hydrofluoric acid mixture (used to remove TaC, NbC, WC), for inorganic acid dissolution; washing and re-washing are used to clean the cermet for 2 to 5 times with deionized water.
  • the invention also provides the application of the above method in recycling waste Ti(C,N)-based cermets.
  • both VC and nickel can react with nitric acid at room temperature and finally dissolve in nitric acid, but the reaction products of VC and nitric acid are too complicated. Only the reaction equation of nickel and nitric acid is given below:
  • Ta, Nb, and W in TaC, NbC, and WC can all be dissolved in nitric acid + hydrofluoric acid mixture at room temperature:
  • Inorganic acid dissolution sequence should be carried out as follows:
  • hydrochloric acid (2) nitric acid; (3) nitric acid + hydrofluoric acid mixture.
  • This sequence can minimize the influence of Cl, while hydrofluoric acid and nitric acid can be removed by irradiation or sintering in the subsequent Ti(C,N)-based cermet preparation process in addition to washing.
  • Ti(C,N)-based cermet raw materials can be dissolved in various inorganic acids except Mo 2 C, which makes it possible to extract different carbides by filtering precipitates.
  • the present invention first breaks the waste Ti(C,N)-based cermets washed with deionized water into pieces by using a hydraulic breaker, and then according to the recovered According to the different components contained in the waste Ti(C,N)-based cermets, hydrochloric acid, nitric acid and nitric acid + hydrofluoric acid mixed solution are used to extract specific carbides.
  • the concentration is too low to react or react too slowly with the corresponding carbide; After the carbide reacts, it cannot be dissolved.
  • the extracted carbides can be finely ground, and the residual acid ions can be evenly distributed in the ball milling solvent, and evaporate with the ball milling solvent in the subsequent drying process.
  • the following conditions need to be met (1) Control the average particle size of the recovered carbide powder to be 0.6 ⁇ m to 5 ⁇ m; (2) Control the quality of the ball milling medium/raw material, ball milling time and ball milling The temperature of the material, under the premise of sufficient ball milling, does not excessively extend the ball milling time to produce ultrafine particles.
  • the carbide reclaimed by the present invention can be directly used in the preparation of Ti(C,N)-based cermets, even if the reclaimed carbide is more than one mixture, the mass ratio of its various carbides is the same as that of the original waste Ti(C,N) N)-based cermets are the same, and can also be used for re-preparation of the original formula Ti(C,N)-based cermets without further chemical treatment.
  • the present invention does not need to carry out complex technological processes such as roasting, leaching, and crystallization, and the implementation steps can be flexibly adjusted according to the components of raw materials contained in the recovered waste Ti(C,N)-based cermets.
  • the extracted raw materials have a relatively stable particle size (average particle size can reach 0.6 ⁇ m ⁇ 5 ⁇ m) and a high purity of 90% to 95% after being dried by wet ball milling.
  • No other metal impurities are introduced.
  • the basic reaction principle of the invention also provides a theoretical basis for the application of recycling other waste cermet raw materials.
  • the recovered waste Ti(C,N)-based cermet consists of: 40% titanium carbonitride, 15% cobalt, and the balance is WC, Mo 2 C;
  • Embodiment 2 reclaims WC and NbC
  • the recovered waste Ti(C,N)-based cermet composition is: 55% titanium carbonitride, 8% nickel, 7% cobalt, and the balance is WC, NbC and Cr 3 C 2 ;
  • Embodiment 3 reclaims TaC
  • the recovered waste Ti(C,N)-based cermet composition is: 55% titanium carbonitride, 8% nickel, 7% cobalt, and the balance is TaC, VC and Cr 3 C 2 ;
  • Embodiment 4 reclaims WC and Mo 2 C
  • the recovered waste Ti(C,N)-based cermet consists of: 50% titanium carbonitride, 9% nickel, 8% cobalt, and the balance is WC, Mo 2 C;
  • Example 5 The TaC recovered in Example 3 is used for the re-preparation of the original formula Ti(C,N)-based cermet
  • the original formula Ti(C,N)-based cermets were prepared by the same process with the commercially available TaC powder and recycled TaC powder, and their mechanical properties were compared.
  • the mechanical performance test samples adopt the standard B style, the standard is GBT3851-2015, GBT7997-2014, JBT12616-2016.
  • the raw materials are weighed: 55% titanium carbonitride, 8% nickel, 7% cobalt, and the balance is TaC, VC and Cr 3 C 2 ; the average particle size of the above raw material powders is 0.6 ⁇ m ⁇ 5 ⁇ m;
  • the obtained green body is placed in a sintering furnace from room temperature to 500°C and kept for 2 hours (heating rate 8°C/min), and then heated to 1500°C (heating rate 10°C/min) and kept for 2 hours; during high temperature sintering Keep the vacuum degree of the sintering environment lower than 100Pa; after the sintering is completed, the furnace is cooled to room temperature to obtain titanium carbonitride-based cermets.

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Abstract

一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法，属于金属陶瓷复合材料制造领域。具体公开了：将Ti(C,N)基金属陶瓷破碎，依次经盐酸、硝酸溶解后，将固液分离得到的固体洗涤、湿磨、干燥，实现碳化物的回收；在经盐酸、硝酸溶解后，还包括经硝酸和氢氟酸混合液溶解的步骤。根据废旧Ti(C,N)基金属陶瓷中所含成分的不同，选用盐酸、硝酸以及硝酸+氢氟酸混合液进行特定碳化物的提取，可以灵活选取实施步骤从而获得Mo 2C、WC、TaC和NbC中的一种或多种。无需进行焙烧、浸取、结晶等复杂工艺流程，回收的碳化物可以直接用于Ti(C,N)基金属陶瓷的制备。

Description

一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法 技术领域
本发明涉及金属陶瓷复合材料制造领域，特别是涉及一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法。
背景技术
碳氮化钛基金属陶瓷作为一类钛系硬质合金，因其较钨钴硬质合金具有更高的红硬性，更好的抗氧化性和更强的耐磨性，被用于制造切削工具、耐磨零件的烧结体,并且因其优异的表面加工质量，常被应用于半精加工和精加工中。
然而，随着碳氮化钛基金属陶瓷的大量应用，废旧碳氮化钛基金属陶瓷也在随之增加，虽然原料中不包含贵金属，但其价格依然坚挺，再加之废旧碳氮化钛基金属陶瓷容易收集，因而研发从废旧碳氮化钛基金属陶瓷回收原料的技术，实现节约资源，保护环境以及原料的再利用具有重大意义。
碳氮化钛基金属陶瓷具有极高的强度，无法直接回收用于再次制造，而在碳氮化钛基金属陶瓷中，碳化物是其中的主要成分之一，具有用量较大，以及除Mo 2C外都与特定无机酸溶液反应等特点，成为最值得从废旧Ti(C,N)基金属陶瓷中回收的原料。然而，利用无机酸溶解、焙烧、浸取、结晶、沉淀等方法从废旧Ti(C,N)基金属陶瓷中分离W、Mo、Ti、Co、Ni等金属成分不但工艺流程复杂，其提取出的金属元素还需进行碳化才能制备出生产Ti(C,N)基金属陶瓷的原料WC、Mo 2C等。
目前针对废旧Ti(C,N)基金属陶瓷中直接回收碳化物还没有成体系的 工艺方法。
发明内容
本发明的目的是提供一种从废旧Ti(C,N)基金属陶瓷中回收碳化物的方法，以解决上述现有技术存在的问题，将Ti(C,N)基金属陶瓷中的特定碳化物分离提取出来，从而实现Ti(C,N)基金属陶瓷中的特定种类碳化物的回收再利用，大大节约了资源。
为实现上述目的，本发明提供了如下方案：
本发明提供一种从Ti(C,N)基金属陶瓷中回收碳化物的方法，包括以下步骤：
将所述Ti(C,N)基金属陶瓷破碎，依次经盐酸、硝酸溶解后，将固液分离得到的固体洗涤、湿磨、干燥，实现所述碳化物的回收；
所述Ti(C,N)基金属陶瓷包括第一陶瓷相、第二陶瓷相和金属相；所述第一陶瓷相为碳氮化钛，第二陶瓷相为第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物；金属相为钴和/或镍。
优选的，所述盐酸的体积分数为20％～30％，所述硝酸的体积分数为30％～40％。
优选的，按质量分数计，所述第一陶瓷相为20％～60％，所述金属相为10～20％，其余为第二陶瓷相。
优选的，所述第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物为Mo 2C、WC、TaC和NbC中的一种或多种，回收方法包括以下步骤：
将所述Ti(C,N)基金属陶瓷破碎，依次经盐酸、硝酸、硝酸和氢氟酸混合液溶解后，将固液分离得到的固体洗涤、湿磨、干燥，实现所述碳化 物的回收。
更优选的，所述第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物还包括VC和/或Cr 3C 2。
优选的，所述硝酸和氢氟酸混合液的体积分数为20％～30％，所述硝酸和氢氟酸混合液中硝酸和氢氟酸的摩尔比为4～5:1。
优选的，所述第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物还包括VC和/或Cr 3C 2。
优选的，所述湿磨采用去离子水或乙醇为湿磨溶剂，溶剂质量/原料质量＝2:1～3:1，硬质合金球或钢球为磨介，磨介质量/原料质量＝5:1～7:1，球磨时间20h～30h，球磨浆料的温度为5℃～25℃；干燥选自喷雾干燥、烘箱干燥、旋转蒸发干燥或冷冻干燥。
本发明所用酸为无机酸，溶解时要根据废旧Ti(C,N)基金属陶瓷具体成分增减以下步骤：将废旧Ti(C,N)基金属陶瓷放入聚丙烯酸解槽中，先加入盐酸使金属陶瓷完全浸泡其中1h～2h，过滤沉淀，固液分离(用于除去其中的Ti(C,N)，Cr 3C 2和钴)，用同样方法依次加入硝酸(用于去除VC和镍)、硝酸+氢氟酸混合液(用于去除TaC，NbC，WC)，进行无机酸溶解；洗涤与再次洗涤均使用去离子水清洗金属陶瓷2～5次。
本发明还提供上述方法在废旧Ti(C,N)基金属陶瓷回收中的应用。
无机酸酸洗的原理如下：由于Ti(C,N)中的Ti，Cr 3C 2中的Cr和钴均能在常温下与浓度大于20％的盐酸发生反应：
2Ti+6HCl＝2TiCl 3+3H 2↑
Co+2HCl＝CoCl 2+H 2↑
2Cr+6HCl＝2CrCl 3+3H 2↑
反应后溶于盐酸，通过固液分离去除。
同理VC和镍均能在常温下与硝酸反应并最终溶于硝酸，但VC与硝酸反应的生成物过于复杂，以下仅给出镍与硝酸的反应方程式：
Ni+6HNO 3→Ni(NO 3) 3+3NO 2+3H 2↑
TaC，NbC，WC中的Ta，Nb，W均能在常温下溶解于硝酸+氢氟酸混合液：
3Ta+5HNO 3+21HF→3H 2[TaF 7]+5NO↑+10H 2O
3Nb+5HNO 3+21HF→3H 2[NbF 7]+5NO↑+10H 2O
W+2HNO 3+6HF→WF 6(g)+2NO(g)+4H 2O
无机酸溶解顺序要按以下进行：
(1)盐酸；(2)硝酸；(3)硝酸+氢氟酸混合液。
这种顺序可以最大程度减少Cl的影响，而氢氟酸和硝酸除洗涤外还可以在后续Ti(C,N)基金属陶瓷制备过程中，通过光照或烧结方式去除。
本发明的技术原理：
现有Ti(C,N)基金属陶瓷原料除Mo 2C以外，都能溶于各种不同的无机酸，这就为过滤沉淀提取不同的碳化物提供了可能。
提取废旧Ti(C,N)基金属陶瓷中的金属成分，一方面会造成工艺过于复杂，成本过高，另一方面提取出来的金属成分不能直接用于Ti(C,N)基金属陶瓷的制备。而在本发明的技术方案中，为实现上述技术目的，本发明先把用去离子水洗涤好后的废旧Ti(C,N)基金属陶瓷利用液压破碎锤破碎成碎块，然后根据所回收的废旧Ti(C,N)基金属陶瓷中所含成分的不同，来选用盐酸，硝酸以及硝酸+氢氟酸混合液进行特定碳化物的提取。
所选取无机酸浓度低于本发明限定含量时，浓度太低无法与对应碳化 物发生反应或反应过慢；高于本发明限定含量时，由于酸的浓度过高难以产生电离，致使酸与对应碳化物反应后无法使之溶解。在球磨过程中，可以将提取出来的碳化物磨细，将残留酸根离子均匀分部在球磨溶剂中，在后续的干燥过程中，随球磨溶剂蒸发。
为实现回收碳化物粉体的质量稳定性，需要满足以下条件(1)控制回收碳化物粉体平均粒径为0.6μm～5μm；(2)控制球磨介质质量/原料质量，球磨时间以及球磨浆料的温度，在充分球磨的前提下，不过度延长球磨时间产生超细颗粒。
本发明公开了以下技术效果：
本发明回收的碳化物可以直接用于Ti(C,N)基金属陶瓷的制备，即使回收的碳化物是一种以上的混合物，但其各种碳化物的质量比与原废旧Ti(C,N)基金属陶瓷一致，也可用于原配方Ti(C,N)基金属陶的再次制备，无需进行再次化学处理。
本发明无需进行焙烧、浸取、结晶等复杂工艺流程，可以根据回收的废旧Ti(C,N)基金属陶瓷所含原料的成分灵活调整实施步骤。提取出来的原料经湿法球磨干燥后具有较稳的粒径(平均粒径可达到0.6μm～5μm)和90％～95％的较高纯度，在无机酸酸洗和去离子水洗涤过程中不会引入其他金属杂质。本发明的反应基本原理还为回收其他废旧金属陶瓷原料的应用提供了理论依据。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更 详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
实施例1回收Mo 2C
(1)回收的废旧Ti(C,N)基金属陶瓷成分为：碳氮化钛40％，钴15％，余量为WC，Mo 2C；
(2)按照体积分数计，配置原料：硝酸35％，盐酸25％，硝酸+氢氟酸混合液(M HNO3:M HF＝4.5:1)25％；
(3)将回收的废旧Ti(C,N)基金属陶瓷用去离子水洗涤干净后用液压破碎锤破碎成碎块，将废旧Ti(C,N)基金属陶瓷放入聚丙烯酸解槽中，先加入盐酸使金属陶瓷完全浸泡其中1.5h，过滤沉淀，固液分离；同上之后依次放入硝酸，硝酸+氢氟酸混合液中浸泡1.5h，过滤沉淀，固液分离后用去离子水洗涤。
(4)称取粉体原料混匀后置于球磨机中，进行湿磨后干燥，得到Mo 2C粉料。经检测，粉料纯度为93％，平均粒径为2.6μm。
其中湿磨条件：采用乙醇为湿磨溶剂，溶剂质量/原料质量＝2:1，硬质合金球为磨介，磨介质量/原料质量＝5:1，球磨时间20h，球磨浆料的温度为5℃；干燥为喷雾干燥。
实施例2回收WC和NbC
(1)回收的废旧Ti(C,N)基金属陶瓷成分为：碳氮化钛55％，镍8％，钴7％，余量为WC，NbC和Cr 3C 2；
(2)按照体积分数计，配置原料：硝酸32％，盐酸24％；
(3)将回收的废旧Ti(C,N)基金属陶瓷用去离子水洗涤干净后用液压破碎锤破碎成碎块，将旧废旧Ti(C,N)基金属陶瓷放入聚丙烯酸解槽中，先加入盐酸使金属陶瓷完全浸泡其中2h，过滤沉淀，固液分离；之后放入硝酸，浸泡2h，过滤沉淀，固液分离后用去离子水洗涤。
(4)称取粉体原料混匀后置于球磨机中，进行湿磨后干燥，得到WC和NbC混合粉料。经检测，WC和NbC混合粉料纯度为91％，平均粒径 为1.81μm。
其中湿磨条件：采用乙醇为湿磨溶剂，溶剂质量/原料质量＝3:1，硬质合金球为磨介，磨介质量/原料质量＝7:1，球磨时间24h，球磨浆料的温度为15℃；干燥为喷雾干燥。
实施例3回收TaC
(1)回收的废旧Ti(C,N)基金属陶瓷成分为：碳氮化钛55％，镍8％，钴7％，余量为TaC，VC和Cr 3C 2；
(2)按照体积分数计，配置原料：硝酸30％，盐酸20％；
(3)将回收的废旧Ti(C,N)基金属陶瓷用去离子水洗涤干净后用液压破碎锤破碎成碎块，将旧废旧Ti(C,N)基金属陶瓷放入聚丙烯酸解槽中，先加入盐酸使金属陶瓷完全浸泡其中1h，过滤沉淀，固液分离；之后放入硝酸，浸泡1h，过滤沉淀，固液分离后用去离子水洗涤。
(4)称取粉体原料混匀后置于球磨机中，进行湿磨后干燥，得到TaC粉料。经检测，粉料纯度为94％，平均粒径为1.46μm。
其中湿磨条件：采用乙醇为湿磨溶剂，溶剂质量/原料质量＝3:1，硬质合金球为磨介，磨介质量/原料质量＝5:1，球磨时间30h，球磨浆料的温度为20℃；干燥为喷雾干燥。
实施例4回收WC和Mo 2C
(1)回收的废旧Ti(C,N)基金属陶瓷成分为：碳氮化钛50％，镍9％，钴8％，余量为WC，Mo 2C；
(2)按照体积分数计，配置原料：硝酸40％，盐酸30％；
(3)将回收的废旧Ti(C,N)基金属陶瓷用去离子水洗涤干净后用液压 破碎锤破碎成碎块，将旧废旧Ti(C,N)基金属陶瓷放入聚丙烯酸解槽中，先加入盐酸使金属陶瓷完全浸泡其中1.8h，过滤沉淀，固液分离；之后放入硝酸，浸泡1.8h，过滤沉淀，固液分离后用去离子水洗涤。
(4)称取粉体原料混匀后置于球磨机中，进行湿磨后干燥，得到WC和Mo 2C混合粉料。经检测，WC和Mo 2C混合粉料纯度为92％，平均粒径为1.64μm。
其中湿磨条件：采用乙醇为湿磨溶剂，溶剂质量/原料质量＝2:1，硬质合金球为磨介，磨介质量/原料质量＝7:1，球磨时间28h，球磨浆料的温度为25℃；干燥为喷雾干燥。
实施例5将实施例3回收的TaC用于原配方Ti(C,N)基金属陶瓷的再次制备
用市售TaC粉料与回收TaC粉料按相同工艺方法进行原配方Ti(C,N)基金属陶瓷制备，对比其力学性能。其力学性能测试样品采用标准B式样，标准为GBT3851-2015，GBT7997-2014，JBT12616-2016。
(1)按照质量分数计，称取原料：碳氮化钛55％，镍8％，钴7％，余量为TaC，VC和Cr 3C 2；以上原料粉体平均粒径为0.6μm～5μm；
(2)称取粉体原料混匀后置于球磨机中，进行湿磨后干燥，然后用压机压制为坯体；
其中湿磨条件：采用乙醇为湿磨溶剂，溶剂质量/原料＝2:1，硬质合金球为磨介，磨介质量/原料质量＝5:1，球磨时间24h，球磨浆料的温度为20℃；干燥为喷雾干燥；
单向模压，压制压力150MPa。
(3)所得坯体置于烧结炉中由室温升温至500℃并保温2h(升温速率8℃/min)，继续升温至1500℃(升温速率10℃/min)，保温2h；高温烧结过程中保持烧结环境真空度低于100Pa；烧结完成随炉冷却至室温，得到碳氮化钛基金属陶瓷。
对市售TaC粉料制备原配方Ti(C,N)基金属陶瓷(A)与回收TaC粉料制备原配方Ti(C,N)基金属陶瓷(B)进行力学性能验证，性能数据见表1。
表1
  硬度HV30 抗弯强度,MPa 断裂韧性，MPa·m 1/2
A 1632 1564 10.2
B 1624 1512 10.3
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (9)

  1. 一种从Ti(C,N)基金属陶瓷中回收碳化物的方法，其特征在于，包括以下步骤：
    将所述Ti(C,N)基金属陶瓷破碎，依次经盐酸、硝酸溶解后，将固液分离得到的固体洗涤、湿磨、干燥，实现所述碳化物的回收；
    所述Ti(C,N)基金属陶瓷包括第一陶瓷相、第二陶瓷相和金属相；所述第一陶瓷相为碳氮化钛，所述第二陶瓷相为第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物；所述金属相为钴和/或镍。
  2. 根据权利要求1所述的方法，其特征在于，所述盐酸的体积分数为20％～30％，所述硝酸的体积分数为30％～40％。
  3. 根据权利要求1所述的方法，其特征在于，按质量分数计，所述第一陶瓷相为20％～60％，所述金属相为10～20％，其余为第二陶瓷相。
  4. 根据权利要求1所述的方法，其特征在于，所述第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物为Mo 2C、WC、TaC和NbC中的一种或多种。
  5. 根据权利要求4所述的方法，其特征在于，所述第Ⅳ、Ⅴ、Ⅵ副族元素的碳化物还包括VC和/或Cr 3C 2。
  6. 根据权利要求4所述的方法，其特征在于，包括以下步骤：将所述Ti(C,N)基金属陶瓷破碎，依次经盐酸、硝酸、硝酸和氢氟酸混合液溶解后，将固液分离得到的固体洗涤、湿磨、干燥，实现所述碳化物的回收。
  7. 根据权利要求4所述的方法，其特征在于，所述硝酸和氢氟酸混合液的体积分数为20％～30％，所述硝酸和氢氟酸混合液中硝酸和氢氟酸的摩尔比为4～5:1。
  8. 根据权利要求1所述的方法，其特征在于，所述湿磨过程中浆料的 温度为5℃～25℃，湿磨时间20h～30h。
  9. 权利要求1-8任一项所述的方法在废旧Ti(C,N)基金属陶瓷回收中的应用。
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