Longgang Ye, Kai Tang, Li Zhang, Zhimei, Xia, Shufen Liu
{"title":"氯化焙烧-水浸结合温和工艺从硬质合金研磨废渣中分离钴钨","authors":"Longgang Ye, Kai Tang, Li Zhang, Zhimei, Xia, Shufen Liu","doi":"10.1016/j.ijrmhm.2025.107303","DOIUrl":null,"url":null,"abstract":"<div><div>Tungsten is primarily used to produce cemented carbide tools, generating substantial amounts of grinding waste of cemented carbide (GWCC) during machining. GWCC mainly comprises tungsten carbide (WC) and cobalt, which have significant economic value and are worth recovering. This work proposes a mildly recovery process involving chloridizing roasting and water leaching, introducing a novel transition and decomposition method for GWCC through chlorination roasting using CaCl<sub>2</sub> as the chlorinating agent. Initially, Co and W in the GWCC are converted into CoCl<sub>2</sub> and CaWO<sub>4</sub>, WO<sub>3</sub> via chloridizing roasting. Subsequently, water leaching of the roasting product yields a CoCl<sub>2</sub> solution and tungstate residue. Pure cobalt hydroxide precipitation is then obtained by adjusting the pH of the solution. The thermodynamic equilibrium of the WC–Co–CaCl<sub>2</sub> system was first calculated, demonstrating that W and Co are entirely transformed into CaWO<sub>4</sub> and CoCl<sub>2</sub> above 400 °C with an initial chlorine-to‑cobalt ratio (<em>n</em><sub>Cl</sub>/<em>n</em><sub>Co</sub> ratio) of 2.0. Detailed roasting experiments reveal that the maximum cobalt leaching efficiency was achieved at 600 °C. The <em>n</em><sub>Cl</sub>/<em>n</em><sub>Co</sub> ratio significantly influences the conversion, and insufficient CaCl<sub>2</sub> and low temperature lead to cobalt tungstate and cobalt chloride formation. Optimal roasting conditions were determined to be a temperature of 600 °C, a <em>n</em><sub>Cl</sub><em>/n</em><sub>Co</sub> ratio of 2.4:1, and a reaction time of 1 h, achieving a cobalt leaching efficiency of 94.32 %. Finally, pure cobalt hydroxide was precipitated, and the separated tungstate residue was a high-quality raw material used for tungsten smelting.</div></div>","PeriodicalId":14216,"journal":{"name":"International Journal of Refractory Metals & Hard Materials","volume":"132 ","pages":"Article 107303"},"PeriodicalIF":4.6000,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Separation of cobalt and tungsten from grinding waste of cemented carbide by a mildly process of chloridizing roasting and water leaching combining\",\"authors\":\"Longgang Ye, Kai Tang, Li Zhang, Zhimei, Xia, Shufen Liu\",\"doi\":\"10.1016/j.ijrmhm.2025.107303\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Tungsten is primarily used to produce cemented carbide tools, generating substantial amounts of grinding waste of cemented carbide (GWCC) during machining. GWCC mainly comprises tungsten carbide (WC) and cobalt, which have significant economic value and are worth recovering. This work proposes a mildly recovery process involving chloridizing roasting and water leaching, introducing a novel transition and decomposition method for GWCC through chlorination roasting using CaCl<sub>2</sub> as the chlorinating agent. Initially, Co and W in the GWCC are converted into CoCl<sub>2</sub> and CaWO<sub>4</sub>, WO<sub>3</sub> via chloridizing roasting. Subsequently, water leaching of the roasting product yields a CoCl<sub>2</sub> solution and tungstate residue. Pure cobalt hydroxide precipitation is then obtained by adjusting the pH of the solution. The thermodynamic equilibrium of the WC–Co–CaCl<sub>2</sub> system was first calculated, demonstrating that W and Co are entirely transformed into CaWO<sub>4</sub> and CoCl<sub>2</sub> above 400 °C with an initial chlorine-to‑cobalt ratio (<em>n</em><sub>Cl</sub>/<em>n</em><sub>Co</sub> ratio) of 2.0. Detailed roasting experiments reveal that the maximum cobalt leaching efficiency was achieved at 600 °C. The <em>n</em><sub>Cl</sub>/<em>n</em><sub>Co</sub> ratio significantly influences the conversion, and insufficient CaCl<sub>2</sub> and low temperature lead to cobalt tungstate and cobalt chloride formation. Optimal roasting conditions were determined to be a temperature of 600 °C, a <em>n</em><sub>Cl</sub><em>/n</em><sub>Co</sub> ratio of 2.4:1, and a reaction time of 1 h, achieving a cobalt leaching efficiency of 94.32 %. Finally, pure cobalt hydroxide was precipitated, and the separated tungstate residue was a high-quality raw material used for tungsten smelting.</div></div>\",\"PeriodicalId\":14216,\"journal\":{\"name\":\"International Journal of Refractory Metals & Hard Materials\",\"volume\":\"132 \",\"pages\":\"Article 107303\"},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2025-06-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Refractory Metals & Hard Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0263436825002689\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Refractory Metals & Hard Materials","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0263436825002689","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Separation of cobalt and tungsten from grinding waste of cemented carbide by a mildly process of chloridizing roasting and water leaching combining
Tungsten is primarily used to produce cemented carbide tools, generating substantial amounts of grinding waste of cemented carbide (GWCC) during machining. GWCC mainly comprises tungsten carbide (WC) and cobalt, which have significant economic value and are worth recovering. This work proposes a mildly recovery process involving chloridizing roasting and water leaching, introducing a novel transition and decomposition method for GWCC through chlorination roasting using CaCl2 as the chlorinating agent. Initially, Co and W in the GWCC are converted into CoCl2 and CaWO4, WO3 via chloridizing roasting. Subsequently, water leaching of the roasting product yields a CoCl2 solution and tungstate residue. Pure cobalt hydroxide precipitation is then obtained by adjusting the pH of the solution. The thermodynamic equilibrium of the WC–Co–CaCl2 system was first calculated, demonstrating that W and Co are entirely transformed into CaWO4 and CoCl2 above 400 °C with an initial chlorine-to‑cobalt ratio (nCl/nCo ratio) of 2.0. Detailed roasting experiments reveal that the maximum cobalt leaching efficiency was achieved at 600 °C. The nCl/nCo ratio significantly influences the conversion, and insufficient CaCl2 and low temperature lead to cobalt tungstate and cobalt chloride formation. Optimal roasting conditions were determined to be a temperature of 600 °C, a nCl/nCo ratio of 2.4:1, and a reaction time of 1 h, achieving a cobalt leaching efficiency of 94.32 %. Finally, pure cobalt hydroxide was precipitated, and the separated tungstate residue was a high-quality raw material used for tungsten smelting.
期刊介绍:
The International Journal of Refractory Metals and Hard Materials (IJRMHM) publishes original research articles concerned with all aspects of refractory metals and hard materials. Refractory metals are defined as metals with melting points higher than 1800 °C. These are tungsten, molybdenum, chromium, tantalum, niobium, hafnium, and rhenium, as well as many compounds and alloys based thereupon. Hard materials that are included in the scope of this journal are defined as materials with hardness values higher than 1000 kg/mm2, primarily intended for applications as manufacturing tools or wear resistant components in mechanical systems. Thus they encompass carbides, nitrides and borides of metals, and related compounds. A special focus of this journal is put on the family of hardmetals, which is also known as cemented tungsten carbide, and cermets which are based on titanium carbide and carbonitrides with or without a metal binder. Ceramics and superhard materials including diamond and cubic boron nitride may also be accepted provided the subject material is presented as hard materials as defined above.