Co对WO3-Co3O4预还原的影响及其产物碳化性能

doi:10.11949/0438-1157.20221018

摘要/Abstract

摘要：

为避免超细WC-Co粉体制备过程中形成对烧结过程及其产物带来不利影响的η相（Co₆W₆C或Co₃W₃C），提出了WO₃-Co₃O₄预还原至WO₂-Co，再深度还原碳化至WC-Co的技术路线。主要考察了600℃，H₂-C₂H₄-Ar气氛条件下，Co含量及钴源粒径对WO₃-Co₃O₄预还原过程的影响规律，并对预还原产物进行了深度还原碳化性能测试。结果表明，Co的存在可催化C₂H₄裂解析出H₂和C，显著加快WO₃预还原速率，且随着Co含量增加其预还原速率显著增加；乙烯析碳速率和析碳量也随Co含量增加而增加。钴源粒径对WO₃还原速率和C₂H₄析碳速率有显著影响，本实验体系下，纳米钴源体系中C₂H₄析碳速率大约是微米钴源体系的2倍；同时，纳米钴源体系中WO₃也具有较快的还原速率。8%Co含量的预还原产物在950℃、甲烷分压1.25%条件下焙烧60 min，可获得无η相的WC-Co复合粉体。

关键词: WO₃-Co₃O₄体系, 流化床, 还原, 粉体

Abstract:

In order to avoid the formation of η phase (Co₆W₆C or Co₃W₃C) that adversely affect the sintering process and its products in the preparation process ultra-fine WC-Co powder, we propose a technical route of pre-reduction of WO₃-Co₃O₄ to WO₂-Co and then deep reduction carbonization to WC-Co. The influence of Co content and cobalt source particle size on the pre-reduction process of WO₃-Co₃O₄ was investigated at 600℃ H₂-C₂H₄-Ar atmosphere in a fluidized-bed reactor, and the deep reduction and carbonization properties of the pre-reduced products were tested. The results show that the presence of Co can catalyze the splitting of C₂H₄to separate H₂and C, significantly accelerate the pre-reduction rate of WO₃, and the pre-reduction rate increases significantly with the increase of Co content. The carbon evolution rate and carbon evolution amount of ethylene also increase with the increase of Co content. Cobalt source particle size has a significant effect on the pre-reduction rate of WO₃ and carbon evolution rate of C₂H₄. In this experimental system, the carbon evolution rate of C₂H₄ in nano cobalt source system is about twice that of micron cobalt source system. Meanwhile, WO₃ in nano cobalt source system also has faster reduction rate. The pre-reduced product was calcined with methane partial pressure of 1.25% at 950℃ for 60 min, and fine WC-Co composite powder without η could be obtained.

Key words: WO₃-Co₃O₄ system, fluidized-bed, reduction, powder

中图分类号:

TQ 026.9

尚慧俊, 黎亨利, 刘家义, 潘锋, 杜占, 孙林兵. Co对WO₃-Co₃O₄预还原的影响及其产物碳化性能[J]. 化工学报, 2022, 73(12): 5592-5604.

Huijun SHANG, Hengli LI, Jiayi LIU, Feng PAN, Zhan DU, Linbing SUN. Effect of Co on the pre-reduction process of WO₃-Co₃O₄ and carbonization performance of its product[J]. CIESC Journal, 2022, 73(12): 5592-5604.

图/表 13

图1 原料XRD谱图

Fig.1 XRD patterns of the raw materials

图2 原料形貌

Fig.2 Morphologies of the raw materials

图3 流化床反应系统示意图1—加热和气体流量控制系统;2—热电偶;3—流化床反应系统;4—气源

Fig.3 Schematic diagram of the fluidized-bed reaction system

表1 不同钨氧化物的K值

Table 1 The RIR values of different tungsten oxides

氧化钨	K
WO₃	6.00
WO_2.9	6.23
WO_2.72	6.65
WO₂	14.69

图4 不同钴含量条件下预还原产物析碳量和析碳速率曲线

Fig.4 Carbon content and carbon deposition rate curves of the pre-reducted products with different cobalt contents

图5 0.3 kmol C2H4-0.4 kmol H2-0.5 kmol Ar体系物相平衡曲线及相关反应的Gibbs自由能变化曲线

Fig.5 Phase equilibrium curves of 0.3 kmol C2H4-0.4 kmol H2-0.5 kmol Ar system and Gibbs free energy change curves of the related reactions

图6 不同Co含量条件下还原产物的还原率、物相含量以及反应体系中相关反应的 Gibbs自由能曲线

Fig.6 The reduction ratio, phase content and Gibbs free energy curves of the related reactions in the reaction system with different Co contents

图7 不同钴含量条件下WO3还原5、30 min形貌

Fig.7 Morphologies of WO3 with different cobalt contents reduced for 5 min and 30 min

图8 不同钴含量产物的拉曼谱图及ID/IG值

Fig.8 Raman spectra and ID/IG values of the products with different cobalt contents

图9 不同粒径Co3O4还原产物析碳量和析碳速率曲线

Fig.9 Carbon content and carbon deposition rate curves of the products under different Co3O4 sizes

图10 不同粒径Co3O4原料预还原产物形貌及粒径分布

Fig.10 SEM images and particle size distributions of the pre-reduced samples with different Co3O4 sizes

图11 不同粒径Co3O4原料预还原产物的XRD谱图、物相含量以及还原率

Fig.11 XRD patterns, phase content, reduction ratio and pre-reduction rate of the pre-reduced products under different Co3O4 with sizes

图12 不同CH4分压下产物的XRD谱图

Fig.12 XRD patterns of the samples obtained under different CH4 partial pressures

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Co对WO₃-Co₃O₄预还原的影响及其产物碳化性能

Effect of Co on the pre-reduction process of WO₃-Co₃O₄ and carbonization performance of its product

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