液相氢还原沉钒制备V2O3及其动力学研究
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作者单位:

1.武汉科技大学资源与环境工程学院, 湖北 武汉 430081 ;2.国家环境保护矿冶资源利用与污染控制重点实验室, 湖北 武汉 430081 ;3.战略钒资源利用省部共建协同创新中心, 湖北 武汉 430081 ;4.湖北省页岩钒资源高效清洁利用工程技术研究中心, 湖北 武汉 430081

作者简介:

胡艺博(1997—),男,安徽宿州人,博士研究生,主要研究方向为液相氢还原沉钒。

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中图分类号:

TF841.3

基金项目:

湖北省科技创新人才及服务专项“黑色页岩系战略性钒资源绿色利用技术”(2022EJD002);国家重点研发计划项目“多金属页岩清洁利用与固废全过程控制关键技术”(2020YFC1909700)


Research of V2O3 preparation via solution-phase hydrogen reduction and its kinetic study
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1.School of Resources and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081 , China ;2.State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control, Wuhan 430081 , China ;3.Collaborative Innovation Center of Strategic Vanadium Resources Utilization, Wuhan 430081 , China ;4.Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource, Wuhan 430081 , China

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    摘要:

    V2O3是制备氮化钒、氮化钒铁和钒铁重要原料。液相氢还原可直接从富钒液制备出V2O3,具有短流程、绿色环保、能耗低的优点。本研究选择低成本的蒽醌和镍粉作为催化剂来替代PdCl2,蒽醌沉钒的主要产物为VO2(H2O)0.5,无法制备出V2O3;镍粉沉钒能获得和PdCl2相同的V2O3产物,沉钒率为99.87%。蒽醌、镍粉与PdCl2催化液相氢还原反应活化能分别为188.83kJ/mol、140.09kJ/mol和38.07kJ/mol。H2分子在Ni或Pd表面发生裂解,同时H原子的s轨道与Pd、Ni的p轨道和d轨道发生了杂化,形成还原性较强的Pd—H或Ni—H键,Pd和Ni对氢气的化学吸附能分别为1.34eV和2.04eV;H2在250~300℃发生裂解,其解吸活化能为9.6994kJ/mol。本研究采用镍粉可替代PdCl2制备出纯度99.21%的V2O3产品。

    Abstract:

    V2O3 has an important application in the preparation of vanadium nitride, ferrovanadium nitride and ferrovanadium. The introduced solution-phase hydrogen reduction (SpHR) can directly prepare V2O3 from V-rich solution, which has the advantages of short process, eco-friendliness, and low energy consumption. Low-cost anthraquinone and Ni powder were selected as catalysts to replace PdCl2 and the products of SpHR with anthraquinone was VO2(H2O)0.5, which showed that V2O3 could not be prepared with anthraquinone, and Ni powder precipitated vanadium can obtain the same V2O3 product as PdCl2 (precipitation ratio was 99.87%). The activation energy of SpHR catalyzed by anthraquinone, Ni powder and PdCl2 were calculated as 188.83kJ/mol, 140.09kJ/mol and 38.07kJ/mol. In the process of catalytic reduction, H2 molecule was cracked on the surface of Ni or Pd, and formed two Pd—H or Ni—H bonds with strong reducibility, and its s orbital is hybridized with the d orbital of Pd and Ni. The chemisorption energies of Pd and Ni for H2 were 1.34eV and 2.04eV, respectively. The H2 was cracked in the range of 250~300℃, and low activation energy of H2 desorption is 9.6994kJ/mol. In this study, Ni powder can be used to replace PdCl2 to prepare V2O3 with purity of 99.21%.

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胡艺博, 张一敏, 薛楠楠, 等. 液相氢还原沉钒制备V2O3及其动力学研究[J]. 中国有色冶金, 2023, 52(5): 42-50.

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  • 收稿日期:2023-05-11
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  • 在线发布日期: 2025-12-23
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