磷矿热还原制取黄磷技术现状及研究进展

doi:10.16085/j.issn.1000-6613.2023-2193

化工进展 ›› 2024, Vol. 43 ›› Issue (7): 3578-3592.DOI: 10.16085/j.issn.1000-6613.2023-2193

• 专栏：热化学反应工程技术 • 上一篇

磷矿热还原制取黄磷技术现状及研究进展

李明霞¹^,²^,³(), 夜晨¹^,²^,³, 李姗¹^,²^,³, 梅毅¹^,²^,³(), 聂云祥¹^,²^,³()

^1.昆明理工大学化学工程学院，云南昆明 650500
^2.云南省磷化工节能与新材料重点实验室，云南昆明 650500
^3.云南省高校磷化工重点实验室，云南昆明 650500

收稿日期:2023-12-13 修回日期:2024-03-19 出版日期:2024-07-10 发布日期:2024-08-14
通讯作者: 梅毅,聂云祥
作者简介:李明霞（1998—），女，博士研究生，研究方向为磷化工节能减排。E-mail：2781158796@qq.com。
基金资助:
云南省重大科技专项(202202AG050001);国家自然科学基金(22068019)

Current status and research progress of thermal reduction technology for producing yellow phosphorus from phosphate rock

LI Mingxia¹^,²^,³(), YE Chen¹^,²^,³, LI Shan¹^,²^,³, MEI Yi¹^,²^,³(), NIE Yunxiang¹^,²^,³()

^1.Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, Yunnan, China
^2.Yunnan Provincial Key Laboratory of Energy Saving in Phosphorus Chemical Engineering and New Phosphorus Materials, Kunming 650500, Yunnan, China
^3.Higher Educational Key Laboratory for Phosphorus Chemical Engineering of Yunnan Province, Kunming 650500, Yunnan, China

Received:2023-12-13 Revised:2024-03-19 Online:2024-07-10 Published:2024-08-14
Contact: MEI Yi, NIE Yunxiang

摘要/Abstract

摘要：

黄磷生产属于“高能耗”和“高污染”行业，电炉法是目前唯一的工业化生产黄磷的方法，但存在电耗高、黄磷尾气难以资源化利用等问题。在“碳达峰、碳中和”背景下，深入打好污染防治攻坚战，实现减污降碳协同增效是必然选择，因此，黄磷生产技术亟待创新。本文总结了磷矿热还原制取黄磷的机制，归纳了SiO₂、Al₂O₃和MgO助熔剂以及炭质还原剂活性对磷矿还原的影响，阐述了高炉法、电炉法、流态化法、熔融电解法、低温碳热还原磷酸法、硅热法和磷煤耦合联产黄磷和一氧化碳法制取黄磷的技术原理、特点以及存在的问题。指出未来黄磷生产技术的总体要求是节能降耗和碳资源高效利用，低品位磷矿利用技术和低磷废弃物中回收磷技术的开发对实现磷资源的可持续开发利用具有重要意义。

关键词: 黄磷, 磷矿, 助熔剂, 热还原, 节能降耗

Abstract:

Yellow phosphorus production is classified as a “high energy consumption” and “high pollution” industry. Currently, the electric furnace method stands as the sole industrialized approach for yellow phosphorus production. However, this method faces challenges such as excessive power consumption and the complexity of efficiently utilizing yellow phosphorus tail gas. Against the backdrop of the “peak carbon dioxide emissions” and “carbon neutrality” initiatives, it is an inevitable choice to fight the battle of pollution prevention and to realize the synergistic effect of pollution reduction and carbon reduction. Therefore, there is a pressing need for innovation in yellow phosphorus production technology. This paper summarizes the mechanism of phosphorus rock thermal reduction to produce yellow phosphorus and elucidates the influence of SiO₂, Al₂O₃, and MgO fluxes, as well as carbonaceous reductant activity, on phosphorus rock reduction. The technical principles, characteristics, and existing issues of the production of yellow phosphorus through blast furnace method, electric furnace method, fluidized bed method, molten electrolysis method, low-temperature carbon thermal reduction of phosphoric acid method, silicothermic process, and the phosphorus-coal coupled production of yellow phosphorus and carbon monoxide method are elucidated. It is emphasized that the overarching objective for future yellow phosphorus production technology is to achieve energy efficiency and optimize the utilization of carbon resources. Significantly, the advancement of technologies for utilizing low-grade phosphate rock and recovering phosphorus from waste with low phosphorus content holds immense importance in realizing the sustainable development and utilization of phosphorus resources.

Key words: yellow phosphorus, phosphorus rock, flux, thermal reduction, energy saving

中图分类号:

TQ028.8

李明霞, 夜晨, 李姗, 梅毅, 聂云祥. 磷矿热还原制取黄磷技术现状及研究进展[J]. 化工进展, 2024, 43(7): 3578-3592.

LI Mingxia, YE Chen, LI Shan, MEI Yi, NIE Yunxiang. Current status and research progress of thermal reduction technology for producing yellow phosphorus from phosphate rock[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3578-3592.

图/表 12

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磷矿来源	温度范围	反应级数	磷矿还原反应活化能/kJ·mol^-1	参考文献
云南	1300～1450℃	介于一级二级之间	192.2	[14]
贵州	800～1200℃	一级	77±1	[15]
湖北	1200～1300℃	—	282.7	[16-17]
云南	1250～1400℃	变级	188.96	[18]
湖北	1450～1550℃	一级	225.106	[19-20]
湖北	1300～1450℃	介于一级二级之间	184.644	[21-22]

磷矿来源	温度范围	反应级数	磷矿还原反应活化能/kJ·mol^-1	参考文献
云南	1300～1450℃	介于一级二级之间	192.2	[14]
贵州	800～1200℃	一级	77±1	[15]
湖北	1200～1300℃	—	282.7	[16-17]
云南	1250～1400℃	变级	188.96	[18]
湖北	1450～1550℃	一级	225.106	[19-20]
湖北	1300～1450℃	介于一级二级之间	184.644	[21-22]

磷矿石来源	实验条件	助熔剂	硅钙质量比	磷矿还原率	参考文献
云南，四川	1350℃，100min	硅石	1.1，1.29，1.1	84.1%，78.9%，91.6%	[27]
云南，湖北	1450℃，60min	硅石	2.57	98%	[21]
云南	1250℃，60min，1Pa（真空）	硅石	0.86	33.09%	[31]
贵州	1400℃，40min	钾页岩	1.02	96.47%	[34]
贵州	1400℃，40min	钾长石	1.02	96.71%	[34]
贵州	1400℃，40min	霞石	1.02	96.12%	[34]
云南	1700℃，20min	煤灰渣	0.8	98.9%	[35]
云南	1430℃，60min	硅石	2.6	80%	[36]
云南	1400℃，120min	硅石	0.76	60%	[37]
云南	1400℃，40min	硅石	1.63	83.98%	[38]

磷矿石来源	实验条件	助熔剂	硅钙质量比	磷矿还原率	参考文献
云南，四川	1350℃，100min	硅石	1.1，1.29，1.1	84.1%，78.9%，91.6%	[27]
云南，湖北	1450℃，60min	硅石	2.57	98%	[21]
云南	1250℃，60min，1Pa（真空）	硅石	0.86	33.09%	[31]
贵州	1400℃，40min	钾页岩	1.02	96.47%	[34]
贵州	1400℃，40min	钾长石	1.02	96.71%	[34]
贵州	1400℃，40min	霞石	1.02	96.12%	[34]
云南	1700℃，20min	煤灰渣	0.8	98.9%	[35]
云南	1430℃，60min	硅石	2.6	80%	[36]
云南	1400℃，120min	硅石	0.76	60%	[37]
云南	1400℃，40min	硅石	1.63	83.98%	[38]

项目	电炉法	高炉法	流态化法	熔融电解法	低温碳热还原磷酸法	硅热法制磷	磷煤耦合联产制磷法
反应温度/℃	1400～1500	—	—	850	1000	1250	1400～1800
磷还原电耗/kW·h·t^-1	13500～15500	0	—	8900	—	—	0
磷源	中、高品位磷矿	中、高品位磷矿	中、高品位磷矿	磷矿、污泥等含磷废弃物	含磷废渣	中、低品位磷矿	低、中、高品位磷矿
工艺复杂程度	简单	简单	较复杂	较复杂	简单	简单	较复杂
磷收率	≥95%	＜50%	>95%	—	50%	≥80%	≥95%
技术现状	已工业化	已淘汰	实验室研究	实验室研究	实验室研究	实验室研究	实验室研究

磷矿热还原制取黄磷技术现状及研究进展

Current status and research progress of thermal reduction technology for producing yellow phosphorus from phosphate rock

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