“双碳”背景下热法黄磷生产技术研究现状及建议

doi:10.16085/j.issn.1000-6613.2023-0560

化工进展 ›› 2024, Vol. 43 ›› Issue (4): 2104-2116.DOI: 10.16085/j.issn.1000-6613.2023-0560

• 资源与环境化工 • 上一篇

“双碳”背景下热法黄磷生产技术研究现状及建议

姚远(), 井红权(), 尹玉婷, 齐帅亮, 王艳语, 侯翠红()

郑州大学化工学院国家钙镁磷复合肥技术研究推广中心，教育部先进功能材料制造工程研究中心，河南郑州 450001

收稿日期:2023-04-10 修回日期:2023-05-21 出版日期:2024-04-15 发布日期:2024-05-13
通讯作者: 井红权,侯翠红
作者简介:姚远（1987—），男，博士研究生，研究方向为固废资源高效利用。E-mail：yaozhikang@live.cn。
基金资助:
“十三五”国家重点研发计划(2018YFC1900201-01);国家磷资源开发利用工程技术研究中心开放基金(NECP2022-02)

Research status and suggestions of yellow hosphorus production technology by thermal processing under peak carbon dioxide emission and carbon neutrality

YAO Yuan(), JING Hongquan(), YIN Yuting, QI Shuailiang, WANG Yanyu. HOU Cuihong

School of Chemical Engineering, Zhengzhou University，National Center for Research & Popularization of Calcium, Magnesium, Phosphate and Compound Fertilizer Technology, Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, Zhengzhou 450001, Henan, China

Received:2023-04-10 Revised:2023-05-21 Online:2024-04-15 Published:2024-05-13
Contact: JING Hongquan

摘要/Abstract

摘要：

黄磷支撑着我国磷酸盐精细化和有机磷化工的发展，是磷化工行业重要的基础原材料。热法黄磷生产高能耗、高污染、高碳排放，因此创新产业可持续发展模式，突破资源、能源、环境的多重制约因素，开发绿色黄磷生产技术是我国黄磷企业今后发展的必经之路。结合“碳达峰、碳中和”的时代背景，本文阐述了黄磷生产技术发展及副产物资源化利用现状，目前黄磷生产存在磷矿资源贫化、副产物低值化利用普遍、能源转型难度高、企业整体能效水平低、产业链链接关键技术不足等问题，提出加快推广黄磷尾气烧结中低品位磷矿成球技术、加大开发资源化增值利用技术、探索黄磷还原新技术、加强企业合作、构建多产业耦合的磷资源产业循环经济五条建议，旨在助力实现黄磷行业节能降碳、绿色发展。

关键词: 低碳, 黄磷, 磷循环经济, 节能减排

Abstract:

Yellow phosphorus is the important basic raw material of phosphorus chemical industry, which supports our phosphate refinement and the development of organic phosphorus chemical industry. Thermal yellow phosphorus production has the characteristics of high energy consumption, high pollution and high carbon emission. It is the only way for Chinese yellow phosphorus enterprises to innovate the sustainable development mode of industry, to break through the multiple constraints of resources, energy and environment, and to develop green yellow phosphorus production technology. Combined with the time background of "carbon peak and carbon neutrality", this paper described the development of yellow phosphorus production technology and the status quo of by-product resource utilization. There were some problems in yellow phosphorus production, such as phosphate ore resource depletion, widespread utilization of low-value by-products, high difficulty in energy transformation, low overall energy efficiency level of enterprises and insufficient key technologies of industrial chain link. In order to realize energy saving and carbon reduction and green development of yellow phosphorus industry, this paper put forward five suggestions: to accelerate the promotion of pelletizing technology of low and medium grade phosphorus ore in tail gas sintering of yellow phosphorus, to increase the development of value-added utilization technology of resources, to explore new technology of yellow phosphorus reduction, to strengthen cooperation between enterprises, and to build a multi-industry coupled circular economy of phosphorus resource industry.

Key words: low carbon, yellow phosphorus, phosphorus recycling economy, energy conservation and emission reduction

中图分类号:

TD985

姚远, 井红权, 尹玉婷, 齐帅亮, 王艳语, 侯翠红. “双碳”背景下热法黄磷生产技术研究现状及建议[J]. 化工进展, 2024, 43(4): 2104-2116.

YAO Yuan, JING Hongquan, YIN Yuting, QI Shuailiang, WANG Yanyu. HOU Cuihong. Research status and suggestions of yellow hosphorus production technology by thermal processing under peak carbon dioxide emission and carbon neutrality[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2104-2116.

图/表 7

图1 我国黄磷的各种用途

图2 我国黄磷生产的基本情况

图3 电炉法制磷生产工艺流程图

表1 生产每吨黄磷的排出物量及成分

排出物	排出量	主要成分	其他成分
炉渣	8010kg（干基）	CaO、SiO₂、Al₂O₃、MgO、P₂O₅	Si、Ca₃P₂、CaC₂、CaS、CaCN₂、SO $4 2 -$ 、Fe₂O₃、CaF₂
尾气	2575m³	CO、CO₂、O₂、CH₄、H₂	N₂、H₂S、PH₃、SiF₄、HF
磷铁	75.62kg	Fe、P、Si、Mn、S、C	Ti、Cr、V、重金属
电除尘灰	约100kg	P₂O₅、SiO₂、K₂O、Na₂O、F^-、C	Fe₂O₃、As、CaO、Al₂O₃
污水	5.67m³	P⁴、F^-、S^2-、CN^-、K₂O、悬浮物	As、Na₂O、酚、K₂SiF₆
磷酸废气	175.62m³	H₃PO₄、P₂O₅、F^-	水蒸气、N₂、O₂
放空废气	12264m³	CO₂、CO、H₂S、HF、NO₂、P₂O₅	水蒸气、N₂、O₂
稀磷酸	131kg	H₃PO₄、H₃PO₃	P、Fe、Mg、Ca、Cr、Ni、Al、Ti、Pb、Si、H₃PO₄
泥磷渣	19.09kg	P₂O₅、F^-、K₂O、CaO、SiO₂	H₂O、Mn、SO $4 2 -$ 、Al₂O₃

表1 生产每吨黄磷的排出物量及成分

排出物	排出量	主要成分	其他成分
炉渣	8010kg（干基）	CaO、SiO₂、Al₂O₃、MgO、P₂O₅	Si、Ca₃P₂、CaC₂、CaS、CaCN₂、SO $4 2 -$ 、Fe₂O₃、CaF₂
尾气	2575m³	CO、CO₂、O₂、CH₄、H₂	N₂、H₂S、PH₃、SiF₄、HF
磷铁	75.62kg	Fe、P、Si、Mn、S、C	Ti、Cr、V、重金属
电除尘灰	约100kg	P₂O₅、SiO₂、K₂O、Na₂O、F^-、C	Fe₂O₃、As、CaO、Al₂O₃
污水	5.67m³	P⁴、F^-、S^2-、CN^-、K₂O、悬浮物	As、Na₂O、酚、K₂SiF₆
磷酸废气	175.62m³	H₃PO₄、P₂O₅、F^-	水蒸气、N₂、O₂
放空废气	12264m³	CO₂、CO、H₂S、HF、NO₂、P₂O₅	水蒸气、N₂、O₂
稀磷酸	131kg	H₃PO₄、H₃PO₃	P、Fe、Mg、Ca、Cr、Ni、Al、Ti、Pb、Si、H₃PO₄
泥磷渣	19.09kg	P₂O₅、F^-、K₂O、CaO、SiO₂	H₂O、Mn、SO $4 2 -$ 、Al₂O₃

图4 黄磷尾气的组成及资源化利用方式[54]

图5 氢气/甲烷还原氟磷酸钙反应热力学分析

图6 多资源耦合的磷资源产业循环经济系统

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“双碳”背景下热法黄磷生产技术研究现状及建议

Research status and suggestions of yellow hosphorus production technology by thermal processing under peak carbon dioxide emission and carbon neutrality

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