高磷锰基合金脱磷剧毒产物的解毒机制及无害化渣系重构研究

CaO-CaF2 slag is usually applied to reduce dephosphorization of manganese ferroalloys containing a high phosphorus, but the dephosphorization production Ca3P2 transferred to this slag is prone to react with H2O and simultaneously produce toxic phosphine, which not only endangers human health but also seriously pollutes environment. This project proposes a new research approach to realize both the dephosphorization of the Mn-based alloy and the harmless treatment of dephosphorization product in one step. Instead of CaO-CaF2 slag, a kind of CaO-SiO2-MxOy slag combining with a kind of Al-based dephosphorizer will be applied to the reduce dephosphorization by an invented deep dephosphorization technology, producing a harmless CaO-SiO2-MxOy-AlPx slag. The project is to research the effects of the constitution of CaO-SiO2-MxOy slag, alkalinity and MxOy on the dephosphorization products AlPx, and to demonstrate the toxicology of the dephosphorization products and detoxification mechanism. The main occurrence states, the multiple coexisting structure, the distribution-zone of AlPx in CaO-SiO2-MxOy-AlPx slag under the multi-conditions should be emphasized, and the crystallization behavior of this slag during cooling should be studied too, clarifying the stability mechanism of AlPx and the restrictive factors of the maximum phosphorus capacity in dephosphorization slag. The optimization of dephosphorization agent and the process parameters can establish the thermodynamic model of CaO-SiO2-MxOy-AlPx slag, and improve the multicomponent and multiphase coexistence theory of dephosphorization slag. The research can provide an innovation technology of Mn-base alloy dephosphorization with highly efficient, energy saving and environmental protection, realizing the harmless discharge as well as the utilization effectively of dephosphorization slag.

高磷锰基合金还原脱磷常采用CaO-CaF2渣系，进入该渣系的脱磷产物遇水生成剧毒磷化氢，危害人类健康，严重污染环境。本项目通过构建一种无氟脱磷渣系CaO-SiO2-MxOy，同时用铝基脱磷剂和专利技术对锰基合金进行还原脱磷，形成CaO-SiO2-MxOy-AlPx无害化渣系，一步法实现脱磷和渣无害化处理。研究CaO-SiO2-MxOy渣系组成、碱度、MxOy等对脱磷产物AlPx的影响，阐明AlPx的毒理及解毒机制；重点研究多变条件下AlPx在CaO-SiO2-MxOy-AlPx渣系中的赋存状态、多元共存结构、优势区域分布，冷却过程结晶行为，阐明AlPx在脱磷终渣中容纳量最大化限制性因素和稳定性机理。通过脱磷剂和过程参数优化，构建CaO-SiO2-MxOy-AlPx渣系热力学模型，完善脱磷渣系多元共存理论，提供一种高效、节能、环保的高磷锰基合金脱磷创新技术，实现脱磷渣无毒无害排放及高效利用。

本课题组在采用国内外冶金工作者普遍采用的CaO-CaF2渣对高磷锰矿冶炼锰基合金还原脱磷研究的基础上，创新性提出了“采用CaO-SiO2-MxOy（M代表Al/Fe/Mn）无氟渣系代替传统的CaO-CaF2渣系，同时使用发明的一种铝基脱磷剂和一种锰硅合金脱磷方法对高磷锰基合金进行深度还原脱磷，形成新的CaO-SiO2-MxOy-AlPx多元无害化渣系，同步实现高磷锰基合金脱磷和渣的无害化处理。”的研究思路。通过系统的深入研究，得到如下系列成果：.（1）阐明了高磷锰基合金脱磷产物的毒理及解毒机制；.（2）构建了一种无氟脱磷渣系CaO-SiO2-MxOy, 一步法实现高磷锰基合金脱磷及脱磷产物无害化处理。经过脱磷渣系重构，合金脱磷后磷含量最低为0.05%，达到了国家I级标准；脱磷后的含磷渣P主要以AlP和AlPO4形式存在，在自然条件下不粉化且无恶臭，实现了合金高脱磷率与脱磷终渣环保治理的理念；.（3）提出了“利用脱磷终渣绿色制备微晶玻璃”的新技术。通过该技术所制备的微晶玻璃性能优良，该方法可以全量利用含磷脱磷渣，并达到高附加值利用。具有重要的学术价值和广阔的应用前景。. 期间培养硕士研究生6名，国内外发表SCI/EI论文8篇，获授权发明专利3项，申请1项，其中授权的1项专利已经转让并实施。