含硫烟气与氧化锰矿协同资源化利用的基础研究

The lack of manganese resources and the increasing of SO2 pollution from industries flue gases have caused big problems in our country. In this project, a new concept in the synergistic resourcefulization and effective utilization of SO2 flue gases coupled with low-grade manganese oxide ores was conceived to recover manganese and control the emission of SO2. The approach was proposed based on the multi-disciplinary consisting of chemical, energy, metallurgical and environmental engineering. Based on the characteristics of the porous structure and the specific oxidizing property of MnO2 as well as the reducing property of SO2, a new idea on the directional reduction from MnO2 to MnSO4 was designed via a gas-solid redox reaction between MnO2 and SO2, targeting at integrating both flue gas desulfurization and manganese extraction in the form of MnSO4 into one-step process. The structural characteristics of micro-, mesoscopic and macro-porous as well as the surfacial physicochemical properties of the manganese oxide ores will be studied by means of structural chemistry and surface chemistry. The first-principles quantum chemistry will be used to study the adsorption mechanism between MnO2 and SO2. The technical approach for in-situ phase transformation and directional reduction of manganese oxide from MnO2 to MnSO4 will be revealed through the study on the reaction mechanism and the technological process between MnO2 and SO2. The techical measures will be found out to enhance the reaction process. A further investigation will be conducted on the enhabcement of the reaction process by cycling fluidization in order to find out the optimal technical parameters. A new technology will be developed for the resourcefulization and effective utilization of industrial flue gases coupled with low-grade manganese oxide ores. Using waste gas to recover the valuable manganese from low-grade ores and utilizing manganese ores to remove SO2 from the flue gases, the economic and environmental benefits will be obviously obtained from the present investigation. It will make a great sense in the fields of metallurgy, environment and energy.

针对我国锰矿资源短缺和SO2烟气污染严重等突出问题，将化学、能源、冶金和环境等学科交叉融合，提出工业烟气与低品位氧化锰矿耦合资源化利用新思路。借MnO2的多孔性和氧化性以及SO2的还原性，在MnO2与SO2发生气固反应之时，实现MnO2→MnSO4的原位相转化定向还原，一步达到烟气脱硫和提取硫酸锰之目的。采用结构化学和表面化学手段，查明不同晶相氧化锰的微观、介观和宏观空隙结构以及表面物理化学性质；运用量子化学第一性原理的计算方法，揭示氧化锰与SO2的吸附机理；基于氧化锰矿与SO2 的反应机理与反应过程研究，查明MnO2→MnSO4原位相转化定向还原的技术途径，找出强化反应的技术措施；通过循环流态化强化反应过程的研究，找出最佳技术参数，初步开发出含硫烟气与低品位氧化锰矿协同资源化高效利用新技术。本项目以废气提锰，以锰矿治废，实现提锰与治废双效共赢，对冶金、环境及能源行业具有重要现实意义。

采用石灰石-石膏湿法或软锰矿浆湿法烟气脱硫存在结垢堵塞、设备腐蚀、副产物污染等问题，需要探索经济、合理的新脱硫方法，有效地解决SO2烟气的环境污染问题。采用悬浮闪速焙烧或回转窑还原工艺处理低品位氧化锰矿，处理难度大，经济效益和环境效益较差。. 因此，本项目利用氧化锰矿自身多孔、反应活性大、氧化性强等特点，吸收烟气中的SO2，一步实现氧化锰定向还原和烟气脱硫作用，对缓解当前我国锰矿资源紧缺的矛盾，确保锰冶金行业的可持续发展具有十分重要的战略意义。. 本项目采用结构化学和表面化学手段，查明不同晶相氧化锰的微观、介观和宏观空隙结构以及表面物理化学性质；运用吸脱附曲线的计算方法，揭示氧化锰与SO2的吸附规律；基于氧化锰矿与SO2的反应机理与反应过程研究，查明MnO2→MnSO4原位相转化定向还原的技术途径，找出强化反应的技术措施；通过循环流态化强化反应过程的研究，找出最佳技术参数，开发出含硫烟气与低品位氧化锰矿协同资源化高效利用的新技术。结果表明锰矿在一体化技术中的脱硫率达到99%以上，脱硝率达到96%。. 本项目发表学术研究论文8篇，SCI收录2篇，授权国家发明专利3项，参加国内外学术合作与交流8人次，培养研究生5人。. 本项目采用含硫烟气直接还原低品位氧化锰矿，实现了含硫烟气与低品位氧化锰矿的协同资源化高效利用。将烟气中的SO2，变废为宝，解决了火电、钢铁等企业的含硫烟气难以经济有效处理的难题，同时增加了中低品位氧化锰矿高效利用的程度，拓宽了锰矿的利用范围。不仅对锰冶金行业低品位氧化锰矿资源的综合利用具有重要的学术意义，而且对火电等行业烟气的治理以及环境保护具有重要的现实意义。