【作者】 柳婷婷；

【导师】 张寿庭；

【作者基本信息】 中国地质大学（北京） ， 矿产普查与勘探， 2011， 博士

【副题名】以黑龙江穆棱沸石矿为例

【摘要】 本研究采用黑龙江穆棱沸石矿的高品位斜发沸石和丝光沸石为研究对象,详细分析了矿石的化学成分与四项物化性能的关系,包括离子交换性,吸附性,热稳定性与耐酸性。研究注重数据,物理化学原理,结果分析的相结合,相关规律的获得对于沸石矿的开发应用具有理论意义和指导作用,从而为快速预测评价当地乃至全国各类型的沸石矿产资源提供了理论基础和保证,分析思路和方法也为以后的资源评价研究提供了全新的参考和开创性的手段。活动性阳离子（K, Na, Ca, Mg）含量主要决定了沸石的交换性和吸附性,Si/Al之值决定了热稳定性和耐酸性。文中分析了两种沸石的化学成分特征;活动性阳离子含量与K⁺,NH4⁺交换量的关系;参数（MgO⁺CaO）/K₂O和MgO/K₂O与酸性气体和水蒸气的吸附量的关系;加热后吸湿能力的变化与沸石类型和Si/Al的关系;酸浸后失重率和结晶度的变化与Si/Al的关系;以及影响天然沸石物化性能的因素和稀土元素、微量元素的地球化学指示意义。研究区所产的高硅天然斜发沸石和丝光沸石以富钠为主,SiO₂/Al₂O₃大于8,绝大部分大于9。丝光沸石内的活动性阳离子总量与离子交换量（K⁺和NH₄⁺）递增关系明显,斜发沸石略差,原因可能在于孔道的离子堵塞作用及蒙脱石的影响。酸性气体吸附实验发现天然斜发沸石和丝光沸石对H₂S和SO₂的吸附专属性较强,对CO₂较弱。参数（MgO⁺CaO）/K₂O和MgO/K₂O与酸性气体的吸附规律弱,但对水蒸气的吸附与其呈递增函数关系。热稳定性和耐酸性主要受SiO₂/Al₂O₃之值影响。对于加热后的吸湿能力,丝光沸石优于斜发沸石,斜发沸石能稳定至400℃左右,而丝光沸石能稳定至800℃左右。富K和Na可能是丝光沸石热稳定性好的因素之一。对于酸浸后的失重率和结晶度,丝光沸石优于斜发沸石,能耐至4M HCl不发生脱Al,且在4M HCl作用下吸湿能力增强。两种高硅沸石在10M HCl作用后仍能保持80%以上的结晶度,在12M HCl作用下,丝光沸石保留的结晶度高于斜发沸石。微量元素中的碱和碱土金属元素（Rb, Cs, Sr, Ba）可以用于指示矿石的阳离子含量,Th⁺U值用于揭示原岩类型。本研究将拓宽和加深对沸石如何发挥其应用优势的认识,并且对该地乃至全国范围内的沸石矿产资源快速评价具有指导性作用。更多还原

【Abstract】 High grade clinoptilolite and mordenite from Muling, Heilongjing Province were taken as the research objects. Relationships between the chemical compositions and four fundamental physicochemical properties, including cation exchangeability, adsorption of acid gas and water vapor, thermal stability and acid resistance, were detailedly analyzed. With an emphasis on the combination of data, physicochemical principles, and result analysis, the consequent disciplines play a theoretical and instructional role in the exploration and application of zeolite ore deposits, thereby serve as the theoretical foundation and guarantee for the rapid prediction/assessment of the local zeolite mineral resources as well as the other localities nationwide. The thoughts and analyzing methodology also provide a wholly new reference and original resort for the resource evaluation research.The content of the mobile cations in zeolites determines the exchangeability and adsorption, while the Si/Al value influences the thermal stability and acid resistance. The following issues were addressed in the research, such as the characteristics of the chemical compositions of the types of zeolites, relationships between the cation content versus exchangeable content of K⁺ and NH4⁺, parameters of （MgO⁺CaO）/K2O and MgO/K2O versus adsorption of acid gases and water vapor, varied moisture absorption capacities after being heated by increasing temperatures versus zeolite types and Si/Al contents, varied rates of weight loss and crystallinities after acid dipping versus Si/Al, the negative factors that impede the physicochemical properties, as well as the geochemical indicator roles played by REE and trace elements.The target samples enrich in Na element, with a SiO₂/Al₂O₃ value higher than 8, or even high than 9 in most cases. Content of mobile cations in mordenite keeps a positive trend with the exchangeable content of K⁺ and NH4⁺, with which clinoptilolite shows a weak connection due to the cation blockage effect and the mixing of montmorillonite. Adsorption experiments using acid gases discovered that both types of zeolites specifically favor H2S and SO₂, but less CO₂. Parameters of （MgO⁺CaO）/K2O and MgO/K2O do not show evident relationship with acid gas adsorption, but link closely and positively with the adsorption of water vapor. Thermal stability and acid resistance depend on SiO₂/Al₂O₃ values. Mordenite shows superior stability to clinoptilolite in terms of moisture adsorption capacity after being heated. Clinoptilolite can stabilize up to 400°C, whereas mordenite can hold up to 800°C. Higher K and Na contents also contribute to the superior thermal stability of mordenite. To estimate the rate of weight loss and crystallinity after acid dipping also results in the discovery that mordenite is also superior to clinoptilolite in terms of acid resistance, for it keeps the crystal structure in 4M HCl solution without losing Al, and even increases its moisture adsorption capacity in the solution mentioned above. Both types of zeolites remain the crystallinity greater than 80% after being leached in 10M HCl solution, but mordenite holds higher crystallinity than clinoptilolite after 12M HCl solution leaching. The alkali and alkaline earth elements among trace elements （Rb, Cs, Sr, Ba） are good indicators of the cation contents in zeolite ores, while value of Th⁺U reveals the origin of parent rock. The research presented will definitely widen and deepen the insight on how zeolites perform their application advantages, and direct the development of the rapid assessment for application of zeolite mineral resources in the target area and all over the country.更多还原