修饰钙基废料重整制氢中捕集CO2机理及循环特性研究

The new progress has been made in the previous National Natural Science Foundation. The breakthroughs have been made in CO2 capture research of calcium-based wastes (CW), that the modified calcium-based wastes (MCW) with high reactivity and mechanical strength have been generated. It is also found that the long-term cyclic reactivity of CO2 carrier is constrained by HCl in a way. Based on the above progress, a new thought about MCW as CO2 carrier coupling to biomass gasification and reforming process for hydrogen production has been proposed in this project. The cyclic reactivity of MCW as CO2 carrier and the effect of HCl on cyclic reactivity of CO2 carrier in the reforming process for hydrogen production are still not clear so far, which are closely associated with the efficiency of hydrogen production. The modification method and design theory of MCW will be deepened and improved. The cyclic CO2 capture behavior and the attrition resistance of MCW in the reforming process for hydrogen production will be investigated. The effect of HCl on cyclic CO2 capture behavior of MCW and their interaction mechanism will be revealed in terms of intrinsic kinetics/macrokinetics, phase and crystallite evolution of product layer, transformation of microstructure, sintering and tribological characteristics of particles in the reaction conditions including steam for hydrogen production. In addition, the cooperative control method of HCl and CO2 will be proposed according to the compatibility and coupling. This work will pave the way for the recycling of the calcium-based industrial wastes and the efficient biomass fuels gasification and reforming to produce hydrogen.

青年科学基金获得新进展：利用钙基废料循环捕集CO2研究获得突破，制得高活性和高强度修饰钙基废料，并发现HCl在一定程度上束缚CO2载体长周期循环性能。基于以上进展，提出把修饰钙基废料作为CO2载体耦合到生物质等燃料重整制氢中的新思路。在重整制氢条件下修饰钙基废料的循环特性及HCl对CO2载体循环性能的影响尚不清楚，而这与制氢效率密切相关。拟深化和完善修饰钙基废料制备方法及设计理论；研究修饰钙基废料重整制氢循环捕集CO2反应规律及其抗磨损性能；从本征/宏观反应动力学、产物层物相/晶相演变、微观结构迁移、烧结及颗粒摩擦学等角度，揭示水蒸气存在等复杂制氢条件下HCl对修饰钙基废料循环捕集CO2影响规律和相互作用机制，并根据反应兼容性和耦合性，提出HCl和CO2协同调控方法，为钙基工业废料资源化与生物质等燃料高效气化制氢相结合的新思路和工艺奠定基础。

提出把修饰钙基废料作为CO2载体耦合到生物质等燃料重整制氢中的新思路。在制氢反应条件下修饰钙基废料的循环特性及HCl对CO2载体循环性能的影响尚不清楚。经过项目组4年的研究得到了以下成果：采用燃烧合成法、模板法和水热合成法等制备了多种高活性修饰钙基废料，揭示了合成方法对修饰废料特定多孔结构生成的影响机制，揭示了修饰钙基废料微观结构对CO2捕集特性的影响机理；获得了HCl对钙基废料捕集CO2过程中碳酸化特性、煅烧特性的影响规律，揭示了捕集CO2条件对钙基废料氯化反应与碳酸化反应竞争的调控机制，揭示了不连续加入HCl提高钙基废料循环捕集CO2性能的机理；提出利用经历多次循环捕集CO2的钙基废料脱除合成气中HCl的方法并揭示脱除机理，揭示了惰性载体对钙基废料捕集CO2和脱除HCl的共同促进机制；揭示碳酸化和煅烧中水蒸气对钙基废料和修饰钙基废料循环碳酸化的影响机理，发现了水蒸气的“双刃效应”；提出在燃料气化重整制氢系统中利用多次捕集CO2的钙基废料脱除H2S的新工艺；研究了修饰钙基废料造粒工艺及其流态化下的抗磨损特性；获得了水蒸气和HCl在循环捕集CO2中对修饰钙基废料造粒颗粒磨损和破碎特性的影响规律。本项目研究为钙基废料大规模资源化利用与气化重整制氢/CO2捕集集成技术路线提供了理论指导和数据支持，有望促进高效低碳能源技术的发展。