新型焦粉链式气化耦合焦炉煤气高值化利用基础研究

Resourceful utilization of coke powder and coke oven gas is a significant way to improve the energy utilization efficiency of coking industry. Chemical looping gasification of coke powder reduces the irreversible exergy loss in the combustion process and realizes fuel energy cascaded utilization by dividing the traditional gasification reaction into two steps using oxygen carrier as oxygen and heat supplier, which averts the expensive investment and energy consumption of oxygen preparation. What’s more, the catalytic performance of oxygen carrier can enhance the gasification reactivity of coke powder, which is beneficial to improving efficiency of coke powder gasification. Besides, the key composition (H2/CO/CO2) of the gasified gas can be adjusted orientedly and controlled in the chemical looping gasification of coke powder by adjusting the gasification atmosphere and conditions. All those advantages of chemical looping gasification of coke powder mentioned above provide useful physical energy and elements for recycling of coke oven gas. .Although coke oven gas integrated with coke powder using chemical looping gasification provides a technical platform for synergistic resourceful utilization of coke powder and coke oven gas, it is needed to re-establish the system matching manners of skills and techniques due to the redistribution of energy flow and substances of the new coupled production system. Understanding the interaction mechanism amongst these functional units and integrating them via system optimization is pivotal for developing efficient, clean and economical technologies of coke powder and coke oven gas..This project focus on the high value utilization of coke oven gas coupled with coke powder using chemical-looping gasification with oxygen uncoupling. A design theory and method for oxygen carrier will be investigated aiming to proactive control composition and quality of coke powder gasified gas, and the evolution law of key elements (C/H), characteristics of gasification reaction, principle of synergic catalytic effect, and the regulation mechanism of components in chemical looping gasification of coke powder under the complex atmosphere will also be disclosed. Furthermore, by illuminating the transfer rules of mass, energy and information in the coupled production systems, engineering cybernetics is applied to syncretize the mass and the energy conversion processes in thermal chemical reactions, chemical engineering and engineering thermodynamic, and the integration theory and method are proposed of resourceful utilization system of coke oven gas coupled with coke powder using chemical-looping gasification, realize balance in energy-element(environment)-economics that are internally related, which finally obtain a synergy and optimization of technology, configuration, products and process route.

焦粉和焦炉煤气的资源化回收利用是提高焦化行业综合能源利用效率的重要途径。焦粉化学链气化在能量梯级利用与组分定向调控方面的特殊匹配属性，为焦炉煤气资源化利用提供了潜在的质/能需求。本项目立足焦粉化学链气化技术与焦炉煤气高值化利用集成体系的有机耦合，研究焦粉气化产物品质主动调控的载氧体颗粒裁剪设计理论和方法，复杂气氛载氧体解耦焦粉化学链气化反应特性与协同催化气化机理，焦粉化学链气化过程关键组分演化规律与气化产物调控机制；阐明焦粉化学链气化耦合焦炉煤气资源化利用系统中质/能量/信息传递规律，寻求系统能流/物流深度集成和协同优化路径与机制，形成以焦粉化学链气化技术为主体耦合焦炉煤气资源化利用的基础理论与方法；从原料源头-转化路径-产品终端-系统优化控制的全局层面，解决焦粉与焦炉煤气高附加值回收利用过程全局能效-元素-经济博弈平衡问题，揭示焦粉化学链气化耦合焦炉煤气资源化利用技术的科学性和合理性。

从原子层面重点探究典型外源活性异质金属离子的引入对功能铁锰复合载氧体反应活性的影响；通过调控微观结构、组分耦合，建立载氧体理化特性与其反应活性之间的映射关系，阐明了载氧体与异质活性金属离子耦合协同机理，获得主动调控焦粉气化产物品质的载氧体材料裁剪设计理论和制备方法；研究铁锰复合载氧体解耦协同催化焦粉化学链气化反应行为及其热力学限度，阐明气化过程中焦粉颗粒-气化介质-载氧体颗粒之间的反应特性及其内在关联，探索了温度场、流体场及载体晶格氧赋存比例等关键气化参数在可行工作域区间交替或同时变化对反应产物组成分布的调控规律，实现焦粉化学链气化源头调控，碳氢氧关键元素的定向演化与高品质合成气制备。建立了焦粉与焦炉煤气碳氢互补联产甲醇-氨系统流程超结构模型，涉及焦粉化学链燃烧解耦制氢子系统、原料气净化单元、CH4/CO2重整单元、甲醇合成单元、合成氨单元等。建立了基于夹点㶲分析方法的能量换热网络集成方法，通过优化关键单元参数和工艺条件，以及系统换热网络集成与优化，实现了甲醇-氨联产过程的元素高效转化与余热回收高效利用。研究表明，与传统焦炉煤气制甲醇和合成氨系统相比，系统㶲效率高达78.7%，CO2相对减排效率为0.67。焦粉与焦炉煤气碳氢互补联产甲醇-氨系统可以根据市场需求灵活调变产品，其中0.576 Mt/y 焦炉煤气和 0.175 Mt/y 的焦粉可以生成甲醇0.44-0.86 Mt/y和合成氨0–0.36 Mt/y。