水泥生料共热耦合原位加氢制合成气  

Co-thermal in situ hydrogenation of cement raw material to synthetic gas

作　　者：张卫涛 于少康 徐明[3] 董猛 郭大冰 杨宇森 邵明飞[1,2] 段雪 ZHANG Weitao;YU Shaokang;XU Ming;DONG Meng;GUO Dabing;YANG Yusen;SHAO Mingfei;DUAN Xue(State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China;Quzhou Resources Chemical Innovation Research Institute,Quzhou 324003,China;College of Chemistry,Chemical Engineering and Resource Utilization,Northeast Forestry University,Harbin 150006,China)

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]衢州资源化工创新研究院,浙江衢州324003 [3]东北林业大学化学化工与资源利用学院,黑龙江哈尔滨150006

出　　处：《洁净煤技术》2024年第4期90-101,共12页Clean Coal Technology

基　　金：国家自然科学基金资助项目(22090031)。

摘　　要：水泥工业是世界第三大能源消耗行业和第二大CO_(2)排放行业,占全球CO_(2)排放的7%。水泥生料(CaCO_(3)、Fe_(2)O_(3)、Al_(2)O_(3)和SiO_(2)的混合物)通过高温(>900℃)煅烧得到水泥熟料,此过程能耗高且释放大量CO_(2)。基于双碳背景,通过球磨法制备水泥生料,采用碳酸盐共热耦合原位加氢还原的创新策略,实现在700℃下水泥生料原位加氢生成CO,其选择性可达94.8%,CO生成速率达0.76 mmol/min,显著降低了碳酸盐的热解温度并抑制了CO_(2)排放,同时获得了均匀多孔的CaO颗粒。采用X射线粉末衍射(XRD)、比表面及孔径分析(BET)、扫描电子显微镜(SEM)、拉曼光谱(Raman)及原位漫反射傅里叶变换红外光谱(In situ DRIFTS)等表征手段,重点探究了反应温度和水泥不同组分(Fe、Si和Al)等因素对碳酸盐加氢性能的影响。结果表明,Fe元素有助于提升CO产物选择性且生成少量甲烷,Si和Al元素的加入降低了碳酸盐加氢反应速率。In situ DRIFTS表明水泥生料加氢生成CO可能遵循甲酸盐中间物种机制。本研究通过水泥生料共热耦合原位加氢制备合成气,实现水泥工业源头降耗与减排增效,为低碳水泥熟料的制备技术提供了新策略与理论依据。The cement industry is the world′s third largest energy consumer and second largest CO_(2)emitter,accounting for 7%of global CO_(2)emissions.Cement raw material(mixture of CaCO_(3),Fe_(2)O_(3),Al_(2)O_(3)and SiO_(2))was calcined at high temperature(>900℃)to obtain cement clinker,which had high energy consumption and releases a huge amount of CO_(2).Based on the dual-carbon background,this paper prepared cement raw material by ball milling method,adopted the innovative strategy of carbonate co-thermal coupling in situ hydrogenation reduction,and realized the in situ hydrogenation of cement raw material to produce CO at 700℃.The selectivity reaches 94.8%,and the CO generation rate reaches 0.76 mmol/min.The pyrolysis temperature of carbonate is significantly reduced,CO_(2)emission is inhibited,and uniformly porous CaO particles are obtained.X-ray powder diffraction(XRD),specific surface area(BET),scanning electron microscopy(SEM),Raman spectroscopy(Raman)and in situ diffuse Fourier transform infrared spectroscopy(In situ DRIFTS)and other characterization methods were used to investigate the effects of reaction temperature and different ponents(Fe,Si and Al)on the hydrogenation performance of carbonate.The results show that Fe helps to improve the selectivity of CO products and produce a small amount of methane,and the addition of Si and Al elements reduces the rate of carbonate hydrogenation.In situ DRIFTS indicate that CO generation from cement raw material hydrogenation may follow the formate intermediate species mechanism.Synthetic gas is prepared by in situ hydrogenation of cement raw materials through co-thermal coupling.This study can reduce consumption and increase efficiency at the source of cement industry,and provide a new strategy and theoretical basis for the preparation technology of low-carbon cement clinker.

关 键 词：水泥生料 碳酸盐 共热耦合 碳减排 合成气 

分 类 号：TQ172[化学工程—水泥工业]