生物质/煤化学链气化研究对于资源的开发利用具有重要意义。本研究采用机械混合-浸渍法制备K2CO3修饰铜铁复合载氧体,利用热重-质谱联用技术,结合脉冲热分析法,考察其加入前后生物质/煤的水蒸气气化反应性能。样品装填量30mg,气化剂(水蒸气)流量3.0g/h,950℃条件下气化20min,结果表明,样品YMYC(玉米芯/羊肠湾煤)气化性能较好,合成气含量及n(H2)/n(CO)分别为81.21%、13.14,在K2CO3修饰铜铁复合载氧体的作用下,体系合成气含量降低了7.60%,n(H2)/n(CO)提高至19.24。从制备高浓度合成气目的出发,K2CO3修饰铜铁复合载氧体是一种适宜的生物质/煤化学链气化载氧体。利用(FWO)Flynm-Wall-Ozawa等转化率法获得反应的活化能E,以及活化能E与生物质/煤转化率α之间的变化关系,结果表明,随着气化温度上升(至650℃左右),转化率增大(大于0.4),气化活化能先增大后减小,说明这一阶段的反应为限速控制转变过程。

The research on chemical looping gasification of Biomass/ Coal has important theoretical significance for the development and utilization of resources. In this study, K CO -modified copper-iron composite oxygen carriers were prepared by impregnation- mechanical mixing method. Thermogravimetric - mass spectrometry and pulse thermal analysis were used to investigate the steam gasification performance of Biomass/ Coal before and after the addition of oxygen carrier. The loading amount of the sample is mg, and the gasification reactions last for minutes under the conditions of gasification agent(water vapor) flow rate of 3. 0 g/ h and ℃. It is found that the sample YMYC(corncob/ Yang chang wan coal) has better gasification performance, and its syngas content and n(H  ) / n( CO) are 81. 21% and 13. 14, respectively. Compared with before addition, it was found that the addition of K CO modified copper-iron composite oxygen carrier could reduce the syngas content of the system by 7. 60%, and increased the n(H ) / n(CO) ratio to 19. 24. For the purpose of preparing high concentration syngas, K CO modified copper-iron composite oxygen carrier is a suitable oxygen carrier for Biomass/ Coal chemical looping gasification. The activation energy E of Biomass/ Coal and K CO modified copper-iron composite oxygen carrier, and the relationship between the activation energy E and the conversion rate α of Biomass/ Coal were obtained by ( FWO) Flynm - Wall - Ozawa isoconversional method. The results show that as the gasification temperature increases(to around 650℃), the conversion rate increases(greater than 0. 4), and the gasification activation energy first increases and then decreases, indicating that this stage of the reaction is a rate-controlling transition process.

               
                    1 实验部分
1.1 实验材料与试剂
1.2 生物质/煤样的制备
1.3 K2CO3修饰铜铁复合载氧体的制备
1.4 气化反应性能评价
1.5 数据处理
1.5.1 气化转化率
1.5.2 气体的摩尔量
1.5.3 合成气的含量
1.5.4 气体的产量
1.5.5 逸出气体摩尔分数
1.5.6 动力学研究
2 结果分析与讨论
2.1 生物质/煤的气化反应性能
2.2 生物质/煤和K2CO3修饰铜铁复合载氧体的气化反应性能
2.3 反应前后载氧体结构分析
2.4 动力学计算与分析
3 结 论