B-ZSM-5酸调控及催化褐煤热解挥发分制轻质芳烃研究  

Catalytic conversion of lignite pyrolysis volatiles for enriching light aromatics over B-ZSM-5

作　　者：杨珍 曹景沛[1] 朱陈 刘天龙 赵小燕 YANG Zhen;CAO Jingpei;ZHU Chen;LIU Tianlong;ZHAO Xiaoyan(Jiangsu Province Engineering Research Center of Fine Utilization of Carbon Resources(Ministry of Education),China University of Mining&Technology,Xuzhou 221116,Jiangsu,China)

机构地区：[1]中国矿业大学江苏省碳资源精细化利用工程研究中心,江苏徐州221116

出　　处：《化工学报》2021年第11期5633-5642,共10页CIESC Journal

基　　金：国家自然科学基金项目(22178374,21978317);江苏省自然科学基金杰出青年基金项目(BK20200028)。

摘　　要：在不同碱性条件下水热合成了B-HZSM-5(B-H5)催化剂用于原位催化褐煤热解挥发分制备轻质芳烃。通过X射线衍射仪、扫描电子显微镜、氨气程序升温脱附仪和N2物理吸附脱附表征了合成条件对分子筛的形貌、酸性和质构特征的影响。在强碱性条件下合成的分子筛表面更光滑、结晶度更高,Na-x B-H5(合成过程加碱)弱酸明显增强。与母体H5相比,Na-x B-H5骨架硼形成的B—OH—Si提供更多的弱酸位点能够吸附乙烯丙烯等中间产物,增加甲基化和烷基化速率。在具有较高的结晶度、丰富的酸位点和微孔/介孔的Na-0.69B-H5(硼添加量为0.69 g)上得到了最高烷基苯产率11.4 mg/g。而过量引入硼则会使骨架Al流失,强弱酸比例减少,抑制芳构化反应,降低轻质芳烃产率。通过骨架硼的引入调控分子筛酸性为褐煤催化热解提高轻质芳烃产率提供了新思路。Under different alkaline conditions,the B-HZSM-5(B-H5)catalyst was hydrothermally synthesized to catalyze the pyrolysis of lignite volatiles to produce light aromatics in situ.X-ray diffraction(XRD),scanning electron microscope(Gemini SEM 500),temperature programmed desorption of ammonia(NH3-TPD),and N2 adsorption-desorption were used to characterize the morphology,acidity and textural properties of x B-HZSM-5.The higher weak acid content and the higher crystallinity of Na-x B-H5(added NaOH)were obtained under a stronger alkaline solution.Compared with parent ZSM-5,the weak acidity assigned to the B—OH—Si groups of Na-x B-H5 provided more active sites to absorb ethylene and propylene to promote methylation and alkylation processes.The highest alkylbenzene yield was obtained(11.4 mg/g)over Na-0.69 B-H5(B content was 0.69 g)with higher crystallinity,sufficient active sites and hierarchical micro/mesopore.However,the excess B also brought a negative effect on aromatization due to the reduced rate of stronger acid and weak acid.The Na-x B-H5 provided a great prospect to enhance the catalyticperformance of lignite vapors by the introduction of B in the framework of H5.

关 键 词：催化剂 沸石 稳定性 传质 芳烃 褐煤热解 B-HZSM-5 

分 类 号：TQ523[化学工程—煤化学工程]