纯硅ZSM-12分子筛的合成及负载Co催化剂用于丙烷脱氢

Synthesis of Pure Silica ZSM-12 Zeolite and ZSM-12-supported Co Catalyst for Propane Dehydrogenation

摘要

丙烷脱氢（PDH）反应因具有产物纯度高、分离能耗低等优势，被认为是最具发展潜力的丙烯生产路线之一.开发高效稳定的新型催化材料是提升PDH反应性能的关键.本文系统研究了具有十二元环孔道结构的纯硅ZSM-12分子筛的可控合成及其热稳定性.通过调变凝胶配比和晶化条件，确定了ZSM-12分子筛的优化合成参数.实验结果表明，经NH₄⁺离子交换处理后的ZSM-12分子筛在1100 ℃高温煅烧后仍能保持较高结晶度，展现出优异的热稳定性.在此基础上，采用“配体保护-原位合成”策略构筑了ZSM-12分子筛封装的高分散Co基催化剂.该催化剂在550 ℃丙烷脱氢反应中表现出良好的催化性能，丙烯生成速率达到16.4 mmol_C3H6·g^-1_cat·h⁻¹；同时，在长时间(1600 min)反应后，经再生处理其活性可基本恢复至初始水平，显示出良好的结构稳定性和再生性能.本研究为大孔纯硅分子筛的合成及高活性、高稳定PDH催化剂的开发提供了参考.

Abstract

Propane dehydrogenation（PDH）is regarded as one of the most promising routes for propylene production owing to its advantages of high product purity and low separation energy consumption.Developing efficient and stable catalytic materials is crucial for improving PDH performance.In this work，the controllable synthesis and thermal stability of pure-silica ZSM-12 zeolite with a twelve-membered-ring pore structure were systematically investigated.By tuning the gel composition and crystallization conditions，the optimized synthetic parameters for ZSM-12 zeolite were established.In addition，the NH⁺₄-exchanged ZSM-12 zeolite retains high crystallinity even after calcination at 1100 ℃，demonstrating excellent thermal stability.On this basis，highly dispersed Co catalyst encapsulated in ZSM-12 zeolite was successfully constructed via a ligand-protected in situ synthesis strategy.The catalyst exhibited excellent catalytic performance in PDH at 550 ℃，achieving a propylene formation rate of 16.4 mmol_C3H6·g^-1_cat·h⁻¹.Moreover，after a long-term reaction of 1600 min，its activity could be nearly restored to the initial level through regeneration，indicating good structural stability and regenerability.This study provides useful guidance for the design and preparation of pure silica large-pore zeolite and the development of efficient and stable PDH catalysts.

关键词

ZSM-12分子筛 / 热稳定性 / 金属负载 / 丙烷脱氢 / 低碳烯烃

Key words

ZSM-12 zeolite / Thermal stability / Metal loading / Propane dehydrogenation / Light olefin

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基金资助

国家重点研发计划项目(2022YFA1506000)

国家自然科学基金(22522204)

国家自然科学基金(22472113)