限域型催化剂Ni@S2对甲烷干重整反应性能影响
收稿日期: 2024-04-29
网络出版日期: 2025-02-20
基金资助
重质油国家重点实验室开放课题项目(SKLHOP202202002);浙江省“尖兵”“领雁”研发攻关计划项目(2023C04021);浙江科技大学科研成果奖培育项目(2023JLZD008)
Effect of confined catalyst Ni@S2 on performance of methane dry reforming reaction
Received date: 2024-04-29
Online published: 2025-02-20
甲烷干重整反应（DRM）能够合理利用CO2和CH4两种温室气体，生产出环保清洁的燃料CO和H2，然而该工艺所使用的镍基催化剂在高温下易发生积炭和烧结，难以满足工业化生产的需求。基于此，采用研磨晶化法制备了限域型Ni@S2（Silicalite-2）催化剂。结果表明，限域型Ni@S2催化剂呈现出橄榄状晶体结构，比表面积大，孔径分布窄，且NiO纳米颗粒均匀地分散在Silicalite-2骨架中，NiO平均晶粒尺寸约为4.63 nm。在700 ℃下进行6 h的甲烷干重整反应［进料流速Fin=40 mL/min，V（CH4）:V（CO2）:V（Ar）=44:44:12］，相较于负载型催化剂10Ni/SiO2，限域型10Ni@S2催化剂的CH4瞬时转化率从65.51%提高至91.91%，CO2的瞬时转化率从71.89%提高至91.14%，积炭率从16.30%降低至1.20%。催化剂优异的催化性能和稳定性得益于其限域结构，不仅避免了活性组分烧结，降低了NiO的颗粒尺寸，还提高了金属与载体间的相互作用力。该研究为低成本、高稳定性的镍基催化剂的开发开辟了新的方向。
关键词： 研磨晶化法; 甲烷干重整反应; Silicate-2沸石; 限域型催化剂; 积炭
朱继成 , 杨期鑫 , 梁浩权 , 王增坤 , 欧阳富贵 , 邸婧 , 盖希坤 . 限域型催化剂Ni@S2对甲烷干重整反应性能影响[J]. 无机盐工业, 2025 , 57(2) : 138 -146 . DOI: 10.19964/j.issn.1006-4990.2024-0242
The dry reforming reaction（DRM） of methane can rationally utilize two greenhouse gases of CO2 and CH4 to produce environmentally friendly and clean fuels of CO and H2.However，the nickel-based catalysts used in this process are susceptible to carbon accumulation and sintering at high temperatures，which makes it difficult to satisfy the demands of industrial production.Based on this，domain-limited Ni@S2（Silicalite-2） catalysts were prepared by the grinding crystallization method.The results showed that the domain-limited Ni@S2 catalyst exhibited an olivine-like crystal structure with a large specific surface area and a narrow pore size distribution，and the NiO nanoparticles were uniformly dispersed in the Silicalite-2 skeleton，with an average NiO grain size of about 4.63 nm.After the dry reforming reaction at 700 ℃ for 6 h［Fin=40 mL/min，V（CH4）:V（CO2）:V（Ar）=44:44:12］，compared with the loaded catalyst 10Ni/SiO2，the confined 10Ni@S2 catalysts exhibited excellent catalytic activity and carbon deposition resistance，the instantaneous conversion of CH4 was increased from 65.51% to 91.91%，the instantaneous conversion of CO2 was increased from 71.89% to 91.14%，and the carbon deposition rate was decreased from 16.30% to 1.20%.The excellent catalytic performance and stability of the catalyst were due to the limited domain structure，which avoided the sintering of the active component，reduced the particle size of NiO，and improved the interaction between the metal and the support.This study opened up a new direction for the preparation of low cost and high stability nickel-based catalysts.
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