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晶种法直接水热合成含磷ZSM-5分子筛及其芳构化性能研究OA北大核心CSTPCD

Study on direct hydrothermal synthesis of phosphorus-containing ZSM-5 zeolites by seeding method and their aromatization performance

中文摘要英文摘要

费托合成油品向高辛烷值汽油转化的流化床体系中,水蒸气的存在极易导致ZSM-5分子筛发生不可逆的水热失活,而磷的引入能提高ZSM-5分子筛的水热稳定性.采用晶种法在无胺体系下直接水热合成了含磷ZSM-5分子筛(HS-P-Z5),并与常规浸渍法得到的含磷ZSM-5分子筛(IM-P-Z5)进行了对比.通过XRD、SEM和N2吸/脱附等对水热处理前后的ZSM-5分子筛进行了表征,通过水洗实验考察了磷元素的流失情况,并以1-辛烯为探针分子评价了ZSM-5分子筛的芳构化性能.结果表明,HS-P-Z5比IM-P-Z5具有更高强度的特征衍射峰、更多的微孔结构和酸量.水洗实验和NMR表征结果表明,HS-P-Z5具有更加稳定的磷铝结构,磷物种不易被洗掉,故其具有更好的水热稳定性,在水热处理后能够保留更多分子筛的微孔结构以及强酸位点.HS-P-Z5-ST(ST表示水热处理)具有最高的芳烃选择性,在反应时间730 min时,其芳烃选择性为23.1%,高于IM-P-Z5-ST(18.4%)以及Z5-ST(11.2%).

In the fluidized bed system for the conversion of Fischer-Tropsch synthetic oil to high octane gasoline,the presence of water vapor can easily lead to the irreversible hydrothermal inactivation of ZSM-5 zeolites,but the introduction of phosphorus can improve the hydrothermal stability of ZSM-5 zeolites.Phosphorus-containing ZSM-5 zeolites were directly hydrothermal synthesized by seeding method(HS-P-Z5)in an amine-free system,and compared with phosphorus-containing ZSM-5 zeolites obtained by conventional impregnation method(IM-P-Z5).The properties of ZSM-5 zeolites before and after hydrothermal treatment were characterized by XRD,SEM,N2 adsorption/desorption,et al.Water washing experiment was conducted to investigate the loss of phosphorus.The aromatization performance of ZSM-5 zeolites was evaluated using 1-octene as probe molecule.The results show that HS-P-Z5 has higher intensity of characteristic diffraction peaks,more micropore structures and acid content than IM-P-Z5.The results of water washing experiment and NMR characterization show that HS-P-Z5 has more stable phosphorus and aluminum structures,and the phosphorus species are not easy to be washed away,making it more hydrothermal stable,and can retain more microporous structures and strong acid sites of zeolites after hydrothermal treatment.HS-P-Z5-ST(ST represents hydrothermal treatment)has the highest aromatics selectivity,with the aromatics selectivity of 23.1%at the reaction time of 730 min,higher than IM-P-Z5-ST(18.4%)and Z5-ST(11.2%).

曹健;郝坤;邢梦姣;王飞;陶智超;杨勇;相宏伟;李永旺

中国科学院 山西煤炭化学研究所 煤炭高效低碳利用全国重点实验室,山西 太原 030001||中国科学院大学,北京 100049中科合成油技术股份有限公司,北京 101400中国科学院 山西煤炭化学研究所 煤炭高效低碳利用全国重点实验室,山西 太原 030001中国科学院 山西煤炭化学研究所 煤炭高效低碳利用全国重点实验室,山西 太原 030001||中科合成油技术股份有限公司,北京 101400

化学工程

含磷ZSM-5分子筛晶种法芳构化水热稳定性

phosphorus-containing ZSM-5 zeolitesseeding methodaromatizationhydrothermal stability

《低碳化学与化工》 2024 (006)

87-94 / 8

中国科学院先导专项(XDA29030700).

10.12434/j.issn.2097-2547.20230295

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