甘油氢解反应中Pt/WO3/Al2O3催化剂的失活行为

doi:10.1016/S1872-2067(20)63549-5

催化学报 ›› 2020, Vol. 41 ›› Issue (8): 1261-1267.DOI: 10.1016/S1872-2067(20)63549-5

甘油氢解反应中Pt/WO₃/Al₂O₃催化剂的失活行为

雷念^a,b, 苗治理^a, 刘菲^a, 王华^a, 潘晓丽^a, 王爱琴^a, 张涛^a

a 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023;
b 中国科学院大学, 北京 100049

收稿日期:2019-11-15 修回日期:2019-12-19 出版日期:2020-08-18 发布日期:2020-08-08
通讯作者: 王爱琴
基金资助:
国家重点基础研究发展计划（2018YFB1501600）；国家自然科学基金（21690080，21690084，21721004，21673228）；中国科学院战略性先导科技专项（XDB17020100）；中国科学院洁净能源创新研究院合作基金（DNL180303）；中国科学院大连化学物理研究所自主部署青年基金（DICP ZZBS 201612）.

Understanding the deactivation behavior of Pt/WO₃/Al₂O₃ catalyst in the glycerol hydrogenolysis reaction

Nian Lei^a,b, Zhili Miao^a, Fei Liu^a, Hua Wang^a, Xiaoli Pan^a, Aiqin Wang^a, Tao Zhang^a

a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, PR China

Received:2019-11-15 Revised:2019-12-19 Online:2020-08-18 Published:2020-08-08
Supported by:
This work was supported by the National Key Projects for Fundamental Research and Development of China (2018YFB1501600), the National Natural Science Foundation of China (21690080, 21690084, 21721004, 21673228), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), DNL Cooperation Fund (DNL180303), CAS and DICP ZZBS 201612.

摘要/Abstract

摘要： 随着生物柴油产业的高速发展，其副产物甘油大量过剩，亟需寻找高效的甘油高值化利用途径来提高整个生物柴油产业链的经济性.在各种甘油转化路线中，甘油选择性氢解制备1，3-丙二醇可用作高端聚酯PTT的单体，因而成为最具应用潜力的高质化路线之一.同时，该反应涉及到仲羟基的选择性脱除，对其它生物质加氢脱氧反应也具有普遍意义.目前，在提高甘油氢解反应活性和1，3-丙二醇选择性方面已经做了大量的研究工作，但是关于催化剂稳定性的研究却鲜有报道，而后者对于整个过程的工业应用是必不可少的.鉴于此，我们以Pt/WO₃/Al₂O₃为催化剂，在连续运行的固定床反应器上对其甘油氢解反应的长期稳定性以及其失活的机理进行了详细的考察.
Pt/WO₃/Al₂O₃催化剂表现出较高的初始活性：甘油的转化率为57.5%，目标产物1，3-丙二醇的选择性可达40.4%，主要副产物1，2-丙二醇、正丙醇和异丙醇的选择性分别为6.3%，37.3%和11.5%.在长达700 h的稳定性测试中，Pt/WO₃/Al₂O₃催化剂呈现缓慢失活的趋势：甘油转化率从57.5%下降到25.1%，而1，3-丙二醇选择性基本不变.通过对失活曲线进行拟合可以得出催化剂的失活呈现三个阶段：第一阶段内（0-100h）催化剂的失活速率最快，甘油转化率由57.5%降至44.9%，失活速率为0.111%/h；第二阶段内（100-600h）催化剂的失活明显变缓，失活速率降至0.037%/h；第三阶段内（600-700h）甘油转化率基本保持不变.
N₂物理吸附、电感耦合等离子体原子发射光谱、热重和程序升温氧化等表征结果显示，活性组分（铂，氧化钨）的流失或积炭都不是催化剂失活的主要原因.同时X射线衍射、高角环形暗场扫描透射电子显微镜和CO化学吸附等表征结果表明，反应过程中Pt/WO₃/Al₂O₃催化剂上Pt颗粒发生了明显的聚集长大，使得Pt的分散度由29.1%降至10.1%.仲丁醇脱水/脱氢探针反应的结果显示，稳定性测试后催化剂在氢气气氛下产生原位B酸的能力显著降低.由此可以得出，反应过程中Pt/WO₃/Al₂O₃催化剂失活的主要原因是催化剂表面Pt颗粒的聚集长大，因而引起催化剂加氢能力的降低，同时Pt-WO_x界面位点的数量下降，使得在氢气气氛下催化剂产生原位B酸的能力大大降低，从而导致了催化剂的失活.

关键词: 甘油, 氢解, 1, 3-丙二醇, 失活, 聚集

Abstract: The selective hydrogenolysis of glycerol to 1,3-propanediol is a highly important reaction for both improving the profitability of biodiesel and valorization of biomass. While intensive research efforts have been devoted to enhancing the catalytic activity and selectivity, little is focused on the stability although the latter is of paramount importance to practical applications. In this work, we investigated the stability of Pt/WO₃/Al₂O₃ and observed a continuous deactivation trend during a 700 h time-on-stream run. Neither the leaching of active W nor the coking was responsible for the deactivation. Instead, XRD, HAADF-STEM and CO chemisorption results clearly showed the occurrence of significant aggregation of Pt particles, which caused a remarkable decrease of Pt-WO_x interfacial sites. As a consequence, strong Brönsted acid sites which were in situ formed by H₂ dissociation at the Pt-WO_x interfacial sites were reduced, leading to the deactivation of the catalyst.

Key words: Glycerol, Hydrogenolysis, 1,3-propanediol, Deactivation, Aggregation/agglomeration

雷念, 苗治理, 刘菲, 王华, 潘晓丽, 王爱琴, 张涛. 甘油氢解反应中Pt/WO₃/Al₂O₃催化剂的失活行为[J]. 催化学报, 2020, 41(8): 1261-1267.

Nian Lei, Zhili Miao, Fei Liu, Hua Wang, Xiaoli Pan, Aiqin Wang, Tao Zhang. Understanding the deactivation behavior of Pt/WO₃/Al₂O₃ catalyst in the glycerol hydrogenolysis reaction[J]. Chinese Journal of Catalysis, 2020, 41(8): 1261-1267.

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甘油氢解反应中Pt/WO₃/Al₂O₃催化剂的失活行为

Understanding the deactivation behavior of Pt/WO₃/Al₂O₃ catalyst in the glycerol hydrogenolysis reaction

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