CO2消除镓氢物种提升Ga2O3/SiO2丙烷脱氢反应性能

doi:10.1016/S1872-2067(21)63900-1

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2225-2233.DOI: 10.1016/S1872-2067(21)63900-1

CO₂消除镓氢物种提升Ga₂O₃/SiO₂丙烷脱氢反应性能

刘怡^a, 张光辉^a^,^*(), 王建洋^a, 朱杰^a, 张新宝^a, Jeffrey T. Miller^b, 宋春山^a^,^c^,^#(), 郭新闻^a^,^$()

^a大连理工大学化工学院宾州-大连联合能源研究中心, 精细化工国家重点实验室, 辽宁大连116024, 中国
^b普渡大学戴维森化学工程学院, 印第安纳州, 美国
^c香港中文大学理学院化学系, 新界沙田, 香港中国

收稿日期:2021-01-04 接受日期:2021-01-04 出版日期:2021-12-18 发布日期:2021-09-10
通讯作者: 张光辉,宋春山,郭新闻
基金资助:
国家自然科学基金(21902019);国家重点研发计划(2016YFB0600902-4);中央高校基本科研业务费(DUT20RC(5)002);辽宁省兴辽英才计划项目

Promoting propane dehydrogenation with CO₂ over Ga₂O₃/SiO₂ by eliminating Ga-hydrides

Yi Liu^a, Guanghui Zhang^a^,^*(), Jianyang Wang^a, Jie Zhu^a, Xinbao Zhang^a, Jeffrey T. Miller^b, Chunshan Song^a^,^c^,^#(), Xinwen Guo^a^,^$()

^aState Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^bDavidson School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, IN 47907, United States
^cDepartment of Chemistry, Faculty of Science, the Chinese University of Hong Kong, Shatin, NT, Hong Kong, China

Received:2021-01-04 Accepted:2021-01-04 Online:2021-12-18 Published:2021-09-10
Contact: Guanghui Zhang,Chunshan Song,Xinwen Guo
About author:$ E-mail: guoxw@dlut.edu.cn
# E-mail: chunshansong@cuhk.edu.hk;
* E-mail: gzhang@dlut.edu.cn;
Supported by:
This work was supported by National Natural Science Foundation of China(21902019);National Key Research and Development Program of China(2016YFB0600902-4);Fundamental Research Funds for the Central Universities(DUT20RC(5)002);LiaoNing Revitalization Talents Program(XLYC 2008032)

摘要/Abstract

摘要：

丙烯是一种基础石油化工原料, 在全球石油化工生产中占有重要地位. 以丙烯为原料可生产许多石油化学品, 如丙烯腈、环氧丙烷和聚丙烯等. 经济快速发展带动了丙烯下游衍生物产业的发展, 进而增加了对丙烯的需求量, 因此尽管近年来丙烯产能逐年上升, 丙烯产量与需求量之间仍存在较大缺口. 传统的丙烯生产路径主要是石脑油蒸汽裂解和重质油催化裂化. 然而, 随着石油资源的短缺和页岩气的发展, 丙烷脱氢作为一种直接生产丙烯的技术, 成为丙烯生产领域的研究热点. 近年来, 镓基催化剂由于其较少的积碳和较高的催化活性受到了越来越多的关注. 镓基催化剂在丙烷脱氢反应中的活性位点也得到了更多研究.

在镓基催化剂中, 镓氧化物具有丙烷脱氢活性, 而丙烷脱氢反应过程中产生的镓氢(Ga^δ⁺-H_x)物种不稳定, 且会造成丙烯选择性降低, 导致丙烯产率降低. 因此, 反应过程中原位消除镓氢物种对于提高丙烷脱氢反应性能具有非常重要的意义. 本文将CO₂作为温和氧化剂引入Ga₂O₃/SiO₂催化的丙烷脱氢反应中, 促进不利的中间产物Ga^δ⁺-H_x的转化, 再生丙烷脱氢的活性位点Ga³⁺-O, 从而提高催化性能. 原位红外光谱实验结果表明, CO₂可有效消除Ga^δ⁺-H_x. 在不同反应温度下, 引入CO₂可显著提高Ga₂O₃/SiO₂催化丙烷脱氢的转化率, 特别是选择性. 反应4.5 h时, 3Ga₂O₃/SiO₂催化丙烷脱氢的选择性从93%降低到89%; 引入CO₂后, 丙烯选择性可提高到并维持在93%. Ga₂O₃负载量由3 wt%提高到10 wt%时, 引入CO₂仍可促进反应性能. 当CO₂:C₃H₈由0.5增加到3时, 引入CO₂带来的反应性能提升基本相同. 同时, 引入CO₂大大减少反应过程中产生的积碳. 本文对镓基催化剂丙烷脱氢活性中心的认识和提高丙烷脱氢反应性能提供了新方向.

关键词: Ga氢化物, Ga₂O₃, CO₂, 丙烷脱氢, 原位红外光谱

Abstract:

Due to the shortage supply of propylene and the development of shale gas, there is increased interest in on-purpose propane dehydrogenation (PDH) technology for propylene production. Ga-based catalysts have great potential in PDH, due to the high activity, low carbon deposit and deactivation. Ga-hydrides formed during PDH reduce the rate, selectivity and yield of propylene. In this contribution, CO₂ is introduced into PDH as a soft oxidant to eliminate the unfavorable intermediate species Ga^δ⁺-H_x re-generating Ga³⁺-O pairs, and also minimize coke deposition thereby improving the catalytic performance. In situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy experiments show that CO₂ can effectively eliminate Ga^δ⁺-H_x. At different temperatures, co-feeding CO₂ during PDH over Ga₂O₃/SiO₂ catalysts with different loadings significantly improves the stability of the conversion and selectivity, especially the latter, and provide a new dimension for improving the performance of PDH process.

Key words: Ga-hydrides, Ga₂O₃, CO₂, Propane dehydrogenation, In situ DRIFT

刘怡, 张光辉, 王建洋, 朱杰, 张新宝, Jeffrey T. Miller, 宋春山, 郭新闻. CO₂消除镓氢物种提升Ga₂O₃/SiO₂丙烷脱氢反应性能[J]. 催化学报, 2021, 42(12): 2225-2233.

Yi Liu, Guanghui Zhang, Jianyang Wang, Jie Zhu, Xinbao Zhang, Jeffrey T. Miller, Chunshan Song, Xinwen Guo. Promoting propane dehydrogenation with CO₂ over Ga₂O₃/SiO₂ by eliminating Ga-hydrides[J]. Chinese Journal of Catalysis, 2021, 42(12): 2225-2233.

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图/表 12

Fig. 1. XRD patterns and propane dehydrogenation performance of Ga2O3/SiO2 with different Ga loadings. (a) XRD patterns; (b) Propane conversion; (c) Propylene selectivity. Reaction conditions: 600 °C, P = 0.05 MPa, GHSV (gas hourly space velocity) = 3900 mL/g/h.

Fig. 2. (a) The amount of carbon deposition on 3Ga2O3/SiO2 and (b) C3H6 yield vs. TOS. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Fig. 3. (a) The rate of C3H6 formation over 8Ga2O3/SiO2. Reaction conditions: 550 °C, 0.05 MPa, GHSV = 19500 mL/g/h, pre-treated in H2 at 650 °C for 1 h. (The C3H8 conversion ranges from 4% to 6%, below the equilibrium conversion of 32% at 550 °C [29].) (b) In situ DRIFT spectra during PDH at 550 °C after 50% H2/N2 pretreatment at 650 °C for 1 h. (c) Peak area of Ga-H (2035 cm?1) vs. time on stream. (d) MS profile obtained during propane dehydrogenation at 550 °C after 50% H2/N2 pretreatment at 650 °C for 1 h.

Fig. 4. In situ DRIFT spectra on Ga2O3. (a) During the treatment of H2; (b) during the treatment of N2 followed by CO2. Conditions: T = 600 °C, ambient pressure.

Fig. 5. In situ DRIFT spectra on 8Ga2O3/SiO2. H2 treatment for 1 h (black), H2 treatment followed by N2 treatment for 20 min (blue), H2 treatment followed by 5%CO2/N2 treatment for 20 min (red), H2 treatment followed by 20%CO2/N2 treatment for 20 min (pink). T = 600 °C, ambient pressure.

Fig. 6. (a) TPSR profiles of 8Ga2O3/SiO2; (b) In situ DRIFT spectra of 8Ga2O3/SiO2. H2 treatment for 1 h (black), H2 treatment followed by 5%CO2/Ar treatment for 20 min (red). T = 600 °C, ambient pressure.

Fig. 7. PDH performance of Ga2O3/SiO2 with different Ga loadings in the presence of CO2. (a) Propane conversion; (b) Propylene selectivity. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h, CO2:C3H8 = 1:1.

Fig. 8. HRTEM images of different samples. (a) Fresh 8Ga2O3/SiO2; (b) 8Ga2O3/SiO2 after PDH without CO2 for 4 h; (c) 8Ga2O3/SiO2 after PDH with CO2 for 4 h.

Fig. 9. (a) TGA profiles of Ga2O3/SiO2 after PDH with or without CO2 for 4 h. Dashed lines indicate the first derivatives of the weight loss curves of the same color; (b) Carbon balance during propane dehydrogenation. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Table 1 Carbon balance during propane dehydrogenation of Ga2O3/SiO2.

CO₂ introduction	3Ga₂O₃/SiO₂	5Ga₂O₃/SiO₂	8Ga₂O₃/SiO₂	10Ga₂O₃/SiO₂
CO₂:C₃H₈= 0:1	97%	92%	87%	86%
CO₂:C₃H₈= 1:1	98%	94%	92%	89%

Fig. 10. PDH performance of 3Ga2O3/SiO2. (a,b) Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h; (c,d) Reaction conditions: 627 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Fig. 11. (a) C3H8-IR spectra of 8Ga2O3/SiO2; (b) CO2-IR spectra of 8Ga2O3/SiO2.

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CO₂消除镓氢物种提升Ga₂O₃/SiO₂丙烷脱氢反应性能

Promoting propane dehydrogenation with CO₂ over Ga₂O₃/SiO₂ by eliminating Ga-hydrides

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