多相催化时空演变的全生命周期表征策略

doi:10.1016/S1872-2067(20)63786-X

摘要/Abstract

摘要：

可持续发展的化学工业需要新型高效的催化材料和催化过程, 尤其需要生态友好、本质安全的新催化过程, 其本质是提高合适反应器内催化剂的选择性、活性和稳定性. 因此, 通过原位技术实时表征反应状态下的催化剂结构并同步测试催化性能, 有助于全面研究真实反应条件下催化剂及其表面物种随时间的演变过程, 深入理解催化剂构效关系的本质, 为开发新一代催化技术提供科学依据.

迄今, 在实际催化体系中实现催化剂从活化、运行到失活的全生命周期表征仍存在巨大挑战. 本文综述了分子筛、金属、金属氧化物三类典型催化剂在甲醇制烯烃、费托合成、丙烷脱氢等催化反应中的全生命周期时空演变, 分析了所采用的表征研究策略, 以期为新型工业催化的应用基础研究提供启示. 据文献报道, 甲醇制烯烃反应案例主要利用了原位紫外-可见光谱和固态核磁共振光谱等获得SAPO-34分子筛催化剂从诱导期、自催化期到失活期的表面烃池物种性质和动态演变; 费托合成反应案例主要利用了同步辐射X射线衍射计算机断层扫描和X射线吸收光谱等技术研究单个毫米级Co/γ-Al₂O₃催化剂颗粒在还原条件和费托合成条件下的催化剂结构演变; 丙烷脱氢反应案例主要结合原位的紫外-可见和拉曼光纤探头分析了CrO_x/Al₂O₃催化剂在700 ml固定床反应器中不同床层积炭的时空演变.

这些研究案例表明, 因受限于表征仪器的时空分辨率和适用工况, 多数重要的催化反应尚未完全实现工业条件下的全生命周期表征; 但通过合理简化非关键变量, 可以获得近似工业条件下的多相催化时空演变规律, 这些原位表征研究拓展了多相催化的新认识新发现. 着眼未来, 近似工业反应条件的原位表征、多尺度的原位表征装置设计、反应条件下的计算模拟等策略将在催化研发中发挥重要作用. 这些全生命周期表征策略反映了催化研究范式的转变, 但将其应用于工业实践仍面临许多科学和工程的挑战. 从实际应用角度看, 还需综合考虑原位表征技术的成本、安全性和准确性, 重视催化剂颗粒及反应器尺度的原位表征, 不断推进新型催化剂的研发.

关键词: 多相催化, 原位表征, 甲醇制烯烃, 费托合成, 丙烷脱氢

Abstract:

The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes, especially eco-friendly and intrinsically safe processes. The idea is to improve the selectivity, activity, and stability of the catalyst in an appropriate reactor. Therefore, it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance. This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions, deepening the understanding of the structure-performance relationship of catalysts, and providing a scientific basis for the development of future generation catalytic technology. Thus far, it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions. In this mini review, we summarize the characterization strategies for heterogeneous catalysts, using zeolite, metal, and metal oxide catalysts as typical examples. The research strategies for the approximation of industrial conditions, multi-scale in-situ characterization devices, and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.

Key words: Heterogeneous catalysis, In-situ characterization, Methanol-to-olefins, Fischer-Tropsch synthesis, Propane dehydrogenation

郑仁垟, 谢在库. 多相催化时空演变的全生命周期表征策略[J]. 催化学报, 2021, 42(12): 2141-2148.

Renyang Zheng, Zaiku Xie. Full life cycle characterization strategies for spatiotemporal evolution of heterogeneous catalysts[J]. Chinese Journal of Catalysis, 2021, 42(12): 2141-2148.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63786-X

https://www.cjcatal.com/CN/Y2021/V42/I12/2141

图/表 7

Fig. 1. An ideal device for full life cycle characterization, containing in-situ probes at specific positions to diagnose the operation level of the reactor and catalyst online. This is of great significance to adjust the real-time process conditions such as temperature, pressure, and reactant feed rate a, b, and c, respectively. Reprinted with permission from Ref. [11]. Copyright 2020 American Chemical Society.

Fig. 2. (a) Schematic of the in-situ device for monitoring the hydrocarbon pool species in the MTO reaction by UV-vis spectroscopy. Reprinted with permission from Ref. [27]. Copyright 2015 American Chemical Society. (b) Conversion and selectivity profiles as a function of methanol throughput and (c) corresponding time-resolved in-situ UV-vis spectra of the MTO reaction. The green, red, blue, and black spectra correspond to the induction period (methanol conversion < 100%), complete conversion period (methanol conversion of 100%), deactivation period (methanol conversion from 100% to 20%), and complete deactivation period (methanol conversion < 20%), respectively. Reaction conditions: WHSV 0.5 h?1, 400 °C. Reprinted with permission from Ref. [28]. Copyright 2017 American Chemical Society.

Fig. 3. (a) Schematic of a glass reactor cell with a 3 mm Co/γ-Al2O3 catalyst pellet for in-situ μ-XRD-CT/μ-PDF-CT characterization. (b) Compositional profile of the different cobalt phases obtained by combined 2D diffraction data. (c) Reconstructed 2D maps for the CoO phase composition during H2 reduction and the FT reaction on Co/γ-Al2O3. The color bar shows the weight percent of CoO, balanced by Co3O4 (150 °C) or metallic Co0 (≥ 310 °C and during the FT reaction). Reaction conditions: 450 °C, 0.1 MPa. Reprinted with permission from Ref. [37]. Copyright 2017 American Chemical Society.

Fig. 4. (a) Photograph and schematic of a 700 mL pilot-scale reactor for the in-situ characterization of PDH over CrOx/Al2O3 pellets. Two UV-vis probes and a Raman fiber probe were used for in-situ characterization of coke deposition on the catalyst bed under real reaction conditions. (b) The Raman intensity (blue) and reaction temperature (black) at the top and bottom of the catalyst bed during the first hour of the two dehydrogenation cycles. Reaction conditions: 550 °C, 0.15 MPa. Reprinted with permission from Ref. [46]. Copyright 2014 Wiley.

Table 1 Summary of the industrial reaction conditions, reaction conditions for characterization, and the features of the characterization techniques.

Typical case	Typical industrial reaction conditions	Characterization reaction conditions	Characterization technique features	Ref.
MTO	SAPO-34 catalyst, 350-500 °C, 0.05-0.3 MPa		Simultaneous monitoring of catalytic performance and surface carbon species by in-situ spectroscopies	[15,28]
MTO	WHSV ∼5 h^-1 a fluidized bed reactor	WHSV 0.5 h^-1, a fixed-bed quartz reactor (50 mg of 200-400 μm catalyst pellets)		[15,28]
FT	Co/Al₂O₃ catalyst, 200-250 °C		Structure evolution characterization of the catalyst pellet, rather than catalyst powder	[37,53]
FT	2-3 MPa a fixed-bed or slurry reactor	0.1 MPa, a quartz tubular reactor (a 3 mm cylindrical catalyst pellet)		[37,53]
PDH	CrO_x/Al₂O₃ catalyst, 550-600 °C		Monitoring the reaction and regeneration of the dehydrogenation catalyst in a pilot-scale reactor by in-situ probes	[45,46,48]
PDH	0.02-0.05 MPa parallel fixed-bed reactors	0.15 MPa, a 700 ml fixed-bed reactor (500 g of 3 mm-sized catalyst pellets)		[45,46,48]

Fig. 5. (a) Linear relationship between the amount of coke deposition and the frequency shift of the characteristic acoustic signal peak. The legends denote the test results at four different gas flow rates in the range of 0.08 to 0.12 m/s. (b) An industrial test device for the in-situ measurement of coke deposition based on acoustic emission signals collected by wave sensor equipment. Reprinted with permission from Ref. [62]. Copyright 2011 American Chemical Society.

Fig. 6. (a) Relationship between the surface free energies of the different facets and CO partial pressure at 227 °C. The numbers beside the curve represent the surface coverage. The yellow dotted line shows the surface energy of Co(100) when carbon deposition is considered. (b) The Wulff equilibrium shape of the Co particles at 227 °C under different CO partial pressures. The equilibrium CO coverages at 1 bar are shown in the inset. Reprinted with permission from Ref. [70]. Copyright 2019 American Chemical Society.

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