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Structured microreactor with gold and palladium on titania: Active, regenerable and durable catalyst coatings for the gas-phase partial oxidation of 1-butanol
Applied Catalysis A: General ( IF 5.5 ) Pub Date : 2018-06-06 , DOI: 10.1016/j.apcata.2018.06.010
Yaseen Khan , Minna Marin , Tiia Viinikainen , Juha Lehtonen , Riikka L. Puurunen , Reetta Karinen

Structured microreactors coated with catalytically active porous layers have emerged as a promising replacement for conventional reactors because they are inherently safe to operate in nearly isothermal conditions within the kinetic regime. Bio-based 1-butanol is commonly produced by acetone-butanol-ethanol (ABE) fermentation and is considered an important platform chemical that will benefit in the share of value-added chemicals through the development of new catalytic processes. In this study, monometallic gold (Au) and palladium (Pd), as well as bimetallic Au-Pd nanoparticles, supported on titania (TiO2) were prepared by a sol-immobilization method, characterized, coated on structured microreactor plates and tested for their catalytic activity in the gas-phase partial oxidation of 1-butanol to n-butyraldehyde. A customized structured catalyst testing microreactor was used. The average noble metal particle size for the catalyst coatings was determined to be approximately 3.6 nm for Au and Au-Pd catalysts, and the noble metal nanoparticles were evenly distributed. The catalyst coating was 17 ± 7 μm in thickness. The studied coated catalysts (TiO2, Au/TiO2, Pd/TiO2, and Au-Pd/TiO2) were all active for the partial oxidation of 1-butanol. The Au/TiO2 (0.6 wt%) catalyst showed the highest yield (20%) of n-butyraldehyde at 300 °C. The introduction of Pd onto Au/TiO2 or TiO2 shifted the product distribution at 250 °C towards retro-hydroformylation and oxidation products (propene, carbon monoxide and carbon dioxide). All of the coated catalysts that were tested were mechanically stable. The nano Au/TiO2 could be regenerated in situ and showed reproducible activities and yields in over 50 test runs. Structured microreactors coated with gold nanoparticles supported on titania show promise as a reusable and mechanically stable device for the process development of n-butyraldehyde production in ABE fermentation plants.



中文翻译:

二氧化钛上具有金和钯的结构化微反应器:活性,可再生且耐用的催化剂涂层,用于1-丁醇的气相部分氧化

涂覆有催化活性多孔层的结构化微反应器已成为常规反应器的有前途的替代品,因为它们在动力学范围内的几乎等温条件下固有地安全运行。生物基1-丁醇通常是通过丙酮-丁醇-乙醇(ABE)发酵生产的,被认为是一种重要的平台化学品,将通过开发新的催化工艺而受益于增值化学品的份额。在这项研究中,通过溶胶固定法制备了负载在二氧化钛(TiO 2)上的单金属金(Au)和钯(Pd)以及双金属Au-Pd纳米颗粒,对其进行了表征,涂覆在结构化微反应器板上并进行了测试。在1-丁醇气相部分氧化为n时的催化活性-丁醛。使用定制的结构化催化剂测试微反应器。对于Au和Au-Pd催化剂,确定催化剂涂层的平均贵金属粒度为约3.6nm,并且贵金属纳米颗粒均匀地分布。催化剂涂层的厚度为17±7μm。所研究的涂层催化剂(TiO 2,Au / TiO 2,Pd / TiO 2和Au-Pd / TiO 2)对1-丁醇的部分氧化均具有活性。在300°C时,Au / TiO 2(0.6 wt%)催化剂显示出最高的丁醛收率(20%)。将Pd引入Au / TiO 2或TiO 2上将产物在250°C下的分布向逆向加氢甲酰化和氧化产物(丙烯,一氧化碳和二氧化碳)转移。所有被测试的涂覆催化剂都是机械稳定的。纳米Au / TiO 2可以原位再生,并在50多次试验中显示出可重现的活性和产率。二氧化钛负载的金纳米颗粒包覆的结构化微反应器有望成为ABE发酵厂生产丁醛工艺开发中可重复使用且机械稳定的装置。

更新日期:2018-06-06
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