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使用负载型铜催化剂强化糠醛合成环戊酮

Intensifying Cyclopentanone Synthesis from Furfural Using Supported Copper Catalysts.

作者信息

Patil Adarsh, Engelbert van Bevervoorde Maurik, Neira d'Angelo Fernanda

机构信息

Sustainable Process Engineering Group, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands.

出版信息

ChemSusChem. 2025 Feb 16;18(4):e202401484. doi: 10.1002/cssc.202401484. Epub 2024 Nov 8.

DOI:10.1002/cssc.202401484
PMID:39340337
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11826132/
Abstract

This work addresses catalytic strategies to intensify the synthesis of cyclopentanone, a bio-based platform chemical and a potential SAF precursor, via Cu-catalyzed furfural hydrogenation in aqueous media. When performed in a single step, using either uniform or staged catalytic bed configuration, high temperature and hydrogen pressures (180 °C and 38 bar) are necessary for maximum CPO yields (37 and 49 %, respectively). Parallel furanic ring hydrogenation of furfural and polymerisation of intermediates, namely furfuryl alcohol (FFA), limit CPO yields. Employing a two step configuration with optimal catalyst bed can curb this limitation. First, the furanic ring hydrogenation can be suppressed by using milder conditions (i. e., 150 °C and 7 bar, and 14 seconds of residence time). Second, FFA hydrogenation using tandem catalysis, i. e., a mix of β-zeolite and Cu/ZrO, at 180 °C, 38 bar and 0.6, allows sufficient time for CPO formation and minimises polymerisation of FFA, thereby resulting in 60 % CPO yield. Therefore, this work recommends a split strategy to produce CPO from furfural. Such modularity may aid in addressing flexible market needs.

摘要

本工作探讨了通过在水相中进行铜催化的糠醛加氢反应来强化环戊酮合成的催化策略,环戊酮是一种生物基平台化学品和潜在的可持续航空燃料(SAF)前体。当采用单步反应,无论是使用均匀催化床配置还是分段催化床配置时,为了获得最高的环戊酮产率(分别为37%和49%),都需要高温和高压氢气(180°C和38巴)。糠醛的呋喃环平行加氢以及中间体糠醇(FFA)的聚合反应限制了环戊酮的产率。采用具有最佳催化床的两步配置可以克服这一限制。首先,可以通过使用较温和的条件(即150°C和7巴,停留时间为14秒)来抑制呋喃环加氢。其次,在180°C、38巴和0.6的条件下,使用串联催化(即β-沸石和Cu/ZrO的混合物)对FFA进行加氢反应,这为环戊酮的形成留出了足够的时间,并使FFA的聚合反应最小化,从而使环戊酮产率达到60%。因此,本工作推荐了一种从糠醛生产环戊酮的分步策略。这种模块化方式可能有助于满足灵活的市场需求。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/c2e486e72685/CSSC-18-e202401484-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/169c805f4903/CSSC-18-e202401484-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/ebf8971c96c2/CSSC-18-e202401484-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/81c0fa5ace83/CSSC-18-e202401484-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/a8c208633a90/CSSC-18-e202401484-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/45adf6bdd2a2/CSSC-18-e202401484-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/4cfbc6c2d2dc/CSSC-18-e202401484-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/cc4909abc374/CSSC-18-e202401484-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/c2e486e72685/CSSC-18-e202401484-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/169c805f4903/CSSC-18-e202401484-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/ebf8971c96c2/CSSC-18-e202401484-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/81c0fa5ace83/CSSC-18-e202401484-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/a8c208633a90/CSSC-18-e202401484-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/45adf6bdd2a2/CSSC-18-e202401484-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/4cfbc6c2d2dc/CSSC-18-e202401484-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/cc4909abc374/CSSC-18-e202401484-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d7a8/11826132/c2e486e72685/CSSC-18-e202401484-g007.jpg

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本文引用的文献

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Furfural to Cyclopentanone - a Search for Putative Oligomeric By-products.糠醛制环戊酮——寻找可能的低聚副产物
ChemSusChem. 2024 Jun 24;17(12):e202400108. doi: 10.1002/cssc.202400108. Epub 2024 Mar 1.
2
Production of cyclopentanone from furfural over Ru/C with AlPO and application in the synthesis of diesel range alkanes.在Ru/C与磷酸铝(AlPO)存在下由糠醛制备环戊酮及其在柴油馏分烷烃合成中的应用
RSC Adv. 2018 Nov 12;8(66):37993-38001. doi: 10.1039/c8ra08757a. eCollection 2018 Nov 7.
3
Efficient synthesis of C fuel precursor by heterogeneously catalyzed aldol-condensation of furfural with cyclopentanone.
通过糠醛与环戊酮的多相催化羟醛缩合高效合成C燃料前驱体。
RSC Adv. 2019 Jan 28;9(7):3661-3668. doi: 10.1039/c8ra09517e. eCollection 2019 Jan 25.
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Hydrogenation of Furfural to Cyclopentanone under Mild Conditions by a Structure-Optimized Ni-NiO/TiO Heterojunction Catalyst.在温和条件下通过结构优化的 Ni-NiO/TiO 异质结催化剂将糠醛加氢转化为环戊酮。
ChemSusChem. 2020 Oct 21;13(20):5507-5515. doi: 10.1002/cssc.202001424. Epub 2020 Aug 28.
5
Single-Pot Reductive Rearrangement of Furfural to Cyclopentanone over Silica-Supported Pd Catalysts.硅胶负载钯催化剂上糠醛单釜还原重排制环戊酮
ACS Omega. 2018 Aug 24;3(8):9860-9871. doi: 10.1021/acsomega.8b00980. eCollection 2018 Aug 31.
6
Sibunit-Supported Mono- and Bimetallic Catalysts Used in Aqueous-Phase Reforming of Xylitol.用于木糖醇水相重整的西布尼特负载的单金属和双金属催化剂。
Ind Eng Chem Res. 2018 Feb 14;57(6):2050-2067. doi: 10.1021/acs.iecr.7b04937. Epub 2018 Jan 25.