Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides
Higher alcohols like 1-butanol are considered important biofuels with superior properties compared to the more readily available bio-ethanol. An attractive route to prepare 1-butanol from ethanol is the Guerbet reaction. We here report the use of hydrotalcite-derived mono- (Cu-PMO or Ni-PMO) and bi-...
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| Format: | Article |
| Language: | English |
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MDPI AG
2020-09-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/10/9/996 |
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| author | Xiao-Ying Xi Zhuo-Hua Sun Hua-Tang Cao Yu-Tao Pei Gert H. ten Brink Peter J. Deuss Katalin Barta Hero J. Heeres |
| author_facet | Xiao-Ying Xi Zhuo-Hua Sun Hua-Tang Cao Yu-Tao Pei Gert H. ten Brink Peter J. Deuss Katalin Barta Hero J. Heeres |
| author_sort | Xiao-Ying Xi |
| collection | DOAJ |
| description | Higher alcohols like 1-butanol are considered important biofuels with superior properties compared to the more readily available bio-ethanol. An attractive route to prepare 1-butanol from ethanol is the Guerbet reaction. We here report the use of hydrotalcite-derived mono- (Cu-PMO or Ni-PMO) and bi-metallic (CuNi-PMO) porous metal oxide catalysts for the Guerbet coupling of ethanol to 1-butanol in a continuous flow reactor (320 °C, 0.1 MPa, LHSV = 15 mL g<sup>−1</sup> h<sup>−1</sup>) at extended times on stream (~160 h). Two distinct regimes with different product distributions were observed for the Cu-PMO and CuNi-PMO catalyst with time on stream. At the start of the run, the initial conversion of ethanol dropped from about 85% to less than 20% after 60 h and acetaldehyde was the main product (regime 1). At prolonged times on stream (60–160 h), fairly constant low conversions of ethanol (14%) were observed and 1-butanol was the main product (regime 2). Performance of the monometallic Cu-PMO catalyst in terms of 1-butanol yield and stability was lower compared to the bi-metallic CuNi-PMO. Detailed catalyst characterization studies (XRD, H<sub>2</sub>-TPR, sorption of acrylic acid, TGA, TEM, HAADF-STEM, and EDS mapping) on both fresh and spent CuNi-PMO taken at various times on stream was performed to determine the changes in catalyst morphology and composition during a run, and particularly to obtain information on changes in catalyst structure operating in regime 1 or 2. The change in chemoselectivity is in line with an increase in basicity of the catalyst at extended runtimes. |
| first_indexed | 2024-03-10T16:39:34Z |
| format | Article |
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| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T16:39:34Z |
| publishDate | 2020-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-359d201f90cc4895955c15898bc83bf42023-11-20T12:09:36ZengMDPI AGCatalysts2073-43442020-09-0110999610.3390/catal10090996Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal OxidesXiao-Ying Xi0Zhuo-Hua Sun1Hua-Tang Cao2Yu-Tao Pei3Gert H. ten Brink4Peter J. Deuss5Katalin Barta6Hero J. Heeres7Green Chemical Reaction Engineering, Engineering and Technology Institute Groningen, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsStratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsDepartment of Advanced Production Engineering, Engineering and Technology Institute Groningen, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG Groningen, The NetherlandsDepartment of Advanced Production Engineering, Engineering and Technology Institute Groningen, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747AG Groningen, The NetherlandsZernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, the NetherlandsGreen Chemical Reaction Engineering, Engineering and Technology Institute Groningen, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsStratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsGreen Chemical Reaction Engineering, Engineering and Technology Institute Groningen, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsHigher alcohols like 1-butanol are considered important biofuels with superior properties compared to the more readily available bio-ethanol. An attractive route to prepare 1-butanol from ethanol is the Guerbet reaction. We here report the use of hydrotalcite-derived mono- (Cu-PMO or Ni-PMO) and bi-metallic (CuNi-PMO) porous metal oxide catalysts for the Guerbet coupling of ethanol to 1-butanol in a continuous flow reactor (320 °C, 0.1 MPa, LHSV = 15 mL g<sup>−1</sup> h<sup>−1</sup>) at extended times on stream (~160 h). Two distinct regimes with different product distributions were observed for the Cu-PMO and CuNi-PMO catalyst with time on stream. At the start of the run, the initial conversion of ethanol dropped from about 85% to less than 20% after 60 h and acetaldehyde was the main product (regime 1). At prolonged times on stream (60–160 h), fairly constant low conversions of ethanol (14%) were observed and 1-butanol was the main product (regime 2). Performance of the monometallic Cu-PMO catalyst in terms of 1-butanol yield and stability was lower compared to the bi-metallic CuNi-PMO. Detailed catalyst characterization studies (XRD, H<sub>2</sub>-TPR, sorption of acrylic acid, TGA, TEM, HAADF-STEM, and EDS mapping) on both fresh and spent CuNi-PMO taken at various times on stream was performed to determine the changes in catalyst morphology and composition during a run, and particularly to obtain information on changes in catalyst structure operating in regime 1 or 2. The change in chemoselectivity is in line with an increase in basicity of the catalyst at extended runtimes.https://www.mdpi.com/2073-4344/10/9/996ethanol1-butanolGuerbet reactionporous metal oxidescatalyst deactivation |
| spellingShingle | Xiao-Ying Xi Zhuo-Hua Sun Hua-Tang Cao Yu-Tao Pei Gert H. ten Brink Peter J. Deuss Katalin Barta Hero J. Heeres Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides Catalysts ethanol 1-butanol Guerbet reaction porous metal oxides catalyst deactivation |
| title | Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides |
| title_full | Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides |
| title_fullStr | Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides |
| title_full_unstemmed | Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides |
| title_short | Catalyst Performance Studies on the Guerbet Reaction in a Continuous Flow Reactor Using Mono- and Bi-Metallic Cu-Ni Porous Metal Oxides |
| title_sort | catalyst performance studies on the guerbet reaction in a continuous flow reactor using mono and bi metallic cu ni porous metal oxides |
| topic | ethanol 1-butanol Guerbet reaction porous metal oxides catalyst deactivation |
| url | https://www.mdpi.com/2073-4344/10/9/996 |
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