Abstract
Copper nanoparticles on silica support are cheap and effective catalysts for dehydrogenation of n-butanol, a biomass-derived building block which is increasingly used. Ultrasonically assisted Cu catalysts are prepared, characterized, and tested for the conversion of n-butanol to n-butanal. The best performance in terms of overall conversion of n-butanol and selectivity to butanal was offered by ultrasound-prepared process of the Cu nanoparticles. In conventional wet impregnation method, Cu nanoparticles on the surface of support tend to aggregate in some sort of cubic aggregates with the size of 4–5 µm and because of this, the percentage of the centers of silica (on which intermolecular dehydration reactions occur) is higher compared to Cu metallic centers (that promotes the dehydrogenation reaction). The ultrasound reduction stage used in the preparation of catalysts provides a better coverage of the catalyst surface by Cu nanoparticles that have a more uniform dimension, which offers a greater selectivity to butanal (more than 95%) and a negligible selectivity to butene.
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Abbreviations
- (00):
-
Catalyst in simple form not exposed to pyridine
- B:
-
Brönsted
- B-Py:
-
Pyridine adsorbed on a Brönsted acid site
- CONV:
-
Conventional wet impregnated catalyst, 10%wt metal load
- Conv:
-
Conversion of n-butanol, %
- d BJH :
-
Average pore diameter computed by BJH from the desorption part of isotherm nm
- EDX:
-
Energy-dispersive X-ray
- FTIR:
-
Fourier transform infrared
- GHSV:
-
Gas hourly space velocity, s−1
- H-Py:
-
Pyridine adsorbed on a Brönsted-H type acid site
- L:
-
Lewis
- L-Py:
-
Pyridine adsorbed on a Lewis acid site
- m1 :
-
Mass of the unreacted n-butanol, mg
- m2 :
-
Mass of the n-butanol introduced in the system, mg
- m3 :
-
Mass of the n-butanal obtained, mg
- m4 :
-
Mass of the n-dibutyl ether obtained, mg
- mCAT :
-
Catalyst sample mass, g
- Mw1 :
-
Molecular weight of n-butanol, kg/kmol
- Mw2 :
-
Molecular weight of butanal, kg/kmol
- Mw3 :
-
Molecular weight of n-dibutyl ether, kg/kmol
- NA :
-
Avogadro’s number, sites/mol
- NPy :
-
Pyridine desorped from catalyst as a difference from the TGA curve for simple catalyst (00) and TGA curve for pyridine-exposed catalyst (Py), mol
- (Py):
-
Catalyst exposed to pyridine
- Py:
-
Pyridine
- S BET :
-
Specific surface area determined with BET method, m2/g
- Sel1 :
-
Selectivity to n-butanal (main product), %
- Sel2 :
-
Selectivity to n-dibutyl ether (secondary product), %
- Sel3 :
-
Selectivity to butene (secondary product), %
- SEM:
-
Scanning electron microscopy
- TGA:
-
Thermogravimetric analysis
- TPD:
-
Temperature programmed desorption
- V tp :
-
Total volume of pores, cm3/g
- UCu :
-
Uniformity with which the copper is distributed on the support surface
- US:
-
Ultrasound
- US10:
-
US impregnated catalyst, 10%wt metal load
- US20:
-
US impregnated catalyst, 20%wt metal load
- 2θ:
-
Diffraction angle
- ν:
-
FTIR wavenumber, cm−1
- Ψ:
-
Total surface acidity of the catalyst, sites/m2CAT
- BET:
-
Brunauer–Emmett–Teller
- BJH:
-
Barrett–Joyner–Halenda
- CAT:
-
Catalyst
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Acknowledgements
The authors acknowledge the financial support received from the mir, Action 1.1.4: Attracting high-level personnel from abroad in order to enhance the RD capacity, project: P_37_471, “Ultrasonic/Microwave Nonconventional Techniques as new tools for nonchemical and chemical processes,” financed by contract: 47/05.09.2016. The authors have no conflict of interest to declare that are relevant to the content of this article.
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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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Chisega-Negrilă, CG., Diacon, A., Călinescu, I. et al. On the ultrasound-assisted preparation of Cu/SiO2 system as a selective catalyst for the conversion of biobutanol to butanal. Chem. Pap. 76, 1443–1455 (2022). https://doi.org/10.1007/s11696-021-01945-9
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DOI: https://doi.org/10.1007/s11696-021-01945-9