Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts
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Introduction
Catalytic hydrogenation of furfural (FFR) is an important industrial reaction since the product furfuryl alcohol (FFA) is widely used in polymers, fine chemicals, and farm chemicals [1], [2]. Gas phase hydrogenation is adopted in most companies, while in some countries, e.g. in China, liquid phase hydrogenation is also frequently employed [3], [4], [5], [6]. During the hydrogenation of FFR, various products may be produced, as shown in the following reaction route [3]:Obviously, the catalyst plays a key role in determining the selectivity to FFA [6]. Up to now, only a few catalysts have been reported for the FFR hydrogenation to FFA [3], [7], among them the Cu-Cr based catalysts are most frequently employed. The disadvantage of the Cu-Cr based catalysts is their high toxicity, which causes severe environmental pollution. The Ni-B amorphous alloy has been proved to be an excellent catalyst for many hydrogenating reactions [8], [9], [10], [11], [12], [13], [14], [15], [16]. However, it exhibits unsatisfactory activity and especially, the low selectivity to FFA when used in the FFR hydrogenation. It is well known that addition of a transition metal to form a bimetallic catalyst may improve both the activity and selectivity and even the stability during the hydrogenation [17]. This paper reports a novel Fe-promoted Ni-B amorphous catalyst (Ni-Fe-B) which seems powerful in the FFR hydrogenation to FFA.
Section snippets
Catalyst preparation
The Ni-Fe-B samples were prepared in the following procedure: at room temperature, 32 ml 2.0 M KBH4 aqueous solution containing 0.2 M NaOH was added dropwise within 2.0 h into 20 ml NiCl2 aqueous solution containing 1.0 g Ni and a certain amount of FeCl3. The KBH4 was greatly excessive to ensure the complete reduction of the metallic ions in the solution. During the addition of KBH4, the solution was stirred vigorously. After complete reaction, the resulting black solid was washed free from Cl− and K+
Results and discussion
Fig. 1 shows the HRTEM morphology of the as-prepared Ni-Fe-B sample, from which one can see that the Ni-Fe-B sample was present in the form of spherical particles with the average diameter around 30 nm. Those particles were surrounded by a large quantity of white gel-like substances. They could be attributed to both the boron and iron oxides which could be confirmed by XPS spectra, as discussed below. The XRD patterns, as shown in Fig. 2, revealed that all the fresh Ni-Fe-B samples were present
Conclusions
At suitable content of the Fe-dopant (χFe), the Fe-doped Ni-B amorphous alloy catalyst exhibited higher activity and better selectivity to FFA during the liquid phase FFR hydrogenation. The optimum χFe was determined as 0.51. The promoting effect of the Fe-dopant on the selectivity to FFA could be mainly attributed to the activation of the CO bond by both the electron-deficient Fe and the Fe3+. Meanwhile, the electron-enrichment of the Ni active sites could also weaken the CO bond by a back
Acknowledgments
This work was supported by the National Natural Science Foundation of China (29973025, G2000048009), the Natural Science Foundation of Shanghai Science and Technology Committee (00XD14019), and the Educational Department of P.R. China.
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