Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts

doi:10.1016/S1381-1169(03)00368-6

Journal of Molecular Catalysis A: Chemical

Volume 203, Issues 1–2, 1 September 2003, Pages 267-275

https://doi.org/10.1016/S1381-1169(03)00368-6 Get rights and content

Abstract

The ultrafine Fe-doped Ni-B amorphous catalyst (Ni-Fe-B) was prepared by reducing mixed FeCl₃ and NiCl₂ with KBH₄ in aqueous solution. At suitable Fe-content (χ_Fe), the Ni-Fe-B amorphous catalyst exhibited much higher activity than the corresponding undoped Ni-B in the liquid phase hydrogenation of furfural (FFR) to furfuryl alcohol (FFA). With the increase of χ_Fe, the activity first increased and then decreased while the selectivity to FFA changed in a contrast way. The Fe-B amorphous alloy itself was inactive for the FFR hydrogenation. The optimum χ_Fe was determined as 0.51, at which the FFA yield reached 100% after reaction for 4 h. Based on various characterizations, the promoting effect of the Fe-dopant was discussed by considering (1) the increase in the surface area, more highly unsaturated Ni active sites, and the more homogeneous distribution of the Ni active sites owing to the presence of Fe₂O₃ as a dopant; (2) the affinity of the Fe³⁺ for the oxygen in the carbonyl group which strengthened the adsorption of the CO bond by the catalyst and thus facilitated its hydrogenation; (3) the electron donation of the metallic Fe to the metallic Ni, making Fe electron-deficient while Ni electron-enriched which activated the CO bond towards the hydrogenation.

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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 (χ_Fe), the Fe-doped Ni-B amorphous alloy catalyst exhibited higher activity and better selectivity to FFA during the liquid phase FFR hydrogenation. The optimum χ_Fe 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 CO bond by both the electron-deficient Fe and the Fe³⁺. Meanwhile, the electron-enrichment of the Ni active sites could also weaken the CO 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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Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts

Abstract

Introduction

Section snippets

Catalyst preparation

Results and discussion

Conclusions

Acknowledgments

J. Catal.

Appl. Catal. A: Gen.

Appl. Catal. A: Gen.

Appl. Catal. A: Gen.

Catal. Today

Stud. Surf. Sci. Catal.

J. Catal.

Appl. Catal. A: Gen.

J. Catal.

Appl. Surf. Sci.

Appl. Catal. A: Gen.

Appl. Catal. A: Gen.

J. Catal.

Appl. Catal. A: Gen.

J. Mol. Catal.

Catal. Lett.

Appl. Catal. A: Gen.