Bimetallic Ru:Ni/MCM-48 catalysts for the effective hydrogenation of d-glucose into sorbitol

doi:10.1016/j.apcata.2016.10.018

Applied Catalysis A: General

Volume 529, 5 January 2017, Pages 49-59

https://doi.org/10.1016/j.apcata.2016.10.018 Get rights and content

Highlights

•
Notable influence of the addition of different amounts of Ru to Ni/MCM-48.
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Ru:Ni ratios higher than 0.45 improved the catalytic behavior of Ni/MCM-48.
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Good stability of Ru:Ni/MCM-48 (0.45) was observed after three reaction cycles.
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Ru:Ni/MCM-48 enhanced selectivity of sorbitol in comparison with Ni/MCM-48.

Abstract

Three different bimetallic Ru:Ni catalysts supported on a mesoporous silica MCM-48 were prepared by consecutive wet impregnations, with a total metal loading of ca. 3% (w w⁻¹). Ru:Ni ratios spanned in the range of 0.15–1.39 (w w⁻¹) and were compared with the corresponding monometallic Ni/MCM-48. The catalysts so prepared were characterized by X-Ray Diffraction, Transmission Electron Microscopy, adsorption/desorption of N₂, Temperature Programmed Reduction, NH₃ − TPD and Atomic Absorption, and tested in the liquid phase hydrogenation of d-glucose into sorbitol in the temperature range 120–140 °C under 2.5 MPa of H₂ pressure. Bimetallic catalysts with Ru:Ni ratios higher than 0.45 enhanced the catalytic behavior of the monometallic Ni/MCM-48 in the reaction, increasing the reaction rate and showing complete selectivity to sorbitol by minimizing the production of mannitol. Ru:Ni/MCM-48 (0.45) was recovered from the reaction media and tested for three reaction cycles, showing good stability under the selected experimental conditions.

Graphical abstract

Introduction

Nowadays, environmental issues such as the poor management of fossil fuels, the depletion of crude-oil reserves and the global warming have promoted a major effort in the valorization of biomass in order to produce fuels, energy and fine chemicals [1]. Lignocellulosic biomass is one of the most promising renewable sources of carbon and it is the only one that can be converted into solid, liquid or gas fuels by thermochemical or biological processes [2]. Essentially, lignocellulosic materials comprise three main fractions, whose average composition is 34–50% cellulose, 19–34% hemicellulose and 11–30% lignin [3], [4] and it is a relatively low-priced source of biomass with a high availability all over the world. In this sense, hydrolytic hydrogenation of cellulose into sugar alcohols has attracted a lot of research interest [5], [6], [7], [8].

Catalytic hydrogenolysis of cellulose consists of two consecutive steps where firstly cellulose is hydrolyzed into d-glucose, which is subsequently hydrogenated into sugar alcohols like sorbitol and mannitol. Sorbitol is a versatile compound which has been used for many different applications, like building block for the synthesis of fine chemicals such as ascorbic acid (intermediate in the synthesis of Vitamin C) [9], [10], as additive in food, cosmetics and paper industries [2], and its annual production is about 700.000 tones/year [11]. Sorbitol is also used as feedstock for hydrolysis − hydrogenation processes in order to produce isosorbide and valuable polyols such as triols, tetrols, glycerol, ethylene glycol and 1,2-propanediol [12]. Most of the sorbitol processing at industrial scale is performed by catalytic hydrogenation of d-glucose, which is a cheap raw material produced from starch and sucrose [13], [14], using Raney–nickel catalysts [15]. Both noble metals (Ru, Rh, Pd and Pt) and non-noble metals (Fe, Ni, Cu or Co) have been used as active phases in hydrogenation reactions. Nickel–based catalysts have achieved a good piece of attention according to their low cost and moderate to good catalytic activity [16]. Nevertheless, nickel–based catalysts are susceptible to show deactivation after its recycling [2], [17], [18] due to leaching of the active nickel into the reaction media [19], sintering of the active metal [18], [20] and poisoning of metallic nickel surface attributed to organic byproducts of the reaction [21]. The current trend consists on the preparation of ruthenium–based catalysts, which show catalytic activities per mass of active metal 20–50 times higher in comparison with nickel [13]. However, the high price of noble metals is the main drawback. Thus, the development of novel bimetallic nickel-based catalysts with comparable high activity to noble metal catalysts still remains a technological challenge. Noteworthy efforts were carried out to enhance catalytic activity of nickel-based catalysts in the catalytic conversion of d-glucose into sorbitol. Hoffer et al. determined that the addition of Mo and Cr had a positive effect promoting Raney − Nickel catalysts activity and stability in the hydrolytic hydrogenation of d-glucose [17]. Bizhanov et al. studied the influence of noble metals such as Pt, Ru, Rh and Pd on Raney nickel catalysts and they observed that Ni/Ru was the most promising option [22]. In that case the catalytic material was an unsupported catalyst; however, to the best of our knowledge, supported Ni-Ru-based catalysts have never been tested in the hydrogenation of d-glucose. With this aim, we present the hydrogenation of d-glucose over bimetallic Ru:Ni catalysts, using MCM-48 as porous support, which has shown an excellent catalytic behavior in previous works [23], [24].

In the present work, we report the catalytic behavior of Ru:Ni-based bimetallic MCM-48 catalysts in comparison with monometallic Ni/MCM-48 for the selective hydrogenation of d-glucose into sorbitol. The influence of the addition of small amounts of ruthenium over Ni/MCM-48 in the catalytic activity is reported in this work.

Section snippets

MCM-48 preparation

MCM-48 has been prepared using a conventional hydrothermal synthesis, according to the procedure described by Schumacher et al. [25]. 2 g of n-Hexadecyltrimethylammonium bromide template (CH₃(CH₂)₁₅N(Br)(CH₃)₃ ≥ 98%, Sigma–Aldrich) was dissolved in 42 cm³ of deionized water, 13 cm³ of ammonium hydroxide (20% as NH₃, Panreac), and 18 cm³ of absolute ethanol (partially denaturated QP, Panreac). The resulting solution was stirred for 15 min and 4 cm³ of tetraethyl orthosilicate (TEOS, purity ≥ 99% GC,

Support characterization

Fig. S1(A) shows Small Angle X-Ray Scattering (SAXS) pattern of MCM-48. Calcined MCM-48 exhibits three main Bragg diffraction peaks in the 2θ range from 2 to 5°, that can be assigned to (211), (220) and (332) planes. These results are in good agreement with the high quality of mesoporous MCM-48, where the cubic phase belongs to a Ia3d space group symmetry [25], [27].

To study adsorption properties of calcined MCM-48 material, typical adsorption/desorption isotherms of N₂ at −196 °C were

Conclusions

As a result of the deposition of different amounts of Ru over Ni/MCM-48, significant differences were observed related to catalyst properties and thus in their behavior during hydrogenation of d-glucose in comparison with monometallic Ni/MCM-48. According to the results presented above, the following conclusions were obtained:

i)
The addition of different amounts of ruthenium over monometallic Ni/MCM-48 improved the reducibility of nickel and ruthenium species into their metallic state,

Acknowledgements

The authors gratefully acknowledge the Spanish Ministry, MINECO, and FEDER funds for the financial support of this project CTQ2015-64892-R (MINECO/FEDER). A. Romero thanks to the program of predoctoral scholarships from Junta de Castilla y León Government for his grant (E-47-2015-0062773).

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Bimetallic Ru:Ni/MCM-48 catalysts for the effective hydrogenation of d-glucose into sorbitol

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

MCM-48 preparation

Support characterization

Conclusions

Acknowledgements

App. Catal. A-Gen.

Catal. Today

J. Supercrit. Fluid.

Prog. Polym. Sci.

J. Fuel Chem. Technol.

Catal. Today

Biomass Bioenergy

App. Catal. A-Gen.

App. Catal. A-Gen.

App. Catal. A-Gen.

Catal. Today

Catal. Today

Catal. Today

App. Catal. A-Gen.

J. Catal.

J. Catal.

Microporous Mesoporous Mater.

Microporous Mesoporous Mater.

J. Colloid Interf. Sci.