Green synthesis of heterogeneous copper-alumina catalyst for selective hydrogenation of pure and biomass-derived 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan

https://doi.org/10.1016/j.apcata.2020.117892Get rights and content

Highlights

  • Catalytic conversion of biomass-derived carbohydrates into bio-based chemicals.

  • Conversion of 5-hydroxymethylfurfural (5-HMF) to 2,5-bis(hydroxymethyl)furan (BHMF).

  • Copper-alumina catalysts were prepared through solvent-free solid-state grinding.

  • Optimized reaction conditions: 3 MPa H2, 130 °C, 1 h.

  • >99 % 5-HMF conversion and 93 % BHMF yield obtained.

Abstract

In this work novel copper-alumina catalysts were prepared through a solvent-free solid-state grinding method ― a low cost and green catalyst preparation method for selective hydrogenation of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(hydroxymethyl)furan (BHMF). Under the optimized reaction conditions (3 MPa H2, 130 °C, 1 h), >99 % 5-HMF conversion and 93 % BHMF yield were obtained by using a 20CA (20 mol%Cu-Al2O3) catalyst. The catalyst characterization results could reveal that the high catalytic activity and selectivity could be attributed to the presence of both metallic and electrophilic copper (Cu°/Cu2+) species and the uniformly distributed copper nanoparticles. Furthermore, an integrated catalytic process was demonstrated for the first time for direct conversion of mono, di, and polysaccharides into the corresponding BHMF, obtained overall BHMF yield in the range of 25 %–48 %.

Introduction

Due to the fast depletion of petroleum-based resources and the awareness of environmental problems triggered by the continuous consumption of fossil deposits, searching for new and alternative feedstocks to synthesize commodity chemicals, fuels, and polymers has attracted significant attention in the past few years [1,2]. Low cost, highly abundant, and carbon-neutral lignocellulosic biomass are considered an ideal feedstock for the synthesis of a variety of platform chemicals and useful industrial products [3]. 5-Hydroxymethylfurfural (5-HMF) is a versatile important platform chemical that can be synthesized directly from lignocellulosic biomass or biomass-derived C6-carbohydrates by the acid-catalyzed dehydration reaction [4,5]. The obtained 5-HMF can be used for the synthesis of various useful industrial chemicals e.g., 2,5-furandicarboxylic acid (FDCA) [6,7], hexanediol, 2,5-dimethylfuran, and 2,5-bis(hydroxymethyl)furan (BHMF) [4] by performing different types of chemical reactions such as oxidation and hydrogenation. For instance, 2,5-furandicarboxylic acid can replace the petroleum-derived terephthalic acid for the synthesis of bio-based polyethylenefuranoate (PET), which can be used for water bottles and packaging applications [8]. Also, 5-HMF can be used in the synthesis of phenol-hydroxymethyl furfural (PHMF), a green alternative to PF resins [9].

Since 5-HMF contains two types of functional groups such as Cdouble bondO and Cdouble bondC; however, hydrogenation of this molecule can produce different reaction products [10]. For example, the carbonyl group selective hydrogenation of 5-HMF can produce a diol - 2,5-bis(hydroxymethyl)furan (BHMF). BHMF can be used as an essential intermediate chemical for various potential industrial applications such as polymers, polyurethane foams, drugs, and other products of the fine chemical industry [10]. Traditionally, BHMF can be synthesized by the stoichiometric hydrogenation of 5-HMF in the presence of NaBH4 or LiAlH4 [11,12]. However, these reagents are moisture sensitive and generate much environmental waste. Alternatively, the catalytic hydrogenation of 5-HMF with hydrogen has been widely studied in recent years [10]. A homogeneous ruthenium-based dinuclear complex was found to be very active for the selective hydrogen of 5-HMF to BHMF, achieved 99 % BHMF yield under mild reaction conditions [13]. However, this catalyst is very expensive, difficult to recover and reuse, and hence has less industrial potential. Alternatively, heterogeneous catalysts that are simple to recover and can reuse for many catalytic cycles are more promising. In this regard, various supported heterogeneous noble metal (Ru, Pt, Pd, Au, Ir, and Re) based catalysts have been reported for selective hydrogenation of 5-HMF to BHMF [[14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25],26]. Although all these catalysts would show remarkable catalytic activity and selectivity, preparation of these metal catalysts' is very costly. Thus, the development of inexpensive and heterogeneous recyclable supported metal-based catalysts for selective hydrogenation of 5-HMF is highly desirable.

Copper-based heterogeneous catalysts are economical and selective catalysts for side-chain carbonyl group hydrogenation without affecting double bonds in 5-HMF molecule [10]. Cao et al. synthesized copper supported on silica (Cu/SiO2) catalyst for the selective hydrogenation of 5-HMF, obtained high BHMF yield after 8 h under 2.5 MPa H2 at 100 °C [27]. In another work, Lima et al. used a commercial Raney®-Cu catalyst for continuous flow hydrogenation of aqueous 5-HMF at 90 °C under 90 bar H2 pressure, attaining 94 % 5-HMF conversion and 84 % BHMF yield, respectively. In contrast, Raney ®-Ni catalyst was less selective under the same reaction conditions [28]. Hassan et al. synthesized bimetallic copper-iron oxide nanoparticles for selective hydrogenation of 5-HMF in the absence of external hydrogen at 150 °C for 5 h in ethanol solvent, and obtained 97 % 5-HMF conversion and 92 % BHMF yield, respectively [29]. Besides, various other heterogeneous copper-based catalysts have also been reported under different reaction conditions, achieving BHMF yields are in the range of 62–99 % [[30], [31], [32], [33]]. Even though all these catalysts were active for the synthesis of BHMF, most of the reported studies were focussed on hydrogenation of commercially available 5-HMF. Recently, an integrated catalytic process for direct conversion of fructose to BHMF was reported [34]. High BHMF yields were reported, whereas fructose is an expensive feedstock for large scale production of BHMF. Therefore, catalytic conversion of inexpensive biomass-derived carbohydrates into BHMF is highly attractive. It should be noted that most of the reported copper-based catalysts for hydrogenation of 5-HMF to BHMF were prepared through conventional precipitation or co-precipitation and impregnation methods, which not only are time consuming, but generate much environmental waste and involve multiple preparation steps. Accordingly, the development of heterogeneous supported copper catalyst prepared through a simple and greener solvent-free method is highly desirable for the selective hydrogenation of 5-HMF to BHMF.

Simple solid-state grinding synthesis of supported metal or metal oxide catalysts have attracted much attention in the past years [[35], [36], [37], [38], [39], [40], [41], [42]]. In this method, various heterogeneous catalysts were prepared through simple physical mixing of metal precursors followed by heat treatment. Interestingly, these catalysts demonstrated better catalytic performance than those prepared via the conventional wet chemistry route. We recently reported the solid-state synthesis of tin phosphate and Co-Mn mixed oxide catalysts [43,44], which also showed much better catalytic performance than the same catalysts prepared in a conventional precipitation method. Moreover, the main advantages of the solid-state grinding method are: it is quick, inexpensive, easy to scale up, and no waste is produced during the catalyst preparation. To the best of our knowledge, no report on the solid-state grinding synthesis of copper-alumina catalysts for selective hydrogenation of biomass-derived 5-HMF into BHMF.

Herein, we report synthesis of various copper-alumina (Cu-Al2O3) catalysts by the one-step solid-state grinding of copper and alumina precursors with oxalic acid followed by calcination and reduction. The as-synthesized catalysts were directly used for the selective hydrogenation of biomass-derived 5-HMF. The effects of various other reaction parameters such as catalyst support, copper loading, hydrogen pressure, solvent, reaction temperature, and time, and the influence of catalyst preparation methods were examined in this work to produce a high BHMF yield. Different catalyst characterization techniques were used to understand the structural properties of the catalysts and their catalytic activities. Additionally, a two-step integration method was demonstrated for direct conversion of simple and complex sugars into BHMF without isolation of the 5-HMF intermediate.

Section snippets

Materials

Reagent grade Al(NO3)3 9H2O, Cu(NO3)2 3H2O, oxalic acid, 5-hydroxymethylfurfural (99 %), glucose, microcrystalline cellulose, cellobiose, sucrose, starch, and 5-methylfurfural were all purchased from Sigma-Aldrich. Niobium phosphate hydrate (NbOPO4·nH2O) was supplied by CBMM (Companhia Brasileira de Metalurgia e Mineraçã). Ethanol, methanol, THF, Toluene, methyl isobutyl ketone (MIBK), Hexane, Water (HPLC grade), acetonitrile (HPLC grade) were obtained from Caledon Laboratories. All reagents

Results

Surface and structural properties of copper-alumina catalysts were characterized by BET, XRD, CO2 and NH3-TPD, H2-TPR, XPS, and HAADF-STEM techniques to gain insight into the structural characteristics of the catalyst materials.

Reaction mechanism

5-HMF contains reactive Cdouble bondC and Cdouble bondO functional groups; however, the bond energy of Cdouble bondO (715 kJ mol−1) is much higher than that of Cdouble bondC (615 kJ mol−1), allowing the hydrogenation of furan ring take place easier especially in the presence of a metal catalyst [76]. Nevertheless, owing to the conjugation of the carbonyl group with furan ring in a 5-HMF molecule, the selective hydrogenation of Cdouble bondO for the synthesis of BHMF could occur at the lower reaction temperature. Based on XPS results, the 20CA

Conclusions

In summary, stable and high-performance copper-alumina catalysts were prepared through a green and sustainable solvent-free solid-state grinding method. The catalysts showed superior performance than other heterogeneous catalysts reported in the literature (prepared generally by precipitation or co-precipitation methods) for selective hydrogenation of 5-HMF to BHMF. It could achieve catalytic activity and selectivity comparable to noble metal-based catalysts, but it is much less expensive. The

CRediT authorship contribution statement

Kasanneni Tirumala Venkateswara Rao: Methodology, Investigation, Formal analysis, Data curation, Visualization, Writing - original draft, Writing - review & editing. Yulin Hu: Investigation, Formal analysis, Writing - original draft. Zhongsun Yuan: Methodology. Yongsheng Zhang: Investigation, Validation. Chunbao Charles Xu: Conceptualization, Funding acquisition, Methodology, Project administration, Supervision, Validation, Writing - review & editing.

Declaration of Competing Interest

The authors report no declarations of interest.

Acknowledgments

The authors acknowledge the financial support from the Natural Sciences and Engineering Research Council of Canada (NSERC) through Discovery Grant and the Western Innovation Fund from Western University, as well as the Program of Processing and Efficient Utilization of Biomass Resources of Henan Centre for Outstanding Overseas Scientists (GZS2018004).

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