Elsevier

Fuel Processing Technology

Volume 138, October 2015, Pages 564-569
Fuel Processing Technology

Research article
Bio-derived fuel additives from furfural and cyclopentanone

https://doi.org/10.1016/j.fuproc.2015.06.036Get rights and content

Highlights

  • Simple synthesis of furan derived bis-cyclic ethers is described.

  • The ethers are suitable as diesel blending agents.

  • Catalytic process is conducted at very mild reaction conditions.

  • Hydrocarbons serve as proper solvents.

  • Crucial effect on selectivity has heterogeneous catalyst.

Abstract

Here, we describe a new method for highly selective catalytic hydrogenation of fully biomass-derived 2,5-bis(2-furylmethylidene)cyclopentan-1-one (F2C) to the corresponding bis-cyclic ethers. The study highlights that by the choice of heterogeneous catalyst and solvent from three kinds of double bonds present in the F2C molecule it is possible hydrogenate only one or both exocyclic Cdouble bondC bonds with selectivities 88 and 95%, respectively, or to obtain mono- or bis-cyclic ethers by saturation of Cdouble bondC bonds in furan rings. Using commercial palladium catalysts supported on activated carbon and hydrocarbons (cyclohexane, n-heptane) as the solvents complete saturation of all Cdouble bondC bonds can be achieved at very mild reaction conditions throughout 20 min in about 90% yield. The complete conversion of F2C and very similar selectivity and products distribution could be achieved after six catalytic runs without extra catalyst treatment or reactivation.

Introduction

The utilization of renewable resources for the preparation of transportation fuels has potential advantages in the reduction of our dependence on fossil resources. In recent years, the development of feasible processes to produce liquid fuels from non-petroleum resources attracted a lot of attention. These fuels have an existing infra-structure and can be utilized by vehicle engines with only a small modification. Biomass-derived fuel range hydrocarbons were prepared by catalytic conversion of C5 and C6 carbohydrates, levulinic acid, furfural or 5-hydroxymethyl furfural and their derivatives [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], by hydrodeoxygenation of condensation or alkylation products of furfural [7], [13] and 2-methylfuran [14], [15]. The biomass-derived precursors of fuels often have high oxygen content originating from hydroxyl, keto and ether groups. The oxygen is usually removed by a hydrodeoxygenation process through cleavage of C–O bonds. The objective of hydrodeoxygenation is to selectively remove oxygen from the molecule of the precursor without cleavage of C–C bonds. It can be achieved by using suitable bifunctional catalysts and operating conditions. The catalysts most frequently studied for hydrodeoxygenation of fuel precursors have been Pd, Pt, Ru, Ni, and Cu metals and metal carbides supported, e.g. on activated carbon, silica, silica-alumina, zeolites, zirconium phosphate, and niobium-based solid acids. The various production routes starting from furfural to various fuel additives were reviewed in the recent publication [16].

An aldol condensation between biomass-derived furanics and various aldehydes has been shown to be an effective way for the selective conversion of the smaller molecules to compounds containing 8–17 carbon atoms that are suitable for upgrading to diesel and jet fuel green components. In addition, during the C–C coupling reaction, oxygen is removed simultaneously. Previous studies on the hydrodeoxygenation of various types of aldol condensation products based on furfural and 4-hydroxymethylfurfural were focused to obtain completely hydrogenated products, i.e. fuel range straight or branched alkanes [17], [18], [19], [20], [21], [22], [23], [24], [25]. Hydrogenation/hydrodeoxygenation reactions occur in the presence of hydrogen (1–15 MPa) at temperatures of 130 to 300 °C with supported metal catalysts.

Adaptation of legislation to improve air quality by reducing emissions has also impact on specifications of diesel fuels. In this context, different oxygenated compounds as high quality products for diesel fuels have been investigated. For example, when the di-n-pentyl-ether is added to a diesel fuel, the blending cetane number, cold flow properties, and density are substantially improved and the ether is free from sulfur and aromatics [26]. Most recently, Bell and co-workers [27], [28] and Liu and Chen [29] reported an alternative for producing usable diesel-range fuels based on cyclic ethers formed through condensation and hydrogenation of biomass-derived furans. Molecules containing cyclic and acyclic ether moieties, in particular furans, have been demonstrated to have good characteristics; for example, cetane number, lubricity, density and energy density [28]. Therefore, based on published studies the high-quality diesel fuels can be formed without necessity of complete oxygen removal from biomass-derived furans. Since deoxygenation reaction involves consumption of large amounts of expensive hydrogen, the diesel blending agents can be produced more economically.

Recently, we have proposed the concept of synthesis of C15 and C17 diesel or jet fuel additives based on the cross-aldol condensation of biomass-derived cyclopentanone with furfural or 5-hydroxymethylfurfural (Scheme 1). These condensation reactions proceed very rapidly and highly selectively in diluted aqueous solutions of hydroxides (furfural:NaOH = 16:1 mol) at about 40 °C and 90 min; e.g. 2,5-bis(2-furylmethylidene)cyclopentan-1-one (F2C) is produced in yields more than 95 mol% [30]. The resulting condensation products are solids insoluble in water, i.e. easily separable. As a consequence of the fact that both aldol condensation and preparation of cyclopentanone from furfural (the yield ~ 92 mol%) are conducted in water it becomes evident that isolation of each reactant from its aqueous solution on the pathway to F2C may not be required which makes the proposed process more economical. Another benefit of this method of synthesis is that theoretically 80% of oxygen might be simultaneously removed from the primary biomass (hemicellulose) without the need of hydrogen.

In the present paper we explore the potential of the product of aldol condensation of furfural with cyclopentanone, 2,5-bis(2-furylmethylidene)cyclopentan-1-one, for the production of corresponding cyclic ether that could be considered as biomass-derived diesel blending agent. Using proper heterogeneous catalysts it is possible to selectively hydrogenate only exocyclic Cdouble bondC bonds, or also unsaturated Cdouble bondC bonds in furan rings while leaving intact the splitting of C–O–C ether bonds in the F2C molecule. The low solubility of the solid F2C in many solvents [31] was because the experiments were performed in a batch reactor in different solvents.

Section snippets

Materials

The 2,5-bis(2-furylmethylidene)cyclopentan-1-one was prepared according to the method described in [30]. Commercial Pd/C, Pt/C and Ru/C catalysts with 5 wt.% metal loading were purchased from Alfa-Aesar. Platinum catalysts supported on alumina Pural SB1 (Sassol) and β-zeolite (Zeolyst) with Si/Al ratio 22 were prepared by the impregnation method using an aqueous solution of H2PtCl6 as metal precursors. After impregnation procedure and drying at 100 °C for 8 h, the catalysts were calcined in air at

Results and discussion

In most solvents the solubility of the aldol condensation product F2C at temperatures < 100 °C is very low [31], and the higher temperatures of hydrogenation result in increased substrate decomposition. In this study the experiments were carried out in cyclohexane, n-heptane and methanol and in the mixture of tetrahydrofuran–water where solubilities of F2C are very limited, and in tetrahydrofuran and acetic acid where solubilities are relatively good. In the reactant, two C–O–C bonds and three

Conclusions

The present paper describes an entirely new route for highly selective preparation of additives for transportation fuels. It is based on a three-step process starting from furfural, which by the base catalyzed aldol condensation with cyclopentanone produces 2,5-bis(2-furylmethylidene)cyclopentan-1-one (F2C) in more than 95 mol% yield. Using 5%Pd/C catalyst complete hydrogenation of F2C can be achieved at 90 °C and 0.3 MPa with more than 83% selectivity to bis-cyclic ethers and with about 91 mol%

Acknowledgment

This work was partly supported by the Slovak Grant Agency VEGA 1/0770/15.

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