Highly Selective and Efficient Rearrangement of Biomass-Derived

Oct 28, 2016 - Biomass-derived furfural was efficiently converted to valuable cyclopentanone over interface-active Ru/carbon nanotubes (CNTs) catalyst...
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Research Article pubs.acs.org/journal/ascecg

Highly Selective and Efficient Rearrangement of Biomass-Derived Furfural to Cyclopentanone over Interface-Active Ru/Carbon Nanotubes Catalyst in Water Yanhua Liu,† Zhihao Chen,† Xiaofeng Wang,‡ Yu Liang,† Xiaomin Yang,*,† and Zichen Wang† †

College of Chemistry and ‡State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

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S Supporting Information *

ABSTRACT: Biomass-derived furfural was efficiently converted to valuable cyclopentanone over interface-active Ru/ carbon nanotubes (CNTs) catalyst in water. The effect of reaction conditions, including furfural concentration, reaction temperature, hydrogen pressure, speed of stirring, and reaction time on the catalytic performance of Ru/CNTs has been studied in detail. The furfural conversion of 99% and cyclopentanone selectivity of 91% were efficiently achieved at very low concentration of Ru/CNTs catalyst (0.26 wt % Ru) under mild reaction conditions (1 MPa H2, 160 °C, 500 rpm). Possible reaction pathways of furfural transformation over Ru/CNTs nanoparticles in water are proposed. KEYWORDS: Carbon nanotubes, Ruthenium nanoparticles, Furfural, Ring rearrangement, Cyclopentanone

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INTRODUCTION Catalytic conversion of renewable biomass resources, as feed stock for the chemical industry, becomes more and more important because of the urgent demand for sustainable and clean fuels and chemicals.1−4 Furfural can be produced from renewable biomass resources by acid-catalyzed dehydration of pentose, which has the potential to be a sustainable substitute for building blocks derived from petrochemical in the production of fuels and fine chemicals.5,6 Catalytic hydrogenation of furfural is an important reaction because it allows for obtaining products such as furfuryl alcohol, tetrahydrofurfurylalcohol, 2-methylfuran, and cyclopentanone.7 Because of the wide variety of available hydrogenation products of furfural, one of the most important themes is the design of catalysts that are highly selective to the desired products. Cyclopentanone is a versatile fine chemical intermediate. It can be used for the synthesis of pharmaceuticals, fungicides, rubber chemicals, and flavor and fragrance chemicals. Traditionally, cyclopentanone can be prepared by the catalytic liquid phase oxidation of cyclopentene with nitrous oxide8 or vaporphase cyclization of 1,6-hexanediol9 or adipic acid esters.10 However, petroleum-based products are used as feed stocks in all of these processes. Recently, furfural was proven to be a good feedstock for synthesizing cyclopentanone,11−19 which has the potential to replace unsustainable fossil fuels. Furfural is the product of acid-catalyzed dehydration of pentose proceeding in water. The process of furfural separation from the formed aqueous solutions increases its cost of production. Therefore, it is highly beneficial to use furfural © 2016 American Chemical Society

aqueous solution as feedstock for preparation of chemicals and fuels. This will significantly reduce the energy needed for furfural production. Recently, Hronec et al. reported new methods for the rearrangement reaction of furfural11−13 and furfuryl alcohol20 to cyclopentanone in aqueous media. They found that some metal catalysts (e.g., Pt/C, Pd−Cu/C, and Nibased catalysts) had good performance in the selective synthesis of cyclopentanone from furfural or furfuryl alcohol in aqueous solution. In other reports, Ni−Cu/SBA-15,14 Cu− Co,15 CuZnAl,16 and CuNiAl hydrotalcite-type catalysts,17 Ru/ MIL-101,18 and Au/TiO219 were also used as efficient catalysts for the furfural rearrangement to cyclopentanone in aqueous solution. In addition, aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Ni/carbon nanotubes (CNTs) and Cu−Mg−Al hydrotalcite-derived catalysts were reported by the Xiao group.21,22 Although some pioneering work has been done in this area, the study is still in its infancy. Gas−water−solid multiphase catalysis reactions often suffer from low catalytic efficiency because of the low solubility of gases in water and the masstransfer resistances between multiphase interfaces.23,24 How to obtain high reaction efficiency for gas−water−solid multiphase catalysis reactions remains a challenge.25 To some degree, this can be done by raising reaction pressure (e.g., 3−8 MPa) and impeller speed (e.g., 1200−1500 rpm), which will require Received: August 30, 2016 Revised: October 1, 2016 Published: October 28, 2016 744

DOI: 10.1021/acssuschemeng.6b02080 ACS Sustainable Chem. Eng. 2017, 5, 744−751

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h in a He stream. After the adsorption, the reactor was purged with He for 1 h at 50 °C. For the desorption measurement, the Ru/CNTs sample was heated from 50 to 500 °C at a rate of 10 K min−1 in a He stream. Furfural Hydrogenation. The selective hydrogenation of furfural was performed in a 100 mL autoclave under stirring. For a typical run, the reaction was carried out with 0.46 g of furfural, 0.020 g of 6 wt % Ru/CNTs, 40 mL of water as solvent, and 1 MPa H2 at 160 °C for 5 h. After each reaction, the catalyst particles were separated from the solution by centrifugation. The liquid phase products were collected, extracted by ethyl acetate, and subsequently analyzed and identified by means of GC (2014C, SHIMADZU) and GC-MS (QP 2010 Plus, SHIMADZU) as well as by comparison with the retention times of the respective standards in GC traces. An HP-INNOWAX capillary column (30 m × 0.32 mm × 0.25 μm) was used for the separation of reaction mixtures. The quantitative determination of the reaction products was carried out by area normalization method and external standard method. All results were evaluated on the basis of the amount of furfural. The conversion of furfural (mol %), the selectivity (mol %) of main products, and carbon balance were calculated as

severe operating conditions. Therefore, developing highly efficient and selective interface-active catalysts in water under mild reaction conditions for furfural rearrangement is still a much-sought-after goal. CNTs have potential application in catalysis due to their unique electron conductivity, thermal stability, high mechanical strength, and so forth.26−34 Compared with traditional catalyst supports, CNTs have high external surface area and aspect ratio, which significantly increase the contact surface between the reactants and active sites of catalysts and greatly minimize the diffusion limitations. These features make CNTs very attractive as catalyst supports in liquid-phase reactions.35−40 It has been found that CNT-supported metal nanoparticles show excellent activity, selectivity, and stability in some redox reactions, which are greatly enhanced and quickened by water.35−37 Therefore, we have immense interest in exploring the novel catalytic properties of CNT-supported metal nanoparticles for biomass-derived platform molecule transformations in a gas−water−solid multiphase catalysis reaction system. Herein, we have investigated the catalytic conversion of biomass-derived furfural to cyclopentanone in aqueous phase, applying CNT-supported Ru nanoparticles as catalyst. The main objective was to develop a novel and efficient interfaceactive catalyst for furfural rearrangement to cyclopentanone in aqueous phase. Various experimental parameters such as furfural concentration, reaction temperature, hydrogen pressure, speed of stirring, and reaction time were studied in detail, aiming to optimize the reaction conditions and to elucidate the reaction pathways of furfural transformation over Ru/CNTs catalysts in aqueous phase.

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conversion = (1 − moles of furfural /moles of furfural loaded initially) × 100%

selectivity of product = (moles of product/moles of furfural converted) × 100% carbon balance = (moles of products/moles of furfural converted)

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× 100%

RESULTS AND DISCUSSION XRD patterns of CNTs and 6.0 wt % Ru/CNTs are shown in Figure 1. For CNTs, there exists a symmetrical and sharp

EXPERIMENTAL SECTION

Materials and Reagents. CNTs with a main diameter range of 30−50 nm, length of 1−2 μm, and N2 surface area of 151 m2/g were purchased from Shenzhen Nanotech Port Co., Ltd. (Shenzhen, China). Furfural before experiments was purified by vacuum distillation and stored at −15 °C. All reagents used in this work were of analytical grade. Catalyst Preparation and Characterization. The Ru/CNTs catalyst with metal loading of 6.0 wt % was made via a wetness impregnation method.35,36 The preparation procedure is as follows. The oxidized CNTs (1 g) were impregnated in an aqueous solution of RuCl3 (40 mL, 0.10 mol/L) under ultrasonic conditions for 30 min, and then the mixture was incubated at room temperature for 12 h. The CNT-supported RuCl3 sample was dried at 110 °C for 12 h under vacuum, reduced at 400 °C in flowing hydrogen for 2 h, and then cooled to room temperature in N2, obtaining 6.0 wt % Ru/CNTs catalyst. For the recycling experiments, the separated Ru/CNTs catalyst was washed first with ethanol and then with water. Thereafter, it was dried at 100 °C for 8 h under vacuum. Before recycling, the obtained catalyst was reduced at 400 °C in flowing hydrogen for 2 h and then cooled to room temperature in an inert atmosphere. The crystalline structure of Ru/CNTs was analyzed by powder Xray diffraction (XRD, D/MAX-2550) using Cu Kα radiation with a scanning rate of 2° min−1. Transmission electron microscopy (TEM) examination was conducted using a JEM-2100F equipped with a CCD camera operated at 200 kV. X-ray photoelectron spectroscopy (XPS) was performed on a Thermo ESCALAB 250 system with Mg Kα source (1254.6 eV). The XPS spectrum was calibrated by adjusting the position of the C 1s peak to 284.6 eV. The temperature-programmed desorption of ammonia (NH3-TPD) experiment was performed using a Micromeritics AutoChem II 2920 automated chemisorption analysis unit with a thermal conductivity detector (TCD) under helium flow. NH3 was adsorbed at 50 °C for 1 h after pretreatment at 300 °C for 1

Figure 1. XRD patterns of CNTs and 6.0 wt % Ru/CNTs.

graphite 002 peak at 26° and a broad graphite 100 peak at 42°. The average interlayer spacing was calculated to be 0.33 nm.41 The layered structure of CNTs was reported to be favorable for the transfer of electrons and for a close interaction between the metal and support by intercalation.42 For 6.0 wt % Ru/CNTs catalyst, no diffraction peak related to metallic Ru is detected (Figure 1), which implies that Ru nanoparticles are of nanometer scale. Typical TEM images and the particle size distribution of the 6.0 wt % Ru/CNTs catalyst are shown in Figure 2, which shows that the Ru nanoparticles with an average size of 2.74 nm are highly dispersed on the surface of CNTs. Figure 3 shows the XPS spectra of the Ru 3p for the 6.0 wt % Ru/CNTs catalyst. Peaks at approximately 462 and 485 eV are attributed to Ru 3p3/2 and Ru 3p1/2, respectively. The 745

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Figure 2. TEM images and particle size distribution of 6.0 wt % Ru/CNTs.

Figure 3. XPS spectra of Ru 3p for 6 wt % Ru/CNTs catalyst. Figure 4. NH3-TPD profile of 6.0 wt % Ru/CNTs catalyst.

XPS spectra indicate that the chemical state of Ru on the surface of Ru/CNTs is metallic. Most of the oxygen-containing functional groups like carboxyl and hydroxyl groups on the CNT surface are acidic sites, which are capable of adsorbing basic molecules like NH3. Therefore, the desorption of preadsorbed NH3 can be used to characterize the surface acidic sites on CNTs.43,44 NH3-TPD profile of 6.0 wt % Ru/CNTs catalyst is shown in Figure 4. The main ammonia TPD peak appeared at approximately 150−200 °C (Figure 4), indicating that most of the ammonia molecules are weakly chemisorbed. Most of the acidic groups act as primary adsorption centers, which bind additional ammonia molecules weakly through hydrogen bonds.43−45 The signal at temperatures above 300 °C originates from the decomposition of the surface functional groups of CNTs.43 According to the TPD-NH3 measurement, the acidity of the catalyst is 991 μmol/g. The aqueous phase hydrogenation of biomass-derived furfural was used to explore the catalytic performance of the

Ru/CNTs catalyst. The effect of reaction temperature on the catalytic performance of Ru/CNTs for the selective hydrogenation of furfural is shown in runs 1−3 in Table 1. Results show that reaction temperature has a significant effect on the selectivity of cyclopentanone. At 160 °C, the selectivity of cyclopentanone is the highest compared with that at 140 and 150 °C, which reveals that 160 °C is an appropriate temperature for the furfural rearrangement to cyclopentanone. The effect of speed of stirring on the catalytic performance of Ru/CNTs for the selective hydrogenation of furfural was also studied, as shown in runs 3 and 4 in Table 1. With the increase of stirring speed from 500 to 800 rpm, the overhydrogenation of cyclopentanone to cyclopentanol is promoted, which causes a decrease of the selectivity of cyclopentanone and the corresponding increase of the selectivity of cyclopentanol. The effect of reaction pressure on the catalytic performance of Ru/CNTs for the selective hydrogenation of furfural was 746

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Table 1. Effects of Reaction Temperature, Hydrogen Pressure, and Speed of Stirring on the Catalytic Performance of Ru/CNTs for Furfural Hydrogenation

a Reaction conditions: 6 wt % Ru/CNTs (20 mg), furfural (0.34 g), solvent (H2O: 40 mL), p (H2) = 1 MPa, 3 h. bReaction conditions: 6 wt % Ru/ CNTs (20 mg), furfural (0.34g), solvent (H2O: 40 mL), p (H2) = 2 MPa, 3 h.

Table 2. Effects of Reaction Time on Conversion and Selectivity for Furfural Hydrogenationa

a

Reaction conditions: 6 wt % Ru/CNTs (20 mg), furfural (0.34 g), solvent (H2O: 40 mL), p (H2) = 1 MPa, 160 °C, 500 rpm.

increases gradually in 1 h of reaction, and it reaches 100% at 2 h. The selectivity of furfuryl alcohol and 2-pentenoic acid decreases gradually in 1 h. The selectivity of cyclopentanol and tetrahydrofurfuryl alcohol (THFAL) increases gradually. The selectivity of cyclopentanone increases in 1 h of reaction and then decreases. According to experimental results and the literature, furfuryl alcohol is an intermediate product, and it is subsequently consumed by further hydrogenation to form THFAL, and THFAL hydrogenolysis to form 1,2-pentanediol, and by rearrangement to form cyclopentanone and cyclopentanol. It should be noted that the cumulative yield of cyclopentanone and cyclopentanol increases from 49 to 91 mol % upon prolonging the reaction time from 0.5 to 3 h. However, the molar ratio of cyclopentanone to cyclopentanol increases in 1 h and decreases afterward. Therefore, high yield and selectivity of cyclopentanone can be achieved by controlling the reaction time.

investigated, as shown in runs 3 and 5 in Table 1. With the increase of hydrogen pressure from 1 to 2 MPa, the selectivity of cyclopentanone decreases from 59 to 0%, and the selectivity of cyclopentanol, tetrahydrofurfuryl alcohol, and 1,2-pentanediol concurrently increases obviously. The cumulative selectivity of cyclopentanone and cyclopentanol decreases from 90 to 70% when the hydrogen pressure increases from 1 to 2 MPa, which reveals that higher hydrogen pressure is not beneficial for the ring-rearrangement of furfural to cyclopentanone and cyclopentanol over Ru/CNTs in aqueous phase. According to our experimental results, the optimum reaction conditions are as follows: reaction temperature of 160 °C, reaction pressure of 1 MPa, and speed of stirring of 500 rpm. For the reaction pathway of furfural hydrogenation to be explored, the evolution of reactant and products with reaction time was studied under the above-mentioned optimal reaction conditions, as shown in Table 2. The conversion of furfural 747

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ACS Sustainable Chemistry & Engineering Table 3. Effects of Solvents on the Catalytic Activity of Ru/CNTs for Furfural Hydrogenationa

a

Reaction conditions: 6 wt % Ru/CNTs (20 mg), furfural (0.45 g), solvent (40 mL), p (H2) = 1 MPa, 160 °C, 5 h, 500 rpm.

CNTs.11−13,20 Then, this intermediate species (*) is converted by consecutive reactions to cyclopentanone over Ru/CNTs catalyst. According to the literature, the intermediate (*) could be 4-hydroxy-2-cyclopentenone.11,13,14,46 Meanwhile, tetrahydrofurfuryl alcohol (THFA) is produced by total hydrogenation of furfural via furfuryl alcohol over Ru/CNTs catalyst in water (reaction 1, Scheme 1). 1,2-Pentanediol was detected under some reaction conditions, which may be formed via furfuryl alcohol hydrogenolysis (reaction 2, Scheme 1).47,48 In water, furfuryl alcohol can be also converted to levulinic acid in the presence of acid catalyst (H3O+).11,13 Then, levulinic acid is converted to 2-pentenoic acid by consecutive hydrogenation, dehydration, and rearrangement reaction in the presence of Ru/CNTs (reaction 4, Scheme 1). In our case, levulinic acid was not detected, but a smaller amount of 2-pentenoic acid was detected under some special reaction conditions. In addition, in the presence of acid catalyst, furfuryl alcohol dissolved in water may undergo condensation and oligomerization reactions to give some undesired byproduct.49,50 For the application potential of the production of cyclopentanone derived from biomass feedstock to be investigated, the effect of furfural concentration on the catalytic activity of Ru/CNTs was studied, as shown in Table 4. A low concentration of furfural aqueous solution was preferred in reported works to reduce the carbon loss.11,12,14 Therefore, the studied furfural concentration was 0.84−2.42 wt % in our research. With the increase of the furfural concentration, the selective rearrangement of furfural to cyclopentanone can be tuned by varying hydrogen pressure and reaction time to obtain high yield and selectivity of cyclopentanone. The furfural conversion of 99% and cyclopentanone selectivity of 91% were efficiently achieved using only 0.26 wt % of Ru with respect to furfural under mild reaction conditions (1 MPa H2, 160 °C, 500 rpm). The knowledge of this dependence offers us the possibility to achieve very high yields of cyclopentanone from aqueous solutions of furfural with different concentrations at relatively low hydrogen pressure and speed of stirring compared with those presented in the literature. According to the literature, the main reason for carbon loss comes from the resinification of furfural or furfuryl alcohol.11−14 Unlike furfural and furfuryl alcohol, cyclopentanone and cyclopentanol are much more stable in hot water. Once cyclopentanone and cyclopentanol were formed,

Effects of solvents on the catalytic activity of Ru/CNTs for the furfural hydrogenation are shown in Table 3. Results show that the highest conversion and selectivity of cyclopentanone are achieved using water as reaction solvent. When CH2Cl2 or ethanol was used as reaction solvent, the furfural rearrangement product of cyclopentanone or cyclopentanol appears, respectively. It should be noted that specified contents of water are in the used dichloromethane and ethanol. For example, the content of water is usually approximately 0.24% in CH2Cl2 at 20 °C. Thus, this content of water can influence the rearrangement reaction, i.e., the rearrangement reaction is influenced not only by the acidity of the catalyst but also water in the reaction system. Similarly, in the case of ethanol, the content of water is even significantly higher. According to our experimental results and the literature data, possible reaction pathways for the furfural transformation over Ru/CNTs nanoparticles in water are proposed as shown in Scheme 1. The dominant reaction pathway is furfural Scheme 1. Proposed Reaction Pathways for the Furfural Transformation over Ru/CNTs Catalyst in Water in which * Denotes Intermediate Species of Furan Ring Rearrangement and Cat. Represents Ru/CNTs Catalyst

rearrangement to cyclopentanone (reaction 3, Scheme 1). The first stage of this pathway is the Ru/CNTs-catalyzed hydrogenation of furfural to furfuryl alcohol. Then, the rearrangement of the furan ring of furfuryl alcohol happens to form an intermediate (*) catalyzed by acid catalyst (H3O+), which may originate from water by self-dissociation according to Hronec’ reports together with the acidic groups on 748

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ACS Sustainable Chemistry & Engineering Table 4. Effect of Furfural Concentration on the Catalytic Activity of Ru/CNTs for Furfural Hydrogenation

a Reaction conditions: 6 wt % Ru/CNTs (20 mg), solvent (H2O: 40 mL), p (H2) = 1 MPa, 160 °C, 1 h, 500 rpm. bReaction conditions: 6 wt % Ru/ CNTs (20 mg), solvent (H2O: 40 mL), p (H2) = 1 MPa, 160 °C, 5 h, 500 rpm. cReaction conditions: 6 wt % Ru/CNTs (20 mg), solvent (H2O: 40 mL), p (H2) = 2 MPa, 160 °C, 2 h, 500 rpm. dReaction conditions: 6 wt % Ru/CNTs (20 mg), solvent (H2O: 40 mL), p (H2) = 2 MPa, 160 °C, 5 h, 500 rpm.

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the carbon loss would be reduced. A higher concentration of furfural would lead to higher carbon loss due to resinification.11−14 For the carbon loss to be reduced, a low concentration of furfural aqueous solution was preferred in reported works. Moreover, the total selectivity of cyclopentanone and cyclopentanol is 82−95% in our research. Therefore, we can infer that the carbon loss is low. For proving this inference, the quantitative determination of C balance was carried out by external standard method, taking run 2 in Table 4 as example. The C balance is 94%. For testing the stability of the Ru/CNTs catalyst, recycling experiments were performed. When the Ru/CNTs catalyst was repeated 3 times for the furfural hydrogenation reaction, furfural conversion of 83% and cyclopentanone selectivity of 95% were achieved. The slight decrease of the yield of cyclopentanone may be due to the leaching of Ru particles during the reaction and/or the catalyst recycling processes. Another possible reason is the aggregation of the Ru particles during the reaction and/or the catalyst regeneration processes. The mechanism of the deactivation and regeneration of catalyst will be carried out in our further studies.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.6b02080. Oxidation of CNTs and SEM images of CNTs and 6.0 wt % Ru/CNTs (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was partly supported by the National Nature Science Foundation of China (No. 51502108), the Research Fund for the Doctoral Program of Higher Education of China (No. 20130061120018), the Development Project of Science and Technology of Jilin Province, China (No. 20150520016JH), the Foundation of Jilin Provence Development and Reform Commission, China (No. 2014N145), and the China Postdoctoral Science Foundation (No. 2013M540242). We thank Dr. Qiming Sun at State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, China for his kind help with the NH3-TPD experiment and helpful discussions.

CONCLUSIONS

In this contribution, carbon nanotube-supported Ru nanoparticles have been demonstrated to be a novel and efficient interface-active catalyst for furfural rearrangement to cyclopentanone in aqueous phase. Results show that the selective rearrangement of furfural can be tuned through controlling the furfural concentration, reaction temperature, hydrogen pressure, speed of stirring, and reaction time. Under relatively mild reaction conditions (1 MPa H2, 160 °C, 500 rpm), 99% conversion of furfural and 91% selectivity of cyclopentanone were efficiently obtained after 5 h of reaction at very low concentration of Ru/CNTs catalyst (0.26 wt % Ru with respect to furfural). Possible reaction pathways of furfural transformation over Ru/CNTs catalyst in water are also proposed.

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DOI: 10.1021/acssuschemeng.6b02080 ACS Sustainable Chem. Eng. 2017, 5, 744−751

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DOI: 10.1021/acssuschemeng.6b02080 ACS Sustainable Chem. Eng. 2017, 5, 744−751