Enhanced Catalytic Transfer Hydrogenation of Ethyl Levulinate to γ

Dec 15, 2016 - Synergetic Catalysis of Bimetallic CuCo Nanocomposites for Selective Hydrogenation of Bioderived Esters. Jun Wu , Guang Gao , Peng Sun ...
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Enhanced catalytic transfer hydrogenation of ethyl levulinate to #-valerolactone over an robust Cu-Ni bimetallic catalyst Bo Cai, Xin-Cheng Zhou, Ying-Chun Miao, Jin-Yue Luo, Hui Pan, and Yao-Bing Huang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b01677 • Publication Date (Web): 15 Dec 2016 Downloaded from http://pubs.acs.org on December 16, 2016

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Enhanced catalytic transfer hydrogenation of

ethyl

levulinate to γ-valerolactone over an robust Cu-Ni bimetallic catalyst Bo Cai,‡ Xin-Cheng Zhou,‡ Ying-Chun Miao, Jin-Yue Luo, Hui Pan, Yao-Bing Huang*a

a

College of Chemical Engineering, Nanjing Forestry University, No 159 Longpan Road,

210037, Nanjing, China. Corresponding author: Y.-B. Huang, Email: [email protected] KEY WORDS: ethyl levulinate, γ-valerolactone, transfer hydrogenation, bimetallic catalyst, stability

ABSTRACT An efficient and robust bimetallic catalyst has been developed for the transfer hydrogenation of biomass derived ethyl levulinate (EL) to γ-valerolactone with 2-butanol as the hydrogen donor. Several bimetallic catalysts were prepared and characterized by BET, TEM, XRD and XPS. They exhibited different catalytic activities in the CTH reaction. Results showed that 10Cu-5Ni/Al2O3 had the highest activity, providing a 97% yield of GVL product in 12 h at 150 oC. The reaction temperature, reaction time and catalyst loading were also investigated and found to affect the product yield. The catalyst was also successfully applied to the CTH of various levulinate esters with different secondary alcohols. Comparing experiments between Cu-Ni and Cu catalysts and the poisoning experiments revealed that the introduction of Ni to Cu remarkably enhanced the catalyst’s activity and stability, showing an outstanding

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recycling ability in the 10 runs recycling experiments without notable loss in the activity. INTRODUCTION The utilization of renewable biomass to produce energy has been considered as a promising solution to the energy crisis and the pollutions that caused by the fast and huge consumption of fossil resource.1,2 The biorefinery industry can produce carbon-containing molecules for drugs or liquid fuels, which are beyond the scope of other renewable energies (e.g. solar, wind).3 Among various biomass feedstocks, lignocellulose is getting more and more attentions due to its abundance and low cost. It can be easily converted to a variety of molecules including alkanes/alkenes,4-6 polyols,7-11 acids,12-15 esters16-18 and aldehydes.19,20 For example, hydrolysis/alcoholysis of cellulose in aqueous/alcoholic solutions provide the important platform chemicals levulinic acid (LA)/levulinate esters.16-18 Through the down-stream processing, they can be easily converted to several useful products such as γ -valerolactone (GVL),21,22 valerate esters23, 24 and 1,4-pentanediol.25,26 Of all these compounds, GVL is the most widely studied molecule with numerous applications such as a fuel additive, solvent, precursor for the production of other chemicals.21,22 To date, many processes have been developed for the production of GVL from LA through hydrogenation reaction.27 These reactions were mainly conducted in the presence of hydrogen with various metal catalysts such as Ir,28 Rh,28 Pd,29,30 Ru,31-33 Pt,34 Co,35 Cu36 and Ni.37-40 In the past few years, formic acid (FA), an in situ hydrogen source, was also applied for the conversion of LA to GVL instead of an external H2 gas. It was demonstrated as an effective and economical method when the upstream carbohydrate hydrolysate (LA and FA aqueous solution) was used as the raw material.41 Apart from LA, levulinate esters was also

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an appealing substrate for preparing GVL. They could be produced from cellulose in alcoholic solutions with high yield under mild conditions. Meanwhile they are much easier and more energy-efficient to be separated from the alcoholic mixture than the separation of LA from water.42,43 Therefore, it is attractive to develop more efficient systems for the catalytic hydrogenation of levulinate esters to GVL. At the same time, the catalytic transfer hydrogenation (CTH) reaction has emerged as an alternative hydrogenating method to conventional H2 method for the reduction of carbonyl compounds,44,45 which is the key step to convert LA or levulinate esters to GVL. For example, Dumesic et al

46

reported the CTH of EL to GVL over ZrO2 catalyst in the presence of

isopropanol, H-donor solvent, at 150 oC. Lin et al47 found that zirconia based hydroxide ZrO(OH)2 could effectively catalyse the CTH of EL to GVL in a supercritical ethanol solution. Song and Han et al48 used Zr-HBA as the CTH reaction catalyst and achieved 94.4% yield of GVL in isopropanol. Kuwahara et al49 demonstrated that ruthenium hydroxides supported on basic oxides could exhibit high catalytic activity in the CTH of EL to GVL. Our group has also reported the CTH of EL over Raney Ni catalyst with an almost quantitative yield at room temperature.50 Several other new systems were also reported as effective for the CTH conversion.51-55 Nevertheless, there still exist some limitations of the above systems such as harsh reaction conditions, low catalyst stability and long reaction time, etc. Therefore, further improvement of the reaction efficiency of the CTH of levulinate esters to GVL with more robust catalyst is highly desired. Previous researches had demonstrated that copper catalysts exhibited excellent catalytic activities in the CTH reactions for the production of various organic chemical.56 However, the

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low stability and easily-oxidized nature of these catalysts severely restrict their applications in other areas. Therefore, a second metal was introduced to the copper catalyst to form a bimetallic catalyst in this study, which can not only stabilize the copper metal particle sites but also enhance the activity of the catalyst.57,58 Herein, we reported a bimetallic Cu-Ni catalyst for the CTH of levulinate esters to GVL in the presence of 2-buthanol as the H-donor (Scheme 1). Several other bimetallic catalysts were also prepared, characterized and tested for the CTH reaction. The influences of the metal ratio, reaction conditions, as well as the stability and recyclability of the catalysts were investigated.

EXPERIMENTAL SECTION Materials Levulinate esters and γ-valerolactone were purchased from TCI Chemical Reagent Company (Shanghai, China). Ni(NO3)2·6H2O, Cu(NO3)2·6H2O and solvents were purchased from Sinopharm Chemical Reagent Company (Shanghai, China). The metal oxide supports were purchased from Saint-Gobain NorPro Company (America). The other chemicals were purchased from the local companies and used without further purification. Preparation of the catalysts The catalysts were prepared by incipient impregnation method. In a typical procedure for preparing the 10%Cu-5%Ni/Al2O3: 1.7g of Al2O3 was firstly impregnated with a aqueous solution containing 0.753 g of Cu(NO3)2·3H2O and 0.495 g of Ni(NO3)2·6H2O, then the mixture was vigorously stirred for 12 h and dried at 110 oC for another 12h. The resulted powder was grinded and calcined at 500 oC for 4 h. The catalyst was then reduced in a flow of

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5% H2/N2: from room temperature to 500 oC at 10 oC/min, then keep at 500 oC for another 2 h. After cooling to room temperature, the catalyst was collected and weighted. This catalyst was denoted as 10%Cu-5%Ni/Al2O3 (10Cu-5Ni/Al2O3). Other catalysts were prepared with similar procedure as 10Cu-5Ni/Al2O3. Catalytic reactions Transfer hydrogenation of EL was carried out in a thick-wall pressured tube. For the model reaction with 10Cu-5Ni/Al2O3: EL 1.0 mmol, catalyst 10Cu-5Ni/Al2O3 100 mg and solvent 2-butanol 3 mL were charged into the reaction tube with a magnetic stirrer. The tube was then purged with nitrogen to remove air. The reaction was allowed to react in a 150 oC oil bath for 12 h at a stirring speed of 600 rmp. Upon the end of the reaction, the tube was removed from oil bath and cooled down to room temperature, and the reaction mixture was sampled and subjected to product analysis. Recycling of the catalyst: the catalyst was centrifuged after the reaction and washed with 2-BuOH for 3 times. All the liquid was collected, combined and subjected to GC analysis. The solid catalyst was directly added to the reaction tube for the next run. Characterization methods The Brunauer-Emmett-Teller (BET) surface area, pore size and pore volume of the catalyst were measured by Automatic Surface Area and Pore Analyzer (Tristar II 3020 M, Micromeritics). X-ray power diffraction (XRD) of the catalysts were recorded on the Rigaku D MAX III VC diffraction system. Transmission electron microscopy (TEM) were acquired on a JEOL-2010 electron microscope. X-ray photoelectron spectra was recorded on the Scientific Escalab 250-X-ray photoelectron spectrometer (XPS).

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The reaction mixture was analyzed on a gas chromatography-mass spectroscopy (GC-MS, Agilent 7890A, Agilent 5975C MSD) and GC (Agilent 7890A) with a DB-5 capillary column (30m×0.25mm×0.25µm, Agilent). The temperature of column increased from 160 to 250 oC at a 15 oC /min rate. Naphthalene was used as the internal standard.

RESULTS AND DISCUSSION Characterization of catalysts Figure 1 shows the XRD patterns of the Cu-Ni catalysts and the support Al2O3. Al2O3 showed four typical reflection peaks at 2θ=37.4o, 39.5 o, 46.1 o and 66.7 o. These peaks can also be easily found in the as-prepared catalysts, indicating a well-dispersed alumina phase in these catalysts during the preparation process. Three new diffraction peaks were observed in the 10Cu-1Ni/Al2O3 catalyst, which can be divided into two groups (partially overlapped, see amplification picture). One group were assigned to the metallic Cu phase (located at 43.3 o, 50.4 o and 74.1 o) while the other were assigned to Cu-Ni alloy species (shoulder peaks located at 43.4 o, 50.6 o and 74.2 o). These result were consistent with the results from the previously reported work.59,60 No obvious diffraction peaks of metal oxides species (e.g. CuxOy or NixOy) were observed in the XRD patterns, possibly attributing to their amorphous state or smaller size (