In this study inexpensive, non-toxic, and noble metal free mono-and bimetallic catalysts on activated carbon were tested in liquid phase catalytic furfural hydrotreatment to a potential biofuel component 2-methylfuran. High yields of 2-methylfuran were achieved in the study, the highest yield was achieved with 10 wt-% Ni/C (48.9%) in 120 minutes and good results were obtained also with bimetallic 2/2 wt-% CuNi/C and CuFe/C (yield 44.2 and 41.0%, respectively). These high yields were achieved applying significantly shorter reaction time (60 -120 min) compared to many published studies. The activity of nickel catalysts was very high resulting eventually in further hydrogenation of 2-methylfuran. With increasing nickel loading also ring-opening and decarbonylation reactions were promoted. Addition of iron to nickel was beneficial for decreasing decarbonylation and other side reactions. Copper/nickel and copper/iron combinations were observed to have beneficial interaction as activity and selectivity to MF increased significantly.
Bio‐based chemicals can be produced from furfural through hydrotreatment. In this study, 2‐methylfuran (MF), a potential biofuel component, was produced with Pt, Ru, and Ni catalysts supported on wood‐based activated carbons. The catalytic hydrotreatment experiments were conducted in a batch reactor at 210–240 °C with 2‐propanol as solvent and 40 bar H2 pressure. Two types of activated carbon supports were prepared by carbonization and activation of lignocellulosic biomass (forest‐residue‐based birch and spruce from Finland). Both types of activated carbons were suitable as catalyst supports, giving up to 100 % furfural conversions. The most important factors affecting the MF yield were the metal dispersion and particle size as well as reaction temperature. The highest observed MF yields were achieved with the noble metal catalysts with the highest dispersions at 240 °C after 120 min reaction time: 3 wt % Pt on spruce (MF yield of 50 %) and 3 wt % Ru on birch (MF yield of 49 %). Nickel catalysts were less active most likely owing to lower dispersions and incomplete metal reduction. Interesting results were obtained also with varying the metal loadings: the lower Pt loading (1.5 wt %) achieved almost the same MF yield as the 3 wt % catalysts, which can enable the production of MF with high yields and reduced catalyst costs. Based on this study, biomass‐based renewable activated carbons can be used as catalyst supports in furfural hydrotreatment with high conversions.
Production of valuable chemicals from furfural through hydrotreatment requires information of hydrogen solubility in furfural and the most often applied solvent, 2-propanol. This study investigates hydrogen solubility in furfural and 2-propanol at the temperature range of 323-476 K and pressure range up to 12.5 MPa. The measured data are compared to prediction with Soave-Redlich-Kwong, Peng-Robinson, and Perturbed-Chain Statistically Associating Fluid Theory (PC-SAFT) equations of state. The most accurate prediction of hydrogen solubility in furfural and 2-propanol was obtained with PC-SAFT.
Hydrogenation of furfural is a possible route to produce potential renewable fuel component 2-methylfuran (MF) on carbon supported nickel catalyst. This study investigates the effect of process conditions on liquid phase hydrotreatment of furfural to 2-methylfuran over 10 wt-% Ni/C catalyst. The most important parameters tested were temperature, hydrogen pressure and metal loading of the catalyst. In addition, the effect of hydrogen addition method, atmosphere in heating, calcination gas, and stirring speed were tested to analyze optimal reaction procedure. As a result, the highest yield of MF achieved was 48.9 % applying 230 8C, 40 bar hydrogen pressure, and 10 wt-% Ni/C. This high yield of 2-methylfuran is higher than typically reported yields and thus the studied catalyst and reaction conditions offer excellent potential for MF production.
In this study, acetone formation was investigated as a side reaction in furfural hydrotreatment applying isopropanol as a solvent. Acetone formation was observed to depend strongly on the metal and metal loading of catalysts as copper, nickel, and iron catalysts supported on activated carbon were studied. Furfural has an important role in acetone formation: the initial formation rate for acetone was high as long as furfural reacted further. After furfural was consumed the acetone formation decelerated except with the catalysts including iron. Two formation mechanisms were derived: first mechanism includes direct and transfer hydrogenation of furfural and isopropanol dehydrogenation, as mechanism two consists only of isopropanol dehydrogenation. Another novel discovery of the study was the confirmation of the formation mechanism for 2-methylfuran through transfer hydrogenation of furfuryl alcohol in the experiments. In conclusion, the acetone formation as a side product was observed significant and could not be totally prevented.
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