Highly Selective Conversion of Furfural to Furfural Alcohol or Levulinate Ester in One Pot over ZrO₂@SBA-15 and Its Kinetic Behavior

Abstract

Biorefinery for the purpose of producing biofuels, chemicals, and materials has received much attention. Furfural alcohol (FOL) and levulinate ester (LE) are important biomassderived platform chemicals, and they are produced from sugar-based furfural (FAL). Unfortunately, the two products are often obtained separately in different reaction systems, which is undesirable; furthermore, it is of significant practical interest to control their selectivity so that the desired product can be accumulated in high yields. Herein, we present an efficient method for the highly selective conversion of FAL to FOL or isopropyl levulinate (IPL) in a one pot system using isopropanol as the hydrogen source and ZrO 2 @SBA-15 as a bifunctional catalyst with both Lewis acid and Brønsted acid sites. Under optimized reaction conditions, high yields of FOL and IPL in up to 90.4% and 87.2%, respectively, were obtained. Based on the experimental results, a kinetic model describing the catalytic conversion of FAL into FOL and IPL process has been established, which has a good correlation (R 2 > 0.92) between the measured and predicted data. The developed kinetics can provide an effective tool to monitor the process and tailor the process conditions to obtain the desired product.

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

“…The favourable formation of 2BMF may be partly due to the fact that Hf-TUD-1(50) was essentially a Lewis acid catalyst ( Table 1 ) [ 43 , 61 , 67 , 68 ]. The furan ring-opening of AMFs to LEs may be favoured by B acidity [ 38 , 43 , 61 , 68 , 69 , 70 ], albeit Hf-TUD-1(50) possessed poor B acidity.…”

“…The kinetic curves of 2BL formation show an induction period for the lower reaction temperature range of 90-130 • C (Figures 5b and S10b The favourable formation of 2BMF may be partly due to the fact that Hf-TUD-1(50) was essentially a Lewis acid catalyst (Table 1) [43,61,67,68]. The furan ring-opening of AMFs to LEs may be favoured by B acidity [38,43,61,[68][69][70], albeit Hf-TUD-1(50) possessed poor B acidity.…”

“…Humins may be removed from the catalysts via thermal treatment at high temperature (>350 °C), which is an issue for several families of materials such as organic–inorganic hybrids and carbon-based ones. Literature studies for the CTH of Fals focused on hexagonally arranged OMSi of the type SBA-15 [ 32 , 36 , 37 , 38 , 39 , 40 , 41 ] and MCM-41 [ 42 , 43 , 44 ] possessing zirconium and using 2-propanol (2PrOH) or 2-butanol (2BuOH) as H-donor. The preparation of these types of OMSi generally requires the use of relatively expensive copolymer organic templates or synthetic surfactant templates, leading to environmental concerns (toxic, non-biodegradable) and requiring more demanding wastewater treatments.…”

Humins with Efficient Electromagnetic Wave Absorption: A By‐Product of Furfural Conversion to Isopropyl Levulinate via a Tandem Catalytic Reaction in One‐Pot

“…[7] Recently, Zhang et al. used ZrO 2 @SBA‐15 catalyst to efficiently and selectively convert FAL to FOL or levulinate ester and conducted a kinetic study [7d] . Galletti et al.…”

Direct Valorization of Furfural in Primary Alcohols Using Rare‐Earth Metal Salts

“…[12] Zr-based bifunctional catalysts have been widely developed due to the superior catalytic transfer hydrogenation ability of Zr. [17,18] The best 95 % of GVL was yielded in iso-propanol with Meso-ZrÀ Al-Beta, [14] and the catalyst incorporated heteropolyacid in the Zr-Beta also offered 90 % of GVL yield. [19] Very recently, Zhang et al developed a magnetically-recoverable multifunctional catalyst (Fe 3 O 4 / ZrO 2 @MCM-41), and realized 81 % yield of GVL from furfural in iso-propanol.…”