Lead/platinum on charcoal as catalyst for oxidation of furfural. Effect of main parameters

doi:10.1016/0926-860X(94)80133-9

Applied Catalysis A: General

Volume 112, Issue 1, 12 May 1994, Pages 1-11

https://doi.org/10.1016/0926-860X(94)80133-9 Get rights and content

Abstract

Catalytic oxidation of furfural leads to 2-furancarboxylic acid. The reaction is carried out in an aqueous alkaline medium under a stream of oxygen in the presence of a bi-metallic lead/platinum deposited on charcoal catalyst. The effect of the main reaction parameters is studied and a reaction scheme is proposed taking in account the results obtained.

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Definitely, it is the bridge connecting biomass raw materials and bio-refining industry. In the methods of electrochemical conversion of furfural, the main products of interest include furoic acid [9,10], 2(5H)-furanone [11], and acyclic dicarboxylic acid derivatives such as succinic acid and maleic acid [12]. In contrast, the two-electron oxidation of furfural to furoic acid is simpler and more direct, without opening the furan ring.
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δ-MnO₂ exhibits excellent activity for furfural oxidation to furoic acid under base-free conditions. However, its poor CH bond breaking capacity leads to lower conversion efficiency per unit mass catalyst than noble metal. Thus, a series of Ru-modified δ-MnO₂ (Ru_x/δ-MnO₂) have been made to enhance its CH bond breaking ability. The result showed that the furfural conversion was greatly enhanced on Ru_x/δ-MnO₂ due to the enhanced capability for breaking the CH bond. Especially for Ru0.25/δ-MnO₂, whose conversion rate per unit mass was 18 times higher than δ-MnO₂. The characterization results showed that the Ru species mainly existed as single atoms or clusters on Ru0.25/δ-MnO₂ and Ru0.5/δ-MnO₂, while started to aggregate to RuO₂ nanoparticles on Ru1/δ-MnO₂ and Ru2/δ-MnO₂. With the increase of Ru particles, the Ru's average oxidation state (AOS) decreased from +6 on Ru0.25/δ-MnO₂ to +4.74 on Ru2/δ-MnO_2. The Ru's TOF (intrinsic activity per Ru) was positively linearly related to the Ru's AOS. The electron-deficient Ru in Ru0.25/δ-MnO₂ can strongly adsorb the H atom of the CH of geminal diol intermediate and accelerate the breakage of its CH bond. As a result, Ru in the Ru0.25/δ-MnO₂ exhibited the highest TOF, which can even reach 29.85 mmol_FF/mmol_Ru/h.
Manifolding active sites and in situ/operando electrochemical-Raman spectroscopic studies of single-metal nanoparticle-decorated CuO nanorods in furfural biomass valorization to H<inf>2</inf> and 2-furoic acid
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FA, which is commonly used as a preservative, fungicide, and pharmaceutical precursor, can be derived from furfural, a product of the acid-catalyzed hydrolysis of hemicellulose sources such as sugar cane [6]. The conventional methods for FA production require either the addition of a strong base (e.g. NaOH) to disproportionate furfural into both FA and furfuryl alcohol (Cannizarro reaction) [7] or the addition of a chemical oxidizer (e.g. O2, H2O2), typically in the presence of a catalyst and at elevated temperature and pressure [8–11]. Electrochemical methods offer a unique opportunity to convert furfural directly to FA without the need to alkalize the acidic aqueous feedstock, provide an oxidizing agent, or perform costly extra separations (Scheme 1) [12].
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2,5-Furandicarboxylic acid (FDCA) can be produced from biomass or its derived sugars or platform chemicals, and has demonstrated to be a very promising substitute for petroleum-derived polymer products. Notably, FDCA in combination with ethylene serves as a copolymer for the production of polyethylene furanoate (PEF), a bioplastic with improved material properties compared to the large-volume polymer polyethylene terephthalate (PET). For FDCA production, far more focus has been directed on oxidative conversion of 5-hydroxymethylfurfural (5-HMF) by chemocatalysis using homogeneous and heterogeneous systems with noble metals. These systems are promising in terms of yield, reaction rate, and product purity but impractical due to their high cost base. Alternatively, have less costly—but also less productive—base metal or metal-free chemocatalyst systems, as well as bio-, electro-, and photocatalytic approaches, also been examined for the oxidation of 5-HMF to FDCA. This chapter surveys recent advances in the production of FDCA with particular focus on applied catalytic systems and highlights applications of FDCA.

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Lead/platinum on charcoal as catalyst for oxidation of furfural. Effect of main parameters

Abstract

Appl. Catal.

Appl. Catal.

Appl. Catal.

Carbohydr. Res.

J. Chem. Soc.

Hoˆkoku

Khim. Geterotsikl Soedin

Ann. Chim. Appl.

Bull. Sci. Facol. Chim. Ind. Bologna

J. Chem. Soc. Faraday Trans.