Sustainable Low-Temperature Hydrogen Production from Lignocellulosic Biomass Passing through Formic Acid: Combination of Biomass Hydrolysis/Oxidation and Formic Acid Dehydrogenation

Abstract

Hydrogen production from renewable resources, such as lignocellulosic biomass, is highly desired, under the most sustainable and mildest reaction conditions. In this study, a new sustainable three-step process for the production of hydrogen has been proposed. In the first step, a crude formic acid (CF) solution, which included typical reaction byproducts, in particular, acetic acid, levulinic acid, saccharides, 5-hydroxymethylfurfural, furfural, and lignin, was obtained through the combined hydrolysis/oxidation of the biomass, in the presence of diluted sulfuric acid/hydrogen peroxide, as homogeneous catalysts. In the second one, the distilled formic acid (DF) solution was obtained by distillation of the CF solution, for example, by isolating liquid byproducts, or the lignin-free CF (LCF) solution was recovered by CF filtration for the elimination of only solid lignin particles. In the final step, hydrogen was produced from the DF or LCF solutions through formic acid dehydrogenation over Pd supported on amine-functionalized mesoporous silica catalysts, in the presence of sodium formate, as an additive. The clean hydrogen, which is produced from biomass passing through formic acid, could be applied as an energy source of fuel cells. This new hydrogen production process is smart, allowing the hydrogen production with mild reaction conditions, eventually starting from different lignocellulosic feedstocks, and it could be integrated within the existing hydrothermal technology for levulinic acid production, which has been already recognized as efficient and sustainable. In addition to the production of hydrogen as an energy source of fuel cells, formic acid derived from biomass could be utilized as a platform chemical for chemical, agricultural, textile, leather, pharmaceutical, and rubber industries.

Hydrophobic Deep Eutectic Solvents for the Recovery of Bio-Based Chemicals: Solid–Liquid Equilibria and Liquid–Liquid Extraction

“…One promising sustainable feedstock is (lignocellulosic) biomass, in which polymeric sugar chains, e.g., cellulose and hemicellulose, and lignin can be converted into a great variety of chemicals [3]. This can be done either by hydrolysis [4][5][6][7], fermentation [8][9][10], or combinations thereof (enzymatic hydrolysis) [11,12]. Typical hydrolysis products [4,7,13] include formic acid, levulinic acid, and furfural, formed via sugars and 5-hydroxymethylfurfural, while products from fermentation can be acetic acid [14,15], propionic acid [14,15], butyric acid [14,15], and L-lactic acid [14][15][16], but valeric acid [17], caproic acid [17], succinic acid [16,18], itaconic acid [16], mandelic acid [16], and alcohols [15] are also known to be produced.…”

“…In this work, a type V DES based on L-menthol and thymol, as shown by Abranches et al [48], or a TOPO and L-menthol DES, inspired by Gilmore et al [45] and Schaeffer et al [46], was applied to two bio refinery-relevant liquid-liquid extractions. Case I is the hydrolysis of lignocellulosic materials followed by an acid-catalyzed conversion of hexose and pentose sugars, which produces platform chemicals, such as levulinic acid, formic acid, and furfural [5,6,55]. The separation case involves the separation of formic acid and levulinic acid.…”

A Review on the Critical Role of H2 Donor in the Selective Hydrogenation of 5‐Hydroxymethylfurfural

“…The simultaneous possession of an aldehyde group, hydroxy group, and furan ring endows HMF with abundant downstream products via oxidation/hydrogenation. It is widely used in chemistry, [9] energy storage, [10] materials, [11] and pharmaceuticals [12] due to its cascaded upgrading. This Review focuses specifically on the selective hydrogenation of HMF to some valorized hydrogenation products, such as 2,5‐bis(hydroxymethyl)furan (BHMF), 2,5‐dimethylfuran (DMF), 1,6‐hexanediol (HDO), 2,5‐dimethyltetrahydrofuran (DMTHF), and so on (as shown in Figure 1), without the utilization of external molecular hydrogen.…”

One-pot synthesis of formic acid via hydrolysis–oxidation of potato starch in the presence of cesium salts of heteropoly acid catalysts

“…2,8,9 Methods for substitution of formic acid for molecular hydrogen in the processes for biofuel production were suggested. [9][10][11][12][13][14] Formic acid can be synthesized as a side product of glucose acidic dehydration into levulinic acid. 15 However, the amount of thus produced formic acid is insufficient.…”