Sustainable Routes for the Synthesis of Renewable Heteroatom-Containing Chemicals

Abstract

One of the biggest discrepancies between the structure of many utilized chemicals and petrochemicals is the ubiquity of heteroatoms in the former and the lack thereof in the latter. Many commodity chemicals and almost all specialty chemicals and pharmaceuticals contain one or more heteroatoms, but introducing functionalities containing oxygen, nitrogen, sulfur or phosphorus into crude oil-derived chemicals is often a very energy- and resource-intensive endeavor. This and the inevitable depletion of fossil resources in the not too distant future are the main reasons for the development of sustainable ways to produce compounds bearing heteroatoms. Synthesis of oxygen-containing compounds from renewable resources such as starch, cellulose and hemicellulose is already well-known, and the production of phenolic compounds from lignin is garnering significant attention recently. In the meantime, there is a surge in the valorization of chitin from waste crustacean and insect shells for the production of various nitrogen-containing compounds. Much less explored is the valorization of sulfur- and phosphorus-containing biomass components, although they find some high market value applications. Catalysis plays a central role to enable the conversion of biomass into value-added products with high activity and selectivity. Further developments made by chemical engineers and process technologists will be required to make those processes economically feasible and competitive with current synthetic schemes from fossil resources. This perspective highlights the most recent advances and the upcoming challenges in the development of renewable and sustainable routes toward heteroatom-containing chemicals.

General Protocol to Obtain D‐Glucosamine from Biomass Residues: Shrimp Shells, Cicada Sloughs and Cockroaches

“…Given such challenges to provide life with biological useful nitrogen, it is crucial to find natural and renewable sources of “fixed” nitrogen . In the past decades, production of useful chemical compounds from biomass residues has grown in importance due to the high consumption of Earth's natural resources . Chitin, a nitrogen‐containing polymer, is the second most abundant natural polymer on Earth, being cellulose the first one.…”

“…The industrial processing of crustaceans for food production generates large amounts of waste, in which 50%–60% of the total dry weight is shells . Such composite structure has low biodegradation rates; therefore, accumulation of large quantities of shells has become a major concern .…”

“…[15][16][17] In the past decades, production of useful chemical compounds from biomass residues has grown in importance due to the high consumption of Earth's natural resources. [18,19] Chitin, a nitrogen-containing polymer, is the second most abundant natural polymer on Earth, being cellulose the first one. Chitin is a linear biomacromolecule composed of N-acetyl glucosamine subunits linked together through covalent β(1 → 4) glycosidic bonds (Figure 1).…”

Leather‐Promoted Transformation of Glucose into 5‐Hydroxymethylfurfural and Levoglucosenone

“…The transformation of lignocellulosic compounds into key platform chemicals has attracted considerable attention in recent years . In particular, the transformation of cellulose and glucose into 5‐hydroxymethylfurfural (5‐HMF) has been extensively investigated because of the low cost and availability of the starting materials combined with the versatility of the product (Scheme ) . In this context, a plethora of metal‐based and nonmetal catalysts have been reported to generate 5‐HMF (see Table S1 in the Supporting Information for examples) .…”

“…[1][2][3][4] In particular, the transformation of cellulose and glucose into 5-hydroxymethylfurfural( 5-HMF) has been extensively investigatedb ecause of the low cost and availability of the startingm aterials combined with the versatility of the product (Scheme 1). [5] In this context,aplethora of metal-based and nonmetal catalysts have been reported to generate 5-HMF (see Ta bleS1i nt he Supporting Information for examples). [6][7][8][9][10][11][12][13][14] Other valuable products that can be derived fromb iomass sourcesi nclude levoglucosenone, furfural, and levulinic acid.…”