Protein‐rich biomass provides a valuable feedstock for the chemical industry. This Review describes every process step in the value chain from protein waste to chemicals. The first part deals with the physicochemical extraction of proteins from biomass, hydrolytic degradation to peptides and amino acids, and separation of amino acid mixtures. The second part provides an overview of physical and (bio)chemical technologies for the production of polymers, commodity chemicals, pharmaceuticals, and other fine chemicals. This can be achieved by incorporation of oligopeptides into polymers, or by modification and defunctionalization of amino acids, for example, their reduction to amino alcohols, decarboxylation to amines, (cyclic) amides and nitriles, deamination to (di)carboxylic acids, and synthesis of fine chemicals and ionic liquids. Bio‐ and chemocatalytic approaches are compared in terms of scope, efficiency, and sustainability.

We report the water-induced transformation of the [Zn2(dobdc)] (dobdc = 2,5-dioxidobenzene-1,4-dicarboxylate) metal-organic framework UTSA-74 to its polymorph MOF-74(Zn), contrary to a previous report on the stability of UTSA-74 under such conditions. This dissolution-recrystallization process was investigated using time-resolved in situ X-ray diffraction and kinetically analyzed using the Gualtieri crystallization model.

While protein-rich biomass waste is nowadays mainly used for animal feed, conversion of its amino acid constituents to nitrogenous chemicals is a potential higher value route. To that end, the hydrogenation of amino acids to amino alcohols was studied in this work. Using a bimetallic Rh-MoOx/SiO2 catalyst, glutamic acid was for the first time hydrogenated to the aminodiol in high yield. By minimizing partial reduction and consecutive hydrogenolysis, and by suppressing the competitive cyclization to pyroglutamic acid (and derivatives thereof), glutamidiol was obtained in 77% yield at 70 bar H2 and 80 °C. High yields (typically > 80%) and selectivities were also achieved for most other natural amino acids, except for the S-containing amino acids 2 cysteine and methionine, which act as catalyst poisons. This limitation was overcome by applying a simple oxidation step with performic acid prior to the hydrogenation. The system was applied successfully to a mixture of amino acids obtained by hydrolysis of pre-oxidized bovine serum albumin. Amino alcohols were produced with high overall conversion (> 90%) and selectivity (88%) without the need for an intermediate, expensive and difficult separation step. The reaction proceeds with very high atom economies for both carbon and nitrogen, and generates only water as a by-product.

By combining experimental adsorption isotherms, microcalorimetric data, infrared spectroscopy and quantum chemical calculations the adsorption behaviour of the CPO-27/MOF-74 series (Ni, Co, Mg, Cu, and Zn) in the desulfurization of fuels is evaluated. The results show a clear influence of the metal ion on the adsorption capacity and affinity for S-heterocyclic compounds, with CPO-27(Ni) being the best performing material both in terms of capacity and affinity. The microcalorimetric data and infrared spectroscopy confirm the high affinity of CPO-27(Ni) for thiophene and similar compounds, while the computational data reveal that the origin of this outstanding adsorption performance is the strong sulfur-metal interaction.

Postsynthetic modification of high-alumina zeolites in hyperalkaline media can be tailored toward alteration of framework topology, crystal size and morphology, or desired Si/Al ratio. FAU, EMT, MAZ, KFI, HEU, and LTA starting materials were treated with 1.2 M MOH (M = Na, K, Rb, or Cs), leading to systematic ordered porosity or fully transformed frameworks with new topology and adjustable Si/Al ratio. In addition to the versatility of this tool for zeolite crystal engineering, these alterations improve understanding of the crystal chemistry. Such knowledge can guide further development in zeolite crystal engineering. Postsynthetic alteration also provides insight on the long-term stability of aluminosilicate zeolites that are used as a sorption sink in concrete-based waste disposal facilities in harsh alkaline conditions.