Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil

Abstract

Asimple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass.T he overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC x / Ci sapromising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired ArÀOH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography,s erving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass,n of urther synthetic steps,a nd no input of additional (e.g., petrochemical) platform molecules.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Bright Side of Lignin Depolymerization: Toward New Platform Chemicals

“…4-Alkylphenols are interesting candidates to serve as replacements for petroleum-derived phenols in several applications 143 , 230 and can also be used as the intermediates for the production of phenols. 231 Several groups have studied the possibilities to obtain phenols by demethoxylation of guaiacols ( Table 3 ) including the most widely applied molybdenum-based catalysts 302 − 308 as well as Re/ZrO 2 , 309 WP/SiO 2 , 310 and Au/TiO 2 ; 311 however, these often suffer either from low activity or low selectivity.…”

Selective valorization of lignin to phenol by direct transformation of C sp2 –C sp3 and C–O bonds

“…4′-Methoxypropiophenone (99%), 4′-methoxyacetophenone (99%), 3′,4′-dimethoxyacetophenone (98+%), 3′,4′,5′-trimethoxyacetophenone (99%), 4′-methoxybutyrophenone (97%), 4-methoxyphenylacetone (97+%), 4-methoxybenzaldehyde (98%), 4-hydroxybenzaldehyde (98%), 3,4-dimethoxybenzaldehyde (99%), 4-hydroxy-3-methoxybenzaldehyde (99%), 3,4,5-trimethoxybenzaldehyde (98%), 4′-hydroxy-3′,5′dimethoxybenzaldehyde (97%), 2-methoxyphenol (98+%), bromoethane (98%), 1-bromohexane (99%), 1-bromododecane (98%), 2-phenylethyl bromide (98%), 1-bromo-3-phenylpropane (98%), (±)-1-phenyl-1-propanol (98+%), magnesium turnings (99+%), 4-npropylphenol (98%), benzoyl chloride (99+%), thionyl chloride (99+%), phosphorus tribromide (99%), triethylamine (99+%), mordenite 10 ammonium zeolite, aluminum oxide (99.5%), silicon dioxide (99.5%), ruthenium(III) chloride (anhydrous; Ru 47.7%), nickel(II) nitrate hexahydrate (98%), zirconium dichloride oxide octahydrate (98%), niobium(V) oxide (99.5%), chromium(III) acetylacetonate (97%), oxalic acid dehydrate (98%), and 4-hydroxybenzoic acid (99%) were purchased from Alfa Aesar. 50 , and MCM-41 were pretreated by calcination at 550°C for 4 hours.…”

“…Biphenyl was used as the internal standard to determine the conversions of substrates, selectivities, and yields of the products. The carbon balance for the transformation of the model compounds was calculated using C aromatics balances, which was given relative to the aromatic products (50). The C aromatics balances for the transformation of the model compounds were larger than 95%.…”

Self-supported hydrogenolysis of aromatic ethers to arenes

“…Identification of the products in the aqueous phase was conducted by 1 H NMR analysis on a Bruker Avance III 400 HD with D 2 O as the solvent. The carbon balance for the transformation of the aromatic ethers was composed of C aromatics and C methoxyl balances, which were given relative to the aromatic and methoxyl-derived products, respectively ( 51 ). The C aromatics and C methoxyl balances for the transformation of small-molecule aromatic ethers were better than 99 and 98%, respectively.…”