Sustainable Continuous Flow Valorization of γ‐Valerolactone with Trioxane to α‐Methylene‐γ‐Valerolactone over Basic Beta Zeolites

Abstract

The need for more sustainable products and processes has led to the use of new methodologies with low carbon footprints. In this work, an efficient tandem process is demonstrated for the liquid‐phase catalytic upgrading of lignocellulosic biomass‐derived γ‐valerolactone (GVL) with trioxane (Tx) to α‐methylene‐γ‐valerolactone (MeGVL) in flow system using Cs‐loaded hierarchical beta zeolites. The introduction of mesopores along with the presence of basic sites of mild strength leads to MeGVL productivity 20 times higher than with the bulk beta zeolite, reaching 0.325 mmol min−1 gcat−1 for the best‐performing catalyst, the highest value reported so far. This catalyst proves stable upon reuse in consecutive cycles, which is ascribed to the partial depletion of the basic sites. The obtained MeGVL is subjected to visible‐light‐induced polymerization, resulting in a final material with similar properties to the widely used poly(methyl) methacrylate.

Pentanoic acid from γ-valerolactone and formic acid using bifunctional catalysis

“…[1][2][3][4][5][6][7][8][9][10] Recently, a large number of reports dealing with the production of chemicals and liquid transportation fuels from lignocellulosic biomass was published. [12][13][14][15][16][17][18][19][20] Among them, the homogeneously and hetero-geneously aqueous-phase hydrogenation of levulinic acid (LA) to pentanoic acid (PA) through γ-valerolactone (GVL) and pentenoic acids (PEAs) has received significant attention. [10][11][12][13][14][15][16][17][18][19][20][21] This correlates to the straightforward and robust production of LA, i.e., via acid catalysis of lignocellulosic biomass, with an equimolar formation of aqueous formic acid (FA).…”

“…[12][13][14][15][16][17][18][19][20] Among them, the homogeneously and hetero-geneously aqueous-phase hydrogenation of levulinic acid (LA) to pentanoic acid (PA) through γ-valerolactone (GVL) and pentenoic acids (PEAs) has received significant attention. [10][11][12][13][14][15][16][17][18][19][20][21] This correlates to the straightforward and robust production of LA, i.e., via acid catalysis of lignocellulosic biomass, with an equimolar formation of aqueous formic acid (FA). The latter crude can be used as an alternative and sustainable source of H 2 , thus avoiding the production of external H 2 , which is currently produced from fossil methane.…”

Graphitic carbon nitride and polymers: a mutual combination for advanced properties

“…First of all, g-C 3 N 4 polymerizations can be operated in the visible light region, which is a benign and abundant trigger. Several monomers were investigated for polymerization via g-C 3 N 4 as photoinitiator, such as styrene, 53 methyl methacrylate (MMA), 54 a-methylene-g-valerolactone (MeGVL), 55 methyl acrylate (MA). 56 On top, photopolymerizations have various useful features, like spatial and temporal control.…”

“…Furthermore, our team has employed g-C 3 N 4 as heterogeneous photocatalyst for free radical polymerization of MeGVL. 55 At first MeGVL is efficiently synthesized from renewable resources via continuous flow reaction from g-valerolactone over hierarchical basic zeolite. MeGVL is structurally similar to methacrylic monomers, and further valorization of this compound via efficient polymerization demonstrates the ability to make novel biomassderived polymer with significant industrial interest.…”

Nickel on nitrogen-doped carbon pellets for continuous-flow hydrogenation of biomass-derived compounds in water

“…S3 †). 64 This system consists of: (i) HPLC pump equipped with a pressure sensor (Knauer Azura P 4.1S Series), (ii) a two-side opened heating mantle equipped with a heat controller (Model # 4848 from the Parr Instrument Company), (iii) massflow controller to supply H 2 (Series SLA5800, Model SLA5850SC1AF1B2A1 from Brooks Instruments), (iv) tee union for gas-liquid mixer (Swagelok SS-400-30) to mix the supplied H 2 with the reaction solution before reaching the pre-heating unit and the catalyst bed, and (v) sampling unit equipped with proportional relief valves as a pressure regulator (Swagelok SS-RL4M8F8-EP). To ensure efficient heat transfer from the oven to the fixed bed reactor, an aluminium cylinder with three different holes was placed inside the oven, i.e., a 1/16″ hole as a pre-heating unit to heat the reactant to the desired reaction temperature before it comes into contact with the catalyst bed, a 1/4″ hole to place the fixed bed reactor (tubular reactor; inner diameter = 4.6 mm, outer diameter = 6.5 mm, and length = 25 mm), and a third hole for the thermocouple (Model # A472E5 from the Parr Instrument Company), cf.…”