Stability of Gamma-valerolactone Under Pulping Conditions as a Basis for Process Optimization and Chemical Recovery

This study investigates the extent of the g-valerolactone (GVL) hydrolysis forming an equilibrium with 4-hydroxyvaleric acid (4-HVA) in aqueous solutions over a wide pH range. The hydrolysis of pure 50 wt% GVL to 4-HVA (3.5 mol%) was observed only at elevated temperatures. The addition of sulfuric acid (0.2×10-5 wt% to 6 wt%) at elevated temperatures (150 – 180°C) and reaction times between 30-180 min caused the formation of 4 mol% 4-HVA but with decreasing acidity, the 4-HVA remained constant at about 3 mol%. The hydrolysis reactions in alkaline conditions were conducted at constant time (30 min) and temperature (180 °C) with variation of the NaOH concentration (0.2×10-6 wt% to 7 wt%). The addition of less than 0.2 wt % of NaOH resulted in the formation of less than 4 mol% of sodium 4-hydroxyvalerate. A maximum amount of 21 mol% of 4-HVA was observed in a 7 wt% NaOH solution. The stability after synthesis was determined by NMR analysis. To verify the GVL stability results obtained under practical conditions, Betula pendula sawdust was fractionated in 50% GVL with and without addition of H2SO4 or NaOH at 180°C and 120 min, and spent liquor was analyzed. The spent liquor contained 5.6 mol% and 6.0 mol% of 4-HVA in a highly acidic (20 kg H2SO4/t wood) and alkaline (192 kg NaOH/ t wood) environment, respectively.