Catalytic hydrodeoxygenation and hydrocracking of Alcell^® lignin in alcohol/formic acid mixtures using a Ru/C catalyst

The catalytic conversion of Alcell^® lignin in iso-propanol/formic acid mixtures (1:1 mass ratio) was explored in a batch set-up using Ru/C as the catalyst (673 K, 4 h, 28% mass lignin intake on solvent). Lignin oils were obtained in good yields (71% mass yields on lignin input) and shown to consist of a mixture of mainly aromatics (10.5% mass yields on lignin input), alkylphenolics (6% mass yields on lignin input), catechols (8.7% mass yields on lignin input), guaiacols (1.3% mass yields on lignin input), and alkanes (5.2% mass yields on lignin input), the remainder being soluble higher molecular weight compounds (GCxGC-FID and GPC). The results for the catalytic experiments using formic acid were compared with those of a non-catalysed experiment and a catalytic hydrotreatment with molecular hydrogen and Ru/C in the absence of a solvent. Distinct differences in product yields and compositions were observed, and highest lignin oil yields were obtained by catalytic solvolysis (71% mass yields on lignin input) versus 18% mass yields on lignin input for non-catalytic solvolysis and 63% mass yields on lignin input for catalytic hydrotreatment. The effect of reaction time on oil yields and product composition was established and a reaction network involving depolymerisation, and hydro(-deoxy)genation pathways is proposed to explain the product yields and composition. Besides iso-isopropanol, the use of ethanol and methanol in combination with formic acid was also explored for catalytic solvolysis. Best results were obtained in methanol (4 h, 673 K) leading to a lignin oil (68% mass yields on lignin input) containing 11% mass yields on lignin input of alkylphenolics and 19% mass yields on lignin input of aromatics.