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Uniformly dispersed 5 wt % ruthenium catalysts supported on Al x SBA-15 (x = Si/Al ratio) were prepared by chemical fluid deposition employing supercritical CO2 as the solvent for hydrogenating dimethyl terephthalate to dimethyl 1,4-cyclohexanedicarboxylate in water. Complete conversion of dimethyl terephthalate was achieved over a Ru5/Al20SBA-15 catalyst having the highest number of Lewis acid sites at 100 °C and 4.14 MPa H2 pressure in 1 h. Here, 100% selectivity with a dimethyl 1,4-cyclohexanedicarboxylate yield of 93.4% was observed in 0.5 h due to complete cutoff of hydrocracking byproducts at shorter reaction times. Al modification enhanced selectivity of the catalysts toward dimethyl 1,4-cyclohexanedicarboxylate by governing the distribution of Lewis and Brönsted acid sites in the support. Water as a functional solvent enriched the hydrogenation of dimethyl terephthalate via an on-water mechanism. The Ru5/Al20SBA-15 catalyst was stable over five cycles. Greener catalyst synthesis, use of water, mild reaction conditions, and high atom economy led the proposed system to be a greener sustainable process.

The solvent free hydrogenation of DOP to DEHHP over an Al modified MCF supported Rh catalyst.