Novel aqueous-phase hydrogenation reaction of the key biorefinery platform chemical levulinic acid into γ-valerolactone employing highly active, selective and stable water-soluble ruthenium catalysts modified with nitrogen-containing ligands

Recent Advances in Ruthenium-Catalyzed Hydrogenation Reactions of Renewable Biomass-Derived Levulinic Acid in Aqueous Media

“…Consequently, numerous steps in classical homogeneous industrial processes are rendered superfluous and process engineering is enormously simplified, resulting in substantial energy savings and lower emissions and (iii) new types of catalytic reactivities have been observed in the aqueous medium. The catalytic activities were much higher in water compared to organic solvents in various and different types of catalytic reactions such as hydrogenation (Moustani et al, 2018), hydrocarboxylation , and hydroformylation reactions (Fremy et al, 1995), which contrasts with the general perception that aqueous-phase catalysis normally exhibits lower rates compared to analogous catalytic reactions in organic solvents. Water-soluble rhodium catalytic complexes with trisulfonated triphenylphosphine ligands (TPPTS, Figure 8) have found important industrial applications such as in the Ruhrchemie/Rhône-Poulenc process for the hydroformylation of the lower olefins propylene and 1-butene, which is rich in the raffinate II mixture [raffinate II consists of 1-butene, 2-butenes (cis/trans) and butanes (n-/iso-) obtained from C 4 -stream of naphtha crackers] and in the Rhône-Poulenc process for the synthesis of vitamin E and A intermediates in aqueous/organic two-phase systems.…”

“…The highest activity of TOF = 210 h −1 was exhibited by the RuCl 3 •3H 2 O/TPPTS catalytic system, whereas with the Ru(acac) 3 /TPPTS system the activity was lower to achieve 202 TOF's per hour, and the conversion of LA and selectivity to GVL were 99 and 97 mol%, respectively. Moustani et al (2018) investigated the hydrogenation reaction of LA using RuCl 3 •3H 2 O, Ru(NO)(OAc) 3 , Ru(NO)(NO 3 ) 3 , Ru(acac) 3 , [Ru(NO)] 2 (SO 4 ) 3, and RuO 2 •H 2 O catalyst precursors modified with water-soluble phosphine and especially with nitrogen-containinig ligands such as TPPTS, PTA, bathophenanthrolinedisulfonic acid disodium salt (BPhDS), bathocuproinedisulfonic acid disodium salt (BCDS), 2-aminoethanesulfonic acid (taurine), nitrilotriacetic acid trisodium salt (NTA•Na 3 ), ethylenediaminetetraacetic acid tetrasodium salt (EDTA•Na 4 ), 2,2'-biquinoline-4,4'dicarboxylic acid dipotassium salt (BQC), tris(2-pyridyl)phosphine (T 2 PyP), N,N'-2,2'-bipyridine-4,4'-dicarboxylic acid (BPyDCA), diethylenetriaminepentakis(methylphosphonic acid) (DTPPA), diethylenetriaminepentaacetic acid pentasodium salt (DTPA•Na 5 ) and 3-pyridinesulfonic acid (3-PSA) (Figure 8) in the aqueous monophasic system. The highest activity of TOF = 3,000 h −1 was obtained with RuCl 3 •3H 2 O/BPhDS catalysts at 140 • C, 80 bar H 2 pressure within 1 h and molar ratios of LA/Ru = 3,000 and BPhDS/Ru=1 with addition of 5 ml of aqueous solvent by a ruthenium concentration of 75 ppm and pH value of 2.43 where the conversion of LA was quantitative with essentially quantitative selectivity to GVL of 99.9 mol% and formation of only 0.1 mol % of the 1,4-PDO byproduct.…”

NNN Pincer‐functionalized Porous Organic Polymer Supported Ru(III) as a Heterogeneous Catalyst for Levulinic Acid Hydrogenation to γ‐Valerolactone

“…( Table 2, entry 9-13 and Figure S16) Interestingly, these results are similar to those reported previously for a homogeneous Ru catalyst with N-based ligands, suggesting that the immobilized Ru/3-bpp-POP catalytic site functions similarly to its homogenous counterparts. [71] However, the catalytic activity of Ru/3bpp-POP decreased to 86.6 % at 30 bar and 26.3 % at 10 bar; therefore, the total reaction pressure was maintained at 50 bar. ( Table 2, entry 7 and 8)…”

Carbonyl Reduction and Biomass: A Case Study of Sustainable Catalysis

“…More recent developments were applied to LA hydrogenation, using water-soluble phenanthroline ligands (BPhDS, Scheme 9C) . [99][100] Scheme 9. Approaches for carbonyl reduction in H2O: A) Using surfactants B) Using watersoluble catalysts C) Application to LA hydrogenation.…”