Catalytic condensation of depithed sugarcane bagasse derived levulinic acid into diphenolic acid

Abstract

Levulinic acid (LA) is a platform chemical that can be produced from biomass. Diphenolic acid (DPA) is a derivative of LA with the potential to replace bisphenol A, a plasticizer. To determine the optimum conditions for DPA production, commercial LA was used with a mild environmentally benign acid, namely, methanesulfonic acid (MsOH). The optimized reaction parameters were time (6 h), temperature (75 °C), and catalyst loading (5.5 g), yielding 65.8% DPA at 90% LA conversion. The response surface methodology (RSM) study indicated that the temperature had the most significant effect on DPA yield, followed by time and catalyst loading. The analysis of variance (ANOVA) revealed that the model was able to satisfactorily predict the DPA yield. To determine the effect of catalyst on DPA production from commercial LA, ionic liquids (ILs), MsOH, and sulfuric acid were used. IL catalysts produced 59 to 68% of DPA, MsOH produced 65.6% of DPA, and sulfuric acid produced the maximum DPA of 74%. The study of LA: phenol ratio revealed that more reactants (2:5) yielded the most DPA (86.35%). The optimized reaction conditions were then used to produce DPA from LA derived from depithed sugarcane bagasse (DSB), which yielded 64.5% of DPA.

Challenges and Opportunities in the Catalytic Synthesis of Diphenolic Acid and Evaluation of Its Application Potential

“…The authors found that HCl led to the highest LA conversion (entry 3, Table 2 , 65 mol%) but also to the lowest p , p ′-DPA/ o , p ′-DPA molar ratio (2.0), whilst the sulfamic acid resulted in the most promising catalyst (entry 10, Table 2 ), showing comparable conversion but with a much higher selectivity towards the p , p ′-DPA isomer ( p , p ′-DPA/ o , p ′-DPA molar ratio of 7.4) and the yield of 51 mol%. Mthembu et al [ 33 ] optimized the Response Surface Methodology (Box–Behnken) for the condensation reaction between commercial LA and phenol by employing methanesulfonic acid as the homogeneous catalyst. The effects of the reaction time, temperature, and acid loading were investigated while keeping constant the LA/phenol molar ratio (3.7).…”

“…Only a slight decrease in the p , p ′-DPA yield up to the value of 85 mol% was observed, which was mainly attributed to some loss of the ionic liquid that occurred during the separation step. Mthembu et al [ 33 ] employed [EMIM][OTs] and [BMim]HSO 4 , considering the catalysis with H 2 SO 4 (entry 5, Table 2 ), p -TSA (entry 9, Table 2 ), and CH 3 SO 3 H (entry 11, Table 2 ), for comparison purposes. Maximum DPA yields of 59 and 68 mol% were obtained with such ionic liquids (entries 78 and 79, Table 6 ), which are comparable to those already reported for the homogeneous catalysts.…”

“…Some niche applications of DPA have been proposed, including the production of thermal paper for printers [ 50 ], coatings, and adhesives [ 51 , 52 , 53 ]. Moreover, DPA and its derivatives show good antioxidant, antiviral, and antibacterial properties, making them suitable for the development of valuable applications in the cosmetic, food, textile, and polymer sectors [ 27 , 33 , 54 , 55 ]. Such materials could be obtained from the diphenolate derivatives.…”

“…These general issues are stimulating the development of new catalysts to perform DPA synthesis with the intention of improving the activity and the selectivity towards the p , p ′-DPA isomer and, above all, overcoming the corrosion and separation problems. In this context, sulfonated acid catalysts [ 19 , 27 , 30 , 31 ], heteropolyacids [ 16 , 18 , 20 , 30 , 32 ], zeolites and oxides [ 18 , 27 ], as well as ionic liquids [ 21 , 22 , 33 ] have been proposed for DPA synthesis in the search for further improvement of the selectivity to the p , p ′-DPA isomer. In this context, the use of a thiolic derivative as a co-catalyst was proposed by Van De Vyver et al [ 30 , 31 ] to further improve the selectivity to the p , p ′-DPA isomer.…”

Selective Conversion of Glucose to Levulinic Acid Catalyzed by HPAs/MOF-5 in a Hydrophilic Eutectic Solvent System

“…In the biological refining industry, 5-HMF is recognized as an important and renewable platform chemical. , Its derivatives include 2,5-furfuryldiamine, 2,5-furfuryldiisocyanate, and 5-hydroxymethyl furfurylidenester, all of which are excellent raw materials for the production of polymers like polyester, polyamide, and polyurethane. − However, 5-HMF is unstable in acidic environments and can easily be further converted into LA. LA is also one of the top 12 bio-based platform chemicals listed by the U.S. Department of Energy and can be used to produce γ-valerolactone, succinic acid, 1,4-pentanediol, bisphenolic acid, maleic anhydride, and other chemicals. − These derivatives can then be used as solvents and fuel additives or in the production of polymers, battery electrolytes, and so forth …”