Search for: All records

Abstract The catalytic hydrothermal liquefaction of biomass under a hydrogen atmosphere is a promising technology to produce stable biocrude oil as a sustainable alternative to petroleum crude. A series of iron‐based non‐noble mix metal‐oxide‐on‐silica catalysts were evaluated to mimic the natural transformation that may have led to the conversion of terrestrial biomass to fossilized fuels. Switchgrass powder was liquefied to a stable bio‐oil with a 71.2% yield by using FeO_x/SiO₂catalyst in ethanol under a 5.5 MPa hydrogen atmosphere at 210 °C. The use of Fe‐MO_x/SiO₂(M = V, Mn, Co, Ni, Cu and Mo) type bimetallic oxide catalysts instead of FeO_x/SiO₂can produce improvements in liquefaction yields by using Mn, Co, Ni, and Cu as the second metal. The highest liquefaction yield of 78.8% was observed with the Fe‐CuO_x/SiO₂catalyst. Liquefaction oils were formed that were composed of complex mixtures of C6‐C12 alcohols, esters, aldehydes, and phenols. The lignin products:holocellulose products ratio changed in the range 0.35 to 0.15 and the composition of oils changed significantly with the use of mixed metal oxides in place of single metal FeO_x/SiO₂The most effective catalyst, Fe‐CuO_x/SiO₂could be reused in five cycles with a small loss in liquefaction yield from 78.8% to 70.0% after four reuse cycles and after regeneration of the catalyst at 500 °C for 3 h in air. 

Energetic ionic liquids (EILs) have various industrial applications because they release chemically stored energy under certain conditions. They can avoid some environmental problems caused by traditionally used toxic fuels. EILs, which are environmentally friendly and safer, are emerging as an alternative source for hypergolic bipropellant fuels. This review focuses on the crucial thermophysical properties of the EILs. The properties of imidazolium and triazolium-based ionic liquids (ILs) are discussed here. The thermophysical properties addressed, such as glass transition temperature, viscosity, and thermal stability, are critical for designing EILs to meet the need for sustainable energy solutions. Imidazolium-based ILs have tunable physical properties making them ideal for use in energy storage while triazolium-based ILs have thermal stability and energetic potential. As a result, it is important to understand and compile thermophysical properties so they can help researchers synthesize tailored compounds with desirable characteristics, advancing their application in energy storage and propulsion technologies. 

Development of efficient catalytic methods for the hydrolysis of cellulose is a major research challenge in sustainable biofuel and polymer areas. In this study five hydroxy sulfonic acids were studied as simple model compounds for cellulase enzyme for the hydrolysis of cellulose. The catalytic activities were measured by analysis of total reducing sugar (TRS) yields produced in a series of reactions carried out at 150–190 °C using 0.050 M aqueous hydroxy sulfonic acid solutions. The highest catalytic activity was observed with isethionic acid, producing 62.7% TRS yield at 180 °C after 4 hr. In the second phase of the work, Density Functional Theory (DFT) calculations were used to study the interactions between hydroxy sulfonic acids and cellulose model compound D-cellobiose to supplement the experimental results. The D-cellobiose – hydroxy sulfonic binding energies and the distance between glycosidic oxygen and -SO3H acidic H were evaluated and the -SO3H to glycosidic oxygen distance was identified as the more important parameter co-related to the catalytic activity. The isethionic acid with highest cellulose hydrolysis activity showed the shortest -SO3H to glycosidic oxygen distance of 1.744 Å. 

aims: Processing of cellulose can be used to produce value added renewable feedstock chemicals. background: Catalytic depolymerization and processing of cellulose can be used to produce value added renewable feedstock chemicals. objective: Development of an acidic ionic liquid - metal ion chloride catalyst system based single-reactor method for processing cellulose to value added products. method: The effect of metal chlorides as co-catalysts on 1-(1-propylsulfonic)-3-methylimidazolium chloride acidic ionic liquid catalyzed degradation of cellulose in 40 % (v/v) aq. ethanol was studied by measuring levulinic acid, ethyl levulinate and 5-hydroxymethylfurfural yields. result: In experiments with Mn(II), Zn(II) chloride co-catalysts at 160 and 170 °C for 12 h, the initial yields of ethyl levulinate and 5-hydroxymethylfurfural improved from ~ 7 % to ~ 12-15% due to co-catalytic effects. The highest enhancements in ethyl levulinate yields were observed with CrCl3, where the yield increased from 6 to 27 % with the addition of 10 mol% co-catalyst. conclusion: All three transition metal chlorides studied produced improvements in yields of secondary products, ethyl levulinate and 5-hydroxymethylfurfural in acidic ionic liquid catalyzed degradation of cellulose in aqueous ethanol. The most significant enhancements in ethyl levulinate yields were observed with CrCl3 as a co-catalyst. other: none 

Background:Polycarboxylic acids are of interest as simple mimics for cellulase enzyme catalyzed depolymerization of cellulose. In this study, DFT calculations were used to investigate the effect of structure on dicarboxylic acid organo-catalyzed hydrolysis of cellulose model compound D-cellobiose to D-glucose. Methods:Binding energy of the complex formed between D-cellobiose and acid (Ebind), as well as glycosidic oxygen to dicarboxylic acid closest acidic H distance were studied as key parameters affecting the turn over frequency of hydrolysis in water. Result:α-D-cellobiose - dicarboxylic acid catalyst down face approach showed high Ebind values for five of the six acids studied; indicating the favorability of down face approach. Maleic, cis-1,2-cyclohexane dicarboxylic, and phthalic acids with the highest catalytic activities showed glycosidic oxygen to dicarboxylic acid acidic H distances 3.5-3.6 Å in the preferred configuration. Conclusion:The high catalytic activities of these acids may be due to the rigid structure, where acid groups are held in a fixed geometry.