Navadol Laosiripojana

Catalytic conversion of sugarcane bagasse, rice husk and corncob in the presence of TiO2, ZrO2 and mixed-oxide TiO2-ZrO2 under hot compressed water (HCW) condition.

The simultaneous hydrolysis/dehydration reaction of sugarcane bagasse, rice husk and corncob was studied under hot compressed water in the presence of TiO(2), ZrO(2) and TiO(2)-ZrO(2) at 473-673K. Among them, the reaction of corncob at 573K in the presence of TiO(2)-ZrO(2) produced the highest furfural and 5-hydroxymethylfurfural (HMF) yields (10.3% and 8.6%) with less by-products (i.e. glucose, fructose, xylose, and 1,6-anhydroglucose) selectivities. It was found that the catalyst preparation procedure and calcination temperature strongly affected its reactivity. Catalysts prepared by (co-) precipitation method gained higher reactivity than those prepared by sol-gel and physical mixing methods. The suitable calcination temperature for TiO(2) and ZrO(2) was at 773K, whereas that for TiO(2)-ZrO(2) was at 873K; the XRD patterns revealed that different portions of phase formation were observed over catalysts with different calcination temperature. The portion of these phase formations affected the acidity-basicity of catalyst and thus the catalyst reactivity.

Hydrolysis/dehydration/aldol-condensation/hydrogenation of lignocellulosic biomass and biomass-derived carbohydrates in the presence of Pd/WO3-ZrO2 in a single reactor.

Hydrolysis/dehydration/aldol-condensation/hydrogenation of lignocellulosic-biomass (corncobs) and biomass-derived carbohydrates (tapioca flour) to produce water-soluble C5-C15 compounds was developed in a single reactor system. WO3-ZrO2 efficiently catalyzed the hydrolysis/dehydration of these feedstocks to 5-hydroxymethylfurfural and furfural, while the impregnation of WO3-ZrO2 with Pd allowed sequential aldolcondensation/hydrogenation of these furans to C5-C15 compounds. The highest C5-C15 yields of 14.8-20.3% were observed at a hydrolysis/dehydration temperature of 573 K for 5 min, an aldol-condensation temperature of 353 K for 30 h, and a hydrogenation temperature of 393 K for 6 h. The C5-C15 yield from tapioca flour was higher than that from corncobs (20.3% compared to 14.8%). Tapioca flour produced more C6/C9/C15, whereas corncobs generated more C5/C8/C13 compounds due to the presence of hemicellulose in the corncobs. These water-soluble organic compounds can be further converted to liquid alkanes with high cetane numbers for replacing diesel fuel in transportation applications.

Optimisation of synergistic biomass-degrading enzyme systems for efficient rice straw hydrolysis using an experimental mixture design

Synergistic enzyme system for the hydrolysis of alkali-pretreated rice straw was optimised based on the synergy of crude fungal enzyme extracts with a commercial cellulase (Celluclast™). Among 13 enzyme extracts, the enzyme preparation from Aspergillus aculeatus BCC 199 exhibited the highest level of synergy with Celluclast™. This synergy was based on the complementary cellulolytic and hemicellulolytic activities of the BCC 199 enzyme extract. A mixture design was used to optimise the ternary enzyme complex based on the synergistic enzyme mixture with Bacillus subtilis expansin. Using the full cubic model, the optimal formulation of the enzyme mixture was predicted to the percentage of Celluclast™: BCC 199: expansin=41.4:37.0:21.6, which produced 769 mg reducing sugar/g biomass using 2.82 FPU/g enzymes. This work demonstrated the use of a systematic approach for the design and optimisation of a synergistic enzyme mixture of fungal enzymes and expansin for lignocellulosic degradation.

Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot compressed water

The phosphates of alkaline earth metals (calcium and strontium) synthesized by precipitation process in acetone-water media system were used as catalysts for converting fructose, glucose, and cellulose to 5-hydroxymethylfurfural (HMF) under hot compressed water condition. It was found that the phosphates of calcium and strontium effectively catalyzed the HMF formation from fructose and glucose dehydration and cellulose hydrolysis/dehydration reaction, as compared with the non-catalytic system. The XRD analysis confirmed the CaP(2)O(6) and α-Sr(PO(3))(2) crystalline phases of the catalyst samples, while acid strength of both catalysts was in a range of +3.3 ≤ H(0) ≤ +4.8. From the study, CaP(2)O(6) and α-Sr(PO(3))(2) showed similar catalytic performance toward the dehydration of sugars, providing the HMF yields of 20-21% and 34-39% from glucose and fructose, respectively; whereas the total yield of glucose and HMF from the hydrolysis/dehydration of cellulose over α-Sr(PO(3))(2) (34%) was higher than that over CaP(2)O(6) (17.4%).

Synthesis of methyl esters from relevant palm products in near-critical methanol with modified-zirconia catalysts

The transesterification and esterification of palm products i.e. crude palm oil (CPO), refined palm oil (RPO) and palm fatty acid distillate (PFAD) under near-critical methanol in the presence of synthesized SO(4)-ZrO(2), WO(3)-ZrO(2) and TiO(2)-ZrO(2) (with various sulfur- and tungsten loadings, Ti/Zr ratios, and calcination temperatures) were studied. Among them, the reaction of RPO with 20%WO(3)-ZrO(2) (calcined at 800 degrees C) enhanced the highest fatty acid methyl ester (FAME) yield with greatest stability after several reaction cycles; furthermore, it required shorter time, lower temperature and less amount of methanol compared to the reactions without catalyst. These benefits were related to the high acid-site density and tetragonal phase formation of synthesized WO(3)-ZrO(2). For further improvement, the addition of toluene as co-solvent considerably reduced the requirement of methanol to maximize FAME yield, while the addition of molecular sieve along with catalyst significantly increased FAME yield from PFAD and CPO due to the inhibition of hydrolysis reaction.

Optimized simultaneous saccharification and co-fermentation of rice straw for ethanol production by Saccharomyces cerevisiae and Scheffersomyces stipitis co-culture using design of experiments.

Herein an ethanol production process from rice straw was optimized. Simultaneous saccharification and co-fermentation (SSCF) using Saccharomyces cerevisiae and Scheffersomyces stipitis co-culture was carried out to enhance ethanol production. The optimal saccharification solid loading was 5%. Key fermentation parameters for co-culture including cell ratio, agitation rate and temperature was rationally optimized using design of experiment (DoE). Optimized co-culture conditions for maximum ethanol production efficiency were at S. cerevisiae:S. stipitis cell ratio of 0.31, agitation rate of 116 rpm and temperature of 33.1°C. The optimized SSCF process reached ethanol titer of 15.2g/L and ethanol yield of 99% of theoretical yield, consistent with the DoE model prediction. Moreover, SSCF process under high biomass concentration resulted in high ethanol concentration of 28.6g/L. This work suggests the efficiency and scalability of the developed SSCF process which could provide an important basis for the economic feasibility of ethanol production from lignocelluloses.

Methane conversion over Nb-doped ceria

Methane steam reforming and dry methane conversion over ceria, and ceria doped with 1.4 and 5% Nb cation has been investigated at 900 °C (a typical solid oxide fuel cell temperature). The influence of the calcination atmosphere on the Nb-doped ceria has also been studied. Use of reducing conditions leads to significantly lower crystallite size, higher specific surface area and greater Nb solubility. Nb-doping lowers activity mainly as a consequence of strong segregation of Nb to the ceria surface. Kinetics of steam reforming are interpreted in terms of a redox mechanism.

Thermodynamic Analysis for Gasification of Thailand Rice Husk with Air, Steam, and Mixed Air/Steam for Hydrogen-Rich Gas Production

Thermodynamic analysis of gasification with air, steam, and mixed air-steam was performed over rice husk to determine the optimum conditions (i.e., equivalence ratio (ER), steam to biomass ratio (SBR) and operating temperature) that can maximize the yield of hydrogen production with low energy consumption. It was found that for air gasification, H2 production is always less than CO production and considerably decreased with increasing ER. For steam gasification, the simulation revealed that H2 production is greater than CO, particularly at high SBR and low temperature; furthermore, H2 yield increased steadily with increasing temperature and SBR until reaching SBR of 3.5-4.0, then the effect of steam on H2 yield becomes less pronounced. As for the mixed steam/air gasification, H2 production yield increased with increasing SBR, but decreased dramatically with increasing ER (up to 0.4). Among these three operations, the highest H2 production yield can be achieved from the steam gasification with SBR of 4.0. Nevertheless, by considering the system efficiency, the combined air-steam gasification provided significant higher hydrogen production efficiency than the other two operations. The optimum condition for combined air-steam gasification can be achieved at 900°C with ER of 0.1 and SBR of 2.5, which provided the efficiency up to 66.5 percent.

Effects of acid and alkali promoters on compressed liquid hot water pretreatment of rice straw.

In this study, effects of homogeneous acid and alkali promoters on efficiency and selectivity of LHW pretreatment of rice straw were studied. The presences of acid (0.25%v/v H2SO4, HCl, H3PO4, and oxalic acid) and alkali (0.25 w/v NaOH) efficiently promoted hydrolysis of hemicellulose, improved enzymatic digestibility of the solids, and lower the required LHW temperature. Oxalic acid was a superior promoter under the optimal LHW conditions at 160 °C, leading to the highest glucose yield from enzymatic hydrolysis (84.2%) and the lowest formation of furans. Combined with hydrolyzed glucose in the liquid, this resulted in the maximal 91.6% glucose recovery from the native rice straw. This was related to changes in surface area and crystallinity of pretreated biomass. The results showed efficiency of external promoters on increasing sugar recovery and saving energy in LHW pretreatment.

Comparison of homogeneous and heterogeneous acid promoters in single-step aqueous-organosolv fractionation of eucalyptus wood chips.

Fractionation of lignocellulosic biomass is a primary step for converting multi-structure biomass to biofuels and other industrial products in integrated biorefinery processes. Here, the effects of homogeneous and heterogeneous acid promoters (HNO3-, HCl-, H2SO4-, and H3PO4-activated carbons) on Clean Fractionation (CF), a single-step aqueous-organosolv fractionation, of eucalyptus wood chips was studied and optimised. The optimised process contained 16.7% w/v biomass in a ternary mixture of methyl isobutyl ketone:methanol:water (25:42:33) with 5% AC-H3PO4 and incubated at 180 °C for 60 min. Under these conditions, 41.2 wt.% cellulose was obtained in enriched solid pulp with the average glucan content of 75.9%. The majority of the hemicelluloses was hydrolysed into the aqueous-methanol phase, which contained 17.8 wt.% monomeric xylose and xylooligomers while 13.7 wt.% lignin was separated into the organic phase. The heterogeneous acid-promoter process is a potent alternative to corrosive homogeneous acids for lignocellulose fractionation in integrated biorefineries.