Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made...Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made of cobalt spinel ferrite and was coated with silica to protect it from oxidation. The silanol groups allowed surface chemical modification of the nanoparticles with the PFS and AS acid functionalities. Thermogravimetric analysis gave a total organic load of 12.6% and 32.5% (w/w) for AS and PFS nanoparticles, respectively. The surface sulfur content was calculated from XPS analysis as 1.37% and 1.93% for PFS and AS nanoparticles, respectively. Wheat straw samples were treated with the acid-functionalized nanoparticles at two different conditions: 80℃ for 24 h and 160℃ for 2 h. These experiments aimed to hydrolyze wheat straw hemicelluloses to soluble oligosaccharides. PFS nanoparticles solubilized significantly higher amounts of hemicelluloses (24.0% ± 1.1%) than their alkyl-sulfonic counterparts (9.1% ± 1.7%) at 80℃, whereas the hydrothermolysis control solubilized 7.7% ± 0.8% of the original hemicelluloses in the sample. At 160℃, PFS and AS nanoparticles gave significantly higher amounts of oligosaccharides (46.3% ± 0.4% and 45 ± 1.2%, respectively) than the control (35.0% ± 1.8%). The hemicelluloses conversion at 160?C reached 66.3% ± 0.9% using PFS nanoparticles and 61.0% ± 1.2% using AS nanoparticles compared with the control experiment, which solubilized 50.9% ± 1.7% of hemicelluloses in the biomass.展开更多
Propyl-sulfonic (PS) acid-functionalized nanoparticles were synthesized, characterized and evaluated as catalysts for pretreatment of corn stover. Silica coated nanoparticles were functionalized with 0.5% mercaptoprop...Propyl-sulfonic (PS) acid-functionalized nanoparticles were synthesized, characterized and evaluated as catalysts for pretreatment of corn stover. Silica coated nanoparticles were functionalized with 0.5% mercaptopropyltrimethoxysilane (MPTMS) at neutral pH in a mixture of water and ethanol. Sulfur contents of the acid functionalized nanoparticles, measured in a CHNS analyzer, varied from 6%-10%, and the acid load ranged from 0.040 to 0.066 mmol H+/g. A Box-Behnken design was employed to calculate the minimum number experiments required to obtain an estimate of the surface response for temperature, catalyst load, and %S content of the catalyst. Pretreatment of corn stover was carried out at three temperature levels 160, 180, and 200°C for 1 h. Three levels of catalyst load were used 0.1, 0.2, and 0.3 g of catalyst per gram of biomass. Hydro-thermolysis controls were carried at each temperature level. The catalyst load did not have an effect on the glucose yield at 160°C, and the average glucose yield obtained at this temperature was 59.0%. The glucose yield was linearly correlated to the catalyst load during pretreatment at 180°C, and a maximum glucose yield of 90% was reached when using 0.2 g of PS nanoparticles that had a total sulfur content of 6.1%. Complete hydrolysis of glucose was reached at 200°C but the average xylose yield was 4.6%, and about 20.2% of the combined glucose and xylose were lost as hydroxymethylfurfural and furfural. Results showed that acid-functionalized nanoparticles can be potential catalysts for the pretreatment of biomass for its later conversion to ethanol.展开更多
基金This project is supported by the NSF award CNET-1033538 and the NSF EPSCoR Kansas Center for Solar Energy ResearchThis material is also based upon work supported by NSF Grant#0903701:“Integrating the Socioeconomic,Technical,and Agricultural Aspects of Renewable and Sustainable Biorefining Program awarded to Kansas State University.”Contribution number 12-367-J from the Kansas Agricultural Experiment Station.
文摘Perfluoroalkylsufonic (PFS) and alkylsufonic (AS) acid-functionalized magnetic nanoparticles were synthesized and characterized, then evaluated for their ability to hydrolyze hemicelluloses. The magnetic core was made of cobalt spinel ferrite and was coated with silica to protect it from oxidation. The silanol groups allowed surface chemical modification of the nanoparticles with the PFS and AS acid functionalities. Thermogravimetric analysis gave a total organic load of 12.6% and 32.5% (w/w) for AS and PFS nanoparticles, respectively. The surface sulfur content was calculated from XPS analysis as 1.37% and 1.93% for PFS and AS nanoparticles, respectively. Wheat straw samples were treated with the acid-functionalized nanoparticles at two different conditions: 80℃ for 24 h and 160℃ for 2 h. These experiments aimed to hydrolyze wheat straw hemicelluloses to soluble oligosaccharides. PFS nanoparticles solubilized significantly higher amounts of hemicelluloses (24.0% ± 1.1%) than their alkyl-sulfonic counterparts (9.1% ± 1.7%) at 80℃, whereas the hydrothermolysis control solubilized 7.7% ± 0.8% of the original hemicelluloses in the sample. At 160℃, PFS and AS nanoparticles gave significantly higher amounts of oligosaccharides (46.3% ± 0.4% and 45 ± 1.2%, respectively) than the control (35.0% ± 1.8%). The hemicelluloses conversion at 160?C reached 66.3% ± 0.9% using PFS nanoparticles and 61.0% ± 1.2% using AS nanoparticles compared with the control experiment, which solubilized 50.9% ± 1.7% of hemicelluloses in the biomass.
基金funded by NSF EPSCoR Kansas Center for Solar Energy Research and facilitated by Kansas State Universitysupported by National Science Foundation Grant:From Crops to Commuting:Integrating the Social,Technological,and Agricultural Aspects of Renewable and Sustainable Biorefining(I-STAR),NSF Award No.:DGE-0903701.
文摘Propyl-sulfonic (PS) acid-functionalized nanoparticles were synthesized, characterized and evaluated as catalysts for pretreatment of corn stover. Silica coated nanoparticles were functionalized with 0.5% mercaptopropyltrimethoxysilane (MPTMS) at neutral pH in a mixture of water and ethanol. Sulfur contents of the acid functionalized nanoparticles, measured in a CHNS analyzer, varied from 6%-10%, and the acid load ranged from 0.040 to 0.066 mmol H+/g. A Box-Behnken design was employed to calculate the minimum number experiments required to obtain an estimate of the surface response for temperature, catalyst load, and %S content of the catalyst. Pretreatment of corn stover was carried out at three temperature levels 160, 180, and 200°C for 1 h. Three levels of catalyst load were used 0.1, 0.2, and 0.3 g of catalyst per gram of biomass. Hydro-thermolysis controls were carried at each temperature level. The catalyst load did not have an effect on the glucose yield at 160°C, and the average glucose yield obtained at this temperature was 59.0%. The glucose yield was linearly correlated to the catalyst load during pretreatment at 180°C, and a maximum glucose yield of 90% was reached when using 0.2 g of PS nanoparticles that had a total sulfur content of 6.1%. Complete hydrolysis of glucose was reached at 200°C but the average xylose yield was 4.6%, and about 20.2% of the combined glucose and xylose were lost as hydroxymethylfurfural and furfural. Results showed that acid-functionalized nanoparticles can be potential catalysts for the pretreatment of biomass for its later conversion to ethanol.
