Todd Lloyd - Academia.edu (original) (raw)

Papers by Todd Lloyd

Bioresource Technology, Dec 1, 2005

A number of previous studies determined dilute acid pretreatment conditions that maximize xylose ... more A number of previous studies determined dilute acid pretreatment conditions that maximize xylose yields from pretreatment or glucose yields from subsequent digestion of the pretreated cellulose, but our emphasis was on identifying conditions to realize the highest yields of both sugars from both stages. Thus, individual xylose and glucose yields are reported as a percentage of the total potential yield of both sugars over a range of sulfuric acid concentrations of 0.22%, 0.49% and 0.98% w/w at 140, 160, 180 and 200°C. Up to 15% of the total potential sugar in the substrate could be released as glucose during pretreatment and between 15% and 90+% of the xylose remaining in the solid residue could be recovered in subsequent enzymatic hydrolysis, depending on the enzyme loading. Glucose yields increased from as high as 56% of total maximum potential glucose plus xylose for just enzymatic digestion to 60% when glucose released in pretreatment was included. Xylose yields similarly increased from as high as 34% of total potential sugars for pretreatment alone to between 35% and 37% when credit was taken for xylose released in digestion. Yields were shown to be much lower if no acid was used. Conditions that maximized individual sugar yields were often not the same as those that maximized total sugar yields, demonstrating the importance of clearly defining pretreatment goals when optimizing the process. Overall, up to about 92.5% of the total sugars originally available in the corn stover used could be recovered for coupled dilute acid pretreatment and enzymatic hydrolysis. These results also suggest that enhanced hemicellulase activity could further improve xylose yields, particularly for low cellulase loadings.

American Chemical Society eBooks, Jul 29, 2004

ABSTRACT

Applied Biochemistry and Biotechnology, 2003

Literature data were collected and analyzed to guide selection of conditions for pretreatment by ... more Literature data were collected and analyzed to guide selection of conditions for pretreatment by dilute acid and water-only hemicellulose hydrolysis, and the severity parameter was used to relate performance of different studies on a consistent basis and define attractive operating conditions. Experiments were then run to confirm performance with corn stover. Although substantially better hemicellulose sugar yields are observed when acid is added, costs would be reduced and processing operations simplified if less acid could be used while maintaining good yields, and understanding the relationship between operating conditions and yields would be invaluable to realizing this goal. However, existing models seldom include the oligomeric intermediates prevalent at lower acid levels, and the few studies that include such species do not account for the distribution of chain lengths during reaction. Therefore, the polymeric nature of hemicellulose was integrated into a kinetic model often used to describe the decomposition of synthetic polymers with the assumption that hemicellulose linkages are randomly broken during hydrolysis. Predictions of monomer yields were generally consistent with our pretreatment data, data reported in the literature, and predictions of other models, but the model tended to overpredict oligomer yields. These differences need to be resolved by gathering additional data and improving the model.

Humana Press eBooks, 2004

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutralize some of the acid during dilute acid pretreatment, reducing its effectiveness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can further reduce hydrogen ion concentrations and compound the effect of neutralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirements to achieve a particular reaction rate unless minerals are removed prior to hydrolysis.

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutral-ize some of the acid during dilute acid pretreatment, reducing its effective-ness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can fur-ther reduce hydrogen ion concentrations and compound the effect of neu-tralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirem...

Wyman/Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals, 2013

ACS Symposium Series, 2004

... Hydrolysis and Subsequent Cellulose Digestion Bin Yang, Matthew C. Gray, Chaogang Liu, Todd A... more ... Hydrolysis and Subsequent Cellulose Digestion Bin Yang, Matthew C. Gray, Chaogang Liu, Todd A. Lloyd, Suzanne L. Stuhler, Alvin O. Converse, and Charles E. Wyman Thayer School of Engineering, Dartmouth College, Hanover, NH 03755 ...

MRS Bulletin, 2008

A sustainable global energy system requires a transition away from energy sources with high green... more A sustainable global energy system requires a transition away from energy sources with high greenhouse emissions. Vast energy resources are available to meet our needs, and technology pathways for making this transition exist. Lowering the cost and increasing the reliability and quality of energy from sustainable energy sources will facilitate this transition. Changing the world's energy systems is a huge challenge, but it is one that can be undertaken now with improvements in energy efficiency and with continuing deployment of a variety of technologies. Numerous opportunities exist for research in material sciences to contribute to this global-scale challenge.

Bioresource Technology, 2005

A number of previous studies determined dilute acid pretreatment conditions that maximize xylose ... more A number of previous studies determined dilute acid pretreatment conditions that maximize xylose yields from pretreatment or glucose yields from subsequent digestion of the pretreated cellulose, but our emphasis was on identifying conditions to realize the highest yields of both sugars from both stages. Thus, individual xylose and glucose yields are reported as a percentage of the total potential yield of both sugars over a range of sulfuric acid concentrations of 0.22%, 0.49% and 0.98% w/w at 140, 160, 180 and 200°C. Up to 15% of the total potential sugar in the substrate could be released as glucose during pretreatment and between 15% and 90+% of the xylose remaining in the solid residue could be recovered in subsequent enzymatic hydrolysis, depending on the enzyme loading. Glucose yields increased from as high as 56% of total maximum potential glucose plus xylose for just enzymatic digestion to 60% when glucose released in pretreatment was included. Xylose yields similarly increased from as high as 34% of total potential sugars for pretreatment alone to between 35% and 37% when credit was taken for xylose released in digestion. Yields were shown to be much lower if no acid was used. Conditions that maximized individual sugar yields were often not the same as those that maximized total sugar yields, demonstrating the importance of clearly defining pretreatment goals when optimizing the process. Overall, up to about 92.5% of the total sugars originally available in the corn stover used could be recovered for coupled dilute acid pretreatment and enzymatic hydrolysis. These results also suggest that enhanced hemicellulase activity could further improve xylose yields, particularly for low cellulase loadings.

Applied Biochemistry and Biotechnology, 2004

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutralize some of the acid during dilute acid pretreatment, reducing its effectiveness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can further reduce hydrogen ion concentrations and compound the effect of neutralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirements to achieve a particular reaction rate unless minerals are removed prior to hydrolysis.

Applied Biochemistry and Biotechnology, 2003

Literature data were collected and analyzed to guide selection of conditions for pretreatment by ... more Literature data were collected and analyzed to guide selection of conditions for pretreatment by dilute acid and water-only hemicellulose hydrolysis, and the severity parameter was used to relate performance of different studies on a consistent basis and define attractive operating conditions. Experiments were then run to confirm performance with corn stover. Although substantially better hemicellulose sugar yields are observed when acid is added, costs would be reduced and processing operations simplified if less acid could be used while maintaining good yields, and understanding the relationship between operating conditions and yields would be invaluable to realizing this goal. However, existing models seldom include the oligomeric intermediates prevalent at lower acid levels, and the few studies that include such species do not account for the distribution of chain lengths during reaction. Therefore, the polymeric nature of hemicellulose was integrated into a kinetic model often used to describe the decomposition of synthetic polymers with the assumption that hemicellulose linkages are randomly broken during hydrolysis. Predictions of monomer yields were generally consistent with our pretreatment data, data reported in the literature, and predictions of other models, but the model tended to overpredict oligomer yields. These differences need to be resolved by gathering additional data and improving the model.

Bioresource Technology, Dec 1, 2005

A number of previous studies determined dilute acid pretreatment conditions that maximize xylose ... more A number of previous studies determined dilute acid pretreatment conditions that maximize xylose yields from pretreatment or glucose yields from subsequent digestion of the pretreated cellulose, but our emphasis was on identifying conditions to realize the highest yields of both sugars from both stages. Thus, individual xylose and glucose yields are reported as a percentage of the total potential yield of both sugars over a range of sulfuric acid concentrations of 0.22%, 0.49% and 0.98% w/w at 140, 160, 180 and 200°C. Up to 15% of the total potential sugar in the substrate could be released as glucose during pretreatment and between 15% and 90+% of the xylose remaining in the solid residue could be recovered in subsequent enzymatic hydrolysis, depending on the enzyme loading. Glucose yields increased from as high as 56% of total maximum potential glucose plus xylose for just enzymatic digestion to 60% when glucose released in pretreatment was included. Xylose yields similarly increased from as high as 34% of total potential sugars for pretreatment alone to between 35% and 37% when credit was taken for xylose released in digestion. Yields were shown to be much lower if no acid was used. Conditions that maximized individual sugar yields were often not the same as those that maximized total sugar yields, demonstrating the importance of clearly defining pretreatment goals when optimizing the process. Overall, up to about 92.5% of the total sugars originally available in the corn stover used could be recovered for coupled dilute acid pretreatment and enzymatic hydrolysis. These results also suggest that enhanced hemicellulase activity could further improve xylose yields, particularly for low cellulase loadings.

American Chemical Society eBooks, Jul 29, 2004

ABSTRACT

Applied Biochemistry and Biotechnology, 2003

Literature data were collected and analyzed to guide selection of conditions for pretreatment by ... more Literature data were collected and analyzed to guide selection of conditions for pretreatment by dilute acid and water-only hemicellulose hydrolysis, and the severity parameter was used to relate performance of different studies on a consistent basis and define attractive operating conditions. Experiments were then run to confirm performance with corn stover. Although substantially better hemicellulose sugar yields are observed when acid is added, costs would be reduced and processing operations simplified if less acid could be used while maintaining good yields, and understanding the relationship between operating conditions and yields would be invaluable to realizing this goal. However, existing models seldom include the oligomeric intermediates prevalent at lower acid levels, and the few studies that include such species do not account for the distribution of chain lengths during reaction. Therefore, the polymeric nature of hemicellulose was integrated into a kinetic model often used to describe the decomposition of synthetic polymers with the assumption that hemicellulose linkages are randomly broken during hydrolysis. Predictions of monomer yields were generally consistent with our pretreatment data, data reported in the literature, and predictions of other models, but the model tended to overpredict oligomer yields. These differences need to be resolved by gathering additional data and improving the model.

Humana Press eBooks, 2004

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutralize some of the acid during dilute acid pretreatment, reducing its effectiveness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can further reduce hydrogen ion concentrations and compound the effect of neutralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirements to achieve a particular reaction rate unless minerals are removed prior to hydrolysis.

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutral-ize some of the acid during dilute acid pretreatment, reducing its effective-ness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can fur-ther reduce hydrogen ion concentrations and compound the effect of neu-tralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirem...

Wyman/Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals, 2013

ACS Symposium Series, 2004

... Hydrolysis and Subsequent Cellulose Digestion Bin Yang, Matthew C. Gray, Chaogang Liu, Todd A... more ... Hydrolysis and Subsequent Cellulose Digestion Bin Yang, Matthew C. Gray, Chaogang Liu, Todd A. Lloyd, Suzanne L. Stuhler, Alvin O. Converse, and Charles E. Wyman Thayer School of Engineering, Dartmouth College, Hanover, NH 03755 ...

MRS Bulletin, 2008

A sustainable global energy system requires a transition away from energy sources with high green... more A sustainable global energy system requires a transition away from energy sources with high greenhouse emissions. Vast energy resources are available to meet our needs, and technology pathways for making this transition exist. Lowering the cost and increasing the reliability and quality of energy from sustainable energy sources will facilitate this transition. Changing the world's energy systems is a huge challenge, but it is one that can be undertaken now with improvements in energy efficiency and with continuing deployment of a variety of technologies. Numerous opportunities exist for research in material sciences to contribute to this global-scale challenge.

Bioresource Technology, 2005

A number of previous studies determined dilute acid pretreatment conditions that maximize xylose ... more A number of previous studies determined dilute acid pretreatment conditions that maximize xylose yields from pretreatment or glucose yields from subsequent digestion of the pretreated cellulose, but our emphasis was on identifying conditions to realize the highest yields of both sugars from both stages. Thus, individual xylose and glucose yields are reported as a percentage of the total potential yield of both sugars over a range of sulfuric acid concentrations of 0.22%, 0.49% and 0.98% w/w at 140, 160, 180 and 200°C. Up to 15% of the total potential sugar in the substrate could be released as glucose during pretreatment and between 15% and 90+% of the xylose remaining in the solid residue could be recovered in subsequent enzymatic hydrolysis, depending on the enzyme loading. Glucose yields increased from as high as 56% of total maximum potential glucose plus xylose for just enzymatic digestion to 60% when glucose released in pretreatment was included. Xylose yields similarly increased from as high as 34% of total potential sugars for pretreatment alone to between 35% and 37% when credit was taken for xylose released in digestion. Yields were shown to be much lower if no acid was used. Conditions that maximized individual sugar yields were often not the same as those that maximized total sugar yields, demonstrating the importance of clearly defining pretreatment goals when optimizing the process. Overall, up to about 92.5% of the total sugars originally available in the corn stover used could be recovered for coupled dilute acid pretreatment and enzymatic hydrolysis. These results also suggest that enhanced hemicellulase activity could further improve xylose yields, particularly for low cellulase loadings.

Applied Biochemistry and Biotechnology, 2004

Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitut... more Dilute acid and water-only hemicellulose hydrolysis are being examined as part of a multiinstitutional cooperative effort to evaluate the performance of leading cellulosic biomass pretreatment technologies on a common basis. Cellulosic biomass, such as agricultural residues and forest wastes, can have a significant mineral content. It has been shown that these minerals neutralize some of the acid during dilute acid pretreatment, reducing its effectiveness, and the higher solids loadings desired to minimize costs will require increased acid use to compensate. However, for sulfuric acid in particular, an equilibrium shift to formation of bisulfate during neutralization can further reduce hydrogen ion concentrations and compound the effect of neutralization. Because the equilibrium shift has a more pronounced effect at lower acid concentrations, additional acid is needed to compensate. Coupled with the effect of temperature on acid dissociation, these effects increase acid requirements to achieve a particular reaction rate unless minerals are removed prior to hydrolysis.

Applied Biochemistry and Biotechnology, 2003

Literature data were collected and analyzed to guide selection of conditions for pretreatment by ... more Literature data were collected and analyzed to guide selection of conditions for pretreatment by dilute acid and water-only hemicellulose hydrolysis, and the severity parameter was used to relate performance of different studies on a consistent basis and define attractive operating conditions. Experiments were then run to confirm performance with corn stover. Although substantially better hemicellulose sugar yields are observed when acid is added, costs would be reduced and processing operations simplified if less acid could be used while maintaining good yields, and understanding the relationship between operating conditions and yields would be invaluable to realizing this goal. However, existing models seldom include the oligomeric intermediates prevalent at lower acid levels, and the few studies that include such species do not account for the distribution of chain lengths during reaction. Therefore, the polymeric nature of hemicellulose was integrated into a kinetic model often used to describe the decomposition of synthetic polymers with the assumption that hemicellulose linkages are randomly broken during hydrolysis. Predictions of monomer yields were generally consistent with our pretreatment data, data reported in the literature, and predictions of other models, but the model tended to overpredict oligomer yields. These differences need to be resolved by gathering additional data and improving the model.