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Title: Carbonic Acid Pretreatment of Biomass

Abstract

This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. 1) Solidify the theoretical understanding of the binary CO2/H2O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments have not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. 2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. 3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenousmore » acids by the substrate. A less acidic substrate such as corn stover would derive benefit from the use of carbonic acid. 4) Quantify the production of microbial inhibitors at selected reaction conditions and severity. It was found that the release of inhibitors was correlated to reaction severity and that carbonic acid did not appear to increase or decrease inhibition compared to pretreatment with water alone. 5) Assess the reactivity to enzymatic hydrolysis of material pretreated at selected reaction conditions and severity. Enzymatic hydrolysis rates increased with severity, but no advantage was detected for the use of carbonic acid compared to water alone. 6) Determine optimal conditions for carbonic acid pretreatment of aspen wood. Optimal severities appeared to be in the mid range tested. ASPEN-Plus modeling and economic analysis of the process indicate that the process could be cost competitive with sulfuric acid if the concentration of solids in the pretreatment is maintained very high (~50%). Lower solids concentrations result in larger reactors that become expensive to construct for high pressure applications.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Bayor University
Sponsoring Org.:
USDOE; USDOE - Office of Solar Thermal, Biomass Power, and Hydrogen Technologies (EE-13)
OSTI Identifier:
882226
Report Number(s):
DOE/GO/11070final
TRN: US200716%%207
DOE Contract Number:
FC36-01GO11070
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; ACTIVATION ENERGY; AGRICULTURAL WASTES; BIOMASS; CARBOHYDRATES; CARBONATES; CARBONIC ACID; ECONOMIC ANALYSIS; ENZYMATIC HYDROLYSIS; FORECASTING; MAIZE; PRODUCTION; SUBSTRATES; SULFURIC ACID; THERMODYNAMICS; TITRATION; WATER; WOOD; biomass, pretreatment, carbonic acid, inhibition, aspen-plus modeling, enzymatic hydrolysis

Citation Formats

G. Peter van Walsum, Kemantha Jayawardhana, Damon Yourchisin, Robert McWilliams, and Vanessa Castleberry. Carbonic Acid Pretreatment of Biomass. United States: N. p., 2003. Web. doi:10.2172/882226.
G. Peter van Walsum, Kemantha Jayawardhana, Damon Yourchisin, Robert McWilliams, & Vanessa Castleberry. Carbonic Acid Pretreatment of Biomass. United States. doi:10.2172/882226.
G. Peter van Walsum, Kemantha Jayawardhana, Damon Yourchisin, Robert McWilliams, and Vanessa Castleberry. 2003. "Carbonic Acid Pretreatment of Biomass". United States. doi:10.2172/882226. https://www.osti.gov/servlets/purl/882226.
@article{osti_882226,
title = {Carbonic Acid Pretreatment of Biomass},
author = {G. Peter van Walsum and Kemantha Jayawardhana and Damon Yourchisin and Robert McWilliams and Vanessa Castleberry},
abstractNote = {This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. 1) Solidify the theoretical understanding of the binary CO2/H2O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments have not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. 2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. 3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenous acids by the substrate. A less acidic substrate such as corn stover would derive benefit from the use of carbonic acid. 4) Quantify the production of microbial inhibitors at selected reaction conditions and severity. It was found that the release of inhibitors was correlated to reaction severity and that carbonic acid did not appear to increase or decrease inhibition compared to pretreatment with water alone. 5) Assess the reactivity to enzymatic hydrolysis of material pretreated at selected reaction conditions and severity. Enzymatic hydrolysis rates increased with severity, but no advantage was detected for the use of carbonic acid compared to water alone. 6) Determine optimal conditions for carbonic acid pretreatment of aspen wood. Optimal severities appeared to be in the mid range tested. ASPEN-Plus modeling and economic analysis of the process indicate that the process could be cost competitive with sulfuric acid if the concentration of solids in the pretreatment is maintained very high (~50%). Lower solids concentrations result in larger reactors that become expensive to construct for high pressure applications.},
doi = {10.2172/882226},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2003,
month = 5
}

Technical Report:

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  • This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. (1) Solidify the theoretical understanding of the binary CO{sub 2}/H{sub 2}O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments havemore » not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. (2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. (3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenous acids by the substrate. A less acidic substrate such as corn stover would derive benefit from the use of carbonic acid. (4) Quantify the production of microbial inhibitors at selected reaction conditions and severity. It was found that the release of inhibitors was correlated to reaction severity and that carbonic acid did not appear to increase or decrease inhibition compared to pretreatment with water alone. (5) Assess the reactivity to enzymatic hydrolysis of material pretreated at selected reaction conditions and severity. Enzymatic hydrolysis rates increased with severity, but no advantage was detected for the use of carbonic acid compared to water alone. (6) Determine optimal conditions for carbonic acid pretreatment of aspen wood. Optimal severities appeared to be in the mid range tested. ASPEN-Plus modeling and economic analysis of the process indicate that the process could be cost competitive with sulfuric acid if the concentration of solids in the pretreatment is maintained very high ({approx}50%). Lower solids concentrations result in larger reactors that become expensive to construct for high pressure applications.« less
  • This report describes one potential biochemical ethanol conversion process, conceptually based upon core conversion and process integration research at NREL. The overarching process design converts corn stover to ethanol by dilute-acid pretreatment, enzymatic saccharification, and co-fermentation. Building on design reports published in 2002 and 1999, NREL, together with the subcontractor Harris Group Inc., performed a complete review of the process design and economic model for the biomass-to-ethanol process. This update reflects NREL's current vision of the biochemical ethanol process and includes the latest research in the conversion areas (pretreatment, conditioning, saccharification, and fermentation), optimizations in product recovery, and our latestmore » understanding of the ethanol plant's back end (wastewater and utilities). The conceptual design presented here reports ethanol production economics as determined by 2012 conversion targets and 'nth-plant' project costs and financing. For the biorefinery described here, processing 2,205 dry ton/day at 76% theoretical ethanol yield (79 gal/dry ton), the ethanol selling price is $2.15/gal in 2007$.« less
  • Our research is aimed at investigating several technical issues associated with carbon dioxide sequestration in calcium carbonate sediments below the sea floor through laboratory experiments and chemical transport modeling. Our goal is to evaluate the basic feasibility of this approach, including an assessment of optimal depths, sediment types, and other issues related to site selection. Through laboratory and modeling efforts, we are studying the flow of liquid carbon dioxide and carbon dioxide-water mixtures through calcium carbonate sediments to better understand the geomechanical and structural stability of the sediments during and after injection. Our modeling efforts in the first year showmore » that the idea is feasible, but requires more sophisticated analysis of fluid flow at high pressure in deep sea sediments. In addition, we are investigating the kinetics of calcium carbonate dissolution in the presence of CO{sub 2}-water fluids, which is a critical feature of the system as it allows for increased permeability during injection. Our experimental results from the first year of work have shown that the kinetics are likely to be fast enough to create dissolution which will affect permeability. However, additional experiments are needed at high pressures, which will be a focus for years 2 and 3. We are also investigating the possibility of carbon dioxide hydrate formation in the pore fluid, which might complicate the injection procedure by reducing sediment permeability but might also provide an upper seal in the sediment-pore fluid system, preventing release of CO{sub 2} into the deep ocean, particularly if depth and temperature at the injection point rule out immediate hydrate formation. Finally, we are in the beginning stages of an economic analysis to estimate costs of drilling and gas injection, site monitoring as well as the availability of potential disposal sites with particular emphasis on those sites that are within the 200-mile economic zone of the United States.« less
  • Our research is aimed at investigating several technical issues associated with carbon dioxide sequestration in calcium carbonate sediments below the sea floor through laboratory experiments and chemical transport modeling. Our goal is to evaluate the basic feasibility of this approach, including an assessment of optimal depths, sediment types, and other issues related to site selection. The results of our modeling efforts were published this past summer in the Proceedings of the National Academy of Sciences. We are expanding on that work through a variety of laboratory and modeling efforts. In the laboratories at Columbia and at Harvard, we are studyingmore » the flow of liquid carbon dioxide and carbon dioxide-water mixtures through calcium carbonate sediments to better understand the geomechanical and structural stability of the sediments during and after injection. We are currently preparing the results of these findings for publication. In addition, we are investigating the kinetics of calcium carbonate dissolution in the presence of CO{sub 2}-water fluids, which is a critical feature of the system as it allows for increased permeability during injection. We are also investigating the possibility of carbon dioxide hydrate formation in the pore fluid, which might complicate the injection procedure by reducing sediment permeability but might also provide an upper seal in the sediment-pore fluid system, preventing release of CO{sub 2} into the deep ocean, particularly if depth and temperature at the injection point rule out immediate hydrate formation. This is done by injecting liquid CO{sub 2} into various types of porous media, and then monitoring the changes in permeability. Finally, we are performing an economic analysis to estimate costs of drilling and gas injection, site monitoring as well as the availability of potential disposal sites with particular emphasis on those sites that are within the 200-mile economic zone of the United States. We present some preliminary results from these analyses. A paper discussing the site selection based on data from the Ocean Drilling Program and Deep Sea Drilling Program is currently in preparation.« less
  • Carbon dioxide injection into deep sea sediments below 2700 m water depth and a few hundred meters to fifteen hundred meters deep in the sediment column may provide permanent geologic storage by gravitational trapping. At high pressures and low temperatures common in deep sea sediments a few hundred meters below sea floor, CO{sub 2} will be in its liquid phase and will be denser than the overlying pore fluid. The lower density of the pore fluid provides a cap to the denser CO{sub 2} and ensures gravitational trapping in the short term. The overall storage capacity for CO{sub 2} inmore » such deep sea formations below the ocean floor is primarily determined by the permeability, and will vary with seafloor depth, geothermal gradient, porosity, and pore water salinity. Furthermore, the dissemination of the injected CO{sub 2} in the sediments and potential chemical reactions between CO{sub 2}, pore fluid and sediments will define its fate in the storage reservoir. The main objectives of our research was to evaluate the potential for sub-seabed CO{sub 2} storage in deep sea sediments using a range of approaches including experiments, permeability analysis, and modeling. Over the course of the three-year award, our results support an important role for sub-seabed storage in a diverse portfolio of carbons sequestration options. Our analysis has shown the feasibility of this type of storage, and also emphasizes that escape or leakage from such sites would be negligible. The most difficult challenge is to overcome the low permeability of typical deep-sea sediments, and a variety of approaches are suggested for future research.« less