Progress 10/01/11 to 09/30/15
Outputs
Target Audience:(1) Graduate and undergraduate students through formal classroom instruction; (2) Peer researchers through publications, invited seminars and presentations at conferences. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? One graduate student participated the research activities of this project. The student was trained to develop the essential skills for scientific research including experimental design, data collection, data interpretation, and result reporting. The student learned the operation and application of many analytical instruments and equipment such as UV, HPLC, GCMS, X-ray diffractometer, NMR, ion-exclusion chromatography, and Paar reactor. The student also attened the 249th ACS annual meeting and gave presentations. Threeundergraduate students participated the project in thefall of 2014, spring and summer of 2015, respectively, as lab assistants. The students were exposed to real research projects and learned many basic skills and hand-on experiences for research. One undergraduate student presented her study at the 249th ACS annual meeting. The results from the studies involving the undergraduate students will be published soon. How have the results been disseminated to communities of interest?(1) Some of the results from the project were used as teaching materials in the course of Biorefining-Energy and Productsfrom Renewable Resources for undergraduate and graduatestudents. The teaching activity made more students aware of thetechnology developed by this project and its impacts; (2) The findings of this project were presented at 2014 AIChE Annual Meeting, November 16-21, 2014, Atlanta, GA; 249th ACS National Meeting & Exposition, March 22 -26, 2015, Denver, CO; and 2015 CPBR Symposium, March 3-4, 2015, Washington D.C.. (3) The findings of the project were presented at an invited seminar at Univesrity of Minnesota:X.J. Pan. New approaches for producing sugars from lignocellulosic biomass. April 14, 2015. University of Minnesota-Twin City. What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
1. Major activities: (1). Preliminary techno-economic analysis of the direct saccharification of lignocellulosic biomass in molten salt hydrate was conducted. (2). A new method for preparing nano-crystal cellulose was developed, based on the saccharification technology developed in this project. (3). The findings of this project were presented at the 2014 American Institute of Chemical Engineers Annual Meeting, November 16-21, 2014, Atlanta, GA; 249th American Chemical Society National Meeting & Exposition, March 22 -26, 2015, Denver, CO; X.J. Pan. Sugar production from biomass in molten salt hydrate. 2015 Consortium for Plant Biotechnology Research Symposium, March 3-4, 2015, Washington D.C. 2. Specific objectives: The specific objectives of the above activities are (1) to evaluate the economic feasibility of the direct saccharification technology of lignocellulosic biomass developed in this project, (2) to develop new method to produce nano-crystal cellulose. 3. Significant results and findings: (1). Preliminary technoeconomic analysis (TEA) indicated that the direct saccharification technology in molten salt hydrate developed in this project is able to produce sugars from lignocellulosic biomass at a lower price, compared to conventional enzymatic processes, because this method does not need cost- and energy-intensive size reduction of biomass, costly pretreatment, and expensive enzymes and enzymatic hydrolysis operation. The TEA results will be further optimized and published soon. (2). It was found that cellulose could be easily dissolved in molten salt hydrate such as lithium bromide trihydrate. When the cellulose solution in the molten salt hydrate was diluted, cellulose could be regenerated in the form of nano-crystal cellulose, which provided an innovative method to produce nano-crystal cellulose. Compared to existing acid hydrolysis and oxidation processes, this method gave much higher yield of nano-crystal cellulose. The produced nano-cellulose had comparable size, shape, and properties with those from acid processes. The new method is under further investigation and optimization and will be reported soon.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
X.J. Pan, N. Li, C.Q. Mei, and L. Shuai. Saccharification and lignin fractionation of lignocellulosic biomass in molten salt hydrate system. 2014 AIChE Annual Meeting, November 16-21, 2014, Atlanta, GA.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2015
Citation:
Ning Li, Joseph Kraft, and Xuejun Pan. Homogeneous saccharification of lignocellulosic biomass in molten salt hydrates. 249th ACS National Meeting & Exposition, March 22 -26, 2015, Denver, CO.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2015
Citation:
Ning Li, Jane Alexander, and Xuejun Pan. Facile quantification of biomass lignin using acidic lithium bromide (ALB) method. 249th ACS National Meeting & Exposition, March 22 -26, 2015, Denver, CO.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2015
Citation:
Melanie Swannell, Chang Geun Yoo, and Xuejun Pan. Effects of halide salt hydrates on isomerization of glucose to fructose. 249th ACS National Meeting & Exposition, March 22 -26, 2015, Denver, CO.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2015
Citation:
X.J. Pan. Sugar production from biomass in molten salt hydrate. 2015 CPBR Symposium, March 3-4, 2015, Washington D.C.
- Type:
Journal Articles
Status:
Published
Year Published:
2016
Citation:
Hongdan Zhang, Ning Li, Xuejun Pan, Shubin Wu, and Jun Xie. Oxidative conversion of glucose to gluconic acid by iron (III) chloride in water under mild conditions. Green Chemistry, 2016, DOI: 10.1039/C5GC02614H.
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Progress 10/01/13 to 09/30/14
Outputs
Target Audience: (1) Graduate and undergraduate students through formal classroom instruction; (2) High-school students through summer workshop on bioenergy and bioproducts; (3) Peer researchers through seminars and presentations at conferences. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? (1) One graduate student participated the research activities of this project. The student was trained to develop the essential skills for scientific research including experimental design, data collection, data interpretation, and result reporting. The student learned the operation and application of many analytical instruments and equipment such as UV, HPLC, GCMS, X-ray diffractometer, NMR, ion-exclusion chromatography, and Paar reactor. (2) Two undergraduate students participated the project in the summer and fall of 2014, respectively, as lab assistants. The students were exposed to real research projects and learned many basic skills and hand-on experiences for research. How have the results been disseminated to communities of interest? (1) Some of the results from the project were used as teaching materials in the course of Biorefining-Energy and Products from Renewable Resources for undergraduate and graduate students. The teaching activity made more students aware of the technology developed by this project and its impacts; (2) The 2nd Summer Workshop on Bioenergy supported by NSF was held in the summer of 2014 for local high school students. The technology developed by this project and its impacts were briefly introduced to the students. (3) The findings of this project were presented at 2014 AIChE Annual Meeting, November 16-21, 2014, Atlanta, GA; the 3rd Frontiers in Biorefining, October 21-24, 2014, St. Simons Island, GA; and the 36th Symposium on Biotechnology for Fuels and Chemicals, April 28-May 1, 2014, Clearwater Beach, FL. What do you plan to do during the next reporting period to accomplish the goals? (1) Further investigate and optimize the separation of salt and sugars using ion-exclusion chromatograph (2) Characterize the lignin separated during the saccharification of lignocellulosic biomass and preliminarily evaluate the potential of the lignin for co-product development. (3) Conduct techno-economic analysis of the saccharification process investigated in this project.
Impacts
What was accomplished under these goals?
(1) Major activities: (a) Separation of LiBr from sugars was investigated using ion-exclusion chromatography. (b) A new method for quantitating lignin and carbohydrates in lignocellulosic biomass was developed, based on the saccharification technology developed in this project. (c) The findings of this project were presented at 2014 AIChE Annual Meeting, November 16-21, 2014, Atlanta, GA; the 3rd Frontiers in Biorefining, October 21-24, 2014, St. Simons Island, GA; and the 36th Symposium on Biotechnology for Fuels and Chemicals, April 28-May 1, 2014, Clearwater Beach, FL. (2) Specific objectives: The specific objectives of the above activities are (1) to develop and demonstrate a method to effectively separate LiBr and sugars based on ion-exclusion chromatography, (2) to develop an easy and fast method to quantitate lignin and carbohydrates in biomass. (3) Significant results and findings: (a) It was found that ion-exclusion chromatography is an effective method to separate LiBr and sugars. Both cationic and anionic exchange resins can be used to separate LiBr and sugars. Results indicated that the ion form, particle size, density of crosslink, and pore size of the resins are the key factors affecting the LiBr-sugar separation. The diameter and length of chromatographic column and concentrations of LiBr and sugars also affect the separation efficiency and capacity. (b) Conversional method for quantitating lignin and carbohydrates in lignocellulosic biomass is based on the Klason method that uses a two-step acid process (72% concentrated sulfuric acid in the first step and 3-4% in the second step) to hydrolyze cellulose and hemicellulose to monosugars and leave lignin as a solid residue. The sugars can be determined using HPLC or GC, while lignin is quantitated by weight. The Klason method is time-consuming, and strong and concentrated acid is involved in the method. Since cellulose and hemicellulose can be completely and quickly hydrolyzed in concentrated LiBr solution at mild conditions, as founded and developed in this project, the LiBr solution can replace sulfuric acid in the Klason method to hydrolyze cellulose and hemicellulose. As a result, a new method was developed for carbohydrates and lignin quantitation. Our results indicated that the new method gives comparable results with Klason method, and the new method is faster, easier, and safer to conduct than the Klason method.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
Xuejun Pan. Molten Salt Hydrate System as a Platform for Saccharification and Conversion of Lignocellulosic Biomass to Sugars, Chemicals, and Fuels. The 36th Symposium on Biotechnology for Fuels and Chemicals, April 28-May 1, 2014, Clearwater Beach, FL.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
X.J. Pan, N. Li, C.Q. Mei, and L. Shuai. One-pot saccharification and fractionation of lignocellulosic biomass in inorganic molten salt hydrate medium to produce high-concentration sugars and high-quality lignin. The 3rd Frontiers in Biorefining, October 21-24, 2014, St. Simons Island, GA.
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2014
Citation:
X.J. Pan, N. Li, C.Q. Mei, and L. Shuai. Saccharification and lignin fractionation of lignocellulosic biomass in molten salt hydrate system. 2014 AIChE Annual Meeting, November 16-21, 2014, Atlanta, GA.
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Progress 01/01/13 to 09/30/13
Outputs
Target Audience: (1) Graduate and undergraduate students through formal classroom instruction; (2) High-school students through summer workshop on bioenergya and bioproducts; (3) Peer researchers through seminar and presentation. Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided? (1) One graduate student participated the research activities of this project. The student was trained to develop the essential skills for scientific research including experimental design, data collection, data interpretation, and result reporting. The student learned hand-on experience on many analytical instruments and equipment such as UV, HPLC, GCMS, X-ray diffractometer, and Paar reactor. (2) One undergraduate student participated the project in the summer of 2013, working on the project as a lab assistant. The student was exposed to a real research project and learned many basic skills for research. How have the results been disseminated to communities of interest? (1) Some of the results from the project were used as teaching materials in the course of Biorefining-Energy and Products from Renewable Resources for undergraduate and graduate students. The teaching activity made more students aware of the technology developed by this project and its impacts; (2) A summer workshop supported by NSF was held in the summer of 2013 for local high school students. The technology developed by this project and its impacts were briefly introduced to the students. What do you plan to do during the next reporting period to accomplish the goals? (1) Further understand the chemistry and mechanism of the saccharification of biomass in concentrated halide salts. (2) Screen and optimize sugar-salt separation method. (3) Preliminarily investigate the changes and behavior of lignin during the saccharification of the biomass.
Impacts
What was accomplished under these goals?
Producing chemicals and liquid fuels from lignocellulosic biomass is one of promising options after oil in the future. One of the approaches for doing so is the so-called sugar-platform, in which sugars are first extracted from the biomass and then converted to the desired fuels and chemicals by biological or chemical means. However, it is still challenging how to produce sugars cost- and energy-effectively from the biomass, which is the bottleneck of the sugar platform. Enzymatic or acid hydrolysis of cellulose and hemicellulose (two of the three major components of the biomass from which sugars are produced) is the existing and also extensively investigated technology for the production of sugars from the biomass. The major issues of the enzyme and acid processes include high capital and operation cost, low sugar yield, and the need of complicated operations. This research is to develop a low-cost and fast chemical process for producing low-cost and high-concentration sugars from biomass. The success of the project will provide an innovative approach for biomass conversion and could greatly promote, even re-direct, the sugar-based economy. (1) Major activities (a) Saccharification of corn stover, hardwood aspen, and softwood spruce in concentrated LiBr was optimized through carefully designed experimental matrixes using Response Surface Methodology to determine optimal conditions (temperature, reaction time, LiBr concentration, ratio of liquid to biomass, and acid dosage) for maximal sugar yield and minimal sugar degradation. (b) Mass balance was established for the saccharification of each feedstock (corn stover, hardwood aspen, and softwood spruce) at their optimal conditions, respectively. (c) Important properties of LiBr-H2O system were investigated, including the solubility of LiBr, acidity of LiBr solution, and toxicity to microbes. (d) Dissolution of cellulose in LiBr solution was carefully investigated to understand why cellulose is quickly hydrolyzed in the LiBr medium. (e) In addition to LiBr, other halides (NaCl, CaCl2, MgCl2, FeCl3, NaBr, CaBr2, KBr) were evaluated for the saccharification of lignocellulosic biomass. (f) Separation of LiBr from sugars was explored, and different methods (ion-exchange, liquid-liquid extraction, boronic acid-mediated solvent extraction) were compared and evaluated. (2) Specific objectives The specific objectives of the above activities are (1) to understand why cellulose and hemicellulose can be dissolved and hydrolyzed in concentrated LiBr solution, (2) to optimize the hydrolysis (saccharification) of biomass in LiBr solution to maximize sugars yield, (3) to look for alternative and less expensive salts rather than LiBr for saccharification of biomass, and (4) to find effective ways to separate and recycle the salt. (3) Significant results and findings (a) LiBr significantly enhances acidity of solution, which is one of the reasons why cellulose and hemicellulose can be hydrolyzed quickly in the presence of LiBr. (b) At approximately 60% concentration (w/w), equivalent to LiBr·3H2O, lithium cations are completely coordinated with water molecules, where bromide anions are free in solution. The free bromide anions can form stronger hydrogen bonds with the hydroxyl groups of cellulose, which breaks the inter- and intra-molecular hydrogen bonds of cellulose and thereby destroys the crystalline structure of cellulose. This is the major reason why cellulose of the biomass can be swelled, dissolved and eventually hydrolyzed easily and quickly in concentrated LiBr solution. (c) In addition to LiBr, CaBr2 is almost equally effective to enhance the hydrolysis of cellulose. CaBr2 is much more abundant in supply and less expensive in production. (d) Lignocellulosic biomass corn stover, aspen and spruce can be quickly hydrolyzed with high sugar yield in concentrated LiBr and CaBr2 solutions. (e) Ion-exchange, liquid-liquid extraction, and boronic acid-mediated solvent extraction are capable of separating LiBr from sugars, but they need further investigation and optimization.
Publications
- Type:
Conference Papers and Presentations
Status:
Published
Year Published:
2013
Citation:
C.Q. Mei and X.J. Pan. Dissolution of cellulose in aqueous lithium bromide solution. 245th ACS National Meeting & Exposition, April 7-11, 2013, New Orleans, LA.
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Progress 01/01/12 to 12/31/12
Outputs
OUTPUTS: The research activities and events during the reporting period included the following: (1) Changes of crystallinity and degree of polymerization of cellulose when dissolved in concentrated LiBr solution were investigated. (2) Saccharification of lignocellulose (spruce) in LiBr was studied, and conditions were preliminarily optimized. (3) Different methods were evaluated for separating sugars and the salt after the saccharification of spruce in LiBr. (4) The effect of residual salt in sugars on fermentation was preliminarily investigated. (5) One graduate student was involved in the project. Dissemination of the project outputs: (1) One abstract was submitted to 2013 ACS annual meeting; (2) Some of the results were used as teaching materials in the course Biorefining-Energy and Products from Renewable Resources for undergraduate and graduate students; (3) An invited presentation was given at University of Delaware on the saccharification of lignocellulosic biomass. PARTICIPANTS: Xuejun Pan, the PI. Chaoqun Mei (graduate student), working on dissolution and hydrolysis of cellulose in concentrated salt solution. TARGET AUDIENCES: (1) Graduate and undergraduate students through formal classroom instruction; (2) peer researchers through seminar and presentation. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The major outcomes and impacts of the project during the reporting period include the following: (1) It was found that degree of polymerization of cellulose significantly decreased during the dissolution in concentrated LiBr. This suggested that concentrated LiBr is not only able to dissolve cellulose but also able to hydrolyze cellulose. (2) It was found that cellulose and lignocellulosic biomass such as softwood and hardwood could be completely hydrolyzed in concentrated salt solution into sugars at moderate temperature (110-130C) within 60 min, dependent on the biomass species and particle size. (3) The results indicated that the methods such as liquid-liquid extraction, ion-exchange chromatography, crystallization, precipitation, and their combination can be used to separate the salt and sugars after the saccharification. The separation methods are under optimization. (4) It was found that small amount of residual salt (such as LiBr) in sugars do not have specific inhibition to the sugar fermentation, compared to other salt (such as NaCl). This suggests that complete separation of the salt from the sugars may not be necessary, considering the cost and complexity of the complete separation.
Publications
- No publications reported this period
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Progress 10/01/11 to 12/31/11
Outputs
OUTPUTS: The research activities and events during the reporting period include: (1). Literature was reviewed in the area of molten salt hydrates as medium for biomass dissolution and fractionation. (2) Dissolution of cellulose from different sources (Avicel and dissolving pulp) in molten salt hydrate was studied. The changes in crystallinity and degree of polymerization of cellulose during the dissolution are under investigation. (3). Saccharification of pure cellulose and real lignocellulosic biomass was preliminarily evaluated. (4). One graduate student was involved in the project. PARTICIPANTS: Xuejun Pan, the PI. Chaoqun Mei (graduate student), working on dissolution and hydrolysis of cellulose in concentrated salt solution. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The major outcomes and impacts of the project during the reporting period include: (1). It was found that cellulose could be dissolved in molten salt hydrate (concentrated salt solution). This finding could lead to a new and green solvent for cellulose processing and derivation. The process conditions are in optimization, and the changes of crystallinity and degree of polymerization of cellulose during the dissolution are under investigation. (2). It was demonstrated that cellulose and lignocellulosic biomass such as softwood and hardwood could be completely hydrolyzed in concentrated salt solution into sugars at moderate temperature (120-140C) within 30 min. Separation of the salt and sugars after the saccharification is under investigation.
Publications
- No publications reported this period
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