OMAFRA New Directions Research Program Project:

Transcription

1 OMAFRA New Directions Research Program Project: Production of Bio-phenols and Phenolic Resins/Adhesives from Agricultural and Forest Biomass Start Date: December 3, 2007 Expected Completion Date: December 2, 2010 Lakehead University Arclin Canada GreenField Ethanol Charles Xu, PhD, P.Eng (PI), Associate Prof., Department of Chemical Engineering Mathew Leitch, PhD (Co-PI), Associate Prof., Faculty of Forestry and Forest Environ.

2 Presentation Outline Project Background and Motivation Objectives Methodologies and Approaches Summary of Key Results On-going and Future Research Project Accomplishments Significance of the Research to Ontario

3 Project Background & Motivation Phenol-formaldehyde (PF) resin Poly-condensation product of phenol (P) and formaldehyde (F). First developed by Baekeland in 1907, and first introduced as binders for particleboard and plywood in the mid 1930 s (Wendler and Frazier, 1996). Used mainly as adhesives for plywood and oriented strand board (OSB), circuit boards, molded products, and fire proof/retarding materials. The PF resin manufacture is an important industry valued approx. $10 billion in the world, or $ 2.3 billion in North America.

4 Project Background & Motivation (Cont d) Phenol More than 95% of phenol is produced from petroleum-derived benzene by the cumene process 3 MPa, 250ºC benzene propylene cumene cumene hydroperoxide phenol 35-40% of phenol produced in the US is used for the production of phenol-formaldehyde (PF) resins. Coal Petroleum Natural Gas 42 Years 60 Year 210 years (Source: Shell Oil) PF resins from renewable resources (biomass)?

5 Project Background & Motivation (Cont d) Bio-Phenols from Lignocellulosic Biomass Agricultural and forest biomass typically contains 10-25% and 20-35% lignin, respectively. Cleavage of the weak β-o-4 ether bonds in lignin yields phenols and derivatives. (Lee and Ohkita, 2003; Alma, et al., 2001; Wang, et al., 2009)

6 Project Background & Motivation (Cont d) Challenge in replacing phenol with lignin or pyrolysis oil for PF resins synthesis Lignin and pyrolysis oil have been successfully used to directly replace phenol in phenolic resin synthesis, but the substitution ratio is generally less than 30-50% due to the much lower reactivity of lignin compared with pure phenol (Van der Klashorst, 1989; Cetin and Ozmen, 2002). Less reactive sites for hydroxy-methylation Steric interactions

7 Objectives Replace petroleum phenol with bio-phenols derived from agricultural and forest biomass for the production of bio-based phenolic resin and adhesives, at a high substitution ratio of >50%. Methodologies/ Approaches Cornstalk, DDGS, wood sawdust Direct liquefaction in hot-compressed phenol, alcohol, water Organosolv extraction Bio-oil Phenol resole Bio-oil resole Methylolation Modified bio-oil Bio-based Pheolic Resins Lignin Pheolic biooil Biophenols Depolymerizatio n Plywood adhesive s

8 Summary of Key Results Liquefy cornstalk, DDGS and pine sawdust in hotcompressed solvents (phenol, alcohols, water) to produce phenol-rich bio-oils. Xu, C., H. Su, D. Cang, Liquefaction of distillers dried grain with solubles (DDGS) in hot-compressed phenol. BioResources, 3(2), Yang, Y., A. Gilbert, C. Xu, Hydro-liquefaction of forestry waste in near- /super-critical methanol for the production of bio-crude. AIChE J., 55, Wang, M., C. Xu, M. Leitch, Liquefaction of corn stalk for the production of phenol-formaldehyde resole resin. Bioresource Technology, 100, Tymchyshyn, M., C. Xu, Liquefaction of biomass in hot-compressed water for the production of phenolic compounds. Bioresource Technology, 101, Cheng, S., I. Dcruz, M. Wang, M. Leitch, C. Xu, Highly efficient liquefaction of woody biomass in hot-compressed alcohol-water co-solvents. Energy Fuels (In press).

9 Summary of Key Results (Cont d) Synthesize bio-oil phenolic resins and plywood Wang, adhesives M., M. Leitch, C. Xu, Synthesis of phenolic resol resins using cornstalk-derived bio-oil produced by direct liquefaction in a hotcompressed phenol-water medium. Journal of Industrial Engineering Chemistry, 15, Cheng, S., I. Dcruz, M. Wang, M. Leitch, C. Xu, Synthesis and characterizations of bio-based phenolic resin using bio-oil obtained by direct liquefaction of pinewood sawdust. European Polymer Journal (to be submitted) Cheng, S., Z. Yuan, M. Leitch, C. Xu, Synthesis and characterizations of biobased phenolic resin using methylolated bio-oil. J. Applied Polymer Science (to be submitted) Wang, M., M. Leitch, C. Xu, Synthesis of novel phenol-glucose resins without using formaldehyde. J. Applied Polymer Science (In press). Xu, C., M. Wang, M. Leitch, Synthesis of Sweet Phenol-Glucose Novolac Resins without Using Formaldehyde. US Patent under application. Research is on-going

10 Summary of Key Results (Cont d) Organosolv extraction of lignin from biomass and depolymerization of lignin to bio-phenols for the production of bio-based phenolic resins Wang, M., M., M. Leitch, C. Xu, Synthesis of phenolformaldehyde resol resins using organosolv pine lignins. European Polymer Journal, 45, Cheng, S., I. Dcruz, M. Wang, M. Leitch, C. Xu,, Catalytic degradation of pinewood-derived organosolv lignin in formic acid. Bioresource Technology (to be submitted). Yuan, Z., S. Cheng, M. Leitch, C. Xu*, Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol. Bioresource Technology (to be submitted). Research is on-going

11 Summary of Key Results (Cont d) Application of bio-based phenolic resins to plywood adhesives Dry strengh Wet strengh Tensile strength / MPa Note: Yellow birch veneer, conditioned 10-12% MC; Adhesive application (250 g/m 2 ) ; Press, 140 o C, 2500 psi, 4 min Wood failure 1 (%) (STEDV) Pure PF 25 % BPF 50 % BPF 75 % BPF Dry 2 89 (± 0.19) 97 (± 0.13) 87 (± 0.36) 22 (± 0.33) Wet 3 65 (± 0.43) 33 (± 0.42) 35 (± 0.41) 15 (± 0.31) Pure PF 25%BPF 50% BPF 75% BPF Type of resol resins 1 Each value represents an average of 20 specimens. 2 Test after conditioning.

12 On-going and Future Research Agricultural / forest biomass Organosolv Extraction of Lignin Lignin Holocellulose Enzymatic Hydrolysis Bio-phenols Resinification 100% Green resins/adhesive s Carbohydrates (Glucose, Xylose) Catalysts (CrCl 2, H 2 SO 4, Ionic liquid) Hydroxy-methylfurfural (HMF) Furfural

13 Project Accomplishments Student and HQP training: - 2 postdoctoral fellows (Dr. Mingcun Wang, Dr. Sean Yuan) - 1 PhD students (Ms. Shuna Cheng), - 2 M.Sc. graduate students (Y. Yang, H. Su) - 3 B.Sc. students. (M. Tymchyshyn, I. DCruz, T. Kennedy) Intellectual property and publications: - 1 patent filed - 6 conference papers and presentations - 12 journal papers (published, submitted or to-be-submitted)

14 Significance of the Research to Ontario Ontario has a strong agri-food sector, annually producing more than 2 million tonnes of wheat and 6 millions tonnes of corn, while leaving about equal (or even more) amounts of crop residues for disposal. Northwestern Ontario has a vitally important forestry sector, where the annual surplus woodwastes was estimated at about 2 million tonnes. There is a large phenolic resin industry valued at US$ 2.3 billion in the North America, and the overall resin demand in North America has increased by as much as 5% annually since In this project, agricultural residues and forest residue and woodwastes are converted into renewable chemical feedstock (bio-phenols and bioaldehydes) for the production of bio-based phenolic resins and plastics. Thus, the implementation and success of the project would yield substantial benefits to the economy of Ontario s agri-food sector and the forestry sector, as well as to the environment.

15 Thank you! New Directions Research Program (OMAFRA) Emerging Technologies Fund (NOHFC/FedNor) Discovery Grant (NSERC) Leaders Opportunity Fund Award (CFI)

16 Mechanisms of Resole Synthesis PF resole synthesis is a step growth polymerization comprising two steps: addition reactions and condensation reactions. Addition Reactions (Witanowski, et al., 1986). To form mono-, di- and tri-substituted hydroxymethylated phenols (HMPs). phenoxide ions Hydrated formaldehyde

17 Introduction Mechanisms of Resole Synthesis (Cont d) Condensation Reactions (Haider, et al., 2000) Quinone methide intermediate Methylene bridge

18 Mechanism of novalac system via electrophilic aromatic substitution.