OMAFRA New Directions Research Program Project: Production

OMAFRA New Directions Research Program Project:

Production of BioProduction of Bio--phenols and Phenolic phenols and Phenolic

Resins/Adhesives from Agricultural and Resins/Adhesives from Agricultural and

Forest BiomassForest Biomass

Lakehead UniversityArclin 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.

Bio-economy Research Highlights Day, April 13, 2010, Guelph, Ontario

Start Date: December 3, 2007Expected Completion Date: December 2, 2010

Presentation OutlinePresentation 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


� 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.

� Phenol-formaldehyde (PF) resin

Project Background & Motivation


� Phenol

3 MPa, 250ºC

cumene cumene hydroperoxide phenol

� More than 95% of phenol is produced from petroleum-derived

benzene by the cumene process

� 35-40% of phenol produced in the US is used for the production of

phenol-formaldehyde (PF) resins.

Petroleum

Coal

Natural Gas

210 years

42 Years

60 Year

PF resins from renewable resources (biomass)?

benzene propylene

(Source: Shell Oil)

Project Background & Motivation (Cont’d)


Cleavage of the weak ββββ-O-4 ether bonds in lignin yields phenols and derivatives.(Lee and Ohkita, 2003; Alma, et al., 2001; Wang, et al., 2009)

Project Background & Motivation (Cont’d)� Bio-Phenols from Lignocellulosic Biomass


Agricultural and forest biomass typically contains 10-25% and 20-35% lignin, respectively.

� 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

Project Background & Motivation (Cont’d)


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%.

Bio-oil Bio-oilresole

Phenolresole

Methodologies/

Approaches

Cornstalk, DDGS, wood sawdust

Pheolic bio-oil

Lignin

Bio-phenols

Bio-based Pheolic Resins

Modified bio-oil

Direct liquefaction in hot-compressed phenol, alcohol, water

Organosolv extraction

De-polymerization

Methylola-tion

Plywood adhesives

Summary of Key Results� Liquefy cornstalk, DDGS and pine sawdust in hot-

compressed solvents (phenol, alcohols, water) to produce phenol-rich bio-oils.

• Xu, C., H. Su, D. Cang, 2008. Liquefaction of distillers dried grain with solubles (DDGS) in hot-compressed phenol. BioResources, 3(2), 363-38.

• Yang, Y., A. Gilbert, C. Xu, 2009. Hydro-liquefaction of forestry waste in near-/super-critical methanol for the production of bio-crude. AIChE J., 55, 807-819.

• Wang, M., C. Xu, M. Leitch, 2009. Liquefaction of corn stalk for the production of phenol-formaldehyde resole resin. Bioresource Technology, 100, 2305-2307.

• Tymchyshyn, M. , C. Xu, 2010. Liquefaction of biomass in hot-compressed water for the production of phenolic compounds. Bioresource Technology , 101, 2483-2490.

• 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).


Summary of Key Results (Cont’d)� Synthesize bio-oil phenolic resins and plywood

adhesives• Wang, M., M. Leitch, C. Xu, 2009. Synthesis of phenolic resol resins using cornstalk-derived bio-oil produced by direct liquefaction in a hot-compressed phenol-water medium. Journal of Industrial Engineering Chemistry, 15, 870-875.• 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)

• Xu, C., M. Wang, M. Leitch, Synthesis of “Sweet” Phenol-Glucose Novolac Resins without Using Formaldehyde. US Patent under application.

Research is on-going…

• Wang, M., M. Leitch, C. Xu, 2010. Synthesis of novel phenol-glucose resins without using formaldehyde. J. Applied Polymer Science (In press).


• Cheng, S., Z. Yuan, M. Leitch, C. Xu, Synthesis and characterizations of bio-based phenolic resin using methylolated bio-oil. J. Applied Polymer Science

(to be submitted)

� Organosolv extraction of lignin from biomass and de-polymerization of lignin to bio-phenols for the production of bio-based phenolic resins

•Wang, M., M., M. Leitch, C. Xu, 2009. Synthesis of phenol-formaldehyde resol resins using organosolv pine lignins. European Polymer Journal, 45, 3380–3388.

Research is on-going…

Summary of Key Results (Cont’d)

• Yuan, Z. , S. Cheng, M. Leitch, C. Xu*, Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol. Bioresource Technology (to be submitted).


• 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).

� Application of bio-based phenolic resins to plywood adhesives

Summary of Key Results (Cont’d)

Pure PF 25%BPF 50% BPF 75% BPF

0.0

0.5

1.0

1.5

2.0

2.5

Ten

sile

str

ength

/ M

Pa

Type of resol resins

Dry strengh

Wet strengh

Wood failure1

(%) (STEDV)Pure PF 25 % BPF 50 % BPF 75 % BPF

Dry2 89 (± 0.19) 97 (± 0.13) 87 (± 0.36) 22 (± 0.33)

Wet3 65 (± 0.43) 33 (± 0.42) 35 (± 0.41) 15 (± 0.31)

Note:• Yellow birch veneer, conditioned 10-12% MC;• Adhesive application (250 g/m2) ;• Press, 140oC, 2500 psi, 4 min

1 Each value represents an

average of 20 specimens.

2 Test after conditioning.3 Test after boiled for

On-going and Future Research

Agricultural /forest biomass

Organosolv Extraction of Lignin

Holocellulose

Carbohydrates(Glucose, Xylose)

Enzymatic Hydrolysis

Lignin

Resinification

100% “Green”resins/adhesivesBio-phenols

Hydroxy-methyl-furfural (HMF)

Furfural

Catalysts (CrCl2, H2SO4, Ionic liquid)


� 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)

Project Accomplishments


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 hasincreased by as much as 5% annually since 2000.

• In this project, agricultural residues and forest residue and woodwastes are converted into renewable chemical feedstock (bio-phenols and bio-aldehydes) 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.

Thank you!Thank you!

New Directions Research Program (OMAFRA)


Emerging Technologies Fund (NOHFC/FedNor)

Discovery Grant (NSERC)

Leaders Opportunity Fund Award (CFI)

� Mechanisms of Resole Synthesis

Addition Reactions (Witanowski, et al., 1986).

• PF resole synthesis is a step growth polymerization comprising two steps: addition reactions and condensation reactions.

To form mono-, di- and tri-substituted hydroxymethylated phenols (HMPs).

phenoxide ions

Hydrated formaldehyde

� Mechanisms of Resole Synthesis (Cont’d) IntroductionIntroduction

Quinone methide intermediate

Methylene bridge

Condensation Reactions (Haider, et al., 2000)

Mechanism of novalac system via electrophilic aromatic substitution.

Documents

OMAFRA New Directions Research Program Project: Production