Ray, Ajay

Siddiqui, Homaira

Xu, Charles

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBioEnergy IV: Innovations in Biomass Conversionfor Heat, Power, Fuels and Chemicals ProceedingsSpring 6-12-2013Process optimization for the production of bio-resins using de-polymerized ligninHomaira SiddiquiICFARCharles XuICFARAjay RayICFARFollow this and additional works at: http://dc.engconfintl.org/bioenergy_ivPart of the Chemical Engineering CommonsThis Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. Formore information, please contact franco@bepress.com.Recommended CitationHomaira Siddiqui, Charles Xu, and Ajay Ray, "Process optimization for the production of bio-resins using de-polymerized lignin" in"BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington StateUniversity, USA Dietrich Meier, Thünen Institute of Wood Research, Germany Raffaella Ocone, Heriot-Watt University, UnitedKingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds, ECI Symposium Series, (2013).http://dc.engconfintl.org/bioenergy_iv/33H O M A I R A  S I D D I Q U IM E S c .  C a n d i d a t e  2 0 1 3W e s t e r n  U n i v e r s i t y  C a n a d aI n s t i t u t e  o f  C h e m i c a l s  a n d  F u e l s  f r o m  A l t e r n a t i v e  R e s o u r c e s  ( I C F A R )C o n t a c t :  h s i d d i q 5 @ g m a i l . c o mC o - S u p e r v i s o r s :  D r s .  C .  X u &  A .  R a yProcess Optimization for the production of Bio-resins using de-polymerized LigninOutlineIntroduction & MotivationObjectivesResearch MethodologiesKey ResultsSummary/ConclusionsAcknowledgements3Introduction: Background & Motivation• Plywood adhesives: High strength and moisture resistance properties• > 95% of phenol from petroleum-derived benzene • Lignocellulosic biomass contains 30-40% lignin; a polyphenolic macromolecule• Thermochemical de-polymerization• Major challenge: reduced reactivity4Introduction: Significance• PF Manufacturing industry valued at $10 billion globally;• US Department of energy: Increase of 23.7% in Compound Annual Growth Rate between 2009 and 2015 (SRI Consulting, 2010);• Cost of PF resins varies from US$ 1,500 to US$ 2,000 per metric ton, mainly due to the high and fluctuating cost of phenol;• Need for lower dependence on non-renewable feedstock and maximization of value of trees.ObjectivesTo produce bio-phenol formaldehyde (BPF) resole resins at varying lignin-to-phenol substitution ratios while maintaining high quality;Multi-objective optimization: To maximize the adhesive strength and minimize the curing temperature of the BPF resole resins Research MethodologiesParameter Variable Level (-1)Level (0)Level(+1)Formaldehyde-to-phenol x1 1.2 2.1 3% Phenol substitution x2 25 50 75Molecular weight of de-polymerized Lignin (DL) (g/mol)x3 7001 1,1002 11,00031 Hydrolytic de-polymerization at 350C & 45 min; 2 Hydrolytic de-polymerization at 300C & 60 min; 3 Hydrolytic de-polymerization at 250C & 45 min (NublaMahmood, 2012)Phenolic Resole Synthesis Reactions Addition Reactions Methylolation of phenolic units Condensation Reactions Formation of Diethyl Ether Bridges Formation of Methylene BridgesPhenolicPhenolic(Methylolated)(Methylolated)Phenolicunit CH2 OCH2 Phenolic(Methylolated)Phenolic(Methylolated)PhenolicH2OPhenolicunit CH2 PhenolicunitCH2OH2Ounitunitunitunitunit8Properties of Phenolic Resoles (Commercial)Property Value Source/NotesViscosity 150-600 cP at 25oC A. Pizzi & Y. Jin (2010)For plywood applicationsSolid Content 40-60% KopfpH 7-13 A. PizziFree formaldehyde 0.19-0.67 Generally lowUnreacted Phenol 5-15% A. PizziMolecular Weight (Mn)1000-2000 g/mol A. PizziShear Strength >2.5 MPa Institute for Research in Construction (2009)Research Methodologies20 wt% Kraft Lignin (FP Innovations)  at varying severitiesWater  NaOHFinal De-polymerized Lignin Product22 barsBio-Phenol Formaldehyde (BPF) resin:*De-polymerized Lignin*Phenol*Formaldehyde*Water & Ethanol*NaOH catalyst: 10 wt%F:P ratioReaction for 2 hLignin De-polymerization BPF Resole SynthesisResearch Methodologies – AnalysisTemperature: 180oC; Pressure: 1.4 MPa; Adhesive application (250 g/m2) BPF Resoles - ViscositySample ID Viscosity (cP) Standard ErrorBPF-25,(-1),2.1 26 (+/-) 1.2BPF-50,(-1),1.2 229 (+/-) 8.5BPF-50,(-1),3 165 (+/-) 7.2BPF-75,(-1),2.1 191 (+/-) 3.5BPF-25,(+1),2.1 124 (+/-) 0.4BPF-50,(+1),1.2 288 (+/-) 0.8BPF-50,(+1),3 137 (+/-) 1.2BPF-75,(+1),2.1 348 (+/-) 0.6BPF-25,(0),1.2 124 (+/-) 0.1BPF-25,(0).3 16 (+/-) 0.1BPF-50,(0),2.1 40 (+/-) 0.1BPF-75,(0),1.2 >5,000BPF-75,(0)3 >5,000LABEL: BPF-%Substitution, Lignin Mw Level, F:P ratio-5.5-4.5-3.5-2.5-1.5-0.50.51.52.53.54.50 20 40 60 80 100 120 140 160 180 200 220 240 260 280Heat Flow (mW)Temperature (degrees Celsius)Effect of Lignin Molecular Weight on Curing Temperature of BPF Resins at 25% SubstitutionBPF-25,(+1),2.1BPF-25,(-1),2.1211oC 216oC-5.5-3.5-1.50.52.54.56.50 20 40 60 80 100 120 140 160 180 200 220 240 260 280Heat Flow (mW)Temperature (degrees Celsius)Effect of Lignin Molecular Weight on Curing Temperature of BPF Resins at Lignin at 75% SubstitutionBPF-75,(+1),2.1BPF-75,(-1),2.1195oC192oC-2.5-2-1.5-1-0.500.511.520 50 100 150 200 250 300 350 400Heat Flow (mW)Temperature (degrees Celsius)Effect of F/P Molar Ratio using Lignin of Mw level (-1) BPF-50,(-1),1.2BPF-50,(-1),3219.50oC200.09oC-2-1.5-1-0.500.511.522.50 50 100 150 200 250 300 350 400Heat Flow (mW)Temperature (degrees Celsius)Effect of F/P Molar Ratio using Lignin of Mw level (+1) BPF-50,(+1),1.2BPF-50,(+1),3Increasing F:P*Higher degree of Methylolation*More cross-linking and rigid structure*Lower Activation Energy228oC191oCEffect of % Substitution0246810Mid Lignin Mw,F:P of 1.2Low Lignin Mw,F:P of 2.1High Lignin M,F:P of 2.1Shear Stress (MPa) Effect of Phenol-to-Lignin Percent Substitution on Shear Stress25%75%Curing Temperature: 180oC; Pressure: 1.4 MPaAdhesive application (250 g/m2) Effect of Lignin Mw 024681012At 25%Subs, F:P of2.1At 50%Subs, F:P of1.2At 50%Subs, F:P of3At 75%Subs, F:P of2.1Shear Stress (MPa) Effect of Lignin Molecular Weight (Mw) on Shear StressLow Lignin MwHigh Lignin MwCuring Temperature: 180oC; Pressure: 1.4 MPaAdhesive application (250 g/m2) Effect of F:P Molar Ratio024681050%Subs, LowLignin Mw50%Subs, HighLignin Mw75% Subs, MidLignin MwShear Stress (MPa) Effect of Molar Ratio on Shear StressMolar Ratio 3Molar Ratio 1.2Curing Temperature: 180oC; Pressure: 1.4 MPaAdhesive application (250 g/m2) Wood Failure (Qualitative)Summary At low percent substitutions, BPF resole qualities are similar to those of pure PF resoles; Relevance of observing BPF qualities at high percent substitutions; High percent substitution: acceptable shear strength, lower wood failure, and exceedingly high viscosity measurements; Increasing F/P ratio reduces the curing temperature and increases the shear strength; Increasing Lignin Mw reduced the curing temperature and increases the shear strength while also increasing the viscosity.Conclusions/Recommendations To obtain high-quality BPF resoles at higher % substitutions: Increase lignin molecular weight; increase F/P ratio; control viscosities of BPF resoles. At 75%, lowest curing temperature (192oC) and highest adhesive strength (9.0 MPa) obtained at high lignin Mw and F:P ratio of 2.1 (348 cp); Pure PF resole: Curing temperature of ~150oC and adhesive strength of 8.3 MPa GPC analysis to determine molecular weight of BPF resoles; TGA analysis to determine thermal stability of BPF resoles.AcknowledgementsH O M A I R A  S I D D I Q U IC o n t a c t :  h s i d d i q 5 @ g m a i l . c o mI n s t i t u t e  o f  C h e m i c a l s  a n d  F u e l s  f r o m  A l t e r n a t i v e  R e s o u r c e s  ( I C F A R )

Process optimization for the production of bio-resins using de-polymerized lignin

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Process optimization for the production of bio-resins using de-polymerized lignin

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