innovative conversion of biomass derivatives to high value...
TRANSCRIPT
Innovative Conversion of Biomass Derivatives to High Value Chemicals by Photocatalysis
Surawut Chuangchote1
Verawat Champreda2 Navadol Laosiripojana3
Takashi Sagawa4
1 Department of Tool and Materials Engineering, Faculty of Engineering, King Mongkut’s University of Technology Thonburi (KMUTT).
2 National Center for Genetic Engineering and Biotechnology (BIOTEC), National Science and Technology Development Agency (NSTDA).
3 The Joint Graduate School of Energy and Environment (JGSEE), KMUTT.4 Graduate School of Energy Science, Kyoto University.
E-mail: [email protected]
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Photocatalysis of Biomass Derivatives
Derivative 1SugarConversion
Derivative 2LigninConversion
Derivative 3BiomassPretreatment
Value-added Fuels & Chemicals
Development of Photocatalysts
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Development of TiO2 Fabrication with CTAB Surfactant
SEM and FESEM images of TiO2 photocatalysts synthesized by different concentrations of CTAB
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SEM images (30000x) of ZeY, TiO2 (5%)/ZeY(95%), TiO2 (15%)/ZeY(85%), TiO2 (30%)/ZeY(70%), TiO2 (45%)/ZeY(55%),and TiO2.
Modification of TiO2 with Supporters
LOGOElectrospinning
Electrospinning is a technique to produce the polymer nanofibers from a wide variety of materials and versatile applications.
Coaxial electrospinning with two-capillary spinneret.
Different methods of electrospinning:
1. Direct electrospinning2. Emulsion electrospinning3. Coaxial electrospinning
LOGOElectrospinning
Internal factors: • Type of polymer,• Type of solvent,• Solution concentration
(viscosity),• Solution conductivity, etc.
External factors:• Collecting distance, • Applied voltage,• Solution flow rate,• Ambient temperature,
humidity, etcExperimental setup
LOGOSEM Images TEM Images
Nanofibers PAN PAN/PMMA PAN/PMMANozzle Single nozzle Coaxial nozzle Inward Normal Outward Illustration
As spun nanofiber(Before calcination)
Carbon Nanofiber(After calcination)
Balance of Inner/Outer Nozzle End
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TiO2 Nanorod Arrays
(a)
(b)
SEM images of (a) ZnOnanorods as templates for producing (b) TiO2
nanotubes
Biomass Derivative 1: Sugar Conversion
LOGOThe results of development of TiO2 fabrication with CTAB surfactant
Photocatalytic conversion of glucose with TiO2synthesized with different concentrations of CTAB in MW.
Product yields of photocatalytic conversion ofglucose with TiO2 photocatalysts synthesized bydifferent concentrations of CTAB
gluconic acid arabinose
xylitol formic acid
Photocatalytic Activity of TiO2 Particles
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ZeolitesZeolites are hydrated aluminosilicate minerals made from interlinked tetrahedral of alumina (AlO4) and silica (SiO4).
(Lutz, 2014).
Basic Zeolite Structure
✓ Improved selectivity✓ High activity ✓ Excellent absorption ability
Advantages of Zeolites
Structure of zeolite A (a) and faujasite-type zeolites X and Y (b) formed by sodalite cages
Modification of TiO2 with Supporters
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Photocatalytic conversion of glucose
The results of modification of TiO2 with zeolite supporter
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Glucoseconv
ersio
n(%)
Irradiationtime (min)
ZeYTiO2(5%)/ZeY(95%)TiO2(15%)/ZeY(85%)TiO2(30%)/ZeY(70%)TiO2(45%)/ZeY(55%)TiO2
Photocatalyst SBET (m2/g)
ZeY 590.76
TiO2(5%)/ZeY(95%) 588.36
TiO2(15%)/ZeY(85%) 524.41
TiO2(30%)/ZeY(70%) 494.57
TiO2(45%)/ZeY(55%) 419.44
TiO2 34.38
Modification of TiO2 with Supporters
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Glu
cose
con
vers
ion
(%)
Irradiation time (min)
TiO2(15%)/ZeY(85%)
TiO2(15%)/SiO2(85%)
TiO2
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TiO2 TiO2(15%)/ZeY(85%) TiO2(15%)/SiO2(85%)
%Yield
FormicacidGluconicacidArabinoseXylitol
Photocatalytic conversion of glucose Product Yields
The results of modification of TiO2 with zeolite supporter
Modification of TiO2 with Supporters
Biomass Derivative 2: Lignin Conversion
LOGO
Photocatalytic activity
Effect of kraft lignin concentration onphotocatalytic conversion of kraft lignin(reaction conditions: 1g/L of P25, 100/0 v/v ofwater to ACN and 400 W of UV-lamp).
Composition of the biomasshttp://www.psb.ugent.be/bio-energy/313-lignin
TiO2
hv
Photocatalytic Conversion of Lignin to High-value Products
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Products Price(THB)/kg Applications
Gluconicacid 337 acidityregulator
Arabinose 1685-5055 sweetener
Xylitol 33.7-168.5 sweetener
Formicacid 16.513-18.53preservativeandantibacterialagent, useincleaningproducts,dyeingandfinishingtextilesproducts,anduseindirectformicacidfuelcell(DFAFC)
Chemicals from glucose conversion
Chemicals from lignin conversion
Products Price(THB)/kg Applications
2-methylnaphtalene 33.7-50.55
textiledyeing,printingandmetalsurfacewatertreatmentandchelating, usedinorganicsynthesis,pesticide,pharmaceuticalanddyneintermedite
4-hydroxy-benzaldehyde 33.7-3370 pharmaceuticalintermediate,antiallergic agentbloodsystemagentandanestheticagents
Vanillin 33.7-505.5 syntheticflavorandfragrance
4'-hydroxy-acetophenone 3370 usedinthemanufacture ofmedicinalreagent
Price of High-value Chemicals
Biomass Derivative 3: Biomass Pretreatment
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Concept of Photocatalytic Pretreatment of Biomass
Biomass structure
Enzymatic hydrolysis
Glucose, fructose, xylose
High-value chemicals
Photocatalytic process
TiO2
Photocatalytic Pretreatment of Biomass
LOGOBlank Pretreatment
①
Photocatalytic Pretreatment ②
Pretreated suspensionfiltrated by vacuum filter
Liquid Product
Further product analysis by HPLC
Solid Product(neutral)
Dilute with DI water
until neutral
Filtration
Further enzymatic hydrolysis
Photocatalytic Pretreatment of Biomass
Conclusion
LOGO
Conclusion
Synthesized Photocatalysts
High-value chemicals
• Xylitol• Gluconic acid• Arabinose• Formicacid
• Vanillin• 2-methylnaphtalene• 4-hydroxy-benzaldehyde• Etc.
Zeolite supported TiO2 TiO2 nanofibers/tubesTiO2 nanoparticles
TiO2 nanowires
LOGO
References
Papers
Patent
• W.Arpavate,S.Chuangchote,N.Laosiripojana,J.Wootthikanokkhan,andT.Sagawa(2016)"ZnONanorod ArraysFabricatedbyHydrothermalMethodUsingDifferentThicknessesofSeedLayersforApplicationsinHybridPhotovoltaicCells,"SensorsandMaterials,28(5),403-408.
• XylitolProductionfromGlucoseandXyloseUsingTitaniumDioxidePhotocatalyst,"PatentSubmissionNo.1401007893.
• M.Wongaree,S.Chiarakorn,S.Chuangchote,andT.Sagawa(2016)"PhotocatalyticPerformanceofElectrospun CNT/TiO2 NanofibersinaSimulatedAirPurifierunderVisibleLightIrradiation,"EnvironmentalScienceandPollutionResearch,23,21395-21406.
• K.Roongraun,N.Laosiripojana,S.Chuangchote(2016)"DevelopmentofPhotocatalyticConversionofGlucosetoValue-addedChemicalsbySupported-TiO2 Photocatalysts,"AppliedMechanicsandMaterials,839,39-43.
• N.Kaerkitcha,S.Chuangchote,andT.Sagawa(2016)"ControlofphysicalpropertiesofcarbonnanofibersobtainedfromcoaxialelectrospinningofPMMAandPANwithadjustableinner/outernozzle-ends,"NanoscaleResearchLetters,11(1),1-9.
• J.Payormhorm,S.Chuangchote,K.Kiatkittipong,S.Chiarakorn,N.Laosiripojana,Xylitol andgluconicacid productions viaphotocatalytic-glucoseconversion using TiO2 fabricated bysurfactant-assisted techniques:Effects of structural and textural properties,MaterialsChemistryand Physics,2017,196,29-36.