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Alexander Cranford
1
2
Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of Biomass: Deriving
More Value from Waste. Science 2012, 337, 695-699.
 Background
 Supercritical Hydrolysis
◦ Method
◦ Results
◦ Discussion
 Applications
3
 Petroleum Use
 Abundance of Biomass
 Fermentation
4
Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of Biomass: Deriving
More Value from Waste. Science 2012, 337, 695-699.
 Non-Supercritical Hydrolysis
◦ Acid Hydrolysis
◦ Enzyme Hydrolysis
 Supercritical hydrolysis
5
http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/Image
Service/Articleimage/2009/GC/b915758a/b915758a-s1.gif
http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/
Articleimage/2010/GC/c0gc00262c/c0gc00262c-s1.gif
http://chemwiki.ucdavis.edu/@api/deki/files/5790/image017.png?revision=1
Sasaki, M.; Adschiri, T.; Arai, K. Kinetics of cellulose conversion at 25 MPa in sub- and supercritical
water. AIChE J. 2004, 50, 192-202.
 Supercritical water
 Kw
 tr
6
http://lessons.chemistnate.com/uploads/5/0/2/9/5029141/__553
6567_orig.png
W. L. Marshall, E. U. Franck, J. Phys. Chem. Ref. Data1981, 10, 295– 304.
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical
Water. ChemSusChem 2015, 8, 1026-1033.
 5-HMF
 Glyceraldehydes
 Pyruvaldehydes
 Radical Reactions
7
http://www.scielo.br/img/revistas/jbchs/v25n12//0103-5053-jbchs-25-12-
2378-gf07.jpg
http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_B
iological_Emphasis/Chapter_13%3A_Reactions_with_stabilized_carbanion_inter
mediates_I/Section_13.3%3A_Aldol_reactions
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical
Water. ChemSusChem 2015, 8, 1026-1033.
 Temperature Control
 Effect on tr
8
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water
hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
9
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis
of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
10
Selectivity of Sugars at 400ºC
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis
of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
11
5-HMF Production
Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in
Supercritical Water. ChemSusChem 2015, 8, 1026-1033.
 P-xylene
 5-HMF
12
Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.;
Dauenhauer, P. J. Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-
Xylene. ACS Catal. 2012, 2, 935-939.
 Opportunities
 Innovations
 Applications
13
 Industrial Use
 Synthesis from Carbohydrates
14
Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J. Cycloaddition of
Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene. ACS Catal. 2012, 2, 935-939.
van Putten, R.; van, d. W.; de Jong, E.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G. Hydroxymethylfurfural, A Versatile Platform
Chemical Made from Renewable Resources. Chem. Rev. 2013, 113, 1499-1597.
Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic
biomass. Green Chem. 2013, 15, 584-595.
 Thank you Dr. Fry
 Thank you for listening
15
 Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Gamma-valerolactone, a sustainable
platform molecule derived from lignocellulosic biomass. Green Chem. 2013, 15,
584-595.
 Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose
Hydrolysis in Supercritical Water. ChemSusChem 2015, 8, 1026-1033.
 Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in
pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour.
Technol. 2013, 135, 697-703.
 Sasaki, M.; Adschiri, T.; Arai, K. Kinetics of cellulose conversion at 25 MPa in sub-
and supercritical water. AIChE J. 2004, 50, 192-202.
 Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of
Biomass: Deriving More Value from Waste. Science 2012, 337, 695-699.
 van Putten, R.; van, d. W.; de Jong, E.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G.
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable
Resources. Chem. Rev. 2013, 113, 1499-1597.
 Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo,
R. F.; Fan, W.; Dauenhauer, P. J. Cycloaddition of Biomass-Derived Furans for
Catalytic Production of Renewable p-Xylene. ACS Catal. 2012, 2, 935-939.
16

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Biomass

  • 2. 2 Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of Biomass: Deriving More Value from Waste. Science 2012, 337, 695-699.
  • 3.  Background  Supercritical Hydrolysis ◦ Method ◦ Results ◦ Discussion  Applications 3
  • 4.  Petroleum Use  Abundance of Biomass  Fermentation 4 Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of Biomass: Deriving More Value from Waste. Science 2012, 337, 695-699.
  • 5.  Non-Supercritical Hydrolysis ◦ Acid Hydrolysis ◦ Enzyme Hydrolysis  Supercritical hydrolysis 5 http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/Image Service/Articleimage/2009/GC/b915758a/b915758a-s1.gif http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/ Articleimage/2010/GC/c0gc00262c/c0gc00262c-s1.gif http://chemwiki.ucdavis.edu/@api/deki/files/5790/image017.png?revision=1 Sasaki, M.; Adschiri, T.; Arai, K. Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water. AIChE J. 2004, 50, 192-202.
  • 6.  Supercritical water  Kw  tr 6 http://lessons.chemistnate.com/uploads/5/0/2/9/5029141/__553 6567_orig.png W. L. Marshall, E. U. Franck, J. Phys. Chem. Ref. Data1981, 10, 295– 304. Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical Water. ChemSusChem 2015, 8, 1026-1033.
  • 7.  5-HMF  Glyceraldehydes  Pyruvaldehydes  Radical Reactions 7 http://www.scielo.br/img/revistas/jbchs/v25n12//0103-5053-jbchs-25-12- 2378-gf07.jpg http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_B iological_Emphasis/Chapter_13%3A_Reactions_with_stabilized_carbanion_inter mediates_I/Section_13.3%3A_Aldol_reactions Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical Water. ChemSusChem 2015, 8, 1026-1033.
  • 8.  Temperature Control  Effect on tr 8 Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
  • 9. 9 Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
  • 10. 10 Selectivity of Sugars at 400ºC Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.
  • 11. 11 5-HMF Production Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical Water. ChemSusChem 2015, 8, 1026-1033.
  • 12.  P-xylene  5-HMF 12 Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J. Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p- Xylene. ACS Catal. 2012, 2, 935-939.
  • 14.  Industrial Use  Synthesis from Carbohydrates 14 Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J. Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene. ACS Catal. 2012, 2, 935-939. van Putten, R.; van, d. W.; de Jong, E.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G. Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources. Chem. Rev. 2013, 113, 1499-1597. Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass. Green Chem. 2013, 15, 584-595.
  • 15.  Thank you Dr. Fry  Thank you for listening 15
  • 16.  Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass. Green Chem. 2013, 15, 584-595.  Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. Governing Chemistry of Cellulose Hydrolysis in Supercritical Water. ChemSusChem 2015, 8, 1026-1033.  Cantero, D. A.; Bermejo, M. D.; Cocero, M. J. High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 2013, 135, 697-703.  Sasaki, M.; Adschiri, T.; Arai, K. Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water. AIChE J. 2004, 50, 192-202.  Tuck, C. O.; Pérez, E.; Horváith, I. T.; Sheldon, R. A.; Poliakoff, M. Valorization of Biomass: Deriving More Value from Waste. Science 2012, 337, 695-699.  van Putten, R.; van, d. W.; de Jong, E.; Rasrendra, C. B.; Heeres, H. J.; de Vries, J. G. Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources. Chem. Rev. 2013, 113, 1499-1597.  Williams, C. L.; Chang, C.; Do, P.; Nikbin, N.; Caratzoulas, S.; Vlachos, D. G.; Lobo, R. F.; Fan, W.; Dauenhauer, P. J. Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene. ACS Catal. 2012, 2, 935-939. 16