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LIGNIN DEPOLYMERIZATION THROUGH
HYDROGENOLYSIS INTO MONOMERIC
   SUBUNITS ON METAL CATALYSTS
             Lis Nimani
       Advisor: Dr. Xuejun Pan
        Master of Science Thesis Defense
                August 3rd, 2012
Outline
 Introduction
   Renewable energy
   Lignocellulosic Biomass
     Polysaccharides
     Lignin
   Conversion Processes of Lignocelluloses to Fuels and
    Chemicals
     Lignocellulose conversion
   Problem Statement
   Objectives
 Hydrogenolysis
   Hydrogenolysis Operation
   Hydrogenolysis of Feedstock
   Lignin Hydrogenolysis
   Polysaccharides Hydrogenolysis
 Conclusion
   Summary
   Future Work
Renewable Energy
 Need for renewable energy
   Depletion of Fossil Fuels
   Global Warming due to Greenhouse Gasses (GHGs)
   National Security




            (Deming, 2000)          (Forster et al., 2007)
   (Akorede et al., 2012)

 Bioenergy
   Corn/Sugarcane (1st Generation)
   Lignocellulosic Biomass (2nd Generation)
Lignocellulosic Biomass
   Lignocellulosic Biomass
     Hardwood
     Softwood
     Herbaceous Plants
   Lignocellulose Complex
                                                                       (Murphy and McCarthy, 2005)
     Cellulose
     Hemicellulose
     Lignin
 The chemical composition make up of the lignocellulosic materials
                     (Sun and Cheng, 2002)

Feedstock      Cellulose (%)         Hemicellulose (%)    Lignin (%)
Hardwood           40-50                  25-40             18-25
Softwood           45-50                  25-35             23-35          (Zhou et al., 2010)
 Grasses           25-40                  35-50             10-30
Polysaccharides
 Cellulose
   Most abundant organic
    chemical on earth.
   Homopolymer
     7,000 to 15,000 monomeric D-
      glucose units
   Crystalline and Amorphous
   Regions
                                                                       (Meyers et al., 2008)
     Up to 65% crystalline regions in             Content and compositional differences between hardwood vs. softwood
      wood.                                                               (Kögel-Knabner, 2002)


 Hemicellulose                          Polyoses
                                                            Deciduous Wood (Hardwood)            Coniferous Wood (Softwood)
                                                             Content (%)       Units              Content (%)         Units
   Branched Heteropolymers                                                 Xylose, 4-O-                         Xylose, 4-O-
     Pentoses (β-D-xylose, α-L-          Xylans             25-30        methylglucuronic        5-10        methylglucuronic
                                                                                acid                                 acid
      arabinose)                                                                                              Mannose, glucose,
     Hexoses (β-D-mannose, β-D-         Mannans              3-5         Mannose, glucose       20-25         galactose, acetyl
                                                                                                                    groups
      glucose, α-D-galactose)                                                Galactose,
                                                                                                                  Galactose,
                                         Galactans           0.5-2           arabinose,           0.5-3
   Xylans and Glucomannans                                                  rhammose
                                                                                                                  arabinose

     Most significant hemicelluloses.
Lignin
 An amorphous three-dimensional bio-polymer of
 three phenylpropane units randomly cross-linked
 with one another.
   Derived generally from three monolignols:
     Para-coumaryl alcohol
     Coniferyl alcohol
     Sinapyl alcohol
   Monolignols produce phenylpropaniod
   units
     Para-hydroxyphenol (H-unit)
                                                (Xu, 2010)
     Guaiacyl (G-unit)
     Syringol (S-unit)

 Lignin is produced by free radical generation
 followed by chemical coupling processes of the
 monolignols.
Lignin
 Lignin content and composition varies
 between lignocellulosic biomass.
  Lignin content
    Softwoods ˃Hardwoods ˃ Herbaceous
  Lignin composition
    Softwood: Guaiacyl (G) lignin
    Hardwood: Guaiacyl-syringol (GS) lignin
    Herbaceous: Gramineae (GSH) lignin
  Lignin linkages
    (1/3) to (1/4) carbon-carbon linkages
    (2/3) to (3/4) ether linkages
Lignin




 (Kögel-Knabner, 2002)
                    Content of the main linkages in lignin               (Faravelli et al., 2010)
    (Achyuthan et al., 2010; Pandey and Kim, 2011; Ralph, 2005; Zakzeski et al., 2010)
      Linkage Type               Softwood (spruce) (%)            Hardwood (birch) (%)
    β-O-4-Aryl ether                       46                               60
    Dibenzodioxocin                      25-30                            5-10
 β-5-Phenylcoumaran                       9-12                               6
      β-β-(Resinol)                        2-6                            3-12
   4-O-5-Diaryl ether                      <4                              <6.5
β-1-(1,2-Diarylpropnae)                    1-2                             1-2
    α-O-4-Aryl ether                     A few                            A few
Conversion Processes of Lignocelluloses to
          fuels and Chemicals




                                       (Menon and Rao, 2012)
        Comparison between the biochemical and thermochemical process (Basu 2010a).

                                          Biochemical Process   Thermochemical Process

            Reactor Type                        Batch                 Continuous

            Reaction Time                     A few Days             A few minutes

            Temperature                       100-200 °C                ˃ °C
                                                                         200

   Water Usage (liter/liter ethanol)           3.5-170                    <1
Lignocellulose Conversion




        (Zheng et al., 2011)
Problem Statement
 Current biochemical
  conversion of lignocellulose for
  fuels and chemicals
   Cellulose and hemicellulose
    converted to ethanol
   Lignin used as a boiler fuel through
    combustion
   Non-simultaneous
 Inefficient utilization of lignin
    2nd most abundant polymer
      15-30% of biomass
    Higher energy content than
     cellulose                             Celunol Corp. http://zfacts.com/p/85.html. 27, July 2012.

      9,000-11,000 Btu/lb vs. 7,300-
       7,500 Btu/lb
    Production of phenols and phenol
Objectives
 Thermochemical conversion of feedstock for fuel
 and chemical precursors
  Polysaccharides followed by lignin conversion
    Ethanol and lignin derived chemicals

  Simultaneous conversion of feedstock
    Polysaccharides and lignin derived chemicals

 Hydrogenolysis of feedstock using noble-metal
 catalysts
  Lignin Hydrogenolysis
    Main focus
    Depolymerization of lignin into fuel and chemical precursors
    Factors affecting lignin hydrogenolysis
    Lignin monomer yield

  Polysaccharides hydrogenolysis
    Conversion of polysaccharides into fuel and chemical precursors
    Factors affecting polysaccharide hydrogenolysis
Hydrogenolysis Operation
                           Reference experiment run:
                           Residence time: 4 hours
                            Temperature: 200 ºC
                             Pressure: 1000 psi
                                Catalyst: Pt/C
                           Mineral acid: Phosphoric
                                     Acid
                           Solvent: Water/dioxane
                                   (1:1, v/v)




Hydrogenolysis Operation            Parr Reactor
Hydrogenolysis of Feedstock
 Conversion of feedstock:
   Based on the weight of feedstock utilized in the reaction and the
    solid recovered after reaction
      Amount dissolved
   Liquid soluble product
      Converted feedstock (%)
   Liquid insoluble product
      Solid residue
 Higher feedstock conversion                                                                                      More fuel
  and chemical precursors possible
   Due to less solid residueFeedstock Conversion
                                                 100

                                                 80
                                Conversion (%)




                                                 60

                                                 40

                                                 20

                                                  0




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                                                                          Feedstock
           Conversion of different feedstocks through catalytic hydrogenolysis. The reaction conditions were: Residence
         time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w);
                                                      solvent: H2O (1:1,v/v).
Hydrogenolysis of Feedstock
   Poplar conversion
 (amount dissolved) for                                                                 Poplar Conversion

    different reaction                                                      100



        conditions                                                          80




                                                           Conversion (%)
 Higher conversion            60

   Higher temperatures
                               40
   Presence of mineral acid
   Water solvent              20
                               15
                               10
                                5
 Lower conversion              0




                                                                              71 a
                                                                               80
                                                                               92
                                                                               39



                                                                               82
                                                                               84
                                                                               72

                                                                               73

                                                                               40
                                                                               47
                                                                               86
                                                                               88
                                                                               90
                                                                               98

                                                                               65

                                                                               67
                                                                               69
                                                                                5




                                                                                9

                                                                                4




                                                                                0

                                                                                2
                                                                              10




                                                                              10

                                                                              10




                                                                              10

                                                                              10
   Lower temperature                 Experimental control run                    a Run #

   Absence of mineral acid Poplar feedstock conversion when an operational variable is changed during catalytic hydrogenolysis. The reaction
                             conditions were: Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
    (phosphoric acid)        phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v), while one of the conditions was changed and the rest kept as
   Ethanol solvent                                                               listed.

 No effect on conversion
   Catalyst and catalyst
Lignin Hydrogenolysis
 Lignin depolymerization into fuels and chemical
 precursors
   Selective cleavage of ether bonds
     Lower temperature
   No carbon-carbon linkage cleavage
     Higher temperature




                                         (Faravelli et al., 2010)




 Isolated lignin i.e. organosolv lignin and alkali
 lignin
   Lignin structure already altered due to isolation
Lignin Hydrogenolysis
 Selective production of
 monomers and/or
 dimers
   Monomers
     Monomer units in the
      native lignin linked to
      other monomer units by
      ether bonds
      depolymerized into
      monomers
   Dimers
     A lignin monomer linked
      to another monomer unit
      through a carbon-carbon
      linkage, while at the     (Yan et al., 2008)
Lignin Hydrogenolysis
 Hydrogen molecules react with
 catalyst
   Hydrogen molecule sigma bond
    broken
   Weaker metal-hydride bond
    formed
 The sigma bond in the C-O
 bond interacts with the metal
 catalyst
   Weakens metal hydride bond
   Hydrogen atom is transferred to
   oxygen(C-O bond)
 Second hydrogen atom is
 transferred from the catalyst to
 carbon
   Weakened sigma bond gets          (Nagy et
                                      al., 2009)
   cleaved
Lignin Hydrogenolysis
 Ideal monomer theoretical yield
   Probability of a monomer linked to two other monomer
    through ether linkages is the square of the ether linkages
    in lignin.
   Ether linkages
     (2/3) to (3/4) of lignin linkages
         Simplified model
     More ether linkages in hardwood than softwood
         Guaiacyl lignin contains less ether linkages
   Resulting in 44-56% theoretical yield for monomers. (Yan
    et al., 2008)
     Assumptions
         All ether linkages cleaved
 Not possible for isolated lignin
   Do not know ether content in isolated lignin
Lignin Hydrogenolysis
 Reference condition
 GC/MS
  Monomers
    Guaiacylpropane
    Syringylpropane
  Dimers
    Not detected

 Reaction conditions
  Peaks with different
   retention times
  Not identified
                                      Gas Chromatography and mass spectrum analysis. The reaction conditions were: Residence
  Guaiacylpropane and               time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; acid: 40%
                                                           (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
   Syringylpropane still
   predominate.
 Previous Studies
  Guaiacylpropanol and
   syringylpropanol in addition to
Lignin Hydrogenolysis
 Factors affecting lignin hydrogenolysis
   The effect of residence time
   The effect of temperature
   The effect of hydrogen pressure
   The effect of feedstock
   The effect of noble-metal catalyst
   The effect of addition of mineral acid
   The effect of solvent
 Compared by lignin yield (%,w/w)
   Based on initial lignin in feedstock
   Guaiacylpropane and syringylpropane end-product
Lignin Hydrogenolysis
 The effect of residence
                                                                                     Residence Time Effect
      time on lignin
                                                                            60
     hydrogenolysis                                                                                                                  2 hrs
   Time needed to reach maximum                                                                                                     4 hrs




                                                            Yield (%,w/w)
     temperature included.                                                                                                           6 hrs
                                                                            40
 Linear relationship between                                                                                                        8 hrs
 residence time and lignin
 yield                                                                      20



   Linear regression analysis                                              0
    statistically significant
                                                                                   s



                                                                                            s



                                                                                                   s



                                                                                                                s
                                                                                 hr



                                                                                          hr



                                                                                                 hr



                                                                                                              hr
   Residence time does a
                                                                                 2



                                                                                         4



                                                                                                6



                                                                                                            8
    somewhat decent job of                               Residence Time (hours)
    predicting lignin monomer yield Lignin product yield during catalytic hydrogenolysis while varying the residence times. The
     R2 = 0.73                    reaction conditions were: temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
                                               phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
 The residence time
Lignin Hydrogenolysis
The effect of temperature
                                                                     Temperature Effect
         on lignin                                      50
     hydrogenolysis                                                                                                   150    (°C)
                                                        40                                                            200    (°C)
 Significant linear




                                        Yield (%,w/w)
                                                                                                                      250    (°C)
  relationship between                                  30                                                            300    (°C)
  temperature and lignin yield                          20
  for (150 to 250 ºC)
                                                        10


   Linear regression analysis not                      0



                                                                 )



                                                                            )



                                                                                      )
    statistically significant between




                                                                                                 )
                                                             (°C



                                                                        (°C



                                                                                  (°C


                                                                                             (°C
                                                          0



                                                                        0



                                                                                  0
    150 to 300 ºC




                                                                                            0
                                                        15



                                                                      20



                                                                                25


                                                                                          30
   Temperature is not a good                                       Temperature
    predictor of lignin monomer         Lignin product yield during catalytic hydrogenolysis while varying the temperature. The reaction
    yield                                  conditions were: Residence time: 4 hours; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C;
                                                     phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
     R2 = 0.61

 The temperature treatments
Lignin Hydrogenolysis
      The effect of
                                                                                  Pressure Effect
   hydrogen pressure
                                                                       60
on lignin hydrogenolysis                                                                                      0 psi
                                                                                                              250 psi




                                                       Yield (%,w/w)
                                                                       40                                     1000 psi
 A minimal pressure
  between 0 and 250 psi is 20
  necessary for initiation of
  hydrogenolysis                        0

 No linear relationship
                                                                              i




                                                                                          i




                                                                                                       i
                                                                            ps




                                                                                        ps




                                                                                                    ps
                                                                            0




                                                                                       0




                                                                                                 00
                                                                                     25
  between pressure and



                                                                                               10
                                                             Pressure (psi)
  lignin yield between 250 psiproduct yield during catalytic hydrogenolysis while varying the hydrogen pressure. The
                              Lignin
  and 1000 psi                reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; catalyst: 10% (w/w)
                                      of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.
 The pressure treatments
  were statistically different.
Lignin Hydrogenolysis
                                                                       Feedstock Effect

The effect of feedstock                             60
                                                                                                                     Agave
                                                                                                                     Poplar
        on lignin




                                   Yield (%,w/w)
                                                    40                                                               Spruce
                                                                                                                     Organosolv Lignin
    hydrogenolysis                                  20
                                                                                                                     Alkali Lignin


 The feedstock treatments
  were statistically different.                     0




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   Poplar generated the highest




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    yield




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 Woods                                                                       Feedstock


   Poplar yield > Spruce yield                               S/Ga (%) versus Feedstock

   S/G ratio                                       5
                                                                                                                     Agave
                                                    4                                                                Poplar
      Spruce contains Guaiacyl
                                    Yield (%,w/w)
                                                                                                                     Spruce
                                                    3
       lignin                                                                                                        Organosolv lignin
                                                                                                                     Alkali Lignin
                                                    2

 Agave                                             1

    S/G ratio ~ 2:1                                0




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    Para-hydroxyphenol unit




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                                                                                                    A
                                                                                   an
 Isolated lignin                                                             O
                                                                                  rg
                                                                              Feedstock
    Organosolv lignin                                   a
                                                             S/G: syrignylpropane to guaiacylpropane

      Small monomer yield        Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the
                                     feedstock. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;
      S/G ratio ~ 4:1               Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O
                                                                             (1:1,v/v).
   Alkali lignin
Lignin Hydrogenolysis
    The effect of noble-metal                                                     Catalyst Effect on Poplar


        catalyst on lignin                                          100
                                                                                                                                    Pt/C
                                                                    80                                                              Pt/G
         hydrogenolysis




                                                    Yield (%,w/w)
                                                                                                                                    Pd/C
                                                                    60
                                                                                                                                    Rh/Ca
Poplar                                                              40
                                                                                                                                    Noneb


 Catalyst is necessary                                             20

                                                                        0
   Lowers the activation energy of




                                                                                                                     Ca



                                                                                                                              b
                                                                                                          C
                                                                                            t/G
                                                                                t/C




                                                                                                                             e
                                                                                                       d/




                                                                                                                          on
                                                                                                                  h/
                                                                            P



                                                                                          P



                                                                                                      P


                                                                                                                 R



                                                                                                                          N
    reaction                                                                                      Catalyst Type
                                                                            a
                                                                                Values greater than theoretical 44%
   Allows for homolytic dissociation of                                    b
                                                                                Same reaction conditions

                                                                                  S/Ga (%) versus Catalyst
    H2 molecules
                                                                    5
                                                                                                                                     Pt/C
 The catalyst treatments were not                                  4                                                                Pt/G




                                                    Yield (%,w/w)
                                                                                                                                     Pd/C
  statistically different for lignin yield.                         3                                                                Rh/C
   Rh/C was not included because                                   2
    produced values greater than theoretical                        1
    yield
                                                                    0
      Outlier




                                                                                                                /C




                                                                                                                             C
                                                                                                /G
                                                                              /C




                                                                                                                          h/
                                                                                                              Pd
                                                                            Pt




                                                                                              Pt




                                                                                                                          R
 Catalyst treatments were                                              a
                                                                                                  Catalyst Type
                                                                            S/G: syrignylpropane to guaiacylpropane
  statistically significant for S/G ratio.
                                                Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the
   Pd/C higher S/G ratio                        catalyst on poplar. The reaction conditions were: Residence time: 4 hours; Temperature: 200
                                                °C; Pressure: 1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v);
      Higher selectivity for syringylpropane                                           feedstock: poplar.
Lignin Hydrogenolysis
      The effect of
  noble-metal catalyst                                   Catalyst Effect on Organosolv Lignin
                                                              15
on lignin hydrogenolysis                                                                                                         Pt/C
                                                                                                                                 Pt/G
Organosolv lignin




                                              Yield (%,w/w)
                                                              10                                                                 Pd/C
 The catalyst treatments                                                                                                        Rh/C

  were statistically different for
                                                              5
  lignin yield.
   Rh/C produced the highest
    yield followed by Pt/G                                    0




                                                                                         /C



                                                                                                         /C
                                                                            /G
                                                                     /C




                                                                                       Pd



                                                                                                       Rh
                                                                   Pt



                                                                          Pt
   Tukey’s Multiple comparison                                             Catalyst Type
                                               Lignin product yield during catalytic hydrogenolysis while varying the catalyst on organosolv
    test
                                             lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure:
     Rh/C statistically different to Pt/C
      and Pd/C                                1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock:
     Pt/G and Rh/C not statistically                                                     poplar.
      different.
Lignin Hydrogenolysis
        The effect of
   noble-metal catalyst on
    lignin hydrogenolysis
          Catalyst loading
Poplar
 Linear relationship between
  catalyst loading and lignin yield            Linear regression of catalalysts loading versus yield of lignin monomers for poplar. The reaction
                                                 conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000 psi; catalyst:
   Linear regression analysis statistically      10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock:
                                                                                             poplar.
    significant
   Catalyst loading can predict lignin
    monomer yield to a certain accuracy.
      R2 = 0.81

 10% and 40% are not statistically
  different
Organosolv lignin
 Linear relationship between                   Linear regression of catalalysts loading versus yield of lignin monomers for organosolv lignin.

  catalyst loading and lignin yield             The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000
                                                psi; catalyst: 10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v);
                                                                                  feedstock: organosolv lignin.
   Linear regression analysis statistically
    significant
Lignin Hydrogenolysis
 The effect of addition mineral acid
      on lignin hydrogenolysis
 Many reactions combine heterogeneous                                       Phosphoric Acid Effect
  catalysis with acid-catalyzed conditions                       50
  to assist in the hydrogenolysis reaction                                                                       No Phosphoric Acid
  (Yan et al., 2008)                                             40                                              Yes Phosphoric Acid




                                                Yield (% ,w/w)
Poplar
                                                                 30
 The acid treatments were
  statistically different for lignin yield.                      20

 Presence of phosphoric acid                                    10
  increased monomer yield
    Assisted in the removal of                                  0




                                                                                                     a
     recalcitrance of lignocellulose




                                                                                 r
                                                                               pla




                                                                                                     OL
                                                                             Po
Organosolv lignin                                                                        Feedstock
 The acid treatments were                                            a
                                                                          Organosolv Lignin
  statistically different for lignin yield.     Lignin product yield during catalytic hydrogenolysis with/without mineral acid on poplar and
                                              organosolv lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;
 Presence of phosphoric acid                  Pressure: 1000 psi; catalyst: 10% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar, organosolv
                                                                                            lignin..
  decreased monomer yield slightly.
    Condensation reactions
      Lignin condensation reactions under
       acidic conditions
Lignin Hydrogenolysis
  The effect of solvent on lignin                                                 Solvent effect on Poplar
                                                                             60
            hydrogenolysis                                                                                                                       Water/Ethanol (1:1,v/v)
                                                                                                                                                 Ethanol




                                                             Yield (%,w/w)
                                                                             40                                                                  Water/Dioxane (1:1,v/v)

Poplar                                                                                                                                           Dioxane
                                                                                                                                                 Water
                                                                             20

 The solvent treatments were
                                                                              0

  statistically different for lignin




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 Water as a solvent did not                                                                        Solvent



  produce guaiacylpropane and                                                      a
                                                                                       Values greater than theoretical value


                                         Lignin product yield during catalytic hydrogenolysis while varying solvent on poplar. The
  syringylpropane.                     reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000 psi;
                                                catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: poplar.
 Water/ethanol (1:1, v/v) highest
                                                            Solvent effect on Organosolv lignin
  yield                                                     8
                                                                                                                                               Ethanol

 Dioxane solvent produced the                              6
                                                                                                                                               Dioxane



                                            Yield (%,w/w)
                                                                                                                                               W ater

  lowest yield.                                             4
                                                                                                                                               W ater/Dioxane (1:1, v/v)



                                                            2
Organosolv lignin                                           0


 The solvent treatments were not
                                                                                                   ne
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  statistically different for lignin
                                                                                                                        xa
                                                                                                                     io
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                                                                                                               er
                                                                                                             at
                                                                                                             W
  yield.                                                                                                Solvent
                                           Lignin product yield during catalytic hydrogenolysis while varying solvent on organosolv lignin.

 Water as a solvent did not
                                            The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000
                                              psi; catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: organosolv lignin.
Polysaccharides Hydrogenolysis
 Polysaccharides are degraded and converted
  concurrently with the depolymerization of lignin
  during hydrogenolysis
 Polysaccharides are converted into
  polysaccharide monomers, polysaccharide
  derived chemicals and insoluble liquid (solid
  residue)
   Homolytic dissociation of H2 (g) into H atoms by
    noble metal catalysts
     Influences hydrolysis
       Spill-over effect
     Cleavage of carbon-carbon and carbon-oxygen
      bonds in cellulose
     Hydrogenation
   Phosphoric acid
     Hydrolysis

                                  (Dhepe and Fukuoka, 2007)
Polysaccharides Hydrogenolysis
 Changes of polysaccharides during
  hydrogenolysis
   Liquid soluble products
     Polysaccharide monomers and
       polysaccharide derived chemicals (PDCs)
   Liquid insoluble products
     Solid residue
 For avicel cellulose, 34% conversion
  of initial cellulose into polysaccharides
  and polysaccharides derived
  chemicals
   ~6% polysaccharide monomers
    identified from original polysaccharides
 For poplar, 64% conversion of
  feedstock.
   ~8% polysaccharide monomers                          Mass balance of cellulose hydrogenolysis. The reaction conditions were:
                                                 Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of
    identified from original polysaccharides          Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: cellulose.
                                                         a
                                                             theoretical weight of un-identifiable saccharides-derived chemicals.

 Reaction conditions produced
  statistically significant conversion
  percentages of polysaccharides
   90-100% conversion of initial
    polysaccharides into PDCs and solid
Polysaccharides Hydrogenolysis
 Trace amounts of
 dehydration chemicals
 from glucose were
 detected
   Glucose converted to HMF,
   furfural, levulinic acid, formic
   acid, acetic acid under
   hydrothermal conditions in
   the presence of acidic                                                          (Liu et al., 2011)
   conditions.
 Cellulose converted into
 polyols such as sorbitol
 through hydrogenation
 using supported metal
 catalysts
     Previous experiments (Shrotri et al.,    Conversion products from catalytic hydrogenolysis of cellulose. (1) glucose, (2)
      2012)                                   sorbitol, (3) sorbitan, (4) isosoribde, (5) xylose, (6) erythritol, (7) glycerol, (8) 1,2-
                                                    (or1,3)propanediol (9) ethanediol, (10) methanol. (Palkovits et al., 2010).
 Chemicals detected by
Summary
 Thermochemical conversion is capable of converting all
  three biopolymers in biomass into fuels and chemical
  precursors simultaneously.
   Biochemical conversion inefficiently utilizes lignin
 Lignin derived chemicals and polysaccharide derived
  chemicals were fractionated with non-polar solvents.
 Lignin is selectively depolymerized into monomeric
  subunits for chemical precursors through catalytic
  hydrogenolysis
     Syringylpropane
     Guaiacylpropane
   Reaction conditions affect the monolignol yield.
 Polysaccharides were degraded through hydrogenolysis
     Polysaccharide monomers
     Polysaccharide derived chemicals
       No dehydration chemicals
       Possible polyols production
   Reaction conditions affect the degradation of polysaccharides
Future Research
 Further investigation of polysaccharide derived
 chemicals (PDCs) produced through hydrogenolysis
   Accurate mass balance
     No assumption necessary
   Energy balance for viability of process
 Design of Experiment (DOE) methodology
   Use factorial experimental designs
     Determine interaction effects

 Investigation into other catalysts
   Increase the selectivity
   Decrease the activation energy
Acknowledgments
 Dr. Xuejun Pan
   I am honored to have Dr. Pan as my mentor
   He has given me a great deal of academic support in
   addition to assistance in my research study.
 Dr. Pan’s Research Group
   There support and knowledge were vital in my research
   studies.
 Dr. Ralph’s Research Group
   I need to thank Dr. John Ralph for allowing me to use his
    laboratory equipment.
   Special thanks to Dr. Fachuang Lu for assistance in gas
    chromatography and mass spectrometry.
 Thesis committee
   I need to thank Dr. Troy Runge and Dr. Fachuang Lu for
   accepting my invitation to be on my thesis committee
     In addition to helping finalize my thesis.
 Biological Systems Engineering
   For the departments support during my undergraduate and
   graduate studies.
Questions




  (Nagy et al., 2009)

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Lignin Depolymerization and Conversion Utilizing Catalytic Hydrogenolysis

  • 1. LIGNIN DEPOLYMERIZATION THROUGH HYDROGENOLYSIS INTO MONOMERIC SUBUNITS ON METAL CATALYSTS Lis Nimani Advisor: Dr. Xuejun Pan Master of Science Thesis Defense August 3rd, 2012
  • 2. Outline  Introduction  Renewable energy  Lignocellulosic Biomass  Polysaccharides  Lignin  Conversion Processes of Lignocelluloses to Fuels and Chemicals  Lignocellulose conversion  Problem Statement  Objectives  Hydrogenolysis  Hydrogenolysis Operation  Hydrogenolysis of Feedstock  Lignin Hydrogenolysis  Polysaccharides Hydrogenolysis  Conclusion  Summary  Future Work
  • 3. Renewable Energy  Need for renewable energy  Depletion of Fossil Fuels  Global Warming due to Greenhouse Gasses (GHGs)  National Security (Deming, 2000) (Forster et al., 2007) (Akorede et al., 2012)  Bioenergy  Corn/Sugarcane (1st Generation)  Lignocellulosic Biomass (2nd Generation)
  • 4. Lignocellulosic Biomass  Lignocellulosic Biomass  Hardwood  Softwood  Herbaceous Plants  Lignocellulose Complex (Murphy and McCarthy, 2005)  Cellulose  Hemicellulose  Lignin The chemical composition make up of the lignocellulosic materials (Sun and Cheng, 2002) Feedstock Cellulose (%) Hemicellulose (%) Lignin (%) Hardwood 40-50 25-40 18-25 Softwood 45-50 25-35 23-35 (Zhou et al., 2010) Grasses 25-40 35-50 10-30
  • 5. Polysaccharides  Cellulose  Most abundant organic chemical on earth.  Homopolymer  7,000 to 15,000 monomeric D- glucose units  Crystalline and Amorphous Regions (Meyers et al., 2008)  Up to 65% crystalline regions in Content and compositional differences between hardwood vs. softwood wood. (Kögel-Knabner, 2002)  Hemicellulose Polyoses Deciduous Wood (Hardwood) Coniferous Wood (Softwood) Content (%) Units Content (%) Units  Branched Heteropolymers Xylose, 4-O- Xylose, 4-O-  Pentoses (β-D-xylose, α-L- Xylans 25-30 methylglucuronic 5-10 methylglucuronic acid acid arabinose) Mannose, glucose,  Hexoses (β-D-mannose, β-D- Mannans 3-5 Mannose, glucose 20-25 galactose, acetyl groups glucose, α-D-galactose) Galactose, Galactose, Galactans 0.5-2 arabinose, 0.5-3  Xylans and Glucomannans rhammose arabinose  Most significant hemicelluloses.
  • 6. Lignin  An amorphous three-dimensional bio-polymer of three phenylpropane units randomly cross-linked with one another.  Derived generally from three monolignols:  Para-coumaryl alcohol  Coniferyl alcohol  Sinapyl alcohol  Monolignols produce phenylpropaniod units  Para-hydroxyphenol (H-unit) (Xu, 2010)  Guaiacyl (G-unit)  Syringol (S-unit)  Lignin is produced by free radical generation followed by chemical coupling processes of the monolignols.
  • 7. Lignin  Lignin content and composition varies between lignocellulosic biomass.  Lignin content  Softwoods ˃Hardwoods ˃ Herbaceous  Lignin composition  Softwood: Guaiacyl (G) lignin  Hardwood: Guaiacyl-syringol (GS) lignin  Herbaceous: Gramineae (GSH) lignin  Lignin linkages  (1/3) to (1/4) carbon-carbon linkages  (2/3) to (3/4) ether linkages
  • 8. Lignin (Kögel-Knabner, 2002) Content of the main linkages in lignin (Faravelli et al., 2010) (Achyuthan et al., 2010; Pandey and Kim, 2011; Ralph, 2005; Zakzeski et al., 2010) Linkage Type Softwood (spruce) (%) Hardwood (birch) (%) β-O-4-Aryl ether 46 60 Dibenzodioxocin 25-30 5-10 β-5-Phenylcoumaran 9-12 6 β-β-(Resinol) 2-6 3-12 4-O-5-Diaryl ether <4 <6.5 β-1-(1,2-Diarylpropnae) 1-2 1-2 α-O-4-Aryl ether A few A few
  • 9. Conversion Processes of Lignocelluloses to fuels and Chemicals (Menon and Rao, 2012) Comparison between the biochemical and thermochemical process (Basu 2010a). Biochemical Process Thermochemical Process Reactor Type Batch Continuous Reaction Time A few Days A few minutes Temperature 100-200 °C ˃ °C 200 Water Usage (liter/liter ethanol) 3.5-170 <1
  • 10. Lignocellulose Conversion (Zheng et al., 2011)
  • 11. Problem Statement  Current biochemical conversion of lignocellulose for fuels and chemicals  Cellulose and hemicellulose converted to ethanol  Lignin used as a boiler fuel through combustion  Non-simultaneous  Inefficient utilization of lignin  2nd most abundant polymer  15-30% of biomass  Higher energy content than cellulose Celunol Corp. http://zfacts.com/p/85.html. 27, July 2012.  9,000-11,000 Btu/lb vs. 7,300- 7,500 Btu/lb  Production of phenols and phenol
  • 12. Objectives  Thermochemical conversion of feedstock for fuel and chemical precursors  Polysaccharides followed by lignin conversion  Ethanol and lignin derived chemicals  Simultaneous conversion of feedstock  Polysaccharides and lignin derived chemicals  Hydrogenolysis of feedstock using noble-metal catalysts  Lignin Hydrogenolysis  Main focus  Depolymerization of lignin into fuel and chemical precursors  Factors affecting lignin hydrogenolysis  Lignin monomer yield  Polysaccharides hydrogenolysis  Conversion of polysaccharides into fuel and chemical precursors  Factors affecting polysaccharide hydrogenolysis
  • 13. Hydrogenolysis Operation Reference experiment run: Residence time: 4 hours Temperature: 200 ºC Pressure: 1000 psi Catalyst: Pt/C Mineral acid: Phosphoric Acid Solvent: Water/dioxane (1:1, v/v) Hydrogenolysis Operation Parr Reactor
  • 14. Hydrogenolysis of Feedstock  Conversion of feedstock:  Based on the weight of feedstock utilized in the reaction and the solid recovered after reaction  Amount dissolved  Liquid soluble product  Converted feedstock (%)  Liquid insoluble product  Solid residue  Higher feedstock conversion More fuel and chemical precursors possible  Due to less solid residueFeedstock Conversion 100 80 Conversion (%) 60 40 20 0 in r e ce se in la av n n ru lo p ig lig g o lu p A L P S el lv i al C so lk o A an rg O Feedstock Conversion of different feedstocks through catalytic hydrogenolysis. The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v).
  • 15. Hydrogenolysis of Feedstock Poplar conversion (amount dissolved) for Poplar Conversion different reaction 100 conditions 80 Conversion (%)  Higher conversion 60  Higher temperatures 40  Presence of mineral acid  Water solvent 20 15 10 5  Lower conversion 0 71 a 80 92 39 82 84 72 73 40 47 86 88 90 98 65 67 69 5 9 4 0 2 10 10 10 10 10  Lower temperature Experimental control run a Run #  Absence of mineral acid Poplar feedstock conversion when an operational variable is changed during catalytic hydrogenolysis. The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; (phosphoric acid) phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v), while one of the conditions was changed and the rest kept as  Ethanol solvent listed.  No effect on conversion  Catalyst and catalyst
  • 16. Lignin Hydrogenolysis  Lignin depolymerization into fuels and chemical precursors  Selective cleavage of ether bonds  Lower temperature  No carbon-carbon linkage cleavage  Higher temperature (Faravelli et al., 2010)  Isolated lignin i.e. organosolv lignin and alkali lignin  Lignin structure already altered due to isolation
  • 17. Lignin Hydrogenolysis  Selective production of monomers and/or dimers  Monomers  Monomer units in the native lignin linked to other monomer units by ether bonds depolymerized into monomers  Dimers  A lignin monomer linked to another monomer unit through a carbon-carbon linkage, while at the (Yan et al., 2008)
  • 18. Lignin Hydrogenolysis  Hydrogen molecules react with catalyst  Hydrogen molecule sigma bond broken  Weaker metal-hydride bond formed  The sigma bond in the C-O bond interacts with the metal catalyst  Weakens metal hydride bond  Hydrogen atom is transferred to oxygen(C-O bond)  Second hydrogen atom is transferred from the catalyst to carbon  Weakened sigma bond gets (Nagy et al., 2009) cleaved
  • 19. Lignin Hydrogenolysis  Ideal monomer theoretical yield  Probability of a monomer linked to two other monomer through ether linkages is the square of the ether linkages in lignin.  Ether linkages  (2/3) to (3/4) of lignin linkages  Simplified model  More ether linkages in hardwood than softwood  Guaiacyl lignin contains less ether linkages  Resulting in 44-56% theoretical yield for monomers. (Yan et al., 2008)  Assumptions  All ether linkages cleaved  Not possible for isolated lignin  Do not know ether content in isolated lignin
  • 20. Lignin Hydrogenolysis  Reference condition GC/MS  Monomers  Guaiacylpropane  Syringylpropane  Dimers  Not detected  Reaction conditions  Peaks with different retention times  Not identified Gas Chromatography and mass spectrum analysis. The reaction conditions were: Residence  Guaiacylpropane and time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar. Syringylpropane still predominate.  Previous Studies  Guaiacylpropanol and syringylpropanol in addition to
  • 21. Lignin Hydrogenolysis  Factors affecting lignin hydrogenolysis  The effect of residence time  The effect of temperature  The effect of hydrogen pressure  The effect of feedstock  The effect of noble-metal catalyst  The effect of addition of mineral acid  The effect of solvent  Compared by lignin yield (%,w/w)  Based on initial lignin in feedstock  Guaiacylpropane and syringylpropane end-product
  • 22. Lignin Hydrogenolysis The effect of residence Residence Time Effect time on lignin 60 hydrogenolysis 2 hrs  Time needed to reach maximum 4 hrs Yield (%,w/w) temperature included. 6 hrs 40  Linear relationship between 8 hrs residence time and lignin yield 20  Linear regression analysis 0 statistically significant s s s s hr hr hr hr  Residence time does a 2 4 6 8 somewhat decent job of Residence Time (hours) predicting lignin monomer yield Lignin product yield during catalytic hydrogenolysis while varying the residence times. The  R2 = 0.73 reaction conditions were: temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.  The residence time
  • 23. Lignin Hydrogenolysis The effect of temperature Temperature Effect on lignin 50 hydrogenolysis 150 (°C) 40 200 (°C)  Significant linear Yield (%,w/w) 250 (°C) relationship between 30 300 (°C) temperature and lignin yield 20 for (150 to 250 ºC) 10  Linear regression analysis not 0 ) ) ) statistically significant between ) (°C (°C (°C (°C 0 0 0 150 to 300 ºC 0 15 20 25 30  Temperature is not a good Temperature predictor of lignin monomer Lignin product yield during catalytic hydrogenolysis while varying the temperature. The reaction yield conditions were: Residence time: 4 hours; Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.  R2 = 0.61  The temperature treatments
  • 24. Lignin Hydrogenolysis The effect of Pressure Effect hydrogen pressure 60 on lignin hydrogenolysis 0 psi 250 psi Yield (%,w/w) 40 1000 psi  A minimal pressure between 0 and 250 psi is 20 necessary for initiation of hydrogenolysis 0  No linear relationship i i i ps ps ps 0 0 00 25 between pressure and 10 Pressure (psi) lignin yield between 250 psiproduct yield during catalytic hydrogenolysis while varying the hydrogen pressure. The Lignin and 1000 psi reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar.  The pressure treatments were statistically different.
  • 25. Lignin Hydrogenolysis Feedstock Effect The effect of feedstock 60 Agave Poplar on lignin Yield (%,w/w) 40 Spruce Organosolv Lignin hydrogenolysis 20 Alkali Lignin  The feedstock treatments were statistically different. 0 in e r e in la v uc gn gn  Poplar generated the highest ga op pr Li Li A P S i lv al so lk yield A o an rg O  Woods Feedstock  Poplar yield > Spruce yield S/Ga (%) versus Feedstock  S/G ratio 5 Agave 4 Poplar  Spruce contains Guaiacyl Yield (%,w/w) Spruce 3 lignin Organosolv lignin Alkali Lignin 2  Agave 1  S/G ratio ~ 2:1 0 in in e r ce la av  Para-hydroxyphenol unit n n ru p lig ig g o p A L P S lv i al so lk o A an  Isolated lignin O rg Feedstock  Organosolv lignin a S/G: syrignylpropane to guaiacylpropane  Small monomer yield Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the feedstock. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;  S/G ratio ~ 4:1 Pressure: 1000 psi; catalyst: 10% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v).  Alkali lignin
  • 26. Lignin Hydrogenolysis The effect of noble-metal Catalyst Effect on Poplar catalyst on lignin 100 Pt/C 80 Pt/G hydrogenolysis Yield (%,w/w) Pd/C 60 Rh/Ca Poplar 40 Noneb  Catalyst is necessary 20 0  Lowers the activation energy of Ca b C t/G t/C e d/ on h/ P P P R N reaction Catalyst Type a Values greater than theoretical 44%  Allows for homolytic dissociation of b Same reaction conditions S/Ga (%) versus Catalyst H2 molecules 5 Pt/C  The catalyst treatments were not 4 Pt/G Yield (%,w/w) Pd/C statistically different for lignin yield. 3 Rh/C  Rh/C was not included because 2 produced values greater than theoretical 1 yield 0  Outlier /C C /G /C h/ Pd Pt Pt R  Catalyst treatments were a Catalyst Type S/G: syrignylpropane to guaiacylpropane statistically significant for S/G ratio. Lignin product yield and monomer selectivity during catalytic hydrogenolysis while varying the  Pd/C higher S/G ratio catalyst on poplar. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v);  Higher selectivity for syringylpropane feedstock: poplar.
  • 27. Lignin Hydrogenolysis The effect of noble-metal catalyst Catalyst Effect on Organosolv Lignin 15 on lignin hydrogenolysis Pt/C Pt/G Organosolv lignin Yield (%,w/w) 10 Pd/C  The catalyst treatments Rh/C were statistically different for 5 lignin yield.  Rh/C produced the highest yield followed by Pt/G 0 /C /C /G /C Pd Rh Pt Pt  Tukey’s Multiple comparison Catalyst Type Lignin product yield during catalytic hydrogenolysis while varying the catalyst on organosolv test lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure:  Rh/C statistically different to Pt/C and Pd/C 1000 psi; catalyst: 10% (w/w); phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock:  Pt/G and Rh/C not statistically poplar. different.
  • 28. Lignin Hydrogenolysis The effect of noble-metal catalyst on lignin hydrogenolysis Catalyst loading Poplar  Linear relationship between catalyst loading and lignin yield Linear regression of catalalysts loading versus yield of lignin monomers for poplar. The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000 psi; catalyst:  Linear regression analysis statistically 10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar. significant  Catalyst loading can predict lignin monomer yield to a certain accuracy.  R2 = 0.81  10% and 40% are not statistically different Organosolv lignin  Linear relationship between Linear regression of catalalysts loading versus yield of lignin monomers for organosolv lignin. catalyst loading and lignin yield The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; pressure: 1000 psi; catalyst: 10% and 40% (w/w) of Pt/C; phosphoric acid: 40% (w/w); solvent: H 2O (1:1,v/v); feedstock: organosolv lignin.  Linear regression analysis statistically significant
  • 29. Lignin Hydrogenolysis The effect of addition mineral acid on lignin hydrogenolysis  Many reactions combine heterogeneous Phosphoric Acid Effect catalysis with acid-catalyzed conditions 50 to assist in the hydrogenolysis reaction No Phosphoric Acid (Yan et al., 2008) 40 Yes Phosphoric Acid Yield (% ,w/w) Poplar 30  The acid treatments were statistically different for lignin yield. 20  Presence of phosphoric acid 10 increased monomer yield  Assisted in the removal of 0 a recalcitrance of lignocellulose r pla OL Po Organosolv lignin Feedstock  The acid treatments were a Organosolv Lignin statistically different for lignin yield. Lignin product yield during catalytic hydrogenolysis with/without mineral acid on poplar and organosolv lignin. The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C;  Presence of phosphoric acid Pressure: 1000 psi; catalyst: 10% (w/w); solvent: H2O (1:1,v/v); feedstock: poplar, organosolv lignin.. decreased monomer yield slightly.  Condensation reactions  Lignin condensation reactions under acidic conditions
  • 30. Lignin Hydrogenolysis The effect of solvent on lignin Solvent effect on Poplar 60 hydrogenolysis Water/Ethanol (1:1,v/v) Ethanol Yield (%,w/w) 40 Water/Dioxane (1:1,v/v) Poplar Dioxane Water 20  The solvent treatments were 0 statistically different for lignin ne ol er v) ) /v an v/ at xa ,v 1, W :1 th io 1: (1 E D l( yield. e o n an xa th io /E /D er er at at W W  Water as a solvent did not Solvent produce guaiacylpropane and a Values greater than theoretical value Lignin product yield during catalytic hydrogenolysis while varying solvent on poplar. The syringylpropane. reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: poplar.  Water/ethanol (1:1, v/v) highest Solvent effect on Organosolv lignin yield 8 Ethanol  Dioxane solvent produced the 6 Dioxane Yield (%,w/w) W ater lowest yield. 4 W ater/Dioxane (1:1, v/v) 2 Organosolv lignin 0  The solvent treatments were not ne ol er ) /v an at xa ,v W th io :1 E D (1 e n statistically different for lignin xa io /D er at W yield. Solvent Lignin product yield during catalytic hydrogenolysis while varying solvent on organosolv lignin.  Water as a solvent did not The reaction conditions were: Residence time: 4 hours; Temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) Pt/C; phosphoric acid: 40% (w/w);); feedstock: organosolv lignin.
  • 31. Polysaccharides Hydrogenolysis  Polysaccharides are degraded and converted concurrently with the depolymerization of lignin during hydrogenolysis  Polysaccharides are converted into polysaccharide monomers, polysaccharide derived chemicals and insoluble liquid (solid residue)  Homolytic dissociation of H2 (g) into H atoms by noble metal catalysts  Influences hydrolysis  Spill-over effect  Cleavage of carbon-carbon and carbon-oxygen bonds in cellulose  Hydrogenation  Phosphoric acid  Hydrolysis (Dhepe and Fukuoka, 2007)
  • 32. Polysaccharides Hydrogenolysis  Changes of polysaccharides during hydrogenolysis  Liquid soluble products  Polysaccharide monomers and polysaccharide derived chemicals (PDCs)  Liquid insoluble products  Solid residue  For avicel cellulose, 34% conversion of initial cellulose into polysaccharides and polysaccharides derived chemicals  ~6% polysaccharide monomers identified from original polysaccharides  For poplar, 64% conversion of feedstock.  ~8% polysaccharide monomers Mass balance of cellulose hydrogenolysis. The reaction conditions were: Residence time: 4 hours; temperature: 200 °C; Pressure: 1000 psi; catalyst: 10% (w/w) of identified from original polysaccharides Pt/C; phosphoric acid: 40% (w/w); solvent: H2O (1:1,v/v); feedstock: cellulose. a theoretical weight of un-identifiable saccharides-derived chemicals.  Reaction conditions produced statistically significant conversion percentages of polysaccharides  90-100% conversion of initial polysaccharides into PDCs and solid
  • 33. Polysaccharides Hydrogenolysis  Trace amounts of dehydration chemicals from glucose were detected  Glucose converted to HMF, furfural, levulinic acid, formic acid, acetic acid under hydrothermal conditions in the presence of acidic (Liu et al., 2011) conditions.  Cellulose converted into polyols such as sorbitol through hydrogenation using supported metal catalysts  Previous experiments (Shrotri et al., Conversion products from catalytic hydrogenolysis of cellulose. (1) glucose, (2) 2012) sorbitol, (3) sorbitan, (4) isosoribde, (5) xylose, (6) erythritol, (7) glycerol, (8) 1,2- (or1,3)propanediol (9) ethanediol, (10) methanol. (Palkovits et al., 2010).  Chemicals detected by
  • 34. Summary  Thermochemical conversion is capable of converting all three biopolymers in biomass into fuels and chemical precursors simultaneously.  Biochemical conversion inefficiently utilizes lignin  Lignin derived chemicals and polysaccharide derived chemicals were fractionated with non-polar solvents.  Lignin is selectively depolymerized into monomeric subunits for chemical precursors through catalytic hydrogenolysis  Syringylpropane  Guaiacylpropane  Reaction conditions affect the monolignol yield.  Polysaccharides were degraded through hydrogenolysis  Polysaccharide monomers  Polysaccharide derived chemicals  No dehydration chemicals  Possible polyols production  Reaction conditions affect the degradation of polysaccharides
  • 35. Future Research  Further investigation of polysaccharide derived chemicals (PDCs) produced through hydrogenolysis  Accurate mass balance  No assumption necessary  Energy balance for viability of process  Design of Experiment (DOE) methodology  Use factorial experimental designs  Determine interaction effects  Investigation into other catalysts  Increase the selectivity  Decrease the activation energy
  • 36. Acknowledgments  Dr. Xuejun Pan  I am honored to have Dr. Pan as my mentor  He has given me a great deal of academic support in addition to assistance in my research study.  Dr. Pan’s Research Group  There support and knowledge were vital in my research studies.  Dr. Ralph’s Research Group  I need to thank Dr. John Ralph for allowing me to use his laboratory equipment.  Special thanks to Dr. Fachuang Lu for assistance in gas chromatography and mass spectrometry.  Thesis committee  I need to thank Dr. Troy Runge and Dr. Fachuang Lu for accepting my invitation to be on my thesis committee  In addition to helping finalize my thesis.  Biological Systems Engineering  For the departments support during my undergraduate and graduate studies.
  • 37. Questions (Nagy et al., 2009)