carbohydrate-presentation by xiaoyounan


									Catalytic Conversion of Carbohydrates as Renewable Raw
Materials to key Platform Chemicals Using Metal Supported
                   Mesoporous Meterials

                    S. Anuradha
                  NCCR, IIT-Madras
                    PART I

           FUEL AND
            ENERGY    BIOGAS




   •   Biomass resources can be divided into
       three general categories:
 Wastes
 Standing forests
 Energy crops – herbaceous woody crops
                Starch crops
                Sugar crops
                Oilseed crops
• As a source of chemicals, biomass has several
  intrinsic advantages over fossil mass

• It is renewable and flexible through crop switching

     Platform molecules identified by the US DOE

            Aspartic acid
            Glutamic acid
            Levulinic acid
            2-Hydroxypropionic acid
            2,5-Furan dicarboxylic acid
            Glucaric acid
            Itaconic acid
            1,4-Diacids (succinic, fumaric and malic)
            3-Hydroxypropionic acid
Hydrolysis of Sucrose, Starch and Cellulose
 •   Catalysts:
  Mineral acids
  Ion-exchange resins
  Protonated dY-Zeolites
  HMM and FSM zeolites
 •   Activation of glycosidic linkage

Ayumu Onda,* Takafumi Ochi and Kazumichi Yanagisawa, Green Chem., 2008, 10, 1033–1037
      Oxidative Decarboxylation of Glucose

• Interest to convert C6 carbohydrates from
  starch or sucrose into C5 and C4 polyols
• Find many applications in food and non-food
• Dehydroxylation reactions leading to deoxy-
• Catalyst – Ru/anthraquinone-2-sulfonate

      L. Fabre, P. Gallezot, A. Perrard, J. Catal. 208 (2002) 247.
    Synthesis of o-Isopropylidene sugar Derivatives

• Monosaccharides which contain two sterically
  adjacent OH groups in the cis-position can be
  reacted with aldehydes or ketones
• Anti-inflammatory and antipyretic active
• a central intermediate product for numerous other
  glucose derivatives
• Drugs - 2-deoxy-D-riboseanilide and amiprilose
• 1,2:5,6-diacetone-D-glucose can be used as a chiral
  ligand in complexes which permit enantioselective
•   Aldoses, Aldosides and ketoses:
    D-galactose, L- and D-arabinose, fructose, sorbose,
    D-xylose, D-mannose, D-ribose, D-mannitol
•   Catalysts:
 Cupric sulphate in acetone
 FeCl3
 Zeolite HY
 VO(OTf)2
 SiO2-H2SO4
• Use of Inorganic acids and salt – Require large
  amount - Disposal
• Use of solid catalysts also presents problems as a
  result of the reactions of caramelisation
• The recovery of ion exchangers involves a great
  deal of expense
Schematic representation of reaction pathways for acid-catalyzed hydrolysis and
dehydration of polysaccharides to 5-hydroxymethylfurfural (HMF) in a biphasic

Juben N. Chheda, Yuriy Roma´n-Leshkov and James A. Dumesic, Green Chem., 2007, 9, 342–350
Synthesis of furane derivatives from carbohydrates
Schematic diagram for production of liquid alkanes from
biomass resources in a biorefinery.

     Juben N. Chheda, James A. Dumesic, Catal. Today 123 (2007) 59–70
Synthesis of Glucamine
• Provides an information about the inhibition of
• Only carbonyl group of an aldose and ketose is
  aminated selectively
• None of the OH groups is transferred to an amino
• Catalyst:
  NH3, Ni

      H.Kelkenberg, Tens.Surf.Det.,25 (1988)1
         Hydrogenation of Glucose

R. Schoevaart, T. Kieboom, Top. Catal. 27 (2004) 3.
    Figure 1. Cellulose structure and the potential monomers formed
         following cleavage of the C-O-C bonds at position a or b.

Ning Yan,† Chen Zhao,† Chen Luo,† Paul J. Dyson,‡ Haichao Liu,*,† and Yuan Kou, J. AM.
                          CHEM. SOC. 2006, 128, 8714-8715
Scheme 1. Proposed Reaction Mechanism under Acidic
Scheme 2. Proposed Reaction Mechanism under Neutral and
                    Basic Conditions
       Schematic representation for catalytic conversion of
                       cellulose into sorbitol

Catalyst: Pt/γ-Al2O3

     Paresh L. Dhepe Æ Atsushi Fukuoka, Catal Surv Asia (2007) 11:186–191
Use of sorbitol as a precursor to fuels and chemicals
• Sorbitol (ca. 800,000 t year-1) - used in food
                                             chemical industries
                                             an additives
• Catalysts
 Raney nickel catalysts promoted with
  electropositive metal atoms such as molybdenum
   and chromium*
 Ruthenium supported on acidic Y-zeolite
 Ruthenium/carbon
 Ru–Pt/C –rate of epimerization decreases
 Pt- increases the stability – prevents the formation of
  oligomeric products
 Prevents the oxidation of Ruthenium
      *P. Gallezot, P. Ce´rino, B. Blanc, G. Fle`che, P. Fuertes, J. Catal. 146 (1994) 93.
         Possible products of oxidation of D-Glucose

S. Hermans, M. Devillers, Applied Catalysis A: General 235 (2002) 253–264
• Varieties of high added value chemicals used in detergents
  & pharmaceuticals (Vitamin C).
• Catalyst
 Hypochlorite mediated by TEMPO (2,2,6,6-tetramethyl-1-
 RuCl2(PPh3)3/TEMPO**
 palladium on charcoal
 Pd–Bi/C catalysts - (5 wt.% Pd, Bi/Pd = 0.1)
 Rate of glucose oxidation to gluconate was 20 times
 Selectivity was high on the fresh and recycled catalysts
 Cocatalyst protecting palladium from                                 over-oxidation
  because of its stronger affinity for oxygen.
*P.L. Bragd, H. van Bekkum, A.C. Besemer, Top. Catal. 27 (2003) 49.
**A. Dijksman, A. Marino-Gonzalez, A. Mairata, I. Payeras, I.W.C.E.Arends, R. heldon,
    J. Am. Chem. Soc. 123 (2001) 6826.
Scheme for the mechanism of glucose oxidation on PdBi catalyst*

     Gold catalysts - active for oxidation with oxygen
      at basic pH - activity was strongly dependent on
      particle size

     The metal-catalyzed oxidation gave comparable
      selectivity and higher productivity than enzymatic
      glucose oxidation

   *M.Besson,F.Lahmer,P.Gallezot, P.Fuertes, G.Fleche,J.Catal. 152 (1995) 116.
    Oxidation of starch by H2O2 by dry method catalysed by
                      metal phthalocyanine complexes

• Active species could be competent to cleave the C2–C3
  bond of an anhydroglucose unit of carbohydrate (AGU)
  having adjacent hydroxyl functions to form aldehyde
  and carboxyl groups

S. L. Kachkarova-Sorokina, P. Gallezot and A. B. Sorokin, C h e m . C ommu n . , 2 0 0 4 , 2 8 4 4.
      PART- II

The Prospect of exciting chemistry of furfural derived
compounds such as 5-Hydroxymethyl furfural, 2,5-furan
dicarbaldehyde and 2,5-furan-dicarboxylic acid is due to its
enormous application

• agrochemistry as fungicides,
• galvanochemistry as corrosion inhibitors
• cosmetic industry and
• flavour agents.

HMF is a good starting material for the synthesis of precursors
of various pharmaceuticals, thermo-resistant polymers and
complex macrocycles.

The synthesis of HMF is based on the triple dehydration of

Various substrates can be used:
    • hexoses
    • oligo- and polysaccharides
    • converted industrial wastes
Scheme 1: The acid catalysed dehydration of Hexose

                        Scheme 1

• Studies performed by a number of independent scientists
  demonstrated that the chemistry of the formation of HMF
  is very complex
• It includes a series of side-reactions, which influence
  strongly on the efficiency of the process.
• The dehydration of hexoses is catalysed by protonic acids
  as well as by Lewis acids.

• First syntheses of HMF were catalysed by oxalic acid1 and till
  now nearly one hundred inorganic and organic compounds
  were positively qualified as catalysts for the HMF synthesis.

• Cottier2 divided catalysts into five groups; they are collected
  in Table 1.

1. Dull, G. Chem. Ztg. 1895, 19, 216.
2. Cottier, L.; Descotes, G. Trend. Heterocycl. Chem. 1991, 2, 233.
• The    problem    with     the     efficient
  preparation      of         pure          5-
  hydroxymethylfurfural is still unresolved.

• No one has found an inexpensive and
  easy-to-use mode of the preparation of
  this compound.
 • Metal phosphates are well known for their acid properties

 • They are characterized by polymeric metal(IV) phosphates
 with layered structures, each layer consisting in a plane of
 tetravalent metal atoms sandwiched between planes of
 different hydrogenphosphate/ phosphate species.

 • Zirconium and Titanium Phosphates3
 • Used as acid catalysts in reactions - alcohols dehydration,
 olefins isomerization and terpenes rearrangements.

3. .Benvenuti,C.Carlini,P.Patrono,A.M.R.Galletti,G.Sbrana,M.A.Massucci,P.Galli,
   Appl.Catalysis A:193 (2000) 147.
Table: 2 Zirconium and Titanium phosphates as well as
       pyrophosphates used for carbohydrates dehydration.
• Batch catalytic experiments were performed under nitrogen
  atmosphere in a 100 ml magnetically stirred glass vessel,
  heated with a thermostatted oil bath at 110°C, equipped
  with a reflux condenser and a vial for sampling the liquid
• All the heterogeneous Titanium and Zirconim based
  catalysts have an ability to dehydrate fructose to HMF in aq.
  solution without any contemporary rehydration of HMF to
  levulinic and formic acids
• The extent of 2-furaldehyde formation is always limited to
  less than 1%.
• Among the investigated catalyst samples, cubic zirconium
  pyrophosphate and γ-titanium phosphate offer the best
  performances, in terms of both activity and selectivity,
  displaying the highest yields to HMF.
Table:3 Fructose and inulin dehydration carried out in aqueous medium in the presence
                    of zirconium-based catalysts(batch experiments)a
• Cubic zirconium pyrophosphate, having the highest
surface area among all the investigated catalysts (Table
2), can be indifferently obtained from α- and γ-ZrP by
thermal treatment at 950°C.
• At this temperature most part of the surface Brønsted
sites are removed and the resulting cubic
pyrophosphate phase is characterized by a large
amount of coordinatively unsaturated octahedrical Zr4+
species located on the external faces of the crystallites.
• Strong Lewis acid sites would be responsible for
significant enhancements of both catalytic activity and
selectivity in the fructose dehydration process.
Table 4. Fructose and inulin dehydration carried out in aqueous
         medium in the presence of titanium-based catalysts (batch
• Cubic titanium pyrophosphate - a low catalytic activity
  was ascertained.

• Lower strength of Lewis acid sites present on the external
  crystal surface of C-TiP2O7 with respect to those on

• Indirectly confirming the importance of the role played by
  the Lewis acid strength in this catalytic process

• Inulin - promising substitute as cheap raw material for a
  potential industrial production of HMF
• The catalytic activity of various niobium-based catalysts has
  been preliminarily tested in the fructose dehydration to HMF4.

• Catalytic experiments were carried out in batch, under
  nitrogen, on aq. 6 wt.% fructose solutions in a stirred glass
  vessel equipped with a condenser and heated with a
  thermostated oil bath at 110°C.

  Table: 5 Niobium-based catalytic systems applied for fructose

  T.Armaroli, G. Busca, C.Carlini, M.Giuttari, A.M.r.Galletti,G.Sbrana, J.Mol.Catal.A:
      151 (2000) 233.
Table:6 Fructose dehydration to HMF in the presence of different
       heterogenous niobium-based catalysts
• The Lewis acidity strength is similar in all the catalysts
examined - assigned to coordinatively unsaturated Nb5+

• The lower reactivity of HMF towards polymerization
processes in the presence of NP catalysts, makes them
more promising from applicative point of view.
• Catalytic properties of niobic acid (Nb2O5.nH2O) and
niobium phosphate (NbOPO4) surfaces were studied.5

• The reaction was performed in a continuous reactor at
different temperatures 90–110°C and pressures (from 2 to 6

• The superior catalytic activity of NBP compared to niobic
acid was due to its higher intrinsic effective acidity in highly
polar and protic media.

5. P.Carniti, A.Gervasini, serena,s.Biella, a.auroux, Catal.Today 118 (2006) 373.
Table:7 Surface properties of the NBO samples
Selectivity to 5-hydroxymethyl-2-furaldehyde (HMF) vs. fructose conversion
for NBO and NBP catalysts at different reaction temperatures (particle size:
20–45 mesh, open symbols; 45–100 mesh, filled symbol).

• Besides the evaluation of activity and selectivity, catalyst
  stability was also explored following the reaction for long time
  on stream, up to 200–220 h.
• Decreasing exponential trend of fructose
conversion against reaction time was observed on
NBP while a lighter decreasing trend was observed
for NBO

    Deactivation of NBO and NBP as a function of time on
    stream at 100 °C for the dehydration of fructose in water.
• Due to the fast deactivation of a part of the
  active acid sites of the NBP surface

• The loss of activity should be likely due to
  deposition of insoluble humines or coke on
  the catalyst surface.
     •The attempt of obtaining, in a one-pot reaction, FDA from
     fructose passing through HMF as an intermediate product
     failed both in water and in a mixed water/methyl isobutyl
     ketone (MIBK) medium.6

            Table:8 Dehydration of fructose to HMF in presence of VOP as
               heterogeneous catalysta
           Entry    VOP(g)   Solvent(ml)         Fructose       Selectivity to
                                                 conversion (%) HMF (%)
              1.         0.6      H2O (30)               50.1              81.5

              2.         0.5      H2O-MIBK (10-30) 49.9                    74.2

              3.         0.6      H2O-MIBK (5-30)        42.0              70.3

    a   Reaction conditions: Fructose: 6 mmol; T=80°C;time:2h; nitrogen atmosphere(PN2 = 0.1MPa).

6. C.Carlini,P.Patrono, A.M.R.Galletti,G.Sbrana, V.Zima, Applied Catalysis A: 289 (2005) 197.
  The modification of the heterogeneous catalysts,
  obtained by partial substitution of VO3+ with different
  metal cations (Fe3+, Cr3+, Ga3+, Mg2+, Cu2+ and Pd2+), did
  not cause any improvement on the performances in this
  • Direct oxidation of HMF to FDA - VOP and N,N-
  dimethylformamide (DMF) - 100°C and room pressure of O2.
Table:10 HMF oxidation to FDA in DMF by the heterogeneous VOP catalystsa
      • On the basis of the collected data, DMF resulted
        in a good solvent for the catalytic oxidation of
        HMF to FDA and VOP exhibited the best
        performances at productivity and selectivity level.

       • HMF is efficiently oxidized to 2,5-diformylfuran
         using Mn(III)–salen catalysts7
       • Sodium hypochlorite - pH 11.3 phosphate
        buffer–CH2Cl2 biphase system at room temperature.
       • Yield - 63–89%

7. Ananda S. Amarasekara *, Dalkeith Green, Erinn McMillan, Catal. Communications 9 (2008) 286
Table:11 Yields of 2,5-diformylfuran(2) and reaction conditions

     All reactions were carried out using 1.0 mmol of HMF (1) in 2.0 mL CH2Cl2 at room
     temperature. Entries 1–6 using 8.0 mmol NaOCl, entry 7 using 5.0 mmol H2O2,
     entries 8,9 under 1 atm. of O2 and 2.0 mmol of butyraldehyde was added in entry 8. a
     Using GC.b Using 1H NMR.c 5-chloromethylfurfural (26%) was the major product.
• Chlorination of the hydroxyl group can be
  completely suppressed by using the pH 11.3
  buffered medium.
• Economical, high yield room temperature oxidation
•   Direct formation of 2,5-furandicarboxylic acid from Fructose8
•   Cobalt acetylacetonate encapsulated in sol–gel silica
•   Bifunctional acidic and redox catalyst
•   Selectivity: 99%          Conversion: 72%.

    8Marcelo   L. Ribeiro, Ulf Schuchardt, Catalysis Communications 4 (2003) 83–86
  Table:12 Yields of 5-hydroxymethyl-2-furfural (2) and of
                2,5-furandicarboxylic acid (3)

a50   ml of MIBK, 7 g of fructose dissolved in 6 ml deionized water with, 0.1 g of catalyst, 88°C, 8 h.
b9.4   ml of MIBK, 0.6 ml deionized water, 0.1 g of catalyst, 40μl of 2, 80°C, 4 h.

• The SiO2-gel catalyst is four times more active in the
  dehydration of fructose to HMF than Co(acac)3..
• This suggests that either another transition state selectivity or
  different proton transfer rates are operating at the active sites
  of the heterogeneous catalyst, favouring the formation of HMF.
            Table:13 Conversions and selectivities in the one-
               pot synthesis of 2,5-furandicarboxylic acid (3)a

a   6 ml deionized water, 0.1 g of fructose, autoclave, 20 bar of synthetic air, 160° C, 65 min.
• The evaluation of the two reaction steps in the
  synthesis of FDA allows the understanding of the
  catalyst action in both systems.
• The SiO2-gel is suitable for the dehydration of fructose,
  avoiding the formation of by-products.
• Activity of free Co(acac)3 depends on the reaction
•    The cooperative effect of the acidic matrix and the
    metal complex occluded therein works properly under
    the more drastic reaction conditions used and FDA is
    obtained with high selectivity, without the formation of
    any by-products.
•   Lanthanoide(III) ions are found to catalyze the
    dehydration of D- glucose to yield HMF.9
    Catalyst : 2.0 X 10-3 mol dm-3
    D-glucose : 0.30 mol dm-3
    water     : 15 cm3

•   The dehydrogenation of D-glucose was carried out
    by heating a stainless bomb (100 cm3) containing
    the glass tube at 140°C under 10 atm of nitrogen

     9. Hitoshi Ishida a’ * , Kei-ichi Seri , J. Mol. Catal. A: 112 (1996) L163.
  Fig. 1. Dependencies of the initial rates of D-glucose dehydration on the
      lanthanoide(III) ion concentration: LaCl3 ( ■), NdCl3 (●), EuCl3 (▲),
      DyCI3 (□), and YbCl3, (○).

• No further decomposition of HMF takes place at least under
  the present reaction conditions.
• The lanthanoide(III) ions coordinate with D-glucose and act
  as Lewis acid catalysts for the present reaction because the
  lanthanoide(III) ions are known to have a high affinity for
  oxygen atoms.
1. Cubic Zirconium pyrophosphate and γ-Titanium
   phosphate offer the best performance in terms of both
   activity and selectivity .
2. The catalytic activity of NP are explained in terms of
   acidity. The Lewis acidity strength can be assigned to
   coordinatively unsaturated Nb5+ sites.
3. VOP has a very low surface area(0.8 m2/g). However,
   high conversion of HMF with low selectivity was found
   when silica supported VOP catalyst was used.
Catalyst   Temp.(°C)      Time(hr)   Conversion   Selectivity
                                         (%)          (%)
C-ZrP2O7   100            0.5        44.4         99.8
                          2.0        52.8         81.4

γ-TiP      100            0.5        36.7         96.1
                          2          56.6         68.7

NP1        100            2          39.0         67.4

NP2        100            2          33.3         71.9

NBO        100            0.5        30           20

NBP        100            1.0        70           35

VOP        80             2          50.1         81.5

Sio-gel    165(H2O)       1          50           100
           88(MIBK/H2O)   8          47           100
4. DMF resulted in a good solvent for the catalytic
   oxidation of HMF to FDA and VOP exhibited the
   best performance at productivity and selectivity
5. Oxidation of HMF was effected by the metal
6. Silica-gel is used for the dehydration with good
7. Main focus is to prevent further hydrolysis of HMF
   to levulinic acid and Formic acid.

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