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CONVERSÃO DA BIOMASSA
          Cesar A. M. Abreu




  UNIVERSIDADE FEDERAL DE PERNAMBUCO
  DEPARTAMENTO DE ENGENHARIA QUÍMICA
  LABORATÓRIO DE PROCESSOS CATALÍTICOS
          RECIFE, PERNAMBUCO
CONVERSÃO DA BIOMASSA



       CONVERSÃO DA BIOMASSA COM VALORIZAÇÃO


Conversão da biomassa
Processos de conversão
Natureza química
Fracionamento
Funcionalização ou degradação
Intermediários
Produtos finais
CONVERSÃO DA BIOMASSA


                 BIOMASSA LIGNOCELULÓSICA


Principais componentes: celulose, hemicelulose, lignina
Outros componentes: cinzas, fenois , acidos graxos, ….

Celulose: polissacarídeo de D-glucose, unidades associadas
via β-1,4-glucosidic ligações.
Hemicelulose: polissacarídeo de xilose, arabinose, manose,
promovendo interações entre a celulose e a lignina
Lignina: polímero baseado em fenilpropano, estruturado em
grupos guaiacil, siringil and p-hidroxifenylpropano
CONVERSÃO DA BIOMASSA

        CONVERSÃO DA BIOMASSA (CANA-DE-AÇÚCAR)

  1 EXTRAÇÃO    SACAROSE       QUÍMICO            GLUCOSE,FRUTOSE

                (MELAÇO)       BIOQUÍMICO         AÇÚCAR INVERTIDO



                                                  CELULOSE
                BIOMASSA       PRÉ-TRAT.
                                                  HEMICELULOSE
                L-CEL          FRACIONAMENTO
                                                  LIGNINA
                (BAGAÇO)
  2 HIDRÓLISE   CELULOSE       ÁCIDO DILUÍDO      GLUCOSE
                HEMICELULOSE   ÁCIDO CATALÍTICO   HMF, DMF
                               ENZIMÁTICO         XILOSE, ARABINOSE,

                                                  FURFURAL,
CONVERSÃO DA BIOMASSA

          CONVERSÃO DA BIOMASSA (CANA-DE-AÇÚCAR)

  3 OXIDAÇÃO     LIGNINA          QUÍMICO      ALDEÍDOS
                                                AROMÁTICOS
                                  CATALÍTICO
                                               ÁCIDOS DERIVADOS




  4 HIDROGENA    SACAROSE         QUÍMICO      POLIÓIS
    ÇÃO
                 GLUCOSE          CATALÍTICO   ÁCIDOS DERIVADOS
    HIDROGENÓ    FRUTOSE                       ÉSTERES
     LISE
                 XILOSE
    OXIDAÇÃO
                 (MELAÇO,
                  HIDROLISADOS)
    ESTERIFICA
     ÇÃO
CONVERSÃO DA BIOMASSA


       CONVERSÃO DO BAGAÇO DE CANA-DE-AÇÚCAR


                                           BAGAÇO
                                              DE
                                        CANA-DE-AÇÚCAR




           CELULOSE              HEMICELULOSE                         LIGNINA




     ACETATO    SORBITOL /   FURFURAL      XILITOL        RESINAS    PLÁSTICOS   VANILINA
        DE       MANITOL                                 FENÓLICAS
     CELULOSE
The acid hydrolysis process
Dilute acid hydrolysis,
Low acid consumption
Maximum monosaccharide yields reached at high
temperatures and short residence times,
Fast reaction rates
Yields circa of 50-60% of the theoretical value
Concentrated acid hydrolysis,
Processed decomposing and dissolving the polysaccharides
Occurs with water deficiency
Production of oligosaccharides
The acid hydrolysis process
Limitations,
Severe conditions (e.g. higher temperature, low pH)
Formations of degradation by-products
Furans and organic acids
Monomeric hexoses and pentoses transformed into HMF and
furfural,
Further degradation into organic acids (e.g. levulinic, humic
acids) and condensation reactions
Dissolved lignin result in the formation of inhibiting phenolic
compounds
Corrosion of the equipment
The acid hydrolysis process
Production process of saccharidic mixtures to further
processing,
Degradation of corn starch or sugarcane hemicellulose in acid
media
Quantification of the oligomeric decompositions
Selection of saccharidic mixtures to further catalytic
treatements
Kinetics of starch and pentosane depolymerization
Consecutive evolutions of the oligomeric components
Identification by the degree of polymerizations (DP6, DP5,
DP4, DP3, DP2, DP1 = glucose, xylose,..).
The acid hydrolysis process
Starch and sugar cane bagasse hydrolysis,
Native corn starch solutions were hydrolyzed at
temperatures ranging 343 K to 373 K, producing
glucose with yield circa 70%
Sugar cane bagasse was hydrolised at 393 K,
producing xylose, with approximate yield of 60%

Abreu, C. A. M. et al. (1995) Biomass and Bioenergy Vol
9, No. 6, 487-492
The acid hydrolysis process
     Mechanism                                         Kinetics

S+         
         AcH 1
            → SH + Ac -              dC S             k'                
                                           = −k ' C S 1 − ((C S O − C G )
                                       dt              k                 
SH + H 2 O 1'
            → DPn + G
DPn + AcH 2   → DPn H + Ac −                                              1/2
                                 dC G                                
                                      = k ' K AcH 1 − ' (C So − C G )         (C So − C G )
                                                       k
DP H + H O 2
                '
     n         → DP
               2       +G
                     n −1
                                  dt               k                 

----------------------------
DP   + AcH n
     2        → DP H + Ac -
                       1

DP1 H + H 2 O n                                                             
                 '
               → G + G
                                    dC OL
                                          = k (C S − C G )1 − ' (C So − C G )
                                                              k
                                     dt                    k                 
AcH ⇔ Ac - + H +
CONVERSION OF CARBOHYDRATES
Processing of raw materials rich in saccharides (sugarcane, starch,
molasse, bagasse,…),
Products with industrial application as polyols and organic
acids
Carbohydrate hydrogenations (saccharides → monosaccharides → polyols)
Carbohydrate oxidations (saccharides → monosaccharides + acids → acids)
Heterogeneous processes with supported catalysts based on
nickel, chromium, ruthenium to hydrogenate glucose,
fructose and sucrose to sorbitol and mannitol
Hydrogenation of carbohydrates
         Heterogeneous mechanism
1st Brazilian Workshop on Green Chemistry


           Hydrogenation of carbohydrates
                               Heterogeneous mechanism
Hydrogenation of carbohydrates
Saccharide hydrogenation process,
Polyol production in a batch three-phase reactor
Glucose conversions of 85% with a selectivity in sorbitol of
99.05% at 413K, under 24 bar, after 3 hours of reaction with
a nickel catalyst (14.75 % weight)/activated carbon
Saccharose conversions of 52% after 3 hours of reaction
Production of glucose and fructose and sorbitol and mannitol

L. C. A. Maranhão, F. G. Sales, J. A. F. R. Pereira, C. A. M. Abreu (2004) React. Kinet. Catal. Lett.
81, 169-175
Hydrogenolysis of carbohydrates

Saccharide hydrogenolysis process,
More drastic temperature and hydrogen pressure conditions
Splitting of carbon-carbon and carbon-oxygen carbohydrate
bonds
Polyols obtained from hydrogenations can be hydrogenolysed
Products: other polyols, glycols and alcohols
Catalysts: noble metals
Continuous production of fine
                   polyols
Scale-up of carbohydrate hydrogenations,
Fine polyols from biomass resources are traditionally
produced in discontinuous processes
Apparatus of great volume in relation to the small quantity of
the obtained products
Scale-up from discontinuous operations to continuous one
Development of the saccharide hydrogenation process into a
continuous operation
Continuous polyol production
Continuous production of fine
                         polyols
Continuous hydrogenation in a three-phase reactor,
Trickle-bed reactor under moderate operation conditions
(1.22 MPa, 413 K)
Glucose conversions of 44% with a polyol selectivity of
99.31%
Yield of 24% in sorbitol and mannitol for the saccharose
hydrogenation
Possibility to develop a process (pressures up to 2.54MPa, low
liquid flow rates) to obtain high conversions

Maranhão, L. A., Abreu, C. A. M. (2005) Industrial and Engineering Chemistry Research. v. 44, p.
9642-9645
Continuous production of fine
          polyols

               0,5
                                                                               dC G                 ′
                                                                                         dC G η G k G C G
                                                                         Dax        − uL     −            =0
               0,4                                                             dz 2
                                                                                          dz   1 + K G CG
               0,3         glucose
 C (mol L-1)




                           sorbitol
                           model
               0,2
                                                                             f e φ G [coth (3φ G f e ) − ( f e 3φ G )]
                                                                  ηG =
               0,1
                                                                               (        )
                                                                         1 + φ G ShLG [coth (3φ G f e ) − ( f e 3φ G )]
               0,0

                     0,0   0,1   0,2   0,3    0,4     0,5   0,6
                                 Axial position (m)




Hydrogenation of glucose at 1.22MPa and 413K in trickle-bed
reactor
Continuous production of fine
               polyols

                              0,3
                                                                                                d 2 C Sac          dC Sac
                                                                                          Dax               − uL                    ′
                                                                                                                          − η Sac k Sac C Sac = 0
                                                                                                  dz 2              dz
                              0,2
                C (mol L-1)




                                                              saccharose
                                                                                       d 2 C Mo    dC Mo                            ′
                                                                                                                                   k Mo C Mo        
                              0,1
                                                              monosaccharides
                                                                                 Dax            −u       + η Mo  k Sac C Sac −
                                                                                                                   ′                               =0
                                                                                                                                                    
                                                              polyols
                                                              model                      dz 2       dz                         1 + K Mo C Mo       

                              0,0


                                    0,0   0,1   0,2    0,3    0,4    0,5   0,6                d 2 C Po        dC Po             ′
                                                                                                                              k Mo C Mo
                                                                                        Dax              −u         + η Po               =0
                                                Axial position (m)
                                                                                                dz   2
                                                                                                               dz          1 + K Mo C Mo



Hydrogenation of saccharose at 1.22MPa and 413K in trickle-
bed reactor.
Continuous production of fine
               polyols
An up grade of the discontinuous to the continuous process for saccharide
hydrogenation may be compared in the following terms:

Discontinuous process (slurry reactor) Continuous       process    (trickle-bed
                                       reactor)
Ni/C catalyst; 413 K, 2.44 MPa         Ni/C catalyst; 413 K, 1.22 MPa
Operation time = 3 hours               Operation time = 3 hours
Concentration of the saccharide feed = Concentration of the saccharide feed =
100.00 g/L                             100.00 g/L
Production = 42.50 g in polyol         Acumulated production = 749.35 g in
                                       polyol
LIGNIN FROM BIOMASS

Biomass conversion into aldehydes and acids,
Lignin degradation: break up into fragments producing
aromatic aldehydes
Polifenate ions, precursors of the aromatic aldehyde
formations
Aldehyde conversion into organic acids
LIGNIN PROCESSING FROM
              SUGARCANE BAGASSE
Lignin oxidation,
Wet air oxidation process (WAO) as an alternative technology
Valorization of lignocellulosic materials
Production of a mixture of aromatic aldehydes of industrial
interest
Catalytic wet air oxidation (CWAO) process using air and
catalysts
Treatment of effluents and by-product of the biomass industry
Catalytic wet oxidation of lignin
                                             H 2COH

                                                  CH
                                                  CO
                                                                                                      H2 COH
                                                                                  OCH3
                                                  1              H2COH                                 HC
                                                                  HC        3       O                      CH
                                      H3CO
                                                  O                   CH
                                                                                  OCH3                     4

                                                                      2                  H2 COH
                                                                                                                 OCH3
                                                                                         HC                O
                                                      H3CO                 OCH3
                                                                      O                      CHO



                                                                           (a)


                H 2COH                                                                                                            HO       O
                                                      H2COH                              H        O
                HC                                                                                                                     C
                                                  H    C     OH                              C
                          O 2 Pd γ − Al2 O
                  CH
                         //  3 →        HO       C     H         2 /γ−Al2
                                                                       Pd/ O3 →
                                                                       O
                                                                                                     + AcH      Pd / γ−Al O3 →
                                                                                                                 2 / 2
                                                                                                                 O
                                                                                                                                      2       + AcH
                                                                                             2

                  2                                                                                                          R1                R2
                                                        2                           R1                R2
                                                                                                                                       OH
                                                                                             OH
         H3CO            OCH3
                 O                           R1                  R2
                                                       OH
                                [ Lignin ]                                        [ Aldehydes ]                               [ Acids ]

                                                                           (b)


Basic structure of lignin and degradation/oxidation
mechanism. (a) basic unit of the Fagus silvatic lignin. (b)
degradation/oxidation reaction steps. R1= H, OCH3 ;
R2 = OCH3 .
Catalytic wet oxidation of lignin
CWAO of lignin from sugar-cane bagasse was evaluated to
produce aromatic aldehydes
Lignin (L) is depolymerized with the productions of
aldehydes, acids and other products of low molecular
weights
The aromatic aldehydes vanillin (V), syringaldehyde (S) and
p-hydroxibenzaldehyde (P) were submitted to subsequent
oxidations
Other products (R), such as organic acids can degrade into
carbon dioxide



              Reaction scheme of the catalytic wet oxidation of lignin
Process operations
Operations in a slurry reactor,
Palladium catalyst, 373-413 K, 2-10 bar/ PO2
Lignin as a by-product from sugarcane bagasse by the DFH
(Dedine Fast Hydrolysis)
Yields of the aromatic aldehydes associated with lignin
consumption and their oxidations to acids
Aromatic aldehyde yields approximately ten to twenty times
higher then with the noncatalytic oxidation process

Sales, F. G. , Maranhão, L. A. , Lima Filho, N. M. , Abreu, C. A. M.( 2006). Industrial & Engineering
Chemistry Research. v. 45, p. 6627-6631
Processo continuo de produção de aldeídos
                      aromáticos
Scale-up of process,
From batch to continuous operations
Aromatic aldehyde productions operated in a continuous
 fluidized-bed reactor
Lignin as a by-product from sugarcane bagasse
Yields of the aromatic aldehydes associated with the lignin
  consumption and their oxidations to acids
Processo continuo de produção de aldeídos
               aromáticos




            Three-phase fluidized-bed reactor
Processo continuo de produção de aldeídos
                           aromáticos
Escalonamento,
Batch operation: 56.24x10-2g of vanillin and
50.01x10-2g of syringaldehyde from a 0.50L-lignin
solution (60.00g/L), 2 h of reaction at 5.00 bar and 393
K
Continuous operation: 65.10x10-1g of vanillin and
114.84x10-1g of syringaldehyde, with a feed
concentration of lignin of 30.00 g/L, 2 h of reaction, at
5.00 bar and 393 K, liquid-phase flow rate of 5.00 L/h

F. G. Sales, L. C.A. Maranhão, N. M. Lima Filho, C. A.M. Abreu (2007) Chemical
Engineering Science 62, 5386 – 5391
Conclusions
Recent technology developments done in the scope of the biorefinery
concept have emerged as alternatives, making production of chemicals
from ligno-cellulosic feedstocks become a reality.

Biomass conversions employ hydrolysis and pretreatments of hemicellulose
and lignin, and acid or enzymatic hydrolysis of cellulose to break the
polymeric structures to their saccharides and lignin components.

In the presence of homogeneous or heterogeneous catalysts the oligomeric
mixtures selected may be processed in order to produce valuable
chemicals.

Through catalytic hydrogenation, hydrogenolysis or oxidation these
mixtures can be converted to polyols, glycols, monoalcohols, aldehydes and
organic acids.

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Conversão da Biomassa

  • 1. CONVERSÃO DA BIOMASSA Cesar A. M. Abreu UNIVERSIDADE FEDERAL DE PERNAMBUCO DEPARTAMENTO DE ENGENHARIA QUÍMICA LABORATÓRIO DE PROCESSOS CATALÍTICOS RECIFE, PERNAMBUCO
  • 2. CONVERSÃO DA BIOMASSA CONVERSÃO DA BIOMASSA COM VALORIZAÇÃO Conversão da biomassa Processos de conversão Natureza química Fracionamento Funcionalização ou degradação Intermediários Produtos finais
  • 3. CONVERSÃO DA BIOMASSA BIOMASSA LIGNOCELULÓSICA Principais componentes: celulose, hemicelulose, lignina Outros componentes: cinzas, fenois , acidos graxos, …. Celulose: polissacarídeo de D-glucose, unidades associadas via β-1,4-glucosidic ligações. Hemicelulose: polissacarídeo de xilose, arabinose, manose, promovendo interações entre a celulose e a lignina Lignina: polímero baseado em fenilpropano, estruturado em grupos guaiacil, siringil and p-hidroxifenylpropano
  • 4. CONVERSÃO DA BIOMASSA CONVERSÃO DA BIOMASSA (CANA-DE-AÇÚCAR) 1 EXTRAÇÃO SACAROSE QUÍMICO GLUCOSE,FRUTOSE (MELAÇO) BIOQUÍMICO AÇÚCAR INVERTIDO CELULOSE BIOMASSA PRÉ-TRAT. HEMICELULOSE L-CEL FRACIONAMENTO LIGNINA (BAGAÇO) 2 HIDRÓLISE CELULOSE ÁCIDO DILUÍDO GLUCOSE HEMICELULOSE ÁCIDO CATALÍTICO HMF, DMF ENZIMÁTICO XILOSE, ARABINOSE, FURFURAL,
  • 5. CONVERSÃO DA BIOMASSA CONVERSÃO DA BIOMASSA (CANA-DE-AÇÚCAR) 3 OXIDAÇÃO LIGNINA QUÍMICO ALDEÍDOS AROMÁTICOS CATALÍTICO ÁCIDOS DERIVADOS 4 HIDROGENA SACAROSE QUÍMICO POLIÓIS ÇÃO GLUCOSE CATALÍTICO ÁCIDOS DERIVADOS HIDROGENÓ FRUTOSE ÉSTERES LISE XILOSE OXIDAÇÃO (MELAÇO, HIDROLISADOS) ESTERIFICA ÇÃO
  • 6. CONVERSÃO DA BIOMASSA CONVERSÃO DO BAGAÇO DE CANA-DE-AÇÚCAR BAGAÇO DE CANA-DE-AÇÚCAR CELULOSE HEMICELULOSE LIGNINA ACETATO SORBITOL / FURFURAL XILITOL RESINAS PLÁSTICOS VANILINA DE MANITOL FENÓLICAS CELULOSE
  • 7. The acid hydrolysis process Dilute acid hydrolysis, Low acid consumption Maximum monosaccharide yields reached at high temperatures and short residence times, Fast reaction rates Yields circa of 50-60% of the theoretical value Concentrated acid hydrolysis, Processed decomposing and dissolving the polysaccharides Occurs with water deficiency Production of oligosaccharides
  • 8. The acid hydrolysis process Limitations, Severe conditions (e.g. higher temperature, low pH) Formations of degradation by-products Furans and organic acids Monomeric hexoses and pentoses transformed into HMF and furfural, Further degradation into organic acids (e.g. levulinic, humic acids) and condensation reactions Dissolved lignin result in the formation of inhibiting phenolic compounds Corrosion of the equipment
  • 9. The acid hydrolysis process Production process of saccharidic mixtures to further processing, Degradation of corn starch or sugarcane hemicellulose in acid media Quantification of the oligomeric decompositions Selection of saccharidic mixtures to further catalytic treatements Kinetics of starch and pentosane depolymerization Consecutive evolutions of the oligomeric components Identification by the degree of polymerizations (DP6, DP5, DP4, DP3, DP2, DP1 = glucose, xylose,..).
  • 10. The acid hydrolysis process Starch and sugar cane bagasse hydrolysis, Native corn starch solutions were hydrolyzed at temperatures ranging 343 K to 373 K, producing glucose with yield circa 70% Sugar cane bagasse was hydrolised at 393 K, producing xylose, with approximate yield of 60% Abreu, C. A. M. et al. (1995) Biomass and Bioenergy Vol 9, No. 6, 487-492
  • 11. The acid hydrolysis process Mechanism Kinetics S+  AcH 1 → SH + Ac - dC S  k'  = −k ' C S 1 − ((C S O − C G ) dt  k  SH + H 2 O 1' → DPn + G DPn + AcH 2 → DPn H + Ac − 1/2 dC G    = k ' K AcH 1 − ' (C So − C G ) (C So − C G ) k DP H + H O 2 ' n → DP 2 +G n −1 dt   k  ---------------------------- DP + AcH n 2 → DP H + Ac - 1 DP1 H + H 2 O n   ' → G + G dC OL = k (C S − C G )1 − ' (C So − C G ) k dt  k  AcH ⇔ Ac - + H +
  • 12. CONVERSION OF CARBOHYDRATES Processing of raw materials rich in saccharides (sugarcane, starch, molasse, bagasse,…), Products with industrial application as polyols and organic acids Carbohydrate hydrogenations (saccharides → monosaccharides → polyols) Carbohydrate oxidations (saccharides → monosaccharides + acids → acids) Heterogeneous processes with supported catalysts based on nickel, chromium, ruthenium to hydrogenate glucose, fructose and sucrose to sorbitol and mannitol
  • 13. Hydrogenation of carbohydrates Heterogeneous mechanism
  • 14. 1st Brazilian Workshop on Green Chemistry Hydrogenation of carbohydrates Heterogeneous mechanism
  • 15. Hydrogenation of carbohydrates Saccharide hydrogenation process, Polyol production in a batch three-phase reactor Glucose conversions of 85% with a selectivity in sorbitol of 99.05% at 413K, under 24 bar, after 3 hours of reaction with a nickel catalyst (14.75 % weight)/activated carbon Saccharose conversions of 52% after 3 hours of reaction Production of glucose and fructose and sorbitol and mannitol L. C. A. Maranhão, F. G. Sales, J. A. F. R. Pereira, C. A. M. Abreu (2004) React. Kinet. Catal. Lett. 81, 169-175
  • 16. Hydrogenolysis of carbohydrates Saccharide hydrogenolysis process, More drastic temperature and hydrogen pressure conditions Splitting of carbon-carbon and carbon-oxygen carbohydrate bonds Polyols obtained from hydrogenations can be hydrogenolysed Products: other polyols, glycols and alcohols Catalysts: noble metals
  • 17. Continuous production of fine polyols Scale-up of carbohydrate hydrogenations, Fine polyols from biomass resources are traditionally produced in discontinuous processes Apparatus of great volume in relation to the small quantity of the obtained products Scale-up from discontinuous operations to continuous one Development of the saccharide hydrogenation process into a continuous operation Continuous polyol production
  • 18. Continuous production of fine polyols Continuous hydrogenation in a three-phase reactor, Trickle-bed reactor under moderate operation conditions (1.22 MPa, 413 K) Glucose conversions of 44% with a polyol selectivity of 99.31% Yield of 24% in sorbitol and mannitol for the saccharose hydrogenation Possibility to develop a process (pressures up to 2.54MPa, low liquid flow rates) to obtain high conversions Maranhão, L. A., Abreu, C. A. M. (2005) Industrial and Engineering Chemistry Research. v. 44, p. 9642-9645
  • 19. Continuous production of fine polyols 0,5 dC G ′ dC G η G k G C G Dax − uL − =0 0,4 dz 2 dz 1 + K G CG 0,3 glucose C (mol L-1) sorbitol model 0,2 f e φ G [coth (3φ G f e ) − ( f e 3φ G )] ηG = 0,1 ( ) 1 + φ G ShLG [coth (3φ G f e ) − ( f e 3φ G )] 0,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6 Axial position (m) Hydrogenation of glucose at 1.22MPa and 413K in trickle-bed reactor
  • 20. Continuous production of fine polyols 0,3 d 2 C Sac dC Sac Dax − uL ′ − η Sac k Sac C Sac = 0 dz 2 dz 0,2 C (mol L-1) saccharose d 2 C Mo dC Mo  ′ k Mo C Mo  0,1 monosaccharides Dax −u + η Mo  k Sac C Sac −  ′ =0  polyols model dz 2 dz  1 + K Mo C Mo  0,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6 d 2 C Po dC Po ′ k Mo C Mo Dax −u + η Po =0 Axial position (m) dz 2 dz 1 + K Mo C Mo Hydrogenation of saccharose at 1.22MPa and 413K in trickle- bed reactor.
  • 21. Continuous production of fine polyols An up grade of the discontinuous to the continuous process for saccharide hydrogenation may be compared in the following terms: Discontinuous process (slurry reactor) Continuous process (trickle-bed reactor) Ni/C catalyst; 413 K, 2.44 MPa Ni/C catalyst; 413 K, 1.22 MPa Operation time = 3 hours Operation time = 3 hours Concentration of the saccharide feed = Concentration of the saccharide feed = 100.00 g/L 100.00 g/L Production = 42.50 g in polyol Acumulated production = 749.35 g in polyol
  • 22. LIGNIN FROM BIOMASS Biomass conversion into aldehydes and acids, Lignin degradation: break up into fragments producing aromatic aldehydes Polifenate ions, precursors of the aromatic aldehyde formations Aldehyde conversion into organic acids
  • 23. LIGNIN PROCESSING FROM SUGARCANE BAGASSE Lignin oxidation, Wet air oxidation process (WAO) as an alternative technology Valorization of lignocellulosic materials Production of a mixture of aromatic aldehydes of industrial interest Catalytic wet air oxidation (CWAO) process using air and catalysts Treatment of effluents and by-product of the biomass industry
  • 24. Catalytic wet oxidation of lignin H 2COH CH CO H2 COH OCH3 1 H2COH HC HC 3 O CH H3CO O CH OCH3 4 2 H2 COH OCH3 HC O H3CO OCH3 O CHO (a) H 2COH HO O H2COH H O HC C H C OH C O 2 Pd γ − Al2 O CH //  3 →  HO C H  2 /γ−Al2 Pd/ O3 → O  + AcH Pd / γ−Al O3 →  2 / 2 O  2 + AcH 2 2 R1 R2 2 R1 R2 OH OH H3CO OCH3 O R1 R2 OH [ Lignin ] [ Aldehydes ] [ Acids ] (b) Basic structure of lignin and degradation/oxidation mechanism. (a) basic unit of the Fagus silvatic lignin. (b) degradation/oxidation reaction steps. R1= H, OCH3 ; R2 = OCH3 .
  • 25. Catalytic wet oxidation of lignin CWAO of lignin from sugar-cane bagasse was evaluated to produce aromatic aldehydes Lignin (L) is depolymerized with the productions of aldehydes, acids and other products of low molecular weights The aromatic aldehydes vanillin (V), syringaldehyde (S) and p-hydroxibenzaldehyde (P) were submitted to subsequent oxidations Other products (R), such as organic acids can degrade into carbon dioxide Reaction scheme of the catalytic wet oxidation of lignin
  • 26. Process operations Operations in a slurry reactor, Palladium catalyst, 373-413 K, 2-10 bar/ PO2 Lignin as a by-product from sugarcane bagasse by the DFH (Dedine Fast Hydrolysis) Yields of the aromatic aldehydes associated with lignin consumption and their oxidations to acids Aromatic aldehyde yields approximately ten to twenty times higher then with the noncatalytic oxidation process Sales, F. G. , Maranhão, L. A. , Lima Filho, N. M. , Abreu, C. A. M.( 2006). Industrial & Engineering Chemistry Research. v. 45, p. 6627-6631
  • 27. Processo continuo de produção de aldeídos aromáticos Scale-up of process, From batch to continuous operations Aromatic aldehyde productions operated in a continuous fluidized-bed reactor Lignin as a by-product from sugarcane bagasse Yields of the aromatic aldehydes associated with the lignin consumption and their oxidations to acids
  • 28. Processo continuo de produção de aldeídos aromáticos Three-phase fluidized-bed reactor
  • 29. Processo continuo de produção de aldeídos aromáticos Escalonamento, Batch operation: 56.24x10-2g of vanillin and 50.01x10-2g of syringaldehyde from a 0.50L-lignin solution (60.00g/L), 2 h of reaction at 5.00 bar and 393 K Continuous operation: 65.10x10-1g of vanillin and 114.84x10-1g of syringaldehyde, with a feed concentration of lignin of 30.00 g/L, 2 h of reaction, at 5.00 bar and 393 K, liquid-phase flow rate of 5.00 L/h F. G. Sales, L. C.A. Maranhão, N. M. Lima Filho, C. A.M. Abreu (2007) Chemical Engineering Science 62, 5386 – 5391
  • 30. Conclusions Recent technology developments done in the scope of the biorefinery concept have emerged as alternatives, making production of chemicals from ligno-cellulosic feedstocks become a reality. Biomass conversions employ hydrolysis and pretreatments of hemicellulose and lignin, and acid or enzymatic hydrolysis of cellulose to break the polymeric structures to their saccharides and lignin components. In the presence of homogeneous or heterogeneous catalysts the oligomeric mixtures selected may be processed in order to produce valuable chemicals. Through catalytic hydrogenation, hydrogenolysis or oxidation these mixtures can be converted to polyols, glycols, monoalcohols, aldehydes and organic acids.