LABORATÓRIO
LABORAT
ÓRIO ASSOCIADO
Laboratory of Separation and Reaction Engineering
Processo integrado de preparação de vanilina
e poliuretanos a partir da lenhina kraft
Equipe de investigação:
Alírio E. Rodrigues
Mª. Filomena F. Barreiro
Eduardo A. B. da Silva
Miriam Zabkova
José Daniel P. Araújo
Carolina A. B. Cateto
- Encontro Ciência em Portugal – Ciência 2008 -
FEUP – julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
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LSRE - FEUP - julho/2008
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Industrial use of biomass from forestry today
Lignin based
Pulp for
specialty chemicals
paper
Burning
Fibres
45 %
Lignin
(Energy and
chemicals recovery)
Specialty
cellulose for
30%
chemicals
Sugars
25%
Pollution
(Dumping into sea or
rivers)
Ethanol
Xylitol
CO2
Yeast
SoyPass
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LSRE - FEUP - julho/2008
Future industrial use of biomass from forestry
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Fiber for plastics
Lignin based
Pulp for
specialty chemicals
paper
Burning
(Energy and
chemicals recovery)
Fibres
45 %
Lignin
Specialty
cellulose for
30%
Bioplastics
chemicals
Sugars
25%
Phenolic chemicals
Ethanol fuel
Basic
chemicals
Xylitol
SoyPass
Ethanol
(diols)
CO2
Pollution
Yeast
SoyPreme
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LSRE - FEUP - julho/2008
Final Products
PART II
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Antioxidant and
antimicrobial properties
Flavoring material
Fragrance
food preservative; antimutagenic effect
Vanillin
THE WORLD
MARKET
Chemical and
pharmaceutical industries
(drags, herbicides, antifoaming agents
air-fresheners, floor polishes)
1800 ton of pods
(price 1200-4000$/kg)
12000 ton industrial
(price 15$/kg)
Chemical Synthesis:
Guaiacol and glyoxylic acid,
acid
black liquors from the paper industry
Vanillin separation
Acidification of the liquor and extraction ( benzene or toluene)
Extraction of sodium vanillate from the alkaline solution by alcohols
Ultrafiltration and ion-exchange process
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LSRE - FEUP - julho/2008
Final Products
PART II
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Antioxidant and
antimicrobial properties
Flavoring material
Fragrance
food preservative; antimutagenic effect
Vanillin
THE WORLD
MARKET
Chemical and
pharmaceutical industries
(drags, herbicides, antifoaming agents
air-fresheners, floor polishes)
1800 ton of pods
(price 1200-4000$/kg)
12000 ton industrial
(price 15$/kg)
Chemical Synthesis:
Guaiacol and glyoxylic acid,
acid
black liquors from the paper industry
Vanillin separation
Acidification of the liquor and extraction ( benzene or toluene)
Extraction of sodium vanillate from the alkaline solution by alcohols
Ultrafiltration and ion-exchange process
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LSRE - FEUP - julho/2008
Final Products
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Biofuels
LIGNIN
Biopolymers
Lignin-based polyurethanes:
Rigid Foams
ElastomerS
ElastomerS
LignoBoost Technology
SealantS
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LSRE - FEUP - julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
8
LSRE - FEUP - julho/2008
Lignin Oxidation Route – Vanillin Production
LABORATÓRIO
LABORATÓRIO ASSOCIADO
high pH
Vanillin concentration and pH (*) versus reaction time.
T= 154 °C, [L]o= 60 g/L, PO2= 4 bar, Ptot=9.7 bar.
C. Fargues, A. Mathias, J.Silva and A. Rodrigues, Kinetics of vanillin
oxidation, Chem. Eng. Technol., 1996, 19, 127-136.
Mathias, A.L., Rodrigues, A. E., Production of vanillin by oxidation of pine
kraft lignins with oxygen., Holzforschung, 1995, 49 (3), 273-278.
Experimental setup for kinetic studies of vanillin
production from Kraft lignin.
Optimal vanillin yield in a batch
reactor (8-10%) [Fargues et al., 1996]:
Oxygen partial pressure= 2.8 bar;
Temperature= 133 ºC;
Initial lignin conc. = 60 g/l;
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LSRE - FEUP - julho/2008
Lignin Oxidation Route – Vanillin Production
(Continuous Process)
LABORATÓRIO
LABORATÓRIO ASSOCIADO
high pH
Schematic of the structured bubble
column reactor (SBCR).
Effect of lignin molecular weight on
the yield of vanillin (CLign. = 60 g/l;
MW= 3050), T = 120 ºC, PO2=6,5
atm).
Sridhar P., Araújo J.D., Rodrigues A.E.; Modelling
of vanillin production in a structured bubble
column reactor; Catalysis Today; Issues 3-4;
Volume 105; p. 574-581; 2005.
10
LSRE - FEUP - julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
11
LSRE - FEUP - julho/2008
Membrane ultrafiltration process for the recovery of
vanillin from Kraft lignin oxidation media
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Lignin+Vanillate
Vanillate
(60kDa) (152 Da)
* Batch concentration mode *
Scheme of the experimental set-up for batch
ultrafiltration.
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LSRE - FEUP - julho/2008
Theoretical models: concentration profile within the
polarization layer and membrane surface concentration.
Mathematical Modelling
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Tubular ceramic membranes.
Histories of the vanillin and lignin concentration in
ultrafiltration - 15 kDa cut-off membrane.
Feed:60/6 g L-1 at
pH=12.5;
Retentate side:
Permeate side:
• M. Zabkova, E.A. Borges da Silva and A. Rodrigues; Recovery of vanillin from lignin/vanillin mixture by using
tubular ceramic ultrafiltration membranes Journ.Memb.Sci.301(1-2);
221-237; ( 2007)
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LSRE - FEUP - julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
14
LSRE - FEUP - julho/2008
Ion-exchange for the system vanillin/NaOH
on Amberlite IR120H
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Salt of vanillin (VNa)
in alkaline condition
Resin-phase:
Amberlite IR120H
Ion-exchange histories of the system Na+ ions, vanillate,
vanillin and pH. Feed solution: mixture of 0.04 equiv/L
NaOH and vanillin (pH=11.4).
Column (15x2 cm, I.D.); Q = 19 cm3 min-1; pHo = 6.1; 20ºC.
Vanillin
Ion-exchange process is
coupled with neutralization
reaction in presence of a buffer
solution (vanillate/vanillin).
• M. Zabkova, E.A. Borges da Silva, A. Rodrigues; Recovery of vanillin from Kraft lignin oxidation by ion-exchange
with neutralization. Sep. Pur. Techn., 55(1), 56-68 (2007).
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LSRE - FEUP - julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
16
LSRE - FEUP - julho/2008
Integrated Process for preparation of vanillin and
polyurethanes from Kraft lignin
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Kraft lignin oxidation for recovery of synthetic vanillin and
biopolymers
high pH (~12)
17
LSRE - FEUP - julho/2008
Lignin based polyurethanes
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Preparation of elastomers (Lignin+PCL+MDI)
In cooperation with • ••••
Initial
sample
PCL1000 (20%)
“GEL-LIKE”
MATERIAL
10, 15, 20
LIGNIN
and 25%
PCL 1000
PCL 750
PCL 400
LINEAR POLYOL
C=O
1
ISOCYANATE
Absorbance
8
BRITTLE
MATERIAL
ELASTIC
MATERIAL
MDI
PCL750 (20%) PCL400 (20%)
6
NCO
OH NH (3100-3600 cm-1)
4
SWELLING TESTS (DMF – 3 days)
1500
20
2
1000
PCL1000
PCL750
PCL400
500
0
0
1600-1800
cm-1
2500
2270
cm-1
300 0
CH2
2870
cm-1
3500
Frequency
15
(cm-1)
1/(1-p)
2 0 00
TYPICAL THREE-DIMENSIONAL PLOT OF AN FTIR EXPERIMENT
• Cateto, C.A., Barreiro M.F., Rodrigues, A.E., “Monitoring of lignin-based polyurethane synthesis
by FTIR-ATR” Industrial Crops and Products, 27, 168-174 (2008).
• Cateto, C.A., Barreiro M.F., Rodrigues, A.E., Belgacem, M.N., “Lignin based polyurethane
elastomers – Mechanical and thermal properties” – To be presented at BIO&POLYMERS (AachenGermany, October-2008)
10
5
0
0
5
10
15
20
25
30
T ime (minutes)
KINETIC STUDIES
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LSRE - FEUP - julho/2008
Lignin based polyurethanes
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Preparation of rigid foams (lignin as filler or as liquid polyol-oxypropylation)
Lignin-based
polyurethane
foams
present
insulating
properties,
dimensional stability and accelerated
ageing properties very similar to those
prepared with commercial polyols.
The natural properties of lignin
contribute to an improvement of
moisture and flame resistance.
In cooperation with • ••••
POLYOL TECHNICAL REQUIREMENTS
300 < IOH < 800 (mg KOH/g)
Viscosity < 300 Pa.s
①
②
③
④
1. Solid lignin; 2. Oxypropylated lignin (liquid polyol); 3. Lignin-based rigid foams; 4. SEM analysis
• Cateto, C.A., Barreiro M.F., Rodrigues, A.E., Belgacem, M.N., “Oxypropylation of lignins and characterization of the ensuing
polyols” Proceedings of 8th ILI Forum, p. 115-119 (2007).
• Cateto, C.A., Barreiro M.F., Rodrigues, A.E., Belgacem, M.N., “Rigid polyurethane foams from lignin-based polyols” – To be
presented at TOP (Ishida - Italy, October-2008)
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LSRE - FEUP - julho/2008
Projects
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Production of vanillin from lignin – process development
(POCTI/EQU/33198/99; Prof. Alírio Rodrigues)
Biodegradable macromolecules from lignins
(CYTED IV.17/2002-2006; Profa. Ma. Filomena Barreiro)–
Purification of vanillin from the lignin oxidation broth
(POCI/EQU/61738/2004; Prof. Alírio Rodrigues/Inv. Eduardo A.B.
da Silva)
Poliuretanos derivados da lenhina: formação, caracterização e
aplicações
(ACÇÃO LUSO-FRANCESA F13/06; Prof. Alírio Rodrigues/ Prof.
Ma. Filomena Barreiro/ Naceur Belgacem (EFPG-INPG) Partners: FEUP|IPB|Institute Polytech. Nationale Grénoble)
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LSRE - FEUP - julho/2008
LABORATÓRIO ASSOCIADO
LABORATÓRIO
LABORATÓRIO ASSOCIADO
Laboratório Associado LSRE/LCM
Laboratory of Separation and Reaction Engineering
Prof. Alírio Rodrigues ([email protected])
Prof. Ma. Filomena Barreiro* ([email protected])
* Instituto Politécnico de Bragança
Dr. Eduardo A.B. da Silva ([email protected])
Dr. Miriam Zabkova ([email protected])
Eng. José Daniel Pacheco de Araújo ([email protected])
Eng. Carolina A. Borges Cateto ([email protected])
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LSRE - FEUP - julho/2008