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Inalbon Ma. CristinaInalbon Ma. Cristina,, Zanuttini MZanuttini M., Marzocchi V.., Marzocchi V.
ITCITC--FIQFIQ--UNLUNL
Mussati M.Mussati M.
INGARINGAR
Santa FSanta Fe, ARGENTINAe, ARGENTINA
MODELING of the ALKALINE MODELING of the ALKALINE
IMPREGNATION IMPREGNATION
of EUCALYPTUS CHIPS. of EUCALYPTUS CHIPS.
REACTIONS and ION TRANSPORTREACTIONS and ION TRANSPORT
id29577156 pdfMachine by Broadgun Software - a great PDF writer! - a great PDF creator! - http://www.pdfmachine.com http://www.broadgun.com
KRAFT
PROCESS
STEAMINGSTEAMING IMPREGNATIONIMPREGNATION
(105 (105 �� 120 120 ººC)C)
COOKING COOKING (165 (165 ººC)C)
Degree of impregnation
A proper impregnation leads to a more homogeneous pulp
A narrower kappa number distribution of the individual fibers can be obtained (Malkov et al. 2003).
Incomplete impregnation leads to:
Uncooked rejects (Gullichsen 1995).
Pulping yield (Gullichsen et al 1992, 1995).
Pulp strength (Gullichsen 1995).
Pulp bleachability (Malkov 2002).
Wood direction of interest
� The critical dimension for alkali
impregnation is the chip thickness
9 % NaOH/wood 9 % NaOH/wood
95 95 ººC C
30 min30 min
Partially impregnated chipPartially impregnated chip
Chip thickness: critical dimension
TangentialTangential
RadialRadial
transverse wood directionstransverse wood directions
Steaming stage and pressurized
impregnation : consequences
If wood has an acceptable permeability:
Steaming rapidly displaces the air from the chip.
Under these conditions, for eucalyptus wood, we have shown that:-Wood results almost saturated with liquid-No evidence of alkali inside wood was found(Inalbon y col. 2005).
A good steaming
+
pressurized impregnation
High liquid uptake
(Malkov et al 2001).
Liquor penetrationand reaction
Spent liquorpenetration
Chip
Liquid reaches the core of the chip
but alkali does not
Assumption
Impregnation (in thickness direction) is
considered:
- Isothermal process
- A diffusion process in wood saturated
with liquid (penetration has finished)
Chemical reactions
� a) Deacetilation.
� b) Acid groups neutralization or
hydrolysis of their esters.
� c) Peeling.
The deacetilation is the main reaction:
It accounts for most of the alkali consumption
(Zanuttini et al, 2003).
It can be taken as indicative of the wood
swelling produced by the alkali treatment
(Zanuttini et.al, 1999).
Chemical reactions consequences
� Alkali consumption (5 � 6 % on wood) � Chemical species
Mobile ions: a) Sodium +b) Hydroxide -c) Acetate -
Fixed: a) Acetyl groupsb) Non ionic acid groupsc) Ionized acid groups -
For the modeling we need:
� Kinetics of reactions
� Diffusion properties of each ion
Kinetics of reactions
a) Deacetylation
For the eucalyptus wood under study we made an experimental kinetic analysis :
Slices of wood (350 ìm) were treated under� different alkali concentrations� at 20º, 45º and 90 ºC.
Deacetylation kinetics
� Obtained expression:
53.1)()( 09.2 OHCAcetylsCkAcetylsR
TR
EAk T exp.)(
The k�constant follows the Arrhenius law:
Hydroxil concentrationCOH - :
Acetyl concentrationCAcetyls :
Specific rate constantk :
Temperature (ºK)T :
Relative activation energyE / R :
Arrhenius constant A :
Acid groups reactions
These reactions represent an additional alkali consumption (1 % NaOH on wood)
Assumption:
We consider them as coupled to deacetylation reaction (they have the same reaction rate)
Acid groups neutralizationAcid groups neutralization
Ester hydrolysisEster hydrolysis
Ion diffusion coefficients
� The concept of effective capillary (Stone 1957)allows considering for each ion
Diffusion
coefficient
in wood
Ion diffusion
coefficient in the
liquid mediumEffective Capillarity
(the same for all ions)
can be obtained
from literatureValues Di
0 can be
interpolated in temperature
using the Nernst-Einstein
equation (ui : ion mobility)
Di = EC. Di0
Di0
Di0 = ui.R.T
Effective capillarity
� We developed a method different from that used by Stone (1957):
Method:
Slices of wood (400 m) a low mass and
thermal diffusion
restriction
The evolution of electrical conductivity through slices,
was followed using laboratory conductivimeter
Electrical
conductivityIon diffusion
EC determination
Slices were placed between electrodes of the
conductivimeter cell
The slice was considered as a series The slice was considered as a series electrical circuit with the solutionelectrical circuit with the solution
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
7 8 9 10 11 12 13 14
pH
Eff
ec
tiv
e c
ap
illa
ry
20ºC-60 min
20ºC
EffectiveEffective CapillarityCapillarity vs. vs. pHpH
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
7 8 9 10 11 12 13 14
pH
Eff
ec
tiv
e c
ap
illa
ry
20ºC-60 min
45ºC-60 min
20ºC
45ºC
T
EffectiveEffective CapillarityCapillarity vs. vs. pHpH
EffectiveEffective CapillarityCapillarity vs. vs. pHpH
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
7 8 9 10 11 12 13 14
pH
Eff
ec
tiv
e c
ap
illa
ry
20ºC-60 min
45ºC-60 min
90ºC-60 min
90ºC
20ºC
45ºC
T
EffectiveEffective CapillarityCapillarity vs. vs. pHpH
0
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
7 8 9 10 11 12 13 14
pH
Eff
ec
tiv
e c
ap
illa
ry
20ºC-60 min
45ºC-60 min
90ºC-60 min
Stone, 25ºC, 24 hs
90ºC
20ºC
45ºC
T
0
0,05
0,1
0,15
0,2
0,25
0,3
0,0 1,0 2,0 3,0 4,0
Acetyl content (%)
Eff
ec
tiv
e c
ap
illa
ry
pH 12
20ºC
EffectiveEffective CapillarityCapillarity vs. vs. AcetylAcetyl contentcontent
0
0,05
0,1
0,15
0,2
0,25
0,3
0,0 1,0 2,0 3,0 4,0
Acetyl content (%)
Eff
ec
tiv
e c
ap
illa
ry
pH 12
pH 13
20ºC
Effective Capillary vs. Acetyl contentEffective Capillary vs. Acetyl content
0
0,05
0,1
0,15
0,2
0,25
0,3
0,0 1,0 2,0 3,0 4,0
Acetyl content (%)
Eff
ec
tiv
e c
ap
illa
ry
pH 12
pH 13
pH 13.5
20ºC
Effective Capillary vs. Acetyl contentEffective Capillary vs. Acetyl content
0
0,05
0,1
0,15
0,2
0,25
0,3
0,0 1,0 2,0 3,0 4,0
Acetyl content (%)
Eff
ec
tiv
e c
ap
illa
ry
pH 12
pH 13
pH 13.5
pH 14
20ºC
Effective Capillary vs. Acetyl contentEffective Capillary vs. Acetyl content
EC depends on:
- Concentration of alkali
- Temperature
- Time
EC EC dependsdepends onon::
-- TemperatureTemperature
-- DeacetilationDeacetilation degreedegree
An empiric equation of Capillarity as a function
of acetyl content and temperature was used for
modeling
EC = EC = f(Acf(Ac, T), T)
Ac : Acetyl content T : Temperature
Modeling
i
iiii
i
i RxRT
cFDz
x
cD
xt
c
DiffusionInteraction
between ions
Chemical
reactions
For each chemical species we consider:
Diffusion coefficient of � i�Di :
Position from the external interphasex :
Time t :
Molar concentration of � i � specieci :
Where:
Differential equations system
Reaction rateRi :
Electric potential :
Faraday constantF :
Charge number of � i �zi :
It involves 9 differential equations and 9 variables
in space and time:
6 chemical species concentrations
Deacetylation rate
Effective Capillary
Electrical potential
ResultsResults
Na+
Co
ncen
tratio
n(m
ol/
l)
Position (cm)
Co= 0.5 M; T=110ºC; 15 minutes
ResultsResults
Co
ncen
tratio
n(m
ol/
l)Co= 0.5 M; T=110ºC; 15 minutes
Position (cm)
OH-
Na+
ResultsResults
Co
ncen
tratio
n(m
ol/
l)Co= 0.5 M; T=110ºC; 15 minutes
Position (cm)
AcetylsOH-
Na+
ResultsResults
Co
ncen
tratio
n(m
ol/
l)Co= 0.5 M; T=110ºC; 15 minutes
Position (cm)
Acetate
AcetylsOH-
Na+
Co
ncen
tratio
n(m
ol/
l)Co= 0.5 M; T=110ºC; 15 minutes
Position (cm)
AG
Acetate
AcetylsOH-
Na+
ResultsResults
nrAG
ResultsResults
Co
ncen
tratio
n(m
ol/
l)Co= 0.5 M; T=110ºC; 15 minutes
Position (cm)
AG
Acetate
AcetylsOH-
Na+
nrAG
Model vs. Experimental Data
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls exp
0.25N ; 105ºC; 5 minutes
Model vs. Experimental Data
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls
acetyls exp
0.25N ; 105ºC; 5 minutes
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls
acetyls exp
Na+ exp
Model vs. Experimental Data
0.25N ; 105ºC; 5 minutes
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls
Na+
acetyls exp
Na+ exp
Model vs. Experimental Data
0.25N ; 105ºC; 5 minutes
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls
Na+
acetyls exp
OH- exp
Na+ exp
Model vs. Experimental Data
0.25N ; 105ºC; 5 minutes
0,25N; 105ºC; 5 minutes
0
0,5
1
1,5
2
2,5
3
3,5
4
0 500 1000 1500 2000
Position (microns)
Con
tent
(%
on
woo
d)
acetyls
OH-
Na+
acetyls exp
OH- exp
Na+ exp
Model vs. Experimental Data
0.25N ; 105ºC; 5 minutes
C0: 0.25 N; 110ºC
1 min
Acetyl Groups
OH-
C0: 0.25 N; 110ºC
5 min
C0: 0.25 N; 110ºC
10 min
C0: 0.25 N; 110ºC
15 min
C0: 0.25 N; 110ºC
20 min
C0: 0.25 N; 110ºC
25 min
C0: 0.25 N; 110ºC
30 min
C0: 0.25 N; 110ºC
35 min
C0: 0.25 N; 110ºC
40 min
C0: 0.25 N; 110ºC
50 min
C0: 0.25 N; 110ºC
70 min
C0: 0.25 N; 110ºC
90 min
Application
For a given wood and set of conditions: For a given wood and set of conditions:
�� A sequence like this can give a criterion A sequence like this can give a criterion
to take a decision regarding the extent of to take a decision regarding the extent of
impregnation stageimpregnation stage
0
0,02
0,04
0,06
0,08
0,1
0,12
0,14
0,16
0,18
0,2
0,22
0 10 20 30 40
Time (minutes)
Po
sit
ion
(c
m)
105ºC-0,25N
Front Position vs. Time
Chip center
Inter-phase
0
0,02
0,04
0,06
0,08
0,1
0,12
0,14
0,16
0,18
0,2
0,22
0 10 20 30 40
Time (minutes)
Po
sit
ion
(cm
)
105ºC-0,25N
105ºC-0,5N
Front Position vs. Time
0
0,02
0,04
0,06
0,08
0,1
0,12
0,14
0,16
0,18
0,2
0,22
0 10 20 30 40
Time (minutes)
Po
sit
ion
(c
m)
105ºC-0,25N
105ºC-0,5N
105ºC-1N
0,25 N1 N 0,5 N
Front Position vs. Time
0
0,02
0,04
0,06
0,08
0,1
0,12
0,14
0,16
0,18
0,2
0,22
0 10 20 30 40
Time (minutes)
Po
sit
ion
(c
m) 105ºC-0,25N
105ºC-0,5N
105ºC-1N
110ºC-0,25N
110ºC-0,5N
110ºC-1N
Temperature
0,25 N1 N 0,5 N
Front Position vs. Time
0
0,02
0,04
0,06
0,08
0,1
0,12
0,14
0,16
0,18
0,2
0,22
0 10 20 30 40
Time (minutes)
Po
sit
ion
(c
m)
105ºC-0,25N
105ºC-0,5N
105ºC-1N
110ºC-0,25N
110ºC-0,5N
110ºC-1N
120ºC-0,25N
120ºC-0,5N
120ºC-1N
Temperature
0,25 N1 N 0,5 N
Front Position vs. Time
Speed of impregnation
� Model shows that a change in alkali concentration
from 0.25 M to 1.0 M speeds up impregnation more than an
increase in temperature from 105 to 120 ºC
Concluding Remarks (1)
This model allows the analysis of the effects
of impregnation variables such as :
external alkali concentration
temperature
time
chip thickness.
For a specific wood:
effective capillary
kinetic parameters
Should be experimentally verified before
the application of the model
Concluding Remarks (2)
Phenomenon: A reaction front is
established which moves to the interior of
the wood and separates an intact inner zone
from a reacted outer zone
The alkali profile differs from Sodium
concentration profile; the latter goes in the
front of the former
Concluding Remarks (3)
Besides the variables here analyzed, the model allows considering:
a) Additional ions such as sulfide; hydrosulfide, carbonate and others
b) Chip thickness distribution
c) Changes in external alkali concentration
including different alkali profiling scenarios
Deacetylation in biofuel production
Capillarity
1) to determine2) to promote it by deacetilation
Are useful to analize the effects of pre-treatments for fermentation processes
Deacetylation and Capillarity
Pretreatment
Fermentation
Biological treatment
Capillarity
Wood
� Thanks for your attention !