itc – fiq – unl - argentina research group20... · 2009. 8. 4. · 3,0 3,5 stoichiometric...
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ResearchResearch groupgroupnn Professor:Professor: Miguel ZanuttiniMiguel Zanuttini
Researchers:Researchers:nn Victorio Victorio MarzocchiMarzocchinn PaulinaPaulina MocchiuttiMocchiuttinn M. Cristina InalbonM. Cristina Inalbon
ITC ITC –– FIQ FIQ –– UNL UNL -- ArgentinaArgentina
Some research topics:Some research topics:nn Chemical pulping (Impregnation)Chemical pulping (Impregnation)
nn Mechanical PulpingMechanical Pulping
nn RecyclingRecycling
nn Fibre characterizationFibre characterization
Alkali ImpregnationAlkali Impregnation
Impregnation of eucalyptus and pine Impregnation of eucalyptus and pine wood in alkaline pulping processes. wood in alkaline pulping processes. Effects of steaming and pressurized Effects of steaming and pressurized impregnationimpregnation
Inalbon et al.Inalbon et al.
ABTCP Conference 2004, October, San Pablo, BrazilABTCP Conference 2004, October, San Pablo, Brazil
Chip Impregnation for pulpingChip Impregnation for pulpingA proper A proper
Penetration of liquidsPenetration of liquids
Diffusion of chemicalsDiffusion of chemicals
Both are necessary for optimal efficiency of:
Chemical pulping Chemical pulping
Chemimechanical pulpingChemimechanical pulping
The alkaline impregnation The alkaline impregnation phenomenon is complex.phenomenon is complex.
It impliesIt implies::••Air removing Air removing
••Penetration in the longitudinal direction Penetration in the longitudinal direction
••Diffusion in all directions.Diffusion in all directions.
••Chemical reactions Chemical reactions
••Wood properties like Wood properties like ““alkali diffusion alkali diffusion coefficientcoefficient”” are chemically modified are chemically modified
Issues not considered in the literatureIssues not considered in the literature
Consumption could be as highConsumption could be as highas 6.0 or 7.0 % NaOH / woodas 6.0 or 7.0 % NaOH / wood
0,00 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,080,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
Stoichiometricconsumption
Original wood
50 oC 70 oC 90 oC
AC
ETYL
S (%
)
CONSUMPTION ( g NaOH / g wood )
•• Deacetylation is the main reaction and is the Deacetylation is the main reaction and is the main responsible for alkali consumption.main responsible for alkali consumption.
WeWe determineddetermined::
The pattern of the pressurized alkaline The pattern of the pressurized alkaline impregnation:impregnation:
Profiles of:Profiles of:
•• alkali alkali concentrationconcentration
•• alkali contentalkali content
pine and eucalyptuspine and eucalyptuswoodwood
steamed woodsteamed wood
•• liquid content liquid content
•• acetyls contentacetyls content
ExperimentalExperimental
200 200 mmmm
Wood treatmentWood treatment
nn Steaming (105oC, 10 minutes)Steaming (105oC, 10 minutes)nn Immersion in liquor (10 gNaOH/L, 110oC)Immersion in liquor (10 gNaOH/L, 110oC)nn Pressurization to 6.0 barPressurization to 6.0 barnn Relief of pressure while wood cube are Relief of pressure while wood cube are
immersedimmersednn Take out from digester and immediate Take out from digester and immediate
immersion of the cubes in liquid Nitrogenimmersion of the cubes in liquid Nitrogen
Slicing of treated cubes Slicing of treated cubes
Wood Wood sample is sample is still frozenstill frozen
Slices are weighed, and chemically analyzedSlices are weighed, and chemically analyzed
Tangential Tangential face of face of
impregnated impregnated woodwood
1 cm
1 cm1 cmWood vesselsWood vessels
0
2
4
6
8
10
12
0.0 0.5 1.0 1.5 2.0
POSITION FROM THE SURFACE (mm)
ALKALI (g NaOH / L) ALKALI (g NaOH / kg) ACETYLS (x10) LIQUID (x5 g water/g) REACTION ZONE
INNER ZONE
REACTION ZONEOUTER ZONE
ACETYLS
ALKALI
EucalyptuEucalyptuss
Mechanism of the chip Mechanism of the chip impregnationimpregnation
Spent liquor penetration
Liquor penetration and reaction
Liquor diffusion and reaction
If the speed of moving front is If the speed of moving front is known, the level of impregnation known, the level of impregnation
can be predictedcan be predicted
00.2
0.40.6
0.81
1.21.4
0 10 20 30 40 50Time (min)
Che
mic
al Im
preg
natio
n (m
m)
The chip The chip halfhalf--thickness thickness distributiondistribution
Fraction of Fraction of impregnated woodimpregnated wood
Conclusions (1)Conclusions (1)
nn Steaming (5 minutes) and pressurized Steaming (5 minutes) and pressurized immersion (6 Bar) can complete immersion (6 Bar) can complete liquid liquid impregnation impregnation
nn Initially alkali does not reach the core a Initially alkali does not reach the core a chipchip
nn The The chemical impregnationchemical impregnation takes place takes place by reaction and diffusion. A front of the by reaction and diffusion. A front of the impregnation is always established.impregnation is always established.
Conclusion (2)Conclusion (2)
The time needed for chemical impregnation The time needed for chemical impregnation (when front reaches the center of the chip) (when front reaches the center of the chip) can be predicted for a given wood and can be predicted for a given wood and determined treatment conditionsdetermined treatment conditions
Marcelo Moreira CostaMarcelo Moreira Costa –– Veracel, EunVeracel, Eunáápolis polis -- BA, BrazilBA, Brazil
JosJoséé LLíívio Gomidevio Gomide -- Universidade Federal de ViUniversidade Federal de Viççosa, osa, ViViççosaosa--MG, BrazilMG, Brazil
Miguel ZanuttiniMiguel Zanuttini –– UNL, Santa FUNL, Santa Féé, Argentina, Argentina
E. SouzaE. Souza and and M. NetoM. Neto -- Cenibra, Belo Oriente Cenibra, Belo Oriente -- MG, BrazilMG, Brazil
ABTCP Conference 2004 San Pablo, BrasilABTCP Conference 2004 San Pablo, Brasil
KRAFT IMPREGNATION STUDIES FOR KRAFT IMPREGNATION STUDIES FOR EUCALYPTUSEUCALYPTUS WOOD CHIPSWOOD CHIPS
Alkali content in the center of the chip at the Alkali content in the center of the chip at the end of impregnationend of impregnation
1,636 2,118 2,601 3,083 3,565 4,048 4,53 5,012 5,495 5,977 above
550 kg/m ³
Time x Time x TemperatureTemperature
Alkali Alkali ConcentrationConcentration
Alkali Alkali ContentContent
Mechanical PulpingMechanical Pulping
Mechanical PulpingMechanical Pulping
We have studied:We have studied:
nn Bagasse Alkaline CMPBagasse Alkaline CMP
nn Alkaline CMP from HardwoodAlkaline CMP from Hardwood
Effects of alkali charge in bagasse Effects of alkali charge in bagasse chemimechanical pulping. Part I and Part II chemimechanical pulping. Part I and Part II
Zanuttini, M.Zanuttini, M. ITC ITC –– ArgentinaArgentina
Christensen P.K.Christensen P.K. –– NTH NTH –– Trondheim Trondheim -- NorwayNorway
Appita 44(3):191 (1991) and 44(4):257 (1991)Appita 44(3):191 (1991) and 44(4):257 (1991)
Study performed at NTH, Trondheim, NorwayStudy performed at NTH, Trondheim, Norway
Grafica Grafica scattering scattering –– traccitraccióónn
Bagasse Bagasse CMPCMP
AlkaliAlkali
RefiningRefining
nn CMP was obtained using the CMP was obtained using the 2020““ Disk Refiner Disk Refiner
nn From different furnishes, From different furnishes, newsprint paper was obtained newsprint paper was obtained for printing testfor printing test
Alkaline Chemimechanical Pulp from Alkaline Chemimechanical Pulp from Poplar. Poplar. Relationship between Chemical State, Relationship between Chemical State, Swelling and PropertiesSwelling and Properties
M. ZANUTTINI and V. MARZOCCHIM. ZANUTTINI and V. MARZOCCHIHolzforschungHolzforschung 57(5) 200357(5) 2003
nn For sulphite CTMP pulp , Sulphonation For sulphite CTMP pulp , Sulphonation degree is a chemical parameter that degree is a chemical parameter that determines pulp properties .determines pulp properties .
nn We have found that for a hardwood alkaline We have found that for a hardwood alkaline CMP, acetyl groups content is a parameter CMP, acetyl groups content is a parameter useful to control propertiesuseful to control properties
ExperimentalExperimental
•Wafers of poplar wood were alkali treated.Variables: Temperature and alkali concentration.
•Treated wafers were hot defibrated in a 300-mm disk mill at 15 % consistency, and then refined in PFI mill at 20 % consistency
RefiningRefining PulpPulp
PropertiesPropertiesAlkali Alkali treatmenttreatment
woodwood
0.0 0.2 0.4 0.6 0.8 1.040
6080
100
0
1
2
3
4
5
6
Con
sum
ptio
n (%
NaO
H /
woo
d)
Tem
pera
ture
(o C)
Alkali (g NaOH / L)
Fig. 1. Response surface of alkali consumption as function of Fig. 1. Response surface of alkali consumption as function of treatment conditions. Alkali concentration is expressed in treatment conditions. Alkali concentration is expressed in
coded unit. coded unit.
0
10
20
30
40
50
0.0 1.0 2.0 3.0
DEACETYLATION (% )
TEN
SIL
E IN
DE
X (N
m/g
) 50ºC70ºC90ºCMechanical pulp
CMP Tensile strength CMP Tensile strength –– deacetylation degreedeacetylation degree
Recycling of unbleached fiberRecycling of unbleached fiber
Ozone applicationOzone application
Upgrading OCC Pulp by MediumUpgrading OCC Pulp by Medium--consistency Ozone Treatmentconsistency Ozone Treatment
M. Zanuttini* and T. McDonough**M. Zanuttini* and T. McDonough*** Institute of Cellulose Technology * Institute of Cellulose Technology -- Santa Fe Santa Fe --ArgentinaArgentina** Institute of Paper Science and Technology ** Institute of Paper Science and Technology ––
Atlanta Atlanta -- USAUSA
2002 ABTCP Conference, San Pablo, Brazil2002 ABTCP Conference, San Pablo, Brazil
nn Low levels of ozone at medium consistency was Low levels of ozone at medium consistency was analyzed. analyzed.
nn Starting materials: Starting materials: §§ OCCOCC: Industrial : Industrial ““Old Corrugating ContainerOld Corrugating Container””§§ Kraft linerKraft liner§§ Fluting:Fluting: Corrugating medium from hardwood Corrugating medium from hardwood
green liquor green liquor semichemicalsemichemical pulppulp
nn A comparison is made with action of alkali and A comparison is made with action of alkali and refining on refining on OCCOCC pulppulp
High Shear MixerHigh Shear MixerCRS ReactorCRS Reactor
(Sweden)(Sweden)
Expandable zoneExpandable zone(2,5 liter) (2,5 liter)
Mixing zoneMixing zone(2,1 liter)(2,1 liter)
Tensile Energy AbsorptionTensile Energy Absorption
0.0
0.5
1.0
1.5
0 0.2 0.4 0.6 0.8 1Ozone (%)
TEA
(J/g
)LinerFlutingOCC
+ 25 %
Concora Crush ResistanceConcora Crush Resistance
110120130140150160170180
0 0.2 0.4 0.6 0.8 1Ozone (%)
CM
T (N
)
LinerFlutingOCC
+ 16 %
Some conclusionsSome conclusions
The application of low level of ozone at The application of low level of ozone at medium consistency can notably medium consistency can notably increase increase CMTCMT, , SSCTSSCT and and internal internal bonding strengthbonding strength..
Similar improvement can be obtained by alkali treatment of OCC. Alkali affects more pulp freeness and produces a higher organic load on the effluents.
Laccase application on Laccase application on highhigh--lignin content pulp lignin content pulp
Hypothesis:Hypothesis:
Delignification and lignin modification Delignification and lignin modification can improve papermaking properties.can improve papermaking properties.
Enzymes from:Enzymes from:••VTT Biotechnology, Espoo, FinlandVTT Biotechnology, Espoo, Finland••Spegazzini Institute, La Plata, Spegazzini Institute, La Plata, ArgentineArgentine
ExperimentalExperimentalFibers from softwood kraft pulp Fibers from softwood kraft pulp (kappa number 90).(kappa number 90).
LaccaseLaccase -- Mediator System:Mediator System:
•• Mediator: HBTMediator: HBT
•• Oxygen bubblingOxygen bubbling
•• Control of the enzyme activity during Control of the enzyme activity during treatmenttreatment
Optimized Alkali TreatmentOptimized Alkali Treatment
ResultsResultsLMS + Alkaline Treatment (45 min- 2% (g/g dried pulp))
20
25
30
35
40
45
0.40 0.41 0.42 0.43 0.44 0.45 0.46 0.47 0.48
Apparent density (g/cm3)
Tens
ile In
dex
(kN
m/k
g)
LMS + Alkaline Treatment
HBT: 3% (g/g dried pulp)Enzyme Charge: 425 (nkat/g dried pulp)
control
LMS
Alkali
LMS + Alkaline Treatment (45 min-2%(g/dried pulp))
20
25
30
35
40
45
17 17.5 18 18.5 19 19.5 20 20.5 21 21.5 22
"k" coefficient (m2/kg)
Tens
ile In
dex
(kN
m/k
g)
LMS
LMS + Alkaline Treatment
HBT: 3% (g/g dried pulp)Enzyme Charge: 425 (nkat/g dried pulp)
Control
ResultsResults onon lacasselacasse aplicationaplication
nn Mocchiutti, P. , M. Zanuttini, K. Kruus And A Mocchiutti, P. , M. Zanuttini, K. Kruus And A SuurnSuurnääkki. kki. ““Improvement of the Fibre Bonding Improvement of the Fibre Bonding Capacity of Unbleached Recycled Pulp by Capacity of Unbleached Recycled Pulp by Laccase/Mediator TreatmentLaccase/Mediator Treatment””. . Tappi JournalTappi Journal(10) 17(10) 17--22, 22, 2008.2008.
Determination of Surface Acidic Determination of Surface Acidic GroupsGroups
Chemical fibre Chemical fibre characterizationcharacterization
Determination of Surface Acid Groups.Determination of Surface Acid Groups. Specific Specific adsorption of adsorption of pDMDAACpDMDAAC vs. equilibrium concentration vs. equilibrium concentration
of the polymer in solution. Adsorption Isotherm.of the polymer in solution. Adsorption Isotherm.
0.00 0.02 0.04 0.06 0.08 0.10 0.12
05
10152025
Spe
cific
adso
rptio
n(µ
eq/g
pul
p)
Equilibrium polymer concentration (µeq/ml)
Mm :amount of polyelectrolyte stoichiometrically adsorbed (µeq/g pulp)
( ) ( )xcx1x1xc
MmM
⋅+−⋅−⋅
=
Proposed Equation:
Surface Acid Groups. Specific adsorption of Surface Acid Groups. Specific adsorption of pDMDAACpDMDAAC onto the pulps dried at 60onto the pulps dried at 60ººC for 48h C for 48h
under NO restraint under NO restraint with 0%, 0.8% and 2% of C.S. with 0%, 0.8% and 2% of C.S. adsorbedadsorbed
0
10
20
30
0.00 0.05 0.10 0.15
Equilibrium polymer concentration (µeq/ml)
Spec
ific
adso
rptio
n ( µ
eq/g
)
0% of starch. Mm= 19.1 ueq/g
0.8% of starch. Mm=12.8 ueq/g
2% of starch. Mm=8.6 ueq/g
Model
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