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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