Recent Developments in - EUCALYPTUS

106th Jan 2009

Recent Developments inE. Globulus Kraft Pulping

Chemistry&Technology

Herbert Sixta, Ewa Rutkowska, Petra Wollboldt, GabrieleSchild, Moritz Leschinsky

4th International Colloquium on Eucalyptus Pulp,May 4-6, Concepción, Chile

206th Jan 2009

outline

o Literature Review

Chemistry of E. globulus Components

Kraft Pulping of E. globulus

o Kraft Pulping

Pulping Kinetics

Lignin Structure

o Autohydrolysis

Effect on wood composition

Effect on lignin structure

o New Generation Kraft Pulps

306th Jan 2009

Literature Review

o Chemistry of E. globulus Components

Xylan Structure

Lignin Structure

o Kraft Pulping of E. globulus

06th Jan 2009

Xylan Structure

506th Jan 2009

Heteroxylan Structure of E. globulus

oo MuchMuch lessless xylanxylan isis dissolveddissolved during kraft pulping ofEucalyptusEucalyptus globulusglobulus,, 5%5% odwodw, as compared to otherhardwoods, e.g. birchbirch, 11%11% odwodw

o Higher xylan retention may be associated withdifferences in their composition and structure:30% of MeGlcA units are branched at O-2 withgalactose and glucose units.

1Pinto, P.C. et al. Carbohydrate Polymers 60 (2005), 489-4972Evtuguin D.V. et al. Carbohydrate Research 338 (2003), 597-604

606th Jan 2009


o Substituted uronic acids may constitute linking pointsbetween xylan and other polysaccharides,contributing to retard xylan degradation.

oo AlsoAlso higherhigher DS:DS: 1010--1212 MeGlcA/100 Xylp inEucalyptusEucalyptus globulusglobulus against 77 for birchbirch.


706th Jan 2009


HighHigh molecularmolecular weightweight of Wood andof Wood and PulpPulp XylanXylan::

E.E. globulusglobulus woodwood xylanxylan 31 kDa31 kDa1

E. globulusE. globulus kraftkraft pulppulp xylanxylan 16 kDa16 kDa1

E. globulusE. globulus pulppulp--CCECCE xylanxylan 17 kDa17 kDa2

BirchBirch woodwood xylanxylan 24 kDa24 kDa1

BirchBirch kraftkraft pulppulp xylanxylan 11 kDa11 kDa1

1Pinto, P.C. et al. Carbohydrate Polymers 60 (2005), 489-4972Sixta, H., Lenzing internal report, 2008

0,0

0,3

0,6

0,9

1,2

0 1 2 3 4 5 6

Molecular Weight

dw

/dlo

gM

W

Xylan isolated from CCE-filtrate

from TCF bleached E. globulus kraft pulp

806th Jan 2009


o Tentative structure of heteroxylan isolated from E. globulus wood1,2

o Xyl : Acetyl : 4MeGlcA = 100 : 61 : 10

o 30% of MeGlcA branched at O-2 with galactosyl and glucosyl unitsoriginating from rhamnoarabinogalactan and glucan backbones

o Acetylation: 34 mol% O-3, 15 mol% O-2, 6mol% O-2,3


06th Jan 2009

Lignin Structure

1006th Jan 2009

Assignment of HSQC to Lignin Structures

O

O

(H3CO) OCH3

HO

HO H3CO

(OCH3)

4'

1

A: -O-4/ 73.9-75.7 / 6.0

O

(H3CO) OCH3

4'

1

B: - / : 85.5 / 4.7

O

O

(OCH3)H3CO

O

1'

'''

O

(H3CO) OCH3

1

C: -5/ : 87.6 / 5.4

OHO

4'5'

OCH3

O

(H3CO)

D: p-hydroxycinnamyl alcohol terminal unit: 61.9 / 4.09 (C -H )

-O-4/ 80.7 / 4.6

- / : 54.1 / 3.0

-5/ : 50.2 / 3.8

Resinol

PhenylcoumaranOH

1106th Jan 2009

O

OH

OHO

OH

O

1

2

3

45

6

E1: 99.6 / 4.4

E2: 70.5 / 4.7

E3: 71.5 / 5.0

E5: 62.2 / 3.3, 3.9

O

OCH3

12

34

5

6

O

OCH3

12

34

5

6

H3CO

G2: 110.9 / 6.9

G6: 119.3 / 6.9

G5: 122.3 / 6.9

S2,6: 103.9 / 6.6

S2,6: 105.8 / 7.1

Assignment of HSQC to Lignin Structures

1206th Jan 2009

Abundance of Lignin Structures

o Predominance of -O-4’-, followed by -’ resinol-type,but low amount of -5’ phenylcoumaran-type linkages.

o Low amount of phenolic, but high amount of primaryaliphatic OH.

o High S/G ratio indicating facilitating delignification

1 Rencoret et al., Holzforschung, 2008, 62, 514-5262Evtuguin, D.V. et al. J.Agric.Food Chem. 2001, 49, 4252-4261

Structures

% side-chains methods per Ar methods

b-O-4 A 69,3 HSQC 0,5613

C

Resinol B 18,2 HSQC 0,1613

C

Phenylcoumaran C 2,9 HSQC

b-1 HSQC

p-Hydroxycinnamyl alcohols D 4,7 HSQC 0,0213

C

primary-OH 0,68 1H

phenol-OH 0,301H

S/G 2,9 HSQC 6,013

C

2,6 Py-GCMS

Milled Wood Lignin[1] DioxaneLignin [2]

06th Jan 2009

Kraft Pulping of E. globulus

1406th Jan 2009

Lignin Structure vs. Cooking Performance

ºPinto,P., Evtuguin, D.V., C. Pascoal Neto. 8th EWLP. 2004, 93-96

Pulps KappaEA HF

% odw Wood Pulp Wood Pulp Wood Pulp

E. globulus 17,8 595 16,4 1,7 1,72 1,15 0,95 0,53 0,39

E. urograndis 22,2 690 15,7 1,4 1,25 1,19 0,69 0,51 0,26

E. grandis 21,1 660 16,1 1,2 1,16 1,14 0,83 0,54 0,27

B. pendula 20,0 690 16,4 1,0 0,71 1,11 0,77 0,55 0,21

A. mangium 26,6 690 15,9 0,6 0,26 0,93 0,27 0,43 0,201) permanganate oxidation

b-O-41HNMR per C9

13CNMR per C9

Cooking S/G1 aliphOH

Kraft Cooking Conditions:L:S = 4:1, heating up 90 min from 30ºC to 160ºC, sulfidity 28%, EAand HF adjusted to obtain Kappa 16

1506th Jan 2009

0,0 0,5 1,0 1,5 2,040

50

60

70

80

S/G [permanganate oxid]

0,10 0,15 0,20 0,25 0,30 0,35 0,40 0,45 0,5040

50

60

70

80C

lO2

con

s,

kg

/odt,

toa

chie

ve

90

%IS

O

-O-4 in pulp lignin, per C9

o Bleachability differs

significantly for the

investigated hardwood

kraft pulps.

o Bleachability correlates

best with the relative

abundanceabundance of S/Gof S/G unitsunits

and the amountamount ofof --OO--

44 structuresstructures.

ºPinto,P., Evtuguin, D.V., C. Pascoal Neto. 8th EWLP. 2004, 93-96

º

1606th Jan 2009

HexA formation - degradation

o HexA formation dependent on T

and EA-charge. Sulfidity has no or

a very minor role

o HexA only decreased at kappa

number below 12

o High amount in unbleached pulp:

o HexA content increases when the

lignin content decreases from

kappa 45 (2828 mmolmmol HexAHexA/kg/kg pulppulp)

to kappa 12 (6868 mmolmmol/kg pulp/kg pulp)2,3.

3Daniel, A.I.D. et al. Tappi J., 2(5),3-8

1Monrroy, M. et al. Appita J., 61(3), 212-215

16.5%EA-155C

22% EA-155C

16.5% EA-165C

22% EA-165C

0

3

6

9

12

Me

Glc

Ao

rH

exA

/10

0xy

lose

MeGlcA HexA

Kappa number 15

EffectEffect of EA andof EA and temperaturetemperature on theon theamountamount ofof carboxyliccarboxylic acidsacids in xylanin xylan1

2Pedroso, A.I. and M.G. Carvalho, JPPS, 29(5), 2003, 150-154

1706th Jan 2009

Pulp Yield Affecting Paramters

E.E. globulusglobulus woodwood LabillLabill..,6-11 a, ENCE Spain:

Tendency of higher yield

with increasing S/G ratio:

delignification requires

less alkali charge which

preserves carbohydrates.

Kraft Pulping: 90 min heating-up, 50 minat 165ºC, S=25%, EA adjusted to achievekappa 16

Del Rio, J.C. et al. J. Anal. Appl. Pyrolysis 74 (2005), 110-115

2 3 4 5 6 7

40

50

60

Pu

lpyie

lda

tK

ap

pa

16

,%

S/G ratio (Py-GC/MS)

1806th Jan 2009

Results

o Composition of E. globulus

o Kraft Pulping

Pulping Kinetics

Lignin Structure

o Autohydrolysis

Effect on wood composition

Effect on lignin structure

o New Generation Kraft Pulps

1906th Jan 2009

Composition of E. globulus*Parameters g/kg woodCarbohydrates 677

Glucan 417Mannan 9Galactan 13Rhamnan 4Xylan 153Arabinan 5Acetyl 33MeGlcA 22

GalA 17

GA 4

Lignin 277Klason Lignin 229Acid soluble Lignin 48

Extractives 17EtOH/Toluene 17

Ash 4

TOTAL 975* origin: UruguayLeschinsky, M. BioResources 4(2), 687-703, 2009

06th Jan 2009

Kraft Pulping Kinetics ofE. globulus

2106th Jan 2009

Delignification Kinetics1

-50 0 50 100 150 200

10

100

imp

reg

na

tio

n

reference

OH-= 0.9

Na+

= 2.5HS

-= 0.0

liquor change

Kappa number on odw

Time, min

j

cba

jji LNaHSOHk

dt

dL ,

tkExptkExpLL LL 32

*

032

Distribution Model2

Reference Conditions:[OH-] = 0.50 M[HS-] = 0.24 M[Na+] = 1.50 M

1Sixta, H., Rutkowska, E. W. O Papel, (2) 54-67, 20072Anderson, N. et al. NPPJ, 18, 200-209, 2003

2

2

x

cD

t

c

RT

EExpTD A710564.0

Diffusion of chemicals

2206th Jan 2009

E. Globulus1

vs. Spruce2

Conditions:[OH-] = 0.50 M[HS-] = 0.24 M[Na+] = 1.50 M

1Sixta, H., Rutkowska, E. W. O Papel, (2) 54-67, 20072Anderson, N. et al. NPPJ, 18, 200-209, 2003

50 100 1500,00

0,05

0,10

0,15

0

50

100

150

Picea abies

reaction rate, k2, min

-1

time, min

Te

mp

era

tur,

CE. globulus

2306th Jan 2009

Carbohydrate Degradation Kinetics

-50 0 50 100 150 2000

1000

2000

3000

4000

5000

2.5 M Na+

DP

time at 160C, min

exp, 1.5 M Na+

exp, 2.5 M Na+

1.5 M Na+

tNaOHTR

EAExpA

DPDP

edC

ntn

0,,

111EAc = 180 kJ/mold = 1.08e = 0.74

Sixta, H., Rutkowska, E. W. O Papel, (2) 68-81, 2007

Model

2406th Jan 2009

Kinetics of Hexenuronic acid reactions2

ii OHHexAkOHMeGlcAkdt

HexAd 21

0 100 200 4000

5

10

15

20

25

He

xA

,m

mo

l/kg

wo

od

Time, min

0.10 M OH-1.50 Na

+0.50 M OH

-0.80 Na

+

0.50 M OH-1.50 Na

+0.90 M OH

-1.50 Na

+

0 100 2000

40

80

120

0

10

20

30

40

He

xA

,m

mo

l/kg

wo

od

MeG

lcA

,m

mol/kg

woo

d

Time at 433 K, min

0.50 M [OH-]

1.50 M [Na+]

iOHMeGlcAkdt

MeGlcAd 1

22

4

2

CNaC

OHNaOH

b

bbi

1Bogren, J. Licentiate Thesis, Chalmers University of Technology, 20062Sixta, H., Rutkowska, E. W. O Papel, (2) 68-81, 20073Leschinsky, M. BioResources, 4(2), 687-703, 2009

Model1

subscript b bulk liquorsubscript i inner liquorC, mol kg-1 c of negatively charged groups in fibre wall[MeGlcA]0 = 116 mmol/kg wood3

0 1 2 30,0

0,2

0,4

0,6

0,8

1,0[OH

-]i/[OH

-]b

[Na+], mol/L

06th Jan 2009

Structural Changes in Lignin duringKraft Cooking of E. globulus

2606th Jan 2009

Effect of Cooking on Lignin Structures

-60 0 30 60 90 120

10

100

K10

K18

K34

K48

K109

Kapp

anum

be

r

Time, min

K141SampleSample YieldYield KLigninKLignin XylanXylanKappa# % % %

K141 100.0 22.7 15.8K109 90.2 19.5 14.6K48 65.0 5.9 10.4K34 52.9 3.0 11.0K18 51.3 1.4 9.1

K10 49.4 0.6 8.7

ImpregnationImpregnation::0.34 M [OH-], 0.15 M [HS-]100ºC, 60 min

Cooking:Cooking:0.50 M [OH-], 0.22 M [HS-]1.50 M [Na+], 160ºC

Rutkowska et al. (2009). “Lignin structure, kraft cook,” BioResources 4(1), 172-193.

Lignin was isolated asDissolved Wood LigninDissolved Wood LigninDWLDWL

2706th Jan 2009

MonitoringMonitoring LigninLignin StructureStructure in Kraftin KraftPulpingPulping

Rutkowska, E.W., Wollboldt, P., Zuckerstätter, G., Weber, H.K., Sixta, H. (2009) H. Bioresources 4(1), 172-193

171 170 169 168

160 140 120 100 80 60 40

-O-4

ArC-O

prim aliph OAc

ppm

ArC-C ArC-H

CDCl3

OMe

phen OAc

sec aliph OAc

2806th Jan 2009

Changes of Lignin Structures

0 50 100 1500,0

0,3

0,6

0,9

phen-OH

-O-4

sec-OH

per Ar

Kappa number

prim-OH

Sixta, H. Workshop Chemical Pulping Processes, Karlstad, Sweden, Nov. 2008

0 50 100 1500,0

0,2

1,5

2,0

2,5

3,0

ArC-C

S/G

per Ar

Kappa number

DWLDWLRutkowska, E.W. et al. Bioresources 4(1), 172-193 (2009)

2906th Jan 2009

Native Kappa-18prim-OH 0,80 0,65

sec-OH 0,73 0,47

phen-OH 0,22 0,19

b-O-4 0,37 0,32

ArC-C 1,72 1,84

b-b 0,20 0,32

S/G 2,58 1,70

Structures

per ArLignin

Sixta, H. Workshop Chemical Pulping Processes, Karlstad, Sweden, Nov. 2008

06th Jan 2009

Effect of Autohydrolysis on WoodComponents

3106th Jan 2009

Fractionation Procedure

Water, L:S = 5:1,Intensities at 170ºC*:P300, P600, P1500

E.E. GlobulusGlobulus2.50 – 3.55 mm

AutohydrolysisAutohydrolysis

t

t

t

t C

TH dtT

Expdtk

kP

00

1510648.40

100

,

EA = 125.6 kJ/mol

AuothydrolysateAuothydrolysate WoodWood ResidueResidue

Cooling

Pressure release, purging with N2

Centrifugation Washing

InsolublesInsolubles,, II--fractionfraction

SolublesSolubles,, SS--fractionfraction

WashWash FiltrateFiltrate

Washed Wood ResidueWRWR

3206th Jan 2009

Xylan

0 300 600 15000

50

100

150

Xn

X

XOS

C5 as xylan, g/kg odw

P-Factor

153

24

35

57

29

F

0 300 600 900 1200 15000

20

40

60percentage of xylan in wood

P-factor

X2

X3

X4

X5

>X5acidXOS

Leschinsky, M. BioResources 4(2), 687-703, 2009

3306th Jan 2009

Glucan

0 300 600 15000

100

200

300

400

Gn

Glucan, g/kg odw

P-factor

G

395417


3406th Jan 2009

Uronic Acids0 300 600 1500

0

3

6

9

0 300 600 15000

10

20

30

40

50

liquid phase

uro

nic

acid

s,

g/k

go

dw

P-Factor

CO

2 ,g

/kg

od

w

S

214 mmol/kg w205 mmol/kg wood

GalA

MeGlcA

GA

GalA

MeGlcA


3506th Jan 2009

Acetyl groups

0 300 600 15000

10

20

30

40

Acety

l,g

/kg

w

P-factor

boundsolid

boundliquid

freeliquid

33

21

6

5


3606th Jan 2009

Lignin

0 300 600 15000

10

210

240

270

300Lig

nin

,g/k

gw

oo

d

P-factor

woo

dre

sid

ue

KL

AL

S-fraction

I-fraction

239229

11

36

10


3706th Jan 2009

MWD of the Lignin in S-fraction

1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,50,0

0,2

0,4

0,6

0,8

1,0

1,2P-factor 300 (Mw = 1.4 kg/mol)P-factor 600 (Mw = 0.9 kg/mol)P-factor 1500 (Mw = 0.4 kg/mol)

Diffe

ren

tia

lw

eig

htfr

actio

n

log molar mass [kg/mol]


06th Jan 2009

Effect of Autohydrolysis onLignin Structure

3906th Jan 2009

Effect on Lignin in Wood Residue

0 500 1000 1500

0,2

0,4

0,6a

bun

da

nce

pe

rA

r

P-factor

-O-4

primary alipha. OHsecundary aliph. OHphenolic OH

MWL

M. Leschinsky et al. Part 1. Holzforschung, Vol 62, 645-652, 2008M. Leschinsky et al. Part 2. Holzforschung, Vol 62, 653–658, 2008

4006th Jan 2009

SEC of MWL samples

12 14 160

25

50

UV

-sig

nal

Retention time [min]

MWL E. nativeMWL WR P320MWL WR P670MWL WR P1540

MW of residual lignin

clearly decreases with

increasing auto-

hydrolysis intensity

4106th Jan 2009

Insoluble Fraction in Hydrolysate

O

(H3CO) OCH3

O

O

(OCH3)H3CO

O

HH

HH

IdentificationIdentification ofof LowLow MolecularMolecular CompoundsCompoundsin Iin I-- andand SS--fractionsfractions 1H1H 13C13C

oo Syringaldehyde, : 9.85 190.9

o Episyringaresinol, 1: 4.44 87.3

o Sinapaldehyde, : 7.40 152

o Stilbene, /: 6.97 128

OCH3

O

(H3CO)

OCH3

O

(OCH3)

M. Leschinsky et al. Part 1. Holzforschung, Vol 62, 645-652, 2008M. Leschinsky et al. Part 2. Holzforschung, Vol 62, 653–658, 2008

Sticky!

Episyringaresinol

Syringyl type stilbene

The abundance of theses structuresincreases with increasing P-factor

4206th Jan 2009

Thermal treatment of Hydrolysate

Thermal treatment of

hydrolysate after separ-

ation from wood results

in the formation of sticky

precipitates, PTPT--fractionfraction,

which originate from the

polycondensation of the

II--fractionfraction

12 14 160

25

50

PT-fraction TT P*1570I-fraction TT P*1570MWL E.native ref

UV

-sig

na

l

Retention time [min]

4306th Jan 2009

New Generation Kraft Process

o Adopting the BiorefineryBiorefinery principleprinciple throughpre- and post-treatments to selectivelyremove hemicelluloses.

o Joint basis for the manufacture of differentpulp grades.

4406th Jan 2009

Technical Concept

Controlled removal of hemicelluloses (xylan) bycold caustic extraction, CCE.

4506th Jan 2009

Single and Double Line Concept

4606th Jan 2009

Controlled Removal of Xylan

3 4 5 6 70,0

0,3

0,6

0,9

1,2

bleachedpaper pulp

XYLAN

dw

/d(l

og

MW

)

log MM

3 4 5 6 70,0

0,3

0,6

0,9

1,2

dw

/(dlo

gM

W)

log Mw

3 4 5 6 70,0

0,3

0,6

0,9

1,2 Standard-CBC CBC-HY

dw

/d(lo

gM

W)

log MW

CCE, depoly

Hemi-lye

HemiHemi--richrich paperpaper pulppulp

HemiHemi--leanlean dpdp

4706th Jan 2009

Yield vs. Purity

84 87 90 93 9635

40

45

50

55

Ble

ach

ed

Pu

lpY

ield

,%

od

Rayon Yield, %

New Generation DP

Conventional DP

06th Jan 2009

Pulp&Cellulose Products

o Hemi-rich Paper Pulp

o Hemi-lean Dissolving Pulp (CCCCEx)

4906th Jan 2009

Hemi-Enriched Paper Pulp

Unbleached E. globulusSodaSoda--AQAQ,, 15:

oo ReferenceReference Pulp:Pulp:YY ~ 50.5%,~ 50.5%, XylanXylan = 17.4%= 17.4%

oo HemiHemi--rich Pulp:rich Pulp:Y ~ 52.4%,Y ~ 52.4%, XylanXylan = 20.0%= 20.0%

0 1000 2000 3000 4000 50003

4

5

6

7

8

Reference Soda-AQ Soda-AQ with hemi-enriched WL

Te

nsile

Stiffn

ess,N

m/g

Beating Degree, min-1

0 10 20 30 40 500,0

0,3

0,6

0,9

Reference Soda-AQ (CBC15)Hemi-rich Soda-AQ (CBC32)

xyl-to

-glu

ratio

peeled mass, %odp

5006th Jan 2009

Dissolving PulpYieldYield AdvantageAdvantage throughthrough PostPost--ExtractionExtraction

94 96 980

3

6

932

36

40

44

autohydrolysis

Cellulose

Yie

ld,

%odw

Alkali Resistance, % R18

Xylan

post-extraction

Eucalyptus GlobulusH. Sixta et al.. PCT Int. Appl. (2007) WO 2007128025

at given cellulose

purity, the modified

paper pulp has up to

8.5% higher abs. yield

than a conventional

dissolving pulp.

5106th Jan 2009

Effect of Post-Extraction on MWD

3 4 5 6 7

REF

CCE100

CCE50

log MW

dw

/d(l

og

Mw

)

Post-extraction

significantly affects

polydispersity:

3.2

5.30.5100

50

PDI

PDIPDICCE

CCE

Eucalyptus Globulus Sixta, H. et al. PCT Int. Appl. (2007) WO 2007128026 A1

5206th Jan 2009

Fibril aggregate dimensions

The fibril aggregate diameters, daggr:CCCCEx pulps: 15.2 nm

Reference PHKReference PHK : 12.2 nm

7577798183858789919395

shift [ppm]

Ib

Ia

Ia+Ib

paracrystalline

hemicelluloses

accessible fibril surface

inaccessible fibril surface

Larsson, P.T., K. Wickholm, and T. Iversen (1997) Carbohydr. Res. 302: 19-25.

C4 region of 13C CP-MAS

2

44

n

nq

n… number of chainsq… signal of accessible

surfaces

5306th Jan 2009

Conversion to Lyocell Fibres (1.3 dtex)

60 80 100 1200

1

34

36

38

40

42best reference

Tena

city

(cond),

cN

/tex

c_NaOH in CCE, g/L

CCEx

5406th Jan 2009

Acknowledgement to my teamAcknowledgement to my teamin Lenzing, Austriain Lenzing, Austria

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