Fundamentals of Extraction Stages

for Kraft Pulps Bleaching

Brian N. Brogdon, Ph.D.
Senior Research Scientist

Kemira
Kemira Chemicals,
Chemicals, Inc.
Inc.
1525
1525 Church
Church St.
St. Extension
Extension
Marietta,
Marietta, GA
GA 30060-1023
30060-1023 USA
USA

Alkali Extraction -- E or (EO) or (EOP)

Purpose
) Solubilize & Disperse oxidized lignin fragments in alkali from

previous acid oxidation stage

) Remove solubilized lignin from the pulp fiber (i.e., washing)
) Re-Activate residual lignin in the fiber toward further
oxidation/modification

Few studies have focused on extraction since the shift from

Chlorine (C or CD or (DC)) to Chlorine Dioxide (D0)
Extraction is often taken for granted as an integrated extension
of the previous oxidation stage

Reactions of Chlorine Dioxide during D0 Stage

[Brogdon, Mancosky & Lucia, IPBC 2002]
R
OCH3

(I)

Phenolic Group

Improved
Improved Lignin
Lignin Solubility
Solubility

OCH3
OH

HO O

Muconic Acid Ester

+ ClO2
R1

R1

(II)

+ CH3OH
O

R1
O

o-Quinone

Primary
Primary Blocking
Blocking Group
Group

Reactions with Alkali During Extraction

[Brogdon, Mancosky & Lucia, IPBC 2002]
R

R
OCH3

R1

HO O

HO

OH
R1

Muconic Acid Ester

+ CH3OH

HO O

Muconic Acid Structure

Alkali causes saponification and improves lignin solubility

Does not make Muconic Structure more reactive towards ClO2 again
R

HO
O

R1
O

o-Quinone

HO
OH

R1
OH

Polyphenol

Alkali transforms quinones to structures more reactive towards ClO2

Alkali Reactions with Chlorolignin Compounds

R
Cl

Cl

Cl

OH

+ HO
Cl

OCH3
OCH3

Chlorinated Organic

+ Cl
Cl

OCH3
OCH3

Partially Dechlorinated
Cpd.

Process Variables for Extraction Stages

Caustic Charge and Previous Oxidation Stage Conditions
Time and Temperature
Consistency
Influence of Oxidative Reinforcement
)Oxygen (EO)
z Pressure
z Time

at Pressure
)Oxygen and Peroxide (EOP)
Examples Taken from R. Berrys 1999 TAPPI Bleaching Short Course

Impact of Caustic Charge on C Stage Pulp

Sufficient NaOH is applied in the E Stage to achieve an end pH ~

10 to 11 (helps to ionize and disperse lignin fragments)
Low end pH (<10) results in less Delignification, while high end
pH results in little additional Delignification

Impact of C Stage Charge (Kappa Factor) on Extraction

Decreasing the Kappa Factor results in less Delignification at a

given NaOH charge
Higher NaOH Charge is required to achieve same Delignification
for lower Kappa Factor

Impact of Shifting from C or (DC) to D0

E stage generally requires less NaOH when converting from C or (DC)

stage to Chlorine Dioxide Delignification (D0)
Less NaCl is generated with D0 treated pulps due to less chlorolignin
compounds vs. C or (DC) Treated Pulps

Effect of Extraction Time and Temperature

Initial rapid delignification phase that occurs within 10 minutes

Majority of Delignification is accomplished in 40 to 60 minutes
Operating at higher temperatures increases Delignification
(improved diffusion of lignin from inside the fiber)

Effect of Extraction Consistency

Consistency has a minor effect on Delignification or Shrinkage

Operating at higher consistencies can reduce steam
requirements for extraction

Extraction Stage with Oxygen and Peroxide

Stabilizer(s)
Stabilizer(s)

Upflow
Upflow Tube
Tube
(pressurized)
(pressurized)

Downflow
Downflow Tube
Tube
(atmospheric)
(atmospheric
(atmospheric)

NaOH
NaOH
Steam
Steam
Pulp
Pulp

OO22&&
HH22OO22

Pulp
Pulp

Impact of Peroxide for E and (EO) Stages

Addition of O2 improves E stage Delignification

Can reduce the amount of active Cl2 (Kappa Factor) by 20% in
the C or (DC) stage to achieve the same level of Delignification

Impact of Oxygen Reinforced Extraction (EO)

Minimum (EO) conditions are 20 psig O2 held at pressure for 3

min. (generally achieved with upflow tower w/ 10 min. retention)
Addition of O2 under typical (EO) conditions has a negligible
effect on Pulp Viscosity [values in parentheses]

Impact of Peroxide for E and (EO) Stages

Addition of peroxide improves E and (EO) Delignification

Can reduce the amount of active Cl2 (Kappa Factor) from 20 to
40% in the C or (DC) stage to achieve the same level of
Delignification

Effect of Peroxide Charge on (EOP) Brightness Development

ISO Brightness (%)

Initial D0 Pulp Brightness = 53.1

78
77
76
75
74
73
72
71
70
69
68
67
66
65
64
63
62
0.00

~70% Increase
in PostExtraction
Brightness vs.
(EO)
0.10

0.20

0.30

0.40

0.50

0.60

% H2O2 in (EOP)

0.70

0.80

0.90

1.00

Improving (EOP) Bleaching Efficiency

Metals management is important for maximizing (EOP)
bleaching efficiency
Current shift in C or (DC) to D0 Delignification

)pH in D0 stages are higher than C or (DC) stages (2.5 - 4 vs. <2)
)Transition Metals, such as Fe and Mn, are typically higher in D0

pulps due to higher end pH vs. C or (DC) stages

)Transition Metals are detrimental to peroxide bleaching in (EOP)

Negative effects of metals can be offset by peroxide stabilizers

z MgSO4

z Chelants

(e.g., DTPA)

(EOP) Bleaching Enhancement of D0(EOP)DND Sequence

Northern Hardwood Kraft Pulp (10-12 Kappa) to 88 ISO Brightness

(EOP) Bleaching Conditions:

) 0.60% H2O2
) 2.5 % NaOH
) 12% Consistency
) Pressurization w/ O2
) Upflow - 20 min. at 0.21 MPa
(30 psig) and 77C (170F)
) Downflow - 40 min. at 0 MPa
(0 psig) and 77C (170F)

Metals Profile of D0 Pulp

Metal Ions
ppm on Pulp
Ca
130
Mg
95
Fe
27
Mn
ND
Cu
8.8

(EOP) Bleach Stabilizers Examined

Aminocarboxylate-Based (AC-Based) Stabilizers
(0.10 - 0.15% on pulp)
) Stabilizer B
) Stabilizer E (MgSO4 replacement)
Organophosphonate-Based (OP-Based) Stabilizers (0.10% on pulp)
) Stabilizer D

(EOP) Brightness Development (Lab)

Initial D0 Pulp Brightness = 53.1
74
73
72
71
70

5%
)
(0
.1
E

(0
.1
0%
)
D

(0
.1
B

on
t

ro
l

0%
)

69

ISO Brightness (%)

75

(EOP) Brightness Development with Peroxide Dosage (Lab)

ISO Brightness (%)

Initial D0 Pulp Brightness = 53.1

78
77
76
75
74
73
72
71
70
69
68
67
66
65
64
63
62
0.00

Stabilizer E (0.15%)

Control (no additive)

0.10

0.20

0.30

0.40

0.50

0.60

% H2O2 in (EOP)

0.70

0.80

0.90

1.00

D1 Brightness Development with ClO2 Dosage (Lab)

for Various (EOP) Treatments
90

ISO Brightness (%)

89
88

Stabilizer
Stabilizer E
E (0.15%)
(0.15%) in
in (EOP)
(EOP)

87
86
85
84
83

Control
Control (no
(no additive)
additive)

82
81
80
0.00

0.25

0.50

0.75

1.00

1.25

% ClO2 in D1

1.50

1.75

2.00

ISO Brightness

(EOP) Mill Trial of Bleach Stabilizer E

Control (no additive)

72.0
71.0
70.0
69.0
68.0
67.0
66.0
65.0
64.0
63.0
62.0
61.0
0

10

20

30

40

50

Stabilizer E (0.10%)

60

70

Observations

80

90 100 110

Summary of Mill Trial (EOP) Bleaching Enhancement

Addition of Stabilizer E to the (EOP) stage
) Increased (EOP) brightness from 64.3 to 68.1 (~ 4 point gain)
) Mill was able to reduce D0 kappa factor from 0.21 to 0.17
) Preliminary results showed an overall ClO2 reduction of

D0(EOP)DND by 4 to 5 lb/ton pulp

) Able to maintain 88 ISO brightness target
) Trial is on-going and continuing to optimize conditions

(EOP) Bleaching Enhancement of D0(EOP)DND Sequence

Southern Softwood Kraft Pulp (~32 Kappa) to 85 ISO Brightness

Bleaching Conditions:
) 0.60% H2O2
) 2.25 % NaOH
) 12% Consistency
) Pressurization w/ O2
) Upflow - 10 min. at 0.21 MPa
(30 psig) and 75C (166F)
) Downflow - 35 min. at 0 MPa
(0 psig) and 75C (166F)

Metals Profile of D0 Pulp

Metal Ions
ppm on Pulp
Ca
80
Mg
40
Fe
90
Mn
ND
Cu
ND

(EOP) Brightness Development (Lab)

Initial D0 Pulp Brightness = 40.0
62
61
60
59
58

(0
.1
E

on
t ro

5%
)

57

ISO Brightness (%)

63

D1 Brightness Development with ClO2 Dosage (Lab)

for Various (EOP) Treatments

ISO Brightness (%)

84

Stabilizer
Stabilizer E
E (0.15%)
(0.15%) in
in (EOP)
(EOP)

83
82

Control
Control (no
(no additive)
additive)

81

80

7 to 8 lb/T ClO2
Reduction

79

78
0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

% ClO2 in D1

1.20

1.30

1.40

1.50

Questions?

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