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CHLORINE DIOXIDE BLEACHING

Presented by:
Scott Carmichael
Senior Process Engineer
Eka Chemicals

PURPOSE OF CHEMICAL BLEACHING

Selectively Remove
Lignin
Brighten Pulp
Remove Contaminants
Remove Extractives

MAJOR WOOD COMPONENTS


AT DIFFERENT STAGES OF
DELIGNIFICATION
100
Extractives

90
Yield, % (On Wood)

Total Pulp Yield

80
70

Lignin Content

60

Bulk Delignification

50

Hemicellulose Content

40
Pure Cellulose Content

30
0

20

40

60

Lignin Removed, %
MacLeod, M., PAPRICAN, TAPPI Kraft Pulping

80

100

FOUR STAGE BLEACH LINE

D0
`

Eop

D1

D2

BLEACHING OF PULP
Sequence Development - Chemical Pulps
Pre-bleaching to remove residual lignin
Fragmentation from the cellulose portion in an
oxidation/substitution step
Solution of fragments for removal in washing
Final bleaching or brightening by oxidation of coloring
material
Chemical selectivity important because of low lignin to
cellulose ratio

BLEACHING AGENTS
Chlorine
Stage Design.
Chem. Form.
Delig. Eff.
Bright. Eff.
Selectivity
Shive Reduct.
Envir. Impact
Total Cost
E = Excellent
I = Inexpensive

C
Cl2
E
P
G
E
P
I

Sodium
Hypochlorite
H
NaOCl
E
E
F/P
E
P
I

Chlorine
Dioxide
D
ClO2
E
E
E
E
G/E
Ex

G = Good
F = Fair
P = Poor
M = Moderate
Ex = Expensive

Oxygen Hydrogen
Peroxide
O
P
O2
H2O2
P/F
F
P
E
F
E
F
F
G/E
G/E
I
M/Ex

Ozone

VE = Very Expensive

Developed from TAPPI: Pulp Bleaching, Principles and Practice

Z
O3
G
G
P
P
G/E
VE

COMMON BLEACHING TERMS

Kappa number (Kp#) measure of lignin content


Lignin~(Kp#)*0.15

Permanganate number (K#) measure of lignin content


K# ~ (Kp#)*0.67

Active chlorine (aCl) term used to relate chlorine based


bleaching compounds
aCl = (2.63* ClO2) + Cl2

Kappa Factor = (aCl as % on pulp)/ (kappa number)


Oxidative Equivalents (OXE) term used to convert bleaching
compounds.
OXE is the quantity of substance that receives one mole of
electrons when a substance is reduced.

OXE FOR BLEACHING CHEMICALS


Chemical

OXE/kg

aCl

Cl2
ClO2
O2
H2O2
O3

28.20
74.12
125.00
58.79
125.00

1.0
2.63
4.43
2.09
4.43

FACTORS EFFECTING
ClO2 PERFORMANCE
Active Chlorine Distribution
pH
Charge
Retention Time / Temperature
Chemical Variants
mixing, lignin, carryover, consistency

MULTI-STAGE BLEACHING
96

Brightness %ISO

92
88
84
80
Do-Eo
D1
D2

76
72
0.2

0.6

1
Chlorine Dioxide, %

1.4

1.8

ClO2 DISTRIBUTION EFFECT ON


TOTAL USAGE

Total ClO2 lb/T

45
43
41
39
37
35
35

45

55

65

75

% of total ClO2 in first D

Sequence: D (EO) D, 14 Kappa (9.4 K#)


Reference: EC bleaching model

85

D1 VERSUS D1+ D2 ClO2 DEMAND FOR


BRIGHTENING
45

92 ISO
90 ISO
88 ISO
87 ISO

Total ClO2 Consumed In D1 and D2 Stages


kg eq.Cl2/t pulp

40
35
30
25
20
15
10
0

25

50

75

100

125

% ClO2 Consumed in the D1 Stage


Reference: Axegard, et al., E2 Stage Improves the Reactivity of
Pulp Towards Chlorine Dioxide

D0 STAGE OPERATIONS

EFFECT OF pH IN D0 STAGE
(SW)
21

45
KF = 0. 23

40

KF = 0. 10

D0 ISO Brightness, %

D0 Kappa N umber

18

15
KF = 0. 17

12
KF = 0. 23

35

KF = 0. 17

30
KF = 0. 10

25
KF = 0. 17 DE

20
1

3
pH

pH

Reference: Basta, et al., New and Improved Possibilities in D100 Bleaching,


Proceedings of 1992 TAPPI Pulping Conference

Eop Kappa #

DELIGNIFICATION EFFICIENCY
12
11
10
9
8
7
6
5
4
3
2

SW
HW

0.1

0.15

0.2
Kappa Factor

0.25

0.3

KAPPA NUMBER VS TIME

Minutes
Source: A Mathematical Model for Chlorine Dioxide Delignification;
Savoie, Martin and Tessier, Patrick, TAPPI Journal June 1997

EFFECT OF COD CARRYOVER


(SW - O2 Delig.)
3.6

E Kappa

3.2
2.8

10 kg/t COD
15 kg/t COD
20 kg/t COD

2.4
2.0
1.6
0.17

0.19

0.21

0.23
KF

0.25

0.27

0.29

BLEACH PLANT OPERATIONS


D0 STAGE SUMMARY

D0 Stage pH optimum at 2.5 - 3.2


Temperature 120 - 130 F, depending on time
Allow for COD carryover in charge
D0 Kappa Factor 0.18 - 0.22 for Economic &
Environmental
Residual not necessary
Charge approx. 50 - 60 % of total active chlorine for D0
Brightness / Kappa relationship difference for Hardwood

D1 STAGE OPERATIONS

EFFECT OF TERMINAL pH ON D1
STAGE
86

1.8

84

1.6

82

1.4

80

1.2
Chlorate + Chlorite

78

1.0
Chlorite

76

0.8

74

0.6
Chlorate

72

0.4

70

0.2

68

0.0
2

pH at End of D1

%Active Chlorine

Brightness at End of D1

Brightness

EFFECT OF pH AND ClO2 CHARGE


ON D1 STAGE BRIGHTNESS
88

K#
K#E1
E1==2.28
2.28
%%ISO
ISOE1
E1==63.5
63.5
Viscosity
E1
Viscosity E1==31.8
31.8cPs
cPs

Brightness D1 % ISO

23 lb/T D (as ClO2)

86
84

15 lb/T D (as ClO2)

82
80
8 lb/T D (as ClO2)

78
1.5

2.5

3.5

4.5

pH D1
O2 - Delignified ECF Softwood Kraft, Kappa # 18 (K# 11.3)
Reference: Basta, et al., Reducing of AOX Levels,
Proceedings of 1991 Appita Annual General Conference

5.5

EFFECT OF END pH IN D1 STAGE ON


SHIVES IN PULP AFTER THE D1 STAGE
22

D1 Washer Shive Count

20
18
16
14
12
10
8
6
4
2
0
3.0

3.5

4.0

4.5

5.0

D1 Tower Terminal pH

Reference: Pulp Bleaching - Principles and Practice; C. Dence & D. Reeve

5.5

6.0

BLEACH PLANT OPERATIONS


D1 STAGE SUMMARY
Maintain residual 0.02-0.05 gpl for brightness
Operate pH 3.5-4.5
Lower pH leads to improved shive bleaching but also
strength and viscosity loss
Temperature range 160-175 F
Charge approx 30-40% of total active chlorine

EFFECT OF RESIDUAL AND


TEMPERATURE ON BRIGHTNESS
86
84
Brightness, % ISO

No residual

Residual ClO2
40 lb/T ClO2

82

30 lb/T ClO2

80
78
76
74

20 lb/T ClO2

120

150

180

210

Time (min)

240

270

3 00

D1 EFFECT ON D2 BRIGHTNESS CEILING

Brightness, %GE

100

D2

90
80

D1

70
60
50
40

D2 ClO2 = 0.5% on pulp

30
0

0.25

0.5

0.75

D1 Chlorine Dioxide, % on Pulp


Rapson, W.H., Bleaching of Pulp. Tappi Monograph

1.25

1.5

BLEACH PLANT OPERATIONS


D2 STAGE SUMMARY
Operate pH 3.5 - 5.0
Temperature range 155 - 175 F
Maintain residual at 0.02 - 0.05 gpl
Residual important for brightness stability
Important to stay away from brightness ceiling

QUESTIONS?