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Presented by:
Scott Carmichael
Senior Process Engineer
Eka Chemicals
Selectively Remove
Lignin
Brighten Pulp
Remove Contaminants
Remove Extractives
90
Yield, % (On Wood)
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
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
Z
O3
G
G
P
P
G/E
VE
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
45
43
41
39
37
35
35
45
55
65
75
85
92 ISO
90 ISO
88 ISO
87 ISO
40
35
30
25
20
15
10
0
25
50
75
100
125
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
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
Minutes
Source: A Mathematical Model for Chlorine Dioxide Delignification;
Savoie, Martin and Tessier, Patrick, TAPPI Journal June 1997
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
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
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
86
84
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
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
5.5
6.0
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
Brightness, %GE
100
D2
90
80
D1
70
60
50
40
30
0
0.25
0.5
0.75
1.25
1.5
QUESTIONS?