PEER REVIEWED PULP BLEACHING

A survey of ClO2 delignification ABSTRACT

Results are reported from a survey of

practices in Canada operating conditions in Canadian mills

that are producing elemental chlo-
rine-free (ECF) grades of bleached
DOUGLAS C. PRYKE AND DOUGLAS W. REEVE pulp. ECF refers to the complete
replacement of chlorine with chlorine
dioxide in the first stage of bleaching.

C
HEMICAL PULP BLEACHING IN to determine, if possible, the opti-
Chlorine dioxide delignification is
Canada continues to ad- mum conditions for maximizing
rapidly becoming the common
vance technologically. In brightness while minimizing costs.
process in the first stage of bleaching.
1988, bleach plants began In 1996 the questionnaire was
This report documents the practical
adopting substantial substitution of sent to forty-two mills. Thirty-eight
conditions utilized in actual mill-scale
chlorine dioxide for chlorine. Today, mills responded. We used the 1995
production of ECF pulps.
in 1997, all bleach plants in Canada survey (1) to estimate the pulp pro-
use substantial substitution of chlo- duction for the mills that did not Application:
rine dioxide in the first stage of respond. We also received and ana- Opportunities are identified for cut-
bleaching (i.e., more than 50%). On a lyzed supplemental questionnaires ting the consumption and costs of
production-weighted basis, pulps for 36 ECF bleaching lines. Here, we bleaching chemicals for conventionally
produced with chlorine dioxide sub- summarize the results of the survey. delignified softwood kraft pulps.
stitution now average 87% for all
bleached chemical pulps. Softwood PULP BLEACHING IN CANADA
grades average 90%, and hardwood Table I summarizes bleached chem-
grades average 79%. ical pulp production in Canada. Most
The number of mills practicing of the pulp is produced to sell as
complete replacement of chlorine market pulp, and most of the pulp is began to grow quickly. ECF pulp is
with chlorine dioxide continues to produced through the kraft process. now produced at 36 of 42 mill sites
grow. These so-called or “elemen- Figure 1 shows the changing and in 47 of 53 bleach plants.
tal chlorine-free” (ECF) pulps are nature of bleached chemical pulp Twenty-three mill sites produce ECF
bleached without elemental chlo- production since 1990. ECF pulp grades exclusively.
rine, Cl2. In 1996, almost 90% of production continues to rise. As the As mentioned, expanded ques-
bleach plants in Canada produced figure shows, ECF pulp accounted tionnaires were issued to those
ECF pulps, totaling about 8.2 million for 67% of bleached chemical pulp bleach plants producing ECF pulps.
metric tons of bleached pulp. The produced in Canada in 1996. In The questionnaires requested infor-
ECF pulps now account for 67% of 1996, totally chlorine-free (TCF) pulp mation on unbleached pulp, process
the total Canadian production of was produced at only two sulfite conditions, chemical consumption,
bleached chemical pulp. Almost 60% mills. mixing, control strategy, and so on.
of bleach plants and over 50% of DEVELOPMENT OF ClO2 Responses were received covering
bleached chemical pulp mill sites in SUBSTITUTION 36 bleach plants—29 softwood and
Canada use ECF bleaching exclu- In 1987, only nine bleach plants in 7 hardwood pulp bleaching plants.
sively. Canada were practicing substantial This report summarizes the
To keep abreast of the develop- substitution of chlorine dioxide (2). bleaching practices from the soft-
ments in bleaching practice, the Since 1988, the number of bleach wood bleach plants within two cate-
CPPA Bleaching Committee issued plants practicing substantial substitu- gories, oxygen-delignified and con-
questionnaires to mills in Canada in tion has been steadily increasing, as ventionally delignified. These two
1994, 1995 and 1996. The question- shown in Fig. 2. In 1996, all of the categories were further subdivided
naires were designed specifically to bleach plants in Canada practised into “low” and “high” categories in
determine the extent and impact of greater than 50% substitution. regard to the relative chemical con-
increased chlorine dioxide substitu- Perhaps even more dramatic is sumption.
tion and complete replacement of the growth of the practice of com- The database for hardwood pulp
chlorine with chlorine dioxide in the plete replacement of chlorine with was not sufficient to characterize
first stage of bleaching. In 1996, the chlorine dioxide in the first stage of practices. The questionnaires and
questionnaire was expanded to bleaching. In 1989, the number of the full data analysis for both soft-
assess ECF bleaching practices and bleach plants producing ECF pulps wood and hardwood pulps can be

VOL. 80: NO. 5 TAPPI JOURNAL 153

PULP BLEACHING

12 60

50 ≥ 50% ClO2
millions of metric tons
10

BLEACH PLANTS
ECF
PRODUCTION,

Other
8 40

6 30

4 20
ECF
10
2
TCF 0
0 1987 1988 1989 1990 1991 1992 1994 1995 1996
1990 1991 1992 1993 1994 1995 1996
2. Bleach plants that substantially substitute chlorine dioxide
1. Production of bleached chemical pulp in Canada have been increasing in number since 1987.

ECF TCF Other* Carryover to the

Total medium consistency. Furthermore,
bleach plant 87% are processes with upflow tow-
Hardwood 1.40 0.006 1.57 2.98 Carryover of un- ers, and only 13% are upflow–down-
Softwood 6.82 0.035 2.42 9.28
wanted chemicals flow towers.
Total 8.22 0.041 3.99 12.26
from pulping to the Retention time is 36 min, with a
bleach plant (i.e., range of 6–120 min. Temperatures
*Pulps bleached with substantial substitution of chlorine dioxide. Softwood and the first chlorine average 54°C, ranging from 35°C to
hardwood pulps average 60% substitution.
dioxide stage) is 65°C. Residual chlorine dioxide is
I. 1996 Canadian bleached chemical pulp production, in million determined by mea- typically zero. Approximately 80% of
metric tons suring the sodium oxygen delignification bleach plants
concentration in and 65% of conventional lines con-
obtained from the CPPA Bleaching the liquor associated with the trol the end pH at 2.5 by adding
Committee. The information report- incoming pulp (unbleached pulp or H2SO4.
ed here, along with some additional oxygen-delignified pulp). This mea- Process control in the first stage
charts and other tabulated data, can sure of carryover is expressed as is dominated by optical and residual
also be found in our earlier paper kilograms of Na2SO4 per air-dried sensors before the tower, with 80%
published in the proceedings for the metric ton. More recently, mills are of the plants controlling to a com-
TAPPI 1996 Pulping Conference (3). beginning to use chemical oxygen pensated brightness setpoint. About
For ECF grades, the dominant demand (COD) to measure carry- 30% of the plants surveyed use a
sequence is D(E+O+P)DED (Fig. 3). over of those chemicals that will post-tower optical sensor as well.
Most grades are bleached to high consume chlorine dioxide in the Approximately 30% of the plants
brightness, commonly 88–90% ISO first stage of bleaching. control to an extracted kappa num-
as shown in Fig. 4. As shown in Figs. 5 and 6, the ber. Of the conventional lines, 35%
carryover ranges from 5 kg to 20 kg have kappa number analyzers.
UNBLEACHED PULP per air-dried metric ton for either Both mechanical and static mix-
Kappa number Na2SO4 or COD. The average value of ers are used in various combinations,
The kappa numbers average 28.7 for both Na2SO4 and COD carryover, for with the distribution of chlorine
conventionally delignified pulps and both conventional and oxygen-delig- dioxide varying widely among mix-
17.5 for oxygen-delignified pulps on nified pulps, is about 8 kg/a.d. metric ers. These differences among mills
entering the bleach plant. ton. probably arose as different mixing
Oxygen delignification and modi- strategies were implemented under
fied cooking are growing in impor- OPERATING CONDITIONS different designs for substituting
tance. Twenty-eight percent of the First chlorine dioxide stage, D0 chlorine dioxide. No doubt, differ-
kraft pulp in Canada is now pro- The typical first stage of chlorine ences in associated hydraulic limita-
duced by oxygen delignification. dioxide bleaching is operated at low tions also contributed to the diver-
This percentage represents 3.5 mil- consistency, reflecting the transition sity. In short, there is no evidence of
lion metric tons of production. Oxy- from chlorine to chlorine dioxide. Of a pattern among the mills for the
gen delignification of softwoods is the bleach plants, 80% operate at low mixing strategy or for chlorine diox-
now practiced at 11 sites. consistency, and 20% operate at ide addition.

154 TAPPI JOURNAL MAY 1997

 25

NUMBER OF GRADES
DEoDED
20 Hardwood
1 Softwood
DEopDE D
15
DEPDED
10
DE2D Hardwood
Softwood 5
Other
0
0 5 10 15 20 25 30 <80 80–86 87–88 89–90 >90
NUMBER OF GRADES FINAL BRIGHTNESS, % ISO
3. Elemental chlorine-free bleaching sequences for hardwoods 4. Most grades are bleached to high brightness, with the final
and softwoods. [1May also be (E+P). 2May also be (E+O) or brightness most commonly reported to be in the range of
(E+O+P).] 88–90% ISO.

5 10
9
BLEACH PLANTS

BLEACH PLANTS
COD 8 COD
4
Na2SO4 Na2SO4
7
3 6
5
2 4
3
1 2
1
0 0
<5 5–10 10–15 15–20 ≥20 <5 5–10 10–15 ≥15
CARRYOVER, kg/a.d. metric ton CARRYOVER, kg/a.d. metric ton
5. Carryover to the bleach plant for oxygen-delignified softwood 6. Carryover to the bleach plant for conventionally delignified
pulps softwood pulps

The kappa factor is higher for 50–134 min, operating at 75°C, with conventional lines, with 40% of the
oxygen-delignified pulps, which aver- a range of 55–85°C. Approximately lines using this parameter, compared
age 0.23 as opposed to an average of 10% of oxygen delignification bleach to only one oxygen delignification
0.20 for conventionally delignified plants and 25% of conventional lines line.
pulps. The kappa factor equals the utilize PapricycleTM to minimize Both hydrogen peroxide and
percent equivalent chlorine on pulp sodium hydroxide consumption. The oxygen are used in the extraction
divided by the incoming kappa num- ratios of NaOH to equivalent Cl2 aver- stage in 90% of the bleach plants.
ber. (The percent equivalent chlorine age 0.45–0.48 without Papricycle Oxygen is applied typically at 5.5
on pulp in the first D-stage equals and 0.25–0.36 with Papricycle. This kg/a.d. metric ton and hydrogen per-
2.63 times the chlorine dioxide mea- difference represents a savings of oxide is applied typically at 3.4
sured as a percent on pulp.) approximately 7–9 kg NaOH/a.d. kg/a.d. metric ton. The E+O+P kappa
Oxygen-delignified pulps are rela- metric ton. number for oxygen-delignified pulps
tively more difficult to further delig- Essentially all stages are con- averages 3.6, compared to 5 for con-
nify with chlorine dioxide. This fact trolled to an end pH of 10.5–10.8, ventional pulps.
is reflected in the higher kappa fac- with 50% of oxygen delignification The kappa factor for the first
tor in the first D-stage. lines and 30% of conventional lines D-stage plus the E+O+P stage is
First extraction stage, E+O+P controlling to an E+O+P brightness higher for oxygen-delignified pulps.
The retention time for the E+O+P target. Controlling to the E+O+P (This kappa factor includes the chlo-
stage is 75 min, with a range of kappa number is more popular in

VOL. 80: NO. 5 TAPPI JOURNAL 155

PULP BLEACHING

5 6
Oxygen Oxygen
delignified 5 delignified
4
BLEACH PLANTS

BLEACH PLANTS
Conventional Conventional
4
3
3
2
2
1 1

0 0
<80 80–82 82–84 84–86 86–88 88–90 ≥90 <88 88–89 89–90 90–91 ≥91
D1 BRIGHTNESS, %ISO FINAL BRIGHTNESS, %ISO
7. Distribution over the bleach plants surveyed for pulp bright- 8. Distribution over the bleach plants surveyed for pulp bright-
nesses in the second chlorine dioxide stage, or the D1-stage nesses in the final chlorine dioxide stage, or the D2-stage

rine dioxide in the D0-stage plus the washer vat. 40% of the oxygen delignification
hydrogen peroxide and oxygen, all Brightness is widely distributed, lines. The retention times for these
expressed as equivalent chlorine.) as Fig. 7 shows. D1-stage brightness stages are in the range of 3–25 min.
Oxygen-delignified pulps average averages 84% ISO for oxygen-deligni- Normal E2-stage retention time is
0.39 in kappa factor, while conven- fied pulps and 83% ISO for conven- 75 min, with a range of 45–120 min,
tionally delignified pulps average tional pulps. Chlorine dioxide is at a temperature of 72°C, with a
0.30. Delignification is typically 90% applied at 9 kg/a.d. metric ton for range of 65–85°C. Both the short and
in both cases, but with oxygen-delig- oxygen-delignified pulps, compared long stages are each controlled to an
nified pulps it takes more oxidizing to 11.3 kg/a.d. metric ton for con- end pH of 10.2–10.3. Approximately
chemical equivalents for each unit of ventional pulps, reflecting the differ- one third of both oxygen-delignified
kappa number decrease. For oxygen- ence in post-extraction kappa num- and conventional lines add hydrogen
delignified pulps, it takes 0.47% ber. The application rate for both peroxide at 1–1.5 kg/a.d. metric ton.
equivalent chlorine for each unit of pulps is approximately 2.3 kg NaOH consumption differs con-
kappa number decrease, compared ClO2/a.d. metric ton per unit E+O+P siderably between the short and long
to 0.35% equivalent chlorine for con- kappa, compared to 2.0 for labora- stages. The short stages consume
ventional pulps. tory-generated values (3). 8–10 kg NaOH/a.d. metric ton, as
Chlorine dioxide brightening: Second extraction stage, E2 opposed to 3–5 kg/a.d. metric ton
D1-stage Recently, a number of mills have for long stages.
The average retention time in the incorporated so-called “short extrac- Chlorine dioxide brightening:
D1-stage is 160 min, with a range of tion” stages for the second E stage. In D2-stage
60–240 min. The operating tempera- some configurations, NaOH is added The average D2-stage retention time
ture is 72°C, with a range of directly to the ring dilution at the is 165 min, with a wide range of
68–81°C. Approximately 40% of oxy- bottom of the D1-stage tower, and 60–255 min, operating at an average
gen delignification bleach plants and the short residence time before the temperature of 75°C, with a range of
85% of conventional lines add NaOH pulp is pumped to the D1-stage 66–82°C. NaOH is usually not added
to control pH. The upflow pH aver- washer is used for extraction. The to control pH. The upflow pH aver-
ages 3.8–3.9, and the end pH is pulp is then washed and forwarded ages 4.5, and end pH averages
3.3–3.8. to the D2-stage. In other configura- 3.7–3.8.
Using pre-tower optical and tions, NaOH is added to the washed Few stages are controlled using
residual sensors, most plants control D1 pulp, and the residence time in pre-tower optical and residual sen-
the D1-stage to a compensated a medium-consistency-pump feed sors. Rather, chlorine dioxide is
brightness target and an end-of- chute is used for extraction. The applied as a percentage on pulp and
tower pulp brightness. A chlorine pulp is not washed in this case, and to a final brightness target. A positive
dioxide residual is retained at the chlorine dioxide is added directly to chlorine dioxide residual is retained
end of the stage, typically in amounts the pulp prior to the D2 tower. Such at the end of the stage, typically in
ranging from trace quantities to 40 short extraction stages are found in amounts ranging from trace quanti-
mg/L as measured in the D1-stage 20% of the conventional lines and in ties to 40 mg/L as measured in the

156 TAPPI JOURNAL MAY 1997

 8 7
7 Oxygen 6 Oxygen
BLEACH PLANTS

BLEACH PLANTS
delignified delignified
6 5 Conventional
Conventional
5
4
4
3
3
2 2
1 1
0 0
<1.25 1.25– 1.50– 1.75– 2.00– 2.25– 2.50– ≥2.75 <30 30–35 35–40 40–45 45–50 50–55 ≥55
1.50 1.75 2.00 2.25 2.50 2.75
BLEACHING CHEMICAL COSTS,
BLEACHING EFFICIENCY, CAD/kappa no. CAD/a.d. metric ton

9. Bleaching efficiency (bleaching chemical costs in Canadian 10. Bleaching chemical costs (bleaching chemical costs in Cana-
dollars divided by the kappa number of the unbleached pulp) dian dollars per air-dried metric ton)

D2-stage washer vat.

Oxygen Conventional
D2-stage brightness averages Low* High* Low* High*
89.8% ISO for oxygen-delignified
pulps and 89.6% ISO for conven- Number of bleach plants 5 2 5 5
tional pulps. The distribution is
Kappa no. to D0-stage 18.4 14.6 28.4 27.6
shown in Fig. 8. Chlorine dioxide is
applied at 2.9 kg/a.d. metric ton for COD carryover, … … … …
kg/a.d. metric ton
oxygen-delignified pulps, compared
Na2SO4 carryover, 6 6 8.4 9.1
to 3 kg/a.d. metric ton for conven-
kg/a.d. metric ton
tional lines. Chlorine dioxide is dis-
tributed at a ratio of 3:1 between the Retention time, min. 39 13 48 30
D1 and D2-stages for oxygen-deligni- Temperature, °C 56 57 53 49
fied pulps and at a ratio of 4:1 for End pH 2.5 2.4 2.4 2.4
conventionally delignified pulps. ClO2, kg/a.d. metric ton 15.6 11.1 20.4 21.8
Kappa factor 0.23 0.20 0.19 0.21
OVERALL BLEACHING CHEMICAL
* Relative chemical consumption.
CONSUMPTION AND COSTS
The kappa factor for the overall II. D(E+O+P)DED bleaching: first chlorine dioxide stage, D0
sequence averages 0.57 for oxygen-
delignified pulps and 0.44 for con-
ventional pulps. The kappa factor for (Exchange rate: 1.37 CAD = 1.00 breakdown of the data for bleaching
the overall sequence is the sum of USD) Figure 9 shows the break- chemical costs. (Assumed costs of
chlorine dioxide in all stages plus down of the data for bleaching effi- bleaching chemicals in Canadian dol-
oxygen and hydrogen peroxide in ciency. lars: ClO2 @ $1/kg, H2O2 @ $1/kg,
the extraction stages, all expressed as Although the overall kappa factor NaOH @ $0.34/kg, O2 @ $0.05/kg.
the percent equivalent chlorine on is higher and the bleaching effi- Excludes cases with Papricycle).
pulp divided by the kappa number ciency is lower for oxygen delignifi-
of the unbleached pulp. cation, the cost of bleaching is lower. OPTIMIZATION ANALYSIS OF
Bleaching efficiency is measured The reason is that the unbleached D(E+O+P)DED BLEACHING
as bleaching chemical costs divided pulps are lower in kappa number for Database
by the kappa number of the the plants bleaching oxygen-deligni- We sorted and analyzed the data sup-
unbleached pulp. In terms of bleach- fied pulps. The average cost for plied both on the nine oxygen-delig-
ing efficiency, the oxygen-delignified bleaching chemicals for oxygen- nified softwood lines and on the
pulps average 2.31 CAD (Canadian delignified pulps was 37.20 CAD/ twenty conventional softwood lines
dollars) per unit of unbleached-pulp a.d. metric ton, compared to 46.44 to see if optimum practices could be
kappa number, while conventional CAD/a.d. metric ton for conventional determined. The data were sorted by
pulps average 1.53 CAD per unit to pulps, a difference of 9.24 CAD/a.d. relative chemical consumption. We
achieve 90% ISO brightness. metric ton. Figure 10 shows the asked, in other words, which mills

VOL. 80: NO. 5 TAPPI JOURNAL 157

PULP BLEACHING

there were five lines with relatively

ASPECT OF BLEACHING low chemical consumption and two
TO EMPHASIZE IN Low consumption lines with relatively high chemical
OPTIMIZATION STRATEGY High consumption
consumption. Similarly, those plants
Minimize bleaching cost bleaching conventionally delignified
Minimize ClO2 pulps fell into two groups as well:
Minimize shives five lines with low chemical
consumption and five with high
Minimize brightness
consumption. Averages for the four
Minimize AOX categories are presented in
Achieve low kappa no. Tables II–VII.
Maximize pulp strength Oxygen-delignified pulps
Compensate for short retention Through the questionnaire, each
Compensate for short sequence bleach plant was assessed to deter-
mine what each was optimized to
Minimize TOX in pulp achieve. As shown in Fig. 11, there
0 1 2 3 4 5 were differences in emphasis
EMPHASIS RATING between the bleach plants having
low chemical consumption and
11. Summary of relative emphasis on various aspects of optimization for low- and high- those plants having relatively high
consumption plants bleaching oxygen-delignified softwood pulps consumption.
All bleach plants emphasized the
importance of minimizing bleaching
Oxygen Conventional costs and the consumption of chlo-
Low High Low High rine dioxide. However, the high-con-
Number of bleach plants 5 2 5 5 sumption bleach plants had greater
emphasis on maximizing brightness
Kappa no. 3.7 5.0 5.0 5.0 and on compensating for short reten-
Brightness, % ISO 55 62 54 54 tion times and short sequences. The
Retention time, min. 89 60 86 79 need to minimize shives was more
Temperature, °C 73 76 79 75 important, on the other hand, in the
low-consumption bleach plants.
NaOH, kg/a.d. metric ton 16.8 16.6 17.4 21.6
NaOH/equivalent Cl2 Kappa factor. The kappa factor
in the D0 stage is lower for the high-
With Papricycle 0.25 … 0.26 0.20
Without Papricycle 0.46 0.56 0.37 0.45 consumption bleach plants than it is
Oxygen addition, 4.2 5.6 5.1 4.8 for the low-consumption plants. This
kg/a.d. metric ton difference probably reflects the
H2O2 addition, 3.2 1.8 2.6 2.9 short retention times for the high-
kg/a.d. metric ton consumption lines (6 and 20 min,
respectively). However, after the
End pH 10.4 10.8 10.7 10.5 E+O+P stage and the D1-stage, the
Delignification, % 82 71 83 83 kappa factor for the high-consump-
Kappa factora 0.36 0.39 0.29 0.31 tion bleach plants becomes greater
Change in % eq. Cl2 per than that for low-consumption
change in kappa no. unitb 0.40 0.57 0.33 0.33
plants.
a
Sum of chlorine dioxide in the first stage plus oxygen and hydrogen peroxide in extraction, all expressed In particular, chlorine dioxide
as % equivalent chlorine on pulp divided by the kappa number of the unbleached pulp.
b
All oxidizing chemicals in the first chlorine dioxide and the first extraction stages, expressed as % equiv- application in the D1 and D2-stages is
alent chlorine divided by the change in kappa number (i.e., the kappa number of the unbleached pulp greater for the high-consumption
minus the kappa number after extraction).
bleach plants, as shown in Fig. 12.
III. D(E+O+P)DED bleaching: first extraction stage, E1 The greater use of chlorine dioxide
in these two stages probably goes to
compensate for the short retention
used the least amounts of oxidizing As mentioned, the database times through the different stages of
chemicals on unbleached pulp of the revealed two groups based on chem- the sequence, as indicated in the
same kappa number to reach the ical consumption. For the plants tables.
same final brightness? bleaching oxygen-delignified pulps,

158 TAPPI JOURNAL MAY 1997

 Brightness development. The
Oxygen Conventional
high-consumption bleach plants Low High Low High
emphasized maximizing final bright-
Number of bleach plants 5 2 5 5
ness to a greater extent than did the
low-consumption bleach plants. As Retention time, min. 175 130 158 142
shown in Fig. 13, the high-consump- Temperature, °C 73 74 72 68
tion bleach plants achieved higher Upflow pH 4.2 … 4.0 3.8
final brightness, at 90.8% ISO as End pH 3.9 … 3.3 3.0
opposed to 89.5% ISO. The effort to Brightness, % ISO 84.8 83.5 82.9 83.6
achieve such a high brightness with
ClO2, kg/a.d. metric ton 8.7 9.8 10.4 13.9
short retention time may explain the
NaOH, kg/a.d. metric ton 0.46 0 … …
relatively higher chemical consump-
H2SO4, kg/a.d. metric ton 0 0 … …
tion in these bleach plants.
Conventionally delignified pulps IV. D(E+O+P)DED bleaching: first ClO2 brightening stage, D1
As shown in Fig. 14, there were dif-
ferences in emphasis between the
low-consumption and the high-con- Oxygen Conventional
sumption bleach plants for conven- Low High Low High
tionally delignified pulps as well. The Number of bleach plants 5 2 5 5
low-consumption plants emphasized
minimizing bleaching cost and mini- Retention time, min.
mizing chlorine dioxide consump- Conventional stage 67 … 72 96
tion, while the high-consumption Short stage 3 7.5 5 …
bleach plants emphasized maximiz- Temperature, °C 68 73 70 70
ing brightness and maximizing pulp
NaOH, kg/a.d. metric ton
strength. Conventional stagea 2.6 … 4.5 5.3
Kappa factor. The kappa factor Short stageb 9.0 8.8 10 …
after each stage is consistently H2O2,c kg/a.d. metric ton 0.8 … 0.7 1.0
higher for the high-consumption
bleach plants, as shown in Fig. 15. End pH 10.4 10.3 10.3 10.3
The kappa factor in the D0-stage and Brightness, % ISO 82.9 … 81.0 …
after E+O+P is 7–10% greater with
a
DED. b(Dn)D. cWhen used.
the high-consumption bleach plants.
After the D1-stage, the difference V. D(E+O+P)DED bleaching: second extraction stage, E2
increases to 15%, and it increases to
17% by the end of the sequence.
Chlorine dioxide application in Oxygen Conventional
the D1 and D2-stages is greater for the Low High Low High
high-consumption bleach plants, as Number of bleach plants 5 2 5 5
shown in Fig. 16. The greater appli-
cation of chlorine dioxide might Retention time, min. 185 110 164 165
serve to compensate for the shorter Temperature, °C 71 75 78 72
retention times in the D1-stage. This Upflow pH 4.2 5.0 4.4 4.4
explanation is not readily apparent End pH 3.9 3.2 3.5 3.9
from the averages given in the Table Brightness, % ISO 89.5 90.8 89.8 89.5
IV: 158 min for low-consumption ClO2, kg/a.d. metric ton 2.3 4.2 2.5 3.8
plants vs. 142 min for high-consump- VI. D(E+O+P)DED bleaching: second ClO2 brightening stage, D2
tion plants. These averages do not
reflect a major difference in the
retention times, as four of the five plant was similar for the cases of low oxidizing equivalents.
low-consumption bleach plants had and high chemical consumption. In Bleaching chemical cost. For
3-h towers and four of the five high- both cases, unbleached pulp of oxygen-delignified pulps, despite the
consumption bleach plants had 2-h kappa no. 28 was bleached to 89.5% relatively high consumption of
towers. ISO brightness. However, the low- chemicals, the bleaching costs for
Brightness development. Bright- consumption bleach plants achieved the high-consumption lines was
ness development across the bleach the same brightness with 17% less lower than for the low-consumption

VOL. 80: NO. 5 TAPPI JOURNAL 159

PULP BLEACHING

90
24 Low consumption
ClO2, kg/a.d. metric ton

Low consumption

BRIGHTNESS, % ISO
High consumption
20 High consumption 80
16

12 70

8
60
4

0 50
D0 D1 D2 Sequence E+O+P D1 D2
STAGE STAGE

12. Distribution of chlorine dioxide consumption for the low- 13. Brightness development for oxygen-delignified softwood
and high-consumption plants bleaching oxygen-delignified soft- pulps in the low-and high-consumption plants
wood pulps

For conventionally delignified

ASPECT OF BLEACHING pulps, the low-consumption bleach-
TO EMPHASIZE IN Low consistency ing lines achieved a bleaching cost
OPTIMIZATION STRATEGY High consistency advantage of approximately 5
Minimize bleaching cost CAD/a.d. metric ton compared to the
Minimize ClO2 high-consumption bleaching lines.
These costs per air-dried metric ton
Minimize AOX
averaged 46 CAD for the low-con-
Achieve low kappa no. sumption lines and 51 CAD for the
Minimize shives high-consumption lines.
Minimize TOX in pulp
Minimize final brightness SUMMARY
Maximize pulp strength The replacement of chlorine dioxide
for chlorine in the first stage of
Compensate for short retention
bleaching is fully compatible with
Compensate for short sequence producing market pulps of 89–90%
0 1 2 3 4 5 ISO brightness. Oxygen-delignified
EMPHASIS RATING softwood pulps require more oxidiz-
ing equivalents per unit of kappa
14. Summary of relative emphasis on various aspects of optimization for low- and high- number in the unbleached pulp.
consumption plants bleaching conventionally delignified softwood pulps On the whole, oxygen-delignified
pulps have an advantage in bleaching
bleaching lines. These costs per air- This difference is due to the sub- chemical costs over conventional
dried metric ton averaged 35.7 CAD stantially lower kappa number for bleached pulps. This advantage is
for the low-consumption lines and the high-consumption case—i.e., roughly 9.24 CAD per air-dried met-
34.3 CAD for the high-consumption 14.6 as opposed to 18.4. The bleach- ric ton of pulp. Finally, operating
lines. ing chemical cost advantage for the with optimized chemical consump-
grades of low kappa number was tion can provide bleaching cost
1.40 CAD/a.d. metric ton. This advantages of 5 CAD/a.d. metric ton
KEYWORDS amount is less than would be for conventional pulps. TJ
Alkaline pulps, bleaching, chemical expected based simply on the kappa
consumption, chemical pulps, chemical number of unbleached pulp. This Douglas C. Pryke is a consultant, RR #1, Erin,
treatment, chlorine dioxide, costs, kraft divergence probably results from the ON, Canada N0B 1T0. Douglas W. Reeve is
pulps, mills (factories), oxides, plant lower bleaching efficiency and the the director of the Pulp & Paper Centre, Uni-
departments, pulp mills, pulps, soft- effort to achieve high brightness. versity of Toronto,Toronto, ON, Canada M5S
wood pulps, surveys. 1A8

160 TAPPI JOURNAL MAY 1997

 0.5 40
Low consumption 36 Low consumption

ClO2, kg/a.d. metric ton

0.4 High consumption 32 High consumption
KAPPA FACTOR

28
0.3 24
20
0.2 16
12
0.1 8
4
0 0
D0 D1 D2 Sequence D0 D1 D2 Sequence
STAGE STAGE
15. Cumulative kappa factors after each stage for conventionally 16. Distribution of chlorine dioxide for the low- and high-
delignified softwood pulps in the low- and high-consumption consumption plants bleaching conventionally delignified
plants softwood pulps

The authors gratefully acknowledge the support of

the CPPA Technical Section Bleaching Committee Oxygen Conventional
Low High Low High
and of Sterling Pulp Chemicals. Most particularly
we wish to thank the mill personnel who took the
time to complete the questionnaires. It is their Number of bleach plants 5 2 5 5
efforts that made this report possible.
ClO2, kg/a.d. metric ton 26.1 25.0 33.3 39.6
Received for review July 24, 1996. O2, kg/a.d. metric ton 4.2 5.6 5.1 4.8
Accepted Dec. 29, 1996. H2O2, kg/a.d. metric ton 3.5 1.8 2.8 3.3
Presented at the 1996 Pulping Conference. NaOH, kg/a.d. metric tona 24.3 21.7 26.7 33.2

Sequence kappa factorb 0.51 0.65 0.41 0.48

Cost, CAD/a.d. metric tonc 35.68 34.30 46.44 51.83
LITERATURE CITED Efficiency, CAD/kappa no. 2.07 2.40 1.53 1.87
Final brightness, % ISO 89.5 90.8 89.8 89.5
1. Pryke, D. C. and McKenzie, D. J., Pulp
Paper Can. 97(1):T1(1996). a
Excludes cases with Papricycle.
b
Sum of chlorine dioxide in all stages plus oxygen and hydrogen peroxide in extraction stages, all
2. Pryke, D. C., Dumitru, M., Cunning- expressed as % equivalent chlorine on pulp divided by the kappa number of the unbleached pulp.
ton, R., et al., “A survey of chlorine c
Assumed costs in Canadian dollars: chlorine dioxide at 1.00 CAD/kg, hydrogen peroxide at 1.00
dioxide substitution in bleached kraft CAD/kg, sodium hydroxide at 0.34 CAD/kg, oxygen at 0.05 CAD/kg. Excludes cases with Papricycle.
mills in Canada,” Technical Section, VII. Overall chemical consumption, costs, and efficiency of D(E+O+P)DED bleaching
CPPA, Montreal, 1992.
3. Pryke, D. C. and Reeve, D. W., TAPPI
1996 Pulping Conference Proceedings,
TAPPI PRESS,Atlanta, Book1, p. 217.
4. Dence, C. W. and Reeve, D. W., Pulp
Bleaching Principles and Practice,TAPPI
PRESS,Atlanta, 1996, p. 387.

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