Development in pulp and bleaching

MFN 0261
N CHAMADA
TITULO Development in pulp and bleaching
AUTOR ES ELLIOTT G
R
EDICAO
IDIOMA ingles
ASSUNTO 3
02 Branqueamento da Pasta Celulosica
TIPO Congresso

EVENTO Congresso Anual de Celulose e Papel 24

PROMOTOR ABTCP
CIDADE Sao Paulo
DATA 25 29
1991
11
IMPRENTA Sao Paulo 1991 ABTCP
PAG VOLUME p
2 69 295
FONTS Congresso Anual de Celulose e Papel 24 1991 Sao
Paulo 269 295
p
AUTOR ENTIDADE
DESCRITOR meio ambiente ozonio antraquinona

RESUMO
 ABTGp

DEVELOPMENTS IN PULP AND BLEACIIING

R G Elliott
Longview Fibre Company
Longview WA U
A
S

Abstract

Current developments in pulping and bleaching are driven by environmental restrictions and the
green movement fiber supply issues prompting concern over pulp yield and competitive
concerns in the emerging world wide market Today
s focus narrows down to chlorine and
chlorine compounds Will we continue to use chlorine in the future Will other chlorine
compoundssuchasch lorinedioxiderenutininuse These questions cannot currently be answered
but certainly current technology is concentrating on minimization of chlorine usage via several
different routes Extended delignification is of major interest via kraft pulping to very low Kappa
Nos oxygen delignification and the use of ozone Very high levels of chlorine dioxide
substitution in the first stage up to 100
70 are being used Yield enhancing additives such as
anthraquinone have moved beyond kraft and soda pulping to neutral sulfite and alkaline sulfite for
much greater yield improvement Solvent pulping long dormant is receiving increased interest
particularly for smaller mills

introduction

Commonlyrecognized problems with chemical pulping which have been studied for several
years such as low yield odor associated with kraft pulping complex chemical recovery
requirements and high capital cost have recently been overshadowed by environmental concerns
These concerns exist not only in requirements to minimize emissions to both airand water but also
in producing environmentally safe products An example of the latter is the demand in Europe
especially Germany for chlorinefree papers Therefore changes currently underway are being
driven not only by regulatory efforts in pollution control but also by product marketing New
technology is evolving rapidly to meet these demands

Extended Delignificalion

Several processes have emerged which involve the addition of kraft cooking liquor in multiple
charges allowing the pulping reaction to continue to low Kappa No or lignin content This allows
a lower alkali concentration at the beginning of the cook and maintenance of residual alkali at the
end of the cook For batch digesting extended delignification is often accompanied by liquor
displacement and cold blowing in systems such as Super Batch marketed by Sunds and Rapid
Displacement I letting RDI I by Beloit Both Super Batch Figure 1 and RDII Figure 2 utilize
hot and warm liquor accumulator tanks for liquor containing low alkali and relatively high
sulfidity is a key to the retention of pulp strength at low Kappa No The processes are quite similar
comparing Figure 1 with Figure 2

Paper presented at the 24th Pulp and Paper Annual Meeting ABTCP Sao Paulo SP Brazil
November 25 to 29 1991
 Figure I

SUPER BATCH SUNDS Enocell

From
White
wash
plant liquor HP Hot
steam water

Wash Hot Hot Hot Warm

filtrate black black white black
C
80 liquor I liquor II liquor liquor
C
167 140
To evaporation
C
160 C
90
plant

V E

WOOD CHIPS
8
LP steam CHIP CHARGE

BLACK LIQUOR
IMPREGNATION i
HOT BLACK
LIQUOR
PRETREATMENT

HOT LIQUOR
B C
CHARGE 165
C

Direct
HP steam HEATINGUP
TO 160 170
C

COOKING
TIME

TERMINAL
DISPLACEMENT A1
A
00
rV
DISCHARGE
 Figure 2

RDH BELOIT Westbrook Calhoun etc

From
White
wash
Hot liquor
water
plant

Cool Hot Hot Warm Wash

I
black black white black filtrate
liquor liquor liquor liquor C
80
C
160 C
157 C
115

I I I I I
A 8 C D E

WOOD

I
t
ICHIPS
Steam Liquor
packing packing
CHIP CHARGE

BLACK LIQUOR
D A
IMPREGNATION

8
HOT BLACK AND
WHITE LIQUOR
CHARGE 157
C
9
C

Direct
HP steam HEATING UP
TO 160 170
C

COOKING
TIME

TERMINAL
D DISPLACEMENT

Pressurized
DISCHARGE
air

J4 PUMP Bennetsville
PULP
Majordifferences include a separate hot black Iiquordisplacement in the Super Batch process and
blowing via compressed air in many of the RDII systems Some of the newer RDIi installations
pulp out the digester contents rather than using compressed air Using two cooking periods these
processes have attained a 5 to 7 Kappa No reduction on softwoods with a 10 to 15 increase in
cooking chemicals resulting in a savings of 20 to 30 chlorine and chlorine dioxide in
bleaching Energy conservation was the major reason for development of these processes with
steam savings of 60 to 85 reported compared to conventional batch digesting 3
7
6
5
4

Modified Continuous Cooking

Modified Continuous Cooking MCC is a process developed by Kamyr to incorporate extended

delignification in Kamyr continuous digesters New digesters equipped with MCC are twovessel
hydraulic with additional white liquor entry and extraction screens for a countercurrent cooking
zone at the end of the cook Figure 1 is a simplified schematic of a two vessel hydraulic digester
equipped for MCC
8 Figure 2 shows the MCC loop in greater detail Several existing digesters
have been converted to MCC using all or part of the wash zone for countercurrent cooking
Modified Continuous Cooking and other extended delignification techniques allow the removal
of a much larger fraction of lignin in the pulping process without loss of pulp strength thereby
substantially reducing the amount of bleaching chemicals required Thus the residual lignin
enters the kraft recovery process rather than the effluent from the bleachery New mills design for
the additional loading to recovery but many existing mills are recovery limited and would have
difficulty incorporating extended delignification techniques into their process 9

Figure 3 Two Vessel Hydraulic Digester

Equipped with MCC
Figure 4 MCC Details

DIGESTER ZONES

1 In S AND LIQUOR

CO CURRENT
COOK ZONE

COUNTER CURRENT
COOK ZONE

HI HEAT
WASH ZONE
At Longview Fibre Company softwood pulp at very low Kappa Nos less than 15 and as low as
9 has been produced in the mill using the modified continuous cooking process MCC in aKamyr
two vessel hydraulic digester The pulp was subsequently mill bleached to 84 G E brightness
using CEI ID C
EPI ID and C
EPD sequences First stage active chlorine applications of less
than 2 were attained Mill effluent and bleach plant effluents were sampled and analyzed for
AOX and dioxins Environmental goals of less than 1 5 KgADMTBP AOX and non detect
8 TCDD were met without chlorine dioxide substitution In addition to the mill studies
7
3
2
numerous bleaching sequences have been studied in the laboratory including sequence using
oxygen Chlorine dioxide substitution at 7
5 n and 21 to 27 further lowered AOX but more
dramatically significantly reduced sodium hydroxide usage and chlorine dioxide in the fourth
stage

The pulp produced at 15 Kappa No and lower using the modified continuous cooking process
proved to be a stronger than batchcooked pulp at approximately 30 Kappa No as determined by
both PFI testing and papermachine testing The traditional relationship between pulp strength and
viscosity does not appear to hold however as low viscosity pulps produced good paper strength
Extensive studies on pulp yield using a solids balance technique indicate a linear relationship with
Kappa No down to approximately Kappa No 18 Below Kappa No 18 yield loss accelerates
slightly down to Kappa No 15 followed by a sharp yield loss at lower Kappa Nos 10
Anthraquinone and QuinoneType Additives

Anthraquinone as an alkaline pulping catalyst was developed by in Canada and millscale

trials were run at Interstate Paper Riceboro Georgia in 1977 Recent approval by the U
S Food
and Drug Administration for use in food packaging papers has spur
dinterest Anthraquinone
a yellow powder material is effective at 0
05 to 0
15 on wood improving pulp yields by 2
5
4 and reducing cooking times by 30 CIL researchers have foii d that anthraquinone and
sulfidity are essentially interchangeable Therefore soda mills can produce quality equal to kraft
via the addition ofanthraquinone Even though anthraquinone AQ is effective at very low dosage
rates the cost per pound is very high Generally speaking some incentive other than yield must
come into play since the cost of AQ generally exceeds the value of the wood saved The cost of
AQ is expected to drop as it becomes more generally used However its greatest use is as a dyestuff
intermediate a relatively small usage and commercial adoption as a pulping catalyst would
require much more than the current world supply Scaling up production to meet a questionable
demand is a difficult problem

The 1980 TAPPI Pulping Conference introduced work in Finland on NS AQ pulping a neutral
sulfite process with anthraquinone added This is a so called alkaline sulfite process with alkali
concentration and liquorto wood ratio similar to kraft The major advantages are a light colored
pulp at yields 7 20 better than kraft Unfortunately the recovery process is complex with
equipment required for the conversion of hydrogen sulfide to sulfur dioxide and for the makeup
of the sodium sulfite cooking liquor

The French have introduced the Alcaper process which uses a soda AQ cook followed by
hydrogen peroxide delignification Pulp at approximately 50 Kappa No is defibered in a refiner
then delignified to about 30 Kappa Number with 0
5 1 hydrogen peroxide at medium

274
consistency in 3 4 caustic on pulp The Alcaper process may offer advantages for bleaching
grade softwood pulps but will require a very large causticizing system to accommodate the high
alkali demand 11

Figure 5
Schematic Flow Diagram of Alkali Peroxide Process

Wood chips
AU

e
Washing

nq
ch
Deli be
iafnq
a to
Caustic
Oda

cooking
1700C
Precooked
chi

ryatem

Currently worldwide some 30 to 40 mills are using anthraquinone or one of its precursors on a
regular basis Mead Corporation Kingsport Tennessee has used AQ full time since 1977 in a
sodaAQ process to provide pulp for manufacturing printing papers On mixed hardwoods at least
3 more pulp is produced in less time using less than 0 1 AQ based on wood Most usage
appears to be for pulps used for fine papers or linerboard Consolidated Bathurst New Richmond
Quebec found that the active alkali level for linerboard basestock production could be lowered
from about 13 to 11 with 0
05 AQ

In Japan approximately 70 of the pulp produced is made with quinone additives The most used
is DDA Dihydrodihydroxyanthracene commonly called SAQ or soluble anthraquinone
12

disodium salt of 1
4 dihydro9
10dihydroxyanthracene

AQ DDA
O ONa

II

II
O Otia

275
Since announced in 1977 more than 200 technical papers have been published on anthraquinone
The consensus is that it is uneconomic in North America to use AQ to save raw materials such
as wood chemicals or energy i lowever it remains an attractive option for debottlenecking a pulp
mill Examples include

Digester limited Kraft Mill

A production gain of approximately 10 can be realized
10 AQon wood The additional production results from a yield increase from 48
using0
to 49
5 plus a more rapid pulping cycle

2 Recovery Furnace Limited Kraft Mill The pulping acceleration can be used to lower
either alkali requirements or energy requirements Choosing the former increased produc
tion results from a gain in yield plus less organic load to the furnace per ton of wood pulped
A similar situation would occur in an alkali limited mill with inadequate causticizing
capability

3 1 ligh Yield Kraft recovery furnace limited This example is similar to the above case except
that a 10 n production increase would be expected using 0 05 AQ on wood

Anthraquinone appears of most interest as a temporary debottlenecking technique in cases where

pulp mills are produced limited yet a market exists and the rest of the mill can handle increased
production The benefits are greater for higher yield pulps than for bleachable grades

Alkaline sulfite anthraquinone ASAQ appears to offer substantial yield advantages over
conventional kraft particularly at high Kappa Nos typically used for containerboard However
the process requires chemical preparation and recovery equipment typical of sulfite pulping Mini
sulfide sulfite anthraquinone MSS AQ has been developed by STFI Sweden for bleachable
grades The prefix mini refers to a low charge of sulfide in an alkaline sulfite pulping liquor
at a ratio of about 0
1 sulfide to sulfite At this ratio a significant minimum in the lignin content
of pulp is attained Yields 8 higher on wood compared to conventional kraft can be obtained in
a single stage process while twostage cooking followed by oxygen delignification resulted in
Kappa Nos less than 10 with strength equivalent to kraft 13

Reaction Mechanism of Anthraquinone The ability of anthraquinone to accelerate pulping was

discovered long before the mechanism was understood The amazing feature of AQ pulping
systems is that only a very small quantity 0
1 or less of anthraquinone is needed for effective
pulping Extensive research discovered that two forms of AQ are present during pulping One
form AQ stabilizes carbohydrates by an oxidation reaction and gives rise to the other form
anthrahydroquinone AilQ The AHQ on the other hand causes the lignin to dissolve by a
reduction reaction and regenerates AQ This results in fast reaction times Little AQ is needed
during pulping because the active chemicals are constantly being regenerated in the digesters via
this redox cycle

Research is underway in thechemical synthesisof anthraquinone from less expensive petrochemi

cal precursors which would allow many pulp mills access to cheaper AQ
 Figure 6

40
KRAFT

36 0

32

z
28
CL
AQ
SODA
Y 24 AQ
KRAFT

9
20 L
46 48 50 52

TOTAL YIELD Y
 TABLE I

Benefits of AQ Addition to Kraft and Soda Cooks 11

Pulp Type
AO Addition Kraft Process Soda Process

Iligh Yield 1015 reduction in Can match normal

Softwood 05 both alkali and 11 kraft with yield
AQ on Wood factor 2 3 yield gain rate equal or
slightly lower
strength compared
to normal kraft

Bleachable Same as above Same as above

Softwood 1015
AQ on wood

1lardwood 10 reduction in Can compare with

5 on Wood
0
025 both alkali and 11 normal kraft yield
factor 1 2 yield gain and strength 10
reduction in both
alkali and 11 factor
53
2 5 yield gain

Organic Solvent Pulping

Pollutionfree pulping processes using alcohols or solvents such as ethylenediamine have been
proposed but not commercialized Most often the cost of the solvent is such that essentially 100
recovery is required and 100 recovery is impractical on a commercial scale This has been the
largest stumbling block to commercialization of solvent pulping processes

Ester pulping is claimed by the University of Wisconsin Department of Forestry to be significantly

less capital intensive than the Kraft process environmentally benign and to provide pulps of
strength comparable to kraft Pulping is by solvent extraction using a mixture of acetic acid ethyl
acetate and water The solvent is a twophase system and after pulping the organic phase contains
quite pure lignin and the aqueous phase contains wood sugars These phases can be easily
separated by decantation for recovery of byproduct lignin if desired It may also be possible to
recover acetic acid ethyl acetate and furfural Current plans include recovery of acetic acid A
pilot plant of about 10 tons per day is planned by Biodyne Chemicals Neenah Wisconsin 14
Early work on ester pulping used aspen and was quite successful however attempts to adapt the
process to additional wood species have been frustrating The Institute of Paper Chemistry has
found ester pulping ineffective for softwoods and uneconomical for hardwoods other than aspen
Alcohol pulping is in operation on hardwoods at a 33 ton per day demonstration plant in New
Brunswick Canada The Alcell process is marketed by Repap Technologies Inc and is similar
to the alcohol pulping and recovery ARP process shown in Figure 7 and Figure S Similar
technology is emerging in Germany termed Organocell The extraction part of the process
operates in a batch mode while the solvent and by product recovery sections operate continuously
Wood yard and bleach plant operations are identical to kraft or sulfite operations In fact for the
demonstration plant in Newcastle N
B Repap is using the bleach plant of the adjacent kraft mill

At the beginning of the process wood chips are loaded into a extractor After preheating within
low pressure steam liquor 60 alcohol from a primary extraction accumulator is circulated
through the extractor and a peak load heat exchanger The temperamreof the mixturequicklyrisec
to between 190C and 2
XC

Following this primary extraction the liquor remaining in the extractor is displaced into the
recovery feed accumulator by the liquor coming from the secondary extraction accumulator At
the completion of this displacement liquor in the extractor is displaced into the primary extraction
accumulator to be used for processing the next batch of wood

Once the extractor is drained it is vented and alcohol rich vapors are condensed in the blowdown
condenser and recycled in the fresh solvent accumulator Pulp left in the extractor then is stripped
with low pressure steam until only trace amounts of alcohol remain The vapors are condensed
in the reboiler of a solvent distillation tower and recycled to the fresh solvent accumulator After
steam stripping the pulp remaining in the extractor is sluiced with water and after screening is sent
to the bleach plant

The duration of this extraction process is about three hours for lowdensity hardwoods and longer
for high density hardwoods 15

Biopulping

Scientists for years have been fascinated by organisms such as white rot fungi in which enzymes
dissolve lignin leaving pockets of pure white cellulose Unfortunately the process is much too
slow to be of interest in pulping requiring several months However a genetic engineering firm
Repligen Corp of Cambridge Massachusetts has identified more than ten of these enzymes The
fungus itself is too difficult to grow in large quantities Hence Repligen intends to clone the genes
controlling enzymes production into another organism is order to produce commercial quantities
They have entered into a joint development agreement with Cellulose du Pin of France 16

A consortium has been organized by the US Forest Products Laboratory and the University of
Wisconsin Madison to explore biopulping The consortium is receiving support from several of
the major forest products companies and research is just getting underway

Oxygen Delignification

This is a grey area as to whether is should be considered pulping or bleaching Predominant usage
is between pulping and bleaching as an extension of the pulping process The major processes are
279
generally segregated according to consistency i
e medium consistency at 8 15 and high
consistency at 25 35 n At the 1987 International Oxygen Delignification Conference in San
iI
egn California U A it was reported that there are 45 operating oxygen delignification
S
systems and the world production capacity is expected to Surpass 10 million metric tons per year
in 1988 17

Figure 7 APR process flow diagram for pulping

To blowdown conde
Chips r T
To other extractors

Peak
load Steam I I
heal

JE
L Ii T iL From other
ex Charmer six extractors
xt ractor
Z ExVaclor Z Ext
ractor
Steam

L
Condensate nd

II I
f Toa from
re i u0 ank
t
Pulp

i From
L 1 J I
fre
Primary extraction liquor
accumulator Fresh liquor tank
eccurnulator
Recovery leed
accumulator
To recovery system

From
Figure B APR processflow diagram for recovery
extractors
overy
Rec Makeup
Second
Flash
r bconde nser steam

I
eff
y tank
Blowdown
conden I First
evaporator
ora

From recovery A eaecl

feed accumulator Black evaporator
liquor a
tank
Vacuum
Lector

Makeup Steam4r Sugars

alcohol I Solvent

To and from Steam

recovery
tower
extractors
4 Centrifugal
Fresh separator
Presoak liquor Condensate
liquor lank Lignin
lank
7

Condensate Feed Clarllier

To fresh l
iquor
accumulator
preheater
Of the operating installations

92 are in kraft mills

60 n are for bleaching softwoods
50 are in Scandinavia and Europe
20 n are in North America
20 n are in Japan
60 use high consistency processes

Oxygen delignification is mandated by the Swedish government for all new bleached pulp mills
as a pollution control measure The economics of oxygen delignification appear favorable only
in Japan where a large amount of very low cost oxygen is available as a byproduct of nitrogen
usage in the semiconductor industry Chlorine and sodium chlorate are also quite expensive in
Japan In most cases the overwhelming reason for choosing oxygen delignification has been
environmental

Pulp Quality The strength properties of oxygen delignified bleached pulps and conventionally
bleached pulps are equivalent if the degree of delignification in the oxygen stage does not exceed
about 50 Oxygen delignified pulps have a much lower viscosity than conventional pulps when
compared at the same strength The traditional relationship between pulp viscosity and pulp
strength does not appear to hold for oxygen delignification Brightness reversion is at least equal
and in the case of some softwoods up to two units less reversion has been reported for oxygen
sequences A marked reduction in pitch deposition has been reported downstream from high
consistency oxygen stages perhaps due to the pressing of the pulp to attain the high consistency
Much lowerdirt counts are reported with oxygen and much less energy isrequired in pulp refining

Environmental Benefits The effluent reduction shown in the following tables is achieved by
washing the dissolved solids from the oxygen stage and recycling them to the pulp mill recovery
system The formation of chlorophenols and chloroform is a growing concern due to toxicity
Since oxygen delignification supplants a large amount of applied chlorine the total amount of
chlorinated organic compounds formed is significantly reduced Note the decrease of 35 50 in
TOCI from softwood bleaching

TABLE II

Effluent Summary
Kraft softwood 0 stage Kappa reduction 45 50

DED
o
E
D
C OC 8 Red

15 21 8 11 40 50
BODt
kg t
COD 65 75 30 40 45 55

Color kg Ptt 200 300 80 120 60 75

TOCI kgt 58 3 4 35 50

Flow 10 1
t 20 25 15 20 25 30
 TABLE III
Effluent summary Kraft hardwood
0 stage Kappa reduction 45 508

C OC 8 Red

10 15 5 7 40 45
BOD t
kgt
COD 40 45 20 25 40 45
Color kQ Pt t 90 125 15 25 40 45

10 I
F1ow t 20 25 15 20 25 30

Note t denotes metric ton

I ligh Consistency Oxygen Delignification The predominant process operates at consistencies of

25 to 28 temperatures of 1
X 125C pressure 5006 X kPa and retention time of 2040
minutes Alkali requirements are high about 21 to 23 Kg per ton of pulp and hence recovery
is necessary in order for the process to be economical A small amount of magnesium compound
such as magnesium carbonate is used as a protector to preserve pulp strength

High consistency is attained via a press and an upper limit of 35 consistency must not be
exceeded because of spontaneous decomposition which results in fires in the oxygen reactor After
the press sodium hydroxide and magnesium protector are added A thick stock pump or screw
feeder is used to compress the pulp into a plug to seal the reactor followed by a Huffer to ensure
good oxygen contact The control strategy is extremely simple A reactor pressure ofpure oxygen
is maintained and as the pulp consumes oxygen the pressure drops signalling for more oxygen
addition Inert gases and carbon monoxide must be purged from the reactor Most reactors are
equipped with continuous hydrocarbon analyzers to prevent combustible concentrations Two
types of reactors are in use a plugflow downflow reactor and a multiple tray downflow tower
equipped with rotating scrapers to scrape the pulp to each succeeding lower tray The traytype
reactor is more expensive to construct and maintain but eliminates any possibility of channeling
which can occur in plug flow reactors

Medium Consistency Oxygen Delignification Pulp from a brown stock washer or decker at 8
14 consistency is treated with sodium hydroxide and magnesium salt preheated in a steam
mixer and pumped through one or more medium consistency oxygen mixers to an upflow
pressurized reactor In some installations oxygen gas is mixed with the sodium hydroxide
solution in a static mixer just prior to injection into the medium consistency mixer Other
variations included the use of the medium consistency pump or a mixer and direct injection of
oxygen gas via a diffuser depending on diffusion for mixing
Figure 9 High consistency oxygen deli
gnification

Figure 10 Medium consistency oxygen delignification

Medium consistency oxygen technology is quite new and is growing rapidly The equipment is
much less expensive and the reactors are inherently safe requiring no venting However MC
systems require more alkali and more steam he issues of capital cost versus chemical and steam
consumption normally dictate the choice between high consistency and medium consistency
oxygen systems Oji Paper Company Ebetsu Japan recently installed a Sunds Defibrator medium
consistency oxygen system and reported a 40n reduction in Kappa No accompanied by a 32
drop in bleaching chemical consumption in DCEO I IWD displacement bleaching 18
Operating data for both high consistency and medium consistency are shown in Table IV

TABLE IV

Typical Operating Data

oxygen Deligni
fication of Kraft Softwood Pulp
High Cs Mad Cs

25 28 10 12
Pulp consistency 1 45 50 40 4S
Deligniticaticn 1 50 60
30
Retention time minutes
100 105 100 105
Initial temp oC

Pressure kPs
500 600 700 800
inlet
outlet 500 600 450 500

Steam consumption kq t 70
lo pc ese 450 kPal 200 300
1140 kPa
press
9ed 73 100
90 110
30 50
evaporator 450 kPa
40 50 35 45
er consumption kWh t
PC 25 I8
Alkali consumption kq t 21 23
20 24 20 24
Oxygen eons umption kqt 5
0 5
0
Mq kq t

Note that steam consumption for the MC system is more than double Additional evaporator steam
must be charged to oxygen systems since the oxygen stage filtrate must be evaporated and burned
along with the pulping spent liquor Of note also is the approximately 20 greater alkali
consumption for medium consistency systems keeping in mind the impact on recovery furnace
and causticizing capacity Because of the high alkali demands of oxygen delignification most
mills use oxidized white liquor rather than purchased sodium hydroxide in order to maintain a
proper chemical balance in the pulp mill

A comparison of kraft cooking with combined cooking and oxygen delignification is shown in
Table V09

A significant yield increase resulted in each case and the Kappa No after oxygen delignification
was the same as the kraft comparison In these cases the load to the kraft recovery furnace would
be the same or less than that for conventional kraft pulping Most often however the process is
used to extend the delignification ahead of the bleaching process thereby increasing the recovery
furnace load and minimizing the effluent discharge
284
 TABLE V

en e Co
d
Cemv l K
ivn fr C
k irh Gembimd Xnfr Ceok
n
nd Og Alkali ien
dfu
G
D

A16G Alkdl 0 4
Y
b dd
Yl r
rA n
ronmmpn N
Y
OH
N o OH
N O O

1 n K
mk
KrJ y

ule m X
Gem6 w
X10

N 44
4 20 1 461 11

J
K w m K
m 10 dJ 3
41

11 KrJ ki m
m 111 O JW
deem fu
As 1
e

r rooWM v IC
Itr m
w10 24 J6

111 ed n JW
0
ro 110
0 1
de
emir n iUo
30
z If 1
4 13 41 11

J nw
K kinr a K
ee
m 30 N 1
46

Chemical Pretreatments for Oxygen Delignification Research activity is extensive in attempts

to improve the selectivity of oxygen delignification and extend it to even lower residual lignin
levels Pretreatment within nitrogen compounds has been studied mainly in Sweden led by Olof
Samuelson of Chalmers University ofTechnology 20 Oxygen bleaching of kraft pulp pretreated
with nitrogen dioxide decreased the Kappa No from 30 to 3 5 without significant pulp degrada
tion Additional variations on the process include the introduction of small amounts ofoxygen to
the pretreatment to minimize the formation of nitric oxide and the use of a low consistency acid
nitrate ripening stage at 5 consistency for 90 minutes Nitrogen dioxide followed by a small
amount of oxygen as a pretreatment has been termed Prenox and is being developed by Sunds
Defibrator A pilot plant at Mo Do flusum Sweden reduces a 31 Kappa No softwood kraft pulp
to 10 Kappa No following oxygen delignification with a retention time of 15 20 minutes in the
Prenox pretreatment stage 21 Pretreatment of pulps with approximately I chlorine has been
found to improve delignification Soteland 22 has proposed a COCO sequence using a total of
2 chlorine resulting in a Kappa No of 3 to 4 with little loss in viscosity without the use of chlorine
dioxide in the chlorination stages Capital equipment however for this sequence would likely be
quite high even at medium consistency Other pretreatments reported include chlorine dioxide
hypochlorite peroxide ozone acidic oxygen sulfur dioxide sulfite and sulfide 23

Developments in Pulp Bleaching

Recent developments in pulp bleaching have emphasized the minimization of molecular chlorine
Chlorine dioxide substitution in the first stage is increasing rapidly with many mills operating at
50 to 75 chlorine dioxide and much of the bleached pulp destined for Europe is produced using

285
 H chlorine dioxide Keep in mind however that most commercial chlorine dioxide contains
I
a small amount of chlorine

These high addition ratesclaim the benefitsof improved pulp cleanliness and brightness and Bless
toxic bleach planteftluent Figure 11 indicates that pulp viscosity reaches amaximumwith asmall
amount of chlorine dioxide approximately 5 and does not regain this viscosity level until
chlorine dioxide substitution was increased to 80

Figure 11
Effect of Substitution of Chlorine Dioxide for Chlorine in the First
Stage on Viscosity after D and D Stages of DCE Bleaching of
Western Hemlock Kraft Pulp

IIAPSON AND MUMILA

35
0

u
U

30

u
0

23
H

yOU
20
100 so so 40 20 O Cl2
0 20 40 60 60 100 C10

OF THE AVAILABLE C11 IN THE CHLORINATION

Ilowever this data was obtained using mixtures of chlorine and chlorine dioxide and recent
technology indicates that sequential or serial addition may be of more benefit Figure 12 shows
the dramatic improvement in pulp viscosity as a chlorine D Q as compared to mixtures
Q
D
 Figure 12

AND ANNERCREN
DENC

E
v

u
0

0 1
0 2
0 3
0 4
0 0
AS ACTIVE CHLORINE
CIO
ROE NO

Medium consistency chlorination 1015 consistency is a recent development spawned from

cost reduction studies in pulp bleaching The development of equipment to allow the removal of
medium consistency pulp from storage tanks without dilution coupled with pumping and mixing
equipment allows pulp processing to be accomplished entirely at medium consistency Medium
consistency chlorination is generally accomplished by the injection of chlorine gas just ahead of
a high shear mixer Diffusion of the gas is rapid since much of the liquid phase is not present and
chlorine utilization efficiency is said to be improved If substantial amounts of chlorine dioxide
are to be added two of the high shear mixers are generally used in series Medium consistency
chlorination is often used with displacement bleaching towers and upflow towers with diffusion
washing but is not common in conventional bleach plants because conventional bleach plant
washers require dilution to a low consistency thereby eliminating most of the advantages

Many chemical additives have been used to boost the efficiency ofcaustic extraction Hypochlo
rite was one of the earliest additives yielding some brightening effect but more commonly added
to reduce the color of the very black extraction stage effluent Hypochlorite addition has been
investigated for many years and interest has recently increased Oxidative extraction E which
involves the addition of molecular oxygen to the extraction stage is a technology which has
mushroomed faster than any other development in pulp bleaching eclipsing the rush to chlorine
dioxide in the early 1960
s Oxidative extraction is a natural spin off from oxygen delignitication
since a highly alkaline environment is required Figure 13 courtesy of IMPCO illustrates the
equipment commonly employed for oxidative extraction and details the benefits achieved Note
that a 2 to 3 point brightness increase has been achieved at equal cost or a savings of 6 to 7 pounds
per ton of chlorine dioxide at equal brightness Equipment for oxidative extraction can be
retrofitted readily into existing plants
287
 Figure 13

Eo
OXIDATIVE EXTRACTION

The E stage was first demonstrated on a commercial scale in Sweden as reported by

Lindstrom Nordem and Carre at the 1980 TAPPI Pulping Conference This was done in an
upflow caustic extraction tower Further developments have shown that the beneficial effect
of oxygen addition can also be achieved in an upflowdownflow tower

This makes the process very attractive as a retrofit in an existing bleach plant The following
benefits can be achieved

An addition of 10 of oxygen per ton of pulp to the first extraction stage in a C

DE
E sequence will save 6 to 7 pounds of chlorine dioxide maintaining the same
D
final brightness This decrease the bleaching cost by about 2 per ton

Addition of oxygen to the first extraction stage will increase the final brightness by 2
to 3 points without increasing the bleaching cost

The short sequence CDE D will reliably produce 85 GE brightness on both soft
wood and hardwood at the same or lower chemical cost as a fourstage or fivestage
sequence Energy and maintenance costs will be drastically reduced

Figure 14 also courtesy of IMPCO shows the Kappa No reduction obtained compared to
conventional caustic extraction

WE
 Figure 14

Ea
OXIDATIVE EXTRACTION
BLEACHING STAGE

TIME MIN

Oxidative extraction is easy to implement and control In practice 8 10 pounds per ton of oxygen
as a gas is mixed with the caustic solution flowing to the caustic mixer A simple static mixer has
been found effective for oxygen mixing and in some cases direct injection of oxygen has been
reported The hydraulic head of an upflow tower or a preretention tube as shown in Figure 13 is
sufficient to allow the reaction of the oxygen with the pulp A minimum hydraulic head pressure
of approximately 138 kPa has been found necessary for good oxygen utilization efficiency
requiring an upflow vessel of about 12 meters in height

Previously mentioned concerns regarding chlorinated organic compounds in bleach plant effluents
have stimulated interest in chlorinefree bleaching A major stumbling block is usually economics
since bleaching with chlorine compounds is generally significantly less expensive than the non
chlorine oxidizing agents

Ozone delignification has been investigated by researchers at Scott Paper Company and Pulp and
Paper Research Institute of Canada frequently in combinations with oxygen and peroxide
resulting in chlorinefree bleaching sequences such as OZEP Z represents ozone Ozone
bleaching has been carried through the pilot plant stage by Scott with satisfactory results on
hardwood pulps using approximately 1 ozone oft pulp Softwood pulps generally require an
oxygen delignification stage to minimize chemical consumption and preserve pulp strength
Ozone is an extremely active oxidizing agent and preservation of pulp strength appears to be a
major problem
289
Union Camp Corporation has announced the installation of ozone delignification at their Franklin
Virginia mill They have established a subsidiary to market the technology Paprican indicated
that a ZF
P sequence could he accomplished essentially in a single stage due to the very fast reaction
time of ozone Ozone would be added to a mixer ahead of a preretention tube similar to EO shown
in Figure 13 At the top of the preretention tube sodium hydroxide and hydrogen peroxide would
he added to complete the stage Softwood pulp brightness of 85 was achieved with 15 Kappa No
oxygen delignified pulp Ozone addition was 0 5 followed by 2 5 hydrogen peroxide 24

Figure 15
High Consistency Ozone Delignification Equipment
WIN POLL PRESS

A side benefit from research on ozone delignification has been the enhancement of bonding
properties such as tensile and bursting strength of highly lignified pulps Ozone treatment of
mechanical pulps at levels of I to 25 n ozone has produced increases of up to 40 in tensile
strength Significant strength increases in recycled fiber waste paper have also been reported via
ozonation

Peroxide bleaching has fallen in and out of favor over many years It can hardly be called a new
development since its usage predates chlorine dioxide However several novel applications have
recently surfaced including the use of peroxide with ozone and oxygen mentioned previously The
use of peroxide to replace the second extraction stage has been reported advantageous for fully
bleached market pulp in sequences such as CEDPD Peroxide is reported to minimize brightness
loss or reversion due to pulp aging The cost of peroxide at equivalent oxidizing power Hence
at present the selection of peroxide as a bleaching agent is normally based on other than economic
decisions This is reportedly not true in Japan where the cost of peroxide is competitive with other
oxidizing agents
M
Current interest in peroxide is most active as an additional reinforcing agent in the caustic
extraction stage i
e EOP A significant increase in delignification is reported over conventional
oxygen reinforced extraction Therefore its use appears attractive as a means of minimizing usage
of molecular chlorine

Although the use of oxygen ozone and peroxide generally consumes less energy in pulp
bleaching consideration must be given to the chlorine caustic balance Chloralkali production
is an electrolytic process which produces nearly equal quantities of both chlorine and caustic
Delignification with oxygen ozone and peroxide requires large amounts of alkali but of course
no chlorine Thus for these processes to receive wide spread use a chlorinefree method of
caustic manufacture must become economical or substantial other uses forchlorine must be found
An additional alternative is the use of oxidized white liquor from the kraft recovery process as a
source of alkali

Development in Chlorine Dioxide Manufacture

Most chlorine dioxide is produced by the R 3 or SVP process which uses a solution of sodium
chlorate and sodium chloride nominally 25 NaCl O and 15 NaC 1 by weight The generator
operates under significant vacuum and at higher temperatures than conventional generators such
that the water introduced is evaporated the vapor acting as a diluent for the chlorine dioxide
leaving crystalline sodium sulfate in the generator solution The sodium sulfate is filtered from
the generator spent acid and the spent acid is recycled back to the generator along with fresh
sulfuric acid makeup Thus the R 3 process operates with no acid effluent The recovered sodium
sulfate is most often used as makeup fora kraft recovery system R 3 generators are reported free
from puffs resulting from chlorine dioxide decomposition due to the steam blanket of water
vapor present with the chlorine dioxide

Most common chlorine dioxide generating processes have two problems associated with by
products 1 Excess saitcake production and 2 a large amount of dilute chlorine gas The
saitcake stream is increasingly more than kraft pulp mill makeup requirements The chlorine
stream is too dilute in air to use in the chlorination stage and is often used to make hypochlorite
The elimination of many hypochlorite stages has compounded the disposal problem

Many new chlorine dioxide processes and sonic not so new such as the revival of theDay Desting
electrolytic process by L
urgi as the Holst or Munich process have been developed to solve the
above problems Although hydrochloric acid has been known to be effective as a reducing agent
for sodium chlorate for many years it is of current interest as a means of minimizing the saitcake
by product Hydrochloric acid is more expensive than sulfuric acid but it provides the reducing
agent in addition to being a source of acidity l fence a mill can vary the saitcake output by
replacing all of part of the sulfuric acid with hydrochloric acid in the R 3 type of generator Pull
replacement is termed the R 5 process

The R 6 process operates with hydrochloric acid but the system s similar to Lurgi in that sodium
chlorate is produced electrolytically from sodiurn chloride Hydrogen from the electrolysis is used
to burn generator by product chlorine and additional make up chlorine to hydrochloric acid
291
The R 7 process is similar to the R3 except that the by product chlorine stream is reacted with
sulfur dioxide and water to produce a mixed acid of hydrochloric and sulfuric which is fed to the
generator This reduces the chlorine by product to 10 20 of the chlorine produced and the
sal akeby product by 25 40 An excess of chlorine must be maintained in the reactor
absorber
cooler during sulfur dioxide reaction to insure that no SO enters the generator The presence of
SO reduces the size of the saltcake crystals causing filtration problems Because of the corrosive
environment thereactor absorber cooler must be fabricated from graphite As acomparison the
R 3 process produces 0
62 kg of chlorine per kg of chlorine dioxide The R 7 process produces
12 to 0
0 16 kg Very large R 7 units are in operation ranging from 30 to 40 TPD of chlorine
dioxide

Figure 16

CL

CL HCL HCL R5 CLOZ

BURNER GENERATOR

O
EXCESS
HZ

POWER GHLORATE CL
Nc
CELLS

Block dlegrem RB system

CLOZ
HZSCA
CLZ CLOZ
NnCL R TYPE
ABSORPTION
G ENERATOR
NaCL03

CONDENSER PRODUCT CLz

R EC
CLE
CHLORINE CLOP SOLUTION
STEAM 502

COMPRESSOR R 7 REACTOR
CONTROLLED
MIXED ACIDS RECYCLE
I
VENT TO

EXHAUST
SYSTEM
Block dlegrem R7 System
The R 8 process is another modification of the R3 process which uses methanol as the reducing
agent for the sodium chlorate drastically reducing the quantity of byproduct chlorine Thus R
8 is similar to the old Solvay process among the first commercial processes for chlorine dioxide
generation The R8 process is a popular retrofit to R 3 generators to markedly increase chlorine
dioxide production and is in operation at Western Pulp Squamish British Columbia Canada and
at Bowater Catawba South Carolina U
A Bowater reported an efficiency increase from 86 to
S
96 and a capacity increase from 11 6 mtday of chlorine dioxide to 172 mtday The R8
generator operates at 9 10 N acidity with 1 to 1
3 M sodium chlorate and 0
02 M sodium chlorate
6 mt sulfuric acid and 2
14 0 mt methanol 25

Figure 17

R8 SCHEMATIC

as
CONDENSER
GENERATOR

mot1 SJ TAIL GAS

STEAM
SCRUBBER

REBOILER
TOP FEED
O
METHANOL FILTER
CHLORATE
lT
1 SALTCAKE I

Monox LTM

Monox L hypochlorous acid HOC I and a cellulose protecting additive is being marketed by
Quantum Technologies Twinsburg Ohio It offers a convenient means for the disposal of the
dilute chlorine byproduct of chlorine dioxide generation by feeding the gas stream to a Monox L
generator likely with additional chlorine needed as makeup Initial work to replace existing
hypochlorite or first chlorine dioxide stages appeared successful Extended mill trials were
conducted at Kymene Juusankoski Finland continuing until a large new chlorine dioxide
generator utilizing methanol to eliminate the chlorine byproduct was installed Georgia Pacific
Brunswick Georgia chose Monox L partly because an onsite chloralkali plant is not equipped
to compress chlorine gas to liquid A second installation at TempleInland Evadale Texas is
exploring the use of Monox L in the first stage Laboratory bleaching has shown non detectable
dioxins and AOX levels comparable to the use of70 chlorine dioxide Best results were obtained
1W c
4 licfienfi nl 061
LI TERATURF CITED

Bowen 1 J and llsu J

L Overview of Emerging Technologies in Pulp and Bleaching
C
Tappi Journal 73
205 1990
9

2 Tikka P Recent Modifications of Kraft Pulping Proceedings Pacific Section TAPPI

Seminar Seattle Washington September 1990

Pettersson B nerfeldt B Advances in Technology Make Batch Pulping as Efficient as

F
Continuous Pulp and Paper 59 11 November 1985 pp 9093
4 Evans J
W Senior Editor RDII Process Boosts Batch Digester Efficiency at U
C S and
Finnish Mills Pulp and Paper 61 5 May 1987 pp 93 95

5 Kaiser M and Pitre R RDII at Owens Illinois Valdosta Georgia The World
s First
Commercial Scale Displacement Cooking Plant Proceedings 1986 TAPPI Pulping
Conference pp 627 632

6 Sjodin L and Pettersson B A Status Report on the Kraft Cold Blow Batch Cooking
Technique Proceedings 1986 TAPPI Pulping Conference pp 633642
7 Silander R New Developments I lave Renewed Interest in Batch Kraft Pulping Pulp and
Paper 59
1 1 November 1985 pp 9689
8 Stromberg B Modified Continuous Cooking An Update Proceedings 1987 TAPPI
Pulping Conference p 453

9 Elliott R G Experience with Modified Continuous Cooking Proceedings University of

Washington Pulp and Paper Foundation Annual Meeting May 1989
10 Elliott R G and Walley C A AOX and Dioxin Emissions Reduction at Longview Fibre
Company Proceedings 1991 International Pulp Bleaching Conference Stockholm
Sweden

11 MacLeod M Chet icalPulpiit g New Processes for a New Decade Pulp and Paper Canada
82 2 46 1981

12 Research and Development Dept Kawasaki Kasei Chemicals Ltd Mill Experiences on
SAQ Application in Pulping Processes of Lignocellulosic Materials and Problems Thereof
May 1 1983 43 pages

13 J et al The Characteristicsof MSS

Dahlbom AQ Pulping A New Pulping Process Tappi
Journal 73
257 1990
3

14 Ilaggin J Ester Pulping Process Avoids Use of Sulfur Compounds Chemical and
Engineering News January 27 1986 pp 25 26
15 Karl W Alcell Plugged as Alternative Pulping Technology 200 and Beyond Supplement
to Tappi Journal February 1990

16 Brooks K Enzymes for Pulping Wood Chemical Week September 3 1986 p 12

17 Tench L and Iloyer S Proceedings 1987 TAPPI International Oxygen Delignification

Conference p 1

18 Proceedings 1986 TAPPI Pulping Conference p 43

19 Singh R
P Editor The Bleaching of Pulp 3rd Edition revised TAPPI PRESS Atlanta
A 1979 p 180
S
U

20 Samuelson O Alternative Pretreatments Before Oxygen Bleaching Proceedings 1987

TAPPI International Oxygen Delignification Conference p 45

21 Proceedings 1986 TAPPI Pulping Conference p 49

22 Soteland N Pretreatment of Pulps with Chlorine Before Oxygen Delignification Proceed

ings 1987 TAPPI International Oxygen Delignification Conference p 63
23 Elliott R G Developments in Pulping and Bleaching Proceedings China Paper 1987
Shanghai China

24 Van Lierop B Bleaching with Ozone and Other Oxygen Containing Compounds Pre
sented to the TAPPI Pulp Bleaching Committee Columbus Mississippi April 2 1991

25 Proceedings 1986 TAPPI Pulping Conference p 403

26 Kenat T A et al Monox L Bleaching Agent in The Chlorination Stage Proceedings

1990 TAPPI Pulping Conference p 809