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The use of ozone in the pulp and paper industry

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 SPECIAL REPORT
The Use of Ozone in the Pulp and Paper Industry
By Jean-Christophe Hostachy, Brendan van Wyk and Alexis Metais
Corresponding Author: jean-christophe.hostachy@xyleminc.com
INTRODUCTION
T he use of ozone in the pulp and paper industry has fol-
lowed a remarkable developmental growth over the
last two decades. Thanks to reliable and economical on-
site ozone production, combined with progresses in pulp
mixing technology, more than 8 million tonnes per year of
chemical pulps are now being bleached with ozone. In
fact, ozone occupies a very unique position in the whole
chemistry involved in P&P manufacture. As a gas, pro-
duced only from oxygen, and reverting back to oxygen
as the final by-product, ozone is an eco-efficient “super
oxidant” that needs to be used straight after generation.
Reacting in seconds to minutes on many of the substances
found in pulping and papermaking, the use of ozone has
been investigated on many materials such as virgin & re-
cycled fibres, sludge, process waters and wastewaters.
Pulp and paper manufacturing is known for its com-
plexity regarding processes, materials, chemicals and
contaminants involved along the production chain. This
paper summarises the latest developments into applica-
tions where ozone has becoming the most advanced
solution:
• Chemical pulp bleaching
• Wastewater treatment
22 March/April 2014 • paperASIA
GREEN OR ECO-EFFICIENT BLEACHING WITH OZONE
Ozone bleaching has been developing as a reliable and
economic technology worldwide since 1992. It is now a
state-of-the-art bleaching process and ozone bleached
pulp capacity is currently around 8 million tonnes per year,
accounting for 8 per cent of the worldwide bleached
chemical pulp capacity. Global leaders having under-
stood the values investing in green technology such as
Fibria, Oji Paper, Lenzing and Nippon Paper have many
fibrelines operating ozone bleaching.
It is also worth noting in Table 1 that most of the mills
operating an ozone bleaching stage are also using chlo-
rine dioxide. Actually, Light-ECF bleaching with ozone
allows for (1):
• Lower operating costs by 20%
• Lower AOX, COD and BOD loads
• Lower brightness reversion
• Similar pulp strengths
• Better pulp cleanliness thanks to direct pitch elimination
with ozone
It has been observed that paper machine runnabilty
using ozone bleached pulp is excellent. For example in
Mondi Ruzomberok (Slovakia), PM18 set a world record
in 2011 as the fastest paper machine of its kind and PM16
is the Metso benchmark leader for lowest percentage in
broke among uncoated fine paper machines (2).
 SPECIAL REPORT
Mondi Ruzomberok is also one of the 6 mills producing
ozone bleached softwood kraft pulp. One of them, SCA
Östrand, operates a Q-(OP)-Z-(PO) bleaching sequence,
and produces 430,000 adt/y of TCF softwood kraft pulp
with brightness up to 90% ISO (3) and same qualities and
costs as ECF (4). With 20 years’ industrial experience, TCF
bleaching with ozone is a mature technology ready to be
implemented (5).
But where do those lower operating costs come from?
Theoretically 1 kg ozone replaces 1.7 kg of pure chlorine
dioxide (6).
Ozone generation is a pure on site technology requiring
only energy and oxygen (usually also produced on site from
a VPSA plant). Ozone (O3) is produced from oxygen (O2)
in an electrical field at a concentration of 12% by weight
according to Figure 1.
Figure 1 - Ozone formation in an electrical field
Production of 1 kg ozone requires a maximum of 10 kWh
and 8.3 kg of oxygen. Common energy requirement for
oxygen production from a VSA plant are 0.28 kWh per kg
oxygen. Therefore, the production of 1 kg ozone requires
12.3 kWh (10 + 8.3 x 0.28) in all.
In comparison producing 1kg chlorine dioxide in a
modern plant requires 1.6 kg of sodium chlorate, a reducing
agent such as methanol or hydrogen peroxide, sulphuric
acid, chemicals storage and deliveries. In the first step, 5
kWh is necessary to produce each kg of sodium chlorate.
Therefore, producing 1 kg chlorine dioxide requires 8 kWh
in addition to what should be considered the cost of pre-
cursors and logistics. Therefore, producing 1.7 kg chlorine
dioxide requires 13.6 kWh, chemicals and logistics!
Reaching the same bleaching efficiency, the use of 1 kg
ozone reduces the energy needs by at least 1.3kWh (con-
sidering only sodium chlorate production) and eliminates
the costs of the other chemicals and logistics.
In terms of safety and chemical usage, ozone is con-
sidered as a non-isolated intermediate meaning that it
is immediately used directly after its generation. In com-
parison, chlorine dioxide generation is based on the use
of large volume of sodium chlorate that needs transport
too and storage on the mill site. As recently shown in the
media, transport of sodium chlorate used in pulp mills can
lead to large disasters, such as the huge explosion after a
train derailed on May 28, 2013 near the city of Baltimore
(7). This can never happen with ozone since the technol-
ogy is pure onsite.
From a chemical production viewpoint, modern tech-
nology for chlorine dioxide generation based on hydrogen
24 March/April 2014 • paperASIA
peroxide always has the potential risk to generate hazard-
ous by-products such as dioxins and furans (8). Concern-
ing ozone, the single raw material for ozone production is
oxygen whereas the final by-product after ozone reaction
is also oxygen. Using ozone is an unchallenged advantage
regarding risk management and safety issues.
Moreover the trend of tightening effluent regulations
is now global: on April 1, 2013 AOX discharge conditions
were lowered from 0.20kg/adt to 0.17 kg/adt for granting
of the EU Ecolabel, and in China and Brazil major green-
field pulp mill projects are asked to fulfill with ever stricter
COD discharge permits. Chlorine dioxide bleaching limits
opportunities in bleach plant filtrate recirculation while
increasing effluent treatment costs is not a sustainable
solution. Ozone is a part of the solution.
New market perspectives: Dissolving pulps and non-wood pulps
The main process change for
conver ting a conventional
kraft pulp mill to dissolving
pulp is the implementation
of a pre-hydrolysis step to re-
move hemicelluloses. It is then
possible to produce dissolving
pulp with the existing fibreline
only by using harsher condi-
tions in both cooking and oxygen delignification. However
such practices significantly impact the pulp yield. Indeed
the combination of specific cooking technology for dis-
solving grades and ozone in the bleach plant increases
the pulp yield by 0.5-1.5% when compared to conventional
technology (9). Ozone offers the possibility of fast and very
selective pulp viscosity adjustment since each kg ozone
in proper operating conditions can decrease kraft pulp
viscosity by 100 ml/g. A further benefit is that it has been
proven that the use ozone lowers amounts of extractives
(pitch) and particles (dirt) in the final bleached dissolving
pulp. It is a benefit for viscose fibre producers as very small
particles are responsible for lower reactivity of the pulp
and results in lower strength properties of the produced
viscose fibre.
Non-wood fibres, such as Bagasse, Bamboo, Straws or
Reeds are used for papermaking and represent a sustain-
able source of raw materials with a significant growth
potential. Whereas there has been no remarkable break-
through in recent decades in the field of non-wood pulp-
ing, pulp bleaching of these particular fibres can benefit
from the development occurring in the wood pulp seg-
ment over the past two decades. Bamboo, Wheat Straw
and Bagasse pulps can be easily bleached with limited
amount of ozone and peroxide to high brightness levels
with significant advantages in terms of fresh water usage,
environmental impact, chemicals usage, safety and eco-
nomic performance. Using 5 kg/adt ozone combined with
5 to 10 kg/adt per tonne of peroxide, it is possible to reach
between 85 to 90% ISO brightness with different sources
of non-wood material (10). Eco-efficient bleaching is now
ready to be implemented into most of the mills in China,
India and other countries where non-wood pulping pre-
 SPECIAL REPORT
dominates. This process should be strongly promoted by
local authorities considering the unique advantages in
terms of fresh water usage, environmental impact, chemi-
cals usage, safety and economic performance.
WASTEWATER TREATMENT
While ozone efficiency in pulp production is already proven,
ozone is of interest to eliminate contaminants found and/or
generated during the papermaking process. Installations
worldwide have already proven the following benefits:
• Ozone, and particularly the combination of ozone and
biofiltration, as a tertiary treatment step represents the
most reliable and economical process for the elimina-
tion of inert COD
• Ozone is a viable technique for color removal from
wastewater
• Ozone for the control and elimination of extractives
during pulping/papermaking process.
Ozone and biofiltration for advanced COD Removal
The paper mill Lang Paper in Germany (Ettringen) is part
of the Finnish group UPM. At Lang Paper, an increased
production capacity of newspaper and magazine paper
required an extension of the existing biological wastewater
treatment plant. But since
increasing COD discharge
loads, mainly caused by
lignin compounds were not
tolerated by public authori-
ties and further purification
by means of biological pro-
cesses alone was not pos-
sible a tertiary treatment
step combining ozonation
and biological fixed-bed
filtration was implement-
ed. The main goal of this
worldwide first large scale
ter tiar y ozone treatment
plant in the paper industry
is to reduce the inert COD
output level of the existing
biological plant [2].
Table 2 - General design parameters of Lang Paper
WWTP
The design of the tertiary treatment process is a sophis-
ticated combination of Ozonation and biological fixed-
bed filtration. The tertiary treatment stage was designed
on the basis that 130 mg/l COD has to be degraded by
the combined process at a design flow of 667 m³/h, with a
specific ozone consumption level of 1 gO3/gCOD elim. (which
was confirmed by pilot trials). Accordingly an ozone plant
with a capacity 100 kgO 3/h and a biofilter with a fixed-bed
26 March/April 2014 • paperASIA
volume of 504 m³ were chosen. The advanced tertiary
treatment stage is designed as a twin line system to provide
highest flexibility and availability at minimum operating
costs. Figure 2 schematically shows one line of the tertiary
treatment plant with Ozonation and Biofiltration.
The biological pre-treated wastewater is pumped into
the recirculation loop of the ozone system. Booster pumps
increase the pressure and transport the water through
venturi injectors.
The flow through the injectors produces a vacuum
which is utilised to suck the ozone into the water and mix it
vigorously. After passing through the injectors, the treated
wastewater flows into a pressurised reaction- and degas-
sing tank. The stainless steel reaction tanks each with a
volume of V=40m³ have in general two functions. At first, the
reaction of the ozone and the non-biodegradable com-
ponents will take place and second the non-dissolved gas
is separated from the water phase. After the reaction, the
water is transferred to holding containers. From the hold-
ing tanks, the water flows by gravity into the biofiltration.
The biofiltration consists of six filters, three per line, each
with a fixed-bed volume of 84 m³. The oxygen demand for
biological COD reduction is provided by oxygen which is
still dissolved in the oxidised wastewater.
Figure 2 - Schematic flowchart of the tertiary treatment
step (Only one line is illustrated!)
In order to keep the operation costs to a minimum level,
a pressurised ozone reaction system was chosen. This allows
for the direct supply of oxygen rich off-gas to the biological
treatment plant. The off-gas is collected in the top of the
degassing tanks and is fed via an ozone destructor into
the biological aeration tanks.
Hard COD cracking for biological digestion
The combination of a conventional biological treatment
facility with a subsequent tertiary stage consisting of an
ozone plant and biofiltration made it possible to increase
total COD reduction from about 87% to 97% (complete
WWTP). As seen in figure 6 the secondary effluent has a
 SPECIAL REPORT
very low BOD 5/COD ratio which makes further biological
COD removal impossible. Only the oxidation by ozone
where long-chained organics are cracked and transferred
to BOD 5 enables a further biological COD reduction in the
subsequent biofiltration unit. Figure 3 records the develop-
ment of BOD5 and the BOD5:COD-ratio in the tertiary stage.
The ratio was improved from 0,059 to 0,21 by oxidation with
ozone. The specific applied ozone dosage was approx. 0,4
gO 3/gCOD inflow. The total COD reduction with the tertiary
treatment stage was for this sample 53,5% based on COD
inflow concentration of 458 mg/l.
Figure 3 - Development of BOD5 in the tertiary treatment
plant
Ozone technology is a process perfectly suited to long-
term wastewater treatment, having very low operating
costs of 0.10-0.18 €/m³. It is only possible with this process,
to keep the strict outflow limits during times of higher bright-
ness production. Similar results are confirmed with the op-
eration from other plants in Europe. Ozone and biofiltration
are now being investigated for many projects in the world,
competing directly with conventional tertiary treatment
technique based on coagulation and flocculation.
CONCLUSION
Ozone for pulp bleaching was born at Lenzing in Austria
and Union Camp in US in the 90s. The combination of
the strictest environmental and economic expectations
explains why ozone bleached pulp capacity is currently
at over 8 million tonnes per year, accounting for 8% of the
worldwide bleached chemical pulp capacity. Promising
growth is expected in the market segments of dissolving
pulps and non-wood fibres.
Concerning wastewater treatment, ozone has the
capability to destroy in situ contaminants and to convert
a part of the pollution back to being biodegradable.
Among chemical and existing treatment techniques for
28 March/April 2014 • paperASIA
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wastewater, this ability is really unique. This explains why
a combination of ozone and biofiltration for Hard COD
elimination and direct use of ozone for color removal is
now selected in many pulp and paper projects.
The time to implement eco-efficient practices is now,
and any pioneering effort to develop processes minimis-
ing water and chemicals usage, conserving resources
and finally protecting biodiversity must be amplified and
promoted.
REFERENCES
1. Métais, A., Germ-
e r, E ., H o s ta c hy,
J . - C . , “A c h i e v e -
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Ozone Bleaching”,
proceedings of the
International Pulp
Bleaching Confer-
ence, 2 011, Po r t-
land, OR, USA
2. h t t p : / / w w w .
risiinfo.com/tech-
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mak ing/Mondi -
SCPu2 019s - PM18 -
beats-own-world-
record-as-fastest-
p a p e r- m a c h i n e -
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(checked on April
12, 2013.)
3. http://w w w.sca.com/en/ppc/Products2/Products1/
Celeste1/Celeste-grades/Celeste/ (checked on April
12, 2013.)
4. Roden, G., “SCA Östrand Builds a “Natural Eco-System”,
April 2005, Pulp & Paper International
5. Germer, E., Métais, A., Hostachy, J.-C., Van Wyk, B., “The
Future is Now” June 2013, Pulp & Paper International
6. 6.Grundelius, R., “Oxidation Equivalents, OXE, an Alter-
native To Active Chlorine”, proceedings of the Inter-
national Pulp Bleaching Conference, 1991, Stockholm,
Sweden
7. http://www.guardian.co.uk/world/2013/may/29/chem-
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8. Pelin K., Perrson F., Stolz E. “Production of Chlorine Di-
oxide” US Patent 2010/0055027
9. Métais, A., Hostachy, J.-C., Van Wyk, B., “Ozone Bleach-
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10. Hostachy, J.-C., Van Wyk, B. “Eco-efficient Bleaching
of Non-wood Pulps”, proceedings of China Paper 2013
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75
11. Rosner M., Rau St., “State of the Art Ozone Systems for Pulp
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