PAPTAC Annual Meeting Proceedings, Montreal, Jan. 2000, p.

B221-224
Combating Odour Problems In a Kraft Mill
Using Hydrogen Peroxide
Tony Christy Dan T. Davies Brian OConnor
Cariboo Pulp & Paper Degussa Canada Ltd. PAPRICAN
Company Surrey BC Pointe Claire, Quebec
Quesnel BC
ABSTRACT:
Many Kraft mills suffer from uncontrolled or accidental releases of offensive odours caused by TRS compounds. These odours can be
health hazards for employees and may generate complaints from neighbours. Common sources of these odours occur through
condensate losses to the sewer and anaerobic activity in holding ponds. Recently, the Cariboo Pulp and Paper mill successfully
employed H
2
O
2
to minimize or eliminate odours related to anaerobic activity in a spill basin and the sewering of treated and foul
condensates. This paper discusses four separate applications of H
2
O
2
for odour control, including a description of the various problem
areas, how the H
2
O
2
was applied in each area and the results of the treatments.
INTRODUCTION:
Kraft pulp mills generate a variety of sulfur compounds, most of which are recovered for re-use in the mill. A small percentage escapes
this recovery process and must be treated separately before release to the environment, in either dissolved or gaseous form. An even
smaller fraction eludes both recovery and treatment. This fraction can require separate treatment outside of NCG systems and
condensate strippers. This paper explores four odour abatement treatments at the Cariboo Pulp & Paper Company Kraft mill in Quesnel
BC. The first application was treatment of an anaerobic effluent from a spill basin. The effluent was to be returned to the effluent
treatment system, to reduce the level in the spill basin in preparation for a major mill shutdown. The H
2
S load in the effluent would have
resulted in unacceptable odour release if the effluent were returned to the clarifier untreated.
The second application was treatment of anaerobic sludge from the spill basin. The basin required dredging to remove accumulated
sludge and restore the capacity of the pond. As the sludge was heavily loaded with TRS compounds, any disturbance could have
released a great deal of offensive odours.
The third application was to minimize sewer odour from the sewering
of treated condensate. This condensate had to be diverted past
workmen during a construction project. Although the condensate
had been steam-stripped (with 80% TRS removal), the remaining
odours were strong enough to be a concern to nearby workers.
In the fourth application, foul condensate was treated with peroxide
during a scheduled shutdown of the steam stripper. Cariboo has no
alternate method for condensate treatment, so this stream is routinely
discharged to the treatment ponds without stripping during stripper
bypass periods. Depending on atmospheric conditions, sewering of
unstripped condensate had resulted in numerous odour complaints
both from the community and from mill personnel.
In all four cases, H
2
O
2
was used to control the odour from the TRS
compounds contained in the treated stream.
EXPERIMENTAL:
Determination of TRS in Aqueous Samples
Some of the condensate samples were characterized for TRS using a method recently developed by Paprican [1]. The method involves
the use of a specially designed glass sparger for nitrogen purging of the aqueous sample followed by collection of the gas in a tedlar
bag and analysis of the individual TRS components by gas chromatography. For the stripped condensates, 50 mL of the sample was
Figure 1 Addition of H2O2 to Liquid Effluent
H
2
O
2
To Effluent
Clarifier
From Spill
Basin
Hand
Valve
P
u
m
p

B
a
c
k

L
i
n
e
2
used in the analysis . For the foul condensates, the samples were usually diluted 10-fold before analysis (i.e., 5 mL of sample diluted to
50 mL with high purity water).
RESULTS AND DISCUSSION:
Application 1: Spill Basin Effluent Treatment
In November 1995, the spill basin had become anaerobic from a series of diversions combined with spill basin aerator downtime. In
total, the basin contained approximately 23 000 m
3
of sludge, 27 000 m
3
of liquid effluent, leaving only 15 000 m
3
of freeboard available
for spills. The effluent layer contained 90 ppm H
2
S and any agitation of the liquid layer resulted in odour complaints both from the
community and from within the mill. The aerator could not be restarted due to odour. Pumpback to lower the liquid level also resulted
in unacceptable odour at the effluent clarifier (>30 ppm H
2
S). Urgency was added to the situation in that the spill basin freeboard
capacity (15 000 m
3
) did not allow enough safety margin for the upcoming major shutdown.
Peroxide Addition
The spill basin liquid level is lowered via pumpback from a submerged pump at the spill basin to the effluent clarifier. The pumpback
line is approximately 250 m long and allows approximately 3 minutes retention time. Peroxide was added at the spill basin directly into
the pumpback line, about 30 cm upstream of a manual throttling valve, which provided good mixing.
For 8 days, 50% H
2
O
2
was metered into the pumpback line at a rate of 1.0 Lpm to treat approximately 27 000 m
3
of liquid. During this
entire period, no additional odours were detected from the effluent clarifier as a result of the effluent pumpback.
Application 2: Spill Basin Dredging:
In 1997, approximately 1000 bdt of solids were dredged and dewatered from the spill basin. The town of Quesnel is situated directly
across the river from the spill basin. As such, odour generation from the solids layer is a constant concern. In particular, the basin had
been dredged in 1995 without any odour control. At that time, the dredging operation was interrupted several times due to odour
concerns and it was clear that odour control would be required in the future.
The nature of the odour was mainly H
2
S and as such H
2
O
2
was deemed suitable to control the odour. Past experience showed that,
during dredging, the majority of the H
2
S was released from the dewatering equipment. This equipment consisted of a grizzly screen, a
large mix tank with agitation, a centrifuge and a belt press and finally a short conveyor to transport the sludge into dump trucks.
Peroxide Addition
A portable H
2
O
2
addition system was positioned near the dewatering equipment where a small metering pump was used to add the
H
2
O
2
. Initially, the H
2
O
2
was added to the pumpback line itself prior
to the grizzly screen. However, pumpback from the dredge was
intermittent in nature, which meant that the H
2
O
2
would also have to
be turned on, and off. Every time the peroxide pump was turned off
some sludge would flow back up the H
2
O
2
line and plug the check
valve. Due to time constraints, rather than solve this addition
problem, the addition point was moved to add the H
2
O
2
directly into
the mix tank.
The dredging rate was 1500 Lpm, during which 1.9 Lpm50% H
2
O
2
was added to the mix tank.
Figure 3 Dosing H
2
O
2
into Treated Condensate
H
2
O
2
Temporary
Pond
U-drain
Figure 2 Addition of H
2
O
2
into Sludge Mix Tank
Untreated
Sludge
Treated
Sludge
H
2
O
2
Agitated
Mix Tank
3
Odour Control Spray
Given that a significant odour was still coming from the grizzly screens, a separate odour control system was used to control odour
from them. This system consisted of a header of foggy nozzles attached to the screens such that they misted an odour-controlling
chemical called Ecosorb in the air above and around the screens. These same foggy nozzles were also attached to the rail around the
floating dredge and were effective in keeping H
2
S levels down on and around the dredge.
Measurement of Success
In past years, H
2
S air concentrations around the dewatering equipment could reach >50 ppm H
2
S. Using peroxide and the odour
controlling spray, H
2
S was significantly reduced, to less than 10 ppm. Dredging was completed after 14 days without one odour
complaint either from the community or mill personnel.
Application 3: Stripped Condensate Diversion:
During a construction project to replace a section of sewer line, the stripped condensate was diverted to a U-drain. This U-drain ran
right past the construction project. Although the condensate had been steam-stripped, the workers on the project were concerned
about odour.
To address their concerns, the stripped condensate was diverted from the normal sewer to a temporary pond. The overflow from the
pond exited through the U-drain, flowed to a sump near the construction site, then to the normal treatment pond.
A temporary H
2
O
2
dosing tank was set up near the exit from the temporary pond. Dosing was accomplished with a simple gravity feed
to the U-drain. When condensate overflow began, 50% H
2
O
2
was added at the entrance of the U-drain. There was sufficient
turbulence in the drain to assure adequate mixing of the H
2
O
2
in the condensate.
Preliminary laboratory tests, performed at Paprican, indicated that a dosage of 200 mg H
2
O
2
per litre of treated condensate would
adequately control odour after a 1.5 minute reaction time. This required a flowrate of 1.3 Lpm of 50% H
2
O
2
into 3800 Lpm treated
condensate.
Initially, about 1.1 Lpm were dosed to an estimated 3800 Lpm condensate flow in the U-drain. This dosage rate eliminated most odours
from the treated condensate. The dosage rate was reduced to about 0.4 Lpm after high residual H
2
O
2
and no odour were detected at the
worksite. There was an estimated 10 minutes retention time from the addition point to the worksite, prior to sampling for H
2
O
2
residual.
The longer retention time in the full scale treatment may have allowed the lower H
2
O
2
dosage.
Application 4: Foul Condensate Treatment
Every 6 to 8 weeks, the mill must perform a routine caustic cleaning of the steam stripper used to treat the foul condensate. This
procedure takes about 8 hours and during this time, the condensate is discharged directly to the treatment ponds without stripping.
Depending on atmospheric conditions, sewering of unstripped condensate has resulted in numerous odour complaints both from the
community and from mill personnel.
Selection of Treatment Method
There are several options for treating the foul condensate, requiring more or less capital investment. As each use was to be of short
duration and widely spaced, a large capital investment was not justified. Therefore, a low capital approach using chemical treatment
was considered. The main source of odours from the condensate is TRS compounds, namely hydrogen sulfide, methyl mercaptan,
dimethyl sulfide and dimethyl disulfide. It was believed that oxidation of the TRS should eliminate most of the odours caused by the
short-term sewering of the foul condensate. Two chemical treatments employing either chlorine dioxide or hydrogen peroxide were
examined in the lab. Although both chemicals could be used successfully there were some differences in efficacy, handling and
control.
TABLE 1: FOUL CONDENSATE LAB TREATMENT
Treatment H
2
S Methyl
Mercaptan
Dimethyl
Sulfide
Dimethyl
Disulfide
None 33 mg/L 35 mg/L 26 mg/L 5 mg/L
H
2
O
2
<1 <1 17 5
ClO
2
<1 0 <1 2
* H
2
O
2
154 mg/L, ClO
2
300 mg/L, 15 minutes reaction time at 80C.
The lab tests proved that either H
2
O
2
or ClO
2
could be used to eliminate 80-98% of the TRS compounds from the untreated condensate.
ClO
2
was more effective at removing the organic sulfides, DMS and DMDS.
4
Both ClO
2
and H
2
O
2
were readily available on site, and H
2
O
2
was selected for handling and safety reasons. Overdosing ClO
2
could
create a problem, as residual ClO
2
could be a hazard. In addition, H
2
O
2
's stability meant that it could be started and stopped with greater
convenience.
Peroxide Addition
A solution of 50% H
2
O
2
was added to the suction of #5 effect condensate transfer pump this ensured adequate mixing of the H
2
O
2
into the condensate. The condensate with H
2
O
2
was pumped to the foul condensate tank, from which it was pumped to the treatment
ponds. Initially, sampling was done after the condensate had left the tank, which gave about 10 minutes reaction time. It was found
that this stream also contained some effluent from acid regeneration,
which depressed the pH, thereby rendering H
2
S analysis inaccurate.
Thereafter, samples were drawn directly from the tank, which allowed
only about 5 minutes reaction time.
Condensate Treatment Trial
A one day trial was planned to test the concepts in this treatment:
mixing, reaction time and effectiveness of the treatment. Prior testing
had shown that the condensates properties and composition did not
vary much. In order to minimize testwork during the trial, samples
were collected only at the start and end of the treatment, and after
major H
2
O
2
dosage changes. In addition, certain samples were held
for later testing by more detailed methods. The treatment was
evaluated by examining the concentrations of H
2
S, Methyl Mercaptan
and H
2
O
2
after treatment. The TRS compounds were analyzed by
potentiometric AgNO
3
titration and the H
2
O
2
by iodometric titration .
Samples were taken and tested immediately, with selected samples frozen for detailed analysis later. The H
2
O
2
dosage was started high,
in order to ensure that odour would not be a problem during the trial. Based on the laboratory treatment experiments (Table 1), for a
TRS level of 100 ppm a dosage of 0.25 L 50% H
2
O
2
per m
3
of condensate would be required to treat the bulk of the TRS components.
However, these calculations were based on the results for only one sample of foul condensate from the mill and the actual TRS
concentrations on site would undoubtedly vary over time. In addition, as the lab work used a 15 minute reaction time, it was expected
that a higher dosage would be required for the shorter reaction time at the mill.
A starting dosage of 1.9 L/m
3
was selected to treat the typical TRS level of 230ppm in the foul condensate. This resulted in an initial
concentration of 1140 mg/L of H
2
O
2
in the condensate. This dosage dropped the titratable TRS to zero and had 530 mg/L residual H
2
O
2
.
The H
2
O
2
dosage was successively lowered until there was detectable TRS, using the titration method. At a dosage of 0.7 L/m
3
, TRS
was detected even though there was 34 mg/L residual H
2
O
2
. The lower dosage rates were sampled after 5 minutes reaction time, which
may have been insufficient reaction time. Allowing further reaction time may have consumed more TRS with the remaining H
2
O
2
.
Figure 4: H
2
O
2
Addition to Foul Condensate
Sample Point
(10 minutes)
Sample Point
(5 minutes)
Foul
Condensate
H
2
O
2
Treated Condensate
Foul
Condensate
Tank
Figure 5: TRS Removal Vs H
2
O
2
Dosage
0
10
20
30
40
50
60
70
0 0.8 1.2 1.9
H
2
O
2
Dosage as 50% (L/m
3
)
T
R
S

(
m
g
/
L
)
0
100
200
300
400
500
600
R
e
s
i
d
u
a
l

H
2
O
2

(
m
g
/
L
)
H 2S
M M
D M S
D M D S
5
Further decreases in H
2
O
2
dosage gave increasing remaining TRS and decreasing H
2
O
2
residual. The lowest H
2
O
2
dosage trialed was
0.4 L/m
3
, which still removed almost 55% of the sulfides and over 85% of the mercaptans, although there was no residual H
2
O
2
.
Analysis of Reserved Samples
Selected samples of treated condensate were frozen for later testing. These tests consisted of chromatographic analysis for H
2
S,
methyl mercaptan, dimethyl sulfide (DMS) and dimethyl disulfide (DMDS). Although the procedure was more accurate, there may have
been some loss of the more volatile components over the storage period. This loss is shown by the lower initial values for H
2
S and
mercaptan respectively, 49 and 26 mg/L by chromatograph, but 71 and 101 mg/L by titration.
The graph in Figure 5 shows the concentration of the TRS compounds at a range of H
2
O
2
dosages. On average, all of the peroxide
treatments resulted in the removal of 80-85% of the TRS in the foul condensate. As with the potentiometric determination, the
concentrations of H
2
S and mercaptan are very low. The analysis also shows that the DMS is mostly removed, while the DMDS is only
slightly affected even at the higher H
2
O
2
dosages. This is similar to the results from the lab tests, but with better removal of the DMS.
CONCLUSION:
Cariboo Pulp & Paper has successfully used H
2
O
2
to treat a variety of TRS odour sources. These treatments have required different
equipment and strategies to be successful. The most important part of these treatments has been the flexibility of the personnel,
adapting the treatments to changing circumstances.
H
2
O
2
has been shown to be a powerful and effective treatment for an assortment of odour problems. It has been particularly useful due
to its ease of handling and control.
The mill will continue to use peroxide as a method of odour control. A permanent dosing system has been designed to dose H
2
O
2
into
the condensate stream during stripper maintenance shutdowns. This will allow treatment of the condensate during shutdown of the
stripper, eliminating concerns about odours. The dosing system will also be used to supplement the steam stripper in periods when the
condensate is particularly heavily loaded with TRS, further reducing odour concerns. The spill basin is due to be dredged again in
1999. The successful combination of H
2
O
2
and Ecosorb will be used again for odour control during this operation.
REFERENCE:
1. B.I. O'Connor and S. Genest, "A method for the analysis of total reduced sulphur (TRS) compounds in aqueous kraft mill process
streams" In Technical Program of the Pittsburgh Conference, No. 1332, New Orleans, Louisiana, March 1-5, 1998.
2. Degussa Standard Method
TABLE 2: FOUL CONDENSATE MILL
TREATMENT
H
2
O
2
Dosage Sulfides Mercaptans H
2
O
2
Residual
L/m
3
* mg/L mg/L mg/L
0 61.6 106.4 0
1.9 0 0 530
1.2 0 0 260
1.2 0 0 280
0.8 0 0 85
0.7 6.6 27.5 34
0.6 20.4 10.2 24
0.4 31.3 14 0
0 70.4 115.5 0
* H
2
O
2
dosage calculated as 50% H
2
O
2
per m
3
of
condensate.
Sampled after 10 minute reaction time
Sampled after 5 minutes reaction time