PII: S0043-1354(00)00322-5

Wat. Res. Vol. 35, No. 3, pp. 745749, 2001

# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0043-1354/01/$ - see front matter

COLOR AND CHLORINATED ORGANICS REMOVAL FROM

PULP MILLS WASTEWATER USING ACTIVATED
PETROLEUM COKE
AYMAN R. SHAWWA*M, DANIEL W. SMITH and DAVID C. SEGO
Department of Civil and Environmental Engineering , 304 Environmental Engineering Building,
University of Alberta, Edmonton, AB, Canada T6G 2M8
(First received 1 December 1999; accepted in revised form 1 May 2000)
Abstract}Delayed petroleum coke, a waste by-product from the oil sand industry, was utilized in the
production of activated carbon. The activated carbon was then evaluated for color and chlorinated
organics reduction from pulp mill wastewater. The activation of the petroleum coke was evaluated using a
fixed bed reactor involving carbonization and activation steps at temperature of 8508C and using steam as
the activation medium. The activation results showed that the maximum surface area of the activated coke
was achieved at an activation period of 4 h. The maximum surface area occurred at burnoff and water
efficiency of 48.5 and 54.3%, respectively. Increasing the activation period to 6 h resulted in a decrease in
the surface area. Methylene blue adsorption results indicated that the activation process was successful.
Methylene blue adsorbed per 100 g of applied activated coke was 10 times higher than that adsorbed by
raw petroleum coke. Adsorption equilibrium results of the bleached wastewater and the activated coke
showed that significant color, COD, DOC and AOX removal (>90%) was achieved when the activated
coke dose exceeded 15,000 mg/L. Adsorption isotherms, in terms of COD, DOC, UV and color were
developed based on the batch equilibrium data. Based on these isotherms, the amount of activated coke
required to achieve certain removal of color and AOX can be predicted. The utilization of the petroleum
coke for the production of activated carbon can provide an excellent disposal option for the oil sand
industry at the same time would provide a cheap and valuable activated carbon. # 2001 Elsevier Science
Ltd. All rights reserved
Key words}AOX, adsorption, color, isotherm, pulp mills, petroleum coke

NOMENCLATURE

B
Ce
K
M
1=n
q
R
Weff
X

burnoff of petroleum coke, %

equilibrium concentration of color, mg color/L
Freundlich parameter, mg color/mg AC
the mass of powdered activated carbon, g
Freundlich parameter, dimensionless
the amount of color adsorbed per mg of applied
activated carbon, mg color/mg AC
mass recovery of carbon, %
water efficiency, %
the adsorbed amount of color, mg

INTRODUCTION

Bleached kraft pulp mill wastewater constitutes one

of the most problematic parts of the entire pulp
industry. These effluents contain high concentrations
of color causing compounds, mainly due to lignin,
measured by absorption at 465 nm. Also, when
*Author to whom all correspondence should be addressed.
Tel.: +1 780-438-7879; fax: +1 780-435-8086; e-mail:
aymanshawwa@hotmail.com
745

chlorine is used for bleaching a high concentration

of chlorinated organic compounds is present in the
wastewater. Discharge of these compounds into a
receiving water body can impact the ecological
balance and cause aesthetic concerns. In addition,
chlorinated organic compounds may be associated
with some toxicity and they show considerable
resistance to biological and chemical degradation.
All pulp mills in Alberta use some sort of
biological treatment systems, which are successful
in the reduction of biological oxygen demand (BOD)
and total suspended solids (TSS) concentration in
their effluent. However, biological treatment is not
very effective for reducing color and chlorinated
organics in pulp mill wastewater (Cecen et al., 1992).
There are other effective treatments alternatives for
color reduction in bleached kraft mill effluent.
Activated carbon adsorption is considered very
effective in the reduction of color, adsorbable organic
halides (AOX) and the nonbiodegradable fraction of
the pulp bleaching wastewater. However, this process
has costs associated with the production of activated
carbon.

746

Ayman R. Shawwa et al.

One option for substantially reducing the high cost

associated with using activated carbon adsorption is
by producing activated carbon from an abundant
and cheap source of raw carbonaceous materials. An
abundant and cheap source in many regions including western Canada is petroleum coke, which is a byproduct of the upgrading of bitumen from oil sands
into synthetic crude oil. This petroleum coke can be
utilized as a cheap and readily available raw material
for the production of more valuable activated carbon
suitable for the removal of color and AOX from pulp
bleaching wastewater. Previous studies on the activation of petroleum coke showed that the activated
coke have adsorptive capacities 10 time greater than
the raw coke (Shawwa et al., 1999). The adsorptive
capacity was attributed to the large surface area and
porosity developed from the activation process.
The objectives of this study are: (i) to evaluate the
production of powdered activated carbon from
petroleum coke using fixed bed reactor involving
carbonization and activation steps and using steam
as the activation media, and (ii) to evaluate the
activated powdered coke for color and AOX reduction from bleached pulp mill wastewater.

EXPERIMENTAL

In this study, delayed petroleum coke from Suncor

Canada was used as the source of raw petroleum coke.
Delayed petroleum coke is produced in a coking drum
heated to 4808C. Volatile material is removed and the
remaining by-product is broken up hydraulically and then
removed from the drum. The delayed coker particles are
irregularly shaped and has an amorphous structure, where
92% of the carbon atoms are aromatic (Majid et al., 1989).
The chemical composition and the ash content (in terms of
w/w%) of delayed coke are given in Table 1. The chemical
characteristics and ash content of the 5-590-A coconut
charcoal, which was used in this study for comparative
purposes, are also shown in Table 1.
Delayed coke samples were dried in a vacuum oven for
24 h at a temperature of 1108C prior to grinding. Samples
were pulverized using a ball mill and the size range between
200 mesh (44 mm) and 325 mesh (75 mm) was utilized for the
activation experiments. The production of the activated
coke involved two stages: the carbonization stage and the

activation stage. The carbonization stage was carried out at

850  28C at an average heating rate of 108C/min. The
activation stage was carried out immediately after the
carbonization using steam. Activation periods ranging from
1 to 6 h were tested. All carbonization and activation
experiments were carried out in a horizontal quartz reactor
with a diameter of 45 mm, as shown in Fig. 1. The reactor
was placed horizontally in a tube furnace with an accurate
temperature controller and under N2 atmosphere. The
carbonization and activation procedures involved placing
10 g of raw petroleum coke sample in the reactor. A metal
thermocouple was inserted in one side of the reactor such
that its tip is just above the sample. Water was introduced to
the reactor by a syringe pump as a steam source for
activation. It was deoxygenated before use by boiling. The
water was introduced into the reactor at a rate of 0.5 mL/
min. A detailed experimental procedure for the activation of
petroleum coke is presented in Shawwa et al. (1999).
The success of activation of the delayed petroleum coke
was evaluated by performing liquid-phase adsorption using
methylene blue dye as adsorbate. Sorption capacities for
methylene blue would provide a valuable indication of the
capacity of the activated carbon to remove color from
wastewater (Sontheimer et al., 1988). The adsorption
procedure followed the ASTM D3860-98 (ASTM, 1999).
Batch adsorption tests were carried out by contacting the
activated coke samples with pulp mill bleaching effluent in
order to generate adsorption isotherms. The characteristics
of the pulp mill bleaching effluent, which was obtained from
Weyerhaeuser Canada Ltd., Alberta, Canada, are given in
Table 2. For this purpose, 250 mL sealed flasks were filled
with 100 mL of the bleaching effluent and different amounts
of activated coke samples were added. The mixture in each
flask was mixed using a tumbler for 24 h. It was assumed
that the equilibrium was achieved in 24 h. Subsequently, the
wastewater was separated from the activated coke by
pressure filtration through 0.45 mm cellulose nitrate filters.
The filtrate was analyzed, according to standard methods
(APHA, AWWA and WEF, 1992), for color measured at
wavelength of 465 nm (color465), ultra violet absorption at
wavelength of 254 nm (UV254), chemical oxygen demand
(COD), dissolved organic carbon (DOC) and AOX.

Table 1. Chemical composition and ash content of delayed petroleum coke and coconut charcoal (after Watkinson et al., 1989 and
Majid et al., 1989)
Parameter

Volatile (wt%)
Moisture content (wt%)
BET-surface area (m2/g)
Iodine number
Ash content (wt%)
SiO2 (wt%)
Al2O3 (wt%)
Fe (wt%)
Ti (wt%)
Ni (wt%)
V (wt%)

Delayed petroleum
coke

5-590-A
coconut charcoal

11.9
1.8
9
28
3
41.7
19.2
16
1.5
1.6
2.8

}
2
1237
1110
7
}
}
}
}
}
}

Fig. 1. Experimental setup for the activation of petroleum

coke.

Table 2. Pulp mill bleaching effluent characteristics

Parameter
COD (mg/L)
DOC (mg/L)
AOX (mg/L as Cl)
UV254 nm (cm 1)
Color465 nm (mg/L PtCo)
pH

Concentration
2126
575
80.2
13.11
2300
2.1

Color and chlorinated organics removal from pulp mills wastewater

RESULTS AND DISCUSSIONS

The activation of delayed petroleum coke consisted

of seven samples, in duplicate, activated with steam
for activation periods ranging from 0 to 6 h. The
activation time of 0 h corresponded to petroleum
coke samples that were subjected to carbonization
only and no activation with steam. The mass
recovery (R) and burnoff (B) of petroleum coke
samples were calculated for each activation period.
The mass recovery (R) is defined as the weight of the
activated coke divided by the original weight of the
sample multiplied by 100%. On the other hand, B is
the mass of carbon that was oxidized as a result of
the activation with steam and is defined as 100% R.
In addition, the amount of water that reacted with
petroleum coke, referred to as the water efficiency
(Weff ), was also calculated. The Weff is defined as the
mass of water, which produced steam and reacted
with the coke sample over the mass of the total water
used in the activation.
The activation results showed that the burnoff of
petroleum coke (B) increased from 8 to 67% as the
activation time increased from 0 to 6 h. The burnoff
of coke resulted from the reaction between steam and
tar deposits inside the initial pore structure of the
coke sample. As the activation time proceeded, the
steam widens the pore structure further and increasing the surface area. The activation process is carried
out until the maximum surface area is achieved in
which 50% of the carbon structure has been burnt
out (Jankowska et al., 1991). This can be illustrated
in Fig. 2, which shows the effect of activation time on
Weff and B.
The results in Fig. 2 indicated that there was a
steady rise in Weff going from 0 to a maximum value
of 54.3% after 4 h of activation. The Weff values then
declined slowly to approximately 40% after 6 h of
activation. These results suggested that there were
few surface sites for carbonsteam reaction to occur
at the start of the activation because of the low
surface area, as indicated by low B values. As the
activation time proceeded, more surface area was
exposed and thus more active sites for carbonsteam
reaction, as indicated by high Weff and B values. The

Fig. 2. Water efficiency of activation as a function of

burnoff.

747

maximum Weff value of 54.3% occurred when the

maximum surface area was achieved (at B value of
48.5%). Beyond this point of activation, further
oxidation starts to burn the walls of the pores
decreasing the surface area and therefore Weff values
decreased.
The success of the activation of delayed petroleum
coke was evaluated by performing liquid-phase
adsorption using methylene blue as adsorbate. The
adsorption capacities for raw petroleum coke,
activated petroleum coke and 5-590-A coconut
charcoal are summarized in Fig. 3. The adsorptive
capacity of raw petroleum coke was 8 mg/g of applied
coke. The methylene blue adsorption ranged from 10
to 100 mg/g for coke samples activated from 0 to 6 h.
The maximum adsorption occurred for coke samples
activated for 4 h with methylene blue adsorption of
100.5 mg/g of applied activated coke. The methylene
blue adsorption for the coconut charcoal had much
higher adsorption capacity of 420 mg/g of applied
activated carbon due to its large surface area (BET
value of 1237 m2/g).
Color removal of the bleaching effluent was
evaluated at different activated carbon dosages using
the 2, 4 and 6 h activated coke samples. Figure 4
shows color465 concentration at activated coke
dosages ranging from 100 to 15,000 mg/L. The results
showed that the 4 h activated coke sample achieved
the highest color removal as the dose increased. This

Fig. 3. Methylene blue adsorption results for different

activation periods.

Fig. 4. Color removal at different activated coke dose and

activation periods.

748

Ayman R. Shawwa et al.

was expected since the maximum surface area of

activated coke was achieved after 4 h of activation. In
the dosage range of 100 to 2500 mg/L, the highest
removal of color was about 33%. As the activated
coke dose increased from 2500 to 15,000 mg/L, color
removal increased to 90%. Similar trends were
observed for COD, DOC, UV254 and AOX.
In addition to the decrease in pollutant concentrations, it was noted that activated coke addition to the
bleached effluent has changed its composition, as
shown in the COD/DOC and color465/DOC versus
activated coke dose diagram, which is illustrated in
Fig. 5. The decrease in the specific oxygen demand
(COD/DOC) with increasing activated coke dose
indicated that the remaining solution contained more
oxidized compounds than the untreated bleached
wastewater (Sontheimer et al., 1988). The COD/
DOC ratio decreased significantly when the activated
coke dose was higher than 2500 mg/L. The activated
coke removed the recalcitrant portion of the organic
compounds present in the bleached wastewater. As a
result, the remaining solution in the bleached wastewater would become more susceptible to biological
treatment (Yin et al., 1990).
In addition, the results in Fig. 5 showed that
significant color465 removal was achieved when the
activated coke dose was higher than 2500 mg/L. The
high color removal exceeded that achieved in COD
or DOC, which indicates the preferential removal of
high molecular weight chlorolignins from bleached
wastewater (Cecen, 1993; Ying and Tucker, 1990).
Activated coke addition also led to a significant
decrease in AOX concentration. The AOX, or
absorbable organic halide, is considered one of the
commonly used surrogate measures for chlorinated
organics concentration in wastewater. It measures
volatile halides that are associated with organic
compounds (Gergov et al., 1988). For activated coke
dose ranging from 100 to 2500 mg/L, the highest
removal of AOX was 26% for coke samples activated
for 4 h. Increasing the carbon dose from 2500 to
15,000 mg/L resulted in 90% reduction in AOX.
Adsorptive capacity for activated petroleum coke
was estimated from adsorption isotherm data for
color465. The Freundlich isotherm is widely used for a

variety of heterogeneous adsorption systems because

it gives more accurate results than the Langmuir
isotherm (Chen and Horan, 1998). Therefore, the
adsorption data were fitted by least-squares regression into the Freundlich equation of the form

Fig. 5. COD/DOC and Color/DOC ratios at different

activated coke dose (4 h-activation period).

Fig. 6. Adsorption isotherm for activated coke with 4 hactivation time.

q X=M KCen
where q is the amount of color465 adsorbed per mg of
applied activated coke, X is adsorbed amount of
color465, M is the weight of carbon, Ce is the
equilibrium concentration of color465 in solution
and K and n are Freundlich adsorption constants.
The Freundlich constant K represents the adsorption
capacity of the carbon for specific adsorbate, at a
given equilibrium concentration Ce . In general, a
high value for K is desirable for higher color
reduction.
Adsorption isotherms for color465, COD, DOC
and UV254 were developed for activated coke with 4 h
activation period. The isotherm data for color465
were plotted as log q versus log Ce shown in Fig. 6.
The bleached effluent contained both easily and
poorly adsorbable compounds, which competed for
activated carbon sites. At activated coke dosages
ranging from 100 to 2500 mg/L, only the easily
adsorbable compounds were removed from the
solution and the equilibrium concentration is determined by the poorly adsorbable compounds left in
the solution (Sontheimer et al., 1988). As a result, a
steep isotherm is obtained, which is shown in region 1
of Fig. 6. Similar trends were observed for COD,
DOC and UV254. The Freundlich constants K and n
based on region 1 were determined as 5  10 22 mg
color/mg activated coke and 6.6, respectively.
The adsorption isotherm for color465 also showed
that as the activated coke dose increased from 2500
to 15000 mg/L, the amount of easily adsorbable
compounds per unit mass decreased. The isotherm
flattened and would reflect only the behavior of
poorly adsorbable compounds, or the high molecular
weight chlorolignins (Chen and Horan, 1998). This
part of the isotherm is represented by region 2 of
Fig. 6. Similar trends were observed for COD, DOC
and UV254. The Freundlich constants K and n based
on region 2 were determined as 0.05 mg color/mg
activated coke and 0.2, respectively.

Color and chlorinated organics removal from pulp mills wastewater

Table 3. Adsorption constants based on region 2 of the adsorption
isotherma
Parameter
COD
DOC
Color465 nm
UV254 nm
a

0.0457
0.0241
0.0514
0.0093

0.2303
0.2541
0.2024
0.4611

The K values for color, COD and DOC are given in mg/mg
activated coke and for UV in cm 1/mg activated coke.

The Freundlich constants K and n based on region

2 were used to calculate the adsorption capacity for
the activated coke because true adsorption of
chlorolignins can be followed in this region. The
adsorption capacity for bleaching effluent that has
color of 2300 mg/L is 0.25 mg color/mg activated
coke.
The adsorption constants K and n expressed as
color465 and UV254 were of the same order of
magnitude as these found in terms of COD and
DOC, as shown in Table 3. In general, better
adsorptivity was obtained when the adsorption was
expressed in terms of color465 than DOC and COD.
The UV analysis is reported to reflect the removal of
halogenated organics better than DOC (Sontheimer
et al., 1988). Therefore, the rapid UV analysis can be
substituted for DOC and COD analysis when
investigating the adsorption of AOX compounds
from bleaching wastewater.
CONCLUSIONS

The results from this study confirmed that the

activation process of petroleum coke was successful.
The maximum surface area of the activated coke was
developed after 4 h of activation with steam at 8508C.
This was confirmed by the methylene blue adsorption
results which showed that the highest adsorption
occurred using the 4 h-activated coke and that the
adsorption capacity was 10 times higher than that for
the raw petroleum coke. The adsorption equilibrium
results showed that significant color and AOX
removal (>90%) from the bleaching wastewater
was achieved when activated coke dose exceeded
15,000 mg/L. The decrease in the specific oxygen
demand (COD/DOC) with increasing activated coke
dose indicated that the remaining solution in the
bleaching wastewater contained more oxidized compounds and as a result it would be more susceptible
to biological treatment. Therefore, adsorption of
color and chlorinated organics with activated coke
can be utilized as a pretreatment step before any

749

biological treatment. Based on the adsorption

isotherms developed in this study, the amount of
activated coke required to achieve certain removal of
color and chlorinated organics can be predicted.
Acknowledgements}This project was funded in part by the
Sustainable Forest Management Network of Centers of
Excellence and part by a research grant from the Natural
Sciences and Engineering Research Council of Canada. The
authors would like to acknowledged Suncore Canada for
providing the petroleum coke samples and Weyerhaeuser
Canada for providing the bleached stage wastewater
samples used in this study.

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