Journal of Environmental Management 214 (2018) 362e369

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Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman

Research article

Evaluation of adsorbent and ion exchange resins for removal of

organic matter from petroleum refinery wastewaters aiming to
increase water reuse

ria da Fonseca b, *
Rodrigo de Abreu Domingos a, Fabiana Vale
a
PETROBRAS, School of Chemistry, Federal University of Rio de Janeiro, Av. Henrique Valadares, 28, Centro, Rio de Janeiro, RJ, 20231-030, Brazil
b
ria, Ilha do Funda
School of Chemistry, UFRJ, Federal University of Rio de Janeiro, Av. Athos da Silveira Ramos 149, Cidade Universita ~o, Rio de Janeiro, RJ,
21941-909, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The oil refinery industry seeks solutions to reduce its water uptake and consumption by encouraging the
Received 3 July 2017 reuse of internal streams and wastewater from treatment systems. After conventional treatment the
Received in revised form petroleum refinery wastewater still contains a considerable quantity of recalcitrant organics and the
11 February 2018
adsorption on activated carbon is currently used in Brazilian refineries, although it is still expensive due
Accepted 5 March 2018
to the difficulty of its regeneration. This study evaluated the use of adsorbent and ion exchange resins for
the removal of organic matter from refinery wastewater after conventional treatment in order to verify
its feasibility, applying successive resin regenerations and comparing the results with those obtained for
Keywords:
Adsorbent resins
activated carbon process. Adsorption isotherms experiments were used to evaluate commercial resins,
Ion exchange resins and the most efficient was subjected to column experiments, where absorbance (ABS) and total organic
Organic matter carbon (TOC) removal were measured. The adsorption isotherm of the best resin showed an adsorptive
Petroleum refinery capacity that was 55% lower than that of activated carbon. On the other hand, the column experiments
Water reuse indicated good removal efficiency, and the amount of TOC in the treated wastewater was as good as has
been reported in the literature for activated carbon. The regeneration efficiency of the retained organics
ranged from 57 to 94%, while regenerant consumption ranged from 12 to 79% above the amount rec-
ommended by the resin supplier for the removal of organic material from natural sources, showing the
great resistance of these recalcitrant compounds to desorption. Finally, an estimate of the service life of
the resin using intermediate regeneration conditions found it to be seven times higher than that of
activated carbon when the latter is not regenerated.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction more resources to treat it. Due to these factors, process optimiza-
tion procedures and reuse actions are being increasingly applied in
Water availability per capita in Brazil is higher than in many order to improve process efficiencies and water recovery.
other countries in the world. However, this water is unevenly The oil industry is included in this context since it is a major water
distributed throughout the territory, with about 80% of the water consumer and, in many cases, is situated in water-scarce regions both
resources being in the Amazon basin, far from most industrial and in Brazil and worldwide. According to PETROBRAS (2015), a Brazilian
more densely populated regions. These regions face critical water petroleum refinery consumes an average of 0.9 m3 water per m3 of
availability levels according to UN classification indexes (ANA, processed oil, with water-based cooling systems and steam gener-
2013). The recent water crisis faced by some Brazilian states ation being the largest consumers (Amorim, 2005; Pombo, 2011). As
worsens the situation and directly affects the industrial sector. The a result, a large amount of wastewater is also generated, which must
industries face increasing costs when purchasing water and spend be treated before disposal since tit contains high levels of pollutants
such as oil, ammonia, phenols, sulfides, heavy metals, and organic
compounds (Nacheva, 2011).
* Corresponding author. Wastewater treatment in refineries primarily consists of two
E-mail addresses: rodrigo.domingos@petrobras.com.br (R. de Abreu Domingos), steps: removal of contaminants (oil and suspended solids) by
fabiana@eq.ufrj.br (F.V. da Fonseca).

https://doi.org/10.1016/j.jenvman.2018.03.022
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369 363

physical and physical-chemical processes, followed by a biological refineries were used in this study. The samples were all collected
step to remove organics and nitrogen compounds. As presented by after membrane bioreactors (MBR) in 20 L bottles after passing
IPIECA (2010) and Tchobanoglous et al. (2003), a third stage, usually through ultrafiltration membranes, making them almost free of
called tertiary treatment, may be required to make the effluent undissolved OM and microorganisms, which also ensured
suitable for disposal or reuse as cooling tower makeup water, improved preservation of their original characteristics.
process water or boiler feed water. The effluents were sampled from two different refineries where
Tertiary treatment processes vary depending on the contaminants MBR are installed, herein called A and B. Refinery A is an industrial-
to be removed. In refineries, clarification, filtration, or membrane scale plant and provided the first samples for the initial isotherms.
separation are commonly applied to remove suspended solids, which Refinery B, which contained a pilot-scale MBR, provided the rest of
is then followed by one or more dissolved salt removal processes, the samples for the adsorption/IEX isotherms and column experi-
such as electrodialysis reversal (EDR), reverse osmosis (RO), or ion ments. The OM content varied between samples due to the use of
exchange (IEX) resins. However, most dissolved salt removal pro- different petroleum sources in the refinery feed and operational
cesses require the reduction or elimination of residual organic com- variations in the wastewater treatment steps. Because of the large
pounds present in the wastewater, since these may foul membranes effluent volume required, samples with the same characteristics
and IEX resins irreversibly. These recalcitrant compounds are difficult could not be used in all the experiments. The initial TOC value for the
to remove using conventional wastewater treatment because they are refineries A and B was 14,2 ± 1,1 and 18,8 ± 0,7 mg/L, respectively.
poorly biodegradable, as indicated by Touma (2013a).
The most widely used process for removing these compounds in 2.2. Adsorbent and IEX resins
industry is adsorption on granular activated carbon (GAC)
(Tchobanoglous et al., 2003; Yang, 2013), which is usually employed The macroporous adsorbent and IEX resins used in this study are
after a biological treatment step as the cost of GAC consumption listed in Table 1, along with their main characteristics as listed by
without prior treatment would make the process economically their manufactures: matrices, functional groups, operational flow
unfeasible. Although GAC adsorption has been used for many years required (in bed volumes per hour), and possible regenerant
for water and wastewater treatment, it has some disadvantages chemicals. The resins were conditioned according to the manu-
when used in refineries. Due to the high levels of organic matter facturer's recommendations by soaking them in water for half an
(OM) present after biological treatment, the GAC is quickly satu- hour in a mixer and then removing the air inside their pores with a
rated and should be replaced with new inventory, or regenerated/ vacuum pump before each experiment. The commercial names of
reactivated. Thermal reactivation of GAC is not usually applied since the resins are not included in order to maintain manufacturer's
it is not performed in situ, requiring GAC to be transported to confidentiality.
reactivation sites that are not always close to the refineries. In Since resin R8 was used throughout all experiments, its true and
addition, it requires a frequent labor force for handling, high capital apparent densities were also obtained according to DOW (2014)
expenditure, and has high GAC losses of 5e10% according to and ASTM D2187-94 (2004), respectively. The true density was
Sufnarski (1999). GAC regeneration also follows this trend and thus 1042 kg m
3, whereas the apparent density was 621 kg m
3. The
is not applied commonly either. calculated porosity based on these values was 0.40. The average
As an alternative to using GAC in refineries, polymeric IEX and particle diameter of these resins was 0.75 mm.
adsorbent resins are based on adsorption and IEX mechanisms.
They are more easily regenerated than GAC (Yang, 2013), as they 2.3. Granular activated carbon
can be regenerated in situ by pH adjustment, solvents, or water
vapor, and they also result in lower losses than seen for GAC (Xu NORIT 1240 W GAC was used in this study. GAC samples were
et al., 2003). This makes them good options for the capture of OM prepared by grinding and sieving the commercial samples (Mesh
from oil refinery wastewaters even though their initial costs are 12  40). After this, GAC was washed several times to remove fine
higher than GAC, as noted by Yang (2013). The use of resins to particles, dried at 100  C in an incubator and had the air inside the
capture some organic compounds, such as fulvic acids and tannins, pores removed using a vacuum pump.
is currently applied using upstream demineralization systems,
usually to protect RO membranes and IEX resins. 2.4. Analytical methods
The main objective of this work is to verify the applicability and
feasibility of a residual OM removal process using adsorbent and The source water and all samples were analyzed for total organic
IEX resins at the laboratory scale, in order to find an alternative to carbon (TOC) and UV254 absorbance. The concentration of TOC was
the use of GAC for tertiary water treatment in oil refineries aiming utilized as the primary marker for performance. TOC testing was
to reduce water consumption by reusing water. Initially, the performed according to APHA (2005) 5310C method using a
adsorption capacities of resins were measured using isotherms and HiPerTOC TOC Analyzer. The UV absorbance was monitored
the best performing material was chosen for column tests. Column following the APHA (2005) 5910 method using an UVmini 1240
experiments were then performed to verify the performance of the Shimadzu UVevisible spectrophotometer.
resin when removing organics from wastewater and its ability to be
regenerated by removing the OMs using regenerant chemicals. 2.5. Equilibrium isotherm experiments
After the experiments, the service life of the resin when performing
intermediate regenerations was estimated and compared with that Equilibrium isotherm experiments were conducted to investi-
of GAC under similar conditions as obtained from literature data gate the capacities of the resins to remove the residual OM from
(Touma, 2013a), with the latter not being regenerated. refinery wastewater through adsorption and IEX mechanisms,
allowing the most efficient resins to be identified and tested in
2. Materials and methods columns. Data collected in these tests were also compared to GAC
isotherm performances. The Langmuir and Freundlich models were
2.1. Effluent source also verified.
Sixteen experiments were conducted, as each resin had two
Effluents from the wastewater treatment plants of Brazilian isotherms, one for each refinery wastewater. They were performed
364 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369

Table 1
Characteristics of evaluated resins.

Resin Type Polymer structurea Functional Group Operation flow (BV/h) Regenerant chemical

R1 e R5 Adsorbent S-DVB None 5e20 NaOH or HCl or ethanol

R6 Adsorbent Chloromethyl S-DVB Amine 2e5 NaOH or HCl
R7 Anionic S-DVB Amine 5e40 NaCl or NaOH
R8 Anionic S-acrylate-DVB Amine 7e20 NaCl and NaOH
a
S-DVB: styrene - divinylbenzene.

by dosing the effluent with 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.2 and 2.0 g of The high ionic strength caused by excess NaCl in water during


resin per liter at 170 rpm in a Nova Etica shaker at 25  C until the regeneration procedure causes the resin to contract and release
equilibrium was achieved. GAC isotherms for each refinery waste- the retained OM particles.
water were obtained followed similar procedures to allow a com- According to the manufacturer recommendation, the flowrate
parison of the isotherms of the resins, using ASTM D3860-98 through resin R8 should be from 8 BV h
1 to 20 BV h
1. For this
(2008) as a reference. experiment, a mean value of 13e14 BV h
1 was chosen.

2.6. Adsorption and regeneration column experiments 2.8. Column experiment 2

Packed-bed column experiments were performed to evaluate This experiment was similar to the previous one, differing only
the adsorption and IEX performances of the resins by extracting in the type and flow of the regenerant chemicals used. The 10% NaCl
their breakthrough curves in order to verify their regeneration solution was supplemented with 2% NaOH solution in an attempt to
capacity, and to test them through several treatment cycles to improve the regeneration efficiency. NaOH increases the pH and
confirm their potential as regenerable resins. Resin regeneration assists in hydrolysis of organics and ion exchange, facilitating the
should be understood to be the process of removing the retained breaking of bonds formed between the resin and the OM molecules.
OM by desorption and IEX through the passage of a regenerant Furthermore, a lower regenerant flow rate was applied to in-
solution. crease the EBCT between the resin and the chemical solution dur-
During the adsorption/IEX step, herein called the “operation ing the regeneration step.
step” or “operation cycle,” the effluent was continuously fed from
the top of the column using a dosing pump. The samples were 2.9. Column experiment 3
collected from the bottom of the column and an automatic sam-
pling valve was used when the column was not directly monitored. The third column experiment evaluated the performance of the
The regenerant solution was also fed from the top of the column resins during consecutive 24 h of test, aiming to check if interme-
during the regeneration/desorption process at flowrates defined diate regenerations allowed the recovery of the initial adsorption
according to the resin manufacturer's lab-scale procedures. The capacity and if the efficiency improved due to the reduced opera-
regeneration step was preceded and followed by deionized water tional cycle duration being less stressful to the resins. The objective
rinses. of these smaller tests was to verify if irreversible adsorption was
The glass column used in the laboratory experiments was occurring in the first two column experiments due to the longer
designed and optimized in order to avoid radial and axial disper- tests lengths.
sion effects, liquid maldistribution, and inadequate flow through In this case, the influent sample TOC was smaller than in column
the bed, while simultaneously seeking to reduce sample con- experiments 1 and 2. Another change was the effluent flow rate
sumption, which was achieved by using smaller diameters. A during operation, which was decreased to the lowest level sug-
schematic draw of the column set-up used in the experiments is gested by the manufacturer, 8 BV h
1, in order to improve the EBCT
present as supplementary material. As a result, an internal column and favor adsorption.
diameter of 12.6 mm and a bed height of 500 mm were chosen,
corresponding to a bed volume (BV) of 64 mL. Correlations based on
2.10. Theoretical models
bed parameters and flow operational conditions were extracted
from Delgado (2006), Inglezakis (2010), Inglezakis and Poulopoulos
There are many solutions for determining the adsorbate mass
(2006), and Thomas and Crittenden (1998) to achieve the desired
balance in a fluid flowing through a packed bed, which depend on
glass column dimensions.
the process conditions and the adsorbate-adsorbent groups. Two
It should be noted that all experiments to evaluate resin effi-
different solutions were used from Richardson and Harker (2002).
ciencies were performed with a single column, giving a lower
Equation (1) considers that equilibrium is achieved between the
empty bed contact time (EBCT) compared to industrial scale sys-
adsorbate in the fluid and in the solid, and that the bed operates
tems, where it is common to find adsorption beds in series to allow
isothermally. On the other hand, equation (2) treats the bed as
higher EBCT and lower outlet OM.
isothermal without reaching equilibrium. According to Ruthven
(1984), small-scale columns approximate isothermal conditions.
2.7. Column experiment 1 In most environment-related applications of adsorption treatment,
such as IEX and catalysis, species are in such low concentrations
This experiment focused on acquiring the breakthrough curve that the effect of the heat of adsorption on the temperature can be
for the selected resin, R8, in a 72 h experiment and on determining neglected (Inglezakis and Poulopoulos, 2006).
the efficiency of the regeneration process using a 10% NaCl solution
as a regenerant after the end of the operation. Experiment duration ut
of 72 h was defined according to the resin limitation of a maximum
¼ z
z0 (1)
1 þ m1i f 0 ðCÞ
of 3 days of operation without regeneration, which aims to avoid
irreversible adsorption.
 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369 365

8 2  39 these results for GAC, it was determined that performing adsorp-

> 3t
1 >
1< = tion/IEX column experiments with resins was of the utmost
C 6 2q 7
¼ 1 þ erf 4 rffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h i 5 (2) importance, since their application would only be feasible
C0 2 >
: 1þ5j >
;
2 compared to GAC if regenerations were efficient enough to allow a
5q
longer service lifetime in order to compensate for their higher in-
In these equations, t is the time; u is the velocity of the particles; vestment and the extra operating costs spent on regenerative
C and C0 are the concentrations at position z and z0 (initial) along chemicals.
the bed, respectively; mi is a bed porosity function, f(C) is the The isotherm data was fitted to the Langmuir and Freundlich
representative function of the considered isotherm; and t, q, and j models. For both refineries, a much higher R-squared value was
are functions of effective diffusivity, time, position, velocity, bed achieved for the Freundlich model compared to the Langmuir
porosity, isotherm, mass transfer coefficient, and particle model. The improved fit of the Freundlich model was expected as it
dimensions. considers the heterogeneity of the active sites of the adsorbent and
the formation of many layers of adsorbate on the adsorbent surface,
whereas the Langmuir model does not. The Freundlich parameters,
3. Results and discussion
Kn, 1/n (n
1), and the adsorption capacity at equilibrium at the
initial sample concentration, (qe)C0, that were obtained for the ef-
3.1. Equilibrium isotherms experiments
fluents of both refineries and the data was presented in
supplementary materials. A better result for the Freundlich model
Adsorption isotherms of the evaluated resins and GAC for the
was also obtained by Li et al. (2004) for polymeric resins in non-
effluents from refineries A and B are shown in Fig. 1, where qe is the
aqueous solutions.
adsorption capacity and Ce is the equilibrium concentration.
The Freundlich parameters obtained for resin R6 indicate that it
Resin R6 showed a slight advantage over the other resins at
possessed a good adsorption capacity. However, R6 had a low
lower equilibrium concentrations; however, it had a reduced ca-
(qe)C0, which is an important parameter for column performance.
pacity at higher concentrations. Resins R5 and R8 also had good
For this parameter, the best resin was R8. Therefore, resin R8 was
results compared to the other five resins. The highest adsorptive
chosen for column experiments since it had one of the best
capacities for the initial sample conditions, Ce ¼ C0, were obtained
isotherm profiles as well as the best performance in terms of (qe)C0.
for resins R5 and R8.
Additionally, resin R8 changed its color as it was contaminated
GAC was favorable and it had a much higher adsorption capacity
(resin R6 maintained its color), allowing observation of the prog-
across the entire concentration range that was monitored. Based on
ress of contamination through the bed.

3.2. Column experiment 1

The adsorption/IEX curve obtained from column experiment 1,

also called a breakthrough curve, is shown in Fig. 3a. It displays the
ratio of the treated effluent TOC to the initial value (C/C0) as a
function of bed volumes treated. Operational data for the first two
column experiments are displayed in Table 2. All column experi-
ments tested resin R8 and used a bed volume of 64 mL (diam-
eter ¼ 12.6 mm and height ¼ 500 mm).
A rapid increase in the treated effluent TOC occurs up to about
200 BV, when the curve reaches an almost constant baseline. This
result does not necessarily indicate a rapid saturation of the bed,
since it keeps adsorbing part of the OM. During this initial increase,
certain recalcitrant organic species that are less favorably retained
through adsorption and IEX rapidly reach the bottom of the bed,
whereas other organic species are more easily retained.
Touma (2013a) presented pilot scale and prototype GAC col-
umns with similar EBCT and effluent TOC levels, resulting in a C/C0
ratio of 0.80 for 900 BV of consumed effluent for a single vessel. The
consumption of the same volume of effluent in present work
experiment resulted in a maximum of C/C0 ¼ 0.62. This shows that
resin R8 had a similar or even better TOC removal efficiency than
GAC.
Fig. 2 shows the regeneration curve (outlet TOC) and the
retained and removed OM from the resins bed during the regen-
eration process. The curve reached the expected profile and TOC
values were almost 4000 mg L
1 at the desorption peak. The
regeneration data for the first two column experiments are shown
in Table 3.
At the end of the experiment, after almost 12 BV of regenerant
consumption, the desorption/regeneration process had removed
around 68% of the initially retained OM on the resin, as determined
Fig. 1. Resins and GAC isotherm and comparison with resins e Refinery A (a) and
by graphical integration, and 1250 g of NaCl per liter of resin had
Refinery B (b). Experimental conditions: Resin concentration (g/L) 0.05, 0.1, 0.2, 0.4, 0.6, been consumed. However, the regeneration could have ended after
0.8, 1.2 and 2.0, T ¼ 25  C, 170 rpm. 4 BV of regenerant consumption, when the outlet TOC had already
366 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369

Table 2
Column experiments 1 and 2 e Operational data.

Column Experiment 1 2
Operation cycle Single Single
Fluid Refinery B effluent Refinery B effluent
Average initial TOC (mg/L) 18.0 17.1
Average flow (BV/h) 12.7 13.0
EBCT (min) 4.7 4.6
Operation cycle duration (h) 68.6 65.7

3.3. Column experiment 2

As expected, the shape of the column experiment 2 break-

through curve was very similar to that seen for experiment 1, since
both tests used the same sample and operational parameters.
Fig. 3a shows that C/C0 did not exceed 0.65 (outlet
TOC ¼ 11.0 mg L
1). As described for experiment 1, the TOC level
stabilized as the treated effluent reached 200 BV. Integrating the
TOC curve showed that about 46% of the total effluent OM was
retained in the resin bed, similar to the amount seen in experiment
1, where 45% of the OM was adsorbed or ion-exchanged.
OM removal in the second regeneration experiment (Fig. 3b)
was better than seen previously, with 80% of the total OM retained
in the resin bed at the beginning of the regeneration procedure
being removed, 12% more than seen for regeneration with only 10%
NaCl, as performed in experiment 1. Even though the total OM
passed through the column was approximately 8% lower than for
experiment 1, which could have contributed to the reduced irre-
versible adsorption in this experiment, the better results could also
have been favored by the greater EBCT due to the decreased
regenerant flow rates, as well as the additional use of NaOH. The
regeneration consumption was the same as seen in column
experiment 1.

3.4. Column experiment 3 e consecutive operation cycles

Fig. 4 shows the outlet TOC values for all operation cycles during
column experiment 3. These values did not exceed 9.3 mg L
1 in all
eight operation cycles, which is equivalent to a maximum C/C0 of
0.61. However, the curves show a tendency for TOC to increase
through the tests, especially in the last three, indicating gradual bed
Fig. 2. Operational breakthrough curve (a) and regeneration curve (b) e Column saturation. The operational and regeneration data obtained from
experiment 1. Experimental conditions: Average flow ¼ 12.7 BV/h; EBCT ¼ 4.7 min; this experiment are displayed in Table 4 and Table 5, respectively.
Operation cycle duration ¼ 68.6 h. Further important evidence is that the breakthrough curves
always began at TOC values above zero, indicating that some OM
compounds had a low tendency towards adsorption or IEX, even
stabilized at low levels. At this point, the regeneration level reached when the bed was not yet contaminated. This portion corre-
430 g of NaCl per liter of resin. This level of regenerant consumption sponded to approximately 24e31% of the refinery wastewater OM.
was 79% above the 240 g NaCl L
1 recommended by the manufac- The presence of non-adsorbable compounds was also shown for
turer in their procedure for the regeneration of resin R8. This GAC by Touma (2013b), where values from 10 to 20% were found.
discrepancy may be possible due to the presence of recalcitrant OM removal efficiency ranged from 57 to 94% (76.1% ± 13.8%) for
organic compounds in this effluent, which are more difficult to the eight regenerations carried out in experiment 3. This does not
desorb than the natural OMs (NOMs) commonly found in surface allow one to conclude if reducing the operation cycle duration from
water and used by the manufacturer as a reference for resin R8 data. 72 h to 24 h decreased irreversible adsorption.

Table 3
Column experiments 1 and 2 e Regeneration step data.

Column Experiment 1 2
Operation cycle Single Single
Fluid/Solution NaCl 10% NaCl 10% and NaOH 2%
Average flow (BV/h) 3.6 2.4
EBCT (min) 16.7 25.2
Regeneration duration (min) 211 340
Regenerant volume consumed (mL) 806 850
 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369 367

These values are smaller than those obtained in the two previous
experiments, but are up to 66% higher than the value provided by
the manufacturer for NOM removal, 240 g NaCl L
1.

3.5. Application of theoretical models

As shown in Fig. 5, the theoretical breakthrough curves calcu-

lated from equations (1) and (2) were compared to the data from
the first operation cycle of experiment 3, since only the first oper-
ation cycle started with a fresh non-contaminated resin.
As can be seen, neither curve agreed with the experimental data.
However, the curve shape under isothermal and equilibrium con-
ditions (obtained using equation (1)) is similar to the experimental
data, since it includes a breakthrough from the starting time. The
disagreement between equation (1) and the experimental data is
primarily caused by the theoretical model not taking into account
non-adsorbable species, which correspond to about 25% of the total
TOC.
In order to adapt the model results to the data obtained in
experiment 3, it was necessary to add the non-adsorbable OM to
the model results. The result of this adjustment for the first oper-
ation cycle of experiment 3 is shown in Fig. 6. According to the
figure, the data for the first operation cycle were in good agreement
with the model when the estimated non-adsorbable OM portion
was added, allowing the results to be used to predict the total
operation cycles for resin as described in the next section.

3.6. Estimate of GAC and resin operation cycles

Fig. 3. Adsorption breakthrough curve (a) and regeneration curve (b) e Column
In order to estimate the maximum GAC and resin operation
experiment 2 and comparison with column experiment 1. Experimental conditions:
Average flow ¼ 13 BV/h; EBCT ¼ 4.6 min; Operation cycle duration ¼ 65.7 h. cycles before saturation, it is necessary to define a breakpoint of
interest. This definition depends on the maximum TOC accepted by
The average regeneration level obtained in experiment 3 was the input specifications of downstream processes, usually for
338 ± 50 g NaCl L
1 resin, ranging from 270 to 400 g NaCl L
1 resin. removal of dissolved solids in tertiary treatment.

Fig. 4. Operation breakthrough curves e column experiment 3. Experimental conditions: Average flow ¼ 7.1e8.3 BV/h; EBCT ¼ 7.2e8.5 min; Operation cycle duration ¼ 21.6e26.5 h.

Table 4
Column experiment 3 e Operational data.

Operation cycle 1 2 3 4 5 6 7 8
Fluid Refinery B effluent
Average initial TOC (mg/L) 14.3 14.3 14.2 13.9 13.9 14.4 14.5 15.3
Average flow (BV/h) 7.8 7.6 8.3 7.1 7.2 7.5 7.4 7.4
EBCT (min) 7.7 7.9 7.2 8.5 8.3 8.0 8.1 8.1
Operation cycle duration (h) 23.6 21.6 24.5 23.7 26.5 24.4 23.5 23.8
Final TOC outlet value (mg/L) 7.3 7.1 6.9 7.2 8.1 8.6 8.6 9.3
368 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369

Table 5
Column experiment 3 e Regeneration data.

Operation cycle 1 2 3 4 5 6 7 8
Fluid/Solution NaCl 10% and NaOH 2%
Average flow (BV/h) 2.0 2.3 2.2 2.1 2,0 2.0 2.2 2.1
EBCT (min) 29.4 26.7 27.3 28.9 29.6 29,3 27.5 28.7
Regeneration duration (min) 139 110 131 108 128 100 99 127
Regenerant volume consumed (mL) 304 283 308 240 278 219 231 284

Fig. 5. Theoretical breakthrough curves e column experiment 3. Experimental conditions: Average flow ¼ 7.1e8.3 BV/h; EBCT ¼ 7.2e8.5 min; Operation cycle
duration ¼ 21.6e26.5 h.

Considering that the average outlet TOC for all column experi- experiments during this study, results were gathered from the
ments performed after achieving a constant baseline was around literature for comparison with resin R8. Touma (2013a) tested GAC
7e11 mg L
1, RO systems could not be used in downstream resins with Brazilian refinery wastewater in rapid small-scale column
beds as most RO membranes do not tolerate TOC values above tests (RSSCT) with the same TOC level as used in experiment 3 of
3e5 mg L
1 without an extensive study of the impact of the TOC on this study and a similar EBCT. To reach C/C0 ¼ 0.70 with a single
the membranes. Moreover, normal IEX systems would also expe- column, Touma (2013a) consumed about 328 BV of effluent.
rience high contamination on anionic resins. On the other hand, An estimate of the total number of resin operation cycles could
EDR membranes can cope with TOC of up to 15 mg L
1 (GE, 2013), not be made using the data from experiment 3 as it had not ach-
and could be used as a dissolved salt removal process after TOC ieved the breakpoint of C/C0 ¼ 0.70. Therefore, the total number of
removal using resin R8 beds. operation cycles was estimated using the theoretical model from
In this work, only experiment 3 ran consecutive operation cycles equation (1), adjusted to consider the non-adsorbable OM as
that could be used to estimate the maximum number of operation described in Section 3.6.
cycles the resin could withstand until the breakpoint is reached. A As shown in Fig. 6, there was a discrepancy between the
breakpoint of about C/C0 ¼ 0.70 will be used as a safe estimate, experimental data for the eight operation cycles and the adjusted
which represents a treated effluent with a TOC of 10 mg L
1. This model curve for the first operation cycle due to bed saturation, with
value is similar to the target TOC used by Touma (2013b) for TOC this discrepancy being especially strong after the fourth adsorption
removal by adsorption using GAC beds. curve. The discrepancy in the retained OM for each operation cycle
Since GAC performance was not tested through column allowed a correlation between the retained OM per operation cycle

Fig. 6. Adjusted equilibrium and isothermal curve e column experiment 3. Experimental conditions: Average flow ¼ 7.1e8.3 BV/h; EBCT ¼ 7.2e8.5 min; Operation cycle
duration ¼ 21.6e26.5 h.
 R. de Abreu Domingos, F.V. da Fonseca / Journal of Environmental Management 214 (2018) 362e369 369

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Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jenvman.2018.03.022.