Resources, Conservation and Recycling 73 (2013) 172179

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Resources, Conservation and Recycling

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Full length article

An analysis of water management in Brazilian petroleum reneries using

rationalization techniques
Felipe Ramalho Pombo , Alessandra Magrini, Alexandre Szklo
Federal University of Rio de Janeiro, Energy Planning Program, Cidade Universitria, C.T., sala C211, 21949-972, Rio de Janeiro, RJ, Brazil

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

Article history: This study assesses the application of rationalization techniques in oil reneries to preserve freshwa-
Received 20 March 2012 ter resources. These techniques include conservation, recycling and reuse of water and Pinch technique.
Received in revised form 1 February 2013 Several reneries in the world use treated household wastewater. In Brazil, a country with expanding
Accepted 4 February 2013
rening capacity, this practice is planned for two reneries. Water conservation and recycling initia-
tives also hold promise, including reduction of losses, replacement of cooling towers with smaller units
Keywords:
and recycling of blowdown into cooling towers and steam generation systems. Some technologies gain
Water management
importance for wastewater reuse, such as ion exchange, nanoltration and advanced oxidative processes.
Efcient use of water
Pinch technology
Finally, the application of the Pinch technique reduces the withdrawal of water and its associated costs.
Oil reneries Thus, this method is appropriate in areas with scarce water, where some new Brazilian reneries are
slated for construction.
2013 Elsevier B.V. All rights reserved.

1. Introduction With the planned construction of new reneries in the country

Brazil is a privileged country in terms of water resources,
with approximately 13% of the worlds freshwater (Mierzwa and
Hespanhol, 2005). On the other hand, this water is unevenly dis-
tributed: some regions have abundance and others shortage (arid
and semi-arid regions). In addition, in highly urbanized regions
(metropolitan areas of major cities, such as Rio de Janeiro and
So Paulo), there are various problems related to water quality
(Hespanhol, 2003).
Moreover, with the implementation of the instruments for
granting and charging for use of water resources in Brazil (National
Water Resource Policy, established by Law 9433 of 1997), the reuse
of industrial efuents became economically attractive, besides
improving the image of companies (Mierzwa and Hespanhol, 2005).
Charging is an instrument that promotes balance between water
supply and demand. The requirement to obtain government per-
mission for a determined period also encourages responsible water
use (Magrini and Santos, 2001).
In 2011, the reneries of Petrobras, the state-controlled Brazil-
ian oil company, processed 226,042 m3 of crude oil per day (ANP,
2012). Given the average water consumption index (WCI) at these
reneries, of 0.9 m3 of water/m3 of oil processed, the estimated
water consumption is 203,438 m3 of water per day.
Corresponding author. Tel.: +55 2562 8767; fax: +55 2562 8777.
E-mail addresses: frpombo@ppe.ufrj.br, feliperamalhop@gmail.com
(F.R. Pombo).
in the next ten years, accounting for an additional installed nominal
atmospheric distillation capacity of 1.46 million barrels of oil per
year (Petrobras, 2011), the increase in water consumption will be
232,140 m3 of water per day. Therefore, water consumption will be
more than double the existing level.
According to Hill (2003), cooling towers and steam generation
systems typically each account for 4045% of water use in rener-
ies. The other uses are mainly the processing units, re ghting
systems and drinking water. Water is also used to remove soluble
inorganic compounds from hydrocarbon streams, while steam is
used in direct contact (water quench) with hydrocarbons, resulting
in the generation of industrial efuents. Therefore, the main users of
water in petroleum rening are presented in Table 1 (Alva-Argez
et al., 2007).
However, is it technically and economically feasible to reduce
the water consumption of petroleum reneries? This paper aims to
answer this question by assessing the reduction of water consump-
tion through rationalization techniques in Brazilian reneries. The
options include conservation, recycling and reuse of water, which
can be reached using the Pinch technique of mass exchange opti-
mization.
Water conservation requires the least effort and investment
costs. It involves the rational use of water by industry, incorporat-
ing measures to prevent physical losses and improve operations
(Matsumura and Mierzwa, 2008). Recycling (with regeneration)
refers to the use of treated wastewater in the place of origin. Finally,
water reuse can occur in the following forms: (a) direct reuse of
wastewater, when the level of contamination does not interfere

0921-3449/$ see front matter 2013 Elsevier B.V. All rights reserved.
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 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179 173

Table 1
Main water users in petroleum rening and the features of their wastewaters (adapted from Alva-Argez et al., 2007).

Water user Origin of the efuent Major pollutants from efuent Comments

Desalting Fresh or foul water stripped Free oil, ammonia, suldes and suspended solids 310% by vol. on crude charge
Distillation Stripping steam Suldes, ammonia, phenols, oil, chlorides, mercaptans Oil sampling lines produce signicant ows
Thermal cracking Overhead accumulators H2 S, ammonia, phenols
Catalytic cracking Stripping steam Oil, suldes, phenols, cyanide, ammonia Alkaline wastewaters
Hydrocraking Stripping steam High in suldes
Polymerization Pretreatment for H2 S removal Suldes, mercaptans, ammonia Low volume but high strength waste

Fig. 1. Scheme of wastewater treatment aiming at reuse in petroleum reneries.

in the next process; and (b) reuse with regeneration, which is the
reuse of treated wastewater in another process (Wang and Smith,
1994).
Primary treatment methods for wastewater reuse in petroleum
reneries are the most conventional alternative for improving the
use of water of these industrial facilities. In this case, oil/water sep-
aration and dissolved air otation deserve attention. In the case
of the secondary treatment, which aims to remove most of the
biodegradable organic material, the use of membrane bioreactors
(MBRs) is gaining importance. This alternative is a combination of
the activated sludge process with membrane separation (micro or
ultraltration UF) (Melin et al., 2006). Finally, the tertiary treat-
ment removes ions (dissolved salts) to obtain adequate quality
for reuse, mainly in cooling towers or steam generation systems.
These processes include reverse osmosis (RO) or reverse electro-
dialysis (EDR). EDR is based on the movement of charged species
in an electrical eld. The polarity of the electrodes is periodically
reversed, inuencing in the direction of the ion movement. This
mechanism reduces the fouling of the ion-exchange membranes
(Chao and Liang, 2008). Fig. 1 shows a typical scheme for wastewa-
ter treatment and reuse in petroleum reneries.
In the case of the Pinch technique, Alva-Argez et al. (2007)
presented a pinch technology-based systematic approach that con-
templates mixed-integer non-linear programming (MINLP). These
authors reached a reduction of water consumption of more than
10% with minimal capital investment. Nabi Bidhendi et al. (2010)
applied the water pinch technique and reduced water consump-
tion by 53% and 63%, considering COD and hardness, respectively,
at a Tehran renery. The analysis of this study complements other
studies, such as Castro et al. (1999), Hallale (2002) and Gomes et al.
(2007).
The next section describes the methodology of this study. Sec-
tion 3 presents the results of the study, which are discussed in
details in Section 4. This section also presents proposals for improv-
ing water use in the existing and new Brazilian reneries. Finally,
the last section presents the nal remarks of the paper.
2. Methodology
This study applies the water consumption index (WCI) and the
processed petroleum for all Brazilian reneries to estimate the
quantity of water used for this industrial activity, in a country that
is expanding its rening capacity. The quantity of additional water
that will be needed with the construction of new reneries is also
estimated, along with data about water use by oil reneries and the
main processes that use water in reneries.
Our analysis is based on the international experiences of water
rationalization in petroleum reneries presented in conference
articles and scientic papers, to help propose new methods and
observe the prospects for water rationalization practices in Brazil-
ian reneries. We then discuss the concepts of conservation,
recycling and reuse of water at petroleum reneries, to propose
the best available techniques.
Finally, the water Pinch technique is applied for two basic data
sets, which represent some processing units found in the new
Brazilian reneries: distillation, hydrodesulfurization (HDS) and
desalting. The data from Takama et al. (1980) and Wang and Smith
(1994) were adjusted to the Brazilian case.
In addition, the software Water Design, developed by Blocher,
Dibicarri, Mann, Tran and Woodson, was used in the Pinch mod-
eling. By using this software, we plot the composite limit curves
for the two mentioned cases, aiming to reach the minimum value
for water ow rate in reneries and the optimum water network,
including reuse opportunities. The results from the water Pinch
application were, then, used for Brazilian Greeneld reneries, to
predict the optimized mass exchange networks in these planned
facilities. This case is particularly relevant for the already men-
tioned context of the expansion of rening capacity in Brazil.
According to Mann and Liu (1999), Water Pinch is divided into
three phases: analysis, where the minimum consumption of fresh-
water in the various operations is determined; design, involving
development of freshwater distribution structure to meet the min-
imum ow rate; and alteration, entailing modifying the structure
of water distribution and wastewater collection to maximize reuse
and minimize generation of wastewater.
The Pinch technique was rstly developed and applied for opti-
mizing the energy use, through a well designed network of heat
exchangers (Szklo and Schaeffer, 2007). Then it was adapted to be
used for minimizing the water use in industrial facilities. Actually,
Wang and Smith (1994) proposed to extend the bottleneck point
technology for mass integration using the concept of composite
limit curve, by estimating the minimum water consumption for
one contaminant and multiple contaminants.
Then, the same authors, Wang and Smith (1995), extended the
methodology, considering restriction and losses of ow rate and
multiple sources of water. The hypothesis for the determination
of minimum water consumption is that water is used to absorb
contaminants. Eqs. (1) and (2) indicate the related mass balances
(Mierzwa and Hespanhol, 2005), the second equation being a con-
sequence of the rst.
P P H2 O H2 O
QP (Ci;in Ci;out ) = QH2 O (Ci;out Ci;in ) (1)
H2 O H2 O
mi;total (kg/h) = QH2 O (t/h) (Ci;out Ci;in ) (ppm) (2)
174 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179
where QP is the ow rate of the most concentrated stream, QH2 O
P and C P
is the ow rate of the least concentrated stream, Ci;in are
i;out
the concentrations of the contaminants that enter and leave the
H2 O and C H2 O are the
most concentrated stream, respectively, and Ci;out
i;in
concentrations that leave and enter the least concentrated stream,
respectively.
The composite curve relates the variation of the contaminant
concentration in the water with the mass of the same contaminant
transferred to the water. With multiple contaminants, it is neces-
sary to choose one as reference, and it might be necessary to make
changes in the concentration of that contaminant. Non-reference
contaminants can determine those changes in order to make reuse
feasible. Eq. (3) is used to calculate the minimum water ow rate.
mi,min
Fmin = 103 (3)
Ci,min
where Fmin is the minimum ow rate, mi,min is the mass variation
of the reference contaminant in the pinch concentration and Ci,min
is the pinch concentration.
3. Results
3.1. International experiences with water rationalization
Esso (the European name of ExxonMobil) carried out a waste-
water reuse project in its Rotterdam renery, using water from
the treatment system as feed for the demineralization plant
(Duyvesteijn, 1998). This renery is located in Rotterdam-Botlek
and its processing capacity is 191,000 barrels of oil per day.
Findings showed that wastewater reuse is limited by the pres-
ence of suspended solids and the relatively high conductivity due to
the presence of chloride ions. The following processes were tested
in a pilot scale (Duyvesteijn, 1998):
Sand ltration for removal of suspended solids and pre-treatment
of UF.
UF for removal of biological contaminants and pre-treatment of
RO.
RO for removal of dissolved salts.
Pemex, the Mexican state-owned oil company, carried out a
wastewater reuse project in its Minatitln renery, which has a
processing capacity of 170,000 barrels of oil per day. The main
objective was to provide water for the cooling towers. Membrane
ltering after biological treatment was used (as secondary treat-
ment). The tertiary treatment consisted of reverse osmosis (Peeters
and Theodoulou, 2005).
According to the same authors, a project was carried out in
the Marathon Ashland Petroleum (MAP) renery, located in Ken-
tucky (USA), with a capacity to process 212,000 barrels of oil per
day. The objective was to make it compliant with the discharge
requirements of city of Ashland. The treatment system chosen was
MBR, and the treated wastewater was discharged into the Ashland
municipal waste treatment system. Table 2 presents the removal
Table 2
BOD, COD, oil/grease and TSS removal by the treatment systems of Lzaro Crdenas
and MAP reneries.
Removal (%)
Renery BOD COD Oil and grease TSS
Lzaro Crdenas 50 54.6 87.5 97.5
MAP 99.7 95.0 97.0 89.4
Notes: (1) The treatment system of MAP Renery is not for wastewater reuse; (2)
BOD, biochemical oxygen demand; COD, chemical oxygen demand; TSS, total sus-
pended solids.
of BOD, COD, oils and greases and TSS by the treatment systems
mentioned.
It can be observed that the treatment system of MAP, which
used MBR, removed an amount of BOD and COD considerably high
when compared to the treatment system of Lzaro Crdenas ren-
ery, which used membrane followed by RO. However, by comparing
the removal rates of oil/grease and TSS by the two treatment sys-
tems, it can be noted that the values are much closer, which shows
that both treatment systems are efcient for these two parameters.
Treated municipal wastewater, usually called reclaimed water,
is often used by industries, among them reneries, which require
cooling water with low levels of phosphate, ammonia and sus-
pended solids. The processes used to achieve these requirements
include softening with lime, reverse osmosis and nitrication.
Additional treatment is required for steam generation, and more
treatment still can be required for water to use in re ghting
systems and other processes (Puckorius et al., 1998).
In Virginia (USA) a cooperative effort between the Hampton
Roads Sanitation District and the Yorktown renery (with capac-
ity of 70,000 barrels of oil per day), owned by Western Rening,
supplies 500,000 gallons per day of highly treated wastewater for
use in cooling towers and other renery processes. Another effort
is the Gold Bar renery, owned by Petro-Canada, in Edmonton,
with capacity to process 135,000 barrels of oil per day. This project
involves the use of tertiary treatment with membranes (UF and RO)
for use in the hydrogen and steam currents of the desulfurization
process.
In Asia, a signicant project is the Yanshan renery in Beijing,
China. It belongs to Sinopec and has processing capacity of 220,883
barrels per day. The project was prompted by the rigorous envi-
ronmental restrictions imposed by the Chinese government. In this
renery, the feed from the treatment unit for reuse contains resid-
ual oil (1.2 mg/L) and high COD (2050 mg/L). The conductivity
(14001900 uS/cm) and hardness (300500 mg/L) are too high for
direct reuse. The system includes a combination of UF and RO to
reduce the level of oil/COD, remove suspended solids and deminer-
alize the output water. The UF system has total capacity of 560 m3 /h
(10 units with capacity of 56 m3 /h). The system also has three RO
units, each with capacity of 103 m3 /h (Tong and Aerts, 2009).
Two other relevant projects were implemented in Mobil Altona
renery, owned by Esso, located in Victoria, Australia, with
processing capacity of 80,000 barrels per day, and in Petromidia
renery complex, owned by Rompetrol, located in Ravodari, Roma-
nia, with capacity of 100,000 barrels per day. Preliminary studies in
the Australian renery (Mobil Altona Renery, 2006) and the Roma-
nian complex identied water savings, minimization of wastewater
discharge and use of treated efuents for re ghting as the main
objectives of the mentioned projects. In addition, the Petromidia
complex adopted as a water conservation measure the replacement
of the cooling towers with smaller units (with energy savings as
well) and the modication and repair of the wastewater treatment
system, and as a recycling measure the reutilization of blowdown
in the steam generation systems.
3.2. Application of water pinch in oil reneries
Table 3 presents important data on the generation of wastew-
aters, water consumption index (WCI) and water consumption in
Brazilian reneries.
Table 4 presents the data on water ow rate, contaminants,
input concentration and output concentration from the following
processes: distillation, hydrodesulfurization (HDS) and desalting.
These data were presented in the works of Takama et al. (1980)
and Wang and Smith (1994).
It can be observed in Table 4 that the ow rate data from Wang
and Smith (1994) are similar to those from Takama et al. (1980),
 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179 175

Table 3
Basic water data of Brazilian petroleum reneries (ANP, 2012; Aquino et al., 2010; Schor, 2006).

Renery Region Crude oil processed in Wastewater Generated WCI (m3 water/m3 oil) Water Consumption
2011 (m3 /day) (m3 /day) (m3 /day)a

LUBNOR Northeast 1263 678 na na

REMAN North 6804 3287 0.450 3062
RECAP Southeast 6826 2194 0.870 5939
REFAP South 23,852 6546 0.800 19,082
REGAP Southeast 21,232 9483 1.060 22,506
RPBC Southeast 24,126 21,381 1.140 27,504
REPAR South 30,915 8852 0.570 17,622
REVAP Southeast 38,469 10,276 0.560 21,543
REDUC Southeast 34,575 25,285 1.190 41,144
RLAM Northeast 38,013 15,989 0.690 26,229
REPLAN Southeast 55,025 13,745 0.690 37,967
RNESTb Northeast 60,305 400600 na 54,275c
COMPERJ Southeast 54,855 dna na 49,370c
Premium I Northeast 99,736 dna na 89,762c
Premium II Northeast 49,868 dna na 44,881c
TOTAL 5,45,864 118,116118,316 dna dna

dna, does not apply; na, not available.

a
Estimates based on the WCI of each renery.
b
RNEST, COMPERJ and Premium I and II are greeneld reneries.
c
Water consumption calculated based on the average WCI of the Petrobras reneries.

Table 4
Limiting process data for two cases of petroleum reneries (adapted from Takama et al., 1980; Wang and Smith, 1994).

Data from Takama et al. (1980) Data from Wang and Smith (1994)

Process Flow rate (te/h) Cont. Cin (ppm) Cout (ppm) Flow rate (te/h) Cont. Cin (ppm) Cout (ppm)

1 45.8 SS 000 2539010 45.0 HC 000 1540035

H2 S H2 S
leo Sal
2 32.7 SS 5050020 6516,890120 34.0 HC 2030045 12012,500180
H2 S H2 S
leo Sal
3 56.5 SS 5020120 8543220 56.0 HC 12020200 220459500
H2 S H2 S
leo Sal

Notes: (1) Process 1 distillation; Process 2 hydrodesulfurization (HDS); Process 3 desalting; (2) SS, suspended solids; Cont., contaminant; HC, hydrocarbon; (3) Cin
input concentration; Cout output concentration.

because the processes considered are basically the same and t
well to the characteristics of the process units of the new Brazilian
reneries, planned to be installed in the next ten years, as men-
tioned before (Szklo et al., 2012). Fig. 2 presents the concentration
composite curve plotted from the data in Table 4, where the red
line is the composite curve and the blue line is the water supply
curve. In this case, the reference contaminant used was H2 S. Fig. 3
presents the same curve plotted using the data from Wang and
Smith (1994) with SS as reference, where the Pinch concentration is
400 ppm. Both chosen reference contaminants are major pollutants
in petroleum reneries, as can be see in Table 1.
From Figs. 2 and 3, the minimum ow rates can be calculated,
being equal to 99.41 and 106.70 te/h, respectively. If foulwater
stripper had been considered for water regeneration, the minimum
ow rate would be 54.20 te/h from the Wang and Smith (1994) data.
Fig. 4 presents the optimum water distribution network from
the data of Wang and Smith (1994). The blue line refers to the supply

Fig. 2. Composite curve for reaching the minimum ow rate of water for reuse Fig. 3. Composite curve for reaching the minimum ow rate of water, for reuse
without regeneration, based on data from Takama et al. (1980) and with the aid of without regeneration, based on data from Wang and Smith (1994) and with the aid
Water Design. of Water Design.
176 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179

Fig. 4. Optimum water distribution network, for reuse without regeneration, based on data from Wang and Smith (1994) and with the aid of Water Design.

Table 5 considered the processing units of the Water Pinch simulation done
Water savings (in %) of existing Brazilian reneries, based on application of the water
in this study.
pinch technique (reuse of water without regeneration).

Renery LUBNOR REMAN RECAP REFAP REGAP RPBC

4. Discussion
Water savings (%) 15.2 60.1 56.9 83.6
4.1. The most promising technologies for wastewater reuse
Renery REPAR REVAP REDUC RLAM REPLAN

Water savings (%) 61.6 18.2 84.1 81.3 The costs of the main technologies employed for wastewater
reuse in petroleum reneries are generally high, such as for mem-
branes for micro and ultraltration. The MBR technology has similar
of freshwater to the processes, the green line to the water reuse and cost, as it uses the membranes mentioned above. Reverse osmo-
the red line the generation of wastewater. From this picture, it can sis and reverse electrodialysis, which are competing technologies,
be noted the reuse from distillation to hydrodesulfurization. The have similar operational costs (Chao and Liang, 2008; OAS, 2010).
result would be similar if the data from Takama et al. (1980) had As mentioned before, these technologies are used in the nal step
been considered. of treatment, aiming at reuse in petroleum reneries, in order to
All existing Brazilian reneries have atmospheric and vacuum remove the chloride ions.
distillation units except for RECAP, which only has the atmospheric Some technologies, not yet applied in large scale for treating
type. All those reneries mentioned in Table 3 have desalting units renery wastewater for reuse, are promising and should be tested
and naphtha hydrodesulfurization units. Therefore, as the units further. Among them are nanoltration, ion exchange, which would
considered in the water pinch applications are well tted to the be useful for the polishing step of reverse osmosis, and advanced
reality of the Brazilian reneries, we are able to estimate the water oxidative processes, which are effective for treating sourwater.
savings that can be achieved with application of the technique in Nanoltration (NF) is a promising technology because its
Brazilian reneries (Tables 5 and 6). removal efciency hovers between that of ultraltration and the
Table 5 shows the water savings estimates based on the reverse osmosis. Hence, NF could be used as a technique immedi-
data of Takama et al. (1980) for reuse without regeneration ately before reverse osmosis or possibly replacing it. Although NF
(2366.9 m3 /day) and Table 6 shows the estimates based on the data membranes are more expensive than other membranes due to their
of Wang and Smith (1994) with regeneration (1290.5 m3 /day). We smaller pore size, its cost might decrease more quickly, possibly
improving its competitiveness, since NFs is a recent technology.
Ion exchange could be used as a polishing step of the reverse
Table 6
osmosis process, since for low salt concentration it is economically
Water savings (in %) of existing Brazilian reneries based on application of the water attractive (Rautenbach and Melin, 2003). Ion exchange could also
pinch technique (reuse of water with regeneration). be used after the reverse osmosis or electrodialysis processes, pos-
Renery LUBNOR REMAN RECAP REFAP REGAP RPBC
sibly reducing the cost of the last step of treatment for chloride
removal from wastewater.
Water savings (%) 53.8 77.6 76.5 91.9
Advanced oxidative processes (AOPs) are also useful for treating
Renery REPAR REVAP REDUC RLAM REPLAN
sourwater from reneries. This kind of wastewater has complex
features, containing emulsied oil, phenols, suldes, mercap-
Water savings (%) 79.1 55.4 91.9 89.8
tans and cyanides. Thus, it has to be segregated. AOPs, such as
 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179
Fenton, Fenton-like and photo-Fenton processes, could be used in
this case, because the sourwater cannot be treated through bio-
logical treatment systems. AOPs contribute to the degradation of
toxic or refractory substances though the production of hydroxyl
radicals.
However, further studies are necessary to assess the feasibility
of these technologies for large-scale application to treat oil renery
wastewater for reuse.
4.2. Prospects for water rationalization in reneries
Reneries worldwide, both existing and under the planning
phase, need to adopt water conservation methods that have already
proved to be effective in existing reneries, such as the use of
treated wastewater as re ghting water, substitution of existing
cooling towers with smaller units and modication and repair of
treatment systems, along with practices to reduce losses in rening
operation.
One form of water recycling involves use of blowdown in cool-
ing towers or steam generation systems. Blowdown is the water
released from these systems to remove impurities and sediment.
This kind of wastewater could be returned to these systems after
adequate treatment.
Several reneries in the world use treated household waste-
water, mainly to feed cooling towers. This type of reuse has been
proposed for two Brazilian reneries: REDUC (in Rio de Janeiro
state, with installed capacity of 242,000 barrels/day) and REPLAN
(in So Paulo state, with installed capacity of 365,000 barrels/day),
and would be a suitable option given the low water availability for
these reneries.
The main treatment technologies are being tested in pilot plants
in the Brazilian REGAP renery (in Minas Gerais state, with installed
capacity of 151,000 barrels/day), and those that prove most suc-
cessful will be incorporated in other reneries owned by Petrobras,
either through retrot in existing ones or inclusion in new projects.
Moreover, those technologies are being studied in the Petrobras
Research Center (CENPES).
A hypothetical example can be envisioned of a renery with
access to plentiful household wastewater. That facility would
mainly use MBR to treat this wastewater. A renery with large
load of heavy metals could use the advanced oxidative processes
after having its efuents segregated. Finally in a renery with saline
wastewater, very common, micro and ultraltration and reverse
osmosis or reverse electrodialysis (the latter two as tertiary treat-
ment) would be the most suitable treatment processes.
Valuable lessons for reneries can also be drawn from the
Energy Star program of the US Environmental Protection Agency
(Worrell and Galitsky, 2005). This is a voluntary labeling pro-
gram originally aimed at identifying and promoting energy efcient
products and opportunities to prevent pollution. The creation of
such a labeling scheme for efcient use of water in oil reneries
would be advantageous worldwide.
The main factors motivating water rationalization in petroleum
reneries are the more restrictive environmental regulations, gov-
ernment policies to improve local water quality and the need to
improve companies reputation due to heightened environmental
awareness. Just as in other countries, these factors are gaining in
importance in Brazil, thus prompting efforts to upgrade existing
reneries and to plan more efcient new ones in regions with water
shortage.
4.3. Pinch technology applied to greeneld reneries
The optimal water network designed in this study (and depicted
in Fig. 4 in Section 3) indicates the water reuse from the oil distilla-
tion unit into the hydrodesulfurization (HDS) unit. This information
177
is crucial to the new Brazilian reneries, whose large hydroren-
ing capacity will produce ultra-specied derivatives (Oil and Gas
Journal, 2012). The optimal network proposed and simulated in
this study depicts that desalting is the principal wastewater gen-
erator. This efuent originates from the mixing of oil with water
to dissolve salts. In the nal step, it removes water from oil, using
chemical or electric processes. There are also good possibilities for
water reuse from processing units to cooling towers and steam
generation systems, as these facilities require lower water quality.
Due to the large volume of water saved with the application of
the water pinch technique in our simulation, it is worth applying
it in Brazilian reneries. In addition to lower water consumption,
this technique has the advantage of reducing the costs associated
with the withdrawal of water, thus resulting in direct economic
gains. This is particularly important for reneries in regions with
water shortage, such as some areas where new reneries are being
built in Brazil - approximately 1 million barrel per day of Green-
eld capacity will be installed in the Northeastern region of the
country (Petrobras, 2011); such region shows low water availability
(Brazilian Government, 2012).
It is also interesting to combine the application of energy and
water Pinch techniques in petroleum reneries, because energy
savings would also result in water savings. For example, Szklo and
Schaeffer (2007) indicate that the lower need for steam as a source
of heat would result in a lower overall water consumption. There-
fore, water and energy Pinch together would result in signicant
gains in terms of water savings, and hence, further cost reduction
related to water withdrawal.
Table 7 indicates the capacities of processing units in existing
and under construction Brazilian reneries according Szklo et al.
(2012). These gures give an idea of the various complexities in the
countrys rening park.
As can be observed in Tables 57, the more complex a renery
is, the larger are the potential gains in terms of water savings with
application of the water pinch technique. However, it is also worth
considering that in more complex reneries (REGAP, RPBC, REDUC,
RLAM and REPLAN), other more sophisticated processes exist in
their various units, such as uid catalytic cracking (FCC), delayed
coking and hydrotreatment (HDT). If these processes were consid-
ered in water pinch applications, the water consumption reduction
would be smaller than presented in Tables 5 and 6, because their
minimum water consumption would be greater.
The data presented here for water savings attained from apply-
ing the water pinch technique in two Brazilian reneries, REMAN
and REVAP, are compatible with the gures obtained by Nabi
Bidhendi et al. (2010). The water savings values in the other rener-
ies are higher, but if other processes are considered, and more
advanced wastewater regeneration techniques, these values will
decline.
To achieve the water savings levels presented, considering
wastewater regeneration and salt as the reference contaminant, the
MBR process followed by reverse osmosis or reverse electrodialysis
has great potential. The cost of MBR membranes is US$ 50.00/m2 ,
while their operating cost is US$ 0.47/m3 . In turn, the cost of reverse
osmosis technology ranges from US$ 1454 to 4483/m3 /day with
operating cost of US$ 0.120.37/m3 , and that of reverse electro-
dialysis is US$ 0.146/m3 . Other technologies, already discussed in
this paper, are promising for treating efuents aiming at reuse at
oil reneries. With respect to advanced oxidative processes, Goi
and Trapido (2002) presented the operating costs for treatment of
nitrophenols.
The observations in the previous paragraphs also apply to the
reneries under construction in Brazil. New installations will have
more complex structures. Hence, they will behave as the most mod-
ern existing Brazilian reneries. RNEST has delayed coking units
(with capacity of 23,800 m3 /day) and two HDT units (one with
178 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179

Table 7
Capacities of the units in Brazilian reneries (Szklo et al., 2012).

Renery Lubnor Reman Recap Refap Regap RPBC Repar

Capacity (m3 /day) 1300a 7300a 8200a 30,000a 24,000a 27,000a 32,000a
1300b 1055b 3600d 6000b 14,000a 12,900b 15,000b
170c 600d 3100d 6800d 10,000d 5100d
7000d 1800e 5200e 10,000d
2400e 4400e 6000f 5000f
4500f 3800e 1000h
3800g 1700i

Renery Revap Reduc Rlam Replan Rnest COMPERJ Premium

a a a a a a
3
Capacity (m /day) 40,000 38,000 44,000 60,000 36,600 26,000 48,000a
20,000b 18,200b 20,042b 31,000b 6,000d 16,000b 31,000b
14,000d 5590c 830c 16,000d 26,000d 5250f 6000f
6000f 7500d 5000d 12,000e 23,800g 2000f 20,500f
6500f 2000f 10,000d 11,700f 8000f 11,500g
6800j 1833f 600j 8250g 14,500k
3000f 9500k
a
Atmospheric distillation.
b
Vacuum distillation.
c
Basic lubricants.
d
FCC.
e
Naphtha hydrodessulfurization.
f
HDT.
g
Delayed coking.
h
Reform.
i
Thermal cracking.
j
Propane De-asphalting.
k
CHC.

capacity of 6000 m3 /day and the other 26,000 m3 /day). COMPERJ
will have a delayed coking unit, with capacity of 8250 m3 /day, and
three HDT units, with capacities of 5250, 2000 and 8000 m3 /day.
Finally, the Premium renery will have a delayed coking unit
with capacity of 11,500 m3 /day, two HDT units with capacities of
6000 m3 /day and de 20,500 m3 /day and a catalytic hydrocracking
(CHC) unit with capacity of 14,500 m3 /day (Szklo et al., 2012).
Finally, it is worth answering the following question: should we
build new reneries designed to minimize water consumption and
maximize reuse of efuents (reneries in project phase), or should
we simply retrot plants that were not designed to minimize water
consumption?
According to the ndings of the application of the water Pinch
technique in this study, the new Brazilian reneries could well
be planned to already incorporate the optimized mass transfer
between contaminants and water stream. This would bring the
largest gains in terms of water savings to the new reneries com-
pared with existing ones. The public data available to these new
reneries do not indicate that their project incorporate water pinch
analysis, though.
Moreover, this would be less costly than modifying the pro-
cesses of an existing renery. Therefore, new reneries would gain
doubly with the application of water Pinch: both because of taking
better advantage of the technique and being less costly to enable
maximum reuse. However, even existing reneries could benet
from the use of this technique, even though they have less spatial
exibility for installation of optimized mass exchange networks.
5. Final remarks
Rationalization techniques contribute signicantly to water
management in petroleum reneries, reducing the need for with-
drawal of water and bringing benets for companies in terms of
economic gains and improved corporate image.
This paper showed that it is technically and economically feasi-
ble to reduce water consumption in Brazilian reneries by applying
the best available techniques for water rationalization. Actually,
the costs of the current and new technologies for water reuse
are decreasing, especially for ion exchange, nanoltration, and
advanced oxidative processes. Water Pinch technique can be help-
ful for improving water reuse and, hence, saving freshwater. While
existing reneries can be retrotted with these technologies, new
reneries can take greater advantage of them. Actually, the exam-
ples run in this paper through the use of Pinch technique indicate
that the minimum ow rate of water can be reduced by almost
4050%. Nevertheless, it is necessary to conduct more thorough
studies of water Pinch in existing Brazilian reneries, encompass-
ing more processing units and considering a wider possibility of
regeneration processes.
Moreover, we suggest the application of the marginal abatement
cost (MAC) curve to evaluate the most suitable strategy for saving
water in Brazilian reneries. This curve represents the added cost
for abatement when the pollution level of a unit is reduced. The
application of this type of analysis would provide a better compar-
ison of the wastewater treatment installations for reuse, in terms
of associated costs, either between existing reneries or between
existing and future reneries. The different shapes of the MAC curve
are related to the characteristics of the efuents generated by two
different reneries.
Acknowledgments
Financial support provided by CNPq and FAPERJ is gratefully
acknowledged.
References
Alva-Argez A, Kokossis AC, Smith R. The design of water-using systems in petroleum
rening using a water-pinch decomposition. Chemical Engineering Journal
2007;8:3346.
Aquino JBC, Medeiros LG, Calmon SV. Renaria Abreu e Lima Uma fbrica de diesel.
In: Rio Oil & Gas Expo and Conference 2010. IBP: Rio de Janeiro; 2010. Article N.
IBP2113 10.
Brazilian Government. Ministry of Social Development. Available at
http://www.mds.gov.br [accessed 14.03.12].
Castro P, Matos H, Fernandes MC, Nunes CD. Improvements for mass-exchange
networks design. Chemical Engineering Science 1999;54:164965.
Chao Y, Liang TM. A feasibility study of industrial wastewater recovery using elec-
trodialysis reversal. Desalination 2008;221:4339.
 F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172179
Goi A, Trapido M. Hydrogen peroxide photolysis, Fenton reagent and photo-
Fenton for the degradation of nitrofenols: a comparative study. Chemosphere
2002;46:13922.
Duyvesteijn CPTM. Water re-use in an oil renery. Desalination 1998;119:3578.
Gomes JFS, Queiroz EM, Pessoa FLP. Design procedure for water/wastewater mini-
mization: single contaminant. Journal of Cleaner Production 2007;15:47485.
Hallale N. A new graphical targeting method for water minimization. Advances in
Environmental Research 2002;6:37790.
Hespanhol I. Potencial de reso de gua no Brasil: Agricultura, indstria, municpios
e recarga de aqferos. In: Mancuso P, Santos H, editors. Manole (USP): So Paulo;
2003.
Hill C. Water use in industries of the future. Portland: 825 NE Multnomah; 2003.
Magrini A, Santos MA. O Modelo Brasileiro de Gerenciamento de Recursos Hdricos.
In: Magrini A, Santos MA, editors. Gesto Ambiental de Bacias Hidrogrcas. Rio
de Janeiro: COPPE/UFRJ; 2001. p. 10113.
Mann JG, Liu YA. Industrial water reuse and wastewater minimization. New York:
McGraw-Hill; 1999.
Matsumura EM, Mierzwa JC. Water conservation and reuse in poultry processing
plant a case study. Resources, Conservation & Recycling 2008;52:83542.
Melin T, Jefferson B, Bixio D, Thoeye C, De Wilde W, De Koning J, et al. Mem-
brane bioreactors technology for wastewater treatment and reuse. Desalination
2006;187:27182.
Mierzwa JC, Hespanhol I. gua na indstria Uso racional e reso. So Paulo: Ocina
de Textos; 2005.
Mobil Altona Renery. Environment improvement plan 20042006. Australia: Mobil
Altona Renery; 2006.
Nabi Bidhendi GR, Mehrdadi N, Mohammadnejad S. Water and wastewater mini-
mization in Tehran oil renery using water pinch analysis. International Journal
of Environmental Research 2010;4:58394.
National Petroleum Agency (ANP, in Portuguese). Available at http://www.
anp.gov.br [accessed 2.2.12].
179
Oil & Gas Journal. Available at http://www.ogj.com [accessed 10.2.12].
Organization of American States OAS Desalination by reverse osmosis. Avail-
able at http://www.oas.org/DSD/publications/Unit/oea59e/ch20.htm [accessed
31.8.10].
Peeters JG, Theodoulou SL. Membrane technology treating oily wastewater for reuse.
In: Corrosion/2005. NACE International: Texas; 2005. Article N. 05534.
Petrobras. Business plan 20112015. Rio de Janeiro: Petrobras; 2011.
Puckorius PR, Loretitsch GA, Tvedt TJ. Reuse water quality for Chemical plants,
reneries, utilities and air conditioning. In: Corrosion/98. NACE International:
California; 1998. Article N. 573.
Rautenbach R, Melin T. Mebranverfahren: Grundlagen der Modul- und Anlage-
nauslegung. 2nd ed. Berlin: Springer-Verlag; 2003.
Schor AR. Riscos e alternativas para o abastecimento de gua em uma renaria de
petrleo Estudo de caso: renaria Duque de Caxias REDUC. Masters Disser-
tation in Civil Engineering. COPPE-UFRJ: Rio de Janeiro; 2006.
Szklo A, Schaeffer R. Fuel specication, energy consumption and CO2 emission in oil
reneries. Energy 2007;32:107592.
Szklo A, Uller VC, Bonf MHP. Fundamentos do reno de petrleo Tecnologia e
economia. 3rd ed. Rio de Janeiro: Intercincia; 2012.
Takama N, Kuriyama T, Shiroko K, Umeda T. Optimal water allocation in a petroleum
renery. Computers & Chemical Engineering 1980;4:2518.
Tong F, Aerts P. RO & Petrochemicals. Water & Wastes Digests
2009(September):267.
Wang YP, Smith R. Wastewater minimization. Chemical Engineering Science
1994;49:9811006.
Wang YP, Smith R. Wastewater minimization with owrate constraints. Chemical
Engineering Resource and Design 1995;73a:885900.
Worrell E, Galitsky C. Energy efciency improvement and cost saving opportunities
for petroleum reneries an energy star guide for energy and plant managers.
Berkeley: Ernest Orlando Lawrence, Berkeley National Laboratory; 2005.