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Resources, Conservation and Recycling 73 (2013) 172–179

Resources, Conservation and Recycling 73 (2013) 172–179 Contents lists available at SciVerse ScienceDirect

Contents lists available at SciVerse ScienceDirect

Resources, Conservation and Recycling

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

journal homepage: www.elsevier.com/locate/resconrec Full length article An analysis of water management in

Full length article

An analysis of water management in Brazilian petroleum refineries using rationalization techniques

Felipe Ramalho Pombo , Alessandra Magrini, Alexandre Szklo

Federal University of Rio de Janeiro, Energy Planning Program, Cidade Universitária, C.T., sala C211, 21949-972, Rio de Janeiro, RJ, Brazil

a r t i

c l e

i n f o

Article history:

Received 20 March 2012 Received in revised form 1 February 2013 Accepted 4 February 2013

Keywords:

Water management Efficient use of water Pinch technology Oil refineries

a b s t r a c t

This study assesses the application of rationalization techniques in oil refineries to preserve freshwa- ter resources. These techniques include conservation, recycling and reuse of water and Pinch technique. Several refineries in the world use treated household wastewater. In Brazil, a country with expanding refining capacity, this practice is planned for two refineries. Water conservation and recycling initia- tives also hold promise, including reduction of losses, replacement of cooling towers with smaller units and recycling of blowdown into cooling towers and steam generation systems. Some technologies gain importance for wastewater reuse, such as ion exchange, nanofiltration and advanced oxidative processes. Finally, the application of the Pinch technique reduces the withdrawal of water and its associated costs. Thus, this method is appropriate in areas with scarce water, where some new Brazilian refineries are slated for construction.

© 2013 Elsevier B.V. All rights reserved.

1. Introduction

Brazil is a privileged country in terms of water resources, with approximately 13% of the world’s 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 São 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 effluents 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 refineries of Petrobras, the state-controlled Brazil- ian oil company, processed 226,042 m 3 of crude oil per day (ANP, 2012). Given the average water consumption index (WCI) at these refineries, of 0.9 m 3 of water/m 3 of oil processed, the estimated water consumption is 203,438 m 3 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).

0921-3449/$ – see front matter © 2013 Elsevier B.V. All rights reserved.

http://dx.doi.org/10.1016/j.resconrec.2013.02.004

With the planned construction of new refineries in the country 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 m 3 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 40–45% of water use in refiner- ies. The other uses are mainly the processing units, fire fighting 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 effluents. Therefore, the main users of water in petroleum refining are presented in Table 1 (Alva-Argáez et al., 2007). However, is it technically and economically feasible to reduce the water consumption of petroleum refineries? This paper aims to answer this question by assessing the reduction of water consump- tion through rationalization techniques in Brazilian refineries. 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

F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172–179

173

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

Water user

Origin of the effluent

Major pollutants from effluent

Comments

Desalting

Fresh or foul water stripped Stripping steam Overhead accumulators Stripping steam Stripping steam Pretreatment for H 2 S removal

Free oil, ammonia, sulfides and suspended solids Sulfides, ammonia, phenols, oil, chlorides, mercaptans H 2 S, ammonia, phenols Oil, sulfides, phenols, cyanide, ammonia High in sulfides Sulfides, mercaptans, ammonia

3–10% by vol. on crude charge Oil sampling lines produce significant flows

Distillation

Thermal cracking

 

Catalytic cracking

Alkaline wastewaters

Hydrocraking

Polymerization

Low volume but high strength waste

Polymerization Low volume but high strength waste Fig. 1. Scheme of wastewater treatment aiming at reuse

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

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 refineries 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 flotation 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 ultrafiltration – 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 field. The polarity of the electrodes is periodically reversed, influencing 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 refineries. In the case of the Pinch technique, Alva-Argáez 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 refinery. 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 refineries. Finally, the last section presents the final remarks of the paper.

2. Methodology

This study applies the water consumption index (WCI) and the processed petroleum for all Brazilian refineries to estimate the quantity of water used for this industrial activity, in a country that is expanding its refining capacity. The quantity of additional water that will be needed with the construction of new refineries is also estimated, along with data about water use by oil refineries and the main processes that use water in refineries.

Our analysis is based on the international experiences of water rationalization in petroleum refineries presented in conference articles and scientific papers, to help propose new methods and observe the prospects for water rationalization practices in Brazil- ian refineries. We then discuss the concepts of conservation, recycling and reuse of water at petroleum refineries, 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 refineries: 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 flow rate in refineries and the optimum water network, including reuse opportunities. The results from the water Pinch application were, then, used for Brazilian Greenfield refineries, 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 refining 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 flow 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 firstly 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 flow 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 first.

Q P × (C

P

i;in C

P

i;out ) = Q H 2 O × (C

H

i;out C i;in

2

O

H 2 O

H

)

2 O

 

(1)

) (ppm)

(2)

m i;total (kg/h) = Q H 2 O (t/h) × (C

H 2 O

i;out C i;in

174

F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172–179

where Q P is the flow rate of the most concentrated stream, Q H 2 O

is the flow rate of the least concentrated stream, C i;in and C

P

P

i;out are

the concentrations of the contaminants that enter and leave the

are the

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 flow rate.

most concentrated stream, respectively, and C

H 2 O

i;out and C i;in

H

2 O

F min = m i,min

C

i,min

× 10 3

(3)

where F min is the minimum flow rate, m i,min is the mass variation of the reference contaminant in the pinch concentration and C i,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 refinery, using water from the treatment system as feed for the demineralization plant (Duyvesteijn, 1998). This refinery 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 filtration 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 Minatitlán refinery, 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 filtering 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) refinery, 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 Lázaro Cárdenas and MAP refineries.

 

Removal (%)

Refinery

BOD

COD

Oil and grease

TSS

Lázaro Cárdenas

50

54.6

87.5

97.5

MAP

99.7

95.0

97.0

89.4

Notes: (1) The treatment system of MAP Refinery 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 Lázaro Cárdenas refin- 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 efficient for these two parameters. Treated municipal wastewater, usually called reclaimed water, is often used by industries, among them refineries, 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 nitrification. Additional treatment is required for steam generation, and more treatment still can be required for water to use in fire fighting systems and other processes (Puckorius et al., 1998). In Virginia (USA) a cooperative effort between the Hampton Roads Sanitation District and the Yorktown refinery (with capac- ity of 70,000 barrels of oil per day), owned by Western Refining, supplies 500,000 gallons per day of highly treated wastewater for use in cooling towers and other refinery processes. Another effort is the Gold Bar refinery, 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 significant project is the Yanshan refinery 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 refinery, the feed from the treatment unit for reuse contains resid- ual oil (1.2 mg/L) and high COD (20–50 mg/L). The conductivity (1400–1900 uS/cm) and hardness (300–500 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 m 3 /h (10 units with capacity of 56 m 3 /h). The system also has three RO units, each with capacity of 103 m 3 /h (Tong and Aerts, 2009). Two other relevant projects were implemented in Mobil Altona refinery, owned by Esso, located in Victoria, Australia, with processing capacity of 80,000 barrels per day, and in Petromidia refinery complex, owned by Rompetrol, located in Ravodari, Roma- nia, with capacity of 100,000 barrels per day. Preliminary studies in the Australian refinery (Mobil Altona Refinery, 2006) and the Roma- nian complex identified water savings, minimization of wastewater discharge and use of treated effluents for fire fighting 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 modification 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 refineries

Table 3 presents important data on the generation of wastew- aters, water consumption index (WCI) and water consumption in Brazilian refineries. Table 4 presents the data on water flow 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 flow 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) 172–179

175

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

Refinery

Region

Crude oil processed in

Wastewater Generated

WCI (m 3 water/m 3 oil)

Water Consumption (m 3 /day) a

 

2011

(m 3 /day)

(m 3 /day)

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

RNEST b

Northeast

60,305

400–600

na

54,275

c

COMPERJ

Southeast

54,855

dna

na

49,370

c

Premium I

Northeast

99,736

dna

na

89,762

c

Premium II

Northeast

49,868

dna

na

44,881

c

TOTAL

5,45,864

118,116–118,316

dna

dna

dna, does not apply; na, not available.

a Estimates based on the WCI of each refinery.

b RNEST, COMPERJ and Premium I and II are greenfield refineries.

c Water consumption calculated based on the average WCI of the Petrobras refineries.

Table 4 Limiting process data for two cases of petroleum refineries (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.

C in (ppm)

C out (ppm)

Flow rate (te/h)

Cont.

C in (ppm)

C out (ppm)

1

45.8

SS

000

2539010

45.0

HC

000

1540035

 

H 2 S Óleo

H 2 S Sal HC

 

2

32.7

SS

5050020

6516,890120

34.0

2030045

12012,500180

 

H 2 S Óleo

H 2 S Sal

3

56.5

SS

5020120

8543220

56.0

HC

12020200

220459500

 

H 2 S Óleo

H 2 S Sal

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

because the processes considered are basically the same and fit well to the characteristics of the process units of the new Brazilian refineries, 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

is the composite curve and the blue line is the water supply Fig. 2. Composite curve

Fig. 2. Composite curve for reaching the minimum flow rate of water for reuse without regeneration, based on data from Takama et al. (1980) and with the aid of “Water Design”.

curve. In this case, the reference contaminant used was H 2 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 refineries, as can be see in Table 1. From Figs. 2 and 3, the minimum flow 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 flow 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

Wang and Smith (1994) . The blue line refers to the supply Fig. 3. Composite curve

Fig. 3. Composite curve for reaching the minimum flow rate of water, for reuse without regeneration, based on data from Wang and Smith (1994) and with the aid of “Water Design”.

176

F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172–179

/ Resources, Conservation and Recycling 73 (2013) 172–179 Fig. 4. Optimum water distribution network, for reuse

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 Water savings (in %) of existing Brazilian refineries, based on application of the water pinch technique (reuse of water without regeneration).

Refinery

LUBNOR

REMAN

RECAP

REFAP

REGAP

RPBC

Water savings (%)

15.2

60.1

56.9

83.6

Refinery

REPAR

REVAP

REDUC

RLAM

REPLAN

Water savings (%)

61.6

18.2

84.1

81.3

of freshwater to the processes, the green line to the water reuse and the red line the generation of wastewater. From this picture, it can be noted the reuse from distillation to hydrodesulfurization. The result would be similar if the data from Takama et al. (1980) had been considered. All existing Brazilian refineries have atmospheric and vacuum distillation units except for RECAP, which only has the atmospheric type. All those refineries mentioned in Table 3 have desalting units and naphtha hydrodesulfurization units. Therefore, as the units considered in the water pinch applications are well fitted to the reality of the Brazilian refineries, we are able to estimate the water savings that can be achieved with application of the technique in Brazilian refineries (Tables 5 and 6). Table 5 shows the water savings estimates based on the data of Takama et al. (1980) for reuse without regeneration (2366.9 m 3 /day) and Table 6 shows the estimates based on the data of Wang and Smith (1994) with regeneration (1290.5 m 3 /day). We

Table 6 Water savings (in %) of existing Brazilian refineries based on application of the water pinch technique (reuse of water with regeneration).

Refinery

LUBNOR

REMAN

RECAP

REFAP

REGAP

RPBC

Water savings (%)

53.8

77.6

76.5

91.9

Refinery

REPAR

REVAP

REDUC

RLAM

REPLAN

Water savings (%)

79.1

55.4

91.9

89.8

considered the processing units of the Water Pinch simulation done in this study.

4. Discussion

4.1. The most promising technologies for wastewater reuse

The costs of the main technologies employed for wastewater reuse in petroleum refineries are generally high, such as for mem- branes for micro and ultrafiltration. The MBR technology has similar cost, as it uses the membranes mentioned above. Reverse osmo- sis and reverse electrodialysis, which are competing technologies, have similar operational costs (Chao and Liang, 2008; OAS, 2010). As mentioned before, these technologies are used in the final step of treatment, aiming at reuse in petroleum refineries, in order to remove the chloride ions. Some technologies, not yet applied in large scale for treating refinery wastewater for reuse, are promising and should be tested further. Among them are nanofiltration, ion exchange, which would be useful for the polishing step of reverse osmosis, and advanced oxidative processes, which are effective for treating sourwater. Nanofiltration (NF) is a promising technology because its removal efficiency hovers between that of ultrafiltration and the reverse osmosis. Hence, NF could be used as a technique immedi- ately before reverse osmosis or possibly replacing it. Although NF membranes are more expensive than other membranes due to their 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 osmosis process, since for low salt concentration it is economically attractive (Rautenbach and Melin, 2003). Ion exchange could also be used after the reverse osmosis or electrodialysis processes, pos- sibly reducing the cost of the last step of treatment for chloride removal from wastewater. Advanced oxidative processes (AOPs) are also useful for treating sourwater from refineries. This kind of wastewater has complex features, containing emulsified oil, phenols, sulfides, mercap- tans and cyanides. Thus, it has to be segregated. AOPs, such as

F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172–179

177

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 refinery wastewater for reuse.

4.2. Prospects for water rationalization in refineries

Refineries worldwide, both existing and under the planning phase, need to adopt water conservation methods that have already proved to be effective in existing refineries, such as the use of treated wastewater as fire fighting water, substitution of existing cooling towers with smaller units and modification and repair of treatment systems, along with practices to reduce losses in refining 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 refineries in the world use treated household waste- water, mainly to feed cooling towers. This type of reuse has been proposed for two Brazilian refineries: REDUC (in Rio de Janeiro state, with installed capacity of 242,000 barrels/day) and REPLAN (in São Paulo state, with installed capacity of 365,000 barrels/day), and would be a suitable option given the low water availability for these refineries. The main treatment technologies are being tested in pilot plants in the Brazilian REGAP refinery (in Minas Gerais state, with installed capacity of 151,000 barrels/day), and those that prove most suc- cessful will be incorporated in other refineries owned by Petrobras, either through retrofit 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 refinery with access to plentiful household wastewater. That facility would mainly use MBR to treat this wastewater. A refinery with large load of heavy metals could use the advanced oxidative processes after having its effluents segregated. Finally in a refinery with saline wastewater, very common, micro and ultrafiltration and reverse osmosis or reverse electrodialysis (the latter two as tertiary treat- ment) would be the most suitable treatment processes. Valuable lessons for refineries 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 efficient products and opportunities to prevent pollution. The creation of such a labeling scheme for efficient use of water in oil refineries would be advantageous worldwide. The main factors motivating water rationalization in petroleum refineries 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 refineries and to plan more efficient new ones in regions with water shortage.

4.3. Pinch technology applied to greenfield refineries

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

is crucial to the new Brazilian refineries, whose large hydrorefin- ing capacity will produce ultra-specified 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 effluent originates from the mixing of oil with water to dissolve salts. In the final 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 refineries. 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 refineries in regions with water shortage, such as some areas where new refineries are being built in Brazil - approximately 1 million barrel per day of Green- field 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 refineries, 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 significant 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 refineries according Szklo et al. (2012). These figures give an idea of the various complexities in the country’s refining park. As can be observed in Tables 5–7, the more complex a refinery 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 refineries (REGAP, RPBC, REDUC, RLAM and REPLAN), other more sophisticated processes exist in their various units, such as fluid 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 refineries, REMAN and REVAP, are compatible with the figures obtained by Nabi Bidhendi et al. (2010). The water savings values in the other refiner- 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/m 2 , while their operating cost is US$ 0.47/m 3 . In turn, the cost of reverse osmosis technology ranges from US$ 1454 to 4483/m 3 /day with operating cost of US$ 0.12–0.37/m 3 , and that of reverse electro- dialysis is US$ 0.146/m 3 . Other technologies, already discussed in this paper, are promising for treating effluents aiming at reuse at oil refineries. 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 refineries under construction in Brazil. New installations will have more complex structures. Hence, they will behave as the most mod- ern existing Brazilian refineries. RNEST has delayed coking units (with capacity of 23,800 m 3 /day) and two HDT units (one with

178

F.R. Pombo et al. / Resources, Conservation and Recycling 73 (2013) 172–179

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

Refinery

Lubnor

 

Reman

 

Recap

 

Refap

Regap

RPBC

Repar

Capacity (m 3 /day)

1300

a

7300

a

8200

a

30,000 a

24,000

a

27,000

a

32,000

a

1300

b

1055

b

3600

d

6000

b

14,000

a

12,900

b

15,000

b

170

c

600

d

3100 d

6800

d

10,000

d

5100 d

 

7000

d

1800

e

5200

e

10,000 d

2400 e

4400

e

6000

f

5000 f

4500 f

3800

e

1000

h

 

3800

g

1700

i

Refinery

Revap

 

Reduc

 

Rlam

Replan

Rnest

COMPERJ

Premium

Capacity (m 3 /day)

40,000

a

 

38,000

a

44,000

a

 

60,000

a

36,600

a

26,000

a

48,000

a

20,000

b

18,200

b

20,042

b

31,000

b

6,000

d

16,000

b

31,000

b

14,000

d

5590

c

830

c

16,000 d

26,000

d

5250 f

 

6000 f

6000

f

7500

d

5000

d

12,000 e

23,800

g

2000 f

20,500 f

6500

f

2000

f

10,000 d

11,700 f

8000 f

11,500

g

6800 j

1833

f

600 j

 

8250 g

14,500

k

 

3000

f

9500 k

 

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 m 3 /day and the other 26,000 m 3 /day). COMPERJ will have a delayed coking unit, with capacity of 8250 m 3 /day, and three HDT units, with capacities of 5250, 2000 and 8000 m 3 /day. Finally, the Premium refinery will have a delayed coking unit with capacity of 11,500 m 3 /day, two HDT units with capacities of 6000 m 3 /day and de 20,500 m 3 /day and a catalytic hydrocracking (CHC) unit with capacity of 14,500 m 3 /day (Szklo et al., 2012). Finally, it is worth answering the following question: should we build new refineries designed to minimize water consumption and maximize reuse of effluents (refineries in project phase), or should we simply retrofit plants that were not designed to minimize water consumption? According to the findings of the application of the water Pinch technique in this study, the new Brazilian refineries 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 refineries com- pared with existing ones. The public data available to these new refineries 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 refinery. Therefore, new refineries 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 refineries could benefit from the use of this technique, even though they have less spatial flexibility for installation of optimized mass exchange networks.

5. Final remarks

Rationalization techniques contribute significantly to water management in petroleum refineries, reducing the need for with- drawal of water and bringing benefits 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 refineries 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, nanofiltration, and advanced oxidative processes. Water Pinch technique can be help- ful for improving water reuse and, hence, saving freshwater. While existing refineries can be retrofitted with these technologies, new refineries can take greater advantage of them. Actually, the exam- ples run in this paper through the use of Pinch technique indicate that the minimum flow rate of water can be reduced by almost 40–50%. Nevertheless, it is necessary to conduct more thorough studies of water Pinch in existing Brazilian refineries, 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 refineries. 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 refineries or between existing and future refineries. The different shapes of the MAC curve are related to the characteristics of the effluents generated by two different refineries.

Acknowledgments

Financial support provided by CNPq and FAPERJ is gratefully acknowledged.

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