Desalination 273 (2011) 235247

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

The treatment of brewery wastewater for reuse: State of the art

Geoffrey S. Simate a,, John Cluett a, Sunny E. Iyuke a, Evans T. Musapatika a, Sehliselo Ndlovu a, Lubinda F. Walubita b, Allex E. Alvarez c
a b c

School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, P/Bag 3, Wits 2050, South Africa TTI - Texas A&M University System, College Station, TX, USA Department of Civil Engineering, University of Magdalena, Santa Marta, Magdalena, Colombia

a r t i c l e

i n f o

a b s t r a c t
The beer brewing process often generates large amounts of wastewater efuent and solid wastes that must be disposed off or treated in the least costly and safest way so as to meet the strict discharge regulations that are set by government entities to protect life (both human and animal) and the environment. It is widely estimated that for every one liter of beer that is brewed, close to ten liters of water is used; mostly for the brewing, rinsing, and cooling processes. Thereafter, this water must be disposed off or safely treated for reuse, which is often costly and problematic for most breweries. As a result, many brewers are today searching for: (1) ways to cut down on this water usage during the beer brewing process, and/or (2) means to costeffectively and safely treat the brewery wastewater for reuse. Based on the available documented literature, this paper provides a review assessment of the current status of the brewery wastewater treatment processes including potential applications for reuse. Key challenges for both brewery wastewater treatment and reuse are also discussed in the paper and include recommendations for future developments. 2011 Elsevier B.V. All rights reserved.

Article history: Received 25 October 2010 Received in revised form 11 February 2011 Accepted 12 February 2011 Keywords: Brewery wastewater Biological oxygen demand Chemical oxygen demand Pretreatment Treatment Reuse

Contents 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . Legislation and environmental management systems . . . Conventional methods of pretreating brewery wastewater 3.1. Physical methods . . . . . . . . . . . . . . . . 3.2. Chemical methods . . . . . . . . . . . . . . . 3.3. Biological methods . . . . . . . . . . . . . . . 3.3.1. Aerobic . . . . . . . . . . . . . . . . 3.3.2. Anaerobic . . . . . . . . . . . . . . . Treatment of brewery wastewater for reuse . . . . . . . 4.1. Membrane ltration . . . . . . . . . . . . . . . 4.2. Non-thermal quenched plasma . . . . . . . . . . 4.3. Membrane bioreactor . . . . . . . . . . . . . . 4.4. Combined anaerobic and aerobic treatment . . . . 4.5. The use of carbon nanotubes . . . . . . . . . . . 4.5.1. Nanosorbents . . . . . . . . . . . . . . 4.5.2. Nanolters . . . . . . . . . . . . . . . 4.6. Electrochemical methods . . . . . . . . . . . . 4.7. Microbial fuel cells . . . . . . . . . . . . . . . 4.8. Carbon . . . . . . . . . . . . . . . . . . . . . Discussion and synthesis of ndings . . . . . . . . . . 5.1. Comparison of processes and technologies . . . . 5.2. Integration of processes and technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236 236 236 237 237 237 237 239 239 240 241 242 242 243 243 244 244 244 244 244 244 245

4.

5.

Corresponding author. Tel.: + 27 11 717 7570, + 27 76 112 6959(Cell); fax: + 27 11 717 7599. E-mail address: simateg@yahoo.com (G.S. Simate). 0011-9164/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2011.02.035

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6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Disclaimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction Despite discharging large volumes of highly polluting efuents throughout the year [1,2], the brewing industry constitute an important economic segment of any country [3,4]. In fact, beer is the fth most consumed beverage in the world behind tea, carbonates, milk and coffee [3]. Beer brewing involves two main steps, i.e., brewing and packaging of the nished product [5]. The byproducts (e.g., spent grains from mashing, yeast surplus, etc) generated from these steps are responsible for pollution when mixed with efuents [5]. In addition, cleaning of tanks, bottles, machines, and oors produces high quantities of polluted water [5]. It is estimated that for the production of 1 L of beer, 310 L of waste efuent is generated depending on the production and specic water usage [1,3,6]. In other words, very large quantities of water are consumed during the beer brewing process. Similarly and because of voluminous water usage, the brewery industry discharges large volumes of highly polluting efuents throughout the year [1,2]. It must also be noted that efuents from individual process steps are variable. For example, bottle washing results in a large wastewater volume, but it contains only a minor part of the total organics discharged from the brewery processes. On the other hand, efuents from fermentation and ltering are high in organics/biochemical oxygen demand (BOD), but generally low in volume, accounting for about 3% of the total wastewater volume but 97% of the BOD [7]. Wastewater from a brewery plant may be discharged in several ways including the following [8,9]: (1) directly into a waterway (oceans, rivers, streams, or lakes), (2) directly into a municipal sewer system, (3) into the waterway or municipal sewer system after the wastewater has undergone some pretreatment, and (4) into the brewery's own wastewater treatment plant. The disposal of untreated (or partially treated) brewery wastewater into water bodies can constitute potential or severe pollution problems to the water bodies since the efuents contain organic compounds that require oxygen for degradation [10]. For example, if water of high organic matter content value ows into a river, the bacteria in the river will oxidize the organic matter consuming oxygen from the water faster than the oxygen dissolves back in the river from the air. Furthermore, as regulations become more and more stringent and the cost of water increases, the call for water recycling is currently gaining a lot of momentum. There are many papers, such as those reviewed by Fillaudeau et al. [3], dealing with several aspects of brewery wastewater treatment. However, a review of this literature shows that only in later years has information become available on water treatment for reuse. It must be noted, however, that wastewater reuse is not common in this type of the industry due to public perception and the possible product quality deterioration problems [11]. However, the future reuse of brewery wastewater seems to be unavoidable, as the issue of water shortage has become a serious global and environmental problem. This is particularly very critical in most developing countries such as the sub-Saharan region where droughts are perpetual, thus every drop of water must be preciously conserved. In this paper, the potential opportunities that may be available for treating brewery wastewater for reuse in two applications are reviewed, namely: (a) primary water used in the production of beer, and (b) secondary water that does not come in contact with beer; e.g. utilities cooling, water used in the packaging process and general cleaning water. Once technology improves and the perceptions have changed regarding the use of recycled water, beer to water ratios is perceived may be reduced to the ratio of about 1:2. Pertinent

challenges as related to brewery wastewater reuse (or recycling) are also discussed in the paper. The treatment, recovery and applications of various brewery byproducts (e.g., spent grains, spent hops, surplus yeast, kieselghur sludge, trub and waste labels) have been extensively documented elsewhere [3,6,8,1214], thus are not discussed in this paper. Accordingly, the paper is organized as follows: a background of the legislation and environmental management systems is presented rst, followed consecutively by brewery wastewater pre- and treatmentmethods. Challenges and future prospects are included in the discussion towards the end. A summary is then provided to conclude the paper. 2. Legislation and environmental management systems Like any other industry, the brewing industry is subject to extensive government regulations. Some of the regulations imposed involve production, distribution, labeling, advertising, trade and pricing practices, credit, container characteristics, and alcoholic content requirements [9]. Governmental entities also levy various taxes, license fees and other similar charges and may require bonds to ensure compliance with applicable laws and regulations. Furthermore, the management of environmental issues is of growing interest nowadays. There is a need to understand the important environmental impacts on the community and then consider the advantages and disadvantages associated with various levels of environmental management [15]. This means that the brewing industry must also comply with numerous environmental protection laws. In fact, the brewing industry has shown increasing awareness for environmental protection and the need of sustainable production processes [16]. Furthermore, most national governments where these industries operate have signed and ratied the Kyoto Protocol aimed at reducing greenhouse gas emissions [17]. Through environmental management systems (EMS) such as, (1) ISO 14001, (2) Eco-Management and Audit Scheme (EMAS), and (3) International Safety Rating System (ISRS), breweries should be able to proactively manage their impacts on the environment. In fact, EMSs should help breweries focus on effective and efcient management of both current and future environmental impacts. The International Finance Corporation (IFC) also has environmental, health and safety (EHS) guidelines for breweries [18]. 3. Conventional methods of pretreating brewery wastewater Brewery wastewater typically has a high chemical oxygen demand (COD) from all the organic components (sugars, soluble starch, ethanol, volatile fatty acids, etc) [9]. It usually has temperatures ranging from 25 C to 38 C, but occasionally reaching much higher temperatures. The pH levels can range between 2 and 12 [9] and are inuenced by the amount and type of chemicals used in cleaning and sanitizing (e.g., caustic soda, phosphoric acid, nitric acid, etc.) [9,16,19]. Sanitizing chemicals which include chlorine compounds ensure that the surfaces are free of any microorganisms harmful to the brewing industry and the public consuming the beer. Nitrogen and phosphorus levels are mainly dependent on the handling of raw material and the amount of yeast present in the efuent [9,16,19]. Table 1 is an example of the physicochemical characteristics of brewery wastewater from the United Breweries in India [20].

G.S. Simate et al. / Desalination 273 (2011) 235247 Table 1 Characteristics of brewery wastewater [20]. Parameter pH Temperature (C) COD (mg L 1) BOD (mg L 1) COD:BOD ratio VFA (mg L 1) Phosphates as PO4 (mg L 1) TKN (mg L 1) TS (mg L 1) TSS (mg L 1) TDS (mg L 1) Value 312 1840 20006000 12003600 1.667 10002500 1050 2580 51008750 29013000 20205940

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methods remove coarse solid matter, rather than dissolved pollutants. It may be a passive process, such as sedimentation to allow suspended pollutants to settle out or oat to the top naturally. In general, these methods have yielded little success; most often resulting in incomplete contaminant removal and/or separation. For example, sedimentation has been found to be unsatisfactory even with the addition of coagulants and other additives [27]. 3.2. Chemical methods Different chemicals can be added to the brewery wastewater to alter the water chemistry [22]. Chemical pretreatment may involve pH adjustment or coagulation and occulation. The acidity or alkalinity of wastewater affects both wastewater treatment and the environment. Low pH indicates increasing acidity while a high pH indicates increasing alkalinity. The pH of wastewater needs to remain between 6 and 9 to protect organisms. Waste CO2 may be used to neutralize caustic efuents from clean-in-places (CIP) systems and bottle washers [28]. The waste CO2 can also be used as a cheap acidifying agent for decreasing the pH of alkaline wastewaters before the anaerobic reactor, thus replacing the conventionally used acids [20]. Neutralization with H2SO4 and HCl acids is usually not recommended because of their corrosive nature and sulfate and chloride discharge limitations [29], which may add to the cost of efuent treatment operations [20]. Coagulation and occulation are physicochemical processes commonly used for the removal of colloidal material or color from water and wastewater. In water and wastewater treatment, coagulation implies the step where particles are destabilized by a coagulant, and this may include the formation of small aggregates by Brownian motion (perikinetic coagulation). On the other hand, the subsequent process in which larger aggregates (ocs) are formed by the action of shear is then known as occulation [30]. After small particles have formed larger aggregates, colloidal material can then be more easily removed by physical separation processes such as sedimentation, otation, and ltration. 3.3. Biological methods Biological waste treatment processes play a central role in the way society manage their wastewaters. It is based on the activity of a wide range of microorganisms, converting the biodegradable organic pollutants in the wastewaters. In fact, brewery efuents having both chemical (with very high organic content) and microbial contaminants are generally treated by biological methods [31]. Therefore, after the brewery wastewater has undergone physical and chemical pretreatments, the wastewater can then undergo biological treatment. Compared to physicochemical or chemical methods, biological methods have three advantages [32]: (1) the treatment technology is mature, (2) high efciency in COD and BOD removal, ranging from 80 to 90%, and (3) low investment cost. However, though biological treatment processes are particularly effective for wastewater treatment, they require a high energy input [33]. Biological treatment of wastewater can be either aerobic (with air/oxygen supply) or anaerobic (without oxygen) [9]. The aerobic and anaerobic processes are shown graphically in Fig. 1 [34]. These processes are discussed in more details in the subsequent sections. Generally, aerobic treatment has successfully been applied for the treatment of brewery wastewater and recently anaerobic systems have become an attractive option [9]. Table 4 presents a general comparison between anaerobic and aerobic biological treatment systems such as activated sludge. 3.3.1. Aerobic Aerobic biological treatment is performed in the presence of oxygen by aerobic microorganisms (principally bacteria) that metabolize the organic matter in the wastewater, thereby producing more

In fact, the brewery wastewater is characterized by large variations in the parameters mentioned in Table 1 [21]. As a result, most large breweries require some degree of wastewater pretreatment. In cases where the brewery does not discharge to the municipal sewer, then primary and secondary treatment of the efuent is required. However, if the brewery is permitted to discharge into a municipal sewer, pretreatment may be required to meet municipal bylaws and/or to lessen the load on the municipal treatment plant. In some cases, sewer discharge fees imposed on efuent volume, and on the suspended and organic loads, by the municipality may encourage the brewery to install its own treatment facility. Pretreatment is meant to alter the physical, chemical, and/or biological properties of feed water [22], thus improving the performance of upstream processes. Therefore, pretreatment is done by physical, chemical, or biological methods, or by a combination of all these methods. Table 2 lists the unit operations included within each category, and detailed schematic representation of a conventional wastewater treatment processes can be found in Spellman's Standard Handbook for Wastewater Operators [23]. Table 3 is a summary of the generic advantages and disadvantages of various wastewater treatment processes as shown in literature [24]. These characteristics (Table 3) generally relate to the cost of construction and ease of operation. Generally, the complexity and cost of wastewater treatment technologies increase with the quality of the efuent produced. In fact, the water management and waste disposal in the brewery industry are considered as signicant cost factors and important aspects in the operations of a brewery plant [25,26]. 3.1. Physical methods Among the rst treatment methods used are physical unit operations, in which physical forces are applied to remove contaminants. Physical

Table 2 Wastewater treatment unit operations and processes. Physical unit operations - Screening - Comminution - Flow equalization - Sedimentation - Flotation - Granular-medium ltration - Chemical precipitation - Adsorption - Disinfection - Chlorination - Other chemical applications - Activated sludge processes - Aerated lagoons - Trickling lters - Rotating biological contactors - Pond stabilization - Anaerobic digestion - Biological nutrient removal

Chemical unit operations

Biological unit operations

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Table 3 Generic advantages and disadvantages of conventional and non-conventional wastewater treatment technologies [24]. Treatment type Aquatic systems Stabilization lagoons Advantages Low capital cost Low operation and maintenance cost Low technical manpower requirements Requires relatively little land area Produces few Undesirable odors Can be used by individual households Easy to operate and maintain Can be built in rural areas Removes up to 70% of solids and bacteria Minimal capital cost Low operation and maintenance requirements and costs Minimal land requirements Relatively low cost Can be used for household scale treatment Easy to operate Highly efcient treatment method Requires little land area Applicable to small communities for local scale treatment and to big cities for regional scale treatment Highly efcient treatment method Requires little land area Applicable to small communities for local scale treatment and to big cities for regional scale treatment Disadvantages Requires a large area of land May produce undesirable odors Requires mechanical devices to aerate basins Produce efuents With a high suspended solids concentration Provides a low treatment efciency Must be pumped occasionally Requires a landll for periodic disposal of sludge and septage Remains largely experimental Requires periodic removal of excess plant material Best used in areas where suitable native plants are available Requires mechanical devices

Aerated lagoons

Terrestrial systems

Septic tanks

Constructed wetland

Mechanical systems

Filtration systems

Vertical biological reactors

Activated sludge

High cost Complex technology Requires technically skilled manpower for operation and maintenance Needs spare parts availability Has a high energy requirement High cost Requires sludge disposal area (sludge usually land-spread) Requires technically skilled manpower for operation and maintenance requirement

microorganisms and inorganic end-products (principally CO2, NH3 and H2O). Aerobic treatment utilizes biological treatment processes, in which microorganisms convert non-settle-able solids to settle-able solids. Sedimentation typically follows; allowing the settle-able solids to settle and separate out. Three options include: Activated sludge process. In the activated sludge process, the wastewater ows into an aerated and agitated tank that is primed with activated sludge. This complex mixture containing bacteria, fungi, protozoans, and other microorganisms is collectively referred to as the

biomass. In this process, the suspension of aerobic microorganisms in the aeration tank is mixed vigorously by aeration devices, which also supply oxygen to the biological suspension. Attached growth (biolm) process. The second type of aerobic biological treatment system is called attached growth (biolm) process and deals with microorganisms that are xed in place on a solid surface. This attached growth type aerobic biological treatment process creates an environment that supports the

sludge 50% Electron acceptor: O2, 1-2mg/L wastewater Aerobic process 50% Heat

methane Electron acceptor: SO4, PO4, organics 90% Anaerobic process 10% sludge
Fig. 1. An illustration of aerobic and anaerobic processes [34].

G.S. Simate et al. / Desalination 273 (2011) 235247 Table 4 Anaerobic treatment as compared to aerobic treatment [16]. Aerobic systems Energy consumption Energy production Biosolids production COD removal (%) Nutrients (N/P) removal Space requirement Discontinuous operation - High - No - High - 9098 - High - High - Difcult Anaerobic systems - Low - Yes - Low - 7085 - Low - Low - Easy

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3.3.2. Anaerobic Anaerobic wastewater treatment is the biological treatment of wastewater without the use of air or elemental oxygen. Anaerobic treatment is characterized by biological conversion of organic compounds by anaerobic microorganisms into biogas, which can be used as a fuel; mainly methane 5575 vol% and carbon dioxide 2540 vol% with traces of hydrogen sulde [35]. In breweries, direct utilization of biogas in a boiler is usually the preferred solution. The reason for this is that investment costs for a combined heat and power unit (CHP) are higher and more extensive biogas treatment is required [36]. In the context of decreasing fossil fuel reserves, anaerobic wastewater treatment makes a brewery more independent from external fuel supply. Furthermore, it contributes to a more sustainable brewing process. Upow Anaerobic Sludge Blanket. One of the most popular anaerobic processes is the Upow Anaerobic Sludge Blanket (UASB). In the UASB reactor, the wastewater enters a vertical tank at the bottom. The wastewater passes upwards through a dense bed of anaerobic sludge where the microorganisms in the sludge come into contact with wastewater substrates [34]. This sludge is mostly of a granular nature (14 mm) having superior settling characteristics (i.e., at a rate of more than 50 m h 1). The organic materials in the solution are attacked by the microbes, which release biogas. As the biogas rises, it carries some of the granular microbial blanket. At the top of the UASB reactor, a so called three-phase separator separates the biomass from the biogas and wastewater [16]. The three-phase separator is also known as the gasliquidsolid-separator [34]. Fig. 2 shows a graphical illustration of the UASB process [34]. Fluidized Bed Reactor. In a Fluidized Bed Reactor (FBR), wastewater ows in through the bottom of the reactor, and up through a media (usually sand or activated carbon) that is colonized by an active bacterial biomass. The media provides a growth area for the biolm. This media is uidized by the upward ow of wastewater into the vessel, with the lowest density particles (those with highest biomass) moving to the top. 4. Treatment of brewery wastewater for reuse The discharged wastewater from the biological pretreatment processes can be further treated. In this section various methods that may be used

growth of microorganisms that prefer to remain attached to a solid material. Trickling lter process. In the trickling lter process, the wastewater is sprayed over the surface of a bed of rough solids (such as gravel, rock, or plastic) and is allowed to trickle down through the microorganism-covered media. Bioltration towers. A variation of a trickling ltration process is the bioltration tower or otherwise known as the biotower. The biotower is packed with plastic or redwood media containing the attached microbial growth. Rotating biological contactor process. The rotating biological contactor process consists of a series of plastic disks attached to a common shaft. Lagoons. These are slow, cheap, and relatively inefcient, but can be used for various types of wastewater. They rely on the interaction of sunlight, algae, microorganisms, and oxygen (sometimes aerated). Sludge treatment and disposal. In general, aerobic treatment systems like the activated sludge system produce relatively large quantities of sludge, which requires disposal. The sludge can undergo a dewatering treatment either by reconsolidated centrifugation, vacuum ltration, or in a pressure lter.

biogas

effluent gas cap baffles

three phase separator

gas bubbles

sludge granules Sludge bed

influent
Fig. 2. UASB anaerobic process [34].

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G.S. Simate et al. / Desalination 273 (2011) 235247 Table 6 Typical characteristics of membrane processes [30]. Process Microltration Ultraltration Nanoltration Reverse osmosis (hyperltration) Operating pressure (bar) b4 210 540 15150 Pore size (nm) 1003000 10200 110 b2 Molecular weight cut-off range N 500,000 10001,000,000 10020,000 b 200 Size cut-off range (nm) 503000 15200 1100 b1

Table 5 Quality standards for rinse and cooling water, and aimed value for drinking water [1]. Quality standard rinsing water COD (mgO2 L 1) Na+ (mg L 1) Cl (mg L 1) pH Conductivity (s cm 1) /: Not specied. 02 0200 50250 6.59.5 / Quality standard cooling water 02 / / 6.59.5 / Quality standard drinking water 02 20 25 6.59.5 400

to treat brewery wastewater for reuse are explored. It must be noted, however, that recycling of regenerated water as brewing water is considered inappropriate and would require that drinking water standards are complied with [1]. Table 5 shows the most important standards for rinsing, cooling and drinking water [1]. Among the parameters in Table 5, the most important parameter for recycling water or required to be measured is the COD [1,37]. COD is a measure of the oxygen equivalent of the organic matter content of a sample that is susceptible to oxidation by a strong oxidant [38]. The COD is considered an appropriate index for showing the amount of organics in water [39]. The COD value of a wastewater mainly represents the biodegradable and nonbiodegradable organic components (Fig. 3), although inorganic compounds may be signicant in certain cases [37]. However, in general, brewery efuents are easily biodegradable with BOD/COD ratio in the range 0.60.7 [19,20,36]. The organic components in the brewery efuent (expressed as COD) consist of sugars, soluble starch, ethanol, volatile fatty acids, etc [1,36]. 4.1. Membrane ltration The separation by porous membranes is of great interest in environmental and chemical engineering processes [4042]. In fact, ltration technology is considered as an integral component of drinking water and wastewater treatment applications [43]. Membrane ltration can be divided into four categories, depending on the effective pore size of the membrane, and hence the size of the impurities removed. In order of decreasing pore size, they are as follows: microltration, ultra ltration, nanoltration, and hyperltration. Table 6 summarizes the essential features of these processes, such as pore size and operating pressure [30]. However, the characteristics listed in Table 6 are not exhaustive, thus different ranges may be quoted elsewhere. Fig. 4 shows two ways of operating a membrane lter, i.e., dead end ltration and cross-ow ltration. In dead-end ltration, all of the feed water ows through the membrane (as permeate) so that all impurities that are too large to pass through the pores accumulate in the lter module. Some means of removing these is necessary. Crossow ltration involves owing the feed water parallel to the membrane surface, with only a proportion passing through the

membrane. The retained impurities remain in the retentate, which is normally recirculated. Membranes can be classied according to their material of construction [34]. There is a variety of materials that are used for the manufacture of membrane lters, e.g., ceramics and polymers [30,44]. Polymer materials used for membrane manufacture are, for instance, cellulose acetate, polyamides, polypropylene, and polysulfone [34]. Ceramic membranes are usually manufactured from metal oxides, such as alumina, often using some form of a solgel process. In wastewater treatment, the use of nanoltration/reverse osmosis for organic/salt removal is normally practiced [45]. Nanoltration (NF) is actually a relatively recent membrane ltration process used most often with low total dissolved solids water such as surface water and fresh groundwater, with the purpose of softening (polyvalent cation removal) and removal of disinfection by-product precursors such as natural organic matter and synthetic organic matter [46]. The nominal pore size of the membrane is typically about 1 nm. However, nanolter membranes (just like other membranes) are typically rated by nominal molecular weight cut-off (MWCO) rather than nominal pore size. The MWCO is an expression of the retention characteristics of the membrane in terms of molecules of known sizes [44]. The nominal MWCO of the membrane may be dened as the relative molecular mass of the component that is rejected by 90% [47]. In other words, MWCO is an attribute of the pore size and is related to the rejection of a spherical solute of a given molecular weight [48]. The reason that the word nominal is used is that the shape and charge on the molecule will inuence its rate of migration through the membrane [44]. The MWCO is typically less than 1000 atomic mass units (daltons). The NF is a cross-ow ltration technology which lies somewhere between ultraltration (UF) and reverse osmosis (RO) (Table 6). These membranes are able to remove particles below 100 nm in size. In addition, the transmembrane pressure (pressure drop across the membrane) required (up to 3 MPa) is considerably lower than the one used for RO, thus reducing the operating cost signicantly. Braeken et al. [1] used NF in an attempt to treat brewery wastewater for recycling. The results of this study showed that the removal of COD, Na+, and Cl (averaging 100%, 55% and 70% removal, respectively) with NF was sufcient for the biologically treated wastewater, whereas the other three wastewater streams (bottle rinsing water, rinsing water of

Total Organic Carbon (TOC)

Non-oxidisable

Chemically oxidisable (COD)

Non-biologically degradable

Biologically degradable (BOD)

Fig. 3. The relationship between the organic carbon fractions in wastewater.

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(a)

pressure

(b)

pressure

Filte caker

feed

retentate

permeate

membranes permeate

Fig. 4. Two forms of membrane ltration, (a) dead-end and (b) cross-ow ltration.

the bright beer reservoir, and rinsing water of the brewing room) were not suitable for recycling using NF. These results clearly show the importance of pretreatment processes. Though nanoltration is vital for the treatment of wastewaters, the major limitation is fouling. However, coagulation/occulation can be used to enhance nanoltration performance towards water reuse and minimization of fouling [49]. This is because coagulation/occulation reduce the concentration of impurities and hence improve the permeate ux after sedimentation. As mentioned earlier, RO is normally practiced for the removal of organic/salt in wastewaters [45]. The RO is the tightest possible membrane process in liquid/liquid separation and therefore produces the highest water quality of any pressure driven membrane process [34]. The RO membranes are classied by percentage rejection of NaCl and ranges from 95 to 99.5% [34]. The success of RO in large-scale desalination and municipal wastewater treatment has led many industries to view this technology as a means of pollution abatement and cost savings through reuse [50]. In fact wastewater treatment using RO have been employed in chemical, textile, petrochemical, electrochemical, pulp and paper, and food industries as well as for municipal wastewater [51]. Madaeni and Mansourpanah [39] reviewed several studies of RO applications and found that RO may decrease the COD of the efuent by more than 90% or completely. In fact, tests to reduce COD values showed that RO is the best method to separate organics from water. RO is also usually combined with other physical separation techniques, as well as biological and physiochemical treatment, to produce efuents suitable for reuse. For example, a combination of ultraltration (UF) and RO have produced high quality water [52,53]. In studies by Madaeni and Mansourpanah [39], biologically treated wastewater from an alcohol manufacturing plant having COD in the range of 900 to 1200 mg L 1 was treated by various polymeric RO and NF membranes. The polyethylene terphetalate RO membrane yielded outstanding results with higher ux (33 kg m 2 h 1) and extreme COD removal (100%). In another study, brewery bio-efuent was obtained using an internal aerobic membrane bioreactor (internal MEMBIOR) [54]. In this study, the COD of brewery wastewater varied strongly from 1500 to 3500 mg L 1, but after the internal MEMBIOR the COD was around 30 mg L 1 regardless of the COD uctuations of the inuent. The suspended solids were completely retained by the at plate membrane. This made the efuent perfectly suited for re-use via reverse osmosis as process water, omitting the need for expensive pretreatment methods. In summary, a review of several literatures has shown that RO is a preferred conditioning method for the brewing industry because of its environmentally friendly applications, its simplicity regarding automation, its user-friendly aspects, and the small amount of space it

requires. Furthermore, it requires no regenerating chemicals, which means no additional salts have to be added for wastewater neutralization.

4.2. Non-thermal quenched plasma Plasma is a highly ionized gas that occurs at high temperatures. The intermolecular forces created by ionic attractions and repulsions give these compositions distinct properties; for this reason, plasma is described as a fourth state of matter [55]. Like gas, plasma does not have a denite shape or a denite volume unless enclosed in a container; unlike gas, in the inuence of a magnetic eld, it may form structures such as laments, beams and double layers. Some common plasmas are stars and neon signs. In summary, a plasma usually results from the increase of the energy of a gas provided by various sources, such as electric, magnetic, mechanical (shock waves and ultrasound), thermal or even optical (laser) sources [56]. A part of the gaseous matter is thus changed from the starting molecules or atoms to an electrically neutral mixture of ions (anions and cations) and electrons, involving other heavy species and photons [56]. Doubla et al. [5] reported the use of humid air plasma created by an electric gliding arc discharge in humid air to lower organic pollutants in brewery wastewater. The gliding arc discharge in humid air generates .NO and .OH radicals, which have strong oxidizing characteristics. The .OH radical is a very powerful oxidizing agent [E0(.OH/H2O) = 2.85 V/NHE] and thus responsible for oxidation reactions with organic targets, both due to its own properties and to its derivative and/or parent molecule H2O2 as shown in Eq. (1) [5]: H2 O2 2 OH 1

Initially, NO leads to the formation of nitrite in neutral mediums, but is further oxidized to nitrate ions as stable species. Additionally, the high standard oxidation-reduction potentials of the HNO2/NO (1.00 V) and NO 3 /HNO2 (1.04 V) systems reect the oxidizing power of the nitrate ion [5]. In other words, the nitrate ions participate in the oxidizing characteristics of the humid air plasma. In the study by Doubla et al. [5], the BOD removal efciency of the process with brewery industrial waters of BOD values of 385 and 1018 mg L 1 were 74 and 98%, respectively. The alkaline wastewaters were also rapidly neutralized due to pH lowering effect of the plasma treatment emanating from the production of nitrate ions [56]. This process can be coupled with biological process treatments to further lower the organic pollutant concentration more easily and rapidly to an acceptable level for reuse [5].

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G.S. Simate et al. / Desalination 273 (2011) 235247 Table 7 Mean operating criteria of anaerobic digestion-ultraltration plants treating various industrial efuents [45]. Operating parameter/ results Volume of digester (m3) Operational period (month) Feed COD (kg/L) Permeate COD (kg/L) COD removal (%) Space load rates (kg COD/m3d) Sludge load rate (kg COD/kg VSSd) HRT (day) Temperature (C) MLSS (kg/m3) Membrane area (m2) Flux (L/m2h) Inlet pressure (kPa) Crossow velocity (m/s) Tube diameter (mm) Brewery Wine Malting Egg Maize distillery process process 0.05 3 6.7 0.18 97 17.0 0.7 0.8 35 3050 0.44 1040 340 1.5 9.0 2.4 18 37 0.26 93 12.0 0.58 3.3 35 50 1.75 4080 400 2.0 12.7 3.0 5 3.5 0.80 77 5.0 0.5 0.8 35 10 9.6 2040 500 1.8 9.0 80 8 8 0.35 95 6.0 0.33 1.3 30 1030 200 1530 500 1.8 12.7 2610 36 415 0.30 97 3.0 0.24 5.2 35 23 800 1070 600 1.6 9.0

Fig. 5. Simplied schematic description of the MBR process [57].

4.3. Membrane bioreactor Depletion of water resources, increasing water price, and stringent regulation has caused the development of various combinations of membranes with other conventional treatment components [45]. Membrane bioreactor (MBR) is becoming one of such ourishing technology in water and wastewater treatment elds [45]. The MBR combines two proven technologies, i.e., enhanced biological treatment using activated sludge, and membrane ltration as shown in Fig. 5 [57]. Depending on how the membrane is integrated with the bioreactor, two MBR process congurations can be identied: side-stream and submerged (Fig. 6). In side-streams MBRs, membrane modules are placed outside the reactor, and the reactor mixed liquor circulates over a recirculation loop that contains the membrane. In submerged MBRs, the membranes are placed inside the reactor, submerged in the mixed liquor. The side-stream MBRs are more energy intensive compared to submerged MBRs [34,58] due to higher operational transmembrane pressures (TMP) and the elevated volumetric ow required to achieve the desired crossow velocity [58]. However, submerged MBRs use more membrane area and operate at lower ux levels [34]. The MBR has been studied not only for wastewater but also for drinking water treatment [59,60], and is applied to municipal wastewater treatment at full scale [61]. Li and Chu [59] found that nearly 60% of inuent total organic carbon (TOC) was removed by MBR, accompanied by more than 75% reduction in trihalomethanes formation potential (THMFP). The MBR technology is also applied to the brewery wastewater for reuse [32]. The COD reduction in MBR inuent (i.e., UASB reactor efuent ranging from 500 to 1000 mg O2 L 1) of up to an average of 96% was reported by Dai et al. [32]. Brewery wastewater was also conducted by various other researchers [6264]. In most of these studies, signicant amounts of COD removals (~90%) were reported. With these promising results, it can be concluded that the MBR process is an attractive option for the treatment and reuse of industrial and municipal wastewaters. Table 7 shows the operating parameters and some of the results of the anaerobic digestion-ultraltration process [45]. Just like other membrane separation processes, membrane fouling is the most serious problem affecting system performance of MBRs and,

therefore need to be cleaned frequently [34]. Membrane fouling can be classied as reversible and irreversible [65]. It results from interaction between the membrane material and the components of the activated sludge liquor, which include biological ocs formed by a large range of living or dead microorganisms along with soluble and colloidal compounds. Fouling leads to a signicant increase in hydraulic resistance, manifested as permeate ux decline or TMP increase when the process is operated under constant-TMP or constant-ux conditions respectively. The organic fouling of the membrane is mainly dependent on several factors including the following [65]: (1) the components of organic matter such as colloidal fraction and dissolved fraction, (2) organic characteristics such as hydrophobicity and molecular size and conguration, (3) solution chemistry such as pH, divalent ions concentration and ionic strength, and (4) membrane properties such as pore size and surface roughness. In practice, membrane fouling can be controlled by two types of approaches, i.e., (1) periodical air scouring, backwashing and chemical cleaning [67], and (2) the addition of adsorbents and pretreatment by coagulation [68,69]. A recent study has shown that direct addition of a coagulant in the bioreactor was able to mitigate membrane fouling [66]. The integration of coagulation into MBR is termed membrane coagulation bioreactor (MCBR). In fact, the most important trend in the development of membrane ltration for water treatment is the integration of different pretreatment strategies to improve the performance of low pressure membranes [22]. 4.4. Combined anaerobic and aerobic treatment Anaerobic and aerobic treatments are often combined in brewery wastewater treatment [16,70,71]. As shown in Fig. 7, there are essentially four types of integrated anaerobicaerobic bioreactors [72]. The attributes

wastewater

wastewater

membrane unit

permeate bioreactor

bioreactor

permeate

Side-stream MBR

Submerged MBR
Fig. 6. Membrane bioreactor congurations [57].

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243

Anaerobic-aerobic treatment

Conventional anaerobic-aerobic system

Anaerobic-aerobic system using high rate bioreactors

Integrated anaerobicaerobic bioreactors

Integrated bioreactors with physical separation of anaerobic-aerobic zone

Integrated bioreactors without physical separation of anaerobicaerobic zone

Anaerobic-aerobic Sequencing Batch Reactor (SBR)

Combined anaerobicaerobic culture system

Fig. 7. Types of combined anaerobic-aerobic system [71].

of integrated anaerobicaerobic bioreactors are as follows [36]: Firstly, in the anaerobic reactor the bulk of the COD, 7085%, is converted into biogas on a small surface area. Secondly, in an aerobic/anoxic post-treatment step, up to 98% of the COD and nutrients are removed. Furthermore, some of the important advantages of combined aerobic/anaerobic treatment of brewery efuent over complete aerobic include a positive energy balance, reduced (bio)sludge production and signicant low space requirements [16]. Recent development of tall slender anaerobic (e.g., internal circulation reactors) and aerobic (e.g., airlift reactors) reactors allows for extreme compact efuent treatment plant design still meeting stringent requirements of surface water quality [16]. 4.5. The use of carbon nanotubes Since the rediscovery of carbon nanotubes (CNTs) in 1991 [73] by Iijima [74], several researchers worldwide cutting across all disciplines have embarked on stimulating research to utilize the myriad unique properties of these nanomaterials. The CNTs consist of honeycomb structures of graphene sheets rolled up into cylinders with a diameter of a few nanometers, but length of many micron or even centimeters [75,76]. A lot of methods and carbon sources for the growth of carbon nanotubes have been actively pursued in the past few years, and these have been outlined in several review papers [7782]. There are typically two forms of CNTs according to the number of rolled up graphene layers that form the tube, i.e., single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT). The model representations of multi-walled CNT and single-walled CNT are shown in Fig. 8 [83,84]. The unique properties of CNTs arise from their special atomic and electronic structures [85]. Owing to their unique structural, mechanical, and electronic properties, CNTs possess great potential in a large variety of promising applications such as chemical sensors, eld emission materials and catalyst supports [75,78,81,86]. Some of the important applications of CNTs with respect to water treatment are discussed below. 4.5.1. Nanosorbents Carbon nanotubes have shown exceptionally good adsorption capability and high adsorption efciency for various organic pollutants [8791] and inorganic pollutants such as uoride [92]. The CNTs have also been found to be superior sorbents for heavy metals [89,93,94]. The CNTs are particularly attractive as sorbents because, on the basis of mass, they have larger surface areas than bulk particles, and can be functionalized with various chemical groups to increase their afnity towards target compounds [95]. The CNTs also have small size, and hollow and layered structures, which are very important characteristic attributes for adsorption [96]. The ability of

functionalized CNTs to adsorb various impurities from wastewater can be extended to the removal of COD from brewery wastewater. A review of the literature has shown that although CNTs have been proven to possess good potential as superior adsorbents, to the best of the authors' knowledge no published work is available regarding their use as coagulants and/or occulants. However, it can be theorized that if CNTs can adsorb on separate colloidal particles, then the particles can be drawn together; a phenomenon known as bridging occulation. Furthermore, the adsorption of CNTs onto particle surfaces can also result in charge neutralization, resulting in a near zero net charge. Once the surface charge has been neutralized, the ionic cloud dissipates and the electrostatic potential disappears so that the contact among colloidal particles occurs freely. Charge neutralization is easily monitored and controlled using zeta potential [97]. From the two phenomena above (adsorption and coagulation), it can be ascertained that for the treatment of wastewaters (including brewery wastewaters) containing both dissolved and suspended organics, CNTs may well be applied to remove dissolved organics by adsorption, and suspended solid organic by heterogeneous coagulation (bridging and neutralization), at the same time. However, a lot of challenges arise in attempting to use CNTs in their present state as coagulants or occulants. Firstly, the CNTs lack dispersion and solubility. However, there have been several successful attempts to prepare water soluble carbon nanotubes by various techniques [98100], and improvements in their dispersivity through

Fig. 8. Models and representation of multi-walled CNT and single-walled CNT [82,83].

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functionalization [101]. Secondly, the CNTs are very expensive, thus they require to be regenerated after use. If the CNTs are applied in the form of slurry, an efcient separation process downstream such as membrane ltration is needed to retain and recycle the CNTs. Retention of nanomaterials is critical not only because of the cost associated with loss of nanomaterials, but also, and more importantly, because of the potential impacts of nanomaterials on human health and ecosystems [102104]. 4.5.2. Nanolters The successful fabrication of carbon nanotube lters have been reported [105]. These ltration membranes consist of hollow cylinders with radially aligned carbon nanotube walls. Srivastava et al. [105] efciently carried out ltration of heavier hydrocarbon species, CmHn (m N 12), from hydrocarboneceous oil for example, petroleum CmHn (n=2m + 2, m=1 to 12), and in the removal of Escherichia coli from drinking water and ltration of the nanometer-sized poliovirus. The high organic content of brewery efuent is classied as high strength waste in terms of COD, from 1000 mg L 1 to 4000 mg L 1 and BOD of up to 1500 mg L 1 [6]. This makes brewery wastewater a good candidate for treatment with these CNT lters. Membranes that have CNTs as pores could be used in desalination and demineralization. Billions of these tubes act as the pores in the membrane. A membrane lter possessing both super-hydrophobicity and superoleophilicity was synthesized from vertically-aligned multi-walled carbon nano-tubes on a stainless steel mesh for the possible separation of oil and water [106]. Both super-hydrophobicity and superoleophilicity could be obtained due to the dual-scale structure, needle-like nano-tube geometry on the mesh with micro-scale pores, combined with the low surface energy [106]. The nano-tube lter could separate diesel and water layers, and even surfactant-stabilized emulsions. The successful phase separation of the high viscosity lubricating oil and water emulsions was also carried out. The separation mechanism can be readily expanded to a variety of different hydrophobic and oleophilic liquids such as brewery wastewater. 4.6. Electrochemical methods Electrochemical method of wastewater treatment came into existence when it was rst used to treat sewage generated onboard by ships [107]. Thereafter, the application of electrochemical treatment was widely received in treating industrial wastewaters that are rich in refractory organics and chloride content [108,109]. The electrochemical method of treatment is well-suited for degrading biorefractory organic pollutants, because it is possible to achieve partial or complete decomposition of the organic substances. The electrochemical methods of treatment are favored, because they are neither subject to failure due to variation in wastewater strength nor due to the presence of toxic substances and require less hydraulic retention time. Vijayaraghavan et al. [108] developed a novel brewery wastewater treatment method based on in situ hypochlorous acid generation. The generated hypochlorous acid served as an oxidizing agent that destroyed organic compounds present in the brewery wastewater. An inuent COD value of 2470 mg L-1 was reduced to 64 mg L 1 (over 97% reduction). The hypochlorous acid was generated using a graphite anode and stainless steel sheet as a cathode in undivided electrolytic reactor. Initially, during electrolysis, chlorine was produced at the anode and hydrogen gas at the cathode. Since the anode and cathode were kept in an undivided electrolytic reactor, the chlorine that was generated undergoes a disproportionation reaction, resulting in hypochlorous acid [108] as indicated in Eq. (2) below: Cl2 H2 OHOCl HCl 2

4.7. Microbial fuel cells Recently, brewery wastewater has been simultaneously treated while generating electricity from organic matter in wastewater [33,110112]. This device that treats wastewater and generates electricity at the same time is termed microbial fuel cell (MFC) [113,114]. The MFC is a combined system with anaerobic and aerobic characteristics. They are designed for anaerobic treatment by bacteria in the solution near the anode, with the cathode exposed to oxygen (or an alternative chemical electron acceptor). Electrons released by bacterial oxidation of the organic matter are transferred through the external circuit to the cathode where they combine with oxygen to form water [33]. Consequently, a combination of anaerobicaerobic processes can be constructed using a double-chamber MFC, in which the efuent of the anode chamber could be used directly as the inuent of the cathode chamber so as to be treated further under aerobic conditions to improve the wastewater treatment efciency [112]. Feng et al. [33] found that with an inuent COD of brewery wastewater of 2 250418 mg L 1, the COD removal efciency was 85% and 87% at 20 C and 30 C, respectively. Performance of sequential anode-cathode MFC achieved COD removal efciency of more than 90% (e.g., COD of 1 250100 mg L 1 was reduced to 60 mg L 1) [112]. Furthermore, up to 94% COD removal has also been reported by other researchers with this method [111]. Since high COD removal efciencies were achieved in these studies, it can be concluded that MFCs, particularly, sequential anode cathode type, can provide a new approach for brewery wastewater treatment while offering a valuable alternative to energy generation. 4.8. Carbon The characteristics of a water treatment plant have a great inuence on the characteristic properties of the end product. Even when the incoming process water is from a municipal drinking water source, the water may contain residual tastes, odors, disinfection byproducts, and free and combined chlorine. Molecules with carbon sulfur bonds often smell and taste bad, but these are often preferentially adsorbed on carbon. The same is true of molecules with aromatic rings. Carbon's de-chlorinating capability results from its ability to act as a reducing agent that reacts with strong oxidizing agents such as hypochlorous acid or chlorine dioxide. The treatment of tannic acid for avor and odor removal is a process application in brewing where carbon adsorption is used. Carbon is also used to remove color from malts for use in clear beers and other avored malt beverages. Several granular and powdered products can be used for this type of application. Activated carbons are an effective treatment to assure water that is contaminant, taste, and odor free. 5. Discussion and synthesis of ndings This section provides a discussion and synthesis of the review ndings of this paper. This discussion includes a comparison and possible integration of the processes and technologies. In a nutshell, the discussion primarily addresses the following two fundamental questions: (a) How do the processes and technologies compare with each other? (b) Can they be integrated with each other, and if so, what are the potential challenges and benets? 5.1. Comparison of processes and technologies This review highlighted the need for treatment of brewery wastewater, and looked at various methods that may be used to safely and cost-effectively treat brewery wastewater for reuse. In addition, some challenges associated with these methods were discussed. It should be noted and emphasized herein that the treatment of brewery wastewater efuent is a costly and relatively

Further disproportion of OCl to ClO 3 was accelerated at high temperature (75 C) and under alkaline conditions (Eq. (3)). 3OCl ClO3 2Cl

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complex activity; particularly with the need to meet governmental regulations and environmental friendliness [6,115]. Conventional separation methods such as coagulation/occulation, centrifugation, and gravity separation exhibit shortcomings including incomplete COD removal. These methods are generally associated with low separation efciency, high operation costs, large setup size, and the generation of secondary pollutants. It was also noticed that biological treatment is widely applied as a pretreatment method. Generally, aerobic treatment has been applied for the treatment of brewery wastewater and recently, anaerobic systems have become an attractive option, among other advantages, because of their high COD content removal. Though these biological methods have found widespread application for the treatment of the characteristically high organic content of the brewery wastewater, further treatment is required for water reuse. Nevertheless, this review has shown some promising results with quenched plasma, MBR, electrochemical methods, and microbial fuel cells. These methods have great potential to be used to treat brewery wastewater for reuse and needs to be further investigated with respect to different challenges and opportunities involved. For example, beer brewery wastewater might be a good source for electricity generation in MFCs due to its nature of high carbohydrates and low ammoniumnitrogen concentration. The authors have also noted that recent advances suggest that many of the recent problems involving water quality could be solved or greatly ameliorated using carbon nanotubes as sorbents. Therefore, it is expected that the brewery industry will also benet from these discoveries. However, the knowledge required for the large-scale design and application of the processes discussed in this review is perhaps still lacking. It is further recommended to carry out some studies to establish estimated capital costs of these promising processes. On the other hand, the application of membrane ltration (e.g., NF and RO) to drinking water treatment and wastewater reuse, though well established, has undergone accelerated development in the past decade with the improvement in membrane quality and the decrease in membrane cost. A very important trend in the development of membrane ltration for water treatment is the integration of different pretreatment strategies to improve their performance. The RO, in particular, has been shown to be an efcient and cost effective process for the treatment of brewery wastewater for reuse. Table 8 shows a summary of some of the studies conducted on brewery wastewater, showing the COD reductions, and whether the efuent is suitable as a primary or secondary water based on the criteria listed in Table 5. It must be noted, however, that these studies had different experimental designs. 5.2. Integration of processes and technologies It can be been seen in Table 8 that none of the methods (apart from RO) can be used individually in brewery wastewater treatment

applications with good economics and high degree of energy efciency. Coupling these processes together as two or three stage processes would be more appropriate. Subsequently, different process combinations are proposed and discussed. The demand for renewable energy in our society is ever increasing [111]. Therefore, the MFCs is recommended to be the rst pretreatment stage of every integrated process particularly with ltration techniques. MFCs have operational and functional advantages over the technologies currently used for generating energy from organic matter [111]. First, the direct conversion of substrate energy to electricity enables high conversion efciency, unlike the biological processes reactors where the metabolized products (e.g., NH3) have to be used in boilers for energy generation. Second, MFCs operate efciently at ambient temperature. Third, an MFC does not require gas treatment because the off-gasses of MFCs are enriched in carbon dioxide and normally have no useful energy content. Fourth, MFCs do not need energy input for aeration provided the cathode is passively aerated [116]. Fifth, MFCs have potential for widespread application in locations lacking electrical infrastructures and can also operate with diverse fuels to satisfy energy requirements. The high COD removal efciency (see Table 8) could also reduce the load in other coupled stages. The uses of other techniques as rst stages in an integrated process do not offer any foreseeable benets. Electrochemical methods can be well suited to be coupled in the latter stages of the integrated process. Sanitizing agents (often called disinfectants) which are present in brewery wastewater contain chlorine compounds. These compounds produce chlorine during electrolysis and, thereafter, chlorine generates hypochlorous acid which oxidizes organic compounds. Chlorine is one of the most widely used disinfectants. It is very applicable and very effective for the deactivation of pathogenic microorganisms. Therefore, electrochemical methods if coupled in the latter stages can serve as an organic oxidation and disinfecting stage. Plasma methods though very effective (see Table 8), the process is expensive because of the high energy requirements by the gas, and the cost of energy sources such as laser. Therefore, if coupled with other methods, the processes can be very expensive. CNTs have shown remarkable adsorption power. Combining CNTs with UF will result in substantial removal of organics. However, the addition of CNTs would rapidly increase the transmembrane pressure rapidly due to the formation of CNT cake on the membrane surface. In this case, CNTs may need to be of large enough diameters to reduce the transmembrane pressure effect. As for the MBR or ltration in general, fouling mitigation can potentially be done by coupling coagulation and occulation to the process [117]. 6. Summary Water is a common element in the lives of all people and societies. Water has been the foundation and sometimes, the undoing of many

Table 8 Summary of brewery wastewater treatment processes. Process Initial COD (mg/L) Final COD (mg/L) COD reduction (%) 98 7391 9098 98 96 97 94 96 100 Potential use Primary (process water) No No No No No No No No Yes Secondary (non-process water) No No No No No No No No Yes [5] [21] [16] [36] [32] [107] [110] [1] [39] Reference

Quenched plasma UASB (*1) Aerobic reactor Combined bioreactor (*1) Membrane bioreactor Electrochemical method Microbial fuel cells (*2) Nanoltration Reverse osmosis
a

1018a 19473079 Not given Not given 5001000 2470 1710 3692 850

18a Not given Not given Not given 40 64 105 143 0

BOD gures; (*1) has added value of energy production from biogas; (*2) has added value of electricity production.

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great civilizations. Today, water continues to be essential for life sustenance (both human and animals), agricultural, economic and industrial activities that help society to develop. Less than a century ago, it was widely assumed that there were enough freshwater supplies in the world for everyone. Yet today, increased use of freshwater for industrial, agricultural, and domestic use has created acute water shortages in some areas of the world, particularly the developing countries. These shortages are stimulating or worsening international conicts over water, which has joined oil as a major commodity triggering wars. The presence of pollutants in raw water due to human activities has also exacerbated the situation. On the other hand, wastewater reclamation and reuse has become an important option, since industrialization and urbanization have accelerated environmental water pollution, making it a limited resource for water supply [118]. When properly treated and recycled, wastewater can be an alternative water source that can benecially and cost-effectively reduce the demands for fresh water. It can be concluded that, along with the growing world population and industrial activities coupled with stringent environmental requirements, the cost of water is increasing. As a result, the demand for water reuse in the brewery industry is expected to increase at an unprecedented rate. Consequently, an increasing need of processes capable of achieving an efcient treatment under extreme operational conditions that simultaneously optimize operational costs can be expected in the future. Information obtained from this review shows that in order to remove impurities efciently, integration of different processes is recommended. Disclaimer The contents of this paper reect the views of the authors who are responsible for the facts and accuracy of the data presented herein and do not necessarily reect the ofcial views or policies of any agency or institute. This paper does not constitute a standard, specication, nor is it intended for design, construction, bidding, contracting, or permit purposes. References
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