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

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DOI: 10.1016/j.desal.2011.02.035

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Desalination 273 (2011) 235–247

Contents lists available at ScienceDirect

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
School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, P/Bag 3, Wits 2050, South Africa
b
TTI - Texas A&M University System, College Station, TX, USA
c
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

Article history: The beer brewing process often generates large amounts of wastewater effluent and solid wastes that must be
Received 25 October 2010 disposed off or treated in the least costly and safest way so as to meet the strict discharge regulations that are
Received in revised form 11 February 2011 set by government entities to protect life (both human and animal) and the environment. It is widely
Accepted 12 February 2011
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,
Keywords:
which is often costly and problematic for most breweries. As a result, many brewers are today searching for:
Brewery wastewater
Biological oxygen demand (1) ways to cut down on this water usage during the beer brewing process, and/or (2) means to cost-
Chemical oxygen demand effectively and safely treat the brewery wastewater for reuse. Based on the available documented literature,
Pretreatment this paper provides a review assessment of the current status of the brewery wastewater treatment processes
Treatment including potential applications for reuse. Key challenges for both brewery wastewater treatment and reuse
Reuse are also discussed in the paper and include recommendations for future developments.
© 2011 Elsevier B.V. All rights reserved.

Contents

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

⁎ 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
236 G.S. Simate et al. / Desalination 273 (2011) 235–247

6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Disclaimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

1. Introduction challenges as related to brewery wastewater reuse (or recycling) are


also discussed in the paper.
Despite discharging large volumes of highly polluting effluents The treatment, recovery and applications of various brewery by-
throughout the year [1,2], the brewing industry constitute an products (e.g., spent grains, spent hops, surplus yeast, kieselghur
important economic segment of any country [3,4]. In fact, beer is sludge, trub and waste labels) have been extensively documented
the fifth most consumed beverage in the world behind tea, elsewhere [3,6,8,12–14], thus are not discussed in this paper.
carbonates, milk and coffee [3]. Beer brewing involves two main Accordingly, the paper is organized as follows: a background of the
steps, i.e., brewing and packaging of the finished product [5]. The by- legislation and environmental management systems is presented first,
products (e.g., spent grains from mashing, yeast surplus, etc) followed consecutively by brewery wastewater pre- and treatment-
generated from these steps are responsible for pollution when methods. Challenges and future prospects are included in the
mixed with effluents [5]. In addition, cleaning of tanks, bottles, discussion towards the end. A summary is then provided to conclude
machines, and floors produces high quantities of polluted water [5]. It the paper.
is estimated that for the production of 1 L of beer, 3–10 L of waste
effluent is generated depending on the production and specific water
2. Legislation and environmental management systems
usage [1,3,6]. In other words, very large quantities of water are
consumed during the beer brewing process.
Like any other industry, the brewing industry is subject to
Similarly and because of voluminous water usage, the brewery
extensive government regulations. Some of the regulations imposed
industry discharges large volumes of highly polluting effluents throughout
involve production, distribution, labeling, advertising, trade and
the year [1,2]. It must also be noted that effluents from individual process
pricing practices, credit, container characteristics, and alcoholic
steps are variable. For example, bottle washing results in a large
content requirements [9]. Governmental entities also levy various
wastewater volume, but it contains only a minor part of the total organics
taxes, license fees and other similar charges and may require bonds to
discharged from the brewery processes. On the other hand, effluents from
ensure compliance with applicable laws and regulations.
fermentation and filtering are high in organics/biochemical oxygen
Furthermore, the management of environmental issues is of
demand (BOD), but generally low in volume, accounting for about 3% of
growing interest nowadays. There is a need to understand the
the total wastewater volume but 97% of the BOD [7].
important environmental impacts on the community and then
Wastewater from a brewery plant may be discharged in several ways
consider the advantages and disadvantages associated with various
including the following [8,9]: (1) directly into a waterway (oceans, rivers,
levels of environmental management [15]. This means that the
streams, or lakes), (2) directly into a municipal sewer system, (3) into the
brewing industry must also comply with numerous environmental
waterway or municipal sewer system after the wastewater has undergone
protection laws. In fact, the brewing industry has shown increasing
some pretreatment, and (4) into the brewery's own wastewater
awareness for environmental protection and the need of sustainable
treatment plant. The disposal of untreated (or partially treated) brewery
production processes [16]. Furthermore, most national governments
wastewater into water bodies can constitute potential or severe pollution
where these industries operate have signed and ratified the Kyoto
problems to the water bodies since the effluents contain organic
Protocol aimed at reducing greenhouse gas emissions [17]. Through
compounds that require oxygen for degradation [10]. For example, if
environmental management systems (EMS) such as, (1) ISO 14001,
water of high organic matter content value flows into a river, the bacteria
(2) Eco-Management and Audit Scheme (EMAS), and (3) Interna-
in the river will oxidize the organic matter consuming oxygen from the
tional Safety Rating System (ISRS), breweries should be able to
water faster than the oxygen dissolves back in the river from the air.
proactively manage their impacts on the environment. In fact, EMSs
Furthermore, as regulations become more and more stringent and the cost
should help breweries focus on effective and efficient management of
of water increases, the call for water recycling is currently gaining a lot of
both current and future environmental impacts. The International
momentum.
Finance Corporation (IFC) also has environmental, health and safety
There are many papers, such as those reviewed by Fillaudeau et al. [3],
(EHS) guidelines for breweries [18].
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, 3. Conventional methods of pretreating brewery wastewater
that wastewater reuse is not common in this type of the industry due to
public perception and the possible product quality deterioration problems Brewery wastewater typically has a high chemical oxygen demand
[11]. However, the future reuse of brewery wastewater seems to be (COD) from all the organic components (sugars, soluble starch,
unavoidable, as the issue of water shortage has become a serious global ethanol, volatile fatty acids, etc) [9]. It usually has temperatures
and environmental problem. This is particularly very critical in most ranging from 25 °C to 38 °C, but occasionally reaching much higher
developing countries such as the sub-Saharan region where droughts are temperatures. The pH levels can range between 2 and 12 [9] and are
perpetual, thus every drop of water must be preciously conserved. influenced by the amount and type of chemicals used in cleaning and
In this paper, the potential opportunities that may be available for sanitizing (e.g., caustic soda, phosphoric acid, nitric acid, etc.)
treating brewery wastewater for reuse in two applications are [9,16,19]. Sanitizing chemicals which include chlorine compounds
reviewed, namely: (a) primary water used in the production of ensure that the surfaces are free of any microorganisms harmful to the
beer, and (b) secondary water that does not come in contact with brewing industry and the public consuming the beer. Nitrogen and
beer; e.g. utilities cooling, water used in the packaging process and phosphorus levels are mainly dependent on the handling of raw
general cleaning water. Once technology improves and the percep- material and the amount of yeast present in the effluent [9,16,19].
tions have changed regarding the use of recycled water, beer to water Table 1 is an example of the physicochemical characteristics of
ratios is perceived may be reduced to the ratio of about 1:2. Pertinent brewery wastewater from the United Breweries in India [20].
G.S. Simate et al. / Desalination 273 (2011) 235–247 237

Table 1 methods remove coarse solid matter, rather than dissolved pollutants. It
Characteristics of brewery wastewater [20]. may be a passive process, such as sedimentation to allow suspended
Parameter Value pollutants to settle out or float to the top naturally. In general, these
methods have yielded little success; most often resulting in incomplete
pH 3–12
Temperature (°C) 18–40 contaminant removal and/or separation. For example, sedimentation has
COD (mg L− 1) 2000–6000 been found to be unsatisfactory even with the addition of coagulants and
BOD (mg L− 1) 1200–3600 other additives [27].
COD:BOD ratio 1.667
VFA (mg L− 1) 1000–2500
Phosphates as PO4 (mg L− 1) 10–50 3.2. Chemical methods
TKN (mg L− 1) 25–80
TS (mg L− 1) 5100–8750 Different chemicals can be added to the brewery wastewater to
TSS (mg L− 1) 2901–3000 alter the water chemistry [22]. Chemical pretreatment may involve
TDS (mg L− 1) 2020–5940
pH adjustment or coagulation and flocculation. The acidity or
alkalinity of wastewater affects both wastewater treatment and the
environment. Low pH indicates increasing acidity while a high pH
In fact, the brewery wastewater is characterized by large variations indicates increasing alkalinity. The pH of wastewater needs to remain
in the parameters mentioned in Table 1 [21]. As a result, most large between 6 and 9 to protect organisms. Waste CO2 may be used to
breweries require some degree of wastewater pretreatment. In cases neutralize caustic effluents from clean-in-places (CIP) systems and
where the brewery does not discharge to the municipal sewer, then bottle washers [28]. The waste CO2 can also be used as a cheap
primary and secondary treatment of the effluent is required. However, acidifying agent for decreasing the pH of alkaline wastewaters before
if the brewery is permitted to discharge into a municipal sewer, the anaerobic reactor, thus replacing the conventionally used acids
pretreatment may be required to meet municipal bylaws and/or to [20]. Neutralization with H2SO4 and HCl acids is usually not
lessen the load on the municipal treatment plant. In some cases, sewer recommended because of their corrosive nature and sulfate and
discharge fees imposed on effluent volume, and on the suspended and chloride discharge limitations [29], which may add to the cost of
organic loads, by the municipality may encourage the brewery to effluent treatment operations [20].
install its own treatment facility. Pretreatment is meant to alter the Coagulation and flocculation are physicochemical processes
physical, chemical, and/or biological properties of feed water [22], commonly used for the removal of colloidal material or color from
thus improving the performance of upstream processes. Therefore, water and wastewater. In water and wastewater treatment, coagu-
pretreatment is done by physical, chemical, or biological methods, or lation implies the step where particles are destabilized by a coagulant,
by a combination of all these methods. Table 2 lists the unit operations and this may include the formation of small aggregates by Brownian
included within each category, and detailed schematic representation motion (perikinetic coagulation). On the other hand, the subsequent
of a conventional wastewater treatment processes can be found in process in which larger aggregates (flocs) are formed by the action of
Spellman's Standard Handbook for Wastewater Operators [23]. shear is then known as flocculation [30]. After small particles have
Table 3 is a summary of the generic advantages and disadvantages formed larger aggregates, colloidal material can then be more easily
of various wastewater treatment processes as shown in literature removed by physical separation processes such as sedimentation,
[24]. These characteristics (Table 3) generally relate to the cost of flotation, and filtration.
construction and ease of operation. Generally, the complexity and cost
of wastewater treatment technologies increase with the quality of the 3.3. Biological methods
effluent produced. In fact, the water management and waste disposal
in the brewery industry are considered as significant cost factors and Biological waste treatment processes play a central role in the way
important aspects in the operations of a brewery plant [25,26]. society manage their wastewaters. It is based on the activity of a wide
range of microorganisms, converting the biodegradable organic pollutants
3.1. Physical methods in the wastewaters. In fact, brewery effluents having both chemical (with
very high organic content) and microbial contaminants are generally
Among the first treatment methods used are physical unit operations, treated by biological methods [31]. Therefore, after the brewery
in which physical forces are applied to remove contaminants. Physical 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
Table 2
Wastewater treatment unit operations and processes. efficiency in COD and BOD removal, ranging from 80 to 90%, and (3) low
investment cost. However, though biological treatment processes are
Physical unit operations - Screening
particularly effective for wastewater treatment, they require a high energy
- Comminution
- Flow equalization input [33]. Biological treatment of wastewater can be either aerobic (with
- Sedimentation air/oxygen supply) or anaerobic (without oxygen) [9]. The aerobic and
- Flotation anaerobic processes are shown graphically in Fig. 1 [34]. These processes
- Granular-medium filtration are discussed in more details in the subsequent sections. Generally,
Chemical unit operations - Chemical precipitation
- Adsorption
aerobic treatment has successfully been applied for the treatment of
- Disinfection brewery wastewater and recently anaerobic systems have become an
- Chlorination attractive option [9]. Table 4 presents a general comparison between
- Other chemical applications anaerobic and aerobic biological treatment systems such as activated
Biological unit operations - Activated sludge processes
sludge.
- Aerated lagoons
- Trickling filters
- Rotating biological contactors 3.3.1. Aerobic
- Pond stabilization Aerobic biological treatment is performed in the presence of oxygen
- Anaerobic digestion by aerobic microorganisms (principally bacteria) that metabolize
- Biological nutrient removal
the organic matter in the wastewater, thereby producing more
238 G.S. Simate et al. / Desalination 273 (2011) 235–247

Table 3
Generic advantages and disadvantages of conventional and non-conventional wastewater treatment technologies [24].

Treatment type Advantages Disadvantages

Aquatic systems Stabilization lagoons –Low capital cost Requires a large area of land
–Low operation and maintenance cost –May produce undesirable odors
–Low technical manpower requirements
Aerated lagoons Requires relatively little land area –Requires mechanical devices to aerate basins
–Produces few Undesirable odors –Produce effluents With a high suspended solids
concentration
Terrestrial systems Septic tanks –Can be used by individual households –Provides a low treatment efficiency
–Easy to operate and maintain –Must be pumped occasionally
–Can be built in rural areas –Requires a landfill for periodic disposal of sludge
and septage
Constructed wetland –Removes up to 70% of solids and bacteria –Remains largely experimental
–Minimal capital cost –Requires periodic removal of excess plant material
–Low operation and maintenance requirements –Best used in areas where suitable native plants
and costs are available
Mechanical systems Filtration systems Minimal land requirements –Requires mechanical devices
–Relatively low cost
–Can be used for household scale treatment
–Easy to operate
Vertical biological –Highly efficient treatment method –High cost
reactors –Requires little land area –Complex technology
–Applicable to small communities for local scale –Requires technically skilled manpower for operation
treatment and to big cities for regional scale and maintenance
treatment –Needs spare parts availability
–Has a high energy requirement
Activated sludge –Highly efficient treatment method –High cost
–Requires little land area –Requires sludge disposal area (sludge usually land-spread)
–Applicable to small communities for local scale –Requires technically skilled manpower for operation and
treatment and to big cities for regional scale treatment maintenance requirement

microorganisms and inorganic end-products (principally CO2, NH3 and biomass. In this process, the suspension of aerobic microorganisms in
H2O). Aerobic treatment utilizes biological treatment processes, in the aeration tank is mixed vigorously by aeration devices, which also
which microorganisms convert non-settle-able solids to settle-able supply oxygen to the biological suspension.
solids. Sedimentation typically follows; allowing the settle-able solids to
settle and separate out. Three options include: Attached growth (biofilm) process. The second type of aerobic
Activated sludge process. In the activated sludge process, the biological treatment system is called “attached growth (biofilm)
wastewater flows into an aerated and agitated tank that is primed process” and deals with microorganisms that are fixed in place on
with activated sludge. This complex mixture containing bacteria, fungi, a solid surface. This “attached growth type” aerobic biological
protozoans, and other microorganisms is collectively referred to as the treatment process creates an environment that supports the

sludge
50%

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

methane
90%
Electron acceptor:
Anaerobic
SO4, PO4, organics
process

10%

sludge

Fig. 1. An illustration of aerobic and anaerobic processes [34].


G.S. Simate et al. / Desalination 273 (2011) 235–247 239

Table 4 3.3.2. Anaerobic


Anaerobic treatment as compared to aerobic treatment [16]. Anaerobic wastewater treatment is the biological treatment of
Aerobic systems Anaerobic systems wastewater without the use of air or elemental oxygen. Anaerobic
treatment is characterized by biological conversion of organic compounds
Energy consumption - High - Low
Energy production - No - Yes by anaerobic microorganisms into biogas, which can be used as a fuel;
Biosolids production - High - Low mainly methane 55–75 vol% and carbon dioxide 25–40 vol% with traces of
COD removal (%) - 90–98 - 70–85 hydrogen sulfide [35]. In breweries, direct utilization of biogas in a boiler is
Nutrients (N/P) removal - High - Low
usually the preferred solution. The reason for this is that investment costs
Space requirement - High - Low
Discontinuous operation - Difficult - Easy 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.
growth of microorganisms that prefer to remain attached to a solid
Upflow Anaerobic Sludge Blanket. One of the most popular anaerobic
material.
processes is the Upflow Anaerobic Sludge Blanket (UASB). In the UASB
reactor, the wastewater enters a vertical tank at the bottom. The
Trickling filter process. In the trickling filter process, the wastewater is wastewater passes upwards through a dense bed of anaerobic sludge
sprayed over the surface of a bed of rough solids (such as gravel, rock, where the microorganisms in the sludge come into contact with
or plastic) and is allowed to “trickle down” through the microorgan- wastewater substrates [34]. This sludge is mostly of a granular nature
ism-covered media. (1–4 mm) having superior settling characteristics (i.e., at a rate of
more than 50 m h− 1). The organic materials in the solution are
Biofiltration towers. A variation of a trickling filtration process is the attacked by the microbes, which release biogas. As the biogas rises, it
biofiltration tower or otherwise known as the biotower. The biotower is carries some of the granular microbial blanket. At the top of the UASB
packed with plastic or redwood media containing the attached microbial reactor, a so called three-phase separator separates the biomass from
growth. the biogas and wastewater [16]. The three-phase separator is also
known as the gas–liquid–solid-separator [34]. Fig. 2 shows a graphical
Rotating biological contactor process. The rotating biological contactor illustration of the UASB process [34].
process consists of a series of plastic disks attached to a common shaft.
Fluidized Bed Reactor. In a Fluidized Bed Reactor (FBR), wastewater flows
in through the bottom of the reactor, and up through a media (usually
Lagoons. These are slow, cheap, and relatively inefficient, but can be sand or activated carbon) that is colonized by an active bacterial biomass.
used for various types of wastewater. They rely on the interaction of The media provides a growth area for the biofilm. This media is
sunlight, algae, microorganisms, and oxygen (sometimes aerated). “fluidized” by the upward flow of wastewater into the vessel, with the
lowest density particles (those with highest biomass) moving to the top.
Sludge treatment and disposal. In general, aerobic treatment systems
like the activated sludge system produce relatively large quantities of 4. Treatment of brewery wastewater for reuse
sludge, which requires disposal. The sludge can undergo a dewatering
treatment either by reconsolidated centrifugation, vacuum filtration, The discharged wastewater from the biological pretreatment process-
or in a pressure filter. es can be further treated. In this section various methods that may be used

biogas

three phase
effluent separator

gas cap baffles

gas bubbles

sludge granules

Sludge bed

influent

Fig. 2. UASB anaerobic process [34].


240 G.S. Simate et al. / Desalination 273 (2011) 235–247

Table 5 Table 6
Quality standards for rinse and cooling water, and aimed value for drinking water [1]. Typical characteristics of membrane processes [30].

Quality standard Quality standard Quality standard Process Operating Pore size Molecular weight Size cut-off
rinsing water cooling water drinking water pressure (bar) (nm) cut-off range range (nm)

COD (mgO2 L− 1) 0–2 0–2 0–2 Microfiltration b4 100–3000 N500,000 50–3000


Na+ (mg L− 1) 0–200 / 20 Ultrafiltration 2–10 10–200 1000–1,000,000 15–200
Cl− (mg L− 1) 50–250 / 25 Nanofiltration 5–40 1–10 100–20,000 1–100
pH 6.5–9.5 6.5–9.5 6.5–9.5 Reverse osmosis 15–150 b2 b200 b1
Conductivity (μs cm− 1) / / 400 (hyperfiltration)

/: Not specified.

to treat brewery wastewater for reuse are explored. It must be noted, membrane. The retained impurities remain in the retentate, which is
however, that recycling of regenerated water as brewing water is normally recirculated.
considered inappropriate and would require that drinking water Membranes can be classified according to their material of
standards are complied with [1]. Table 5 shows the most important construction [34]. There is a variety of materials that are used for the
standards for rinsing, cooling and drinking water [1]. Among the manufacture of membrane filters, e.g., ceramics and polymers [30,44].
parameters in Table 5, the most important parameter for recycling Polymer materials used for membrane manufacture are, for instance,
water or required to be measured is the COD [1,37]. COD is a measure of cellulose acetate, polyamides, polypropylene, and polysulfone [34].
the oxygen equivalent of the organic matter content of a sample that is Ceramic membranes are usually manufactured from metal oxides, such
susceptible to oxidation by a strong oxidant [38]. The COD is considered an as alumina, often using some form of a sol–gel process.
appropriate index for showing the amount of organics in water [39]. The In wastewater treatment, the use of nanofiltration/reverse osmosis for
COD value of a wastewater mainly represents the biodegradable and non- organic/salt removal is normally practiced [45]. Nanofiltration (NF) is
biodegradable organic components (Fig. 3), although inorganic com- actually a relatively recent membrane filtration process used most often
pounds may be significant in certain cases [37]. However, in general, with low total dissolved solids water such as surface water and fresh
brewery effluents are easily biodegradable with BOD/COD ratio in the groundwater, with the purpose of softening (polyvalent cation removal)
range 0.6–0.7 [19,20,36]. The organic components in the brewery effluent and removal of disinfection by-product precursors such as natural organic
(expressed as COD) consist of sugars, soluble starch, ethanol, volatile fatty matter and synthetic organic matter [46]. The nominal pore size of the
acids, etc [1,36]. membrane is typically about 1 nm. However, nanofilter membranes (just
like other membranes) are typically rated by nominal molecular weight
4.1. Membrane filtration cut-off (MWCO) rather than nominal pore size. The MWCO is an
expression of the retention characteristics of the membrane in terms of
The separation by porous membranes is of great interest in molecules of known sizes [44]. The nominal MWCO of the membrane may
environmental and chemical engineering processes [40–42]. In fact, be defined as the relative molecular mass of the component that is
filtration technology is considered as an integral component of drinking rejected by 90% [47]. In other words, MWCO is an attribute of the pore size
water and wastewater treatment applications [43]. Membrane filtration and is related to the rejection of a spherical solute of a given molecular
can be divided into four categories, depending on the effective pore size of weight [48]. The reason that the word ‘nominal’ is used is that the shape
the membrane, and hence the size of the impurities removed. In order of and charge on the molecule will influence its rate of migration through the
decreasing pore size, they are as follows: microfiltration, ultra filtration, membrane [44]. The MWCO is typically less than 1000 atomic mass units
nanofiltration, and hyperfiltration. Table 6 summarizes the essential (daltons). The NF is a cross-flow filtration technology which lies
features of these processes, such as pore size and operating pressure [30]. somewhere between ultrafiltration (UF) and reverse osmosis (RO)
However, the characteristics listed in Table 6 are not exhaustive, thus (Table 6). These membranes are able to remove particles below 100 nm
different ranges may be quoted elsewhere. in size. In addition, the transmembrane pressure (pressure drop across the
Fig. 4 shows two ways of operating a membrane filter, i.e., dead end membrane) required (up to 3 MPa) is considerably lower than the one
filtration and cross-flow filtration. In dead-end filtration, all of the used for RO, thus reducing the operating cost significantly.
feed water flows through the membrane (as permeate) so that all Braeken et al. [1] used NF in an attempt to treat brewery wastewater
impurities that are too large to pass through the pores accumulate in for recycling. The results of this study showed that the removal of COD,
the filter module. Some means of removing these is necessary. Cross- Na+, and Cl− (averaging 100%, 55% and 70% removal, respectively) with
flow filtration involves flowing the feed water parallel to the NF was sufficient for the biologically treated wastewater, whereas the
membrane surface, with only a proportion passing through the other three wastewater streams (bottle rinsing water, rinsing water of

Total Organic Carbon


(TOC)

Chemically oxidisable
Non-oxidisable
(COD)

Biologically degradable
Non-biologically degradable
(BOD)

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


G.S. Simate et al. / Desalination 273 (2011) 235–247 241

pressure
(a) pressure
(b)

Filte caker retentate


feed

membranes
permeate
permeate

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

the bright beer reservoir, and rinsing water of the brewing room) were requires. Furthermore, it requires no regenerating chemicals, which
not suitable for recycling using NF. These results clearly show the means no additional salts have to be added for wastewater
importance of pretreatment processes. neutralization.
Though nanofiltration is vital for the treatment of wastewaters, the
major limitation is fouling. However, coagulation/flocculation can be
used to enhance nanofiltration performance towards water reuse and 4.2. Non-thermal quenched plasma
minimization of fouling [49]. This is because coagulation/flocculation
reduce the concentration of impurities and hence improve the Plasma is a highly ionized gas that occurs at high temperatures.
permeate flux after sedimentation. The intermolecular forces created by ionic attractions and repulsions
As mentioned earlier, RO is normally practiced for the removal of give these compositions distinct properties; for this reason, plasma is
organic/salt in wastewaters [45]. The RO is the tightest possible described as a fourth state of matter [55]. Like gas, plasma does not
membrane process in liquid/liquid separation and therefore produces have a definite shape or a definite volume unless enclosed in a
the highest water quality of any pressure driven membrane process container; unlike gas, in the influence of a magnetic field, it may form
[34]. The RO membranes are classified by percentage rejection of NaCl structures such as filaments, beams and double layers. Some common
and ranges from 95 to 99.5% [34]. The success of RO in large-scale plasmas are stars and neon signs. In summary, a plasma usually results
desalination and municipal wastewater treatment has led many from the increase of the energy of a gas provided by various sources,
industries to view this technology as a means of pollution abatement such as electric, magnetic, mechanical (shock waves and ultrasound),
and cost savings through reuse [50]. In fact wastewater treatment thermal or even optical (laser) sources [56]. A part of the gaseous
using RO have been employed in chemical, textile, petrochemical, matter is thus changed from the starting molecules or atoms to an
electrochemical, pulp and paper, and food industries as well as for electrically neutral mixture of ions (anions and cations) and electrons,
municipal wastewater [51]. Madaeni and Mansourpanah [39] involving other heavy species and photons [56].
reviewed several studies of RO applications and found that RO may Doubla et al. [5] reported the use of humid air plasma created by an
decrease the COD of the effluent by more than 90% or completely. In electric gliding arc discharge in humid air to lower organic pollutants
fact, tests to reduce COD values showed that RO is the best method to in brewery wastewater. The gliding arc discharge in humid air
separate organics from water. RO is also usually combined with other generates .NO and .OH radicals, which have strong oxidizing
physical separation techniques, as well as biological and physiochem- characteristics. The .OH radical is a very powerful oxidizing agent
ical treatment, to produce effluents suitable for reuse. For example, a [E0(.OH/H2O) = 2.85 V/NHE] and thus responsible for oxidation
combination of ultrafiltration (UF) and RO have produced high quality reactions with organic targets, both due to its own properties and to
water [52,53]. its derivative and/or parent molecule H2O2 as shown in Eq. (1) [5]:
In studies by Madaeni and Mansourpanah [39], biologically treated
wastewater from an alcohol manufacturing plant having COD in the
H2 O2 ↔2  OH ð1Þ
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 flux (33 kg m− 2 h− 1) and extreme Initially, NO leads to the formation of nitrite in neutral mediums,
COD removal (100%). In another study, brewery bio-effluent was but is further oxidized to nitrate ions as stable species. Additionally,
obtained using an internal aerobic membrane bioreactor (internal the high standard oxidation-reduction potentials of the HNO2/NO
MEMBIOR) [54]. In this study, the COD of brewery wastewater varied (1.00 V) and NO− 3 /HNO2 (1.04 V) systems reflect the oxidizing power
strongly from 1500 to 3500 mg L− 1, but after the internal MEMBIOR of the nitrate ion [5]. In other words, the nitrate ions participate in the
the COD was around 30 mg L− 1 regardless of the COD fluctuations of oxidizing characteristics of the humid air plasma.
the influent. The suspended solids were completely retained by the In the study by Doubla et al. [5], the BOD removal efficiency of the
flat plate membrane. This made the effluent perfectly suited for re-use process with brewery industrial waters of BOD values of 385 and
via reverse osmosis as process water, omitting the need for expensive 1018 mg L− 1 were 74 and 98%, respectively. The alkaline wastewaters
pretreatment methods. were also rapidly neutralized due to pH lowering effect of the plasma
In summary, a review of several literatures has shown that RO is a treatment emanating from the production of nitrate ions [56]. This
preferred conditioning method for the brewing industry because of process can be coupled with biological process treatments to further
its environmentally friendly applications, its simplicity regarding lower the organic pollutant concentration more easily and rapidly to
automation, its user-friendly aspects, and the small amount of space it an acceptable level for reuse [5].
242 G.S. Simate et al. / Desalination 273 (2011) 235–247

Table 7
Mean operating criteria of anaerobic digestion-ultrafiltration plants treating various
industrial effluents [45].

Operating parameter/ Brewery Wine Malting Egg Maize


results distillery process process

Volume of digester (m3) 0.05 2.4 3.0 80 2610


Operational period (month) 3 18 5 8 36
Feed COD (kg/L) 6.7 37 3.5 8 4–15
Permeate COD (kg/L) 0.18 0.26 0.80 0.35 0.30
COD removal (%) 97 93 77 95 97
Space load rates (kg COD/m3·d) 17.0 12.0 5.0 6.0 3.0
Sludge load rate (kg COD/kg VSS·d) 0.7 0.58 0.5 0.33 0.24
Fig. 5. Simplified schematic description of the MBR process [57]. HRT (day) 0.8 3.3 0.8 1.3 5.2
Temperature (°C) 35 35 35 30 35
MLSS (kg/m3) 30–50 50 10 10–30 23
4.3. Membrane bioreactor Membrane area (m2) 0.44 1.75 9.6 200 800
Flux (L/m2·h) 10–40 40–80 20–40 15–30 10–70
Depletion of water resources, increasing water price, and stringent Inlet pressure (kPa) 340 400 500 500 600
Crossflow velocity (m/s) 1.5 2.0 1.8 1.8 1.6
regulation has caused the development of various combinations of
Tube diameter (mm) 9.0 12.7 9.0 12.7 9.0
membranes with other conventional treatment components [45].
Membrane bioreactor (MBR) is becoming one of such flourishing
technology in water and wastewater treatment fields [45]. The MBR
therefore need to be cleaned frequently [34]. Membrane fouling can be
combines two proven technologies, i.e., enhanced biological treatment
classified as reversible and irreversible [65]. It results from interaction
using activated sludge, and membrane filtration as shown in Fig. 5 [57].
between the membrane material and the components of the activated
Depending on how the membrane is integrated with the bioreactor,
sludge liquor, which include biological flocs formed by a large range of
two MBR process configurations can be identified: side-stream and
living or dead microorganisms along with soluble and colloidal
submerged (Fig. 6). In side-streams MBRs, membrane modules are placed
compounds. Fouling leads to a significant increase in hydraulic resistance,
outside the reactor, and the reactor mixed liquor circulates over a
manifested as permeate flux decline or TMP increase when the process is
recirculation loop that contains the membrane. In submerged MBRs, the
operated under constant-TMP or constant-flux conditions respectively.
membranes are placed inside the reactor, submerged in the mixed liquor.
The organic fouling of the membrane is mainly dependent on several
The side-stream MBRs are more energy intensive compared to submerged
factors including the following [65]: (1) the components of organic matter
MBRs [34,58] due to higher operational transmembrane pressures (TMP)
such as colloidal fraction and dissolved fraction, (2) organic characteristics
and the elevated volumetric flow required to achieve the desired cross-
such as hydrophobicity and molecular size and configuration, (3) solution
flow velocity [58]. However, submerged MBRs use more membrane area
chemistry such as pH, divalent ions concentration and ionic strength, and
and operate at lower flux levels [34].
(4) membrane properties such as pore size and surface roughness. In
The MBR has been studied not only for wastewater but also for
practice, membrane fouling can be controlled by two types of approaches,
drinking water treatment [59,60], and is applied to municipal wastewater
i.e., (1) periodical air scouring, backwashing and chemical cleaning [67],
treatment at full scale [61]. Li and Chu [59] found that nearly 60% of
and (2) the addition of adsorbents and pretreatment by coagulation
influent total organic carbon (TOC) was removed by MBR, accompanied
[68,69]. A recent study has shown that direct addition of a coagulant in the
by more than 75% reduction in trihalomethanes formation potential
bioreactor was able to mitigate membrane fouling [66]. The integration of
(THMFP). The MBR technology is also applied to the brewery wastewater
coagulation into MBR is termed membrane coagulation bioreactor
for reuse [32]. The COD reduction in MBR influent (i.e., UASB reactor
(MCBR). In fact, the most important trend in the development of
effluent ranging from 500 to 1000 mg O2 L− 1) of up to an average of 96%
membrane filtration for water treatment is the integration of different
was reported by Dai et al. [32]. Brewery wastewater was also conducted
pretreatment strategies to improve the performance of low pressure
by various other researchers [62–64]. In most of these studies, significant
membranes [22].
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 4.4. Combined anaerobic and aerobic treatment
shows the operating parameters and some of the results of the anaerobic
digestion-ultrafiltration process [45]. Anaerobic and aerobic treatments are often combined in brewery
Just like other membrane separation processes, membrane fouling is wastewater treatment [16,70,71]. As shown in Fig. 7, there are essentially
the most serious problem affecting system performance of MBRs and, four types of integrated anaerobic–aerobic bioreactors [72]. The attributes

wastewater wastewater

membrane
unit
permeate

bioreactor permeate bioreactor

Side-stream MBR Submerged MBR


Fig. 6. Membrane bioreactor configurations [57].
G.S. Simate et al. / Desalination 273 (2011) 235–247 243

Anaerobic-aerobic
treatment

Conventional Anaerobic-aerobic Integrated anaerobic-


anaerobic-aerobic system using high aerobic bioreactors
system rate bioreactors

Integrated bioreactors Integrated bioreactors Anaerobic-aerobic Combined anaerobic-


with physical separation without physical Sequencing Batch aerobic culture
of anaerobic-aerobic separation of anaerobic- Reactor (SBR) system
zone aerobic zone

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

of integrated anaerobic–aerobic bioreactors are as follows [36]: Firstly, in functionalized CNTs to adsorb various impurities from wastewater
the anaerobic reactor the bulk of the COD, 70–85%, is converted into biogas can be extended to the removal of COD from brewery wastewater.
on a small surface area. Secondly, in an aerobic/anoxic post-treatment A review of the literature has shown that although CNTs have been
step, up to 98% of the COD and nutrients are removed. Furthermore, some proven to possess good potential as superior adsorbents, to the best of
of the important advantages of combined aerobic/anaerobic treatment of the authors' knowledge no published work is available regarding their
brewery effluent over complete aerobic include a positive energy balance, use as coagulants and/or flocculants. However, it can be theorized that
reduced (bio)sludge production and significant low space requirements if CNTs can adsorb on separate colloidal particles, then the particles
[16]. Recent development of tall slender anaerobic (e.g., internal can be drawn together; a phenomenon known as bridging floccula-
circulation reactors) and aerobic (e.g., airlift reactors) reactors allows for tion. Furthermore, the adsorption of CNTs onto particle surfaces can
extreme compact effluent treatment plant design still meeting stringent also result in charge neutralization, resulting in a near zero net charge.
requirements of surface water quality [16]. Once the surface charge has been neutralized, the ionic cloud
dissipates and the electrostatic potential disappears so that the
4.5. The use of carbon nanotubes contact among colloidal particles occurs freely. Charge neutralization
is easily monitored and controlled using zeta potential [97]. From the
Since the ‘rediscovery’ of carbon nanotubes (CNTs) in 1991 [73] by two phenomena above (adsorption and coagulation), it can be
Iijima [74], several researchers worldwide cutting across all disciplines ascertained that for the treatment of wastewaters (including brewery
have embarked on stimulating research to utilize the myriad unique wastewaters) containing both dissolved and suspended organics,
properties of these nanomaterials. The CNTs consist of honeycomb CNTs may well be applied to remove dissolved organics by adsorption,
structures of graphene sheets rolled up into cylinders with a diameter of a and suspended solid organic by heterogeneous coagulation (bridging
few nanometers, but length of many micron or even centimeters [75,76]. and neutralization), at the same time.
A lot of methods and carbon sources for the growth of carbon nanotubes However, a lot of challenges arise in attempting to use CNTs in
have been actively pursued in the past few years, and these have been their present state as coagulants or flocculants. Firstly, the CNTs lack
outlined in several review papers [77–82]. dispersion and solubility. However, there have been several successful
There are typically two forms of CNTs according to the number of attempts to prepare water soluble carbon nanotubes by various
rolled up graphene layers that form the tube, i.e., single-walled carbon techniques [98–100], and improvements in their dispersivity through
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, field 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 efficiency for various organic pollu-
tants [87–91] and inorganic pollutants such as fluoride [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 affinity 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 Fig. 8. Models and representation of multi-walled CNT and single-walled CNT [82,83].
244 G.S. Simate et al. / Desalination 273 (2011) 235–247

functionalization [101]. Secondly, the CNTs are very expensive, thus 4.7. Microbial fuel cells
they require to be regenerated after use. If the CNTs are applied in the
form of slurry, an efficient separation process downstream such as Recently, brewery wastewater has been simultaneously treated
membrane filtration is needed to retain and recycle the CNTs. while generating electricity from organic matter in wastewater
Retention of nanomaterials is critical not only because of the cost [33,110–112]. This device that treats wastewater and generates
associated with loss of nanomaterials, but also, and more importantly, electricity at the same time is termed microbial fuel cell (MFC)
because of the potential impacts of nanomaterials on human health [113,114]. The MFC is a combined system with anaerobic and aerobic
and ecosystems [102–104]. characteristics. They are designed for anaerobic treatment by bacteria
in the solution near the anode, with the cathode exposed to oxygen
4.5.2. Nanofilters (or an alternative chemical electron acceptor). Electrons released by
The successful fabrication of carbon nanotube filters have been bacterial oxidation of the organic matter are transferred through the
reported [105]. These filtration membranes consist of hollow cylinders external circuit to the cathode where they combine with oxygen to
with radially aligned carbon nanotube walls. Srivastava et al. [105] form water [33]. Consequently, a combination of anaerobic–aerobic
efficiently carried out filtration of heavier hydrocarbon species, CmHn processes can be constructed using a double-chamber MFC, in which
(mN 12), from hydrocarboneceous oil for example, petroleum CmHn the effluent of the anode chamber could be used directly as the
(n=2m+2, m=1 to 12), and in the removal of Escherichia coli from influent of the cathode chamber so as to be treated further under
drinking water and filtration of the nanometer-sized poliovirus. The high aerobic conditions to improve the wastewater treatment efficiency
organic content of brewery effluent is classified as high strength waste in [112].
terms of COD, from 1000 mg L− 1 to 4000 mg L− 1 and BOD of up to Feng et al. [33] found that with an influent COD of brewery wastewater
1500 mg L− 1 [6]. This makes brewery wastewater a good candidate for of 2 250±418 mg L− 1, the COD removal efficiency was 85% and 87% at
treatment with these CNT filters. 20 °C and 30 °C, respectively. Performance of sequential anode-cathode
Membranes that have CNTs as pores could be used in desalination and MFC achieved COD removal efficiency of more than 90% (e.g., COD of 1
demineralization. Billions of these tubes act as the pores in the membrane. 250±100 mg L− 1 was reduced to 60 mg L− 1) [112]. Furthermore, up to
A membrane filter possessing both super-hydrophobicity and super- 94% COD removal has also been reported by other researchers with this
oleophilicity was synthesized from vertically-aligned multi-walled carbon method [111]. Since high COD removal efficiencies were achieved in these
nano-tubes on a stainless steel mesh for the possible separation of oil and studies, it can be concluded that MFCs, particularly, sequential anode–
water [106]. Both super-hydrophobicity and superoleophilicity could be cathode type, can provide a new approach for brewery wastewater
obtained due to the dual-scale structure, needle-like nano-tube geometry treatment while offering a valuable alternative to energy generation.
on the mesh with micro-scale pores, combined with the low surface
energy [106]. The nano-tube filter could separate diesel and water layers, 4.8. Carbon
and even surfactant-stabilized emulsions. The successful phase separation
of the high viscosity lubricating oil and water emulsions was also carried The characteristics of a water treatment plant have a great
out. The separation mechanism can be readily expanded to a variety of influence on the characteristic properties of the end product. Even
different hydrophobic and oleophilic liquids such as brewery wastewater. when the incoming process water is from a municipal drinking water
source, the water may contain residual tastes, odors, disinfection by-
products, and free and combined chlorine. Molecules with carbon–
4.6. Electrochemical methods
sulfur bonds often smell and taste bad, but these are often
preferentially adsorbed on carbon. The same is true of molecules
Electrochemical method of wastewater treatment came into existence
with aromatic rings. Carbon's de-chlorinating capability results from
when it was first used to treat sewage generated onboard by ships [107].
its ability to act as a reducing agent that reacts with strong oxidizing
Thereafter, the application of electrochemical treatment was widely
agents such as hypochlorous acid or chlorine dioxide.
received in treating industrial wastewaters that are rich in refractory
The treatment of tannic acid for flavor and odor removal is a process
organics and chloride content [108,109]. The electrochemical method of
application in brewing where carbon adsorption is used. Carbon is also
treatment is well-suited for degrading biorefractory organic pollutants,
used to remove color from malts for use in clear beers and other flavored
because it is possible to achieve partial or complete decomposition of the
malt beverages. Several granular and powdered products can be used for
organic substances. The electrochemical methods of treatment are
this type of application. Activated carbons are an effective treatment to
favored, because they are neither subject to failure due to variation in
assure water that is contaminant, taste, and odor free.
wastewater strength nor due to the presence of toxic substances and
require less hydraulic retention time. Vijayaraghavan et al. [108]
5. Discussion and synthesis of findings
developed a novel brewery wastewater treatment method based on in
situ hypochlorous acid generation. The generated hypochlorous acid
This section provides a discussion and synthesis of the review
served as an oxidizing agent that destroyed organic compounds present in
findings of this paper. This discussion includes a comparison and
the brewery wastewater. An influent COD value of 2470 mg L-1 was
possible integration of the processes and technologies. In a nutshell,
reduced to 64 mg L− 1 (over 97% reduction). The hypochlorous acid was
the discussion primarily addresses the following two fundamental
generated using a graphite anode and stainless steel sheet as a cathode in
questions: (a) How do the processes and technologies compare with
undivided electrolytic reactor. Initially, during electrolysis, chlorine was
each other? (b) Can they be integrated with each other, and if so, what
produced at the anode and hydrogen gas at the cathode. Since the anode
are the potential challenges and benefits?
and cathode were kept in an undivided electrolytic reactor, the chlorine
that was generated undergoes a disproportionation reaction, resulting in
5.1. Comparison of processes and technologies
hypochlorous acid [108] as indicated in Eq. (2) below:

Cl2 þ H2 O→HOCl þ HCl ð2Þ This review highlighted the need for treatment of brewery
wastewater, and looked at various methods that may be used to
Further disproportion of OCl− to ClO− 3 was accelerated at high safely and cost-effectively treat brewery wastewater for reuse. In
temperature (75 °C) and under alkaline conditions (Eq. (3)). addition, some challenges associated with these methods were
discussed. It should be noted and emphasized herein that the
− − −
3OCl →ClO3 þ 2Cl ð3Þ treatment of brewery wastewater effluent is a costly and relatively
G.S. Simate et al. / Desalination 273 (2011) 235–247 245

complex activity; particularly with the need to meet governmental applications with good economics and high degree of energy
regulations and environmental friendliness [6,115]. Conventional efficiency. Coupling these processes together as two or three stage
separation methods such as coagulation/flocculation, centrifugation, processes would be more appropriate. Subsequently, different process
and gravity separation exhibit shortcomings including incomplete combinations are proposed and discussed.
COD removal. These methods are generally associated with low The demand for renewable energy in our society is ever increasing
separation efficiency, high operation costs, large setup size, and the [111]. Therefore, the MFCs is recommended to be the first pretreat-
generation of secondary pollutants. It was also noticed that biological ment stage of every integrated process particularly with filtration
treatment is widely applied as a pretreatment method. Generally, techniques. MFCs have operational and functional advantages over
aerobic treatment has been applied for the treatment of brewery the technologies currently used for generating energy from organic
wastewater and recently, anaerobic systems have become an matter [111]. First, the direct conversion of substrate energy to
attractive option, among other advantages, because of their high electricity enables high conversion efficiency, unlike the biological
COD content removal. Though these biological methods have found processes reactors where the metabolized products (e.g., NH3) have to
widespread application for the treatment of the characteristically high be used in boilers for energy generation. Second, MFCs operate
organic content of the brewery wastewater, further treatment is efficiently at ambient temperature. Third, an MFC does not require gas
required for water reuse. treatment because the off-gasses of MFCs are enriched in carbon
Nevertheless, this review has shown some promising results with dioxide and normally have no useful energy content. Fourth, MFCs do
quenched plasma, MBR, electrochemical methods, and microbial fuel not need energy input for aeration provided the cathode is passively
cells. These methods have great potential to be used to treat brewery aerated [116]. Fifth, MFCs have potential for widespread application in
wastewater for reuse and needs to be further investigated with locations lacking electrical infrastructures and can also operate with
respect to different challenges and opportunities involved. For diverse fuels to satisfy energy requirements. The high COD removal
example, beer brewery wastewater might be a good source for efficiency (see Table 8) could also reduce the load in other coupled
electricity generation in MFCs due to its nature of high carbohydrates stages. The uses of other techniques as first stages in an integrated
and low ammonium–nitrogen concentration. The authors have also process do not offer any foreseeable benefits.
noted that recent advances suggest that many of the recent problems Electrochemical methods can be well suited to be coupled in the
involving water quality could be solved or greatly ameliorated using latter stages of the integrated process. Sanitizing agents (often called
carbon nanotubes as sorbents. Therefore, it is expected that the disinfectants) which are present in brewery wastewater contain
brewery industry will also benefit from these discoveries. However, chlorine compounds. These compounds produce chlorine during
the knowledge required for the large-scale design and application of electrolysis and, thereafter, chlorine generates hypochlorous acid
the processes discussed in this review is perhaps still lacking. It is which oxidizes organic compounds. Chlorine is one of the most widely
further recommended to carry out some studies to establish estimated used disinfectants. It is very applicable and very effective for the
capital costs of these promising processes. deactivation of pathogenic microorganisms. Therefore, electrochem-
On the other hand, the application of membrane filtration (e.g., NF ical methods if coupled in the latter stages can serve as an organic
and RO) to drinking water treatment and wastewater reuse, though oxidation and disinfecting stage.
well established, has undergone accelerated development in the past Plasma methods though very effective (see Table 8), the process is
decade with the improvement in membrane quality and the decrease expensive because of the high energy requirements by the gas, and
in membrane cost. A very important trend in the development of the cost of energy sources such as laser. Therefore, if coupled with
membrane filtration for water treatment is the integration of different other methods, the processes can be very expensive.
pretreatment strategies to improve their performance. The RO, in CNTs have shown remarkable adsorption power. Combining CNTs
particular, has been shown to be an efficient and cost effective process with UF will result in substantial removal of organics. However, the
for the treatment of brewery wastewater for reuse. addition of CNTs would rapidly increase the transmembrane pressure
Table 8 shows a summary of some of the studies conducted on rapidly due to the formation of CNT cake on the membrane surface. In
brewery wastewater, showing the COD reductions, and whether the this case, CNTs may need to be of large enough diameters to reduce
effluent is suitable as a primary or secondary water based on the the transmembrane pressure effect. As for the MBR or filtration in
criteria listed in Table 5. It must be noted, however, that these studies general, fouling mitigation can potentially be done by coupling
had different experimental designs. coagulation and flocculation to the process [117].

5.2. Integration of processes and technologies 6. Summary

It can be been seen in Table 8 that none of the methods (apart from Water is a common element in the lives of all people and societies.
RO) can be used individually in brewery wastewater treatment Water has been the foundation and sometimes, the undoing of many

Table 8
Summary of brewery wastewater treatment processes.

Process Initial COD Final COD COD Potential use Reference


(mg/L) (mg/L) reduction
Primary Secondary
(%)
(process water) (non-process water)

Quenched plasma 1018a 18a 98 No No [5]


UASB (*1) 1947–3079 Not given 73–91 No No [21]
Aerobic reactor Not given Not given 90–98 No No [16]
Combined bioreactor (*1) Not given Not given 98 No No [36]
Membrane bioreactor 500–1000 40 96 No No [32]
Electrochemical method 2470 64 97 No No [107]
Microbial fuel cells (*2) 1710 105 94 No No [110]
Nanofiltration 3692 143 96 No No [1]
Reverse osmosis 850 0 100 Yes Yes [39]
a
BOD figures; (*1) has added value of energy production from biogas; (*2) has added value of electricity production.
246 G.S. Simate et al. / Desalination 273 (2011) 235–247

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