Journal of Environmental Chemical Engineering 8 (2020) 104418

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Journal of Environmental Chemical Engineering

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

Minimal Liquid Discharge (MLD) and Zero Liquid Discharge (ZLD)

strategies for wastewater management and resource recovery – Analysis,
challenges and prospects
Argyris Panagopoulos *, Katherine-Joanne Haralambous
School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechniou St., Zografou, 15780, Athens, Greece

A R T I C L E I N F O A B S T R A C T

Editor: Teik Thye Lim Brine is a saline wastewater generated from several industries (e.g., desalination, energy and oil production) and
its disposal can have adverse environmental impacts. To address this issue, brine treatment seems to be a
Keywords: promising option to eliminate the wastewater discharge, while also recovering extra freshwater and valuable
Minimal liquid discharge materials such as salts. This can be achieved through minimal liquid discharge (MLD) and zero liquid discharge
Zero liquid discharge
(ZLD) strategies. In this work, MLD and ZLD frameworks are analyzed and evaluated under 9 criteria (framework
Brine treatment
stages, technologies, freshwater recovery target, feed brine salinity, energy consumption of each technology,
High-salinity wastewater treatment
Resource recovery GHGs emissions, cost impact, resource recovery and social impact). Moreover, a case-study is presented under
Industrial wastewater treatment two different scenarios, Scenario 1 (MLD system) and Scenario 2 (ZLD system). Results showed that the energy
consumption of the ZLD system is 10.43 kW h/m3 which is 1.93 times higher than the energy consumption of the
MLD system (5.4 kW h/m3). The total freshwater recovery of the MLD system is 84.6 %, whereas the total
freshwater recovery of the ZLD system is 98.15 %. Overall, the results suggest that the MLD and ZLD strategies
can be valuable strategies for wastewater utilization, reuse, and resource recovery.

freshwater and have an average freshwater recovery of 40 %, according

1. Introduction
Increasing urbanization and industrialization have resulted in high
demands for freshwater in many regions of the world. Freshwater
shortages are one of the major international problems that pose a sig­
nificant threat to water quality, health, ecosystems, and economic
development [1]. Freshwater is extensively used in many industries,
thus generating large quantities of wastewater. When wastewater is
released into water bodies without proper treatment, it can cause sig­
nificant pollution that negatively impacts the marine environment and
hence public health [2,3,4,5]. Saline wastewater is commonly known as
‘brine’ or ‘concentrate’, comes from different sources such as desalina­
tion plant, oil and gas production industry, textile industry, food in­
dustry, leather industry, etc. and has become a major cause of pollution
and threat to aquatic ecosystems. The brine produced has a high salt
concentration (up to 400,000 mg/L total dissolved solids (TDS)) as well
as several toxic or non-toxic chemicals used in the processes [6,7,8,9,10,
11]. The quantity of brine produced per day by the different industries is
significantly high. Taking into account, for example, that desalination
plants worldwide currently produce about 142,000,000 m3/day of
to the authors, the desalination brine produced is estimated at 128,652,
000 m3/day [12]. It is worth noting that the previously mentioned
quantity of desalination brine produced per day is sizeable since it is
equivalent to the volume of water of 56,800 Olympic-style pools.
Currently, several disposal methods have adopted in brine management
such as sewer discharge, deep-well injection, surface water discharge,
evaporation ponds [6]. Nevertheless, these disposal strategies have
recently been considered unsustainable due to environmental negative
effects, stricter discharge standards and increased attempts to recover
useful resources from brine (brine mining) [13,14]. For instance,
evaporation pond requires a significantly large footprint area, deep-well
injection is inappropriate in countries with an intense seismic activity (e.
g. Greece), sewer discharge and land use are practiced only for limited
quantities of brine, and surface water discharge has a direct adverse
effect on the aquatic ecosystem [6]. This is why consideration is given to
alternative brine management approaches that are not based on disposal
but on minimizing waste (to achieve the maximum freshwater produc­
tion and the minimum solid waste production) [15]. In order to avoid
the negative aspects of brine rejection, increased attention is paid to
brine concentration and zero liquid discharge (ZLD) framework. Under

* Corresponding author.
E-mail address: argyrispan@hotmail.com (A. Panagopoulos).

https://doi.org/10.1016/j.jece.2020.104418
Received 4 July 2020; Received in revised form 21 August 2020; Accepted 21 August 2020
Available online 1 September 2020
2213-3437/© 2020 Elsevier Ltd. All rights reserved.
A. Panagopoulos and K.-J. Haralambous Journal of Environmental Chemical Engineering 8 (2020) 104418

Nomenclature LCAs Life-cycle assessments

MCr Membrane crystallization
Abbreviations MD Membrane distillation
BC Brine concentrator MED Multi-effect distillation
BCr Brine crystallizer MLD Minimal liquid discharge
COD Chemical oxygen demand MSF Multi-stage flash distillation
EC Electrocoagulation NF Nanofiltration
ED Electrodialysis OARO Osmotically assisted reverse osmosis
EDM Electrodialysis metathesis RES Renewable energy sources
EDR Electrodialysis reversal RO Reverse osmosis
EFC Eutectic freeze crystallization SD Spray dryer
FGD Flue gas desulfurization TDS Total dissolved solids
FO Forward osmosis TOC Total organic carbon
GHGs Greenhouse gases WAIV Wind-aided intensified evaporation
HPRO High-pressure reverse osmosis ZLD Zero liquid discharge
IEX Ion exchange

Table 1
Characteristics of brine effluents from different industries [9,6,24,25,26,27,28,29,30,31].
Source Total dissolved Osmotic Major ions Other parameters
solids (TDS) (mg/L) pressure (bar)

Brackish water 7,500-22,000 6.35-18.65 Ca2+ (600-1,900 mg/L), Mg2+ (300-1,600 mg/L), Na+ (900-5,000 mg/L), K+ (70- TOC (0-15 mg/L)
desalination 500 mg/L), Cl- (3,000-15,000 mg/L), SO2-4 (900-9,000 mg/L), HCO3- (800-1,400
mg/L)
2+ 2+
Seawater desalination 50,000-82,000 42.39 -69.53 Ca (500-900 mg/L), Mg (1,700-2,900 mg/L), Na+ (15,000-26,000 mg/L), K+ TOC (2-10 mg/L)
(500-900 mg/L), Cl- (20,000-44,000 mg/L), SO2-
4 (4,000-7,000 mg/L), HCO3- (100-
1,900 mg/L)
Textile industry 1,500-50,000 1.27-42.39 Ca2+ (50-600 mg/L), Mg2+ (50-1,700 mg/L), Na+ (220-3,500 mg/L), Cl- (2,000- COD (40-7,000 mg/L)
16,000 mg/L), SO2-4 (500-2,800 mg/L)
Flue gas 5,000-50,000 4.24-42.39 Ca2+ (700-4,800 mg/L), Mg2+ (1,100-5,400 mg/L), Na+ (600-5,200 mg/L), Cl- COD (50-400 mg/L)
desulfurization (1,500-28,000 mg/L), SO2-4 (1,500-8,000 mg/L), SiO2 (5-80 mg/L)
(FGD)
Oil and gas flowback 20,000-130,000 16.95-110.23 Ca2+ (1,000-3,800 mg/L), Mg2+ (50-300 mg/L), Na+ (10,000-15,000 mg/L), K+ COD (80-1,200 mg/L),
water (100-400 mg/L), Cl- (10,000-16,000 mg/L), SO2-
4 (4,000-7,000 mg/L), HCO3- (100- DOC (5-50 mg/L)
1,900 mg/L), Br- (10-400 mg/L), Ba2+ (50-250 mg/L), Sr2+ (200-1,400 mg/L), CO2-3
(100-900 mg/L)
2+ 2+
Oil and gas produced 5,000-400,000 4.24-339.18 Ca (400-18,100 mg/L), Mg (20-3,200 mg/L), Na (1,100-80,000 mg/L), K
+ +
COD (20-8,500 mg/L)
water (20-2,900 mg/L), Cl- (5,000-150,000 mg/L), SO2-
4 (10-200 mg/L), Ba
2+
(50-12,000
mg/L), Sr2+ (40-6,800 mg/L)
Landfill leachate 1,000-50,000 0.84-42.39 Ca2+ (100-1,800 mg/L), Na+ (300-19,000 mg/L), Cl- (400-22,000 mg/L), SO2- 4 (50- COD (40-7,800 mg/L),
4,000 mg/L), TOC (20-400 mg/L)
Dairy industry 8,000-120,000 6.78-101.75 Ca2+ (50-2,400 mg/L), Na+ (700-33,000 mg/L), Cl- (900-48,000 mg/L) COD (100-20,000 mg/L)
Municipal wastewater 600-4,000 0.50-3.39 Ca2+ (40-220 mg/L), Mg2+ (10-150 mg/L), Na+ (90-1,100 mg/L), K+ (15-110 mg/ COD (10-30 mg/L), TOC
L), Cl- (100-1,900 mg/L), SO2-
4 (85-300 mg/L), HCO3- (150-450 mg/L) (10-30 mg/L)

the ZLD framework, approximately 100 % of freshwater is recovered
and a solid salt is produced which can be disposed of in a more envi­
ronmentally friendly way [16,17,18,19,20]. In addition to ZLD, the
minimal liquid discharge (MLD) framework has recently attracted in­
terest due to lower capital costs and energy demands compared to the
ZLD framework, as the freshwater recovery goal is up to 95 % [21,22]. In
this review article, we analyze and evaluate the MLD and ZLD strategies
for wastewater management and resource recovery. Initially, the char­
acteristics of brine effluents and categories of pretreatment and treat­
ment technologies are analyzed and discussed. Subsequently, both MLD
and ZLD strategies are analyzed and evaluated under 9 criteria (frame­
work stages, technologies, freshwater recovery target, feed brine
salinity, energy consumption of each technology, GHGs emissions, cost
impact, resource recovery, social impact). Furthermore, a case-study is
presented under two different scenarios, Scenario 1 (MLD system) and
Scenario 2 (ZLD system). Finally, current challenges, prospects and
future research needs on MLD and ZLD systems are highlighted.
2. Characteristics of brine effluents and categories of treatment
technologies
2.1. Brine effluents
Brine is a saline reject stream containing dissolved salts, organic
matter, metals, nutrients and pathogenic substances. Many industries,
such as desalination plants, oil and gas production industries, textile
industries, dairy industries, etc., produce these reject streams [6,7,8,9,
10,11]. Table 1 illustrates the principal characteristics of brine effluents
from various industries. With regard to desalination brine, its compo­
sition depends on the quality of the feedwater, the technology category,
the recovery rate, the purity of the freshwater produced, the pretreat­
ment methods and the chemical additives (e.g., antiscalants, flocculants,
coagulants in the desalination industry) [23,6]. High recovery and
heavy use of chemical additives lead to a more concentrated and less
pure brine. Furthermore, it is interesting to mention that brine from
brackish water or seawater desalination plants presents low total
organic carbon (TOC), up to 15 mg/L. In contrast, industrial brine such
as brine from the textile industry can have chemical oxygen demand

2
A. Panagopoulos and K.-J. Haralambous
Table 2
Comparison of pretreatment technologies and processes used in MLD & ZLD systems.
Technology Removal targets Cost impacts
3
Chemical precipitation Hardness US$0.82–0.93/m
3
Chemical coagulation Organic matter US$0.09–0.12/m
Electrocoagulation (EC) Hardness, organic matter and silica US$0.25–0.35/m3
Ion exchange (IEX) Hardness and silica US$0.08–0.21/m3
Nanofiltration (NF) Hardness, organic matter and silica US$0.08–0.12/m3
(COD) of up to 7,000 mg/L. Industrial brines, as presented in Table 1,
have a wide range of characteristics as they depend on the activities of
each industry. Among others, brines from oil and gas production have
the highest total dissolved solids (TDS), reaching up to 400,000 mg/L
[10]. It should also be noted that differentiation in composition can be
observed even in brines from the same category of industry (e.g., dairy)
as a product is manufactured with different quality characteristics.
2.2. Pretreatment and treatment technologies
Before determining the appropriate treatment technologies for a
given brine effluent, an analysis of the various compounds present in
brine effluent is required. Based on the nature of the contaminations (e.
g., organic, inorganic, etc.), several processes and technologies can be
used for pretreatment. Pretreatment is necessary to address fouling is­
sues (e.g., organic, biological, physical, chemical) as these four fouling
mechanisms can have an adverse impact on the performance of the
treatment technologies under the MLD/ZLD frameworks. In particular,
scaling ions (Ca2+, Mg2+ and SO2-
4 ), organic matter, and silica (SiO2) are
the principal drivers of fouling [23,32]. With regard to hardness ions
(Ca2+ and Mg2+), chemical precipitation is the most commonly used
pretreatment process, as it can effectively remove hardness and thus
minimize membrane fouling from magnesium and calcium precipitates
[33,34]. Nonetheless, organic fouling and silica scaling are not suffi­
ciently addressed. In addition, a by-product is co-produced during
chemical precipitation which has to be disposed of, thus increasing the
economic costs even more [35,36]. However, extensive efforts are being
made to enhance the chemical precipitation (e.g., by adding seed ma­
terial to enhance the growth of crystals) or to seek alternative strategies
that may involve techniques of various kinds [37,38]. Even after these
drawbacks, chemical precipitation remains very important in MLD &
ZLD systems, as other pretreatment methods and technologies are still to
be thoroughly assessed to conclude on their technical and economic
sustainability. Concerning organic matter, chemical coagulation has
shown good results in removing organic matter from municipal brine
effluents [39]. However, the analysis revealed significant operating
costs due to the heavy use of chemicals and the demand for sludge
disposal [40,39]. An alternative to the chemical coagulation process is
electrocoagulation (EC) which produces lower volumes of sludge and
has a smaller footprint than chemical coagulation [41,42]. EC has ach­
ieved over 80 % removal of hardness ions in brine effluents, while
research studies have shown that EC can be used efficiently in organics
and silica removal, however, more research studies are needed to
investigate these aspects [43,44,42,45]. Ion exchange (IEX) is an effi­
cient process for hardness removal in brine effluents. This process has
shown particularly good results in desalination brine pretreatment while
being considered a cost-effective process (US$0.08–0.21/m3) [46,47].
The primary driver of the cost is the regeneration of the membranes, and
it has been proposed to recycle brine as a regenerant to minimize costs
[47,48]. However, the performance of the process is affected by the resin
type and the brine solution’s TDS, while the ability to remove silica
varies among IEX membranes [49,50]. To improve the efficiency of the
IEX process, the implementation of multiple resins to simultaneous
remove different substances has been proposed [51]. Nanofiltration
3
Journal of Environmental Chemical Engineering 8 (2020) 104418
Limitations References
- Performance is affected by the brine’s composition [36,35]
- A by-product is generated, and its safe disposal is therefore required
A by-product is generated, and its safe disposal is therefore required [40,39,94]
A by-product is generated (less than in chemical coagulation), [41,42,44]
and its safe disposal is therefore required
Performance is affected by the resin type and the brine solution’s TDS [47,48,49]
- Fouling problems [55,56,57,95]
- Limited to low-salinity brine effluents
(NF) is a membrane-based technology that has been used in the pre­
treatment of the brine since it is fairly reliable and does not produce
sludge [23,52,53,54]. Several schemes were evaluated, such as NF with
electrodialysis (ED) or NF with reverse osmosis (RO) [55,56,57]. NF has
the potential to address scaling ions, organic matter, and silica, ac­
cording to several studies [58,56,59]. Nevertheless, NF as a
membrane-based process poses fouling problems while its adoption is
limited to low-salinity brines (<55,000 mg/L TDS) due to osmotic
pressure constraints [6]. Overall, a summary of pretreatment processes
and methods is presented in Table 2.
The treatment technologies used in MLD & ZLD systems can be
grouped into two categories: membrane-based and thermal-based. The
membrane-based technologies include RO, high-pressure reverse
osmosis (HPRO), forward osmosis (FO), osmotically assisted reverse
osmosis (OARO), membrane distillation (MD), membrane crystallization
(MCr), ED, electrodialysis reversal (EDR) and electrodialysis metathesis
(EDM) [6]. While RO may be the most widely adopted desalination
technology, due to limitations in salinity (<70 g/L TDS) and low re­
covery (<50 %), RO is rarely used as the principal technology in MLD &
ZLD [60,61,62]. An improved version of RO called HPRO can concen­
trate the brine 1.7 times more but also has comparatively poor perfor­
mance with brine effluents; however, newly designed membranes have
the potential to boost HPRO performance [63,64,65]. More recently, a
new membrane-based technology called OARO has shown a higher re­
covery (up to 72 %) compared to RO/HPRO at higher feed salinities (up
to 140 g/L TDS). However, its economic cost is significantly high (US
$2.40/m3) since it includes multiple RO/FO stages [66,67]. FO is more
cost-effective compared to previously mentioned technologies and can
be used at even higher feed salinities (up to 200 g/L TDS). Nevertheless,
membrane problems and lack of generic draw solution are the primary
issues that hinder its usage [68,69] In addition to FO, two
thermal-driven membrane-based technologies, MD and MCr, have great
potential because they significantly increase the feed salinity concen­
tration to 350 g/L TDS; however, membrane issues (e.g., membrane
fouling and wetting) are also presented [70,71,72]. As far as
electrical-driven membrane-based technologies (ED, EDR, and EDM) are
concerned, these technologies are not as effective as FO and MD; how­
ever, they are effective in concentrating silica-contaminated brine ef­
fluents because silica is neutrally charged [73,74,75]. EDM is more
interesting of the three approaches, as it separates problematic salts
from the brine and hence improves recovery without the need for
multiple stages [76,77,78]. On the other side, thermal-based technolo­
gies include brine concentrator (BC), brine crystallizer (BCr),
multi-stage flash distillation (MSF), multi-effect distillation (MED),
spray dryer (SD), eutectic freeze crystallization (EFC) and wind-aided
intensified evaporation (WAIV) [6]. Concerning the commercial brine
treatment technologies, BC and BCr, while their performance is excep­
tional (up to 99 % freshwater recovery), both their costs (capital and
operational) are significantly high, resulting in the need for different
options [79,80,81,82]. For instance, evaporation technologies such as
MSF and MED are alternative options that have lower energy demands.
Nevertheless, scaling is a major issue for these systems, even when
pretreatment is performed [83,15,84,85]. SD is a commercial crystalli­
zation technology that can produce solid salt products with desired
A. Panagopoulos and K.-J. Haralambous Journal of Environmental Chemical Engineering 8 (2020) 104418

Table 3
Comparison of treatment technologies used in MLD & ZLD systems.
Technology Maximum feed brine Maximum freshwater Limitations Energy consumption Cost Impacts References
salinity (mg/L TDS) recovery (%) (kWh/m3)

RO 70,000 50 - Not effective as a stand-alone technology in 2-6 US$0.75/m3 [60,61,62]

brine treatment
- Membrane fouling issues
- Intensive pretreatment required
HPRO 120,000 50 - Membrane fouling issues 3-9 US$0.79/m3 [63,64,65]
- Intensive pretreatment required
OARO 140,000 72 - Multiple RO/FO stages 6-19 US$2.40/m3 [66,67]
- Lack of a generic draw solution
- Membrane fouling issues
- Intensive pretreatment required
FO 200,000 98 - Lack of a generic draw solution 0.8-13 US$0.63/m3 [68,69]
- Membrane fouling issues
- Intensive pretreatment required
MD 350,000 90 - Membrane fouling and wetting issues 39-67 US$1.17/m3 [70,71,72]
- Intensive pretreatment required
3
MCr 350,000 90 - Membrane fouling and wetting issues 39-73 US$1.24/m [70,71,72]
- Intensive pretreatment required
ED & EDR 200,000 86 - Energy cost increases with increasing feed 7-15 US$0.85/m3 [73,74,75]
salinity
- Membrane fouling issues
- Intensive pretreatment required
EDM 150,000 92 - Energy cost increases with increasing feed 0.6-5.1 US$0.60/m3 [76,77,78]
salinity
- Membrane fouling issues
- Intensive pretreatment required
BC 250,000 99 High capital costs due to the expensive anti- 15.86-26 US$1.11/m3 [79,80,81,
corrosion materials (stainless steel or titanium) 82]
BCr 300,000 99 High capital costs due to the expensive anti- 52-70 US$1.22/m3 [79,80,81,
corrosion materials (stainless steel or titanium) 82]
MSF 180,000 85 - Scaling issues 12.5-24 US$1.40/m3 [83,15,84,
- Moderate capital costs 85]
MED 180,000 85 - Scaling issues 7.7-21 US$1.10/m3 [83,15,84,
- Moderate capital costs 85]
SD 250,000 No recovery - Highly unlikely to be economically viable on a 52-64 US$0.09/kgsolid [86,87,88]
large scale. produced
- No freshwater recovery
EFC 250,000 98 - High capital costs 43.8-68.5 US$1.42/m3 [89,90]
- This technology hasn’t been applied extensively
in multicomponent brine solutions
WAIV 100,000 No recovery - No freshwater recovery 0.3-1 US$1.37/ [91,92,93]
- No selective salt production m3evaporated

quality standards. To utilize this advantage, however, the feed brine
effluent must contain specific ions, (e.g., Mg2+ and Cl-) to generate the
desired high-purity salt (e.g., MgCl2) and decrease the treatment cost
[86,87,88]. Unlike SD, EFC has no restriction in the feed composition
since it generates high-purity solid salts (>90 % purity). Even so, its
capital expenditures are high, and there are only a few studies on the
brine treatment aspect [89,90]. WAIV is a straightforward crystalliza­
tion technology for brine crystallization and has a small footprint.
However, just like the SD, this technology doesn’t recover freshwater
[91,92,93]. A summary of membrane-based and thermal-based treat­
ment technologies is presented in Table 3. Overall, both pretreatment
and treatment technologies are illustrated in Fig. 1.
3. Minimal and zero liquid discharge (MLD and ZLD)
frameworks
3.1. Concept and current status
Recently, the demand for freshwater has become very high, and
therefore alternative strategies to obtain freshwater have to be found.
One such solution is the wastewater recycling and reuse. This approach
allows for the recovery of both freshwater and other useful materials. In
addition, it is an approach that is based on the circular economy model
which is a modern sustainable development concept promoted by the
European Union [96,97]. Furthermore, increasing public awareness of
the adverse impacts of brine effluents on the environment has
contributed to the adaptation of stricter regulations for brine disposal
that may restrict several disposal methods in the coming years [98,99].
Under these conditions, treatment systems should be designed that can
maximize the freshwater recovery and achieve resource recovery by
minimizing the volume of the brine effluent (Fig. 2). Hence, the devel­
opment and adoption of ZLD systems can achieve this goal. ZLD systems
incorporate numerous desalination technologies to produce freshwater
and remove completely the liquid waste [16,100,17]. The freshwater
generated from the ZLD systems is of high purity and can be used for
domestic or industrial use. Besides the freshwater, the compressed solid
salt that is produced can either be sold, used by the industry itself, or
discarded in an environmentally friendly manner. In more detail, when
the technologies are properly selected, the production of multiple
high-purity salts can be achieved instead of a compact mixed solid salt
[6]. Early implementation of the ZLD systems started in the 1970s when
power plants near the Colorado River introduced ZLD systems due to the
increasing salinity of river water. As of now, most of the ZLD systems
around the world are operating in the US [60,101]. The global ZLD
market size reached US$0.71 billion in 2018 and is expected to reach US
$1.76 billion by 2026, demonstrating a compound annual growth rate of
12.1 % over the forecast timeframe. There are many companies involved
in the ZLD market all over the world, with the following being the main:
Condorchem Envitech (Spain), Aquarion Group (Switzerland), SafBon
Water Technology (US), Toshiba Infrastructure Systems & Solutions
Corporation (Japan), Arvind Envisol (India), Fluence Corporation
Limited (US), Veolia Water Technologies (France), Hydro Air Research

4
A. Panagopoulos and K.-J. Haralambous
Fig. 1. Classification of pretreatment and treatment technologies in the MLD and ZLD systems.
Fig. 2. Key motivations to adopt MLD and ZLD systems.
(Italy), Lenntech (Netherlands), Samco Technologies Inc. (India),
Aquatech (US), Shiva Global Environmental Private Limited (India)
[102]. Whereas for some industries ZLD strategy is a sustainable solu­
tion, it is not the most reasonable choice for all given the high costs. To
this end, when regulatory and environmental needs and requirements
are fulfilled, the MLD strategy appears to be a promising and more
cost-effective option for industries. As discussed in more detail below,
the MLD strategy is similar to the ZLD strategy because it uses common
technologies, but the technologies have been combined to recover up to
95 % of freshwater [22,103]. The General Motors vehicle assembly
5
Journal of Environmental Chemical Engineering 8 (2020) 104418
plant, which was built in San Luis Potosi (Mexico) in 2008, is an example
of the MLD strategy. It is a plant with an annual vehicle production
capacity of 160,000 and is located in an arid area, 400 km northwest of
Mexico City. By integrating various technologies and processes such as
RO, IEX, etc., the plant can turn up to 90 % of the wastewater into
reusable water, leaving less than 10 % of the liquid waste to be disposed
of in adjacent solar ponds for evaporation [104].
3.2. Analysis and assessment of the MLD and ZLD frameworks
This review article performs an analysis and assessment of the two
strategies for the management and utilization of brine effluents. The
assessment will be carried out using criteria covering all the aspects
(performance, economy, environment and society). The criteria used in
this study are: (1) framework stages, (2) technologies, (3) freshwater
recovery, (4) feed brine salinity, (5) energy consumption of each tech­
nology, (6) GHGs emissions, (7) cost impact, (8) resource recovery, and
(9) social acceptance (Fig. 3). A key feature of both MLD and ZLD sys­
tems is the number of stages that they consist of. A conventional ZLD
system is composed of four stages. The stages are (i) pretreatment, (ii)
preconcentration, (iii) evaporation, and (iv) crystallization (Fig. 4). The
pretreatment stage consists of membrane-based or chemical processes
aiming to remove contaminants that may adversely affect the perfor­
mance of the preceding stages [6,91]. Generally, the clearer the brine
effluent is, the less pretreatment is needed. Afterwards, in the second
stage, freshwater recovery and reduction of the effluent’s volume are
accomplished via membrane-based technologies. This stage is important
from an economic perspective, as it greatly decreases the size of the next
two very costly stages. Finally, freshwater recovery (up to 100 %),
reduction of the volume of the brine, total elimination of the liquid
waste and production of one or more solid products are accomplished in
the succeeding two stages primarily through thermal-based technologies
[6,105]. In contrast to the ZLD systems, MLD systems consist of 2 stages
(pretreatment and preconcentration) rather than 4 stages, as the fresh­
water recovery goal is set at 95 % (Fig. 5) [106]. As for the types of
A. Panagopoulos and K.-J. Haralambous Journal of Environmental Chemical Engineering 8 (2020) 104418

Fig. 3. The nine criteria used in the assessment of the MLD and ZLD strategies.

Fig. 4. The four stages in the ZLD framework. The stages are pretreatment, preconcentration, evaporation, and crystallization.

Fig. 5. The two stages in the MLD framework. The stages are pretreatment and preconcentration.

technology, MLD systems integrate only membrane-based technologies,

while ZLD systems implement both membrane-based and thermal-based
technologies [103]. Furthermore, it is important to emphasize that there
is a wide variety of technology combinations and arrangements in the
MLD/ZLD systems, and that having a standardized MLD or ZLD system is
not feasible. Hence, MLD/ZLD systems can incorporate more than two
technologies. The freshwater recovery target in the MLD systems is 95 %
while the freshwater recovery target in the ZLD systems is 100 %.
Treatment technologies with variable recovery rates exist in both ap­
proaches, from very low to very high or even without freshwater re­
covery (e.g., WAIV) [93]. Although the maximum feed brine salinity can
be the same (350 g/L TDS) for both frameworks, generally ZLD systems
typically have higher feed brine salinity limits than MLD systems. This is
associated with the last stage (crystallization stage) of the ZLD strategy
in which several crystallization technologies can treat high-salinity
brine effluents (over 250 g/L TDS) [107,6]. MLD systems are more
efficient than ZLD systems with respect to energy demands. This can be
explained by the fact that only membrane-based technologies are
implemented in the first systems. Membrane-based technologies use
electric energy and have energy consumptions ranging from 0.6 kW Fig. 6. The energy consumption of the technologies used in MLD and
h/m3 to 19 kW h/m3, as presented in Table 3. However, the only ZLD systems.
exception to that rule is the MD technology as it is a thermal-driven
membrane-based, having significant high energy consumption (39-69 energy-intensive systems, are associated with higher emissions than
kWh/m3) [108,81]. In addition to membrane-based technologies, ZLD MLD systems. For example, as reported in the literature, GHGs emissions
systems also have phase-changing thermal-based technologies that are in MED (18 kg CO2/m3 H2O) and MSF (24 kg CO2/m3 H2O) are multiple
associated with heat losses during evaporation and condensation [109, times higher than in RO (1.8 kg CO2/m3 H2O) since membrane-based
110]. As a result, the energy consumption of thermal-based technologies technologies have lower consumptions [50]. With regard to economic
starts at 7.7 kW h/m3 and can reach up to 72 kW h/m3 at the crystal­ costs, ZLD systems are more costly than MLD systems, as they have
lization stage (Fig. 6) [6]. High energy consumption is strongly linked thermal-based technologies such as MED, BCr, etc. The explanation
with air pollutants and greenhouse gases (GHGs) emissions since fossil behind this is that the materials of the thermal-based technologies must
fuels generate the required energy. Hence, ZLD systems, as more be made of corrosion-resistant metallic materials (e.g., super/hyper

6
A. Panagopoulos and K.-J. Haralambous
Fig. 7. Sale prices of different salts that can potentially be extracted from
brine effluents.
duplex stainless steels, titanium) and thus, as explained in a case-study
below, the capital costs are increasing significantly [84,111,112].
MLD systems subsequently have significantly lower costs than ZLD
systems but they can also be expensive as they frequently require
membrane changes and replacements. Although ZLD systems were
originally designed to eliminate liquid waste and recover as much
freshwater as possible, it has been perceived that useful resources such
as salts (e.g., sodium chloride, magnesium chloride) can be recovered
through appropriate technology combinations [6]. The salts produced
can either be sold or used internally by the industry, thereby reducing
the economical treatment expense in the ZLD/MLD systems. Fig. 7 il­
lustrates the sale prices of different salts which can potentially be
extracted from brine effluents [113]. Brine effluents are thus not
considered as waste to be rejected, but as a valuable resource that can be
transformed into a variety of valuable products such as freshwater and
salts. Society’s acceptance of ZLD and MLD systems is positive as both
systems support the transition from linear to the circular economy,
where waste production is kept to a minimum, low carbon dioxide
emissions are limited, and resource utilization is made more efficient
[114,115,116]. At the same time, industries using such brine treatment
and exploitation systems are becoming more environmentally friendly,
Table 4
Assessment of the MLD and ZLD frameworks.
No Criteria
1 Framework stages
2 Technologies
3 Freshwater recovery target
4 Feed brine salinity
5 Energy consumption of each technology
6 GHGs emissions
7 Cost impact
8 Resource recovery
9 Social impact
Fig. 8. The arrangement of the technologies used in the MLD system (scenario 1).
7
Journal of Environmental Chemical Engineering 8 (2020) 104418
and promoting the importance of recycling and environmental protec­
tion to the local community [117,118]. Overall, the results for the
analysis and assessment carried out for MLD and ZLD systems are
summarized in Table 4.
3.3. Case-study: MLD and ZLD scenarios
In order to have a better understanding of the two brine treatment
frameworks, we evaluate a case-study under two different scenarios.
Scenario 1 considers an MLD system comprising of RO and FO, whereas
Scenario 2 considers an ZLD system comprising of all Scenario 1 tech­
nologies (namely, RO and FO), but also two additional technologies, BC
and BCr. In particular, the technology arrangement in the MLD system is
RO-FO (Fig. 8), while the technology arrangement in the ZLD system is
RO-FO-BC-BCr (Fig. 9). The data and assumptions for the technologies
used in both scenarios are described in Table 5. For the first scenario, the
total freshwater recovery is 84.6 % and the energy required to recover
84.6 m3 of freshwater is 457.2 kW h. The energy consumption of the
MLD system is therefore 5.40 kW h/m3. In the second scenario, the ZLD
system is made up of exactly the same technologies (RO and FO), but the
brine produced by FO is imported for further treatment in BC and finally
in BCr. As a result, 6.16 m3 of freshwater with an energy consumption of
123.2 kW h are recovered from BC while 7.39 m3 of freshwater with an
energy consumption of 443.52 kW h are recovered from BCr. As a result,
the total freshwater recovery is 98.15 % and the energy required to
recover 98.15 m3 of freshwater is 1023.92 kW h. The energy con­
sumption of the ZLD system is therefore 10.43 kW h/m3 which is 1.93
times higher than the energy consumption of the MLD system. It is
therefore interesting to note that the energy consumption for the further
recovery of freshwater after the use of FO increases is increased by 7.74
times, as can be clarified by the sharp increase in Fig. 10. This is the
crucial point at which any industry should decide whether the prospect
of further treatment and the development of a ZLD system is worthwhile,
given that the cost of the next two technologies (evaporation and crys­
tallization) is between 60 and 70 % of the total capital cost [6].
3.4. Challenges and future prospects
While MLD/ZLD systems have the main objective of increasing the
production of freshwater and reducing waste generation up to zero (in
the case of the ZLD system), their adoption may contribute to unin­
tended environmental consequences. Typically, these systems aim
ZLD MLD
4 2
Membrane-based and thermal-based Membrane-based
up to 100 % Up to 95 %
up to 350,000 mg/L TDS up to 350,000 mg/L TDS
0.6-72 kW h/m3 0.6-69 kWh/m3
High Moderate
High Moderate
Yes Yes
Positive Positive
A. Panagopoulos and K.-J. Haralambous Journal of Environmental Chemical Engineering 8 (2020) 104418

Fig. 9. The arrangement of the technologies used in the ZLD system (scenario 2).

odors that may affect wildlife or perhaps even present a risk of leakage
Table 5 [119]. Consequently, in order to avoid potential spoilage from these
Data and assumptions used in the case-study. by-products, impervious liners and systematic monitoring systems are
Parameter Value needed [120]. Recently, in addition to the recovery of freshwater, a
Feed volume (m3) 100 recent approach is directed at the recovery of valuable resources. As far
Feed salinity (mg/L TDS) 35,000 as ZLD systems are concerned, there is a potential not to produce
Feed effluent source Seawater compact mixed solid salts, but to produce several solid salts of high
RO recovery (%) 40 purity. In this manner, we accomplish three objectives: (1) reduction of
RO energy consumption (kWh/m3) 4
costs and need for brine disposal (2) the opportunity to market the
FO recovery (%) 70
FO energy consumption (kWh/m3) 7 produced salts, while following a circular economy policy and (3) the
BC recovery (%) 40 opportunity to use the produced solid salts internally in the industry.
BC energy consumption (kWh/m3) 20 Several salts such as MgCl2, CaCO3, CaCl2, NaCl can be produced
BCr recovery (%) 40
depending on the feed composition, while the commercial sale price of
BCr energy consumption (kWh/m3) 60
these salts can range from US$65/ton to US$400/ton [113]. On the
other hand, while the need for brine disposal remains in MLD systems,
the high-purity concentrated streams can be used internally by the in­
dustry, thus lowering the cost of chemicals. As a result, a wide range of
MLDs and ZLDs can be designed to adopt a circular economy strategy
through the recovery, recycling and reuse of both freshwater and valu­
able resources [121,122,123]. As mentioned earlier, desalination tech­
nologies in MLD/ZLD systems consume massive quantities of energy,
resulting in considerable emissions of GHGs and air pollutants. To
address this challenge, the authors recommend the integration of
renewable energy sources (RES) or industrial waste heat with MLD/ZLD
systems. RES include solar energy, hydropower, wind power,
geothermal energy, etc. [124,71]. For example, as reported in the
literature, the GHGs emissions in RO powered by fossil fuels are 1.8 kg
CO2/m3 H2O, while the GHGs emissions in RO powered by wind power
are only 0.2 kg CO2/m3 H2O [50]. As a consequence, this practice is
considered to decrease GHGs associated with MLD/ZLD systems. Ac­
cording to the authors, future efforts should be made to improve the
multiple perspectives of the treatment systems. In particular, new ma­
terials with sophisticated characteristics, low-cost and cost-effective
materials, advanced system configurations, etc. may improve the effi­
ciency of the MLD and ZLD systems. In this effort, new membranes (e.g.,
Fig. 10. Energy consumption versus recovery rate in Scenarios 1 and 2. omniphobic, janus, superhydrophobic) have recently demonstrated
tremendous promise in this scope [125,126,127]. In addition, process
exclusively on the liquid waste elimination aspect of the treatment simulations, techno-economic assessments and life-cycle assessments
process. As a result, these systems generate mixed solid salts (in ZLD) or (LCAs) are required to assess the feasibility of the different MLD and ZLD
multi-component concentrated streams (in MLD). Hence, there is a need systems. Finally, the major issues in the MLD and ZLD systems are
to reject the very concentrated streams/mixed solid salts in evaporation outlined in Fig. 11, whereas the present and future prospects are illus­
ponds, however, this tactic poses a danger as these by-products create trated in Fig. 12.

Fig. 11. Major issues in the MLD and ZLD systems.

8
A. Panagopoulos and K.-J. Haralambous
Fig. 12. Present and future prospects in the MLD and ZLD systems.
4. Conclusions
In this review article, an analysis and evaluation of the MLD and ZLD
strategies under nine criteria is presented. Initially, the analysis revealed
that they are several pretreatment and treatment technologies that can
be combined to treat brine effluents from different industries. In addi­
tion to the positive environmental impacts of the two strategies, these
strategies help the transition from a linear economy to a circular econ­
omy, where valuable resources such as salts are recovered. ZLD systems
can be very effective in the treatment of brine effluents (up to 100 %
freshwater recovery); however, their viability is strongly limited by the
high capital and operating costs. On the other side, MLD systems have
lower freshwater recovery range (up to 95 %) but are more cost-effective
as they comprise only of membrane-based technologies. Furthermore,
the results of the case-study investigated showed that the energy con­
sumption of the ZLD system is nearly twice as high (10.43 kW h/m3) as
that of the MLD system (5.4 kW h/m3). In the coming years, several
aspects of both frameworks can be improved, while future research
studies should focus on coupling RES with MLD/ZLD systems or novel
materials/configurations for the brine treatment technologies. Overall,
the results suggest that MLD and ZLD strategies can be valuable
wastewater strategies.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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