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Process Safety and Environmental Protection 146 (2021) 656–669

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Process Safety and Environmental Protection

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Techno-economic assessment of minimal liquid discharge (MLD)

treatment systems for saline wastewater (brine) management and
treatment
Argyris Panagopoulos
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

Article history: The management and treatment of brine (saline wastewater) are of great importance, as its discharge
Received 13 October 2020 to the environment poses a significant threat. A new strategy called minimal liquid discharge (MLD)
Received in revised form 7 December 2020 appears to be a promising and more cost-effective option than zero liquid discharge (ZLD) as it uses only
Accepted 8 December 2020
membrane-based technologies, leading to up to 95 % freshwater recovery. This research study intro-
Available online 11 December 2020
duces and presents for the first time a techno-economic assessment of five MLD treatment schemes
that can be implemented in the brine treatment. The technologies included are reverse osmosis (RO),
Keywords:
high-pressure RO, forward osmosis (FO), osmotically assisted RO (OARO), and membrane distillation
Minimal liquid discharge (MLD)
Zero liquid discharge (ZLD)
(MD). Results showed that the MLD schemes costs ranged from US$0.79/m3 to US$1.36/m3 , while the
Brine management freshwater recovery ranged from 78 % to 89 %. In schemes 2 and 5, the implementation of MD substan-
High-Salinity wastewater treatment tially increased the energy consumption (>20 kW h/m3 ), however, these schemes were more economical
Industrial wastewater treatment (<US$1/m3 ) than the other 3 schemes. If the produced freshwater is sold, then the profit from the MLD
Techno-economic analysis treatment can reach up to US$2.21/m3 . Furthermore, the costs of MLD schemes are at the same level as
the subsurface water supplies, so MLD schemes can be valuable in countries relying on subsurface water
sources.
© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Sahebi et al., 2020; Bagheri et al., 2018). Recently, the increase in
the production of brine effluents has become a reason for concern.
Brine is a by-product of various industries such as desalina- As estimated by the author, the volume of brine generated only
tion plants, oil and gas industries, petrochemical industries, textile from desalination plants is approximately 128,652,000 m3 /day in
industries, steel industries, etc. Generally, brine effluents have high 2019 which is comparable to the water volume of 56,800 Olympic-
concentrations of total dissolved solids (TDS) (up to 400 g/L), heavy size swimming pools (Panagopoulos and Haralambous, 2020b). In
metals, and organics (Table 1) (Lester et al., 2015; Blondes et al., the previous decade, brine management practices included direct
2016; Jiménez et al., 2018; Panagopoulos and Haralambous, 2020b; disposal to oceans and rivers, deep-well injection, disposal into
sewage plants, evaporation ponds, and land use. Recently, these dis-
charge practices have been deemed unsustainable due to harmful
environmental impacts on the marine environment (e.g., eutroph-
Abbreviations: BC, Brine concentrator; BCr, Brine crystallizer; CA, Cellulose ication, alteration of the water’s pH/salinity) (Panagopoulos et al.,
acetate; CFRO, Counterflow reverse osmosis; COD, Chemical oxygen demand;
2019a; Kress, 2019; Panagopoulos, 2020a; Zhuang et al., 2019;
COMRO, Cascading osmotically mediated reverse osmosis; CTA, Cellulose triacetate;
EDM, Electrodialysis metathesis; EDR, Electrodialysis reversal; FO, Forward osmosis; Panagopoulos and Haralambous, 2020a). Furthermore, due to
GHGs, Greenhouse gases; HPRO, High-pressure reverse osmosis; IEX, Ion exchange; increasing environmental issues and stricter regulations, differ-
MD, Membrane distillation; MEC, Minimum energy consumption; MED, Multi- ent approaches for the management of the brine effluent are
effect distillation; MLD, Minimal liquid discharge; MMM, Mixed matrix membranes; being considered (Panagopoulos et al., 2019a; Sadhwani Alonso and
MSF, Multi-stage flash distillation; MVC, Mechanical vapor compression; OARO,
Osmotically assisted reverse osmosis; PA, Polyamide; PA-TFC, Polyamide thin-film
Melián-Martel, 2018; Roberts et al., 2012).
composite; PE, Polyethylene; PP, Polypropylene; PTFE, Polytetrafluoroethylene; PV, To this aim, research focuses on the implementation of a
Pervaporation; PVDF, Poly(vinylidene fluoride); RES, Renewable energy sources; zero liquid discharge (ZLD) framework, in which both freshwater
RO, Reverse osmosis; TDS, Total dissolved solids; TOC, Total organic carbon; TVC, and salt(s) are recovered without wastewater effluent genera-
Thermal vapor compression; ZLD, Zero liquid discharge.
tion. Approximately 100 % of freshwater is recovered under a
E-mail address: argyrispan@[Link]

[Link]
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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Table 1
Characteristics of brine effluents from different industries.

Industry Total dissolved solids Osmotic pressure Total organic carbon Chemical oxygen References
(TDS) (mg/L) (bar) (TOC) (mg/L) demand (COD)
(mg/L)

Seawater desalination 68,967 58.48 – – (Gude, 2018)

Oil and gas 39,450 33.45 420 – (Franks et al., 2009)
Mining 27,400 23.4 – – (Randall et al., 2011)
Steel 14,300 12.13 25–35 120−150 (Zhou et al., 2011)
Leachate 74,166 62.89 – 17,650 (Cingolani et al., 2017)
Textile 47,000 39.85 – 67,000 (Praneeth et al., 2014)

ZLD system and the solid salt(s) can be discarded in a more assisted reverse osmosis (OARO), high-pressure reverse osmosis
environmentally sustainable manner (DuPont, 2020; Hermsen, (HPRO), etc. (Nicolaisen, 2003; Padaki et al., 2015; Dyer et al., 2000;
2016). A ZLD system involves two or more desalination tech- Panagopoulos et al., 2019a). MLD framework is a strategy that, like
nologies combined into one hybrid system. In ZLD systems, both the ZLD framework, follows the circular economy model, a new
membrane-based and thermal-based technologies are commonly concept of viable development recently supported by the Euro-
implemented (Panagopoulos and Haralambous, 2020b). A conven- pean Union (Bonviu, 2014; Ismail and Matsuura, 2016). The General
tional ZLD system is one comprising of a thermal-based brine Motors Assembly Plant (San Luis Potosi - Mexico) is an example of
concentrator (BC) and a thermal-based brine crystallizer (BCr). The the MLD strategy as 90 % of the plant’s wastewater is recovered as
saline wastewater is processed initially into the BC and afterward freshwater with a combination of membrane-based technologies,
into the BCr. As a result, the freshwater produced is collected, while namely reverse osmosis (RO), ion exchange (IEX), etc. (Veolia Water
the remaining solid salts are either utilized or disposed of. Another Technologies, 2014).
ZLD system variation is the one incorporating the membrane-based To determine the feasibility and economic efficiency of ZLD
reverse osmosis (RO), before inserting the saline wastewater into schemes, numerous research studies have been carried out. Such
the BC. This modification resulted in a decrease in energy and cost studies have been carried out for desalination (Guo et al., 2016;
demands; however, due to osmotic pressure constraints, RO can- Wyk et al., 2020; Panagopoulos, 2020c), textile (Mohan et al., 2020;
not be implemented in the treatment of effluents with significantly Bahadur and Bhargava, 2019; Rajakumari and Kanmani, 2008), food
high salinity (Escobar and Schäfer, 2009; Sridhar, 2018). As a result, (Tabassum et al., 2015), oil and gas industries (Li et al., 2014; Han
the disadvantages of high energy usage and high capital costs have et al., 2020), etc. Nonetheless, it should be emphasized that all
limited the widespread adoption of ZLD systems (Mickley, 2008; results were exclusively linked to ZLD after a thorough literature
Yusuf, 2018; Xiong and Wei, 2017). Recently, some studies have review by the author. To my knowledge, this is the first time that
been carried out on the use of only membrane-based technologies MLD treatment schemes are introduced and assessed. This research
for ZLD desalination where MD is applied instead of thermal-based article provides an assessment of five MLD treatment schemes that
BC, BCr, etc. The main reason behind this selection is that MD does can be used in the treatment of desalination brine. All treatment
not face state-of-the-art technology limitations (namely, high pres- schemes consist only of membrane-based technologies (RO, HPRO,
sures in RO and material corrosion in thermal-based technologies) FO, OARO and MD) and are evaluated for their overall performance.
(Zhao et al., 2020; Schwantes et al., 2018). Furthermore, brine treatment through MLD schemes is compared
A novel alternative option for the sustainable management of with brine discharge practices and conventional water sources.
brine effluents is the minimal liquid discharge (MLD) framework. The research article is structured as follows: Section 2 describes
The MLD approach has recently gained attention as it has sig- both the MLD treatment schemes and the membrane-based tech-
nificantly lower energy and cost demands, while the freshwater nologies used in these treatment schemes, while the findings of
recovery target is very high (up to 95 %). In MLD systems, two the five MLD schemes assessment as well as the current status
or more desalination systems are combined into one hybrid sys- and prospects are discussed in Section 3. Finally, conclusions are
tem, as in ZLD systems. However, the implementation of only pointed out in Section 4.
membrane-based technologies in the MLD systems leads to sig-
nificant advantages (Panagopoulos and Haralambous, 2020b). The 2. Desalination technologies and MLD treatment schemes
lower energy and cost demands can be attributed to the fact
that membrane-based technologies are primarily used in MLD This section includes two paragraphs. The first presents the basic
treatment schemes in contrast to ZLD schemes that adopt both principles of the membrane-based technologies used in this study.
membrane-based and thermal-based technologies (Panagopoulos The second describes the five MLD treatment schemes which are
et al., 2019a). Thermal-based technologies such as multi-stage flash intended to treat the brine effluent from a seawater desalination
distillation (MSF), multi-effect distillation (MED), mechanical vapor plant.
compression (MVC), thermal vapor compression (TVC), etc. are
phase-changing processes with high energy intensity due to the
2.1. Membrane-based technologies
high enthalpy of water vaporization (40.65 kJ/mol) (Panagopoulos,
2020a; Jaffe and Taylor, 2018). Membrane-based technologies, on
2.1.1. Reverse osmosis (RO)
the other hand, have the advantages of low operational energy
The pressure-driven RO is the most widely adopted membrane-
requirements and a relatively simplified operating process. This
based process for desalinating saline water. In RO, hydraulic
is why membrane-based systems are used to separate a broad
pressure is used and saline water is divided into freshwater and
range of fluids such as water, wastewater, oil, chemical mixtures
a more saline effluent (brine) (Nagy, 2019; Panagopoulos et al.,
(e.g., separation of ethyl acetate/ethanol/water mixture), etc. (Meng
2019a). RO is currently considered to be the most energy-efficient
et al., 2020; Wu et al., 2020; Sridhar, 2018). Membrane-based
desalination process and has become the most widely used tech-
technologies include several technologies such as RO, electro-
nology for the desalination of seawater. In particular, with regard
dialysis (ED), electrodialysis reversal (EDR) pervaporation (PV),
to desalination technology, 74 % of desalination plants world-
forward osmosis (FO), membrane distillation (MD), osmotically
wide implemented RO in 2019 (Panagopoulos and Haralambous,

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 2. The conceptual diagram of RO and HPRO.

Fig. 1. The decade-by-decade timeline of the minimum reported energy consump-

tion in RO.

2020a). This large implementation can be explained by the fact

that the consumption of RO energy has been reduced from 16 kW
h/m3 in the 1970s to around 2 kW h/m3 in 2020, as illustrated in
Fig. 1 (Panagopoulos et al., 2019a; Panagopoulos and Haralambous,
2020a). Conventional seawater RO modules currently operate at a Fig. 3. The conceptual diagram of FO.
pressure of 50−82 bar while recovering 35–50 % of feed water as
freshwater and discharging brine of 60−70 g/L TDS (Alspach, 2014;
Panagopoulos et al., 2019a). Several research studies have been (ROTREAT, 2016; The Dow Chemical Co., 2017). The conceptual
conducted with regard to the fabrication of RO membranes. Poly- diagram of both RO and HPRO is presented in Fig. 2.
meric and ceramic membranes have been used extensively in the
desalination and water treatment industry. Nowadays, polyamide
(PA) is widely used in the manufacture of commercial RO mem- 2.1.3. Forward osmosis (FO)
branes. In particular, PA thin-film composite (PA-TFC) membranes In contrast to RO and HPRO, FO is a technology based on
have experienced tremendous growth and are dominant in the membranes that employs osmotic pressure gradients instead of
global market due to their exceptional salt-rejection and high- hydraulic pressure. In this process, a solution of relatively high
water flux (Kucera, 2015; Ismail et al., 2018). Even so, polymeric concentration (draw solution) is required to generate an osmotic
membrane implementation has encountered a range of critical pressure gradient over a semipermeable membrane, forcing water
challenges, such as fouling, scaling, the trade-off between water molecules to be transferred from the less concentrated solution to
permeability and salt rejection, etc. This has attracted the attention the more concentrated solution (draw solution) (Abdullah et al.,
of researchers to produce membranes from different materials and 2019; Panagopoulos et al., 2019a). Commercially, FO units able to
to improve membrane performance through a variety of membrane treat brine at a concentration greater than 70 g/L TDS have been
modification approaches (Kucera, 2015; Koohi and Rahimpour, developed by companies, such as Fluid Technology Solutions Inc.
2020). Thus, besides polymeric and ceramic membranes, mixed and Oasys Water Inc (Fluid Technology Solutions Inc., 2019; Eyvaz
matrix membranes (MMM) or hybrid membranes have been devel- et al., 2018). A great variety of draw solutions can be used such
oped. The primary aim of developing this novel material was to as organic, inorganic, nanoparticle-based solutions, etc. (Nguyen
combine the favorable properties of the two membrane types and et al., 2015; Cui and Chung, 2018; Zhou et al., 2015). Currently,
improve the overall effectiveness of the RO process (Kheirtalab there is no draw solution for each case, while the main issue in
et al., 2020; Hailemariam et al., 2020). this process is the draw solution recovery. Furthermore, concen-
tration polarization issues as well as fouling issues are present in
2.1.2. High-pressure osmosis (HPRO) this process. Nonetheless, the findings have shown significantly
Recent advances in RO membrane technology have now allowed higher freshwater recoveries (up to 98 %) than the technologies pre-
the production of HPRO systems capable of operating at pressures viously described (Johnson et al., 2018; Panagopoulos et al., 2019a;
of up to 120 bar (Panagopoulos et al., 2019a). HPRO shares the Liden et al., 2019). A large variety of membranes have been used for
same principles as RO, but HPRO can treat brine effluents at a con- FO, including cellulose acetate (CA), cellulose triacetate (CTA), PA-
centration greater than 70 g/L TDS. In the last 5 years, companies TFC, and biomimetic membranes (Linares et al., 2017; Shon et al.,
including Dow Chemical Company, Saltworks Technologies Inc, Pall 2015). The latest research efforts have concentrated on the sur-
Corporation, etc. have developed membranes and modules suit- face modification of current membranes and the manufacture of
able for higher pressures (Saltworks Technologies Inc., 2019; The innovative membranes to enhance antifouling and increase sur-
Dow Chemical Co., 2017, 2016). The major problem associated with face hydrophilicity (Panagopoulos et al., 2019a). Recently, materials
both RO and HPRO is the scaling deposition and fouling due to for surface modification such as polydopamine and nanoparticle-
the potentially high degree of brine hardness (Panagopoulos et al., decorated nanosheets of graphene oxide (AgNP-GO) have been
2019a). Regarding the materials used in HPRO membranes, these utilized and encouraging findings have been reported (Guo et al.,
materials are the same as those used in conventional RO; however, 2018; Soroush et al., 2016). The conceptual diagram of FO is pre-
as reported, HPRO membranes can withstand higher pressures sented in Fig. 3.

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 4. The conceptual diagram of OARO and COMRO.

Fig. 5. The conceptual diagram of CFRO.

2.1.4. Osmotically assisted reverse osmosis (OARO) principle of MD, a temperature gradient between the two surfaces
The latest membrane-based technology is the OARO. It is a of the membrane contributes to a difference in vapor pressure that
process that shares the principles of both RO and FO technolo- generates a flux of vapor across the membrane (Ashoor et al., 2016;
gies (Bartholomew et al., 2017; Panagopoulos et al., 2019a). The Panagopoulos et al., 2019a; Tibi et al., 2020). Through this process,
OARO system involves a sequence of OARO stages and a final salt rejection is higher than 99 %, resulting in the production of high-
RO stage (Peters and Hankins, 2019). Regarding the principle of purity freshwater. Unlike other membrane-based technologies, MD
OARO, OARO employs hydraulic pressure, like RO, to transfer water can treat significantly high-TDS effluents (up to 350 g/L TDS) (Tun
through a semipermeable membrane against the osmotic pres- and Groth, 2011). Research studies on MD have shown signifi-
sure difference between feed and permeate. In contrast to RO cantly high freshwater recoveries (<90 %), however; MD addresses
where permeate salinity is significantly low, OARO has a permeate- issues such as fouling, pore wetting, flux reductions due to temper-
side saline sweep solution (also called ‘draw solution’) to decrease ature polarization (Panagopoulos, et al., 2019a; Fortunato, et al.,
the osmotic pressure difference across the membrane. This alter- 2018; Ali, et al., 2015). To date, MD is based on hydrophobic poly-
ation increases the recovery of water and allows higher-salinity meric membranes, with the most frequently studied polymeric
water solutions to be desalinated without exceeding the membrane membranes being polypropylene (PP), polyethylene (PE), polyte-
burst pressure (Bartholomew et al., 2017). OARO has also been trafluoroethylene (PTFE) and poly(vinylidene fluoride) (PVDF) (Lu
referred to as counterflow RO (CFRO), while a relevant approach and Chung, 2019; Benyahia, 2019). Recently, ceramic membranes
is the cascading osmotically mediated RO (COMRO). All employ that are chemically modified have great potential because they
the same core technology but organize their stages/modules into have high mechanical power, thermal resistance and increased
different configurations (Bouma and Lienhard, 2018; Chen and lifespan (Yang et al., 2017; Hubadillah et al., 2019). Addition-
Yip, 2018). The difference is that the stages are placed in a ally, surface modification strategy includes the modification of
cascading counterflow pattern in COMRO, while the stages are conventional hydrophobic MD membranes to superhydropho-
connected by closed re-circulating loops in OARO/CFRO. It is not bic/omniphobic membranes or janus membranes (Chew et al.,
a straightforward desalination procedure since it is a dilution 2019; Li et al., 2019). The conceptual diagram of MD is presented
through series-organized stages. OARO can treat 100−140 g/L TDS in Fig. 6.
brine effluents with up to 72 % freshwater recovery (Bartholomew
et al., 2017; Panagopoulos et al., 2019a). Commercially, Hyrec has
recently developed an OARO system that has successfully concen- 2.1.6. Evaluation of the membrane-based technologies
trated seawater brine at 250 g/L TDS (WDR, 2018). OARO faces, A summary of the membrane-based treatment technologies
as is easily understood, both the issues of RO and FO technolo- used in this study is given in Table 2. Although RO is the most com-
gies. In addition, OARO, just like FO, has a more complex operation monly adopted desalination process, due to salinity restrictions
than RO/HPRO (Panagopoulos et al., 2019a). Regarding the mate- (<70 g/L TDS) and relatively low recovery (<50 %), this process can-
rials used in OARO membranes, current commercial FO and RO not be used extensively in the treatment of high-salinity effluents.
membranes are used for this process (Chen and Yip, 2018). The The more advanced version of RO, the HPRO, operates at higher
conceptual diagram of OARO/COMRO is presented in Fig. 4, while pressures and thus HPRO can treat 1.7 times more saline effluents.
the conceptual diagram of CFRO is presented in Fig. 5. OARO, along with its variations (namely, CFRO and COMRO), is the
newest technology that accomplishes higher recovery (<72 %) at
higher feed salinities in contrast to RO and HPRO. Nevertheless,
2.1.5. Membrane distillation (MD) OARO is still the costliest technology due to the combination of
MD is a thermal-driven membrane-based technology that several FO/RO stages. FO is much more cost-effective and appropri-
employs a microporous membrane. The membrane is hydrophobic ate for much higher salt concentrations (<200 g/L TDS) compared
as it is only permeable to water vapor. With regard to the operation to previous processes. Even so, the lack of a generic draw solution

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Fig. 6. The conceptual diagram of MD.

Table 2
Comparison of the desalination technologies used in MLD treatment schemes (Panagopoulos et al., 2019a).

Technology Driving force Status Highest feed Highest recovery (%) Energy Cost
concentration (g/L consumption
TDS) (kWh/m3 )

RO Hydraulic pressure Well-established 70 50 2−6 US$0.75/m3

HPRO Hydraulic pressure Emerging 120 50 3−9 US$0.79/m3
OARO/COMRO/ CFRO Osmotic and hydraulic pressure Emerging 140 72 6−19 US$2.40/m3
FO Osmotic pressure Emerging 200 98 0.8−13 US$0.63/m3
MD Vapor pressure difference Emerging 350 90 39−67 US$1.17/m3

and membrane issues are the primary considerations that hinder scheme. Furthermore, in scheme 3, a different technology (FO) was
its wider implementation. MD can treat extremely high-TDS brine added in the last stage (Fig. 10). The difference between schemes 1
effluents, but the use of thermal energy results in high MD energy and 5 is that in the fifth scheme, the number of stages was reduced
consumption. from 3 to 2, while they share one common technology, namely RO.
RO is placed on the first stage in both schemes; however, a different
2.2. Description of the MLD treatment schemes technology (MD) is placed in the second stage in the fifth scheme.
These five schemes were selected based on their efficiency to treat
The technologies involved in the study are RO, HPRO, FO, OARO, high-salinity brine. In particular, as previously described, RO has
and MD. Treatment schemes appropriate for MLD treatment of the lowest feed salinity limit compared to other technologies. For
desalination brine effluents were developed as shown in Figs. 7–11. this reason, RO was placed in the first stage of schemes 1, 3 and 5.
The following five technology integration schemes were analyzed, In contrast, MD has the highest feed salinity limit, which is why it
including RO-HPRO-OARO (Scheme 1), FO-MD (Scheme 2), RO- was placed in the final stage of schemes 2 and 5.
OARO-FO (Scheme 3), HPRO-OARO-FO (Scheme 4) and RO-MD The analysis was carried out taking into account a steady flow
(Scheme 5). In all treatment schemes, the treatment technologies rate and composition of the feed water to be treated. In more
are arranged in series. Schemes 1, 3 and 4 have three stages while detail, the feed water flow rate is equal to 100 m3 /day, while the
schemes 2 and 5 have two stages. With regard to the technol- feed water salinity is 38 g/L TDS, a typical salinity for Eastern
ogy maturity, schemes 1, 3 and 5 contain both well-established Mediterranean seawater (Negewo, 2012). In the MLD treatment
and emerging technologies, while schemes 2 and 4 consist only of schemes, the operating conditions of the technologies were taken
emerging technologies. from peer-reviewed literature. Overall, the data and assumptions
The first treatment scheme, given in Fig. 7, is taken as a bench- for treatment technologies applied in all MLD treatment schemes
mark and, in terms of their variations with respect to the first, the are presented in Table 3.
others are described. In the first treatment scheme, feed water is
inserted into the RO unit. The freshwater produced by the RO unit 3. Results and discussion
(RO permeate) is collected, and the brine co-produced becomes the
feed effluent of the HPRO unit. Subsequently, freshwater produced This section has five paragraphs to it. In particular, the first
by the HPRO unit (HPRO permeate) is collected and the brine co- paragraph presents the freshwater recovery and the flow rates
produced becomes the feed effluent of the OARO unit. Finally, both of each stream in the five MLD treatment schemes. The second
freshwater produced (OARO permeate) and concentrated brine are presents the results of the energy and economic analysis conducted
collected. The difference between schemes 1 and 2 is that in the sec- in the present study of the five MLD treatment schemes. The third
ond scheme, the number of stages was reduced from 3 to 2, while describes comparing the MLD treatment schemes with the prac-
the type of technology was also completely changed, as none of the tices of brine discharge, while the fourth compares MLD treatment
scheme 1 technologies (RO, HPRO, or OARO) were used in the sec- schemes in terms of cost with conventional water sources. Finally,
ond scheme (Fig. 8). On the other side, schemes 1 and 3 share two the fifth paragraph sets out the current status and prospects for the
common technologies, namely RO and OARO. RO is placed in the future.
first stage in both schemes; however, OARO is placed in the second
stage in the third scheme and not in the third stage as was the case 3.1. Freshwater recovery and stream flow rates of each MLD
in the first scheme. Furthermore, in scheme 3, a different technol- treatment scheme
ogy (FO) was added (Fig. 9). In the same manner as in scheme 3,
schemes 1 and 4 share two common technologies, namely HPRO Freshwater recovery is defined as the volume ratio between
and OARO. However, OARO is placed in the second stage in the the freshwater produced and the feed water. A higher freshwater
fourth scheme and not in the third stage as was the case in the first recovery is valuable as lower quantities of brine effluent are pro-

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 7. Schematic representation of the first MLD treatment scheme (RO-HPRO-OARO technology combination).

Fig. 8. Schematic representation of the second MLD treatment scheme (FO-MD technology combination).

Fig. 9. Schematic representation of the third MLD treatment scheme (RO-OARO-FO technology combination).

Fig. 10. Schematic representation of the fourth MLD treatment scheme (HPRO-OARO-FO technology combination).

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Fig. 11. Schematic representation of the fifth MLD treatment scheme (RO-MD technology combination).

duced and higher quantities of freshwater are recovered. In this

respect, Fig. 12 presents the freshwater recovery in the five MLD
treatment schemes. As shown in Fig. 12, in the five schemes, the
recovery ranges from 78 % to 89 % and is considered sufficient as
the freshwater recovery is up to 95 % in the MLD systems. The high-
est recovery (89 %) was achieved in treatment scheme 3, while the
lowest recovery (78 %) was achieved in treatment scheme 5. With
regard to the percentage participation of each treatment technol-
ogy in the freshwater production of each scheme, an analysis is
illustrated in Fig. 13. As shown in Fig. 13, the highest freshwater
production is achieved in the first stage in all schemes, which can
be explained by the low salinity of the feed solution (38 g/L), while
in the later stages the feed solution becomes more concentrated,
with the result that not all technologies can be equally efficient.
Moreover, the highest freshwater production is carried out by RO
in schemes 1 (54 %), 3 (49.5 %) and 5 (57 %), in scheme 2 (71 %)
by FO, while in scheme 4 it is almost shared between HPRO (40.4
%) and OARO (37.4 %). Another interesting thing to note is that Fig. 12. Freshwater recovery in MLD treatment schemes 1, 2, 3, 4 and 5. The blue
while all five MLD treatment schemes generate freshwater that dashed line indicates the maximum freshwater recovery in MLD systems.

is acceptable according to the standards of drinking water (<500

mg/L TDS), schemes 2 and 5 produce freshwater of high purity

Fig. 13. The percentage participation of each treatment technology in the total freshwater production in MLD treatment schemes 1, 2, 3, 4 and 5.

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Table 3 3.2. Energy and economic evaluation of each MLD treatment

Data and assumptions used in the five MLD treatment schemes (The Dow Chemical
scheme
Co., 2016, 2017; E.D.E.Y.A, 2019; Panagopoulos et al., 2019a; Benyahia, 2019; Linares
et al., 2017).
Initially, a detailed analysis of the percentage of each technol-
Item Value
ogy’s participation in the total energy consumption of each MLD
Feed water temperature (◦ C) 25 treatment scheme is carried out. To this end, the energy percent-
Feed water flow rate (m3 /day) 100 ages of the technologies involved in each of the five treatment
Feed water salinity (g/L TDS) 38
schemes are shown in Fig. 15. The results of this figure show that
Feed water composition (g/L TDS) Ca2+ (0.425), Na+ (11.865), K+
(0.465), Cl− (22.672), SO4 2− (1.201), OARO is the primary energy driver of the total energy consump-
Mg2+ (1.41) and HCO3 − (0.05) tion of schemes 1, 3 and 4, as OARO accounts for more than 48 %
Feed water source Seawater of the energy demands of each scheme. In schemes 2 and 5, on the
Location Eastern Mediterranean
other hand, the main energy driver is MD, which accounts for 67
RO recovery (%) 44
RO energy consumption (kWh/m3 ) 3.3 % and 92 % of total energy consumption, respectively. To have a
RO specifications 114 m2 (membrane area) better understanding of the energy consumption of each scheme,
HPRO recovery (%) 35 the energy consumption per freshwater produced of each scheme
HPRO energy consumption 5.1 is presented in Fig. 16. Scheme 5 has the highest energy consump-
(kWh/m3 )
tion per freshwater produced (23.09 kW h/m3 ), as shown in Fig. 16,
HPRO specifications 60 m2 (membrane area)
FO recovery (%) 9.9 while scheme 1 has the lowest energy consumption per produced
FO energy consumption (kWh/m3 ) 7 freshwater (5.76 kW h/m3 ). It is interesting to note that schemes 2
FO specifications 98 m2 (membrane area) (21.41 kW h/m3 ) and 5 (23.09 kW h/m3 ) have a significantly higher
OARO recovery (%) 59
energy consumption than the other three schemes since scheme 2
OARO energy consumption 12.4
(kWh/m3 )
has a 2.4-fold higher energy consumption than the third-highest
OARO specifications 128 m2 (membrane area) energy consumption scheme (scheme 4). Although only two tech-
MD recovery (%) 60 nologies (FO and MD, RO and MD) are included in schemes 2 and 5,
MD energy consumption (kWh/m3 ) 49 this significantly higher energy consumption of both schemes 2 and
MD specifications 41 m2 (membrane area), 70 ◦ C
5 can be attributed to the fact that they are the only MLD treatment
(feed temperature)
Remaining brine discharge 0.2 schemes that involve MD. As reported earlier in Section 2, MD is the
(US$/m3 ) only membrane-based technology that depends on thermal energy
for its operation (Ashoor et al., 2016). It is interesting to compare the
energy consumption of each of the five schemes with the thermo-
dynamically minimum energy consumption (MEC) required for the
same recovery, provided that one standalone technology could be
used to achieve the same recovery. As the author reports, the MECs
for the necessary recovery in each scheme ranges from 1.6 kW h/m3
to 2.4 kW h/m3 (Panagopoulos, 2020a). As shown in Fig. 16, the
actual energy consumption in each scheme is at least three times
higher than the MEC, however, this was reasonable as energy losses
due to irreversibility are present in actual MLD systems. In treat-
ment schemes 2 and 5, the differentiation is significantly higher
(over 10 times higher) as MD is a thermal-driven membrane-based
technology and thus losses such as heat losses in the environment
or frictional heat losses are considered (Panagopoulos et al., 2019a,
b).
An analysis of the percentage participation of each treatment
technology in the total cost formulation of each scheme is pre-
sented in Fig. 17 to evaluate the degree to which technology
combinations affect the total cost of the MLD system. Similar to
energy consumption analysis, Fig. 17 showed that OARO is the pri-
mary cost driver of the total cost formulation of schemes 1, 3 and
Fig. 14. Outlet flow rates in MLD treatment schemes 1, 2, 3, 4 and 5. 4, as OARO accounts for more than 45.4 % of the cost demands of
each scheme. This can be attributed to the requirement for several
RO/FO units as well as to OARO’s technical immaturity since the first
(<50 mg/L TDS) (Panagopoulos, 2020a). In particular, MD produces OARO study was published 3 years earlier (in 2017) (Bartholomew
24.6 m3 /day high-purity freshwater (MD permeate) in scheme 2 et al., 2017). On the other hand, in scheme 2, the cost is relatively
and 33.6 m3 /day high-purity freshwater (MD permeate) in scheme balanced between the two technologies, however; FO contributes
5, since MD is the only phase-changing membrane technology in more (56 %) to the total cost. Similarly, in scheme 5, the cost is
which only vapor is transferred through the hydrophobic mem- relatively balanced between the two technologies, however; MD
brane and then condensed as freshwater (Ali et al., 2015; Fortunato contributes more (54 %) to the total cost. The freshwater produced
et al., 2018). The production of high-purity freshwater can there- cost of each scheme is presented in Fig. 18. As shown in Fig. 18,
fore be useful in industries such as pharmaceuticals, where the scheme 2 has the lowest freshwater produced cost (US$0.79/m3 )
freshwater salinity needs to be significantly low (<50 mg/L TDS) even though this scheme had the second-highest energy con-
(Panagopoulos, 2020a). Finally, for each MLD treatment scheme, sumption (21.41 kW h/m3 ) among the other schemes. This can be
we present a summary of the stream results in Fig. 14. Treatment attributed to the fact that only two technologies are included in
scheme 3 has the highest freshwater volume (89 m3 /day) and the this scheme, as opposed to schemes 1, 2 and 4, which include three
lowest brine volume (11 m3 /day) amongst all treatment schemes technologies. In addition, by combining a relatively cheap tech-
as a direct result of the freshwater recovery. nology (FO at US$0.63/m3 ) with a relatively expensive technology

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 15. The percentage participation of each treatment technology in the total energy consumption in MLD treatment schemes 1, 2, 3, 4 and 5.

that would otherwise be discharged as wastewater. With that in

mind, Fig. 19 provides a cost correlation between the discharge
practices and the MLD treatment schemes proposed. It is worth
noting that the discharge cost refers to m3 of the feed brine while
the treatment cost refers to m3 of the freshwater produced. More-
over, in order to have a detailed understanding of the economic
aspect of the MLD schemes, it is considered that the remaining
small amount of highly concentrated brine is rejected. As shown
in Fig. 19, the cost of the evaporation pond is at least 2.4 times
higher than the treatment cost by either of the five MLD treat-
ment schemes. With the regard to the cheapest treatment scheme
(scheme 2), its cost (US$0.99/m3 ) is close to the minimum cost
of land application (US$0.75/m3 ). In addition, it is interesting to
note that, under certain conditions, all five MLD treatment schemes
can be cheaper than deep-well injection and land application prac-
tices. The contribution of the proposed MLD treatment schemes is
that these schemes produce freshwater that can be marketed. We,
Fig. 16. Bar charts with the energy consumption per freshwater produced in MLD therefore, consider that the income of each treatment scheme is
treatment schemes 1, 2, 3, 4 and 5. The pink horizontal line indicates the MEC equal to the income from the selling of the freshwater generated
required to achieve the equivalent recovery in each MLD system.
at market price in the Eastern Mediterranean (e.g., US$3.2/m3 in
Greece) (Panagopoulos, 2020b). In this respect, Fig. 20 depicts the
(MD at US$1.17/m3 ), the lowest cost of freshwater produced can analysis of profit and loss for MLD treatment schemes and brine
be clarified. In a similar manner, scheme 5 has the second-lowest discharge practices. As can be seen in Fig. 20, only expenses are
freshwater produced cost (US$0.93/m3 ) even though this scheme present in brine discharge practices. This was expected as these
had the highest energy consumption (23.09 kW h/m3 ). The cost approaches do not reclaim freshwater. Profit, on the other side, is
of freshwater produced from the other three schemes ranges from present in all five treatment schemes. In more detail, the profit is
US$1.13/m3 to US$1.36/m3 , with the fourth scheme being the most the highest in scheme 2 (US$2.21/m3 ), while the lowest profit is in
expensive scheme (US$1.36/m3 ). scheme 4 (US$1.64/m3 ). It should be noted that in countries with
a higher freshwater market price, such as Canada (US$4.11/m3 ) or
3.3. MLD treatment schemes versus brine discharge practices France (US$3.6/m3 ), the profit of the MLD schemes can be even
higher (Panagopoulos, 2020a; EurEau, 2017).
There are different practices for brine discharge, as stated earlier
in Section 1. Nevertheless, these practices lack the focus on environ-
mental conservation and so several environmental concerns have 3.4. MLD treatment schemes versus conventional water sources
arisen. Surface water contamination, marine pollution, groundwa-
ter pollution, soil salinization, eutrophication are such concerns The conventional water sources include surface and subsurface
(Latteman, 2010; Larramendy and Soloneski, 2016; Panagopoulos sources, while their costs vary due to different geographical and
and Haralambous, 2020a). In contrast, feed water is used as a mate- political conditions. Fig. 21 shows the cost of freshwater generated
rial resource by the MLD treatment schemes to reclaim freshwater in the MLD treatment schemes and the cost of freshwater col-

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 17. The percentage participation of each treatment technology in the total cost formulation in MLD treatment schemes 1, 2, 3, 4 and 5.

Fig. 18. Bar charts with the freshwater produced cost in MLD treatment schemes 1, 2, 3, 4 and 5.

lected by conventional water sources (National Research Council, implementation can lead to unwanted environmental impacts.
2012; Raudales et al., 2017). As seen in Fig. 21, the cost of fresh- Such systems commonly focus solely on the liquid waste manage-
water collected from surface water sources (from US$0.32/m3 ment dimension of the treatment procedure. As a consequence,
to US$0.69/m3 ) is substantially smaller than the cost of fresh- these systems produce concentrated multi-component streams
water produced from treatment schemes (from US$0.99/m3 to that have to be discarded in evaporation ponds. Nonetheless, the
US$1.56/m3 ). On the other hand, the freshwater cost collected from disposal of such streams increases the risks of leakage and pro-
subsurface water sources is relatively on the same levels as the cost duces odors that may damage the ecosystem (Water Environment
of freshwater produced from treatment schemes 1 and 2. It is inter- Research, 2012). As a reaction, impermeable liners and networks
esting to note, for instance, that two-thirds of the water in Israel, of surveillance are necessary to prevent possible spoilage from
a country in the Eastern Mediterranean, comes from underground these streams (Sridhar, 2018). In this decade, a new concept (brine
sources (KKL JNF, 2020). In this case, MLD treatment systems can mining) is being taken to reclaim valuable resources, in paral-
be beneficial as they can produce freshwater at comparatively the lel to freshwater reclamation. Although the demand for discharge
same prices as those in the freshwater production from subsurface remains in the MLD systems, industries can make internal use of
sources. Furthermore, if we consider that the freshwater produced high-purity concentrated streams, reducing the cost of raw mate-
from treatment schemes is being marketed, then MLD systems can rials. To this aim, MLD systems can be appropriately designed and
be profitable as stated in Section 3.3. configured to recover usable raw material streams and follow a cir-
cular economy strategy (Sorour et al., 2014; Liu et al., 2016; Ji et al.,
2018).
3.5. Current status and prospects
Although membrane-based technologies in MLD systems con-
sume substantially less energy than ZLD systems that employ
Although the primary goal of MLD systems is to increase fresh-
both thermal-based and membrane-based technologies, the energy
water generation and decrease waste generation by up to 95 %, their

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 19. MLD treatment schemes (yellow bars) versus brine discharge practices (blue bars).

Fig. 20. Profit and loss analysis for MLD treatment schemes and brine discharge practices.

demands still result in considerable emissions of greenhouse gases expected to increase the maximum operating pressure at HPRO in
(GHGs) and air pollutants. The author recommends that renew- the coming years. Overall, prospects for MLD systems are illustrated
able energy sources (RES) such as solar energy, geothermal, wind in Fig. 22.
energy, etc. or industrial waste heat can be incorporated into MLD
to tackle this challenge (Sorour et al., 2014; Liu et al., 2016; Ji
et al., 2018). In particular, solar RO’s GHGs emissions (0.2 kg of CO2
4. Conclusions
per m3 H2 O) are 9 times lower than GHGs emissions of conven-
tional fossil-fuel-powered RO (1.8 kg of CO2 per m3 H2 O) (Kucera,
Since the direct discharge of brine effluents is regarded as a prac-
2019). In this respect, the integration of MLD systems with RES is
tice with adverse impacts on the environment, it is a technological
considered to reduce the emissions of GHGs. To improve the perfor-
challenge to quest for environmentally sustainable management
mance of MLD systems, the technologies used in such systems must
strategies. An emerging approach for wastewater management and
first be enhanced. Novel membranes such as omniphobic (Chen
resource recovery is the MLD strategy. Five MLD treatment schemes
et al., 2018; Deng et al., 2018), janus (Chew et al., 2019; Li et al.,
are introduced and proposed for the first time in this research paper
2019), and superhydrophobic (Xiao et al., 2019; Yang et al., 2017),
to treat hyper-saline effluent (brine) from the seawater desali-
for example, have recently shown great potential to enhance MD
nation plant and to recover additional freshwater. The schemes
performance. Moreover, advanced membranes and modules are
included different combinations of desalination technologies (RO,

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A. Panagopoulos Process Safety and Environmental Protection 146 (2021) 656–669

Fig. 21. MLD treatment schemes (yellow bars) versus conventional water sources (red bars).

Fig. 22. Prospects for MLD systems.

HPRO, FO, OARO/COMRO/CFRO and MD) in two (schemes 2 and 5) treatment of brine effluents. The results of this study can have
or three stages (schemes 1, 3 and 4). major implications for the various industries that produce brine,
The results showed that the freshwater recovery ranges from as they can make a significant contribution to improving the sus-
78 % to 89 % in all five schemes with the highest recovery (89 %) tainability of the brine treatment process and at the same time
observed in scheme 3. Additionally, the results revealed that OARO suggesting financially viable MLD treatment schemes for brine
(in schemes 1, 3 and 4) and MD (in schemes 2 and 5) are the main utilization. Future research should focus on the improvement of
energy drivers in the total energy consumption of the MLD systems. membrane-based technologies (e.g., novel membranes, advanced
Schemes 2 (FO-MD) and 5 (RO-MD) have at least 2.4 times higher configurations) and the incorporation of more environmentally
energy consumption than the other three schemes because MD sustainable energy sources, such as RES and waste heat, in order
is the only thermal-driven membrane-based technologies. How- to enhance efficiency and increase the adoption of MLD systems.
ever, schemes 2 and 5 present the lowest freshwater produced
cost (US$0.79/m3 and US$0.93/m3 , respectively) mainly due to the Declaration of Competing Interest
reduced stages (two stages instead of three) as well as due to the
combination of an expensive technology with two comparatively The author declares that he has no known competing finan-
cheaper technologies (MD and FO/RO, respectively). The treatment cial interests or personal relationships that could have appeared
schemes are cheaper than the discharge practice of evaporation to influence the work reported in this paper.
pond, while MLD brine treatment can be profitable if revenue from
the sale of the freshwater is considered. In particular, the profit
from the MLD treatment can reach up to US$2.21/m3 . Acknowledgements
Overall, the findings suggest that the five proposed MLD sys-
tems can be sustainable and cost-effective in the management and This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.

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