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Waste conversion and resource recovery from wastewater by ion exchange membranes: state-of-the-art and prospective Wen-Yan Zhao, Miaomiao ZHOU, Binghua Yan, Xiaohan Sun, Yang Liu, Yaoming Wang, Tongwen Xu, and Yang Zhang Ind. Eng. Chem. Res., Just Accepted Manuscript • Publication Date (Web): 05 Apr 2018 Downloaded from http://pubs.acs.org on April 5, 2018

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Industrial & Engineering Chemistry Research

1

Waste conversion and resource recovery from wastewater by ion

2

exchange membranes: state-of-the-art and prospective

3

Wen-Yan Zhao1,3,5, Miaomiao Zhou1,3,5, Binghua Yan1,2, Xiaohan Sun1,2, Yang Liu1,2,

4

Yaoming Wang 4, Tongwen Xu 4, Yang Zhang 1,2,5*

5

1 Waste Valorization and Water Reuse Group (WVWR), Qingdao Institute of Bioenergy and

6

Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Laoshan District,

7

Qingdao 266101, China

8

2 Qingdao Key Laboratory of Functional Membrane Material and Membrane Technology,

9

Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences,

10

Qingdao 266101, China

11

3 State Key Laboratory of Petroleum Pollution Control, Beijing, 102206, PR China

12

4 CAS Key Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of Chemistry

13

for Energy Materials, School of Chemistry and Material Science, University of Science and

14

Technology of China, Hefei 230026, PR China

15

5 University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing 100049, China

16 17

*Corresponding Author: Yang ZHANG, PhD

18

Email Address: [email protected]

19 20

Invited review from Industrial & Engineering Chemistry Research, to the Special

21

Issue of 2018 Class of Influential Researchers

22 1

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

1

Abstract

2

Wastewater treatment is in a dilemma: more energy and efforts have to be put to

3

obtain an effluent with better quality; while significant amount of sludge is generated,

4

and the treatment or disposal expenses are high. Even the sludge is disposed properly,

5

the components can be released and pollute the environment again. Therefore,

6

conversion and recovery of the contaminants to resources is the way out of the

7

dilemma. Ion exchange membrane (IEM) is a special type of membrane, which allows

8

charged solutes pass through it while retains uncharged components. Attributes to this

9

character, IEMs are taking more important roles in separation and conversion

10

processes recently. They act as key elements in many resource recovery systems, such

11

as in separation and concentration, salt valorization, energy conversion, and even in

12

microbial systems. This review summarizes the important processes for waste

13

conversion and resource recovery from wastewaters by using IEMs. Drawbacks and

14

prospective are concluded in view of the development of the processes and the

15

membranes.

16 17

Keywords: Waste conversion; resource recovery; ion exchange membrane; energy

18

conversion; wastewater

19 20

2


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1

Abbreviations

2

Anion Exchange Membrane (AEM)

3

Bipolar Membrane Electrodialysis (BMED)

4

Cation Exchange Membrane (CEM)

5

Conventional Electrodialysis (CED)

6

Diffusion Dialysis for Power Generation (DD Power)

7

Electrodeionization (EDI)

8

Electrodialysis (ED)

9

Electrodialysis Metathesis (EDM)

10

Electro-electrodialysis Bipolar Membrane (EEDBM)

11

Electro-ion Substitution (EIS)

12

Ion Exchange Membranes (IEMs)

13

Membrane Distillation (MD)

14

Microbial Electrolysis Cell (MEC)

15

Microbial Electrosynthesis System (MES)

16

Microbial Fuel Cell (MFC)

17

Polymer Inclusion Membranes (PIMs)

18

Resource Recovery Systems (RRS)

19

Reverse Electrodialysis (RED)

20

Reverse Osmosis (RO)

21

Salinity Gradient Power (SGP)

22

Selectrodialysis (SED)

23

Supported Liquid Membranes (SLM)

24

Two-phase Electrodialysis (TPED)

25

Wastewater Treatment Plant (WWTP)

26

Water Loop Closure (WLC)

27

Zero Liquid Discharge (ZLD)

28

3



11.

1 Introduction

2

Water shortage has become an urgent problem due to unequal spatial distribution

3

of water resources, rapid development of global economy, urbanization with a large

4

and growing population and inefficient use of resource.1-3 About one third of Earth’s

5

population live in water stressed areas, and the number is predicted to rise nearly

6

two-third by 2025.4

7

Traditional domestic wastewater treatment focuses on removing of pollutants,

8

while ignoring the recovery of potential resources. This leads to over consumption of

9

energy and chemicals. It is reported that domestic Wastewater Treatment Plants

10

(WWTP) consume more than 5% of global electricity.5 Moreover, nutrients from

11

wastewater are accumulated in sewage sludge, and disposal of the sludge may result

12

in dispersion of the nutrients into aquatic environment. Considering that phosphorous

13

is a depleting resource and significant amount of energy has been put to produce

14

ammoniacal nitrogen in ammonia industry, the necessity arises to recover these

15

nutrients. Therefore, with the requirements of energy and resource recovery,

16

conceptual design of WWTP with Resource Recovery Systems (RRS) has been drawn

17

great attention in recent years.6

18

On the other hand, it is an essential requirement to improve water recovery rate

19

for industrial wastewater treatment system, especially in arid and semi-arid area or the

20

discharge of total dissolved solid (TDS) is restricted. This pushes the development of

21

water loop closure (WLC) and zero liquid discharge (ZLD) concepts. However, both

22

WLC and ZLD concentrate TDS and require intensive energy input. Operational 4


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1

expenditures and disposal fees may be significantly reduced if salt and energy can be

2

yielded from these industrial wastewater treatment processes from the above

3

mentioned concepts.7

4

Membrane technology is one of the most fast-growth processes in chemical

5

engineering. Among the category of membranes, ion exchange membrane is a special

6

one since this type of membrane transfers solutes (proton or hydroxyl, ions or charged

7

molecules) instead of solvent (water). This property allows ion exchange membrane

8

to be used for resource (nutrients, metals, salts, organic acids, or even

9

chemical/electrical potential) recovery from wastewater. Furthermore, ion exchange

10

membrane can convert solutes to new chemicals like acid, base or new salts by

11

applying bipolar membrane electrodialysis (BMED), electrodialysis metathesis (EDM)

12

or other ion exchange membranes based processes.

13

This work reviews the recent development of ion exchange membranes on waste

14

conversion and resource recovery with regard to yield water, resources and energy

15

from domestic and industrial wastewaters, as illustrated in Figure 1. Recent

16

development of ion exchange membrane based physical-chemical, electro-chemical,

17

and biological processes, like Reverse Electrodialysis (RED)8, Microbial Fuel Cell

18

(MFC), Microbial Electrolysis Cell (MEC), Microbial Electrosynthesis System

19

(MES)9 etc., are also reviewed in this work. Last but not least, prospective on the

20

development of ion exchange membranes used in waste conversion and resource

21

recovery from wastewater will be discussed.

5



1 2

Figure 1: Frame of this review: water, resources and energy are yielded from domestic

3

and industrial wastewaters through ion exchange membrane

4 52.

2 Recovery of inorganic salt

6

With the wastewater discharge tolerance limit on TDS has been set to a lower

7

level in many countries, recovery of inorganic salts has been drawing great attention

8

in recent years. Recovery and valorization of inorganic salts from industrial

9

wastewater not only gets salt products for reuse, more importantly, it eliminates the

10

disposal cost of the waste salts. Recovery of salts also avoids the potential threat from

11

landfill saline leakage to the groundwater and surface water. In this section, salt

12

fractionation and concentration, acid and base production, heavy metal extraction

13

technologies are reviewed to discuss how ion exchange membrane takes important

14

roles in these technologies.

15 6


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1

2.1 Salt concentration and fractionation

2

Conventional electrodialysis (CED) is of significance in the recovery of

3

inorganic salt, which has been widely applied to concentrate brine solutions. A CED

4

stack is composed of anion exchange membranes and cation exchange membranes

5

arranged alternately. Under the influence of an electrical potential, cation migrates

6

towards the cathode and it only passes through the cation exchange membrane but

7

retains by the anion-exchange membrane (vise versa for anion migration).10

8

In recent years, CED has been applied to concentrate Reverse Osmosis (RO)

9

retentate to improve the overall water recovery rate.11 It reduces the volume of

10

wastewater to cut down the disposal or evaporation cost in (near) ZLD systems. CED

11

elevates salt concentration up to 20%, which is very competitive as a

12

pre-concentration process prior to evaporation process (like Multi-Effect Distillation

13

or Mechanical Vapor Recompression), if it is compared with spiral wound RO system

14

(may elevates salt concentration to 8-9% w/w).12 Tong and Elimelech reported a

15

comparison of CED and RO as a pre-concentration step of a ZLD system. It showed

16

that the energy consumption of CED was 7-15 kWh/m3 of wastewater, which can lift

17

the salinity up to 200 000 mg/L.13 Ghyselbrecht et al.14 applied a CED to remove

18

NaCl and KCl from industrial saline water. Results showed that chloride was reduced

19

by half and the NaCl/KCl mixed concentrate can be reused in the secondary

20

aluminum industry.

21

Water transport through ion exchange membranes hinders the further

22

concentration of salts. Han et al. reported that water transport in ED attributes to 7



1

osmosis from concentration gradient and electro-osmosis (water co-migration with

2

ions).15 This work further pointed out that electro-osmosis dominants water migration

3

through ion exchange membranes. To reduce water migration, several membrane

4

fabrication strategies have been applied, including reduce membrane hydrophilicity

5

and water content, increase membrane cross-linkage, and coat a dense top layer to

6

reduce the permeated ion hydration number.16

7

On the other hand, mixed salt streams are obtained from conventional salt

8

concentration processes (like CED or RO). As mentioned above, mixed salts disposal

9

cost and the potential threat to the aquatic environment are of major concerns in ZLD

10

projects. Therefore, salt fractionation technologies are needed to obtain more pure

11

products and hence fulfill the requirements of salt reuse. As known, monovalent ions

12

can be discriminated from multivalent ions when monovalent selective ion exchange

13

membranes are installed in a CED stack. However, this kind of stack still can not

14

effectively fractionate ions, since those commercialized selective membranes have

15

limited separation efficiency.

16

In order to improve membrane selectivity, various efforts have been paid to

17

investigate ion transport mechanisms with regard to the degree of membrane

18

cross-linkage and membrane surface potential. Li and Xu17 prepared pre-cross-linked

19

BPPO anion exchange membranes with pyridinium groups and found that this method

20

was effective for separation of anions in view of their hydration energy. It is reported

21

that the separation factor of fluoride to chloride was around 0.2 while the factor of

22

iodine to chloride could reach around 3.5 by adjusting the membrane cross-linkage. 8


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1

On the other hand, recent studies revealed that membrane permselectivity is

2

influenced by co-ion and counter-ion spices through ion-membrane interaction which

3

shifts the membrane surface potential18-20. More specifically, higher counter-ion

4

binding affinity and higher co-ion polarizability both may result in lower

5

permselectivity20.

6

To improve separation efficiency, Zhang et al.21 invented a electrodialytic stack,

7

named “Selectrodialysis” (SED), to fractionate bivalent ions from monovalent ones.

8

Different from CED, a standard ion exchange membrane and a monovalent selective

9

ion exchange membrane are installed in SED stack to form a “product” compartment

10

which retains bivalent ions while permeates monovalent ones. The work further

11

investigated on fractionation of sulfate from chloride. Results showed that the

12

separation efficiency was significantly improved and the purity of fractionated sulfate

13

reached over 85%. SED has been used to recover phosphate22, industrial salts23, and

14

heavy metals 24.

15

Furthermore, to overcome membrane scaling caused by bivalent ions during

16

up-concentration of saline water, a Nanofiltration (NF) – Electrodialysis Metathesis

17

(EDM) integrated process was proposed by Zhang et al.21. This process is called

18

“Fracsis”, which utilizes NF to retain bivalent salt (c.a. CaSO4) while to permeate

19

monovalent salt (c.a. NaCl). Afterwards, the retentate (mainly bivalent salt) and the

20

permeate (only monovalent salt) is pumped into two different compartments of the

21

EDM stack to metathesize highly soluble salts (i.e., CaCl2 and Na2SO4),

22

simultaneously.25 By using this method, the salt streams can be further concentrated 9



1

and the system water recovery rate is enhanced. Fracsis exhibits high water recovery,

2

no membrane scaling, no chemical consumption and no sludge treatment

3

expenditures.

4 5

2.2 Convert salt to acid and base

6

Many industrial processes, such as metal surface treatment, graphite production,

7

titanium oxide production etc., consume acid or/and base. This wastewater has to be

8

neutralized to meet the pH requirement prior to discharge. However, under the

9

legislation of TDS control, this kind of wastewater cannot be discharged directly

10

anymore. In this case, the salts in these saline wastewaters should be converted back

11

to acid and base to avoid discharge and achieve a circular economy. Membrane

12

electrolysis and bipolar membrane electrodialysis are of fundamental importance to

13

convert salts to acid and base, as shown in Figure 2. Membrane electrolysis is a

14

widely used method to convert salt to acid and base, e.g., NaCl is succeeded in

15

collecting chlorine, hydrogen and sodium hydroxide simultaneously, as seen in Figure

16

2 (a).

17

Furthermore, bipolar membrane electrodialysis (BMED) can also convert the

18

concentrated salts into their corresponding acids and bases. A bipolar membrane

19

consists of a cationic layer, an anionic layer and a junction layer (with catalysis for

20

water splitting). Under an electrical field, protons and hydroxyl ions are generated

21

from bipolar membrane due to water is split in the junction layer. By using this way,

22

salt (MX) is converted to HX (acid) and MOH (base), as shown in Figure 2 (b). 10


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1

2 3

Figure 2: Schematic diagram of ion exchange membranes applied to convert salts to

4

acid and base.(a) membrane electrolysis;(b) bipolar membrane electrodialysis. BP:

5

bipolar membrane; AEM: anion exchange membrane; CEM: cation exchange

6

membrane; M+: cation; X−: anion; H+: hydrogen ion; OH−: hydroxide ion.

7 8

Owning to its advantages on less byproduct generation, low voltage drop, space

9

saving and simpler installation, BMED has found more applications with regard to

10

cleaner production of inorganic/organic acid and base in various processes. However,

11

there are still some bottlenecks on BMED process, these bottlenecks lead to the

12

product concentration (acid and base) is limited (usually less than 10%). Among all

13

the bottlenecks, proton leakage through anion exchange membrane (AEM) is the most

14

significant problem. Although anion exchange membrane is positively charged, which

15

blocks other cations, proton can still permeate through the membrane by Grotthuss

16

and “vehicle transport” mechanisms with the assistance of water molecules.

17

Commercialized proton blockage anion exchange membranes (also called “acid 11



1

blocker”) have been available, but the efficiency still needs to be improved.

2

In addition, due to the complicated fabrication procedures and the relatively

3

small market, the high price of bipolar membrane still limits its industrialization.

4

Heterogeneous bipolar membrane may be a good alternative with regard to the price

5

(can be as low as 1/5 of the homogeneous one), but the quality is still not satisfying

6

(difficult to produce the acid and base higher than 2 M). Therefore, substantial amount

7

of research is needed for improving of the bipolar membrane properties and

8

optimizing of related processes for new applications to open the market.

9 10

2.3 Recovery of valuable metal

11

With the expansion of electronic manufacturing industries and more stringent

12

legislations for the protection of the environment, more attention is paid to the

13

recovery and recycling of toxic and valuable metals from these streams.26 Many

14

methods have been tried to remove metal ions include chemical precipitation, ion

15

exchange, adsorption, solvent extraction, membrane technologies, electrochemical

16

treatment technologies, etc.27 Compared to other separation technologies, ion

17

exchange membrane based processes performed many advantages, such as low waste

18

rejection, low consumption of chemicals, and high modularity, which is considered to

19

be an effective method for the treatment of wastewater containing toxic and valuable

20

metal ions.28-30 Large numbers of literatures reported the recovery or removal of metal

21

ions from various aqueous, such as Li+, Pb2+, Ni2+, Cu2+, Cr3+, Mn2+, and Fe3+, etc.

22

Some of novel reported examples are given in Table S1 (in Supporting Information). 12


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1

Most recently, Reig et al.31 proposed the separation of As (V) from Cu (II) and Zn (II)

2

by using SED that integrating standard ion exchange membrane and monovalent

3

selective membrane, which open new opportunities for the use of SED technology in

4

the recovery of metal ions from waste water or secondary resources. In this work,

5

around 80% of Cu(II), 87% of Zn(II) and 95% of As(V) from the feed solution have

6

been recovered.

7

Although CED qualifies as an effective technology for removal of metal ions, the

8

cell resistance increases when the ions are removed from the diluate compartment,

9

which turns in higher energy consumption and lower efficiency to remove metal

10

ions.32,33 In order to facilitate the ion transport rate in CED, Electrodeionization (EDI)

11

has also been employed for the effective removal of metal ions, particularly when the

12

concentrations of metal ions are low and a polarization concentration phenomenon

13

emerges.28, 34, 35 Furthermore, EDI reduces the energy consumption when the feed

14

conductivity is low (lower than 500 µS/cm) in comparison to the amounts used for

15

CED.36, 37 It should be pointed that in a EDI system, the ion exchange resin bed plays

16

a major role as a permanent ionic conductive medium in the diluate compartment38,

17

while the ion exchange membranes lead to the depletion and concentration of the

18

solutions, respectively.39,40 Therefore, EDI has received great attention in purification

19

of wastewater containing metal ions in recent years (Table S1).

20

BMED technology has also been studied for the recovery of valuable metal ions

21

from aqueous solutions, especially for the recovery of Lithium (Table S1).41 In the

22

separation and recovery of lithium and boron from aqueous solution by BMED 13



1

process, Li+ and B(OH)4− are recovered as LiOH and H3BO3, respectively.42 The

2

recovery efficiency increased with an increase in applied voltage but decreased with

3

an increase in initial sample volume with the best values are around 88% for lithium

4

and 71% for boron, respectively. Thus, BMED process is capable to overcome the

5

difficulty of separation of lithium and boron from the same stream. Furthermore,

6

Jiang et al.43 reported the possibility to produce LiOH with a purity of 95% from a

7

solution of Li2CO3 by using electro-electrodialysis bipolar membrane (EEDBM)

8

process. In their work, high current efficiency and low energy consumption were

9

obtained at saturated Li2CO3 solution.

10

As illustrated above, although ED and related technologies has been proposed for

11

the removal and recovery of metal ions from wastewaters, separating ions from

12

mixtures of various ions is difficult by employing these technologies suffers from a

13

lack of selectivity for metal ions with similar valences.28, 44 Two potential methods

14

have been devoted to improve the selectivity of the ED based techniques44: 1)

15

multistage process or pre, post, or coupled treatment operations; 2) the chemical

16

modification of membrane surfaces or the synthesis of new materials in order to

17

increase the selectivity of membranes.

18

The selectivity of ED can be enhanced by the addition of various complexing

19

agents, which are known to create highly stable complexes with particular metal ions

20

(Table 1 summarized some examples).28 Separation of Ni(II) from Co(II) using ED in

21

the presence of EDTA was studied by Chaudhary et al.28. The hydrated Co2+ ions were

22

transferred from the feed solution to the ED catholyte chambers, while Ni-(EDTA)2− 14


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1

complex was removed to the ED anolyte chamber, respectively. Similarly, Cu2+ and

2

Zn2+ are transferred in the form of negatively charged complexes ([Cu-EDTA]2- and

3

[Zn-EDTA]2-) into the anodic concentrate side, whereas Ag+ is transferred to the

4

cathodic concentrate side.45 Separation of lithium and cobalt in the recycling of waste

5

lithium-ion batteries via BMED coupled with metal-ion chelation has been proposed

6

by Iizuka et al.46. The selectivity for each metal ion in the metal recovery cells was

7

higher than 99%.

8 9

Table 1: Separation of metal ions by using ED enhanced with complex formation Metal ions +

Remarks

2+

2+

Ag and Zn ; Cu

Excellent extraction (≥99%) and high separation performances for both Ag/Zn

and Cd2+

and Cu/Cd systems (EDTA as complexing agent).44

Zn2+ and Fe3+

Zn2+ recovery exceeded 86.6% with Fe3+ retention coefficient equal to 92.36% (Citric as complexing agent).28

Cu2+ and Ni2+

Permselectivity increased with increased stoichiometric ratio of complex agent (citric acid and glycine) to metal ions and solution pH, but decreased with an increased current density.47

Co2+ and Ni2+

Complete removal of nickel from cobalt can be achieved with an EDTA:Ni mole ratio of 1:0.85.48

Co2+ and Ni2+

EDI process was more effective than ED process for selective separation of Ni2+/Co2+ when EDTA was used as complexing agent; Ni2+/Co2+ ions molar ratio increased from 3 to 155.49

+

2+

2+

Ag , Zn and Cu

Complexation by EDTA in ammonia medium gave rise to a separation of Ag+ from [Cu-EDTA]2- and [Zn-EDTA]2-.45

10 11

Furthermore, it is important to develop functionalized membranes which contain

12

ligand or functional group with high permeability, low electrical resistance, and high

13

stability that can be used for the separation of metal ions with similar properties.

14

Developed from supported liquid membranes (SLM), polymer inclusion membranes

15

(PIMs) are considered to be an effective method for selective separation of metal 15



1

ions.50 Figure 3 shows the recovery of Cr(VI) by using the PIMs containing Aliquat

2

336. PIMs are usually composed of carrier (molecular or ionic liquid), a base polymer

3

and a plasticizer or modifier. The carrier encapsulated in the polymeric structure is

4

responsible for selectively binding with the target chemical species while the base

5

polymer provides the mechanical strength of the membrane.51, 52

6 7

Figure 3: Schematic drawing of the setup for the transporting of Cr(VI) by using

8

PIM.53

9 10

Attribute to high stability and good selectivity of PIMs, this technology shows

11

tremendous potential in different applications. Nghiem et al.54 and Almeida et al.55

12

have reviewed the recovery of metal ions and other compounds by using PIMs

13

containing different kinds of carriers. Table S2 (in Supporting Information) listed

14

several kinds of extractants which could be used as carrier for the preparation of PIMs.

15

The totally separation of Co(II) from Ni(II) from solutions containing 7 mol L-1 HCl

16

has been obtained by using an Aliquat 336/ PVC-based PIM.56 Separation of Co(II) 16


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1

from

Mn(II)

could

be

achieved

by

using

a

N-[N,N-di(2-ethylhexyl)

2

aminocarbonylmethyl] glycine (D2EHAG) containing PIM.57 Although lots of work

3

has been reported on the separation of metal ions by using PIMs, only a few PIMs as a

4

role of ion exchange membranes under electro-driven have been tried on the transport

5

of metal ions58. This might be caused by the high membrane resistance and lower

6

stability affected by existence of electric field. Around 98% of Cr(VI) was removed

7

from aqueous solutions after 40 min under constant DC electric current.59 Despite the

8

transport of Cr(VI) was facilitated by employing electric field, 50-100 V voltage

9

should be provided. Therefore, the modification of PIMs should be employed to

10

decrease the membrane resistance and enhance the stability, thus can be used in ED

11

process for the effective separation and recovery of metal ions.

12 13

2.4 Recovery of nutrients by electrodialytic processes

14

Eutrophication of natural water bodies becomes an increasingly severe problem

15

due to the discharge of nutrient containing wastewater. Tertiary treatment processes

16

remove nutrients, but the nutrient elements are enriched in the (biological) sludge,

17

which has to be further disposed as a solid waste. The nutrient enriched sludge may

18

bring a secondary pollution to the environment. More importantly, nutrients have to

19

be recovered in view of the facts that phosphorus is depleting, while ammonia

20

production is energy intensive. Therefore, the recovery of nutrients from wastewater

21

becomes urgent and necessary.

22

Phosphorus is a non-renewable resource derived from phosphate rock and 17



1

current global reserves may be depleted in 50-100 years60. This is why there are

2

increasing efforts to recycle phosphorus from wastewater. About 95% of phosphorus

3

is existed in the form of phosphate. There are various methods which can be applied

4

for phosphate recovery, such as chemical precipitation, filtration, membrane processes,

5

Enhanced Biological Phosphorus Removal (EBPR) and adsorption based processes.

6

The last two techniques for phosphorus removal from wastewater are commonly used,

7

but the recovered phosphors cannot be directly used as fertilizer.

8

On the other hand, phosphorous can be directly recovered as fertilizer through

9

magnesium ammonium phosphate (struvite) crystallization. However, phosphate

10

concentration is not high enough to efficiently produce struvite in most wastewaters.61

11

Therefore, a pre-concentration of phosphate prior to the struvite production is needed.

12

Zhang et al.22 integrated SED - struvite reactor process to improve phosphate recovery

13

from wastewater. In this process, SED was employed to concentrate phosphate to a

14

desired concentration. Results showed that phosphate concentration was increased

15

from 0.93 mmol/L to 6.64 mmol/L, and 93% of phosphate from the wastewater was

16

recovered.

17

Another possibility is to recover phosphate from the sludge or the adsorbent.

18

Phosphorus recovery rate from sewage sludge and its ash can reach up to 90%62.

19

Wang et al.63 investigated phosphate recovery from a broth extracted from the

20

activated sludge by using conventional electrodialysis (CED) and bipolar membrane

21

electrodialysis (BMED). In this study, phosphate was concentrated through CED, and

22

the concentrated phosphate was further converted to phosphoric acid by BMED. 18


Page 18 of 51

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1

In wastewater, nitrogen mostly presents in inorganic forms as ammonium (NH4+)

2

and nitrate (NO3−). Wastewater treatment plants always convert nitrogen to N2 by

3

nitrification-denitrification process to avoid secondary pollution. However, since

4

ammonia synthesis is energy intensive in fertilizer industry, recovery of ammonia and

5

nitrate for fertilization may be energy and cost effective in view of the life cycle

6

assessment.

7

Various technologies are available to recover nitrogen, including gas stripping64,

8

pervaporation through gas permeable membranes65, and electrodialysis66. Among

9

nitrogen recovery technologies from aqueous phase, ED may be the most efficient one.

10

ED shows several advantages in nitrogen recovery such as lower energy consumption,

11

less pre-treatment, high water recovery, and no/low chemical consumption.

12

Recently, studies are focusing on human urine as an alternative resource since

13

nitrogen in domestic wastewater is mostly from urine. K+ and NH4+ can be also

14

recovered from urine and used as a natural fertilizer. Bioelectrochemical systems with

15

ion exchange membranes used for resource recovery are widely studied in recent

16

years. This will be further discussed in “Resource recovery by bioelectrochemical cell”

17

section of this review.

18 193.

3 Recovery of organic acids

20

In wastewater treatment, anaerobic process has been drawn great attention in

21

recent years due to its low energy consumption (without aeration), no/low sludge

22

generation and low CO2 production, since the process converts most of the organic 19



1

compounds to methane or organic acids. With regard to the economic value, organic

2

acids are more interesting than methane. Ion exchange membranes have been proved

3

their stronger economic and environmental competence than traditional separation

4

method like precipitation and acidification, extraction, crystallization, distillation,

5

ion-exchange, and adsorption in separation of organic acids. Huang et .al67 reviewed

6

many related ion exchange membrane processes, such as electrodialysis metathesis

7

(EDM), electro-ion substitution (EIS), electro-electrodialysis (EED), bipolar

8

membrane electrodialysis (BMED), and two-phase electrodialysis (TPED), which can

9

be used to produce organic acid, while conventional electrodialysis (CED) and

10

electrodeionization (EDI) can be used to concentrate organic acids or organic salts.

11

Among these processes, BMED attracts much attention for organic acid

12

production since BMED generates hydroxyl to replace organic ions and adjust pH in

13

the feed compartment with anaerobic (fermented) wastewater, while it generates

14

proton simultaneously in another compartment which acidify the received organic

15

ions to organic acids, as shown in Figure 4. In anaerobic wastewater treatment,

16

organic acids inhibit anaerobic digestion. Therefore, in-situ organic acid removal is

17

desired to improve the efficiency of anaerobic digestion.

20


Page 20 of 51

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1 2

Figure 4: Schematic diagram of the integration of BMED and fermentation. BM:

3

bipolar membrane; M+: cation; X−: anion.

4 5

Recently, BMED is widely adapted in in-situ production and separation of acetic

6

acid68, monoprotic, diprotic, and triprotic organic acids,69 sebacic acid,70

7

carboxylate,71 and succinic acid72. Wang et al. studied the operational compatibility

8

and uniformity of BMED intensified fermentation process to produce lactic acid

9

and achieved a continuous operation

73

74

. Jones et al.75 applied conventional

10

electrodialysis to remove VFAs from hydrogen fermentation broth to intensify the

11

process. In-situ carboxylate recovery and simultaneous pH control was achieved with

12

tailor-configured bipolar membrane electrodialysis during continuous mixed culture

13

fermentation.71 Since CED is advantageous in concentrating organic salts while

14

BMED provides H+ and OH-, some investigations76, 77 integrated CED and BMED to

15

improve the extraction efficiency of organic acid and elevate the concentration

16

simultaneously.

17

Ion exchange membrane related processes have great potential on the production 21



1

of organic acids, especially in assistance with anaerobic digestion processes. However,

2

membrane fouling during in-situ product recovery should be solved prior to industrial

3

applications. Furthermore, organic ion selective ion exchange membrane is desired to

4

separate targeted organic acids. Zhang et al.78 used layer-by-layer method to fabricate

5

an anion exchange membrane with dense layer to separate hexanoic acid from formic

6

acid. Results showed that the migrated formate was 13.62 times higher than that of

7

hexanoate. Since most of homogeneous ion exchange membranes exhibit their

8

“molecular weight cut-off” (internal cavity) around 300-400, larger organic ions (or

9

charged organic molecules) are difficult to permeate through the membranes. Ion

10

exchange membranes with more loose structure may need to be developed to separate

11

those organic compounds.

12 134.

4 Energy recovery by RED or DDPower

14

With the rapid development of world economy, the demand of energy is

15

increasing. This leads to the requirements of renewable and sustainable energies.

16

Saline wastewaters are produced from various industries and process effluents.

17

Salinity gradient or chemical potential can be directly converted to electrical potential

18

by ion exchange membranes (IEMs) based processes, such as Reverse Electrodialysis

19

(RED) and a novel Diffusion Dialysis (namely DD Power). In this section, the

20

application of IEMs used in renewable and sustainable energy exploration will be

21

summarized and discussed.

22 22


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1

4.1 Reverse Electrodialysis (RED)

2

Similar as ED, RED comprises alternatively arranged cation exchange membrane

3

(CEM) and anion exchange membrane (AEM), as shown in Figure 5. High salinity

4

stream and low salinity stream are feed into adjacent compartments, simultaneously.

5

Driven by salinity gradient (SG), cations and anions in high salinity compartments are

6

transmitted across the CEM and AEM to adjacent low salinity compartments,

7

respectively. This process can generate electricity by redox reaction in the electrode

8

compartments on both sides of membrane stack.

9 10

Figure 5: Schematic diagram of RED stack for electrical power generation from a

11

salinity gradient.

12 13

Salinity gradient power exists widely between saline water (such as seawater,

14

industrial wastewater or RO concentrates) and fresh water (such as surface water or

15

domestic wastewater)8. Various investigations have been done by using different kinds 23



1

of salts as high salinity streams in RED process79-81. Development of IEMs with lower

2

ohmic resistance is one of the key points to generate a higher power density. By using

3

the current membranes, the power density generated by RED is reported between 0.17

4

W/m2 and 4.32 W/m2 82-86. Apart from the fabrication of IEMs, a number of studies

5

have been conducted to develop the RED stack, such as design new stack

6

configuration and spacer87, 88, investigate the composition of anolyte/catholyte and

7

develop novel electrodes89, 90.

8

However, the use of natural waters (like seawater and surface water) may

9

consume more energy by transporting of water and pretreatment to control membrane

10

fouling and spacer blockage80, 91. Instead, RO retentate from desalination plant can be

11

used as the saline water and UF/MBR treated domestic wastewater can be used as the

12

fresh water to feed RED for energy generation. This concept solves the bottlenecks (as

13

mentioned above) of using natural water bodies 92.

14

Furthermore, RED may serve as a energy recovery step of RO / ED to reduce

15

energy consumption of desalination 93. As a result, the researchers demonstrated that

16

RED could improve the desalination efficiency by 47%.

17

Apart from RO retentate, low-grade (waste) thermal sources can also be

18

converted to SGP, which are accessible as solar thermal, geothermal, and industrial

19

waste heat.

20

further concentrated by membrane distillation (MD). This concentrated solution is fed

21

into a RED stack together with a fresh water to generate salinity power, hence, waste

22

heat is indirectly converted to electric power. Long et al. reported an integrated system

94

. By using these low-grade heats, saline industrial wastewater can be

24


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1

consisting of a MD (20 ℃ -60 ℃ waste heat) and a RED, a energy conversion

2

efficiency (from heat to electric power) of 1.15% was obtained.

3

On the other hand, ammonium hydrogen carbonate (NH4HCO3) is a thermally

4

unstable salt, which decomposes to NH3, CO2 and water at 40℃-60℃. Thus, it is

5

considered as a suitable thermolytic solution used in RED to reuse low-grade heat for

6

power generation. According to an integrated model of a RED unit and a regeneration

7

unit for saline water regeneration, Bevacqua et al.95 reported that a maximum power

8

density could reach 9 W/m2 when the concentrations of the saline water and the fresh

9

water were 2.6 M and 0.075 M, respectively. An energy conversion efficiency of 22%

10

was obtained in this above mentioned work. Another investigation was reported by

11

Luo et al.96, the maximum power density and energy conversion efficiency were 0.33

12

W/m2 and 31%, respectively. A higher power density of 0.77 W/m2 was obtained by

13

Kwon et al.97.

14

These works mainly focus on the operating conditions including concentration of

15

feed water and flow rate96, 97, membrane type97, the design of fluid flow to reduce the

16

effect of bubbles98, junction potential99 and the modeling set-up95, 100. More effect

17

should be put for enhancing power density and energy efficiency by tailored

18

membrane design and improved heat exchange system.

19

For practical applications, RED can be act as a power source or a

20

pre-desalination process. A hybrid RED/ED system for treating phenol-containing

21

wastewater was investigated by Wang et al.

22

from 25.32 kWh/m3 to 17.65 kWh/m3 with RED as a pre-desalination technology and

101

. The energy consumption decreased

25



1

Page 26 of 51

the recovery of SGP was 0.35 kWh/m3.

2

Furthermore, a single stack combining with ED and RED configurations called

3

“energy self-sufficient desalination stack”, was reported by Chen et al.102. In this

4

concept, RED and ED were configured in a same stack. By using this way, SGP from

5

mixing of seawater and brackish water was used to desalinate the brackish water

6

without any external power. It is believed that, this design can effectively solve water

7

shortage problem without electricity supply in remote area.

8

As reviewed above, RED may be a promising process to recover electrical

9

energy from various saline wastewaters. Therefore, it is suggested that more

10

investigations should be done to develop tailored IEMs and stacks to reduce the

11

internal resistance and improve the efficiency of power generation..

12 13

4.2 Diffusion Dialysis for Power Generation (DD Power)

14

High concentration of waste acids are generated in various industries such as

15

steel production, metal-refining, electroplating etc.103. DD Power is a novel process

16

and the apparatus was suggested by Zhang and Helsen

17

and simultaneously generate electricity by SGP from the acids. Two types of anion

18

exchange membranes alternatively are installed in DD Power stack: ones allow proton

19

pass through (diffusion dialysis membrane, as AFN, Astom, Japan) and another only

20

permit anion across but block the proton (proton blockage anion exchange membrane,

21

as ACM, Astom, Japan). As seen in Figure 6, this design enables protons and anions

22

move to different directions, thus the chemical potential is converted to electrical

104, 105

26


to recover waste acids

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1

potential.

2

As an example in Figure 6, a wastewater stream containing HCl and Fe2+ and a

3

deionized water stream are fed into dialysate compartment and diffusate compartment,

4

respectively. Driven by chemical gradient, H+ and Cl- move to different directions and

5

transfer across the membranes, while Fe2+ is blocked since the stack is configured

6

only with anion exchange membranes. Hence, electricity is generated with a purified

7

HCl stream through the DDPower stack. Results showed that the maximum power

8

density was 27.53 µW·cm-2 with 3.0 mol/L HCl, meanwhile, the acid flux was 9.12

9

mol/m2 in average. These results are comparable with the power generation efficiency

10

of RED and the acid recovery rate of conventional DD. Thus, DD Power as a new

11

application of IEMs shows economic and environmental values.

12 13

Figure 6: Schematic diagram of DDPower stack for electrical power generation and

14

simultaneous acid purification from a waste acid stream.

15 27



15.

5 Resource recovery by bioelectrochemical cell

2

In recent years, bioelectrochemical cells (BECs) is gaining increasing attention106.

3

Standard BECs compose of an anode and a cathode that typically separated by an ion

4

exchange membrane in between. As shown in Figure 7, BECs can be applied in

5

bioelectrochemical conversion of bio-electricity or synthesis of fuels and chemicals in

6

the anode or cathode107,

7

microbial electrolysis cells (MECs). Besides, microbial electrosynthesis system (MES)

8

which converts electric energy to chemical energy, has become a hot topic and has

9

been developing rapidly recently.

108

which is operated as microbial fuel cells (MFCs) or

10

11 12

Figure 7: An overview of the bioelectrochemical cells.

13 14

5.1 Recovery and utilization of bio-electricity

15

MFCs and MECs are processes that use biofilms on an anodic electrode to

16

degrade organic wastes and generate electric current, which are proposed as 28


Page 28 of 51

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1

sustainable technologies for wastewater treatment 109. Bio-electricity can be harvested

2

as the final product, or it can be used in-situly to drive other thermodynamic

3

unfavorable reactions at the cathode.

4

In MFCs, electrochemically active microbes in the anode can oxidize organic 106

5

substrates to CO2, proton and electron with electrode as final electron acceptor

6

Electrons from anode electrode are transported to cathode via external circuit. While

7

in the cathode, oxygen in the atmosphere/solution together with the proton transferred

8

from the anode through a cation exchange membrane is reduced to water. The cation

9

exchange membrane between the anode and cathode chamber acts as a separator of

10

the chambers, which allows proton transfer to complete the anode-cathode reaction

11

but prevents anion ions exchange.

12

MFCs has been developed for more than a century

.

107

. Nowadays, production of

13

biologically electricity through MFCs is an easy task. Microbes in the anode utilizes a

14

wide range of substrates, such as VFAs 110, alcohols 111, glucose 112 and phenol 113 and

15

even the complex organic wastes 114 in wastewater can be used as substrates in MFCs

16

to produce electricity. In other words, MFCs is a technology, with which organic

17

compounds in wastewater are degraded to CO2 and H+, as a result, chemical energy in

18

the wastes is converted to electrical energy. Hence, it is recognized as a promising

19

technology that offers both environmental and energetic benefits.

20

A critical standard to evaluate the performance of MFC is electricity generation

21

from degradation of organic matters, and this has been set as the key target by most of

22

researches in this area. In previous studies, strategies such as modification of 29



Page 30 of 51

1

electrodes 115, acclimation of biofilm 116, alteration of reactor design 117, selection of

2

separators

3

improve the output power density. These efforts resulted in the power density

4

increased from 0.01 mW·m-2

5

Especially when MFCs were combined with RED membrane stacks, the maximum

6

power outputs reached 5.6 W·m-2

7

that produced without RED.

118

and optimization of operational conditions

120

119

have been executed to

in early days to 2.72 W·m-2 in recent research

121

.

122

, this power density is significantly higher than

8

Despite of the aforementioned advantages of MFCs as power sources, high

9

investment and comparatively low power density are still the challenges for the

10

application of MFCs. Further measures to increase the power density and decrease the

11

cost of the installation are required. Solutions, electrodes and membranes are the main

12

components of MFCs which affect the power output and overall cost. Among these

13

components, membranes affect internal resistance and ions transport efficiency, which

14

have great influence on the efficiency of MFCs. Until now, various types of

15

membranes have been used for separation of anode and cathode chamber in MFCs,

16

such as CEMs, AEMs and porous membranes

17

membrane selectivity, oxygen diffusion and membrane fouling should be considered

18

to choose a proper membrane for MFCs.

123

. The cost, membrane resistance,

19 20

5.2 Energy utilization for resource recovery

21

Over the past decade, the application of BECs has been extended beyond

22

electrogenesis to the recovery of value-added products, and the process was defined as 30


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1

microbial electrolysis cells (MECs). With electricity supplying in MECs, organics are

2

degraded in the anode with electron production. Meanwhile, the proton transfers

3

through a cation exchange membrane and is reduced to hydrogen in the cathode,

4

which results in hydrogen production124. Since MECs was reported to produce H2 in

5

the 70s of the last century

6

development. Until now, the products in MECs have extended from simple H2 to

7

many other compounds such as hydrogen peroxide, methane, ethanol, formic acid and

8

acetate 126, and this further expand the application of MECs.

125

, it has drawn lots of attention and gained significant

9

Membranes are employed in MECs to prevent the products generated in cathode

10

transferring to anode and being consumed by bacteria in anode chamber. However,

11

since the membrane surface area is relatively small between the anolyte and the

12

catholyte cuvettes and membrane fouling occurs during the process, low ions transfer

13

efficiency and significant internal resistance can be brought by the membrane. Hence

14

the current efficiency of MECs is reduced. Zhang et al.127 patented a “side-stream”

15

bioelecrochemical reactor, which consists of separate anode and cathode cuvettes and

16

an ion exchange membrane stack. The components in the anolyte and the catholyte

17

are transferred (or exchanged) through the membranes in the stack. Hence, the

18

membrane surface area is not restricted by the connection of the cuvettes anymore,

19

and the membranes can be easily cleaned.

20

Recently, microbial electrosynthesis system (MES) as an electric driven

21

biochemical process has attracted increasing attention. MES converts organic or

22

inorganic compounds to chemical products by consumes electric energy108. Unlike 31



Page 32 of 51

1

MFCs, MES is operated in electrolytic mode in which external electricity is supplied

2

to reduce compound in the biocathode, rather than galvanostatic mode in which

3

electricity is produced by microbial respiration. In the anode of MES, water is usually

4

oxidized to oxygen, which is different with the conversion of organics in MECs.

5

While in the cathode of MES, microorganisms on the electrode catalyze the fixation

6

of CO2 by consuming electrons on a cathode or other reductive products 106, 107, 128.

7

Nevin et al. first investigated the reduction of CO2 to acetate and 2-oxobutyrate

8

by acetogen Sporomusa ovata with 85% of electrons consumed in MES

129

9

Subsequently, microbial electrosynthesis with CO2 for production of methane

130

131

, ethanol

132

, glycerol 133, butyrate and butanol

134

. ,

10

acetate

were demonstrated with

11

pure culture or mixed microbes. The MES process can be used to reduce greenhouse

12

gas emission in wastewater treatment with the CO2 as substrate. Besides CO2,

13

organics such as fumarate or VFAs in wastewater can be used as the organic substrate

14

in biocathode. For instance, conversion of fumarate to succinate in MES has been

15

achieved with pure culture Shewanella oneidensis

16

were reduced by H2 to produce alcohols 136and, thus it is believed that VFAs also can

17

be reduced in the cathode of MES. One research has shown that when acetate was

18

used as substrate in cathode chamber of MES, ethanol was produced with butyrate as

19

the by-product with mixed microbial community 137.

135

. In a previous research, VFAs

20

Microbes in cathode of MES are mostly sensitive to oxygen. Hence, ion exchange

21

membrane is used to separate anode and cathode chamber for the reduction of oxygen

22

diffusion. However, there are rooms for improvement of membrane performance, such 32


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1

as increase the ions transport rate, increase ions selectivity, lower membrane

2

resistance and enhance biofouling resistance. In addition, the above mentioned

3

“side-stream” bioelecrochemical reactor can also be applied to improve the efficiency

4

of MES. Owning to the external membrane separation device, the limitation of

5

membranes area can be eliminated, which results in the enhancement of ion transport.

6

Moreover, it is easier to clean the fouled membranes to recover the membrane

7

performance and prolong the membrane lifetime. By applying different stack

8

configuration, selective ion separation from the MES system and addition of

9

substrates to the MES system may be achieved.

10

When MES is used to produce valuable chemicals, some drawbacks in cathodic

11

reaction need to be overcome. For instance, activation overpotential which reduces the

12

current efficiency exists during the reductive reaction in the biocathode. Some

13

measures such as addition of biological/chemical catalyst may be needed to decrease

14

the activation overpotential. Moreover, products inhibition appears with the

15

accumulation of products in the cathode chamber. Separation technologies, especially

16

in-situ separation is required for long-term operation.

17

As reviewed in the previous section, nitrogen and phosphorus are the essential

18

elements for life, however, the abuse of them will lead to pollution even a disaster of

19

the ecosystem. Some wastes like sanitary wastewater and animal excrements contain

20

considerable amount of ammonium and phosphorous. It is widely aware that the

21

recovery and reuse of ammonium and phosphorous are not only environmentally

22

friendly but also economically viable. MECs have been reported to recover 33



Page 34 of 51

1

ammonium or phosphorus from wastewater, a schematic diagram of this concept can

2

be seen in Figure 8. It is reported 138 that when ammonium rich wastewater was fed

3

into the cathode chamber of MECs, the ammonium was recovered as ammonia gas

4

due to the high pH in the cathode.

5

Moreover, phosphorous in wastewater can be recovered as struvite crystallization 139

6

(MgNH4PO46H2O) with the hydrogen production in MECs

. As known, urea is

7

another form of nitrogen and rich in urine. A recent research 140 raised a new design of

8

three-chamber MECs which could recover nitrogen, phosphorus and potassium from

9

urine in the middle chamber. Finally, relatively pure ammonium bicarbonate crystals

10

were obtained. This novel design utilized the permselectivity of anion and cation

11

exchange membrane, which possibly can expand the applications of MEC on resource

12

recovery from various wastewaters.

13

In view of the present researches, MECs can be used as a promising method to

14

recover nutrients from wastewater. More studies should be carried out to further

15

improve the recovery efficiency as well as find more possibilities for the recovery of

16

other nutrients.

34


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1 2

Figure 8: MEC for recovery of ammonia (cathode) and simultaneous degradation of

3

organic pollutants (anode) from wastewater.

4 5

Conclusion and prospective

6

To reduce the energy and resources obtained from the nature, and minimize the

7

impact of the waste discharge to the environment, water and resources recycling are

8

highly desirable by the current industrialized society. Ion exchange membrane and its

9

related processes clearly exhibit effectiveness on waste conversion and resource

10

recovery from wastewaters. More specifically, CED shows its competitiveness on salt

11

concentration and metal ion extraction; BMED is in ascendant on inorganic/organic

12

acid and base production and recovery; SED and EDM present their specialty on ion

13

fractionation; RED and DDPower exhibit their strength on energy recovery from

14

chemical potential; BECs (including MFC, MEC, MES etc.) illustrate their

15

advantages on energy and resource recovery from organic and inorganic compounds.

16

However, there are still bottlenecks which hinder full-scale applications of these 35



1

processes: one of the essential hurdles is the price of IEM. Comparing with RO

2

membrane, the price of IEMs may be twice or even higher (bipolar membrane could

3

be more than ten times higher). This is mainly due to the fact that the market of IEMs

4

is still under development. Besides, as discussed in this review, tailored selective

5

membrane for specific ions (monovalent ion, proton, metal etc.) is desired to improve

6

the efficiency of resource recovery in the IEM based processes. To achieve this,

7

transport mechanisms of the ions through IEMs should be intensively studied to

8

develop the theories on selectivity.

9

Based upon this, new membrane fabrication methods should be invented to

10

produce highly selective and low resistance IEMs. Membrane selectivity and

11

resistance exhibit trade-off effect, but if new fabrication methods are introduced, it

12

may turn to be a win-win effect. As an example, composite IEMs are developed in

13

recent years, and these methods are probably inspired from the fabrication of

14

nanofiltration membranes141, 142. These composite IEMs consist of functionalized top

15

layers which show higher monovalent ion selectivity with lower electrical resistance.

16

With the innovation of membrane fabrication methods, it is promising to obtain more

17

ideal membranes.

18

Water permeation and inorganic/organic fouling should also be controlled.

19

Although these two problems are, more or less, unavoidable, they should be paid

20

more attention since the current efficiency is severely reduced in various applications.

21

They especially hurdle the application of IEM processes on deep concentration of

22

saline solution and on bioelectrochemical systems. It is suggested that, more strength 36


Page 36 of 51

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1

has to be paid to fabricate IEMs with less water permeability and better fouling

2

resistance to promote the application of IEMs in these two promising fields.

3

Last but not least, more robust IEM stacks with more innovative and practical

4

processes should be designed to fulfill the scale-up demands and to develop the

5

markets on waste valorization and resource recovery from industrial and domestic

6

wastewaters. As the population of scientists and engineers in IEM field is increasing

7

rapidly (an example is the participants in electro-membrane related conferences

8

dramatically increase in recent years), and more publications and patents have been

9

published, it is believed that IEMs will share more important roles in membrane and

10

resource recovery fields.

11 12

Supporting Information

13

Summary of the literature reports on the recovery and removal of metal ions by using

14

CED, EDI, and BMED is shown in Table S1. Commonly used molecule extractants

15

and ionic liquids for the preparation of PIMs are listed in Table S2. The Supporting

16

Information is available free of charge via the Internet at http://pubs.acs.org.

17 18

Acknowledgement

19

This invited contribution is part of the I&EC Research special issue recognizing

20

the 2018 Class of Influential Researchers. The authors would like to appreciate the

21

financial support of the National Natural Science Foundation of China (No.

22

51508548), the National Science and Technology Major Project of the Ministry of 37



1

Science and Technology (2016ZX05040-003), the Belt and Road Science and

2

Technology Collaboration Program of the Chinese Academy of Sciences

3

(211134KYSB20170010), and the Shandong Provincial Key R&D Program

4

(2016CYJS07A02).

5 6

38


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43

References: (1) Rao Z.; Debski, D.; Webb, D.; Harbin, R. Genetic algorithm-based optimization of water resources allocation under drought conditions. Water Sci. Technol.: Water Supply 2010, 10, 517. (2) Kummu, M.; Guillaume, J. H. A.; de Moel, H.; Eisner, S.; Florke, M.; Porkka, M.; Siebert, S.; Veldkamp, T. I. E.; Ward, P. J. The worldʹs road to water scarcity: shortage and stress in the 20th century and pathways towards sustainability. Sci. Rep. 2016, 6, 38495. (3) Jiang, Y. China's water scarcity. J. Environ. Manage. 2009, 90, 3185. (4) Service, R. F. Desalination Freshens Up. Science 2006, 313, 1088. (5) Deslauriers, S.A.; Kanzaki, M.; Bulkley, J.W.; Keoleian, G.A. U.S. Wastewater Treatment; University of Michigan: Ann Arbor, 2004. (6) Guest, J. S.; Skerlos, S. J.; Barnard, J. L.; Beck, M. B.; Daigger, G. T.; Hilger, H.; Jackson, S. J.; Karvazy, K.; Kelly, L.; Macpherson, L.; Mihelcic, J. R.; Pramanik, A.; Raskin, L.; Van Loosdrecht, M. C. M.; Yeh, D.; Love, N. G. A New Planning and Design Paradigm to Achieve Sustainable Resource Recovery from Wastewater. Environ. Sci. Technol. 2009, 43, 6126. (7) Logan, B. E.; Rabaey, K. Conversion of Wastes into Bioelectricity and Chemicals by Using Microbial Electrochemical Technologies. Science 2012, 337, 686. (8) Logan, B. E.; Elimelech, M. Membrane-based processes for sustainable power generation using water. Nature 2012, 488, 313. (9) Rozendal, R. A.; Hamelers, H. V. M.; Rabaey, K.; Keller, J.; Buisman, C. J. N. Towards practical implementation of bioelectrochemical wastewater treatment. Trends Biotechnol. 2008, 26, 450. (10) Strathmann, H. Electrodialysis, a mature technology with a multitude of new applications. Desalination 2010, 264, 268. (11) Korngold, E.; Aronov, L.; Daltrophe, N. Electrodialysis of brine solutions discharged from an RO plant. Desalination 2009, 242, 215. (12) Korngold, E.; Aronov, L.; Belayev, N.; Kock, K. Electrodialysis with brine solutions oversaturated with calcium sulfate. Desalination 2005, 172, 63. (13) Tong, T. Z.; Elimelech, M. The Global Rise of Zero Liquid Discharge for Wastewater Management: Drivers, Technologies, and Future Directions. Environ. Sci. Technol. 2016, 50, 6846. (14) Ghyselbrecht, K.; Huygebaert, M.; Van der Bruggen, B.; Ballet, R.; Meesschaert, B.; Pinoy, L. Desalination of an industrial saline water with conventional and bipolar membrane electrodialysis. Desalination 2013, 318, 9. (15) Han, L.; Galier. S.; Roux-De Balmann, H. Ion hydration number and electro-osmosis during electrodialysis of mixed salt solution. Desalination, 2015, 373, 38. (16) Zhang, Y. F.; Liu, R.; Lang, Q. L.; Tan, M.; Zhang, Y. Composite anion exchange membrane made by layer-by-layer method for selective ion separation and water migration control. Sep. Purif. Technol. 2018, 192, 278. (17) Li, Y.; Xu, T. W. Permselectivities of monovalent anions through 39



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

pyridine-modified anion-exchange membranes. Sep. Purif. Technol. 2008, 61, 430. (18) Geise, G. M.; Cassady, H. J.; Paul, D. R.; Logan, B. E.; Hickner, M. A. Specific ion effects on membrane potential and the permselectivity of ion exchange membranes. Phys. Chem. Chem. Phys. 2014, 16, 21673. (19) Imteyaz, S.; Rafiuddin. Effects of monovalent ions on membrane potential and permselectivity: evaluation of fixed charge density of polymer based zirconium aluminophosphate composite membrane. RSC Adv. 2015, 5, 96008. (20) Cassady, H. J.; Cimino, E. C.; Kumar, M.; Hickner, M. A. Specific ion effects on the permselectivity of sulfonated poly(ether sulfone) cation exchange membranes. J. Membr. Sci. 2016, 508, 146. (21) Zhang, Y.; Van der Bruggen, B.; Pinoy, L.; Meesschaert, B. Separation of nutrient ions and organic compounds from salts in RO concentrates by standard and monovalent selective ion-exchange membranes used in electrodialysis. J. Membr. Sci. 2009, 332, 104. (22) Zhang, Y.; Desmidt, E.; Van Looveren, A.; Pinoy, L.; Meesschaert, B.; Van der Bruggen, B. Phosphate Separation and Recovery from Wastewater by Novel Electrodialysis. Environ. Sci. Technol. 2013, 47, 5888. (23)Reig, M.; Valderrama, C.; Gibert, O.; Cortina, J. L. Selectrodialysis and bipolar membrane electrodialysis combination for industrial process brines treatment: Monovalent-divalent ions separation and acid and base production. Desalination 2016, 399, 88. (24)Reig, M.; Vicino. X.; Valderrama, C.; Gibert, O.; Cortina, J. L. Application of selectrodialysis for the removal of As from metallurgical process waters: Recovery of Cu and Zn. Sep. Purif. Technol. 2018, 195, 404. (25) Zhang, Y. F.; Liu, L.; Du, J.; Fu, R. Q.; Van der Bruggen, B.; Zhang, Y. Fracsis: Ion fractionation and metathesis by a NF-ED integrated system to improve water recovery. J. Membr. Sci. 2017, 523, 385. (26) Mahmoud, A.; Hoadley, A. F. A. An evaluation of a hybrid ion exchange electrodialysis process in the recovery of heavy metals from simulated dilute industrial wastewater. Water Res. 2012, 46, 3364. (27) Fu, F. L.; Wang, Q. Removal of heavy metal ions from wastewaters: a review. J. Environ. Manage. 2011, 92, 407. (28) Babilas, D.; Dydo, P. Selective zinc recovery from electroplating wastewaters by electrodialysis enhanced with complex formation. Sep. Purif. Technol. 2018, 192, 419. (29) Chen, Q.B.; Ji, Z.Y.; Liu, J.; Zhao, Y.Y.; Wang, S.Z.; Yuan, J.S. Development of recovering lithium from brines by selective-electrodialysis: Effect of coexisting cations on the migration of lithium. J. Membr. Sci. 2018, 548, 408. (30) Benvenuti, T.; Krapf, R. S.; Rodrigues, M. A. S.; Bernardes, A. M.; Zoppas-Ferreira, J. Recovery of nickel and water from nickel electroplating wastewater by electrodialysis. Sep. Purif. Technol. 2014, 129, 106. (31) Reig, M.; Vecino, X.; Valderrama, C.; Gibert, O.; Cortina, J. L. Application of selectrodialysis for the removal of As from metallurgical process waters: Recovery of Cu and Zn. Sep. Purif. Technol. 2018, 195, 404. (32) Alvarado, L.; Ramírez, A.; Rodríguez-Torres, I. Cr(VI) removal by continuous 40


Page 40 of 51

Page 41 of 51 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

electrodeionization: Study of its basic technologies. Desalination 2009, 249, 423. (33) Alvarado, L.; Chen, A. C. Electrodeionization: Principles, Strategies and Applications. Electrochim. Acta 2014, 132, 583. (34) Feng, X.; Wu, Z. C.; Chen, X. F. Removal of metal ions from electroplating effluent by EDI process and recycle of purified water. Sep. Purif. Technol. 2007, 57, 257. (35) Zheng, X.Y.; Pan, S. Y.; Tseng, P. C.; Zheng, H. L.; Chiang, P. C. Optimization of resin wafer electrodeionization for brackish water desalination. Sep. Purif. Technol. 2018, 194, 346. (36) Pan, S. Y.; Snyder, S. W.; Ma, H. W.; Lin, Y. J.; Chiang, P. C. Development of a Resin Wafer Electrodeionization Process for Impaired Water Desalination with High Energy Efficiency and Productivity. ACS Sustainable Chem. Eng. 2017, 5, 2942. (37) Bouhidel, K. E.; Lakehal, A. Influence of voltage and flow rate on electrodeionization (EDI) process efficiency. Desalination 2006, 193, 411. (38) Xu, T. W.; Huang, C. H. Electrodialysis-based separation technologies: A critical review. AIChE J. 2008, 54, 3147. (39) Arar, Ö.; Yüksel, Ü.; Kabay, N.; Yüksel, M. Removal of Cu2+ ions by a micro-flow electrodeionization (EDI) system. Desalination 2011, 277, 296. (40) Alvarado, L.; Rodríguez-Torres, I.; Balderas, P. Investigation of Current Routes in Electrodeionization System Resin Beds During Chromium Removal. Electrochim. Acta 2015, 182, 763. (41) Bunani, S.; Yoshizuka, K.; Nishihama, S.; Arda, M.; Kabay, N. Application of bipolar membrane electrodialysis (BMED) for simultaneous separation and recovery of boron and lithium from aqueous solutions. Desalination 2017, 424, 37. (42) Bunani, S.; Arda, M.; Kabay, N.; Yoshizuka, K.; Nishihama, S. Effect of process conditions on recovery of lithium and boron from water using bipolar membrane electrodialysis (BMED). Desalination 2017, 416, 10. (43) Jiang, C. X.; Wang, Y. M.; Wang, Q. Y.; Feng, H. Y.; Xu, T. W. Production of Lithium Hydroxide from Lake Brines through Electro–Electrodialysis with Bipolar Membranes (EEDBM). Ind. Eng. Chem. Res. 2014, 53, 6103. (44) Frioui, S.; Oumeddour, R.; Lacour, S. Highly selective extraction of metal ions from dilute solutions by hybrid electrodialysis technology. Sep. Purif. Technol. 2017, 174, 264. (45) Cherif, A. T.; Elmidaoui, A.; Gavach, C. Separation of Ag+, Zn2+ and Cu2+ ions by electrodialysis with monovalent cation specific membrane and EDTA. J. Membr. Sci. 1993, 76, 39. (46) Iizuka, A.; Yamashita, Y.; Nagasawa, H.; Yamasaki, A.; Yanagisawa, Y. Separation of lithium and cobalt from waste lithium-ion batteries via bipolar membrane electrodialysis coupled with chelation. Sep. Purif. Technol. 2013, 113, 33. (47) Huang, T. C.; Wang, J. K. Preferential transport of nickel and cupric ions through cation exchange membrane in electrodialysis with a complex agent. Desalination 1992, 86, 257. (48) Chaudhary, A. J.; Donaldson, J. D.; Grimes, S. M.; Yasri, N. G. Separation of nickel from cobalt using electrodialysis in the presence of EDTA. J. Appl. 41



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

Electrochem. 2000, 30, 439. (49) Taghdirian, H. R.; Moheb, A.; Mehdipourghazi, M. Selective separation of Ni(II)/Co(II) ions from dilute aqueous solutions using continuous electrodeionization in the presence of EDTA. J. Membr. Sci. 2010, 362, 68. (50) Wang, D.; Hu, J. G.; Liu, D. B.; Chen, Q. Y.; Li, J. Selective transport and simultaneous separation of Cu(II), Zn(II) and Mg(II) using a dual polymer inclusion membrane system. J. Membr. Sci. 2017, 524, 205. (51) Vera, R.; Gelde, L.; Anticó, E.; de Yuso, M. V. M.; Benavente, J.; Fontàs, C. Tuning physicochemical, electrochemical and transport characteristics of polymer inclusion membrane by varying the counter-anion of the ionic liquid Aliquat 336. J. Membr. Sci. 2017, 529, 87. (52) Mahanty, B.; Mohapatra, P. K.; Raut, D. R.; Das, D. K.; Behere, P. G.; Afzal, M.; Verboom, W. Polymer Inclusion Membrane Containing a Tripodal Diglycolamide Ligand: Actinide Ion Uptake and Transport Studies. Ind. Eng. Chem. Res. 2016, 55, 2202. (53) Gherasim, C. V.; Bourceanu, G.; Olariu, R. I.; Arsene, C. A novel polymer inclusion membrane applied in chromium (VI) separation from aqueous solutions. J. Hazard. Mater. 2011, 197, 244. (54) Nghiem, L. D.; Mornane, P.; Potter, I. D.; Perera, J. M.; Cattrall, R.W. ; Kolev, S. D. Extraction and transport of metal ions and small organic compounds using polymer inclusion membranes (PIMs). J. Membr. Sci. 2006, 281, 7. (55) Almeida, M. I. G. S.; Cattrall, R. W.; Kolev, S. D. Recent trends in extraction and transport of metal ions using polymer inclusion membranes (PIMs). J. Membr. Sci. 2012, 415, 9. (56) Blitz-Raith, A. H.; Paimin, R.; Cattrall, R. W.; Kolev, S. D. Separation of cobalt(II) from nickel(II) by solid-phase extraction into Aliquat 336 chloride immobilized in poly(vinyl chloride). Talanta 2007, 71, 419. (57) Baba, Y.; Kubota, F.; Goto, M.; Cattrall, R. W.; Kolev, S. D. Separation of cobalt(II) from manganese(II) using a polymer inclusion membrane withN-[N,N-di(2-ethylhexyl)aminocarbonylmethyl]glycine (D2EHAG) as the extractant/carrier. J. Chem. Technol. Biotechnol. 2016, 91, 1320. (58) Chaudhury, S.; Bhattacharyya, A.; Goswami, A. Electrodriven Transport of Cs+through Polymer Inclusion Membrane as “Solvent Separated Ions”. Ind. Eng. Chem. Res. 2016, 55, 3120. (59) Kaya, A.; Onac, C.; Alpoguz, H. K. A novel electro-driven membrane for removal of chromium ions using polymer inclusion membrane under constant D.C. electric current. J. Hazard. Mater. 2016, 317, 1. (60) Cordell, D.; Drangert, J. O.; White, S. The story of phosphorus: Global food security and food for thought. Global Environ. Change 2009, 19 , 292. (61) Desmidt, E.; Verstraete, W.; Dick, J.; Meesschaert, B. D.; Carballa, M. Ureolytic phosphate precipitation from anaerobic effluents. Water Sci. Technol. 2009, 59, 1983. (62) Cornel, P.; Schaum, C. Phosphorus recovery from wastewater: needs, technologies and costs. Water Sci. Technol. 2009, 59, 1069. (63) Wang, X. L.; Wang, Y. M.; Zhang, X.; Feng, H. Y.; Li, C. R.; Xu, T. W. Phosphate 42


Page 42 of 51

Page 43 of 51 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

Recovery from Excess Sludge by Conventional Electrodialysis (CED) and Electrodialysis with Bipolar Membranes (EDBM). Ind. Eng. Chem. Res. 2013, 52, 15896. (64) Liao, P. H.; Chen, A.; Lo, K. V. Removal of nitrogen from swine manure wastewaters by ammonia stripping. Bioresour. Technol. 1995, 54, 17. (65) EL-Bourawi, M. S.; Khayet, M.; Ma, R.; Ding, Z.; Li, Z.; Zhang, X. Application of vacuum membrane distillation for ammonia removal. J. Membr. Sci.2007, 301, 200. (66) Mondor, M.; Masse, L.; Ippersiel, D.; Lamarche, F.; Masse, D. I. Use of electrodialysis and reverse osmosis for the recovery and concentration of ammonia from swine manure. Bioresour. Technol.2008, 99, 7363. (67) Huang, C. H.; Xu, T. W.; Zhang, Y. P.; Xue, Y. H.; Chen, G. W. Application of electrodialysis to the production of organic acids: State-of-the-art and recent developments. J. Membr. Sci. 2007, 288, 1. (68) Yu, L. X.; Guo, Q. F.; Hao, J. H.; Jiang, W. J. Recovery of acetic acid from dilute wastewater by means of bipolar membrane electrodialysis. Desalination 2000, 129, 283. (69) Wang, Y. M.; Zhang, N.; Huang, C. H.; Xu, T. W. Production of monoprotic, diprotic, and triprotic organic acids by using electrodialysis with bipolar membranes: Effect of cell configurations. J. Membr. Sci. 2011, 385, 226. (70) Zhang, F; Huang, C. H.; Xu T. W. Production of Sebacic Acid Using Two-Phase Bipolar Membrane Electrodialysis. Ind. Eng. Chem. Res. 2009, 48, 7482. (71) Arslan, D.; Zhang, Y.; Steinbusch, K. J. J.; Diels, L.; Hamelers, H. V. M.; Buisman, C. J. N.; De Wever, H. In-situ carboxylate recovery and simultaneous pH control with tailor-configured bipolar membrane electrodialysis during continuous mixed culture fermentation. Sep. Purif. Technol. 2017, 175, 27. (72) Szczygiełda, M.; Antczak, J.; Prochaska, K. Separation and concentration of succinic acid from post-fermentation broth by bipolar membrane electrodialysis (EDBM). Sep. Purif. Technol. 2017, 181, 53. (73) Wang, X. L.; Wang, Y. M.; Zhang, X.; Xu, T. W. In situ combination of fermentation and electrodialysis with bipolar membranes for the production of lactic acid: operational compatibility and uniformity. Bioresour. Technol. 2012, 125, 165. (74) Wang, X. L.; Wang, Y. M.; Zhang, X.; Feng, H. Y.; Xu, T. W. In-situ combination of fermentation and electrodialysis with bipolar membranes for the production of lactic acid: continuous operation. Bioresour. Technol. 2013, 147, 442. (75) Jones, R. J.; Massanet-Nicolau, J.; Guwy, A.; Premier, G. C.; Dinsdale, R. M.; Reilly, M. Removal and recovery of inhibitory volatile fatty acids from mixed acid fermentations by conventional electrodialysis. Bioresour. Technol. 2015, 189, 279. (76) Novalic, S.; Kongbangkerd, T.; Kulbe, K. D. Recovery of organic acids with high molecular weight using a combined electrodialytic process. J. Membr. Sci. 2000, 166, 99. (77) Wang, Y. M.; Zhang, X.; Xu, T. W. Integration of conventional electrodialysis and electrodialysis with bipolar membranes for production of organic acids. J. Membr. Sci. 2010, 365, 294.. (78) Zhang, Y. F.; Liu, R.; Lang, Q. L.; Tan, M.; Zhang, Y. Composite anion exchange 43



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

membrane made by layer-by-layer method for selective ion separation and water migration control. Sep. Purif. Technol. 2018, 192, 278. (79) Liu, F.; Coronell, O.; Call, D. F. Electricity generation using continuously recirculated flow electrodes in reverse electrodialysis. J. Power Sources 2017, 355, 206. (80) Kingsbury, R. S.; Liu, F.; Zhu, S.; Boggs, C.; Armstrong, M. D.; Call, D. F.; Coronell, O. Impact of natural organic matter and inorganic solutes on energy recovery from five real salinity gradients using reverse electrodialysis. J. Membr. Sci. 2017, 541, 621. (81) Tedesco, M.; Cipollina, A.; Tamburini, A.; Micale, G. Towards 1 kW power production in a reverse electrodialysis pilot plant with saline waters and concentrated brines. J. Membr. Sci. 2017, 522, 226. (82) Weinstein, J. N.; Leitz, F. B. Electric Power from Differences in Salinity: The Dialytic Battery. Science 1976, 191, 557. (83) YuSafronova, E.; Golubenko, D. V.; Shevlyakova, N. V.; Dʹyakova, M. G.; Tverskoi, V. A.; Dammak, L.; Grande, D.; Yaroslavtsev, A. B. New cation-exchange membranes based on cross-linked sulfonated polystyrene and polyethylene for power generation systems. J. Membr. Sci. 2016, 515, 196. (84) Zhang, B. P.; Hong, J. G.; Xie, S H..; Xia, S. M.; Chen, Y. S. An integrative modeling and experimental study on the ionic resistance of ion-exchange membranes. J. Membr. Sci. 2017, 524, 362. (85) Pawlowski, S.; Geraldes, V.; Crespo, J. G.; Velizarov, S. Computational fluid dynamics (CFD) assisted analysis of profiled membranes performance in reverse electrodialysis. J. Membr. Sci. 2016, 502, 179. (86) Yip, N. Y.; Elimelech, M. Comparison of Energy Efficiency and Power Density in Pressure Retarded Osmosis and Reverse Electrodialysis. Environ. Sci. Technol. 2014, 48, 11002. (87) Kwon, K.; Park, B. H.; Kim, D. H.; Kim, D. Comparison of spacer-less and spacer-filled reverse electrodialysis. J. Renewable Sustainable Energy 2017, 9, 044502. (88) Gurreri, L.; Tamburini, A.; Cipollina, A.; Micale, G. CFD analysis of the fluid flow behavior in a reverse electrodialysis stack. Desalin. Water Treat. 2012, 48, 390. (89) Scialdone, O.; Guarisco, C.; Grispo, S.; DʹAngelo, A.; Galia, A. Investigation of electrode material – Redox couple systems for reverse electrodialysis processes. Part I: Iron redox couples. J. Electroanal. Chem. 2012, 681, 66. (90) Burheim, O. S.; Seland, F.; Pharoah, J. G.; Kjelstrup, S. Improved electrode systems for reverse electro-dialysis and electro-dialysis. Desalination 2012, 285 , 147. (91) Vermaas, D. A.; Kunteng, D.; Saakes, M.; Nijmeijer, K. Fouling in reverse electrodialysis under natural conditions. Water Res. 2013, 47, 1289. (92) Brauns, E. An alternative hybrid concept combining seawater desalination, solar energy and reverse electrodialysis for a sustainable production of sweet water and electrical energy. Desalin. Water Treat. 2010, 13, 53. (93) Li, W. Y.; Krantz, W. B.; Cornelissen, E. R.; Post, J. W.; Verliefde, A. R. D.; Tang, C. Y. Y. A novel hybrid process of reverse electrodialysis and reverse osmosis for low 44


Page 44 of 51

Page 45 of 51 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

energy seawater desalination and brine management. Appl. Energy 2013, 104, 592. (94) Logan, B. E.; Elimelech, M. Membrane-based processes for sustainable power generation using water. Nature 2012, 488, 313. (95) Bevacqua, M.; Tamburini, A.; Papapetrou, M.; Cipollina, A.; Micale, G.; Piacentino, A. Reverse electrodialysis with NH4HCO3-water systems for heat-to-power conversion. Energy 2017, 137, 1293. (96) Luo, X.; Cao, X. X.; Mo, Y. H.; Xiao, K.; Zhang, X. Y.; Liang, P.; Huang, X. Power generation by coupling reverse electrodialysis and ammonium bicarbonate: Implication for recovery of waste heat. Electrochem. Commun. 2012, 19, 25. (97) Kwon, K.; Park, B. H.; Kim, D. H.; Kim, D. Parametric study of reverse electrodialysis using ammonium bicarbonate solution for low-grade waste heat recovery. Energy Convers. Manage. 2015, 103, 104. (98) Hatzell, M. C.; Logan, B. E. Evaluation of flow fields on bubble removal and system performance in an ammonium bicarbonate reverse electrodialysis stack. J. Membr. Sci. 2013, 446, 449. (99) Huang, W.; Walker, W. S.; Kim, Y. Junction potentials in thermolytic reverse electrodialysis. Desalination 2015, 369, 149. (100) Kim, D. H.; Park, B. H.; Kwon, K.; Li, L.; Kim, D. Modeling of power generation with thermolytic reverse electrodialysis for low-grade waste heat recovery. Appl. Energy 2017, 189, 201. (101) Wang, Q.; Gao, X. L.; Zhang, Y. S.; He, Z. L.; Ji, Z. Y.; Wang, X. Y.; Gao, C. J. Hybrid RED/ED system: Simultaneous osmotic energy recovery and desalination of high-salinity wastewater. Desalination 2017, 405, 59. (102) Chen, Q.; Liu, Y. Y.; Xue, C.; Yang, Y. L.; Zhang, W. M. Energy self-sufficient desalination stack as a potential fresh water supply on small islands. Desalination 2015, 359, 52. (103) Xu, T. W.; Yang, W. H. Sulfuric acid recovery from titanium white (pigment) waste liquor using diffusion dialysis with a new series of anion exchange membranes — static runs. J. Membr. Sci. 2001, 183, 193. (104) Zhang, Y.; Helsen, J. Apparatus and method for product recovery and electrical energy generation, [patent] WO2015028685. (105) Zhang, Y.; Helsen, J. A Novel Diffusion Dialysis Stack for Acid Recovery with Simultaneous Power Generation. In International Congress on Membranes and Membrane Processes (ICOM), Suzhou, China, 2014. (106) Rabaey, K.; Rozendal, R. A. Microbial electrosynthesis - revisiting the electrical route for microbial production. Nat. Rev. Microbiol. 2010, 8, 706. (107) Pant, D.; Singh, A.; Van Bogaert, G.; Olsen, S. I.; Nigam, P. S.; Diels, L.; Vanbroekhoven, K. Bioelectrochemical systems (BES) for sustainable energy production and product recovery from organic wastes and industrial wastewaters. RSC Adv. 2012, 2, 1248. (108) Sharma, M.; Aryal, N.; Sarma, P. M.; Vanbroekhoven, K.; Lal, B.; Benetton, X. D.; Pant, D. Bioelectrocatalyzed reduction of acetic and butyric acids via direct electron transfer using a mixed culture of sulfate-reducers drives electrosynthesis of alcohols and acetone. Chem. commun. 2013, 49, 6495. 45



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44

(109) Oh, S. T.; Kim, J. R.; Premier, G. C.; Lee, T. H.; Kim, C.; Sloan, W. T. Sustainable wastewater treatment: how might microbial fuel cells contribute. Biotechnol. adv. 2010, 28, 871. (110) Chae, K. J.; Choi, M. J.; Lee, J. W.; Kim, K. Y.; Kim, I. S. Effect of different substrates on the performance, bacterial diversity, and bacterial viability in microbial fuel cells. Bioresour. Technol. 2009, 100, 3518. (111) Kim, J. R.; Jung, S. H.; Regan, J. M.; Logan, B. E. Electricity generation and microbial community analysis of alcohol powered microbial fuel cells. Bioresour. Technol. 2007, 98, 2568. (112) Rahimnejad, M.; Ghoreyshi, A. A.; Najafpour, G.; Jafary, T. Power generation from organic substrate in batch and continuous flow microbial fuel cell operations. Appl. Energy 2011, 88, 3999. (113) Song, T. S.; Wu, X. Y.; Zhou, C. C. Effect of different acclimation methods on the performance of microbial fuel cells using phenol as substrate. Bioprocess and biosyst. Eng. 2014, 37, 133. (114) Koók, L.; Rózsenberszki, T.; Nemestóthy, N.; Bélafi-Bakó, K.; Bakonyi, P. Bioelectrochemical treatment of municipal waste liquor in microbial fuel cells for energy valorization. J. Cleaner Prod. 2016, 112, 4406. (115) Zhang, F.; Cheng, S. A.; Pant, D.; Van Bogaert, G.; Logan, B. E. Power generation using an activated carbon and metal mesh cathode in a microbial fuel cell. Electrochem. Commun. 2009, 11, 2177. (116) Zhang, L. X.; Zhou, S. G.; Zhuang, L.; Li, W. S.; Zhang, J. T.; Lu, N.; Deng, L. F. Microbial fuel cell based on Klebsiella pneumoniae biofilm. Electrochem. Commun. 2008, 10, 1641. (117) Wang, H. Y.; Bernarda, A.; Huang, C. Y.; Lee, D. J.; Chang, J. S. Micro-sized microbial fuel cell: A mini-review. Bioresour. Technol. 2011, 102, 235. (118) Pant, D.; Van Bogaert, G.; De Smet, M.; Diels, L.; Vanbroekhoven, K. Use of novel permeable membrane and air cathodes in acetate microbial fuel cells. Electrochim. Acta 2010, 55, 7710. (119) Manohar, A. K.; Mansfeld, F. The internal resistance of a microbial fuel cell and its dependence on cell design and operating conditions. Electrochim. Acta 2009, 54, 1664. (120) Kim, B. H.; Kim, H. J.; Hyun, M. S.; Park, D. H. Direct electrode reaction of Fe(III)-reducing bacterium, Shewanella putrefaciens. J. Microbiol. Biotechnol. 1999, 9, 127. (121) Xing, D. F.; Zuo, Y.; Cheng, S. A.; Regan, J. M.; Logan, B. E. Electricity generation by Rhodopseudomonas palustris DX-1. Environ. Sci. Technol. 2008, 42,4146. (122) Cusick, R. D.; Kim, Y.; Logan, B. E. Energy Capture from Thermolytic Solutions in Microbial Reverse-Electrodialysis Cells. Science 2012, 335, 1474. (123) Leong, J. X.; Daud, W. R. W.; Ghasemi, M.; Ben Liew, K.; Ismail, M. Ion exchange membranes as separators in microbial fuel cells for bioenergy conversion: A comprehensive review. Renewable Sustainable Energy Rev. 2013, 28, 575. (124) Kundu, A.; Sahu, J. N.; Redzwan, G.; Hashim, M. A. An overview of cathode 46


Page 46 of 51

Page 47 of 51 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


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material and catalysts suitable for generating hydrogen in microbial electrolysis cell. Int. J. Hydrogen Energy 2013, 38, 1745. (125) Blanchard, G. C.; Foley, R. T. The Operation of an Ion‐Membrane Fuel Cell with Microbially‐Produced Hydrogen. J. Electrochem. Soc. 1971, 118, 1232. (126) Zhang, Y. F.; Angelidaki, I. Microbial electrolysis cells turning to be versatile technology: recent advances and future challenges. Water Res. 2014, 56, 11. (127) Zhang, Y., Yan, B. H., Du, J. A method and apparatus to couple electrosynthesis with a membrane stack.[Patent] CN 201510339417. (128) Srikanth, S.; Maesen, M.; Dominguez-Benetton, X.; Vanbroekhoven, K.; Pant, D. Enzymatic electrosynthesis of formate through CO2 sequestration/reduction in a bioelectrochemical system (BES). Bioresour. Technol. 2014, 165, 350. (129) Nevin, K. P.; Woodard, T. L.; Franks, A. E.; Summers, Z. M.; Lovley, D. R. Microbial electrosynthesis: feeding microbes electricity to convert carbon dioxide and water to multicarbon extracellular organic compounds. mBio, 2010,1, e00103-10. (130) Marshall, C. W.; Ross, D. E.; Fichot, E. B.; Norman, R. S.; May, H. D. Electrosynthesis of commodity chemicals by an autotrophic microbial community. Appl. Environ. Microbiol. 2012, 78, 8412. (131) Gildemyn, S.; Verbeeck, K.; Slabbinck, R.; Andersen, S. J.; Prevoteau, A.; Rabaey, K. Integrated Production, Extraction, and Concentration of Acetic Acid from CO2 through Microbial Electrosynthesis. Environ. Sci. Technol. Lett. 2015, 2, 325. (132) Bajracharya, S.; Yuliasni, R.; Vanbroekhoven, K.; Buisman, C. J. N.; Strik, D. P. B. T. B.; Pant, D. Long-term operation of microbial electrosynthesis cell reducing CO2 to multi-carbon chemicals with a mixed culture avoiding methanogenesis. Bioelectrochemistry 2017, 113, 26. (133) Soussan, L.; Riess, J.; Erable, B.; Delia, M. L.; Bergel, A. Electrochemical reduction of CO2 catalysed by Geobacter sulfurreducens grown on polarized stainless steel cathodes. Electrochem. Commun. 2013, 28, 27. (134) Ganigue, R.; Puig, S.; Batlle-Vilanova, P.; Balaguer, M. D.; Colprim, J. Microbial electrosynthesis of butyrate from carbon dioxide. Chem. Commun. 2015, 51, 3235. (135) Ross, D. E.; Flynn, J. M.; Baron, D. B.; Gralnick, J. A.; Bond, D. R. Towards electrosynthesis in shewanella: energetics of reversing the mtr pathway for reductive metabolism. PloS one, 2011, 6, e16649. (136) Steinbusch, K. J. J.; Hamelers, H. V. M.; Buisman, C. J. N. Alcohol production through volatile fatty acids reduction with hydrogen as electron donor by mixed cultures. Water Res. 2008, 42 , 4059. (137) Steinbusch, K. J. J.; Hamelers, H. V. M.; Schaap, J. D.; Kampman, C.; Buisman, C. J. N. Bioelectrochemical Ethanol Production through Mediated Acetate Reduction by Mixed Cultures. Environ. Sci. Technol. 2010, 44, 513. (138) Wu, X.; Modin, O. Ammonium recovery from reject water combined with hydrogen production in a bioelectrochemical reactor. Bioresour. Technol. 2013, 146, 530. (139) Cusick, R. D.; Logan, B. E. Phosphate recovery as struvite within a single chamber microbial electrolysis cell. Bioresour. Technol. 2012, 107, 110. 47



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(140) Ledezma, P.; Jermakka, J.; Keller, J.; Freguia, S. Recovering Nitrogen as a Solid without Chemical Dosing: Bio-Electroconcentration for Recovery of Nutrients from Urine. Environ. Sci. Technol. Lett. 2017, 4, 119. (141) Ge, L.; Wu, B.; Li, Q. H.; Wang, Y. Q.; Yu, D. B.; Wu, L.; Pan, J. F; Miao, J. B.; Xu, T. W. Electrodialysis with nanofiltration membrane (EDNF) for high-efficiency cations fractionation. J. Membr. Sci. 2016, 498, 192. (142) Hong, S. U.; Malaisamy, R.; Bruening, M. L. Separation of fluoride from other monovalent anions using multilayer polyelectrolyte nanofiltration membranes. Langmuir 2007, 23, 1716.

Wen-Yan Zhao earned her B. Eng. in Environment Science from Xiangtan University (2017). In 2017, she joined Prof. Zhang Yang’s group. She is currently a Ph.D. student at the Waste Valorization & Water Reuse Group, Qingdao Institute of Bioenergy & Bioprocess Technology, Chinese Academy of Sciences. Her current research focuses on membrane technology.

Miaomiao Zhou earned her B.S. in Pharmaceutical Engineering from East China University of Science and Technology and M.S. in Biological Engineering from Institute of Oceanology, Chinese 48


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Academy of Sciences. She started her research in Professor Zhang’s group in the summer of 2015 as a Ph.D. student. Her work focused on the wastewater valorization and microbial electrochemical synthesis. She will defend her Ph.D. degree in Chemical Engineering at Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences in June 2018

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Professor Tongwen Xu (University of Science and Technology of China) received his BSc (1989) and MSc (1992) from Hefei University of Technology and his Chemical Engineering PhD (1995) from Tianjin University. He was a postdoctoral researcher at Nankai University (1995-1997). He was visiting scientist at University of Tokyo (2000), Tokyo Institute of Technology (2001) and Gwangju Institute of Science and Technology (Brain Pool Program Korea award recipient) (2007). He is the Fellow of the Royal Society of Chemistry (2015-now). He was recipient of a National Science Fund for Distinguished Young Scholars (2010) and Cheung Kong Scholars Programme. His research interests cover membranes and related processes, particularly ion exchange membranes and for energy and environmental applications.

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Dr. Yang Zhang is the leader of Waste Valorization and Water Reuse Group at Qingdao Institute of Bioenergy and Bioprocess Technology (QIBEBT), Chinese Academy of Sciences (CAS). He obtained his B.E. from Ocean University of China (Qingdao, China) in 2003, M.Sc. from Chalmers University of Technology (Gothenburg, Sweden) in 2005 and Ph.D. from KULeuven (Leuven, Belgium) in 49



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2011. He received the financial support through “Hundred-Talent Program of Chinese Academy of Sciences (CAS)” and joined QIBEBT as a professor in 2015. His research mainly focuses on solute transport mechanisms in membranes and membrane integrated systems for water purification, wastewater reuse, salt fractionation and resource recovery.

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