Alkhadra Et Al. 2019 - Continuous Separation of Radionuclides From Contaminated Water by SED

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Remediation and Control Technologies

Continuous separation of radionuclides from
contaminated water by shock electrodialysis
Mohammad Alkhadra, Kameron Conforti, Tao Gao, Huanhuan Tian, and Martin Z. Bazant
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.9b05380 • Publication Date (Web): 03 Dec 2019
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Page 1 of 31 Environmental Science & Technology
Continuous separation of radionuclides from

contaminated water by shock electrodialysis
Mohammad A. Alkhadra,†,¶ Kameron M. Conforti,†,¶ Tao Gao,† Huanhuan
Tian,† and Martin Z. Bazant∗,†,‡
†Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,

MA 02139, USA
‡Department of Mathematics, Massachusetts Institute of Technology, Cambridge, MA 02139,
USA
¶Equal Contribution
E-mail: bazant@mit.edu
Nuclear Reactor Shock Electrodialysis
Turbine Waste Clean water

Generator
Steam
Cooling water
(Condenser)
Supply
Condensate electricity
Core
Boric Acid Lithium
Lithium
Cobalt Cobalt
Cesium Cesium Contaminated water
1
ACS Paragon Plus Environment
Environmental Science & Technology Page 2 of 31
1 Abstract
2 The increasing popularity of nuclear energy necessitates development of new meth-
3 ods to treat water that becomes contaminated with radioactive substances. Because
4 this polluted water comprises several dissolved species (not all of which are radioac-
5 tive), selective accumulation of the radionuclides is desirable to minimize the volume
6 of nuclear waste and to facilitate its containment or disposal. In this article, we use
7 shock electrodialysis to selectively, continuously, and efficiently remove cobalt and ce-
8 sium from a feed of dissolved lithium, cobalt, cesium, and boric acid. This formulation
9 models the contaminated water commonly found in light-water reactors and in other
10 nuclear processes. In a three-pass process, a consistent trade-off is observed between
11 the recovery of decontaminated water and the percentage of cobalt removed, which
12 offers flexibility in operating the system. For example, 99.5% of cobalt can be removed
13 with a water recovery of 43%, but up to 66% of the water can be recovered if deioniza-
14 tion of cobalt is allowed to drop to 98.3%. In general, the energy consumed during this
15 process (ranging between 1.76 and 4.8 kW h m−3 ) is low because only charged species
16 are targeted and virtually no energy is expended removing boric acid, the most abun-
17 dant species in solution.
18 1 Introduction
19 Nuclear waste is matter that undergoes radioactive decay, a spontaneous process by which
20 an unstable atomic nucleus emits radiation and concomitantly transforms into smaller
21 daughter nuclei. 1 Although radioactive decay is stochastic at the level of individual nuclei,
22 the expected rate of decay for a collection of radionuclides can be characterized in terms of
23 an observable decay constant such as the half life. 1 Radioactive waste is often a byproduct
24 in the industrial generation of nuclear power and is hazardous to the environment and to
25 nearly all forms of life. Indeed, high-energy radiation can ionize atoms or even generate
26 free radicals (e.g., hydroxyl from radiolysis of water) that react with the cellular compo-
27 nents of an organism, which may cause aberration of chromosomes, mutation of nucleic
2
28 acids, or death of cells. 2,3 Given the harmful nature of such radiation, the scientific com-
29 munity has sought to develop methods to isolate, manage, and dispose of nuclear waste.
30 In this article, we adapt an emerging electrokinetic deionization method known as shock
31 electrodialysis 4–8 (SED) to continuously treat water contaminated with radioactive ions.
32 This study focuses on the basic physics and design principles needed to selectively remove
33 cobalt (59 Co) and cesium (133 Cs), while recovering a reasonable fraction of the water fed
34 and minimizing the energy cost of the process. Since SED is an electrokinetic method,
35 separation of ions is based primarily on charge and is insensitive to mass, 4,5 which implies
36 that our results should also be applicable to radioactive isotopes of cobalt and cesium.
37 The principal aim of our methodology is to concentrate nuclear waste in a contained dis-
38 charge stream and, in turn, minimize the volume of waste that would need management,
39 recycling, or disposal in subsequent processes.
40 Our strategy for separation is based on the phenomenon of deionization shock waves 9
41 by which a sharp gradient in the concentration of salt propagates near an ion selective
42 surface, such as a cation exchange membrane 4,5 or metal electrodeposit. 10,11 Moreover,
43 our system comprises a weakly charged porous medium to sustain overlimiting current—at
44 which transport of ions is faster than by diffusion alone—as the conductivity of the solu-
45 tion diminishes near this surface. 5,10,12,13 The shock wave splits the system into a region
46 that is concentrated and another that is deionized. These regions are then continuously
47 separated by driving flow perpendicular to the applied electric field. 4 This system can
48 therefore achieve electrically tunable and “membraneless” separation within the porous
49 material without any physical barriers in the direction of flow. In contrast to conventional
50 electrodialysis in which overlimiting current is often sustained by chemical or hydrody-
51 namic instabilities, 14 overlimiting current in SED is sustained by electrokinetic phenomena
52 at the scale of pores, namely surface conduction and electroosmosis. 5,12,13,15 Experimen-
53 tally, concentration polarization was first observed in glass microchannels emanating from
54 nanoscopic junctions 16–18 or membranes. 15 SED, however, relies on the propagation of
3
55 macroscopic shock waves across a network of charged pores, which is necessary for flow
56 fractionation, 5,7 , scale-up to practical flow rates, 4 , and improvement of both desalina-
57 tion 5,13 and water recovery 4 by leveraging electroosmotic flow.
Nuclear Reactor Shock Electrodialysis x
Turbine
y
z
Generator e−
Anolyte Anolyte Out
Steam 1
/4O Anode (+)
1
/2H O 2
2
Q CEM (Nafion) Q
Enriched
H+ A− C+ Brine
Porous Frit
N
Contaminated QB
Cooling water
(Condenser)
Depleted
E Splitter
Q′ (< Q) Fresh
N
QF
Deionized
Boric Acid CEM (Nafion)
Condensate Lithium Catholyte Catholyte Out
Core Cobalt H+ 1
/2H C+ Cathode (−)
2
Cesium
Q Q
e−
Figure 1. Operating principles of a light-water nuclear reactor and the SED device used for decon-
tamination. (left) Simplified schematic of a boiling water reactor (a type of light-water reactor) used
to generate electrical power by heating water that turns into steam and drives a turbine. Several
radionuclides are present in this water and contaminate the reactor components outside the core;
refer to 2 for details. (right) A rectangular cross section of the SED device shows water splitting at
the anode and formation of molecular hydrogen at the cathode (maintained under acidic conditions
to prevent precipitation of metal hydroxides), which are the primary electrochemical reactions that
provide current to the cell. Contaminated water in the frit is then subjected to an electric field (~E)
that transports charged species (labeled C+ for cations and A− for anions) perpendicular to the
flow. Anions are blocked by cation exchange membranes (CEMs), and neutral species (labeled
N) are unaffected by the electric field. Here, flow rate is denoted by the letter Q, and streams are
colored based on relative concentration of ions.
58 The first laboratory scale prototype to successfully demonstrate SED was designed,
59 built, tested, and patented by our group. 5–8 To achieve continuous operation, subsequent
60 iterations of this system introduced a novel cross-flow architecture, in which the feed flows
61 into a porous glass frit placed between identical cation exchange membranes, as shown in
62 Figure 1. 4 The frit was made of sintered borosilicate glass, a porous material with nega-
63 tive charges bound to the surfaces of its pores, which were nominally 1 micron in size. By
64 placing a splitter downstream of the frit, the exiting fluid was separated into enriched and
65 deionized streams on the anodic and cathodic sides of the shock wave, respectively. Previ-
4
66 ous work showed that SED can continuously deionize electrolytes comprising monovalent
67 cations, including NaCl, KCl, KNO3 , and Na2 SO4 . 4 (These measurements were made by
68 quantifying changes in electrical conductivity of the solution.) This work also revealed
69 that water recovery (defined as the fraction of fluid recovered as desalinated water from
70 the concentrated feed) can be increased to over 80% by increasing the applied current and
71 without repositioning the splitter. Improved water recovery was attributed to electroos-
72 motic flow perpendicular to the imposed flow, which conveniently delivered more fluid to
73 the depleted region.
74 The present study is motivated by the recently discovered capability of SED to separate
75 specific ions from multicomponent electrolytes. In particular, recent work demonstrated
76 selective removal of magnesium—a divalent cation—from an aqueous mixture of NaCl
77 and MgCl2 with (retention) selectivity of up to 200:1 in the extreme case. 19 Since many
78 radionuclides and harmful products of corrosion are dissolved in water as multivalent ions,
79 this result suggests that SED can be used to purify water contaminated with radioactive
80 ions and byproducts of various nuclear processes.
81 2 Background and Experimental Design

82 In treating radioactive water, the goal is often to separate the fluid into two streams. The
83 first of these has low enough activity for safe discharge into the environment, and the
84 second (with the smallest possible volume) is concentrated in radionuclides for further
85 management. Existing methods for treatment can be broadly categorized into physical
86 methods, which focus on extracting uncontaminated water, and chemical methods, which
87 focus on extracting radionuclides. Physical methods include evaporation, reverse osmosis,
88 nanofiltration, ultrafiltration, and microfiltration. 20–23 In these methods, water is driven
89 across an interface (either a membrane, or a gas–liquid interface in the case of evapora-
90 tion) that retains dissolved species in a concentrated brine. The inclusion of an excess of
91 boric acid (commonly done in the process water of various nuclear reactors for neutron
5
92 poisoning 24,25 ) complicates the use of several physical methods and makes them more
93 energy intensive. This radioactively inert salt increases the osmotic pressure in membrane
94 technologies such as reverse osmosis and is highly corrosive 26 when concentrated. For
95 these reasons, selective removal is preferable to indiscriminately concentrating all dis-
96 solved species. 27
97 Chemical methods, which are typically (but not always) selective in molecular sepa-
98 rations, include solvent extraction (using liquid phase compounds), precipitation, chela-
99 tion, ion exchange, and electrodeionization (EDI, sometimes called hybrid ion-exchange
100 electrodialysis). 21,22 These methods target ions based on chemical reactivity (adsorption,
101 chelation, precipitation), 28,29 solubility and partition coefficient (solvent extraction), 30
102 affinity for charged or functionalized surfaces (ion exchange, EDI), 31–33 or response to
103 electric fields in solution (EDI). 32 Apart from SED, EDI is the only technology that involves
104 electrochemistry, and is the only chemical method that can operate continuously without
105 the need for additives or solvents. 32 The remaining methods require the use of sacrificial
106 chemicals, such as carriers or additives (adsorption, chelation, precipitation), non-aqueous
107 solvents (solvent extraction), or ion-exchange resins with regenerating acids and salts (ion
108 exchange), the disposal of which has been deemed challenging. 31,34
109 In light-water reactors (LWRs, see Figure 1 for a simplified schematic), the most com-
110 mon and active byproducts include cobalt-60 and cesium-137. 35,36 Cobalt-60 is the main
111 contributor to high levels of radiation because it has a short half life (5.3 years) and emits
112 high-energy gamma rays (1.17 and 1.33 MeV). 35 Cesium-137, on the other hand, has a
113 longer half life (30 years) and is not as active as cobalt-60, but it is one of most abun-
114 dant radionuclides produced from fission of uranium-235. 36,37 Moreover, this species poses
115 long-term risks because, like cobalt-60, it produces high-energy beta particles and gamma
116 rays. 38 Cesium in general is an alkaline metal that becomes a monovalent ion in solution
117 and is chemically similar to sodium and potassium. Radioactive cesium is therefore read-
118 ily taken up by biological organisms, in which it can deposit on soft tissue and, over time,
6
119 induce thyroid cancer. 36 Compared to other radionuclides, cesium-137 has been deemed
120 difficult to remove because of its small radius of hydration and high (mass) diffusivity. 36
Table 1. Concentrations of Prevalent Species in Practical Water, the Non-Radioactive Analog of

Contaminated Process Water in Nuclear Reactors
Species Concentration (ppm [mM]) Role

Boron 4,000 [370] Present in boric acid; boron-10 serves as neutron poison 24
Lithium-7 2.2 [0.32] Used (as LiOH) to stabilize pH and control corrosion 39
Cobalt-59 20 [0.34] Cobalt-60 is the main contributor to high levels of radiation 35
Cesium-133 100 [0.75] Cesium-137 is one of most abundant fission byproducts 36
121 In this study, we prepared model radioactive water (referred to hereafter as “practical
122 water”) with the composition outlined in Table 1, as proposed by our sponsor, Mitsubishi
123 Heavy Industries. This solution includes non-radioactive isotopes of the ions most abun-
124 dant and active in the process water of LWRs, namely cobalt and cesium. 35,36 Boric acid is
125 included abundantly as it is often used as neutron poison in these reactors because boron-
126 10 can reduce the likelihood of thermal fission by absorbing neutrons. 24 Lastly, lithium-7 is
127 used (in the form of LiOH) as an additive to control water chemistry and minimize the cor-
128 rosive effects of boric acid. 39,40 During operation, small amounts of hazardous corrosion
129 and fission byproducts (e.g., cobalt and cesium) are released into the process water, such
130 that non-radioactive species may undergo radioactivation near the hot reactor core. 36,41–43
131 (For example, cobalt-60 is produced when its precursor, cobalt-59, is bombarded with ther-
132 mal neutrons; cobalt-59 is the naturally occurring isotope of cobalt with 100% abundance,
133 and it is used in alloys that are required to possess thermal and mechanical resilience. 44 )
134 These species are then able to settle onto surfaces of the cooling system and recirculation
135 pipes, and the quantity of undesired deposits of radionuclides increases with time. 41,45
136 Accumulation of radioactive matter in the structural portions of nuclear reactors is thus an
137 occupational hazard to those who work in the vicinity of these systems and are exposed to
138 such radiation. We note, however, that demineralization of process water in LWRs is only
139 one possible application of SED, and the study of selective removal of cobalt and cesium is
140 generally relevant to treatment of nuclear (waste)water. 20,21,46,47
7
141 3 Materials and Experimental Methods

142 The device used here was based on a design recently published by our group. 19 This contin-
143 uous, laboratory scale architecture is illustrated in Figure 2. Our device included 3 inlets,
144 2 to transport fluid to the electrodes and a third to deliver contaminated feed, as well as 4
145 outlets, 2 to transport fluid from the electrodes and the other 2 to generate fresh and brine
146 streams at the splitter. All fluids were transported through 1/8th -inch Tygon® tubing (Saint-
147 Gobain) glued onto portplates made of cast acrylic. These portplates were used to seal
148 liquids inside the device and to support the rubber tubing in which fluid flows. Moreover,
149 four 1/16th -inch Viton® rubber gaskets (DuPont) were used to conformally seal the device
150 and simultaneously provide channels for the electrode solutions (catholyte and anolyte).
151 The electrodes in this device were platinum meshes (Sigma–Aldrich) that were connected
152 to a Gamry Reference 3000™ potentiostat/galvanostat using titanium wires (Alfa Aesar).
153 The electrodes and wires were secured in place by compressible Viton® gaskets. Cation
154 exchange membranes (nafion N115, Ion Power) with a thickness of approximately 130 µm
155 served as fluidic barriers between the electrode channels and the porous medium, which
156 in this study was a borosilicate frit (Adams & Chittenden Scientific Glass) with ultrafine
157 pores (nominally ranging from 0.9 to 1.4 µm in size), an internal surface area of 1.75 m2 g−1
158 based on Brunauer–Emmett–Teller (BET) theory, a mass density of 1.02 g m−3 , a porosity
159 of 0.31, and dimensions of 0.9 cm × 2 cm × 1 cm. Prior to assembly, the frit was glued onto
160 an acrylic frame using Devcon 2 Ton Epoxy (McMaster-Carr). The splitter (placed midway
161 down the frit for ease of assembly) was made of cast acrylic and was sealed against the top
162 face of the frit using 0.04-inch GORE™ expanded polytetrafluoroethylene (ePTFE) gasket
163 tape. Holes in all of the acrylic slabs and rubber gaskets were formed using a laser cutter
164 (Universal Laser Systems) and refined with a drill press (Palmgren 10-inch, 5-speed bench
165 model). These layers were then stacked and held together with nuts, bolts, and washers
166 made of 316 stainless steel.
8
Cat
holy
te Catholy
te O
ut
10 μm
Fresh
Capped
Brine
Capped
Platinum Mesh
Titanium Wire
z Ano
lyte Ano
ly te O
ut
Con Cap
y tam ped
ina
ted
x
Figure 2. Photographs and 3D illustration of the SED device that shows assembly. A working de-
vice consists of platinum electrodes, titanium wire, and a microporous borosilicate frit sandwiched
between identical nafion membranes which permit passage of only cations. The inlet (outlet)
streams are labeled contaminated, anolyte (anolyte out), and catholyte (catholyte out); fluid leav-
ing the top edge of the frit is split into fresh and brine streams. The close-up image of a glass frit
was taken by scanning electron microscopy.
9
167 To prepare practical water with the composition shown in Table 1, we formulated
168 stock solutions with 1000 times the target concentrations made from lithium hydroxide
169 monohydrate (LiOH · H2 O), cobalt(II) chloride hexahydrate (CoCl2 · 6H2 O), and cesium
170 chloride (CsCl). Appropriate volumes of these solutions were then diluted in deionized
171 water, followed by the addition of solid boric acid (H3 BO3 ) to achieve a concentration of
172 370 mM. (All reagents were purchased from Sigma–Aldrich and used as received.) We note
173 that H3 BO3 is a weak acid with a first pKa of 9.24 in pure water at room temperature; with
174 the following equation for dissociation equilibrium,
) H+ + H2 BO3 −
H3 BO3 * (1)
175 we determined the concentration of H2 BO3 − to be approximately 0.015 mM in solution.

176 This weak dissociation implied that virtually all of the boron was present as electrically
177 neutral boric acid and thus was not separated by SED. We recognized, however, that H3 BO3
178 could have influenced the pH of practical water, the dynamics of proton transport, and
179 the extent of ionic separation. The pH of practical water (assumed here to be an ideal
180 solution) was indeed calculated assuming partial dissociation of H3 BO3 as well as complete
181 dissociation of LiOH. By definition of the equilibrium constant Ka , we obtained
[H+ ][H2 BO3 − ]

= Ka = 10−pKa =⇒
[H3 BO3 ]
(2)
[H+ ]([LiOH]0 + [H+ ])
= 10−pKa
[H3 BO3 ]0 − [LiOH]0 − [H+ ]
182 where brackets denote concentration (molarity), [H3 BO3 ]0 = 0.37 M, [LiOH]0 = 0.32 mM,
183 and pKa = 9.24. Solving this algebraic equation gave
[H+ ] = 6.6 × 10−7 M =⇒ pH = − log([H+ ]) = 6.2 (3)
10
184 In preparing practical water, the anolyte and contaminated feed were identical in compo-
185 sition, whereas the catholyte included an additional dose of hydrochloric acid (HCl) with
186 a concentration of 10 mM. This dose of HCl was deliberately added to prevent precipita-
187 tion of cobalt hydroxide that could have formed as a result of hydrogen evolution in the
188 otherwise basic catholyte.
189 With these solutions prepared, experiments began by setting the flow rates of all streams.
190 In this report, all flow rates were held constant: 0.21±0.01 mL min−1 for the electrode
191 streams (anolyte and catholyte) and 0.065±0.003 mL min−1 for the contaminated feed. To
192 transport these streams to the SED device, we used peristaltic pumps equipped with Tygon®
193 Chemical tubing (Saint-Gobain). With such pumps—and at low speeds of rotation—the
194 flow would be pulsed, though it was made smooth by incorporating a small buffering tank
195 known commonly as a hydraulic accumulator (or capacitor) just upstream of the device.
196 In our deign, the accumulators were capped glass vials that held a small volume of (com-
197 pressible) air above the (incompressible) liquids being pumped at the bottom to smooth
198 out pulsations. With flow rates set and tubing connected, the accumulators were left to
199 pressurize and the system to equilibrate overnight, after which the Gamry was set to oper-
200 ate in galvanostatic mode. (Air inside the accumulators became pressurized over time until
201 the fluidic resistance downstream—such as that created by the porous frit—was overcome
202 by the pumped liquid.) The measured voltage was allowed to stabilize for at least 1 hour
203 until it reached steady state.
204 Samples were collected directly from the device in graduated cylinders and stored in
205 conical centrifuge tubes for analysis, which included measurement of volume, conductiv-
206 ity, pH, and composition of cations. Conductivity and pH were measured using Mettler
207 Toledo analytical instruments (SevenCompact pH/Cond S213), and composition was de-
208 termined using inductively coupled plasma mass spectrometry (Agilent 7900 ICP–MS). The
209 plasma in ICP–MS was made from argon gas and was supplemented by helium, which is
210 normally needed to analyze elements with high ionization energies (e.g., Co) for which
11
211 argon plasma alone is not a sufficient source of ionization. 48 To improve the accuracy of
212 our data and subsequent analysis, we incorporated an internal standard that introduced
213 100 ppb of indium to all of our samples. Since the output of ICP–MS was numerical (in
214 counts per second), quantitative analysis required calibration of the measurements, which
215 was achieved by processing a set of reference standards and producing a calibration curve,
216 an example of which is shown in Figure S1 (Supporting Information). These standards
217 (Li, Co, Cs, and In) were purchased from Sigma–Aldrich and serially diluted to prepare
218 a set of samples encompassing the concentrations relevant to this study. All samples and
219 standard solutions were diluted in 2 vol% nitric acid prior to analysis by ICP–MS.
220 4 Results and Discussion

221
222 4.1 Principles and Performance of Shock Electrodialysis
a Lithium (Li+) b Cobalt (Co2+) c Cesium (Cs+)

2 100 15 100 80 100
Concentration (ppm)
Concentration (ppm)
Concentration (ppm)
80 80 80
Deionization (%)
Deionization (%)
Deionization (%)
1.5 60
10
60 60 60
1 40
40 40 40
5
0.5 20
20 20 20
Fresh
0 0 0 0 0 0
5 5 5
Concentration (ppm)
Concentration (ppm)
Concentration (ppm)
8
60 300
Enrichment
Enrichment
Enrichment
4 4 4
Brine 6
3 40 3 200 3
4
2 2 2
20 100
2 1 1 1
0 0 0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5 0 1 2 3 4 5
Dimensionless Current Dimensionless Current Dimensionless Current
Figure 3. Quantitative analysis of the deionization of (a) lithium, (b) cobalt, and (c) cesium in prac-
tical water. The upper (lower) half of each panel shows measured concentration and calculated
deionization (enrichment) in the fresh (brine) stream as functions of dimensionless current. The
concentration of ions in the feed was 1.41 mM, with compositions outlined in Table 1. Each data
point represents the arithmetic mean of 4 samples, and the shaded areas correspond to the range
of those samples.
12
223 The key phenomenon that governs deionization in SED is propagation of a shock wave
224 across which concentration varies drastically and a depletion zone is formed. This shock is
225 generated by providing the system with an overlimiting current, which is current in excess
226 of the flow-limited current (Ilim ) defined as
Ilim = ∑ νkCk FQ0 (4)

k
227 where ν is valence (charge), C is molar concentration, F is Faraday’s constant, Q0 is the

228 volumetric flow rate of the feed, and the sum is taken over all cations k. This definition
229 of Ilim can be interpreted as the rate of forced convection of positive charge carriers into
230 the device, and it was assumed that the flux of anions is 0 at steady state in the presence
231 of ideal cation exchange membranes. Using the composition of practical water in Table
232 1 and with Q0 = 0.065 mL min−1 , we found that Ilim = 180 µA. We verified this value ex-
233 perimentally by performing a conventional voltage sweep from 0 to 10 V and measuring
234 the current, as shown by the I–V curve in Figure S2 (Supporting Information). After
235 exceeding Ilim , the (overlimiting) current increased linearly with voltage and effected con-
236 stant conductance, which was consistent with the governing theory as well as previous
237 experimental observations in negatively charged porous media. 4,12
238 Based on a previous study by our group, we operated our SED system in galvanostatic
239 mode (see Figure S3 in the Supporting Information) because it facilitates the formation
240 of a stable deionization shock wave when supplying overlimiting current. 4 (Potentiostatic
241 operation, on the other hand, tends to result in overshoot and oscillation about a desired
242 overlimiting current and is associated with variability in the shock wave. 17 ) Our results for
243 treatment of practical water are presented in Figure 3, where deionization (the percentage
244 removed of a given species, DI) is defined as

Cfresh
DI = 100% × 1 − (5)
Cfeed
13
a b
90 0.08
P = I×V
Cost Rate (cents year−1)

0.06
Power (kWh year−1)

Water Recovery (%)
80 2
70 0.04 1.5
tts
Fresh
e
us
ch
0.02 sa 1
60 as
M tal
To
US
50 0 0.5
na
isia
Brine Lou
40 0
0 1 2 3 4 5 0 1 2 3 4 5
Dimensionless Current Dimensionless Current
c d
2 27,200 ft2 (2,530 m2)
Energy Density (kWh m−3)
Cost Density (cents m−3)
Ê = P÷Q
1.5 40
tts
VPrudential = 576,000 m3
se
1 30
hu
CD = 14.2 cents m−3

ac
s
as
l
M
ota Cost = $81,800 US
748 ft (228 m)
0.5 T 20
(c) US
0 na 10
isia
Lou
5′10′′ (178 cm)
0
0 1 2 3 4 5
Dimensionless Current BFM$
40x
Figure 4. Quantitative analysis of the water recovery and energy demand/cost corresponding
to the results shown in Figure 3. (a) Water recovery as a function of dimensionless current;
graduated cylinders portray relative proportions of the fresh and brine products, and each data
point represents the arithmetic mean of 4 samples with the shaded area corresponding to the
range of those samples. (b) Power and cost rate as well as (c) energy density and cost density
as functions of dimensionless current; cost rate (cost density) is equal to power (energy density)
multiplied by the residential cost of electricity, which varies between states in the US. (d) Cartoon
schematic to aid with visualization of the cost needed to apply 3 times the dimensionless current
to a body of water with volume equal to that of the Prudential Tower in Boston, MA; CD is cost
density from (c).
14
245 enrichment factor (EF) as

Cbrine
EF = (6)
Cfeed
246 and dimensionless current (I)

e as Ie = I/Ilim . The upper half of this figure illustrates that
247 the concentration of cations (Li+ , Co2+ , and Cs+ ) in the fresh stream decreased—by up
248 to 92% for both Co2+ , and Cs+ —with current. Moreover, the lower half shows that the
249 concentration of cations in the brine stream increased with current. Deionization that
250 occurred with no applied current was most likely due to exchange of H+ (abundant in the
251 cathode) with cations in practical water across the lower membrane.
252
253 4.2 Water Recovery and Energy Cost
254 Given the importance of water recovery and energy efficiency in desalination systems,
255 we analyzed the recovery ability and energy demand of SED when used to treat practical
256 water. Water recovery (WR), sometimes referred to the recovery ratio, is defined as
QF
WR = (7)
Q0
257 where QF is the volumetric flow rate of the fresh stream, and it is shown in Figure 4a
258 to increase (up to 80%) with current. This increase in water recovery is predominantly
259 due to electroosmotic flow (see Figure 3d and the Supporting Information in ref 4);
260 the position of the splitter was not changed in this study, although it could be adjusted in
261 future designs for improved water recovery. Analysis of the electrical energy needed for
262 deionization is shown in Figure 4b & c, where power P is the product of applied current
263 and (steady) voltage, and energy density Ê is power divided by the volumetric flow rate
264 of the feed. Although electrical power is the more natural measure of energy transport,
265 it is extensive and does not scale with the size of a system (particularly with flow rate).
266 Energy density is therefore of greater value in quantifying the energy efficiency of SED. In
15
267 treating practical water, the energy density increases quadratically with current, though it
268 was on the order of 1 kW h m−3 for dimensionless currents between 3 and 5. Moreover, the
269 cost of fluidic pumping in our laboratory scale system was negligible compared to the cost
270 of electrical energy:
= N Q0 ∆pfrit + Q ∆panoylte + ∆pcatholyte

Ppump
= 2.0 × 10−3 kW h year−1

(8)

Êpump = N Êfrit + Êanolyte + Êcatholyte
= 4.2 × 10−2 kW h m−3
271 where N is the number of passes (3 here), ∆p is pressure drop (6.1 psi across the frit and
272 0.67 psi across each of the electrodes), and Q = 0.21 mL min−1 is the volumetric flow rate of
273 the electrode streams. At commercial scales, however, we expect that the cost of pumping
274 will become important and will increase according to the desired level of throughput.
275 A more intuitive way of understanding the energy efficiency of SED is to consider cost
276 rate (Figure 4b) or cost density (Figure 4c), which are equal to power or energy density,
277 respectively, multiplied by the cost of residential electricity per kilowatt hour. We present
278 average electricity data for a state in which electricity is expensive (MA, $0.21 kWh−1 ) and
279 in the other cheap (LA, $0.09 kWh−1 ) relative to the US total ($0.13 kWh−1 ); costs are based
280 on 2018 data gathered from the US Energy Information Administration (EIA). 49 Figure 4d
281 is a cartoon that helps visualize the cost needed to apply 3 times the dimensionless current
282 (enough to remove 82% of Li+ , 91% of Co2+ , and 85% of Cs+ ) to a body of water with
283 a volume equal to that of the Prudential Tower in Boston, MA. For comparison, a nuclear
284 reactor with an electrical power output of 1.7 GWe, such as the US Advanced Pressurized
285 Water Reactor, requires coolant at a flow rate of approximately 28 m3 s−1 . 50 This flow rate
16
286 corresponds to 8.8 × 108 m3 (> 1500 times the volume of the Prudential Tower) of water
287 that passes through the reactor core annually. The simple economic analysis introduced
288 here will be useful when SED is being scaled up for use at commercial scale.
a Species Deionization (%) c

100 100
20 Li+ Co2+ Cs+ 20
Li+
Dimensionless Current
Total Deionization (%)

Co2+
80 80
15 15
Cs+
60 60
10 10
40 40
5 5
20 20
1 1
0 0
1 2 3 1 2 3 1 2 3
20
Pass Number Pass Number Pass Number
Water Recovery (%)

90
15
b C1st
feed
= 1.41 mM (of Li+, Co2+, Cs+); I = 5 × Ilim 80
Cumulative Deionization (%)

10
99.6
100 70
97.6
5
96.3
90 60
1
80 50
Energy Density (kWh/m3)

20
70
100
Deionization Per Pass (%)
100 1st Pass 2nd Pass 3rd Pass 15
80 10 10−1
60
5
40 10−2
1
20
10−3
0 1 2 3
Li+ Co2+Cs+ Li+ Co2+Cs+ Li+ Co2+Cs+ Pass Number
Figure 5. Simulation of a 3-step process for deionization of practical water by feeding serially di-
luted solutions in turn to the same device; neglecting boric acid, concentrations of the feed to each
pass are 1.41 mM (Ilim = 180 µA), 0.282 mM (5× dilution, Ilim = 36 µA), and 0.0564 mM (25× dilution,
Ilim = 7.2 µA), respectively. (a) Two-dimensional array of deionization as a function of dimension-
less current in each pass. (b) Deionization per pass (bottom) and cumulative deionization (top) for
each species with a dimensionless current of 5; each data point represents the arithmetic mean
of 3 samples with errors bars corresponding to the range of those samples. (c) Two-dimensional
arrays of total deionization (top) for the 3 target species, water recovery (middle), and energy den-
sity (bottom) as functions of dimensionless current in each pass. Zones of diagonal black stripes
in (a) and (c) correspond to parameters that were not tested.
289
17
290 4.3 Implementation of a Multi-Step Process
291 For common desalination technologies, performance is improved and energy consump-
292 tion is reduced by using multiple units or stages of the technology in series, and by operat-
293 ing each stage at lower power. 51,52 Such an approach is especially suitable for SED because
294 power increases quadratically with current (Figure 4), even though deionization eventu-
295 ally plateaus (Figure 3). 53 To demonstrate this claim, we developed a new configuration
296 for our system that involved a 3-step process for deionization of practical water. Because
297 the throughput of our laboratory scale device was low, we accelerated experimentation
298 with this process by feeding serially diluted solutions in turn to the same device. A dilu-
299 tion factor of 5 was chosen for the second step and 25 for the third based on deionization
300 of the target species in the first 2 steps for a dimensionless current of 5. In other words,
301 concentrations of the feed to each pass were 1.41, 0.282, and 0.0564 mM, neglecting boric
302 acid. In Figure 5a, we present two-dimensional arrays of deionization for each species
303 as a function of dimensionless current in each pass. In these experiments, dimensionless
304 current ranged from 1 to 20, though deionization typically plateaued at some moderate
305 value. To examine the performance of our system at one such value, we report deioniza-
306 tion per pass and cumulative deionization for each species at a dimensionless current of 5,
307 as shown in Figure 5b. In the first and second passes, all 3 species were removed in nearly
308 equal proportions, whereas in the third pass, Co2+ was preferentially removed (see Fig-
309 ure S4 in the Supporting Information for discussion of this observation). This selective
310 separation of the divalent ion agreed with a previous experimental study by our group, in
311 which magnesium was selectively removed from an aqueous mixture of NaCl and MgCl2 . 19
312 Figure 5b also shows that our 3-step process led to a high cumulative deionization for
313 each species, ranging from 96.3% for Cs+ to 99.6% for Co2+ . Based on its ability to remove
314 target ions from practical water, SED could function as a novel method for treatment of
315 radioactive waste.
316 In addition to removal of target ions, effective methods for decontamination of water
18
317 must also optimize total deionization, water recovery, and energy density. These quantities
318 are shown for our 3-step process in Figure 5c and are consistent with previously observed
319 trends: total deionization often plateaus at some moderate value of dimensionless cur-
320 rent, whereas water recovery and energy density increase monotonically with current. It
321 is striking to learn that our device can sustain water recovery at over 92% (Ie= 20) only by
322 electroosmotic flow 4 and even though the splitter is positioned midway along the width
323 of the frit. Moreover, successive steps in this process contribute little energy in addition
324 to that consumed in the first step (see Figure S3 in the Supporting Information), which
325 implies that a contaminated feed can be repeatedly passed through the device for greater
326 deionization at a reduced cost. This proportionality between energy demand and concen-
327 tration of the feed—even in the dilute limit—gives SED an advantage over conventional
328 purification techniques, which typically require an input of energy that is bounded from
329 below as the feed becomes more dilute. As with other desalination methods, removal of
330 more ions by multi-step SED comes at the expense of water recovery, which diminishes in
331 every pass. We will address this challenge in future generations of our device by introduc-
332 ing a recycle scheme that feeds the brine stream from a later pass back to an earlier pass
333 in which the original feed is of comparable concentration.
334 So far, we quantified the ability of SED to remove target species from practical water
335 and identified general rules to optimize the design of a real system that can treat nuclear
336 waste. In particular, we inferred a complex coupling between the extent of deionization—
337 convoluted by the selective nature of separation by SED (Figure S4 in the Supporting
338 Information)—water recovery, and energy demand. The relationship between these pa-
339 rameters is nonlinear, and indeed we observe quadratic growth in energy density with
340 applied current (Figure 4b & c and Figure 5c). Moreover, deionization varies between
341 species and is not monotonic, and water recovery appears to increase sublinearly with
342 applied current (Figure 4a and Figure 5c). These results suggest that there is an in-
343 herent trade-off between deionization, water recovery, and energy efficiency, which poses
19
a 2
= DICo WR Elin
b 2
= DItot WR Elin
c 2
= DItot WR 2
Co tot WR
0.60 0.60 0.60
20 20 20
0.45 0.45 0.45
15 15 15
10 0.30 10 0.30 10 0.30
5 5 5
0.15 0.15 0.15
1 1 1
0 0 0
1 2 3 1 2 3 1 2 3
Pass Number Pass Number Pass Number
Figure 6. Quantitative characterization of the performance of the 3-step process shown in Figure
5. Figure of merit Ψ (as defined in Eq. 9) based on (a) deionization of cobalt only DICo , (b)
total deionization DItot , and (c) water recovery WR (weighted quadratically, and with no penalty on
energy demand) as functions of dimensionless current in each pass; light blue (a), dark red (b),
and orange (c) stars indicate which steps in the sequence of passes maximize Ψ (see Table 2).
Zones of diagonal black stripes in the upper left corners correspond to parameters that were not
tested.
344 a significant challenge to satisfactorily treat nuclear waste while minimizing the demand
345 for power. We addressed this challenge from the perspective of systems engineering by
346 introducing a new figure of merit (Ψ) defined as
Ψ = DI 2 × WRn × f (Ê) (9)
347 where DI is deionization (squared to emphasize this metric), WR is water recovery, n is a

348 positive integer (either 1 or 2 here), and f (Ê) is a dimensionless function of energy density
349 that ranges from 0 to 1. This function may be constant:
f (Ê) = 1 (no penalty on energy demand) (10)
350 linear:
Ê
f (Ê) = E lin ≡ 1 − (11)
max Ê
20
351 or nonlinear with respect to Ê:
s
1 − Ê/ max Ê
f (Ê) = E quad ≡ (12)
1 − min Ê/ max Ê
352 where “min” and “max” operate on the entire array of energy densities in Figure 5c.
353 Although we only considered Eq. 10 and Eq. 11 in this study, a nonlinear function such
354 as Eq. 12 could be used to detract from the merit of steps that operate at high power,
355 such that this penalty would become increasingly severe as Ê approaches max Ê. In any
356 case, all terms in the expression for Ψ (and hence Ψ itself) would range from 0 to 1.
357 Introducing a figure of merit allows us to quantitatively decide which operating con-
358 ditions in each pass maximize deionization in our system. Characterization of the perfor-
359 mance of our 3-step process is shown in Figure 6 based on several variations of Ψ. For
360 example, Ψ may be based on deionization of cobalt only (Figure 6a) or total deionization
361 (Figure 6b). These variations of Ψ, both with n = 1, suggest the same value of dimension-
362 less current in only the first pass (Ie = 5), but suggest different values in the second and
363 third passes (as designated by the colored stars). This difference can be rationalized by the
364 fact that deionization of Co2+ (and not of Li+ or Cs+ ) is often greatest at low to moderate
365 dimensionless current (Figure 5a).
366 To select the most suitable operating conditions, we compared total (and individual)
367 deionization, water recovery, and energy density, all of which are summarized in Table
368 2, for the sequence of passes that maximizes the corresponding variation of Ψ. The se-
369 quence that maximizes ΨCo in each step, for instance, leads to relatively low water recov-
370 ery, but the energy density it consumes is also the least. In comparison, the sequence that
371 maximizes Ψtot in each step gives water recovery of 58%, and it maintains almost 99%
372 deionization of Co2+ with little additional demand for energy. This level of water recov-
373 ery is similar to those achieved by conventional purification technologies, though it can be
374 increased by selecting an alternate sequence in our process. To make a quantitatively moti-
21
375 vated selection, more weight is given to water recovery by setting n = 2 and f (Ê) = 1 in our
376 definition of Ψ, as shown in Figure 6c. With this modification, the sequence that maxi-
377 mizes ΨWR in each step gives a water recovery of 66%. In response, however, consumption
378 of energy increases considerably. It then seems that water recovery can be improved in re-
379 turn for higher energy consumption (or lower deionization, by repositioning the splitter)
380 depending on the targets set by the operator.
Step 1 Porous Carbon Electrode

e−
Anolyte Out Separator or membrane
/4O Anode (+) ... A−

1
1
/2H O 2
2
E Waste
CEM (Nafion) (Co2+, Cs+)
Enriched Li+
H+ A− C+ Brine Separator or membrane
Porous Frit
N
Lithium Iron Phosphate Electrode
Depleted
E Splitter
Fresh Step 2 Porous Carbon Electrode
N
Separator or membrane
Deionized
A−
CEM (Nafion) Recycle
Catholyte Out E
C+ Cathode (−) ... Li+ (Li+)
H+ 1
/2H
2
Separator or membrane
e−
Lithium Iron Phosphate Electrode
Figure 7. Process intensification of SED by using CDI to recycle Li+ in 2 steps. The first step
involves selective capture of Li+ in the CDI unit from the brine stream discharged by SED. Selec-
tivity is achieved by intercalation of Li+ into an iron phosphate electrode, which becomes lithium
iron phosphate (Lix FePO4 ) upon insertion of Li+ . The second step involves release of Li+ into the
fresh stream exiting the SED device by reversing the direction of electric field.
381
382 4.4 Process Intensification for Lithium Recovery
383 For all cases shown in Table 2, total deionization is approximately 98%, and deion-
Table 2. Summary of Total (and Individual) Deionization DI, Water Recovery WR, and Energy Den-
sity Ê For the Sequence of Passes That Maximizes the Figure of Merit Ψ in Figure 6 (Designated
by Light Blue (a), Dark Red (b), and Orange (c) Stars)
DItot (%) DILi (%) DICo (%) DICs (%) WR (%) Ê (kW h m−3 )
Optimal Sequence for ΨCo 98.1±0.2 98.0±0.2 99.5±0.1 97.3±0.5 43±2 1.76±0.04
Optimal Sequence for Ψtot 98.6±0.1 98.8±0.2 98.9±0.3 98.3±0.2 58±2 2.18±0.05
Optimal Sequence for ΨWR 98.2±0.2 98.5±0.3 98.3±0.4 98.1±0.2 66±2 4.8±0.2
22
384 ization of Co2+ is even greater in our 3-step process. Another practical result is the high
385 deionization of Li+ , which is used (as LiOH) in nuclear reactors for corrosion control by
386 alkalizing the process water. 39 For this application, LiOH is isotopically enriched in lithium-
387 7 which does not interfere with nuclear reactions (unlike lithium-6), and it is sometimes
388 used in demineralizers (also known as ion exchangers) to remove radioactive contami-
389 nants from the process water. 54 Lithium can be selectively captured and recycled in our
390 system (or reused elsewhere) by integrating capacitive deionization (CDI) with intercala-
391 tion materials 55,56 as a second operation following SED. This process intensification can in
392 principle be achieved in two steps, as illustrated in Figure 7. In the first step, SED is used
393 to concentrate waste in the brine stream, from which Li+ is selectively captured in the CDI
394 unit by intercalation into an appropriate electrode such as iron phosphate 57 (Fe(III)PO4 ,
395 often prepared by deintercalation of Li+ from LiFe(II)PO4 ) or lithium manganese oxide 58
396 (LiMn2 O4 ). During this process, all cations are driven towards the intercalation electrode,
397 but only Li+ can be inserted into its crystal lattice because Cs+ is too large and Co2+
398 will exhibit strong Coulomb repulsion (vacancies in FePO4 are fitted for small monovalent
399 cations 57 ). Moreover, the anions are inserted into a porous carbon electrode where they
400 are electrostatically trapped by the applied potential. Fluid leaving the device in this first
401 step will therefore be depleted of lithium and its counterion(s). In the second step, the
402 fresh stream produced by SED is passed through the CDI unit. By reversing the direction
403 of electric field, lithium and its counterion(s) are released from the electrodes back into
404 solution and are recovered for later use.
405 Author Information
406 Corresponding Author
407
∗ E-mail: bazant@mit.edu
23
408 ORCID
409 MA Alkhadra: 0000-0003-3866-709X

410 MZ Bazant: 0000-0002-8200-4501
411 Notes
412 The authors declare no competing financial interest.
413 Acknowledgments
414 This research was supported by a grant from Mitsubishi Heavy Industries Limited. The
415 authors thank the Center for Environmental Health Sciences (CEHS) at MIT for use of
416 ICP–MS.
417 Supporting Information Available
418 The Supporting Information is available free of charge on the ACS Publications website
419 at DOI: 00.0000/00000000.
420 The following files are available free of charge
421 • Supporting Information: representative calibration curve for ICP–MS, current and
422 voltage data, analysis of species selectivity, conductivity and pH data
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31

Alkhadra Et Al. 2019 - Continuous Separation of Radionuclides From Contaminated Water by SED

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Remediation and Control Technologies

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Continuous separation of radionuclides from

Mohammad A. Alkhadra,†,¶ Kameron M. Conforti,†,¶ Tao Gao,† Huanhuan

Tian,† and Martin Z. Bazant∗,†,‡

†Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,

Nuclear Reactor Shock Electrodialysis

Turbine Waste Clean water

2 The increasing popularity of nuclear energy necessitates development of new meth-

5 tive), selective accumulation of the radionuclides is desirable to minimize the volume

10 nuclear processes. In a three-pass process, a consistent trade-off is observed between

17 dant species in solution.

Nuclear Reactor Shock Electrodialysis x

81 2 Background and Experimental Design

Table 1. Concentrations of Prevalent Species in Practical Water, the Non-Radioactive Analog of

Species Concentration (ppm [mM]) Role

141 3 Materials and Experimental Methods

175 we determined the concentration of H2 BO3 − to be approximately 0.015 mM in solution.

[H+ ][H2 BO3 − ]

[H+ ] = 6.6 × 10−7 M =⇒ pH = − log([H+ ]) = 6.2 (3)

220 4 Results and Discussion

222 4.1 Principles and Performance of Shock Electrodialysis

a Lithium (Li+) b Cobalt (Co2+) c Cesium (Cs+)

Ilim = ∑ νkCk FQ0 (4)

227 where ν is valence (charge), C is molar concentration, F is Faraday’s constant, Q0 is the

Cost Rate (cents year−1)

Power (kWh year−1)

Cost Density (cents m−3)

CD = 14.2 cents m−3

ota Cost = $81,800 US

245 enrichment factor (EF) as

246 and dimensionless current (I)

253 4.2 Water Recovery and Energy Cost

= N Q0 ∆pfrit + Q ∆panoylte + ∆pcatholyte

= 2.0 × 10−3 kW h year−1

= 4.2 × 10−2 kW h m−3

a Species Deionization (%) c

Total Deionization (%)

Water Recovery (%)

Cumulative Deionization (%)

Energy Density (kWh/m3)

100 1st Pass 2nd Pass 3rd Pass 15

290 4.3 Implementation of a Multi-Step Process

10 0.30 10 0.30 10 0.30

Ψ = DI 2 × WRn × f (Ê) (9)

347 where DI is deionization (squared to emphasize this metric), WR is water recovery, n is a

f (Ê) = 1 (no penalty on energy demand) (10)

351 or nonlinear with respect to Ê:

Step 1 Porous Carbon Electrode

/4O Anode (+) ... A−

Fresh Step 2 Porous Carbon Electrode

382 4.4 Process Intensification for Lithium Recovery

405 Author Information

406 Corresponding Author

409 MA Alkhadra: 0000-0003-3866-709X

412 The authors declare no competing financial interest.

417 Supporting Information Available

525 (41) Lister, D. H. The Transport of Radioactive Corrosion Products in High-Temperature

553 (51) Ahunbay, M. G.; Tantekin-Ersolmaz, S. B.; Krantz, W. B. Energy optimization of

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