Subscriber access provided by Eastern Michigan University | Bruce T. Halle Library
Article
Enhanced Flux and Electrochemical Cleaning of Silicate Scaling on Carbon Nanotube-Coated Membrane Distillation Membranes Treating Geothermal Brines Li Tang, Arpita Iddya, Xiaobo Zhu, Alexander V Dudchenko, Wenyan Duan, Craig Turchi, Johan Vanneste, Tzahi Y. Cath, and David Jassby ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b12615 • Publication Date (Web): 13 Oct 2017 Downloaded from http://pubs.acs.org on October 17, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Applied Materials & Interfaces is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 44
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
ACS Applied Materials & Interfaces
Enhanced Flux and Electrochemical Cleaning of Silicate Scaling on Carbon Nanotube-Coated Membrane Distillation Membranes Treating Geothermal Brines
Li Tang a,⊥*, Arpita Iddyaa, ⊥, Xiaobo Zhu a, Alexander V. Dudchenko a, Wenyan Duan a, Craig Turchi b, Johann Vanneste c, Tzahi Y. Cath c, and David Jassby a,* a
b
c
Department of Chemical and Environmental Engineering, University of California, Riverside, California 92521, United States
National Renewable Energy Lab, Department of Energy, Golden, Colorado 80401, United States
Department of Civil and Environmental Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
* Corresponding author: David Jassby, E-mail:
[email protected], Phone: 1-951-827-6475 * Corresponding author: Li Tang, E-mail:
[email protected] ⊥
These authors contributed to the work equally
ACS Paragon Plus Environment
ACS Applied Materials & Interfaces
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
The desalination of inland brackish groundwater offers the opportunity to provide potable
3
drinking water to residents and industrial cooling water to industries located in arid regions.
4
Geothermal brines are used to generate electricity, but often contain high concentrations of
5
dissolved salt. Here, we demonstrate how the residual heat left in spent geothermal brines can
6
be used to drive a membrane distillation (MD) process and recover desalinated water. Porous
7
polypropylene membranes were coated with a carbon nanotube (CNT)/poly (vinyl alcohol)
8
layer, resulting in composite membranes having a binary structure that combines the
9
hydrophobic properties critical for MD with the hydrophilic and conductive properties of the
10
CNTs. We demonstrate that the addition of the CNT layer increases membrane flux due to
11
enhanced heat transport from the bulk feed to the membrane surface – a result of CNT’s high
12
thermal transport properties. Furthermore, we show how hydroxide ion generation, driven by
13
water electrolysis on the electrically conducting membrane surface, can be used to efficiently
14
dissolve silicate scaling that developed during the process of desalinating the geothermal brine,
15
negating the need for chemical cleaning.
16 17
Keywords:
18
cleaning.
Membrane distillation; silicate scaling; carbon nanotubes; electrochemical
19 20 21 22 23 24 25 26 27 28 29
2
ACS Paragon Plus Environment
Page 2 of 44
Page 3 of 44
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
ACS Applied Materials & Interfaces
1 2
Graphical Abstract
3
4 5 6 7 8 9 10 11 12 13 14
3
ACS Paragon Plus Environment
ACS Applied Materials & Interfaces
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
1. Introduction
4
The desalination of inland brackish groundwater has the potential of addressing water
5
shortages across many regions. Over the last several decades, membrane-based desalination
6
technologies, such as reverse osmosis (RO), and membrane distillation (MD) have attracted
7
significant research attention. MD, which relies on thermal energy to drive the desalination
8
process, is an attractive and cost-effective technology when an abundant low-grade heat source
9
is available, or when high salinity brines require treatment 1-3. Such a heat source can be found
10
in geothermal brines, which are often exploited for power generation in geothermal power
11
plants
12
concentrations as high as 254,000 mg/l measured in deep brines near the Salton Sea, CA 5. In
13
the power generation process, heat from the brines is extracted and used to power a turbine and
14
generate electricity, with the spent brines pumped back into the ground 6. However, not all of
15
the heat is extracted in the process, and the spent brine is returned to the environment with
16
temperatures as high as 70 °C, which are sufficient to drive brine desalination 7. Thus, capturing
17
the residual heat in the spent geothermal brines and using it to drive a desalination process
18
offers an attractive option to arid inland regions that often struggle to secure potable water
19
resources.
4
; the salinity of these brines depends on the underlying geology, with TDS
20
In the direct-contact MD (DCMD) process, a hot brine flows over a hydrophobic
21
microporous membrane, with cold water flowing on the opposite (distillate) side of the
22
membrane; due to the temperature difference across the membrane, a vapor pressure difference
23
emerges, which drives water vapor from the hot feed to the cold distillate, generating a
24
desalinated stream. Because the membrane is hydrophobic, liquid water does not transport
25
across the membrane, and dissolved species, such as ions, remain in the hot feed and do not
26
cross the hydrophobic barrier. Because MD does not rely on pressure as a driving force, and
27
because water vapor pressure is only moderately impacted by salinity, the technology can be
28
used to desalinate high salinity brines that have an osmotic pressure that is too high for
29
desalination by RO. In addition, MD requires less specialized mechanical equipment compared
30
to high-pressure desalination systems 8-11.
4
ACS Paragon Plus Environment
Page 4 of 44
Page 5 of 44
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
ACS Applied Materials & Interfaces
1
Even though MD technology was first proposed in the late 1960s 12, it has yet to be applied
2
in large-scale industrial applications. One of the key technical challenges that hinder the wide-
3
spread use of MD is membrane fouling, and in particular, membrane mineral scaling
4
mineral scaling, supersaturated conditions along the membrane surface, which develop due to
5
water leaving the brine during the desalination process, lead to the nucleation and growth of
6
mineral deposits on the membrane surface (heterogeneous nucleation) as well as nucleation and
7
growth in the feed stream itself (homogeneous nucleation), which results in the deposition of
8
solids on the membrane surface, although there have been several demonstrations of
9
fluorosilicone surface coatings that have reduced (although not completely prevented) scaling, 13-16
13
. In
10
including silica scaling
11
of pore clogging or surface blockage. In addition, scaling exacerbates temperature and
12
concentration polarization, and can lead to a drop in salt rejection due to pore wetting and
13
membrane material damage
14
desalinating brackish groundwater
15
water 27-28. During the MD process, silicate monomers accumulate along the membrane surface,
16
and under certain concentration and pH conditions begin to polymerize
17
multivalent cations in natural waters (e.g., iron, aluminum, calcium, magnesium, and barium
18
ions) favors and promotes the polymerization process 29-30. This polymerization process leads to
19
the formation of a dense and sticky “gel” layer, which is a complex and amorphous product that
20
is difficult to remove. Membrane cleaning using a high pH solution provides an effective
21
method to recover membrane performance because of the dissolution of silicates at high pH
22
19, 26
23
interruptions, which leads to an increase in O&M costs 13, 17, 26, 31.
. Once scaling occurs, MD performance rapidly deteriorates because
15, 17-21
. Silicate scaling, in particular, is a challenge when
22-26
. Silicates of various forms are ubiquitous in natural 19
. The presence of
13,
. However, this cleaning process requires the use of chemicals and results in process
24
Recently, thanks to the discovery of the unique electrical, thermal, and mechanical
25
properties of carbon nanotubes (CNTs), interest in the utilization of these materials in
26
membrane separation processes has been increasing. In particular, the ability to form porous,
27
electrically conducting composite polymeric materials has attracted significant attention due to
28
the exceptional anti-fouling and self-cleaning properties enabled through the application of an
29
electrical potential to the membrane surface
30
cleaning mechanisms include simple electrostatic repulsion, electrochemical redox reactions,
31
micro-environmental pH changes, and micro-bubble generation 37-38. Among these mechanisms,
2, 32-37
5
. The electrochemical anti-fouling and self-
ACS Paragon Plus Environment
ACS Applied Materials & Interfaces
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
Page 6 of 44
1
manipulating pH in the microenvironment of the membrane surface serves as a very promising
2
method to remove silicate scale in the MD process because silicate scales can be readily
3
dissolved under high pH conditions. This approach can be realized by forming a CNT/polymer
4
composite material that consists of a layer of electrically conducting CNTs deposited on a
5
microporous hydrophobic support. By applying an electrical potential to the membrane surface,
6
with the membrane as a cathode, water splitting can be facilitated, which generates hydroxide
7
ions and increases the pH on the membrane surface.
8
In addition to their electrical properties, CNTs also possess remarkable heat transfer
9
properties. The thermal conductivity of CNTs ranges between 2000-6000 W m–1 K–1 at room 39
10
temperature
11
feed and distillate streams; however, as water vapor passes through the hydrophobic membrane,
12
the feed solution cools down, resulting in the formation of thermal polarization
13
thickness of the temperature boundary layer is dependent on several factors, including
14
hydrodynamic (mixing) conditions along the membrane surface, the temperature difference
15
between the feed and distillate streams, and membrane morphological architecture
16
Ultimately, for the distillation process to proceed, heat from the bulk stream must transfer
17
across the thermal boundary layer to the membrane/feed interface to drive vapor formation 41, 43,
18
48
19
mixing, the rate of this conductive heat transfer is fundamentally determined by the thermal
20
conductivity of water, which is 0.6 W m–1 K–1 at room temperature
21
higher thermal conductivity of CNTs, a layer of CNTs deposited on a microporous hydrophobic
22
support and extending into the bulk stream could increase conductive heat transfer from the
23
bulk to the membrane surface, which would reduce thermal polarization and increase membrane
24
performance 45.
. The MD process relies on the maintenance of a thermal gradient between the 40-43
. The
44-47
.
. Ignoring advective transport of water from the bulk feed to the membrane surface through 49
. Considering the far
25
The main objective of this research was to examine the effectiveness of using a
26
CNT/polymer composite MD membrane to decrease thermal polarization and for in-situ
27
electrochemical cleaning to remove silicate scales from the membrane surface. In this study,
28
microporous polypropylene (PP) base membranes were spray-coated with a thin film of CNTs
29
by a custom-made spray coater, which are then crossed-linked with a hydrophilic polymer
30
(poly(vinyl alcohol) (PVA)). Because the CNT films are spray coated on the membrane surface,
31
the underlying hydrophobic properties of the PP support are maintained, and the composite
6
ACS Paragon Plus Environment
Page 7 of 44
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
ACS Applied Materials & Interfaces
1
material functions as an MD membrane, albeit having a top hydrophilic layer. A laboratory-
2
scale MD system was used to treat a synthetic geothermal brine that had high silicate
3
concentrations with and without electrochemical cleaning. Membrane flux and electrical
4
conductivity were continuously monitored and recorded in real time throughout the silicate
5
scaling and electrochemical cleaning processes. In addition, flux differences between the coated
6
and uncoated membranes were evaluated as a function of the temperature difference and
7
hydrodynamic conditions in the feed channel. Our results show that the membrane modified
8
with CNT thin films can facilitate rapid in-situ cleaning of silica scaling. In addition, we
9
demonstrate that the addition of the CNT film increases membrane flux by enhancing heat
10
transfer from the bulk to the membrane surface, compressing the thermal polarization layer.
11 12
2. Materials and methods
13
2.1
Materials
14
PP membranes having a nominal pore size of 0.45 µm were provided by 3M (Charlotte, NC)
15
and were used directly without any treatment as the base membranes on which CNT thin films
16
were spray coated. 50 wt% glutaraldehyde (GA) solution was purchased from Fisher Scientific
17
and used as received. 146,000–186,000 MW PVA, sodium dodecylbenzenesulfonate (DDBS),
18
Na2SiO3·5H2O, AlCl3·6H2O, BaCl2·2H2O, FeCl6· H2O, KCl, CaCl2·2H2O, MgCl2·6H2O, and
19
Na2SO4 were purchased from Sigma Aldrich and used as received. Multi-Walled CNTs
20
functionalized with carboxylic groups (-COOH) via plasma treatment were purchased from
21
CheapTubes (Cheaptubes Inc., Brattleboro, VT) and used without any further purification.
22
Based on the specification provided by the manufacture, the CNTs are reported to have an outer
23
diameter of 13-18 nm, a length of 1-12 µm and purity >99%, with a functional group content of
24
7.0 ± 1.5%.
25 26 27
2.2
Membrane surface modification CNT suspensions were prepared using previously reported methods
33-34
. Briefly, CNT
28
powder was suspended in deionized water at 1.0 wt% concentration with 1:10 ratio of CNT:
29
DDBS. The suspension was sonicated with a horn sonicator (Branson, Danbury, CT) for 30 min
30
to fully disperse the CNT powder. A 0.1 wt% PVA solution was prepared by dissolving PVA in
31
deionized water at 95-100 °C with stirring. To modify the base PP membranes with CNT thin
7
ACS Paragon Plus Environment
ACS Applied Materials & Interfaces
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
films, CNT suspension were sprayed evenly on top of membrane surfaces with a surface mass
2
of either 0.09 mg cm–2 (CNT_009), 0.19 mg cm–2 (CNT_019), or 0.37 mg cm–2 (CNT_037). A
3
final thin layer of PVA was sprayed on top of the CNTs-modified membrane surface, with a
4
surface density of 0.004 mg cm–2. The prepared membranes were washed using deionized water
5
for at least 2 hrs to remove DDBS and then the membranes were dried in oven at 90 °C for 10
6
minutes. Following that, the dried membranes were submerged into a crosslinking solution
7
consisting of 11.3 g L–1 GA as the cross linker and 4.4 g L–1 hydrochloric acid as the catalyst
8
and heated at 70 °C for 1 hr. The membranes were then removed from the crosslinking solution,
9
dried at 90 °C for 10 min, and used without any further treatment.
10 11
2.3
Membrane characterization
12
Membrane surfaces and cross sections were imaged using scanning electron microscopy
13
(SEM, FEI NNS540). All samples were affixed onto SEM stubs with carbon tape and sputter
14
coated with Pd/Pt before imaging (Sputter coater 108 Auto, Cressington, UK). Quantitative
15
chemical analysis of the membrane surface was performed by energy dispersive X-ray (EDX)
16
spectroscopy. Water flux was measured and compared between the base membrane (bare PP)
17
and the CNT_037 membrane, as a representative of the CNTs-modified membranes, at three
18
different feed temperatures (50, 60, and 70 °C). Membrane surface roughness was measured
19
using atomic force microscopy (AFM, Bruker, Billerica, MA) in tapping mode. The membrane
20
sheet resistance was measured using a 4-point conductivity probe (Mitsubishi, MCP-T610).
21
Contact angle measurements were performed using a contact angle goniometer (Rame-Hart,
22
Model 250, Netcong, NJ), using the captive bubble method. Attenuated total reflectance Fourier
23
transform infrared spectroscopy (ATR-FTIR, Thermo Scientific, Waltham, MA) was performed
24
on all samples to analyze and compare the functional groups before and after membrane
25
modification.
26
Measurements of the relative potential of the membrane vs. a Ag/AgCl reference electrode
27
at an applied cell potential of 15 V were performed by connecting a membrane sample (working
28
electrode), a titanium (Ti) sheet (counter electrode), and a reference electrode (Ag/AgCl
29
solusion) to a potentiostat (CH Instruments, Austin, TX) following a similar procedure as
30
previously described
31
reference electrode were placed in an electrochemical cell, with the open-circuit potential on the
50
. Briefly, the membrane sample, the Ti counter electrode, and the
8
ACS Paragon Plus Environment
Page 8 of 44
Page 9 of 44
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
ACS Applied Materials & Interfaces
1
membrane surface measured once a 15 V cell potential was applied to the membrane and Ti
2
counter electrode using a DC power source (KORAD KA3005P).
3 4
2.4
Design and operation of the MD system
5
An automated laboratory-scale cross flow MD system (with a polycarbonate membrane flow
6
cell) was used to perform all of the experiments (Figure 1). Each portion of the flow cell has an
7
open channel with the dimensions of 100 mm in length, 40 mm in width, and 3.80 mm in
8
height. A Ti sheet, located 3 mm above the membrane surface, was used as the counter
9
electrode. A peristaltic pump (Cole Parmer, Pump Drive Model 7553-70, Pump Head Model
10
77200-50, Vernon Hills, IL) with temperature resistant tubing was used to circulate the hot feed
11
solution, while a gear pump (Greylor, PQ-12/24, Cape Coral, FL) was used to circulate the cold
12
distillate solution on the opposite side of the membrane. Feed and permeate spacers were placed
13
in the flow channels. The circulation flow rates were monitored using two rotameters. The
14
conductivity of the circulating distillate was measured continuously with a conductivity meter
15
(Thermo Scientific, Orion Star A322) to monitor salt rejection and membrane wetting.
16
The feed solution was heated using an immersion heater (Process Technology, VX1111,
17
Mentor, OH) immersed in the feed tank, with a temperature sensor (Vktech, DS18b20)
18
suspended in the hot water. Another temperature sensor was placed immediately prior to the
19
inlet of the feed channel. The two temperature sensors were connected to a temperature control
20
unit and the inlet temperature of the hot feed solution could be maintained at a constant value
21
with a PID cascade loop 51. A vertically mounted level float switch (Madison, M8000, Branford,
22
CT) was suspended in the hot water tank to maintain a constant water level throughout the
23
experiments. A temperature sensor was placed immediately before the inlet of the distillate
24
channel, and the inlet temperature of the cold distillate solution was maintained constantly at
25
20 °C using a chiller (PolyScience, 6500 Series, 1/2 HP) through a stainless-steel heat-exchange
26
coil. A digital balance (Fisher Scientific Education Precision Balance) was used to weigh the
27
excess produced distillate for the determination of water flux. When comparing the flux of the
28
CNT-coated membranes and the bare PP membranes, deionized water was used as the feed at
29
different temperatures (50, 60, and 70 °C), with the distillate maintained at 20 °C. In these
30
experiments, the membrane was tested in the presence and absence of a feed-side spacer, at
9
ACS Paragon Plus Environment
ACS Applied Materials & Interfaces
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
three different flow rates (0.75, 1.5, and 2 L min–1); these flow rates correspond to a cross-flow
2
velocity of 10.4, 20.8, and 27.7 cm s–1, respectively.
Page 10 of 44
Control Program on PC Microcontroller
Chilling Unit Tcold1
Tcold2 Distillate Solution Tank
Membrane Liquid Level Sensor
Balance Thot1
Thot2
Feed Solution Tank
3 4
Buffer Tank
Figure 1. Schematic of the MD testing system.
5 6
2.5
Preparation of silicate scaling solution
7
A simulated brine solution, with a composition similar to that found in geothermal brines
8
used for power generation in Nevada, was prepared by dissolving representative salts in
9
deionized water; salts (type and concentrations) used to prepare the solution are summarized in
10
Table 1. In an effort to limit the time required for fouling experiments, the concentration of salts
11
was increased by a factor of six over what is naturally found in Nevada geothermal fluids. Thus,
12
the concentrations in Table 1 are 6X what is naturally found in the environment.
13
Table 1. Solution chemistry of the feed solution Salts NaSiO3·5H2O AlCl3·6H2O BaCl2·2H2O FeCl3·6H2O CaCl2·2H2O KCl MgCl2·6H2O Na2SO4
Concentration (mg L–1) 1906 10 2 6 176 85 102 92
Concentration (mM) 8.985 0.051 0.010 0.026 1.439 1.372 0.605 0.774
14 15
2.6
Silicate scaling and electrochemical cleaning procedure 10
ACS Paragon Plus Environment
Page 11 of 44
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
ACS Applied Materials & Interfaces
1
MD scaling experiments on the CNT-modified membranes were started with 10 L of the 6X
2
brine solution in the feed tank and 1 L of deionized water as the initial fluid in the distillate
3
tank. The temperatures of the feed and distillate were maintained at 60 °C and 20 °C,
4
respectively. Both the feed and distillate were circulated at a flowrate that resulted in a flow
5
velocity of 14 cm s–1 in the flow channels. The flux and the conductivity of the permeate was
6
recorded in real time.
7
The first electrochemical cleaning cycle was initiated when the flux declined by 40%
8
compared to its original value. During the cleaning, deionized water and the distillate streams
9
were circulated with the temperature difference maintained at 40 °C (60 °C feed and 20 °C
10
distillate). The cleaning was first conducted for 20 min without applying any electrical potential
11
until water flux was stable. Then, a constant DC current (20 mA) was applied across the
12
membrane (cathode) and the Ti counter electrode (anode) using a DC power source for 50 min
13
until the water flux was recovered to the original level. A freshly prepared feed solution, with
14
6X higher feed concentration than that found naturally in geothermal brines from Nevada, was
15
used to re-foul the membrane after it was cleaned electrochemically. Since the initial feed
16
concentrations in the feed were already near saturation with regards to silica, the system was
17
always operated in constant concentration mode, as increasing the concentration (by not
18
returning the permeate to the feed tank) would lead to silicate formation in the feed tank.
19
Following the cleaning, a new round of scaling was initiated on the same membrane with a
20
freshly prepared feed solution. The scaling experiment continued until the flux declined by
21
40%, and then the second cleaning was initiated. A round of scaling and cleaning followed. In
22
addition, a continuous silicate scaling experiment without any electrochemical cleaning was
23
performed as a control. All scaling experiments were conducted in duplicate using new
24
membranes in each round.
25 26
2.7
27
The driving force for mass transfer in DCMD is the partial vapor pressure difference of water
28
across the membrane. This difference arises from the difference in the feed and distillate
29
temperatures on the opposite sides of the membrane. When modeling the flux through MD
30
membranes, it is important to account for changes in the vapor pressure within the concentration
31
polarization layer, which can be accomplished using different modeling methods
Modeling vapor flux in DCMD
11
ACS Paragon Plus Environment
52
. In our
ACS Applied Materials & Interfaces
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
Page 12 of 44
1
experiments, the feed stream was DI water, and as a result, we neglected changes in the partial
2
vapor pressure along the membrane surface. Mass transport occurs as water from the bulk of the
3
feed stream is brought to the membrane surface where it evaporates to form water vapor. The
4
vapor is then transported across the membrane to the distillate side, where it condenses to form
5
water.
6
The relationship of vapor pressure (P in Pa units) as a function of temperature (T in K units)
7
is given by the Antoine equation:
8
= exp ( −
9
)
(1)
where A, B, and C are Antoine constants 23.238, 3841.273 and 45, respectively, for water 53.
10
The temperature difference also leads to heat transport from the hot feed to the cold distillate.
11
This transport occurs over three regions: (1) bulk of feed to membrane surface, primarily
12
through convection, (2) through the membrane, primarily through conduction, and (3) from the
13
surface of the membrane to the bulk of distillate, primarily through convection.
The heat flux in each domain is given by Equations 2-4, where represents the heat
14 15 16 17 18
flux over the respective domain: the subscripts represent the feed (f), membrane (m), and
permeate (p). In addition, ℎ is the convective heat transfer coefficient, is the conductive heat transfer coefficients of the membrane, and is the thickness of the membrane. The bulk
temperatures of the feed and permeate are denoted by / , while & , denote the
19
temperatures at the membrane-feed and membrane-permeate interface, respectively (Figure 2a).
20
In Equation 3, J is the vapor flux, and H the enthalpy of vaporization.
21
= ℎ −
22 23 24
=
(2)
− + (! ∗ #)
(3)
= ℎ ( − )
(4)
25
At steady state, the heat flux across the membrane is constant for flat sheet DCMD membranes
26
45
27
:
= =
(5)
28
Substituting equations 2-4 into equation 5, yields the temperatures at the feed-membrane and
29
membrane-permeate interfaces:
12
ACS Paragon Plus Environment
Page 13 of 44
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
ACS Applied Materials & Interfaces
%
%
,∗-∗
%
,∗-∗
1
= − $ ( ∗ ) + ∗ ) − +
2
= + $ ( ∗ ) + ∗ ) − +
3
where U is the overall heat transfer coefficient, given by:
4
/ = $
5
The convective heat transfer coefficient for the feed and permeate is calculated using:
6
ℎ/ =
7
&'
*
&.
*
%
%
&'
+
+
%
&.
+
+
(
(6) (7)
(8)
01'/. ∗ '/.
(9)
2-
where, / is the conductivity of heat in water in the feed/permeate and dH is the hydraulic
8
diameter of the flow system. The Nusselt number (34/ ) is dependent on the flow conditions;
9
in our model we use one of the two following correlations to calculate the Nusselt number for
10
laminar and turbulent flow conditions 45, 54:
11
a. For laminar flow
12
34 = 4.36 +
13
b. For turbulent flow
9.9:;∗?∗(2-/@)
%A9.9%%[?∗)
(10)
CD G.H +] E
2-
34 = 0.036 ∗ JK 9.L ∗ M %/: ∗ ( @ )9.9NN
14
(11)
15
where Re and Pr are the Reynolds and Prandtl numbers, respectively. The vapor flux through
16
the membrane is obtained by modelling mass transfer across the membrane using the dusty gas
17
model for the DCMD 55. The criteria for the mode of vapor transport through the membrane is
18
given by the Knudsen number, which is the ratio of the mean free path of molecules to the
19
radius of the membrane pore. If the mean free path of molecules is of the order of the pore size,
20 21 22 23 24 25 26
i.e., OP >1, the molecule-pore wall collisions are dominant and Knudsen diffusion is responsible
for mass transfer. For the case where the mean free path is much smaller than the pore size, OP