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Electrodialysis/Reverse Osmosis To Recover Dissolved Organics From Seawater
Electrodialysis/Reverse Osmosis To Recover Dissolved Organics From Seawater
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Overview
•Source: NASA
3 Index
•http://earthobservatory.nasa.gov/Library/CarbonCycle
Earth scientists would like to know:
• Composition of carbon reservoirs
• Origin/fate of carbon reservoirs
Aminosugars
Aromatics
Polysaccharides
Humic Species
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How do you detect marine dissolved
organic carbon (DOC)?
Not a trivial issue: reasonably accurate part-per-billion level
analysis for organic carbon in a high-salt (chloride) matrix.
Shimadzu TOC-VCSN high-temperature catalytic oxidation
analyzer
Sample is acidified to remove inorganic carbon, then
combusted over Pt catalyst and CO2 is detected by infrared
Many papers, book chapters, and meetings are dedicated to
this issue. Perdue at Georgia Tech is one of the well known
experts on this.
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The issue: recover pure DOC for scientific
analysis. The problem: salt
Water
Process
Solid DOC
sample
Salt
35 g/L salts
7 ~ 0.001 g/L=1 ppm DOC Index
State of the Art Recovery
Ultrafiltration Adsorption Methods
Seawater
Tangential Flow Porous
Salt Non-polar
~30% DOC Resin
Pore Resin
Columns
100-300 μm
Reverse
Osmosis
Process Freeze Dry
Salt
35 g/L salts ED removes salt with minimal loss of
uncharged species
9 ~ 1 ppm DOC Index
RO
ED
The Processes
Electrodialysis Reverse Osmosis
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Electrodialysis Spacers and
Membranes
11 Astom AMX/CMX
Index
Electrodialysis
Diluate Return
Concentrate Return
C A C A C C
+ Cl- Na+
Na+
--
+
Cl-
Cl- Na+
Na+ Cl-
Na+
Concentrate
Diluate/Feed
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Electrodialysis Characterization
Limiting Current (Ilim)
30
25
Limiting 20 Reapp = 90
Limiting
Current
15
Current
Density
(Amps) 10
(Amps)
Reapp = 38
5 4 R h v
Re apparent
Temperature: 25°C
0
0 10 20 30 40 50
Conductivity (mS/cm)
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RO
ED
The Processes
Electrodialysis Reverse Osmosis
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Reverse Osmosis
~ Pure Water
Higher High Pressure
Flow
Concentration
PolyamideRetentate
barrier 0.2 μm Water Salt
Water
Microporous
40 μm
polysulfone
Polyester 120 μm
fabric
Salt
Water
Discarded Permeate
Low
Concentration
Feed
15 http://www.dow.com/PublishedLiterature/ Index
Spiral Wound RO Module
http://www.purewaterplanet.com/images/ROMembrane.jpg
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Reverse Osmosis Characterization
40
35
205 psi
30
40 180 psi
0.35
Retentate
25
Permeate
150 psi Retentate Permeate
35
Permeate
20
CA
Qs K s
Flowrate (mL/s)
0.3
205120psi
psi
15 90 psi
Tm
30 0.99 mS/cm
180 psi
10 60 psi
0.25
15 90 psi
0.3
12.12 mS/cm
0.1 0.99 mS/cm
10 0.25 60 psi
4.11 mS/cm
0.05 0.2
5
Stage Cut
7.80 mS/cm
0.15
0
0 0.1
12.12 mS/cm
0 50 100 150 200
0 2 4 6 8 10 12 14 16 18
High Feed
0.05 Low
Operating Pressure Feed
(psi)
Flow Rate Conductivity
Flow(mS/cm)
Rate
0
0 50 100 150 200
17 Operating Pressure (psi) Index
Combined Process Operation
RO
Unit
Electrodialysis
Stack
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Overall
Retrieve
Drive to seawater Purge ED/RO
site sample systems
(200- 400 l)
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Experimentation
Experiment Date Starting Concentration (ppm) Sample Type Experimental Objective
7/12/2005 0.18 Artificial Seawater
9/28/2005 0.11 Artificial Seawater
10/18/2005 0.05 Artificial Seawater Determination of operating
11/9/2005 0.01 Artificial Seawater parameters and modes
3/6/2006 0.22 Artificial Seawater
4/3/2006 0.06 Artificial Seawater
5/26/2006 1.95 Brackish Water
Examine recovery of natural
6/8/2006 2.24 Brackish Water
DOC species
7/3/2006 3.30 Brackish Water
7/18/2006 1.20 Seawater (ship board)
7/19/2006 0.93 Seawater (ship board)
7/20/2006 1.19 Seawater (ship board) Recovery of DOC from various
7/20, 7/21/2006 1.21 Seawater (ship board) locations and depths
7/21/2006 0.82 Seawater (ship board)
7/22/2006 1.10 Seawater (ship board)
7/23/2006 0.20 Blank (ship board) Examine DOC leaching
7/24, 7/25/2006 1.22 Seawater (ship board) Adjustment of ED operation
7/25, 7/26/2006 1.10 Seawater (ship board) Attempt total desalination
7/26, 7/27/2006 1.02 Seawater (ship board) Examine high concentration
7/27/2006 5.08 Brackish Water (ship board) Comparison of DOC recovery
8/14/2006 0.96 Seawater Lab reproduction of seawater
8/18/2006 1.08 Seawater Test new membranes
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100
Salt
75 S
%
removed 50
Water
25
ED ED & RO ED
Examples: 0
0 2 4 6
Three shipboard Time [hrs]
experiments 240
200
Start with 200 liter
160
seawater DOC
retained 120
[mg]
80
ED ED & RO ED
40
0
0 2 4 6
Time [hrs]
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ED: follow the limiting current density
20
applied
18
current
16
14
12 limiting
ED current initial
10
current seawater sample
[A] 8 201 liters
initial ED only
6
30
Brackish
20
10
Seawater Lab Lab Lab Lab Lab
0
1
5-26 2
6-8 3
7-3 4
7-18 5
7-19 6 7-21
7-20 7 8
7-21 9
7-22 10 7-25
7-24 11 12
7-26 13 8-14
7-27 14 15
8-18
Date of Experiment
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Conclusions
• ED/RO can recover a significant
fraction of DOC from seawater
(60%-90%)
• The process is fast, allowing
treatment of large volumes of
samples
• We are able to reduce salt
concentration and water volume to
make a sample ready for freeze
drying
• Preliminary results by NMR:
differences from the high MW
fraction that was previously
available.
• Scientists and engineers think
differently but can communicate
and collaborate successfully
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Outlook
• Examine the impact of
temperature
• Further minimize losses to the
ED concentrate, possibly with
different membranes
• Examine modulation of the ED
current to optimize DOC
recovery
• Applications for recovery of
sensitive molecules (proteins,
enzymes)?
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Acknowledgements
• This work is supported by the National Science
Foundation, Grants No. 0425624 and 0425603.
(Any opinions, findings, and conclusions or recommendations expressed
in this material are those of the authors and do not necessarily reflect the
views of NSF)
• Dr. Mary Rezac who initiated the contact between
scientists and engineers that made this work
possible.
• Poulomi Sannigrahi for help at sea and in the
laboratory.
• We would especially like to thank Captain
Raymond Sweatte and the excellent crew of the
R/V Savannah for two great and productive
cruises.
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