Index

1
Electrodialysis/Reverse Osmosis to
Recover Dissolved Organics from
Seawater
Peter H. Pfromm, Tarl Vetter
Department of Chemical Engineering,
Kansas State University
Manhattan, Kansas

E. Michael Perdue, Ellery Ingall,
Jean-Franois Koprivnjak
School of Earth and Atmospheric Sciences
Georgia Institute of Technology
Atlanta, Georgia
Index
2
Overview


Introduction and Motivation

Electrodialysis

Reverse Osmosis

Combined Process

Process Characterization

Experiments/Results


Conclusions and Outlook
Index
3
Source: NASA
http://earthobservatory.nasa.gov/Library/CarbonCycle
Units: Gigatons C, GtC/yr
(1 GtC= 10
9
tons of carbon)
Index
4
Earth scientists would like to know:
Composition of carbon reservoirs

Origin/fate of carbon reservoirs

The problem with DOC in the
oceans:
Only 1 gram of carbon in 1000 liters of
seawater......

Salt
The approach:
Engineers and scientists collaborate
Develop a new separation approach
Index
5
What is marine dissolved organic
carbon (DOC)?
~30wt% of DOC is high molecular weight (HMW) >1000 Da
~70wt% of DOC is low molecular weight (LMW) <1000 Da
DOC is composed of many types of molecules, examples:
Humic Species
Aminosugars
Polysaccharides
Aromatics
Index
6
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 CO
2
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.
Index
7
35 g/L salts
~ 0.001 g/L=1 ppm DOC
Solid DOC
sample
Salt
Water
Process
The issue: recover pure DOC for scientific
analysis. The problem: salt
Index
8
State of the Art Recovery
Ultrafiltration Adsorption Methods
Pore
Tangential Flow
Water Salt LMW DOC
Salt
~30% DOC
Only recovers High Molecular Weight
DOC (>1000 Da)
Salt still present in final sample
Seawater
Resin
Columns
Porous
Non-polar
Resin
Seawater with
remaining DOC
Only recovers select species (humic, etc)
Must use pH or other method to desorb
100-300 m
Index
9
35 g/L salts
~ 1 ppm DOC
Solid DOC
sample
Salt
Water
Process
Reverse
Osmosis
Electro-
dialysis
New Approach:
RO removes fresh water concentrating
salt and DOC
ED removes salt with minimal loss of
uncharged species
Freeze Dry
Index
10
RO
ED
The Processes
Electrodialysis
Reverse Osmosis
Index
11
Electrodialysis Spacers and
Membranes
Astom AMX/CMX
Index
12
Electrodialysis
+
C C C C A A
-
Na
+

Cl
-

Cl
-

Cl
-

Na
+

Na
+

Na
+

Na
+

Diluate/Feed
Diluate Return
Cathode Anode
Concentrate Return
Concentrate
+
C C C C A A
-
Na
+

Cl
-

Cl
-

Cl
-

Na
+

Na
+

Na
+

Na
+

Diluate/Feed
Diluate Return
Cathode Anode
Na
+

Concentrate Return
+
-
Index
13
Electrodialysis Characterization
Limiting Current (I
lim
)

0
5
10
15
20
25
30
0 10 20 30 40 50
Conductivity (mS/cm)
Limiting
Current
Density
(Amps)
Re
app
= 38
Re
app
= 90

v R
h
apparent
4
Re =
Limiting
Current
(Amps)

Temperature: 25C
Index
14
RO
ED
The Processes
Electrodialysis
Reverse Osmosis
Index
15
Water
Salt
~ Pure Water
Low
Concentration
Feed
Higher
Concentration
Retentate
Water
Salt
Flow
High Pressure
Discarded Permeate
0.2 m
http://www.dow.com/PublishedLiterature/
Reverse Osmosis
Water
Polyester
fabric
120 m
40 m
Microporous
polysulfone
Polyamide
barrier
Index
16
Spiral Wound RO Module
http://www.purewaterplanet.com/images/ROMembrane.jpg
Index
17
0
5
10
15
20
25
30
35
40
0 2 4 6 8 10 12 14 16 18
Conductivity (mS/cm)
Permeate
Flowrate (mL/s)
180 psi
205 psi
150 psi
120 psi
90 psi
60 psi
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0 50 100 150 200
Operating Pressure (psi)
Stage Cut
0.99 mS/cm
4.11 mS/cm
7.80 mS/cm
12.12 mS/cm
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0 50 100 150 200
Operating Pressure (psi)
Stage Cut
0.99 mS/cm
4.11 mS/cm
7.80 mS/cm
12.12 mS/cm
0
5
10
15
20
25
30
35
40
0 2 4 6 8 10 12 14 16 18
Conductivity (mS/cm)
Permeate
Flowrate (mL/s)
180 psi
205 psi
150 psi
120 psi
90 psi
60 psi
Permeate Retentate Permeate Retentate
High Feed
Flow Rate
Low Feed
Flow Rate
Small Stage
Cut
Large Stage
Cut
|
|
.
|

\
|
A
=
m
s s
T
CA
K Q
Reverse Osmosis Characterization
Index
18
RO
Unit
Electrodialysis
Stack
Combined Process Operation
Index
19
Overall
Drive to
site
Purge ED/RO
systems
Freeze
~10 l
Freeze dry
NMR....
Retrieve
seawater
sample
(200- 400 l)
ED/RO
200 l seawater
Hope for good weather!
Index
20
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
11/9/2005 0.01 Artificial Seawater
3/6/2006 0.22 Artificial Seawater
4/3/2006 0.06 Artificial Seawater
5/26/2006 1.95 Brackish Water
6/8/2006 2.24 Brackish Water
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)
7/20, 7/21/2006 1.21 Seawater (ship board)
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
Determination of operating
parameters and modes
Examine recovery of natural
DOC species
Recovery of DOC from various
locations and depths
Experimentation
Index
21
Examples:

Three shipboard
experiments

Start with 200 liter
seawater
0
40
80
120
160
200
240
0 2 4 6
Time [hrs]
DOC
retained
[mg]
ED & RO ED ED
0
25
50
75
100
0 2 4 6
Time [hrs]
%
removed
ED & RO ED ED
S
Salt
Water
Index
22
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50
Diluate (seawater) conductivity [mS/cm]
ED
current
[A]
initial
seawater sample
201 liters
initial ED only
RO&ED: water removal
balanced by salt removal
to maintain conductivity
limiting
current
applied
current
final ED
ED: follow the limiting current density
Index
23
0
10
20
30
40
50
60
70
80
90
100
Diluate DOC
Recovery (%)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Date of Experiment
5-26 6-8 7-3 7-18 7-19 7-20 7-21 7-21 7-22 7-24 7-25 7-26 7-27 8-14 8-18
Brackish
Seawater Lab Lab Lab Lab Lab
Summary
24
14
21
21
15
21
17
15
26
103
6
7
6
3
2
Final DOC ppm
Index
24
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
Index
25
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)?
Index
26
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.