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-François Koprivnjak
School of Earth and Atmospheric Sciences
Georgia Institute of Technology
Atlanta, Georgia

1 Index
 Overview

• Introduction and Motivation

• Electrodialysis
• Reverse Osmosis
• Combined Process
• Process Characterization
• Experiments/Results
• Conclusions and Outlook
2 Index
 Units: Gigatons C, GtC/yr
(1 GtC= 109 tons of carbon)

•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

The problem with DOC in the

oceans:
• Only 1 gram of carbon in 1000 liters of
seawater......
• Salt
The approach:
• Engineers and scientists collaborate
4 • Develop a new separation approach Index
 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:

Aminosugars

Aromatics

Polysaccharides
Humic Species

5 Index
 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.

6 Index
 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

Water Salt LMW DOC

Seawater with
Only recovers High Molecular Weight remaining DOC
DOC (>1000 Da) Only recovers select species (humic, etc)
Salt still present in final sample Must use pH or other method to desorb
8 Index
 New Approach:
RO removes fresh water concentrating
salt and DOC
Water

Reverse
Osmosis
Process Freeze Dry

Electro- Solid DOC

dialysis sample

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

10 Index
 Electrodialysis Spacers and
Membranes

11 Astom AMX/CMX
Index
 Electrodialysis
Diluate Return

Concentrate Return

C A C A C C

Anode Cl- Cathode

Na+
Na+ Cl
-
Na+
Na+ Na+
Na+

+ Cl- Na+
Na+
--
+
Cl-
Cl- Na+

Na+ Cl-
Na+

Concentrate

Diluate/Feed

12 Index
 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)
13 Index
 RO

ED
The Processes
Electrodialysis Reverse Osmosis

14 Index
 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
16 Index
 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

Small25Stage5 150 psi Large Stage 4.11 mS/cm

Permeate Cut 0 Cut
0.2
0 2 4 6 8 10 12 14 16 18
Stage Cut 20
Flowrate (mL/s) 120 psi Conductivity (mS/cm) 7.80 mS/cm
0.15 0.35

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

18 Index
 Overall
Retrieve
Drive to seawater Purge ED/RO
site sample systems
(200- 400 l)

ED/RO Freeze Freeze dry

200 l seawater ~10 l NMR....

Hope for good weather!

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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

20 Index
 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]
21 Index
 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

4 RO&ED: water removal

balanced by salt removal
2 to maintain conductivity
final ED
0
0 10 20 30 40 50

Diluate (seawater) conductivity [mS/cm]

22 Index
 Summary
100 103
6 7 Final DOC ppm 15
90
14 3
80 21 26
24
6 21 15
70 21 2
17
60
Diluate DOC
50
Recovery (%)
40

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
23 Index
 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
24 Index
 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)?

25 Index
 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.

26 Index