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
1

Index

Overview

Introduction and Motivation

Electrodialysis
Reverse Osmosis
Combined Process
Process Characterization
Experiments/Results

Conclusions and Outlook

Index

Units: Gigatons C, GtC/yr

(1 GtC= 109 tons of carbon)

Source: NASA
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:
4

Engineers and scientists collaborate

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

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.

Index

The issue: recover pure DOC for scientific

analysis. The problem: salt
Water

Process
Solid DOC
sample

35 g/L salts
7~ 0.001 g/L=1 ppm DOC

Salt
Index

State of the Art Recovery

Ultrafiltration
Tangential Flow

Salt

~30% DOC

Adsorption Methods
Seawater
Porous
Non-polar
Resin
Resin
Columns

Pore

100-300 m

Water

Salt

LMW DOC

Seawater with
remaining DOC

Only recovers High Molecular Weight

DOC (>1000 Da)

Only recovers select species (humic, etc)

Salt still present in final sample

Must use pH or other method to desorb

Index

New Approach:
RO removes fresh water concentrating
salt and DOC

Water

Reverse
Osmosis
Process
Electrodialysis

35 g/L salts
9

~ 1 ppm DOC

Freeze Dry

Solid DOC
sample

Salt
ED removes salt with minimal loss of
uncharged species

Index

RO
ED

The Processes

Electrodialysis

10

Reverse Osmosis

Index

Electrodialysis Spacers and

Membranes

11

Astom AMX/CMX

Index

Electrodialysis
Diluate Return
Concentrate Return
C

Anode
Na+

Cathode

Cl-

Na+

Cl

Na+
Na+

Na+

+
+

Cl-

Na+
Na+

Na+
Cl-

Cl-

--

Na+
Na+

Na+

Cl-

Concentrate
Diluate/Feed

12

Index

Electrodialysis Characterization
Limiting Current (Ilim)

Limiting
Current
(Amps)

Temperature: 25C

13

Re apparent

4 R h v

Index

RO
ED

The Processes

Electrodialysis

14

Reverse Osmosis

Index

Reverse Osmosis
Higher
Flow
Concentration
PolyamideRetentate
barrier

0.2 m

High Pressure

Water

~ Pure Water

Salt
Water

Microporous
40 m
polysulfone
Polyester 120 m
fabric
Salt
Water

15

Discarded Permeate
Low
Concentration
Feed

http://www.dow.com/PublishedLiterature/

Index

Spiral Wound RO Module

16

http://www.purewaterplanet.com/images/ROMembrane.jpg

Index

Reverse Osmosis Characterization

40
35
30

40
0.35

205 psi

180 psi

25
150
psi
Retentate
Permeate

Permeate
35
20
Flowrate (mL/s)
15

90 psi

Small25Stage5
0.2
Permeate Cut 0

Stage Cut

Flowrate (mL/s)

20

0.15

0.99 mS/cm

180 psi
60 psi

10

0.25

CA

Qs K s
Tm

psi
205120psi

0.3

30

Retentate Permeate

Large Stage
Cut

150 psi
0

120 psi

10

12

4.11 mS/cm
14

Conductivity (mS/cm)

7.80 mS/cm

90 psi

0.3

12.12 mS/cm

0.1

10

0.99 mS/cm

60 psi

0.25

4.11 mS/cm

0.2

5
Stage Cut

7.80 mS/cm

0.15

0
0

0.1

50

High Feed
Flow
Rate
0

0.05

17

18

0.35

15

0.05

16

100

12.12 mS/cm

10

150

Operating Pressure
(psi)
Low
Feed

12

14

200

16

18

Conductivity
(mS/cm)
Flow
Rate

50

100

Operating Pressure (psi)

150

200
Index

Combined Process Operation

RO
Unit
Electrodialysis
Stack

18

Index

Overall
Drive to
site

Retrieve
seawater
sample
(200- 400 l)

ED/RO
200 l seawater

Purge ED/RO
systems

Freeze
~10 l

Freeze dry
NMR....

Hope for good weather!

19

Index

Experimentation
Experiment Date Starting Concentration (ppm)
Sample Type
Experimental Objective
7/12/2005
0.18
Artificial Seawater
9/28/2005
0.11
Artificial Seawater
Determination of operating
10/18/2005
0.05
Artificial Seawater
parameters and modes
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
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)
Recovery of DOC from various
7/20/2006
1.19
Seawater (ship board)
locations and depths
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

20

Index

Examples:
Three shipboard
experiments
Start with 200 liter
seawater

21

Index

ED: follow the limiting current density

22

Index

Summary
100

90

14

80

70

24

103

15

Final DOC ppm

3
21
21

17

60

Diluate DOC
Recovery (%)

15

21

26

50
40

Brackish
Seawater

30
20
10
0

Lab Lab Lab

1
5-26

2
6-8

3
7-3

Lab Lab
4
7-18

5
7-19

6 7-21
7
7-20

8
9
7-22
7-21

10 7-25
11
7-24

12
7-26

13 8-14
14
7-27

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