ICDEMOS, 13 – 16 April 2014,
1/40
Sultan Qaboos University, Muscat, Sultanate of Oman
Desalination Process Advancement
by Hybrid and New Material
beyond the seaHERO R&D Project
In S. Kim
Global Desalination Research Center (GDRC)
Global Desalination
Research Center
Global Warming & Climatic Changes
Excessive dependence of fossil fuel
Source: San Diego state university
Between 1950 and 2000,World fossil fuel
consumption increased fourfold.
Global Desalination
Research Center
2/40
Global warming & Climatic calamity
Source: NASA Goddard Institute for Space Studies
The global temperature is forecast to rise
4 ℃ by the end of 21st century.
Urbanization & Industrialization
Continuous increase of water consumption
Global Desalination
Research Center
3/40
Solutions for Water Shortage
Solutions for water Crisis
•
•
•
Water conservation techniques and
technologies
Better management of water resources
Production of additional fresh water from
saline water or impaired water sources
In particular, producing fresh water from
alternative sources is inevitable in the future
New sources of water
Seawater
Global Desalination
Research Center
Wastewater
4/40
Seawater Desalination
•
•
5/40
Producing fresh water from seawater
Key technology: MSF(Thermal) and Reverse Osmosis(membrane)
MSF (Multistage Flash)
Global Desalination
Research Center
RO (Reverse Osmosis)
Issues for Fresh Water from New Sources
Seawater Desalination & Wastewater Reuse
Water Safety
Water Security
Energy Efficiency
Guarantee of
safe water quality
Enough water
availability
Low production
cost
Which technologies ?
Membrane and nano technologies
Global Desalination
Research Center
6/40
Needs for Membrane Technologies
 Higher Flux
 Higher Removal
 Lower Fouling
 Lower Energy demand
Global Desalination
Research Center
7/40
 New desalination process
- Forward osmosis
- Membrane distillation
- Hybrid process (FO-RO and etc.)
 New material for membrane
- Graphene & Carbon nanotube
- Zeolite, Aquaporins and etc…..
 New O&M approaches
- Closed Circuit Desalination (CCD)
- Cleaning (Osmotic Backwashing)
SeaHERO R&D program
8/40
SeaHERO: Seawater Engineering Architecture High Efficiency Reverse Osmosis
Value
Creator (VC)
- 10
Head center: GIST
Exe. Director: Prof. In Kim
Period: 2007. 3 ~ 2014. 8
►
New growth engine
Budget: 180 billion KRW
►
Green growth
Supported by Ministry of Land,
Global
Top – 5 Tech.
Infrastructure and Transport
(MOLIT)
Development of World-leading Seawater desalination technology
Global Desalination
Research Center
Technical Objectives : 3L
Energy consumption,
< 4kWh/m3
Unit Train Size,
~ 8MIGD
(~36,000 tons/day)
•
•
•
•
•
•
The biggest unit train in the
world
Big Train-Standard of large
scale plant
High opportunity of energy
saving
Essential factor affecting O&M Cost
Stabilization of water price
Energy recovery system
development
Fouling Reduction as a new
index, < 50%
•
•
Reliability increasing
Most important factor in SWRO
“Focus on how to get EPC/O&M Cost
minimization and Energy Saving”
Global Desalination
Research Center
9/40
SeaHERO R&D program
10/40
CT1: Development of core technologies for future SWRO plant
1
URP 1: Development of the infrastructure and the support system of seawater desalination
URP 2: Development of optimal pretreatment process adjusted to seawater characteristics
URP 3: Monitoring technology for SWRO process: Development of RO process sensors and
network based monitoring systems
URP 4: Post treatment of R/O processed water and risk assessment of condensed water
URP 5: Next Generation RO membrane analysis and operation diagnosis
CT 2: Localization of SWRO Membrane/Pump Components and Development
- 4 Core fields
-13 main + 27
commissioned projects
-250 research staff
-25 Univ. + 6 National
Institutes + 28 Industries
2
of Systems Integration Technologies for SWRO Desalination Plant
URP 1: Systems engineering technology development for seawater desalination systems
Integration
URP 2: Development of high performance polyamide RO membrane for SWRO desalination plant
construction
URP 3: Development of novel SWRO membranes with high durability and chemical resistance for
seawater desalination
URP 4: Development of high efficiency, high capacity high pressure pump and ERD for desalination
Plant
3
CT 3: Development of large-scale SWRO Desalination Plant Design and
Construction Technology
URP 1: Development of large-scale SWRO desalination plant design and construction technology
(Test bed: 45,000 cubic meter/day of drinking water production)
URP 2: Development of evaluation technology of domestic device’s site application characteristic
on Test-Bed plant
4
Global Desalination
Research Center
CT 4: Development of Innovative O&M technology for large-scale SWRO plant
URP 1: Development of optimization technology for large-scale SWRO plant
URP 2: Development of diagnosis and control system for large-scale SWRO plant
Research Outputs of SeaHERO
Global Desalination
Research Center
11/40
History & Perspective of Desal. Tech.
Beginning
of desalination Application of
(Kuwait)
desalination process
1956
1956
1970
1970
Present
1980
1980
1990
1990
2000
2000
2005
2005
Market leading tech. : Thermal type
Energy 10 kWh/ton
2010
2010
2015
2015
2020
2020
Market leading tech. : Reverse osmosis
Energy 4 kWh/ton
RO
Development
1st technical innovation
2nd technical innovation
1st Energy reduction periods
MSF
RO
2nd Energy reduction periods
RO
SeaHERO
2nd Energy reduction periods
1.
Innovative enhancement in efficiency of RO process
2.
Development of new desalination technology
or
Global Desalination
Research Center
12/40
????
After SeaHERO Projects..
Energy-intensive process
13/40
Environmental load
(Brine treatments, CO2 emission)
We still need further development for energy and
environmental issues of desalination.
Global Desalination
Research Center
Steps of Desalination Technology
4
SeaHERO
Project
Global Desalination
Research Center
5
Development of
hybrid system
+
Material
improvement
14/40
Two ways: Hybrid Desalination
1. Innovative unit processes
(with FO, PRO, MD, ..)
Global Desalination
Research Center
15/40
2. Hybrid with renewable energy
(Solar, wind, geothermal, ..)
Conventional Hybrid Desalination Plant
16/40
RO with Thermal Process
 Operating at the optimal temperature
 increase of the efficiency
 Increasing the recovery rate compared to the
typical RO
 reduction of operating cost & water cost
 Blending RO product water and MSF product
water
 improving the product water quality
 Example)
Fujairah(UAE) plant
(constructed by Doosan)
62.5 MIGD MSF + 37.5 MIGD SWRO
(source: O.A. Hamed, Desalination 186, 2005; Ho-Sun Yu, Korean Plant Society, 2007)
Global Desalination
Research Center
Future Hybrid Desalination Plant
17/40
Key issues:
Energy Reduction & Minimum Environmental load
Reduction & Reuse of brine
(MD, PRO)
► Low usage of chemical agents
(Low fouling process → FO)
►
Energy
Energy-efficient process (FO, MD)
► Osmotic energy production
(PRO, RED)
► Use of various energy resources
►
Global Desalination
Research Center
Hybrid
Desalination
Plant
Environmental Load
SWRO + Membrane Distillation (MD)
18/40
Heater
steam
fresh water
seawater
Product
< Hybrid RO-MD >
membrane
- Thermally driven process
- Driving force: vapor pressure
difference
- Hydrophobic porous membrane
is required.
< Hybrid FO-MD:
Draw solution recovery>
Reduction of brine & increase of recovery by MD
→ Toward zero discharge desalination (source: Lucy Mar Camacho et al., Water, 2013)
Global Desalination
Research Center
Forward Osmosis (FO) & Pressure Retarded
Osmosis (PRO):
19/40
Water & Energy production: FO & PRO
Energy consumption of FO
process
≈ 1 kWh/m3 (Theoretical)
Low
Energy
Low pressure
P 〈△π
High pressure
P 〉△π
Water
Production
Energy
Production
Water
Production
More osmotic power can be
recovered by using brine in PRO.
(Feasible power density = 5 W/m2)
(source: Yale Univ., 2006, guy Z. Ramon et al., Energy & Environmental Sci., 2011)
Global Desalination
Research Center
SWRO + Forward Osmosis (FO)
20/40
Osmotic Dilution by FO-RO hybrid
 FO stage 1 :
Seawater is diluted by an impaired
water stream
 RO :
diluted seawater is processed to
produce potable water
 FO stage 2 :
osmotic dilution can be
implemented to dilute the RO brine
 Dilution of seawater (RO feed) by FO stage 1
 Reducing the energy consumption
 Decreasing the salinity of the discharged RO brine via FO stage 2
 Minimizing the environmental impact of RO brine
(source: T.Y. Cath et al., IDA Journal, 2010)
Global Desalination
Research Center
SWRO + Forward Osmosis (FO)
21/40
Predictions on Performance
FO-RO hybrid desalination system may have… (at same recovery)
- 10-30% less Specific Energy Consumption (SEC) than 2-Pass RO
- However, greater total membrane area than 2-Pass RO
(Source : Shaffer et al., JMS ,2012)
Global Desalination
Research Center
SWRO + Pressure Retarded Osmosis (PRO) 22/40
Osmotic energy production
** 1 MJ
: the work generated by when
1 ton truck(160km/h) hits a wall
Brine + River water
Draw
(5 mol/l)
(0.01mol/l)
10 MJ
1.4 MJ
15 MJ
Brine + Sea water
(5 mol/l)
(0.5mol/l)
Sea water + River water
(0.5 mol/l)
(0.01mol/l)
(Source : J. W. Post, “Blue energy: electricity production from salinity gradient by reverse electrodialysis”, 2009)
Global Desalination
Research Center
SWRO + PRO
23/40
PRO research in Mega-ton Project (Japan)
RO
 Demo plant (Kitakyushu, Japan)
: 1,500 m3/d sewage & 500 m3/d seawater
 140,000 m3/d product water (industrial
use)
 Energy-saving efficiency is higher than
UF+RO
 More than 30% of operating pressure
reduction
 Dilution of concentrated RO brine  Cost reduction of RO brine disposal
 Utilization of RO brine as PRO draw solution  Enhancement of PRO
power generation
(source: M. Kurihara and M. Hanakawa, Desalination 308, 2013)
Global Desalination
Research Center
SWRO + Reverse Electrodialysis (RED)
24/40
④
①
Sea water (Brine)
②
River water (Dilute)
③
① Driving force of RED  Electro-chemical potential difference between brine and dilute
② Concentrated brine from RO is supplied as the high salinity feed solution
 high power density
③ Decreasing the salinity of the discharged brine via RED process
 minimizing the environmental impact of RO brine
④ In the case (a) RED ⇒ RO, pre-treating the feed solution through the RED process
 reducing the energy consumption of RO process
Global Desalination
Research Center
(source: W. Li et al., Applied Energy 104, 2013)
Next Hybrid Desalination Projects
seaHERO-MVP
seaHERO-FWER
Concentrates & Valuables
Management Enhanced
Product Water&Energy
Enhanced
MD/Valuables/PRO Hybrid
Process
Global Desalination
Research Center
FO/Water-Energy/RO
hybrid Process
25/40
New Materials for Membrane
26/40
New Materials for Membrane
Nanomaterials
- Metal oxide (TiO2)
- Silver nanoparticle
- Biopolymer
Aquaporin
- Cellular
membrane protein
Inorganic
materials
- Zeolite
- Ceramic
membrane
Carbon
materials
Etc.
- Graphene
- CNT (SWNT, MWNT)
New generation membranes should have :
1.
2.
3.
4.
High performance (high water flux & salt rejection, …)
High feasibility (Simple fabrication & low cost, …)
Long lifetime (high chemical/physical resistance, ...)
Special characteristics (Antimicrobial, antifouling, conductive, …)
Global Desalination
Research Center
Research Trends of Nanoparticles
27/40
Types of nanomaterials in antifouling membrane
Total No. of Paper = 134
(from 2001 to present)
Search engine : www.scopus.com
TITLE-ABS-KEY(membrane AND (antifouling OR fouling)) AND PUBYEAR AFT 2000
Global Desalination
Research Center
New Membrane Materials
28/40
What kind of materials can have
1. Commercial feasibility,
2. High performance?
Source : Mary et al., EES, 2011
Global Desalination
Research Center
Graphene for Membrane
Graphene
•
•
A single layer of carbon packed in a
hexagonal (honeycomb) lattice
29/40
Table 1. Graphene characteristics
Characteristics
Graphene
Structure
2-dimension
(thickness：0.34 nm)
Young’s modulus
1 Tpa
Tensile Strength
130 Gpa
Thermal stability
∼2,800 ℃ under Ar
Density
2.2 g/cm3
A carbon-carbon distance of 0.142 nm
As active layer of membrane
1. 2D structure with atomic thickness  Ultra thin active layer
2. Well-ordered rigid structure  High potential for excellent salt rejection
But, need of supporting structure!
Global Desalination
Research Center
New material : Graphene & Ceramic 30/40
Seawater & Wastewater
H2O
Graphene nanosheet (Active layer)
- Ultrathin
- High selectivity
- Superior chemical & physical property
Solutes
Combination
Ceramic membrane (Support layer)
- High strength
- High uniformity
- Outstanding chemical resistance
Ceramic-based graphene membrane
(CbGM)
Pure water production !
Global Desalination
Research Center
 High performance, Chemical inertness, High
structural strength, Long lifetime
Issues in graphene membrane
31/40
③ Control of pores
① Graphene synthesis
& Rejection mechanism
(Kind of graphene)
② Combining and
interaction between
graphene and ceramic
Graphene nano-sheet
Ceramic substrate
④ Mass transport
& Mechanism
⑤ Characteristics & Performance
evaluation
Figure source: K. S. Novoselov et al., Nature review, 2012
Global Desalination
Research Center
Graphene Membrane Fabrication
1. Starting materials
32/40
2. Combining between
- Graphenes (flakes or sheets)
- Graphene and ceramic
1 Graphene flakes
(ex)Graphene oxide (GO), Reduced GO,(rGO))
Graphene
2 Graphene nanosheet
(Graphene prepared by CVD methods)
Ceramic Substrate
Providing - 1. high structural strength
2. chemical inertness
Global Desalination
Research Center
Potential transport mechanism
33/40
 Ion rejection by what mechanisms
1.Physical size exclusion ?
2.Electrostatic force ?
Graphene
layer
Porous
ceramic
membrane
 Transport of water molecule
through interspacing nanochannel ?
Global Desalination
Research Center
 Transmission of water
molecule through defects
on graphene sheet ?
Water
Ions
Comparison of Fabrication Methods
34/40
 Drop-casting (DC) method
Raw ceramic
membrane
1 time
4 times
16 times
8 times
 Filtration-assisted assembly (FAA) method
rGO
393.0 mg/m2
rGO
786.0 mg/m2
rGO
1572.0 mg/m2
Two kinds of membrane (prepared by DC and FAA method)
 Uniformity difference (FAA > DC methods)
Global Desalination
Research Center
Surface Morphology – SEM image
Plane view
Cross-sectional
view
Raw ceramic membrane
Plane view
35/40
Cross-sectional
view
rGO 393.0 mg/m2
Thickness: ~2 μm
rGO 786.0 mg/m2
Thickness: ~6 μm
Global Desalination
Research Center
rGO 1572.0 mg/m2
Thickness: ~12 μm
Comparison of surface morphology-SEM
Old results
Plane view
Cross-sectional view
New results
Plane view
rGO 1205.6 mg/m2
Thickness: ~1.7 μm
rGO 2411.2 mg/m2
Thickness: ~ 3.1 μm
 Surface fully covered with 130 time less GO than rGO 2411.2 mg/m2
 With highly superior graphene interlocking & Uniformity
Global Desalination
Research Center
36/40
Cross-sectional view
GO 15.09 mg/m2
Thickness: ~ 28 nm
GO 30.18 mg/m2
Thickness: ~ 65 nm
Application : Fouling & Cleaning
Antimicrobial activity of graphene oxide
37/40
Connection between graphene layers
- Van der Waals force
- Hydrogen bonding
Juanni Chen et al., 2014
Hyo Won Kim et al., 2014
1. Fouling characteristics & resistance
- Antimicrobial characteristics of graphene nanosheets
 Biofouling reduction on graphene membrane?
2. Cleaning efficiency & resistance
- Chemical bonding strength between graphene nanosheets
Cleaning  Detachment of graphene nanosheet & chemical resistance
CbGM
Global Desalination
Research Center
Summary & Conclusion
38/40
1. Hybrid desalination approaches are appropriate and required
for energy consumption reduction and environmental
sustainability of desalination plant.
- W/ innovative unit processes (FO, PRO, MD, ..)
- W/ renewable energy sources (Solar, wind, ..)
2. Various membrane with new materials under testing
- Nanomaterials (TiO2, Silver, …)
- Biomimetic (Aquaporin)
- Inorganic materials (Zeolite, ceramic, …)
- Carbon materials (Graphene, CNT, …)
 Carbon-based materials are hot issue in recent year
Global Desalination
Research Center
Global Networking
39/40
International Desalination Workshop (IDW)
1
- Date : 2007.11.16∼17
- Attendee : 91 peoples (8 countries)
- Place : GIST (Korea)
- 30 presentations
The 7th IDW2014 (Nov. 5-8, Lotte City 2
Hotel) will be held in Jeju Island,
South Korea.
3
(by GDRC + EDS)
- Date : 2008.10.08∼09
- Attendee : 116 peoples (12 countries)
- Place : GIST (Korea)
- 58 presentations
- Date : 2010.11.03∼06
- Attendee : 180 peoples (15 countries)
- Place : Jeju island (Korea)
- 109 presentations
- Date : 2011.11.16∼19
- Attendee : 250 peoples (15 countries)
- Place : Jeju island (Korea)
- 82 presentations
Join and make global networking in desalination field!
5
- Date : 2012.10.28∼31
- Attendee : 160 peoples (15 countries)
- Place : Jeju island (Korea)
- 120 presentations
Global Desalination
Research Center
4
The 6th IDW2013:
Nov. 28-29, 2013,
Melbourne, Australia
Technology – Need harmony by height
“Thank you”
Global Desalination
Research Center
40/40