Desalination Process Advancement by Hybrid and New ...Global Desalination Research Center In S. Kim...
Transcript of Desalination Process Advancement by Hybrid and New ...Global Desalination Research Center In S. Kim...
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Global Desalination Research Center
In S. Kim
Global Desalination Research Center (GDRC)
ICDEMOS, 13 – 16 April 2014,
Sultan Qaboos University, Muscat, Sultanate of Oman
Desalination Process Advancement by Hybrid and New Material
beyond the seaHERO R&D Project
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Global Warming & Climatic Changes Excessive dependence of fossil fuel Global warming & Climatic calamity
Between 1950 and 2000,World fossil fuel consumption increased fourfold.
The global temperature is forecast to rise 4 ℃ by the end of 21st century.
Source: NASA Goddard Institute for Space Studies Source: San Diego state university
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Continuous increase of water consumption
Urbanization & Industrialization
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Solutions for Water Shortage
• Water conservation techniques and technologies
• Better management of water resources • Production of additional fresh water from
saline water or impaired water sources
Solutions for water Crisis
New sources of water
Seawater Wastewater
In particular, producing fresh water from alternative sources is inevitable in the future
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Seawater Desalination • Producing fresh water from seawater • Key technology: MSF(Thermal) and Reverse Osmosis(membrane)
MSF (Multistage Flash) RO (Reverse Osmosis)
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Issues for Fresh Water from New Sources
Seawater Desalination & Wastewater Reuse
Water Safety Water Security Energy Efficiency
Which technologies ?
Enough water availability
Low production cost
Guarantee of safe water quality
Membrane and nano technologies
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Higher Flux
Higher Removal
Lower Fouling
Lower Energy demand
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)
Needs for Membrane Technologies
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Global Desalination Research Center
SeaHERO R&D program
Development of World-leading Seawater desalination technology
Head center: GIST
Exe. Director: Prof. In Kim
Period: 2007. 3 ~ 2014. 8
Budget: 180 billion KRW
Supported by Ministry of Land,
Infrastructure and Transport
(MOLIT)
SeaHERO: Seawater Engineering Architecture High Efficiency Reverse Osmosis
Value Creator (VC)
- 10
Global Top – 5 Tech.
► New growth engine ► Green growth
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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
• Reliability increasing • Most important factor in SWRO
• Essential factor affecting O&M Cost • Stabilization of water price • Energy recovery system
development
Fouling Reduction as a new index, < 50%
Energy consumption, < 4kWh/m3
“Focus on how to get EPC/O&M Cost minimization and Energy Saving”
Technical Objectives : 3L
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SeaHERO R&D program
- 4 Core fields -13 main + 27 commissioned projects -250 research staff -25 Univ. + 6 National Institutes + 28 Industries
1 CT1: Development of core technologies for future SWRO plant 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
2 CT 2: Localization of SWRO Membrane/Pump Components and Development
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 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
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Research Outputs of SeaHERO
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1956
Beginning of desalination
(Kuwait)
1970
Application of desalination process
1980 1990 2000 2005 2010 2015 2020
Market leading tech. : Thermal type
Energy 10 kWh/ton Energy 4 kWh/ton
1st technical innovation
RO Development
1st Energy reduction periods MSF RO
2nd Energy reduction periods RO ????
History & Perspective of Desal. Tech.
1956 1970 1980 1990 2000 2005 2010 2015 2020
2nd technical innovation
Market leading tech. : Reverse osmosis
SeaHERO
1. Innovative enhancement in efficiency of RO process
2. Development of new desalination technology
Present
2nd Energy reduction periods
or
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After SeaHERO Projects..
We still need further development for energy and environmental issues of desalination.
Environmental load (Brine treatments, CO2 emission)
Energy-intensive process
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Steps of Desalination Technology
SeaHERO Project
Development of hybrid system
+ Material
improvement
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Two ways: Hybrid Desalination 1. Innovative unit processes (with FO, PRO, MD, ..)
2. Hybrid with renewable energy (Solar, wind, geothermal, ..)
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(source: O.A. Hamed, Desalination 186, 2005; Ho-Sun Yu, Korean Plant Society, 2007)
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
Conventional Hybrid Desalination Plant RO with Thermal Process
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Future Hybrid Desalination Plant
Key issues: Energy Reduction & Minimum Environmental load
► Reduction & Reuse of brine (MD, PRO) ► Low usage of chemical agents (Low fouling process → FO)
Energy
Environmental Load ► Energy-efficient process (FO, MD) ► Osmotic energy production (PRO, RED) ► Use of various energy resources
Hybrid Desalination
Plant
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< Hybrid RO-MD >
< Hybrid FO-MD: Draw solution recovery>
SWRO + Membrane Distillation (MD)
Reduction of brine & increase of recovery by MD → Toward zero discharge desalination
membrane
seaw
ater
Heater
fresh water
stea
m
Product
- Thermally driven process - Driving force: vapor pressure
difference - Hydrophobic porous membrane
is required.
(source: Lucy Mar Camacho et al., Water, 2013)
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Forward Osmosis (FO) & Pressure Retarded Osmosis (PRO):
Water & Energy production: FO & PRO
Low Energy
High pressure P 〉△π
Low pressure P 〈△π
Water Production
Energy Production
Water Production
Energy consumption of FO process
≈ 1 kWh/m3 (Theoretical)
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)
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SWRO + Forward Osmosis (FO)
(source: T.Y. Cath et al., IDA Journal, 2010)
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
Osmotic Dilution by FO-RO hybrid
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(Source : Shaffer et al., JMS ,2012)
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
Predictions on Performance
SWRO + Forward Osmosis (FO)
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SWRO + Pressure Retarded Osmosis (PRO) Osmotic energy production ** 1 MJ
: the work generated by when 1 ton truck(160km/h) hits a wall
Sea water + River water (0.5 mol/l) (0.01mol/l)
Brine + Sea water (5 mol/l) (0.5mol/l)
Brine + River water (5 mol/l) (0.01mol/l)
10 MJ
15 MJ 1.4 MJ
(Source : J. W. Post, “Blue energy: electricity production from salinity gradient by reverse electrodialysis”, 2009)
Draw
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SWRO + PRO
(source: M. Kurihara and M. Hanakawa, Desalination 308, 2013)
PRO research in Mega-ton Project (Japan)
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
RO
Dilution of concentrated RO brine Cost reduction of RO brine disposal Utilization of RO brine as PRO draw solution Enhancement of PRO
power generation
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SWRO + Reverse Electrodialysis (RED)
(source: W. Li et al., Applied Energy 104, 2013)
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
Sea water (Brine)
River water (Dilute)
①
②
③
④
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seaHERO-MVP
Concentrates & Valuables Management Enhanced
seaHERO-FWER
Product Water&Energy Enhanced
FO/Water-Energy/RO hybrid Process
MD/Valuables/PRO Hybrid Process
Next Hybrid Desalination Projects
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New Materials for Membrane
New generation membranes should have : 1. High performance (high water flux & salt rejection, …) 2. High feasibility (Simple fabrication & low cost, …) 3. Long lifetime (high chemical/physical resistance, ...) 4. Special characteristics (Antimicrobial, antifouling, conductive, …)
New Materials for Membrane
Nanomaterials Aquaporin Inorganic materials
Carbon materials
- Graphene - CNT (SWNT, MWNT)
- Metal oxide (TiO2) - Silver nanoparticle - Biopolymer
- Cellular membrane protein
Etc.
- Zeolite - Ceramic membrane
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Research Trends of Nanoparticles 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
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New Membrane Materials
Source : Mary et al., EES, 2011
What kind of materials can have 1. Commercial feasibility, 2. High performance?
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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
Graphene for Membrane
• A single layer of carbon packed in a hexagonal (honeycomb) lattice
• A carbon-carbon distance of 0.142 nm
Graphene Table 1. Graphene characteristics
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!
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Graphene nanosheet (Active layer) - Ultrathin - High selectivity - Superior chemical & physical property
Ceramic membrane (Support layer) - High strength - High uniformity - Outstanding chemical resistance
Pure water production !
Combination
Ceramic-based graphene membrane (CbGM)
New material : Graphene & Ceramic
H2O
Solutes
High performance, Chemical inertness, High structural strength, Long lifetime
Seawater & Wastewater
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Issues in graphene membrane
Ceramic substrate
Graphene nano-sheet
① Graphene synthesis
(Kind of graphene)
② Combining and interaction between graphene and ceramic
③ Control of pores
& Rejection mechanism
④ Mass transport
& Mechanism ⑤ Characteristics & Performance
evaluation
Figure source: K. S. Novoselov et al., Nature review, 2012
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Ceramic Substrate
Graphene Graphene flakes (ex)Graphene oxide (GO), Reduced GO,(rGO))
Graphene nanosheet (Graphene prepared by CVD methods)
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Graphene Membrane Fabrication
Providing - 1. high structural strength
2. chemical inertness
1. Starting materials 2. Combining between - Graphenes (flakes or sheets) - Graphene and ceramic
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Water
Ions
Porous ceramic
membrane
Graphene layer
Ion rejection by what mechanisms 1.Physical size exclusion ?
2.Electrostatic force ?
Transmission of water molecule through defects on graphene sheet ?
Transport of water molecule through interspacing nano-channel ?
Potential transport mechanism
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rGO 393.0 mg/m2
rGO 786.0 mg/m2
rGO 1572.0 mg/m2
Comparison of Fabrication Methods
Raw ceramic membrane
4 times 8 times 16 times 1 time
Drop-casting (DC) method
Filtration-assisted assembly (FAA) method
Two kinds of membrane (prepared by DC and FAA method)
Uniformity difference (FAA > DC methods)
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Surface Morphology – SEM image
Raw ceramic membrane
Plane view Cross-sectional view
rGO 393.0 mg/m2
Thickness: ~2 μm
rGO 786.0 mg/m2 rGO 1572.0 mg/m2
Plane view Cross-sectional view
Thickness: ~6 μm Thickness: ~12 μm
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Plane view Plane view Old results New results
rGO 2411.2 mg/m2
rGO 1205.6 mg/m2
GO 30.18 mg/m2
GO 15.09 mg/m2
Thickness: ~1.7 μm
Thickness: ~ 3.1 μm Thickness: ~ 65 nm
Thickness: ~ 28 nm
Comparison of surface morphology-SEM Cross-sectional view Cross-sectional view
Surface fully covered with 130 time less GO than rGO 2411.2 mg/m2
With highly superior graphene interlocking & Uniformity
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CbGM
Application : Fouling & Cleaning
1. Fouling characteristics & resistance
2. Cleaning efficiency & resistance
- Antimicrobial characteristics of graphene nanosheets Biofouling reduction on graphene membrane?
Cleaning
Juanni Chen et al., 2014
Antimicrobial activity of graphene oxide Connection between graphene layers
Hyo Won Kim et al., 2014
- Van der Waals force - Hydrogen bonding
- Chemical bonding strength between graphene nanosheets Detachment of graphene nanosheet & chemical resistance
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Summary & Conclusion 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
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- Date : 2007.11.16∼17 - Attendee : 91 peoples (8 countries) - Place : GIST (Korea) - 30 presentations
- 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
- Date : 2012.10.28∼31 - Attendee : 160 peoples (15 countries) - Place : Jeju island (Korea) - 120 presentations
International Desalination Workshop (IDW)
Global Networking
The 6th IDW2013: Nov. 28-29, 2013,
Melbourne, Australia
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The 7th IDW2014 (Nov. 5-8, Lotte City Hotel) will be held in Jeju Island,
South Korea. (by GDRC + EDS)
Join and make global networking in desalination field!
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Technology – Need harmony by height
“Thank you”