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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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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4 5

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

http://www.scopus.com/

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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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2

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



International Desalination Workshop (IDW)

Global Networking

The 6th IDW2013: Nov. 28-29, 2013,

Melbourne, Australia

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2

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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”

desalination process advancement by hybrid and new ...global desalination research center in s. kim...

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