Desalination Process Advancement by Hybrid and New Material beyond the seahero R&D Project

Transcription

1 ICDEMOS, April 2014, Sultan Qaboos University, Muscat, Sultanate of Oman 1/40 Desalination Process Advancement by Hybrid and New Material beyond the seahero R&D Project In S. Kim Global Desalination (GDRC)

2 Global Warming & Climatic Changes 2/40 Excessive dependence of fossil fuel Global warming & Climatic calamity Source: San Diego state university Source: NASA Goddard Institute for Space Studies Between 1950 and 2000,World fossil fuel consumption increased fourfold. The global temperature is forecast to rise 4 by the end of 21 st century.

3 Urbanization & Industrialization 3/40 Continuous increase of water consumption

4 Solutions for Water Shortage 4/40 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 Wastewater

5 Seawater Desalination 5/40 Producing fresh water from seawater Key technology: MSF(Thermal) and Reverse Osmosis(membrane) MSF (Multistage Flash) RO (Reverse Osmosis) Global Desalination

6 Issues for Fresh Water from New Sources 6/40 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

7 Needs for Membrane Technologies 7/40 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)

8 SeaHERO R&D program 8/40 SeaHERO: Seawater Engineering Architecture High Efficiency Reverse Osmosis Value Creator (VC) - 10 Global Top 5 Tech. New growth engine Green growth Head center: GIST Exe. Director: Prof. In Kim Period: ~ Budget: 180 billion KRW Supported by Ministry of Land, Infrastructure and Transport (MOLIT) Development of World-leading Seawater desalination technology

9 Technical Objectives : 3L 9/40 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 Energy consumption, < 4kWh/m 3 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

10 SeaHERO R&D program 10/40 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 - 4 Core fields -13 main + 27 commissioned projects -250 research staff -25 Univ. + 6 National Institutes + 28 Industries 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 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 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

11 Research Outputs of SeaHERO 11/40

12 History & Perspective of Desal. Tech. 12/40 Beginning of desalination Application of (Kuwait) desalination process Present Market leading tech. : Thermal type Market leading tech. : Reverse osmosis Energy 10 kwh/ton RO Development Energy 4 kwh/ton 1 st technical innovation 1 st Energy reduction periods MSF RO 2 nd technical innovation 2 nd Energy reduction periods RO???? 2 nd Energy reduction periods Global Desalination SeaHERO 1. Innovative enhancement in efficiency of RO process or 2. Development of new desalination technology

13 After SeaHERO Projects.. 13/40 Energy-intensive process Environmental load (Brine treatments, CO2 emission) We still need further development for energy and environmental issues of desalination.

14 Steps of Desalination Technology 14/ SeaHERO Project Development of hybrid system + Material improvement

15 Two ways: Hybrid Desalination 1. Innovative unit processes 2. Hybrid with renewable energy (with FO, PRO, MD,..) (Solar, wind, geothermal,..) 15/40 Global Desalination

16 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 MIGD SWRO (source: O.A. Hamed, Desalination 186, 2005; Ho-Sun Yu, Korean Plant Society, 2007) Global Desalination

17 Future Hybrid Desalination Plant 17/40 Key issues: Energy Reduction & Minimum Environmental load Energy Energy-efficient process (FO, MD) Osmotic energy production (PRO, RED) Use of various energy resources Hybrid Desalination Plant Reduction & Reuse of brine (MD, PRO) Low usage of chemical agents (Low fouling process FO) Environmental Load Global Desalination

18 SWRO + Membrane Distillation (MD) 18/40 Heater Product seawater steam fresh water < 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)

19 Forward Osmosis (FO) & Pressure Retarded Osmosis (PRO): Water & Energy production: FO & PRO 19/40 Energy consumption of FO process 1 kwh/m 3 (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)

20 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

21 SWRO + Forward Osmosis (FO) Predictions on Performance 21/40 FO-RO hybrid desalination system may have (at same recovery) % less Specific Energy Consumption (SEC) than 2-Pass RO - However, greater total membrane area than 2-Pass RO (Source : Shaffer et al., JMS,2012)

22 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 Draw 10 MJ Brine + River water (5 mol/l) (0.01mol/l) 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)

23 SWRO + PRO 23/40 PRO research in Mega-ton Project (Japan) RO Demo plant (Kitakyushu, Japan) : 1,500 m 3 /d sewage & 500 m 3 /d seawater 140,000 m 3 /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

24 SWRO + Reverse Electrodialysis (RED) 24/40 1 Sea water (Brine) 4 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 (source: W. Li et al., Applied Energy 104, 2013)

25 Next Hybrid Desalination Projects 25/40 seahero-mvp Concentrates & Valuables Management Enhanced seahero-fwer Product Water&Energy Enhanced MD/Valuables/PRO Hybrid Process Global Desalination FO/Water-Energy/RO hybrid Process

26 New Materials for Membrane 26/40 New Materials for Membrane Nanomaterials Aquaporin Inorganic materials Carbon materials Etc. - Metal oxide (TiO2) - Silver nanoparticle - Biopolymer - Cellular membrane protein - Zeolite - Ceramic membrane - Graphene - CNT (SWNT, MWNT) 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, ) Global Desalination

27 Research Trends of Nanoparticles 27/40 Types of nanomaterials in antifouling membrane Total No. of Paper = 134 (from 2001 to present) Search engine : TITLE-ABS-KEY(membrane AND (antifouling OR fouling)) AND PUBYEAR AFT 2000

28 New Membrane Materials 28/40 What kind of materials can have 1. Commercial feasibility, 2. High performance? Global Desalination Source : Mary et al., EES, 2011

29 Graphene for Membrane 29/40 Graphene Table 1. Graphene characteristics A single layer of carbon packed in a hexagonal (honeycomb) lattice A carbon-carbon distance of nm Characteristics Structure Young s modulus Tensile Strength Thermal stability Density Graphene 2-dimension (thickness:0.34 nm) 1 Tpa 130 Gpa 2,800 under Ar 2.2 g/cm3 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!

30 Solutes New material : Graphene & Ceramic Seawater & Wastewater H 2 O 30/40 Graphene nanosheet (Active layer) - Ultrathin - High selectivity - Superior chemical & physical property Combination Ceramic membrane (Support layer) - High strength - High uniformity - Outstanding chemical resistance Ceramic-based graphene membrane (CbGM) Pure water production! High performance, Chemical inertness, High structural strength, Long lifetime

31 Issues in graphene membrane 31/40 1 Graphene synthesis (Kind of graphene) 3 Control of pores & Rejection mechanism 2 Combining and interaction between graphene and ceramic Graphene nano-sheet Ceramic substrate 4 Mass transport & Mechanism Global Desalination 5 Characteristics & Performance evaluation Figure source: K. S. Novoselov et al., Nature review, 2012

32 Graphene Membrane Fabrication 32/40 1. Starting materials 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

33 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? Transmission of water molecule through defects on graphene sheet? Water Ions

34 Comparison of Fabrication Methods Drop-casting (DC) method 34/40 Raw ceramic membrane 1 time 4 times 8 times 16 times Filtration-assisted assembly (FAA) method rgo rgo rgo mg/m mg/m mg/m 2 Two kinds of membrane (prepared by DC and FAA method) Uniformity difference (FAA > DC methods)

35 Surface Morphology SEM image 35/40 Plane view Cross-sectional view Raw ceramic membrane Plane view rgo mg/m 2 Cross-sectional view Thickness: ~2 μm rgo mg/m 2 rgo mg/m 2 Thickness: ~6 μm Thickness: ~12 μm

36 Comparison of surface morphology-sem 36/40 Old results Plane view Cross-sectional view rgo mg/m 2 Plane view New results GO mg/m 2 Cross-sectional view Thickness: ~1.7 μm Thickness: ~ 28 nm rgo mg/m 2 GO mg/m 2 Thickness: ~ 3.1 μm Thickness: ~ 65 nm Surface fully covered with 130 time less GO than rgo mg/m 2 With highly superior graphene interlocking & Uniformity Global Desalination

37 Application : Fouling & Cleaning 37/40 Antimicrobial activity of graphene oxide Connection between graphene layers - Van der Waals force - Hydrogen bonding Juanni Chen et al., 2014 Hyo Won Kim et al., Fouling characteristics & resistance - Antimicrobial characteristics of graphene nanosheets Biofouling reduction on graphene membrane? Cleaning 2. Cleaning efficiency & resistance - Chemical bonding strength between graphene nanosheets Detachment of graphene nanosheet & chemical resistance CbGM Global Desalination

38 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 (TiO 2, Silver, ) - Biomimetic (Aquaporin) - Inorganic materials (Zeolite, ceramic, ) - Carbon materials (Graphene, CNT, ) Carbon-based materials are hot issue in recent year

39 International Desalination Workshop (IDW) Global Networking - Date : Attendee : 91 peoples (8 countries) - Place : GIST (Korea) - 30 presentations The 7 th IDW2014 (Nov. 5-8, Lotte City - Date : Attendee : 116 peoples (12 countries) - Place : GIST (Korea) - 58 presentations Hotel) will be held in Jeju Island, South Korea. - Date : Attendee : 180 peoples (15 countries) - Place : Jeju island (Korea) presentations (by GDRC + EDS) - Date : Attendee : 250 peoples (15 countries) - Place : Jeju island (Korea) - 82 presentations Join and make global networking in desalination field! - Date : Attendee : 160 peoples (15 countries) - Place : Jeju island (Korea) presentations 39/ The 6th IDW2013: Nov , 2013, Melbourne, Australia

40 Technology Need harmony by height 40/40 Thank you