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Science and Technology for
    Sustainable Water Supply

                   Menachem Elimelech
            Department of Chemical Engineering
            Environmental Engineering Program
                     Yale U i
                     Y l University
                                 it

Seminar, University of Oklahoma, February 20,
2009
The “Top 10” Global Challenges
for the New Millennium
1.
1     Energy
2. Water
3.    Food
4.    Environment
5.    Poverty
6.    Terrorism and W
      T     i     d War
7.    Disease
8.
8     Education           Richard E Smalley Nobel
                                  E. Smalley,
9.    Democracy           Laureate, Chemistry, 1996,
10.   Population          MRS Bulletin, June 2005
International Water Management Institute
Regional and Temporal Water
Scarcity
S    it




 National Oceanic and Atmospheric Administration
How Do We Increase the Amount
of Water Available to People?
 Water conservation repair of infrastructure
       conservation,          infrastructure,
 and improved catchment and distribution
 systems ― improve use not increasing
                     use,
 supply!
 Increase water supplies t gain new waters
 I           t      li to i           t
 can only be achieved by:
   Reuse of wastewater
   R       f    t     t
   Desalination of brackish and sea waters
Many Opportunities
We are far from the thermodynamic limits for
separating unwanted species f
      ti          t d    i from water
                                    t
Traditional methods are chemically and
                                     y
energetically intensive, relatively expensive,
and not suitable for most of the world
New systems based on nanotechnology can
dramatically alter the energy/water nexus
           y               gy
Dr. Menachem Elimelech - Water Technologies to Solve Increasing Global Water Scarcity
Wastewater Reuse
W t    t R
Reclaimed Wastewater in
Singapore (NEWater)
                      Source of water
                      supply f
                           l for
                      commercial and
                      industrial sectors
                      (10% of water
                      demand)

                      4 NEWater p a ts
                             ate plants
                      supplying 50 mgd
                      of NEWater.

                      Will meet 15% of
 5 miles
                      water demand by
                      2011
Reuse of Wastewater in Orange
 County,
 County California
  www.gwrsystem.com               Groundwater Replenishment
                                      System (70 MG/day))
Prado
Dam




                      Santa Ana River Facilities
GWR System for Advanced Water
  Purification (Orange County)
            Microfiltration   Reverse   Ultraviolet
                (MF)          Osmosis   Light with
                               (RO)        H2O2
  OCSD
Secondary
   WW                                                 Recharge
 Effluent                                              Basins
Namibia,
Namibia Africa
Natural Beauty … but not Enough
Water
Windhoek’s Solution: Wastewater
  Reclamation for Direct Potable Use

Goreangab Reclamation Plant (Windhoek)
                                         “Water should not be
                                          Water
                                         judged by its history,
                                         but by its quality.”
                                              y     q     y
                                         Dr. Lucas Van Vuuren
                                         National Institute of Water
                                         Research, S th Af i
                                         R       h South Africa


 The only wastewater reclamation plant
         y
 in the world for direct potable use
The Treatment Scheme: A
Multiple Barrier Approach
Most Important: Public Acceptance
and T
  d Trust i the Q li of W
          in h Quality f Water
 Breaking down th psychological b i (th
 B ki d         the       h l i l barrier (the
 “yuck factor”) is not trivial
 – Ri
   Rigorous monitoring of water quality after every
                it i    f   t      lit ft
   process step
 – Final product water is thoroughly analyzed (data
   made available to public)
 The citizens of Windhoek have a genuine
 pride in the reality that their city leads the
 world in direct water reclamation
Wastewater Reuse: Membrane
   Bioreactor (MBR)-RO System




Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
Fouling Resistant UF Membranes:
   Comb (PAN-g-PEO) Additives
  amphiphilic copolymer added
     hi hili       l       dd d                             segregate & self-organize
                                                                   t      lf      i
       to casting solution                                   at membrane surfaces

                                                                                          PEO brush
                                                                                           layer on
                                                                                         surface and
                                                                                         inside pores

     Casting            Doctor
     Solution           Blade                                 Heat
                                                           Treatment
                                                                                         Fouling
     Casting Solution
                                       Coagulation
                        Doctor Blade
                                                            Heat Treatment
                                            Bath
                                        Coagulation Bath         Bath


                                                                                        Resistance


Asatekin, Kang, Elimelech, Mayes, Journal of Membrane Science, 298 (2007) 136-146.
Fouling Reversibility (with
    Organic Matter)
    O             )



                                                                     White: Pure water
                                                                     Whit P        t

                                                                    Gray: recovered flux
                                                                    after fouling/cleaning
                                                                    (following “physical”
                                                                    cleaning (rinsing)
                                                                    with no chemicals)



Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
AFM as a Tool to Optimize
        Copolymer for Fouling Resistance
             4
             2
      N/m)




             0
F/R (mN




             -2
             -4                                   PAN (P0-0)
                                                  P50-5
             -6                                   P50-10
                                                  P50 20
                                                  P50-20
             -8
Kang, Asatekin, Mayes, Elimelech, Journal of Membrane Science, 296 (2007) 42-50.
Force Distribution Provides the
Necessary Information
                 60
                            PAN (P0-0)                                     60         P50-5
                 45
            %)



                                                                           45
  requency (%




                                                                      %)
                                                             equency (%
                 30                                                        30

                 15                                                        15




                                                           Fre
 Fr




                  0                                                         0
                      -12 -10 -8   -6   -4   -2   0                         -12 -10 -8 -6 -4 -2 0   2   4
                            F/R (mN/m)                                              F/R (mN/m)


                 60
                            P50-10                                         60
                                                                                   P50-20
                 45                                                        45

                                                                     %)
            %)




                                                          Frequency (%
  requency (%




                 30                                                        30

                 15                                                        15
 Fr




                 0                                                         0
                       -1    0      1        2        3                    0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
                            F/R (mN/m)                                              F/R (mN/m)
Wastewater Reuse: Membrane
   Bioreactor (MBR)-RO System




Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
One Step NF MBR System?
         NF-MBR




        NF
Antifouling NF Membranes for
    MBR (PVDF g POEM)
          (PVDF-g-POEM)
      Filtration of activated sludge from MBR
       – PVDF-g-POEM NF: no flux loss over 16 h filtration
       – PVDF base: 55% irreversible flux loss after 4 h

                           1.4
                           1.2
            malized flux




                           1.0
                           0.8
                                         PVDF-g-POEM (●,●)
                           0.6
         Norm




                                           PVDF base (• •)
                                                     (•,•)
                           0.4
                           0.2
                           0.0
                                 0                       12
                                     Time (hours)
Asatekin, Menniti, Kang, Elimelech, Morgenroth, Mayes: J. Membr. Sci. 285 (2006) 81-89
MBR and the Sanitation Crisis in
D
Developing C
    l i Countries
               ti
1.1 billion people ⎯ or one
sixth of the world’s population
⎯ lack access to safe water
2.4 billion are without
adequate sanitation
Between 2 to 4 million deaths
a year are attributed to unsafe
water,
water mostly due to water
                      water-
borne preventable diarrheal
diseases
MBR as a Decentralized Sewage
Treatment Option
T t     t O ti




Centralized sewage treatment (wastewater treatment
plants) is not realistic (long-term goal)
MBR may be ideal for localized, decentralized sewage
treatment in the developing world
Advantages: small footprint, flexible design, and
automated operation
Desalination:
Reverse Osmosis
Population Density Near Coasts
Dr. Menachem Elimelech - Water Technologies to Solve Increasing Global Water Scarcity
Dr. Menachem Elimelech - Water Technologies to Solve Increasing Global Water Scarcity
Dr. Menachem Elimelech - Water Technologies to Solve Increasing Global Water Scarcity
Seawater Desalination
Augmenting and diversifying water supply
Reverse osmosis and thermal desalination
(MSF and MED) are the current desalination
technologies
Energy intensive (cost and environmental
impact)
Reverse osmosis is currently the leading
technology
Reverse Osmosis
Major improvements in the past 10 years
Further improvements are likely to be
incremental
Recovery limited to ~ 50%:
  Brine discharge (
  B i di h        (environmental concerns)
                      i      t l         )
  Increased cost of pre-treatment
Use prime (electric) energy (~ 2.5 kWh per
cubic meter of product water)
Minimum Energy of Desalination
                           Minimum energy needed to desalt water is
                           independent of the technology or mechanism of
                           desalination                           V                2
                                                                         1
                           3.5
                           35                                      W=             ∫Π        dV
Minimum Energy (kW-h/m )




                                                                      V1 − V2
3




                                                                                       os
                                                    O
                           3.0                 100 C                              V1
                                                  O
                                                25 C
                           2.5
                           25
               (




                           2.0
                                                                   Minimum theoretical energy
                                                                   for desalination:
                           1.5
                           15
                                                                      0% recovery: 0.7 kWh/m3
                           1.0
                                                                      50% recovery: 1 kWh/m3
                           0.5
                           05
M




                                 0   20   40   60       80   100
                                     Percent Recovery
Nanotechnology May Result in
Breakthrough Technologies
“These nanotubes are so beautiful
that they must be useful for
something. . .”, Richard Smalley
(1943-2005).
Aligned Nanotubes as High Flux
Membranes for Desalination?




                 Hinds et al, “Aligned multi-walled carbon nanotube
                 membranes”, Science, 303, 2004.
Research on Nanotube Based
Membranes




                  Mauter and Elimelech,
                  Environ. Sci. Technol., 42
                  (16), 5843-5859, 2008.
Next Generation Nanotube
Membranes
M b



                                      Mauter and Elimelech,
                                                  Elimelech
                                      Environ. Sci. Technol., 42
                                      (16), 5843-5859, 2008.



 Single-walled carbon nanotubes (SWNTs) with a pore
 size of ~ 0.5 nm are critical for salt rejection
 Higher
 Hi h nanotube d
              t b density and purity
                        it     d     it
 Large scale production?
Bio-inspired High Flux
Membranes for Desalination
Natural aquaporin proteins extracted from living
organisms can be incorporated into a lipid bilayer
membrane or a synthetic polymer matrix
BUT …. Energy is Needed Even for
   Membranes with Infinite Permeability

                                                     Minimum theoretical
                                                     energy for desalination at
                                                         gy
                                                     50% recovery: 1 kWh/m3
                                                     Practical limitations: No
                                                     less than 1.5 kWh/m3
                                                     Achievable goal:
                                                                g
                                                     1.5 − 2 kWh/m3



Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
Desalination:
Forward Osmosis
The Ammonia-Carbon Dioxide Forward
Osmosis Desalination Process
                                    Nature, 452, (2008) 260


                                                               Energy
                                                               Input




McCutcheon, McGinnis, and Elimelech, Desalination, 174 (2005) 1-11.
NH3/CO2 Draw Solution
         NH3(g)     CO2(g)
NH3(g)                       CO2(g)



             NH4HCO3(aq)
            (NH4)2CO3(aq)
           NH4COONH2(aq)


             HEAT
High Water Recovery with FO
                            RO           FO
          450
          400                                      Seawater π
          350
          300
          250
π (atm)   200
          150
          100
           50
            0
                0 10 20 30 40 50 60 70 80 90 100
                        Recovery (%)
                        R
Energy Use by Desalination
Technologies (Equivalent Work)
               6
                                                    MSF
                                                    MED-TVC
               5                                    MED-LT
                                                    RO
                                                    FO-LT
               4
      3
       kWh/m




               3

               2

               1
                                                              Contribution from
                                                              Electrical Power
               0

  McGinnis and Elimelech, Desalination, 207 (2007) 370-382.
Waste Heat   Geothermal Power
Concluding Remarks
              g
We are far from the thermodynamic limits
                           y
for separating unwanted species from water
Nanotechnology and new materials can
significantly advance water purification
technologies
Advancing the science of water purification
           g                    p
can aid in the development of robust, cost-
effective technologies appropriate for
                   g     pp p
different regions of the world
Acknowledgments

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Dr. Menachem Elimelech - Water Technologies to Solve Increasing Global Water Scarcity

  • 1. Science and Technology for Sustainable Water Supply Menachem Elimelech Department of Chemical Engineering Environmental Engineering Program Yale U i Y l University it Seminar, University of Oklahoma, February 20, 2009
  • 2. The “Top 10” Global Challenges for the New Millennium 1. 1 Energy 2. Water 3. Food 4. Environment 5. Poverty 6. Terrorism and W T i d War 7. Disease 8. 8 Education Richard E Smalley Nobel E. Smalley, 9. Democracy Laureate, Chemistry, 1996, 10. Population MRS Bulletin, June 2005
  • 4. Regional and Temporal Water Scarcity S it National Oceanic and Atmospheric Administration
  • 5. How Do We Increase the Amount of Water Available to People? Water conservation repair of infrastructure conservation, infrastructure, and improved catchment and distribution systems ― improve use not increasing use, supply! Increase water supplies t gain new waters I t li to i t can only be achieved by: Reuse of wastewater R f t t Desalination of brackish and sea waters
  • 6. Many Opportunities We are far from the thermodynamic limits for separating unwanted species f ti t d i from water t Traditional methods are chemically and y energetically intensive, relatively expensive, and not suitable for most of the world New systems based on nanotechnology can dramatically alter the energy/water nexus y gy
  • 9. Reclaimed Wastewater in Singapore (NEWater) Source of water supply f l for commercial and industrial sectors (10% of water demand) 4 NEWater p a ts ate plants supplying 50 mgd of NEWater. Will meet 15% of 5 miles water demand by 2011
  • 10. Reuse of Wastewater in Orange County, County California www.gwrsystem.com Groundwater Replenishment System (70 MG/day)) Prado Dam Santa Ana River Facilities
  • 11. GWR System for Advanced Water Purification (Orange County) Microfiltration Reverse Ultraviolet (MF) Osmosis Light with (RO) H2O2 OCSD Secondary WW Recharge Effluent Basins
  • 13. Natural Beauty … but not Enough Water
  • 14. Windhoek’s Solution: Wastewater Reclamation for Direct Potable Use Goreangab Reclamation Plant (Windhoek) “Water should not be Water judged by its history, but by its quality.” y q y Dr. Lucas Van Vuuren National Institute of Water Research, S th Af i R h South Africa The only wastewater reclamation plant y in the world for direct potable use
  • 15. The Treatment Scheme: A Multiple Barrier Approach
  • 16. Most Important: Public Acceptance and T d Trust i the Q li of W in h Quality f Water Breaking down th psychological b i (th B ki d the h l i l barrier (the “yuck factor”) is not trivial – Ri Rigorous monitoring of water quality after every it i f t lit ft process step – Final product water is thoroughly analyzed (data made available to public) The citizens of Windhoek have a genuine pride in the reality that their city leads the world in direct water reclamation
  • 17. Wastewater Reuse: Membrane Bioreactor (MBR)-RO System Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
  • 18. Fouling Resistant UF Membranes: Comb (PAN-g-PEO) Additives amphiphilic copolymer added hi hili l dd d segregate & self-organize t lf i to casting solution at membrane surfaces PEO brush layer on surface and inside pores Casting Doctor Solution Blade Heat Treatment Fouling Casting Solution Coagulation Doctor Blade Heat Treatment Bath Coagulation Bath Bath Resistance Asatekin, Kang, Elimelech, Mayes, Journal of Membrane Science, 298 (2007) 136-146.
  • 19. Fouling Reversibility (with Organic Matter) O ) White: Pure water Whit P t Gray: recovered flux after fouling/cleaning (following “physical” cleaning (rinsing) with no chemicals) Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
  • 20. AFM as a Tool to Optimize Copolymer for Fouling Resistance 4 2 N/m) 0 F/R (mN -2 -4 PAN (P0-0) P50-5 -6 P50-10 P50 20 P50-20 -8 Kang, Asatekin, Mayes, Elimelech, Journal of Membrane Science, 296 (2007) 42-50.
  • 21. Force Distribution Provides the Necessary Information 60 PAN (P0-0) 60 P50-5 45 %) 45 requency (% %) equency (% 30 30 15 15 Fre Fr 0 0 -12 -10 -8 -6 -4 -2 0 -12 -10 -8 -6 -4 -2 0 2 4 F/R (mN/m) F/R (mN/m) 60 P50-10 60 P50-20 45 45 %) %) Frequency (% requency (% 30 30 15 15 Fr 0 0 -1 0 1 2 3 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 F/R (mN/m) F/R (mN/m)
  • 22. Wastewater Reuse: Membrane Bioreactor (MBR)-RO System Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
  • 23. One Step NF MBR System? NF-MBR NF
  • 24. Antifouling NF Membranes for MBR (PVDF g POEM) (PVDF-g-POEM) Filtration of activated sludge from MBR – PVDF-g-POEM NF: no flux loss over 16 h filtration – PVDF base: 55% irreversible flux loss after 4 h 1.4 1.2 malized flux 1.0 0.8 PVDF-g-POEM (●,●) 0.6 Norm PVDF base (• •) (•,•) 0.4 0.2 0.0 0 12 Time (hours) Asatekin, Menniti, Kang, Elimelech, Morgenroth, Mayes: J. Membr. Sci. 285 (2006) 81-89
  • 25. MBR and the Sanitation Crisis in D Developing C l i Countries ti 1.1 billion people ⎯ or one sixth of the world’s population ⎯ lack access to safe water 2.4 billion are without adequate sanitation Between 2 to 4 million deaths a year are attributed to unsafe water, water mostly due to water water- borne preventable diarrheal diseases
  • 26. MBR as a Decentralized Sewage Treatment Option T t t O ti Centralized sewage treatment (wastewater treatment plants) is not realistic (long-term goal) MBR may be ideal for localized, decentralized sewage treatment in the developing world Advantages: small footprint, flexible design, and automated operation
  • 32. Seawater Desalination Augmenting and diversifying water supply Reverse osmosis and thermal desalination (MSF and MED) are the current desalination technologies Energy intensive (cost and environmental impact) Reverse osmosis is currently the leading technology
  • 33. Reverse Osmosis Major improvements in the past 10 years Further improvements are likely to be incremental Recovery limited to ~ 50%: Brine discharge ( B i di h (environmental concerns) i t l ) Increased cost of pre-treatment Use prime (electric) energy (~ 2.5 kWh per cubic meter of product water)
  • 34. Minimum Energy of Desalination Minimum energy needed to desalt water is independent of the technology or mechanism of desalination V 2 1 3.5 35 W= ∫Π dV Minimum Energy (kW-h/m ) V1 − V2 3 os O 3.0 100 C V1 O 25 C 2.5 25 ( 2.0 Minimum theoretical energy for desalination: 1.5 15 0% recovery: 0.7 kWh/m3 1.0 50% recovery: 1 kWh/m3 0.5 05 M 0 20 40 60 80 100 Percent Recovery
  • 35. Nanotechnology May Result in Breakthrough Technologies “These nanotubes are so beautiful that they must be useful for something. . .”, Richard Smalley (1943-2005).
  • 36. Aligned Nanotubes as High Flux Membranes for Desalination? Hinds et al, “Aligned multi-walled carbon nanotube membranes”, Science, 303, 2004.
  • 37. Research on Nanotube Based Membranes Mauter and Elimelech, Environ. Sci. Technol., 42 (16), 5843-5859, 2008.
  • 38. Next Generation Nanotube Membranes M b Mauter and Elimelech, Elimelech Environ. Sci. Technol., 42 (16), 5843-5859, 2008. Single-walled carbon nanotubes (SWNTs) with a pore size of ~ 0.5 nm are critical for salt rejection Higher Hi h nanotube d t b density and purity it d it Large scale production?
  • 39. Bio-inspired High Flux Membranes for Desalination Natural aquaporin proteins extracted from living organisms can be incorporated into a lipid bilayer membrane or a synthetic polymer matrix
  • 40. BUT …. Energy is Needed Even for Membranes with Infinite Permeability Minimum theoretical energy for desalination at gy 50% recovery: 1 kWh/m3 Practical limitations: No less than 1.5 kWh/m3 Achievable goal: g 1.5 − 2 kWh/m3 Shannon, Bohn, Elimelech, Georgiadis, and Mayes, Nature 452 (2008) 301-310.
  • 42. The Ammonia-Carbon Dioxide Forward Osmosis Desalination Process Nature, 452, (2008) 260 Energy Input McCutcheon, McGinnis, and Elimelech, Desalination, 174 (2005) 1-11.
  • 43. NH3/CO2 Draw Solution NH3(g) CO2(g) NH3(g) CO2(g) NH4HCO3(aq) (NH4)2CO3(aq) NH4COONH2(aq) HEAT
  • 44. High Water Recovery with FO RO FO 450 400 Seawater π 350 300 250 π (atm) 200 150 100 50 0 0 10 20 30 40 50 60 70 80 90 100 Recovery (%) R
  • 45. Energy Use by Desalination Technologies (Equivalent Work) 6 MSF MED-TVC 5 MED-LT RO FO-LT 4 3 kWh/m 3 2 1 Contribution from Electrical Power 0 McGinnis and Elimelech, Desalination, 207 (2007) 370-382.
  • 46. Waste Heat Geothermal Power
  • 47. Concluding Remarks g We are far from the thermodynamic limits y for separating unwanted species from water Nanotechnology and new materials can significantly advance water purification technologies Advancing the science of water purification g p can aid in the development of robust, cost- effective technologies appropriate for g pp p different regions of the world