[PPT] - New Advancement of Seawater Desalination Reverse Osmosis Membranes PowerPoint Presentation

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New Advancement of Seawater Desalination Reverse Osmosis Membranes (SWRO)

Dr. Masaru Kurihara

Toray I ndustries, I nc.

11 March 2008

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UN Target: “Halve the proportion of people without access to drinking water or sanitation facilities“ - Not yet achieved. The water issue is a global challenge required to be resolved together with the food and energy issues. The water issue is a global challenge that should be dealt with on the same basis as the carbon dioxide issue. UN Target: “Halve the proportion of people without access to drinking water or sanitation facilities“ - Not yet achieved. The water issue is a global challenge required to be resolved together with the food and energy issues. The water issue is a global challenge that should be dealt with on the same basis as the carbon dioxide issue.

T h e W a t e r I s s u e i s a G l

b

a l C h a l l e n g e 5 . 8 1 3 . 8 3 9 . 7 5 2 . 4

2 4 6 1 9 1 9 5 2 2 2 5

[100 billion liters]

Source: UNESCO

(Estimate)

I n c r e a s i n g G l

b

a l W a t e r C

n

s u m p t i

n

Reference: Council for Science and Technology Policy, 67th Meeting (held on May 18, 2007) Material 3: Recent Trends of Science and Technology “Japanese Technologies Contributing to the World – An Example of Japanese Water Treatment Technologies －”1

R e l a t i

n

s h i p b e t w e e n W a t e r , E n e r g y a n d F

d

Water Energy Food

People in the World

Agriculture Desalination Electric Power Generation Food Production Bio-fuel Virtual Water

No data

FAO: Food and Agriculture Organization

World Water Resources and Water Issues

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Increase of World Population and Development of Water Treatment Technologies

Difficult to secure volume and quality of water only by natural purification due to the increase of rapid increase of population Membrane treatment technology, which enable control of high precise water quality and high speed treatment, is essential in 21 century Membrane treatment technology, which enable control of high precise water quality and high speed treatment, is essential in 21 century

World population 2000 1800 1900 1700 Population (Billion) Natural purification ⑤Membrane treatment ④Evaporation 2100 ①Slow filtration ③Rapid filtration ②Microorganism treatment Industrial Revolution

【 Toray Estimate】

10.0 8.0 6.0 4.0 2.0

Reference: Tambo, N. et. ; "Infrastructure Development under Decreasing Population" - A Design from Expansion to Shrink -. Japan Society of Civil Engineers. 2002, p.10. (Japanese)

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1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 M E D M S F N F R O 2,000,000 4,000,000 6,000,000 8,000,000 10,000,000 12,000,000 14,000,000 16,000,000 18,000,000 MED MSF NF RO

Authority: IDA Inventory no19

Trend of Cumulative Capacities of Water Production Facilities by Technology

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Types of Membranes and Toray’s Membrane Products

Toray’s membrane products Types Separation materials Size HF membrane

(PVDF Hollow Fiber)

NF (Nanofiltration)

RO (Reverse Osmosis）

UF (Ultrafiltration） MF (Microfiltration) 0.001 ㎛ 0.01 ㎛ 0.1 ㎛ 1 ㎛ 10 ㎛ RO membrane High molecular weight polymer Ion, Low molecule weight organics Colloid Clay

Trihalomethane Monovalent Ions Agricultural & Organic Material

Virus Cryptosporidium Coliform

Multivalent Ions

Bacteria NF membrane MF membrane

(PVDF Hollow Fiber) PVDF Immersed membrane for MBR Ultrapure Water, Seawater Desalination, Advanced Water Treatment Softening, Removal of Toxic substance Municipal Drinking Water, Reuse of Wastewater, Pretreatment for RO Process Sewage Water Treatment

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Ultra low Low High Ultra high 0.3 0.5 1.0 2.0 5.5 10.0 Operating Pressure [MPa] Recovery = 40% Recovery = 60％ High TOC removal High quality Cost reduction Notes High TDS removal High boron removal Super low High TDS removal High boron removal Cost reduction Low-fouling Ultra pure water Lower pressure Waste water reuse Low-fouling Cost reduction 2nd stg. 1st stg.

SWRO BW RO

Technical Trends of RO Membranes

High Recovery Energy- Saving

Energy saving membrane with retaining conventional performance will be expected.

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10 5 10 15 ５．東レグループ水処理事業の現状と拡大戦略

Technical Trends on SWRO Membrane

SWRO = Salt rejection was the most important factor. 1) At the time of initial stage in SWRO

The boron regulation guideline value in drinking water (1998).
The report for toxicity of boron in drinking water (2003).
New boron regulation guideline will be discussed in the IDA congress (2007).

Energy (kWh/m3)

I. Energy saving
II. Changes in the required water quality

Two technical requirements for SWRO membrane

12.0 8.1 5.0 3.7 1.6

2) In current years WHO actions against the boron regulation (in addition to item 1))

Period

Requirement for further improvement · High flux membrane at low

perating pressure

· More effective energy recovery device

2.1

2.3

ADC 1970 1980 1990 2000 2006 2007

(Without boron regulation)

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WHO 0.3mg/l 0.5mg/L (guidline) 1993 19971998 2000 1990 2005 2001 1996 Okinawa Fukuoka 1.5mg/L Trinidad Israel Singapore Abu Dhabi 0.4mg/L 1.0mg/L 1.0mg/L Spain Not required 136

×1,000m3/d

272 136 227 40 50 42 Boron regulation Not required Not required World Japan

Boron regulation has been getting tougher especially after 2000.

0.5mg/L (Pub.Com.)

Recent trends of boron regulation and requirement.

2007

Changes in Boron Regulation

California 1.5mg/L 1.0 mg/L 0.5 mg/L 0.3 mg/L

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Seawater Zone I I : 2 to 4 stages SWRO with boron regulation (ex. : Ashkelon, Tuas , Shuaiba III ) Product water Seawater (A) SWRO membrane (High boron rejection) (B) SWRO (High boron rejection, High water productivity) (C) BWRO (High boron rejection, High productivity, Alkaline (pH10) tolerance Product water Alkaline dosing, High pH Membrane Manufacturers are competing with each

ther in these A - D types, respectively.

Zone I I I : Single stage SWRO without boron regulation (ex. : Point Lisa, Al-Jubail, Okinawa) (D) SWRO (High water productivity, Low energy type) Zone I : Single stage SWRO with boron regulation (ex. : Las Palmas III, Barcelona, Malta)

Flow Diagram of SWRO Desalination Plant with Boron Regulation & without Boron Regulation

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History and Prospect of Boron Rejection Performance

Toray has been investigating SWRO membranes with focusing on boron rejection.

Boron rejection performance (%) 80 90 95 99 Period

2000

2000-2003 2003-2007

Toray Others

“Early” 50 “Conventional” “Improved” 2008- “Renovative”

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2. Scientific Research on Boron Removal Mechanism

by RO Membrane 1) Positron Annihilation Lifetime Spectroscopy 2) Solid-state 13C NMR Spectroscopy 3) Molecular Dynamics Simulations

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Conventional RO membrane structural analyses

Membrane Surface

Separating functional layer

Cross-linked aromatic polyamide, 0.2µm Support layer Poly sulfone, 60µm Substrate Non-woven fabric substrate, 150µm

Imaginative chemical structure

Insoluble to any solvent How large is the pore?

Purpose

Structure of RO membrane Predicted pore size distributions by removable substances RO NF UF

Small Mol. Large Mol. Ion Organic Chemicals Bacteria Colloid Virus

roughly 5Å roughly 50Å

Purpose in this work:

1. To establish a certain pore size

analysis method

2. To acquire some basic

physicochemical information for MD simulations

Poor information

Predictions Substances O H N H N O H N H N H N O O CO2H O NH

10Å 100Å

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Boron removal performance of SWROs 88 90 92 94 96 98 100 0.0 0.2 0.4 0.6 0.8 1.0 Flux (m3/m2/day) Boron removal rate (%) S1 (90%) S2 (92%) S3 (94%) S4 (95%)

Candidate Membranes for Analyses

The SWRO membranes with different boron removal rate were prepared, even though SWRO membranes had same NaCl rejection and water flux.

Test condition: feed solution; TDS 35000 mg/l, temperature; 25 degree C., pH; 6.5,

perating pressure; 800 psig (5.5 MPa), flow rate; 3.5 L/min.

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ﾋﾞｰﾑ

22Na

e+ e+

基板薄膜

Separation Layer Support layers

Beam For measurement of separation layer alone, positron beam method is applied

Pore size

Small Large

Positron Annihilation Lifetime

Short Long

Atom Molecule Pore Positron Electron

e+ e- e+ e+ e- e- e- e-

Controllable positron energy

Beam method

22Na method

Pore size is estimated from Positron Annihilation Lifetime

Analysis of RO Membrane Pore Size by Positron Annihilation Lifetime Spectroscopy (PALS)

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18 0.000 0.005 0.010 0.015 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 Pore size (Å) Relative intensity 100 200 300 400 500 600 700 800 900 5.0 6.0 7.0 Pore size (Å) Boron permeability (x10 -9 m/s)

S1 S2 S3 S4

1. Any SWRO has 5.6-7.0 Å of pore.
2. Pore sizes in SWROs show clear correlation with those of

boron removal performance.

Pore size distribution2a)

Comparison of Pore Size between SWROs

Correlation between pore size2b) and boron permeability in SWROs

2) a) MELT: A. Shukla, L. Hoffmann, A. A. Manuel, M. Peter, Materials Science Forum, 255-257, 233-237 (1997). b) POSITRONFIT: P. Kirkegaard and M. Eldrup, Computer Physics Communications, 3, 240 (1972).

S1 S2 S3 S4

SLIDE 19

19 Dissolve polysulfone layer Peel off substrate

Remaining functional layer = Cross-linked aromatic polyamide

HNC=O Ar.C–NH2 Ar.C DD/MAS 13C NMR spectrum of Membrane S1 (90% boron removal) HOOC

Prospective chemical shift3)

1 1.2 Ratio (mol) Aromatic acid halide Aromatic amine Moiety Mol ratio of each moiety

1. All of peaks characteristic to

each moiety are observed.

2. A chemical structural model

unit of polyamide is estimated by the ratio of moiety.

172 HOOC 165 HNC=O 147 ArC-NH2 107-139 Aromatic C (except for ArC-NH2) δ (ppm) Type of carbon

Estimation of Chemical Structure by Solid-State 13C NMR

3) by ChemDraw Ultra 7.0.1 Original spectrum Resolved peaks

Estimating presumable chemical structure

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MD simulations were performed with initial structure (determined by 13C NMR).

Optimized structure (relaxation state) Delete H2O Insert probes 20Å H2O

Investigation of RO Membrane Pore via MD Simulations Analyses

Connolly surface calculation

Larger probes than pore size cannot be inserted. The probe diameter when the Connolly surface reached zero should be pore size. The calculated pore size was 6 - 8 Å.

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Comparison between Pore Size and Referential Substances

Pore size sphere Boric acid B(OH)3 Hydrated sodium ion (Na+-6H2O) 6Å 8Å

Hydrated state of boric acid and sodium ion were calculated

as referential substances for pore size.

Boric acid is hardly hydrated in neutral pH region.

Only a little difference in the size between pore and substances, including the difference between hydrated states, must dominate the removal performance.

4Å 1.9Å

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New High Boron Removal SWROs

1. From the viewpoint of water quality, a high boron removal type (for

Zone I , type A), TM800A, was commercialized. New High Boron Removal SWRO membranes were developed by special molecular design controlling the pore size of membrane in sub-nanometer level.

2. From the viewpoint of energy saving, a high productivity with high boron

removal type (for Zone I I , type B), TM800C and TM800E, and a high boron removal BWRO (for type C), TM700C, were also commercialized. Seawater Product water

Zone I , type A membrane

Seawater Product water Alkaline dosing, High pH

Zone I I , type B membrane type C BWRO membrane

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Israel 92,960 m 3/d Israel 92,960 m

3/d

84,000 m 3/d 84,000 m3/d

●
● ●
●
●
Singapore

136,000 m 3/d Singapore 136,000 m3/d Kuwait 320,000 m 3/d Kuwait 320,000 m 3/d Saudi 91,000 m 3/d* Saudi Arabia 91,000 m3/d* Trinidad 136,000 m 3/d Trinidad and Tobago 136,000 m3/d * Joint delivery with other companies 40,000 m 3/d* Okinawa 40,000 m3/d* Algeria 200,000 m 3/d Algeria 200,000 m3/d Australia 66,000 m 3/d Australia 66,000 m3/d Saudi 150,000 m 3/d Saudi Arabia 150,000 m3/d Seawater Desalination Seawater Desalination Brackish Water Desalination Brackish Water Desalination Waste Water Reuse Waste Water Reuse

as of January 2008

Korea

Cum ulative installation: about 1 1 ,7 5 0 ,0 0 0 m 3/ day ( as of seaw ater desalination: over 2 ,3 0 0 ,0 0 0 m 3/ day) Cum ulative installation: about 1 1 ,7 5 0 ,0 0 0 m 3/ day ( as of seaw ater desalination: over 2 ,3 0 0 ,0 0 0 m 3/ day)

Equivalent to water for daily use of about 50,000,000 people

Water Treatment Plants in the World using Toray RO Membrane “ROMEMBRA”

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10,000m3/d of water is equivalent to daily life water of 40,000 people

4. World Large Water Treatment Projects

as of January 2008 *1 Total output of all units *2 The year in which the plant was commissioned, ( ) shows a project *3 Toray's initial installation (Notes)

1989 Drinking & Pro c e ss Wa te r 36,000 Al Buka riya h Sa udi Ara b ia 16 1989 Drinking & Pro c e ss Wa te r 36,000 Al Ra ss Sa udi Ara b ia 16 *3 : 30,000 m 3/ d 1997 Se a wa te r De sa lina tio n 40,000 Okina wa Ja pa n 15 2006 Drinking & Pro c e ss Wa te r 45,000 Co llie r Unite d Sta te s 14 re pla c e me nt fo r thre e pla c e s 2007 Se a wa te r De sa lina tio n 53,500 Gha r L a psi, e tc . Ma lta 13 2001 Pro c e ss Wa te r 60,000 Suwo n K

re a

12 e xpa nsio n: 15,000m 3/ d (2006) 2002 Se a wa te r De sa lina tio n 65,000 Alic a nte Spa in 11 *3 : 23,100 m 3/ d 2001 Se a wa te r De sa lina tio n 69,300 Ma llo rc a Spa in 10 2001 Pro c e ss Wa te r 80,000 Da e sa n K

re a

9 1997 Pro c e ss Wa te r 84,000 Da e sa n/ HPC K

re a

8 *3 : 24,240 m 3/ d 2000 Se a wa te r De sa lina tio n 90,909 Al Jub a il-I I I Sa udi Ara b ia 7 2007 Se a wa te r De sa lina tio n 92,250 Pa lma c him I sra e l 6 2001 Pro c e ss Wa te r 100,000 F a jr I ra n 5 2005 Se a wa te r De sa lina tio n 136,000 T ua s Sing a po re 3 2002 Se a wa te r De sa lina tio n 136,000 Po int L isa s T rinid a d & T

b a g o

3 (2009) Se a wa te r De sa lina tio n 150,000 Shua ib a h Sa udi Ara b ia 2 (2008) Se a wa te r De sa lina tio n 200,000 Ha mma Alg e ria 1 Notes Oper ation Year *2 Pur pose Capac ity *1 m3/ d L

cation

Countr y No.

Large Scale Desalination Plants in the World with Toray “ROMEMBRA” Elements

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25 UF/MF membrane RO (reverse osmosis) membrane Sterilization

Industrial water Agricultural water Indirect drinking water Wastewater Secondary effluent (was discharged)

4. World Large Water Treatment Projects

*1 Total output of all units *2 The year in which the plant was commissioned, ( ) shows a project *3 ROMEMBRA(RO/NF), TORAYFIL(UF/MF), MEMBRAY(MBR) (Notes)

2006 Munic ipa l ME MBRAY 1,975

UK

15 2006 I nd ustria l T ORAYFI L 2,160

Philippine s

13 2006 I nd ustria l T ORAYFI L 2,160 Be ijin China 13 2006 Munic ipa l ME MBRAY 2,400

Ne the rla nd s

12 (2008) Munic ipa l ME MBRAY 2,400

Ba hra in

11 (2008) Munic ipa l ME MBRAY 2,500

Ca na d a

10 F

r T

e xtile I nd ustry (2008) I nd ustria l ME MBRAY 11,200

I

nd ia 9 (2008) Munic ipa l ME MBRAY 15,000

UAE

8 2004 Munic ipa l ROME MBRA 24,000 Se le ta r Sing a po re 6 2004 Wa ste wa te r Re use ROME MBRA 24,000 Se le ta r Sing a po re 6 F

r Pa pe r I

nd ustry 2005 I nd ustria l ROME MBRA 25,000 Do ng g ua n China 5 2006 Munic ipa l ROME MBRA 30,000 T ia njin China 3 2006 Wa ste wa te r Re use ROME MBRA 30,000 T ia njin China 3 (2008) Wa ste wa te r Re use ROME MBRA 66,000 L ug g a g e Po int Austra lia 2 2005 Munic ipa l ROME MBRA 320,000 Sula ib iya K uwa it 1 Notes Oper ation Year *2 Pur pose Membr ane Br and Name *3 Capac ity *1 m3/ d L

cation

Countr y No

Advanced Wastewater Treatment & Reclamation Plant in the World with Toray "ROMEMBRA", "TORAYFIL" and "MEMBRAY"

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1. With the Pore size analyses studies,

Conclusion

a. The nondestructive method of measuring pore size

in RO membrane was established, and reliable values, 5.6-7.0Å, almost agreeing with predictions, were respectively acquired.

b. The clear correlation between pore size and boron

removal performance of SWRO membrane was revealed.

2. Back to basic, the scientific knowledge on RO

membrane was accumulated. Based on these new knowledge, the new high boron removal membranes were obtained.

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SWC4+

TM800H (2001)

High Salinity, High Temperature SWC3+ SW30HR TM800 (2001) Standard SWC5 SW30XLE TM800L (2001) Ultra Low Energy SWC4+ SWC5 SW30XHR (2007) TM800A (2007) TM800C (2007) High Boron rejection

SU-800BCM (1997)

Ultra High Salinity SW30HRLE TM800E (2007) Low Energy Coverage Hydranautics Dow Toray Manufacturer

*( ): Year in which the product is launched. SWRO products lineup corresponding to various coverage released from each company*.

Many types of SWROs for energy saving & water quality have been announced.

SWRO Membrane Lineup of Typical Membrane Manufacturer

Energy Saving Water Quality

New Advancement of Seawater Desalination Reverse Osmosis Membranes - - PowerPoint PPT Presentation