Focus on Membrane Technology for Water Treatment
FocusFocus onon MembraneMembrane TechnologyTechnology forfor WaterWater TreatmentTreatment
Toray Industries, Inc.
1 September 2003 Dr. Masaru Kurihara CONTENTCONTENT
1.1. WorldWorld WaterWater ProblemProblem
2.2. WaterWater TreatmentTreatment MembranesMembranes
3.3. RORO MembranesMembranes && NFNF MembranesMembranes
4.4. UFUF MembranesMembranes && MFMF MembranesMembranes -- DrinkingDrinking WaterWater ProductionProduction --
5.5. ImmersedImmersed MembranesMembranes forfor WastewaterWastewater TreatmentTreatment
6.6. ConclusionConclusion 2 IntroductionIntroduction ofof DoctorDoctor M.M. KuriharaKurihara Title: Toray Industries, Inc. Senior Director In charge of Water Treatment Division, Technology Center (Water Treatment Technology Center), and Research & Development Division Director of International Desalination Association (IDA) Vice President of Japan Desalination Association (JDA) Director of Japan Membrane Society, Part-time lecturer at Kyoto University Personal History: 1963 Joined Toray Ind., Inc. 1970 Doctoral Dissertation at the University of Tokyo Membrane Research with Prof. J.K. Stille at the University of Iowa as Post-Doctoral Fellow 1991 General Manager, Polymers Research Labs Awards: 1992 Chemical Society of Japan Technical Award 2002 International Desalination Association Presidential Award 2003 Okochi Memorial Production Prize 3 TorayToray –– TheThe LeaderLeader inin ““AdvancedAdvanced MaterialsMaterials””
AchievingAchieving High High Growth Growth by by Constantly Constantly Supplying Supplying “Advanced “Advanced Materials”Materials” – – Developed Developed withwith ourour CoreCore TechnologiesTechnologies –– into into ourour Three Three Growth Growth Areas Areas (an (an expansion expansion of of our our four four strategic strategic businessbusiness areas)areas)
- Nanofibers Four Strategic - High-performance Fibers
4 WorldWorld WaterWater ShortageShortage -- NowNow andand FutureFuture (WMO and others, 1996) 1995 Main regions which have high water shortage percentages of more than 20%
Water 1995: Shortage More than 1) >40% : Middle East, Singapore, 40% = Korea, Pakistan 40 - 20% 2) 20 - 40%: India, Mexico, Europe 20 - 10% Less than (excluding UK and France), 10% Taiwan, South Africa 2025
2025: 1) >40% : Middle East, Korea, Pakistan, India, Algeria, South Africa, etc. 2) 20 - 40%: Mexico, China, USA, Water shortage presumed to continue worldwide Europe (excluding Water shortage presumed to continue worldwide UK) especially in Europe, the U.S.A., and China by 2025 especially in Europe, the U.S.A., and China by 2025 5 WaterWater ProblemProblem andand MeMembranembrane TechnologyTechnology Water Problem Membrane Technology for Water Treatment Water Region, Country Water Fresh Water Wastewater Resource Desalination Reuse & Pollution Treatment Shortage Reclamation United States Problem Problem In operation In operation Construction Benelux Problem Being applied In operation UK, France Problem In operation Being applied Spain Problem Problem Being applied In operation Being applied Saudi Arabia Severe In operation Planning Kuwait Severe In operation Construction China Problem Severe Being applied Being Planning applied Singapore Severe In operation In operation In operation Japan Problem In operation In operation
Water resources are extending from fresh water 6 to sea water and wastewater. WaterWater TreatmentTreatment MembranesMembranes
7 MembranesMembranes andand RelativeRelative SizeSize ofof CommonCommon MaterialsMaterials
Ultrafiltration Microfiltration MF Nanofiltration UF Membrane Reverse Osmosis NF RO Size (micrometer) 0.0001 0.001 0.01 0.1 1 10
Cl- ion Pesticide, Organic Material Influenza Virus Algae, Mad Relative Size Na+ion of Zn2+ion Vibrio Cholerae Common F- ion Virus 2+ Polio Virus Coliform Materials Pb ion Cryptosporidium NO -ion 3 Hepatitis A Virus Trihalomethane Bacillus anthracis Sea Water Desalination Wastewater Treatment Application Brackish Water Desalination Drinking Water 8 Wastewater Treatment Drinking Water Drinking Water SeparationSeparation CharacteristicsCharacteristics ofof VariousVarious MembranesMembranes
RO/NF Membranes UF/MF Membranes
Low MW Middle to high organic materials MW materials (Mw <= 200) (Mw >200) Ions Dissolved Suspended Solid Monovalent ions Multivalent ions Matter Particles Permeation Water and Water Rejection Membrane Membrane
RO: Molecular interaction MF: Dynamic separation Separation Solution diffusion Size exclusion Mechanism Electric repulsion NF: Size exclusion UF: Electric repulsion
RO: <1 nm UF: 10~100 nm Pore Size NF: 1~10 nm MF: >100 nm 9 GlobalGlobal CapacityCapacity ofof MembraneMembrane FiltrationFiltration PlantsPlants
Cumulative 12,0000 Annual Total
) Cumulative Total Estimated 3 Crypto outbreak RO&NF Cumulative 10,0000 Contracted /d x10 3 Potential New 8,0000 Cumulativ e Es timate RO+NF 6,0000 Potentiality MF&UF Cumulative 4,0000 Crypto outbreak Number of 2,0000 Contracts Installed Capacity (m
00 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9 0 1 2 8 8 8 8 8 9 9 9 9 9 9 9 9 9 9 0 0 0 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2
MF&UF Annual 10 Membrane Applications - Conventional & New Technologies : New membrane products ( ) : in R & D Water treatment processes Technical target Toray’s products
Multi Stage Flush (MSF) RO membrane with high boron Single Stage Low cost removal SWRO
Conventional (=High recovery) Sea- Drinking water water NF membrane for NF Multi stage High quality flush (MSF) scaling inhibition (Low boron conc.) Desalination
New Brine conversion RO membrane NF Two-stage SWRO for brine conversion system
Coagulation & Sand PAN hollow fiber River Sedimentation Filter Security UF membrane Conv. Drinking Lake conservation water Ground Removal of Coagulation & MF/UF PVDF hollow fiber
production cryptosporidium New Sedimentation membrane MF(UF) membrane Drinking water Drinking
Activated PVDF MF/UF flat Sludge Sedimentation Discharge sheet membrane for Conv. Sewage High quality MBR & for reuse and Ind. MF/UF Membrane Low-fouling Drinking Low-fouling RO treatment reclamation 11 Wastewater Wastewater New Bio-Reactor (MBR) RO water membrane TorayToray’’ss MembranesMembranes && ApplicationsApplications
ate TM rme 1. RO & NF Membrane Romembra * ube Pe uct t Prod 1) Seawater & brackish water desalination e Brin al e se rin acer 2) Ultra pure water production B h sp Mes er wat Feed ane 3) Harmful material removal mbr me RO rrier e ca ater eat d w Perm 4) Wastewater reuse Fee eate Perm 2. PAN Hollow Fiber UF Membrane Torayfil TM* 1078mm 1) Industrial process water production 2) Drinking water production
3) Wastewater reuse 114mm (diameter)
12 TorayToray’’ss MembranesMembranes && ApplicationsApplications
3. PVDF Hollow Fiber MF Membrane 8 inches Torayfil-F TM* 2m length 1) Drinking water production 2) Industrial process water production 3) Pre-treatment for seawater desalination 4) Wastewater reuse Element 4. PVDF Flat Sheet MF Membrane Permeate for MBR 1) Municipal and industrial wastewater treatment 2) Municipal and industrial wastewater reuse
13 RORO MembranesMembranes && NFNF MembranesMembranes
14 StructureStructure ofof RORO MembraneMembrane ElementElement Separation Membrane Feed Crosslinked Aromatic Polyamide 0.2 micrometer
Structure of RO Membrane Support Membrane Polysulfone 45 micrometer Structure of RO Element
ate me e Per Tub ter Cen
Polyester Taffta rine B ter l Wa Sea ne Bri ter Wa ed r Substrate Fe ace Sp eed F ter Wa ne Polyester Taffta bra Mem RO ter Filtrate 150 micrometer Wa ate ed me 15 Fe ate Per cer me pa Structure of Composite Membrane Per S ApplicationApplication ofof RORO MembranesMembranes
1. Industrial Ultra Pure Water Industrial Process Water 3. Wastewater Pure Water for Boilers Recovery of Valuables Reuse & Food Industry Process Water Reclamation
Industry RO Membranes Agriculture Indirect Drinking 2. Drinking Water Water
Sea Water Desalination Brackish Water Desalination
16 WaterWater ProductionProduction CostCost Sea Water
) Desalination 3 100 (MSF) Sea Water Desalination (RO) Wastewater Reuse (MF + RO)
50 Ground water Surface Water Treatment (MF)
Water Production Cost (yen/m Water 0 e) 1) ) ) ur 00 04 02 at (2 20 20 er e ) ) ( n ) ( it or 3 /d d io 3 d (l p it 3 / at / F ga (m a (m m (m S in 00 uw 0 sti 0 M S ,0 K 00 E 00 36 0, 0, 1 31 10
WaterWater resourceresource cancan bebe chosenchosen byby country.country. 17 ProgressProgress ofof RORO SeawatSeawaterer DesalinationDesalination PlantsPlants
1980‘s 1990‘s 2000‘s
Recovery % 25 40 -50 55 -65
psig 1,000 1,200 1,400 Operational Pressure (MPa) (6.9) (8.25) (9.7)
Product Water mg/l 500 300 <200 Quality (TDS)
Energy kWh/kgal 45 21 17.4 Consumption (kWh/m3) (12) (5.5) (4.6)
I. Moch, Pre-prints of ADA Conference in Lake Tahoe (2000) Progress of membrane technology realized Progress of membrane technology realized 18 goodgood qualityquality andand energyenergy saving.saving. SeaSea WaterWater DesalinationDesalination RORO MembranesMembranes inin GlobalGlobal MarketMarket
Module Type Supplier Product Material Morphology Toray SU-800 Dow/ SW-30 Filmtech Composite Spiral Crosslinked Koch/ Membrane TFCL-HP Aromatic Polyamide Fluidosystems Nitto Denko/ NTR-SWC Hydranautics Asymmetric Hollow Fiber Toyobo HOLLOSEP Cellulose Triacetate Membrane
CrosslinkedCrosslinked aromatic aromatic polyamide/spirpolyamide/spiralal modulemodule isis globalglobal standard.standard. ToyoboToyobo isis thethe onlyonly hollowhollow fiberfiber modulemodule supplier.supplier. DuPontDuPont withdrew withdrew fromfrom thethe hollowhollow fiberfiber RORO modulemodule businessbusiness inin MarchMarch 2001.2001. 19 TechnologicalTechnological TrendsTrends ofof RO/NFRO/NF MembranesMembranes
Operating Super low Ultra low Low High Ultra high Pressure Notes [MPa] 0.3 0.5 1.0 2.0 5.5 10.0 Recovery = 60% High TDS removal Pressure durability
2nd stg. High boron removal
SWRO Recovery = 40% High TDS removal N Co., D Co. High boron removal 1st stg. 1st Cost reduction RO BW Low-fouling Lower pressure N Co., H Co. High TOC removal
Reverse osmosis Reverse High quality pure Ultra water N Co. Cost reduction Low-fouling
reuse D Co., N Co., H Co. water Cost reduction Waste
Toxic mat. removal
water D Co., N Co. Cost reduction Product. Drinking
Scale removal Nanofiltration Pre- Ttreat. of SWRO 20 in R & D by Toray D Co. : Dow N Co. : Nitto Denko H Co.: Hydranautics ProgressProgress ofof RORO MembraneMembrane PerformancePerformance
Changing of Controlling of Interfacial Polycondensation 99.8 Material and/or Reaction, and use of Catalyst Morphology of Membrane II III IV 99.5 I
99.0 CA (1987) (1988) (1996) (1999) Asymmetric UTC-70 UTC-70L UTC-70U UTC-70UL Membrane Crosslinked Aromatic PA Composite Membrane 98.0 (1970's)
NaCl Rejection (%) Crosslinked PA Composite Membrane 95.0 (1980's)
90.0 Flux 00.20.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 (m3/m2 day MPa) Operating Pressure 5.0 3.0 2.0 1.5 1.0 0.8 0.7 0.5 (MPa/(m3/m2 day)) Medium Low Pressure Ultra Low Super Ultra Low
World’sWorld’s No.No. 11 MembraneMembrane PerformancePerformance 21 ConventionalConventional OneOne--StageStage RORO SeaSea WaterWater DesalinationDesalination SystemSystem
Pretreatment Cartridge Filter RO Element Pressure<7MPa*)= NaHSO3 FeCl3 High Pressure Pump Chlorine Chlorine Motor H2SO4
Energy Recovery Turbine Brine Product Sea Water Sea Water Tank Feed Tank Water
*) Spiral element 22 OkinawaOkinawa SeaSea WaterWater DesalinationDesalination PlantPlant (Capacity:(Capacity: 40,000 m³/d, 1996)
40,000m³/d: Tap water for 160,000 people
RO Module Installation (each unit produces 5,000m³/d)
TorayToray modulemodule isis usedused inin Japan’sJapan’s largestlargest plant.plant. 23 LargestLargest SeaSea WaterWater DesalinationDesalination PlantsPlants inin thethe WorldWorld
CapacityNumber ContractOperation Plant Membrane No. Country Plant Site (m3/d) of Units (year) Manufacturer Manufacturer 1 Trinidad Trinidad 136,000 8 99 2002 Ionics Toray 2 Saudi Arabia Yanbu RO2 128,000 15 92 98 MHI Toyobo 3 Saudi Arabia Al Jubail III 91,000 15 93 2000 Preussag DuPont, Toray 4 Saudi Arabia Jeddah RO1 56,800 10 86 89 MHI Toyobo 4 Saudi Arabia Jeddah RO2 56,800 10 91 94 MHI Toyobo 6 Spain Marbella 56,400 10 97 99 Inima DuPont 7 Malta Penbroke 54,000 10 - 94 Polymetric DuPont 8 Bahrain Al Dur 45,000 8 84 89 Weirwest garthgeDuPont 9 Spain Bl Mallorca 42,000 6 96 98 Degremont DuPont, Toray 10 Japan Okinawa 40,000 8 94 - 95 96 - 97 Kurita, etc. Toray, Nitto * DuPont withdrew from RO business in 2001 RORO seasea waterwater desalinationdesalination seemsseems veryvery difficultdifficult inin thethe ArabianArabian Gulf,Gulf, becausebecause troublestroubles occurredoccurred atat allall ofof DuPont’sDuPont’s RO RO plants.plants. 24 AlAl JubailJubail IIIIII isis thethe firstfirst successfulsuccessful plant.plant. Typical Flow Diagram of Brine Conversion Two Stage RO Seawater Desalination System Brine Conversion Two Stage RO Seawater Desalination System
Conventional System High Pressure Product Seawater RO Element Water (100) Pump 1st Stage (40) Total C=3.5% SW 6.5MPa Product Water Pretreatment (40+20)
Brine Water Water (60) RO Element Recovery C=5.8% SW 2nd Stage 60%
Booster Pump Product Water (20) 6.5 --- 9.0MPa Brine Water (40) ( ): Water Flow Ratio C=8.8% SW
Toray’s Patent: Japanese Patent Application 1994-245184(1994), US: 6187200(2001), CA: 216033(2001),25 RC: 302294(1997), AU: 691649(1998), EU(granted 2002), KR: 204608(1999), Pending - JP, CH Performance Trends of RO MembranesMembranes for Seawater Desalination
35,000 mg/L Seawater Ultra High Pressure Spiral PA 10.0 Composite Membrane (Toray 1996)
9.0 Spiral PA Composite Membrane (1998) High Pressure Hollow Fiber PA 8.0 Membrane (1992) High Pressure 7.0 Hollow Fiber PA Hollow Fiber CA Membrane Membrane (1969) ( 1998) Membrane Elements (MPa) Elements Membrane 6.0 Spiral PA Composite Membrane Pressure Resistance Level of RO RO of Level Resistance Pressure (1978-1979) 5.0 01020 30 40 50 60 Water Recovery Ratio from 3.5% seawater (%) Toray’sToray’s membranemembrane performanceperformance forfor seasea waterwater desalinationdesalination isis world’sworld’s No.1.No.1. 26 GlobalGlobal InstallationsInstallations ofof TorayToray SeaSea WaterWater DesalinationDesalination RosRos
KAE Curacao Mas Palomas Mas Palomas (Netherlands, Antilles) (Spain, Canary Island) (Spain, Canary Islands) 11,400 (m3/d) No. 1 Plant 4,500 (m3/d) No. 2, 3 Plant 9,000 (m3/d) Okinawa (Japan) 40,000 (m3/d) ● ● ● ● ● ● ●● ● ● ● ●● ● ● ● ●●● ● ●● ●● ●●● ●● ●● ● ● ● ●●● ● ● ● Tortola ● ● ● ● ● (British, Virgin Islands) ● ● 690 (m3/d) ● ●
●
● :Toray’s 2-Stage RO Systems ● :Conventional RO Systems Trinidad and Tobago Al Jubail 136,000 (m3/d) (Saudi Arabia) 91,000 (m3/d) 27 ResultsResults ofof MembraneMembrane BiofoulingBiofouling (MBP)(MBP) AssayAssay
Surface Bad (Orange County water district: Dr.Ridgway) (High attachment) 0.14 Cross 600nm section RO 0.12 Mycobacteria (hydrophobic cell surface) 0.10 Flavobacteria (hydrophilic cell surface) 0.08 Surface 0.06 Cross 600nm section 0.04 Low-fouling RO 0.02 Good BacterialAttachment (B/F ratio) Standard level (Low attachment) 0.00 (Cellulose Acetate Membrane) RO Low-fouling RO Fouling : Deterioration of membrane performance caused by stains TorayToray less-foulingless-fouling RORO membranemembrane hashas extremelyextremely lowlow bacteriabacteria attachment.attachment. WastewaterWastewater ReclamationReclamation && ReuseReuse PlantsPlants
Disinfections Wastewater MF RO Reclamation Reuse
Capacity MF/UF RO Plant (Country) Installation (m3/d) Supplier Supplier Jewel (Singapore) 30,000 2000 Dow Luggage Point (Australia) 14,000 2000 Pall Dow Bedok (Singapore) 10,000 2000 US Filter Hydranautics Bedok (Singapore) 32,000 2003 Zenon Hydranautics Kranji (Singapore) 40,000 2003 US Filter Hydranautics Seleta (Singapore) 24,000 2003 Hyflux Toray Sulaibiya (Kuwait) 310,000 2004 Norit Toray Orange County (USA) 220,000 2004 US Filter Piloting Ulpandan (Singapore) 140,000 2004 Piloting Piloting
TorayToray less-foulingless-fouling RORO waswas selectedselected atat thethe world’sworld’s largestlargest RORO plant.plant.29 CumulativeCumulative InstallationsInstallations ofof TorayToray ROsROs byby ApplicationApplication
2,500,000 /d)
3 2,000,000
1,500,000
1,000,000
500,000 Cumulative Installation Installation (m Cumulative 0 1987 1988
1989 3 1990 (thousand m /d) 1991 1992
1993 Ultra pure water 1,470 1994 Year年度 1995 1996 Brackish water 2,940 1997
1998 Sea water desalination 650 Global Demand Extension 1999 2000 Others 13 2001 2002 Ultra pure water production Wastewater reuse Sea water desalination Brackish water desalination & reclamation30 TorayToray GroupGroup’’ss BusinessBusiness BasesBases andand GlobalGlobal OperationsOperations
Flat Sheet Membrane Flat Sheet ● ● Membrane
● ● ● ● ● ● ● ●
●
Toray Ropur TMA Flat Sheet Membrane Production Three Main Element Production Production Base 31 ConclusionConclusion –– RORO••NFNF MembranesMembranes
1. The RO seawater desalination system has entered a stable growth stage and the business is expanding steadily.
2. Wastewater reuse and reclamation is expected to be a new RO application.
3. Expansion of the NF membrane businesses is expected in the pretreatment of seawater desalination, and in highly efficient water purification systems.
32 UFUF MembranesMembranes && MFMF MembranesMembranes -- DrinkingDrinking WaterWater ProductionProduction --
33 UF & MF Membranes – Breakdown of World Applications -
Others Industrial Water
Wastewater Drinking Water Treatment
Ref: David H. Furukawa, WATERMARK, October 17, 2002
3 Total Water Production: 4.9 million m /d 34 Market for Hollow-fiber Membranes for Drinking Water Production 200 US /d) 3 EU Total Drinking Water m
4 150 4 3 Large Plant Production (x10 m /d) In Operation US: 2900 100 Japan: 6900 Regulation Cryptosporidium 50 Outbreak Cumulative (x10 Cumulative Japan
0 0 1990 1992 1994 1996 1998 2000 2002 (year) Cryptosporidium parvum (4 ~ 8micrometer)1993 400,000 people experienced intestinal illness in Milwaukee. At least 50 died of the disease. 1996 8,000 people infected in Ogose, Saitama, Japan 1998 Enhanced regulations of surface water treatment EnhancementEnhancement ofof PathogenPathogen RegulationsRegulations causedcaused marketmarket expansion.expansion.35 MembraneMembrane FiltrationFiltration PlantsPlants forfor DrinkingDrinking WaterWater inin JapanJapan Capacity Location Engineering Membrane Installation (m3/d) Supplier (Year) 4,000 Saitama, Ogose Kurita Kuraray (UF) 1998 6,200 Hokkaido, Nishisorachi Orugano Daiseru (UF) 1999 2,400 Ooita, Notsu Hitachi Toray (UF) 1999 10,000 Tochigi, Imaichi Orugano Daiseru (UF) 2000 1,900 Fukui, Miyazaki Suido Kiko Asahi Kasei (UF) 2000 1,600 Fukushima, Aizuwakamatsu Orugano Daiseru (UF) 2000 6,000 Miyagi, Onagawa NKK Memcore (MF) 2001 5,000 Mie, Kiho Ebara Mitsubishi (MF) 2001 1,900 Fukui, Eiheiji Maezawa Toray (UF) 2001 4,500 Gifu, Ena Suido Kiko Asahi Kasei (UF) 2001 1,900 Gunma, Showa Suido Kiko Asahi Kasei (UF) 2001 5,000 Suido Kiko Toray (MF) 2002 8,000 Suido Kiko Toray (MF) 2003
ApplicationApplication ofof UF/MFUF/MF membranesmembranes isis expandingexpanding inin Japan.Japan. 36 CumulativeCumulative installationsinstallations areare 200,000200,000 (m(m33/d)/d) asas ofof JuneJune 2003.2003. PANPAN--basedbased HollowHollow FibFiberer UFUF MembraneMembrane
Cross section Pore size: 0.01 micrometer
Outer surface37 CasingCasing TypeType ModuleModule
10 78 mm
) er et am di ( m 4m 11
Membrane area: 12 m2 Water production: 10 m3/d Drinking water production plant
38 TankTank TypeType ModuleModule D
Merit - Low Initial Cost H - Small Footprint - Easy Maintenance
Flux (m3/d) 70 200 500 800 Membrane area (m2) 84 228 576 960 Diameter (D) (cm) 45 75 120 150
Height (H) (cm) 200 230 250 25039 DesignDesign ConceptConcept ofof PVDFPVDF HollowHollow FiberFiber MFMF MembraneMembrane
Operation Functional Requirement 1. High Water Flux 1. High Water Permeability 2. Low Operational Pressure 2. Precise Pore Size 3. Frequent Physical Washing 3. High Physical Stability 4. Frequent Chemical Rinse 4. Good Chemical Resistance
PVDF(Poly Vinylidene Fluoride) polymer is suitable
Performance of hollow fiber membrane Proprietary spinning process depends highly on spinning process
High Permeability & High Physical Strength 40 TorayToray PVDFPVDF HollowHollow FiberFiber MembraneMembrane
Spinning Method Feature Outer surface Lumen Extraction Melt spinning with pore High Strength formation agent and extraction High Cost Drawing High Strength Melt spinning and drawing Low Cost Melt Spinning
Non-solvent Induced UF/MF Applicable Phase Separation Low Cost Permeability and Polymer solution is High-strength coagulated by non-solvent inconsistent Water flow Thermally Induced Phase Separation High Strength Polymer solution is cooled High Flux Solution Spinning Solution down to phase separation Low Cost 41 temperature Comparison of Hollow Fiber Membrane with Other Companies * Pure Water, at 50 kPa
Supplier U Company Z Company N Company A Company Toray
Material PPPVDF PVDF PES PVDF PVDF
* Permeability - (m3 / m2-d) 4.8 1.5 3.0 5.3 6.7
Membrane Area (m2) 30- 56 35 50 72
Module
PP: Polypropylene, PVDF: Poly (Vinylidene Fluoride), PES: Poly (Ether Sulfone)
Toray’sToray’s hollow hollow fiber fiber membranes membranes are are World’s World’s No.1 No.1 inin permeabilitypermeability andand thethe largestlargest module.module. 42 ComparisonComparison ofof StrengthStrength && ElongationElongation - Membrane Material -
PVDF
PAN
CA
PS
15 10 5 0 050 100 150 Strength (MPa) Elongation (%)
PhysicalPhysical propertyproperty dependsdepends highlyhighly on on materialmaterial && spinningspinning method.method. 43 Comparison of Chemical Stability of PVDF Hollow Fiber -Accelerated Oxidation-
Purpose: Confirmation of stability against strong oxidation agent
1.0 Accelerated oxidation PVDF
1. Evaluation of membrane PE configuration PS 2. Evaluation under cleaning
condition StrengthStrength / Initial / Initial 0.5 PAN (5,000 ppm as H2O2 with FeSO4) CA
Results
StrengthStrength after aftersoak soak 0 1. PVDF-MF membrane is very stable 0 50 100 150 200 250 under strong oxidation conditions. Soaking period (h) 2. PVDF-MF membrane can be cleaned with a concentrated oxidation agent. Comparison of Oxidation Resistance44 Comparison of Chlorine Resistance of PVDF Hollow Fiber
Purpose: Confirmation of stability against chlorine
1.0 Evaluation condition 1. Evaluation of membrane PVDF configuration PE 2. Evaluation under cleaning PAN condition PS (1,000 ppm as Chlorine, pH=10) 0.5 CA
Results 1. PVDF MF membrane is very Elongation after soak / Elongation soak Initial after Elongation 0 stable in a concentrated chlorine solution. 0 200 400 600 800 1000 2. PVDF-MF membrane can be cleaned Soaking period (h) with a concentrated chlorine solution. Comparison of Chlorine Resistance PVDFPVDF MFMF MembraneMembrane 88”” ModuleModule
Specifications Permeate Back Wash
Air out PVDF-HF large Module (& Circulate) 8 inches, 2m length
PAN-HF Module 4 inches, 1m length
1724
2160 216
Items Toray 8B Module Module Size [mm] 216 (8B) dia. x 2,160L Feed Membrane Area [m2] 72 Flux (pure water) [m3/h/50kPa] 20 (Feed) Drain Temperature [deg.] 0 – 40 &Air 46 HFMHFM--20202020 StandardStandard OperationalOperational ConditionsConditions Pretreated Water River & Lake Surface Feed Water Type Clean Ground Water Water Filtration Flux (m3/m2/d) 2 – 5 1 - 2 Flux: 1 - 2 times of filtration flux Chlorine dosing: 1 - 10 ppm Backwash Condition Time: 30 – 60 sec. Frequency: every 0.3 – 2 h Air flow: 4 – 10 Nm3/h/Module Scrubbing Condition Time: 30 – 120 sec. Frequency: every 0.3 – 2 h
Operation Temp. (degrees C) =<40 Operation pH 1 – 10 (1) CIP (Clean In Place): every 3 - 6 months (2) Trans-Membrane pressure Chemical Cleaning (3 - 5 times of initial, or 150 kPa) (3) Chemicals: 1N-HCl + 3,000 ppm NaClO47 LargeLarge ScaleScale GroundGround WatWaterer FiltrationFiltration PlantPlant ((5,000 m3/d, for 20,000 people)
4 m 2 m
48 CompactCompact andand HighHigh ProductivityProductivity OutlineOutline ofof SuidoSuido KikoKiko Kaisha,Kaisha, Ltd.Ltd. Profile Established : 1936 Net Sales : 200 million dollars Function : One of the largest water system and equipment companies in Japan Alliance with Toray : Toray owns 20% of shares - Joint water business venture - Development of new systems and membrane products - Sharing and exchange of technical and business information
Domestic position Positioned in 15th place as a water treatment company, second, behind Ebara, in the drinking water production business, and first in membrane filtration systems (Orugano second, Ebara third) 49 TorayToray CollaborationCollaboration withwith SuidoSuido KikoKiko
Suido Kiko’s Advantages Toray’s Advantages
- Pioneer and first-ranking - Capable of meeting diverse demand with a manufacturer in the drinking wide range of products from MF to RD water systems business membranes - Experience in Government and Public - Operating businesses in Japan, the U.S., and Businesses Europe
Development into an Overall Water Treatment System Business
Japan : Supplies Membranes to Suido Kiko Korea/China : Jointly Launched Business - Toray Supplies Membrane Technology, Suido Kiko Offers Engineering Technology 50 Water Treatment Related National Projects
Year Title Toray’s R&D Theme 1992 Project Membrane Aqua Century 21 (MAC21) 1993 1994 New Membrane Aqua Century 21 - Highly efficient water purification system (MAC21) utilizing NF membranes 1995 (Toray Engineering Co.) 1996 1997 Advanced Aqua Clean Technology for the 21st [Search for New Technology Application of Membrane Filtration] Century - Development of efficient coagulation and sedimentation technology to 1998 (ACT21) be applied in the UF pretreatment -Development of operational stability during the NF advanced water 1999 purification process 2000 [Development of Advanced Water Purification System of River Water] - Technological examination of combination of conventional water 2001 purification systems and membrane filtration 2002 Environmental, Ecological, Energy Saving and Group 1: Development of large-capacity membrane filtration Economical Water Purification System technology (Kawai,Yokohama/Shinishikawa,Okinawa) 2003 (e-Water) Group 2: Total water purification system 2004 (Ayase,Yokohama/Otogane,Fukuoka) Group 3: Observation technology at the drinking water supply source 51 Participation in National Project (e-water) Water Drinking Production Plant Order Award Requirements: 1. Qualification of the Facility 2. Approval of Construction Work 3. Acquisition of National Licenses 4. Actual Experience in Plant Delivery
Water Purification Plant Feed Water Subject Participants/ Toray’s Expected Role
Kawai, Fresh Water - Comparative Experiments of 6 - Toray/Suido Kiko Joint Team Yokohama Groups, including Ebara - Toray; Experiment Supervisor, June/03 - Basic Design, Manufacture of Mar/05 - Case Trial - 200,000 m3/d Experimental Facility, Follow-up of Operations Ayase, Fresh Water - Examination of Appropriate - Co-R&D of 38 Companies Yokohama Operating Conditions - Toray; Basic Design, Supply of Aug/03 - Mar/05 PVDF Modules Otogane, Fresh Water - Comparative Experiments of 5 - Suido Kiko as the Supervisor Fukuoka Groups including Maezawa and - Toray; Supplies PVDF Sept/03 - Shinko Pantec Modules, Supports System Mar/05 - Case Trial - 110,000 m3/d Examination
Ishikawa, Fresh Water - MF Pretreatment+NF Membrane - Nishihara; Supervisor, Joint Okinawa (to confront Ozone + Activated Team of Suido Kiko, Ebara, Carbon Method) Kubota, and Toray Oct/03 - - Only Successful Group to actually - Toray; Basic Design and Mar/05 demonstrate use of membranes Supply of PVDF and NF - Case Trial - 50,000 m3/d Modules 52 Conclusion - UF/MF Membranes for Drinking Water
1. The Drinking Water Production Market is expanding rapidly, centering on the U.S. and Europe.
2. Toray has developed highly water-permeable and highly stable PVDF hollow fiber large modules suitable for drinking water production. 3. Although still in the experimental stage, Toray’s technology is highly appraised, and we are aiming to enter the market as soon as possible.
53 ImmersedImmersed MembraneMembrane ModulesModules forfor WastewaterWastewater TreatmentTreatment
54 ImmersedImmersed MembraneMembrane ModuleModule SystemSystem MBR (Membrane Bioreactor)
Wastewater Discharge
MF P Reuse RO Reclamation
Activated Sludge in MBR Immersed Membrane Module
Features good water quality, small footprint, reduced excess Features good water quality, small footprint, reduced excess 55 sludge,sludge, andand thethe marketmarket isis yetyet undeveloped.undeveloped. FiltrationFiltration MechanismMechanism andand RequiredRequired CharacteristicsCharacteristics Sludge Element Effluent
Feed Water
Aeration Bubble Feed Water Effluent (Activated Sludge) Support Membrane
Requirement Physical Stability Impact of bubble and sludge. Vibration. Stability Chemical Stability Chlorine, acid, oxidation agent, alkaline Initial Permeability High permeability Permeability Durability Prevention for clogging 56 DesignDesign ConceptConcept ofof ImmersedImmersed MembraneMembrane 1. Membrane Material HH Poly (Vinylidene Fluoride): PVDF n High stability for chemicals : fluorine polymer FF High physical strength : high molecular weight (MW=300,000 400,000)
2. Membrane Form Fiber reinforced (non-woven) PVDF flat sheet membrane Fiber Membrane
3. Surface Pore Diameter 1) Small pore diameter Good permeate quality 2) Narrow pore diameter distribution Prevention of clogging 3) Numerous pores High flux 57 BasicBasic CharacteristicsCharacteristics ofof ImmersedImmersed MembranesMembranes
1.5 2 PVDF Membrane / m / m ) 12 1 Type B
東レBF014 0.5 クボタ
0 3.0 micron 3.0 micron 0 0.2 0.4 0.6 0.8 Number of pores (10 Pore diameter (micron) PVDF membrane Type B
FE-SEM photographs of Pore diameter distribution of surface Flat sheet membrane surface (Estimated from SEM photos)
IdealIdeal membrane membrane micro micro structure structure is is achieved. achieved. 58 ImmersedImmersed MembraneMembrane ElementElement && ModuleModule
Housing 1,500mm
Aeration 500mm Module Element
Toray’sToray’s modulesmodules featuresfeatures highhigh performanceperformance perper footprint.footprint. 59 ComparisonComparison ofof MoModuledule PerformancePerformance
Module Performance Membrane Performance Membrane Area = X = (m3/footprint) (m3/m2) (m2) 2 (Compared to (1.4) (1.5) other modules) Rinse 2.0 /d)
3 Differential pressure = 2 kPa 1.5
1.0 Toray: 0.8 (m3/d) 0.5 Other: 0.4 (m3/d)
0.0
Module Performance (m Performance Module 0 1000 2000 3000 4000 5000 6000 7000 8000 Operation (h)
TorayToray modulemodule performanceperformance isis twicetwice asas competentcompetent asas others.others.60 OperationalOperational TechnologyTechnology
1. Roll of Operational Technology
1) To maintain efficiency and stability of the performance of modules and module elements 2) To achieve module performance targets at low cost 3) Required as software in case of selling modules and module elements 2. Alliance with SKG* 1) Joint pilot tests in Europe and Singapore
2) Joint businesses in Europe, Singapore, and China
* SKG (Seghers Keppel Technology Group): More than 200 Activated Sludge System installations Worldwide
61 PilotPilot TestTest atat BeverwijkBeverwijk WWTPWWTP (the(the Netherlands)Netherlands) Consulting company DHV conducts tests of MBR suppliers and immersed membranes
2000
The Absolute Group in Europe’s Wastewater Treatment Business
PilotPilot test test is is showing showing goodgood performance.performance.62 Conclusion - Immersed Membranes for Wastewater Treatment
1. Performances such as good water quality, small footprint, and reduced surplus sludge are expected in MBR technology, and the market is still globally new. 2. Toray has developed highly stable, highly permeable and reduced clog types of PVDF flat sheet membrane modules.
3. Toray making progress in pilot tests in Europe, Singapore, and China, and aiming at entering the market at an early stage.
63 Conclusion - Toray’s Membrane Separation Technology for Water Treatment
1. Toray is a synthetic membrane manufacturer whose products cover all types - RO, NF, UF, and MF.
2. Placing top priority on seawater desalination, drinking water production, and wastewater treatment, Toray intends to expand its membrane technology business throughout the world.
3. High water quality and an Integrated Membrane System (IMS), a combination of several membranes, is required in the future market. Toray, possessing all types of membranes, is in an advantageous position in expanding business utilizing the IMS.
64 TorayToray cancan contributecontribute toto ensuringensuring sustainablesustainable waterwater resourcesresources withwith membranemembrane technology.technology.
River, Lake, Ground Water Sea Water Wastewater
65