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 Brenntag Seminar
5 Dec 2017

Presented by
Brenntag
and
Hydranautics, a Nitto Group Company

Slide 1
 Brenntag Seminar
7 Dec 2017

Presented by
Brenntag
and
Hydranautics, a Nitto Group Company

Slide 2
Nitto Denko Corporation
Company Profile

Slide 3
 Nitto Denko Corporation
President Hideo Takasaki

Founded 1918 October 25th

Head Office Osaka, Japan

Capital 26.7B JPY*

Sales (consolidated) 768B JPY*

Employees (group) 29,617*

Head Office
*as of 31 Mar 2017
Slide 4
 Products
Nitto provides over 15,000 products to over 70 various industries

Industrial
Tapes
Double Sided Tape Paint Protection Tape Plate Reinforcement Protection Film Heat Avulsion Sheet

Optical &
Electronics
LCD polarizing film Retardation film Transparent Metallic coating Dicing tape for
for LCD conductive film circuit board silicon wafer

Medical &
Membrane
Transdermal drug Medical surgical Particles for Nucleic Seawater Waste water reuse
delivery patches tape dressing Acid Synthesis desalination facility facility
Slide 5
 Global Membrane Division

Hydranautics, A Nitto Group Company

Slide 6
 Our Milestone
Nitto has over 40 years experience of membrane development since 1970’s

1963 Hydranautics is founded in California, USA

1973 Start R&D for industrialization of separation membrane
1978 Commercialized prototype of capillary & spiral
1983 Release ultrapure UF membrane for semiconductor
1986 Shiga Plant started up as the world first RO/UF plant
1987 Acquisition of Hydranautics in California, USA
1988 Release of Low-pressure aromatic PA-RO product – CPA2
1991 Release Seawater desalination aromatic PA RO product - SWC1
1995 Release ultra-low pressure RO product – ESPA1
1997 Release fouling-resistant RO product – LCF1
2002 Spiral membrane assembly started in Shanghai
2002 Introduced the new ESNA1-LF low fouling NF membrane
2003 Introduced high boron-removal RO membrane product
2008 SWC5 wins Nikkei Superior Products and Services Awards
2009 Start new plant operation in Shiga Plant
2010 Released patented vented seal carrier
2015 Released new RO/NF projection software IMSDeign®2015
2016 Rolled out high flow and high salt rejection elements (ESPA2-LD MAX & CPA7-LD)
Slide 7
 Global Membrane Division
Nitto covers demands of market and customers with the well organized global network

Nitto China, Songjiang

Assembling 4” RO
element

●
● Shiga, Japan
● HQ of Membrane Div.
● ● ●●
●● R&D and Production Hydranautics, CA
●●
● ●
RO / UF / NF / MF R&D and Production
●
●
RO / UF / NF / MF
●

● R&D and Production

● Sales & Tech Service office
Slide 8
Global Membrane Division (GMD)
Manufacturing Facilities

Slide 9
 World Class RO Manufacturing Facility (Shiga)

New Plant Profile

•Completed Time: May, 2009
•Total Area: 15,000㎡
(Steel structure 4-story building)
•Manufacturing Item: RO membrane element

ND/HY enhanced the production capacity to meet increasing water demand

Slide 10
Global Membrane Division (GMD)
Manufacturing Facilities

Slide 11
 Large Scale Projects
Europe China
Carboneras ES 126 MLD 2002 Potable Yinglite 60 MLD 2012 Power
Barcelona ES 200 MLD 2009 Potable Baotou 100 MLD 2013 Steel
Beckton UK 150 MLD 2015 Potable Shenhua 50 MLD 2013 Coal Chem
Yanchang 50 MLD 2013 Coal Chem

Middle East USA

Fujairah 170 MLD 2003 Power Orange County 264 MLD 2006 Municipal
Rabiegh 192 MLD 2008 Petrochem Boca Raton 150 MLD 2015 Municipal
Barka 2 125 MLD 2009 Power
Sorek
Singapore
400 MLD 2014 Potable
Ras Al Khair 300 MLD 2015 IWPP Japan Bedok I 32 MLD 2002 Municipal
Okinawa 40 MLD 1997 Potable Kranji I 40 MLD 2002 Municipal
Fukuoka 50 MLD 2005 Potable Ulu Pandan 156 MLD 2006 Municipal
Bedok II 55 MLD 2008 Municipal
INDIA Changi II 228 MLD 2016 Municipal
Chennai Metro 100 MLD 2009 Municipal
Adani Power 100 MLD 2012 Power
Brazil
P-66 39 MLD 2016 Offshore
P-74 48 MLD 2016 Offshore
P-69 39 MLD 2017 Offshore
Algeria
Beni Saf 200 MLD 2008 Potable
Australia Chile
Hamma 200 MLD 2008 Potable Gold Coast 132 MLD 2012 Potable Antofagasta 50 MLD 2003 Mining
Tlemcen 200 MLD 2009 Potable Adelaide 300 MLD 2013 Potable Copiapo 54 MLD 2013 Mining
Honaine 200 MLD 2009 Potable Melbourne 400 MLD 2013 Potable Escondida 200 MLD 2016 Mining
Slide 13
 Separation Ranges of Membranes
(nm) 0.1 1 10 102 103 104
Dimensions

(μm) 0.0001 0.001 0.01 0.1 1 10

(m) 10-10 10-9 10-8 10-7 10-6 10-5

Reverse osmosis (RO) Membranes

membrane
Type of

Nanofiltration (NF) Membranes

Ultrafiltration (UF) Membranes
Microfiltration (MF) Membranes

Ions Proteins Viruses Bacteria

Pseudomonas
Ions Sucrose Poliomyelitis diminuta Algae and mud
Cl- Vitamin B Polio Salmonella enterica
Target Separation Substances

Japanese
NO3- Insulin Vibrio cholerae
encephalitis
OH- Cytochrome C Hepatitis A Giardia
Pepsins Influenza Escherichia
K+ coli
Na+ Albumins Smallpox Cyptosporidium
Ca2+ γ-Globulin Shigella bacteria
Mg2+ Colloidal silica
Agrochemicals and
Diameters of organic substances
hydrated ions

Trihalomethanes
Slide 13
 Product Overview

REVERSE OSMOSIS (RO) NANO FILTRATION (NF)

CPA, ESPA, LFC, SWC, SANRO ESNA, NANOSW, HYDRAcore

ULTRA FILTRATION (UF) MEMBRANE BIO REACTOR (MBR)

HYDRAcap, HYDRAcapMAX, NTU3306K6R HYDRAsub

Slide 14
 Spiral Wound Element – RO Membrane
Model: SWC / CPA / ESPA / LFC
Size: 4” / 8” / 16” x 1,016mm
Material : Composite Polyamide
Feed water

Feed water

Concentrate

Permeate
Permeate
Core Tube Spacer
Feed / Brine RO / UF
Spacer Membrane
Slide 15
 Capillary Element – Pretreatment
HYDRAcap MAX : OUT-side-IN HYDRAcap : IN-Side-OUT

PVDF TIPS
Fiber PES Fiber
Slide 16
Products Applications

Slide 17
 Product lineup – Standard RO membrane
Main application
Pressure
Product name Specialty Sea Ultra pure Waste
level Brackish Process
water water water
SWC5 MAX, -LD Balance

High SWC4 MAX, -LD High Rejection ◎ ○

SWC6 MAX, -LD High Flow

CPA3
CPA5 MAX, -LD High Rejection
Low CPA7-LD ◎ ◎ ○
Tolerance to
LFC3-LD
surfactant

ESPA1
High Flow ◎ ◎ ○
Ultra low ESPA2 MAX, -LD

ESPAB MAX High Boron Rej. ◎ ○

Super
ESPA4 MAX, -LD High Flow ○
ultra low Slide 18
 Product lineup – Specialty membrane
Main application
Membrane
Product name Specialty
type Ultra pure Waste
Sea water Brackish Process
water water

NTR-7400HG series
NF
Hydracore series
Heat
resistance
◎
NTR-70HG
High Rejection
NTR-759HG

SanRO series Heat resistance ◎

Sanitary DairyUF series

DairyNF Dairy ◎
DairyRO

Ultra low ESNA1-LF2-LD

pressure ESNA1-LF-LD
High Flow ◎ ○

Slide 19
 Product lineup – Capillary UF
Main application
Membrane
Product name Specialty Ultra pure Water Aseptic Waste
type
water purification water water

K6R-HP High particle Rejection

NTU-3306-K6R High flow ◎ ○

Outside in NTU-3306-K4R MWCO : 20,000
PVDF
Hydracap MAX
Pore size : 0.08μm ○ ◎
series
Max turbidity : 300

NTU-3006-C3RM Pyrogen free ◎

NTU-3050-C3R MWCO : 20,000 ◎

Inside out
PES
Hydracap series Pore size : 0.02μm ◎ ○
Max turbidity : 100

Slide 23
The Newater (Singapore) Story – Hydranautics,
First RO membrane used in Newater

Slide 21
 The Newater (Singapore) Story – Hydranautics,
First RO membrane used in NEWater
Capacity
Plant Start Up RO Qty (pcs) RO Manufacturer
(m3/d)
Bedok Demo 2000 10,000 624 Nitto Denko/Hydranautics
Bedok I 2002 32,000 2,044 Nitto Denko/Hydranautics
Bedok II 2008 55,000 432 (16inch) Nitto Denko/Hydranautics
Kranji I 2002 40,000 2,555 Nitto Denko/Hydranautics
Kranji II 2006 16,000 1,022 Woongjin
Kranji + 2007 26,000 1,778 Woongjin
Kranji III 2016 22,500 1,500 Nitto Denko/Hydranautics
Seletar 2003 24,000 1,449 Nitto Denko/Hydranautics
Ulu Pandan 2006 156,000 9,100 Nitto Denko/Hydranautics
Ulu Pandan Stage 3 2017 14,800 938 Nitto Denko/Hydranautics
Changi 2009 228,000 13,860 Toray
Slide 22
Changi II 2016 228,000 15,000 Nitto Denko/Hydranautics
Bedok NEWater Factory (Phase II – 16 inch)

Location Singapore
End User PUB, Singapore
Application Wastewater Reclamation
Capacity 55,000 m3/day
Membrane Model ESPA2-16-1570 (16inch)
Membrane Quantity 288 pcs Slide 23
Kranji Newater Factory Expansion
Location Singapore

End User PUB, Singapore

Application Wastewater Reclamation

Plant Capacity 22,730 m3/day

Membrane Model ESPA2-LD

Membrane Quantity 1,512 pcs

• ST Marine has secured a new contract from Public Utilities Board

(PUB) Singapore, to expand the existing Kranji NEWater Factory
(KNF).
• The contract will be managed by STSE Engineering Services Pte Ltd
(STSE), a fully owned subsidiary of ST Marine and is completed in
2016.
Slide 24
Singapore Changi NEWater Plant II
Location Singapore

Main Contractor United Engineers Ltd

End User BEWG

Application Wastewater Reclamation

Plant Capacity 228,000 m3/day

Membrane Model ESPA2 MAX

Membrane Quantity 15,680 pcs

Slide 25
Keppel Ulu Pandan 3rd Stage – ESPA2-LD MAX
Location Singapore

End User Keppel

Application Wastewater Reclamation

Plant Capacity 14,800 m3/day

Membrane Model ESPA2-LD MAX

Membrane Quantity 938 pcs

The Business Times, 10 April 2017

Slide 26
100 MLD Maynilad Putatan RO Replacement
Location Philippines

End User Maynilad

Application River Water Treatment

Plant Capacity 100,000 m3/day

Membrane Model ESPA2 MAX

Membrane Quantity 1500 pcs

• Due to the drought season, possibly resulted by El Nino effect, there is an intrusion of
Sea Water into the Laguna Lake that causes high dissolved solids in the feed water.
The incumbent membranes are not able to meet the required quality.
• Hydranautics responded immediately by supply of brackish water membranes. At the
same time, technical support is rendered to the team on site.
Slide 27
Beenyup - Advanced Water Replenishment
Plant (AWRP)
Location Perth, Australia

Western Australia’s Water

End User
Corporation

Application Wastewater Reclamation

Plant Capacity 35,000 m3/day
Membrane Model ESPA2-LD
Membrane Quantity 3000 pcs

• The first wastewater recycling project of its type

in Australia and is a major step in progressing
the Water Corporation’s strategy for climate
resiliency
• Completed in 2016/17

Slide 28
 Singapore : 136 MLD Tuas 3 Desalination
• National water agency PUB announced on Monday (Nov 16) that HSL Constructor Pte Ltd has
won the tender to design and build Singapore's third desalination plant at Tuas.
• The plant is expected to begin operating in 2017 and will add another 30 million gallons, or
136,000 cubic metres, of water per day (mgd) to Singapore's water supply. It will be owned
and operated by PUB.
• PUB said the open tender attracted bids from eight reputable companies. HSL won with the
most competitive tender bid of S$217 million.

Location Singapore

End User PUB

Application Seawater Desalination

Plant Capacity 136,000 m3/day

Membrane Model SWC4 MAX (10,332pcs)

and Quantity ESPA2 MAX (4,116 pcs)
Slide 29
 Marina East Desalination Plant : 138MLD

Location Singapore
End User PUB
Application Seawater Desalination
Plant Capacity 138,000 m3/day
SWC4 MAX & SWC5 MAX
Membrane Model
(9408 pcs)
and Quantity
ESPA2-LD MAX (6,300 pcs)
To be completed by Dec, 2019
Slide 30
200MLD Independent Water Plant in Qurayyat
Location Sultanate of Oman

• Hyflux Utility (Oman) Pte Ltd

• Hyflux International Pte Ltd.
End User
Modern Channels Services
LLC (MCS) )

Application Seawater Desalination

Plant Capacity 30,000 m3/day

Membrane Model SWC4-LD and SWC5-LD

Membrane
17,864 pcs
Quantity

Slide 31
 Organization Structure of SEA & Oceania

Tanihiro Takahashi Senior Asia Sales Director

Satish Chilekar Technical Consultant

Laurine Lim Senior Manager, Regional Sales

Australia & Oceania South East Asia

Tom McCrisken Keith Andes Technical : Sales :

Lee Chin Ling Carol Chew
Pacific Rim Lim YangJun Sarah Nasir
Sales Manager
Technical Manager
(Australia & Oceania)
(SEA & Oceania)
Slide 32
 Our Specialists
Satish Chilekar, Technical consultant / Trainer
• 37 years in water treatment, specializing in water separation technology

Keith Andes, Technical Expert / Trainer

• 34 years with Hydranautics, specializing in plant commissioning & Troubleshooting

David Shin, UF & MBR Specialist

• Specialize in UF & MBR design, troubleshooting and commissioning for Hydranautics

Max Echizen, Chief Engineer & Process NF specialist

• Involve in R&D and product development of RO & NF.

Hiroki Fujioka, Final Filter UF specialist / Product Manager

• Involve in Final UF application and development Slide 33
Thank You
Slide 34
RO Operation and Maintenance
Training

Presented by
Brenntag
and
Hydranautics, a Nitto Group Company

Slide 35
 Content
1. RO Membrane
2. Pretreament Functions and Monitoring
3. RO Feed Water Monitoring
4. RO Start Up & Shut Down
5. RO Performance Monitoring
6. RO Cleaning
7. RO Troubleshooting
Slide 36
 Part 1
RO Membrane

37
 Spiral Wound Element – RO Membrane
Model: SWC / CPA / ESPA / LFC
Size: 4” / 8” / 16” x 1,016mm
Material : Composite Polyamide
Feed water

Feed water

Concentrate

Permeate
Permeate
Core Tube Spacer
Feed / Brine RO / UF
Spacer Membrane
Slide 38
 Part 2
Pretreatment Functions and Monitoring

Slide 39
 Typical Process Units in Power Plants
SMBS Antiscalant

Cartridge
Clarifier Media Filter or Activated
Filter
Ultra-Filtration Carbon
(5um)

Ion Brackwish Seawater

Product Exchanger Reverse Osmosis Reverse Osmosis
(BWRO) (SWRO)

Slide 40
 Clarifier
• Objective is to reduce suspended solids in incoming
seawater
• It can remove suspended solids to about 10 NTU
turbidity
• Close monitoring and jar test is required optimize
coagulant / flocculant dosage.
• Monitoring influent & effluent: Turbidity

Slide 41
 Media Filter
• Objective is to remove Colloids
• Pros
– it can remove colloids to low levels, about 1 NTU
turbidity
– Simple to design, construct and operate
• Cons –
– Can not handle > 25 NTU feed turbidity
– Carry over can increase the outlet turbidity to high
levels (> 1 NTU) that will create problems in
downstream units.
• Monitoring influent & effluent : Turbidity & SDI

Slide 42
 Ultra-Filtration (UF)
• Objective is to remove colloids and bacteria
• Pros
– it removes colloids almost completely producing < 0.2
NTU turbidity water
– It removes bacteria, 6 log removal
– Simple to design, construct and automatically
operable
– Low pressure design requires lower costs
– Long membrane life (5 years), lower operating cost
• Monitoring influent & effluent : Turbidity & SDI
Slide 43
 Activated Carbon Filter
• Objective is to remove free chlorine and organics
• Pros :
– it can remove free chlorine completely
– it can remove organics based on their nature
– Simple to design, construct and operate
• Cons
– Can not handle any turbidity > 1 NTU
– Will increase micro biological counts in the outlet
waters.

Slide 44
 Sodium Meta Bi-Sulphite (SMBS) Dosing
• Objective : remove free chlorine effectively.
• Free chlorine (or any other oxidants) will oxidize
polyamide layer, causing conductivity to increase.
• Recommended preparation : every few days
• Monitoring effluent : Free Chlorine & ORP

Antiscalant Dosing
• Objective : prevent scaling formation
• Scale forms due to solubility limits are exceeded.
Slide 45
Poor Pretreatment :

Slide 48
 Poor Pretreatment :

• Feed Spacer Displacement

• Membrane layer delamination
Slide 49
 Typical Process Units in Power Plants
SMBS Antiscalant

Cartridge
Clarifier Media Filter or Activated
Filter
Ultra-Filtration Carbon
(5um)

•Turbidity •Turbidity •Turbidity •Turbidity & SDI (Opt)

•O&G •SDI (Opt) •SDI •Free Chlorine/ORP
•Conductivity

Ion Brackwish
Product Reverse Osmosis Seawater
Exchanger
(BWRO) Reverse Osmosis
(SWRO)
•Conductivity •Conductivity •Conductivity
/ Resistivity Slide 50
 Part 3
RO Feed Water Monitoring

Slide 51
 RO Feed Water Limiting Conditions
• Turbidity <1NTU (0.3NTU)*
• SDI <5.0 (3.0)*
• Temperature <45oC
• Oil & Grease Absent
• Free Chlorine <0.1ppm (Dechlorination is recommended)
• Organics Free of harmful organics
• pH 3-10
Remark:
1. Pretreatment is required to achieve above
2. If there is no monitoring / treatment unit for transition metals, it’s
strongly recommended not to have any free chlorine in RO feed
3. *with MF/UF pretreatment
Slide 52
Silt Density Index (SDI)

Slide 53
 Silt Density Index (SDI)
• A measurement of the rate that a 0.45 micron filter pad
plugs. A standard method used to predict the rate of
membrane fouling.
• Membrane manufacturers recommend <5 SDI for a 15
minute test.

Slide 54
 Silt Density Index (SDI)

• Ti = Initial time (seconds) required to collect 500 ml sample

• Tf = Time (seconds) required to collect 500 ml sample after 15
minutes or less.
• T= Total test time in minutes (must be a 15 minute test)

Slide 55
 Part 4
RO Start Up & Shut Down

Slide 56
Start Up : Step 1 – Preservative Flushing
• To preserve elements from biological growth and to help
maintain performance over time, Hydranautics
Composite Polyamide type membranes are stored in
dionized water, a 0.99% sodium bisulfite solution, or a
combination of 0.99% sodium bisulfite and 10%
propylene glycol solution.
• It is therefore advised to flush membranes prior to use to
eliminate residual preservatives in the product stream.

Slide 57
 Start Up : Step 2 – RO System Start-Up
• A low pressure flush to purge air from the membranes is
always recommended before a high pressure startup
• This can be accomplished through the use of a soft-start
mechanism, or a variable frequency drive.
• Failure to do this can result in a water hammer that can
cause physical damage to the RO/NF membranes.
• The permeate valves should always be open to drain
during this flush to prevent damage to the membranes.
• After the air has been purged from the system the feed
pressure should be increased gradually up to the working
pressure of the RO unit Slide 58
 Start Up : Step 3 – RO System Monitoring
• Monitor the plant performance and re-adjust them in
case they change.
• Membrane systems are operated based on constant flow
rates and recovery.
• Pressures can varying depending upon feed water
composition, water temperature, membrane condition,
and operating parameters such as recovery.

Slide 59
RO System Shut Down –Seawater Systems
• Upon shutdown for seawater systems, a flush with RO/NF
permeate is recommended to remove the high
concentration of salts from the membranes.
• The permeate valves should be open to drain during this
flush to prevent damage to the membranes.
• If RO permeate is temporarily unavailable, the membranes
should be flushed with RO feed at low recovery (with brine
valve wide open).
• The membranes should then be flushed with RO permeate
as soon as it is available.
• The seawater RO system should not be left unflushed with
a high concentration brine on the membrane surface. Slide60
 RO System Shut Down – Short Term
Short Term Membrane Storage in Pressure Vessel:
• Normally 1 to 5 day intervals (based on biological
activity)
• Perform normal Post-Service Flush and Air Venting with
Feed Water
• Reflush at 5 day intervals (up to 30 days)
• Flushing with 1 % sodium bisulfite reduces risk of bio-
growth

Slide 61
 RO System Shut Down – Long Term
Long Term Membrane Storage in Pressure Vessel:
• Normally more than 30 days
• Clean the RO elements in place
• Flush and store with approved biocide (15% Isothiazalon,
1% sodium bisulfite or 0.1-1% formaldehyde)
• Re-flush and store in biocide every 30 days if temp is < 27
C
• Re-flush and store in biocide every 15 days if temp is >28
C

Slide 62
 Part 5
RO System Monitoring

Slide 63
RO System Monitoring

Slide 64
 Parameters affect RO Performance
• Recovery
• Feed Water Temperature
• Feed Water TDS
• Feed Water pH
• Operating Pressure

65
 RO Data Normalization
• Normalization allows comparison operation at a specific
set of conditions to a reference set of conditions
• This allows the user to determine whether changes in
flow or rejection are caused by fouling, damage to
membrane, or are just due to different operating
conditions

Slide 71
 RO System Parameters to Monitor
Measured Parameters
1. Pressure
– Feed, Reject & permeate
2. Flow
– Feed, Reject & permeate
3. Conductivity
– Feed, Reject & permeate
4. Feed Temperature
Calculated Parameters
1. Pressure drop
2. Salt passage
3. Normalized permeate flow
4. Normalized salt passage
5. Normalized pressure drop
Slide 72
 Normalization of Operating Data
• Normalize membrane permeate flow, salt passage and
pressure drop
• Normalization removes effects of
– Temperature
– TDS
– Recovery
– Pressure
– Flow
• Above values are compared to those of the plant
commissioning values
Slide 73
Normalized Salt Passage

Slide 74
Normalized Permeate Flow

Slide 75
Normalized Differential Pressure

Slide 76
 Part 6
RO Cleaning

Slide 77
 When do we clean a RO?
• When normalized permeate flow decreases 10-15%
from last cleaning
• When normalized permeate quality decreases 10-
15% from last cleaning
• When normalized pressure drop (feed-to-reject)
increases 10-15% from last cleaning
• Prior to a long-term shutdown
• As a matter of routine maintenance
Slide 78
General RO Chemical Cleaning Procedures
RO Cleanup Skid

10-micron RO Stage
Clean-up Filter
RO Clean-up Pump
Tank

Concentrate

Permeate

Slide 79
 General RO Chemical Cleaning Procedures
(SWRO)
• Flushing with permeate to remove all seawater in membrane
Step 1

• High pH cleaning (pH10.5-11.5)

Step 2 • Recirculation, Soaking, Recirculation

• Flushing with permeate until reject pH similar to feed pH

Step 3

• Low pH cleaning (pH2.5-3)

Step 4 • Recirculation, Soaking, Recirculation

• Flushing with permeate until reject pH similar to feed pH

Step 5
Slide 80
 Part 7
RO Troubleshooting

Slide 81
 Initial Troubleshooting Steps
• Get normalized data
• Get plant history (i.e. cleaning history, any
membrane change-outs, past problems)
• Check instrumentation and verify that
everything is properly calibrated
• Determine if problem is with salt passage or
product flow (fouling/scaling)

Slide 82
 Salt Passage Problems
• Do a complete pressure vessel profile
• Probe any vessels that show higher than
expected conductivity
• Remove elements from high conductivity
vessels and inspect o-rings, adapters,
interconnectors, and elements

Slide83
 Vessel Profiling

25 27 24 1st stage

28 24 118 1st stage

49 224 52 2nd stage

Slide 84
 Vessel Probing
• Insertion of tubing into permeate tubes to
determine conductivity levels along length of
vessel (see TSB 114).
• Points of higher conductivity indicate leakage
areas.
• Need to determine whether o-ring leakage or
element leakage is the cause.

Slide 85
 Bubble Test Unit

Slide 87
 Fouling/Scaling Problems
• Check Delta P’s by stage to determine if fouling is at the
front end or back end of the RO system (fouling/scaling
never starts in the middle of the system, it always starts
at the front or back and spreads to the middle)

• If unsure, remove lead and tail elements, drain for 5

minutes and weigh the elements. If one element is much
heavier than the other then this is usually where the
fouling is occurring

Slide 88
 Front End High DP Causes
• High Delta P’s in the front of the RO system can be
caused by:
a) Particulates (sand, PVC pipe shavings, carbon fines,
etc.). Could be due to possible bypassing of cartridge
filters
b) Biological fouling – it is very important to sanitize the
feed lines after cleaning the RO membranes for
biological fouling, therwise the bugs will spread right
back into the RO system
c) Colloidal or metal oxide fouling

Slide 89
 Possible Solutions for Front End Fouling
• Remove lead elements and reverse direction (move brine
seal to other end of element) and put in a tail position in
the system. This will help to flush out the foulant.
• If the system allows it, you can flush the elements from
the brine to feed end and this will help to flush out any
debris on the feed end of the elements.

Slide 90
 Back End High DP Causes
• Precipitation of sparingly soluble salts (scaling).
Some of the most common scaling salts are calcium
carbonate, calcium sulfate, barium sulfate, strontium
sulfate, calcium phosphate (in wastewater plants)
and polymerized silica.

Slide 91
 Trouble Shooting Questions (1)
1. Better to run some trains 24/7 rather than all trains
some of the time.
2. Break Tank
– What kind of material is used?
– Check for biogrowth
– Protected from sunlight (black tank) or is the tank
translucent?
3. Startup. Was the system properly flushed before
loading elements?

Slide 92
 Trouble Shooting Questions (2)
4. SDI. How frequent are they taken?
5. Check Chemical injection
– Cl2, SBS, H2SO4,NaOH
6. Cartridge Filter
– 1 to 10 micron. Watch CF Dp closely. Check filters
within the first 24 hours of startup to ensure proper
seating and confirm integrity.
7. Check lead elements for debris and tail elements for
scale

Slide 93
 Trouble Shooting Questions (3)
9. Check calibration and location of instrumentation
10. How frequently does the system operate? Is it flushed
at shutdown?
11. Ensure proper placement and seating of O-rings and
Interconnectors
12. Has permeate backpressure been accounted for?
13. Is concentrate line sized to accommodate flushing and
cleaning?
14. Feed Water Quality
– Consider Scaling Potential
Slide 94
Some Common RO System Problems

Slide 95
 1. Permeate Backpressure
When a RO system shuts down, the permeate pressure
should be very minimal. If the permeate pressure
exceeds 0.35 bar (5 psi), damage to the glue lines can
occur.

Remedies :
• Install check valves or pressure relief valves on permeate
lines.
• Make sure the permeate from individual vessels are
isolated if they are removed from service.
• In 2 pass – Single pump systems – design system to
release the 1st pass permeate pressure correctly.
Slide 96
 2. Permeate Valve Closed During a Flushing or
Cleaning Operation
When a permeate valve is closed during flushing or
cleaning, the permeate pressure will equal the feed
pressure. If there is significant pressure loss from feed to
concentrate, this can result in the permeate pressure at
the tail end of the RO system being much higher than the
concentrate pressure. This results in glue line damage at
the brine end of the tail elements.

Remedies :
• Do not install valves on permeate lines. If valves are
required, be sure to design so that the permeate
pressure can never exceed the concentrate pressure.
• Install pressure relief valves.

Slide 97
 3. Permeate Suckback with Chemical Addition
When a RO system shuts down, osmotic forces tend to pull
permeate water back into the RO elements to dilute the
high concentration of salts on the membrane surface.
This can result in membrane damage if the permeate has
been treated with chlorine, caustic, etc.

Remedies :
• Permeate flush upon shutdown.
• Install spring check valves on permeate line.
• Have permeate dump into a tank so that it cannot be
drawn back into system.
• Install vacuum breakers.

Slide 98
Thank You
Slide 99
Low Differential (LD) Technology

Hydranautics, a Nitto Group Company

Slide 100
The Low Differential Technology: Features

1. Enhanced Membrane Chemistry

• For increased chemical resistance

2. Innovative Spacer Design

• To minimize trapping of small colloidal particles

3. Proprietary Vented Seal Carrier

• To eliminate pressure shock damage during system startup

Slide 101
 NaOH tolerance of the CPA5-LD

100
99.70% Testing Conditions:
~99.69% • pH 12 NaOH soln.
Rej. Retention Rate (%)

• 3 hrs/soaking
99 • Temp 20o C
• NaCl Conc.: 2000 mg/l
• Pressure: 225 psi (1.55
MPa)
98
• Recovery: 15%

97
0 20 40 60 80 100
Number of pH 12 NaOH Soaking
Slide 102
 2. Improved Feed Spacer Design

✓ Thick spacer with modified geometry

✓ Same membrane surface area per element

Advantages :
• Lower Differential Pressure
• Lower Fouling Potential
• Improves the Effectiveness of Membrane Cleanings
• Improved Flux Distribution Between the Lead and Tail
Elements

Slide 103
Lower Differential Pressure for improved spacer
Differential Pressure (kPa)

Brine Flow rate (m3/h)

Slide 104
 Lower Fouling Potential

Innovative feed
Improved Flux
spacer design Chemically Improves the
Distribution
prevents enhanced to Effectiveness of
Between the
trapping of prevent Membrane
Lead and Tail
small colloidal biofouling Cleanings
Elements
particles

Particle
A

A
Filament

Flow

Innovative Feed Feedspacer Conventional Feedspacer

Clearance A of 34mil is 20% wider than 28mil’s

Slide 105
 Lower Fouling Potential
Flow

Particles Plugged flow

pass through channel of
34mil spacer 28mil spacer

Slide 106
 Lower DP &Fouling Potential
5

28 mil
Delta-Pressure of 1st stage (bar)

4 CIP
CIP CIP
CIP
3
CIP

2
31 mil
CIP
1
34 mil
0
0 30 60 90 120 150 180 210 240 270
Operation Period (days)

Actual operational test data

•Feed: city water with SDI 4-5 (Max = 6)
•4 elements in a pressure vessel first stage
•28 mil, 31 mil, 34 mil Slide 107
 3. New ATD Design

Prevents accidental pressure shocks to element shell !

Slide 109
 New ATD Design

Possible to release air between element and vessel reduces

element burst risk
Slide 110
 Pressure behavior in vessel

Residual Air :Air

Pin P1 P2

:Water

High flow Diff. Press. At

1stElement Outer shell 3rdElement
(internal > external)

Vessel
ATD

Brine Seal

P in : Feed
P1 : Outer shell of 1st. Ele.
P2 : Outer shell of 2nd. Ele. Slide 111
 Pressure Profile After Start Up
Conventional New ATD

Pin: Feed
P1: Outer
shell of
1st. Ele.
P2: Outer
shell of
2nd. Ele.
Slide 112
 Demonstration of start-up

LD technologyTM Company A

Slide 113
LD Technology : Key Benefits

Longer Reduced
Membrane Cleaning
Life Costs

Improved
Increased
Permeate
Productivity
Quality

Slide 114
Thank You
Slide 115
 Confidential

Ion Exchange Resins of MCC

for Power Plant Application

Mitsubishi Chemical Corporation

Separation Materials Department
Dec. 2017

1
 About Mitsubishi Chemical Holdings
Mitsubishi Chemical Holdings Corporation

Established October 3, 2005

Head office 1‐1, Marunouchi 1‐Chome, Chiyoda‐ku, Tokyo
President & CEO Hitoshi Ochi
Paid-in capital ¥50.0 billion Hitoshi Ochi
Representative Corporate Executive Officer
Listings Tokyo Stock Exchange President & CEO
Profile＊ Activities Management of the Group companies
(Development of Group strategies, allocation of financial resources, etc.)
Performance Products, Industrial Materials, and Health Care
Business domains ¥3,823.1 billion ( About 35 billion USD )
Consolidated net sales ¥280.0 billion ( About 2.5 billion USD )
Consolidated operating
income 68,988
Group employees http://www.mitsubishichem‐hd.co.jp/english/
Website
*All figures are for the year ended March 2016（FY2015）.
5th Largest
The Mitsubishi Chemical Holdings Group consists of about 750 companies:
the holding company Mitsubishi Chemical Holdings, its about 500 consolidated subsidiaries including
Mitsubishi Chemical, Mitsubishi Tanabe Pharma, Mitsubishi Plastics, Mitsubishi Rayon,
Life Science Institute, Taiyo Nippon Sanso, and its about 80 equity-method affiliates.
Source: Latest data for each company from
Under our corporate brand “THE KAITEKI COMPANY,” Thomson Reuters FORTUNE Global 500 (as of Sept. 2017)
we promote corporate activities aiming to realize KAITEKI. Industry : Chemicals

2
 Organization
Holding company Function-sharing companies
Mitsubishi Chemical Holdings Corporation* The KAITEKI Institute, Inc. Apr. 2009~

Mitsubishi Chemical Holdings America, Inc. Nov. 2010~

Consolidated net sales: ¥3,823.1 billion 100％
Mitsubishi Chemical Holdings (Beijing) Co., Ltd. Jan. 2011~
Employees: 68,988
Mitsubishi Chemical Holdings Europe GmbH Nov. 2012~

* Listed <Business domain> Mitsubishi Chemical Holdings Corporate Staff, Inc. Apr. 2013~
All figures are for the year
ended March 2016 (FY2015) Performance Products
MCHC R&D Synergy Center, Inc. Apr. 2014~
Industrial Materials

Health Care

To be integrated as Mitsubishi Chemical Corporation on April 1, 2017 Operating companies

100％ 100％ 100％ 56.3％ 100％ 50.6%

Mitsubishi Chemical
Corporation
Oct. 2005~
Consolidated net sales:
¥1,746.0 billion
Group employees
22,709
[ Line of businesses ]
Performance products,
Industrial materials etc.
Mitsubishi Plastics, Mitsubishi Rayon
Inc. Co., Ltd.
Apr. 2008~ Mar. 2010~
Consolidated net sales: Consolidated net sales:
¥480.8 billion ¥548.5 billion
Group employees Group employees
9,486 9,396
[ Line of businesses ] [ Line of businesses ]
Chemicals, Plastics,
Plastics products,
Synthetic fibers,
Inorganic fiber materials
Carbon fibers &
etc.
composite materials,
Water treatment etc.
Mitsubishi Tanabe Life Science Taiyo Nippon Sanso
Pharma Corporation* Institute, Inc. Corporation*
Oct. 2007~ Apr. 2014~ Nov. 2014~
Consolidated net sales: Consolidated net sales: Consolidated net sales:
¥431.7 billion ¥136.0 billion ¥641.5 billion
Group employees Group employees Group employees
8,125 4,751 14,127
[ Line of businesses ] [ Line of businesses ] [ Line of businesses ]
Health and Medical ICT,
Pharmaceuticals etc. Industrial gases
Advanced Medication
& related equipment /
Drug Development and
devices etc.
Manufacturing Solutions

Group companies Group companies Group companies Group companies Group companies Group companies

Separation Material Department 3

Mitsubishi DIAION

- Long history over 70 years (since 1946)

- Wealth of experience and know-how
- The most stable quality in the world
- Excellent technical support and services
- Around 40% market share in Japan
- We expanded production capacity
starting with new production site
in Korea.

MCC head office in Tokyo

4
Overseas Operation of DIAION

HALAL
Samyang Fine
Resindion s.r.l.
Technology (Korea) New factory from 2016
(EU, ME, Africa)
Itochu Chemical
America
Mitsubishi Chemical
Tokyo head office (Japan)
HALAL
MCI (India) Mitsubishi Chemical
Kurosaki Plant (Japan)
MCT (Thailand) HALAL
MCS (Singapore) Tai-Young Chemical (Taiwan)

MCCI (Indonesia)

Production site / Sales office

Sales office

5
Contents Confidential

1. Ion Exchange Resin and Manufacturing Process

2. Power Plants and Ion Exchange Resin

3. Ion Exchange Resin for Power Plants

6
DIAION’s Brand Separation Material Confidential

Cation resins
Ion exchange resins
Anion resins

Chelating resins

MCC has approx. 300 grades.

Synthetic adsorbents
MCC has produced IER products
Protein separation materials for 70 years!

MCI® GEL
Separation materials for analysis (e.g. HPLC)

7
What is IER Confidential

Plastic beads
Particle size: 0.2～0.8 mm

Cation Exchange Resin ： Exchange cation

Anion Exchange Resin ： Exchange anion

Cation Exchange Resin Anion Exchange Resin

-CH2CH2- -CH2CH2- -CH2CH2- -CH2CH2-

COO-

SO3- CH2-N(CH3)3+ CH2-N(CH3)2

<Strongly Acidic> <Weakly Acidic> <Strongly basic> <Weakly basic>

8
Deionization by IERs Confidential

9
Manufacturing Process of IER Confidential

Polymerization Anion Exchange resin

STM DVB
Animation
＋
CH2Cl CH2NR3Cl

Chelate resin

CH2COOH
Gel type N
CH2COOH

Cation Exchange Resin

Porous type

Sulfonation
High Porous SO3 Na
Synthetic adsorbent

10
Polymerization Confidential

CH CH2 CH CH2
Cross‐linkage (%)

CH CH2
= 100
Monomer
Styrene Divinylbenzene
water (St) (DVB)

Polymerization
Stirring Stirring/heat

Polymer

11
Functionalization Confidential

12
Porous Types Confidential
CH CH2 CH CH2

X
CH CH2
Monomer
Styrene Divinylbenzene Porogen
water (St) (DVB)

Polymerization
Stirring Stirring/heat
X X X
Polymer X X
X

13
Porosity control Confidential

MR
Porous Gel MR 高大孔型
Macroreticuler
(Macroreticuler)
Macro Porous

Macro pore Micro pore Macro pore

(10～10000Å) (～300Å) (10～1000Å)

DVB (%): 2% < Porous, Gel < 14～16% < MR

Reaction Rate: Porous > Gel > MR
Osmotic Resistance: MR > Porous > Gel
Porous: reaction rate, osmotic resistance, resistant to organic fouling
Gel: Oxidation-resistant, physical strength
14
Resins with Uniform Particle Size Confidential

Gaussian Type Uniform type

SK1B UBK08

SA12A UBA120

15
Resins with Uniform Particle Size Confidential

Particle size distribution

Cation exchange resin Anion exchange resin

Particle size (μm) Particle size (μm)

16
DIAION Product Line up Confidential

Resin Type Ion-exchangeable groups DIAION Grade

Strongly acidic ＳＫ series

－ＳＯ ３ Ｎａ
－ ＋ ＰＫ２００ series
Cation resins ＵＢＫ series

Strongly basic ＳＡ１０Ａ series

－Ｎ ＋（ＣＨ ３） ３Ｃｌ －
Anion resins ＰＡ３００ series
（TypeⅠ）
－Ｎ ＋（ＣＨ ３） ２（ＣＨ ２ＣＨ ２ＯＨ）Ｃｌ － ＳＡ２０Ａ
（TypeⅡ） ＰＡ４００ series
Weakly acidic ＷＫ１０,１１
－ＣＯＯＨ ＷＫ４０
Cation reins
Weakly basic －ＮＨ-（ＣＨ ２ＣＨ ２ＮＨ） ｎ ＷＡ２０，２１J
ＷＡ１０
Anion resins －Ｎ（ＣＨ ３） ２ ＷＡ３０
－ＣＨ ２Ｎ（ＣＨ ２ＣＯＯＮａ） ２ ＣＲ１１
－ＣＨ ２ＮＨ（ＣＨ ２ＣＨ ２ＮＨ） ｎＨ ＣＲ２０
Chelating resins
－ＣＨ ２Ｎ(CH 3)ＣＨ ２ （ＣＨOH） ４ＣＨ ２ＯＨ ＣＲＢ０３，０５

ＨＰ series
Synthetic ＳＰ２００ series
No ion-exchangeable group ＳＰ８００ series
adsorbents
ＨＰＭＧ series

17
Contents Confidential

1. Ion Exchange Resin and Manufacturing Process

2. Power Plants and Ion Exchange Resin

3. Ion Exchange Resin for Power Plants

18
Purpose of Water Chemical Control in Power PlantsConfidential

1. Maintain the safety, stability and Ion exchange resin:

reliability of plants’ constituent Cleanup circuit water
materials
Needs:
2. Keep the safety, stability and reliability
of fuel, and prevent fuel damage Ion exchange

3. Reduce radiation expose on workers Oxidation resistance

4. Decrease the quantity of radioactive

Crud removal
waste

※ CRUD : Chalk River Unidentified Deposition

Particulate and /or colloidal metal corrosion products

19
 IER for Thermal Power Plants Confidential

Generator
タービン
Turbine 発電機；Ｇ
脱硫
SOx ＥＰ 脱硝
NOx ；T
removal removal 定子冷却水
Stator固定子冷却；
cooling water：
ＳＭＮ1
SMN1
Desulfurization Denitration
Boiler Condenser
復水器 ；Cond.
脱硫排水処理で
Waste water treatment：
Fuel:
燃料 ； 火炉
ＣＯＤ吸着用
WA30C 石炭、
ＷＡ３０Ｃ Coal
油 、
Heavy
ＬＮＧ等oil
LNG, etc.

給水加熱器 CP Condensate；ＣＰ
復水ポンプ pump
Feed water heater
Make up water system
脱塩（
Raw４Ｂ ５Ｔ）
water Regen.
再生 Regen.
再生
Condensate Polishing
CO2

(CP)
Resin for CP （MB）：
W.C S.C W.A S.A ＰＫ２２８Ｇ／ＰＡ３１２Ｌ
CSK40/CPA12
D.G
Deionized CPK80/CPA02 20 20
water
Contents Confidential

1. Ion Exchange Resin and Manufacturing Process

2. Power Plants and Ion Exchange Resin

3. Ion Exchange Resin for Power Plants

21
 IER for Thermal Power Plants Confidential

Generator
タービン
Turbine 発電機；Ｇ
脱硫
SOx ＥＰ 脱硝
NOx ；T
removal removal 定子冷却水
Stator固定子冷却；
cooling water：
ＳＭＮ1
SMN1
Desulfurization Denitration
Boiler Condenser
復水器 ；Cond.
脱硫排水処理で
Waste water treatment：
Fuel:
燃料 ； 火炉
ＣＯＤ吸着用
WA30C 石炭、
ＷＡ３０Ｃ Coal
油 、
Heavy
ＬＮＧ等oil
LNG, etc.

給水加熱器 CP Condensate；ＣＰ
復水ポンプ pump
Feed water heater
Make up water system
脱塩（
Raw４Ｂ ５Ｔ）
water Regen.
再生 Regen.
再生
Condensate Polishing
CO2

(CP)
Resin for CP （MB）：
W.C S.C W.A S.A ＰＫ２２８Ｇ／ＰＡ３１２Ｌ
CSK40/CPA12
D.G
Deionized CPK80/CPA02 22 22
water
 Technical Trend of Thermal Power Plants in Japan Confidential

Purpose of water quality control of thermal power plants：

‐ Keep good quality of water and steam, and prevent scale formation
and corrosion of materials at boiler, turbine and other equipment.

‐ Maintain plants in good situation, improve the efficiency of power

generation.
Large scale, high steam pressure → requires higher quality of water.

23
 Technical Trend of Thermal Power Plants in Japan Confidential

IER for condensate polishing：

Combination of porous type CER and porous type AER are wildly
selected.
→ Merits：Easy separation of CER/AER, resistant to organic fouling,
higher osmotic strength.
Recently, SO42‐ level in water is controlled more strictly
→ Some customers consider using high cross‐linkage gel type CER and
porous type AER
Ionic form:
It depends on customer. Some customers purchase H/OH form resins,
because it is easier to control the water quality at operation start‐up.

24
IER for Make‐up Water System Confidential
Raw water
condition
System WAC SAC MB WBA SBA
Hard water Softener UBK08

Type I
(Standard UBK08 D
Deionizer) 2B3T or UBK10 G UBA100

Type II
UBK08 D
UBA200
or H
UBK10 G

D Type I
UBK08
High salt 3B4T or H
UBK10 G WA30 UBA100
Type I
High Ca, Mg UBK08 D
and high salt
4B5T WK40L
or H
UBK10 G WA30 UBA100

(High purity UBA100P

Small scale)
MB UBK08 OH H
H OH or UBA200P
25
2B3T: 2 Beds 3 Towers, MB: Mix Bed, DG: Degasifier, H and OH: Ionic form
IER for Condensate Polishing Confidential

Gel type Porous type

Na‐form H‐form CL‐form OH‐form

UBK10B UBK10BH
Cation resins CPK80 CPK80H
CSK40 CSK40H
High cross‐linkage

CPA12 CPA12OH
Anion resins UBA10A UBA10AOH

CER：CSK40H：
High cross‐linkage（14%）gel type： Oxidation resistance, less leachables

AER：CPA12OH：
Porous type： Resistant to organic fouling, high PSS adsorption capacity
＊PSS：Leachables of CER（polystyrene sulfonate）.
PSS could cause organic fouling of AER.
26
Development and Design of IER Confidential

Factors ：
‐ Ion Exchange Capacity
‐ Reaction Rate
‐ Ion Selectivity
‐ Leachable
Initial Leachables
Oxidation Leachables: CER
Heat‐decomposition Leachables: AER
‐ Adsorption of Organic Substances
PSS adsorption capability of Anion resin
(PSS: polystyrene sulfonate)

27
Exchange Capacity and Reaction Rate Confidential

High cross‐linkage % → High IE capacity, low reac on rate

IE Capacity （Gel type CER） Reaction Rate （Na+ adsorption of Gel type CER）
90 2.8
IE Capacity 50

80 2.4
40

Reaction Time（Sec.)
IE Capacity（mmol/mL）
Water Content（%）

70 2
Cap. 30
60 Water 1.6
20
50 1.2
Water 10
40 0.8
0
30 0.4 0 5 10 15 20
0 5 10 15 20
DVB (%)
DVB (%)

28
Ion Selectivity Confidential

‐ Different ion‐exchangeable groups → different ion selectivity.

‐ High Cross‐linkage (%) → high ion selec vity.
→High DVB%：molecular sieve effect!
‐ Strongly acidic CER （SK, PK）
AL3+ >> Ba2+ > Ca2+ > Mg2+ >> K+ > NH4+ > Na+ > H+
High ion valency → High selec vity

‐ Weakly acidic CER （WK）

H+ > Ba2+ > Ca2+ > Mg2+ >>> Na+
High H+ selectivity（Easy regeneration）

‐ Strongly basic AER（SA, PA）

SO42‐ > NO3‐ > CL‐ > HCO3‐ > SiO2 > OH‐
High ion valency → High selec vity

‐ Weakly basic AER （WA）

OH‐ > SO42‐ >NO3‐ > CL‐
High OH‐ selectivity （Easy regeneration）
29
Leachables Confidential

Initial Leachables

Oxidation Leachables: CER

Heat‐decomposition Leachables: AER

30
Leachables from IER Confidential

Leachables of resins

AER
AER’s leachables
CER’s leachables CER

AER’s leachables AER’s leachables

CER’s leachables
CER’s leachables

AER’s leachables
CER’s leachables
AER’s leachables
CER’s leachables
AER CER

Surface fouling
CER’s leachables AER’s leachables
In mixed beds：
-CER adsorbs AER’s leachables
31
-AER adsorbs CER’s leachables
Oxidation Leachables (CER) Confidential

・CER could be oxidized easily.

・Main components of leachables are PSS（polystyrene sulfonate）
・Oxidation resistance of CER can be enhanced by increasing cross‐linkage %.

Decomposition of CER DVB% vs. Oxidation‐resistance of CER

100
‐ CH‐CH2‐CH‐CH2‐

Remaining IE capacity (%)

95
DVB 12%
90
85
DVB 10% Swelling by oxidation
‐ CH‐CH2‐ ＳＯ3‐ 80
Oxidation 75
70 DVB 8%

H2SO4 ‐ CH‐CH2‐ 65
60 Oxidation resistance
Decomposition 55 ：12% 〉10% 〉8%
of IE groups
ＳＯ3‐ 50
0 0.5 1 1.5 2

High MW leachables (PSS) Run time (years)

32
Oxidation Leachables (CER) Confidential

图6 陽樹脂の架橋度vs溶出物
DVB% of CER vs. Leachables

1200 80
Oxidation‐resistant CER

TOC (ppm) (TOC ppm)

1000 70

Reaction
800 60

反応時間
Amount of leachables

600 50

time
(秒)(sec.)
400 40

200 30

0 20
5 10 15 20
DVB%(%)
交联度

14% cross‐linkage：DIAION CSK40H

33
Oxidation Leachables (CER) Confidential

Cross‐linkage % vs. MW distribution of PSS

MW distribution of leachabls (PSS) MW distribution of leachabls (PSS)

20 12

Before use Before use

10
16
After oxidation

ratio %
ratio %

存在比率（％）
存在比率（％）

8
12

After oxidation

Existing
6
Existing

8
4

4
2

0 0
1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
分子量（MW）
MW
分子量（MW） MW

Gel type CER with 14% cross‐linkage Gel type CER with 8% cross‐linkage

Gel type CER with high DVB% has good oxidation‐resistant ability！
34
Heat‐decomposition Leachables (AER) Confidential

・AER could be decomposed by heat easily.

・Main components of leachables are trimethylamine（TMA）

Decomposition
強塩基樹脂の分解 of strongly basic AER 水処理使用強塩基樹脂の劣化例
Time course of IE capacity of AER in water treatment use

70

交換容量低下率（％）
CH CH2
弱塩基化

of IE capacity (%)
Change into weakly basic AER SSCⅡaerated
60
CH CH2 CH3 50 SSCⅡdeaerated
CH2 N
CH3 40
＋ TotalⅡ
CH3 30
CH3OH SSCⅠ
CH2 N CH3 20
Reduction ＴｏｔａｌⅠ
CH3 CH CH2
10
CH3 0
+
交換基脱落
Decomposition of CH2OH
N
CH3
CH3
0 1 2 3 4
ion exchange groups
TMA 使用時間（年）
Run time (years)
使用年数（年）

35
Adsorption Capacity of Organic PSS (AER) Confidential

・CER’s leachables (PSS) can removed by AER.

・Regarding PSS adsorption, porous type AER has high capability.

PSA（分子量59
PSS (MW5000) 00）吸着量の比較
adsorption capacity of each type of resin
0 .8
of PSS adsorption (mmol/L‐R)

DIAION
0 .7 Porous
吸附量（mmol/L‐R）

0 .6
PSSPSA吸着量(mmol/L-R)

0 .5 PA312LT
DIAION
SA12AOH
0 .4 Gel
SA10AOH
Dow550A
Other Brand
0 .3 DIAION
Gel
0 .2
Amount

0 .1 Gel

0 Porous type AER：

0 0 .2 0 .4 0 .6 0 .8 DIAION CPA12OH
添 加 したPSS（mmol/L‐R）
Added PSA量 （ mmo l/ L- R)

Porous type AER：Resistant to organic fouling ！ 36

Adsorption Capacity of Organic PSS (AER) Confidential

阴树脂的物理结构和PSS的吸附性能
图11
Column阴树脂的物理构造和PSS吸着性能
test of PSS adsorption of AER
（用交换柱的动态实验）
（用交换柱的连续通水实验）
0.030
in treated water (mmol/L)

0.025
出水的PSS浓度(mmol/L)

Gel type
0.020
凝胶型阴树脂 大孔型阴树脂 通液条件
Conditions:
0.015 树脂量 : 10 mL
Resin: 10mL, 树脂层
Height: : 47mm
47mm
Porous type PSS分子量: 4600
MW of PSS: 4600
PSS浓度 : 0.025
PSS conc.: mmol/L
0.25mmol/L
0.010
流速 : SV = 30
PSS conc.

Flow rate: SV=30

温度 : 室温( 23 ℃ )
Temp.: room temp. (23C)
0.005 交换柱 : 内径16.5mmφ玻璃柱
Column: 16.5mmφ

0.000
0 5 10 15 20 25 30 35 40 45 50
Volume处理水量（BV）
of treated water (BV)

Porous type AER is resistant to organic fouling！

Porous type AER：
DIAION CPA12OH 37
Adsorption of Organic Substance (PSS)

AER’s
图12 PSS Adsorption Model
PSS对于阴树脂吸着的模式

Gel
凝胶型type Porous
大孔型 type

Porous type AER：Highly resistant to organic fouling！

38
Organic fouling of AER Confidential

‐ Organic substances cause organic fouling of AER, and affect its performance.
‐ PSS with high MW could easily cause severe organic fouling of AER.
PSS MW vs. Ion 吸着量の脱塩に及ぼす影響
Exchange Capability of AER
PSS分子量/吸着量对于阴树脂脱盐能力方面的影响
PSA分子量/
通 水 条 件 ：Column
Conditions: ｶﾗﾑ3
柱 0Φ 30 × 1 0 0 0 mmH
X 1000mmH
樹脂量： 3 5 7 mL 層高： 5 0 c m
Resin vol.: 357mL, Bed depth: 50cm 流 速 ： S V 7 0
原 液 ： N a2 S O 4 3 0 μ S / c m
Inlet water: Na2SO4 30μS/cm, flow rate: SV=70
20
18
16
水比抵抗（MΩ・cm）
（MΩ・ｃｍ）

14
12
10
处理水的电阻值
resistivity

8
6
処理
Outlet

4 MW10000
MW50000
2 MW500000

0
0 0 .1 0 .2 0 .3 0 .4 0 .5
PA3 1 2 在阴树脂上附着的PSS量
LTに吸着したPSA量（ mmo l/ L- R)
AER’s PSS adsorption (mmol/L‐R) 39
Organic fouling of AER Confidential

Column test of PSS adsorption

图8 PSS吸着试验 : Impact of MW
- PSS分子量的影响
0.025
分子量 4600
in treated water (mol/L)

0.020
出水的PSS浓度(mmol/L)

MW:4600 分子量 3610

0.015 Conditions:
通液条件
Resin: :10mL,
树脂量 10 mLHeight:
树脂层47mm
: 47mm
MW:3610 PSS conc.: 0.25mmol/L
PSS浓度 : 0.025 mmol/L
0.010 Flow: SV
流速 rate: SV=30
= 30
温度 : 室温( 23temp.
Temp.: room ℃ ) (23C)
Column: 16.5mmφ
交换柱 : 内径16.5mmφ玻璃柱
PSS conc.

0.005

0.000
0 5 10 15 20 25 30 35 40 45 50
Volume处理水量（BV）
of treated water (BV)

Important!：
Control the amount of leachables of CER
Control the MW of leachables of CER
40
Comparison (Cross‐linkage%) Confidential

Low DVB% High DVB%

Ion exchange capacity Low High
Reaction rate High Low
Ion selectivity Low High
Oxidation resistance Low High
Leachables Much Less
Adsorption capability High Low
of organic substances
CRUD removal capability* High Low
＊Regarding CRUD removal, many factors could influence the removal capability,
for example, type of CRUD, surface structure of resin beads and so on.

41
Comparison (Physical Structure) Confidential

Gel type Porous type

Ion exchange capacity High Low
Reaction rate Low High
Ion selectivity － －
Oxidation resistance High Low
Leachables Less Much
Adsorption capability Low High
of organic substances
CRUD removal capability* Low High
＊Regarding CRUD removal, many factors could influence the removal capability,
for example, type of CRUD, surface structure of resin beads and so on.

42
 Confidential

Products Line‐up of DIAIONTM

for Power Plants Application

43
IER for Make‐up Water System Confidential
Raw water
condition
System WAC SAC MB WBA SBA
Hard water Softener UBK08

Type I
(Standard UBK08 D
Deionizer) 2B3T or UBK10 G UBA100

Type II
UBK08 D
UBA200
or H
UBK10 G

D Type I
UBK08
High salt 3B4T or H
UBK10 G WA30 UBA100
Type I
High Ca, Mg UBK08 D
and high salt
4B5T WK40L
or H
UBK10 G WA30 UBA100

(High purity UBA100P

Small scale)
MB UBK08 OH H
H OH or UBA200P
44
2B3T: 2 Beds 3 Towers, MB: Mix Bed, DG: Degasifier, H and OH: Ionic form
IER for Condensate Polishing Confidential

Gel type Porous type

Na‐form H‐form CL‐form OH‐form

UBK10B UBK10BH
Cation resins CPK80 CPK80H
CSK40 CSK40H
High cross‐linkage

CPA12 CPA12OH
Anion resins UBA10A UBA10AOH

CER：CSK40H：
High cross‐linkage（14%）gel type： Oxidation resistance, less leachables

AER：CPA12OH：
Porous type： Resistant to organic fouling, high PSS adsorption capacity
＊PSS：Leachables of CER（polystyrene sulfonate）.
PSS could cause organic fouling of AER.
45
 Specifications of IER for Condensate Polishing Confidential
Cation Exchange Resin Anion Exchange Resin
Grade CPK80H CSK40H CPA12OH
Structure Type Porous Gel Porous
Ionic Form H Form H Form OH Form
Whole bead Count （%） ≥95 ≥95 ≥95
Apparent Density (g/mL) 0.76-0.86 0.78-0.88 0.66-0.74
Salt Splitting Capacity (mmol/mL) ≥１.9 ≥2.4 ≥0.9
Water Content (%） 42 - 48 33 - 43 58 - 68
True Density (g/mL) 1.20-1.28 1.22-1.32 1.05-1.09
Effective Size (mm) 0.550 - 0.800 0.550 - 0.700 0.500 - 0.710
Mean Particle Size (mm) － (0.600 - 0.700) -
Uniformity Coefficient ≤1.4 ≤1.2 ≤1.4
Particle Size Distribution (%）
≥1180μm ≤5 - ≤5
500-850μm ≥95 -
＜500μm ≤1 ≤1 -
＜425μm - ≤2
SAOA （%）
- ≥90 ≥90
(Sphericity after osmotic-attrition)
Ionic Form (eq%) H Form ≥99 H Form ≥99 OH Form ≥90
Ionic Form (eq%) Na Form ≤0.1 Na Form ≤0.1 CL Form ≤0.2
CO3 Form ≤10
CER：CSK40H：
High cross‐linkage（14%）gel type： Oxidation resistance, less leachables
AER：CPA12OH：
Porous type： Resistant to organic fouling, high PSS adsorption capacity
46
Specifications of IER for Condensate Polishing Confidential

Gel Type Resins with Uniform Particle Size

- Cation Exchange Resin Anion Exchange Resin
Grade - UBK10BH UBA10AOH
Structure Type - Gel Gel
Ionic Form - H Form OH Form
Whole Bead Count (%) - ≥95 ≥95
Apparent Density g/mL 0.78-0.84 0.67-0.75
Salt Splitting Capacity mmol/mL ≥2.0 ≥0.9
Water Content % 40-50 55-65
Ture Density g/mL 1.20-1.26 1.05-1.09
Effective Size mm 0.550-0.700 0.500-0.710
Mean Particle Size μm （600-700） （500-600）
Uniform Coefficient - ≤1.2 ≤1.2
Particle Size Distribution
500-850μm ≥95
＜500μm % ≤1
400-800μm ≥95
＞800μm ≤1
Sphericity after
% ≥90 ≥90
osmotic-attrition
Ionic Form eq% H Form：≥99 OH Form：≥90
Ionic Form Na Form：≤0.1 CL Form：≤1
eq%
CO3 Form：≤10
47
DIAION Customers of Thermal Power Plants in Japan Confidential

Condensate polishing use（600MW or larger）

Company Unit Plant type Capacity MW Start year CP resins
A-1 Thermal 600 1990 PK/PA
A-2 Thermal 600 1991 PK/PA
KS Power A-3 Thermal 600 1991 PK/PA
B-1 Thermal 600 1987 PK/PA
B-2 Thermal 600 1987 PK/PA
A-1 Thermal 1,000 1987 PK/PA
TK Power A-2 Thermal 1,000 1991 PK/PA
B-1 Thermal 1,000 2003 PK/PA
TH Power A-1 Thermal 1,000 1983 PK/PA
A-1 Thermal 1,000 1990 PK/PA
J Power A-2 Thermal 1,000 1997 PK/PA
B-2 Thermal 600 2009 PK/PA
CB Power A-4 Thermal 700 1981 UBK14/PA

48
DIAION Customers in China (Condensate Polishing Use) Confidential

Ningxia Lingwu
2×1000MW
Air‐cooled plant

49
Application for CP of Air‐Cooled Plants Confidential

Combination of high cross‐linkage gel type CER and porous type AER

Merits：High water quality, high oxidation resistance, high durability

→ Suitable for using in air‐cooled power units with high condensate temp.

DIAION resins, CSK40(high cross‐linkage) and CPA12(porous), are used in Ningxia

Lingwu Power Plant, which is the first 1000MW scale air‐cooled unit in the world, and
achieve high water quality.

50
DIAION’s Customer in China Confidential

Place Power Station Type Capacity (MW) CP resins Start operation

Commercially operating
ML China Ningxia LW Thermal (Coal) 2 X 1,000 CSK40/CPA12 2011
ML China Inner Mongolia SD Thermal (Coal) 2 X 600 CSK40/CPA12 2011
ML China Guangdong HY Thermal (Coal) 2 X 600 UBK10BH/UBA10AOH 2011
ML China Jiangsu JR Thermal (Coal) 2 X 1,000 UBK10B/UBA10A 2013
ML China Guizhou TZ Thermal (Coal) 2 X 600 CSK40/CPA12 2013
ML China Fujian HS Thermal (Coal) 1 X 1,000 UBK10BH/UBA10AOH 2014
ML China Anhui LA Thermal (Coal) 2 X 600 UBK10BH/UBA10AOH 2014
ML China Zhejiang LH Thermal (Coal) 2 X 1,000 CSK40H/CPA12OH 2014
ML China Hebei XJ Thermal (Coal) 2 X 300 CSK40/CPA12 2014
ML China Zhejiang TZ Thermal (Coal) 2 X 1,000 CSK40H/CPA12OH 2015
ML China ZhejiangWZ Thermal (Coal) 2 X 600 CSK40/CPA12 2015
ML China Inner Mongolia TY Thermal (Coal) 2 X 600 CSK40/CPA12 2016
ML China Hunan CD Thermal (Coal) 2 X 600 UBK10B/UBA10A 2016
Constructing
ML China Guizhou LZ Thermal (Coal) 2 X 600 UBK10BH/UBA10AOH 2016
ML China Chongqing AW Thermal (Coal) 2 X 600 UBK10BH/UBA10AOH 2016
ML China Chongqing FJ Thermal (Coal) 2 X 600 UBK10BH/UBA10A 2016
ML China Ningxia WZ Thermal (Coal) 2 X 300 CSK40H/CPA12OH 2016

51
 Confidential

Thank you for your attention!

52