Water Treatment How do membrane position today?Albert Jansen & Matias Bikel

Seminar: Developing future water technologies – MembranesDipoli, Espoo, Finland June 8 , 2011

10-6-20111

TNO: Market Themes & Water Issues

Health: Water quality, EDC’s, Legionella,

Industrial innovation: Water technologies, sensors, modules

Energy: Energy efficiency, Oil and gas market

Built environment: Vital city, rainwater applications, water reuse, energy from water

Integral safety

Mobility: Transport by water

Information society: Sensor and control for decentralized systems

10-6-20112

TNO Water Treatment

Apeldoorn

Earth, Environment & Life (xxx fte) Markets

• Water Technology

• Energy Efficiency

• Separation Technology

• Analytical Devices

• Sustainability (LCA)

• Health

•`Sensors

• Modelling

• Water industry

• Water boards

• Industry

• Governments

Apeldoorn Utrecht

10-6-20113

Mission: Development of decentralized and sustainable water treatment technologies

Water & Health: EDC’s, Environment, Ground water (As); Decentralized (fresh)

Water & Reuse: Industrial: WaterFit4Use, E4Water , EWA, minerals recovery

Water & Energy: Use of waste heat for ST and power production

10-6-20114

Business Model: Cooperation in Technology Development

Fundamental Research

1. Proof of Principle

2. Proof of Concept

3. Proven Design

4. Pilot Plant

5. Full Scale Demo

TNOIndustrial partnersUniversity partners

6. Licensing Or start ups

Applied Research

MarketDevelopment

€ £

Time

Royalty's$

¥

10-6-20115

Water scarcity

Increasing demand for water by fast growing world population.Drinking water (also higher quality)Agriculture for foodAgriculture for energyIndustrial processes

Climate change (droughts and melting ice and snow)

Decreasing amount of suitable groundwater

Conclusion: Water stress is emerging

10-6-20116

Solutions for water production

Rainwater harvesting

Surface water treatment

Reuse of waste water (industrial and communal)

Brackish and seawater desalination

10-6-20117

Water treatment

Techniques (non complete)Chemical treatmentBiotechnology Precipitation/flocculationCrystallization ( EFC)FiltrationSedimentationDistillationAdvanced oxidation (UV or ozone)

and

Membranes!

10-6-20118

Water treatment with membranes

Silver bullets don’t exist, but membranes should help!

10-6-20119

Membrane Technology (container concept)

Materials: organic, metal, inorganic, hybrid materials

Membrane: porous, non porous, asymmetric,

Membrane geometry: hollow fiber, tubes, flat sheets, discs

Membrane modules: stacks (plate and frames), spiral wounds, shell and tube.

Driving forces: ΔP, ΔT, ΔV, ΔC

10-6-201110

Why Membrane Technology?

No Chemicals (?)

Highest Quality Water

Membranes are versatile

Lowest cost

Energy consumption?

10-6-201111

Membranes processes

RO/HF Desalination (ΔP)NF Softening, Metals, (ΔP)UF Pretreatment RO (ΔP)MF Disinfection, L-S separation (ΔP)MBR Membrane Bioreactor (ΔP)Pervaporation Dewatering, Organics (ΔP)Electro dialysis Desalination (ΔV)CMC Oxidation/hydrogenation (ΔC)Dialysis Water extraction (ΔC)Pertraction Solvent extraction(ΔC)Membrane distillation Dewatering (ΔT)CDI Desalination (ΔV)

10-6-201112

History membrane technology

The process of osmosis through semi-permeable membranes was first observed in 1748 by Jean Antoine Nollet Researchers from both UCLA and the University of Florida (Reid) successfully produced fresh water from seawater in the mid-1950s with cellulose acetate RO (fluxes too low)Loeb and Sourirajan made asymmetric CA membrane in the sixties with high fluxesSeventies and eighties: new materials, standardization/optimizationNineties: lowering energy consumption; control of foulingTwenty one century: breakthrough of RO followed by (UF, MF, NF,…)

10-6-201113

Membrane Issues

Bio fouling

Scaling

Cleaning (Chemical/back flushing)

Retentate: concentrated streams

10-6-201114

Separation demands

Na/K separation

Removal of minor components (ppb and ppt) (FWD)

Breaking emulsions (oils and gas industry)

Separation organics from inorganics

Organics to reuse/energy

Product recovery (white biotechnology)

Ultra pure water

10-6-201115

Challenges ~ Performance: COSTS

Memstill

vs.

MEDMSFRO

10-6-201116

Desalination market

10-6-201117

Facts and Figures

The desalination market 2005 - 2015 will generate expenditure in the region of $95 billion, of which around $48 billion will be derived from new capacity ($30 billion of cap-ex and $18 billion of op-exMembrane treatment market for industrial water and waste water is expected to grow at a Compound Annual Growth Rate (CAGR) of 13% from $2.3 billion in 2008 through 2015 to reach $5.5 billion. Globally, microfiltration membrane treatment is likely to witness 15% CAGR growth during 2008 to 2015 [Global Markets Direct]

10-6-201118

Trends

Introduction of nano technologiesparticles in/on membranes

Membrane structuring

Membranes with micro sieves (uniform pores)

Pressure exchanger

Decentralization (downsizing of processes)

Backwashing and pre treatment

10-6-201119

RO Membrane flowsheet

10-6-201120

Water Treatment Technologies

Membrane distillation (Memstill®): desalination with waste heatFACT/MAC: softening of drinking water Pertraction: removal of organicsEmulsion Pertraction: selective removal of metalsMAAS: selective removal of organics/metalsF/MBR: high flux and improved O2 transferCatalytic Membrane Contactor: O2 and NO3 removalPeroxsite: DisinfectionPuridrain: Water treatment in natureMembrine®: From brine to solid salt and fresh waterMempower: Power and fresh water from heat and (salt) waterDenutritor: prevention RO biofoulingPrevscale: Preventation of scaling

10-6-201121

Memstill® Potential vs. State of the Art MED

Memstill®

MED 4700 m3/day

10-6-201122

Memstill® Basic Principle

10-6-201123

Memstill® Applications

Large-scale production of drinking water from seawater

Production of fresh water on ships and in offshore industry

Production of ultra pure water, boiler feed water, etc.

Consumer market applications

10-6-201124

Memstill Pilot Singapore: Location at Senoko

10-6-201125

Memstill Singapore Pilot

10-6-201126

First Memstill-Desalinated Water Produced in Singapore

10-6-201127

Water Production Costs: Memstill vs. RO(seawater: 105 m3/day, incl. intake&pre/post treatment)

Memstill Memstill RO

“minimum”

RO

“Wilf”Cogeneration

LP steam

Cogeneration85 C

Waste heat

Energy costs

Heat (MJ /m3 ) (cost in €/GJ)

231 (2.00)

231 (0.80)

139(0.80)

231 (0.10)

Electricity (kWh /m3) 0.75 0.75 0.75 0.75 2.5 4.5

Heat cost (€ /m3) 0.46 0.19 0.11 0.02

Electricity cost, 0.07 /kWh (€ /m3) 0.05 0.05 0.05 0.05 0.18 0.32

Fixed costs

Hardware (excl. membranes) (€ per m3-day)

165 165 750 1000

Modules/elements (€ per m3-day)

214 233 35 49

Hardware cost (€ /m3) 0.05 0.05 0.05 0.05 0.23 0.30

Module cost (€ /m3) 0.11 0.11 0.12 0.12 0.02 0.03

Auxilary: (€/ / m3)

O&M, chemicals., filters etc.0.03 0.03 0.03 0.03 0.09 0.09

Water costs-total (€ /m3) 0.70 0.43 0.36 0.27 0.52 0.74

10-6-201128

Advantages Memstill

Low cost (<0,50 €/m3 at large scale)

High purity (salt reduction: 10.000 times, < 1 µS/cm)

Compact

Low or no electricity demand

Minimal site work

High sustainability (no CO2, low heat and salt emission and no chemicals)

10-6-201129

Today

Licensed to AquaStill and Keppel Seghers (development of module PT)

Running Pilots/demo’s Aquastill (25 m3/day):Shell, Cosun Friesland Foods, Fuji, ..

Planned Pilot/demo’s Keppel Seghers:Singapore refinery (100 m3/day) July 2011

TNO:Flux-, energy performance and new bonding techniquesDevelopment of household, solar units and waste heat applications.Testing of new applications (waste water, industrial flows)Membrane Distillation: Getting Ahead

10-6-201130

FACT: Optimal Crystallization + Optimal Filtration

CrystallizerHard water Soft water

Recycle seedCausticsolution

Filter

Membrane Assisted Crystallization (MAC): WO9411309, EP0669898 Filtration Assisted Crystallization Technology (FACT): US Patent

Short residence time Cake filtration with good filtrability

10-6-201131

Control Parameters in Heterogeneous Crystallization: Surface Area

d (µm) S.S.A. (m2/kg)seed

1 2400

20 120

600 4

Small seeds = large surface area = fast process = compact setup

Size seed materials: - In pellet reactor: 500 µm- In FACT: 10-15 µm

10-6-201132

Heterogeneous Crystallization: Crystal-Seed Interaction

FACT seeds create extra degrees of freedom:Less limited in seed density and seed size

Homogeneous nucleation leads to fines

B

metastable region:operation regime

FACT/pellet reactor

Supersaturation

Nuc

leat

ion

rate

homogeneousheterogeneous

C

A

idealseed

seed efficiency

B

metastable region:operation regime

FACT/pellet reactor

Supersaturation

Nuc

leat

ion

rate

homogeneousheterogeneous

C

A

idealseed

seed efficiency

10-6-201133

Comparison of Effects of Heterogeneous Seeds for Pellet Reactor and FACT

FACT: Small seeds faster than big seeds -> small and compact apparatus

1.0 wt% small seeds (10 µm)0.4 wt% small seeds (10 µm)0.1 wt% small seeds (10 µm)10 wt% seed (500 µm)No seeds

1.0 wt% small seeds (10 µm)0.4 wt% small seeds (10 µm)0.1 wt% small seeds (10 µm)10 wt% seed (500 µm)No seeds

10-6-201134

PilotsSoftening of ground water for the production of potable water (Vitens and Lyonaisse des Eaux)

Softening of process water paper- and pulp industry (IWE)

Full scale demonstration at Sappi Maastricht 2011

New development on Struvite production for phosphate recovery from communal waste water with Siemens Water Technology and Waterboard Zuiderzeeland

10-6-201135

Pilot Equipment (Softening Plant Goor, Vitens)

Crystalliser FilterPilot Equipment Capacity:1 m3/hr

10-6-201136

Current FACT/MAC Projects

Piloted at Vitens site

Demonstrated on 10 m3/hr scale in Eerbeek

Project with Degremont for Lyonnaisse de Eaux (F)

Full scale demonstration in AquaFit4Use with at Sappi (Maastricht)

New contacts in Belgium and USA

10-6-201137

Recovery of Organics from Aqueous SolutionFirst Industrial Pertraction Plant

procesfeed-stock

biowaste water15 m3/h

Envista (former Hoechst ) - Vlisssingen

since 1999

aromatics

• Apolar hydrocarbons

• Aromatic compounds

• Halogenated HC’s

• Polycyclic HC’s

• Range: 1 ppb – 1000 ppm (< 100 m3/h)

aqeousstream

productrecovery

cleanedwater

Energy savings

10-6-201138

Pertraction Pilot

Energy savings

10-6-201139

Offshore Pertraction Applications

Technology required:Compliance with (future) targets/regulationAcceptable costsReliableLow volume & weight

Test program in preparation:Produced water oil production platformProduced water gas production platform

10-6-201140

Principle Emulsion Pertraction

10-6-201141

Emulsion Pertraction Installation at Rogal Enschede

Licensed to Suez/Ondeo

10-6-201142

Membrane Assisted Adsorption Separation (MAAS)

Features:Small affinity particlesSelective adsorptionSeparation by membrane filtration

Adsorptionsection

Filtrationsection

Contaminated water Purified water

Regeneration section

Residues

10-6-201143

Status MAASMarket Drinking water Waste water Other

Target component

R&D period

R&D budget

Project funding

Status

TOC, Color, Humic Acids, Pesticides

2000- ..1999- 2003 (textile)2001- 2004 (metals)

700 k€

Consortium

Co-finance

Vitens, WLB, WML, Hatenboer Water

Dyes, Heavy metals (Ni, Zn, ..)

900 k€ (textile)500 k€ (metals)

Amino acidsMBTE, Xeno oestrogens

EET / EU EET

Textile branch, WUR, Paques, Umicore (B)

o.a.Catch Mabs, WUR, DSM, ATO, ….

2003-2006

3 M€

Proof of concept Pilot Proof of concept

No commercial application yet

10-6-201144

Peroxsite (Disinfection)

Peroxsite: onsite production of hydrogen peroxide (O2 + H2O -> H2O2)

Advantages Accurate dosing of H2O2 (varying electric current)No transport/storage of H2O2

Applications: DisinfectionBreakdown HFC’sBiological growth limiting...

10-6-201145

Peroxsite/UV- Combination(Demo: pH control, 3*4 cells buffer vessel, UV, AC)

10-6-201146

Current activities TNO FBR/MBR research

Joint research MBR Varsseveld (DHV, Wetsus, Waterboard) Demonstration technical feasibility Full scale treatment (750 m3/h)Research focus on:

Pre-treatmentOverall performanceSludge qualityOxygen inputProcess controlMembrane filtration (operation/cleaning)Fouling

TNO is coordinating and performing several research tasks

10-6-201147

Aeration: New Design Plate & Frame Modules

Benefits:Experiments indicates energy reduction of 10-50%Enhanced oxygen transfer at high viscosities

Current status:New conceptProposed in WSSTP pilot urban city

10-6-201148

Filtration: Improved Flux by New Filter Design

New approach for high fluxes using a perforated plate separator (5-150 micron holes)

Potential benefits Low investments (cheap materials)High fluxes Good cleaning abilities

Current status:New concept Proposed in pilot urban city

150 micron

Perforatedplate

Dynamic Sludge layer

10-6-201149

Catalytic Membrane Contactor (CMC): Principle

Catalytic-Hydrogen-based membrane biofilmreactor

NO3-

H2

N2

Biofilm

Palladium

10-6-201150

Catalytic Membrane Contactor: Applications

Removal of nitrate / nitrite groundwater Removal of bromate (desinfection byproduct ozon)Removal of oxygen for process industryRemoval of chlorinated solvents, pesticides

10-6-201151

Puridrain: Water Treatment in Drainage Systems

Design/geometry

10-6-201152

Denutritor: Mechanism Membrane Biofouling

membrane

Bacterial cell

Step 1:

Initial approach Step 2:

EPS biosynthesis

Step 3:

cel growth

RBOC, nutrients

10-6-201153

Denutritor: Symptoms & Effects Biofouling RO

Product quality

Costs

Water supply

reduction membrane flux >50% lower production

reduction salt retention 2x higher salt passage

Increase TMP up to 2x or more

10-6-201154

DeNutritor: New type of Bio filter

Filter material with good adsorption characteristics Porous material (low pressure drop) Compact design Continuous processIn-line regeneration

On site tests surface water

10-6-201155

DeNutritor: Controlled growth of Bio fouling

microbes

DeNutritor RO membrane

readily biodegradable organic matter

slowly biodegradable organic matter

10-6-201156

Prevscale; prevention of scalingScaling is precipitation of dissolved metal salts. In most cases this is e.g. calcium, magnesium, barium, sulfate and carbonate

PrevScale (patent pending) can prevent scale formation, which will:reduce down-timereduce usage of chemicalsenhance longer equipment life timeefficiency improvement (heat or mass transfer)lower pressure dropssafetytaste influences in food industrycontribute to disinfection low energy requirement

Prevscale is an electrochemical technique without addition of chemicals

10-6-201157

Prevscale principle

RO

permeate

10-6-201158

Proof of Principle: Flux of water during RO experiments

10-6-201159

Proof of principle: RO retentate clearness

Without Prevscale With PrevScaleConcentration factor 12 Concentration factor 23Turbid Clear

10-6-201160

Energy Requirement

Expected energy requirement:< 0.2 kWh/m3 feed flow;

Costs:

10-6-201161

Membrine®: Membrane Distillation Crystallizationa hybrid combination of Memstill and MAC/FACT

10-6-201162

Membrine® Principle

BRINE

PURE WATER

CONCENTRATE(< 1%)

SALT 1SALT 2SALT 3

MEMBRANE

CONDENSOR

INPUT WASTE HEAT

WATER VAPOR

MDC MODULE

10-6-201163

Potential products from 1000 m3 seawater

980 m3 potable- or process water (10 micro S)30 ton NaCl1 ton NaCl/KCl/MgSO4/MgCl2/.6H2O1 ton CaCO3/CaSO40,1 ton BaSO40,01 ton other salts0,2 kg lithium (and other minerals)<3 m3/h (<0,3%) waste stream with organics and waste waters (bitters) and waterMinerals (Lithium, …)

10-6-201164

Project

Consortium:Oasen Drinking waterShell Production waterFrieslandCampina DairyProductschap Tuinbouw HorticultureGeneral Electric System supplier

Start: December 15, 2010

Duration: 2,5 years

Budget: k€ 1.200

10-6-201165

Lab test equipment for Membrine

10-6-201166

Mempower®

A new energy and water conversion technology (patent pending)

Energy: from waste or solar heat to power

Water: non potable water to pure water

Application: Markets with water and power needs

10-6-201167

Current position

Rainwater harvesting MF

Surface water Bio fouling – UF – RO

Industrial waste water reuse Many membrane technologies

Communal waste water MBR - RO

Desalination UF- RO / MD

10-6-201168

Forecast

Membrane fluxes will slightly improve (Concentration polarization)

Selectivity will further increase (higher quality water)

Price of membranes goes further down by competition

Energy consumption will be further optimized (energy integration)

Bio fouling and scaling on RO will disappear

Life time of membranes will strongly increase lowering Opex

New hybrid processes will emerge (membranes in the centre)

10-6-201169

Conclusions

Membranes: young history (50 years)

No silver bullet solution but helpful technology

Strong market position

New materials: optimization of membranes

Processes will become more sustainable (energy and environment)

Membranes can solve the (future) problem of water scarcity

10-6-201170

With MemBrains to the Market