1. 1st SUMMER SCHOOL
Barcelona 26-30 September 2011
MEMBRANE TECHNOLOGY IN WATER TREATMENT
Dr. Xavier Martinez
Environmental Technology Department
Fundació CTM Centre Tecnològic
irene.jubany@ctm.com.es

2. 1st Summer School
Groundwater Restoration
SOME EXAMPLES
Membrane: Selective barrier between two phases

3. 1st Summer School
Groundwater Restoration Història
A LITTLE BIT OF HISTORY
Ionic Membranes 2000
1700 1800 1900
Pore Model
Scientific Knowledge
Osmosis Electroosmosis Dialysis Irreversible t
hermodynamics
Diffusion Membrane potentials
Membrane equilibrium
Osmotic pressure
Electrolyte transport
Electrodialysis Gas Separation
Hemodyalisis
Development of processes
Nanofiltration
Reverse Osmosis
M. Mulder. Basic Principles of Membrane Ultrafiltration
Technology. Ed. Kluwer Academic. 1997 Microfiltration

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Groundwater Restoration
DEFINITIONS
Membrane: Selective barrier between two phases
A B A AA BB
B B B A A B B
A A A B
B B A A B
Disorder (Entropy) ↑ Order (Entropy) ↓
W > ΔG = ΔH - T ΔS Energy

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Groundwater Restoration
WHERE DOES THE ENERGY COME FROM?
Hydraulic pressure
Concentration
Temperature
Electric potential

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Groundwater Restoration
CHARACTERISTICS
Membrana: Selective barrier between two phases
Cf Cp Permeability (l·s-1·m-2bar-1)
feed Cf Cp permeate
Cp
Selectivity 1
Cf
σ = 0 : Non-selective membrane
Cc
0 < σ < 1 : Solute transport
concentrate
σ = 1 : Ideal membrane
Recovery (%)
High Permebility ΔP↓
High Selectivity σ↑

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Groundwater Restoration
WHERE DOES THE ENERGY COME FROM?
Hydraulic Concentració Temperature Electric Potential
pressure
Microfiltration Pervaporation Thermosmosis Electrodyalisis
Ultrafiltration Gas Separation Membrane Distillation Electrosmosis
Nanofiltration Vapor Permeation Membrane Electrolysis
Reverse Osmosis Dialysis

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Groundwater Restoration
PRESSURE DRIVEN MEMBRANE PROCESSES
AA
A A
A
A
ΔP
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis

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Groundwater Restoration
PRESSURE DRIVEN MEMBRANE PROCESSES
Microfiltration < 2 bar Particles Particle Size
Ultrafiltration 1 – 10 bar Macromolecules Particle Size
Nanofiltration 5 – 20 bar Charged solutes, Solubility
organic matter
Diffusivity
Electrical Charge
Na+, Cl-, ...
Reverse Osmosis 10 – 60 bar ...

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Groundwater Restoration
FILTRATION CONFIGURATIONS
Concentration Polarization
Feed Permeate Feed Permeate
Backflush
Concentrate Concentrate

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Groundwater Restoration
MODULE GEOMETRIES
FLAT SHEET
TUBULAR

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Groundwater Restoration
MODULE GEOMETRIES
HOLLOW FIBER
SPIRAL WOUND

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Groundwater Restoration
MICROFILTRATION
· Retains large suspended solids
· Retains bacteria
· Passes some suspended solids and all dissolved material
· Pore ranges from 0.1 micron to 3 micron

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Groundwater Restoration
ULTRAFILTRATION
· Retains oils, particulate matter, bacteria and suspended solids large
macromolecules and proteins
· Passes most surfactants, water, acid and alkaline compounds
· Pore sizes ranging from 0.005 – 0.1 micron; 1K – 500K MWCO
· Permeate is clear (non-turbid) solution void of suspended solids

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Groundwater Restoration
MF UF MEMBRANE MATERIALS
POLIMERIC PS, HPS, PVDF, CA, PA, ...
CERAMIC TiO2, Al2O3 , ZrO2, SiO2
Durability ↑
Robustness: T, chemicals, pH ↑
Cost ↑

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Groundwater Restoration
MF UF MODULES

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Groundwater Restoration
MF/UF IN DRINKING WATER TREATMENT
Solids Removal

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Groundwater Restoration
MF/UF IN WASTEWATER TREATMENT
Membrane Biorreactors (MBR)

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Groundwater Restoration
MF/UF IN WASTEWATER TREATMENT
Membrane Biorreactors (MBR)
BOD < 2 mg/L
TSS < 0.5 mg/L
NH3-N < 0.5 mg/L
Turbidity < 0.2 NTU
Fecal Coliform < 10 CFU/100 mL
WASTEWATER REGENERATION

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Groundwater Restoration
OPERATIONAL CONSIDERATIONS
Periodical backwashes: water or air
Chemical enhanced backwashes (CEB)
HClO
HCl
NaOH
Cleaning in place

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Groundwater Restoration
NANOFILTRATION
• Retains divalent salts and organics
• Passes monovalent salts, water, acid and alkaline compounds
• Pore sizes ranging between UF and RO

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Groundwater Restoration
REVERSE OSMOSIS
• Retains salts and organics
• Passes essentially only water
• Passes molecules in the range of 5 Angstroms (0.0005 micron)
or 100 MWCO

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Groundwater Restoration
MEMBRANE MATERIALS
· Cellullose acetate
· Polyamide
Selective Barrier
Poliamide
Polysulfone
Polyester
Support
20 μm

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Groundwater Restoration
REQUIREMENTS
Chlorine < 0.1 ppm → Sodium metabisulfite
pH 2-11
SDI < 5
Scaling and fouling prevention
Antiscalant addition: SHMP, organophosphonates,
polyacrylates
Scale control: CaCO3, CaSO4, SrSO4, BaSO4, …
Media filtration: sand, antrhacite
UF/MF
20 μm
Cartridge MF

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Groundwater Restoration
DRINKING WATER TREATMENT PLANT
Remove contaminants: pesticides, DBP precursors, color, inorganic contaminants...
Remove hardness: Ca2+, Mg2+, SO42-...
Brackish water desalination
17500 m3/d
85 % Recovery
Feed pressure: 10 bar
0.35 kWh/m3 = 0.015 €/m3
9120 Membrane modules
B Cyna. Two years of nanofiltration at the Méry-sur-
Oise plant, France. Desalination (2002) 147:69-75

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Groundwater Restoration
PERFORMANCE
ORGANIC MATTER + Chlorine ↔ THMs
Lab Scale Pilot Scale
(Membrane Selection) (Membrane Performance)
160
4000
140 3500 Feed
120 3000 Permeate
TOC (ppm C)
100 2500
PFTHM
80 2000
60 1500
40 1000
20 500
0 0
06/06/2011
25/08/2011
07/04/2011
27/04/2011
17/05/2011
26/06/2011
16/07/2011
05/08/2011
14/09/2011
04/10/2011
RW UF E1.1 E1.2 E2

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Groundwater Restoration
SEAWATER DESALINATION
Llobregat desalination plant
60 hm3/year
Conversion: 45%
Pressure 50-80 bar
4 kWh/m3 = 0.21 €/m3

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Groundwater Restoration
ELECTRODIALYSIS REVERSAL
Hydraulic Concentració Temperature Electric Potential
pressure
Microfiltration Pervaporation Thermosmosis Electrodyalisis
Ultrafiltration Gas Separation Membrane Distillation Electrosmosis
Nanofiltration Vapor Permeation Membrane Electrolysis
Reverse Osmosis Dialysis

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Groundwater Restoration
ELECTRODIALYSIS REVERSAL
Electrodialysis: Electrically driven membrane process used to demineralize brackish water
Ion exchange membranes: Anionic or cationic

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Groundwater Restoration
ELECTRODIALYSIS REVERSAL

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Groundwater Restoration
ELECTRODIALYSIS REVERSAL
Llobregat drinking water treatment plant
Objective: THM reduction
0.2 hm3/day
345000 membranes
> 90 % recovery
Salt rejection 60-80%
0,8 kWh/m3 = 0.2 €/m3
F Valero. Desalination of brackish river water using Electrodialysis Reversal
(EDR). Control of the THMs formation in the Barcelona (NE Spain) area.
Desalination (2010) 253.

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Groundwater Restoration
NEW PROCESSES
FORWARD OSMOSIS
Draw solution Membrane
High solubility High rejection
McGinnis R., Elimelech M. (2007).
Energy requirements of ammonia– High osmotic pressure Chemical Stability
carbon dioxide forward osmosis Easily recovered Concentration
desalination.
polarisation

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Groundwater Restoration
NEW PROCESSES
CARBON NANOTUBES MEMBRANES
CN vs FILMTEC SW30HR-380
maximal pore density 2.5 × 1011 pores per cm2
size salt flow rate improveme flow rate improveme
rejection nt nt
(5,5) 100% 45.2 682 0.16 2.42
(6,6) 100% 78.8 1189 0.27 4.21
(7,7) 95% 119.5 1801 0.42 6.39
(8,8) 58% 182.9 2759 0.65 9.76
Membranes
High fluxes (x4 NF) Increase selectivity
Corry B. Designing Carbon Nanotube High rejections Lower production costs
Membranes for Efficient Water Desalination.
The Journal of Physical Chemistry B (2008) Lower hydrofobicity

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Groundwater Restoration
THANK YOU FOR YOUR ATTENTION
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