1.
TECNALIA
ENERGY &
ENVIRONMENT
Materials for water treatment
Retos y Oportunidades del
Sector del agua en Euskadi:
“Foro del Agua“
Bilbao 22 de enero de 2014
1

2.
1.
Overview
2.
Introduction
3.
Main applications
4.
Infrastructure and equipment
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3.
1.
Overview
2.
Introduction
3.
Main technologies
4.
Infrastructure and equipment
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

4.
1. Overview
FUNDACION TECNALIA RESEARCH & INNOVATION
is a private non profit research centre.
Generating and developing
business opportunities through
applied research.
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5.
1. Overview
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6.
1. Overview
Organized in 7 fully interconnected sectorial Business
Divisions.
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7.
1. Overview
ENERGY & ENVIRONMENT DIVISION
We generate and develop business opportunities for the different
actors of the value chains of the Energy and Environment sectors.
8 Areas:
01. BIOREFINERY & CO2
02. MARINE ENERGY
03. MATERIALS FOR ENERGY & ENVIRONMENT
04. METEROLOGY
05. SMART GRIDS
06. SOLAR ENERGY
07. THERMAL ENERGY
08. URBAN ENVIRONMENT & LAND SUSTAINABILITY
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8.
1. Overview
Advanced
surface
technology
Catalysts
Ionic Liquids
Materials for
extreme
environments
Membranes
Technology
Dry (Plasma) & Wet
technologies
Improved
(nano)coating ,
multilayers, surface
functionalization, dry
lubricants, …
Electrocatalyst,
nanocatalysts
Elecrolytes for
electrochemical
devices (i.e.
advanced batteries
and supercapacitors)
Surface treatments &
Coatings
Corrosion-related
failure analysis &
Monitoring.
Advanced materials
& processing for
thermal, radiation,
corrosion, wear
protection,..
Gas separation (i.e.
H2, Air, CO2,..) &
Energy conversion
membranes (i.e.
batteries, fuel cells,
electrolysers,..)
Nanomaterials for
energy &
environment
Loss of functional
properties &
Environmental
implications of
nanomaterials
Nano-enabled
materials/products
Water
Photocatalysis
Filtration
Water purification
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9.
1. Overview
Staff: 30
15
15
11 PhD
6 PhD students
Jon Zúñiga, Ekain Fernández, Miren Etxeberría, Sara Miguel, Saioa
Sáenz de Urturi, Amets Etxeberría, Andrés Del Barrio, Jean Baptiste
Jorcin, Marta Tejero, Marta Brizuela, Patricia Santa Coloma, Uxoa
Izagirre, Cecilia Agustín, Juan Mari Hernández, Iñigo Ibáñez, José Angel
Sanchez, Laura Sánchez, Amal Siriwardana, Jose Luis Viviente, Iñigo
Braceras, Alfredo Tanaka, Oguz Karvan, Fabiola Brusciotti, Pablo
Corengia, Ainhoa Unzurrunzaga, Saioa Zorita, Pablo Benguria, José
Antonio Martínez, Yolanda Belaustegui, José Manuel González
50%
7 Nationalities
San Sebastian &
Derio (Spain)
Margot Llosa, Jon Meléndez, Alba Arratibel
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10.
1.
Overview
2.
Introduction
3.
Main technologies
4.
Infrastructure and equipment
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11.
2. Introduction
Improving wastewater treatment from the point of view of materials
 Disruptive approaches in cross-cutting technologies that can be tailored to improve current
water treatment technologies.
 We develop new materials for water treatment, not turnkey plants
 We need from water engineering companies for the plant construction and scale up to pilot
plants.
 As a result of former R&D projects, we developed a variety of lab/pilot scale plants.
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

12.
1.
Overview
2.
Introduction
3.
Main technologies
4.
Infrastructure and equipment
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

13.
3. Main technologies
3. Main technologies
a.
Degradation of organic emerging pollutants from water
b.
Removal of pollutants from industrial wastewater
c.
Detection of trace pollutants from water
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14.
3. Main technologies
3. Main technologies
a.
Degradation of organic emerging pollutants from water
b.
Removal of pollutants from industrial wastewater
c.
Detection of trace pollutants from water
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15.
3. Main technologies
Photocatalysis for water treatment
Objective
 New photocatalytic materials with enhanced
properties
 Study of photocatalytic fundamentals under
real environments
Technology’s key parametres
 Photocatalytic coatings based on nano-TiO2
• Synthesis via sol-gel  high versatility to adapt to
different substrates and to include different NPs
• Strong adhesion to substrates: no need of posttreatment filtration
• Strong resistance to leaching
 Composite graphene-metal oxide platelets
• Patent pending synthesis method (WO2011/132036
A1)
• Improved photoactivity due to:
 High surface area (nanoparticles dispersed
on both graphene surfaces)
 Reduced rate of e- hole recombination
 Adsorption of chemical species on the
surface
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16.
3. Main technologies
Patent pending photocatalytic reactor
Objective
 Development of a robust, efficient and cost
effective photocatalytic reactor for the
elimination of emerging organic pollutants
from water
 Applicable as a tertiary treatment to urban
and industrial wastewater and to drinking
water.
Technology’s key parametres
 Complete mineralization of organic pollutants: no
degradation subproducts
 No chemical consumables
 Based on TiO2 nanoparticles supported in coatings
 Patent pending photoreactor with a maximized
degradation efficiency (WO2012/156548 A1)
 Collaboration with Oxital and University of
Cantabria
 Work in progress to increase photoreactor’s
efficiency
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17.
3. Main technologies
3. Main technologies
a.
Degradation of organic emerging pollutants from water
b.
Removal of pollutants from industrial wastewater
c.
Detection of trace pollutants from water
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

18.
3. Main technologies
Pollutant adsorption by polymeric beads
Objective
Technology’s key parametres
 Synthesis of functionalized adsorbents
supported in polymeric beads
 Taylor made solutions to selectively extract
pollutants in trace concentration from
water
 Solid liquid extraction of pollutants from water:
functionalization of macroporous polymeric
beads with different functional groups (physic
adsorption, covalent or ionic bonds). Examples:
ZrO2 can extract fluoride, As and Se
Zirconium phosphate can extract Pb (II)
Chromotopic acid to extract borate
Maleic anhidride with cysteine selective to Pb (II) and Cd
(II)
• Other pollutants such Se(IV), Al, or Cu (II), can also be
effectively extract from water in trace levels
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 Enhanced surface-volume ratio by supporting
the adsorbents in macroporous polymeric beads
 Stability: adsorption of pollutants are not
affected by interfering ions
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19.
3. Main technologies
Membrane technologies
Objective
 Improvement of current processes:
industrial wastewater treatment and
effluent minimization
 Recovery of valuable materials from
wastewater for recycling
Technology’s key parametres
 Pervaporation
• Elimination of VOCs from drinking water
• Recycling of phenols from wastewater
 Liquid-liquid extraction
• Formaldehyde, phenol and methanol recycling
from wastewater from phenolic resins fabrication
 Membrane technologies (ultrafiltration,
nanofiltration)
• Membrane functionalization for the recovery of
specific substances
• Filtration of nanoparticles (TiO2, ZnO and Ag)
• Membrane technologies (ultrafiltration,
nanofiltration)
Filtration pilot plant
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20.
3. Main technologies
Electrochemical processes
Technology’s key parametres
Objective
 Two main techniques:
 Removal of redox active metals and
metalloids from wastewater
 Recovery of pure metals for recycling
 Ions (metals) selectivity and versatility
• Potentiostatic deposition: metal ions in solution are
reduced by applying a constant potential to the metal
electrode (cathode)
• Cementation: metal ions are reduced to zero valence at
a solid metallic interface.
 Environmental compatibility: the main agent used
is the electron, which is a clean reagent.
 Cost effectiveness: simple and relatively
inexpensive equipment and operations
Schematic of an electrochemical cell
Electrochemical cell
 Amenability to automation: variables used
(current, I, and voltage, E) are well suited for easing
data acquisition, process automation and control.
 Elimination of pollutants from a variety of industrial
wastewater (i.e: painting processes, photographic
processes, bleaching processes)
Lab scale: Pure Cd deposited over Al cathode
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21.
3. Main technologies
Ionic liquids
Technology’s key parametres
Objective
 Removal of organic and inorganic pollutants
from water
 New coatings as corrosion inhibitors,
antiscalants, biocides, algaecides and
bactericides
 Improvement of coagulation and flocculation
during removal of solids in suspension from
wastewater
 Solid liquid extraction of pollutants from water
• Incorporating functional groups ILs are capable of
interacting selectively with the pollutant into solid
materials: extraction of fluoride, As, Se, Bo, Pb(II),
Cd(II),...
• The extraction process with methimazole based ILs
does not require the addition of a complexing agent
or pH control of the mixture
 Highly tuneable
• ILs can be tailored to have selective functional
groups.
• Functionalized ILs can be impregnated in porous
supports for water purification (i.e. membranes,
polymer beads).
 Cost effective
• Ionic liquids can be recycled and used again in a cost
effective process
• Easy to synthesize in large scale
• Environmentally friendly (no eco-human toxicity)
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22.
3. Main technologies
3. Main technologies
a.
Degradation of organic emerging pollutants from water
b.
Removal of pollutants from industrial wastewater
c.
Detection of trace pollutants from water
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

23.
3. Main technologies
Detection systems
Some examples
Objective
 Simple detection of pollutants from drinking
water at trace levels
 Different configuration of the adsorbents:
polymeric beads, membranes, etc.
 The presence of pollutants such fluoride and
arsenic in drinking water causes chronic diseases
and death in many parts of the world
• Fluorescent detection system of fluoride ions in
aqueous media
• Not affected by other ion interferences
• Tunable to detect other harmful substances such
as arsenic and mercury
 Onsite detection of trace ppb levels of Pb(II) in
real samples (i.e. wastewater from mining)
Fluorescent detection system of fluoride
ions in aqueous media
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24.
1.
Overview
2.
Introduction
3.
Main technologies
4.
Infrastructure and equipment
(CONFIDENTIAL - Disclosure or reproduction without prior permission of Tecnalia is prohibited).

25.
4. Infrastructure and equipment
Lab/pilot scale plants - Water
Electrosynthesis
plant
Nanofiltration plant
Electrosynthesis plant
Electroembrane plant
Microfiltration plant
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26.
4. Infrastructure and equipment
Lab/pilot scale plants - Water
Lab scale photoreactor
Pilot scale filtration plant
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27.
4. Infrastructure and equipment
Lab/pilot scale plants - Materials
Hollow fiber spinning
lines
Plasma surface processing
Automatic pilot-plant (10 L
tanks) for surface treatments
Automatic pilot-plant (30L tanks) for surface
treatments
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28.
4. Infrastructure and equipment
Laboratory equipment - Water
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Test platforms for the measurement of
photocatalytic activity in water
Lab scale photocatalytic continuous reactor
for water treatment
Zeta-sizer
Water analysis:
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High pressure liquid chromatography (HPLCDAD)
Inductively coupled plasma optical emission
spectroscopy (ICP/OES)
Atomic absorption spectrometer
UV Spectrophotometer
Turbidimeter
Conductivity meter, NaCl analyzer and TDS
TOC analyzer
Centrifuge
Speed-Vac
SPE manifold….
Climatic chamber
Wheel and brush erosion system
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29.
4. Infrastructure and equipment
Laboratory equipment - Materials
Optical Microscopy
X Ray Diffraction
(Glancing Angle)
Sol preparation
XPS/Auger Spectroscopy
Atomic Force Microscopy
Rotary evaporator
Scanning Electron Microscopy
and EDS analysis
Organic compounds
characterization
FTIR
µ RAMAN
Sol-gel deposition (dip
coating)
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