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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

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1. Overview

2. Introduction

3. Main applications

4. Infrastructure and equipment

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1. Overview

2. Introduction

3. Main technologies

4. Infrastructure and equipment

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1. Overview

Generating and developing business opportunities through applied research.

FUNDACION TECNALIA RESEARCH & INNOVATION is a private non profit research centre.

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1. Overview

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Organized in 7 fully interconnected sectorial Business Divisions.

1. Overview

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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

ENERGY & ENVIRONMENT DIVISION

1. Overview

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Dry (Plasma) & Wet technologies Improved (nano)coating , multilayers, surface functionalization, dry lubricants, …

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,..)

Elecrolytes for electrochemical devices (i.e. advanced batteries and supercapacitors) Surface treatments & Coatings

Loss of functional properties & Environmental implications of nanomaterials Nano-enabled materials/products

Electrocatalyst, nanocatalysts

Advanced surface technology

Materials for extreme environments

Membranes Technology

Ionic Liquids Catalysts

Nano-materials for energy & environment

Water Photocatalysis Filtration Water purification

1. Overview

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Staff: 30

15

11 PhD 6 PhD students 50%

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

Margot Llosa, Jon Meléndez, Alba Arratibel

15

7 Nationalities

San Sebastian & Derio (Spain)

1. Overview

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1. Overview

2. Introduction

3. Main technologies

4. Infrastructure and equipment

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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.

2. Introduction

Improving wastewater treatment from the point of view of materials

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1. Overview

2. Introduction

3. Main technologies

4. Infrastructure and equipment

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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

3. Main technologies

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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

3. Main technologies

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Photocatalysis for water treatment

Objective Technology’s key parametres

New photocatalytic materials with enhanced properties

Study of photocatalytic fundamentals under real environments

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 post-

treatment 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

3. Main technologies

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Patent pending photocatalytic reactor

Objective

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

Technology’s key parametres 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.

3. Main technologies

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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

3. Main technologies

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Objective

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

Enhanced surface-volume ratio by supporting the adsorbents in macroporous polymeric beads

Stability: adsorption of pollutants are not affected by interfering ions

Technology’s key parametres

Pollutant adsorption by polymeric beads

3. Main technologies

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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

3. Main technologies

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Electrochemical processes

Objective

Removal of redox active metals and metalloids from wastewater

Recovery of pure metals for recycling Ions (metals) selectivity and versatility

Two main techniques: • 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

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

Schematic of an electrochemical cell

Technology’s key parametres

Electrochemical cell

3. Main technologies

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Ionic liquids

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)

Technology’s key parametres

3. Main technologies

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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

3. Main technologies

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Detection systems

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)

Some examples

3. Main technologies

Fluorescent detection system of fluoride ions in aqueous media

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1. Overview

2. Introduction

3. Main technologies

4. Infrastructure and equipment

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Lab/pilot scale plants - Water

4. Infrastructure and equipment

Electrosynthesis plant

Nanofiltration plant Electrosynthesis plant

Electroembrane plant Microfiltration plant

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Lab/pilot scale plants - Water

Lab scale photoreactor Pilot scale filtration plant

4. Infrastructure and equipment

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Lab/pilot scale plants - Materials

Automatic pilot-plant (10 L tanks) for surface treatments

Automatic pilot-plant (30L tanks) for surface treatments

Plasma surface processing

Hollow fiber spinning lines

4. Infrastructure and equipment

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Laboratory equipment - Water

4. Infrastructure and equipment

• Test platforms for the measurement of photocatalytic activity in water

• Lab scale photocatalytic continuous reactor for water treatment

• Zeta-sizer • Water analysis:

– High pressure liquid chromatography (HPLC-DAD)

– 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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Laboratory equipment - Materials

Atomic Force Microscopy

X Ray Diffraction (Glancing Angle)

XPS/Auger Spectroscopy

Optical Microscopy

Scanning Electron Microscopy and EDS analysis

FTIR µ RAMAN Organic compounds characterization

Sol preparation

Sol-gel deposition (dip coating)

4. Infrastructure and equipment

Rotary evaporator