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PCATDES Report Summary

Project ID: 309846
Funded under: FP7-NMP
Country: United Kingdom

Periodic Report Summary 2 - PCATDES (Photocatalytic Materials for the Destruction of Recalcitrant Organic Industrial Waste)

Project Context and Objectives:
Scarcity and misuse of fresh water pose a serious and growing threat to sustainable, global, industrial development and the protection of ecosystems and the environment in the 21st century. More effective management of water and land resources is required.
Organic pollutants from the agricultural (e.g. olive or palm oil) and seafood industries are of particular concern. These enterprises are frequently in remote locations, with poor infrastructure and limited access to power. Spending money on extra, on-site treatment options is unaffordable.

The PCATDES project, funded by the EC’s FP7 Programme, aims to provide a cost effective, solar powered method for mineralising the recalcitrant organic pollutants, currently left in waste water, produced by these agricultural and seafood industries, that biological methods cannot remove. The project unites cross disciplinary teams based in ASEAN and EU countries and the resulting sharing of expertise between centres of excellence will generate new knowledge on photo-catalytic materials and processes.

The basic waste-water purification system, typically used, employs filtration and microbiological treatment. This provides a cheap means to eliminate solids and some organic matter. However, anaerobic and aerobic digesters are inefficient and remove only ~95% of the organic matter. As a result, wastewater cannot be reused without further treatment.

In contrast, complete mineralization of the residual “recalcitrant” material, (including humic acid and palmitic, oleic and linoleic triglycerides) currently requires energy intensive and relatively expensive treatments to meet legislative standards. Small Palm Oil mills, Olive Oil pressing industries, and small scale fish farming businesses, are ubiquitous to South East Asia and Southern Europe, and are often situated in rural areas where power is scarce and/or expensive. These industries, are unable to afford water treatment to meet required standards.

Photo-catalysis has huge potential for the remediation of low concentrations of organic pollutants in waste-water and offers a cost effective and inherently “clean” solution to this issue for SME’s. However, major scientific and technical obstacles must be overcome to increase oxidation efficiency and facilitate successful introduction of large-scale operations. The multidisciplinary PCATDES consortium drawn from across the ASEAN and EU regions has the necessary skills in nanotechnology, materials design, modelling, electronic and chemical engineering to:

* 1. Nanoengineer the structural and electronic properties of semiconductor photo-catalysts to enhance the response to solar and UV irradiation and charge separation characteristics.
* 2. Establish methods for artificially boosting natural UV radiation by using advanced UV light emitting diodes (LEDs) to greatly enhance the photo-catalytic process.
* 3. Bring together the “key enabling technologies (KET)” developed in steps (i) and (ii) to realize a prototype autonomous reactor powered by solar cells to establish systems with a design capacity of purifying contaminated water to meet EU council directive 98/83/EC.

The challenge for the PCATDES Consortia is to design an innovative, energy efficient, cost effective photocatalytic reactor that will be attractive and affordable for SMEs in the target Industries.

Project Results:
The PCATDES Project has made its anticipated progress over the first Two Reporting Periods with all original Deliverables and Milestones being achieved, although time frames for some milestones were amended to allow Partners to achieve better outcomes.

PCATDES recognised that standardisation of experimental protocols was essential, allowing 11 different partners to make informed decisions. The Standard Test Reactor, designed and assembled by URJC, Madrid and University of Bath, UK shows the benefit of standardisation.

Bath’s LED lighting system, demonstrated at the 2014 STI Days Event, is significant component of the Reactor which was distributed to 10 out of 11 PCATDES Partners in Autumn 2014. The Reactor gives excellent illumination characteristics than that obtained with alternative UV illumination sources and thus reaction kinetics is much faster.

Similarly, to establish a standard reaction test protocol, Cinnamic acid (CA) was chosen as a standard test compound for PCATDES because of its aromatic ring which is also present in the humic acids in the palm oil and seafood industry wastewaters

Bath installed the 4 standard reactors in the ASEAN Partners laboratories not only emphasised their commitment to the Project but helped to build the strong collaboration that exists within PCATDES.

Catalyst development has centred on a large range of materials being investigated as replacements for the standard P25 TiO2 powder including TiO2 Films doped with non-metal precursors using vapour deposition methods, with N, S, P, F, Al, Mo and W dopants show improvements in performance compared to the pure TiO2. The development of layers of different TiO2 polymorphs: anatase-rutile bilayers show outstanding extended photocatalytic activity in the UV range. A nanostructured WO3/TiO2 coating deposited by chemical vapour deposition (CVD) is also promising.
Additionally, Hierarchically-structured ZnO structures, have also shown excellent promise. But perhaps the most promising non-TiO2 photocatalysts with enhanced visible light activity have been the carbon nitrides.
A multi-wavelength LED board has been developed to test the new materials in the visible regime,

The photocatalyst in the Pilot Reactor needs a morphology that allows excellent water permeation. After trialling TiO2 pellet, foam and nanotubes created by anodisation of titanium wire meshes, TiO2 foams will replace the nanotube concept in the Reactor Design on the grounds of stability and reactivity. Foams of different pore sizes have been tested against palm oil wastewater - coated catalysts tested against Fisheries waste-water.

The physical & optical properties of the catalyst foams have been investigated and first kinetic models of the prototype photocatalytic reactor and the LED array devised. Assessment of the optimum coating process sol-gel versus CVD is currently under investigation

Significant progress in exploring the mechanism of the photocatalytic degradation of organic species in aqueous systems has been made, with the effects of a variety of common poisons, particularly the chloride ion studied. An in-situ LED illuminated ATR flow cell has been designed that will permit spectroscopy of reactive species during photocatalytic reactions, and has identified the most prominent adsorbed intermediates and explored the influence of pH.

An alternative approach utilizing GC/MS has examined the molecules present in the solution during the photodecomposition reaction of some of the target molecules and shown how the presence of chloride ions may lead to an increased rate of decomposition and open up an alternative pathway replacing the OH radical as the primary scavenging agent. A fast Laser Pump-probe system together with time-resolved spectroscopy has been constructed to study electron dynamics with catalyst particles during UV excitation.

Potential Impact:
The PCATDES Consortia is expecting to evidence that a prototype, photocatalytic reactor developed by the Project is capable of helping the targeted Palm Oil and Fisheries Industries to remove the recalcitrant pollutants currently left in wastewater. This project fully aligns with the Water, Energy and Food Security Nexus which is central to the Green Economy and the consideration of sustainability development goals.

The United Nations Sustainable Development Goal 6 on availability and sustainable management of water and sanitation by 2030 states: “we will have to improve water quality by reducing pollution, eliminating dumping and minimizing the release of hazardous chemicals and materials, halving the proportion of untreated wastewater and substantially increasing recycling and safe reuse globally.” Projects, such as, PCATDES can make a contribution to these lofty goals.
The Consortia believes that 3 scaled up reactors, deployed in the ‘field’ in South East Asia, during the final Period of the Project, and possibly beyond, will confirm that the Reactor Design, featuring an innovative LED rig, novel materials, catalysts and coatings developed as part of the Project, will not only show how sunlight, assisted by science and technology, can not only clean-up industrial waste water but also be of technical, commercial and environmental interest to others. The ability to recycle ‘industrial’, waste water, with minimal energy, should hopefully attract the attention of industrialists, environmentalists, governments, scientists and be of interest to similar or following projects.
The collaboration and cooperation between the 11 EU/ASEAN Partners in the PCATDES Consortia is one of its key strengths. The Consortia will ensure that the scaled up reactors are properly installed and supported; will liaise closely with the Industries at the South-East Asian test sites and will continue to advance their research to the Project End and possibly beyond.

The PCATDES Consortia is aware of the environmental damage being caused by many small scale agricultural and fisheries industries’ being unable to access cheap, efficient energy and/or being unable to afford extra plant to clean-up waste water. Photocatalytic Reactors will offer the opportunity to remove pollutants; recycle water, using a low energy solution. PCATDES has conducted REACH assessments to ensure that their proposed solution is as safe as possible.

PCATDES shall showcase its progress and Final Results in an International Workshop, scheduled for Hanoi, Vietnam in January 2017. The Consortia remains confident that its outputs, relating to the use of a photocatalytic reactor, will have the potential to help targeted industries and the environment and be of scientific and technical interest to others.

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