Final Report Summary - BIONEXGEN (Development of the next generation bioreactor system)
Executive Summary:
According to the World Health Organisation (WHO), the most dangerous threat for health of mankind emerging within the next years is polluted water. Though polluted water and water shortages demand for a sustainable water usage and recycling of wastewater, the barriers are high to adopt these outside of Europe: Clean water as basis for health and good living conditions is too far out of reach for the majority of the population. Thus, neither sustainable consumption nor reinforcement of governmental regulations are effective drivers to force the industry to adopt sustainability policies.
Membrane bioreactor (MBR) technology is regarded as a key element of advanced wastewater reclamation and reuses schemes and can considerably contribute to sustainable water management. MBR technology is used for wastewater treatment and reuse in municipal, agricultural and a variety of industrial sectors in Europe and Middle East and North Africa (MENA).
The overall objective of BioNexGen is to develop and test on pilot scale a new class of functional low fouling membranes for membrane bioreactor technology with high water flux and high rejection of organic pollutants with low molecular weight. The field tests with these newly developed membranes will be carried out with wastewater from 3 different industries (cosmetics, textiles and olive oil industry) which play an important role in the MENA countries and will be compared to conventional, commercially available membranes for benchmarking.
The consortium will develop a novel single step Nano-Filtration (NF) MBR operated with low energy consumption; small footprint, flexible design, and automated operation make it ideal for localized, decentralized wastewater treatment and recycling in the European and MENA countries.
Project Context and Objectives:
The overall objective of this project period was first of all to continue providing basic benchmarking data for all BioNexGen R&D activities. To this end benchmarking pilot trials using the existing MN membrane and practical industrial wastewater have been pursued by the partners CMRDI, CBS and HsKA. Besides that laboratory work on novel membrane materials such as PBM coating, CNTs and layer-by-layer technology has been conducted. Cost estimate for the potential BioNexGen manufacturing process has been carried out. Moreover computer modelling and laboratory activities continued with focus on modifying the existing commercial MN membrane. The emphasize was given on theoretically studying structures-properties relationships of CNTs and incorporating vertically aligned CNTs in the existing MN membranes as well as casting a novel nano-scale layer with tailored pore size onto the membrane surface. Characterisation of novel membranes regarding surface morphology, water flux and rejection of model compounds were conducted. Preparation of technical module envelopes for pilot trials in MENA countries were done. Finally field tests using these novel membrane based modules were carried out with textile wastewater, olive mill wastewater and cosmetic wastewater and the results were reported in different deliverables.
The specific objectives of the project were:
WP1:
• Securing benchmarking data with existing MBR modules in short term by running small-scale pilot units with real wastewater from olive mill, textile and cosmetics industry.
• Preparation of a systematic market research for MBR application
• Defining potential membrane, module and process chemical materials under economic, technical and health related constraints
• Conducting laboratory tests (water flux, rejection) with membrane samples with PBM coating prepared by ITM-CNR
• Update of cost estimate for potential BioNexGen PBM membrane manufacturing process as well as Layer-by-layer technique in cooperation with ITM-CNR, FORTH and IZTECH
WP2:
• Structures-properties relationships related to organic solutes rejection from CNTs as well as theoretical study of water flow through CNT doped MN membranes.
WP3:
• Incorporation of CNTs in the existing MN polymer membranes by filtration in combination with tip sonication
• Functionalization of CNTs by hydroxyl groups
WP4:
• Synthesis of polymerisable surfactant for PBM technique
• Modification of the existing MN membranes towards nanostructured membranes with tailored pore size by PBM techniques.
• Provision of flat sheet membrane samples for laboratory tests on water flow and solute rejection
WP5:
• Starting initial experiments to synthesis antimicrobial nanoparticles
• Modification of the existing MN through layer-by-layer technique in order to increase antimicrobial properties
• Continuation of experiments to synthesis antimicrobial nanoparticles
• Provision of antimicrobial nanoparticles for being incorporated in layer-by-layer coating
WP6:
• Laboratory activities to study surface and cross sections of membranes to gain: surface roughness measurements, characterisation of surface morphology, changes to cross section of membranes and foulant layer thickness.
• Characterisation of novel membrane samples with regard to water flux and rejection of model compounds
WP7:
• Preparation of technical module envelopes for upcoming pilot trials in the MENA countries. The main focus was on selection of a low-temperature glue for lamination process of the envelopes since the novel PBM membrane material is not as temperature stable as the commercial material.
WP8:
• To conduct field tests with olive mill wastewater
• To conduct field tests with textile effluent
• To conduct field tests with cosmetic effluent
Apart from R&D WPs, specific objectives were also set for the WPs dedicated to the following activities: dissemination, exploitation (WP9) and management (scientific (WP10), administrative and financial (WP11)).
WP9:
• To create the first step-stones for marketing activities necessary for the exploitation of the project’s results
• To give visibility of BioNexGen objectives, activities and benefits by answering to the different needs of target groups
• To disseminate BioNexGen aims, evolution and results through printed (brochures, booklets, etc) and electronic (website, quarterly electronic newsletter) sources.
• To manage the access to partner’s background IP necessary for the project
• To manage and protect the consortium’s foreground IP
• To avoid patent infringement
• To assure a successful technology and knowledge transfer between the academic partners and the SMEs
• To create interest in the BioNexGen concept from potential customers in Europe as well as in the MENA region
• Organisation of the first training workshop focusing on basic principles and state-of-the-art of "Membrane based wastewater treatment and reuse" at CBS in Sfax, Tunisia. This workshop took place on the 8th and 9th of March 2012. The deliverable D9.4 “Report on the 1st training workshop on novel MBR technology” provides an overview of the presentations given during the workshop.
• Organisation of the second training workshop on “Functionalized membranes for Wastewater Treatment - Nanoparticles and surface modifications” which took place in May 15-17th, 2013 in Cetraro, Italy.
• Organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and clarify some aspects concerning the ownership and the use of these results
• Updates on patents search
• To continue the dissemination activities through the website, the newsletters, the participations to conferences and the networking activities.
WP10:
• Smooth and effective collaboration within the consortium
• Delivery of deliverables and milestones in time
• High quality of the project results
• Tracking and effective mitigation of risks
• Anticipation unexpected developments or new opportunities
WP11:
• To ensure that all the administrative documents (grant agreement and the consortium agreement) were understood and signed by all the partners.
• To distribute the pre-financing among the partners and
• To remind the partners’ role, level of involvement in the project and the budget planned for their participation in BioNexGen.
• To choose and the set-up of the management platform.
• To provide assistance to the partners on administrative and financial aspects
• To get the partners acquainted with the reporting process
• To perform the first periodic reporting in accordance with the criteria defined by the EC.
• To ensure that all the administrative and financial documents (Form Cs) were understood, signed by all the partners and delivered on time to the EC for the first periodic reporting
• To maintain updated the management platform
• To solve the issues concerning the Syrian partner ABU
• To prepare the amendment
Project Results:
Resuls obtained within period M1-M12
During the reporting period starting from the 01.09.2010 - 31.08.2011 WP1 through WP5 and WP9 through WP11 have been started.
Within WP1 benchmarking data were obtained with the existing MBR membrane from MN by testing industrial wastewater (olive mill, textile, and cosmetics). Small scale MBR pilot trials have been successfully started in the laboratories of the partners ABU, CBS and CMRDI using practical wastewater from olive mill, cosmetics and textile industry. In parallel, HSKA has started small pilots using model olive mill wastewater and practical wastewater for which the findings can be compared with the results of ABU. The results are summarized in a report (D1.2). In addition laboratory experiments with model foulants (humic acid, proteins and alginate) were conducted using a flat sheet membrane cell. The MBR market in Europe and the MENA countries has been studied by performing a SWOT analysis. For this analysis, a specific questionnaire has been developed for collecting the data among BioNexGen partners. The results are summarized in the deliverable D1.1. The potential membrane and module materials, as well as the potential membrane manufacturing processes of the BioNexGen membranes have been defined additionally an initial cost estimate for novel materials involved has been made in cooperation with CNR-ITM and FORTH. The results are summarized in the deliverables (D1.4 and D1.5). The health and safety aspects have been studied based on a matrix based risk analysis including all potential chemicals for manufacturing the novel membranes. The deliverable D1.6 highlights the findings. Deviation: The report on short-term results (D1.2) has been finalized only in month 12 instead of month 6 as initially planned but this does not affect the further progress of the work. No other deviation from the workplan occurred and the respective deliverables have been issued.
WP2 addressed theoretical aspects through computer modelling. FORTH and CNR-ITM were responsible for the tasks under this work package and were supported by HSKA and NTX. Within the overall aim of the WP2 investigation of structures-properties relationships, necessary in the development and design of innovative materials, the main progress is the subdivision of pollutants (textile, olive mill, cosmetics) into three groups as function of the ratio between the cross sections of the CNTs and those of pollutants. By analysing the ratios between the cross sections, it is possible to conclude that CNTs with diameters less than 3 nm can work as molecular sieves for medium (II group) and large (I group) sized solutes since the cross sectional ratios are smaller than 1. The calculations indicate that the existing CNTs with diameter larger than 3 nm cannot be used as molecular sieves to separate the larger part of the considered pollutants. Nevertheless, dynamic effects could cause deviations from this prediction. This is important since it allowed defining a computational strategy for the subsequent simulations aiming at calculation of the rejection of organic solutes of small size (III group) by the CNTs of NTX with diameter smaller the 3 nm. In fact, efficient solutes rejection could be driven by an unfavourable trapping of these molecules in the considered CNTs. For example the Tyrosol shows an unfavourable electronic free energy when embedded in a CNT with diameters of 1.66 nm. Multi-scale simulations (QC and MC) have been planned for the next six months to explore this possibility in advance. This WP has started earlier than planned in the DoW and the deliverable D2.1 has been submitted at M12.
Within WP3, FORTH has started to experiment the formation of vertically aligned CNTs in the existing commercial MN membrane as well as in a custom-made track-etched membrane through filtering. The active layer of the MN membrane consists of PES with an average pore size of 50 nm. Experiments have been performed by using the less expensive CNTs which are the MWCNTs with an external diameter of around 40 nm. The incorporation of CNTs has been attempted by using an improved common filtration system. The incorporation of the CNTs in the pores of both membranes has been monitored by SEM images of the membrane surface and cross-section as well. The consequent next steps will be to test water permeability and retention efficiency in a small test cell and in addition to improve and optimize the infiltration process. In addition initial experiments on functionalization of the MWCNTs by hydroxyl groups have been started. Moreover, decorated MWCNTs with polymers such as PMMA and PGMA have been also prepared. This WP has started earlier than planned in the DoW.
The main work of WP4 has been done on the preparation of “loose” hydrophilic nanofiltration membranes with tailored pore size. Two different types of NF membranes have been produced made of 1) polyvinyl alcohol (PVA) and 2) polymerisable bicontinuous microemulsion (PBM). The PVA membranes prepared so far proofed to be too “dense” to be applied over MN membranes (this has been observed by performing water permeability tests). Therefore two different approaches (addition of additives, low quantity of polymer in solution) will be studied in detail within the next 6 months. The symmetric PBM membranes have been produced using two different types of surfactants. The first one has been newly synthesized (together with the subcontracting, UNICAL) and the other one is commercially available (SDS type). Both types of membranes have been successfully made on lab scale using UV and redox initiators. Furthermore, the PBM membranes have been successfully coated on commercial MN membranes and their preliminary characterisation tests have supported their great potentialities and validated that the coating has been well performed. Further characterisation tests are now in progress to verify the interconnectivity of the pores of the respective membranes. However, the membranes need to be further optimised also for being applied in MBRs. This WP has started earlier than planned in the DoW.
Within WP5 initial experiments were started to prepare antimicrobial nanoparticles such as AgCl/TiO2 and chitosan which can be incorporated into nanofilms through PBM or PVA techniques (see WP4). The initial syntheses of these two nanoparticles have been conducted. Sol-gel synthesized Ag/TiO2 materials and chitosan nanoparticles were found to be antimicrobial against E.coli. The existing MN MBR membrane was modified by layer-by-layer (LBL) technique by alternating layers of chitosan and layers of alginates. The water flux and rejection for a model foulant (such as humic acid) were measured by HSKA. The water flux measured in the first samples was too low for expecting an application in MBRs. However, the process has been modified and further experiments will be carried within the next 6 months. This WP has started earlier than planned in the DoW.
WP9 supported dissemination, exploitation and training activities. The main objectives of this period were the development of the dissemination tools (project’s website and brochure) as well as an analysis of the intellectual property mechanisms suitable for the dissemination and the exploitation of BioNexGen outcomes. A corporate identity has been developed with the help of a professional communication agency. From this collaboration, a logo and a slogan have been created. In January 2011, the website has been finally opened to the public under the following address: http://www.bionexgen.eu The brochure is available in English since April 2011 and in Arabic, Greek, Turkish, Italian and German since August 2011. Several partners have started to communicate on the project through participation to conferences and press releases. Furthermore, the first issue of the BioNexGen newsletter has been released in August 2011. This newsletter can be downloaded on BioNexGen website.
Finally, a first report on the IP mechanisms, trademarks and patent survey has been worked out. The results obtained during this study are presented in the deliverable D9.7 submitted to the EC in August 2011. Some deviations have occurred in this WP but they are not affecting the progress of the project.
WP10 is related to scientific and technical coordination. The organization of the kick-off meeting in Karlsruhe 7-8th November 2010 has been done in collaboration between HSKA and SEZ. After that, monthly telephone conferences have been launched. This has created a high team spirit among the partners allowing a smooth and efficient collaboration among them. The second partner meeting has been held in Patras, Greece and hosted by our partner FORTH. This meeting has been the occasion to present the first technical progresses of the project. The first interim progress report (Deliverable D10.1) has been submitted in May 2011.
Deviation: The kick-off meeting was originally planned 4-5th October 2010. However due to the uncertainty to be able to effectively start the project in September 2010, HSKA and SEZ have decided, at the end of August 2010, to postpone the kick-off meeting to 8-9th November.
WP11 is related to project management. SEZ was responsible for this WP. The first action within this workpackage was to ensure that all administrative documents were understood and signed by all partners. Then a scenario concerning the budget distribution among the partners and through the complete duration of the project has been elaborated. Furthermore, each partner has been reminded on his role and level of involvement in the project as well as on the budget planned for his participation in BioNexGen. The first payment to the partners was slightly delayed and has been mainly released in November 2010 due to the time needed to decide which payment plan was the most suitable for the project and also due to the time necessary to obtain official bank data from the partners. The money transfer to ABU in Syria could not yet be accomplished since HSKA administration came to know that the bank of ABU is on the black list. HSKA administration is working on this issue to get the problem settled. Another objective of this WP was the set-up of the financial management platform. The German company EMDESK has been selected for their very competitive offer and the quality of the interface for the management. The programming of EMDESK platform has been finalised in December 2010. To set up the platform, the data have been retrieved from the Annex I and the Grant preparation forms. From January 2011, the BioNexGen partners have been granted by an access to EMDESK. In March 2011, an internal budget reporting has been realised among BioNexGen partners. The costs spent by each partner have been analysed in order to evaluate if there was no major financial deviation occurring. Each partner has been contacted individually in order to clarify which are the costs that can be declared and in some cases to define some correctives actions. In April 2011, the second payment has been released. However, the coordinator was still unable to transfer the two first payments to the Syrian partner ABU.
Resuls obtained within period M13-M30
During the reporting period starting from the 01.09.2011 - 28.02.2013 WP1 through WP7 and WP9 through WP11 have been continued.
Within WP1 benchmarking data were obtained with the existing MBR membrane from MN by testing industrial wastewater (textile and olive mill wastewater) and model textile dye wastewater (MTDW). Small scale MBR pilot trials have been successfully pursued in the laboratories of the partners CBS and CMRDI using practical wastewater from textile and olive mill industry. In parallel, HSKA has continued small pilots using model textile dye wastewater. In addition laboratory experiments with model foulants (humic acid and alginate) were conducted using a flat sheet membrane cell. The water permeability and rejection with selected model compounds were also tested. A potential membrane manufacturing process of the BioNexGen PBM membranes has been designed. Additionally a cost estimate for the novel PBM material and CNTs has been made in cooperation with ITM-CNR and FORTH. Deviation: Pilot trial with olive mill wastewater have been done by CBS since ABU left the BioNexGen consortium due to political turmoil.
WP2 addressed theoretical aspects through computer modelling. ITM-CNR and FORTH were responsible for the tasks under this work package. The subdivision of pollutants into three groups according to their effective diameters has been made. However, in the last period, the solutes rejection has been analyzed on the basis of another molecular descriptor that is: the Minimum! cross-section! projection of the solute atoms on the opening of CNTs. In fact, in this way, it is possible to obtain more indicative information regarding the rejection ability of CNTs by ‘size exclusion’. According to solute Minimum! cross-section! a new classification has been performed. In order to investigate the possibility of having rejection through a mechanism different from size exclusion, the evaluation of the trapping energy of the solutes in the CNT with diameter equal to 1.66 nm is also carried out. Efficient solutes rejection could be driven by an unfavourable trapping energy (activated diffusion process) although the aforementioned analysis on the solute sizes gives a different response. Multi-scale simulations (QC and MC) have been planned for the next six months to explore this possibility. However it has been shown that for CNTs with diameter of 1.66 and molecules like tyrosol this is not the case. Calculations of the water flow rate as function of CNT diameters have been also carried out in this period by ITM-CNR to predict the number of MWCNTs to be used in the porous MN membranes in order to improve the total water flow. Various parameters such as the MWCNTs length and internal and external diameter were considered in this computational analysis. Quantum Mechanics calculations about the adsorption of antimicrobial particles on the active layers by means of CTAB, DTAB and AUTEAB surfactants have been carried out. These calculations concern the activity of the Task 2.2. Concerning the activity of the Task 2.1b nano-scale sorption of water molecules inside smooth single wall carbon nanotubes (SWCNTs) with different diameters has been simulated using a Grand Canonical Monte Carlo (GCMC). Armchair (n,n) SWCNTs with tube diameter of 8.14 10.86 13.58 16.28 and 27.14 (Å), respectively, with lengths equal to 40 (Å), have been used in this work. After thermodynamic equilibration has been reached, the water molecular structure and organization inside the CNT is examined as a function of CNT diameter. Hence, the ordering of the water molecules inside the CNTs was examined as a function of CNT diameters. Moreover, in this period, nano-scale sorption of small model molecules such as tyrosol, vanillic and p-coumaric acid inside SWCNTs with the aforementioned diameters has been simulated. The solute molecular structure and organization inside the CNT is examined as a function of CNT diameter, in addition to the ordering of the solute molecules inside these CNTs. The main objectives of Task 2.1c include: calculation of water (or ethanol) permeability and flow features / characteristics in the interior of composite membranes; simulation of motion of CNTs as they approach the polymer matrix. The objective of the Task 2.3 is the 3D representation of the aforementioned active layers. Active layer reconstruction stages initially included imaging techniques for retrieving 2D data of the material. SEMs of the active layer prepared by bi-continuous micro emulsion at several resolution levels were received from ITM-CNR. Image processing was carried out at FORTH/ICE-HT and several geometrical and topological data of the materials, such as the (surface) porosity and the autocorrelation function, were extracted and the milestone MS2 has been submitted at M18.
Within WP3, NTX in strong cooperation with FORTH has developed the optimum protocol for the incorporation of CNTs in membranes using the facilities of the company. Moreover, the effect of this process on the functional groups of CNTs was studied and the results showed that there is no effect on the amount of functional groups attached to the tube. During the last months, a new protocol for the incorporation of CNTs in the membranes has been under development. This new protocol aims at developing an easier and economical way for the large scale production of the new enhanced membranes with CNTs. The incorporation of CNTs into UP150T Microdyn-Nadir membranes has been attempted with the help of simple or dead-end filtration system. Different attempts have been performed. Basically, the protocol is the following: the infiltration of CNTs is carried out through the PET side, and below, the water flow rate is measured through the active PES side of the membrane in a dead-end filtration system. However, infiltration of CNTs has been also carried out through PES side. The infiltration of the CNTs is achieved in combination with tip sonication.
During this period, FORTH has focused their experiments on MWCNTs, Thin-MWCNTs, Thin-MWCNT-OH and Thin-MWCNT-COOH all provided by NTX, but also on SWCNTs and DWCNTs purchased from Cheap Tubes (USA). Substitution of the carboxylic acid groups (-COOH) with carboxyl anion groups (-COO-) where further prepared and infiltrated. The embedment of CNTs into the porous membrane was performed either from the support layer or directly to the thin selective layer. Study of dispersion of CNTs in suspensions has been achieved. CNT functionalized with deprotonation of carboxy groups (-COO-) present improved dispersion of CNTs in water facilitating the incorporation of CNTs in the MN membrane. The incorporation of CNTs to the membranes has been substantiated with the help of SEM images as well as with AFM images.
The best results with respect to water flow have been obtained with the membranes infiltrated with DWCNT and SWCNT through PES side and with the membranes infiltrated with Thin-MWCNT-COOH through PET side. In these cases the membrane rejection was was probed for model textile dye waste, composed principally by Acid Red (380 Dalton) and Remazol Brilliant Blue R (630 Dalton), and Reactive black (990 Dalton). Since the UP150 Microdyn-Nadir membrane belongs to the category of ultrafiltration membranes with a molecular weight cut off, MWCO, 150 kDalton and the model foulants used for the retention measurements present a MWCO of 1000 Dalton at most, that means they need a nanofiltration membrane to be retained, the retention ability improvement due to the incorporation of CNTs into the UP150 MN membrane will be progressively examined using Polyethylene glycol (PEG) model compounds of different molecular weights between the two above mentioned MWCOs.
Moreover, a thin film of polyethersulfone/CNT blend has been coated on existing commercial Nadir? microfiltration polymer membranes and water flux and MWCO will be also tested. Polyethersulfone/ CNT blend membrane can be produce from polyethersulfone/solvent/no solvent system by the immersion phase inversion process in water bath.
NTX has produced CTNs functionalized with a carboxy (-COOH) group. These functionalised CNTs were delivered to FORTH either for the incorporation in the membranes, or for further functionalization. The MWCNTs with 97% purity were functionalized with the protocol of NTX and the result led to 5% over the nanotubes weight of functional groups, while the thin-MWCNTs were functionalized with two different protocols achieving percentages of functional groups of 7 and 12% respectively. 2 grams of each of these materials were delivered to FORTH for further experiments.
NTX has also participated to the realization of cytotoxicity experiments, by developing the protocol for the dispersion of CNTs in PF127. For the development of this protocol several parameters were studied, while the facilities of the company were used. In our experiments, its toxicity was evaluated as internal control of the assay. In all of our experiments, we observed a cell viability of 80-90% with the 1% PF-127 which is the internal control of the assay and the effect of CNTs on cell viability is compared with PF-127 treated cells. The experiments are conducted at human lung fibroblasts. The toxicity of the compounds was evaluated in terms of cell viability and hemolytic potential of CNTs of interest. We assayed a range of concentrations of 0,125µg/mL to 25µg/mL for all synthesized CNTs. Pristine MWCNTs revealed a dose-dependent effect on the toxicity with the ranging from 50-70% cell viability, while SWCNTs and DWCNTs, according also to the literature exhibited higher toxicity compared with MWCNTs. MWCNTs-OH maintain high viability even at high concentrations (50% cell viability at the highest concentration) compared to pristine. A similar pattern is also exhibited by –COOH functionalized. Functionalization with water soluble polymer PSSNa also results in maintenance of high viability compared to pristine MWCTs.
Non-covalent interactions of phosphonium and ammonium groups with SSNa-functionalized CNTs lead to high toxicity profile at concentrations higher than 2,5µg/mL and 25µg/mL, respectively. The high antimicrobial activity of phosphonium groups is also depicted with high cytotoxicity profile. It is worth noticing that in lower concentrations tested the cell viability reaches the levels of the internal control of the assay. The covalent attachment of vinylic monomers onto phenol-functionalized CNTs exhibits no statistical significant changes in cell viability in the concentrations tested from 5 to 0,125µg/mL for thin-MWCNTs, whereas further introduction to vinylic monomers of the cytotoxic ammonium groups resulted in a balanced toxicity profile. The range of concentrations used in the cell proliferation assays did not exhibit any hemolytic activity nor the high concentrations tested (50µg/mL & 100µg/mL) for incubation intervals of 30min, 1, 2 and 3 h. The antimicrobial properties of polymer modified carbon nanotubes were also assayed in a range of bacterial populations. It seems that there is a different effect depending on the type of bacteria (gram positive or negative). However, the dispersion media, used for the toxicity assays, seems not to be optimal for such experiments.
The main work of WP4 has been done on the preparation of “loose” hydrophilic nanofiltration membranes with tailored pore size. The synthesis of Acryloyloxyundecyltriethyl ammonium bromide (AUTEAB) has still been synthesized following the consolidated route and used as surfactant for Polymerisable Bicontinuous Microemulsion (PBM) preparation. A new commercial surfactant Dodecyltrimethylammonium bromide (DTAB) was employed for PBM preparation in order to decrease membrane final cost.
PBM membranes prepared with AUTEAB were used as coating material for PES membranes from Microdyn-Nadir and sent to the partner HSKA for rejection tests with fouling model compounds and water permeability tests. Some variables, which can affect membrane polymerization procedure, were taken into account and evaluated (e.g. temperature and HEMA concentration). Different antimicrobial agents prepared by IZTECH, ITM-CNR and CMRDI were incorporated into the bicontinuous microemulsion which was polymerised following the traditional procedure used on MN PES membranes. The prepared membranes have been sent to IZTECH for the evaluation of antimicrobial activity. However PBM membranes themselves showed antimicrobial activity due to the presence of cationic surfactant (AUTEAB or DTAB). Thus, the addition of further antimicrobial agents was not required. Many efforts have been evaluated in order to embed CNTs into the PBM matrix, such as: increasing the viscosity of the microemulsion (varying CNTs concentration and chemical composition of the microemulsion), increasing the affinity between CNTs and the microemulsion (deprotonation of CNTs), temporary closing the pores of the commercial membranes (pre-treatment, double coating). Nevertheless no one of the applied techniques was found to be a viable method to incorporate CNTs into the PBM matrix. PBM membranes were characterised by SEM, AFM (Swansea University), contact angle measurements, permporometry tests, conductivity measurements and weight loss determination. In order to determine membrane cut-off, Gel Permeation Chromatography (GPC) analyses will be performed. New PBM membranes will be prepared and characterised with the commercial surfactant DTAB and they will be sent to Microdyn-Nadir for the assembly of a second MBR module.
Within WP5, Ag nanoparticles were synthesized by co-precipitation and new hydrothermal techniques. These Ag nanoparticles were characterized using transmission electron microscope. In addition, chitosan nanoparticles using TPP and POM as two alternative crosslinking agents were also synthesized. Their average size and their size distribution were determined by dynamic light scattering and their antibacterial activities against E. coli were determined. The cytotoxicities of chitosan /TPP nanoparticles on the lung fibroblast cells were measured. Furthermore, the Microdyn-Nadir membranes were modified with alginate and chitosan by changing polyelectrolyte concentration, number of layers, ionic strength and pH of the polyelectrolyte solution and deposition time. The water fluxes through both modified and unmodified membranes were measured and their antifouling properties were determined. The results have shown that all types of chitosan nanoparticles show antibacterial activity and the cytotoxicities depend on their concentration in the medium. Initial filtration experiments conducted in a small dead-end ultrafiltration module indicated that it could be possible to enhance antifouling properties of the MN membranes by layer-by-layer deposition of alginate and chitosan without significantly reducing the water fluxes through these membranes. In addition, antibacterial membranes with better water flux can be attained by incorporation of AgCl/TiO2 in the chitosan solution used for building the outmost layer of the modified commercial membranes. It has been indicated that higher rejection can be acquired by appropriately modifying the membranes.
The objective of WP6 is to characterize the surface and cross section morphology of the prepared membranes samples and to analyse the foulant properties on their surface subsequent to the fouling experiments with model waters. This work will support the optimisation of the membrane materials development within WP 2, 3, 4, 5. The work will be carried out through close cooperation between SU and HSKA and it will give the necessary feed-back to the WPs 2, 3, 4, 5. Within WP6 for this reporting period, for task 6.1 AFM and SEM measurements on the surfaces of membranes have been carried out to examine membrane structure and to assess fouling of membranes used for cross-flow filtration of model foulant wastewater (as part of task 6.3). These measurements have shown the surface morphology of fouled and unfouled membranes, produced measurements of surface roughness, thickness of adhering foulant layers. Pristine membranes showed a much lower surface roughness than membranes which were fouled with humic acid. Correlations were found between measured surface roughness and foulant layer thickness, showing that for the polymer membranes measured surface roughness can be used as a corollary for the degree of surface fouling. Deliverable report 6.1 was issued for this task. For task 6.2 colloid probes were produced containing a covalently bound coating layer of humic acid as a model membrane foulant. Force measurements were carried out between these coated colloid probes in both high purity water and in model textile dye wastewater (as provided by HsKA). This has allowed the membranes tested in this way to be ranked according to adhesion forces between model foulant and the membrane surfaces in two different conditions. Deliverable report 6.2 was submitted for this task. Long term cross-flow filtration tests with model foulant and industrial wastewaters were carried out (task 6.3). A deliverable report (D6.3) has been issued for this task. Task 6.4 filtration of activated sludge in a side-stream MBR laboratory reactors has been carried out. For task 6.5 three different types of membranes called layer by layer membranes, CNTs incorporated membranes and PBM coated prepared by BioNexGen project partners, IZTECH, FORTH/NTS and ITM-CNR respectively were tested with pure water, model foulant and biological sludge.
The purpose of WP7 is to prepare small three-envelope membranes with the novel materials for the upcoming pilot trials in the MENA countries Tunisia and Egypt. The commercial lamination process of MN has to be modified since the novel membrane materials are not as temperature stable as the commercial one. Therefore a commercial low-temperature glue (T< 100°C) was selected and tested in the technical laboratory of MN. The new three panel membrane prepared by the low temperature lamination process showed sufficient mechanical stability in long-term laboratory tests. After final selection of the target membrane material the sheets will be laminated by this process for the upcoming pilot trials within WP8.
WP9 supported dissemination, exploitation and training activities. During this period, several newsletters were produced and used as dissemination tools for BioNexGen results. These newsletters can be downloaded on BioNexGen website. Several partners have participated to conferences and presented by BioNexGen through posters and oral presentations. Two scientific publications have been released during this period. The first training workshop focusing on basic principles and state-of-the-art of "Membrane based wastewater treatment and reuse" has been held at CBS in Sfax, Tunisia. This workshop took place on the 8th and 9th of March 2012. The deliverable D9.4 “Report on the 1st training workshop on novel MBR technology” provides an overview of the presentations given during the workshop. The second training workshop on “Functionalized membranes for Wastewater Treatment - Nanoparticles and surface modifications” has been organised during this period and it will take place in May 2013 (15-17th) in Cetraro, Italy. In addition, technology watch activities have been performed by the mean of patents searches.
Furthermore, the exploitation activities have been started with the organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and clarify some aspects concerning the ownership and the use of these results.
WP10 is related to scientific and technical coordination. This work has been conducted in close cooperation between HSKA and SEZ. An active support has been provided to the partners for the organization of the partners meetings. Monthly telephone conferences have been continued. This keeps high team spirit among the partners and this allows a smooth and efficient collaboration among them. HsKA also initiated a variety of bilateral discussions with all partners. This support was necessary to orientate the research performed within the project towards industrial expectations. HsKA and SEZ have also organised meetings with the industrial partner MN in order to keep them update about the progresses of the project.
WP11 is related to administrative and financial management of the project. SEZ is responsible for this WP. The first two months of this period (01.09.2011-31.10.2011) have been fully dedicated to the finalisation of the first periodic reporting. The activities and the Form Cs have been all submitted to the EC on the 31.10.2011. Since March 2011, the Syrian Arab Republic is facing major political turmoil which has lead to a great instability. Unfortunately, this political situation has also some consequences on BioNexGen project. Indeed, the partner ABU is located in Homs (which is the center of the opposition to the Syrian regime). Over the last months the situation in Homs has been seriously altered. Unfortunately, this political context has posed a challenging scenario and has imposed several constrains for the implementation of ABU’s work within BioNexGen. In March 2012, the coordinator has been informed that ABU was excluded from the first interim payment due to the sanctions taken by the EU against Syria. During the M24 partner meeting, the steering committee has voted for the termination of ABU’s participation starting from the 1st of March 2012. ABU has been informed of our decision and has accepted the consortium’s choice.
Once the sanctions against Syria will be removed, the coordinator will try to pay ABU for costs incurred within the first 18 months of BioNexGen if these costs are accepted by the European Commission. Since the consortium has to submit an amendment for ABU’s participation termination, it was decided to submit requests for technical modification at the same time. Indeed after 24 months, it becomes clear that some of the tasks planned for the project were actually no longer feasible due to results obtained so far. The third and the fourth instalments from the pre-financing have been transferred to the partners in October 2011 and April 2012 respectively. Furthermore, the project coordinator has received in March 2012 the first interim payment based on the costs declared during the first periodic reporting. However due to the sanctions taken by the EU against the Syrian regime, ABU’s has been excluded from the first interim payment. The respective share of the interim payment has been established for all partners. This share of the interim payment will be distributed to the partners over 2 instalments. The first instalment has been transferred in October 2012 and the second will be transferred in April 2013.
Deviations from the work plan:
An amendment is preparation concerning ABU’s participation termination and the major technical deviations.
Only one partner (ABU, Syria) has been not paid since the beginning of the project. Many attempts have been tried to transfer the money until March 2012. Since March 2012, the coordinator did not further try to transfer any payment to ABU due to the official EC letter concerning ABU’s payment suspension
Resuls obtained within period M31-M42
During the reporting period starting from the 01.03.2013 - 28.02.2014 WP1 has been finished; WP2 through WP7 and WP9 through WP11 have been continued and WP8 has been started.
Within WP2 three Tasks: Task2.1 task2.2 and task2.3 has been carried out.
Tasks 2.1 is divided in three other tasks: 2.1a 2.1b 2.1c. In particular in Task 2.1a advanced quantum chemical calculations have been carried out. Instead, advanced MC and MD calculations are performed in the Task 2.1b while calculation of water (or ethanol) permeability and flow features in the interior of membranes, in addition to simulation of CNTs motion as they approach the polymer matrix have been carried out in the Task 2.1c. In Task 2.2 the final aim of the work was to figure out (to predict by computational modelling) whether a good adhesion of POM antibacterial nanoparticles on the active membrane coating is possible without loss of their activity. Finally, the purpose of the last Task 2.3. is the computational 3D representation of the active layer (membrane coating) of composite membranes impregnated with CNTs, in order to provide guidance to the preparation process.
The WP3 consists of six Tasks: 3.1 3.2 3.3 3.4 3.5 and 3.6. of which tasks 3.1 and 3.6 are already completed. Task 3.2 is dealing with Incorporation of carbon nanotubes in commercial polymer membranes from Microdyn Nadir. Nadir® microfiltration polyethersulfone (PES) hydrophilic polymer membranes have been preferably utilized. Task 3.3. According to the valid amended version of the Annex I (description of work), the synthesis of carbon nanotubes/polyethersulfone blend membranes via the phase inversion method is the new target for this task. Prior to membrane synthesis, thin-Multiwall carbon nanotubes have been functionalized with carboxylic groups and afterwards de-protonated, providing the CNT with COO- groups. Functionalization increases dispersion of CNT in solvents. Water flux test as well as molecular weight cut-off (MWCO) of the blend membrane will be determined. Task 3.4 In the present reporting period, optimization of the crosslinking reaction of carbon nanotubes, functionalized with PGMA moieties, embedded in the nanoporous filters, was detected by testing various crosslinking methods, at different temperature values, reaction time and crosslinker quantity. In the previous reporting polymer-functionalized CNTs were further modified by incorporation, through non-covalent attachment, of antimicrobial quaternized phosphonium (PSSPhC16) and ammonium salts (PSSAmC16) in task 3.5. CNTs functionalized, either covalently or non-covalently, with biocidal groups have been developed and their toxicity studies have been conducted. In addition to this, the covalent attachment of biocidal groups on functionalized CNTs has also taken place, using polymerization of vinylic monomers and subsequent quaternization with proper amines (P(AA25-co-VBCHAM)). The above mentioned systems have been studied in order to find the optimum experimental conditions. In the present reporting period, for comparison reasons, the synthesis of amine functionalized monomers (VBCTEAM) and the subsequent polymerization on the surface of carbon nanotubes was tested in order to be further studied in terms of toxicity.
Within WP4 main work carried for the last period (M31-M42) of BioNexGen project has been focused on:
1. The synthesis of a cationic polymerisable surfactant AUTEAB. The possibility to use a commercial surfactant (DTAB) was also evaluated and applied (task 4.1).
2. 30x30 cm PBM membranes preparation by coating the bicontinuous microemulsion on MN PES membranes and sent to Microdyn Nadir for the preparation of 2 MBR modules. In order to reduce cost impact of AUTEAB on PBM membrane preparation, a new commercial surfactant (DTAB) was used (task 4.2).
3. RuPOM-AUTEAB nanoparticles were incorporated into the PBM membrane and their catalytic activity was evaluated (task 4.3).
4. PBM membranes were characterised at laboratory scale by SEM, AFM (Swansea University), contact angle measurements and permporometry tests. Membrane cut-off measurements by Gel Permeation Chromatography (GPC) analysis, acquired in this project, were carried out on PES commercial membrane and are, at the moment, in progress on PBM membranes prepared with the commercial surfactant (task 4.4).
Highlighting the results obtained
1. DTAB surfactant was successfully applied for PBM preparation allowing to decrease the final membrane cost.
2. Commercial surfactant DTAB allowed to obtain a well dispersed and homogenous bicontinuous microemulsion. The use of DTAB allowed to decrease membrane final costs. The cost of 1 m2 of PBM coating was about 5€.
3. RuPOM nanoparticles were successfully entrapped within the microemulsion structure and their activity was preserved and tested.
4. From characterisation tests PBM membranes showed good antifouling properties, higher hydrophilicity, higher rejection to organic molecules (model dyes) and a reduced pore size in comparison to PES commercial membranes.
The overall objective of the WP5 is to prepare antimicrobial nanoparticles which can be incorporated into nanofilms through polymeric bicontinuous microemulsion (PBM) technique and modify the nanofilms and commercial MN membranes with the layer-by-layer technique. Overall work done within this workpackage during this period can be summarized as follows:
a) Based on water fluxes, the antifouling behavior and the antibacterial activities of unmodified and LBL modified membranes, 9 membranes were selected and sent to Swansea University to characterize with the scanning electron microscope and atomic force microscope.
b) The polyelectrolytes with different ionic strength, ( 0, 0.5 and 1 M NaCl), concentration (0.1 1 and 2 mg/ml), pH (pH 5 or 6 for chitosan solution ) and number of layers (1.5 2.5 and 3.5 bilayers) were directly deposited on the commercial membrane. The rejection properties of these membranes were determined with dextran (Mw=73,000 ) and raffinose (Mw=594 ).
c) Different macromolecules (Polyvinyl alcohol (PVA) Mw=~31,000-50,000; Polyvinylpyrrolidone (PVP) Mw=~55,000; Polyethylene glycol (PEG) Mw=~40,000 and Polysodium 4-styrenesulfonate (PSS) Mw=~70,000) were permeated through the commercial membrane under 0.7 bar pressure and their dextran rejection values were determined.
d) Polyelectrolytes were deposited on PVA infiltrated commercial membrane and the rejection properties were determined with the raffinose.
e) Based on highest raffinose rejection values obtained, two membranes were selected and prepared with 30 cm x 30 cm sizes and they were sent to HSKA for testing their performances in 2 cross flow units and in a side stream MBR as well. Pure water and humic acid permeability as well as red and blue dye rejection values of these membranes were measured .
f) The influences of heat treatment applied during lamination of membrane sheets on the water fluxes and rejection properties of the membranes were investigated in a small scale filtration unit at IZTECH and in a larger scale cross flow filtration units at HSKA.
g)The effect of coating both surfaces and only active surface of the commercial membrane on the rejection values of the membranes was first investigated in a small dead-end filtration unit at IZTECH. Based on the results, two membrane samples selected based on highest raffinose rejection values were sent to HSKA for further tests in cross flow units.
h) New commercial PES membrane with a lower molecular weight cut off value than the one used throughout the project was also modified with polyelectrolyte deposition to improve its water permeation characteristics. Parameters tested to modify membranes were number of bilayers, polyelectrolyte concentration, use of two polycations on the outermost top layer and blending a hydrophilic polymer , polyethylene glycol (PEG) with the polyelectrtolytes in each layer.
Highlights of the results obtained
a) The dextran rejection of around 90 % was obtained by coating the commercial membrane with 0.1mg/ml chitosan/0.1 mg/ml alginate /1 mg/ml chitosan where 0.5 M NaCl was added to each polyelectrolyte solution.
b) Molecular weight cut off value of the commercial membrane decreased by infiltrating the hydrophilic polymers under pressure.
c) Both the charge and molecular weight of the polymer used for infiltration are important for decreasing the molecular weight cut off value of the existing membrane.
d) Layer by layer deposition of polyelectrolytes on the PVA permeated commercial membrane improved the rejection properties of the membranes.
e) Deposition of polyelectrolytes on the unmodified commercial membrane and then permeating PVA through layer by layer deposited polyelectrolytes also gave similar rejection values compared to the case when polyelectrolytes were deposited on the PVA infiltrated commercial membrane.
f) PVA permeated commercial membrane coated with 1 mg/ml chitosan solution (Altink_01) and commercial membrane coated with 0.1 mg/ml chitosan /0.1 mg /ml alginate /1 mg/ml chitosan including 0.5 M NaCl and then infiltrated with 10 g/l PVA (Altink_02) showed considerably higher pure water as well as humic acid permeabilites than that of commercial membranes.
g) The regain of the flux after flushing three times with pure water was around 70 % for Altink_02 sample and 33 % for Altink_01 sample , however, for commercial membrane the regain always fluctuated between 10 and 20 %.
h) The humic acid rejection values of modified membranes were similar to that of commercial membranes while the dye water permeability was slightly higher than that of commercial PES membrane.
i) The rejection of red and blue dyes of the Altink_01 membrane was found similar to the values obtained with commercial membrane while Altink_02 membrane showed higher blue dye and lower red dye rejection values.
j) Altink_02 membrane in a side stream MBR showed a sudden increase in the permeability at the end of 15 days which remained higher than that of the commercial membrane after 15 days.
k) Heating the membrane without glycerol coating caused a decrease in water flux while heat treated membranes after glycerol treatment showed significantly higher water fluxes compared to the Altink_02 membrane not subjected to heating.
l) Heat treatment applied to the Altink_02 membrane did not significantly change its rejection property.
m) The results obtained at HSKA showed that that pure water permeability of commercial membrane decreased significantly with time while that of modified membranes remained stable and heat treatment enhanced the permeability of the Altink_02 membrane.
n) All LBL modified membranes showed higher dye water permeabilities than the commercial membrane while their red and blue dye rejection values were similar to that of the commercial membrane.
o) Application of layer of layer deposition of polyelectrolytes on both surfaces of the commercial membrane or just on its active surface was found to affect the rejection properties of the membranes.
p) For the new commercial PES membrane with a lower molecular weight than the one used throughout the project, the highest water flux was measured with 1.5 bilayer membranes (CS/ALG/CS) prepared with 0.05 mg/ml polyelectrolyte concentration.
q) Blending chitosan (CS) with another polycation, whey protein isolate, at a ratio of 1:1 did not change the water flux values of 1.5 bilayer membranes prepared from new support membrane.
r) Similarly, blending PEG with CS at a ratio of PEG/CS: 1/5, 1/10 to form a single layer on the new commercial membrane or blending both CS and Alginate with PEG in each layer at a ratio of 1/1 to form 1.5 bilayer membrane did not improve the water flux values compared to the cases where polyelectrolytes were used alone for coating.
Within WP6, for task 6.1 AFM and SEM analysis of membrane samples received from various partners were undertaken to characterise the surface and cross sectional morphology of fabricated membranes and membranes fouled by filtration tests. Task 6.2 continued with force measurements carried out using silica glass colloidal probes to simulate the attachment of silica foulants to several PBM membranes in clean water and model dye wastewater. These measurements were carried out to complement previous measurements in this tasks using a humic acid coated probe. In addition filtration tests were carried out with practical wastewaters and using membrane bioreactors with side stream modules under anaerobic conditions for tasks 6.3 and 6.4. For task 6.5 filtration with commercial and layer by layer prepared membranes were carried out using clean water, model wastewater and activated sludge to give a comparison of the performance of the fabricated membranes compared to commercially available membranes.
WP7 addresses the modification of the production process and testing of small prototype membrane modules (stack of 3 laminate sheets 25*25 cm²). The work will be conducted with the findings resulting from WP6 and supported through SU and HSKA.
Within WP8 the following tasks were carried out
Field study with olive mill wastewater
In this reporting period, CBS has just started two MBR units working in parallel with real olive mill wastewater (OMW). The first pilot MBR was running with the commercial Microdyn-Nadir membrane (MBR1) and the second MBR with the PBM coated membranes (MBR2). The trials were started with diluted OMW at a flux of 2 L/h/m2. The flux was increased stepwise to 3 L/h/m2. Under these operating conditions, the COD removal efficiency was quite similar for both MBR units reaching 26.47% and 23.53% for MBR1 and MBR2, respectively after 8 days of continuous treatment.
A report of the results achieved in Task 8.1 will be prepared and is planned to be submitted as deliverable D8.1 as agreed.
Field study with textile effluent
During M31-M42, CBS has started two MBR units working in parallel with real textile wastewater (TWW). The first pilot MBR was running with the commercial Microdyn-Nadir membrane (MBR1) and the second MBR with the PBM coated membranes (MBR2). In this task, long term trials with textile effluent studying crucial parameters such as suction pressure, BOD, TOC, dissolved O2, COD and colour removal efficiencies, drying residues, pH, temperatures, conductivity etc have been investigated. The trials were started with diluted TWW at an average OLR of 0.7 g COD/l, a flux of 2 l/h/m2 and a HRT of 3.5 days. Under these operating conditions, the COD removal efficiency was quite similar for both MBR units with average of 94 and 95% for MBR1 and MBR2, respectively while, the TOC removal efficiency was higher for MBR2 with an average of 96% (MBR1 91%).
After the start-up period, the flux was gradually increased to 6 l/h/m2, The COD removal efficiency were quite similar for MBR 1 and MBR 2 with values of 79.80% and 80.20% for MBR1 and MBR2, respectively. At this flux, colour removals were also quite similar reaching 58.97% for MBR2 and 54.18% for MBR 1. However, under the same flux the TMP of MBR1 increased to 1 bar while MBR TMP remained at 100 mbar. Both units were stopped after 147 days of continuous treatment.
A report of the results achieved in Task 8.2 will be prepared and is planned to be submitted as deliverable D8.2 as agreed.
Field study with cosmetic wastewater
During M31-M42, CBS has also started one MBR unit running with the PBM-coated Mn-membranes and working with real cosmetic wastewater. The trial was started in parallel with OMW trials. In this task, The MBR was fed with diluted cosmetic wastewater at a flux of 2 L/h/m2. The flux was increased stepwise to 3 L/h/m2. Under these operating conditions, the COD removal efficiency reached 82.97% while the anionic surfactant removal was 98.57% after 6 days of continuous treatment. The TMP was steady at 100 mbar under the same flux.
A report of the results achieved in Task 8.3 will be prepared and is planned to be submitted as deliverable D8.3 as agreed.
Within WP9 the following objectives were achieved. The objectives of this period were the following:
• Organisation of the second training workshop focusing on basic principles and state-of-the-art of "Functionalized membranes for wastewater treatment - Nanoparticles and surface modifications". The workshop took place in Cetraro, Italy from 15th to 17th May 2013.
o The deliverable D9.5 “Report on the 2nd training workshop on novel MBR technology” provides an overview of the presentations given during the workshop.
• Organisation of BioNexGen final conference under the topic “Use of nanotechnology in membrane for water treatment”. The conference was held from 8th-10th October 2013 in Izmir, Turkey.
o The deliverable D9.6 “Report on the final international conference” provides an overview of the presentations given during the final conference.
• Organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and to clarify some aspects concerning the ownership and the use of these results.
o The deliverable D9.9 “Technology Implementation Plan” provides an overview of the exploitable results obtained during the project.
• Updates on patents search and IPR to implement for protecting BioNexGen exploitable results.
o The deliverable D9.8 “IPR Report” provides an overview on the IPR foreseen for the exploitable results plus an overview of the relevant patents families.
• To continue the dissemination activities through the website, the newsletters, the participations to conferences and the networking activities.
o The issues 5th and 6th of BioNexGen were produced and made available on the project website.
o The deliverable D9.10 “Review of Dissemination Activities” provides an overview on all the dissemination activities performed by the partners (oral presentations, posters, articles, internet presence and the newsletters published).
The objective of WP10 is to ensure an efficient and pro-active scientific coordination of the project and monitoring of the technical components of the project. The following objectives have been achieved:
• Smooth and effective collaboration within the consortium
• Delivery of deliverables and milestones in time
• High quality of the project results
• Tracking and effective mitigation of risks
• Anticipation unexpected developments or new opportunities
The following significant results can be highlighted:
• Successful M30, M36 and M42 partners meetings
• Effective collaboration among the partners
• Smooth scientific coordination through monthly telephone conferences
The objective of this WP11 is to ensure an efficient and pro-active coordination of the project by administration, organisation and monitoring of the administrative and financial components of the project.
Therefore, this period was dedicated:
- To perform the second periodic reporting in accordance with the criteria defined by the EC.
- To ensure that all the administrative and financial documents (Form Cs) were understood, signed by all the partners and delivered on time to the EC for the second periodic reporting
- To distribute the EC contribution received by the coordinator among the partners
- To maintain updated the management platform
- To provide assistance to the partners on administrative and financial aspects
- To finalise the amendment request regarding the termination of Al Baath University (ABU) participation and some technical modifications in the Annex I.
Potential Impact:
Socio-economic impact:
Wastewater reuse is an accepted practice in Europe and the MENA countries with limited rainfall and very limited water resources. Wastewater reuse has become already an integral effective component of long term water resources management.
MBR technology is an effective solution for transforming various wastewaters into high-quality effluent suitable for discharge and/or for reuse. Experts believe that the market potential of MBR technology in the next 5 to 10 years is high since an increase in treated wastewater demand is expected.
Furthermore, MBR technology presents many advantages over conventional activated sludge such as high flexibility, interoperability, high performance, low footprint.... Of course this technology possesses also drawbacks such as high investment and operating costs or membrane fouling that could prevent a wider implementation.
Moreover, some countries have developed comprehensive water treatment and reuse standards to provide direction, and, encourage and finance wastewater reuse programmes.
It is clear that treated wastewater reuse plays an important and increasing role. State regulation should ensure safe wastewater reuse practices locally. However the difference in standards between EU member state regulations can cause confusion over what is best practice and sustainable for local situations and type of applications.
Next challenges to overcome are the costs reduction for producing treated wastewater production and the increase of treated wastewater availability.
BioNexGen project aimed at developing a MBR technology that has important impacts on the implementation of water reclamation and purification plants. Indeed, this one-step process technology has achieved breakthroughs by:
• Increasing the efficiency and the operational time due to less membrane fouling which permits a constant high membrane flux
• Decreasing operational and maintenance costs
• Improving the quality of the filtration by retaining micro-pollutants
• Increasing the performance of the biological degradation by improving the permeability of the membrane to salts and reducing the generation of toxic sludge
To attain these breakthroughs, three novel membrane materials were developed by applying different novel techniques. The developed membranes were prepared by the following ways:
(1) Functionalization of membranes through Layer by Layer (LBL) Technique
(2) Polymersiable bicontinuous microemulsion (PBM) coating on commercial PES membranes incorporated with functionalized CNTs
(3) PBM coating with a cost effective surfactant
The performances of the three different types of BioNexGen membranes were evaluated with DI water, model foulants, micro-pollutants and biological sludge treatment.
From the technological performance and economic analysis, it can be concluded that DTAB based PBM membrane material can be considered as the best overall performing membrane materials with possibility of producing variable performing membranes by changing the chemical compositions of the membranes during the preparation process.
The process is technically efficient and the membranes are economically viable because of their high fouling resistance. The new membranes are advantageous as they reduce the operating and investment costs on an industrial scale by an average of 25 %.
Further details can be found in the deliverable D6.5 “Report on techno - economical evaluation of membrane development”.
In conclusion, we believe that most of current weaknesses of MBR technology will be overcome by the new membrane developed in BioNexGen and consequently high market potential can be achieved.
Dissemination:
All BioNexGen project partners have been very active throughout the course of the project with disseminating the project and their research results. This constituted in many event participations, general publications and peer-reviewed articles. Even beyond the project’s termination, several articles related to BioNexGen project outcomes will be published, as those are currently being prepared.
BioNexGen’s website can be consulted under the following address: http://www.bionexgen.eu.
Further details can be found in the deliverable D9.1 “Project Website”.
In addition a project brochure was developed. This brochure was used as a promotional instrument and it has been utilised to increase visibility of BioNexGen and to disseminate the project’s objectives. The project’s brochure contains the main elements of the BioNexGen project (project summary and objectives, information and logos of the partners, contact details for further information). The project brochure was available in English and a translated inlay was available in German, Turkish, Greek and Arabic.
Further details can be found in the deliverable D9.2 “Project’s brochure”.
During the project 10 scientific papers were published, 1 scientific paper is under review, 6 scientific papers are in preparation, 3 PhD dissertations were achieved (Federica Bisignano - CNR-ITM, Francesco Galiano -CNR-ITM, Shamim A. Deowan - HSKA) and 2 PhD dissertations will be achieved in 2014 (John Anastasopoulos - FORTH, Inès Friha - CBS). Furthermore, the partners have been involved in more than 100 dissemination activities. 6 electronic public newsletters were produced.
Further details can be found in the deliverable D9.10 “Review of dissemination activities”.
Within BioNexGen, three events of high relevance for the project have been set-up:
1) First Training Workshop in Tunisia (March 2012)
2) Second Training Workshop in Italy (May 2013)
3) BioNexGen Final International Conference in Turkey (October 2013)
First Training Workshop:
The First Training Workshop “Membrane based Wastewater Treatment and Reuse” was held at Centre de Biotechnologie de Sfax in Sfax, Tunisia on 8th & 9th March 2012. It was organised within the scope of Task 9.4 “Organisation and implementation of training workshop on novel MBR technology” of the Description of Work.
The organization of the first workshop on MBR technology has been done in collaboration with CBS, SEZ, HSKA and CNR-ITM. The programme of this two-day event has been co-developed by CBS, HSKA and CNR-ITM. An electronic flyer has been created by SEZ for the workshop announcement. In addition to the e-flyer, the workshop has been also announced on BioNexGen project website as well as in some partners’ websites. Approximately 80 external participants have been registered to the workshop among them many companies were also present. In total, around 100 persons have attended to the workshop.
Further details can be found in the deliverable D9.4 “Report on the 1st training workshop on novel MBR technology”.
Second Training Workshop:
This second workshop has focused on basic principles and state-of-the-art of "Functionalized membranes for wastewater treatment - Nanoparticles and surface modifications". It has been hosted by CNR-ITM from the 15th to the 17th of May 2013 in Cetraro, Italy. Besides theoretical seminars, this workshop has been combined with a visit at CNR-ITM laboratories.
The organization of the second workshop on MBR technology has been done in collaboration with SEZ, and CNR-ITM. The programme of this event has been co-developed by HSKA and CNR-ITM. An electronic flyer has been created by SEZ for the workshop announcement. In addition to the e-flyer, the workshop has been also announced on BioNexGen project website as well as in some partners’ websites.
Approximately 40 participants from different companies, universities, research institutes and companies coming from European and MENA countries have attended to the workshop. During this 3-days workshop, 20 oral presentations were given and 11 posters were presented. This workshop has focused on functionalised membranes, antimicrobial materials, nano-particles, carbon nano-tubes and membrane applications in wastewater treatment, which are BioNexGen’s main research topics.
Further details can be found in the deliverable D9.5 “Report on the 2nd training workshop on novel MBR technology”.
BioNexGen Final International Conference:
The final conference was the main part of the Task 9.6 “Final International Conference” which aims at fostering the dissemination of the project’s results to the academic community as well as to industrial and NGO stakeholders, and at raising mutual understanding and awareness for water related problems and for wastewater treatment technologies.
This final conference was called NANOMEMWATER international conference and has focused on application of nanotechnology in membranes for water treatment. It has been hosted by IZTECH from the 8th to the 10th of October 2013 in Izmir, Turkey. For the location the partner IZTECH was chosen as conference venue, since Turkey is the gateway between European and the MENA countries. Besides talks on the second and the third day, the conference opened with a poster presentation on the first day.
The organization of the NANOMEMWATER final conference has been done in collaboration with SEZ and IZTECH. The conference website www.nanomemwater.org has been created by IZTECH to raise the awareness on the conference. Approximately 80 external participants have been registered to the conference. In total, around 70 persons have attended the conference.
Further details can be found in the deliverable D9.6 “Report on the final conference”.
Participation in Clustering events:
As networking and clustering have been defined as important aspects of the dissemination strategy, the consortium actively engaged in several workshops and clustering events to present their research performed within BioNexGen. Hence, especially the nano4water Cluster has played an important role as a dissemination platform for the project consortium. The members of the nano4water Cluster are project committees of EU-funded research projects dealing with the topic of nanotechnologies for water treatment. In the framework of this cluster’s annual dissemination workshop BioNexGen project partners have regularly given presentations to researchers working in related areas.
Exploitation of results:
In the course of the BioNexGen project, the technological developments were continuously and carefully monitored in order to identify the generated foreground and to correctly assign the foreground to the involved partner(s) (Task 9.8: Exploitation strategy).
The assessment of the technological developments and of the generated foreground was performed during the exploitation strategy seminars. Three of them were organised during BioNexGen.
1st Exploitation strategy seminar (M18) with the support of an expert from the ESIC-team
2nd Exploitation strategy seminar (M30)
3rd Exploitation strategy seminar (M36)
Through these seminars the following outcomes were obtained and discussed:
1) Identification of novel developments = BioNexGen foregrounds
2) Definition of exploitable results
3) Assessment of the exploitation potential of the foregrounds identified
4) Determination of partner in charge (for a given exploitable result)
5) Characterization of results (result characterization sheets)
6) Establishment of individual exploitation claims
It is worth to note that over the 10 exploitable results identified in the project, 6 of them will be protected by a patent application.
Result 1:
A new technical process based on membrane bioreactor technology using either MN membranes or MN modified ones for efficient treatment of textile (dyes) and olive (polyphenols) wastewaters.
Owned by: CBS and HSKA
IP protection: Licenses or confidentiality agreements
Partners interested in exploitation: CBS and HSKA
Result 2:
Software that defines optimal CNTs diameters and functionalization for an efficient rejection of solutes
Owned by: CNR-ITM
IP protection: Copyrights, licenses
Partners interested in exploitation: CNR-ITM
Result 3:
Tailored made CNTs for the efficient incorporation in membranes
Owned by: NTX
IP protection: Non disclosure agreement, Know-how, Trade secret, licenses
Partners interested in exploitation: NTX
Result 4:
CNT embedment in anisotropic polymer membranes.
Owned by: FORTH and NTX
IP protection: Patent, Non disclosure agreement, trade secret, licenses or copyright if scientific publication
Partners interested in exploitation: FORTH and NTX
Result 5:
Decoration of carbon nanotubes with functional polymers.
Owned by: FORTH and NTX
IP protection: Patent, Non disclosure agreement, trade secret, licenses or copyright if scientific publication
Partners interested in exploitation: FORTH and NTX
Result 6:
Detection of CNTs in water via SERS
Owned by: FORTH
IP protection: Patent application will be submitted
Partners interested in exploitation: FORTH
Result 7:
Preparation of a novel coating based on Bicontinuous Microemulsion Polymerisation (PBM).
Owned by: CNR-ITM and HSKA
IP protection: Patent application submitted
Partners interested in exploitation: CNR-ITM and HSKA
Result 8:
A sol-gel procedure to prepare a mixed oxide containing TiO2, AgCl nanoparticles and commercial POM (H3PW12O40).
Owned by: IZTECH
IP protection: Patent application will be submitted
Partners interested in exploitation: IZTECH
Result 9:
Development of use of colloidal probe technique to screen polymer membranes for screening based on favourable foulant attachment forces under process conditions
Owned by: SU
IP protection:
Partners interested in exploitation: SU and HSKA
Result 10:
Modification of LBL technique to convert ultrafiltration into nanofiltration membranes.
Owned by: IZTECH
IP protection: Patent application will be submitted
Partners interested in exploitation: IZTECH and HSKA
The deliverable D9.9 “Technology implementation plan” provides an overview of the exploitable results generated during BioNexGen.
List of Websites:
http://www.bionexgen.eu/
According to the World Health Organisation (WHO), the most dangerous threat for health of mankind emerging within the next years is polluted water. Though polluted water and water shortages demand for a sustainable water usage and recycling of wastewater, the barriers are high to adopt these outside of Europe: Clean water as basis for health and good living conditions is too far out of reach for the majority of the population. Thus, neither sustainable consumption nor reinforcement of governmental regulations are effective drivers to force the industry to adopt sustainability policies.
Membrane bioreactor (MBR) technology is regarded as a key element of advanced wastewater reclamation and reuses schemes and can considerably contribute to sustainable water management. MBR technology is used for wastewater treatment and reuse in municipal, agricultural and a variety of industrial sectors in Europe and Middle East and North Africa (MENA).
The overall objective of BioNexGen is to develop and test on pilot scale a new class of functional low fouling membranes for membrane bioreactor technology with high water flux and high rejection of organic pollutants with low molecular weight. The field tests with these newly developed membranes will be carried out with wastewater from 3 different industries (cosmetics, textiles and olive oil industry) which play an important role in the MENA countries and will be compared to conventional, commercially available membranes for benchmarking.
The consortium will develop a novel single step Nano-Filtration (NF) MBR operated with low energy consumption; small footprint, flexible design, and automated operation make it ideal for localized, decentralized wastewater treatment and recycling in the European and MENA countries.
Project Context and Objectives:
The overall objective of this project period was first of all to continue providing basic benchmarking data for all BioNexGen R&D activities. To this end benchmarking pilot trials using the existing MN membrane and practical industrial wastewater have been pursued by the partners CMRDI, CBS and HsKA. Besides that laboratory work on novel membrane materials such as PBM coating, CNTs and layer-by-layer technology has been conducted. Cost estimate for the potential BioNexGen manufacturing process has been carried out. Moreover computer modelling and laboratory activities continued with focus on modifying the existing commercial MN membrane. The emphasize was given on theoretically studying structures-properties relationships of CNTs and incorporating vertically aligned CNTs in the existing MN membranes as well as casting a novel nano-scale layer with tailored pore size onto the membrane surface. Characterisation of novel membranes regarding surface morphology, water flux and rejection of model compounds were conducted. Preparation of technical module envelopes for pilot trials in MENA countries were done. Finally field tests using these novel membrane based modules were carried out with textile wastewater, olive mill wastewater and cosmetic wastewater and the results were reported in different deliverables.
The specific objectives of the project were:
WP1:
• Securing benchmarking data with existing MBR modules in short term by running small-scale pilot units with real wastewater from olive mill, textile and cosmetics industry.
• Preparation of a systematic market research for MBR application
• Defining potential membrane, module and process chemical materials under economic, technical and health related constraints
• Conducting laboratory tests (water flux, rejection) with membrane samples with PBM coating prepared by ITM-CNR
• Update of cost estimate for potential BioNexGen PBM membrane manufacturing process as well as Layer-by-layer technique in cooperation with ITM-CNR, FORTH and IZTECH
WP2:
• Structures-properties relationships related to organic solutes rejection from CNTs as well as theoretical study of water flow through CNT doped MN membranes.
WP3:
• Incorporation of CNTs in the existing MN polymer membranes by filtration in combination with tip sonication
• Functionalization of CNTs by hydroxyl groups
WP4:
• Synthesis of polymerisable surfactant for PBM technique
• Modification of the existing MN membranes towards nanostructured membranes with tailored pore size by PBM techniques.
• Provision of flat sheet membrane samples for laboratory tests on water flow and solute rejection
WP5:
• Starting initial experiments to synthesis antimicrobial nanoparticles
• Modification of the existing MN through layer-by-layer technique in order to increase antimicrobial properties
• Continuation of experiments to synthesis antimicrobial nanoparticles
• Provision of antimicrobial nanoparticles for being incorporated in layer-by-layer coating
WP6:
• Laboratory activities to study surface and cross sections of membranes to gain: surface roughness measurements, characterisation of surface morphology, changes to cross section of membranes and foulant layer thickness.
• Characterisation of novel membrane samples with regard to water flux and rejection of model compounds
WP7:
• Preparation of technical module envelopes for upcoming pilot trials in the MENA countries. The main focus was on selection of a low-temperature glue for lamination process of the envelopes since the novel PBM membrane material is not as temperature stable as the commercial material.
WP8:
• To conduct field tests with olive mill wastewater
• To conduct field tests with textile effluent
• To conduct field tests with cosmetic effluent
Apart from R&D WPs, specific objectives were also set for the WPs dedicated to the following activities: dissemination, exploitation (WP9) and management (scientific (WP10), administrative and financial (WP11)).
WP9:
• To create the first step-stones for marketing activities necessary for the exploitation of the project’s results
• To give visibility of BioNexGen objectives, activities and benefits by answering to the different needs of target groups
• To disseminate BioNexGen aims, evolution and results through printed (brochures, booklets, etc) and electronic (website, quarterly electronic newsletter) sources.
• To manage the access to partner’s background IP necessary for the project
• To manage and protect the consortium’s foreground IP
• To avoid patent infringement
• To assure a successful technology and knowledge transfer between the academic partners and the SMEs
• To create interest in the BioNexGen concept from potential customers in Europe as well as in the MENA region
• Organisation of the first training workshop focusing on basic principles and state-of-the-art of "Membrane based wastewater treatment and reuse" at CBS in Sfax, Tunisia. This workshop took place on the 8th and 9th of March 2012. The deliverable D9.4 “Report on the 1st training workshop on novel MBR technology” provides an overview of the presentations given during the workshop.
• Organisation of the second training workshop on “Functionalized membranes for Wastewater Treatment - Nanoparticles and surface modifications” which took place in May 15-17th, 2013 in Cetraro, Italy.
• Organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and clarify some aspects concerning the ownership and the use of these results
• Updates on patents search
• To continue the dissemination activities through the website, the newsletters, the participations to conferences and the networking activities.
WP10:
• Smooth and effective collaboration within the consortium
• Delivery of deliverables and milestones in time
• High quality of the project results
• Tracking and effective mitigation of risks
• Anticipation unexpected developments or new opportunities
WP11:
• To ensure that all the administrative documents (grant agreement and the consortium agreement) were understood and signed by all the partners.
• To distribute the pre-financing among the partners and
• To remind the partners’ role, level of involvement in the project and the budget planned for their participation in BioNexGen.
• To choose and the set-up of the management platform.
• To provide assistance to the partners on administrative and financial aspects
• To get the partners acquainted with the reporting process
• To perform the first periodic reporting in accordance with the criteria defined by the EC.
• To ensure that all the administrative and financial documents (Form Cs) were understood, signed by all the partners and delivered on time to the EC for the first periodic reporting
• To maintain updated the management platform
• To solve the issues concerning the Syrian partner ABU
• To prepare the amendment
Project Results:
Resuls obtained within period M1-M12
During the reporting period starting from the 01.09.2010 - 31.08.2011 WP1 through WP5 and WP9 through WP11 have been started.
Within WP1 benchmarking data were obtained with the existing MBR membrane from MN by testing industrial wastewater (olive mill, textile, and cosmetics). Small scale MBR pilot trials have been successfully started in the laboratories of the partners ABU, CBS and CMRDI using practical wastewater from olive mill, cosmetics and textile industry. In parallel, HSKA has started small pilots using model olive mill wastewater and practical wastewater for which the findings can be compared with the results of ABU. The results are summarized in a report (D1.2). In addition laboratory experiments with model foulants (humic acid, proteins and alginate) were conducted using a flat sheet membrane cell. The MBR market in Europe and the MENA countries has been studied by performing a SWOT analysis. For this analysis, a specific questionnaire has been developed for collecting the data among BioNexGen partners. The results are summarized in the deliverable D1.1. The potential membrane and module materials, as well as the potential membrane manufacturing processes of the BioNexGen membranes have been defined additionally an initial cost estimate for novel materials involved has been made in cooperation with CNR-ITM and FORTH. The results are summarized in the deliverables (D1.4 and D1.5). The health and safety aspects have been studied based on a matrix based risk analysis including all potential chemicals for manufacturing the novel membranes. The deliverable D1.6 highlights the findings. Deviation: The report on short-term results (D1.2) has been finalized only in month 12 instead of month 6 as initially planned but this does not affect the further progress of the work. No other deviation from the workplan occurred and the respective deliverables have been issued.
WP2 addressed theoretical aspects through computer modelling. FORTH and CNR-ITM were responsible for the tasks under this work package and were supported by HSKA and NTX. Within the overall aim of the WP2 investigation of structures-properties relationships, necessary in the development and design of innovative materials, the main progress is the subdivision of pollutants (textile, olive mill, cosmetics) into three groups as function of the ratio between the cross sections of the CNTs and those of pollutants. By analysing the ratios between the cross sections, it is possible to conclude that CNTs with diameters less than 3 nm can work as molecular sieves for medium (II group) and large (I group) sized solutes since the cross sectional ratios are smaller than 1. The calculations indicate that the existing CNTs with diameter larger than 3 nm cannot be used as molecular sieves to separate the larger part of the considered pollutants. Nevertheless, dynamic effects could cause deviations from this prediction. This is important since it allowed defining a computational strategy for the subsequent simulations aiming at calculation of the rejection of organic solutes of small size (III group) by the CNTs of NTX with diameter smaller the 3 nm. In fact, efficient solutes rejection could be driven by an unfavourable trapping of these molecules in the considered CNTs. For example the Tyrosol shows an unfavourable electronic free energy when embedded in a CNT with diameters of 1.66 nm. Multi-scale simulations (QC and MC) have been planned for the next six months to explore this possibility in advance. This WP has started earlier than planned in the DoW and the deliverable D2.1 has been submitted at M12.
Within WP3, FORTH has started to experiment the formation of vertically aligned CNTs in the existing commercial MN membrane as well as in a custom-made track-etched membrane through filtering. The active layer of the MN membrane consists of PES with an average pore size of 50 nm. Experiments have been performed by using the less expensive CNTs which are the MWCNTs with an external diameter of around 40 nm. The incorporation of CNTs has been attempted by using an improved common filtration system. The incorporation of the CNTs in the pores of both membranes has been monitored by SEM images of the membrane surface and cross-section as well. The consequent next steps will be to test water permeability and retention efficiency in a small test cell and in addition to improve and optimize the infiltration process. In addition initial experiments on functionalization of the MWCNTs by hydroxyl groups have been started. Moreover, decorated MWCNTs with polymers such as PMMA and PGMA have been also prepared. This WP has started earlier than planned in the DoW.
The main work of WP4 has been done on the preparation of “loose” hydrophilic nanofiltration membranes with tailored pore size. Two different types of NF membranes have been produced made of 1) polyvinyl alcohol (PVA) and 2) polymerisable bicontinuous microemulsion (PBM). The PVA membranes prepared so far proofed to be too “dense” to be applied over MN membranes (this has been observed by performing water permeability tests). Therefore two different approaches (addition of additives, low quantity of polymer in solution) will be studied in detail within the next 6 months. The symmetric PBM membranes have been produced using two different types of surfactants. The first one has been newly synthesized (together with the subcontracting, UNICAL) and the other one is commercially available (SDS type). Both types of membranes have been successfully made on lab scale using UV and redox initiators. Furthermore, the PBM membranes have been successfully coated on commercial MN membranes and their preliminary characterisation tests have supported their great potentialities and validated that the coating has been well performed. Further characterisation tests are now in progress to verify the interconnectivity of the pores of the respective membranes. However, the membranes need to be further optimised also for being applied in MBRs. This WP has started earlier than planned in the DoW.
Within WP5 initial experiments were started to prepare antimicrobial nanoparticles such as AgCl/TiO2 and chitosan which can be incorporated into nanofilms through PBM or PVA techniques (see WP4). The initial syntheses of these two nanoparticles have been conducted. Sol-gel synthesized Ag/TiO2 materials and chitosan nanoparticles were found to be antimicrobial against E.coli. The existing MN MBR membrane was modified by layer-by-layer (LBL) technique by alternating layers of chitosan and layers of alginates. The water flux and rejection for a model foulant (such as humic acid) were measured by HSKA. The water flux measured in the first samples was too low for expecting an application in MBRs. However, the process has been modified and further experiments will be carried within the next 6 months. This WP has started earlier than planned in the DoW.
WP9 supported dissemination, exploitation and training activities. The main objectives of this period were the development of the dissemination tools (project’s website and brochure) as well as an analysis of the intellectual property mechanisms suitable for the dissemination and the exploitation of BioNexGen outcomes. A corporate identity has been developed with the help of a professional communication agency. From this collaboration, a logo and a slogan have been created. In January 2011, the website has been finally opened to the public under the following address: http://www.bionexgen.eu The brochure is available in English since April 2011 and in Arabic, Greek, Turkish, Italian and German since August 2011. Several partners have started to communicate on the project through participation to conferences and press releases. Furthermore, the first issue of the BioNexGen newsletter has been released in August 2011. This newsletter can be downloaded on BioNexGen website.
Finally, a first report on the IP mechanisms, trademarks and patent survey has been worked out. The results obtained during this study are presented in the deliverable D9.7 submitted to the EC in August 2011. Some deviations have occurred in this WP but they are not affecting the progress of the project.
WP10 is related to scientific and technical coordination. The organization of the kick-off meeting in Karlsruhe 7-8th November 2010 has been done in collaboration between HSKA and SEZ. After that, monthly telephone conferences have been launched. This has created a high team spirit among the partners allowing a smooth and efficient collaboration among them. The second partner meeting has been held in Patras, Greece and hosted by our partner FORTH. This meeting has been the occasion to present the first technical progresses of the project. The first interim progress report (Deliverable D10.1) has been submitted in May 2011.
Deviation: The kick-off meeting was originally planned 4-5th October 2010. However due to the uncertainty to be able to effectively start the project in September 2010, HSKA and SEZ have decided, at the end of August 2010, to postpone the kick-off meeting to 8-9th November.
WP11 is related to project management. SEZ was responsible for this WP. The first action within this workpackage was to ensure that all administrative documents were understood and signed by all partners. Then a scenario concerning the budget distribution among the partners and through the complete duration of the project has been elaborated. Furthermore, each partner has been reminded on his role and level of involvement in the project as well as on the budget planned for his participation in BioNexGen. The first payment to the partners was slightly delayed and has been mainly released in November 2010 due to the time needed to decide which payment plan was the most suitable for the project and also due to the time necessary to obtain official bank data from the partners. The money transfer to ABU in Syria could not yet be accomplished since HSKA administration came to know that the bank of ABU is on the black list. HSKA administration is working on this issue to get the problem settled. Another objective of this WP was the set-up of the financial management platform. The German company EMDESK has been selected for their very competitive offer and the quality of the interface for the management. The programming of EMDESK platform has been finalised in December 2010. To set up the platform, the data have been retrieved from the Annex I and the Grant preparation forms. From January 2011, the BioNexGen partners have been granted by an access to EMDESK. In March 2011, an internal budget reporting has been realised among BioNexGen partners. The costs spent by each partner have been analysed in order to evaluate if there was no major financial deviation occurring. Each partner has been contacted individually in order to clarify which are the costs that can be declared and in some cases to define some correctives actions. In April 2011, the second payment has been released. However, the coordinator was still unable to transfer the two first payments to the Syrian partner ABU.
Resuls obtained within period M13-M30
During the reporting period starting from the 01.09.2011 - 28.02.2013 WP1 through WP7 and WP9 through WP11 have been continued.
Within WP1 benchmarking data were obtained with the existing MBR membrane from MN by testing industrial wastewater (textile and olive mill wastewater) and model textile dye wastewater (MTDW). Small scale MBR pilot trials have been successfully pursued in the laboratories of the partners CBS and CMRDI using practical wastewater from textile and olive mill industry. In parallel, HSKA has continued small pilots using model textile dye wastewater. In addition laboratory experiments with model foulants (humic acid and alginate) were conducted using a flat sheet membrane cell. The water permeability and rejection with selected model compounds were also tested. A potential membrane manufacturing process of the BioNexGen PBM membranes has been designed. Additionally a cost estimate for the novel PBM material and CNTs has been made in cooperation with ITM-CNR and FORTH. Deviation: Pilot trial with olive mill wastewater have been done by CBS since ABU left the BioNexGen consortium due to political turmoil.
WP2 addressed theoretical aspects through computer modelling. ITM-CNR and FORTH were responsible for the tasks under this work package. The subdivision of pollutants into three groups according to their effective diameters has been made. However, in the last period, the solutes rejection has been analyzed on the basis of another molecular descriptor that is: the Minimum! cross-section! projection of the solute atoms on the opening of CNTs. In fact, in this way, it is possible to obtain more indicative information regarding the rejection ability of CNTs by ‘size exclusion’. According to solute Minimum! cross-section! a new classification has been performed. In order to investigate the possibility of having rejection through a mechanism different from size exclusion, the evaluation of the trapping energy of the solutes in the CNT with diameter equal to 1.66 nm is also carried out. Efficient solutes rejection could be driven by an unfavourable trapping energy (activated diffusion process) although the aforementioned analysis on the solute sizes gives a different response. Multi-scale simulations (QC and MC) have been planned for the next six months to explore this possibility. However it has been shown that for CNTs with diameter of 1.66 and molecules like tyrosol this is not the case. Calculations of the water flow rate as function of CNT diameters have been also carried out in this period by ITM-CNR to predict the number of MWCNTs to be used in the porous MN membranes in order to improve the total water flow. Various parameters such as the MWCNTs length and internal and external diameter were considered in this computational analysis. Quantum Mechanics calculations about the adsorption of antimicrobial particles on the active layers by means of CTAB, DTAB and AUTEAB surfactants have been carried out. These calculations concern the activity of the Task 2.2. Concerning the activity of the Task 2.1b nano-scale sorption of water molecules inside smooth single wall carbon nanotubes (SWCNTs) with different diameters has been simulated using a Grand Canonical Monte Carlo (GCMC). Armchair (n,n) SWCNTs with tube diameter of 8.14 10.86 13.58 16.28 and 27.14 (Å), respectively, with lengths equal to 40 (Å), have been used in this work. After thermodynamic equilibration has been reached, the water molecular structure and organization inside the CNT is examined as a function of CNT diameter. Hence, the ordering of the water molecules inside the CNTs was examined as a function of CNT diameters. Moreover, in this period, nano-scale sorption of small model molecules such as tyrosol, vanillic and p-coumaric acid inside SWCNTs with the aforementioned diameters has been simulated. The solute molecular structure and organization inside the CNT is examined as a function of CNT diameter, in addition to the ordering of the solute molecules inside these CNTs. The main objectives of Task 2.1c include: calculation of water (or ethanol) permeability and flow features / characteristics in the interior of composite membranes; simulation of motion of CNTs as they approach the polymer matrix. The objective of the Task 2.3 is the 3D representation of the aforementioned active layers. Active layer reconstruction stages initially included imaging techniques for retrieving 2D data of the material. SEMs of the active layer prepared by bi-continuous micro emulsion at several resolution levels were received from ITM-CNR. Image processing was carried out at FORTH/ICE-HT and several geometrical and topological data of the materials, such as the (surface) porosity and the autocorrelation function, were extracted and the milestone MS2 has been submitted at M18.
Within WP3, NTX in strong cooperation with FORTH has developed the optimum protocol for the incorporation of CNTs in membranes using the facilities of the company. Moreover, the effect of this process on the functional groups of CNTs was studied and the results showed that there is no effect on the amount of functional groups attached to the tube. During the last months, a new protocol for the incorporation of CNTs in the membranes has been under development. This new protocol aims at developing an easier and economical way for the large scale production of the new enhanced membranes with CNTs. The incorporation of CNTs into UP150T Microdyn-Nadir membranes has been attempted with the help of simple or dead-end filtration system. Different attempts have been performed. Basically, the protocol is the following: the infiltration of CNTs is carried out through the PET side, and below, the water flow rate is measured through the active PES side of the membrane in a dead-end filtration system. However, infiltration of CNTs has been also carried out through PES side. The infiltration of the CNTs is achieved in combination with tip sonication.
During this period, FORTH has focused their experiments on MWCNTs, Thin-MWCNTs, Thin-MWCNT-OH and Thin-MWCNT-COOH all provided by NTX, but also on SWCNTs and DWCNTs purchased from Cheap Tubes (USA). Substitution of the carboxylic acid groups (-COOH) with carboxyl anion groups (-COO-) where further prepared and infiltrated. The embedment of CNTs into the porous membrane was performed either from the support layer or directly to the thin selective layer. Study of dispersion of CNTs in suspensions has been achieved. CNT functionalized with deprotonation of carboxy groups (-COO-) present improved dispersion of CNTs in water facilitating the incorporation of CNTs in the MN membrane. The incorporation of CNTs to the membranes has been substantiated with the help of SEM images as well as with AFM images.
The best results with respect to water flow have been obtained with the membranes infiltrated with DWCNT and SWCNT through PES side and with the membranes infiltrated with Thin-MWCNT-COOH through PET side. In these cases the membrane rejection was was probed for model textile dye waste, composed principally by Acid Red (380 Dalton) and Remazol Brilliant Blue R (630 Dalton), and Reactive black (990 Dalton). Since the UP150 Microdyn-Nadir membrane belongs to the category of ultrafiltration membranes with a molecular weight cut off, MWCO, 150 kDalton and the model foulants used for the retention measurements present a MWCO of 1000 Dalton at most, that means they need a nanofiltration membrane to be retained, the retention ability improvement due to the incorporation of CNTs into the UP150 MN membrane will be progressively examined using Polyethylene glycol (PEG) model compounds of different molecular weights between the two above mentioned MWCOs.
Moreover, a thin film of polyethersulfone/CNT blend has been coated on existing commercial Nadir? microfiltration polymer membranes and water flux and MWCO will be also tested. Polyethersulfone/ CNT blend membrane can be produce from polyethersulfone/solvent/no solvent system by the immersion phase inversion process in water bath.
NTX has produced CTNs functionalized with a carboxy (-COOH) group. These functionalised CNTs were delivered to FORTH either for the incorporation in the membranes, or for further functionalization. The MWCNTs with 97% purity were functionalized with the protocol of NTX and the result led to 5% over the nanotubes weight of functional groups, while the thin-MWCNTs were functionalized with two different protocols achieving percentages of functional groups of 7 and 12% respectively. 2 grams of each of these materials were delivered to FORTH for further experiments.
NTX has also participated to the realization of cytotoxicity experiments, by developing the protocol for the dispersion of CNTs in PF127. For the development of this protocol several parameters were studied, while the facilities of the company were used. In our experiments, its toxicity was evaluated as internal control of the assay. In all of our experiments, we observed a cell viability of 80-90% with the 1% PF-127 which is the internal control of the assay and the effect of CNTs on cell viability is compared with PF-127 treated cells. The experiments are conducted at human lung fibroblasts. The toxicity of the compounds was evaluated in terms of cell viability and hemolytic potential of CNTs of interest. We assayed a range of concentrations of 0,125µg/mL to 25µg/mL for all synthesized CNTs. Pristine MWCNTs revealed a dose-dependent effect on the toxicity with the ranging from 50-70% cell viability, while SWCNTs and DWCNTs, according also to the literature exhibited higher toxicity compared with MWCNTs. MWCNTs-OH maintain high viability even at high concentrations (50% cell viability at the highest concentration) compared to pristine. A similar pattern is also exhibited by –COOH functionalized. Functionalization with water soluble polymer PSSNa also results in maintenance of high viability compared to pristine MWCTs.
Non-covalent interactions of phosphonium and ammonium groups with SSNa-functionalized CNTs lead to high toxicity profile at concentrations higher than 2,5µg/mL and 25µg/mL, respectively. The high antimicrobial activity of phosphonium groups is also depicted with high cytotoxicity profile. It is worth noticing that in lower concentrations tested the cell viability reaches the levels of the internal control of the assay. The covalent attachment of vinylic monomers onto phenol-functionalized CNTs exhibits no statistical significant changes in cell viability in the concentrations tested from 5 to 0,125µg/mL for thin-MWCNTs, whereas further introduction to vinylic monomers of the cytotoxic ammonium groups resulted in a balanced toxicity profile. The range of concentrations used in the cell proliferation assays did not exhibit any hemolytic activity nor the high concentrations tested (50µg/mL & 100µg/mL) for incubation intervals of 30min, 1, 2 and 3 h. The antimicrobial properties of polymer modified carbon nanotubes were also assayed in a range of bacterial populations. It seems that there is a different effect depending on the type of bacteria (gram positive or negative). However, the dispersion media, used for the toxicity assays, seems not to be optimal for such experiments.
The main work of WP4 has been done on the preparation of “loose” hydrophilic nanofiltration membranes with tailored pore size. The synthesis of Acryloyloxyundecyltriethyl ammonium bromide (AUTEAB) has still been synthesized following the consolidated route and used as surfactant for Polymerisable Bicontinuous Microemulsion (PBM) preparation. A new commercial surfactant Dodecyltrimethylammonium bromide (DTAB) was employed for PBM preparation in order to decrease membrane final cost.
PBM membranes prepared with AUTEAB were used as coating material for PES membranes from Microdyn-Nadir and sent to the partner HSKA for rejection tests with fouling model compounds and water permeability tests. Some variables, which can affect membrane polymerization procedure, were taken into account and evaluated (e.g. temperature and HEMA concentration). Different antimicrobial agents prepared by IZTECH, ITM-CNR and CMRDI were incorporated into the bicontinuous microemulsion which was polymerised following the traditional procedure used on MN PES membranes. The prepared membranes have been sent to IZTECH for the evaluation of antimicrobial activity. However PBM membranes themselves showed antimicrobial activity due to the presence of cationic surfactant (AUTEAB or DTAB). Thus, the addition of further antimicrobial agents was not required. Many efforts have been evaluated in order to embed CNTs into the PBM matrix, such as: increasing the viscosity of the microemulsion (varying CNTs concentration and chemical composition of the microemulsion), increasing the affinity between CNTs and the microemulsion (deprotonation of CNTs), temporary closing the pores of the commercial membranes (pre-treatment, double coating). Nevertheless no one of the applied techniques was found to be a viable method to incorporate CNTs into the PBM matrix. PBM membranes were characterised by SEM, AFM (Swansea University), contact angle measurements, permporometry tests, conductivity measurements and weight loss determination. In order to determine membrane cut-off, Gel Permeation Chromatography (GPC) analyses will be performed. New PBM membranes will be prepared and characterised with the commercial surfactant DTAB and they will be sent to Microdyn-Nadir for the assembly of a second MBR module.
Within WP5, Ag nanoparticles were synthesized by co-precipitation and new hydrothermal techniques. These Ag nanoparticles were characterized using transmission electron microscope. In addition, chitosan nanoparticles using TPP and POM as two alternative crosslinking agents were also synthesized. Their average size and their size distribution were determined by dynamic light scattering and their antibacterial activities against E. coli were determined. The cytotoxicities of chitosan /TPP nanoparticles on the lung fibroblast cells were measured. Furthermore, the Microdyn-Nadir membranes were modified with alginate and chitosan by changing polyelectrolyte concentration, number of layers, ionic strength and pH of the polyelectrolyte solution and deposition time. The water fluxes through both modified and unmodified membranes were measured and their antifouling properties were determined. The results have shown that all types of chitosan nanoparticles show antibacterial activity and the cytotoxicities depend on their concentration in the medium. Initial filtration experiments conducted in a small dead-end ultrafiltration module indicated that it could be possible to enhance antifouling properties of the MN membranes by layer-by-layer deposition of alginate and chitosan without significantly reducing the water fluxes through these membranes. In addition, antibacterial membranes with better water flux can be attained by incorporation of AgCl/TiO2 in the chitosan solution used for building the outmost layer of the modified commercial membranes. It has been indicated that higher rejection can be acquired by appropriately modifying the membranes.
The objective of WP6 is to characterize the surface and cross section morphology of the prepared membranes samples and to analyse the foulant properties on their surface subsequent to the fouling experiments with model waters. This work will support the optimisation of the membrane materials development within WP 2, 3, 4, 5. The work will be carried out through close cooperation between SU and HSKA and it will give the necessary feed-back to the WPs 2, 3, 4, 5. Within WP6 for this reporting period, for task 6.1 AFM and SEM measurements on the surfaces of membranes have been carried out to examine membrane structure and to assess fouling of membranes used for cross-flow filtration of model foulant wastewater (as part of task 6.3). These measurements have shown the surface morphology of fouled and unfouled membranes, produced measurements of surface roughness, thickness of adhering foulant layers. Pristine membranes showed a much lower surface roughness than membranes which were fouled with humic acid. Correlations were found between measured surface roughness and foulant layer thickness, showing that for the polymer membranes measured surface roughness can be used as a corollary for the degree of surface fouling. Deliverable report 6.1 was issued for this task. For task 6.2 colloid probes were produced containing a covalently bound coating layer of humic acid as a model membrane foulant. Force measurements were carried out between these coated colloid probes in both high purity water and in model textile dye wastewater (as provided by HsKA). This has allowed the membranes tested in this way to be ranked according to adhesion forces between model foulant and the membrane surfaces in two different conditions. Deliverable report 6.2 was submitted for this task. Long term cross-flow filtration tests with model foulant and industrial wastewaters were carried out (task 6.3). A deliverable report (D6.3) has been issued for this task. Task 6.4 filtration of activated sludge in a side-stream MBR laboratory reactors has been carried out. For task 6.5 three different types of membranes called layer by layer membranes, CNTs incorporated membranes and PBM coated prepared by BioNexGen project partners, IZTECH, FORTH/NTS and ITM-CNR respectively were tested with pure water, model foulant and biological sludge.
The purpose of WP7 is to prepare small three-envelope membranes with the novel materials for the upcoming pilot trials in the MENA countries Tunisia and Egypt. The commercial lamination process of MN has to be modified since the novel membrane materials are not as temperature stable as the commercial one. Therefore a commercial low-temperature glue (T< 100°C) was selected and tested in the technical laboratory of MN. The new three panel membrane prepared by the low temperature lamination process showed sufficient mechanical stability in long-term laboratory tests. After final selection of the target membrane material the sheets will be laminated by this process for the upcoming pilot trials within WP8.
WP9 supported dissemination, exploitation and training activities. During this period, several newsletters were produced and used as dissemination tools for BioNexGen results. These newsletters can be downloaded on BioNexGen website. Several partners have participated to conferences and presented by BioNexGen through posters and oral presentations. Two scientific publications have been released during this period. The first training workshop focusing on basic principles and state-of-the-art of "Membrane based wastewater treatment and reuse" has been held at CBS in Sfax, Tunisia. This workshop took place on the 8th and 9th of March 2012. The deliverable D9.4 “Report on the 1st training workshop on novel MBR technology” provides an overview of the presentations given during the workshop. The second training workshop on “Functionalized membranes for Wastewater Treatment - Nanoparticles and surface modifications” has been organised during this period and it will take place in May 2013 (15-17th) in Cetraro, Italy. In addition, technology watch activities have been performed by the mean of patents searches.
Furthermore, the exploitation activities have been started with the organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and clarify some aspects concerning the ownership and the use of these results.
WP10 is related to scientific and technical coordination. This work has been conducted in close cooperation between HSKA and SEZ. An active support has been provided to the partners for the organization of the partners meetings. Monthly telephone conferences have been continued. This keeps high team spirit among the partners and this allows a smooth and efficient collaboration among them. HsKA also initiated a variety of bilateral discussions with all partners. This support was necessary to orientate the research performed within the project towards industrial expectations. HsKA and SEZ have also organised meetings with the industrial partner MN in order to keep them update about the progresses of the project.
WP11 is related to administrative and financial management of the project. SEZ is responsible for this WP. The first two months of this period (01.09.2011-31.10.2011) have been fully dedicated to the finalisation of the first periodic reporting. The activities and the Form Cs have been all submitted to the EC on the 31.10.2011. Since March 2011, the Syrian Arab Republic is facing major political turmoil which has lead to a great instability. Unfortunately, this political situation has also some consequences on BioNexGen project. Indeed, the partner ABU is located in Homs (which is the center of the opposition to the Syrian regime). Over the last months the situation in Homs has been seriously altered. Unfortunately, this political context has posed a challenging scenario and has imposed several constrains for the implementation of ABU’s work within BioNexGen. In March 2012, the coordinator has been informed that ABU was excluded from the first interim payment due to the sanctions taken by the EU against Syria. During the M24 partner meeting, the steering committee has voted for the termination of ABU’s participation starting from the 1st of March 2012. ABU has been informed of our decision and has accepted the consortium’s choice.
Once the sanctions against Syria will be removed, the coordinator will try to pay ABU for costs incurred within the first 18 months of BioNexGen if these costs are accepted by the European Commission. Since the consortium has to submit an amendment for ABU’s participation termination, it was decided to submit requests for technical modification at the same time. Indeed after 24 months, it becomes clear that some of the tasks planned for the project were actually no longer feasible due to results obtained so far. The third and the fourth instalments from the pre-financing have been transferred to the partners in October 2011 and April 2012 respectively. Furthermore, the project coordinator has received in March 2012 the first interim payment based on the costs declared during the first periodic reporting. However due to the sanctions taken by the EU against the Syrian regime, ABU’s has been excluded from the first interim payment. The respective share of the interim payment has been established for all partners. This share of the interim payment will be distributed to the partners over 2 instalments. The first instalment has been transferred in October 2012 and the second will be transferred in April 2013.
Deviations from the work plan:
An amendment is preparation concerning ABU’s participation termination and the major technical deviations.
Only one partner (ABU, Syria) has been not paid since the beginning of the project. Many attempts have been tried to transfer the money until March 2012. Since March 2012, the coordinator did not further try to transfer any payment to ABU due to the official EC letter concerning ABU’s payment suspension
Resuls obtained within period M31-M42
During the reporting period starting from the 01.03.2013 - 28.02.2014 WP1 has been finished; WP2 through WP7 and WP9 through WP11 have been continued and WP8 has been started.
Within WP2 three Tasks: Task2.1 task2.2 and task2.3 has been carried out.
Tasks 2.1 is divided in three other tasks: 2.1a 2.1b 2.1c. In particular in Task 2.1a advanced quantum chemical calculations have been carried out. Instead, advanced MC and MD calculations are performed in the Task 2.1b while calculation of water (or ethanol) permeability and flow features in the interior of membranes, in addition to simulation of CNTs motion as they approach the polymer matrix have been carried out in the Task 2.1c. In Task 2.2 the final aim of the work was to figure out (to predict by computational modelling) whether a good adhesion of POM antibacterial nanoparticles on the active membrane coating is possible without loss of their activity. Finally, the purpose of the last Task 2.3. is the computational 3D representation of the active layer (membrane coating) of composite membranes impregnated with CNTs, in order to provide guidance to the preparation process.
The WP3 consists of six Tasks: 3.1 3.2 3.3 3.4 3.5 and 3.6. of which tasks 3.1 and 3.6 are already completed. Task 3.2 is dealing with Incorporation of carbon nanotubes in commercial polymer membranes from Microdyn Nadir. Nadir® microfiltration polyethersulfone (PES) hydrophilic polymer membranes have been preferably utilized. Task 3.3. According to the valid amended version of the Annex I (description of work), the synthesis of carbon nanotubes/polyethersulfone blend membranes via the phase inversion method is the new target for this task. Prior to membrane synthesis, thin-Multiwall carbon nanotubes have been functionalized with carboxylic groups and afterwards de-protonated, providing the CNT with COO- groups. Functionalization increases dispersion of CNT in solvents. Water flux test as well as molecular weight cut-off (MWCO) of the blend membrane will be determined. Task 3.4 In the present reporting period, optimization of the crosslinking reaction of carbon nanotubes, functionalized with PGMA moieties, embedded in the nanoporous filters, was detected by testing various crosslinking methods, at different temperature values, reaction time and crosslinker quantity. In the previous reporting polymer-functionalized CNTs were further modified by incorporation, through non-covalent attachment, of antimicrobial quaternized phosphonium (PSSPhC16) and ammonium salts (PSSAmC16) in task 3.5. CNTs functionalized, either covalently or non-covalently, with biocidal groups have been developed and their toxicity studies have been conducted. In addition to this, the covalent attachment of biocidal groups on functionalized CNTs has also taken place, using polymerization of vinylic monomers and subsequent quaternization with proper amines (P(AA25-co-VBCHAM)). The above mentioned systems have been studied in order to find the optimum experimental conditions. In the present reporting period, for comparison reasons, the synthesis of amine functionalized monomers (VBCTEAM) and the subsequent polymerization on the surface of carbon nanotubes was tested in order to be further studied in terms of toxicity.
Within WP4 main work carried for the last period (M31-M42) of BioNexGen project has been focused on:
1. The synthesis of a cationic polymerisable surfactant AUTEAB. The possibility to use a commercial surfactant (DTAB) was also evaluated and applied (task 4.1).
2. 30x30 cm PBM membranes preparation by coating the bicontinuous microemulsion on MN PES membranes and sent to Microdyn Nadir for the preparation of 2 MBR modules. In order to reduce cost impact of AUTEAB on PBM membrane preparation, a new commercial surfactant (DTAB) was used (task 4.2).
3. RuPOM-AUTEAB nanoparticles were incorporated into the PBM membrane and their catalytic activity was evaluated (task 4.3).
4. PBM membranes were characterised at laboratory scale by SEM, AFM (Swansea University), contact angle measurements and permporometry tests. Membrane cut-off measurements by Gel Permeation Chromatography (GPC) analysis, acquired in this project, were carried out on PES commercial membrane and are, at the moment, in progress on PBM membranes prepared with the commercial surfactant (task 4.4).
Highlighting the results obtained
1. DTAB surfactant was successfully applied for PBM preparation allowing to decrease the final membrane cost.
2. Commercial surfactant DTAB allowed to obtain a well dispersed and homogenous bicontinuous microemulsion. The use of DTAB allowed to decrease membrane final costs. The cost of 1 m2 of PBM coating was about 5€.
3. RuPOM nanoparticles were successfully entrapped within the microemulsion structure and their activity was preserved and tested.
4. From characterisation tests PBM membranes showed good antifouling properties, higher hydrophilicity, higher rejection to organic molecules (model dyes) and a reduced pore size in comparison to PES commercial membranes.
The overall objective of the WP5 is to prepare antimicrobial nanoparticles which can be incorporated into nanofilms through polymeric bicontinuous microemulsion (PBM) technique and modify the nanofilms and commercial MN membranes with the layer-by-layer technique. Overall work done within this workpackage during this period can be summarized as follows:
a) Based on water fluxes, the antifouling behavior and the antibacterial activities of unmodified and LBL modified membranes, 9 membranes were selected and sent to Swansea University to characterize with the scanning electron microscope and atomic force microscope.
b) The polyelectrolytes with different ionic strength, ( 0, 0.5 and 1 M NaCl), concentration (0.1 1 and 2 mg/ml), pH (pH 5 or 6 for chitosan solution ) and number of layers (1.5 2.5 and 3.5 bilayers) were directly deposited on the commercial membrane. The rejection properties of these membranes were determined with dextran (Mw=73,000 ) and raffinose (Mw=594 ).
c) Different macromolecules (Polyvinyl alcohol (PVA) Mw=~31,000-50,000; Polyvinylpyrrolidone (PVP) Mw=~55,000; Polyethylene glycol (PEG) Mw=~40,000 and Polysodium 4-styrenesulfonate (PSS) Mw=~70,000) were permeated through the commercial membrane under 0.7 bar pressure and their dextran rejection values were determined.
d) Polyelectrolytes were deposited on PVA infiltrated commercial membrane and the rejection properties were determined with the raffinose.
e) Based on highest raffinose rejection values obtained, two membranes were selected and prepared with 30 cm x 30 cm sizes and they were sent to HSKA for testing their performances in 2 cross flow units and in a side stream MBR as well. Pure water and humic acid permeability as well as red and blue dye rejection values of these membranes were measured .
f) The influences of heat treatment applied during lamination of membrane sheets on the water fluxes and rejection properties of the membranes were investigated in a small scale filtration unit at IZTECH and in a larger scale cross flow filtration units at HSKA.
g)The effect of coating both surfaces and only active surface of the commercial membrane on the rejection values of the membranes was first investigated in a small dead-end filtration unit at IZTECH. Based on the results, two membrane samples selected based on highest raffinose rejection values were sent to HSKA for further tests in cross flow units.
h) New commercial PES membrane with a lower molecular weight cut off value than the one used throughout the project was also modified with polyelectrolyte deposition to improve its water permeation characteristics. Parameters tested to modify membranes were number of bilayers, polyelectrolyte concentration, use of two polycations on the outermost top layer and blending a hydrophilic polymer , polyethylene glycol (PEG) with the polyelectrtolytes in each layer.
Highlights of the results obtained
a) The dextran rejection of around 90 % was obtained by coating the commercial membrane with 0.1mg/ml chitosan/0.1 mg/ml alginate /1 mg/ml chitosan where 0.5 M NaCl was added to each polyelectrolyte solution.
b) Molecular weight cut off value of the commercial membrane decreased by infiltrating the hydrophilic polymers under pressure.
c) Both the charge and molecular weight of the polymer used for infiltration are important for decreasing the molecular weight cut off value of the existing membrane.
d) Layer by layer deposition of polyelectrolytes on the PVA permeated commercial membrane improved the rejection properties of the membranes.
e) Deposition of polyelectrolytes on the unmodified commercial membrane and then permeating PVA through layer by layer deposited polyelectrolytes also gave similar rejection values compared to the case when polyelectrolytes were deposited on the PVA infiltrated commercial membrane.
f) PVA permeated commercial membrane coated with 1 mg/ml chitosan solution (Altink_01) and commercial membrane coated with 0.1 mg/ml chitosan /0.1 mg /ml alginate /1 mg/ml chitosan including 0.5 M NaCl and then infiltrated with 10 g/l PVA (Altink_02) showed considerably higher pure water as well as humic acid permeabilites than that of commercial membranes.
g) The regain of the flux after flushing three times with pure water was around 70 % for Altink_02 sample and 33 % for Altink_01 sample , however, for commercial membrane the regain always fluctuated between 10 and 20 %.
h) The humic acid rejection values of modified membranes were similar to that of commercial membranes while the dye water permeability was slightly higher than that of commercial PES membrane.
i) The rejection of red and blue dyes of the Altink_01 membrane was found similar to the values obtained with commercial membrane while Altink_02 membrane showed higher blue dye and lower red dye rejection values.
j) Altink_02 membrane in a side stream MBR showed a sudden increase in the permeability at the end of 15 days which remained higher than that of the commercial membrane after 15 days.
k) Heating the membrane without glycerol coating caused a decrease in water flux while heat treated membranes after glycerol treatment showed significantly higher water fluxes compared to the Altink_02 membrane not subjected to heating.
l) Heat treatment applied to the Altink_02 membrane did not significantly change its rejection property.
m) The results obtained at HSKA showed that that pure water permeability of commercial membrane decreased significantly with time while that of modified membranes remained stable and heat treatment enhanced the permeability of the Altink_02 membrane.
n) All LBL modified membranes showed higher dye water permeabilities than the commercial membrane while their red and blue dye rejection values were similar to that of the commercial membrane.
o) Application of layer of layer deposition of polyelectrolytes on both surfaces of the commercial membrane or just on its active surface was found to affect the rejection properties of the membranes.
p) For the new commercial PES membrane with a lower molecular weight than the one used throughout the project, the highest water flux was measured with 1.5 bilayer membranes (CS/ALG/CS) prepared with 0.05 mg/ml polyelectrolyte concentration.
q) Blending chitosan (CS) with another polycation, whey protein isolate, at a ratio of 1:1 did not change the water flux values of 1.5 bilayer membranes prepared from new support membrane.
r) Similarly, blending PEG with CS at a ratio of PEG/CS: 1/5, 1/10 to form a single layer on the new commercial membrane or blending both CS and Alginate with PEG in each layer at a ratio of 1/1 to form 1.5 bilayer membrane did not improve the water flux values compared to the cases where polyelectrolytes were used alone for coating.
Within WP6, for task 6.1 AFM and SEM analysis of membrane samples received from various partners were undertaken to characterise the surface and cross sectional morphology of fabricated membranes and membranes fouled by filtration tests. Task 6.2 continued with force measurements carried out using silica glass colloidal probes to simulate the attachment of silica foulants to several PBM membranes in clean water and model dye wastewater. These measurements were carried out to complement previous measurements in this tasks using a humic acid coated probe. In addition filtration tests were carried out with practical wastewaters and using membrane bioreactors with side stream modules under anaerobic conditions for tasks 6.3 and 6.4. For task 6.5 filtration with commercial and layer by layer prepared membranes were carried out using clean water, model wastewater and activated sludge to give a comparison of the performance of the fabricated membranes compared to commercially available membranes.
WP7 addresses the modification of the production process and testing of small prototype membrane modules (stack of 3 laminate sheets 25*25 cm²). The work will be conducted with the findings resulting from WP6 and supported through SU and HSKA.
Within WP8 the following tasks were carried out
Field study with olive mill wastewater
In this reporting period, CBS has just started two MBR units working in parallel with real olive mill wastewater (OMW). The first pilot MBR was running with the commercial Microdyn-Nadir membrane (MBR1) and the second MBR with the PBM coated membranes (MBR2). The trials were started with diluted OMW at a flux of 2 L/h/m2. The flux was increased stepwise to 3 L/h/m2. Under these operating conditions, the COD removal efficiency was quite similar for both MBR units reaching 26.47% and 23.53% for MBR1 and MBR2, respectively after 8 days of continuous treatment.
A report of the results achieved in Task 8.1 will be prepared and is planned to be submitted as deliverable D8.1 as agreed.
Field study with textile effluent
During M31-M42, CBS has started two MBR units working in parallel with real textile wastewater (TWW). The first pilot MBR was running with the commercial Microdyn-Nadir membrane (MBR1) and the second MBR with the PBM coated membranes (MBR2). In this task, long term trials with textile effluent studying crucial parameters such as suction pressure, BOD, TOC, dissolved O2, COD and colour removal efficiencies, drying residues, pH, temperatures, conductivity etc have been investigated. The trials were started with diluted TWW at an average OLR of 0.7 g COD/l, a flux of 2 l/h/m2 and a HRT of 3.5 days. Under these operating conditions, the COD removal efficiency was quite similar for both MBR units with average of 94 and 95% for MBR1 and MBR2, respectively while, the TOC removal efficiency was higher for MBR2 with an average of 96% (MBR1 91%).
After the start-up period, the flux was gradually increased to 6 l/h/m2, The COD removal efficiency were quite similar for MBR 1 and MBR 2 with values of 79.80% and 80.20% for MBR1 and MBR2, respectively. At this flux, colour removals were also quite similar reaching 58.97% for MBR2 and 54.18% for MBR 1. However, under the same flux the TMP of MBR1 increased to 1 bar while MBR TMP remained at 100 mbar. Both units were stopped after 147 days of continuous treatment.
A report of the results achieved in Task 8.2 will be prepared and is planned to be submitted as deliverable D8.2 as agreed.
Field study with cosmetic wastewater
During M31-M42, CBS has also started one MBR unit running with the PBM-coated Mn-membranes and working with real cosmetic wastewater. The trial was started in parallel with OMW trials. In this task, The MBR was fed with diluted cosmetic wastewater at a flux of 2 L/h/m2. The flux was increased stepwise to 3 L/h/m2. Under these operating conditions, the COD removal efficiency reached 82.97% while the anionic surfactant removal was 98.57% after 6 days of continuous treatment. The TMP was steady at 100 mbar under the same flux.
A report of the results achieved in Task 8.3 will be prepared and is planned to be submitted as deliverable D8.3 as agreed.
Within WP9 the following objectives were achieved. The objectives of this period were the following:
• Organisation of the second training workshop focusing on basic principles and state-of-the-art of "Functionalized membranes for wastewater treatment - Nanoparticles and surface modifications". The workshop took place in Cetraro, Italy from 15th to 17th May 2013.
o The deliverable D9.5 “Report on the 2nd training workshop on novel MBR technology” provides an overview of the presentations given during the workshop.
• Organisation of BioNexGen final conference under the topic “Use of nanotechnology in membrane for water treatment”. The conference was held from 8th-10th October 2013 in Izmir, Turkey.
o The deliverable D9.6 “Report on the final international conference” provides an overview of the presentations given during the final conference.
• Organisation of exploitation seminars in order to determine the potential exploitable results developed within BioNexGen and to clarify some aspects concerning the ownership and the use of these results.
o The deliverable D9.9 “Technology Implementation Plan” provides an overview of the exploitable results obtained during the project.
• Updates on patents search and IPR to implement for protecting BioNexGen exploitable results.
o The deliverable D9.8 “IPR Report” provides an overview on the IPR foreseen for the exploitable results plus an overview of the relevant patents families.
• To continue the dissemination activities through the website, the newsletters, the participations to conferences and the networking activities.
o The issues 5th and 6th of BioNexGen were produced and made available on the project website.
o The deliverable D9.10 “Review of Dissemination Activities” provides an overview on all the dissemination activities performed by the partners (oral presentations, posters, articles, internet presence and the newsletters published).
The objective of WP10 is to ensure an efficient and pro-active scientific coordination of the project and monitoring of the technical components of the project. The following objectives have been achieved:
• Smooth and effective collaboration within the consortium
• Delivery of deliverables and milestones in time
• High quality of the project results
• Tracking and effective mitigation of risks
• Anticipation unexpected developments or new opportunities
The following significant results can be highlighted:
• Successful M30, M36 and M42 partners meetings
• Effective collaboration among the partners
• Smooth scientific coordination through monthly telephone conferences
The objective of this WP11 is to ensure an efficient and pro-active coordination of the project by administration, organisation and monitoring of the administrative and financial components of the project.
Therefore, this period was dedicated:
- To perform the second periodic reporting in accordance with the criteria defined by the EC.
- To ensure that all the administrative and financial documents (Form Cs) were understood, signed by all the partners and delivered on time to the EC for the second periodic reporting
- To distribute the EC contribution received by the coordinator among the partners
- To maintain updated the management platform
- To provide assistance to the partners on administrative and financial aspects
- To finalise the amendment request regarding the termination of Al Baath University (ABU) participation and some technical modifications in the Annex I.
Potential Impact:
Socio-economic impact:
Wastewater reuse is an accepted practice in Europe and the MENA countries with limited rainfall and very limited water resources. Wastewater reuse has become already an integral effective component of long term water resources management.
MBR technology is an effective solution for transforming various wastewaters into high-quality effluent suitable for discharge and/or for reuse. Experts believe that the market potential of MBR technology in the next 5 to 10 years is high since an increase in treated wastewater demand is expected.
Furthermore, MBR technology presents many advantages over conventional activated sludge such as high flexibility, interoperability, high performance, low footprint.... Of course this technology possesses also drawbacks such as high investment and operating costs or membrane fouling that could prevent a wider implementation.
Moreover, some countries have developed comprehensive water treatment and reuse standards to provide direction, and, encourage and finance wastewater reuse programmes.
It is clear that treated wastewater reuse plays an important and increasing role. State regulation should ensure safe wastewater reuse practices locally. However the difference in standards between EU member state regulations can cause confusion over what is best practice and sustainable for local situations and type of applications.
Next challenges to overcome are the costs reduction for producing treated wastewater production and the increase of treated wastewater availability.
BioNexGen project aimed at developing a MBR technology that has important impacts on the implementation of water reclamation and purification plants. Indeed, this one-step process technology has achieved breakthroughs by:
• Increasing the efficiency and the operational time due to less membrane fouling which permits a constant high membrane flux
• Decreasing operational and maintenance costs
• Improving the quality of the filtration by retaining micro-pollutants
• Increasing the performance of the biological degradation by improving the permeability of the membrane to salts and reducing the generation of toxic sludge
To attain these breakthroughs, three novel membrane materials were developed by applying different novel techniques. The developed membranes were prepared by the following ways:
(1) Functionalization of membranes through Layer by Layer (LBL) Technique
(2) Polymersiable bicontinuous microemulsion (PBM) coating on commercial PES membranes incorporated with functionalized CNTs
(3) PBM coating with a cost effective surfactant
The performances of the three different types of BioNexGen membranes were evaluated with DI water, model foulants, micro-pollutants and biological sludge treatment.
From the technological performance and economic analysis, it can be concluded that DTAB based PBM membrane material can be considered as the best overall performing membrane materials with possibility of producing variable performing membranes by changing the chemical compositions of the membranes during the preparation process.
The process is technically efficient and the membranes are economically viable because of their high fouling resistance. The new membranes are advantageous as they reduce the operating and investment costs on an industrial scale by an average of 25 %.
Further details can be found in the deliverable D6.5 “Report on techno - economical evaluation of membrane development”.
In conclusion, we believe that most of current weaknesses of MBR technology will be overcome by the new membrane developed in BioNexGen and consequently high market potential can be achieved.
Dissemination:
All BioNexGen project partners have been very active throughout the course of the project with disseminating the project and their research results. This constituted in many event participations, general publications and peer-reviewed articles. Even beyond the project’s termination, several articles related to BioNexGen project outcomes will be published, as those are currently being prepared.
BioNexGen’s website can be consulted under the following address: http://www.bionexgen.eu.
Further details can be found in the deliverable D9.1 “Project Website”.
In addition a project brochure was developed. This brochure was used as a promotional instrument and it has been utilised to increase visibility of BioNexGen and to disseminate the project’s objectives. The project’s brochure contains the main elements of the BioNexGen project (project summary and objectives, information and logos of the partners, contact details for further information). The project brochure was available in English and a translated inlay was available in German, Turkish, Greek and Arabic.
Further details can be found in the deliverable D9.2 “Project’s brochure”.
During the project 10 scientific papers were published, 1 scientific paper is under review, 6 scientific papers are in preparation, 3 PhD dissertations were achieved (Federica Bisignano - CNR-ITM, Francesco Galiano -CNR-ITM, Shamim A. Deowan - HSKA) and 2 PhD dissertations will be achieved in 2014 (John Anastasopoulos - FORTH, Inès Friha - CBS). Furthermore, the partners have been involved in more than 100 dissemination activities. 6 electronic public newsletters were produced.
Further details can be found in the deliverable D9.10 “Review of dissemination activities”.
Within BioNexGen, three events of high relevance for the project have been set-up:
1) First Training Workshop in Tunisia (March 2012)
2) Second Training Workshop in Italy (May 2013)
3) BioNexGen Final International Conference in Turkey (October 2013)
First Training Workshop:
The First Training Workshop “Membrane based Wastewater Treatment and Reuse” was held at Centre de Biotechnologie de Sfax in Sfax, Tunisia on 8th & 9th March 2012. It was organised within the scope of Task 9.4 “Organisation and implementation of training workshop on novel MBR technology” of the Description of Work.
The organization of the first workshop on MBR technology has been done in collaboration with CBS, SEZ, HSKA and CNR-ITM. The programme of this two-day event has been co-developed by CBS, HSKA and CNR-ITM. An electronic flyer has been created by SEZ for the workshop announcement. In addition to the e-flyer, the workshop has been also announced on BioNexGen project website as well as in some partners’ websites. Approximately 80 external participants have been registered to the workshop among them many companies were also present. In total, around 100 persons have attended to the workshop.
Further details can be found in the deliverable D9.4 “Report on the 1st training workshop on novel MBR technology”.
Second Training Workshop:
This second workshop has focused on basic principles and state-of-the-art of "Functionalized membranes for wastewater treatment - Nanoparticles and surface modifications". It has been hosted by CNR-ITM from the 15th to the 17th of May 2013 in Cetraro, Italy. Besides theoretical seminars, this workshop has been combined with a visit at CNR-ITM laboratories.
The organization of the second workshop on MBR technology has been done in collaboration with SEZ, and CNR-ITM. The programme of this event has been co-developed by HSKA and CNR-ITM. An electronic flyer has been created by SEZ for the workshop announcement. In addition to the e-flyer, the workshop has been also announced on BioNexGen project website as well as in some partners’ websites.
Approximately 40 participants from different companies, universities, research institutes and companies coming from European and MENA countries have attended to the workshop. During this 3-days workshop, 20 oral presentations were given and 11 posters were presented. This workshop has focused on functionalised membranes, antimicrobial materials, nano-particles, carbon nano-tubes and membrane applications in wastewater treatment, which are BioNexGen’s main research topics.
Further details can be found in the deliverable D9.5 “Report on the 2nd training workshop on novel MBR technology”.
BioNexGen Final International Conference:
The final conference was the main part of the Task 9.6 “Final International Conference” which aims at fostering the dissemination of the project’s results to the academic community as well as to industrial and NGO stakeholders, and at raising mutual understanding and awareness for water related problems and for wastewater treatment technologies.
This final conference was called NANOMEMWATER international conference and has focused on application of nanotechnology in membranes for water treatment. It has been hosted by IZTECH from the 8th to the 10th of October 2013 in Izmir, Turkey. For the location the partner IZTECH was chosen as conference venue, since Turkey is the gateway between European and the MENA countries. Besides talks on the second and the third day, the conference opened with a poster presentation on the first day.
The organization of the NANOMEMWATER final conference has been done in collaboration with SEZ and IZTECH. The conference website www.nanomemwater.org has been created by IZTECH to raise the awareness on the conference. Approximately 80 external participants have been registered to the conference. In total, around 70 persons have attended the conference.
Further details can be found in the deliverable D9.6 “Report on the final conference”.
Participation in Clustering events:
As networking and clustering have been defined as important aspects of the dissemination strategy, the consortium actively engaged in several workshops and clustering events to present their research performed within BioNexGen. Hence, especially the nano4water Cluster has played an important role as a dissemination platform for the project consortium. The members of the nano4water Cluster are project committees of EU-funded research projects dealing with the topic of nanotechnologies for water treatment. In the framework of this cluster’s annual dissemination workshop BioNexGen project partners have regularly given presentations to researchers working in related areas.
Exploitation of results:
In the course of the BioNexGen project, the technological developments were continuously and carefully monitored in order to identify the generated foreground and to correctly assign the foreground to the involved partner(s) (Task 9.8: Exploitation strategy).
The assessment of the technological developments and of the generated foreground was performed during the exploitation strategy seminars. Three of them were organised during BioNexGen.
1st Exploitation strategy seminar (M18) with the support of an expert from the ESIC-team
2nd Exploitation strategy seminar (M30)
3rd Exploitation strategy seminar (M36)
Through these seminars the following outcomes were obtained and discussed:
1) Identification of novel developments = BioNexGen foregrounds
2) Definition of exploitable results
3) Assessment of the exploitation potential of the foregrounds identified
4) Determination of partner in charge (for a given exploitable result)
5) Characterization of results (result characterization sheets)
6) Establishment of individual exploitation claims
It is worth to note that over the 10 exploitable results identified in the project, 6 of them will be protected by a patent application.
Result 1:
A new technical process based on membrane bioreactor technology using either MN membranes or MN modified ones for efficient treatment of textile (dyes) and olive (polyphenols) wastewaters.
Owned by: CBS and HSKA
IP protection: Licenses or confidentiality agreements
Partners interested in exploitation: CBS and HSKA
Result 2:
Software that defines optimal CNTs diameters and functionalization for an efficient rejection of solutes
Owned by: CNR-ITM
IP protection: Copyrights, licenses
Partners interested in exploitation: CNR-ITM
Result 3:
Tailored made CNTs for the efficient incorporation in membranes
Owned by: NTX
IP protection: Non disclosure agreement, Know-how, Trade secret, licenses
Partners interested in exploitation: NTX
Result 4:
CNT embedment in anisotropic polymer membranes.
Owned by: FORTH and NTX
IP protection: Patent, Non disclosure agreement, trade secret, licenses or copyright if scientific publication
Partners interested in exploitation: FORTH and NTX
Result 5:
Decoration of carbon nanotubes with functional polymers.
Owned by: FORTH and NTX
IP protection: Patent, Non disclosure agreement, trade secret, licenses or copyright if scientific publication
Partners interested in exploitation: FORTH and NTX
Result 6:
Detection of CNTs in water via SERS
Owned by: FORTH
IP protection: Patent application will be submitted
Partners interested in exploitation: FORTH
Result 7:
Preparation of a novel coating based on Bicontinuous Microemulsion Polymerisation (PBM).
Owned by: CNR-ITM and HSKA
IP protection: Patent application submitted
Partners interested in exploitation: CNR-ITM and HSKA
Result 8:
A sol-gel procedure to prepare a mixed oxide containing TiO2, AgCl nanoparticles and commercial POM (H3PW12O40).
Owned by: IZTECH
IP protection: Patent application will be submitted
Partners interested in exploitation: IZTECH
Result 9:
Development of use of colloidal probe technique to screen polymer membranes for screening based on favourable foulant attachment forces under process conditions
Owned by: SU
IP protection:
Partners interested in exploitation: SU and HSKA
Result 10:
Modification of LBL technique to convert ultrafiltration into nanofiltration membranes.
Owned by: IZTECH
IP protection: Patent application will be submitted
Partners interested in exploitation: IZTECH and HSKA
The deliverable D9.9 “Technology implementation plan” provides an overview of the exploitable results generated during BioNexGen.
List of Websites:
http://www.bionexgen.eu/