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Zawartość zarchiwizowana w dniu 2024-06-18

Biogas Reforming and Valorisation Through PEM Fuel Cells

Final Report Summary - BIOGAS2PEM-FC (Biogas Reforming and Valorisation Through PEM Fuel Cells)

Executive Summary:
Biogas2PEM-FC is an industrial research project that aims to develop, according to participating SMEs needs, the technologies that compose a novel and integrated solution for biogas valorisation through proton exchange membrane fuel cells (PEM). As a solution, this project proposes to couple several technologies in order to achieve a sustainable valorisation approach for olive mill waste. Specifically, Olive Mill Waste (OMW) and Solid olive Mill Waste (SOMW) will be anaerobically digested, thus producing biogas. In order to tap as much as possible the potential that biogas has, this stream is used in a steam reforming process in order to obtain a H2 stream to be fed to a PEM-FC, thus obtaining heat and electricity that could be used within the valorisation process or latter in the cooperative.

In order to develop such solution, the following research has been conducted:

-Research for the increase of biogas production yield, using physic-chemical and biological pre-treatment technologies at laboratory scale for enhancing anaerobic digestion effectiveness. After optimization of pre-treatment technologies, different inoculates and co-substrates have been investigated and used in laboratory experiments for maximization of biogas production: high methane and hydrogen content with minimum CO2 and CO production ratio.
-Development and optimization of current biogas reforming technologies: new catalysts for an efficient conversion of biogas to hydrogen as well as pre and post treatment of reforming unit inputs strategies.
-Research for the integration of PEM technologies using hydrogen produced from biogas by studying its performance when operating with different impurities in the fuel cell feed and with different MEAs.
-Design, construction and field test operation of a pilot plant located in a San Isidro de Loja, a real olive oil mill exploitation.
-Techno-economic and environmental evaluation of power generation using integrated Biogas2PEM-FC technology.
-Dissemination and exploitation activities of Biogas2PEM-FC project results for the feasibility demonstration of low cost biogas reforming and power generation.

This way, main results obtained from the project are the improvement of each subsystem that compose the integrated solution as well as an operative and working prototype able to valorise olive mill waste and produce heat and electricity at the same time. This approach provides several advantages, for example:

(1) Decrease of the electricity consumption cost of the olive mill cooperative since the electricity produced by the PEM-FC can be used by the cooperative itself as well as the heat generated at the same time (which can be used as an extra thermal input);

(2) OMW storage and evaporation ponds will be no longer needed, hence all the odour, emissions and leaking problems attached to them can be avoided. Land occupation will be no longer necessary;

(3) On-site valorisation process, avoiding waste transport or storage for long periods.
Project Context and Objectives:
Biogas2PEM-FC firstly came up as an answer to the needs of the Andalusian Agrarian Cooperatives Union (participating end-user FAECA). As an agrarian sector representative, FAECA is specifically searching a way to treat and valorise olive oil mill (solid and liquid) wastes. The extraction of olive oil generates huge quantities of wastes that have a great impact on land and water environments because of their high phytotoxicity. These wastes include olive pomace (SOMW), a mixture of liquid and solid wastes with 55-60% water content. Because of SOMW characteristics (higher water content and organic compound concentration such as carbohydrates, pectins and polyphenols), a huge disposal and potentially pollution problem for the industry is generated.

Additionally, olives are cleaned producing washing wastewater containing emerging pollutants like pesticides, and olive oil produced is centrifuged producing oil washing wastewater (OMW) representing high pollution impact because of its acidity, high salinity and organic load. As a consequence, wastewater discharge into public wastewater collectors and/or use for crop land irrigation is limited. Then, the extensive practice for management of both types of wastes (solid and liquid) is the disposal into vessels. When vessels are filled up, the need for new vessels creates new problems such as increase of land use, overflowing, economic sanctions and activity, stop-up of industrial production, atmospheric pollution (odors), insect plagues and other problems in locations with high pluviometry. Several studies have proven the negative effects of these wastes on soil microbial populations, on aquatic ecosystems and even in air medium. Therefore, there is a need for guidelines to manage these wastes through technologies that minimize their environmental impact and lead to a sustainable use of resources. For many years, olive oil mill wastes has been the most pollutant and troublesome waste produced by olive mills in all Mediterranean countries, being very difficult to be treated and valorised.

After analysing and considering the OMW and SOMW characteristics it was found that the best available treatment technology that brings together environmental remediation and energetic valorisation of mentioned industrial wastes is the biogas production through anaerobic digestion. In order to explore in more detail this possibility, IDENER (Biogas2PEM-FC coordinator) contacted participating SME MARCHES-BIOGAS as an anaerobic digestion expert, which provided information about which problems this technology should overcome and also showed their interested in participating in a related research project. Mentioned limitations based on anaerobic digestion reliability using olive wastes are the following:
-Lipids and polyphenols are difficult to be degraded by micro-organisms or may inhibit certain microbial groups.
-Olive oil mill waste has a very low nitrogen content, which is needed by microorganisms for their growth at a concentration depending on the organic matter in the feed. The value of 20/1 has been suggested as the optimum C/N ratio, while the Olive oil mill waste may have double or an even higher value of this ratio.
-Olive oil mill waste has a low alkalinity, which is necessary however as it contributes to the stability of anaerobic digestion.
-Olive oil mill waste is seasonally available, as it is produced between November and February– March in most cases. This means that sufficient storage facilities are required. Otherwise, the digesters must be over-dimensioned to treat the wastes while being out of operation for an extended period of the year.
-Sources of Olive oil mill waste (olive mills) are usually in highly dispersed and so it is difficult to be cost efficient, as most of the digesters should be of small, and hence not economic size.

The specialized SME INGENOSTRUM developer of renewable energy plants suggested that, in order to valorise the biogas generated in small agrarian cooperatives, a modular system combining efficiently the heat and electricity generation should be developed. By going deeper with this idea, the development of a system able to integrate biogas production and PEM-FC was proposed. However, such a system would require an intermediate stage where biogas generated by anaerobic digestion needs to be converted to hydrogen as pure as possible. Regarding this requirements, contacts were made with HELBIO SME as biogas reforming expert and with POWERCELL as PEM-FC specialized SME, which soon showed great interest for the project.

HELBIO stated that in order to achieve a cost-effective hydrogen production, actions relating to biogas characterization and purification, as well as to the development of the fuel processor unit should be needed to be carried out. In addition, the selection of proper catalytic materials for biogas reformation, the design of the own novel process and of the basic sub-systems of the fuel processor should be developed too. In parallel, POWERCELL considered that to study the impurities tolerance of PEM-FC is mandatory, and also the development of novel PEM-FC that could use the hydrogen from reforming technologies.

Summarizing the aforementioned SME research needs, Biogas2PEM-FC project creates a framework where SMEs shows their needs for advanced research in order to obtain a novel, cost-effective, efficient and integrated system to jointly valorise SOMW and OMW:
-FAECA needs the development of an olive mill waste bioremediation and valorisation system
-INGENOSTRUM needs a cost-effective integrated modular system for energy and heat production from biowastes
-HELBIO needs to go deep into biogas reforming through the development of new catalysts, new reactor designs looking for the maximization of process efficiency for biogas conversion to hydrogen.
-POWERCELL needs the development of a novel and efficient PEM-FC able to accept hydrogen impurities at least in some degree in order to be fed by hydrogen from reforming technologies.

In order to overcome the aforementioned SME needs and thus a marketable solution, some project objectives in each of the corresponding areas are expected to be achieved.
-Regarding anaerobic digestion, an optimization of the process should be carried out, so an objective of around 0,005 m3/kg olive mill waste in co-digestion is expected and realistic.
-As for the reforming process, the developed reformer should consume around 0.45 Nm3/h of biogas (assuming composition of ~65% CH4) in order to produce 1 Nm3/h of hydrogen (in reformate gas) demanding no more than 0.8kW. The latter is produced by burning biogas in the combustion side of the reformer (also the unreacted reformate from the fuel cell can be recycled and directed it in the burner, reducing the biogas needed for the combustion).
-As for the PEM-FC, membranes suited to the reformate hydrogen while providing service life of about 40.000 hours are also advisable.
-Last but not least, the system to be developed should integrate all the aforementioned technologies in a modular, robust and easy-to-intall&operate way, also taking advantage as much as possible of heat&energy recovery. An overall efficiency of up to 80% (electricity + thermal) is expected.
-The objective price of the overall solution in a commercial format should not exceed 20.000 €/kW installed in order to achieve a return on investment (ROI) of about 10 years.

Moreover, the project objectives are not restricted to olive mill waste valorisation. Once they are achieved, project results could be extrapolated to the valorisation of other agricultural wastes just with little technological modifications, making the project potential impact and interest of European and international SMEs bigger.

According to the “Research for the benefit of SME” programme definition, the selected project objectives require research and development activities that the SMEs cannot afford by themselves, both technically and economically (since usually only well specialized RTD performers have the resources to conduct such activities). This is why first-class RTD performers where searched in order to be subcontract by the participating SMEs. Specifically, next RTD performers are going to participate in Biogas2MEM-FC project:
-IDENER, research SME specialized in systems integration and control optimization formed by a leading systems and automation R&D University group that will focus on the development of the modular system of valorisation and the reforming research tasks
-LEITAT, non-profit research centre that will focus con anaerobic digestion tasks
-KTH, Royal Institute of technology, public university with wide experience in PEM-FC research studies

Hence, the list of project participants is as follows: (please see the table enclosed in attached file)

Finally, the following figure shows the main areas where research will be conducted as well as the partners involved. The flow of knowledge exchange is also represented (from the RTD performers to the SMEs, adopting the “Research for the benefit of SMEs” approach).

Fig. 1. Biogas2PEM-FC S/T methodology (see attached file)

Project Results:
Main S&T results obtained from the project form the foreground held by the participating SMEs after project accomplishment. Hence, the knowledge that has been generated can be divided according to main areas of the project, i.e. main process stages of the proposed technology.

The following pages summarise main project results obtained during project execution.

Anaerobic digestion development

-Biological pre-treatment is an efficient method for TP and COD degradation. The requirement of pig manure as co-substrate for fungal pre-treatment also favours the AD performance. The main disadvantage on the use of fungal pre-treatment is the requirement of a previous sterilization of the organic waste, which will involve an additional capital and operating cost to the system.

-With regard to non-biological pre-treatment, ozonation technology is efficient for the reduction of TP (more than sonication). On the other hand, the existence of inhibitory compounds in AD tests, the low methane production demonstrated in BMP tests, and the related capital and operating costs of the technology could limit their implantation at semi-pilot and pilot scale.

-Considering the main conclusions obtained, it is worth mentioning that the use of new inoculates and co-substrates such as pig manure are really necessary for the success of AD of SOMW:OMW.

-The system has been initially operated in batch mode with the optimal SOMW:OMW (O) ratio together with pig manure (P) in a 3P:1O ratio. Once stabilised it has been switched to the continuous mode and, aiming to increase olive residue valorisation, the feed has been enriched with O in relation to P feeding 3P:2O and 1P:1O.

-Organic matter degradation around 40.0 g O2/L of TCOD, 5.0 g O2/L of SCOD and 4.2g O2/L of BOD5 in the effluent are maintained during the whole continuous process. That represents TCOD reductions of 30% when feeding 3P:1O, 54% when feeding 3P:2O and 63% when feeding 1P:1O. Final SCOD and BOD5 removal during the whole process is approximately 85%. This indicates the system is able to adapt to the increase of organic matter in the feed by increasing its capacity of TCOD degradation.

-A stable concentration of solids is achieved during the whole continuous process (35.0-37.0 g/L TSS). This represents a 6% reduction is achieved with 3P:1O, 59% when feeding 3P:2O and 67% when feeding 1P:1O. This again indicates an adaptation of the inoculum happening in the process which allows for a higher hydrolytic capacity of the insoluble matter when mixtures with higher olive content are fed to the digester.

-No inhibition by VFA, LCFA and polyphenol accumulation was achieved during the overall performance of the AD system. The system, then, could tolerate high organic load while maintaining biogas production and quality.

-Biogas flow and quality: Methane content in the biogas decreases with increasing olive content in the mixture (70:30 for 3P:1O, 65:35 for 2P:1O and 62:38 for 1P:1O) which also causes a reduction in the methane to TCOD removed ratio. Daily production increases with increasing olive content in the mixture (1.9L/day for 3P:1O, 2.7L/day for 3P:2O and 2.5L/day for 1P:1O).

-Digestates material obtained in Biogas2PEM-FC project are considered as amendment Type C. The most of obtained values were below the minimum limits, except for Zn and Ni content, which classify the three digestate as a low quality amendment. Digestate samples obtained in Biogas2PEM-FC project seem to contain higher nutrients (NPK) and minerals than values reported by bibliography, so fertilizer properties in terms of oligonutrients is higher for digestate samples analysed in Task 1.5. Finally, according to the BOD5/TCOD ratio, all digestate samples are stable in terms of biodegradability (<0.2).

Biogas reforming process

-Selection of adsorption technology for biogas purification; selection, purchase and testing of suitable commercial absorbers and acquisition of crucial data for defining the parameters required for the design and construction of the final biogas purification setup.

-Literature study shown that adsorption is a common technology that is used for biogas purification. Its main advantages are that is an easy manageable technology offering a “plug and play” operation, it requires low capital investments, while presents no complexities. Currently, there are numerous adsorbing materials which are commercially available and used for purification applications. It was found that a combination of different adsorbents in series is the most appropriate way for optimizing and maximizing the total impurities uptake from the biogas fuel. For this reason, a number of materials based on activated carbon, copper oxide on synthetic alumosilicate, zeolite and manganese-copper oxides, purchased from a commercial supplier and tested for their capability in biogas purification. Experiments done with artificial mixture simulating biogas and “real” biogas as well shown very attractive results. Even in the case of real biogas feed, the total sulphur capacity of the selected materials found to be twice as compared with the reported in literature corresponding values. The above experiments gave important data which will help to the design and construction of the final biogas purification setup which will be used for the needs of the Biogas2PEM project. However, when the composition of the biogas which will be produced from OMW during the project will be finalised may be some minor modifications should take place on the final design in order to maximize the efficiency of purification materials.

-Acquisition of preliminary crucial data for defining the parameters for design and construction of the reforming reactor.

-Development of a suitable catalyst for biogas reforming (Ru-based catalyst) in structured form, suitable to be placed inside the plate type reformer.

-Testing of the abovementioned catalyst under biogas reforming conditions. The ruthenium based reforming catalyst was successfully deposited onto Fecralloy corrugated sheets in order to be capable to be placed inside the innovative, compact reactors (HIWAR) that Helbio has developed during the previous years. These reactors are very compact and efficient exhibiting high heat integration. Fecralloy exhibits very good performance in heat transfer phenomena supporting the HIWAR concept, while it is very resistant in high temperatures and mechanical frictions.

-Experiments with the ruthenium structured catalyst shown that this material exhibits high activity and high selectivity towards hydrogen production under conditions of biogas reforming. Results shown that reforming reactions, and thus hydrogen production, are favoured at high temperatures and low space velocities. In addition, the structured catalyst presented very good stability as a function with time on stream. The operating parameters for the reforming catalyst were defined keeping in mind the optimization of catalytic activity and efficiency. It was found that the abovementioned catalyst can perfectly operate at space velocities lower than 8000 h-1 in order to present high methane conversions (>95%).

-Selection of the technology for reformate treatment for CO minimisation (Water Gas Shift followed by selective methanation of CO) and definition of its operating parameters and optimization of its catalytic performance.

-The process for reformate treatment in order to reducing the CO in levels suitable for feeding a LT PEM fuel cell was defined after comparing the available methods for final CO removal. The selected scheme for CO minimization after biogas reformation is the following: High Temperature Water Gas Shift, Low Temperature Water Gas Shift and CO selective methanation reaction. Methanation reaction was selected among other competitive processes, mainly the CO oxidation, due to the advantages that presents. The most important of them is that is an oxygen free process, in contrary with PROX, since no air needs to be added to the fuel processor. This results in avoiding hydrogen dilution by air’s nitrogen, hydrogen oxidation to water and creation of hot spots in reactor due to the exothermicity of the oxidation reaction. Moreover, better temperature control of the reaction is expected since the methanation reaction of carbon oxides are less exothermic than the oxidation of CO and H2, while there is no need of additional equipment for air feeding (like air blower) in terms of process simplicity. The biggest drawback of the SMET process is the consumption of hydrogen; however, this amount is rather small in absolute values.

-Testing of commercially available catalytic materials for the CO minimization reactions. Experiments with all catalysts that will be present in the fuel processor shown that the combination of these materials possess the activity and efficacy characteristics required in the application. The biogas can be effectively reformed to hydrogen while the CO minimization catalysts can reduce the carbon monoxide to amounts lower than 20 ppm. The overall catalytic performance, simulating perfectly the operation of fuel processor, seems to be very stable with time on stream, ensuring that the reformate quality, in terms of hydrogen and CO concentrations, meet the standards of LT PEM fuel cell demands.

-Testing of all catalytic reactors in series, simulating the operation of the fuel processor. Different commercial catalysts were tested for their performance for each CO minimization process. Catalysts A, D and H exhibited the best results for the reactions of HTWGS, LTWGS and SMET, respectively, and were selected for further testing. It was found that CO contents in the reformate gas can be reduced in the level of few ppms, less than ten, using the abovementioned scheme. The operating parameters of each reaction were defined keeping in mind the optimization of catalytic activity and efficiency. It was found that there is a temperature window where the abovementioned catalyst can perfectly operate. In specific, this temperature range is between 280-300 0C, 250-270 0C, and 205-225 0C for the HTWGS, LTWGS and SMET catalysts, respectively. The corresponding windows for the operating space velocities are the following: 10.000-15.000 h-1, 6.000-10.000 h-1 and 4.000-7.000 h-1.

-Definition of all operating parameters and optimization of the overall performance. This way the production of reformate gas suitable to feed a LT PEM fuel cell stack can be achieved.

-Acquisition of all data required for the design and construction of the fuel processor.

PEM-FC operation

-A comprehensive literature survey of different possible contaminants in polymer electrolyte fuel cells was done. A majority of the studies presented in literature is done on Pt catalysts. From literature it was shown that the most severe contaminants for the fuel cell are carbon monoxide, hydrogen sulphide and ammonia. The former two impurities poison the catalyst particles (occupying active sites on the catalyst) and thereby affect the activation polarization in a negative way. PtRu catalysts have a much better tolerance for CO contaminations, but such a positive effect of PtRu is not shown for H2S. Ammonia is an impurity affecting the membrane in negative way, due to presence of ammonium cations in the membranethat decreases the membrane conductivity.

-Electrochemical measurements performed in a lab scale fuel cell with PtRu catalyst show that using clean reformate gas for the anode, i.e. 67% H2 and 33% CO2 without any traces of other compounds, will hardly at all affect the performance of the fuel cell. However, diluting the hydrogen with higher amounts of CO2 will reduce the performance remarkably. The performance loss is in accordance with thermodynamics, i.e. the loss is only a consequence of the lower partial pressure of hydrogen and not due to poisoning of the anode catalyst by CO2.

-Based on the literature survey done, and with knowledge about what impurities are already studied thoroughly in previous investigations, Powercell and KTH have agreed that nitrogen compounds are interesting pollutants to study. The PEM fuel cell in our study will be operated by air and also placed in an agricultural area, where the air may contain this type of contaminants affecting negatively the fuel cell performance. For this project NOx and NH3 in the cathode were therefore selected as the most important impurities to start with.

-Using a clean reformate gas at 70 ⁰C at the anode (67% H2 and 33% CO2) will hardly affect the performance of the fuel cell. However, diluting the hydrogen with higher concentrations of CO2 will reduce the performance remarkably. The loss is only a consequence of the lower partial pressure of hydrogen and not due to poisoning of the anode catalyst by CO2.

-Nitrogen compounds showed a detrimental effect on the fuel cell performance. Ammonia has a negative effect not only on the membrane, but also on the catalyst and ionomer, while nitrogen dioxide has influence only on the catalyst.

-Propane showed no effect on the fuel cell performance when it was operated with PtRu-alloy catalyst, but it did affect the performance when Pt catalyst was used.

-The fuel cell stack was operated using three different commercial MEAs, and the performance was studied by electrochemical methods. The studies made by polarization curves showed that the MEA from supplier A has the best performance, and also a higher OCV. By operating with pure hydrogen a better performance than expected was reached.

-The normalized polarization curves depicted that the MEAs from supplier A and B were both fabricated in a successful way, although the MEA from supplier A had a higher OCV.

-The influence of stoichiometry indicated that the MEA from supplier A is the most stable for both current densities. Accumulation of water was seen as ‘noise’ when it was operated at lower stoichiometry, which means that there is a lower gas flow and therefore less pressure to pull the water drops inside of the fuel cell.

-Humidification was also studied and it was seen that the MEAs are dependent on the cathode dewpoint. Instability was visualized due to the low operating stoichiometry (1.25/1.8) and water management of the membrane. By making a deeper diagnostic, electrochemical impedance spectroscopy was done. The membrane conductivity was analysed at different cathode dewpoints where a decrease in resistance was revealed with the increasing of temperature, thus facilitating the proton conduction. The MEA from supplier A was the most stable.

-According to this study the MEA from supplier A presented the best performance whether changing the stoichiometry or the relative humidity. Additionally, it was the most stable MEA.

-The energy balance shows that 50% of the input hydrogen energy is converted into electricity and the other 50% into heat. Assuming a single cell of 200 cm2, 34 cells in the stack are needed to produce 1 kW of electricity.

-The fuel cell stack was studied by different electrochemical methods. The polarization curves show a stable performance and a wide operation range. The pressure drop at the cathode at higher current densities is higher than at the anode, due to the high flow rate required and amount of water production. The pressure drop at the anode and cathode may in any case be considered low.

-The cathode pressure sensitivity analysis shows that the stack has a good heat and water management, and the performance is not affected by the mass transport losses.

-The influence of the stoichiometry indicates that both electrodes, anode and cathode, are stable when operated at stoichiometry above 1.2 at the anode and above 1.8 at the cathode. In both cases, the stack operates efficiently above those stoichiometries, for anode and cathode, without supplying large quantities of hydrogen and air.

-The fuel cell stack showed a stable performance and a wide operation range. The pressure drop was considered low, and the stack also presented a good heat and water management.

-The effect of 25 ppm of carbon monoxide was completely mitigated when it was operated with air bleed.

Modular system for olive mill waste valorization

-The modular system integrates the anaerobic digester that produces biogas using olive mill waste, the fuel processor that carries out the reforming process and the PEM-FC that transforms the hydrogen stream from the reformate into energy. It also comprehends a variable load that modifies and consumes the generated electrical current. To allow the whole modular system to be operated and controlled, a distributed control system is implemented, consisting on a personal computer that communicates and masters the sensors, actuators and PLCs of each sub-module.

-The complete design was realized. As part of this design process, a set of technical data was also generated, including Process Flow Diagram (PFD), Piping and Instrumentation diagram (P&ID), Mass and Energy balances (MB & EB), safety recommendations and overall blueprints. As for the different process stages, the following designs have been produced:

Anaerobic digester pilot scale design. An 800 litres anaerobic digester with its associated 800 litres bell-over-water gas holder was designed. Deposits for feeding and digestate extraction purposes were also considered. The digester vessel is to be equipped with a level transmitter, a pressure sensor, a pH transmitter and two temperature sensors, so that optimal conditions can be ensured for the anaerobic digestion. Meanwhile, the gas holder has a pressure indicator and a level transmitter. A flowmeter is placed inline between both vessels to quantify the amount of generated biogas. A set of auxiliary equipment was also included in the design for heating and agitation purposes.

Fuel processor unit pilot scale design. The reforming subsystem was completely defined. Various stages has been considered such as the purification of raw biogas is done by means of its circulation through subsequent vessels containing adsorbents; and Water Gas Shift reactions and selective methanation to convert the purified biogas into a hydrogen rich stream (each one of these operations are performed in specific tubular reactors containing proper catalysts). Finally, a condenser has been included to meet temperature and humidity criteria for the fuel cell inlet. All the equipment is integrated within the reforming unit, except the pre-treatment vessels, which are placed inside an external metallic box.

PEM-FC definition. The fuel cell subsystem was designed including its auxiliary equipment. The elements that compound the membrane were selected according to main results from WP3 to ensure proper operation with the amount of impurities that the biogas is expected to carry. Adequate monitoring devices are included to track the voltage of each cell of the stack and to ensure that they are within a safety operating range. Auxiliary devices to expel generated heat and to manage fuel humidity and temperature were also considered.

-Pilot scale modular system construction. A complete semi-pilot scale prototype for the Biogas2PEM-FC concept was built and deployed. It is formed by the integration of three main subsystems, namely AD subsystem, reforming subsystem and Fuel Cell subsystem, along with other auxiliary, supervisory and control subsystems. An adequate olive mill was selected for the prototype to be installed in. The deployment of the semi-pilot scale plant was realized according to the project specifications.

-Field test of the developed modular system. The proper functioning of the constructed prototype has been demonstrated. In addition, the following conclusion regarding each process stage have been drafted:
---The anaerobic digester has been capable of maintaining the desired operating conditions thus assuring that the requirements for a proper anaerobic digestion of the wastes are fulfilled. It has to be considered that, when scaling up AD to semi-pilot scale, pH conditions will be controlled during all the process. The agitation system will also ensure more homogeneous working conditions. The control of these parameters can help improving the performance of the system. Therefore, working conditions can be kept at the mentioned values during the start-up (3P:1O if mesophilic, 2P:1O if thermophilic) but once the system starts working in a continuous mode it could be fed with a mixture that has, progressively, a higher content of olive waste.
---The reformer has been able to process the produced biogas and has reduced (combined with the initial biogas filter designed in previous WPs) the amount of CO present in the biogas to levels suitable for the operation of the FC.
---The FC, and specifically its membrane, has been capable of working with the fuel provided by the reformer, thus demonstrating a significant advance on membrane capabilities compared to current state of the art devices.

-Summarising, the tests conducted have demonstrated the feasibility of the concept behind the Biogas2PEM-FC project and thus, a future scale up of the project is recommended.

-Pictures from the modular system implementation are included next: (please see the attached file)
Fig. 2. (a) Anaerobic digester at pilot scale; (b) Helbio Biogas reformer and prototype structure
Fig. 3. (a) Helbio biogas reformer control and display; (b) Powercell PEM-F
Fig. 4. (a) Pilot prototype shipment; (b) Pilot prototype installation at olive mill cooperative
Fig. 5. (a) Partial view of the prototype, anaerobic digester; (b) Partial view of the prototype, reformer, fuel cell and control PC
Potential Impact:
Biogas2PEM-FC system development will overcome current technological and economical barriers of on-site power generation using PEM fuel cell technologies and biogas as fuel obtained from olive oil extraction liquid wastes. Given high potential market opportunities for Biogas2PEM-FC outcomes, the results of the project will improve the competitiveness of the SME participants by providing them with a valuable know-how. The potential impact of carrying the project in terms of economic growth and employment is difficult to be specified, but the SME participants have roughly estimated that Biogas2PEM-FC could lead to a 15%-40% increase of their market activity. To that end, a proper market strategy will be conducted within and after the finalisation of the project, and it will be focused on the market segment composed of agricultural cooperatives of small-medium size, taking advantage of the distribution channels currently utilised by the SMEs participants and also thinking on new distributors taking also advantage of the participation of FAECA as end user. Specifically, main Biogas2PEM-FC project benefits for each individual SME participant are summarised next:

-MARCHES-BIOGAS Novel inoculates and codigestates to allow efficient biogas generation from olive mill waste in combination with other biomass residues; and cost-effective anaerobic digesters especially suited to such substrates
- HELBIO Novel catalysts for the increase of biogas reforming yields
- POWERCELL Suitable PEM-FC with selected MEA and operable at high temperatures for a sustainable power generation using hydrogen generated from biogas
- INGENOSTRUM Novel on-site integrated system optimally combining the aforementioned technologies

The proposed research project cost effectiveness analysis (CEA) can be derived taking into account the overall cost of the project in relation to the following direct benefits:
-Increase in project quality, mainly derived from the research subcontracting to key RTD performers in the areas of interest.
-Increase in project scope, derived from the European dimension of Biogas2PEM-FC, uniting the efforts of SMEs of different countries in order to develop a novel technology with a potentially large impact on economic growth and employment.
-Reduction of project time-to-market, speeding the research and development phase of the proposed technology thanks to the European Framework Programme financial support. The estimated time-to-market after the end of the project is 1 year, which is the time needed to finish the commercial presentation of the solution.
The objective price of the overall solution in a commercial format is expected not exceed 20.000 €/kW installed in order to achieve a return on investment (ROI) of about 10 years.

Innovation impacts

Moreover, the technologies to be developed herein are also extendable to other digestible agricultural wastes, such as sugar beet tops and straw. Regarding the potential new markets of these outcomes, two phases olive mil waste (TPOMW) has become a critical environmental problem in the Mediterranean areas where the 2-phase extraction process of olives is used. Millions of tons of TPOMW are produced every year, most of them in Southern Mediterranean regions, as Spain, which is the world leader in the production of olives (1,200,000 Tn) and produces more than 4 million tons of TPOMW.

In addition, in other countries where other extraction techniques dominates the market (such as the three-phase techniques) the average amount of olive mill wastewater (OMW) produced during the milling process using the three stages process is 1.2-1.8 m3/t. In the olive-growing countries of the Mediterranean area approximately 30 million m3 OMW effluents are produced as by-products per year, of which about 370,000 m3 are produced in the Middle Eastern region. In these countries, OMW is a potential and active source of environmental pollution due to its high content of polyphenols, tannins, and lipids, which exhibit phytotoxic and antimicrobial activities, as well as a high potential to contaminate surface and ground water. In these countries Biogas2PEM-FC technology also represents a challenging opportunity to introduce new waste valorisation processes.

Not only limited to olive mill waste energy valorisation, Biogas2PEM-FC technology can also be extrapolated to other digestible agricultural wastes in the EU in order to expand the related existing markets. There are quite a few biogas process volumes at the current wastewater treatment plants, landfill gas installations, and industrial biowaste processing facilities. However, the largest volume of produced biogas will, by 2020, originate from farm biogas and from large co-digestion biogas plants, integrated into the farming- and food-processing structures. The EU policy concerning renewable energy (RES) has set forward a fixed goal of supplying 20% of the European energy demands from RES. It is without doubt, that a major part of the renewable energy will originate from European farming and forestry: as biomass conversion to gaseous, liquid and solid biofuels. The gaseous part – the biogas production - has its own, more and more consolidated platform. The forecasts look promising. At least 25% of all bioenergy in the future can originate from biogas, produces from wet organic materials, like animal manure, whole crop silages, wet organic food/feed wastes etc.

Smaller CHP (combined heat and power) plants using local energy sources (solid biomass, peat) have only become competitive in recent years due to technological innovations and financial support. CHP as percentage of gross electricity production (2007) is the largest in the EU in Denmark, 44%, followed by Latvia, 41% and Finland, 34%. Electricity production from biogas in the EU in 2008 was 20 TWh. 42% was in Germany and 27% in the United Kingdom, both using primarily electricity-only plants. Nordic (Denmark, Sweden and Finland combined) electricity production from biogas is small, 0.3 TWh, but it is practically all CHP based. Most Member States produce biogas primarily from sewage sludge and landfills, though Germany and Austria have an overwhelming bias toward other sources (mostly decentralized agricultural plants etc.). Nordic production of electricity from solid, renewable municipal waste is twice that of the UK, but still only half of Germany’s 4.5 TWh. Gross electricity production from solid biomass in the European Union reached almost 60 TWh in 2008. Finland, Sweden and Germany are the big players, each producing about 10 TWh.

As an added benefit, the modularity of the proposed system will allow efficient decentralization of the production of biogas. Europe is beginning a transition from a centralized and largely fossil-fuel and nuclear-based power system delivering electricity to passive consumers toward a more decentralized power system relying to a larger extent on small-scale (sometimes intermittent) generation from renewable energy sources (RES) allowing greater active participation of consumers by becoming producers themselves and/or by smarter demand response management of their own energy use.

This profound change is brought about by a combination of converging drivers:
-The necessity to combat Climate change by reducing greenhouse gas emissions by 20% by 2020 from the 1990 level;
-The rise of renewables: Europe has set itself a goal of achieving a share of 20% of RES in its energy mix by 2020;
-The widely recognized necessity to use energy in a more efficient manner: Europe will have to improve energy efficiency by 20% by 2020;
-A growing concern over the security of European energy supply due to the increasing share of intermittent power production from RES;
-Rising electricity demand throughout European countries, and
-The liberalization of Europe’s energy markets.

The natural gas network is a very centrally oriented operation. The main decentralized aspect is the possibility of supplementing biogas to the gas network. This is a way of turning a decentralized (renewable) energy source into a centrally used alternative. Biogas networks are also a possibility, either in areas where there is no natural gas grid or when the upgrading of biogas to natural gas quality is seen as too expensive. This might be the case if biogas is only used for heating, for example.

These potential markets are an example of the great impact that a biogas valorisation modular system could have in order to enlarge the competitiveness of the participating SMEs. The system that will be developed will, on the one hand, open a new market as the olive mill waste valorisation and, on the other hand, expand the anaerobic digestion market by using conventional substrates in modular systems ready to be used by small-scale cooperatives.

Economic impacts

Regarding economic profitability of the proposed approach, a financial analysis has been carried out, being the following the main findings:
-Financial Net Present Value on investment is negative for power installations of 250, 500 and 1000 kWe when foreseen to 10 years. However they result positive for 15 and 30 years-long time horizons. This leads to the need to plan plants with a relatively long expected lifespan and, where maintenance and replacement costs have to be curbed.
-Models show a high sensitivity to some variables, such as digestate price and season duration. The effect of these variables must be completely characterized in order for the rest of the Cost Benefit Analysis to be realistic.
-The costs per installed and produced kW of electricity are far below the objectives outlined during the project proposal. Financing costs might cause a rise in this costs, but it is expected that, even so, both costs will be inside the margins.


Environmental impacts

Concerning environmental impact of the proposed solution for olive mill waste valorisation, it has been compared to the traditional procedure and the following conclusions can be drafted:
-In the midpoint, the deployment of the proposed solution would have a positive impact in abiotic depletion (due to land preservation since no longer storage ponds would be needed), global warming (since it produces energy, decreasing this way the energy consumption of the olive cooperative since it could use its own produced energy) and human toxicity (since no emissions and leakage from the ponds would take place).
-From and endpoint approach, the main positive impact is climate change, respiratory inorganics, minerals and fossil fuels. This is due to the long-term effect of the decrease of energy production, i.e. the use of renewable energies. This is fully aligned with the European targets related to the use of renewable energy, helping this way to address planned scenarios.
-Moreover, a sensitive study has been conducted in order to study the contribution to the environmental impact of the pig manure transportation (as this is one of the main hypothesis of the LCA). It has been stated that in the midterm the difference between having a pig manure 10km or 100km far way is slightly significant (especially for ozone layer depletion, due to the traction emissions). However, in the long term and using a single score approach it can de concluded that the same impact is caused by both possibilities. Thus, it can be concluded that the pig manure availability is not an issue of concern when estimating environmental impact (but it would be needed to be considered as for the economic analysis of the whole solution).

In brief, the use of the prototype as alternative to traditional approach when valorising agrarian waste might have a positive impact in the environment, especially concerning the use of fossil fuels and global warming, and could help Europe to meet its targets concerning renewable energy.


Dissemination and exploitation activities

The following activities have been carried out in order to disseminate and exploit project results.

-Project branding
The graphical identity of the project has been created and is in line with the public website and the general brochure and poster. It is important to follow the graphical identity since good use of it will help to consistently communicate and disseminate the project. Guidelines and templates will also save time and effort for the members of the consortium, since no further design work will be necessary.

An important item to establish the project’s identity is the project’s logo. This logo was created by project partners and is usually included in all presentations, reports, documents, etc., of the project. In addition, a poster, a flyer (where information from each partner can be included), presentations and deliverable templates have been produced. All this material is labelled with the project and EU FP7 logos, making easier for the public to recognise them and relate them to the project concept and the Seventh Framework Programme from EU.

Fig. 6.Biogas2PEM-FC project logo (please see attached file)

All this material has been provided to the partners using the Alfresco share tool linked to the project website private area.
Furthermore, a label was placed at the prototype site installation in order to provide information about the EU project under its funding the prototype implementation was being carried out.

-Events
Biogas2PEM-FC project has achieved a good success rate in relation to the participation of the partners in conferences, exhibitions and meetings.

Specific mention must be made in relation to the type of audience each event can be targeted, since the dissemination activities performed approached an array of interested parties, coming from different fields and areas of interest. Universities and academic institutions, technology institutes and potential end-users are some examples of the type of audience the dissemination activities aimed at. Specifically, for end-users the main link between the project’s core and them will be FAECA, the Spanish Association of Andalusian agrofarms.

All events had a wide geographic approach, targeting audiences in Europe and took place over the entire time span of the project’s second reporting period, thus maintaining a dynamic momentum of interest at a constant pace.
Concerning the audiences, events that have taken place can be listed as follows.

Events targeted to scientific audience
Scientific audience is an important target in order to share project results, assess its content and exchange new ideas about potential developments that could increase the performance of the process or the project impact. Hence, the project participants have attended the following events in order to disseminate main results achieved:
-“Development of pre-treatment technologies for the enhancement of biogas production from olive oil residues”, Sergio Martínez-Lozano, Elena Genescà, Julia García-Montaño Lorenzo Bautista, Jordi Mota, Jose García-Torres (LEITAT). Wastes 2013, 2nd International conference. Braga, Portugal. 11-13 September 2013.
-“Development of an on-site power generation modular system for agricultural wastes valorisation”, Macias Aragones, Marta, Leyva Guerrero, Carlos, del Real Torres, Alejandro J. (IDENER). Wastes 2013, 2nd International conference. Braga, Portugal. 11-13 September 2013.
-”From olive oil residues to electricity via a PEM fuel cell”, Yasna Acevedo-Gomez, Carina Lagergren, Göran Lindbergh, poster presented at the “KTH Energy dialogue 2013”, 7 November, 2013.
-“Pre-treatment technologies for the enhancement of the anaerobic digestion of industrial semi-liquid wastes”, E. Genescà, S. Martínez-Lozano, E. Borràs, J. García-Torres, L. Bautista, J. Mota, A. Surribas, J. García Montaño (LEITAT). V Workshop about WWTP sludge treatment and management. Barcelona, Spain. 20th November 2013.
-"Reformate from biogas used as fuel in a PEM fuel cell", Yasna Acevedo-Gomez, Göran Lindbergh, Carina Lagergren, short proceeding and poster contribution, European Fuel Cell 2013, Rom, Italien, 11-13 December, 2013.
-”Ammonia contamination of the proton exchange membrane (PEM) fuel cell”, Göran Lindbergh, presentation at WHEC 2014, Gwangju Metropolitan City, Korea, 15-20 June, 2014.
-”Ammonia contamination of the proton exchange membrane (PEM) fuel cell”, Göran Lindbergh, presentation at meeting of Annex 22, IEA Advance Fuel Cells, South Korea, June, 2014.
-“Anaerobic co-digestion of olive oil mill wastes and pig manure in batch and continuous mode for the maximization of biogas production” E. Genescà, S. Martínez-Lozano, E. Borràs, A. Surribas, J. García Montaño (LEITAT). 13th Mediterranean Congress of Chemical Engineering. Barcelona, Spain, September30-October 2, 2014
-”Hydrogen and air contaminants in PEM fuel cells”, Yasna Acevedo-Gomez, Göran Lindbergh, Carina Lagergren, Rakel Wreland Lindström, abstract sent to the conference CARISMA 2014, going to be held in Cape Town, South Africa, 1-3 December, 2014.

Events targeted to wider public
Wider public is also a target for the dissemination activities planned in the project since results end-users (olive cooperatives) are included in this group. Moreover, another SMEs that could take advantage of the generated knowledge (by acquiring subsystems of the whole process, e.g. the anaerobic digester, the reformer or the robust PEM-FC) are targeted.

Events targeted to wider public where project partners have presented project concept and main results are:
-”The fuel cell – the efficient energy converter”, Carina Lagergren, presentation for teachers participating in ”Technology Initiative”, a project for teachers in technology in the elementary school in Stockholm, 7 November, 2013.
-”What President Obama did see!”, Carina Lagergren and Göran Lindbergh, presentation at Vallentuna Naturskyddsförening (a local association within the Swedish Society for Nature Conservation), 10 March, 2014.
-“IDENER – SME success case”, Marta Macias Aragonés (IDENER). Vision 2020: Third pan-European SME event. Barcelona, Spain. 4th April 2014.
-“Energy related opportunities in the agro-food industry” and “Precise agriculture” oral presentations (by Ingenostrum) at the Workshop held in the Universidad Catalina de Temuco, Santiago de Chile, Chile. 30th May 2014.

Events targeted to politicians and policy makers
A way to increase the impact of the project is to let us know politicians and policy makers about SMEs needs and how can them be solved thanks to the solution developed through Biogas2PEM-FC. Hence, it has been crucial for maximising this project impact, to carry out some exhibitions and seminars with them in order to share main problems that are happening regarding the olive mill waste treatment and management. These events have been:
-“Fuel Cells” Göran Lindbergh, Carina Lagergren, a seminar at KTH in the presence of Barack Obama, president of United States of America, September 2013.
Fig. 7. Barack Obama at KTH
-“Fuel cells”, Göran Lindbergh, Carina Lagergren, Rakel Wreland Lindström, Presentation at “Energy systems for tomorrow”, a seminar at KTH in the presence of His Majesty the King, Carl XVI Gustav, 4 November, 2013.
-”Fuel cells and power-to-gas”, Carina Lagergren and Göran Lindbergh, Presented at the visit to KTH of the German delegation led by Federal Minister for Economics and European Affairs, Ralf Chrostoffers, 14 November, 2013.
-”The fuel cell – the efficient energy converter”, Carina Lagergren and Rakel Wreland Lindström, presentation for the Swedish Ministry of Defence, 12 June, 2014.
-”The fuel cell – the efficient energy converter”, Göran Lindbergh, Carina Lagergren and Rakel Wreland Lindström, presentation at the visit to KTH by the Chinese Embassy in Stockholm, 19 September, 2014.

-Website
The project website (www.biogas2pemfc.eu) acts as a dissemination platform with the aim to establish an efficient and effective dissemination and communication tool for the Biogas2PEM-FC consortium for the duration of the project. The website construction consists of one of the main dissemination tools of the project, which will ensure the successful use of project results and non-confidential information to the widest possible audience (including the industrial, academic community and potential end-users).

The website has a clear structure with two types of webpage navigation depending on the type of user i.e. visitor (public) or Consortium member (private area). The potentials for navigation, document uploading and website alterations differ for each type of user. The aim of the website is on one hand to inform general public about the project and on the other hand to constitute a tool to communicate and to exchange information on the project between partners. Project website is often updated through the insertion of news, new data and events and activities that are related to the project area and could be interesting for website visitors. Concerning project website updates, information has been added to the website often.

-Publications
Publications, either in the form of Press Releases or as scientific papers with the intention of being published and/or in the process of being published, have played a significant role in the dissemination of the project and are elevated at an equal bearing as any other type of activities performed during this time.

The project has been disseminated in various newspaper articles mainly on the internet such as Tierra cooperative and chil.org both Spanish publications targeting agrarian sector. These Press Releases were aimed primarily at the local audience, particularly end-users such as small and medium agriculture cooperatives who usually deal with the problems related to olive mill waste valorisation and management. This medium has proved particularly useful since it has disseminated the project at large to a wide public which would not be easily identified via standardized methods of dissemination such as events and scientific conferences.

In addition, links to these publications have been disseminated using new tools such as twitter, specifically from the account of @red_chil, the media account from chil.org.

As for scientific publications, contributions to conferences has provided the chance to publish project results in the corresponding proceedings, e.g. for WASTES 2013, V Workshop about WWTP sludge treatment and management, European Fuel Cell 2013 and 13th Mediterranean Congress of Chemical Engineering.

-Project reports
Dissemination of projects results by making deliverables publicly available is regarded as one of the most important means to publish results. For that reason this project consortium team is considering to review the dissemination level of deliverables (after the end of the project) in order to have more public reports published on the project website. These documents will be published on the projects website.

All public deliverables that have been produced have been added to the website according to the DoW.

-PhD positions
PhD and MSc theses contribute to the dissemination of Bioogas2PEM-Fc results in the academia by involving other academic institutions and the people working in them. Additionally, this is a way to increase impact of project results since opens a new way of spreading generated knowledge across Europe (since PhD students usually spend time in other universities or RTD centres exchanging knowledge and techniques).
Within this project, the following PhD and MSc theses have taken place: “PEM-FC predictive control development” and “Modelling and optimisation using predictive control of co-generation in an olive oil waste valorisation plant”, both MSc thesis at IDENER and “Influence of fuel and air contaminants on the PEM fuel cell performance”, PhD thesis work at KTH

-Other dissemination material
According to the DoW and the Plan for Use and Dissemination of project results, a Wikipedia and a Video clip have been produced. The video clip has been uploaded to YouTube in order to increase its impact (https://www.youtube.com/watch?v=H7vHfGm_XcI).
List of Websites:
www.biogas2pemfc.eu
As for contacting the consortium, please send your mails to contact@biogas2pemfc.eu.