Biogas membrane reformer for decentralized production

Newsletter – Issue 2 – 2nd half 2016

This Newsletter Previous release  Membrane & Catalysts  Industrial development specifications  Reference case  First results @ Lab scale  First membrane &  First release of LCA catalyst release analysis

March September March September March September

2016 2017 2018 Editorial

Dear BIONICO friends I am glad to welcome you to the second project newsletter! The last project meeting was held at the end of August, allowing all the consortium members to take stock of the situation: in the second six months of the project new membranes, membrane supports and catalyst specifically designed for operating with biogas have been tested at TU/e labs and soon new promising finger-like porous asymmetric ceramic supports will be tested. The information collected allow now the Abengoa Hidrogeno engineering team to start with the design of the pilot scale reactor that will contain around 100 membranes! The scale of the project represents a strong step forward for CMR technology. Not only experimental, but also simulation work was performed by POLIMI in order to have benchmark cases for BIONICO. At the same time environmental performance of these technologies is being evaluated by Quantis, in order to demonstrate not only improved efficiency performance but also environmental ones for the BIONICO technology!

I hope you will find the info in this newsletter interesting. On our website www.bionicoproject.eu you will find public presentations, all the public deliverables of the project and many other interesting news. Stay tuned!

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu In this Issue:

Editorial ...... 1 Latest News: Around the world to make Bionico known ...... 2 Why is BIONICO? ...... 3 A life with membranes ...... 6 BIONICO in progress ...... 7 Novel catalysts and supported membranes for Biogas Reforming process ...... 7 Lab-scale reformer development ...... 8 Life cycle assessment ...... 8 BIONICO second progress meeting, August 2016, Sonning Common, UK ...... 9 Highlights ...... 10

Latest News: Around the world to make Bionico known During summer, Bionico partners travelled for thousands of kilometers to disseminate the BIONICO projects and its achievements in this first year. Posters, presentations, leaflets and pens were used to increase the impact of the communication. Conference attendees showed their interest in the project, looking forward for the pilot plant in Chamusca to be ready and running. Still 18 months to go for the pilot plant to run. In the meanwhile, you can keep up to date about the intermediate results on www.bionicoproject.eu and in the membrane reactor linkedin group https://www.linkedin.com/groups/8513530

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu Why BIONICO? In the first year of the project, two reference cases are identified to benchmark the performance of the BIONICO concept. The first case is based on a steam- reformer (SMR) reactor, while the second one on an autothermal reformer (ATR). These two cases reflect the state of the art of hydrogen production from biogas, being the steam methane reformer the most diffused configuration. Both cases are based on the same layout consisting of a reforming section (either steam or autothermal reformer), two water gas shift reactors and a pressure swing adsorption system. The systems are designed for a hydrogen production of 100 kg/day with a purity of 4.0 (99.99%).

After defining the layout of the two selected configurations, the operating conditions are determined to maximize the system efficiency. The main performance indexes, which are consistent with literature data, are reported in Table 1.

Table 1 Main results for the two benchmark technologies1 Results units SMR ATR Biogas feed Nm3/h 35.7+14.6 47.0 Total Biogas Input kW 221 207

System efficiency %LHV 59.2 55.4 Hydrogen delivery pressure bar 13.3 13.3 Equipment costs €*h/Nm3 14520 12342 Hydrogen production cost €/Nm3 0.408 0.398

The target of BIONICO is a system efficiency above 70%LHV, which is about 20% higher than SMR. The higher efficiency together with equipment savings will end up in lower hydrogen production costs making more competitive with respect to conventional processes.

The concept

Biogas production in EU28 is expected to enjoy a remarkable growth in the next decades, increasing the production up to 40 Mtoe in 2020. Biogas, which mainly consists of methane and carbon dioxide, can be upgraded to biomethane by CO2 separation. Hydrogen production from biogas is even more complex since it can have variable gas compositions depending on primary matter sources. In addition, traditional conversion technologies are energy and capital intensive as several process steps are involved. Consequently, there is a need for shifting from traditional conversion technologies to a novel and flexible technology.

The BIONICO project proposes an integral solution throughout the whole building value chain. By using the novel intensified reactor, direct conversion of biogas can be achieved in a single step producing and separating pure hydrogen in situ, which results in an increase of the overall efficiency and strong decrease of volumes and auxiliary heat management units. This will guarantee a higher efficiency in the conversion of biogas and a higher penetration of this fuel into the market.

1 D2.2: Definition of the reference case http://www.bionicoproject.eu/dissemination/deliverables

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu Project objectives

The BIONICO project will develop, build and demonstrate a novel reactor concept integrating H2 production and separation in a single vessel in a biogas production plant. The hydrogen production capacity will be of 100 kg/day. In particular, by integrating the separation of hydrogen in situ during the reforming reaction, the methane in the biogas will be converted to hydrogen at a much lower temperature compared with a conventional reforming system. The adoption of a membrane reactor (MR) can improve the conversion efficiency due to combining the biogas conversion to hydrogen and its separation in one single reactor. MR has advantages in terms of costs because the equipment is reduced and also because of the lower maximum temperature: cheaper materials can be adopted. Additionally, the reactor will be integrated with an advanced control system such that the flexibility of the system towards several parameters (temperature, pressure, flow rates, etc.) is improved. Dedicated tests with different biogas compositions will be carried out to show the flexibility of the process with respect to feedstock types.

ATR-MR Retentate H2

Vac.P.

HX-4 HX-2 air+H2Oreaction

CMPNG Airbrn EUNG

Exhaust Sep Burner HX-1

HX-0 Sep

water rec. AirATR

H2Oreaction CMPair P-1 Figure 1 Schematic BIONICO layout

Compared with any other MR projects in the past, BIONICO will demonstrate the MR at a much larger scale, so that more than 100 membranes will be implemented in a fluidized bed MR, making BIONICO’s concept a real demonstration unit, paving the way towards a market exploitation of the reactor concept.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu Partnership In order to achieve maximum impacts on the European industry, the BIONICO consortium gathers 8 organisations from 7 countries including top level European Research Institutes, Universities (3 RES) and representative top industries (1 SME and 3 IND) in different sectors. The consortium brings together multidisciplinary expertise of catalysts synthesis, membranes development, chemical and process engineering development and construction of turn-key solution in the energy sector including operation and maintenance (i.e. biogas recovery plants design, other energy plants), modelling and simulation, LCA and industrial risk study.

Project structure

The project scheduled work plan includes activities related to the whole system design, construction and prototype demonstration. It is broken down in nine work packages covering three years of work following the focus of the development of a flexible biogas gas membrane reformer to provide pure hydrogen. BIONICO also takes advantage of the previous FP7/JU projects carried out by the partners, thus the technical work packages are limited and focused to the optimization and scale up production of the components for the final membrane reformer.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu

A life with membranes by Ekain Fernandez

My name is Ekain and I’m researcher at the Membrane Technology department at TECNALIA (San Sebastian, Spain). Within BIONICO project I’m developing thin Pd-based membranes for their use in membrane reactors for biogas reforming and also leading the Work Package of Membranes. When I finished my chemical engineering degree at the Engineering School at Bilbao, I obtained a grant for working on membranes at TECNALIA (former INASMET-TECNALIA). It has been nine years since that time and I learned a lot from many people and different experiences. In the beginning, I started preparing few amount of very short tubular Pd-based supported membranes of max. 5-10 cm long. After being involved in some European projects (DEMCAMER, REFORCELL, FERRET, FLUIDCELL), now in BIONICO project our objective is to manufacture more than 100 membranes of 50 cm length together with RAUSCHERT that will provide the supports. This means a quantum leap in the scale up and Technology Readiness Level of the membranes. In that initial period, I also worked on polymeric membrane preparation for a short time and learned the fundamentals on membranes for gas separation (e.g. transport phenomena). Almost 5 years ago, a big change in my career occurred: I started my PhD on palladium membranes for membrane reactors at TU/e that I have defended this June under the supervision of Prof. Martin van Sint Annaland and Dr. Fausto Gallucci from TU/e and Dr. Alfredo Pacheco Tanaka from TECNALIA. The nice collaboration that we have had with TU/e during the last years has been essential for my growth on this topic and on improving my skills on research and project management. After many efforts and collaborations with other project partners we have scaled up the membranes and improved the sealing for their use in membrane reactors for hydrogen production. In these years we moved from fundamental research to applied research with the aim of introducing the palladium membrane technology into the market. During this years and trip, I learned to take special care at small details since we are targeting almost pure hydrogen at very high fluxes. In addition, other aspects that in the beginning seemed less important turned crucial. For example, a key issue for integrating these membranes in reactors is the sealing as Niek de Nooijer already explained very well in the BIONICO’s 1st newsletter. After these years, I believe that the collaboration is the key point for the success in any discipline. Thus, we are open to collaborate with new partners for bringing the membrane technology closer to the market and fulfill industrial needs.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu BIONICO in progress

The latest news on the different WP activities are reported:

Novel catalyst and supported membranes for Biogas Reforming process

JM are developing novel, highly active reforming catalysts designed to convert biogas into . To improve reactor performance at the relatively low temperatures used in the system, a catalyst has been developed which can operate under dry, steam or autothermal reforming conditions. Catalyst interaction with the membrane reactor tubes has been investigated by TU/e and reaction kinetic information by AH.

RAUSCHERT is developing new finger-like porous asymmetric ceramic supports in which one of the ends of the tube is a closed porous part. In this sense, only one seal based on Swagelok-graphite will be needed compared to the two seals needed for conventional both open-end tubular supported Pd-based membranes for their integration in the reactor. Thus, the probability for leaks through seals will be reduced as well as the cost of one Swagelok will be saved. Thin Pd-Ag layers have been deposited at TECNALIA onto the first 50 cm long finger-like supports (see Figure 2). The stability of the finger-like supported membranes will be evaluated at TU/e under the operating conditions (fluidization regime, temperature, etc.).

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu

Figure 2 Ceramic supported (finger-like) Pd-Ag membranes (length: 50 cm long, 14/7 mm outer/inner diameter).

Lab-scale reformer development

TUE is testing the stability and performance of the membranes and catalyst delivered by TECNALIA and JM. The membranes are tested in pure gas conditions such as nitrogen, hydrogen and mixtures containing CO or H2S. After these test the membranes are immersed in a fluidized bed containing the catalyst of JM. The membrane in contact with the catalyst shows stable performance regarding the hydrogen permeance. However the fluidization results in a decrease of selectivity due to the increase of leakage. The next goal is to identify the critical points of operation for this increase in leakage. Knowing this critical point will allow for better selection of the operation conditions to ensure a longer durability of the membranes. In parallel the catalyst reaction kinetics are being obtained to include in the model, which will later can describe the lab scale reactor.

Life cycle assessment

Quantis has refined goal & scope of this studies, in particularly, with further clarifications with regard to reference systems, level of details of inventory modelling and system boundaries, i.e., cradle to gate, as shown in Figure 3. Furthermore, data collection is improved for key data points, such as biogas input, conversion efficiency, energy and water use related to conversion processes.

Figure 3 Life cycle assessment modelling and system boundaries.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu The first preliminary LCA results demonstrated that the BIONICO CMR technology might be potentially environmentally preferable than reference technology systems (i.e., SMR and ATR for all indicators (climate change, human health, water use, resources and ecosystem quality) under conditions examined in this study; however, the conclusion and validity need to be further examined under refined data quality, assumptions and scenarios.

BIONICO second progress meeting, August 2016, Sonning Common, UK

The second progress meeting of BIONICO was hosted by Johnson Matthey research head quarter in Sonning Common. The partners presented the advancement status on each work package and discussed aspects regarding coordination and distribution of short term tasks. The assembly was decisive for the agreement on following dissemination strategies and activities to implement during the next months.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu Highlights

Workshop on Membrane Reactors: SAVE THE DATE!

On 9 and 10 March 2017, the Third European Workshop on Membrane Reactors will be held in Italy. The first workshop was organised back in November 2012 (Italy) and was entitled “Pd-based membranes and reactor scale-up”. The second workshop, “Catalytic Membrane Reactors: what’s next” was held in April 2015 in the Netherlands. More information on these two events is available from the CARENA website.

This third one is jointly organised by ROMEO, MEMERE, Fluidcell, Bionico, and Ferret, 5 major European projects on membrane reactors.

During these two days, there will be presentations on fundamental membrane-related science, process design and applications, industrial applications. There will also be a poster session and a company visit. More information will be provided on our website so watch that space and save the date for what promises to be a very fruitful workshop!

Just like ROMEO, MEMERE is a EU Horizon 2020 - SPIRE-05-2015 project. Bionico is a EU Horizon 2020 Research and Innovation Programme Hydrogen Europe and N.ERGHY. Fluidcell and Ferret are projects supported by the European Union’s Seventh Framework Programme for the Fuel Cells and Hydrogen Joint Technology Initiative.

Dissemination activities, publications and presentations:

 BIONICO public presentation available on the website http://www.bionicoproject.eu/dissemination/presentations

 M. Binotti, G. Di Marcoberardino, G. Manzolini, F. Gallucci, N. Ibanez Lirio, Biogas

membrane reformer for decentralized H2 production, European Biogas Association Conference (EBA 2016), 27-29 September 2016, Ghent, Belgium.

 G. Di Marcoberardino, M. Binotti, G. Manzolini, J. L. Viviente, F. Gallucci, L. Roses, N. Ibanez Lirio, Achievements of EU projects on membrane reactor for hydrogen production, 11th Conference on Sustainable Development of Energy, Water and Environment Systems (SDEWES 2016), 4-9 September 2016, Lisbon, Portugal.

 D.A. Pacheco Tanaka, E. Fernandez, J. Melendez, A. Arratibel, A. Helmi, J.A. Medrano, N. Nooijer, K. Coenen, V. Spallina, J.L. Viviente, J. Zuñiga, M. van Sint Annaland, F. Gallucci, Fluidized bed membrane reactors for hydrogen production using thin Pd-based (< 5 μm) supported membranes, 14th International Conference on Inorganic Membranes (ICIM 2016), 10-13 July 2016, Atlanta, USA.

 N.C.A. de Nooijer, J. Melendez, K. Coenen, E. Fernandez, F. Gallucci, M. van Sint Annaland, P.L. Arias, D.A. Pacheco Tanaka, Effect of the addition of Au in Pd-Ag alloy

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu membranes on the hydrogen permeation performance under the presence of H2S, 14th International Conference on Inorganic Membranes (ICIM 2016), 10-13 July 2016, Atlanta, USA.

 J. Meléndez, D. A. Pacheco Tanaka, A. Arratibel, N. de Nooijer, E. Fernandez, M. van Sint Annaland, P. L. Arias, F. Gallucci, Preparation and characterization of thin Pd-Ag-Au supported membranes for hydrogen separation, European Membrane Society Summer School on "Membranes and Membrane Processes Design”, 26 June – 1 July 2016, Bertinoro, Italy.

 N.C.A. de Nooijer, J. Melendez, E. Fernandez, D.A. Pacheco Tanaka, M. van Sint Annaland, F. Gallucci, of biogas in a fluidized bed membrane reactor for pure hydrogen production, Dutch membrane society Jubilieum posterday, June 2016, Apeldoorn, The Netherlands.

 E. Fernandez, A. Helmi, J. A. Medrano, K. Coenen, A. Arratibel, J. Melendez, N. de Nooijer, V. Spallina, J. L. Viviente, J. Zuñiga, M. van Sint Annaland, D.A. Pacheco Tanaka, F. Gallucci, Palladium based membranes and membrane reactors for hydrogen production and purification, 21st World Hydrogen Energy Conference (WHEC 2016), 13- 16 June 2016, Zaragoza, Spain.

 M. Binotti, G. Di Marcoberardino, Biogas membrane reformer for decentralized H2 production, 21st World Hydrogen Energy Conference (WHEC 2016), 13-16 June 2016, Zaragoza, Spain.

A picture from the WHEC conference in Zaragoza

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu Upcoming events:

18 – 20 October 2016 9th EFIB, The European Forum for Industrial Biotechnology and the Bioeconomy, Glasgow, Scotland http://www.efibforum.com/

2 – 3 November 2016 16th Aachener Membran Kolloquium, Aachen, Germany http://www.avt.rwth-aachen.de/AMK/

5 – 8 December 2016 9th IMSTEC, International Membrane Science and Technology Conference, Adelaide Convention Centre, Australia http://www.imstec.com.au/

29 – 30 December 2016 18th ICCB 2016, International Conference on and Bioenergy, Paris, France https://www.waset.org/conference/2016/12/paris/ICBB/home

31 January – 2 7th International Conference on ”Fundamentals & Development February 2017 of Fuel Cells, Stuttgart, Germany http://www.nerghy.eu/

24 February 2017 Biogas Italy 2017, Rome, Italy http://www.biogasitaly.com/

10 – 11 May 2017 4th REGATEC 2017, International Conference on Renewable Energy Gas Technology, Italy http://regatec.org/

12 – 15 June 2017 25th EUBCE 2017, European Biomass Conference & Exhibition, Stockholm, Sweden http://www.eubce.com/home.html

2 – 5 July 2017 7th WHTC World Hydrogen Technologies Convention, Prague, Czech Republic http://www.whtcprague2017.cz/

10 – 13 July 2017 13th ICCMR, International Conference on in Membrane Reactors, Houston, USA http://iccmr.tamu.edu/

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu

BIONICO in figures:

 8 partners (3 RES, 3 IND, 2 SME)  7 countries

 3.4 M€ project

 Start September 2015  Duration: 36 months

 Key Milestones:  February 2017 – Validation of lab-scale reactor

 December 2017 – Pilot scale prototype ready

 February 2018 – System integrated at biogas producer facility

 September 2018 – Validation of the pilot plant

Project manager: Technical manager: Dr. Marco Binotti Dr. Fausto Gallucci Politecnico di Milano TU/e [email protected] [email protected]

Dissemination manager: Exploitation manager: Dr. Gioele Di Marcoberardino Dr. Noelia Ibáñez Lirio Politecnico di Milano Abengoa Idrogeno [email protected] [email protected]

More information on BIONICO available at the project website: http://www.bionicoproject.eu

Acknowledgements:

The BIONICO project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 671459. This Joint Undertaking receives support from the European Union’s Horizon 2020 research and innovation programme and Italy, Spain, Netherlands, United Kingdom, Germany, Portugal, Switzerland.

Disclosure: The present document reflects only the author’s views, and neither the FCH- JU nor the European Union is liable for any use that may be made of the information contained therein.

BIONICO newsletter - Issue 2 – 2nd half 2016 www.bionicoproject.eu

Biogas membrane reformer for decentralized hydrogen production

Summary: The BIONICO project will develop, build and demonstrate a novel reactor concept integrating H2 production and separation in a single vessel in a biogas production plant. The hydrogen production capacity will be of 100 kg/day. By using the novel intensified reactor, direct conversion of biogas to pure hydrogen is achieved in a single step, which results in an increase of the overall efficiency and strong decrease of volumes and auxiliary heat management units.

A membrane assisted fluidized bed reactor for biogas reforming will be designed and tested. Novel high flux membranes supplied and novel catalysts will be assembled in the reactor: particular attention will be devoted to the design in order to avoid problems due to membrane vibration and to improve the bubble breckage and thus reduce fuel slip through the bubble phase. The control of the reformer will be developed as integral part of the reactor, to achieve full flexibility of the system. The experimental work carried out on the reactor will also validate the models to be used for the scale-up of the system. Finally, the final prototype of membrane reactor will be designed, constructed and tested in a facility where biogas is produced.

Contact: Dr. Marco Binotti Politecnico di Milano [email protected]

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