Periodic Report Summary 1 - FERRET (A Flexible natural gas membrane Reformer for m-CHP applications)
Project Context and Objectives:
The potential for fuel CHP units in Europe as a large market in the future is in general well recognised. Although the size of this market is large and is undisputed when the cost targets of m-CHP units is reached, it is often overlooked that it is a very segmented market. All micro-CHP units, as new heating appliances, will have to be certified against the Gas Appliance Directive (90/396/CE). The latest legislation in Europe and some specific countries, which is expected will be adopted by other countries will lead to a broader range of natural gas specifications per country with larger differences of natural gas qualities. And last and most important: the gas quality is allowed to change more rapidly in time.
In future, more oxygen will be present in natural gas. Now, in Europe actions are taken (regulatory actions) to allow even larger fluctuations of the gas composition. This means that not only the fuel processor should be efficient in reforming NG to hydrogen, but should be also very robust and flexible, reducing the possibility of hot spots and low selectivity when the composition changes. Within FERRET, we will design the reactor, balance of plant and revise the controls to allow the sudden change of natural gas specification that
can be expected in the field in the coming years.
According to the problems mentioned above, FERRET project will (in the first reporting period):
• Design a flexible reformer in terms of catalyst, membranes and control for different natural gas compositions.
• Use hydrogen membranes to separate pure hydrogen and help shifting all the possible H2 production reactions towards the products, thus reducing side reactions.
• Scale up the new H2 selective membranes and catalysts production
• Simulate the reformer integration with the entire system.
Project Results:
Development of a catalyst stable to fluidization is one of the objectives of WP2. This was achieved by use of a strong stable support material that also wouldn’t degrade the membranes developed in WP3.
The catalyst has also to be stable to a varying natural gas feed ranging from higher ethane fractions to larger nitrogen fractions and almost pure methane. Additionally the catalyst has to produce enough hydrogen to meet the project objectives and maintain an equilibrium conversion of ~95% converted methane at 600 oC.
Finally catalyst has to be scalable from a lab based preparation to provide over 3 kg of catalyst for the FERRET reformer unit.
WP3 developed this Pd membranes and pore filled membranes for the lab scale reactor. The thin film membranes have characteristics that meet the FERRET targets. For the pore filled membranes still the selectivity is too low, mainly due to the low permeation flux. Thus the thin Pd membranes have been selected for the scale-up in the prototype. All membranes required for the prototype including spare membranes, have been produced and delivered to TUE for the sealing. After sealing these membranes will be delivered at HyGear for integration in the fluidized bed reactor.
WP4 concentrated on the integration of catalyst and membranes and the testing of the reactor at lab scale. The catalyst was tested from the very beginning together with the membranes to check if any interaction occurs. No interaction was found (i.e. the membrane flux does not decrease and the catalyst is not damaged). During last period (M10-M14) catalysts received from JM were characterized before and after some reactive test in presence of a Pd-Ag-Au membrane provided by Tecnalia.
The catalyst was integrated in a MR and some reactive experiments were carried out. SMR and ATR reactions were performed at 500 °C and 550 °C at different pressures and steam to carbon ratios. For ATR experiment O/C ratio was fixed to 0.25 (close to the real value for autothermal operation). The catalyst showed high methane conversion, close to the theoretical ones for both conventional reactor and membrane reactors.
No interaction between catalysts and membrane was found. However, the selectivity of membrane decrease dramatically while experiment was running, due to the nitrogen permeation was increasing. After the experiments, leakages from the membrane surface and the sealing were detected at 0.5 bar of pressure difference.
In WP5 the prototype reactor was designed based on the results of the catalyst behaviour and characteristics and the membrane behaviour. All material has been ordered while also membranes and catalyst are under preparation.
Concerning WP6, a m-CHP system model was developed by POLIMI and validated using experimental results from tests performed at HyGear. The results from this analysis were used as reference case within the project. The performance of FERRET unit will be compared to this reference system: 28% for the net electric efficiency and 86% for the total efficiency of the CHP system. Furthermore, the natural gas compositions across Europe have been investigated and among the 37 different NG compositions available, 4 cases were selected as representative of the entire European situation.
Starting from the interaction between industrial partners and POLIMI, the input required for the modelling and assessment of the CHP system integrated with the fuel processor were defined. The layout of FERRET fuel cell CHP-system was identified: a good compromise between efficiency and membrane area occurs at 8 bar and 873 K with a net electric and total respectively higher than 41 % and 97%. In this particular case, a sweep gas is adopted in the membrane reactor to enhance hydrogen permeation.
The impact of NG composition on system design and performances was evaluated both at rated and partial load conditions. Results showed that the adoption of the most diluted natural gas (NL case) is suggested in order to guarantee a high efficiency at any NG composition.
The WP7 goals were about the dissemination of the achievements in FERRET project as well as the identification of results to be exploited. In order to achieve these goals, significant effort has been made by the consortium. A first document summarizing the plan for use and dissemination of the project result has been composed after agreement with all partners of the FERRET project. The document has been submitted with the deliverable D7.9. The dissemination is proceeding as planned. It is worth noting that among the different dissemination events, FERRET results were presented in the International Conference on Catalysis in Membrane Reactors, where the work on pore-filled membranes has been granted the Best Poster presentation prize. Additionally, two papers are under review in the International Journal of Hydrogen Energy. One paper is a collaboration between TECNALIA and TUE and a second one is collaboration between TUE and POLIMI, which also shows the good collaboration between partners of the project.
Potential Impact:
The project aim at developing a novel reformer for pure hydrogen production to be used in fuel cell CHP systems. The reformer integrates separation and reaction in one vessel resulting in a decrease of process steps (from 4 for conventional system to 1 for novel reactor), and increase the performance of the component.
The components of the novel reformer including advanced hydrogen separation membranes and catalyst will be improved and the analysis of production costs and scale up of the membrane production technology, catalyst production and reactor manufacturing will be carried out.
A lower reforming temperature (<700 °C compared to >900 °C of conventional systems together with limited membrane area required (i.e. by reducing the mass transfer limitations thanks to fluidized bed system) will allow to decrease the overall costs to <2000 €/kW for industrial and <5000 €/kW for domestic micro CHP by 2020. Estimated cost reduction of membrane reforming reactor vs. state-of-the-art fuel processing technology is about 15-20 %.
The new technology has a great environmental and societal impact. In particular, the project will reduce specific CO2 emissions as well as other pollutants as NOx and SOx thanks to the higher energy conversion efficiency, simultaneous heat and power generation, and lower temperatures;
Limit the number of additional power plant required to satisfy the increasing demand of electricity.
The smaller and lower temperature reforming will also result in a reduction of risks and hazard with positive implication for the public acceptance of the hydrogen based economy.
List of Websites:
http://www.ferret-h2.eu/
The potential for fuel CHP units in Europe as a large market in the future is in general well recognised. Although the size of this market is large and is undisputed when the cost targets of m-CHP units is reached, it is often overlooked that it is a very segmented market. All micro-CHP units, as new heating appliances, will have to be certified against the Gas Appliance Directive (90/396/CE). The latest legislation in Europe and some specific countries, which is expected will be adopted by other countries will lead to a broader range of natural gas specifications per country with larger differences of natural gas qualities. And last and most important: the gas quality is allowed to change more rapidly in time.
In future, more oxygen will be present in natural gas. Now, in Europe actions are taken (regulatory actions) to allow even larger fluctuations of the gas composition. This means that not only the fuel processor should be efficient in reforming NG to hydrogen, but should be also very robust and flexible, reducing the possibility of hot spots and low selectivity when the composition changes. Within FERRET, we will design the reactor, balance of plant and revise the controls to allow the sudden change of natural gas specification that
can be expected in the field in the coming years.
According to the problems mentioned above, FERRET project will (in the first reporting period):
• Design a flexible reformer in terms of catalyst, membranes and control for different natural gas compositions.
• Use hydrogen membranes to separate pure hydrogen and help shifting all the possible H2 production reactions towards the products, thus reducing side reactions.
• Scale up the new H2 selective membranes and catalysts production
• Simulate the reformer integration with the entire system.
Project Results:
Development of a catalyst stable to fluidization is one of the objectives of WP2. This was achieved by use of a strong stable support material that also wouldn’t degrade the membranes developed in WP3.
The catalyst has also to be stable to a varying natural gas feed ranging from higher ethane fractions to larger nitrogen fractions and almost pure methane. Additionally the catalyst has to produce enough hydrogen to meet the project objectives and maintain an equilibrium conversion of ~95% converted methane at 600 oC.
Finally catalyst has to be scalable from a lab based preparation to provide over 3 kg of catalyst for the FERRET reformer unit.
WP3 developed this Pd membranes and pore filled membranes for the lab scale reactor. The thin film membranes have characteristics that meet the FERRET targets. For the pore filled membranes still the selectivity is too low, mainly due to the low permeation flux. Thus the thin Pd membranes have been selected for the scale-up in the prototype. All membranes required for the prototype including spare membranes, have been produced and delivered to TUE for the sealing. After sealing these membranes will be delivered at HyGear for integration in the fluidized bed reactor.
WP4 concentrated on the integration of catalyst and membranes and the testing of the reactor at lab scale. The catalyst was tested from the very beginning together with the membranes to check if any interaction occurs. No interaction was found (i.e. the membrane flux does not decrease and the catalyst is not damaged). During last period (M10-M14) catalysts received from JM were characterized before and after some reactive test in presence of a Pd-Ag-Au membrane provided by Tecnalia.
The catalyst was integrated in a MR and some reactive experiments were carried out. SMR and ATR reactions were performed at 500 °C and 550 °C at different pressures and steam to carbon ratios. For ATR experiment O/C ratio was fixed to 0.25 (close to the real value for autothermal operation). The catalyst showed high methane conversion, close to the theoretical ones for both conventional reactor and membrane reactors.
No interaction between catalysts and membrane was found. However, the selectivity of membrane decrease dramatically while experiment was running, due to the nitrogen permeation was increasing. After the experiments, leakages from the membrane surface and the sealing were detected at 0.5 bar of pressure difference.
In WP5 the prototype reactor was designed based on the results of the catalyst behaviour and characteristics and the membrane behaviour. All material has been ordered while also membranes and catalyst are under preparation.
Concerning WP6, a m-CHP system model was developed by POLIMI and validated using experimental results from tests performed at HyGear. The results from this analysis were used as reference case within the project. The performance of FERRET unit will be compared to this reference system: 28% for the net electric efficiency and 86% for the total efficiency of the CHP system. Furthermore, the natural gas compositions across Europe have been investigated and among the 37 different NG compositions available, 4 cases were selected as representative of the entire European situation.
Starting from the interaction between industrial partners and POLIMI, the input required for the modelling and assessment of the CHP system integrated with the fuel processor were defined. The layout of FERRET fuel cell CHP-system was identified: a good compromise between efficiency and membrane area occurs at 8 bar and 873 K with a net electric and total respectively higher than 41 % and 97%. In this particular case, a sweep gas is adopted in the membrane reactor to enhance hydrogen permeation.
The impact of NG composition on system design and performances was evaluated both at rated and partial load conditions. Results showed that the adoption of the most diluted natural gas (NL case) is suggested in order to guarantee a high efficiency at any NG composition.
The WP7 goals were about the dissemination of the achievements in FERRET project as well as the identification of results to be exploited. In order to achieve these goals, significant effort has been made by the consortium. A first document summarizing the plan for use and dissemination of the project result has been composed after agreement with all partners of the FERRET project. The document has been submitted with the deliverable D7.9. The dissemination is proceeding as planned. It is worth noting that among the different dissemination events, FERRET results were presented in the International Conference on Catalysis in Membrane Reactors, where the work on pore-filled membranes has been granted the Best Poster presentation prize. Additionally, two papers are under review in the International Journal of Hydrogen Energy. One paper is a collaboration between TECNALIA and TUE and a second one is collaboration between TUE and POLIMI, which also shows the good collaboration between partners of the project.
Potential Impact:
The project aim at developing a novel reformer for pure hydrogen production to be used in fuel cell CHP systems. The reformer integrates separation and reaction in one vessel resulting in a decrease of process steps (from 4 for conventional system to 1 for novel reactor), and increase the performance of the component.
The components of the novel reformer including advanced hydrogen separation membranes and catalyst will be improved and the analysis of production costs and scale up of the membrane production technology, catalyst production and reactor manufacturing will be carried out.
A lower reforming temperature (<700 °C compared to >900 °C of conventional systems together with limited membrane area required (i.e. by reducing the mass transfer limitations thanks to fluidized bed system) will allow to decrease the overall costs to <2000 €/kW for industrial and <5000 €/kW for domestic micro CHP by 2020. Estimated cost reduction of membrane reforming reactor vs. state-of-the-art fuel processing technology is about 15-20 %.
The new technology has a great environmental and societal impact. In particular, the project will reduce specific CO2 emissions as well as other pollutants as NOx and SOx thanks to the higher energy conversion efficiency, simultaneous heat and power generation, and lower temperatures;
Limit the number of additional power plant required to satisfy the increasing demand of electricity.
The smaller and lower temperature reforming will also result in a reduction of risks and hazard with positive implication for the public acceptance of the hydrogen based economy.
List of Websites:
http://www.ferret-h2.eu/