A Flexible natural gas membrane Reformer for m- CHP applications FERRET This project is supported by the European Union s Seventh Framework Programme (FP7/2007-2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement nº 621181 Duration: 3 years. Starting date: 01-Apr-2014 Contact: f.gallucci@tue.nl The present publication reflects only the author s views and the FCH JU and the Union are not liable for any use that may be made of the information contained therein. 31/03/2017 / Page 1 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Summary FERRET aims at developing a high efficient heat and power cogeneration system based on: i) design, construction and testing of a flexible advanced reformer for pure hydrogen production from a broad range of natural gas with optimization of all the components of the reformer (catalyst, membranes, heat management etc.) and ii) the design and optimization of all the BoP for the integration of the novel reforming technology in a CHP system. The main idea of FERRET is to develop a novel more efficient and cheaper multi-fuel membrane reformer for pure hydrogen production in order to intensify the process of hydrogen production through the integration of reforming and purification in one single unit 31/03/2017 / Page 2 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Partnership Multidisciplinary and complementary team: 6 top level European organisations from 4 countries: 3 Research Institutes and Universities and 3 top industries in different sectors (from hydrogen production to catalyst developments to boilers etc.). TU/e, Netherlands TECNALIA, Spain POLIMI, Italy ICI, Italy HyGear, Netherlands Johnson Matthey (UK) 31/03/2017 / Page 3 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Project objectives Scale-up of membranes and development of new pore-filled membranes more resistant to fluidized bed membrane reactor configuration and using less amount of Pd per m 3 /h of hydrogen production Reduction of fuel processor costs Development of methods for recycling and repairing of Pd-based membranes Improvement of catalyst for reforming of different natural gas compositions Scale up the catalyst production for fluidized bed applications Improvement of a novel fluidized bed membrane reforming reactor of different natural gas compositions Improvement of a novel fluidized bed membrane reforming reactor for longterm performance. Protection of Fuel cell stack (e.g. Cr release), CO poisoning Integration of the novel reforming in a CHP system Optimization of the BoP for the novel reforming CHP system Simulation and optimization of the reformer integration with the entire system 31/03/2017 / Page 4 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Work structure 31/03/2017 / Page 5 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Partnership synergies 31/03/2017 / Page 6 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Catalyst development Objectives: Develop an autothermal reforming catalyst to convert a mixture of natural gas, steam and air into syngas (hydrogen, carbon monoxide, carbon dioxide, nitrogen). The catalyst needs to be mechanically durable and operate as a fluidized bed inside a membrane reactor. The catalyst needs to maintain activity under membrane reactor operating conditions. Scale up of catalyst production 31/03/2017 / Page 7 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Catalyst development Catalyst Testing: Catalyst development focused transition metal oxide supports Chosen for mechanical and thermal stability Catalysts made by doping PGM on to support materials Additional metal dopants strengthened activity and long term stability of the catalyst 31/03/2017 / Page 8 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Catalyst development Status: Catalyst surpasses activity and stability targets for the FERRET project Displays activity across a wide range of natural gas compositions Stable to fluidization testing without loss of particle size or sphericity Scalable preparation methods 31/03/2017 / Page 9 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Catalyst development Particle size distribution of catalysts before sieving, after sieving and after cold and hot fluidization in air. 31/03/2017 / Page 10 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Membranes development Objectives: Development of Pd based tubular membranes, for application in natural gas autothermal reforming catalytic membrane reactors Improved flux and selectivity Temperature 600 ºC Improved sulphur resistance Resistant to fluidization regime Process scaling up 31/03/2017 / Page 11 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pd-Ag membranes by direct PVD deposition Sample Pd-Ag thickness (µm) N 2 permeance x10-9 (mol m -2 s -1 Pa -1 ) at 25 ºC Al 2 O 3 200 nm ZrO 2 3 nm PVD on ZrO 2 3 nm ---- 24,600 ±434 ~ 0.5 15,143 ±1,292 The Pd-Ag film is not dense on porous supports. It is not possible to prepare suitable Pd-Ag membranes by one step direct PVD deposition onto porous supports. Suitable membranes could be obtained by a double process: PVD + ELP or ELP+PVD. PVD could be used for increasing the Ag amount as well as for adding a 3 rd metal (i.e. Au, Ru,..) to Pd-Ag membranes developed by ELP. 31/03/2017 / Page 12 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Membranes by direct PVD deposition: PVD-MS at Tecnalia could coat up to 78 supports (Ø10 mm) simultaneously. Ru and Au will be deposited on Pd-Ag membranes by PVD-MS Thickness profile at various target levels +30 mm 31/03/2017 / Page 13 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pd-Ag-Au membranes by ELP Au layer was deposited by ELP on a Pd-Ag membrane The Pd76-Ag12-Au10 was formed by thermal treatment H 2, N 2 permeation test (550ºC, ~1 bar) H 2 permeation increases until a plateau is reached at around 500 min H 2 permeance=1.6 x 10-6 mol m -2 s -1 Pa -1 ; Ideal H2/N2 selectivity= ~1600 31/03/2017 / Page 14 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pd-Ag membranes for the prototype Pd-Ag membranes supported onto ZrO 2 tubular porous supports (Ø10 mm) prepared by simultaneous Pd & Ag ELP deposition. Length of the Pd-Ag membrane 22-23 cm ( 50% longer than planned) Thickness of the selective layer: 3-4 µm 21 Pd-Ag membranes have been already delivered. 31/03/2017 / Page 15 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pd pore filled membrane Composite nano porous membranes Packed with Palladium panoparticles (pore filled membranes) Al Pd Thin Pd film membrane Al Pore-fill type Pd membrane Advantages of pore filled over conventional membranes - Less Pd is used (a fraction of conventional) - Protection under fluidization regime 31/03/2017 / Page 16 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pd pore filled membrane Membrane preparation Long term permeation test PF-A45 Al 2 O 3 (100 nm) 1 st coating Protective layer + 60YSZ/40γ-Al 2 O 3 + Seedings + 60YSZ/40γ-Al 2 O 3 + Platings Selectivity and H 2 permeation still low Thicker nanoporous layer are being prepared to increase permeation properties 31/03/2017 / Page 17 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Lab scale reformer Objectives: Selection of ATR-CMR components: catalysts, membranes and supports, and sealing based. Integration of these elements in lab scale reactors specifically designed for ATR. Validation of the lab scale reactors performances and identification of the best design for prototype pilot. 31/03/2017 / Page 18 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Lab scale reformer Methane conversion at different pressures of experiment carried out at 550 C and S/C=3. For ATR O/C=0.25 31/03/2017 / Page 19 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pilot scale catalytic membrane reformer Objectives: Design the pilot scale catalytic membrane reactor (CMR) Construct and assemble the pilot scale catalytic membrane reactor including controls Perform functionality tests before integration into Fuel Cell CHP-system 31/03/2017 / Page 20 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Pilot scale catalytic membrane reformer Specifications: Maximum H 2 output 5 Nm3/h Partial loads 30 % (1.5 Nm3/h) Sweep gas (steam) Design operating temperature up to 600 ºC 7 bar Permeate ~ 200 mbarg Hydrogen recovery up to 90 % 31/03/2017 / Page 21 (Disclosure or reproduction without prior permission of FERRET is prohibited).
System assembly: Portable skid; reduced footprint Pilot scale catalytic membrane reformer Safeguarding stability of fragile membranes during transport Reactor Methanator Flow controllers DeS Steam generators Control cabinet Pumps 31/03/2017 / Page 22 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Test results: Tests at 550 C Steam-to-Carbon Feed flow Pilot scale catalytic membrane reformer 31/03/2017 / Page 23 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Test results: Tests at 550 C Sweep flow Pilot scale catalytic membrane reformer 31/03/2017 / Page 24 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Test results: Pilot scale catalytic membrane reformer NG specifications from different sources NG type Species Unit NL UK IT ES CH 4 %mol 81.23 92.07 99.581 81.57 C 2 H 6 %mol 2.85 3.41 0.056 13.38 C 3 H 8 %mol 0.37 0.76 0.021 3.67 n-c 4 H 10 %mol 0.08 0.18 0.002 0.40 i-c 4 H 10 %mol 0.06 0.14 0.006 0.29 n-c 5 H 12 %mol 0.02 0.05 0 0 i-c 5 H 12 %mol 0.02 0.06 0.002 0 C 6+ %mol 0.08 0.09 0.007 0 CO 2 %mol 0.89 0.87 0.029 0 N 2 %mol 14.4 2.37 0.296 0.69 LHV MJ/kg 38.0 46.7 49.7 48.6 LHV MJ/mol 0.708 0.819 0.801 0.939 H 2 potential mol H 2 /mol NG 3.52 4.07 3.99 4.66 x in CxHy - 0.89 1.04 1.00 1.22 Wobbe index MJ/Nm3 43.6 52.0 53.1 56.6 31/03/2017 / Page 25 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Test results: Pilot scale catalytic membrane reformer Stable operation with four NG compositions tested Composition with high content of C 3 H 8 showed lower conversion 31/03/2017 / Page 26 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Integration & Validation in CHP-System Definition of fuel cell CHP-model based on existing fuel cell CHP-system Integrating the FERRET reformer into existing CHP-system Evaluation of the FERRET CHP-system feeding different natural gas compositions Compare performance of the FERRET CHP-system with existing CHP-system Perform techno-economic analysis of the FERRET CHP-system 31/03/2017 / Page 27 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Integration & Validation in CHP-System Activities: Definition of the reference case lay-out and assessment of the performances. Survey of different NG composition around Europe. Investigation on different lay-out and operating conditions for the FERRET system. Investigation on layout flexibility under different NG compositions. 31/03/2017 / Page 28 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Results: Integration & Validation in CHP-System Among the 37 different NG compositions available, 4 cases were selected as reference for the project, representing the entire European situation. A m-chp system model was developed and validated using experimental results from tests performed. The results from this analysis will be used as reference case within the project. The performance of FERRET unit is compared to this reference system: 28% for the net electric efficiency and 86% for the total efficiency of the CHP system. The layout of FERRET fuel cell CHP-system was defined. A good compromise between efficiency and membrane area occurs at 8 bar and 873 K for the sweep gas case with a net electric and total respectively higher than 41 % and 97%. Influence of the four NG qualities on the performances of FERRET unit was investigated. 31/03/2017 / Page 29 (Disclosure or reproduction without prior permission of FERRET is prohibited).
Results: Integration & Validation in CHP-System In general terms, the system flexibility is demonstrated by the limited efficiency variation with the load and under different NG compositions The net electric efficiency of the system increases s up to 70% of the rated load when it starts to drop as consequence of the polarization curve of the PEM fuel cell. The thermal efficiency reduces in the first part because of the higher electric efficiency 31/03/2017 / Page 30 (Disclosure or reproduction without prior permission of FERRET is prohibited).
PES (%) Eq. hours ( 10 3 h) Micro-CHP target cost ( /kw) Results: Integration & Validation in CHP-System The Ferret solution was applied to the different European residential loads as well as economic boundaries. The resulting yearly energy balance reveals that the PES is higher than 10% in most of the cases; The adoption of the micro-chp system can reduce the annual operating cost of around 1500. The target micro-chp specific cost can be around 2000 /kw which is not the current cost of the system but it can be achieved when the system is industrialized and available in hundreds of thousands of units. 35 32 29 26 23 20 Primary Energy Savings Equivalent hours NL UK IT ES 5.0 4.5 4.0 3.5 3.0 2.5 3000 2500 2000 1500 1000 500 0 NL UK IT ES 31/03/2017 / Page 31 (Disclosure or reproduction without prior permission of FERRET is prohibited).
A Flexible natural gas membrane Reformer for m- CHP applications FERRET Thank you for your attention Contact: f.gallucci@tue.nl 31/03/2017 / Page 32 (Disclosure or reproduction without prior permission of FERRET is prohibited).