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FIRST YEARD1.2 Project Internet platform - Website (PUBLIC)
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D1.11 Annual data report, year 1 (PUBLIC)
D2.2 Definition of the reference case (PUBLIC)
D2.4 Industrial specification (PUBLIC)
A preliminary configuration of the system to produce hydrogen from biogas with catalytic membrane reactor technology has been defined including plant specifications, general considerations for the design (location, onsite conditions, raw material specifications, noise limitations) and a preliminary process design.
The process design includes general considerations (location, onsite conditions, raw material specifications, noise limitations) and a description of the process to produce hydrogen from biogas considering the balance of plant required represented on a schematic plant layout.
The process proposed does not require the upgrading of biogas to biomethane, performing the direct conversion of biogas to hydrogen. Nevertheless, a pre-cleaning stage is required to remove hydrogen sulphide and other components of the biogas that could cause catalyst and membranes poisoning reducing the process lifetime.
D5.1 Preliminary design of the lab scale membrane reactor (PUBLIC)
D5.4 First model of novel reforming membrane reactor system (PUBLIC)
Furthermore the influence of the presence of the dry reforming reaction is studied. Currently the kinetics for the catalyst used in the final process is still being studied. A rate equation for DR is assumed to describe the dry reforming kinetics. The results show that the production of hydrogen in the first part of the reactor increases however the overall equilibrium conversion of methane is lowered.
For the final model the experimentally obtained kinetics will be implemented in the model. Furthermore a description of the mass transfer resistance near the membrane will be included. To validate the model experimental results of a single membrane reactor and the lab scale reactor will be used.
D5.5 Final model of novel reforming reactor system (PUBLIC)
The 1D fluidized bed membrane model is extended with a film layer description of concentration polarization. Permeation experiments show that the thickness δ which describes the mass transfer resistance can be fitted. The results also show that the flow conditions significantly affect the mass transfer resistance. The delta used to validate the model is obtained from a fitting to one base case experiment and shows to predict the other experiments accurately.
The model is then used to optimize and scale up the system. An important design parameter is introduced, the load to surface ratio. Showing that higher temperatures and pressures are beneficial. The scale up is dependent on the thickness of δ if delta changes significantly with scale up this can have significant effects on the predictability of the model. Scale up experiments can give a more accurate prediction of the behaviour of δ at higher pressures and different flow conditions. Autothermal conditions increase the conversion, however give lower hydrogen recovery.
SECOND YEARD1.12 Annual data report, year 2 (PUBLIC)
D3.7 Development of a fluidizable biogas reforming catalyst (PUBLIC)
D5.2 Integrated catalyst, membranes and sealing in lab scale membrane reactor (PUBLIC)
B-L1 and E507 are both brought in contact with respectively catalyst support and loaded catalyst under fluidization. For both the performance and stability of the H2 permeance was measured. The H2 permeance slightly increased when the membranes where brought under fluidization due to surface roughening. No interaction between the catalyst and the membrane active layer is suspected. However the selectivity decreases when the membrane is brought under fluidization conditions with the loaded catalyst. In both cases the appearance of the surface of the membrane was more dull then the fresh membrane layer.
The membranes E505 PdAg, E505 PdAgAu and E506 PdAgAu were exposed to different amounts of H2S during hydrogen permeation. The results show that the presence of H2S decreases the hydrogen flux through the membrane. For the PdAg and the PdAgAu membrane with 5% of gold the decrease did not change with increasing content of H2S. The PdAgAu with 7% of gold had a relatively smaller decrease on exposure with H2S. However when increasing H2S concentration the membrane reached a similar relative decrease as the other two membranes.
This work will be expanded for the next deliverable (D5.3) in M18. The report is expected to include the following points by month M18:
• Integration of catalyst and membranes containing gold.
• Long term test for both stability and selectivity of the membrane
• Post characterization of the membranes
• Expansion of the work with H2S
• Post characterization of the membranes exposed to H2S
• Catalyst activity and stability
D5.3 Report on Characterization and Validation of the lab scale reformer (PUBLIC)
Permeance test where performed at different temperatures to characterize the membrane flux and selectivity. An activation energy of 9.26 kJ/mol with a pre-exponential factor of 8.74 ∙ 10-3 mol m-2 s-1 pa-0.5 have been measured. The initial ideal perm-selectivity was found to be 18000 at 545 °C and 1 bar pressure difference.
To experiments performed to validate the system are methane steam reforming and Biogas steam reforming. In all experiments the steam to methane ratio was kept 3. The system was tested at different CO2/CH4 ratios, pressures and temperatures.
The CO2/CH4 ratio showed a decrease in methane conversion, due to the equilibrium effects of CO2 as a product. As expected, the selective removal of hydrogen through the membrane shifted the equilibrium to higher methane conversions. However the overall trend also with selective removal showed still a decrease with increasing CO2 in the feed. The effect of the CO2/CH4 ration on the separation factor could not be measured due to the system dilution. The increase of CO concentration did not seem to influence the separation via the membrane at 485 °C. The hydrogen purity showed a decrease when more CO2 was present in the feed.
The pressure was varied between 2 and 5 bar. The equilibrium conversion is decreased with increasing pressure; however, when hydrogen is selectively extracted, this decrease is reduced. More membrane area and thus more hydrogen permeation would result in an increase of conversion with pressure. The hydrogen separation factor and HRF both increase with pressure. A slight decrease in purity was obtained with the increase of pressure.
The temperature improves the equilibrium conversion due to the overall endothermic nature of the system. Selective removal of hydrogen shifts the equilibrium. The separation factor is not changed a lot however due to the increase in methane conversion with temperature the HRF is increased significantly. The hydrogen purity is increased due to the increase in permeability of hydrogen.
The system showed stable behaviour during the experiment. Although the nitrogen permeance of the membrane was slightly increased over the experimental period. The maximum hydrogen purity obtained was 99.88% at 535 °C, maximum amount of CO measured in the permeate stream was 184 ppm. However it should be noted that the tested period was relatively short and long term data is required to show the system stability.
D6.1 Definition of the BIONICO operating conditions andperformances (PUBLIC)
BIONICO system model is implemented in Aspen Plus and Aspen Custom Modeler to perform respectively the balance of plant with thermal integration and a detailed fluidized bed membrane reactor design. Two permeate side configurations, sweep gas and vacuum pump, were modelled and compared.
The BIONICO system outperforms the reference cases by 10% points achieving a hydrogen production efficiency around 67-69% assuming a delivery pressure of 13.3 bara. In addition, the membrane reactor operates at lower temperature and pressure of the reference cases.
Between the two permeate side configurations investigated, sweep gas and vacuum pump, the former is penalized by (i) the low hydrogen partial pressure in the feed side and (ii) the limited amount of sweep flowrate available. The resulting system efficiency and membrane for the sweep cases were 22% lower and two times larger than the vacuum pump ones.
Afterwards, the preliminary economic assessment was carried out accounting for both the capital and operating costs to determine the hydrogen production costs. The hydrogen cost production of the BIONICO case ranges from 4.16 to 4.28 €/kgH2, while the reference case resulted 4.35 €/kgH2 and 4.48 €/kgH2 for the SR and ATR respectively. With respect to the steam reforming reference case, the BIONICO one has lower biogas and capital costs, but higher electricity costs (as consequence of the hydrogen compression consumptions), while it has lower biogas and electricity cost with respect to the ATR case. Between the landfill and anaerobic digestion cases, no big differences can be outlined.
D8.1 Preliminary environmental LCA of the developed technology (PUBLIC)
Overall, it shows that higher system energy efficiency of technologies is not necessarily translated into better environmental performance, due to large difference in environmental impacts of feedstock or energy types and their sourcing variations. Also, climate change impact indicator is a poor proxy to represent all impact categories. CMR technology can be either better or worse than alternatives, depending on specific situations considered and chosen indicators. The CMR technology has a lower impact on climate change: i) when biogas is taken away from those otherwise would be flared, also electricity comes from additional generation from biogas; the less CO2 emitted directly from H2 conversion is better; ii) when biogas is taken away from those otherwise would be used for bioelectricity production, resulting in marginal carbon-intensive electricity generated to satisfy energy demand; the less biogas input is better; iii) when part of impact from landfill is allocated to biogas that dominates the life cycle GHG impact; the less biogas input is better. On the other hand, the CMR technology may have a higher impact on climate change: i) when fugitive biogas is additionally captured for H2 production, resulting in avoided methane emissions. Counter-intuitively, the more biogas input the better; and ii) when biogas is taken away from those otherwise would be flared and electricity comes from carbonintensive grid mix; as biogas bears no climate change impact, the more electricity consumption is worse. With sensitivity analysis, key influencing parameters are identified, including: i) landfill gas emission and utilization rate, leachate rate, and price of green electricity; ii) yield of biogas, biodegradability and fossil carbon content from degraded waste; iii) time horizon; iv) variation of biogas impact accounting; v) variation of marginal electricity supply from different locations, timing, technologies, and fuel efficiencies. The LCA results presented are limited to the predefined scenarios, just preliminary based on BIONICO CMR concepts that will be further updated. Also, the choice of 1 MJ of H2 as function unit will be further discussed within the consortium and might be changed later. Other key limitations include omission of infrastructure and biogas pre-cleaning, which will be also improved in the second phase of the project. When this study is communicated to stakeholders, the magnitude and nature of the limitations should be communicated at the same time. The next step will also explore the trade-off among techno-economic and environmental aspects to guide the design of CMR concepts.
THIRD YEARD1.13 Annual data report, year 3 (PUBLIC)
FOURTH & FIFTH YEARD1.15 Annual data report, year 4 (PUBLIC)
D4.12 Membrane development (PUBLIC)
The membranes are composed of thin Pd-based membranes (up to ~5 microns thick) deposited at TECNALIA onto 14/7 mm o.d./i.d. asymmetric finger-like alumina porous supports (100 nm pore size) developed by RAUSCHERT during this project.
The final length of the membranes after the sealing is ~35-45 cm. The membranes meet the target on N2 permeance (leakage) at room temperature defined in the project for the membranes in the prototype.
D6.4 Design and manufacturing of novel biogas catalytic membrane reformer (PUBLIC)
D8.2 Final environmental LCA of the developed technology (PUBLIC)