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Periodic Report Summary 2 - FASTCARD (FAST industrialisation by CAtalysts Research and Development)

Project Context and Objectives:
Overall summary
The overall goal of FASTCARD is to enable short- and long-term implementation of advanced biofuel production based on rapid and risk reducing industrialisation of nano-catalytic processes through the two major catalysis based value chains, combined with micro-kinetic and process design level modelling to guide and give insight to the mechanisms and economics of the processes.
This will be achieved through demonstration both at laboratory and relevant pilot level (WP7) to achieve significant reduction (up to 50%) in the time for development to industrial scale. For the two selected value-chains, key objectives focus on energy and resource efficiency:

Gas based value chain
• Hydrocarbon Reforming (WP1) of producer gas from biomass fluidized bed gasification aims to reduce biofuels production costs by 20%. This being based on two routes: (1) a higher risk single step reforming catalyst or (2) or a low-risk two-step steam reforming approach.
• Next generation supported iron Fischer-Tropsch (FT) catalysts (WP2) will aim at small delocalised 500-3000 bpd BTL plants addressing performance robustness with respect to higher temperature, high CO2 feeds and improved durability. This will target improvement in C5+ productivity of at least 10%, energy savings of 3%, and CAPEX reduction of at least 15%.

Liquid based value chain
• Hydrotreating (WP3) will develop new generation catalysts on two levels of hydrotreating, i.e. for bio-oil stabilization and for further upgrading in a more severe hydrodeoxygenation (HDO), to produce co-feed to existing FCC units minimizing the overall level of treatment. Challenges are the robustness of catalyst performance, lowering the hydrogen consumption, reducing process severity (lower pressure and temperature, and higher space velocity), to improve durability, and increase selectivity in relation to oxygen removal.
• Co-FCC (WP4) will develop a catalyst able to co-process bio-feeds and crude oil distillates in a FCCU, showing similar or better performances than a State-of-art FCC catalyst, designed for co-processing 2nd generation bio feed blended in conventional feed. It is targeted to maximize the oxygen content of the co-FCC feed blend, either by increasing the blending level or decreasing pre-treatment severity for the bio component. The new catalyst should match specification of hydrothermal stability and price competitive production route, as well as a reduced usage of strategic resources like rare earths and precious metals by at least 20%.

Micro kinetic and process design modelling
Microkinetic modeling tools (WP5) are being developed to establish fundamental Quantitative Structure Activity Relationships (QSARs). These relationships will support the rational design of nanoscale catalysts within WP1 to WP4 and will be validated by the actual synthesis and performance testing of new generations of catalysts and the Down-scale/Upscale pilot testing.
For metal catalysis, relevant for WP1, 2 and 3, the quantitative models (QSARs) will be supported by the synthesis of series of supported metal nanoparticles with very well controlled size and surface composition.
Process design and evaluation (WP6) will translate and link the catalyst & pilot research results to individual process designs/modifications and integrate these designs, including techno-economic evaluations & sensitivities into integrated designs with acceptable overall energy requirements. This WP is also expected to provide process consequences and feedback/guidance for the individual catalyst research issues in both the gasification and the pyrolysis value chains.

Project Results:
WP1 – Hydrocarbon Reforming
Significant advances have been achieved in the development of improved steam reforming catalysts. State-of-the-art reforming catalysts from JM were firstly selected and tested under realistic biomass gasification conditions. First tools in the toolbox were created, including ship-in-bottle for size selectivity, and synthesis of bi-metallic and tri-metallic materials for increased carbon resistance during reforming. The effect of Ni and/or Pd alloying with Fe on catalytic properties was investigated.
The 2 x 100-h duration tests performed at ECN under relevant gasification conditions on M34-M35 revealed that the addition of the pre-catalyst in dual bed configuration is very positive for the improvement of the stability of the downstream catalyst.

WP2 – CO2 FT
A global kinetic model based on cobalt FT catalysts has been modified using literature parameters and real data from the SoA catalyst. Initial reactor modelling indicated the productivity of the reactor is low, reinforcing the importance of both selectivity and activity in the FT process. The SoA catalyst has been extensively tested under various conditions for benchmarking. Information on the effects of pre-treating the catalyst, the many complex iron phases present during the FT reaction, and has given options for deactivation mechanisms – e.g. metal sintering, complex formation and surface carbon deposition. Testing results show that these materials are active for FT, and may exhibit reverse-Water Gas Shift (WGS) activity in the presence of CO2. Isotopically labelled CO2 experiments show CH4, CO and small amounts of C2-C4 products are produced from CO2.

WP3 - Hydrotreating
Catalysts with improved durability and increased selectivity in relation to oxygen removal from biomass pyrolysis oils (PO) are developed, and process conditions optimized for lowering the hydrogen consumption. SoA catalysts were applied, showing stand times up to 500 h. Kinetic screening study of the first generation HDO catalysts have been performed and publications are in progress. A base case 1stG HDO catalyst system was selected for up-scaling and tested with real PO, but this deoxygenation catalyst lack stability. Preparation of a 2nd generation HDO catalyst is now completed, and performance evaluation and characterization is on-going.

WP4 – Co-FCC
Bio-oils of different qualities were used to establish the state-of-the-art baseline defined at REPSOL’s pilot plant, co-feeding fully HDO bio-oil with VGO. Bench scale and pilot plant deactivation and testing was aligned between all partners. Novel zeolites, including hierarchical and nanocrystalline materials, were synthesized and checked for hydrothermal stability. Intermediate pilot scale co-FCC tests revealed the opportunity to switch from partially hydrodeoxygenated bio-oil to stabilized pyrolysis oil as bio component. This renders the overall liquid value chain – consisting of hydrodeoxygenation and co-FCC – economically more feasible and environmentally friendlier.

WP5 - Nanoscale probing and modelling
Within Tasks 5.3 and 5.4, a kinetic model has been developed simulating the effect of the presence of tars and sulphur in the feed on the catalyst performance for Hydrocarbon Reforming (HR, WP1), while for Fischer-Tropsch Synthesis (FTS, WP2) ab initio calculations of rate coefficients for the key elementary steps within the microkinetic model have been performed. For HydroDeOxygenation (HDO, WP3) the construction of the microkinetic model for the anisole HDO was finalized while the propionic acid HDO microkinetic model is under way. Regarding co-Fluid Catalytic Cracking (co-FCC, WP4) a kinetic model was developed including selective deactivation functions to simulate the co-FCC (C10 / EP) reaction.

WP6 - Conceptual process design and energy efficiency
Industrial processes for three of the conversions processes has been conceptually designed. The former two have been integrated in a value chain from wood to FT waxes. Techno-economic evaluations have been performed for this value chain and for the hydrotreating of pyrolysis liquid. The value chain based on gasification as currently envisaged is not economically feasible, but this is largely due to the prohibitive CAPEX for the gasification technology. Other choices of gasification technologies will be considered, which are expected to considerably reduce the production cost of the FT wax produced. The production of hydrotreated pyrolysis liquid seems more competitive, but the economic evaluation still has to be extended to the whole value chain including co-feeding in an FCC unit.

Potential Impact:
Gas based value chain
WP1 will prove selected possible pathways of producing syngas from biomass under realistic conditions during long-term tests. It will involve newly developed and upscaled catalysts and possibly apply a novel process scheme. WP1 will finally result in the catalyst(s) needed to more efficiently produce fuels and chemicals through syngas from biomass. Furthermore, advances in design of nano-catalysts will establish a fundamental platform that can be applied to other energy applications. The project will therefore speed up industrialization of safer, greener and stable catalysts.
The expected final result of WP2 is to have invented novel supported iron catalysts that have increased activity, increased C5+ selectivity and stability to operating at temperatures in excess of 250°C, under fluctuating and sub-stoichiometric syngas conditions. Because the syngas for the process will be coming from a biomass source, the ability to tailor the catalyst to the operating conditions to generate the optimum hydrocarbon blend, should minimize downstream processing. Novel catalysts must be prepared using industrially scaleable processes.

Liquid based value chain
The expected final results of WP3 is a process (operating conditions and catalyst) that allows the accelerated use of biomass in existing refineries – by subsequent fast pyrolysis and hydrotreating of pyrolysis liquid to liquid products to be co-fed in FCC – with focus in the treatment step on (i) improved carbon efficiency, (ii) reduced hydrogen consumption, (iii) improved catalyst activity and stability, and (iv) reduced overall costs.
Ultimate goal of the work packages 4 and 5 is to define the optimum value chain for the incorporation of biomass into the conventional refinery stream via pyrolysis, hydrodeoxygenation and co-FCC in terms of cost, as well as carbon and energy efficiency. It has been decided to follow up the high risk option for catalyst development, using novel zeolite types and their modifications for the co-processing of bio-feed, alongside with optimizations around the low risk option (faujasite based catalysts). Final goal of the project will be the development of a catalyst which enables the processing of either higher levels (<10%) of bio-feed, and/or to allow to process a less deeply hydrotreated bio-oil.

Micro kinetic and process design modelling
• Adequate kinetic models for the various reactions investigated within FASTCARD. These models will assist in
o the identification of promising next generation catalysts, as well as in
o the scale-up from the laboratory to the industrial scale
• Tailored nanoparticle catalysts with dedicated activity and selectivity performance for reforming and FTS
• Optimized pore structure catalysts for co-processing of oxygenates in conventional hydrocarbon streams.

The expected final results are twofold:
• Integrated conceptual process designs integrated in value chains (a gasification and a pyrolysis route) from biomass to fuels, including the fruits of feedback provided to the catalyst developers from a process design perspective.
• Techno-economic evaluation of these value chains and evaluation of their overall energy efficiency.

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