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Bifunctional Zeolite based Catalysts and Innovative process for Sustainable Hydrocarbon Transformation

Periodic Reporting for period 3 - BIZEOLCAT (Bifunctional Zeolite based Catalysts and Innovative process for Sustainable Hydrocarbon Transformation)

Reporting period: 2022-01-01 to 2022-12-31

BIZEOLCAT addressed the use of light alkanes as raw material for specialty chemical industry and not as feedstockfor fuels in the current oil refining process governing the transition to a sustainable economy
BIZEOLCAT’s main objective was to obtain light olefins and aromatics using light hydrocarbons (C1, C3 and C4) by implementing new procedures, involving innovative catalysts synthesis methodologies and novel reactor designs and processing, demonstrating their improvement in sustainability and economic scalability in existing industrial processes.

The project is addressing the catalytic transformation of hydrocarbon in line with the H2020 focus area of “Connecting economic and environmental gains” in a circular economy approach.
Three key elements are addressed:

• using resources efficiently, since light hydrocarbons will be transformed into products of added value
• reduce waste and environmental pollution, decreasing the availability of raw materials for fuel
• creating competitive advantages for companies and creating opportunities for new business since 3 large companies are interested in results with the aim of improving their competitiveness.

Life Cycle Assessment performed on the proposed propane, butane dehydrogenation and aromatization processes have shown a considerable reduction of greenhouse gas emissions of more than 80% in the production of butadiene and aromatics and a reduction of use of fossil fuels of 85% and 60% respectively. The reduction in the production, operating costs and the fixed capital for investment are always higher than 10% compared to the benchmark technologies and in aromatics production the values reach up to 50% of benefit.
Validation at TLR5 has been achieved, a patent has been published, two doctoral thesis presented in catalyst development and exploitation plan will run in parallel with the technology maturity plan.
BIZEOLCAT’s innovative schemes are based on the concept of considering the integration of a catalytic membrane reactor with innovative catalyst formulation, optimized ad hoc and including hydrogen removal during the reaction step, helping to reduce the operating temperature, thereby limiting the formation of coke on the catalyst, reducing the overall energy use and the environmental impact of the process.
Therefore, the quantified process schemes have been developed (based on values of the corresponding benchmark technology to determine the actual performance and limitations of the technologies and catalysts used at industrial scale). A benchmark technology, currently commercialized at industrial scale, was selected for each process.

The catalyst preparation has included different tasks related to the synthesis of mesoporous materials, the catalytic elements by the introduction organometallics supported on the materials surface and the support of metal nanoparticles on the mesoporous material Catalytic evaluation of the materials developed has been performed and after optimizing conditions, were obtained catalysts with high activity and selectivity in both dehydrogenation and aromatization of hydrocarbons with exploitable results.

Kinetic modelling and Catalysts upscaling experiments were taken place at pilot plant scale (150 g of catalyst) and promising results obtained were reproducing previous results at lab scale (2g of catalyst).

After mapping out the production routes for the innovative production processes and benchmark conventional routes in detailed data according to the defined schemes and scenarios, assessment of CAPEX, OPEX, LCA, Human Risk Assessment and Environmental Risk Assessment and HAZOP were done.

Articles about modelling, catalysts and membrane reactors have been published (up to nine) and others are under preparation.

A published patent out of BIZEOLCAT, filed by Eurecat on Feb 2021, which reference is EP21382154 and title is “Alkane dehydrogenation nanocatalyst and process for its preparation” and a CEN Workshop Agreement (CWA) approved and published to create an standard about the catalyst preparation methodology
*Progress beyond the state of the art in nanocatalysts

The obtention of new light hydrocarbon dehydrogenation catalysts. new preparation methodology and new aromatization catalyst supported on different materials with improved performances (activity, selectivity, and stability) at lab scale using as reference other benchmark catalysts and results have been reproduced at pilot plant stage. Currently, we have already validated at TRL5 all the proposed new synthetic routes conceived in the context of this project.

Feedstock variability was studied, Additionaly such catalysts are stable at air. In the case of single site catalysts the presence of CO, CO2 or NH3 leads to a decrease in activity in all of them, However, the selectivity in Aromatics decreases due to the poisonning of brønsted sites.
In the catalysts made of nanoparticles the activity and selectivity in propene is slightly affected in presence of 50 ppm of NH3 and CO2 in the feed. The presence of 50 ppm of CO, Me2S or O2 in the feed leads to a decrease of the activity of the catalysts PtSn/Li-Al2O3
Using fluidized bed membrane reactors with PDH improved performance towards the propane conversion (+21%) and propylene yield (+43%) related to a conventional fluidized bed. However, the average hydrogen recovery factor obtained was below 50% due to coke formation.

*Progress beyond the state of the art in reaction modelling: A total multi-scale description was applied for reactors using the 3 optimal catalyst materials for light hydrocarbon conversion mechanisms. Providied detailed understanding of full reaction mechanisms, both for desired and undesired reactions (re. coke formation

The socio-economic impact of the investment and operations phases of the novel PDH process was estimated quantitatively with the use of a macro-economic model populated with the input-output data from all EU-countries. The model estimates the added value for every industry in every EU-country from a hypothetical production facility placed in Spain. Baseline studies for all Eastern ENP countries and an overall study of the EU area was carried out for a qualitative socio-economic impact assessment (SEIA) and guidelines on establishing viable operation in European Neighbourhood Policy countries

For PDH the reduction in VOC (Variable Operation Cost) of about 18% and a reduction in cost of production (COP) of about 14% and CAPEX of 10%
For BDH showed a reduction in VOC of about 31% and a reduction in cost of production of about 10% and CAPEX of 4%
In the case of propane aromatization a reduction of about 50% both in Variable Operating Cost and Cost of Production can be achieved.
A reduction of 20% in carbon footprint has been achieved in 2 of the 3 case studies analysed and in the only case, the PDH in which it has not been achieved, a 15% reduction has been obtained.
Another indicator that has been monitored is the Abiotic depletion in fossil fuels, ADPff, which objective was to achieve a 30% reduction. This has been accomplished in two of the innovative process BDH and PAr but not in PDH which reduction was not that significant (4%).
Another relevant indicator was the reduction in the use of fossil fuels. There was a significant reduction in the case of BDH and Par (more than 80%) and less significant in PDH (4% reduction).
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