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PROcess intensification through the development of innovative MEmbranes and CAtalysts

Periodic Reporting for period 2 - PROMECA (PROcess intensification through the development of innovative MEmbranes and CAtalysts)

Período documentado: 2019-01-01 hasta 2022-10-31

The transition from fossils to renewable feedstocks is one of the main challenges in course worldwide in both industrial and energy production. The PROMECA project fits into this context by proposing bioethanol as renewable feedstock for hydrogen production, and it is developing suitable process schemes for both centralized and distributed hydrogen production. These novel schemes are based on the introduction of innovative structured catalysts for the ethanol steam reforming and water gas shift reaction, and of Pd-membranes for pure hydrogen separation by which the process can achieve a better performance than a conventional process. In such a way the overall environmental benefit is dual, being represented by the use of a renewable feedstock instead of fossil, and by an enhanced process performance through an action of Process Intensification (PI).
Among several industrial processes, hydrogen production aroused great interest in the research and industrial scenarios, due to the possibility, in particular aiming to exploit hydrogen as an energy vector (also through distributed generation). On the other hand, up to now, really sustainable hydrogen production (i.e. with lower environmental impact and the use of new raw materials) represents one of the main obstacles toward a true hydrogen-based economy.
The technology of Membrane Reactor (MR) plays an important role in the PI and is based on a device combining a membrane-based separation and a catalytic chemical reaction in one unit. Every catalytic industrial process can potentially benefit from the introduction of catalytic membranes and membrane reactors instead of the conventional reactors.
Today membrane reactors are being proposed for a variety of reactions (especially in the H2 production processes). But there are still several barriers to be overcome for their successful deployment at industrial level.
The PROMECA project’s strategic objective is to substantially contribute to the increase of knowledge, skills, and competitiveness in the European research area and industry, through the design and deployment of a thorough plan of research and secondment of researchers between top-level academia and industrial partners, thus advancing the knowledge on membrane reactors for process intensification in hydrogen production and relevant applications in a multidisciplinary way, thus contributing to the main European Policies on innovation (e.g. Europe 2020 and Innovation Union flagship initiative).
PROMECA will develop, test, and validate an innovative membrane reactor integrating new structured catalysts and selective membranes to improve the overall performance, durability, cost effectiveness, and sustainability over different industrially interesting processes, with distributed hydrogen production as the main focus of the project.
The project will bring substantial impacts in terms of skills and knowledge development of the researchers, as well as higher R&I output, contributing to convert more ideas into products. Organizations involved will strongly boost their capacity to carry out R&I activities in multidisciplinary and inter-sectorial collaborations. Finally, the project will enhance the innovation potential and competitiveness of the EU industry, reinforcing its world leadership as a true knowledge-driven industry.
Regarding the four main objectives listed above, the work carried out during the reporting period towards the achievement of each listed objective is detailed below.
Support career development and training of several researchers: the international and inter-sectoral mobility among all the partners was continuously assured and monitored to reach this objective

Up to 31/10/2022, 7 project meetings were performed, as planned, in order to (i) assess and validate research findings in a systematic way, and (ii) monitor the discrepancy among the project objectives and the obtained results. The performed meetings are detailed in the following T1.5 paragraph.
7 dedicated workshops were organized and performed, each with a different focus, in order to increase the competences of all the participants. These workshops were open to the scientific and industrial community, in order to increase the visibility of the PROMECA project.
PROMECA will develop, test, and validate an innovative membrane reactor: in all the project a big effort was spent by all partners in order to develop new structured catalysts and selective membranes, with the aim to obtain an important process intensification in the field of distributed hydrogen production. In parallel, detailed modelling of hydrogen plant schemes integrating membrane reactors have been developed.
Anyway, the Covid-19 pandemic did not allow to complete all the secondments as planned.
Progress beyond state-of-the-art on membranes
PROMECA aims at the development of ≤4 microns thick Pd-based supported membranes with H2 selectivity >10.000 (to other gases) and high H2 permeance (>3 x10-6 mol m-2 s-1 Pa-1@400 ºC) for long periods (>1000 h) at 600 ºC for NG reforming membrane reactor. The prepared membranes need to be resistant under catalyst fluidization regime. Ternary Pd-based alloys and new supports will be developed in order to get long-term stable membranes at 600 ºC.Progress beyond state-of-the-art on Catalysts
PROMECA aims to intensify industrial processe through the development of high thermal conductivity supported catalysts. The optimization of catalytic system through structured catalyst development is candidate to improve the overall thermal efficiency of reforming process systems, by increasing heat transfer rate towards catalytic volume, thus reducing heating medium temperature. Such aspects could reflect on reaction system materials, and its resistance to thermal stresses. Moreover, more flat thermal profiles result in a more uniform catalyst exploiting.
On the other hand, very high conductive structured carriers, coupled with optimized formulations for the low temperature water-gas shift, aims to achieve “quasi-isothermal” process, by heat redistribution from the end to the inlet of the catalytic bed. Such aspect will result very higher conversions despite a considerable reduction in catalytic volume.

On top of the above-mentioned advancement on the state of the art, PROMECA will also address advancement in energy analysis and modelling in support of the process intensification and optimization, i.e. through the use of ab initio calculations for membranes and by embedding detailed reactors/membrane reactor models into Aspen Plus simulator tool.

Some dedicated experimental tests have been performed by using the lab-scale reactor, in order to assess the catalytic activity of the structured catalyst. The operating conditions have been the following:

The results of the experimental tests are shown in Figure 1 as CO conversion vs temperature

The results of the experimental tests evidenced the very good catalytic activity of the structured catalyst, which was able to approach the thermodynamic equilibrium values in terms of CO conversion under the operating conditions of the PROMECA project demonstrator (point 2) starting at temperatures of about 300 °C, perfectly in line with the project target.
CO conversion vs T in the experimental tests with the structured catalysts. P = 1 bar; T = 200 – 400