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Production, control and Demonstration of structured hybrid nanoporous materials for Industrial adsorption Applications

Periodic Reporting for period 2 - ProDIA (Production, control and Demonstration of structured hybrid nanoporous materials for Industrial adsorption Applications)

Reporting period: 2017-05-01 to 2018-10-31

Within the past 20 years, new classes of nanoporous materials (NMP) have been discovered in the form of amorphous micro- and mesoporous aluminosilicates and more recently metal organic frameworks (MOF). Despite the great potential of these new classes of materials, to date there has been only modest success in applying their unique properties commercially.
One of the main limitations to commercialisation is that these materials are not readily produced on pilot nor semi-industrial scale (10s-100s kg) which therefore makes their cost prohibitive to penetrate many potential markets. Furthermore, many of the application areas where these materials would be ground breaking require the solid powdered NPMs to be shaped bodies and at present fabrication techniques are immature.
In respect to these issues, the overall objectives of ProDIA are:
- to develop scalable production technologies for a variety of MOFs and aluminosilicates, producing high quality material enabling enhanced adsorption/separation properties.
- to set up pilot line production facilities, including shaping, at TRL 6-7 to produce high performing and price competitive NPMs, which fulfil safety requirements allowing the NPM to be commercially sold, distributed and used by customers.
PRODIA is developing three innovative processes for the cost-effective production of NPMs to meet industrial expectations of reliability and repeatability at the pilot-scale. The industrial markets in which these NPMs will be demonstrated are in adsorption based applications of gas storage (ANG), air purification, heat pump and health care.
Prodia has successfully set-up four pilot lines of MOF production in Europe. It includes batch synthesis of >6 MOFs from 1 kg to 140 kg scale (TRL5/6), mechano-chemical synthesis using negligible amount of solvent of 5 MOFs at >10 kg scale (TRL5/6), and syntheses of one MOF by spray-drying using at >15 kg scale (TRL6). Particular attention has been given to producing these selected NPMs at scale in a cost-competitive manner; high reaction yields and throughput with negligible use of organic solvents, if any.
In addition, the sustainable syntheses of a series of second generation NPMs with enhanced performances for the four chosen applications (gas storage, air purification, heat pump and health care) have have been developed.

In parallel with the NPM powder upscaling studies various shaping techniques for the chosen NPMs have been evaluated and optimized for the selected applications. Methods such as dry pressing, extrusion, freeze granulation, suspension casting and spheronation using cross-bonded biopolymers have all been studied. The focus has been on conserving the gravimetric properties of the NPM powder, such as pore volume and surface area, while densifying the material into usable granules, tablets and spheres. The shaped materials have been tested with respect to equilibrium and kinetic adsorption properties and chemical and physical stability. Beside the materials ease of production, also projected cost of production, HSE aspects, freedom to operate, stability and performance for the selected application were used to select a limited number of NPMs to be used in pilot line demonstartions of the four applications. An evaluation of the readiness of the demonstrators for each of the application areas was used to plan the processes required to produce successful demonstrators within the timeline of the project .

Four application demonstrations were completed. For the methane storage (ANG) application, 10 kg MOF produced by mechanosynthesis were shaped by dry compression into solid discs to completly fill a specially designed ANG tank containing internal water cooling/heating. 4.4 kg shaped adorbent were used to fill the tank. Results from the testing campeign shows good thermal behaviour of the pilot, however, the volumetric and gravimnetric storage capacity of the tank islower than the target set (225 L/L). The air purification pilot (TIC) was based on a MOF shaped by granulation and by extrusion. For ammonia adsorption the shaped MOF adsorbent gave longer breakthrough times than state-of-art adsorbents at all NIOSH-conditions used. For the heat pump pilot line, 2 kg of shaped MOF sphers were produced and tested in a dedicated pilot unit by subcontracting. Also for this application, the shaped MOF performed twice better than state-of-art silica based adsorbents. The last demonstration case, health care, is based on the controlled release of antimicrobials from MOF coatings. The chosen MOF coatings reached the goal with respect to release profile of antimicrobial components. All in all, for three out of four application cases at demonstrator scele, the shaped NPMs performed either better than existing adsorbent or better than the goal. We believe that further improvement will be achieved for all four applications by further optimization at the system levels.
At the end of the project the following targets have been achieved:
• Pilot production of first generation MOFs >5-10 kg/day, HKUST-1 at >15 kg scale with a space-time-yield of >900 kg.m-3day-1
• Production of a series of aluminosilicates with well controlled pore sizes
• Successful and scalable water based synthesis of three second generation MOFs at > 1 kg scale
• Successful mechanochemical synthesis of two second generation MOFs at >1 kg/day
• Tableting procedure for selected MOFs achieving >80% of crystal density while maintaining structure integrity
• Extrusion and spheronizing procedures for selected NPMs achieving > 80% of original micropore volume/surface area
• MOF/polymer formulations and coatings prepared with targeted release profiles of active agents achieved
• Successful demonstration of the four chosen applications of NPMs at TRL 5-6

Expected potential impact at end of project:
In terms of commercial exploitation, ProDIA’s four selected application areas can be split into two groups: NPMs in healthcare and air purification are pioneering and are therefore high value add propositions for their specific markets areas. Whereas NPMs for natural gas storage and adsorption driving heat-pump applications, albeit cutting edge technologies, have to compete with current technologies where the price of adopting a new technology is tightly linked to energy prices and government incentives.
• Established that a shaped MOFs produced by scalable methods at kg scale show enhanced performance in the capture of a TIC under the industrial standard test conditions (EN, NIOSH) than current state-of-art commercial adsorbents. Commercialisation to be expected within 3-4 years if competitive price point can be achieved. The same MOFs offer new adsorbent solutions to overcome challenges in VOC removals for indoor and industrial applications in which state of the art adsorbents show major limitations.
• MOFgen Ltd, a spin-off company from USTAN secured VC investment in November 2016. This funding will facilitate further development of the commercialization of MOFs into the healthcare markets. The initial target application is to penetrate antimicrobial coatings for medical devices. The global catheter market is forecast to reach $42.5billion in 2020, with the largest sectors growing at >5% CAGR. The industry is actively seeking novel alternatives to current offerings due to lack of performance and cost of silver based products.
The ProDIA project approach