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Report

Teaser, summary, work performed and final results

Periodic Reporting for period 1 - POROUS4APP (PILOT PLANT PRODUCTION OF CONTROLLED DOPED NANOPOROUS CARBONACEOUS MATERIALS FOR ENERGY AND CATALYSIS APPLICATIONS)

Teaser

Summary

There has been a growing interest in new applications of nanoporous carbons because of their chemical stability, conductive property, high surface area, mechanical resistance as well as their abilities to support catalysts and to adsorb contaminants. Porous carbon materials have been applied in a wide range of applications, including electrodes for batteries and fuel cells, catalyst supports for fine chemical products and catalyst support materials for biomass conversion process. According to this, global demand on battery for personal electronic devices and electrical vehicle was valued at approximately US$32 billion in 2014. With a CAGR1 of 7,7%, the market is expected to approach US$50 billion by 2020. Global catalysts demand which include fine chemical fabrication and biomass conversion was 6,259.3 kilo tons in 2013 and is expected to reach 7,803.4 kilo tons by 2020 which represent US$27 billion, growing at a CAGR of 3.2% from 2014 to 2020.

What POROUS4APP project will bring to the European community is the development of new metal/metal-oxide doped/undoped-nanoporous carbonaceous materials based on a known technology: STARBON from renewable resources like starch. This technology needs to be upscaled and modified to enable a full flexibility of the material characteristics to be applied to various industrial applications:

(i) doped-nanoporous carbon materials such as NMC/C, LMO/C and LTO/C (LTO) for Li-ion battery having faster charge and discharge rate and longer battery life time.

(ii) doped-nanoporous carbon materials such as metal/C, metal oxide/C for improved conventional catalysis reaction and biomass conversion to produce fine pharmaceuticals and chemicals respectively.

Due to the scarcity of fossil resources, the use of renewable resources can be considered a new low cost option as raw material source for the industrial production of carbonaceous materials having porosity in the nanometer range. Moreover, this technology will mean a reduction on the carbon footprint in comparison with the synthesis of other types of nanoporous materials made from ceramics, etc. The energy storage, biomass conversion and catalysis applications in the project will all contribute to the EU 20-20 target for 2020: 20% reduction of GHG compared to 1990, 20% rise in share of renewable energy sources and 20% improvement of EU efficiency.

Work performed

In the first stage of the project, the different specifications regarding the material properties and the process to accomplish with the applications and the modeling approach have been defined in the associated deliverables. Moreover, a document that will be updated each 6 months has been created to track progress in the project against the performance criteria defined in D1.1.

The fabrication of nanoporous carbon from starch and alginic acid has been up-scaled (up to 0.5Kg) using up-scalable equipments: a RoboQbo equipment for the gelation (up to 15Kg/h T<100ÂºC), a semi-pilot scale freeze drier (up to 1.1Kg/batch) and a customized dean stark like set-ups for the carbonization (yielding up to 70g/batch porous carbon). Key process steps for up-scaling fabrication of materials have been identified and first process optimizations have been realized.

First results on the control of the porosity by mixing starches with different quantity of amylose (30-70%) and using ionic liquids have been obtained. Other investigations including the synthesis of N-containing porous carbons using chitosan or urea, the preparation of mesoporous carbon beads to be used in flow reactors and the study on the cross-linking of expanded polysaccharides to increase the final carbon yield have been realized at lab scale.

The first synthesized metal/metal-oxide doped porous carbons (Pd, Co, Pt, LTO) produced at lab-scale using impregnation and sol-gel techniques have been tested as catalysts for fine chemicals and biomass conversion and as electrodes in batteries.

A multifaceted computational model with an innovative three-dimensionally-resolved model of a lithium ion battery that resolves both the ionic transport in the electrolyte and the lithium transport in the active material for performance simulation of rechargeable batteries has been developed.

For the first application (energy storage) all partners have been focused on the establishment of test setup and conditions to ensure comparability of results between partners. The performance of POROUS4APP nanoporous carbons have been compared with reference materials (commercially available porous carbons as cathodes). For the catalytic properties of POROUS4APP material, metal-doped porous carbons have been tested in two model hydrogenation systems and the furfural decarbonylation reaction to evaluate the catalystsâ€™ activity, selectivity, shelf-life stability, leaching and reusability.

The exposure scenarios for their fabrication have been defined and evaluated mainly focused on the occupational exposure to airborne metal and metal oxide nanomaterials during the processing and manufacturing phase. Moreover, the MPAS (Multi-Perspective Application Selection) method has been applied to assess and identify the most promising application fields interesting for these new materials.

A website and a project brochure has been delivered as well as the establishment of social media communications. A first draft structure of the business plan and the development of an IPR ownership strategy has been done.

A constant contact with all partners regarding contractual and financial information has been stablished. Each Work Package leader has been in charge of the specific tasks of the Work Package and the associated Deliverables in collaboration with each Task and Deliverable responsible according to the DoA, assisting the Coordinator in the overall coordination of the project.

Final results

Main reached results in POROUS4APP can be summarized as follows:

- The optimization of gelation-drying processes has been investigated and a reduction in the energy consumption and processing time during the gelation process has been achieved (gelation at kg scale within minutes at T<100ÂºC, allowing for atmospheric pressure operation). A semi-pilot scale freeze drying process has also been developed (1kg/batch, t=100h).

- Up to 0.5Kg of porous carbon from AA and starch has been produced.
- The use of IL as solvents for the mixing of different starches has been studied to influence on the final porosity. In this studies the IL can be quantitatively recovered.
- Several procedures (sol-gel and impregnation) for the production of metal and metal oxide doped porous carbons have been investigated.
- First tests in hydrogenation catalysis are promising showing higher selectivity that the commercial ones.
- For the battery applications higher capacities are measured with the new materials for Litium ion batteries.
- An innovative 3D resolved model of a Li-ion battery and first simulations have been developed using COMSOL Multiphysics.
The further expected results can be summarized as follows:
- Design and construction of a production line for the doped-nanoporous carbonaceous materials, including post-process quality control procedures.
- Process demonstration and technological validation of the doped-nanoporous carbonaceous materials production process with the capacity of up to 20 kg/day.
- Economic assessment of the POROUS4APP doped-nanoporous carbonaceous materials production process.