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PILOT PLANT PRODUCTION OF CONTROLLED DOPED NANOPOROUS CARBONACEOUS MATERIALS FOR ENERGY AND CATALYSIS APPLICATIONS

Periodic Reporting for period 3 - POROUS4APP (PILOT PLANT PRODUCTION OF CONTROLLED DOPED NANOPOROUS CARBONACEOUS MATERIALS FOR ENERGY AND CATALYSIS APPLICATIONS)

Reporting period: 2019-03-01 to 2020-02-29

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 application including advanced carbon materials such as battery for personal electronic devices and electrical vehicle was valued at approximately US$32 billion in 2014 and global catalysts demand was 6,259.3 kT in 2013.
Due to the scarcity of fossil resources, the use of renewable resources as raw material source can be considered a low-cost alternative for industrial production of carbonaceous materials having porosity in the nanometer range. In addition, by using raw material made carbon for catalyst support application, a reduction on the carbon footprint in comparison with the synthesis of other types of nanoporous materials made from ceramics will be achievable.
Thus, what POROUS4APP project brings to the European community is the development of new metal/metal-oxide doped/undoped-nanoporous carbonaceous materials from Starbon® technology using renewable resources like starch. This technology needed to be upscaled and modified to enable a full flexibility of the material characteristics to be applied to various industrial applications:
(i) nanoporous carbon-doped metal oxides such as C/NMC, C/LMO and C/LTO for Li-ion battery (LIB) having faster charge and discharge rate and longer battery lifetime.
(ii) metal-doped nanoporous carbon materials such as Pd/C and Co/C for improved conventional catalysis reaction and biomass conversion to produce fine pharmaceuticals and chemicals, respectively.
As conclusions, POROUS4APP project has made possible the upscaling production of nanoporous carbons using an optimized Starbon process at a scale of 5.3Kg/week and at cheaper price. These carbons showed to be promising as supports for catalysts in biomass conversion and as cathodic material in post-lithium batteries.
Nanoporous carbons have been produced from starch, alginic acid, chitosan and urea at lab-scale using a Starbon-based process. Nanoporous carbons hybrid materials with metal/metal oxides or nitrogen have been prepared using both impregnation and sol-gel techniques: Pd/C, Co/C, C/LTO, C/LMO, C/TiO2 and N/C. Moreover, ionic liquid-based routes have shown to be promising allowing polysaccharides blending as well as direct carbonization. All this work has resulted in two patents, four published papers and four papers that are under preparation.
The fabrication of nanoporous carbon from starch and alginic acid (with/without LTO or N-doping) has been up-scaled (up to 900 g / batch) using up-scalable equipments: RoboQbo equipment for gelation, pilot scale freeze drier and pilot scale furnace for carbonization. Key process steps for up-scaling fabrication of materials have been identified and process optimizations have been realized.
The reaction mechanisms involved in the catalytic processes have been computationally identified. For that, Kinetic Monte Carlo (KMC) simulations and Density Functional Theory calculations have been performed. Moreover, three generations of 3D-resolved performance models of composite electrodes for LIBs have been developed. The third-generation model allowed to investigate the influence of the spatial distribution and electronic conductivity of the carbon additive on the overall discharge capacity. Main conclusions were that more porosity is needed to see improvements in terms of discharge capacity and binder ratio optimization in the formulation is needed, as too much binder limits lithium transport. Data base of the developed models are already available (open access) for Pd catalysts and will be available in the next six months also for carbon catalysts. All this work has resulted in five publications.
Carbon doped metal oxides (C/LTO, C/LMO, C/TiO2) have shown promising results regarding high rate capability in lithium ion batteries. N/C or Co/C have shown also very promising cyclabilities and capacities in lithium-air batteries. POROUS4APP Pd/C samples have shown similar activity as commercial ones in case of hydrogenation reactions with improved selectivity. In case of biomass conversion, Pd/C samples have shown promising competitive materials regarding existing catalysts. All this work has given five open-access publications and one patent under preparation.
From sustainability assessment and taking into consideration the safety precaution principles currently implemented, the whole process has been declared as safe. Main conclusion of the LCA studies with the three different applications to improve the efficiency of the entire production processes is that the recovery of Pd and its re-use to bring up to 98% environmental impact savings. From these studies four papers are under preparation.
A website and a project brochure have been delivered as well as the establishment of social media communications and an Industrial Exploitation Board (IEB). A final workshop has been organized and partners have assisted to several conferences. A continuously updated business plan with focus on batteries and catalysis has been realized and the development of an IPR ownership strategy has been done. A complete market analysis report focused on batteries has been delivered.
Main reached results in POROUS4APP can be summarized as follows:
- Highly nanoporous carbons with tunable porosity have been synthesized from different polysaccharides: alginic acid, starch and chitosan (up to Vtotal > 1 cm3/g).
- These carbons showed to be promising as cathodic materials in Li-air batteries and as supports in Pd-based biomass conversion reactions.
- Low cost nanoporous carbons can be obtained by direct carbonization of previously blended starches using an ionic liquid, that can be recovered and reused (30% price reduction).
- Carbon doped metal oxides nanocomposites (C/LTO, C/LMO, C/TiO2) have been prepared and showed to be promising as electrodes in LIB.
- Pilot scale production of nanoporous carbons has been performed (up to 900g/batch) from Starbon-based process and using starch or alginic acid. Production costs are highly reduced (more than 20 times) from current commercially available Starbon-derived carbons.
- Nitrogen doped nanoporous carbons (up to 10%N) have been synthesized at large scale from alginic acid and urea, which show to be promising as catalyst.
- Innovative 3D resolved models for the Li-ion battery and the two catalytic reactions have been developed. The models have been used to simulate the different user cases.
- No relevant safety issues have been detected during the evaluation of the fabrication process and a 98% environmental impact saving can be reached with the recovery and re-use of the Pd in Pd/C catalysts used for the biomass conversion.
- A detailed market analysis and business plan for the biomass conversion user case has been performed.
- 14 scientific publications and 2 patents have been created.
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