Final Report Summary - PLASCARB (Innovative plasma based transformation of food waste into high value graphitic carbon and renewable hydrogen)
Executive Summary:
Estimated food waste in the EU27 in 2012 was approximately 89M tonnes p.a. (179kg per person), rising to 126M tonnes p.a. by 2020. This waste, w o u l d generate 170M tonnes of CO2 p.a. equivalent to 3% of all EU27 Greenhouse Gas (GHG) emissions, a n d is considered by the European Parliament to be an unsustainable resource waste. PlasCarb project (2013-2016) was a €3.8M initiative funded by EU’s FP7 Programme, using innovative technology to produce – EU identified critical and valuable products graphitic carbon and renewable hydrogen from food waste.
Most c a r b o n a n d hydrogen used by industry is from fossil derived sources, primarily imported into the EU from politically unstable or competitive regions. PlasCarb integrates technical innovation to promote future market uptake. Industry and research will collaborate to combine anaerobic digestion (AD), innovative low temperature microwave plasma processing and leading edge control of carbon morphology and purification.
During the first period of the project, a comprehensive year- long study was undertaken looking at the seasonal variations, composition and quality of Anaerobic Digestion (AD) biogas (CH4 and CO2) generated from mixed food waste this was extremely important for the plasma system. The plasma system was optimised for the processing of a range of potential bio gas compositions for the formation of high value carbon materials and RH2. A quantitative analysis and evaluation of the full sustainability, i.e. environmental, economic and social viability, of PlasCarb using the in the industry and academic accepted LCA approach started. Also the analysis and characterisation commenced to look at the morphology of the produced carbon generated by the PlasCarb plasma process.
For the second period of the project, the original intent of WP6 and WP7 was to design, build and trial an integrated process plant containing AD plant, biogas upgrading unit, buffer tank, PlasCarb reactor, Renewable PlasCarbon handling, and RH2 separation and storage unit, the latter only if economically feasible. It was demonstrated early in the project that the off-gas containing RH2 could only be used as a fuel at this scale and that RH2 separation was not feasible. Furthermore, due to reductions in UK renewable energy tariffs and incentives, the AD plant build was put on hold for the duration of the project as from an investors perspective it was no longer economically viable. An existing AD plant was therefore identified and the biogas upgrading unit was operated at this plant during a five-day biogas upgrading trial from 11th – 15th July 2016, to produce the required Biomethane feed. The biomethane was stored in high pressure cylinders and transported to the PlasCarb reactor where it was let down to provide the reactor feed. In line with WP7, a one- month pilot plant trial was then run to process this Biomethane thus produced, from 18th July – 19th August 2016. The intent of the project, to operate an integrated system and run the PlasCarb reactor on biogas, was therefore realised despite the severe limitation of no AD plant operated by a project partner. The high pressure storage in effect provided the buffer tank that was part of the original scope. It was identified early in the project that the values quoted in WP7 for RPC and RH2 production rates were incorrect, and the correct theoretical values were given according to the mass balance. From the production trial 7.8 kg of carbon were produced, the amount produced was lower because of the challenge of undertaking the trial with bio-derived methane in the absence of the AD plant within the consortium, because of the changes already identified considerable effort was put in place, finding a source of gas, procuring the gas purification at the scale required, undertaking design, safety and scheduling exercises to bring the activity to a successful conclusion on time. Much staff time was required to ensure this success.
Also throughout this period work continued on the Carbon morphology of the graphitic carbon produced via natural gas and bio-methane from food waste leading to a defined characterisation of the material important to identify the best possible end use applications for the material. A number of uses were identified including conductive inks, conductive rubbers, as a catalyst in processes and potentially within fuel Cell technology.
The quantitative analysis and evaluation of the full sustainability, environmental, economic and social viability, of PlasCarb using accepted Life Cycle Assessment (LCA) approach based on ISO 14040/14044 (2006) has continued and concluded. The main result was to confirm the sustainability of PlasCarb, also in comparison to the state of the art treatment technologies.
During this period an economic optimisation of the process/products was completed in order to assess the viability of the technology, gauge likely funding options, potential applications and to enable the future market uptake. Different CAPEX (capital expenditure) models were assessed together with the indicative OPEX (Operational Expenditure) costs and all potential realisable revenue streams. With this robust financial modeling at its core, a business model and assessment of market viability with an overall SWOT (Strength, Weakness, Opportunity and Threat) analysis was performed and for a number of different scenarios namely UK, Hungary and Germany.
The project went beyond the objectives and identified unique dissemination opportunities for maximizing the impact of the project results.
Project Context and Objectives:
PlasCarb was stimulated by a transnational consortium of R&D performing SME’s in partnership with specialist scientific resource, Life Cycle thinking experts, industrial customers and access to risk finance to facilitate future market uptake. The aim was to integrate commerce with research; transforming a widespread urban solid waste environmental problem into a sustainable source of significant economic added value (high value graphitic carbon and renewable hydrogen). The vast majority of carbon and hydrogen used today in industry are derived from fossil petroleum sources, the majority of which are imported into the EU from regions which are often politically unstable or competitive.
PlasCarb aim was to integrate an established technology (Anaerobic Digestion) with innovative, low temperature microwave plasma processing and leading edge control of Carbon Morphology and purification. This project extended beyond current Best Available Techniques (BAT) in the valorisation of food waste of anaerobic digestion to generate renewable energy; it transformed (and purified) the now bio-methane output from AD using an innovative low energy microwave plasma to split bio-methane into high value graphitic carbon and potentially renewable hydrogen, however within the course of the project it was identified that at the project output scale it was not commercially viable, that said at higher volumes this should be possible.
The quality and economic value of the carbon was subsequently maximised through the integration of research and industrial process engineering
The specific Work Package objectives include:
WP1 - Management: to manage the PlasCarb project consortium and co-ordinate project delivery. To ensure that all deliverables and milestones are met on time and to budget. Fulfil the formal reporting and administrative requirements out lined in the Grant Agreement.
WP2 – Biogas Generation: to generate representative biogas from an AD process with a feedstock rate of 1800 tonnes mixed food waste per annum, noting seasonal CH4:CO2 variations and impurity leves versus seasonal input variations over 12 month period. Assess and incorporate an economically viable process to remove trace impurities from biogas to less than 4ppm H2S and less than 6ppm in total. Define the biogas output from anaerobic digestion of representative food waste over a period of 12 months, noting variations in CH4:CO2 yields and purification requirements for input into microwave plasma process.
WP3- Plasma Process: Define and validate a microwave plasma process design for biogas generated from the anaerobic digestion of food waste from WP2. Optimise nozzle geometries and gas flows to enable optimal carbon formation in WP5 from biogas using a 12kW microwave plasma reactor. Investigate the use of pre-separated CO2 to enhance the carbon formation from the methane.
WP4-Gas solid separation: Define and validate gas/solid and gas/gas separation unit operations. Develop an optimal process to separate the combined carbon species and then the renewable hydrogen from any other gases present from the gas stream output from WP3.
WP5- Carbon Morphology: Develop a methodology whereby the appropriate size, shape and form of carbon generated by the integrated process. Desired form of carbon is graphitic rather than amorphous or glassy. The desired size and shape is that most appropriate to maximise the economic yield of graphitic carbon, both in the synthesis and the separation process. Will closely interact with WP3 and WP4.
WP6- Process Integration: Integrate and optimise the outputs of WP2-5. This involves the integration of the separate unit operations of process plant, along with appropriate process control. The control operations of the integrated plant will then be refined, to enable both local and remote monitoring and control. Integrate a working pilot scale PlasCarb plant including one AD unit processing 1800 tonnes per annum of mixed food waste and at least one 12kW microwave plasma reactor to process a proportion of the biogas generated.
WP7-Pilot Trials: Operate an integrated plant continuously for a period of at least one month transforming over 150 tonnes of mixed food waste into over 25 thousand m3 of biogas. Over 2400m3 of this biogas will then be transformed into over 240kg of RH2 and 700Kg of highly graphitic carbon, enabling economic validation to be undertaken as part of WP8 and demonstration to the research community, industry and the wider public in WP10. As highlighted in this final report together with the Period 2 report, the project was unable to use it's own AD plant due to political and financial issues and therefore biogas (biomethane) was sourced from another AD facility, purified and sent via cylinders to GasPlas (CNS) for processing into graphitic carbon.
WP8-Economic Optimisation: Optimise the project results and the economics of all aspects of the technology to enable future market uptake. The OPEX (operating expenditure), CAPEX (capital expenditure) and revenues (determined by end user techno-economic validation of the RH2 and graphitic carbon produced in WP7) to be validated. An optimal business deployment strategy (size and location) to be prepared. Financial mechanisms that can be applied to different regions of Europe will be selected. Preparation of an integrated financial and business package for wider deployment.
WP9-Sustainability: Verify the full environmental, economic and social viability of PlasCarb (WP2 to WP8) using a recognised Life Cycle Assessment (LCA) approach based on ISO 14040/44 (2006). Validate the net benefits compared with State of the Art (SoA) food waste management and sustainable material supply. To include an evaluation of the regional and political waste management strategies from across Europe. Verify the technology development as being Best Available Technology (BAT) using the EU Environmental Technology Verification pre-programme.
WP10-Exploitation & Dissemination: Protect project results and disseminate results for maximum impact. Project results protection to include the filing of at least one patent. Dissemination to include publicising project achievements via international industry seminars, scientific and technical papers, publications and conference proceedings and a dedicated open access web site. Project results to be publicised in over ten disclosures (presentations, publications, web sites). Dissemination activities to operate both during the project and for at least five years post-project, the monitoring of the economic and environmental impacts of the project achievements.
Project Results:
Main S&T results/foregrounds
Environmental value and circular economy contribution
Natural graphite is listed as one of 20 critical raw materials in the EU. The global demand for graphitic materials and carbon allotropes is fast growing i.e. the market demand carbon black is forecasted to increase to more than 15 million tonnes by 2022. Carbon black is to 99% sourced from fossil raw materials such as heavy aromatic oils by partial combustion processes (several forms of carbon black exist) or from light and medium aromatic oils or natural gas by thermal processes (e.g. acetylene black).
Renewable PlasCarbon (RPC) and potential market applications
The cracking of biomethane by microwave plasma yielded graphitic nano carbons (“Renewable PlasCarbon”) in turbostratic packing motif, comparable to those produced by the same process from Natural Gas. The quality of the generated graphitic nano carbon depends inversely on the carbon dioxide concentration applied during the plasma process. The PlasCarbon contains valuable graphitic domains plus amorphous parts which can be removed by heat treatment. For the various samples characterised, ca 12 % -15 % amorphous material can be removed that way. In the solid material, the graphitic domains of the samples are randomly oriented (turbostratic) with primary particles (“pucks”) in the range between 20-30 nm. However, stacked aggregates are up to the micrometer range. The bigger aggregates may be split apart and the most valuable part of the sample, the few layered graphene (FLG), may be isolated by means of aqueous dispersion followed by centrifugation. Here, the size calibrated dispersion is made of particles of ca 30-80 nm in lateral size and 3 nm in thickness. Raman spectroscopy on a statistical basis shows that edges and point defects actually represent most if not all of the defects, underlining the quality of these materials. Therefore, generating large quantities of sustainable graphitic nano carbons appear to be feasible and technologically relevant. Due to its intrinsic size and defined chemical structure, PlasCarbon may be used to formulate conductive inks with superior conductive properties, providing access to printable electronics. Therefore, these materials fit well between graphene and carbon black and constitute a promising and exciting alternative to established carbon blacks due to their well-defined nature, conductivity performances, and sustainability. PlasCarbon appears to be of high quality, similar to or better than previous graphitic materials characterised by CNRSThe material generated by the PlasCarb process can be classified as particles of graphitic nanocarbon (Renewable PlasCarbon, RPC). It can be classified to fit between graphene and carbon black. PlasCarb has developed a process chain to produce high value RPC from the renewable feedstock food waste, namely through the integration of innovative technologies such as Anaerobic Digestion, biogas upgrading and a cold microwave plasma process.
The original intent of WP6 and WP7 was to design, build and trial an integrated process plant containing AD plant, biogas upgrading unit, buffer tank, PlasCarb reactor, Renewable PlasCarbon handling, and RH2 separation and storage unit, the latter only if economically feasible. It was demonstrated early in the project that the off-gas containing RH2 could only be used as a fuel at this scale and that RH2 separation was not feasible. Furthermore, due to reductions in renewable energy tariffs and incentives, the AD plant build was put on hold for the duration of the project as it was no longer economically viable. An existing AD plant was therefore identified and the biogas upgrading unit was operated at this plant during a five-day biogas upgrading trial from 11th – 15th July 2016, to produce the required Biomethane feed (this is discussed fully in D6.1 Process Integration report). The biomethane was stored in high pressure cylinders and transported to the PlasCarb reactor where it was let down to provide the reactor feed. In line with WP7, a one- month pilot plant trial was then run to process this Biomethane thus produced, from 18th July – 19th August 2016 (this is reported in D7.1 report). The intent of the project, to operate an integrated system and run the PlasCarb reactor on biogas, was therefore realised despite the severe limitation of no AD plant operated by a project partner. The high pressure storage in effect provided the buffer tank that was part of the original scope. It was identified early in the project that the values quoted in WP7 for RPC and RH2 production rates were incorrect, and the correct theoretical values were given according to the mass balance.
The 12 kW PlasCarb reactor has 2 nozzles. Due to operational problems caused mainly by contaminated biomethane storage cylinders, only one nozzle was operational for much of the trial period. To prove continuous operation on both nozzles once problems were resolved, the PlasCarb reactor was run continuously and without any downtime for an additional week in September 2016).
The WP7 trial plan was for the reactor to be operated continuously for 8 hours a day, then the system purged and shut-down overnight due to manning and safety issues. Once the PlasCarbon collection pot was purged and cooled, it was isolated from the reactor vessel by means of a gate valve; the pot was then removed to a safe location for sealed emptying under local extraction. A second, empty pot was attached and the gate valve opened; the reactor was then ready to be brought back on line for the following day’s operation.
The main findings from the trial were:
• Each nozzle produced approx. 100 g/h for a total of up to 200 g/h of Renewable PlasCarb material.
• Gaseous products such as hydrogen were burnt during the trial due to the very low flowrates precluding beneficial use. A desktop purification study has been completed as part of WP4 for potential separation and storage for the use of gaseous products on a larger scale.
• The results of the pilot trial are a very powerful proof-of-concept for the feasibility of the PlasCarb project’s technology operating on biomethane.
• To begin with there were some commissioning problems. In particular, three weeks of commissioning issues occurred due to:
▪ Flow fluctuations due to contamination of flow controllers
▪ Damage to reactors caused by flow fluctuations
▪ Stoppage of auxiliary equipment
• Fourth week had four straight days running the reactor for 8 hours per day.
• Flow fluctuations reappeared in final week and again caused damage to reactor.
• Final day of trial, both nozzles on reactor ran for 5 hours before having to stop due to an auxiliary equipment error not related to reactor and previous operational issues.
• Main issue with operating reactor initially was related to flow fluctuations due to contaminated flow controllers, due to contamination within the high pressure cylinders. Once identified, this issue was resolved, after which the reactor ran on both nozzles ran with minimal issues.
• Operation of reactor is now fairly simple and requires little operator intervention during production.
• 7.8 kg of carbon were produced at the end of the trial period, the amount produced was lower because of the challenge of undertaking the trial with bio-derived methane in the absence of the AD plant within the consortium, because of the changes already identified considerable effort was put in place, finding a source of gas, procuring the gas purification at the scale required, undertaking design, safety and scheduling exercises to bring the activity to a successful conclusion on time. Much staff time was required to ensure this success.
This corresponded to an average yield 106.3 g/h from one nozzle.
Main achievements specific to the trial and project include:
- Successful removal of impurities from the Biogas ie H2S
- Purification of the biogas
- Process integration including the development of a design pack (general assembly layout, Process Flow Diagrams (PFD's), Process control mass balance. Process & Instrumentation Diagrams (P&ID), Aspen process modelling.
- Hazard & Operation (HAZOP) studies including risk assessments, Method statements.
- Pilot trial report which included CAPEX and OPEX finance models (see Deliverables D6.1 7.1 and 7.2 together with WP8 deliverables)
- Class B front end engineering design report.
In terms of the size of the Plasma technology (12kW, 75kW, 100kW) from a CAPEX and OPEX perspective this was reviewed in D7.2 from this the CAPEX and OPEX required for the 12kW plasma reactor (which the project was carried out on) would be approximately £447K and £70K respectively. For more full scale plants these would be approximately: for 75kW £620K and £290K, for 100kW £1M and £380K. In terms of the optimum scale, this would clearly depend on the available biogas from AD and opportunities for the material in terms of applications, that said the highlighted CAPEX and OPEX cost will assist.
The generated material was subject to extensive research and industrial engineering by a number of the project partners CNRS, Abalonyx, CPI and CNS. One of the research outcomes is available as a published open access study by researchers of CNRS and CNS. RPC produced by the PlasCarb technology has promising properties in two aspects, namely (a) its added value for a range of industrial applications and (b) its environmental value and the contribution to a circular economy.
Sustainable production of Renewable Hydrogen (RH2)
The complexity of the mixture and nature of the non-H2 species in the off-gas results in a significant challenge in defining ways of producing pure H2 from it. A variant study was undertaken to identify the options for generating RH2 from the off-gas mixture, taking into account all the available processing/separation options currently available. From this, the most preferred technique of separating H2 from the off-gas was identified.
The technique identified as the best to apply to this separation challenge is that of Pressure Swing Adsorption (PSA), although gas reforming to simplify the gas composition and increase the concentration of H2 might also be applied. Sorbents can be obtained for all of the non-H2 components of the gas, whether reformed or otherwise, and a high purity of H2 can be achieved (>99.99%). However, at the 12kW scale of plasma reactor, the amount of H2 generated is below a level at which carrying out the separation is economically viable (see D4.2). Consequently, the separation investigations were terminated within the project, but it must be emphasized that a larger-scale operation might well lead to the opposite conclusion, that the RH2 generated would be an economical amount, and this process would be included in the overall flow sheet.
Added value for economy and industry
The qualitative characteristics of RPC were tested by CNRS and Abalonyx to estimate the substitution potential for similar market available carbon products such as carbon black (esp. acetylene black) and for state-of-the-art industrial applications. Physio-chemical characterisation, dispersibility and electric conductivity are the traits which were discovered to be strongly represented in RPC. These traits are at the same time essential for a range of applications in the industry.
The material produced by PlasCarb by the plasma- “PlasCarbon” broadly belongs to the group of graphene types produced in plasma processes, with the advantages and disadvantages related to material quality and scalability. However, the PlasCarb process is unique in the sense that it is different from other graphene materials, as the material properties can be tuned in different directions by adjusting reaction parameters.
Technological Assessment
A number of potential markets for high value graphitic forms of carbon as one of the main results of the PlasCarb process and has been identified and thoroughly scrutinised in conjunction with many of the PlasCarb partners (Abalonyx, GasPlas, CNRS, CPI, Geonardo). With a view on the potential exploitation opportunities for high value graphitic carbon, the following markets are listed and reviewed:
• Inks for 2D and 3D printing
• Electronics and Energy applications,
o Batteries
o Super- and ultra-capacitors
o H2-Storage
o Illumination / LED
o Sensors
• Polymers e.g. Composites and coatings
• Biomedical and Healthcare
• Catalysts e.g. filtration/separation, process catalysts
The electronics and energy segment are going to account for a significant upsurge in the demand for natural or synthetic graphite. Lithium-ion batteries require a large amount of high purity graphitic spherical graphite, which could be provided through RPC. As most high-tech appliances, equipment and electric vehicles use lithium-ion batteries and as the market for the latter is predicted to grow by 3 million vehicles by 2017, the importance of high value graphitic forms of carbon is going to increase immensely. Synthetic graphite embodies 60% of the global graphite market by tonnage and 90% of the total market by value, with the EU having the second biggest global share in demand.
Conductive inks and coatings
The conductive ink market is estimated to be worth $2.5 billion- $3 billion (€2.4-2.88 billion) per annum. The addressable market size of graphene in coating applications is over $3 billion (€2.88 billion) per annum
Stable aqueous dispersions of RPC were produced to formulate inks with narrow size distribution. The inks were formulated by the dispersion of RPC with water and an optimised surfactant. Additionally, it was possible to use the inks further to generate conductive membranes that exhibited properties within the range of carbon nanotube inks. Further optimisation of the generation of the conductive membranes could lead to products that may outperform established inks based on carbon allotropes.
Applications were identifies, namely for hand-writing and for inkjet printing which were tested on their practical functionality. The viscosity of the ink has been adjusted to give good results in both pens and inkjet cartridges.
Conductive inks can be applied in several industrial domains. Printed electronics (e.g. RFID-tags, antennas, sensors, displays, printed batteries, capacitors, photovoltaic and piezo electric materials) are a number of the major potential markets. Electronic smart packaging, consumer packaged units that have electronic functionality, is another market where conductive inks and coatings from PlasCarb could be taken up.
Conductive rubber composites
It is assumed that RPC of 0.1wt% is applied as nano-composite material in 10% of annual global carbon fibre products which would require 142,000 kg of RPC annually. With an assumed market value of €117.40 (£100) this would add to an annual revenue of approximately €16.7 million.
Conventionally, carbon black is used in the rubber industry to reinforce properties of polymers such as natural rubber. Due to the size of the graphitic nanocarbon particles in RPC this material is a promising alternative as conductive fillers in natural rubber as well as for functional materials. The properties of RPC in nanocomposites between natural rubber and RPC have been investigated. The aim of the investigation was to extend application possibilities of the composite material while maintaining low cost and high stability.
Tests showed that it was possible to prepare composites of natural rubber and RPC (see below) so that characteristics of both materials are preserved.
The investigations showed that one set of the composites prepared obtained well dispersed particles with increased mechanical properties. The other set of composites showed the formation of a network of particles with superior electrical properties. Overall, by adding RPC to natural rubber the resulting composite materials exhibit thermal, mechanical, electrical and piezo resistive properties superior in comparison to pure natural rubber.
Further research will continue in the fields of conductive rubber nanocomposites based on RPC with the aim to generate a market-ready product.
Extensive efforts were taken to disseminate the scientific findings using RPC for the creation of conductive nanocomposites. A presentation under the title "High Value Forms of Nanocarbon from Food Waste" was presented at the 5th Meeting of INCT Carbon Nanomaterials at the Federal University of Minas Gerais, Belo Horizonte, Brazil on the 19 November 2014. Rubbers and RPC-composite materials with different concentrations of RPC were exhibited at the PlasCarb industry seminars at the ANM2016 in Portugal and RWM2016 event in Birmingham UK and the use of RPC as fillers in conductive rubber is a topic of the doctoral dissertation of Katerina Kampioti, from CNRS.
45S5 Bioglass®-RPC composites
The global market for biomaterials used in orthopaedic applications was predicted to be $9.6 billion (€9.2 billion) for 2016. A product in bone tissue engineering (BTE) based on 3D scaffolds (45S5 Bioglass/RPC ink) could be placed in this commercial segment which takes up about 85% of the market share with further growth to be expected. With an assumption that 10 million operations per year worldwide would be carried out with the 3D scaffold (assumed value of $1000 per scaffold) this would represent a total value of $10 billion (€9.6 billion).
In regards to the fabrication of 3D printable inks, the global market for 3D printing has been estimated to be USD 7 billion (€6.7 billion) in 2016 and predicted to reach a total of USD 21 billion (€20.2 billion) in 2020. The market share for medicine is the largest within the 3D printing market with 25% followed by electronics (20%), consumer products/toys (20%) and automotive (10%).
This potential application of RPC contains the fabrication of three-dimensional porous structures called ‘scaffolds’ which provide the mechanical support during repair and regeneration of damaged or diseased bone. The research and testing conducted for this application has been published by a colleague from Abalonyx. Conventionally, scaffolds for bone tissue engineering are produced from ceramics but one important limitation is the intrinsic brittleness and the resulting inability for load-bearing applications. Abalonyx has prepared and tested 3D scaffolds based on 45S5 Bioglass® reinforced with RPC for bone tissue engineering to increase properties and usefulness of the Bioglass scaffolds.
3D porous scaffold produced by robocasting from A) 45S5 bioglass ink (ceramic based) and B) 45S5 bioglass/RPC ink
The investigation shows that RPC-induced scaffold possess improved mechanical properties in comparison to traditional ceramic based bioglass scaffolds. The addition of 1% RPC to the bioglass ink increased the compressive strength of the scaffold by 45% and its fracture toughness by 280%.
Electrodes for Batteries
The following assumption has been applied for batteries used in the electro-mobility sector. Assuming, that 6 million electric cars will be produced in 2020 and each car currently requires 265 kg of carbon for the batteries (currently in the form of graphite), this equates to 1.59 million tons. We assume that RPC replaces 10% of this graphite need (159 kt) and with an assumed market value of 17.82 € (15 GBP) per kg RPC this would result in a net revenue of €284.6 million in the electro car sector only.
A number of PlasCarb partners investigated the application of RPC in Li-ion Batteries and evaluated the possibility to substitute the therein conventionally used substance carbon black.
Two samples of purified RPC were tested as additive to LFP (Lithium iron phosphate)-cathodes for Li-ion batteries. The results of the test are publicly available on the PlasCarb webpage under the title “Test Report: Application of Renewable PlasCarbon in Batteries”. The cathodes were prepared with RPC and a solvent for two kinds of cathode binders PVDF and CMC, respectively.
The conclusion drawn from this test work was that the purified RPC was a potential alternative to carbon black for high carbon electrode formulations.
The electrochemical characterisation from the tests provided an insight into the functionality of the RPC in comparison to carbon black. However further research is still required to fully explore the potential of RPC.
Supercapacitors from conductive inks
The potential annual requirement of graphitic carbon in the field of supercapacitors is estimated at 16 kt. With an assumed market value of 17.82 € (15 GBP) per kg RPC for this application, the potential revenue could be ca. €285 million.
Supercapacitors are an emerging and very promising energy storage alternative to electrochemical batteries. Supercapacitors are superior to normal capacitors due to their high power density and high charge/discharge rates and are thus suitable for a wide range of commercial and industrial applications.
The chemical properties of carbon-based inks (especially high relative surface area of carbon nanoparticles) prove to be an asset to produce supercapacitors, resulting in a highly effective yet cheaper alternative to silver or polymer-based energy storage devices.
By using RPC-based inks for printing, it has been possible to produce and test supercapacitors on different surfaces such as A4 printing paper, (UV-ozone treated) PET and SiO2. The conductive RPC inks were prepared with a glycol to produce dispersions with different concentrations to be applied in cartridges of a Canon PIXMA IP7250 office ink jet printer.
The laboratory tests encompassed the printing of three different products: Electrical circuits on UV-ozone treated PET, in-plane supercapacitors with 4 micro-electrodes on office paper and a sandwich structure supercapacitor.
It has been shown that RPC-induced supercapacitors are well suited for a range of different applications in industrial scale. In-plane supercapacitors as printed devices on conventional paper contribute significantly to the aim of creating easy-to-recycle end-products. Sandwich structure supercapacitors from RPC-based ink have been shown to be functional also under bending influence which makes them suitable for flexible electronic devices. The conductive RPC-based ink employed in the test devices exhibits clear benefits regarding the sustainability and carbon footprint in comparison to conventionally used high-conductive silver nanoparticles. The supercapacitors developed and tested could be used for a range of different application possibilities such as smartphone chargers, flashlights or other devices which must rely on quickly accessible energy.
Addressable markets for supercapacitors based on PlasCarbon include the smartphone market, the electric car market, electric grid stabilisation and the recently popularized concept of a home off the Grid with Solar.
Electrocatalyst for fuel cell technology
RPC can be used to prepare composite materials with iron nanoparticles for the utilisation as electrocatalysts in two oxygen electrocatalysis reactions.
Fuel cells constitute a significant group of high-tech energy storage devices which require high performance on energy efficiency. Oxygen electrocatalysis has a dramatic influence on the energy efficiency of the fuel cell technology in regards to energy storage and conversion. Two important oxygen electrocatalysis reactions are: Oxygen reduction and Oxygen evolution reactions.
However, both reaction types have large kinetic limitations decreasing the energy efficiency. Although platinum would embody a great catalyst for electro-catalytic reactions, it is too expensive and scarce to be deemed viable. Earth-abundant catalysts, though technically promising, are still not researched enough to be widely deployed as they exhibit low intrinsic catalytic activity, chemical stability and limitations in mass transportation.
A promising option is the synergistic combination of nanomaterials with well-defined catalytically active particles. To this end, graphene seems to be an appropriate material that combines remarkable electronic properties with chemical stability.
Within the project RPC was used to produce a composite material consisting of nano-sized graphene sheets decorated with iron oxide nanoparticles.
Catalyst for Heterogeneous Catalysis
The economic potential of this application, the global catalyst market value was estimated to USD 16 billion (€15.4 billion) in 2012, where the largest share was assigned to chemical (40%), followed by refining (35%) and polymers (24%). These market calculations however, excluded environmental catalysts that are estimated to reach USD 6.4 billion (€6.2) in 2018 according to Transparency Market Research.
Catalysis is the substantial chemical process of accelerating the breaking or building of chemical bonds, essential for energy and resource efficiency. They facilitate chemical reactions from the starting material to the product. In our everyday life, catalysts enable the usage of automobiles, aircrafts and other motor-driven applications.
To switch from a fossil-based economy to a sustainable one, it is important to adapt catalysts accordingly. This could prove to be a difficult task in light of the highly specialised nature of industrial catalysts, based mainly on hydrocarbons. Renewable starting materials for catalysts are in contrast generated from feedstocks rich in oxygen and carbon. For the creation of catalysts from renewable feedstocks parameters such as energy efficiency the yield, the life time and the selectivity are important.
Two different concepts for exploiting catalysts in chemical processes are available: in homogeneous or heterogeneous phases.
Both concepts are widely used in the chemical industry but the homogeneous catalysis is more frequently applied in fine chemical synthesis or pharmacy whereas platform chemicals are produced predominantly using heterogeneous catalysis. The advantages of homogeneous catalysis are in general the yield and activity (high turnover numbers and high turnover frequency). In heterogeneous catalysis, the active material is compressed in pellets and is directly inserted in the chemical process.
Photoluminescence
The estimated market for optoelectronics was valued in USD 33 billion (€31.7 billion) in 2016 and it is estimated to reach USD 38 billion (€36.6 billion) by 2019.
Four different solutions and/or dispersions of RPC in organic and liquid media were prepared to carry out preliminary investigations of the photoluminescence behaviour (PL) of RPC. Subsequently, the four samples were characterised with absorption spectroscopy and atomic force microscopy (AFM) imaging.
It was found that RPC exhibits in liquid media strong blue photoluminescence which could be used in applications such as optoelectronics and biological labelling.
Potential Impact:
Potential/expected impact
Reducing landfill of food waste: The microwave plasma reactors as core part of the PlasCarb technology is operating on the feed stock food waste and is hence able to substantially decrease food wastage going to landfills.
Creation of new jobs and businesses. An adoption of the PlasCarb technology at conventional biogas sites across Europe would induce a boost in several sectors of the economy to adjust to a circular economy model.
Creation of new business streams at biogas sites. The PlasCarb technology could be applied either in a facility which is being new-built or as a bolt-on scheme in existing methane- or biogas producing plants e.g. AD plants.
Major contribution to various industries in the carbon nanoproducts and the hydrogen economy. The microwave plasma reactor was able to produce Renewable PlasCarbon (RPC) in significant quantities that possesses high-quality features and thus able to compete against conventional carbon nanoproducts (high grades of carbon black) on the market. RPC has been found to lead to efficient electrocatalytic activity for fuel cell technology (ORR, Oxygen reduction reaction) and water splitting (OER, Oxygen evolution reaction). Notably, the developed Fe/RPC composites are as efficient as Pt or Rh based commercial electocatalysts, while being made only of carbon Iron and oxygen. A patent has been filed and research is actively going on in CNRS partner to develop actual electrocatalysts. Likewise, awaiting further financing, sustainable supercapacitors, conductive rubbers and inks for printable electronics could be developed.
The dissemination activities of PlasCarb have been aimed at increasing the visibility of the project for the target groups, scientific communities in nanotechnology as well as industries and SMEs from waste management within the graphitic carbon and hydrogen economy. The project has seen effective dissemination activities over the entire duration of the project through both the proactive participation of all partners and the overview of dissemination tasks by the WP 10 leader Geonardo.
The beginning of the project was dedicated to develop dissemination strategies for continuous use throughout the rest of the project. The unique PlasCarb visual identity and the set of dissemination protocols (Power point protocols, poster templates, local email signatures, web usage specifications, newsletter) have been integral parts in establishing a strong presence of the project on international as well as local level from an early stage on.
The PlasCarb visual identity: The project logo and the graphical icons for Food Waste, Microwave Plasma Processing, Renewable Hydrogen and Renewable PlasCarbon.
As a way to increase the wider dissemination, the visual identity and the dissemination protocols were used by the partners of the consortium to present the work of the project as well as their specific topic areas at multiple locations. The PlasCarb webpage (www.plascarb.eu) and partner’s online networks were used to publish scientific and technological project results. The results were presented in the form of articles for special or general interest among the target groups, press release, newsletters, event announcements, downloadable general as well as specific material (http://www.plascarb.eu/downloads/) on-line applications such as the PlasCarb Viability Assessment (post project engagement portal) or the project video.
The PlasCarb webpage as dissemination medium for partner related and general project related information
PlasCarb produced a range of project information material which presents the development of the project over time. This served the partners as information material to be disseminated at physical events along with more specific, tailor made materials of the separate partner topic areas. The project information material encompasses the following:
• Project Flyers (Issue 1 and 2)
• Project Newsletters (Issues 1, 2 and 3)
• Project poster
• Project banner – ‘the PlasCarb process’
• PlasCarb pens, notepads and business cards
These materials were available in printed/produced version to equip all partners and allow them to appear on partner-related events with the PlasCarb visual identity and most up-to date project information. As many consortium partners have a strong presence on public events (academic, scientific, industrial, other media) they designed tailor-made content posters and presentations in the PlasCarb visual identity for suitable project presentations. A collection of the dissemination activities, articles and presentations of the PlasCarb consortium can be downloaded as Deliverable 10.7 Articles for Publication.
Moreover, two large dissemination events were conducted in the second half of the project with the participation and support of the entire project consortium. The events were organised as industry seminars to transfer the knowledge and information of the PlasCarb technology to the target groups, scientific and academic communities in nanotechnologies and industry and SMEs in waste management, graphitic carbon and hydrogen sectors. The two events the PlasCarb industry were co-organised was the ANM 2016 - 7th international conference on Advanced Nanomaterials, 25th - 27th July 2016, Aveiro, Portugal and the RWM 2016 - 13th - 15th September 2016, Birmingham, United Kingdom. A detailed description and results of the two events can be downloaded as Deliverable 10.6 Industry Seminars.
A Policy Brief has been established to inform the interested public about the main idea of PlasCarb and to advocate policy recommendations towards policy makers. The policy recommendations to enable a better implementation for PlasCarb on European scale lay mainly in the fields of waste legislations and reporting duties on national and regional scale as well as in eco-innovations and green market technologies.
The exploitation potential of the PlasCarb technology and its products has been tested and elaborated on by several consortium partners. GasPlas as the provider of the microwave plasma reactor applied in PlasCarb will seek further opportunities to exploit this technology on a commercial basis. The work of Abalonyx and CNRS has shown that one of the PlasCarb products, Renewable PlasCarbon, possesses unique properties as a “few-layer graphene” and thus applicable in a range of industrial applications. Some results which describe these properties and applications have been published and are available on the download section of the PlasCarb webpage. The PlasCarb technology has successfully carried out a proof of concept in the form of a one-month pilot test trial. Resulting from this and other achievements to-date shows that the PlasCarb consortium is seeking to exploit the technology on a commercial basis across Europe. Direct or indirect end-users as well as adopters of the technology are AD-plant operators, Investors in biotechnological engineering projects, industries with a need for graphene or graphitic carbon etc. The PlasCarb Viability Assessment is an easy to use application to provide people interested in PlasCarb from a business perspective with a preliminary viability assessment of the technology for a custom specified environment. The application is directly accessible on the project home page and a detailed description of the tool can be download a Deliverable 10.8.
List of Websites:
www.plascarb.eu
Mr Neville Slack
Neville.slack@uk-cpi.com
+44 7742413292
Estimated food waste in the EU27 in 2012 was approximately 89M tonnes p.a. (179kg per person), rising to 126M tonnes p.a. by 2020. This waste, w o u l d generate 170M tonnes of CO2 p.a. equivalent to 3% of all EU27 Greenhouse Gas (GHG) emissions, a n d is considered by the European Parliament to be an unsustainable resource waste. PlasCarb project (2013-2016) was a €3.8M initiative funded by EU’s FP7 Programme, using innovative technology to produce – EU identified critical and valuable products graphitic carbon and renewable hydrogen from food waste.
Most c a r b o n a n d hydrogen used by industry is from fossil derived sources, primarily imported into the EU from politically unstable or competitive regions. PlasCarb integrates technical innovation to promote future market uptake. Industry and research will collaborate to combine anaerobic digestion (AD), innovative low temperature microwave plasma processing and leading edge control of carbon morphology and purification.
During the first period of the project, a comprehensive year- long study was undertaken looking at the seasonal variations, composition and quality of Anaerobic Digestion (AD) biogas (CH4 and CO2) generated from mixed food waste this was extremely important for the plasma system. The plasma system was optimised for the processing of a range of potential bio gas compositions for the formation of high value carbon materials and RH2. A quantitative analysis and evaluation of the full sustainability, i.e. environmental, economic and social viability, of PlasCarb using the in the industry and academic accepted LCA approach started. Also the analysis and characterisation commenced to look at the morphology of the produced carbon generated by the PlasCarb plasma process.
For the second period of the project, the original intent of WP6 and WP7 was to design, build and trial an integrated process plant containing AD plant, biogas upgrading unit, buffer tank, PlasCarb reactor, Renewable PlasCarbon handling, and RH2 separation and storage unit, the latter only if economically feasible. It was demonstrated early in the project that the off-gas containing RH2 could only be used as a fuel at this scale and that RH2 separation was not feasible. Furthermore, due to reductions in UK renewable energy tariffs and incentives, the AD plant build was put on hold for the duration of the project as from an investors perspective it was no longer economically viable. An existing AD plant was therefore identified and the biogas upgrading unit was operated at this plant during a five-day biogas upgrading trial from 11th – 15th July 2016, to produce the required Biomethane feed. The biomethane was stored in high pressure cylinders and transported to the PlasCarb reactor where it was let down to provide the reactor feed. In line with WP7, a one- month pilot plant trial was then run to process this Biomethane thus produced, from 18th July – 19th August 2016. The intent of the project, to operate an integrated system and run the PlasCarb reactor on biogas, was therefore realised despite the severe limitation of no AD plant operated by a project partner. The high pressure storage in effect provided the buffer tank that was part of the original scope. It was identified early in the project that the values quoted in WP7 for RPC and RH2 production rates were incorrect, and the correct theoretical values were given according to the mass balance. From the production trial 7.8 kg of carbon were produced, the amount produced was lower because of the challenge of undertaking the trial with bio-derived methane in the absence of the AD plant within the consortium, because of the changes already identified considerable effort was put in place, finding a source of gas, procuring the gas purification at the scale required, undertaking design, safety and scheduling exercises to bring the activity to a successful conclusion on time. Much staff time was required to ensure this success.
Also throughout this period work continued on the Carbon morphology of the graphitic carbon produced via natural gas and bio-methane from food waste leading to a defined characterisation of the material important to identify the best possible end use applications for the material. A number of uses were identified including conductive inks, conductive rubbers, as a catalyst in processes and potentially within fuel Cell technology.
The quantitative analysis and evaluation of the full sustainability, environmental, economic and social viability, of PlasCarb using accepted Life Cycle Assessment (LCA) approach based on ISO 14040/14044 (2006) has continued and concluded. The main result was to confirm the sustainability of PlasCarb, also in comparison to the state of the art treatment technologies.
During this period an economic optimisation of the process/products was completed in order to assess the viability of the technology, gauge likely funding options, potential applications and to enable the future market uptake. Different CAPEX (capital expenditure) models were assessed together with the indicative OPEX (Operational Expenditure) costs and all potential realisable revenue streams. With this robust financial modeling at its core, a business model and assessment of market viability with an overall SWOT (Strength, Weakness, Opportunity and Threat) analysis was performed and for a number of different scenarios namely UK, Hungary and Germany.
The project went beyond the objectives and identified unique dissemination opportunities for maximizing the impact of the project results.
Project Context and Objectives:
PlasCarb was stimulated by a transnational consortium of R&D performing SME’s in partnership with specialist scientific resource, Life Cycle thinking experts, industrial customers and access to risk finance to facilitate future market uptake. The aim was to integrate commerce with research; transforming a widespread urban solid waste environmental problem into a sustainable source of significant economic added value (high value graphitic carbon and renewable hydrogen). The vast majority of carbon and hydrogen used today in industry are derived from fossil petroleum sources, the majority of which are imported into the EU from regions which are often politically unstable or competitive.
PlasCarb aim was to integrate an established technology (Anaerobic Digestion) with innovative, low temperature microwave plasma processing and leading edge control of Carbon Morphology and purification. This project extended beyond current Best Available Techniques (BAT) in the valorisation of food waste of anaerobic digestion to generate renewable energy; it transformed (and purified) the now bio-methane output from AD using an innovative low energy microwave plasma to split bio-methane into high value graphitic carbon and potentially renewable hydrogen, however within the course of the project it was identified that at the project output scale it was not commercially viable, that said at higher volumes this should be possible.
The quality and economic value of the carbon was subsequently maximised through the integration of research and industrial process engineering
The specific Work Package objectives include:
WP1 - Management: to manage the PlasCarb project consortium and co-ordinate project delivery. To ensure that all deliverables and milestones are met on time and to budget. Fulfil the formal reporting and administrative requirements out lined in the Grant Agreement.
WP2 – Biogas Generation: to generate representative biogas from an AD process with a feedstock rate of 1800 tonnes mixed food waste per annum, noting seasonal CH4:CO2 variations and impurity leves versus seasonal input variations over 12 month period. Assess and incorporate an economically viable process to remove trace impurities from biogas to less than 4ppm H2S and less than 6ppm in total. Define the biogas output from anaerobic digestion of representative food waste over a period of 12 months, noting variations in CH4:CO2 yields and purification requirements for input into microwave plasma process.
WP3- Plasma Process: Define and validate a microwave plasma process design for biogas generated from the anaerobic digestion of food waste from WP2. Optimise nozzle geometries and gas flows to enable optimal carbon formation in WP5 from biogas using a 12kW microwave plasma reactor. Investigate the use of pre-separated CO2 to enhance the carbon formation from the methane.
WP4-Gas solid separation: Define and validate gas/solid and gas/gas separation unit operations. Develop an optimal process to separate the combined carbon species and then the renewable hydrogen from any other gases present from the gas stream output from WP3.
WP5- Carbon Morphology: Develop a methodology whereby the appropriate size, shape and form of carbon generated by the integrated process. Desired form of carbon is graphitic rather than amorphous or glassy. The desired size and shape is that most appropriate to maximise the economic yield of graphitic carbon, both in the synthesis and the separation process. Will closely interact with WP3 and WP4.
WP6- Process Integration: Integrate and optimise the outputs of WP2-5. This involves the integration of the separate unit operations of process plant, along with appropriate process control. The control operations of the integrated plant will then be refined, to enable both local and remote monitoring and control. Integrate a working pilot scale PlasCarb plant including one AD unit processing 1800 tonnes per annum of mixed food waste and at least one 12kW microwave plasma reactor to process a proportion of the biogas generated.
WP7-Pilot Trials: Operate an integrated plant continuously for a period of at least one month transforming over 150 tonnes of mixed food waste into over 25 thousand m3 of biogas. Over 2400m3 of this biogas will then be transformed into over 240kg of RH2 and 700Kg of highly graphitic carbon, enabling economic validation to be undertaken as part of WP8 and demonstration to the research community, industry and the wider public in WP10. As highlighted in this final report together with the Period 2 report, the project was unable to use it's own AD plant due to political and financial issues and therefore biogas (biomethane) was sourced from another AD facility, purified and sent via cylinders to GasPlas (CNS) for processing into graphitic carbon.
WP8-Economic Optimisation: Optimise the project results and the economics of all aspects of the technology to enable future market uptake. The OPEX (operating expenditure), CAPEX (capital expenditure) and revenues (determined by end user techno-economic validation of the RH2 and graphitic carbon produced in WP7) to be validated. An optimal business deployment strategy (size and location) to be prepared. Financial mechanisms that can be applied to different regions of Europe will be selected. Preparation of an integrated financial and business package for wider deployment.
WP9-Sustainability: Verify the full environmental, economic and social viability of PlasCarb (WP2 to WP8) using a recognised Life Cycle Assessment (LCA) approach based on ISO 14040/44 (2006). Validate the net benefits compared with State of the Art (SoA) food waste management and sustainable material supply. To include an evaluation of the regional and political waste management strategies from across Europe. Verify the technology development as being Best Available Technology (BAT) using the EU Environmental Technology Verification pre-programme.
WP10-Exploitation & Dissemination: Protect project results and disseminate results for maximum impact. Project results protection to include the filing of at least one patent. Dissemination to include publicising project achievements via international industry seminars, scientific and technical papers, publications and conference proceedings and a dedicated open access web site. Project results to be publicised in over ten disclosures (presentations, publications, web sites). Dissemination activities to operate both during the project and for at least five years post-project, the monitoring of the economic and environmental impacts of the project achievements.
Project Results:
Main S&T results/foregrounds
Environmental value and circular economy contribution
Natural graphite is listed as one of 20 critical raw materials in the EU. The global demand for graphitic materials and carbon allotropes is fast growing i.e. the market demand carbon black is forecasted to increase to more than 15 million tonnes by 2022. Carbon black is to 99% sourced from fossil raw materials such as heavy aromatic oils by partial combustion processes (several forms of carbon black exist) or from light and medium aromatic oils or natural gas by thermal processes (e.g. acetylene black).
Renewable PlasCarbon (RPC) and potential market applications
The cracking of biomethane by microwave plasma yielded graphitic nano carbons (“Renewable PlasCarbon”) in turbostratic packing motif, comparable to those produced by the same process from Natural Gas. The quality of the generated graphitic nano carbon depends inversely on the carbon dioxide concentration applied during the plasma process. The PlasCarbon contains valuable graphitic domains plus amorphous parts which can be removed by heat treatment. For the various samples characterised, ca 12 % -15 % amorphous material can be removed that way. In the solid material, the graphitic domains of the samples are randomly oriented (turbostratic) with primary particles (“pucks”) in the range between 20-30 nm. However, stacked aggregates are up to the micrometer range. The bigger aggregates may be split apart and the most valuable part of the sample, the few layered graphene (FLG), may be isolated by means of aqueous dispersion followed by centrifugation. Here, the size calibrated dispersion is made of particles of ca 30-80 nm in lateral size and 3 nm in thickness. Raman spectroscopy on a statistical basis shows that edges and point defects actually represent most if not all of the defects, underlining the quality of these materials. Therefore, generating large quantities of sustainable graphitic nano carbons appear to be feasible and technologically relevant. Due to its intrinsic size and defined chemical structure, PlasCarbon may be used to formulate conductive inks with superior conductive properties, providing access to printable electronics. Therefore, these materials fit well between graphene and carbon black and constitute a promising and exciting alternative to established carbon blacks due to their well-defined nature, conductivity performances, and sustainability. PlasCarbon appears to be of high quality, similar to or better than previous graphitic materials characterised by CNRSThe material generated by the PlasCarb process can be classified as particles of graphitic nanocarbon (Renewable PlasCarbon, RPC). It can be classified to fit between graphene and carbon black. PlasCarb has developed a process chain to produce high value RPC from the renewable feedstock food waste, namely through the integration of innovative technologies such as Anaerobic Digestion, biogas upgrading and a cold microwave plasma process.
The original intent of WP6 and WP7 was to design, build and trial an integrated process plant containing AD plant, biogas upgrading unit, buffer tank, PlasCarb reactor, Renewable PlasCarbon handling, and RH2 separation and storage unit, the latter only if economically feasible. It was demonstrated early in the project that the off-gas containing RH2 could only be used as a fuel at this scale and that RH2 separation was not feasible. Furthermore, due to reductions in renewable energy tariffs and incentives, the AD plant build was put on hold for the duration of the project as it was no longer economically viable. An existing AD plant was therefore identified and the biogas upgrading unit was operated at this plant during a five-day biogas upgrading trial from 11th – 15th July 2016, to produce the required Biomethane feed (this is discussed fully in D6.1 Process Integration report). The biomethane was stored in high pressure cylinders and transported to the PlasCarb reactor where it was let down to provide the reactor feed. In line with WP7, a one- month pilot plant trial was then run to process this Biomethane thus produced, from 18th July – 19th August 2016 (this is reported in D7.1 report). The intent of the project, to operate an integrated system and run the PlasCarb reactor on biogas, was therefore realised despite the severe limitation of no AD plant operated by a project partner. The high pressure storage in effect provided the buffer tank that was part of the original scope. It was identified early in the project that the values quoted in WP7 for RPC and RH2 production rates were incorrect, and the correct theoretical values were given according to the mass balance.
The 12 kW PlasCarb reactor has 2 nozzles. Due to operational problems caused mainly by contaminated biomethane storage cylinders, only one nozzle was operational for much of the trial period. To prove continuous operation on both nozzles once problems were resolved, the PlasCarb reactor was run continuously and without any downtime for an additional week in September 2016).
The WP7 trial plan was for the reactor to be operated continuously for 8 hours a day, then the system purged and shut-down overnight due to manning and safety issues. Once the PlasCarbon collection pot was purged and cooled, it was isolated from the reactor vessel by means of a gate valve; the pot was then removed to a safe location for sealed emptying under local extraction. A second, empty pot was attached and the gate valve opened; the reactor was then ready to be brought back on line for the following day’s operation.
The main findings from the trial were:
• Each nozzle produced approx. 100 g/h for a total of up to 200 g/h of Renewable PlasCarb material.
• Gaseous products such as hydrogen were burnt during the trial due to the very low flowrates precluding beneficial use. A desktop purification study has been completed as part of WP4 for potential separation and storage for the use of gaseous products on a larger scale.
• The results of the pilot trial are a very powerful proof-of-concept for the feasibility of the PlasCarb project’s technology operating on biomethane.
• To begin with there were some commissioning problems. In particular, three weeks of commissioning issues occurred due to:
▪ Flow fluctuations due to contamination of flow controllers
▪ Damage to reactors caused by flow fluctuations
▪ Stoppage of auxiliary equipment
• Fourth week had four straight days running the reactor for 8 hours per day.
• Flow fluctuations reappeared in final week and again caused damage to reactor.
• Final day of trial, both nozzles on reactor ran for 5 hours before having to stop due to an auxiliary equipment error not related to reactor and previous operational issues.
• Main issue with operating reactor initially was related to flow fluctuations due to contaminated flow controllers, due to contamination within the high pressure cylinders. Once identified, this issue was resolved, after which the reactor ran on both nozzles ran with minimal issues.
• Operation of reactor is now fairly simple and requires little operator intervention during production.
• 7.8 kg of carbon were produced at the end of the trial period, the amount produced was lower because of the challenge of undertaking the trial with bio-derived methane in the absence of the AD plant within the consortium, because of the changes already identified considerable effort was put in place, finding a source of gas, procuring the gas purification at the scale required, undertaking design, safety and scheduling exercises to bring the activity to a successful conclusion on time. Much staff time was required to ensure this success.
This corresponded to an average yield 106.3 g/h from one nozzle.
Main achievements specific to the trial and project include:
- Successful removal of impurities from the Biogas ie H2S
- Purification of the biogas
- Process integration including the development of a design pack (general assembly layout, Process Flow Diagrams (PFD's), Process control mass balance. Process & Instrumentation Diagrams (P&ID), Aspen process modelling.
- Hazard & Operation (HAZOP) studies including risk assessments, Method statements.
- Pilot trial report which included CAPEX and OPEX finance models (see Deliverables D6.1 7.1 and 7.2 together with WP8 deliverables)
- Class B front end engineering design report.
In terms of the size of the Plasma technology (12kW, 75kW, 100kW) from a CAPEX and OPEX perspective this was reviewed in D7.2 from this the CAPEX and OPEX required for the 12kW plasma reactor (which the project was carried out on) would be approximately £447K and £70K respectively. For more full scale plants these would be approximately: for 75kW £620K and £290K, for 100kW £1M and £380K. In terms of the optimum scale, this would clearly depend on the available biogas from AD and opportunities for the material in terms of applications, that said the highlighted CAPEX and OPEX cost will assist.
The generated material was subject to extensive research and industrial engineering by a number of the project partners CNRS, Abalonyx, CPI and CNS. One of the research outcomes is available as a published open access study by researchers of CNRS and CNS. RPC produced by the PlasCarb technology has promising properties in two aspects, namely (a) its added value for a range of industrial applications and (b) its environmental value and the contribution to a circular economy.
Sustainable production of Renewable Hydrogen (RH2)
The complexity of the mixture and nature of the non-H2 species in the off-gas results in a significant challenge in defining ways of producing pure H2 from it. A variant study was undertaken to identify the options for generating RH2 from the off-gas mixture, taking into account all the available processing/separation options currently available. From this, the most preferred technique of separating H2 from the off-gas was identified.
The technique identified as the best to apply to this separation challenge is that of Pressure Swing Adsorption (PSA), although gas reforming to simplify the gas composition and increase the concentration of H2 might also be applied. Sorbents can be obtained for all of the non-H2 components of the gas, whether reformed or otherwise, and a high purity of H2 can be achieved (>99.99%). However, at the 12kW scale of plasma reactor, the amount of H2 generated is below a level at which carrying out the separation is economically viable (see D4.2). Consequently, the separation investigations were terminated within the project, but it must be emphasized that a larger-scale operation might well lead to the opposite conclusion, that the RH2 generated would be an economical amount, and this process would be included in the overall flow sheet.
Added value for economy and industry
The qualitative characteristics of RPC were tested by CNRS and Abalonyx to estimate the substitution potential for similar market available carbon products such as carbon black (esp. acetylene black) and for state-of-the-art industrial applications. Physio-chemical characterisation, dispersibility and electric conductivity are the traits which were discovered to be strongly represented in RPC. These traits are at the same time essential for a range of applications in the industry.
The material produced by PlasCarb by the plasma- “PlasCarbon” broadly belongs to the group of graphene types produced in plasma processes, with the advantages and disadvantages related to material quality and scalability. However, the PlasCarb process is unique in the sense that it is different from other graphene materials, as the material properties can be tuned in different directions by adjusting reaction parameters.
Technological Assessment
A number of potential markets for high value graphitic forms of carbon as one of the main results of the PlasCarb process and has been identified and thoroughly scrutinised in conjunction with many of the PlasCarb partners (Abalonyx, GasPlas, CNRS, CPI, Geonardo). With a view on the potential exploitation opportunities for high value graphitic carbon, the following markets are listed and reviewed:
• Inks for 2D and 3D printing
• Electronics and Energy applications,
o Batteries
o Super- and ultra-capacitors
o H2-Storage
o Illumination / LED
o Sensors
• Polymers e.g. Composites and coatings
• Biomedical and Healthcare
• Catalysts e.g. filtration/separation, process catalysts
The electronics and energy segment are going to account for a significant upsurge in the demand for natural or synthetic graphite. Lithium-ion batteries require a large amount of high purity graphitic spherical graphite, which could be provided through RPC. As most high-tech appliances, equipment and electric vehicles use lithium-ion batteries and as the market for the latter is predicted to grow by 3 million vehicles by 2017, the importance of high value graphitic forms of carbon is going to increase immensely. Synthetic graphite embodies 60% of the global graphite market by tonnage and 90% of the total market by value, with the EU having the second biggest global share in demand.
Conductive inks and coatings
The conductive ink market is estimated to be worth $2.5 billion- $3 billion (€2.4-2.88 billion) per annum. The addressable market size of graphene in coating applications is over $3 billion (€2.88 billion) per annum
Stable aqueous dispersions of RPC were produced to formulate inks with narrow size distribution. The inks were formulated by the dispersion of RPC with water and an optimised surfactant. Additionally, it was possible to use the inks further to generate conductive membranes that exhibited properties within the range of carbon nanotube inks. Further optimisation of the generation of the conductive membranes could lead to products that may outperform established inks based on carbon allotropes.
Applications were identifies, namely for hand-writing and for inkjet printing which were tested on their practical functionality. The viscosity of the ink has been adjusted to give good results in both pens and inkjet cartridges.
Conductive inks can be applied in several industrial domains. Printed electronics (e.g. RFID-tags, antennas, sensors, displays, printed batteries, capacitors, photovoltaic and piezo electric materials) are a number of the major potential markets. Electronic smart packaging, consumer packaged units that have electronic functionality, is another market where conductive inks and coatings from PlasCarb could be taken up.
Conductive rubber composites
It is assumed that RPC of 0.1wt% is applied as nano-composite material in 10% of annual global carbon fibre products which would require 142,000 kg of RPC annually. With an assumed market value of €117.40 (£100) this would add to an annual revenue of approximately €16.7 million.
Conventionally, carbon black is used in the rubber industry to reinforce properties of polymers such as natural rubber. Due to the size of the graphitic nanocarbon particles in RPC this material is a promising alternative as conductive fillers in natural rubber as well as for functional materials. The properties of RPC in nanocomposites between natural rubber and RPC have been investigated. The aim of the investigation was to extend application possibilities of the composite material while maintaining low cost and high stability.
Tests showed that it was possible to prepare composites of natural rubber and RPC (see below) so that characteristics of both materials are preserved.
The investigations showed that one set of the composites prepared obtained well dispersed particles with increased mechanical properties. The other set of composites showed the formation of a network of particles with superior electrical properties. Overall, by adding RPC to natural rubber the resulting composite materials exhibit thermal, mechanical, electrical and piezo resistive properties superior in comparison to pure natural rubber.
Further research will continue in the fields of conductive rubber nanocomposites based on RPC with the aim to generate a market-ready product.
Extensive efforts were taken to disseminate the scientific findings using RPC for the creation of conductive nanocomposites. A presentation under the title "High Value Forms of Nanocarbon from Food Waste" was presented at the 5th Meeting of INCT Carbon Nanomaterials at the Federal University of Minas Gerais, Belo Horizonte, Brazil on the 19 November 2014. Rubbers and RPC-composite materials with different concentrations of RPC were exhibited at the PlasCarb industry seminars at the ANM2016 in Portugal and RWM2016 event in Birmingham UK and the use of RPC as fillers in conductive rubber is a topic of the doctoral dissertation of Katerina Kampioti, from CNRS.
45S5 Bioglass®-RPC composites
The global market for biomaterials used in orthopaedic applications was predicted to be $9.6 billion (€9.2 billion) for 2016. A product in bone tissue engineering (BTE) based on 3D scaffolds (45S5 Bioglass/RPC ink) could be placed in this commercial segment which takes up about 85% of the market share with further growth to be expected. With an assumption that 10 million operations per year worldwide would be carried out with the 3D scaffold (assumed value of $1000 per scaffold) this would represent a total value of $10 billion (€9.6 billion).
In regards to the fabrication of 3D printable inks, the global market for 3D printing has been estimated to be USD 7 billion (€6.7 billion) in 2016 and predicted to reach a total of USD 21 billion (€20.2 billion) in 2020. The market share for medicine is the largest within the 3D printing market with 25% followed by electronics (20%), consumer products/toys (20%) and automotive (10%).
This potential application of RPC contains the fabrication of three-dimensional porous structures called ‘scaffolds’ which provide the mechanical support during repair and regeneration of damaged or diseased bone. The research and testing conducted for this application has been published by a colleague from Abalonyx. Conventionally, scaffolds for bone tissue engineering are produced from ceramics but one important limitation is the intrinsic brittleness and the resulting inability for load-bearing applications. Abalonyx has prepared and tested 3D scaffolds based on 45S5 Bioglass® reinforced with RPC for bone tissue engineering to increase properties and usefulness of the Bioglass scaffolds.
3D porous scaffold produced by robocasting from A) 45S5 bioglass ink (ceramic based) and B) 45S5 bioglass/RPC ink
The investigation shows that RPC-induced scaffold possess improved mechanical properties in comparison to traditional ceramic based bioglass scaffolds. The addition of 1% RPC to the bioglass ink increased the compressive strength of the scaffold by 45% and its fracture toughness by 280%.
Electrodes for Batteries
The following assumption has been applied for batteries used in the electro-mobility sector. Assuming, that 6 million electric cars will be produced in 2020 and each car currently requires 265 kg of carbon for the batteries (currently in the form of graphite), this equates to 1.59 million tons. We assume that RPC replaces 10% of this graphite need (159 kt) and with an assumed market value of 17.82 € (15 GBP) per kg RPC this would result in a net revenue of €284.6 million in the electro car sector only.
A number of PlasCarb partners investigated the application of RPC in Li-ion Batteries and evaluated the possibility to substitute the therein conventionally used substance carbon black.
Two samples of purified RPC were tested as additive to LFP (Lithium iron phosphate)-cathodes for Li-ion batteries. The results of the test are publicly available on the PlasCarb webpage under the title “Test Report: Application of Renewable PlasCarbon in Batteries”. The cathodes were prepared with RPC and a solvent for two kinds of cathode binders PVDF and CMC, respectively.
The conclusion drawn from this test work was that the purified RPC was a potential alternative to carbon black for high carbon electrode formulations.
The electrochemical characterisation from the tests provided an insight into the functionality of the RPC in comparison to carbon black. However further research is still required to fully explore the potential of RPC.
Supercapacitors from conductive inks
The potential annual requirement of graphitic carbon in the field of supercapacitors is estimated at 16 kt. With an assumed market value of 17.82 € (15 GBP) per kg RPC for this application, the potential revenue could be ca. €285 million.
Supercapacitors are an emerging and very promising energy storage alternative to electrochemical batteries. Supercapacitors are superior to normal capacitors due to their high power density and high charge/discharge rates and are thus suitable for a wide range of commercial and industrial applications.
The chemical properties of carbon-based inks (especially high relative surface area of carbon nanoparticles) prove to be an asset to produce supercapacitors, resulting in a highly effective yet cheaper alternative to silver or polymer-based energy storage devices.
By using RPC-based inks for printing, it has been possible to produce and test supercapacitors on different surfaces such as A4 printing paper, (UV-ozone treated) PET and SiO2. The conductive RPC inks were prepared with a glycol to produce dispersions with different concentrations to be applied in cartridges of a Canon PIXMA IP7250 office ink jet printer.
The laboratory tests encompassed the printing of three different products: Electrical circuits on UV-ozone treated PET, in-plane supercapacitors with 4 micro-electrodes on office paper and a sandwich structure supercapacitor.
It has been shown that RPC-induced supercapacitors are well suited for a range of different applications in industrial scale. In-plane supercapacitors as printed devices on conventional paper contribute significantly to the aim of creating easy-to-recycle end-products. Sandwich structure supercapacitors from RPC-based ink have been shown to be functional also under bending influence which makes them suitable for flexible electronic devices. The conductive RPC-based ink employed in the test devices exhibits clear benefits regarding the sustainability and carbon footprint in comparison to conventionally used high-conductive silver nanoparticles. The supercapacitors developed and tested could be used for a range of different application possibilities such as smartphone chargers, flashlights or other devices which must rely on quickly accessible energy.
Addressable markets for supercapacitors based on PlasCarbon include the smartphone market, the electric car market, electric grid stabilisation and the recently popularized concept of a home off the Grid with Solar.
Electrocatalyst for fuel cell technology
RPC can be used to prepare composite materials with iron nanoparticles for the utilisation as electrocatalysts in two oxygen electrocatalysis reactions.
Fuel cells constitute a significant group of high-tech energy storage devices which require high performance on energy efficiency. Oxygen electrocatalysis has a dramatic influence on the energy efficiency of the fuel cell technology in regards to energy storage and conversion. Two important oxygen electrocatalysis reactions are: Oxygen reduction and Oxygen evolution reactions.
However, both reaction types have large kinetic limitations decreasing the energy efficiency. Although platinum would embody a great catalyst for electro-catalytic reactions, it is too expensive and scarce to be deemed viable. Earth-abundant catalysts, though technically promising, are still not researched enough to be widely deployed as they exhibit low intrinsic catalytic activity, chemical stability and limitations in mass transportation.
A promising option is the synergistic combination of nanomaterials with well-defined catalytically active particles. To this end, graphene seems to be an appropriate material that combines remarkable electronic properties with chemical stability.
Within the project RPC was used to produce a composite material consisting of nano-sized graphene sheets decorated with iron oxide nanoparticles.
Catalyst for Heterogeneous Catalysis
The economic potential of this application, the global catalyst market value was estimated to USD 16 billion (€15.4 billion) in 2012, where the largest share was assigned to chemical (40%), followed by refining (35%) and polymers (24%). These market calculations however, excluded environmental catalysts that are estimated to reach USD 6.4 billion (€6.2) in 2018 according to Transparency Market Research.
Catalysis is the substantial chemical process of accelerating the breaking or building of chemical bonds, essential for energy and resource efficiency. They facilitate chemical reactions from the starting material to the product. In our everyday life, catalysts enable the usage of automobiles, aircrafts and other motor-driven applications.
To switch from a fossil-based economy to a sustainable one, it is important to adapt catalysts accordingly. This could prove to be a difficult task in light of the highly specialised nature of industrial catalysts, based mainly on hydrocarbons. Renewable starting materials for catalysts are in contrast generated from feedstocks rich in oxygen and carbon. For the creation of catalysts from renewable feedstocks parameters such as energy efficiency the yield, the life time and the selectivity are important.
Two different concepts for exploiting catalysts in chemical processes are available: in homogeneous or heterogeneous phases.
Both concepts are widely used in the chemical industry but the homogeneous catalysis is more frequently applied in fine chemical synthesis or pharmacy whereas platform chemicals are produced predominantly using heterogeneous catalysis. The advantages of homogeneous catalysis are in general the yield and activity (high turnover numbers and high turnover frequency). In heterogeneous catalysis, the active material is compressed in pellets and is directly inserted in the chemical process.
Photoluminescence
The estimated market for optoelectronics was valued in USD 33 billion (€31.7 billion) in 2016 and it is estimated to reach USD 38 billion (€36.6 billion) by 2019.
Four different solutions and/or dispersions of RPC in organic and liquid media were prepared to carry out preliminary investigations of the photoluminescence behaviour (PL) of RPC. Subsequently, the four samples were characterised with absorption spectroscopy and atomic force microscopy (AFM) imaging.
It was found that RPC exhibits in liquid media strong blue photoluminescence which could be used in applications such as optoelectronics and biological labelling.
Potential Impact:
Potential/expected impact
Reducing landfill of food waste: The microwave plasma reactors as core part of the PlasCarb technology is operating on the feed stock food waste and is hence able to substantially decrease food wastage going to landfills.
Creation of new jobs and businesses. An adoption of the PlasCarb technology at conventional biogas sites across Europe would induce a boost in several sectors of the economy to adjust to a circular economy model.
Creation of new business streams at biogas sites. The PlasCarb technology could be applied either in a facility which is being new-built or as a bolt-on scheme in existing methane- or biogas producing plants e.g. AD plants.
Major contribution to various industries in the carbon nanoproducts and the hydrogen economy. The microwave plasma reactor was able to produce Renewable PlasCarbon (RPC) in significant quantities that possesses high-quality features and thus able to compete against conventional carbon nanoproducts (high grades of carbon black) on the market. RPC has been found to lead to efficient electrocatalytic activity for fuel cell technology (ORR, Oxygen reduction reaction) and water splitting (OER, Oxygen evolution reaction). Notably, the developed Fe/RPC composites are as efficient as Pt or Rh based commercial electocatalysts, while being made only of carbon Iron and oxygen. A patent has been filed and research is actively going on in CNRS partner to develop actual electrocatalysts. Likewise, awaiting further financing, sustainable supercapacitors, conductive rubbers and inks for printable electronics could be developed.
The dissemination activities of PlasCarb have been aimed at increasing the visibility of the project for the target groups, scientific communities in nanotechnology as well as industries and SMEs from waste management within the graphitic carbon and hydrogen economy. The project has seen effective dissemination activities over the entire duration of the project through both the proactive participation of all partners and the overview of dissemination tasks by the WP 10 leader Geonardo.
The beginning of the project was dedicated to develop dissemination strategies for continuous use throughout the rest of the project. The unique PlasCarb visual identity and the set of dissemination protocols (Power point protocols, poster templates, local email signatures, web usage specifications, newsletter) have been integral parts in establishing a strong presence of the project on international as well as local level from an early stage on.
The PlasCarb visual identity: The project logo and the graphical icons for Food Waste, Microwave Plasma Processing, Renewable Hydrogen and Renewable PlasCarbon.
As a way to increase the wider dissemination, the visual identity and the dissemination protocols were used by the partners of the consortium to present the work of the project as well as their specific topic areas at multiple locations. The PlasCarb webpage (www.plascarb.eu) and partner’s online networks were used to publish scientific and technological project results. The results were presented in the form of articles for special or general interest among the target groups, press release, newsletters, event announcements, downloadable general as well as specific material (http://www.plascarb.eu/downloads/) on-line applications such as the PlasCarb Viability Assessment (post project engagement portal) or the project video.
The PlasCarb webpage as dissemination medium for partner related and general project related information
PlasCarb produced a range of project information material which presents the development of the project over time. This served the partners as information material to be disseminated at physical events along with more specific, tailor made materials of the separate partner topic areas. The project information material encompasses the following:
• Project Flyers (Issue 1 and 2)
• Project Newsletters (Issues 1, 2 and 3)
• Project poster
• Project banner – ‘the PlasCarb process’
• PlasCarb pens, notepads and business cards
These materials were available in printed/produced version to equip all partners and allow them to appear on partner-related events with the PlasCarb visual identity and most up-to date project information. As many consortium partners have a strong presence on public events (academic, scientific, industrial, other media) they designed tailor-made content posters and presentations in the PlasCarb visual identity for suitable project presentations. A collection of the dissemination activities, articles and presentations of the PlasCarb consortium can be downloaded as Deliverable 10.7 Articles for Publication.
Moreover, two large dissemination events were conducted in the second half of the project with the participation and support of the entire project consortium. The events were organised as industry seminars to transfer the knowledge and information of the PlasCarb technology to the target groups, scientific and academic communities in nanotechnologies and industry and SMEs in waste management, graphitic carbon and hydrogen sectors. The two events the PlasCarb industry were co-organised was the ANM 2016 - 7th international conference on Advanced Nanomaterials, 25th - 27th July 2016, Aveiro, Portugal and the RWM 2016 - 13th - 15th September 2016, Birmingham, United Kingdom. A detailed description and results of the two events can be downloaded as Deliverable 10.6 Industry Seminars.
A Policy Brief has been established to inform the interested public about the main idea of PlasCarb and to advocate policy recommendations towards policy makers. The policy recommendations to enable a better implementation for PlasCarb on European scale lay mainly in the fields of waste legislations and reporting duties on national and regional scale as well as in eco-innovations and green market technologies.
The exploitation potential of the PlasCarb technology and its products has been tested and elaborated on by several consortium partners. GasPlas as the provider of the microwave plasma reactor applied in PlasCarb will seek further opportunities to exploit this technology on a commercial basis. The work of Abalonyx and CNRS has shown that one of the PlasCarb products, Renewable PlasCarbon, possesses unique properties as a “few-layer graphene” and thus applicable in a range of industrial applications. Some results which describe these properties and applications have been published and are available on the download section of the PlasCarb webpage. The PlasCarb technology has successfully carried out a proof of concept in the form of a one-month pilot test trial. Resulting from this and other achievements to-date shows that the PlasCarb consortium is seeking to exploit the technology on a commercial basis across Europe. Direct or indirect end-users as well as adopters of the technology are AD-plant operators, Investors in biotechnological engineering projects, industries with a need for graphene or graphitic carbon etc. The PlasCarb Viability Assessment is an easy to use application to provide people interested in PlasCarb from a business perspective with a preliminary viability assessment of the technology for a custom specified environment. The application is directly accessible on the project home page and a detailed description of the tool can be download a Deliverable 10.8.
List of Websites:
www.plascarb.eu
Mr Neville Slack
Neville.slack@uk-cpi.com
+44 7742413292