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Towards a green strategy for materials recycling. Two focusing domains: high added materials & CO2 for innovative applications

Green strategy for material recycling opens the way for circular economy and news industrial processes; however, the pillars of this challenge are the strategic materials, the carbon cycle and the water consumption.

Scope

One of the new challenge is to develop circular economy for each kind of materials, however we can distinguish the byproducts of the process from the mine to the elaborated material and the deconstruction of each kind of product at the end of its life.

Generally in a thermodynamic strategy we speak of enthalpy and entropy, the second one take into account the mass balance and the energy balance of the byproducts and permit an optimization of the process.

Today we mix to kind of proposals the mass balance with the material recycling and the byproducts, and the energy balance with the carbon energy efficiency that is why the question of the carbon content seems to be a strategic parameter to evaluate each kind of process.

However, the question of the carbon taxes (ETS) through the international trading system is the hidden parameter of the black box. For the waste treatment without international references in the stock exchange, and an anarchic environmental rules any kind of economical simulation processes does not take care of the waste treatment and the carbon emission. The economic optimization as we see around the world consist of Stockpiling waste for the next generation.

If we modify the paradigm and qualify the waste as a field of raw materials or a storage of energy we can open a new engineering research strategy and develop new education proposals.

In front of us we have the recycling of electronic materials from computers, mobile phones, the recycling of batteries, the recycling of rubber from tires, the recycling of rare earths from magnets, the polymers recycling, the zinc and copper from electronic hardware. But today we have no rules for an industrial recycling with specific processes which probably need more dry techniques, including innovative approaches, to replace wet dirty processes.

One of the question behind the recycling and the mineral extraction is the amount of waste produces during the treatment. But e-waste recycling creates new opportunities, as the waste provides a higher concentration of metals higher than in the mined ore. However waste is also mixed with other materials and compounds so new processes are needed and new co-products could also be generated, which could be harnessed under well-defined recycling pathways.

To open a new symposium we can suggest two main ways one about a critical value-added material and a second one about carbon dioxide emission from the processes but in every case we have to point out the byproducts and the water consumption.

At the same time we have to point out the environmental risks of waste transformations into value-added materials which are more complex than the usual materials. Because some mixtures contain a variety of materials with many possible outcomes and need specific rules or new processes and open the question of new researches, new industrial techniques, which are the goal of a more safe and sustainable world.

Today waste or end-of-life products from many industries and other sources could reach those countries were the environmental rules and the human risks are not taken into account, and in doing this through unfortunate circumstances way we produce geopolitical conflicts, water pollution and toxic air emissions.

Under the umbrella of UNESCO for the education and the ONU for the international trade it seems that an international agreement is needed to manage recycling, waste treatment and circular economy needed with an increasing world population.

Hot topics to be covered by the symposium

  • First balance of the main waste material production including the carbon ones
  • Management tools for the waste control for materials (toxicity, time life, European directives)
  • Waste transformations and material recycling for electronic, batteries, glasses, polymers, magnets and harmful materials to regenerate valuable materials and develop new technologies for selective synthesis of materials from waste through microrecycling.
  • Bacteria processes for new extraction from deep field and carbon loop
  • Innovative processes for turbine efficiency
  • Circular economy and waste: how to manage the new wastes, and build on the new science of microrecycling

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General introduction of the meeting and workshop program : J. Amouroux (E-MRS) & A. Igartua (EUMAT)
08:30
Authors : Jacques Amouroux
Affiliations : E-MRS/UPMC

Resume : Material recycling and circular economy seem to be the two sides of a main strategy: how to decrease the waste byproducts and the carbon dioxide emission. The first step of this new challenge is to develop recycling in order to give an added value to many materials from waste treatment and develop innovation processes with a green chemical engineering. The second step is to control the byproducts production, the energy efficiency and the water consumption including some very toxic products which need a specific treatment, the final balance in carbon dioxide gives us a new tool for the best choice in term of economic investment and environmental management. In the goal of material recycling the challenge is much more complex than expected because the complexity of multilayer materials such as in microelectronic, in optic for antireflective properties such as in photovoltaic layers or complex multifiber composites for wind turbine etc… the deconstruction and the recycling model are far away than the usual chemical engineering knowledge ;the cost or the acid byproducts are worse than the waste storage The goal of rare earth recycling, main metal recycling, and the environmental rules point out our difficulties in front of the COP 21 and the energy requires to do that, the waste management, the water control and the carbon dioxide finger print are a very complex equation for our future of chemical engineering processes.

O.0.1
 
Scientific presentations on material recycling : Jacques Amouroux
08:50
Authors : Jean Pierre Massué
Affiliations : -

Resume : In promoting the purchase of recyclables, the recent efforts of private companies and public interest groups deliberately challenge several recycling myths. Myth 1: Recycled products cost too much. Myth 2: The quality of recycled products is bad. Myth 3: Recycled products aren’t available when you need them. The ethical approach consists in rethinking the architecture by including in urban planning places of recycling and storage in accordance with the populations . It is therefore a political action which must be associated with strong educational initiatives. The legal recognition of landscape and the cultural heritage implies ethical considerations, rights and responsibilities on the part of all institutions,industries and citizens of Europe towards their physical surroundings in the context of a circular economy Society. We need to take into consideration the ethical and legal recognition of the importance of landscape, the cultural heritage and the environment implies rights and responsibilities.

O.1.1
09:10
Authors : Koji Hashimoto
Affiliations : Institute for Materials Research, Tohoku University, Sendai, Japan

Resume : tba

O.1.2
09:40
Authors : Claude Degueldre
Affiliations : Engineering Department, Lancaster University, UK

Resume : Nuclear energy as applied with the ‘once and out’ half nuclear fuel cycle for electricity production can reach a ERoI factor of about 100 when applied during a 5 year irradiation in a Light Water Reactor (LWR). This is an excellent yield compared to the other energy vector conversions. Nuclear circular economy becomes reality when dissolving the spent fuel and reprocessing it. Actually by applying separations not only the non-used fissile uranium can be directly recycled, but also plutonium can be reused in the form of uranium – plutonium mixed oxides. This is done since about 50 years. In addition if recent a study has proved at fission products are difficult to be reused as inactive elements some other long-live radioactive elements such as technetium could be extracted and reused for medical application. Now, the use of fuel cycles through molten salt reactors (MSR), with their potential on-line reprocessing allows better neutronic economy compared to LWR’s. With MSR’s the in-line separation of fission product isotopes becomes so fast that short-live radionuclides can be extracted and used as useful isotopes in medicine and industry. As an example radio-xenon can be produced and used for lung diagnostic and therapy.

O.1.3
10:00 Coffee break    
10:20
Authors : Christian Thomas
Affiliations : Terra Nova Development, France

Resume : tba

O.1.4
10:40
Authors : Blet V., Miguirditchian M., Penet F., Bouyer E.
Affiliations : Blet V.; CEA, DEN, DMRC, F30207 Bagnols sur Cèze cedex, France Miguirditchian M.; CEA, DEN, DMRC, F30207 Bagnols sur Cèze cedex, France Penet F.;CEA, DRT, SBEM, F 38054 Grenoble Cedex 9, France Bouyer E.;CEA, DRT, LITEN, F 38054 Grenoble Cedex 9, France

Resume : For a decade, rare earth elements (REEs) have been recognized by the European Commission as highly critical metals for European industry. Despite their importance, only a few companies in Europe produce and recycle REEs, and in particular NdFeB permanent magnets that represent the main segment. Today, China largely controls the entire REEs value chain, from the extraction of REE to magnet production. Nevertheless, in the face of mounting health-related issues, environmental considerations are becoming more and more stringent for China’s extraction industry thus potentially leading to risk of price increases or/and supply of REEs. In that context, CEA is looking to develop innovative and eco-friendly recycling REEs processes, either based on a direct remanufacturing of new permanent magnets incorporating up to 30% by weight of recycled NdFeB material, or based on a patented process to recover separated REEs before remanufacturing. The economic viability of these two complementary routes will essentially depend on the accessible volume of used magnets, which itself will depend on the lifespans of magnets in circulation in different end-uses, and on the cost and technical performance of collection and dismantling. Worth noting is that this viability will also depend on the progress in substitution of REEs and finally in political incentive . This example highlights the importance of strategic market analysis (or economic intelligence) prior to any process development in the raw material sector.

O.1.5
11:00
Authors : Frederic Rousseau∗; Jonathan Cramer*; Frederic Prima*;Daniel Morvan*; Alice Bizouard+
Affiliations : ∗ Chimie ParisTech, Institut de Recherche de Chimie Paris, Paris Sciences et Lettres University, Paris, 75006, France. Email: frederic.rousseau@chimie-paristech.fr + Eco-systèmes, Direction Technique, Courbevoie, 92400, France.

Resume : The technological revolution of recent decades has profoundly reshaped society and electronic devices are now widely used throughout the world. The production of primary resources sometimes strives to meet the growing demand for electronic devices, and to demonstrate industrial responsiveness. New recycling processes are therefore needed to address this supply risk. The aim of this doctoral project is to study the potential offered by the plasma chemistry in order to selectively extract critical elements contained in a metal matrix made from electronic waste. Thus, an experimental study was conducted on matrices of typical "printed circuit board" compositions to show the contribution of plasma for elementary pyrometallurgical extraction operations. In parallel, a theoretical study using simulation tools increased the level of understanding in order to optimize the process. By combining these two approaches, it was possible to process CuSn26wt%. binary matrices under oxidizing atmosphere to extract Sn with high selectivity (>90%). An extraction mechanism to calculate kinetic parameters has also been proposed. Indium could also be extracted from CuSn26wt%. + In matrices (150 ppm.) and recovered with a concentration enrichment factor ranging from 30 to 400. Finally, tantalum capacitors were pyrolyzed and thermochemically treated by the plasma in order to recover tantalum at high purity (>99%) in a dry process.

O.1.6
11:20
Authors : Bartosz Michalski, Mateusz Szymański, Katarzyna Wiercińska, Marcin Leonowicz
Affiliations : Warsaw University of Technology, Faculty of Materials Science and Engineering, 141 Woloska St., 02-507 Warsaw, Poland

Resume : Waste, sintered, neodymium-iron-boron magnets can be considered as a secondary ore of the rare earth metals. The scrap magnets can succesfully be recycled into new, polymer bonded magnets, by Hydrogen Decrepitation (HD) followed by dehydrogenation and further binding with polymer. The NdFeB powder particles, obtained as a result of the hydrogen treatment, are however of flake-like shape and thus hinder injection moulding process by increasing viscosity of the polymer-based mixture. Ball milling was tested to modify the size, shape and properties of the recycled powders. It was found that shorter milling times as well as smaller ball/powder mass ratio are beneficial for improving of the magnetic properties of the powders. Further studies are carried out to investigate morphology of the powders and viscosity of the polymer-based mixture.

O.1.7
11:40
Authors : T.DEGABRIEL, G. LEFEVRE
Affiliations : Institut de Recherche de Chimie Paris, CNRS−Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005 Paris, France

Resume : New technologies as electronic devices (capacitors), green energy (turbines), super-alloys (aerospace) and medical implants depend on refractory metals. At the end of their life, the recycling of refractory metals oxides contained in these products is facing to two problems: - current processes to extract and purify metals from wastes use various strong acids (as hydrofluoric acid) as well as organic solvents, so effluent and final waste are chemically problematic, - e-wastes and scraps are low-grade materials, consequently recycling is not economically viable. In order to provide a sustainable circular economy from e-wastes and scraps we propose a new and ecofriendly process of recycling refractory metals. Our method is based on the layered double hydroxide (LDH) abilities to provide anionic exchange with highly charged anionic species. Indeed, refractory metals form polyoxometallates (POMs) which are highly negative charged species, thus, by using LDH we are able to extract and release selectively refractory metals. Results were obtained for the WEEEs treatment, and the totality of tantalum contained in the e-waste samples was found to be recovered by the LDH process. Moreover, this process has several advantages: it is non-toxic and ecological friendly, based on cheap chemicals, does not generate problematic effluents or wastes (no concentrated acid or base), selective, and allowing to treat low concentrated scraps or ores (which is not valuable in the classic industrial process).

O.1.8
12:00
Authors : Emmanuel Billy, Julie Andrez, Adrien Boulineau
Affiliations : Université Grenoble Alpes, F-38000 Grenoble, France and CEA,LITEN, F-38054 Grenoble, France

Resume : The Li-Ion battery (LiB) market is currently growing strongly due to new applications mainly related to the emergence and development of all-electric vehicles. LiBs composition varies from one technology to another, depending on their application. Complex transition metal oxides are currently the main cathode active materials used in Li-ion battery cells. The electric revolution happening in many sectors and the environmental urgency impose to recycle the LiBs with sustainable recycling processes and aspire to close the loop for resource circulation. Currently there are different recycling strategies to recover the valuable metals from a mixed LiB feed.[1-4] The major industrial goal is to treat a mix of spent LiBs as a secondary feed with new precursors for battery active material production. The initial step consists in dismantling the LiBs, before a deactivation step to prevent fires caused by reactive elemental Li oxidation with air and water. Many industrial processes as Umicore, Snam, Sony-Sumitomo, Accurec, Inmetco, Glencore (formerly Xstrata) use a thermal treatment. Another approach, used by Retriev technologies (formerly Toxco Inc.), is a cryogenic cooling to control the reactivity of lithium. The third category of process, used by industrials such as Recupyl, Akkuser, Battrec and AEA Technology, consists in opening the cells under an oxygen and water controlled atmosphere with specific technology according to the process. In view to develop a sustainable approach, we have to consider a representative black mass in terms of nature and structure of material. It involves to consider a mix of cathodes, and a black mass subjected and non-subjected to a thermal pretreatment. These considerations affect strongly the chemistry and thus, the sustainability of the process. As recently mentioned in a critical review,[5] significant work still needs to be done to guide the selection of leaching reagent and operating conditions. Providing insight into the reaction mechanism during the leaching will be, thus, very helpful. This study aims a better understanding of the impact of the thermal pre-treatment and the effect of the cathode mixing on both the leaching and the elimination steps. In order to reach this goal, we first study and compare the dissolution mechanisms involved during the leaching of pristine LFP/NMC materials and pre-treated mixed cathode material. We will then focus on the elimination step considering the pre-treatment influence, regarding the economic and environmental aspects.. 1. Sonoc, A., J. Jeswiet, and V.K. Soo, Opportunities to Improve Recycling of Automotive Lithium Ion Batteries. Procedia CIRP, 2015. 29: p. 752-757. 2. Valio, J., Critical review on Li ion battery recycling technologies, in Chemical Engineering2017, Aalto University. 3. Ekberg, C. and M. Petranikova, Chapter 7 - Lithium Batteries Recycling, in Lithium Process Chemistry, A. Chagnes and J. Światowska, Editors. 2015, Elsevier: Amsterdam. p. 233-267. 4. Winslow, K.M., S.J. Laux, and T.G. Townsend, A review on the growing concern and potential management strategies of waste lithium-ion batteries. Resources, Conservation and Recycling, 2018. 129: p. 263-277. 5. Lv, W., et al., A Critical Review and Analysis on the Recycling of Spent Lithium-Ion Batteries. ACS Sustainable Chemistry & Engineering, 2018. 6(2): p. 1504-1521.

O.1.9
12:20 ROUND TABLE: materials recycling and circular economy: challenges    
12:20
Authors : Florian Sauer, Bum-Ki Choi, Gesa Beck
Affiliations : Mairec Eedelmetallgesellschaft mbH; Fraunhofer Applied Research Center for Resource Efficiency, Germany

Resume : tba

O.1.10
12:40 LUNCH    
14:00 General introduction: Jacques Amouroux - Amaya Igartua    
 
Workshop EUMAT strategy in the materials area in Europe : Amaya Igartua
14:20
Authors : Jarosław Piekarski
Affiliations : Krajowy Punkt Kontaktowy Programów Badawczych Unii Europejskiej ul. Wawelska 14 02-061 Warszawa

Resume : tba

O.2.1
14:40
Authors : Jean-François Renault
Affiliations : Forschungszentrum Jülich

Resume : tba

O.2.2
15:00
Authors : Roland Gauss
Affiliations : EIT Raw Materials

Resume : tba

O.2.3
15:20
Authors : Jan Meneve
Affiliations : EUMAT responsible of working group on materials for the circular economy

Resume : tba

O.2.4
15:40
Authors : Amaya Igartua
Affiliations : Fundación TEKNIKER, PARKE TEKNOLOGIKOA, C/ Iñaki Goenaga, 5 - 20600 Eibar, Gipuzkoa (Spain)

Resume : tba

O.2.5
16:00
Authors : Anne Chloe Devic
Affiliations : REPSOL SA, Spain

Resume : tba

O.2.6
16:20 Coffee break    
16:40
Authors : Gilles Dennler
Affiliations : CT-IPC, France

Resume : tba

O.2.7
17:00 Perspectives for green strategic collaborations and innovative recycling proposals in Europe (Possibility to present Pitch for project ideas, 5 minutes presentation, reception deadline 10th September, amaya.igartua@tekniker.es)    
17:25 Education strategy for materials recycling - Ecole des Mines - Paris Tech - PSL    
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09:30 PLENARY SESSION    
12:30 Lunch    
 
Scientific presentations on material recycling II : Jacques Amouroux
14:00
Authors : Jacques Amouroux, Koji Hashimoto
Affiliations : UPMC –EMRS; Tohoku University Japan

Resume : tba

O.3.1
14:20
Authors : Jean-Christophe P. GABRIEL1,2, Ange Maurice,2 Johannes THEISEN1, Christophe PENISSON1, Asmae EL MAANGAR1, Thomas ZEMB1
Affiliations : 1: CEA, France; 2: NTU, Singapore

Resume : We will report on a newly developed liquid-liquid extraction microfluidic device. We will first report of our studies of solvent chemical activities [1, 2, 3]. We will then show that, when associated with X-ray fluorescence, It enabled us to investigate the synergy effect in liquid-liquid extraction of rare earths. We will show unpublished results obtained enabling the study of both the kinetic and the equilibrium of such reactions. This approach has allowed us to determine the variation of the free energy of transfer for five rare earths mixed together in solution with iron, a non-target ion and thus at different pH and temperature. We finally will discuss these results in regards of the various terms contributing to the free energy associated with this synergy effect.[4] [1] V. Kokoric, J. Theisen, A. Wilk, C. Penisson, G. Bernard, B. Mizaikoff, J.C.P. Gabriel, Determining the Partial Pressure of Volatile Components via Substrate-Integrated Hollow Waveguide Infrared Spectroscopy with Integrated Microfluidics, Analytical Chemistry, 90 (2018) 4445-4451. [2] A.W. C. Penisson, J. Theisen, V. Kokoric, B. Mizaikoff, J.C.P. Gabriel, Water activity measurement of NaCl/H2O mixtures via substrate-integrated hollow waveguide infrared spectroscopy with integrated microfluidics, in: Nanotech 2018, CRC Press, Anaheim, CA, USA, 2018, pp. 198-201. [3] J. Theisen, C. Penisson, J. Rey, T. Zemb, J. Duhamet, J.C.P. Gabriel, Submitted. [4] T. Zemb, C. Bauer, P. Bauduin, L. Belloni, C. Dejugnat, O. Diat, V. Dubois, J.F. Dufreche, S. Dourdain, M. Duvail, C. Larpent, F. Testard, S. Pellet-Rostaing, Recycling metals by controlled transfer of ionic species between complex fluids: en route to "ienaics", Colloid and Polymer Science, 293 (2015) 1-22.

O.3.2
14:40
Authors : A.K. Ola Hekselman, David J. Payne
Affiliations : Department of Materials, Imperial College London, South Kensington Campus, London, UK

Resume : Lead-acid batteries are a mature and well-optimised technology with an established supply chain and end-of-life system. Despite being in the shadow of advancements in the Li-ion field, the technology still made significant technical progress in the last 20 years, e.g. with extending battery life by up to 35%. Moreover, lead-acid batteries remain the dominant battery technology on the market today and new, emerging applications such as grid energy storage are expected to sustain the growth of this market in the future. However, a major challenge facing lead-acid technology is its toxicity and the environmental impact of lead. Current recycling technologies are energy intensive and highly polluting. In our work, we develop new low-temperature chemical and electrochemical routes for lead recycling via solution-based processing. We lower overall energy usage and significantly reduce lead-to-air emissions from lead recovery process by using deep eutectic solvents (DES). These solvents are composed of low-cost, easy to handle, environmentally benign chemicals and, most importantly, they have an ability to dissolve a wide range of inorganic compounds - including oxides. The talk will provide an insight into this unique behaviour by analysing speciation of Pb in DES. The resulting electrodeposition mechanism of lead, morphology and phase analysis of lead materials recovered from commercial battery waste will be also discussed.

O.3.3
15:00
Authors : Yang Peng
Affiliations : Institute of electronic engineering, China Academe of Engineering Physics

Resume : Epoxy resins are used in a wide range of applications. However, recycling at the end of their life cycle is very difficult because of the cross-linked nature of the resin. Owing to the serious concerns regarding the environment and finite natural resources, new recycling technologies for thermoset resins are urgently needed. In this work, we have used polyethylene/NaOH to solvolyze anhydride-cured epoxy resin. Dissolution was carried out in a 250 mL three-necked round-bottomed flask, equipped with a reflux condenser and a mechanical stirrer. Typically, NaOH (0.8 g) was dissolved in PEG200 (40 mL), and then mixed with the model epoxy resin (2.0 g). Then the solvolysis products has been separated and characterized. A high decomposition efficiency has been proved for that the epoxy resin can be completely solubilized at 180 °C in 50 min under atmospheric pressure. The structure of the solvolysis products has been characterized by FT-IR, 1H-NMR, 13C-NMR, GPC and ESI-MS, indicating the decomposition of the curing bond through ester hydrolysis accompanied by transetherification as the plausible solvolysis mechanism. Solvolysis of anhydride-cured epoxy resin using PEG/NaOH shows high efficiency under mild reaction conditions. The main solubilization mechanism is ester hydrolysis accompanied by the transetherification reaction. Optimization of the reaction conditions will further increase the solvolysis efficiency, stressing more the potential to recycle of anhydride-cured thermosetting composites using the PEG/NaOH catalytic system.

O.3.4
15:20
Authors : Suman Nandy; Sumita Goswami; Arghya Narayan Banerjee (#); Rodrigo Martins; Elvira Fortunato
Affiliations : i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology, Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus deCaparica, 2829-516, Caparica, Portugal # School of Mechanical Engineering, Yeungnam University, Gyeongsan, 712-749, South Korea

Resume : Waste management systems are of prime concern now-a-days to reach the sustainable development goals. Reduce, reuse and recycle these three `R´ factors are the building blocks towards managing waste products not only of the industries but also from house-holds. Obviously, carbon based materials are the lion´s share of such waste products as well as of the raw materials. Here, waste car-bon from cooking oven has been directly percolated into polyaniline (PANi), via in-situ polymerization procedure, without any prior chemical purification or modification. The excellent properties of π-electron delocaliza-tion at the backbone of conjugate polymer like PANi can be initiator of charge transfer mechanism with the incorporated carbon na-noparticles resulting tunibility of electronics dynamics within the composites. Aim of our work is to develop novel strate-gies for recycling biowaste-derived carbon after functionalizing with PANi via simple cost-effective techniques towards multifunctional applicability. Based on the charge transfer mechanism between PANi matrix and waste carbon particles, composites have been used for next-generation charge trap-ping memory device, microelectrodes for supercapacitors, sensitive ion (Fe+3) detectors etc. Such kind of advanced multifunctional materials derived from waste carbon-polyaniline by a cheap and eco-friendly process, having unique synergy in their physico-chemical properties, can surely enrich the green technology towards sustainability.

O.3.5
15:40
Authors : K. Rahmani, M. Nikravech
Affiliations : Laboratoire LSPM-CNRS, Université Paris 13, Université Sorbonne Paris Cité 99 Ave Jean Baptiste Clément 93430 Villetaneuse France Corresponding author: nikravech@lspm.cnrs.fr

Resume : Degradation of agricultural wastes leads to produce greenhouse gases CH4 and CO2 mixtures named commonly Biogas. Valorization of Biogas by cogeneration or by injection into the network is economically reliable only for the farms producing at least 200 kWe and able to be connected to gas and electric networks. A recent study in France demonstrated that more than 42% of Biogas is produced in remote areas that cannot be valorized by the mentioned paths. Therefore, direct transformation of Biogas into high value liquid chemicals as methanol and ethanol in low temperature and easy running processes will constitute an alternative valorizing way for Biogas produced in remote farms. These chemicals formed by retaining the elements of CH4 and CO2 molecules participate to reduce the greenhouse gas emissions and have high energetic storage capacity. We developed an efficient dielectric barrier discharge reactor permitting to achieve 45% and 23% conversion of CH4 and CO2 respectively. More than 11 chemical species liquid at room temperature are detected. The yield of the liquid species reaches 3 to 5 %wt in addition to the production of syngas (H2 + CO), C2H6 and C2H4. The major liquid products are acetaldehyde, acetone, methanol, ethanol and acetic acid. These results express the catalytic role of steam during the reaction.

O.3.6
16:00
Authors : R.A. Geioushy *, S.M. El-Sheikh, I.M. Hegazy, Ahmed Shawky, S. El-Sherbiny, Abdel-Hakim T. Kandil
Affiliations : Nanomaterials and Nanotechnology Department, Advanced Materials Division, Central Metallurgical R & D Institute (CMRDI), P.O. Box, 87 Helwan, 11421 Cairo, Egypt

Resume : Herein, hydrothermal synthesis of 2D structure of MoS2 sheets followed by a simple annealing step was reported. The XRD pattern revealed the co-existence of 2H and 3R MoS2 phases. FE-SEM clearly showed the observation of stacked layers of MoS2. Moreover, Raman analysis revealed that more than 10 layers stacking of MoS2 sheets was synthesized. Furthermore, XPS analysis confirmed the presence of Mo4+ species that belongs to MoS2. The CO2 photoreduction over MoS2 was operated under UV light and the results displayed a significant performance towards methanol and acetaldehyde production using different aqueous solutions. The maximum production yield of methanol was estimated to be 109.5 µmol/g in 0.5 M NaHCO3, however, acetaldehyde yield was 19.2 µmol/g in 0.5 M NaCl. The high-speed transition of excited electrons along MoS2 sheets would reflect a high separation between charge carriers, which addressed for the impressive photocatalytic performance of MoS2 to reduce CO2.

O.3.7
16:20
Authors : Jéssica D. C. Santos 1, Idalina Gonçalves 1, Cláudia Nunes 1, Paula Ferreira 2, Manuel A. Coimbra 3
Affiliations : 1-CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal 2-CICECO-Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal 3-QOPNA & LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal

Resume : Calcium carbonate is commonly used as filler in the plastics industry. However, its inherent high density limits the amount that can be added into plastic formulations. To overcome this phenomenon, in this work, eggshells, known by their high porosity, were used as a source of calcium carbonate for the development of lightweight fillers. The influence of organic membrane in the physicochemical and morphological properties of ball-milled eggshell-derived calcium carbonate was studied. In addition, the effect of adding starch, recovered from potato washing slurries, during the eggshells ball milling stage was verified. Commercial calcium carbonate was used for comparison reasons. Both eggshell powders, with or without membrane, showed FTIR profiles typical of calcium carbonate, that was in the calcite form, according to X-ray diffraction pattern. Their specific surface areas (BET) were higher than those observed for the commercial calcium carbonate, whereas their particle sizes were similar. The density of eggshell powders decreases in 6% when compared to commercial calcium carbonate. In the presence of starch, the powders density was 8 and 16% lower than commercial calcium carbonate, depending on the presence or not of the organic membrane, respectively. Moreover, their particle specific surface areas and sizes slightly increased when compared with the control. This study reveals that eggshells can be an alternative source of lightweight calcium carbonate. Moreover, adding starch during the eggshells milling contributes to decrease the calcium carbonate density, offering a new sustainable strategy to develop lightweight fillers while adding value to agrofood byproducts. Acknowledgments: Thanks are due to the University of Aveiro and FCT/MCTES for the financial support of QOPNA (FCT UID/QUI/00062/2019) and CICECO-Aveiro Institute of Materials (FCT Ref. UID/CTM/50011/2019) through national funds and, where applicable, co-financed by the FEDER, within the PT2020 Partnership Agreement, and to the Portuguese NMR Network. The authors acknowledge to PLASTICOLIGHT project (POCI-01-0247-FEDER-33848), financed by FEDER through POCI, to “Isolago – Indústria de Plásticos, S. A.”, the project leader, and to “Derovo” group for providing eggshells. FCT is also thanked for the Investigator FCT program (PF), Scientific Employment Stimulus program (IG), and in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19 (CN). References: [1] A. F. Lemos and J. M. F. Ferreira, Mater. Sci. engineering, 11 (2000) [2] R. K. Das, S. K. Brar, and M. Verma, Waste Biomass Valorization, 6 (2015) [3] Ncobela, C. N., Kanengoni, A. T., Hlatini, V. A., Thomas, R. S., & Chimonyo, M. Animal Feed Science and Technology, 227 (2017).

O.3.8
16:40 Coffee break    
 
Poster session with the session: 5 min for each poster : Jacques Amouroux
17:00
Authors : Linh Nguyet Thi Ho, Dieu Minh Ngo, Hyun Min Jung*
Affiliations : Dept.of Applied Chemistry, Kumoh National Institute of Technology, Yangho-dong 1, Gumi, Korea; Dept.of Applied Chemistry, Kumoh National Institute of Technology, Yangho-dong 1, Gumi, Korea; Dept.of Applied Chemistry, Kumoh National Institute of Technology, Yangho-dong 1, Gumi, Korea

Resume : In recent decades, poly cycohexanedimethyl terephthalate (PCT) has become one of the most popular polymers utilized in manufacturing containers, automotive and optical films because of its excellent heat resistance and good mechanical properties. PCT is a modified – glycol PET in which all ethylene glycol units are replaced by 1,4 – cyclohexanedimethanol (CHDM) in polymer backbone. However, it is presumed that these cyclohexylene rings in PCT structure have a significantly negative effect on the glycolysis, an important chemical recycling route of the PET derivative. To investigate the influence of the steric hindrance groups in the decomposition reaction of PCT, bis((4-(hydroxymethyl)cyclohexyl)methyl) terephthalate (BHCHT), a model compound of PCT, was synthesized by the transesterification of bis(2-hydroxyethyl) terephthalate (BHET) and 1,4-cyclohenxanedimethanol (CHDM), and compared with BHET, a monomer of PET, in transesterification with zinc catalyst conditions. The BHCHT transesterification had a reduction in speed and it was just one-third of that of BHET case with the primary zinc acetate catalyst. However, this retarded reaction rate dramatically risen up to 4 times under the presence of alkoxy species in zinc catalyst conditions. The combined zinc catalysts were applied to the glycolysis of PCT and the reaction rate was enhanced up to 3 times than that of the conventional zinc acetate and the conversion of this process was 82% yield.

O.P.1
17:00
Authors : Atsushi Nakano 1, Masato Imai 1, Koki Kamimizutaru 2, Kentaro Sakai 1 and Kenji Yoshino 2
Affiliations : 1; Center for Collaborative Research and Community Cooperation, University of Miyazaki, 1-1 Gakuen Kibanadai-nishi, Miyazaki 889-2192, Japan 2; Department of Applied Physics and Electronics Engineering, Faculty of Engineering, University of Miyazaki, 1-1 Gakuen Kibanadai-nishi, Miyazaki 889-2192, Japan

Resume : Ni-P coating is widely accepted in engineering application due to its excellent characteristics such as the corrosion resistance, wear and abrasion resistance, ductility, lubrication and solderability. Though the electroless plating is commonly used for Ni-P coating, has disadvantages such as limited solution life, plating-bath toxicity, the difficulty of plating large parts. Stremsdoerfer et al developed the low cost technology which is based on spraying separate aqueous solutions containing metallic ions and reducing agent. In this study, the spray pyrolysis method which is used the deposition of ZnO thin film [1], is applied for Ni-P deposition using aqueous solution containing Ni sulfate and sodium hypophosphate in order to reduce solution and apply for large parts. The apparatus consists of spray nozzle, syringe pump, heating system and scanning function in a wide area. The Ni-P films are deposited by varying the substrate temperature and the solution composition. The deposited films are characterized with XRD, SEM and AFM for the physical property, XPS and SEM/EDX for the composition ratio of films. The Ni-P film deposited at 90°C is amorphous, and P content is about 11%, similar to Ni-P film coated by the conventional electroless method. The relationship between the property of film and process condition, and the comparison with the conventional plating process are discussed from the view of economy and waste. [1] M. Imai et al, Phys. Status Solidi A2017, 1700406

O.P.2
17:00
Authors : Atsushi Nakano 1, Yuzo Nakamura 2, Shingo Kubo 3, Sueyoshi Hidekazu 4 and Wataru Oshikawa 5
Affiliations : 1 Center for Collaborative Research and Community Cooperation, University of Miyazaki, 1-1 Gakuen Kibanadai-nishi, Miyazaki-City, Miyazaki, 889-2192, Japan 2 Department of Mechanical Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima, 890-0065, Japan 3 Division of Instrumental Analysis, Kagoshima University, 1-21-40 Korimoto, Kagoshima, 890-0065, Japan 4 Emeritus Professor, Kagoshima University 5 Energy and Environmental Program, Faculty of Engineering, University of the Ryukyus, 1 Nakagamigun Nishiharachou Senbaru-nishi, Okinawa, 903-0213, Japan

Resume : Japan is one of the eminent volcano countries in the world, and there are many volcanoes active lively now. An active volcano, Sakurajima, in Kagoshima located the south of Japan is very close to an urban area. Recently, Sakurajima has shown many eruptions, which accompany a large amount of fall out of ejecta. The volcanic ejecta consists of three kinds of lava, pyroclastic deposits (volcanic ashes) and the volcanic gas, and it is thought that the volcanic gas has an extremely great effect on the corrosion of metals. In this study, two types of austenitic stainless steel were exposed to the atmosphere involving Sakurajima ejecta about 23 years, and their corrosion behaviors were evaluated using the several analytical techniques. Weather monitoring equipment was installed at the exposure site to measure and record rainfall, chloride deposition rate and sulfur oxide deposition rate. The maximum pit depth evaluated by extreme value analysis. After visual observation, the surface analysis of each specimen was characterized by confocal fluorescence microscopy, and the elemental distributions were identified using an electron probe microanalyzer. In an active volcanic environment, Sakurajima, it was found that stainless steel exposed for about 23 years maintained high resistance corrosion performance. In addition, pit corrosion progressed from under the volcanic ashes which covered the surface. It is considered that the evaluation through the comparison between corrosion behavior and corrosion environment of the stainless steel contributes for solving societal issues of structural steel from a viewpoint of economic circulation and maintenance of metals.

O.P.3
17:00
Authors : Atsushi Nakano 1, Wataru Oshikawa 2, Teppei Koba3 and Shinya Inoue 3
Affiliations : 1 Center for Collaborative Research and Community Cooperation, University of Miyazaki, 1-1 Gakuen Kibanadai-nishi, Miyazaki 889-2192, Japan 2 Energy and Environmental Program, School of Engineering, Faculty of Engineering, University of the Ryukyus, 1 Nakagamigun Nishiharachou Senbaru, Okinawa 903-0213, Japan 3 Department of Mechanical System Engineering, Faculty of Engineering, University of the Ryukyus, 1 Nakagamigun Nishiharachou Senbaru, Okinawa 903-0213, Japan

Resume :  The south of Japanese Islands in the subtropical environment is in an extremely severe environment for the corrosion of metals. As another characteristic of the weather of Japan, a typhoon comes several times in a year. It is thought that the intense wind and rain and airborne salt in the typhoon environment promote the corrosion than a mild environment.  In this study, corrosion monitoring in the typhoon environment was carried out using Atmospheric Corrosion Monitor (ACM) sensor, consisting of a Fe-Ag galvanic couple. It is possible to evaluate corrosion environments quantitatively by measuring the ACM sensor output. Corrosion rate of carbon steel was determined by conventional mass loss method in the typhoon environment exposure test. After checking both data of ACM sensor and rainfall, these output time were in agreement. Thus, it was also demonstrated that this ACM sensor could be applicable to the evaluation of corrosivity in a typhoon environment. In addition, corrosion rate [CR] was closely correlated with electricity [Q/day] which is the ACM type corrosion sensor output, and formula predicting corrosion rate of carbon steel in a typhoon environment has been proposed.  It is considered that the evaluation through the comparison between corrosion rate of carbon steel and the ACM sensor output in typhoon environment contributes for solving societal issues of structural steel from a viewpoint of economic circulation and maintenance of metals.

O.P.4
 
General conclusion and world innovation processes : J. Amouroux
17:20
Authors : J. Amouroux, S.Dresvin, K. Hashimoto
Affiliations : E-MRS / UPMC

Resume : Some innovative industrial processes and companies open the field of the recycling and circular economy, so it is a pleasure to give a brief list of those who develop a new strategy to be in agreement with the carbon print balance and the material recycling This list was published in an economic new paper INVESTIR but I suppose that many new lists appear for a strategic financial classification as the new green evaluation for green investment groups, while at the same time some insurance group develop climate risk department for a prediction of financial risk and financial investment “management". As we know "no risk no fun" but with Artificial intelligence and supercomputers of 10 Peta –flops and more we expect to predict our future, that is the challenge, energy and material are still present from the Lavoisier Law “nothing gets lost, nothing shines all turns” except the energy balance which gives us entropy.

O.4.1
17:40 Round table: recycling and circular economy, green processes and collaborative strategy: a dream or a challenge for the scientists and the education in chemical engineering and a more innovative Europe between Scientists and Industry    

No abstract for this day


Symposium organizers
Hans FECHTUlm University

Institute of Functional Nanosystems FNS, Albert-Einstein-Allee 47, 89081 Ulm, Germany

hans.fecht@uni-ulm.de
Jacques AMOUROUXUniversité Pierre et Marie Curie

ENSCP / PSL, Paris, France

jacques.amouroux@gmail.com
Veena SAHAJWALLACentre for Sustainable Materials Research and Technology (SMaRT)

UNSW Sydney, NSW 2052, Australia

veena@unsw.edu.au