Eco-efficient Processes Research Articles

Iron-Catalyzed Laser-Induced Graphitization - Multiscale Analysis of the Structural Evolution and Underlying Mechanism.

The transition to sustainable materials and eco-efficient processes in commercial electronics is a driving force in developing green electronics. Iron-catalyzed laser-induced graphitization (IC-LIG) has been demonstrated as a promising approach for rendering biomaterials electrically conductive. To optimize the IC-LIG process and fully exploit its potential for future green electronics, it is crucial to gain deeper insights into its catalyzation mechanism and structural evolution. However, this is challenging due to the rapid nature of the laser-induced graphitization process. Therefore, multiscale preparation techniques, including ultramicrotomy of the cross-sectional transition zone from precursor to fully graphitized IC-LIG electrode, are employed to virtually freeze the IC-LIG process in time. Complementary characterization is performed to generate a 3D model that integrates nanoscale findings within a mesoscopic framework. This enabled tracing the growth and migration behavior of catalytic iron nanoparticles and their role during the catalytic laser-graphitization process. A three-layered arrangement of the IC-LIG electrode is identified including a highly graphitized top layer with an interplanar spacing of 0.343nm. The middle layer contained γ-iron nanoparticles encapsulated in graphitic shells. A comparison with catalyst-free laser graphitization approaches highlights the unique opportunities that IC-LIG offers and discuss potential applications in energy storage devices, catalysts, sensors, and beyond.

All-Graphene Quantum Dot-Derived Battery: Regulating Redox Activity Through Localized Subdomains.

In the quest for materials sustainability for grid-scale applications, graphene quantum dot (GQD), prepared via eco-efficient processes, is one of the promising graphitic-organic matters that have the potential to provide greener solutions for replacing metal-based battery electrodes. However, the utilization of GQDs as electroactive materials has been limited; their redox behaviors associated with the electronic bandgap property from the sp2 carbon subdomains, surrounded by functional groups, are yet to be understood. Here, the experimental realization of a subdomained GQD-based anode with stable cyclability over 1000 cycles, combined with theoretical calculations, enables a better understanding of the decisive impact of controlled redox site distributions on battery performance. The GQDs are further employed in cathode as a platform for full utilization of inherent electrochemical activity of bio-inspired redox-active organic motifs, phenoxazine. Using the GQD-derived anode and cathode, an all-GQD battery achieves a high energy density of 290Wh kgcathode -1 (160Wh kgcathode+anode -1 ), demonstrating an effective way to improve reaction reversibility and energy density of sustainable, metal-free batteries.

Electrodialysis Processes an Answer to Industrial Sustainability: Toward the Concept of Eco-Circular Economy?-A Review.

Wastewater and by-product treatments are substantial issues with consequences for our society, both in terms of environmental impacts and economic losses. With an overall global objective of sustainable development, it is essential to offer eco-efficient and circular solutions. Indeed, one of the major solutions to limit the use of new raw materials and the production of wastes is the transition toward a circular economy. Industries must find ways to close their production loops. Electrodialysis (ED) processes such as conventional ED, selective ED, ED with bipolar membranes, and ED with filtration membranes are processes that have demonstrated, in the past decades and recently, their potential and eco-efficiency. This review presents the most recent valorization opportunities among different industrial sectors (water, food, mining, chemistry, etc.) to manage waste or by-product resources through electrodialysis processes and to improve global industrial sustainability by moving toward circular processes. The limitations of existing studies are raised, especially concerning eco-efficiency. Indeed, electrodialysis processes can be optimized to decrease energy consumption and costs, and to increase efficiency; however, eco-efficiency scores should be determined to compare electrodialysis with conventional processes and support their advantages. The review shows the high potential of the different types of electrodialysis processes to treat wastewaters and liquid by-products in order to add value or to generate new raw materials. It also highlights the strong interest in using eco-efficient processes within a circular economy. The ideal scenario for sustainable development would be to make a transition toward an eco-circular economy.

(Invited) Searching for High Potential Organic Cathode Materials for High Energy Green and Sustainable Batteries

Thanks to the use of abundant chemical elements, organic chemistry provides great opportunities for discovering innovative electrode materials, which could be prepared (i) from renewable resources (biomass) and (ii) via eco-efficient processes, making the concept of greener and sustainable batteries possible [1]. We are putting a lot of efforts on greener and sustainable organic non-aqueous and aqueous batteries at the IMN. In this communication, we report on novel crystallized organic positive electrode materials for the non-aqueous application of organic batteries. However the synthesis of high-voltage lithiated materials is rather challenging, so very few examples of all-organic Li-ion cells currently exist. Compounds of the Mn+ 2/n-p-DHT (with Mn+ = Li+, Mg2+, Ca2+ and Ba2+) family were studied to better understand the effect of substitution chemistry on the redox properties of the Li-diphenolate cycle of p-DHT. This innovative chemical approach makes it possible to tune the redox potential of lithiated organic electrode materials, by playing on the nature and the ionic potential of a spectator cation in the host structure. Indeed, by adjusting the attractor/donor electron effects in the organic redox-active backbone, it is possible to modify the redox potential of the molecule by inductive effect. We show that substituting magnesium (2,5-dilithium-oxy)-terephthalate for lithium (2,5-dilithium-oxy)-terephthalate enables an outstanding voltage gain of 800 mV, leading to a high operating voltage of 3.4V vs. Li+/Li [2]. This Mg(Li2)-p-DHT compound is the first lithiated organic positive electrode material with an operating potential as high as that of LiFePO4. Based on this finding, full organic Li-ion cells with an output voltage of 2.5V and long cycle life have been achieved, thus making a big step forward the design of high energy green and sustainable organic batteries.

Eco-efficient processes for biodiesel production from waste lipids

Abstract The paper proposes innovative eco-efficient processes for converting waste lipid feedstock with up to 35% free fatty acids into biodiesel. Free fatty acids pre-treatment is a key issue, which can be handled by esterification with methanol or glycerol, using hetero- or homogeneous catalyst. The integration with the transesterification stage is possible using methods based on process intensification and heterogeneous catalysis. Three integrated continuous processes are investigated. The first performs the esterification with methanol by reactive absorption and superacid solid catalyst, followed by transesterification by reactive distillation with alkali catalyst. The second method applies the esterification with glycerol at high temperature, coupled with transesterification by heterogeneous catalyst in a variable residence-time plug-flow reactor. The third alternative replaces the second reaction stage with vacuum distillation. In all cases, biodiesel fulfills the specifications of D6751 and EN14214 norms. This result is obtained by kinetic simulation of reactors including free fatty acids esterification and glycerides transesterification. A techno-economic analysis pinpoints the pros and cons of each process. The first process is suited for low free fatty acids content, as used cooking oils. The second and third processes can be applied for higher content of free fatty acids, such as animal fats and greases. Particularly the third process can deliver biodiesel of highest quality, conforming to the cold soak filtration test.

Novel Organic Electrode Materialsfor Innovative Thick Electrode Based Aqueous Batteries

Thanks to the use of abundant chemical elements, organic chemistry provides great opportunities for discovering innovative electrode materials, which could be prepared (i) from renewable resources (biomass) and (ii) via eco-efficient processes, making the concept of greener and sustainable batteries possible [1]. Two types of reaction mechanisms can be used: n-type involving charge transfer with cation release/uptake and p-type involving anion uptake/release [2-5]. We are putting a lot of efforts on greener and sustainable organic batteries. In this communication, we report on novel materials, their uncommon reaction mechanism, and the performance of full aqueous cells. We focus on aqueous organic batteries as a new promising green technology, barely studied yet, for which negative electrodes are missing. We have designed and synthesized novel mixed p- and n-type “bi-block” oligomer negative electrodes with repeating units made of naphthalene diimide and bipyridinium units [6]. They demonstrate optimal potential, extremely fast kinetics and highly competitive capacity and cyclability in both neutral aqueous Na and Mg electrolytes, including ocean water. Based on these findings, full organic cells bearing millimeter thick electrodes were assembled and tested [7]. These findings make a big step forward the design of low-cost rocking-chair dual-ion aqueous batteries. References 1) P. Poizot, F. Dolhem, Energy Environ. Sci. 4, 2003 (2011). 2) Z. Song and H. Zhou, Energy Environ. Sci. 6, 2280 (2013). 3) S. Gottis, A.-L. Barrès, F. Dolhem, P. Poizot, ACS Appl Mater Interfaces 6, 10870 (2014). 4) E. Deunf, P. Moreau, E. Quarez, D. Guyomard, F. Dolhem, P. Poizot, J. Mater. Chem. A, 4, 6131 (2016). 5) E. Deunf, P. Jimenez, D. Guyomard, F. Dolhem, P. Poizot, Electrochem. Comm., 72, 64 (2016). 6) S. Perticarari, Y. Sayed-Ahmad-Baraza, C. Ewels, P. Moreau, D. Guyomard, P. Poizot, F. Odobel, J. Gaubicher, Adv. Energy Mater., 8, 1701988 (2018). 7) S. Perticarari, E. Grange, T. Doizy, Y. Pellegrin, E. Quarez, K. Oyaizu, A. J. Fernandez, D. Guyomard, P. Poizot, F. Odobel and J. Gaubicher, Chem. Mat., in revision

Assessing Industrial Biotechnology Products with LCA and Eco-Efficiency.

Biotechnology is applied in many industrial areas and uses microorganisms, enzymes, or precursors replacing chemicals to produce goods, including chemicals, plastics, food, agricultural and pharmaceutical products, and energy carriers from renewable raw materials and increasingly also from waste from agriculture and forestry (BIOPRO Baden-Württemberg GmbH, Facts and Figures. Biotechnologie.de. https://www.biooekonomie-bw.de/en/articles/dossiers/industrial-biotechnology-biological-resources-for-industrial-processes/ , 2013). In comparison with conventional processes, industrial biotechnology processes often run under relatively mild reaction conditions, moderate temperatures, and the use of aqueous media. They might reduce in general the energy requirements and the number of by-products. Since product concentration and formation rate are often very low, the resulting products need to be purified and recovered in marketable quantities in a process that is referred to as downstream processing. Product quantity can also be increased by optimizing the manufacturing processes or biocatalysts used (OECD, the application of biotechnology to industrial sustainability. www.oecd.org/sti/biotechnology , 2001).In this context, developing a sustainable bio-based economy that uses eco-efficient processes is one of the key strategic challenges for the twenty-first century. Decisions in the technology development are often supported by sustainability assessment results using different types of sustainability assessment methods. In the last decades, we developed different types of sustainability assessment methods evaluating aspects of economy, ecology, and society to support decision-making processes. We show in this chapter how different types of questions can be answered, how more sustainable solutions can be identified, and how this information can be used for marketing and research activities.

Development of Some Eco-Efficient and Selective Chemical Processes and Products Using Sustainable and Green Chemistry Approaches

Development of Some Eco-Efficient and Selective Chemical Processes and Products Using Sustainable and Green Chemistry Approaches

From a Sequential Chemo-Enzymatic Approach to a Continuous Process for HMF Production from Glucose

Notably available from the cellulose contained in lignocellulosic biomass, glucose is a highly attractive substrate for eco-efficient processes towards high-value chemicals. A recent strategy for biomass valorization consists on combining biocatalysis and chemocatalysis to realise the so-called chemo-enzymatic or hybrid catalysis. Optimisation of the glucose conversion to 5-hydroxymethylfurfural (HMF) is the object of many research efforts. HMF can be produced by chemo-catalyzed fructose dehydration, while fructose can be selectively obtained from enzymatic glucose isomerization. Despite recent advances in HMF production, a fully integrated efficient process remains to be demonstrated. Our innovative approach consists on a continuous process involving enzymatic glucose isomerization, selective arylboronic-acid mediated fructose complexation/transportation, and chemical fructose dehydration to HMF. We designed a novel reactor based on two aqueous phases dynamically connected via an organic liquid membrane, which enabled substantial enhancement of glucose conversion (70%) while avoiding intermediate separation steps. Furthermore, in the as-combined steps, the use of an immobilized glucose isomerase and an acidic resin facilitates catalyst recycling.

(Keynote) Conducting Redox Polymer Batteries

Organic matter based battery materials have attracted large interest due to their inherent ability to provide an environmentally benign alternative to inorganic batteries because such materials can be produced from renewable resources via eco-efficient processes. Conducting redox polymers (CRPs) is an attractive class of materials for organic matter based electrical energy storage. CRPs are composed of a conducting polymer backbone with redox active pendant groups covalently linked to the polymer backbone. The conducting polymer backbone renders the material conductive and, due to the large molecular size, prevents material dissolution thus mastering two of the most significant obstacles in achieving powerful and stable battery materials from organic compounds. The pendant redox group, on the other hand, can provide high charge storage capacities to the material. Combining conducting polymers with high charge storage capacity pendants thus has the possibility to form powerful materials for battery applications provided that the individual properties of the backbone and the redox group can be preserved and operate in synergy in the CRP. This requires careful matching of the redox chemistry of the pendant group and the CP backbone as CPs are only conducting in specific potential regions. In this work design principles for CRPs are outlined and we present results suggesting that CRPs can show semi-metallic electron transport properties and that redox conversion rates on the sub-second time-scale can be accomplished with this type of materials [1]. In addition we present an all-organic proton battery composed of quinone CRPs as both anode and cathode [2]. [1] M. Sterby, et al., Electrochim. Acta, 2017, 235, 356-364 [2] R. Emanuelsson, et al., J. Am. Chem. Soc., 2017, 139 (13), 4828-4834. Figure 1

Intelligent, model-based control towards the intensification of downstream processes

Process Intensification (PI) has been gaining increasing interest as industrial trends urge a shift towards more eco-efficient processes of significantly decreased operation and capital costs. In this direction we focus on the development of advanced control strategies of the Multicolumn Countercurrent Solvent Gradient Purification Process (MCSGP), an industrial, semi-continuous, chromatographic process, used for the purification of several biomolecules. We present a novel control approach that manages to drive the process towards continuous, sustainable operation. The presented controllers are designed within the PARametric Optimization and Control (PAROC) framework/software platform that enables the development of intelligent, model-based controllers through a step-by-step approach. The controllers are successfully tested against various disturbance profiles and they manage to track the predefined setpoints without significant offset.

Biotechnological and Biochemical Utilization of Lignin.

This chapter provides an overview of the biosynthesis and structure of lignin. Moreover, examples of the commercial use of lignin and its promising future implementation are briefly described. Many applications are still hampered by the properties of technical lignins. Thus, the major challenge is the conversion of lignins into suitable building blocks or aromatics in order to open up new avenues for the usage of this renewable raw material. This chapter focuses on details about natural lignin degradation by fungi and bacteria, which harbor potential tools for lignin degradation and modification, which might help to develop eco-efficient processes for lignin utilization.

Innovation on Environmental Management Systems towards Firms’ Eco-Efficiency for Malaysia Polypropylene Industries

This paper presents the findings of a research that examined eco-efficiency on ISO14000 certified polypropylene firms. Polypropylene poses pollution threat to air, water and landfill due to its non-biodegradable products. Polypropylene firms are expected to demonstrate continual improvements in their environmental performances, objectives and targets, controls on environmental impacts and promote best practices. Environmental programs and innovations are needed not only for eco-efficiency and environmental performances, but also to comply with the global and market pressures towards sustainable green technology and businesses. Findings of the research revealed that employees’ involvements, innovations integration in the production systems towards eco-efficient production processes, producing substituted environmentally-friendly products, minimization of wastes and reducing environmental impacts are crucial for polypropylene industries in Malaysia. Additionally, organizational compliances towards government regulations and corporate social responsibility have implications on EMS and organizational performances towards green technology and business sustainability. In conclusion, innovations in EMS support eco-efficiencies in polypropylene industries and simultaneously protect the environment for future generation

C-A-S-H gels formed in alkali-activated slag cement pastes. Structure and effect on cement properties and durability

The development of alternatives to traditional Portland cement produced with more eco-efficient processes (lower energy consumption and CO 2 gas emissions) is an item on climate change and innovation agendas. Alkaline cements and concretes are an effective alternative to traditional cements.The structure of the C-S-H gel in Portland cements consists mostly of 14-nm tobermorite (with a chain length of five) and jennite (2-link chain). The mechanical properties of C-S-H gels can be explained in terms of the three types of packing found in these gels: low density (LD), high density (HD) and ultra-high density (UHD).The main reaction product in alkali-activated slag (AAS) cements is a C-A-S-H gel, which adopts different structures depending on the nature of the alkaline activator. When the activator is a NaOH solution (4 % Na 2 O by slag weight), the C-A-S-H gel formed has an intermediate structure between 14-nm tobermorite with a chain length of five links and 11-nm tobermorite with 14 links. When the activator is a waterglass solution (4 % Na 2 O by slag weight), traits characteristic of 14-nm tobermorite with 11-link chains and 11-nm tobermorite with a chain length of 14 co-exist in the structure of the C-A-S-H gel formed. This densely packed structure (with three HD states) yields excellent mechanical properties. Like the C-A-S-H gels obtained in NaOH (4% Na2O)-activated AAS paste, the C-A-S-H gels forming in AAS gels activated with waterglass have no UHD states.The structure and composition of these C-A-S-H gels determine strength development in AAS mortars and concretes as well as their resistance to aggressive chemicals.

Biomineralized α-Fe2O3: texture and electrochemical reaction with Li

Sustainable batteries call for the development of new eco-efficient processes for preparation of electrode materials based on low cost and abundant chemical elements. Here we report a method based on bacterial iron biomineralization for the synthesis of α-Fe2O3 and its subsequent use as a conversion-based electrode material in Li batteries. This high-yield synthesis approach enlists (1) the room temperature formation of γ-FeOOH via the use of an anaerobic Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1 and (2) the transformation of these BoFeN1/γ-FeOOH assemblies into an alveolar bacteria-free α-Fe2O3 material by a short heat treatment under air. As the γ-FeOOH precursor particles are precipitated between the two membranes of the bacterial cell wall (40 nm-thick space), the final material consists of highly monodisperse nanometric ([similar]40 × 15 nm) and oriented hematite crystals, assembled to form a hollow shell having the same size and shape as the initial bacteria (bacteriomorph). This double level of control (nanometric particle size and particle organization at the micrometric scale) provided powders exhibiting (1) enhanced electrochemical reversibility when fully reacted with Li and (2) an impressive high rate capability when compared to non-textured primary α-Fe2O3 particles of similar size. This bacterially induced eco-efficient and scalable synthesis method opens wide new avenues to be explored at the crossroads of biomineralization and electrochemistry for energy storage.

2nd International Symposium on Green Chemistry (ISGC-2): Renewable Carbon and Eco-efficient Processes (May 21–24, 2013, La Rochelle, France)

Article 2nd International Symposium on Green Chemistry (ISGC-2): Renewable Carbon and Eco-efficient Processes (May 21–24, 2013, La Rochelle, France) was published on February 1, 2013 in the journal Green Processing and Synthesis (volume 2, issue 1).

Renewable carbon and eco-efficient processes

A graphical abstract is available for this content

Bio-based solvents: an emerging generation of fluids for the design of eco-efficient processes in catalysis and organic chemistry

Biomass and waste exhibit great potential for replacing fossil resources in the production of chemicals. The search for alternative reaction media to replace petroleum-based solvents commonly used in chemical processes is an important objective of significant environmental consequence. Recently, bio-based derivatives have been either used entirely as green solvents or utilized as pivotal ingredients for the production of innovative solvents potentially less toxic and more bio-compatible. This review presents the background and classification of these new media and highlights recent advances in their use in various areas including organic synthesis, catalysis, biotransformation and separation. The greenness, advantages and limitations of these solvents are also discussed.

Sociedade, indústria e design: percepções, atitudes e caminhos rumo a uma sociedade sustentável

Sustainable development, since the introduction of its concept, has been neglected, and among the greatest challenges to the paradigm shift towards a sustainable society are the formation and consolidation of a society based on consumption and disposal of industrial products. However, despite these challenges, several public opinion polls reveal some new business opportunities leveraged by the new green market that is in the process of expansion. In addition, other environmental reasons, economic and legal are gradually forcing the private sector to produce products and create more eco-efficient processes. In this new scenario, the participation of social actors is seen as essential in the process of materialization of a green economy. It should be emphasized that the role of design is increasingly recognized as essential to the process of change. In this sense, the ecodesign strategies, aimed at developing more sustainable products, can disrupt the flow of high consumption of raw materials, streamline production methods, minimize pollutant emissions and waste generation, shifting consumption systems for the formation of an ecological mindset.

Understanding and Promoting the Rapid Preparation of the Triplite-Phase of LiFeSO4F for Use as a Large-Potential Fe Cathode

The development of new electrode materials, which are composed of Earth-abundant elements and that can be made via eco-efficient processes, is becoming absolutely necessary for reasons of sustainable production. The 3.9 V triplite-phase of LiFeSO(4)F, compared to the 3.6 V tavorite-phase, could satisfy this requirement provided the currently complex synthetic pathway can be simplified. Here, we present our work aiming at better understanding the reaction mechanism that govern its formation as a way to optimize its preparation. We first demonstrate, using complementary X-ray diffraction and transmission electron microscopy studies, that triplite-LiFeSO(4)F can nucleate from tavorite-LiFeSO(4)F via a reconstructive process whose kinetics are significantly influenced by moisture and particle morphology. Perhaps the most spectacular finding is that it is possible to prepare electrochemically active triplite-LiFeSO(4)F from anhydrous precursors using either reactive spark plasma sintering (SPS) synthesis in a mere 20 min at 320 °C or room-temperature ball milling for 3 h. These new pathways appear to be strongly driven by the easy formation of a disordered phase with higher entropy, as both techniques trigger disorder via rapid annealing steps or defect creation. Although a huge number of phases adopts the tavorite structure-type, this new finding offers both a potential way to prepare new compositions in the triplite structure and a wealth of opportunities for the synthesis of new materials which could benefit many domains beyond energy storage.