Tobacco plants are grown worldwide by thousands of families who are financially dependent on the crop for cigarette production. The stricter tobacco laws force these producers to find alternatives to sell this product. In addition, in this regard, the European Union must look to develop its own greener processes giving at the same time independence from eastern countries. Nearly 50 % of the current overall market for nicotine, which is being used, as a bioactive compound, comes from China. The present study compares the environmental life cycle impacts of different methods to extract nicotine from tobacco leaves (the maceration and the mechanochemical process). These have been compared with an ecoefficiency analysis in terms of environmental performance (with life cycle assessment methodology), financial performance (with an economic analysis of the operational costs) and assessing energy consumption as a transversal indicator. The maceration process would be more advisable in the case that energy supply is considered a limiting resource. Even though, this might be compensated using solar panels or other renewable energy sources. In addition, the mechanochemical process achieves higher nicotine extraction rate (1.91 wt%) than the maceration process (1.78 wt%). After the complete evaluation, it has been concluded that the highest nicotine extraction rate of the mechanochemical process compensates for its higher energy consumption. Therefore, when considering the whole life-cycle, the mechanochemical process presents about 7 % lower environmental impacts and slightly better (2 %) economic balance than the maceration process.

Reline, a deep eutectic solvent (DES), was employed as the reaction medium for the selective catalytic oxidation of phenylmethanol derivatives using either N-bromosuccinimide (NBS) or a combination of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and [bis(acetoxy)iodo]benzene (PIDA). Various reactor setups, including a stirred glass tank reactor, a planetary ball mill, and the impact in continuous flow heated mechanochemistry (ICHeM) system, were evaluated for the selective synthesis of 4-bromobenzaldehyde. Starting from solid components-primary or secondary alcohols, NBS or TEMPO/PIDA oxidizing agents, choline chloride, and urea-the ICHeM technology simultaneously enabled the in situ formation of the reline DES medium and the synthesis of 12 different aldehydes and ketones in yields ranging from 11% to 97% with 100% selectivity. The reactions were completed within a residence time of 9.4 to 10.9 min, achieving space-time yields of 0.750 kg h-1 L-1 for 4-bromobenzaldehyde, 0.780 kg h-1 L-1 for 4-iodobenzaldehyde, and 0.470 kg h-1 L-1 for p-tolualdehyde.

Impact in Continuous Flow Heated Mechanochemistry (ICHEM) technology was used for the first biphasic continuous flow esterification of choline chloride-based deep eutectic solvents (DESs) with nonmiscible acetic, hexanoic, and octanoic anhydrides, resulting in the synthesis of novel hydrotropic DESs. The reaction was first optimized in batch using acetic anhydride, and then scaled up to continuous flow in an 80 mL WAB Research Lab ICHEM reactor, achieving 90-95% yields at lab scales of 50-100 g. The physicochemical properties of the three new DESs were analyzed, revealing that esterification via the ICHEM process had minimal impact on these properties compared to the conventional batch method. Furthermore, the potential of these new hydrotropic DESs as anticorrosive agents was evaluated, demonstrating their effectiveness as corrosion inhibitors.

Several MgO materials have been prepared throughout wet flow semi-continuous mechanochemical treatment of the Mg(OH)2 precursors and their subsequent calcination. This mechanochemical treatment of the precursors has shown a clear influence on the textural properties and the amount and strength of basic sites of the MgO catalysts after its calcination, obtaining higher values than that observed in a MgO sample synthesized without mechanochemical treatment. An in-depth investigation was conducted on the effects of the mechanochemical treatment on the catalytic performance in the catalytic transfer hydrogenation of furfural, and a positive effect on the activity of the catalysts was found after short mechanochemical treatment times. The highest conversion values at shorter reaction times were obtained after a mechanochemical treatment of 15 min, reaching a furfuryl alcohol yield of 79% after 2 h of reaction at 90 degrees C, using 2-propanol as both hydrogen donor and solvent. This data notably improves that obtained for the untreated material, which only reaches a conversion of 48% under the same experimental conditions. The stability of the material in the reaction media as well as their reusability were also investigated, and the interaction nature of 2-propanol with the MgO surface has been elucidated by attenuated total reflection spectroscopy and 2-propanol adsorption studies.

Impact in Continuous Flow Heated Mechanochemistry (ICHeM) was utilized for the biphasic acetylation of glycerol with immiscible acetic anhydride in the presence of homogeneous acid catalysts. This innovative technology combines efficient phase dispersion with continuous flow, offering the following benefits: (i) improved mixing of the two immiscible components (liquid glycerol and highly reactive acetic anhydride); (ii) mechanochemical energy generated by bead impact in continuous flow, eliminating the need for additional heating energy; and (iii) an alternative to single- and double-screw extruders, which are ineffective with liquid reaction media. Under our optimized conditions, triacetin "t" can be obtained with a 99% yield (100% conversion and 99% selectivity) in a solvent-free biphasic continuous flow process with a residence time of 15-30 min, using efficient homogeneous Lewis acids like iron triflate II or Bronsted acids like sulfuric acid.

This study discloses the synthesis of Ag- and Cu- modified ZIF-8 materials using a novel, sustainable beadsassisted flow reaction in a continuous-flow mechanochemical system. This approach offers an efficient, environmentally friendly route to producing antimicrobial materials with promising applications. Antimicrobial tests against Escherichia coli, Staphylococcus aureus, and Candida albicans revealed that pristine ZIF-8 showed no relevant biological activity. Ag@ZIF-8 comparably demonstrated strong bactericidal activity against E. coli and S. coli at 0.1 mg mL- 1, while Cu@ZIF-8 exhibited moderate antibacterial activity against S. aureus (0.5 mg mL- 1, 5 % Cu loading) and no activity against E. coli or C. albicans. Notably, bimetallic Ag-Cu@ZIF-8 composite (5 % Ag + 5 % Cu) displayed enhanced antibacterial efficacy including antifungal activity against C. albicans at a concentration of 0.1 mg mL- 1, likely due to a synergistic effect between Ag and Cu ions.

In this work, hydrocalumite, a layered double hydroxide with formula Ca2Al(OH)6Cl·2H2O, has been prepared for the first time using flow semi-continuous mechanochemistry with a DYNO®-MILL RESEARCH LAB (Willy A. Bachofen AG, Switzerland), with stoichiometric amount of reactants in water, after only 5 min at 25 °C. Hydrocalumite, before and after thermal treatment, was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG–DTA) and N2 sorption at − 196 °C. Moreover, calcined hydrocalumite has been evaluated as catalyst for the isomerization of glucose to fructose, a catalytic process which has also been performed in the same flow semi-continuous mechanochemical reactor. This mechanochemical system, unlike conventional ball milling, allows working in semi-continuous and/or continuous mode, using solvents and allowing heating control up to temperatures of 80 °C. The isomerization of glucose to fructose was successfully carried out in this reactor, demonstrating that hydrocalumite prepared by mechanochemistry is more active than that prepared by co-precipitation. The optimization of several experimental variables (reaction temperature and time, glucose/catalyst weight ratio and concentration of glucose in water) has resulted in a 23.5

This article presents a study of cadmium removal from nitrate medium using adsorption in calcined mesoporous silica (MCM-C), mesoporous silica doped (MCM_DIOPA), and calcined and impregnated mesoporous silica (MCM@DIOPA), with diisooctylphosphinic acid (DIOPA). The sorbents were synthesized via a sol–gel method. Several characterization techniques, such as XRD, FTIR spectroscopy, N2 sorption and elemental analysis, have been used to determine the main structural, textural, and chemical properties of prepared sorbents. Batch adsorption and kinetics tests were carried out, where the influence of pH and contact time of the sorbents and their role in cation removal were studied. Experimental results show poor sorption efficiencies with MCM-C and MCM_DIOPA at pH 5.85. At the same pH, better cadmium extraction was attained by MCM@DIOPA and was achieved within 30 min. The pseudo-second-order model is the most appropriate model to describe the elimination mechanism of Cd(II) ions. The Langmuir equation was used to model the sorption isotherm and the maximum sorption capacity of Cd(II) is 22.16 mg/g (200 mmol/kg). The complex type of the probable extracted species isCdL2-HL.

The need to explore contemporary alternatives for industrial production has driven the development of innovative techniques that address critical limitations linked to traditional batch mechanochemistry. One particularly promising strategy involves the integration of flow processes with mechanochemistry. Three noteworthy technologies in this domain are single-screw extrusion (SSE) and twin-screw extrusion (TSE) and Impact (Induction) in Continuous-flow Heated Mechanochemistry (ICHeM). These technologies go beyond the industrial production of polymers, extending to the synthesis of active pharmaceutical ingredients, the fabrication of (nano) materials, and the extraction of high-added value products through the valorisation of biomass and waste materials. In accordance with the principles of green chemistry, ball milling processes are generally considered greener compared to conventional solvothermal processes. In fact, ball milling processes require less solvent, enhance reaction rates and reaction conversion by increasing surface area and substituting thermal energy with mechanochemical energy, among others. Special attention will be given to the types of products, reactants, size of the milling balls and reaction conditions, selecting 60 articles after applying a screening methodology during the period 2020-2022. This paper aims to compile and analyze the cutting edge of research in utilizing mechanochemistry for green chemistry applications.

A series of Pd-based catalysts supported on oxides with different acid-base properties has been prepared, characterized, and used for the valorization of furfural into value-added chemicals, with polymethylhydroxysiloxane (PMHS) as a reducing agent being an alternative to the use of hydrogen gas and alcohols as hydrogen donors. PMHS is a polymeric waste product of the silicone industry and is also recognized as a sustainable reductant for epoxide hydrosilylations and diastereoselective radical reduction in organic chemistry. Moreover, it is nontoxic, water/air insensitive, and soluble in most organic solvents due to its low viscosity. So, PMHS has been employed for the reduction of furfural in the presence of supported Pd catalysts. Although all catalysts tested are catalytically active, those supported on Al2O3 and SiO2 showed complete conversion after 30 min of reaction at 303 K, whereas 27.7% was attained using MgO as support. 1PdAl(2)O(3) (1 wt % Pd) catalyst was initially very selective to furfuryl alcohol (80.4% yield of FOL), which was hydrogenated to tetrahydrofurfuryl alcohol (THFA) at longer reaction times, reaching yields of 48.8 and 33.4% of FOL and THFA, respectively, after 6 h. By increasing the amount of Pd until 5 wt %, the reaction evolves toward the formation of more hydrogenated products (THFA), although the amount of nondetected products also increases. The best FOL productivity data has been achieved with 1PdAl(2)O(3), with a TOF value of 397 h(-1) (mol(FOL)mol(Pd)(-1)h(-1)) at 303 K after 30 min, with 180 mu L of PMHS in ethanol, as solvent, while increasing both the amount of Pd to 2.5 wt % (2.5PdAl(2)O(3)) and that of PMHS until 360 mu L; under similar experimental conditions, 100 mol(THFA) mol(Pd)(-1)h(-1) can be produced.

This article evaluates two processes, wet milling and chemical depolymerization, for the end-of-life of wood waste in terms of environmental performance (ex ante life cycle assessment), energy balance, and economic analysis of the operating costs. Cellulose, hemicellulose, and lignin are essential components with numerous applications. The study provides valuable insights for industry stakeholders, policymakers, and researchers of the wet milling process (WMP), which is scarcely reported in the literature. The chemical depolymerization process (CDP) is discontinuous and more energy-intensive, while the WMP is a continuous reaction demanding milder conditions and shorter times. However, the milling process requires a pretreatment to reduce the wood chip size. Economic analysis shows that the CDP has lower operational costs when considering the average European electricity price in 2019. This is a result of the price differences between steam and electricity. For lower electricity prices such as in France or using utility-scale solar photovoltaics, the WMP has lower operational costs. The WMP also outperforms the CDP in most environmental indicators, such as global warming potential, particularly when using green electricity technologies.

Nitroaromatic compounds (NACs) are a group of organic chemicals containing one or more nitro functional groups attached to an aromatic ring. These compounds are considered emerging pollutants (EPs) in wastewater due to their potential environmental and human health impacts. These NACs can enter wastewater through various sources, including the production and use of explosives, dyes, pesticides, or pharmaceuticals. 4-nitrophenol (4-NP) is considered a priority pollutant due to its toxicity and potential environmental and health hazards. Thus, its removal is crucial. For that purpose, a novel strategy to carry out Zr-MOFs syntheses has been developed employing I-CHEM technology (Impact Continuous flow Heated Mechanochemistry), an improved wet-milling process. The resulting materials have demonstrated efficacy as catalysts in the reduction of 4-NP towards 4-aminophenol (4-AP), a precursor to paracetamol. Notably, the most promising outcomes were achieved with Zr-MOF prepared through continuous flow mechanochemical processes utilizing Zr-methacrylate clusters as precursor (Zr-MOF/2@RL). 4-NP removal was successfully carried out at room temperature, with an outstanding optimal time of removal of 14 min, 30% faster than with synthesized by conventional methodologies. These findings underscore the innovation brought about by the I-CHEM synthetic approach, where more effective collisions are reached, as well as opening avenues for broader applications of MOFs. The wet-mechanochemical procedure not only demonstrates its novelty, but also presents the potential for scalability under continuous flow conditions, further enhancing the feasibility of largescale production.

Impact in Continuous flow Heated Mechanochemistry (ICHEM) was used for the production of solketal at 60 °C using glycerol and acetone in the presence of homogeneous FeCl3.6H2O (1 mol

ICHeM technology (Impact Continuous Heated Mechanochemical) was developed for the preparation of different deep eutectic solvents (DESs) such as choline chloride–urea (1:2, mol/mol), choline chloride–glycerol (1:2, mol/mol), choline chloride–oxalic acid (1:1, mol/mol), and choline chloride–zinc chloride (1:2, mol/mol) with graduate formation challenges. The designed DESs were obtained without external heating with a productivity ranging from 4.8 to 254 g min–1. Moreover, characterization of DESs using NMR, FT-IR (ATR), ICP-MS, differential scanning calorimetry, viscosity, and relative permittivity showed identical physicochemical properties compared with DESs obtained using conventional processes. In all cases, even and almost for more challenging DESs, the beads’ mechanochemical assisted continuous flow process showed incomparable advantages in comparison with traditional batch preparation processes, in terms of performance, energy, operating time, security, economics, and thus industrial-scale reality. This new process opens the routes to meet the industry’s new expectations for DES production to follow the future drastic development of this green solvent-based process in many fields.

The potential of combining continuous flow and mechanochemistry for biomass valorization was explored in this work. Vanillin production employing isoeugenol and vanillyl alcohol as sustainable biomass-derived feedstocks was chosen due to the relevance of this flavoring molecule and the current need to find alternative starting materials to industrially used petro-based compounds. The combination of continuous flow and mechanochemistry led to outstanding results in terms of conversion, selectivity, and yield of vanillin by performing the reaction in the absence of catalysts from the lab to scale-up results (a 0.5-1 L DYNO-MILL Multi Lab reactor). The transformation of vanillyl alcohol toward vanillin was additionally performed in a DYNO-MILL Research Lab, a laboratory scale flow mechanochemical reactor (Willy A. Bachofen AG, Switzerland), observing optimum values of conversion, selectivity, and yield of the product of interest.

The urge of developing modern alternatives regarding indus-trial production has led to the creation of novel techniques that help overcome critical disadvantages from traditional batch mechanochemistry. One promising strategy includes the merging of flow processes with mechanochemistry. Two tech-nologies are herein highlighted: twin-screw extrusion (TSE) and Impact (induction) in Continuous flow HEated Mechano-chemistry (I-CHEM) allowing not only the industrial production of polymers but also active pharmaceutical ingredients, syn-thesis of (nano)materials, and the obtention of high-added value products from biomass and wastes valorization.

The world's energy transition from fossil to renewable energy is unthinkable without further research in energy storage. Decreasing the environmental impacts from the production of energy storage technologies is essential for achieving a green energy transition. Calcium Zincate (CAZN) is used as active material in rechargeable zinc-based batteries (and other products, such as heterogeneous catalysts for biodiesel or antifungal products). They present a low-cost, safer, alternative to Lithium based batteries and are targeted as replacement solutions for lead-acid batteries. We propose a novelty in the synthesis of CAZN, the hydro-micro-mechanical process (HMMS). The residence time of this new route is about 20 times lower than the traditional processes, so its production needs less infrastructure and can deliver quicker at an industrial scale. In addition, laboratory tests indicate that HMMS CAZN has more reaction surface area and the activation of the battery is 1.77 times faster. Using the life cycle assessment (LCA) method, we compare this new process with the current best option, hydro-thermal synthesis (HTS). The cradle-to-gate results per kg of CAZN already indicates that HMMS is an environmentally better alternative for all indicators; especially when considering the normalization of the results with the residence time and the surface area, HMMS delivers better results, with improvements of 97 % in global warming, for instance. With this, we demonstrate that, outside of the cradle-to-gate, variables that make the final products better service units or give more function should be considered as valuable additional information when deciding among alternatives. This also highlights the importance of life cycle thinking when working with chemical processes and substances. In the sensitivity analysis, we developed 7 scenarios related to the energy demand of the processes, and we incorporated the projection in the European electricity mix for 2030 and 2050.

This work is aimed at the development of a semi-continuous mechanochemical process for biodiesel production and the subsequent valorization of glycerol, its by-product, via its conversion into calcium diglyceroxide using the same mechanochemical reactor. This basic solid catalyzes the methanolysis of vegetable oils. The implementation of a semi-continuous process allows both the preparation of the solid catalyst and the methanolysis process, overcoming the miscibility problems of methanol and oil. Thus, a biodiesel yield higher than 90% is reached using a methanol:oil molar ratio close to stoichiometric value and 1.5 wt. % catalyst, after passing through the reactor with a flow rate between 4 and 45 L/h. This new process for biodiesel production can easily be scaled up and applied to the conversion of used cooking oils, without any significant yield decrease. A cost study was also performed, demonstrating that this is more economical than the conventional batch stirring-based process. (C) 2020 Elsevier Ltd. All rights reserved.

The development of an innovative and sustainable high-throughput reaction platform allows optimizing a wide range of chemical processes (materials synthesis and catalysis, among others) to tackle the Green Deal. This tool unifies, for the first time, the benefits of mechanical energy, thermal and pressure activation in continuous flow with an induction in situ heating system, facilitating the incorporation of inputs (liquids, solids and gases) with controlled pressure. As a result of the synergistic effect of this simultaneous activation, this technology will: (i) shorten reaction times; (ii) decrease temperature; (iii) improve reactions kinetics as mass transfer limitations are reduced; (iv) minimize the use of solvents; (v) decrease the reaction steps; (vi) increase the volume treated, enabling a real scale-up; and (vii) enhance the yields and/or selectivity. This new high-throughput reactor is used for the synthesis of calcium diglyceroxide (CaDG), minimizing the reaction steps and cost, to obtain a pure CaDG. This heterogeneous catalyst is used for biodiesel production and valorization of the glycerol generated as a by-product. An efficient synthesis protocol of CaDG has been developed, requiring shorter time, without heating, and no need for a solvent. This new process facilitates oil–methanol mixing in the transesterification process, thus minimizing the mass transfer limitations associated with the immiscibility of reactants. In addition, this process has been optimized by using CaDG as a solid catalyst.