In recent years, we have witnessed an increasing interest in the application of mechanochemical methods for processing materials in biomass refining techniques. Grinding and mechanical pretreatment are very popular methods utilized to enhance the reactivity of polymers and plant raw materials; however, the choice of devices and their modes of action is often performed through trial and error. An inadequate choice of equipment often results in inefficient grinding, low reactivity of the product, excess energy expenditure, and significant wear of the equipment. In the present review, modern equipment employing various types of mechanical impacts, which show the highest promise for mechanochemical pretreatment of plant raw materials, is examined and compared—disc mills, attritors and bead mills, ball mills, planetary mills, vibration and vibrocentrifugal mills, roller and centrifugal roller mills, extruders, hammer mills, knife mills, pin mills, disintegrators, and jet mills. The properly chosen type of mechanochemical activation (and equipment) allows an energetically and economically sound enhancement of the reactivity of solid-phase polymers by increasing the effective surface area accessible to reagents, reducing the amount of crystalline regions and the diffusion coefficient, disordering the supramolecular structure of the material, and mechanochemically reacting with the target substances.

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The surface area is an important parameter in setting any biorefining technology. The aim of this study was to investigate the applicability of sorption of methylene blue to characterize the surface of the main biomass carbohydrates: α-cellulose, sigmacell cellulose, natural gum, β-glucan, and starch. The morphology of particles of the model objects was studied by scanning electron microscopy. Nitrogen adsorption isotherms demonstrate that the selected carbohydrates are macroporous adsorbents. The monolayer capacities, the energy constants of the Brunauer–Emmett–Teller (BET) equation, and specific surface areas were calculated using the BET theory, the comparative method proposed by Gregg and Sing, and the Harkins–Jura method. The method of methylene blue sorption onto biomass carbohydrates was adapted and mastered. It was demonstrated that sorption of methylene blue proceeds successfully in ethanol, thus facilitating surface characterization for carbohydrates that are either soluble in water or regain water. It was found that the methylene blue sorption values correlate with specific surface area determined by nitrogen adsorption/desorption and calculated from the granulometric data. As a result of electrostatic attraction, the presence of ion-exchanged groups on the analyte surface has a stronger effect on binding of methylene blue than the surface area does. Sorption of methylene blue can be used in addition to gas adsorption/desorption to assess the accessibility of carbohydrate surface for binding large molecules.

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This study aimed at estimating peat adsorption properties for copper ion removal from aqueous solutions during peat modification. Two peat modifications have been studied using batch tests and quantitatively reproduced with instrumental analysis by using spectrometric, potentiometric, and thermodynamic modeling methods. The first variation—mechanical activation—was carried out in a planetary mill; for the second one—mechanochemical activation—dry sodium percarbonate (Na2CO3∙1.5H2O2) was added. The adsorption of copper ions was studied in the concentration range from 10–150 mg/L with an interaction time from 0.25–12 h. Both modifications led to significant changes in the interaction energy in the adsorption layer; thus, the acceptor properties of macromolecules were enhanced from natural peat to mechanically activated peat and mechanochemically activated peat. FTIR spectra, specific surface area characteristics, and sorption experiments show the predominantly chemical nature of copper sorption. Maximum adsorption capacity was determined to be 24.1, 42.1, and 16.0 mg/g for natural peat, mechanically activated peat, and mechanochemically activated peat, respectively. The example of peat mechanochemically oxidized with Na2CO3∙1.5H2O2 shows that the improvement in the physicochemical properties (CBET and specific surface area) plays a smaller role in the sorption capacity in relation to copper ions than the presence of phenolic and carboxyl groups, the content of which decreases during oxidation.

Permittivity analysis for detection of unbound water in coal and analysis of its effect on mechanochemical reactions and technology realization.

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