Effect of synthesis conditions on the porous texture of activated carbons obtained from Tara Rubber by FeCl3 activation.

This paper presents the results of an unique analysis of the influence of the mass ratio of activator FeCl3 to precursor and the temperature of the activation process on the formation of the porous structure of activated carbons obtained from Tara Rubber by FeCl3 activation. The study used the new numerical clustering based adsorption analysis method and the quenched solid density functional theory, taking into account, among other things, the heterogeneity of the analysed surface which is a new approach rarely used in the analysis of the porous structure of adsorbents. On the basis of the calculation results, it was concluded that the activated carbon with the most developed porous texture was obtained at a mass ratio (FeCl3:Tara Rubber) of 2, at an activation process temperature of 800 °C. This activated carbon is also characterised by the lowest degree of surface heterogeneity and at the same time, however, the widest range of micropores compared to activated carbons obtained at other mass ratios. The analyses carried out further demonstrated the valuable and complementary information obtained from the structure analysis methods and their high utility in practical applications, especially in the development of new industrial technologies for the production of adsorbents and the selection of optimal conditions for their production.

Numerical analysis of the porous structure of spherical activated carbons obtained from ion-exchange resins.

This paper presents the results of an analysis of the porous structure of spherical activated carbons obtained from cation-exchange resin beads subjected to ion exchange prior to activation. The study investigated the effects of the type of cation exchange resin, the concentration of potassium cations in the resin beads and the temperature of the activation process on the adsorption properties of the resulting spherical activated carbons. The numerical clustering-based adsorption analysis method and the quenched solid density functional theory were used to analyse the porous structure of spherical activated carbons. Based on original calculations and unique analyses, complex relationships between preparation conditions and the porous structure properties of the obtained spherical activated carbons were demonstrated. The results of the study indicated the need for simultaneous analyses using advanced methods for the analysis of porous structures, i.e., the numerical clustering-based adsorption analysis method and the quenched solid density functional theory. This approach allows a reliable and precise determination of the adsorption properties of the materials analysed, including, among other things, surface heterogeneities, and thus an appropriate selection of production conditions to obtain materials with the expected adsorption properties required for a given industrial process.

Analysis of the Influence of Activated Carbons' Production Conditions on the Porous Structure Formation on the Basis of Carbon Dioxide Adsorption Isotherms.

The results of a study of the impact of activation temperature and the mass ratio of the activator to the carbonised precursor on the porous structure of nitrogen-doped activated carbons obtained from lotus leaves by carbonisation and chemical activation with sodium amide (NaNH2) are presented. The analyses were carried out via the new numerical clustering-based adsorption analysis, the Brunauer-Emmett-Teller, the Dubinin-Raduskevich, and the density functional theory methods applied to carbon dioxide adsorption isotherms. Carbon dioxide adsorption isotherms' analysis provided much more detailed and reliable information about the pore structure analysed. The analyses showed that the surface area of the analysed activated carbons is strongly heterogeneous, but the analysed activated carbons are characterised by a bimodal pore structure, i.e., peaks are clearly visible, first in the range of pore size from about 0.6 to 2.0 nm and second in the range from about 2.0 to 4.0 nm. This pore structure provides optimal adsorption performance of carbon dioxide molecules in the pore structure both for adsorption at atmospheric pressure, which requires the presence of narrow pores for the highest packing density, as well as for adsorption at higher pressures, which requires the presence of large micropores and small mesopores. However, there are no micropores smaller than 0.5 nm in the analysed activated carbons, which precludes their use for carbon dioxide adsorption for processes conducted at pressures less than 0.01 MPa.

Mathematical analysis of the effect of process conditions on the porous structure development of activated carbons derived from Pine cones.

This paper presents the results of a study on the influence of the degree of impregnation and activation temperature on the formation of the porous structure of activated carbons (ACs) obtained from Pine cones by the chemical activation process using potassium hydroxide as an activator. The advanced new numerical clustering based adsorption analysis (LBET) method, together with the implemented unique numerical procedure for the fast multivariant identification were applied to nitrogen and carbon dioxide adsorption isotherms determined for porous structure characterization of the ACs. Moreover, the Quenched Solid Density Functional Theory (QSDFT) method was chosen to determine pore size distributions. The results showed a significant influence of the primary structure of Pine cones on the formation of the porous structure of the developed ACs. Among others, it was evidenced by a very high degree of surface heterogeneity of all the obtained ACs, irrespective of the degree of impregnation with potassium hydroxide and the activation temperature. Moreover, the analysis of carbon dioxide adsorption isotherms showed, that the porous structure of the studied ACs samples contains micropores accessible only to carbon dioxide molecules. The results also showed a significant advantage of the LBET method over those conventionally used for porous structure analysis based on Brunauer-Emmett-Teller (BET) and Dubinin-Raduskevich (DR) equations, because it takes into account surface heterogeneities. The novel analyses methods were more fully validated as a reliable characterization tool, by extending their application to the isotherms for ACs developed from the same precursor by phosphoric acid activation, and for samples arising from these ACs, further subjected to additional post-treatments. The effect of the raw material used as precursor was moreover analysed by comparison with previous reported results for other ACs. The complementarity of the results obtained with the LBET and QSDFT methods is also noteworthy, resulting in a more complete and reliable picture of the analyzed porous structures.

Computer Analysis of the Porous Structure of Activated Carbons Derived from Various Biomass Materials by Chemical Activation.

In this study, the preparation of activated carbons from various materials of biomass origin by activation with potassium hydroxide and a comprehensive computer analysis of their porous structure and adsorption properties based on benzene (C6H6) adsorption isotherms were carried out. In particular, the influence of the mass ratio of the activator's dry mass to the char mass on the formation of the microporous structure of the obtained activated carbons was analysed. The summary of the analyses carried out based on benzene adsorption isotherms begged the conclusion that activated carbon with a maximum adsorption volume in the first adsorbed layer and homogeneous surface can be obtained from ebony wood at a mass ratio of the activator to the char of R = 3. The obtained results confirmed the superiority of the new numerical-clustering-based adsorption analysis (LBET) method over simple methods of porous structure analysis, such as the Brunauer-Emmett-Teller (BET) and Dubinin-Raduskevich (DR) methods. The LBET method is particularly useful in the evaluation of the influence of the methods and conditions of production of activated carbons on the formation of their porous structure. This method, together with an appropriate economic analysis, can help in the precise selection of methods and conditions for the process of obtaining activated carbons at specific manufacturing costs, and thus makes it possible to obtain materials that can successfully compete with those of other technologies used in industrial practice and everyday life.

Computer Analysis of the Effect of Activation Temperature on the Microporous Structure Development of Activated Carbon Derived from Common Polypody.

This paper presents the results of a computer analysis of the effect of activation process temperature on the development of the microporous structure of activated carbon derived from the leaves of common polypody (Polypodium vulgare) via chemical activation with phosphoric acid (H3PO4) at activation temperatures of 700, 800, and 900 °C. An unconventional approach to porous structure analysis, using the new numerical clustering-based adsorption analysis (LBET) method together with the implemented unique gas state equation, was used in this study. The LBET method is based on unique mathematical models that take into account, in addition to surface heterogeneity, the possibility of molecule clusters branching and the geometric and energy limitations of adsorbate cluster formation. It enabled us to determine a set of parameters comprehensively and reliably describing the porous structure of carbon material on the basis of the determined adsorption isotherm. Porous structure analyses using the LBET method were based on nitrogen (N2), carbon dioxide (CO2), and methane (CH4) adsorption isotherms determined for individual activated carbon. The analyses carried out showed the highest CO2 adsorption capacity for activated carbon obtained was at an activation temperature of 900 °C, a value only slightly higher than that obtained for activated carbon prepared at 700 °C, but the values of geometrical parameters determined for these activated carbons showed significant differences. The results of the analyses obtained with the LBET method were also compared with the results of iodine number analysis and the results obtained with the Brunauer-Emmett-Teller (BET), Dubinin-Radushkevich (DR), and quenched solid density functional theory (QSDFT) methods, demonstrating their complementarity.

Analysis of the Effect of Conditions of Preparation of Nitrogen-Doped Activated Carbons Derived from Lotus Leaves by Activation with Sodium Amide on the Formation of Their Porous Structure.

This paper presents results of the analysis of the impact of activation temperature and mass ratio of activator to carbonized precursor R on the porous structure of nitrogen-doped activated carbons derived from lotus leaves by carbonization and chemical activation with sodium amide NaNH2. The analyses were carried out via the new numerical clustering-based adsorption analysis (LBET) method applied to nitrogen adsorption isotherms at -195.8 °C. On the basis of the results obtained it was shown that the amount of activator, as compared to activation temperatures, has a significantly greater influence on the formation of the porous structure of activated carbons. As shown in the study, the optimum values of the porous structure parameters are obtained for a mass ratio of R = 2. At a mass ratio of R = 3, a significant decrease in the values of the porous structure parameters was observed, indicating uncontrolled wall firing between adjacent micropores. The conducted analyses confirmed the validity of the new numerical clustering-based adsorption analysis (LBET) method, as it turned out that nitrogen-doped activated carbons prepared from lotus leaves are characterized by a high share of micropores and a significant degree of surface heterogeneity in most of the samples studied, which may, to some extent, undermine the reliability of the results obtained using classical methods of structure analysis that assume only a homogeneous pore structure.

An Evaluation of the Impact of the Amount of Potassium Hydroxide on the Porous Structure Development of Activated Carbons.

This paper presents the results of an evaluation of the impact of the amount of potassium hydroxide on the obtained porous structure of the activated carbons derived from the shells of pistachios, hazelnuts, and pecans by carbonization and subsequent chemical activation with potassium hydroxide by different adsorption methods: Brunauer-Emmett-Teller, Dubinin-Raduskevich, the new numerical clustering-based adsorption analysis, Quenched Solid Density Functional Theory, and 2D-Non-linear Density Functional Theory for Heterogeneous Surfaces, applied to nitrogen adsorption isotherms at -196 °C. Based on the conducted research, a significant potential for the production of activated carbons from waste materials, such as nut shells, has been demonstrated. All the activated carbons obtained in the present study at the activator/char mass ratio R = 4 exhibited the most developed porous structure, and thus very good adsorption properties. However, activated carbons obtained from pecan shells deserve special attention, as they were characterized by the most homogeneous surface among all the samples analyzed, i.e., by a very desirable feature in most adsorption processes. The paper demonstrates the necessity of using different methods to analyze the porous structure of activated carbons in order to obtain a complete picture of the studied texture. This is because only a full spectrum of information allows for correctly selecting the appropriate technology and conditions for the production of activated carbons dedicated to specific industrial applications. As shown in this work, relying only on the simplest methods of adsorption isotherm analysis can lead to erroneous conclusions due to lack of complete information on the analyzed porous structure. This work thus also explains how and why the usual characterizations of the porous structure of activated carbons derived from lignocellulosic biomass should not be taken at face value. On the contrary, it is advisable to cross reference several models to get a precise idea of the adsorbent properties of these materials, and therefore to propose the most suitable production technology, as well as the conditions of the preparation process.

An Evaluation of the Reliability of the Results Obtained by the LBET, QSDFT, BET, and DR Methods for the Analysis of the Porous Structure of Activated Carbons.

This paper presents the results of an analysis of the impact of the activator to the product of carbonized materials mass ratio on the porous structure of activated carbons obtained from mahogany, ebony, and hornbeam wood by carbonization and chemical activation with potassium hydroxide. The analyses were carried out on nitrogen adsorption isotherms using the Brunauer-Emmett-Teller (BET), Dubinin-Radushkevitch (DR), and Quenched Solid Density Functional Theory (QSDFT) methods, as well as the numerical clustering-based adsorption analysis (LBET) method. The activated carbons with the best adsorption properties and homogeneous surfaces were obtained at a mass ratio of R = 3. The analyses suggest the significant potential of producing adsorbents characterized by a large surface area and adsorptive capacity from raw materials such as mahogany, ebony, and hornbeam wood. The analyses in question also included an evaluation of the usability and reliability of the results obtained with the employed methods of structural analysis. Particular focus was placed on the limitations of adsorption models and on critically analyzing the output data. Our study shows the unique advantages of the LBET method compared to the other methods used. The LBET method allowed us, for example, to determine the degree of heterogeneity of the surface of the studied activated carbons and the shape of the clusters of adsorbate molecules formed in the pores of the studied material, as well as obtain information about the distribution of adsorption energy on the first adsorbed layer. This study also demonstrates the limitations of the methods used and the necessity to use LBET and QSDFT methods simultaneously for porous structural analysis. The simultaneous analysis of the adsorption isotherms via the LBET and the QSDFT methods makes it possible to choose the optimal preparation conditions while considering the properties of the original raw material. The analyses also suggest the complementary character of the employed methods and the scope of the useful and reliable information that can be obtained with these methods.

An evaluation of the reliability of the characterization of the porous structure of activated carbons based on incomplete nitrogen adsorption isotherms.

The paper presents the results of research devoted to reliability evaluation of the analysis of results of the porous structure of activated carbons based on incomplete nitrogen adsorption isotherms using the BET, t-plot, and NLDFT methods, as well as the LBET method comprising the unique numerical fast multivariant procedure of adsorption system identification. The research involved the application of the nitrogen adsorption isotherms obtained for five samples of activated carbons produced from waste materials of organic origin by way of chemical activation with potassium hydroxide, sodium hydroxide, and potassium carbonate with the use of microwave heating. The analyses performed pointed to a good correlation between the results obtained using the BET, t-plot, NLDFT, and LBET methods. Moreover, the parameters of the porous structure determined using these methods based on incomplete adsorption isotherms of nitrogen are in fact as reliable as these methods allow.

Numerical studies of the effects of process conditions on the development of the porous structure of adsorbents prepared by chemical activation of lignin with alkali hydroxides.

This paper presents the results of the application of the advanced LBET and QSDFT methods compared to the BET and DR approach to the comprehensive analysis of the porous structure of activated carbons obtained by chemical activation of demineralised Kraft lignin with potassium and sodium hydroxides. Based on the analysis of nitrogen adsorption isotherms, the influence of the preparation process conditions on the porous structure formation was investigated. Particularly, the impact of the type of activating agent, the activation temperature, the hydroxide to lignin mass ratio, and the flow rate of inert gas on the porous structure formation was assessed. This work proves how useful the used methods of structure analysis are when evaluating the influence of preparation conditions on the formation of the porous structure of activated carbons.

Use of fast multivariant identification of the parameters of adsorption systems to study the impact of activating agent on microporous structure formation during activation.

The possibility of using fast multivariant identification of adsorption system parameters to evaluate the influence of the activation conditions on the microporous structure of carbonaceous adsorbents was examined. The fitted models used in the procedure are based on a unique approach to the modeling of adsorption processes, which is a significant development of the conventional BET approach. This takes into account the occurrence of branched clusters and surface heterogeneity. The approach considers heterogeneity from the perspectives of both geometry and energy, and discusses geometrical and energy limitations of creating clusters and the adhesive forces in layers above the first one.

Computer analysis of the microporous structure of activated carbon fibres using the fast multivariant identification procedure of adsorption system parameters.

The paper presents the results of the research on possible employment of the new fast multivariant identification procedure of adsorption system parameters as a tool for analysis of the microporous structure of activated carbon fibres. This research should provide information on what significant advantages can be drawn from applying the proposed new method of porous structures description in comparison to the classical approaches, as well as show how the results obtained using this method should be interpreted and what calculation results and additional information will be obtained from analysing the adsorption isotherms using a more sophisticated tool as compared to the classical models. Particularly, in presented method it is possible to easily acquire not only information regarding the values of the obtained structure parameters, but also, more importantly, precise information on the reliability of these parameter calculations. A characteristic feature of the procedure used in the paper is also the fact that the properties of adsorption system can be considered independently of the applied adsorbate. Consequently, the description of microporous structure is independent of experimental conditions, hence will hopefully prove valuable for technologists.

Computer analyses of new numerical methods for the description of adsorption process and the reliability of identification of microporous structure parameters.

The aim of this work was the computer analysis of numerical properties of the original mathematical method of the description of adsorption process and the reliability of the identification of structure parameters. The method is based on the theory of multilayer adsorption, the derivation and further theoretical discussion of which was presented in the author's earlier works. The following tasks were given special attention in this paper: the influence of the assumed structure parameters, the influence of the high-pressure section of adsorption isotherms and the influence of the number of simultaneously fitted adsorption isotherms on the quality of identification and the errors of microporous structure parameters. This research provides a basis for the evaluation of the reliability of the parameters calculated for real adsorption systems.

Numerical analysis of nitrogen adsorption isotherms on active carbons by an employment of the new LBET class models.

The reported research concerns properties of the new LBET class models designed to describe the heterogeneous adsorption on microporous carbonaceous materials. In particular, the new adsorption models were used for the analysis of the microporous structure of two active carbons on the basis of nitrogen adsorption isotherms. This paper gives more information on the properties of the proposed identification technique.

Computer analysis of microporous structure by employing the LBET class models with various variants of the adsorption energy distribution in comparison to the classical equations.

The paper presents a properties study of the new LBET class models for heterogeneous multilayer adsorption and its applicability to analysis of microporous carbonaceous adsorbents in comparison to the selected classical equations. This paper shows that the LBET formulas give a good insight into the pore size distribution and dominant pore shape. Moreover, they provide more reliable evaluation of material surface area than the popular classical equations. This research constitutes a significant development and completion of the author's earlier works and provides a basis for the evaluation of reliability of parameters calculated for real systems.

Computer modeling and analysis of heterogeneous structures of microporous carbonaceous materials.

The aim of this work was to study the problems connected with computer modeling and analysis of heterogeneous structures of microporous carbonaceous materials. The research was focused on the numerical properties of original mathematical models for heterogeneous multilayer adsorption on microporous carbonaceous materials presented in our earlier papers and their applicability to examination of real microporous materials. These models are aimed at drawing information on pore structure and capacity on the basis of adsorption isotherms of small molecule adsorbates. They easily fit typical adsorption data in wide relative pressure ranges. In the theory presented, adsorption of small nearly spherical molecules in irregular pores of molecular size has been considered and side adsorbate-adsorbate interactions are neglected. The molecules mentioned are located in pores by forming aggregates, the size of which is limited by the geometry of the pores. The set of adsorbate molecules, which were adsorbed mainly due to adhesive interactions with the adsorbent matter, is treated as the first layer adsorption. Joining further molecules is viewed as the second, third,... layer adsorption. The main idea of the approach to modeling microporous structure presented, consists of introducing of realistic relationships between geometrical properties of pores and adsorption energy. Special attention was focused on the analysis of the influence of the number of model parameters on identification reliability and evaluation errors of porous structure parameters. This paper gives more information on properties of the identification technique presented in our earlier papers. The five-parameter and six-parameter identification reliability is analyzed in more detail, for different values of the system parameters. In this context, the efficiency of simultaneous examination of two isotherms is also studied.