The study of the reactivity of catalysts requires one to assess chemical kinetics and mechanisms in the absence of mass transport artifacts. Despite the existence of models and criteria for assessing the presence of mass transfer limitations during catalytic tests for gas-phase reactions in isothermal fixed bed reactors, the literature does not present straightforward protocols for performing the latter calculations. In this work, we present a systematic protocol for the calculations above. Particularly, we present protocols for estimating the effectiveness factor for external and the Weisz-Prater number for the internal mass transfer limitations. Data previously published on the oxidation of propane over mixed vanadium–aluminum (hydr)oxides was taken as a case study. Based on these protocols, we did a sensitivity study of the models used for calculations. Results showed that the model for calculating the effectiveness factor was poorly sensitive to all the above modifications. Meanwhile, the Weisz-Prater number was much more sensitive to the studied modifications, even reaching deviations up to ∼200%.

The so-called mechanochemical method for the synthesis of zeolites reduces the generation of liquid residues and gaseous pollutants as compared to the conventional solvothermal method. Different types of zeolites have been synthesized at the laboratory scale with this method using mostly pestle and mortar. However, such an approach hinders both the systematic comprehension of the effects of the input variables of the milling process and its further scale-up towards the synthesis of the zeolites and their catalytic application. This work investigates the influence of key factors involved in the ball milling stage of the mechanochemical route for the synthesis of MFI done with the assistance of a commercial MFI seed and in the absence of solvents over the most salient physicochemical properties of this type of materials, i.e. the recovery percentage, production cost, morphology, surface area and porosity, crystallinity, acidity of the protonated MFI and catalytic performance. The synthesis of the materials was planned and executed following a full 2 4 factorial experiment whose input variables were the Na2O/SiO2 and H2O/SiO2 molar ratios and the milling time and speed. The effects of both main and interaction factors over key physicochemical properties, and catalytic behavior of the synthesized materials on the alkylation of phenol with tert-butyl alcohol were established within the explored sampling space. Results showed that the Na2O/SiO2 molar ratio plays a key role for the mechanochemical synthesis of MFI, since this variable may direct the synthesis to the preferential production of MOR instead of MFI. On the other hand, it was found that the milling time and speed and their interactions markedly impact the textural properties of MFI. Furthermore, the triple interaction between the input variables affected the concentration of Lewis acid sites of the produced materials. These effects were rationalized by considering that sodium can act as a structure directing agent during the mechanochemical synthesis of MFI and also can promote the incorporation of aluminum to its structure. On the other hand, the milling time and speed are non-linearly correlated to the milling energy required for forming the aluminosilicate precursor that crystallizes during the hydrothermal stage of the process. Overall, all the zeolites synthesized by the mechanochemical route were less crystalline than both the MFI used as seed and an MFI synthesized by solgel. This was associated to the formation of amorphous agglomerates around the zeolitic crystals. Finally, the catalytic behavior of the mechanochemical MFI zeolites in the studied reaction was found to be linearly and positively correlated with both the concentration of BrØnsted of sites and with the density of acid sites. The catalytic tendencies were consistent with the proposal of a stepwise Langmuir-Hinshelwood mechanism for the alkylation of phenol with tert-butyl alcohol.

Despite the humongous volume of literature aiming to present the synthesis of innovative, more selective, stable, and active solid catalysts, the catalysts that come to be used at the industrial level, known as technical catalysts, are scarcely studied and poorly understood starting from the fact that most of the information on their manufacturing remains as an industrial secret. Therefore, many knowledge gaps and uncertainties in the techniques suitable to transform catalytic powders into technical catalysts lie ahead of those researchers who decide to engage in the development and study of applied catalysis. Therefore, this review seeks to provide guidance on the process for manufacturing technical catalysts from catalytic powders while also providing insight into the targeted properties of such materials. Specifically, this review examines the aspects related to the manufacture of technical catalysts spanning from the operations related to the mixture of their components to the thermal treatments to which the corresponding shaped bodies are submitted. Furthermore, we define and discuss the properties considered as key when evaluating the catalytic performance of the shaped materials.

No abstract

The so-called mechanochemical method for the synthesis of zeolites reduces the generation of liquid residues and gaseous pollutants as compared to the conventional solvothermal method. Different types of zeolites have been synthesized at the laboratory scale with this method using mostly pestle and mortar. However, such an approach hinders both the systematic comprehension of the effects of the input variables of the milling process and its further scale-up towards the synthesis of the zeolites and their catalytic application. This work investigates the influence of key factors involved in the ball milling stage of the mechanochemical route for the synthesis of MFI done with the assistance of a commercial MFI seed and in the absence of solvents over the most salient physicochemical properties of this type of materials, i.e. the recovery percentage, production cost, morphology, surface area and porosity, crystallinity, acidity of the protonated MFI and catalytic performance. The synthesis of the materials was planned and executed following a full 24 factorial experiment whose input variables were the Na2O/SiO2 and H2O/SiO2 molar ratios and the milling time and speed. The effects of both main and interaction factors over key physicochemical properties, and catalytic behavior of the synthesized materials on the alkylation of phenol with tert-butyl alcohol were established within the explored sampling space. Results showed that the Na2O/SiO2 molar ratio plays a key role for the mechanochemical synthesis of MFI, since this variable may direct the synthesis to the preferential production of MOR instead of MFI. On the other hand, it was found that the milling time and speed and their interactions markedly impact the textural properties of MFI. Furthermore, the triple interaction between the input variables affected the concentration of Lewis acid sites of the produced materials. These effects were rationalized by considering that sodium can act as a structure directing agent during the mechanochemical synthesis of MFI and also can promote the incorporation of aluminum to its structure. On the other hand, the milling time and speed are non-linearly correlated to the milling energy required for forming the aluminosilicate precursor that crystallizes during the hydrothermal stage of the process. Overall, all the zeolites synthesized by the mechanochemical route were less crystalline than both the MFI used as seed and an MFI synthesized by sol-gel. This was associated to the formation of amorphous agglomerates around the zeolitic crystals. Finally, the catalytic behavior of the mechanochemical MFI zeolites in the studied reaction was found to be linearly and positively correlated with both the concentration of BrØnsted of sites and with the density of acid sites. The catalytic tendencies were consistent with the proposal of a stepwise Langmuir-Hinshelwood mechanism for the alkylation of phenol with tert-butyl alcohol.

The so-called mechanochemical method for the synthesis of zeolites reduces the generation of liquid residues and gaseous pollutants as compared to the conventional solvothermal method. Different types of zeolites have been synthesized at the laboratory scale with this method using mostly pestle and mortar. However, such an approach hinders both the systematic comprehension of the effects of the input variables of the milling process and its further scale-up towards the synthesis of the zeolites and their catalytic application. This work investigates the influence of key factors involved in the ball milling stage of the mechanochemical route for the synthesis of MFI done with the assistance of a commercial MFI seed and in the absence of solvents over the most salient physicochemical properties of this type of materials, i.e. the recovery percentage, production cost, morphology, surface area and porosity, crystallinity, acidity of the protonated MFI and catalytic performance. The synthesis of the materials was planned and executed following a full 24 factorial experiment whose input variables were the Na2O/SiO2 and H2O/SiO2 molar ratios and the milling time and speed. The effects of both main and interaction factors over key physicochemical properties, and catalytic behavior of the synthesized materials on the alkylation of phenol with tert-butyl alcohol were established within the explored sampling space. Results showed that the Na2O/SiO2 molar ratio plays a key role for the mechanochemical synthesis of MFI, since this variable may direct the synthesis to the preferential production of MOR instead of MFI. On the other hand, it was found that the milling time and speed and their interactions markedly impact the textural properties of MFI. Furthermore, the triple interaction between the input variables affected the concentration of Lewis acid sites of the produced materials. These effects were rationalized by considering that sodium can act as a structure directing agent during the mechanochemical synthesis of MFI and also can promote the incorporation of aluminum to its structure. On the other hand, the milling time and speed are non-linearly correlated to the milling energy required for forming the aluminosilicate precursor that crystallizes during the hydrothermal stage of the process. Overall, all the zeolites synthesized by the mechanochemical route were less crystalline than both the MFI used as seed and an MFI synthesized by sol-gel. This was associated to the formation of amorphous agglomerates around the zeolitic crystals. Finally, the catalytic behavior of the mechanochemical MFI zeolites in the studied reaction was found to be linearly and positively correlated with both the concentration of BrØnsted of sites and with the density of acid sites. The catalytic tendencies were consistent with the proposal of a stepwise Langmuir-Hinshelwood mechanism for the alkylation of phenol with tert-butyl alcohol.

The study of the reactivity of solid catalysts requires assessing chemical kinetics and mechanism in the absence of mass transport artifacts. These artifacts consist of the formation of concentration gradients either on the external or internal (inside nanopores) surface of the solid. Despite the existence of models and criteria for assessing the presence of mass transfer limitations during catalytic tests for gas-phase reactions in isothermal fixed bed reactors, the literature does not present straightforward protocols for performing the latter calculations. In this work, we present a systematic and complete protocol for the calculations above. The developed protocol serves as a tutorial for students and researchers. Particularly, the effectiveness factor for external and the Weisz-Prater number for the internal mass transfer limitations were developed. The oxidation of propane over mixed vanadium-aluminum (hydr)oxides was taken as a case study. Based on these protocols we perform a sensitivity study of the models for the following modifications: (i) the equation of state for modeling the thermodynamic properties of the gas phase, (ii) the particle size, (iii) the conversion of propane at two different temperatures and, (iv) the reactant used as a basis of the calculations; i.e., switching from propane to oxygen. Results showed that the model for calculating the effectiveness factor was poorly sensitive to all the above modifications. Meanwhile, the Weisz-Prater number was much more sensitive to the studied modifications, even reaching deviations up to ~200%.

The study of the reactivity of catalysts requires assessing chemical kinetics and mechanism in the absence of mass transport artifacts. Despite the existence of models and criteria for assessing the presence of mass transfer limitations during catalytic tests for gas-phase reactions in isothermal fixed bed reactors, the literature does not present straightforward protocols for performing the latter calculations. In this work, we present a systematic protocol for the calculations above. Particularly, the effectiveness factor for external and the Weisz-Prater number for the internal mass transfer limitations were developed. The oxidation of propane over mixed vanadium-aluminum (hydr)oxides was taken as a case study. Based on these protocols we perform a sensitivity study of the models. Results showed that the model for calculating the effectiveness factor was poorly sensitive to all the above modifications. Meanwhile, the Weisz-Prater number was much more sensitive to the studied modifications, even reaching deviations up to ~200%.