Ullrich Stahl

This study presents a sustainable approach for Methylene Blue (MB) dye removal using pristine, non-activated biochar derived from orange peel waste via Microwave-Assisted Pyrolysis (MAP). The key novelty lies in the systematic comparison of the biochar’s adsorption performance under both pH-controlled (constant pH 4) and unregulated pH conditions, demonstrating that pH regulation is essential for optimizing adsorption efficiency. The resulting biochar exhibited a high fixed carbon content (60.89%), an alkaline surface (Point of zero charge (pH_pzc) = 11.20, ZPotential = 0.1 mV @ pH 9), and oxygenated functional groups. Best MB removal of 83% was achieved at pH 4, despite the expected electrostatic repulsion. Kinetic studies showed the best fit with the Elovich model, indicating a heterogeneous surface. The Langmuir isotherm accurately described the equilibrium data, revealing a maximum adsorption capacity (q_max) of 20.57 mg g⁻¹ under pH-controlled conditions, representing an 83% increase over the 11.24 mg g⁻¹ obtained in the unregulated scenario. Thermodynamic analysis confirmed the process is spontaneous (ΔG° < 0), endothermic (ΔH° = + 4.88 kJ mol⁻¹ at constant pH), and governed by physisorption mechanisms, including hydrogen bonding and π-π interactions. This work demonstrates that pristine orange peel biochar generated via MAP is a highly effective adsorbent and highlights the critical impact of pH control on improving adsorption capacity and elucidating the dominant physisorption mechanisms.

Waste valorization is a necessary activity for the development of the circular economy. Pyrolysis as a waste valorization pathway has been extensively studied, as it allows for obtaining different fractions with diverse and valuable applications. The joint analysis of results generated by thermogravimetry (TGA) and analytical pyrolysis (Py-GC/MS) allows for the characterization of waste materials and the assessment of their potential as sources of energy, value-added chemicals and biochar, as well as providing awareness for avoiding potential harmful emissions if the process is performed without proper control or management. In the present study, these techniques were employed on three greenhouse plant residues (broccoli, tomato, and zucchini). Analytical pyrolysis was conducted at eight temperatures ranging from 100 to 800 °C, investigating the evolution of compounds grouped by their functional groups, as well as the predominant compounds of each biomass. It was concluded that the decomposition of biomass initiates between 300–400 °C, with the highest generation of volatiles occurring around 500–600 °C, where pyrolytic compounds span a wide range of molecular weights. The production of organic acids, ketones, alcohols, and furan derivatives peaks around 500 °C, whereas alkanes, alkenes, benzene derivatives, phenols, pyrroles, pyridines, and other nitrogenous compounds increase with temperature up to 700–800 °C. The broccoli biomass exhibited a higher yield of alcohols and furan derivatives, while zucchini and tomato plants, compared to broccoli, were notable for their nitrogen-containing groups (pyridines, pyrroles, and other nitrogenous compounds).

The present study focuses on the kinetics of the Knoevenagel condensation reaction between 7-methoxy-1-tetralone (1) and glyoxylic acid (2), catalyzed by potassium tert-butoxide in tert-butanol as a solvent, using a batch-type system under nitrogen atmosphere. The objective of this study was to synthesize the product (E)-2-(7-methoxy-1-oxo-3,4-dihydronaphthalen-2(1H)-ylidene) acetic acid (3). The reaction was conducted under controlled temperature conditions (65 °C, 75 °C and 85 °C), considering five specified time intervals to monitor its progress by thin layer chromatography (TLC) and high-performance liquid chromatography (HPLC). The kinetic data obtained was analyzed through three different mathematical methods: integral, differential, and nonlinear regression method, in order to determine the most suitable kinetic model. Applying the power law, the findings indicated that the pseudo-second order model, which was estimated via nonlinear regression, showed the best fit with the experimental data, characterized by minimal discrepancy between the calculated and observed values. The kinetic constants (k) obtained at temperatures of 65 °C, 75 °C and 85 °C were 0.89, 1.77 and 3.42 mL mmol⁻¹ min⁻¹, respectively. The pre-exponential factor (A) was calculated to be 2.194 × 10¹⁰ mL mmol⁻¹ min⁻¹, and the activation energy (Ea) was determined to be 67.22 kJ mol⁻¹. The product yield at these temperatures was 17.01%, 81.40% and 72.59%, respectively. The final product was characterized by GC-MS, FTIR, and UV-Vis. In conclusion, the kinetic study of the reaction was able to determine the optimal Knoevenagel condensation reaction conditions between (3) and (2) catalyzed by potassium tert-butoxide, and to facilitate understanding of the mechanism involved.

The main objective of the current work is to evaluate the effect of adding biochar obtained by pyrolysis of a mixture of greenhouse waste to agricultural soil, measuring its effectiveness as an amendment. A mixture of broccoli, zucchini, and tomato plant residues was pyrolyzed in a lab-scale reactor at 450 °C, obtaining a biochar yield of 35.6%. No carrier gas was used in the process. A thorough characterization of the biochar obtained was performed, including elemental and proximal analysis, density, pH, electrical conductivity, cation exchange capacity, surface area, and metal content. Since the raw material had a high percentage of ash (approximately 20%), the resulting biochar contained around 50% inorganic matter, with potassium and calcium being the major metals detected (10–11%). This biochar had a 29% fixed carbon content, a high heating value of 11.5 MJ kg⁻¹, a cation exchange capacity of 477 mmol kg⁻¹, and an electrical conductivity of 16 mS cm⁻¹.The biochar was mixed with greenhouse soil and fertilizer to form a substrate to grow bean seeds, the crop selected for the study. Different experiments were carried out, varying the biochar, fertilizer, and soil percentages. By adding 0.5% biochar to a substrate containing 1% fertilizer, the bean production was increased by 24.5%. It is worth noting that by adding only 0.5% biochar to soil, the bean production reached higher values than when adding 1% fertilizer. Biochar produced from the studied biomass improved the productivity of agricultural soils. The avoidance of selective collection by farmers as well as the non-use of carrier gas in the pyrolysis process made the implementation of the pyrolysis system in situ easier. Consequently, this research has great potential for practical application in modest agricultural areas.

In this work we present, a kinetic study of the Knoevenagel condensation reaction between 5-methoxy-1-tetralone and glyoxylic acid, catalyzed by sulfuric acid, to produce (E)-2-(5-methoxy-1-oxo-3,4-dihydronaphthalen-2(1H)-ylidene)acetic acid. The reaction was carried out in a batch system at 400 rpm for 24 h at temperatures of 75, 80 and 85 °C. The yields obtained at these temperatures were 90.30, 93.75 and 94.16%, respectively. The reaction was monitored by TLC and HPLC. For the kinetic analysis, three mathematical methods were used: integral, differential and non-linear regression. The results showed an excellent fit of the experimental data to the pseudo-first-order kinetic model.

The MAP process involved placing acid-pretreated biomass (CPH) in a domestic microwave oven at 600 W for 15 min. This was followed by a doping process with iron salts (+2, +3) to obtain BCCPH-Fe. Characterization of BCCPH-Fe was carried out using surface analysis (BET), TGA analysis and FTIR. Subsequently, the photodegradation process was performed using three different light sources (solar, UV 254 nm and UV 356 nm), with tartrazine as the adsorbate. The effect of pH on photodegradation was studied, and the percentage of degradation was evaluated through equilibrium and kinetic studies. The amount of BCCPH-Fe, tartrazine concentration, and exposure time to the light source were also evaluated. The best conditions for the photodegradation process were: light source was 254 nm, pH of 5, 1 g of BCCPH-Fe over 100 mL of tartrazine, 25 ppm tartrazine concentration, and 40 h exposure time. Under these conditions, a 93.45% removal of tartrazine was achieved. The experimental data of the adsorption equilibrium best fit the Langmuir-Hinshelwood model, while the adsorption kinetics best fit the pseudo-first-order model. The apparent kinetic constant was 0.04053 [h⁻¹], and the correlation coefficient was 0.98667. In conclusion, photodegradation using BCCPH-Fe can be an effective method for the removal of tartrazine from wastewater, offering a sustainable alternative to traditional methods.

The optimal conditions of the catalytic activation of allophane were evaluated for possible use as a catalyst within a fluidized bed catalytic cracking unit (FCC). The physicochemical properties of natural allophane and activated allophane were studied by using an alkaline activating agent, followed by a hydrothermal treatment. For the characterization, analytical techniques were used: Fourier transform infrared spectroscopy, particle size, (BET) surface area, thermogravimetry (TGA), X-ray diffraction (XRD), chemisorption, X-ray fluorescence (XRF), atomic force microscopy (AFM), and chromatography. The catalytic evaluation was determined by the (MAT) micro activity test equipment constructed according to ASTM D-3907/D3907M-2019. In addition, the Navier–Stokes 3D equations (nonlinear partial derivatives) were studied, which allow studying molecular dynamics contributing substantively to chemical kinetics describing the process of decomposition of crude oil in thermal cracking, determining the maximum temperature at which it retains its properties through the action of heat.

James Wei, profesor del «Department of Chemical Engineering-MIT» empleó el concepto de paradigma en 1988, introducido por T. Kuhn, para caracterizar las etapas evolutivas de la ingeniería química. Wei identificó 3 períodos: el preparadigmático, un primer paradigma que lo relaciona con la publicación del texto Principles of Chemical Engineering, y un segundo paradigma asociado al texto: Transport Phenomena, de Bird, Stewart and Lightfoot, en 1960. Los paradigmas de Wei son reduccionistas y limitados y deben ser ampliados y actualizados. En el presente trabajo se identifican 3 etapas: el preparadigmático, el paradigma de las operaciones unitarias, y el paradigma de la ciencia de la ingeniería química. Se hace referencia a las nuevas fronteras de la ingeniería química y a la necesidad de incluir nuevas disciplinas académicas y nuevas técnicas de enseñanza-aprendizaje.

Arrays with polymer-coated acoustic sensors, such as surface acoustic wave (SAW) and surface transverse wave (STW) sensors, have successfully been applied for a variety of gas sensing applications. However, the stability of the sensors’ polymer coatings over a longer period of use has hardly been investigated. We used an array of eight STW resonator sensors coated with different polymers. This sensor array was used at semi-annual intervals for a three-year period to detect organic solvent vapors of three different chemical classes: a halogenated hydrocarbon (chloroform), an aliphatic hydrocarbon (octane), and an aromatic hydrocarbon (xylene). The sensor signals were evaluated with regard to absolute signal shifts and normalized signal shifts leading to signal patterns characteristic of the respective solvent vapors. No significant time-related changes of sensor signals or signal patterns were observed, i.e., the polymer coatings kept their performance during the course of the study. Therefore, the polymer-coated STW sensors proved to be robust devices which can be used for detecting organic solvent vapors both qualitatively and quantitatively for several years.