Conversion Range Research Articles

Improving In Situ Combustion for Heavy Oil Recovery: Thermal Behavior and Reaction Kinetics of Mn(acac)3 and Mn-TO Catalysts

In this research work, the catalytic performances of two manganese-based catalysts, manganese (III) acetylacetonate (Mn(acac)3) and manganese tallate (Mn-TO), were studied during the process of Ashalcha heavy oil oxidation under in situ combustion conditions. DSC analysis shows distinct thermal behavior of both ligated catalysts during low- and high-temperature oxidation phases (LTO and HTO); for example, the shifting in peak temperature (Tp) in the HTO at a heating rate of 10 °C/min was reduced by approximately 5.3% for Mn-TO and 2.24% for Mn(acac)3 when compared with uncatalyzed heavy oil. Combined isothermal kinetic analyses using the Friedman and Kissinger–Akahira–Sunose analytic methods have provided insights about activation energies and frequency factors over the whole conversion range, where the catalytic performance of Mn-TO showed low activation energies in both LTO and HTO (Eα of Mn-TO was approximately 13.33% (LTO) and 7.68% (HTO) less than with the heavy oil alone). In addition, calculations of the effective rate constant confirmed the increased oxidation rate trend of both catalysts, with Mn-TO exhibiting the highest values. The findings highlight the potential of these manganese-based catalysts, the Mn-TO catalyst in particular, in optimizing heavy oil oxidation processes. The overall results further contribute to developing more efficient ligand catalyst complexes for sustainable heavy oil recovery while continuously improving their efficient application during in situ combustion in the petroleum industry.

A review on the heterogeneous catalyst for effective conversion of lignocellulosic biomass

This study examines a review of the heterogeneous catalyst for effective conversion of lignocellulosic biomass. In light of the challenges posed by a growing global population and the depletion of natural resources, there is an urgent need for alternative solutions. One such solution is the conversion of biomass into fuel, which has the potential to be a cost-effective and widely available substitute for fossil fuels. Solid catalysis and a range of chemical conversions effectively convert biomass into value-added chemicals. A critical factor in this process is the development of a highly efficient and selective catalysis system, along with the necessary chemical reactions. This review provides a comprehensive discussion of the various sources of biomass and their essential chemical composition. It also covers the conversion of biomass into a value-added chemical and the indispensable role of catalysis in the conversion process. Additionally, the review explores various conversion techniques for transforming biomass into useful forms of energy, and highlights their potential applications. By providing a detailed analysis of this process, this review aims to contribute constructively to the ongoing search for sustainable and effective solutions to energy challenges.

Pyrolysis characteristics and kinetic analysis of coating pitch derived from ethylene tar using model-free and model-fitting methods

This work conducted the pyrolysis of coating pitch derived from the ethylene tar through thermogravimetry analysis. The thermogravimetry-mass spectrometry and solid-state 13C nuclear magnetic resonance spectroscopy were performed to correlate the structural characteristics with the pyrolysis behavior. Meanwhile, the pyrolysis kinetics were estimated with model-free and model-fitting methods. The TG-DTG results showed that the pyrolysis process was generally divided into drying, fast pyrolysis, and polycondensation stages, accompanied by the decomposition of active functional groups like the aliphatic carbons bonded to oxygen (falO), the pyrolysis of relatively stable groups like the non-protonated aromatic carbon (faH), and the condensation of high bonding-energy aromatic structure like aromatic bridgehead carbon (faB). The activation energy obtained from model-free analysis ranged from 78.12 to 150.92kJ/mol with the increasing conversion, indicating the pyrolysis process as a multi-step reaction mechanism. Furthermore, the reaction model A1/3 (gα=[−ln(1−α)]3) was identified as the most suitable model for the pyrolysis of coating pitch in the conversion range of 0.25-0.8. The modeling values matched well with the experimental data, indicating the accuracy and feasibility of the results.

Improving precision base editing of the zebrafish genome by Rad51DBD-incorporated single-base editors

Single-base editors, including cytosine base editors (CBEs) and adenine base editors (ABEs), facilitate accurate C⋅G to T⋅A and A⋅T to G⋅C, respectively, holding promise for the precise modeling and treatment of human hereditary disorders. Efficient base editing and expanded base conversion range have been achieved in human cells through base editors fusing with Rad51 DNA binding domain (Rad51DBD) such as hyA3A-BE4max. Here, we show that hyA3A-BE4max catalyzes C-to-T substitution in the zebrafish genome and extends editing positions (C12–C16) proximal to the protospacer adjacent motif. We develop the codon-optimized counterpart zhyA3A-CBE5, which exhibits substantially high C-to-T conversion with 1.59- to 3.50-fold improvement compared to the original hyA3A-BE4max. With these tools, disease-relevant hereditary mutations can be more efficaciously generated in zebrafish. We introduce human genetic mutation rpl11Q42∗ and abcc6aR1463C by zhyA3A-CBE5 in zebrafish, mirroring Diamond-Blackfan anemia and Pseudoxanthoma Elasticum, respectively. Our study expands the base editing platform targeting the zebrafish genomic landscape and the application of single-base editors for disease modeling and gene function study.

Bioenergy potential from Ecuadorian lignocellulosic biomass: Physicochemical characterization, thermal analysis and pyrolysis kinetics

Lignocellulosic biomass offers a sustainable and renewable method for producing high-quality fuels and value-added chemicals. In this study, residues from peach palm (top, inner sheath, and meristem), sugarcane (top), and pineapple (mother plant) were characterized based on their physicochemical properties and thermal degradation behavior to estimate their bioenergy potential. The biomass residue kinetic constraints were analyzed using three isoconversional models: the Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), and differential Friedman (DF) models. Physicochemical characterization showed the peach palm top's notably high cellulose content of 35.71 ± 0.47 % wt. Calorific values of the residues ranged from 13.73 ± 0.08 to 16.91 ± 0.90 MJ kg−1. X-ray diffraction analysis indicated the carbonaceous and crystalline nature of the biomass residues. Mean activation energy values ranged from 105.02 to 370.10 kJ mol−1 for KAS, 111.50–360.99 kJ mol−1 for FWO, and 108.60–360.27 kJ mol−1 for DF. Finally, thermodynamic analysis revealed the endothermic nature of the pyrolysis process across the entire conversion range for the samples. Overall, these samples demonstrate major potential as feedstock for biorefineries and the development of Ecuador's circular economy.

New single-switch buck–boost converter with continuous input/output currents and a wide conversion range

The main aim of this paper is to introduce a new high step-up/down buck-boost converter with a minimum number of switches which provides the benefit of having the continuity of the input/output current. This single-switch semi-quadratic converter is suitable for high step-up applications while being able to provide step-down voltage gains. Also, by applying some minor changes to the circuit elements, another single-switch buck-boost converter is suggested which has two operative outputs with different voltage gains. One of the outputs of this topology has quadratic buck-boost converter voltage gain which is appropriate for high step-up/step-down applications. The other output could vary from input voltage to minus infinity, ideally. After studying the steady-state operation of the proposed converters in Continuous Conduction Mode (C.C.M), the simulation results are presented. In addition, a comparison among related converters proposed in the literature is made. Finally, experimental results are evaluated by implementing a laboratory prototype of the proposed converter in both step-down and step-up modes. Theoretical, simulation, and experimental results are compatible with each other.

Protonic conduction on oxide surfaces—role and applications in electrochemical energy conversion

Abstract Protonic conduction on surfaces of oxides has over the last two decades drawn attention for its possible utilisation in electrolytes for energy conversion at low temperatures and for its roles in enhancement of catalytic activity. This has led to deeper investigation and increased understanding of the phenomenon and development of quantifiable models. Along with this has emerged apparent demonstrations of use of such conduction in low-drain fuel cells as well as acknowledgement of the role of surface protonic conduction in electrodes for solid-state electrochemical and photoelectrochemical cells. Here is provided a brief review and elaboration of the fundamentals of the interaction of water and hydrogen with oxide surfaces, and models for the resulting protonic conduction in chemisorbed and physisorbed layers. We finally discuss aspects of surface protonic conduction in a range of applications, including sensors, catalysis, and electrochemical and photoelectrochemical energy conversion.

Enhancing oxidative desulfurization using sludge-derived ferrate (VI) for dibenzothiophene: An optimization study

Sulfur emissions pose a substantial threat to human health and the environment. To address this, stringent regulations limit sulfur content in fuels, and innovative desulfurization technologies are under active investigation. Oxidative desulfurization (ODS) employs oxidants to convert sulfur compounds into more readily recoverable sulfones. This study explores high-shear mixing in ODS, known as mixing-assisted oxidative desulfurization (MAOD), focusing on dibenzothiophene (DBT) oxidation in model fuels and pyrolysis oil. Fe(VI) derived from drinking water treatment sludge via wet oxidation is utilized in the MAOD process. The research evaluates the impact of ferrate concentration (400–600 ppm), phase transfer agent (PTA) concentration (100–300 mg per 50 mL of fuel), agitation speed (4,400 to 10,800 rpm), and temperature (40–60 °C) on % DBT conversion. Experimental sulfur conversions range from 63.4 % to 99.6 %. Through response surface methodology, optimal parameters of 537 ppm Fe(VI), 114 mg PTA per 50 mL of model fuel, 8,157 rpm agitation speed, and 41.7 °C are determined. These parameters are applied to pyrolysis oil, achieving a desulfurization efficiency of 53.2 %. Notably, increasing Fe(VI) concentration, agitation speed, and temperature significantly enhances sulfur reduction. The study underscores the potential of using potassium ferrate derived from drinking water treatment sludge in MAOD for effective desulfurization and provides insights into the impact of operating conditions on desulfurization efficiency. Ultimately, the research contributes to advancing environmentally friendly and cost-effective desulfurization technologies.

Thermokinetic study of tannery sludge using combustion and pyrolysis process through non-isothermal thermogravimetric analysis

Sludge from the tannery is produced in enormous amount. This work has investigated the thermal analysis behaviour of the tannery sludge by use of the thermogravimetric analysis (TGA). The TGA experiments is carried out in both air and nitrogen environment at the varied heating rates of 5, 10, 20 and 40 °C/min from the temperature range of 30–900 °C. In the assessment of kinetic parameters, the model fitting (Combined kinetics) method was employed. It was investigated that thermal degradation of the tannery sludge sample occurred in three stages. Majorly the conversions were observed in stage II for both in air and nitrogen environment. The activation energy (Ea) value for the combustion is 165.9 kJ/mol while for the pyrolysis the Ea value is obtained as 65.2 kJ/mol from the conversion range between 0.2 and 0.8 which is a promising approximation supported by a strong R2 value of 0.9719 and 0.93 for combustion and pyrolysis respectively. It is estimated from the master plots that six ideal models A1/2, A1/3, A1/4, F3, F4 and D5 were probably in approximation with the linear fitted data for both air and nitrogen. Various thermodynamic parameters which include the ΔH, ΔG and ΔS are also complimented that indicates the formation of activated complex and non-spontaneity of the reaction. The detailed thermokinetic study of the tannery sludge in combustion and pyrolysis offers a novel approach to understanding how this waste material decomposes under different temperature conditions. This holistic perspective contributes valuable insights into waste management practices, environmental impacts, resource recovery, and process optimization within the leather industry. Furthermore, the optimization of leather production processes on a large scale can minimize waste generation and enhance energy efficiency, strengthening the competitiveness and sustainability of the leather industry.

A Configurable Resolution Time-to-Digital Converter with Low PVT Sensitivity for LiDAR Applications

This paper presents an all-digital and configurable resolution time-to-digital converter (TDC) with low process–voltage–temperature (PVT) sensitivity for light detection and ranging (LiDAR) applications. The proposed TDC offers configurable resolution, allowing it to provide an appropriate conversion resolution according to the system’s requirements, thereby optimizing overall system performance. In addition, because the proposed TDC has high immunity to process–voltage–temperature (PVT) variations, it provides more stable time-converting results. The proposed design uses 0.18 μm CMOS technology, and the measurement results demonstrate a resolution ranging from 36 ps to 1193 ps, with a conversion range from 0.1 ns to 36 ns and an average error of 20.59 ps. Furthermore, the proposed TDC is implemented in an all-digital manner, making it highly suitable for system integration.

Farm to Fork Stability of Phytochemicals and Micronutrients in Brassica oleracea and Allium Vegetables.

Brassica oleracea and Allium vegetables are known for their unique, family specific, water-soluble phytochemicals, glucosinolates, and S-alk(en)yl-l-cysteine sulfoxides, respectively. However, they are also important delivery systems of several other health-related compounds, such as carotenoids (lipid-soluble phytochemicals), vitamin C (water-soluble micronutrient), and vitamin K1 (lipid-soluble micronutrient). When all-year-round availability or transport over long distances is targeted for these often seasonal, locally grown vegetables, processing becomes indispensable. However, the vegetable processing chain, which consists of multiple steps (e.g., pretreatment, preservation, storage, preparation), can impact the nutritional quality of these vegetables corresponding to the nature of the health-related compounds and their susceptibility to (bio)chemical conversions. Since information about the impact of the vegetable processing chain is scattered per compound or processing step, this review targets an integration of the state of the art and discusses needs for future research. Starting with a discussion on substrate-enzyme location within the vegetable matrix, an overview is provided of the impact and potential of processing, encompassing a wide range of (nonenzymatic) conversions.

Interpretable machine learning model for activation energy prediction based on biomass properties

A thorough understanding of pyrolysis kinetics for biomass is crucial for the process design, feasibility assessment, and scale-up in industrial scenarios. To reduce the time and economic cost invested in obtaining experimental kinetic data by performing the thermogravimetric analysis, a data-driven machine learning method was proposed in the present work. Random forest (RF), gradient boosting decision tree (GBDT), and extreme gradient boosting (XGB) algorithms were utilized to predict the activation energy versus conversion range with ten input features from biomass characteristics. Among these XGB has shown the most competitive prediction accuracy with a coefficient of determination (R2) higher than 0.98 and a root mean squared error (RMSE) = 7.7 kJ/mol. To enhance the model interpretability of the derived model, a visualized analysis for individual impact and interactions of variables was conducted by Shapley additive explanation (SHAP). The top three significant inputs for the model established by the current dataset are conversion rate, volatile content, and moisture content. This work provides a quick and accurate kinetic prediction method for unexploited biomass and favors detailed insights into the complicated associations between biomass characteristics and pyrolysis kinetics.

Solar energy EV charging system using integrated Zeta-Luo converter

This paper focuses on a grid-incorporated solar electric vehicle (EV) charging station that maximizes the acceptance of EVs in agricultural areas and reduces the over-reliance on the grid of urban cities. Since photovoltaic (PV) systems are widely available and easy to install, they are an excellent choice for EV charging applications. Hence, the aim of this work is to combine PV and EV, in order to achieve the objectives of both decarbonized energy generation and transportation. A Modified Zeta Integrated Luo Converter (MZILC), which provides a large conversion range combined with lower voltage stress, is proposed intending to increase the voltage level of the PV system. Furthermore, the converter generates a stable output devoid of fluctuations with the usage of the Grey Wolf–Grasshopper Optimized Proportional Integral (GW-GOPI) controller. Electricity for BLDC motors is generated by PV power during the day and supplied by a single-phase grid at night. The efficiency of the suggested grid-connected PV-based EV charging station is examined in MATLAB environment.

Mesoscale modeling of random chain scission in polyethylene melts

Polyolefins account for more than half of global primary polymer production, however only a small fraction of these polymers are currently being recycled. Fragmentation of polymer chains into shorter chains with a targeted molecular weight distribution with the goal of reusing these fragments in subsequent chemical synthesis can potentially introduce an alternative approach to polyolefins recycling. Herein we develop a mesoscale framework to model degradation of polyethylene melts at a range of high temperatures. We use the dissipative particle dynamics approach with modified segmental repulsive potential to model the process of random scission in melts of linear polymer chains. We characterize the fragmentation process by tracking the time evolution of the distribution of degrees of polymerization of chain fragments. Specifically, we track the weight average and the number average degrees of polymerization and dispersity of polymer fragments as a function of the fraction of bonds broken. Furthermore, we track the number fraction distribution and the weight fraction distribution of polymer fragments with various degrees of polymerization as functions of the fraction of bonds broken for a range of high temperatures. Our results allow one to quantify to what extent the distribution of polymer chain fragments during random scission can be captured by the respective analytical distributions for the range of conversions considered. Understanding the thermal degradation of polyolefins on the mesoscale can result in the development of alternative strategies for recycling a range of thermoplastics.

Assessing effects of climate and technology uncertainties in large natural resource allocation problems

Abstract. The productivity of the world's natural resources is critically dependent on a variety of highly uncertain factors, which obscure individual investors and governments that seek to make long-term, sometimes irreversible, investments in their exploration and utilization. These dynamic considerations are poorly represented in disaggregated resource models, as incorporating uncertainty into large-dimensional problems presents a challenging computational task. In this paper, we apply the SCEQ algorithm (Cai and Judd, 2023) to solve a large-scale dynamic stochastic global land resource use problem with stochastic crop yields due to adverse climate impacts and limits on further technological progress. For the same model parameters and bounded shocks, the range of land conversion is considerably smaller for the dynamic stochastic model than for deterministic scenario analysis.

Pyrolysis behavior of densified refuse-derived fuels (d-RDFs) via TGA: Investigating the impact of densification degree on thermal kinetics and thermodynamics

The conversion of municipal solid waste (MSW) into its energy-rich fraction, known as refuse derived fuel (RDF), addresses both MSW management and energy demand. RDF comprises a diverse blend of various non-hazardous waste streams, making it challenging to predict physical properties and chemical compositions. However, densification can help overcome these challenges. This work aims to explore the effect of densification degree on kinetic and thermodynamic parameters during the degradation of densified refuse-derived fuels (d-RDFs) in inert atmosphere. Herein, three d-RDFs samples obtained with varying degree of densification and die temperatures ranging from 55 °C to 118 °C, as well as a mixed fines (MF) sample produced during the pelletization process, were analyzed. Pyrolysis potential of d-RDFs and MF were determined using thermogravimetric analysis in the temperature range from 30 to 800 °C, at multiple heating rates of 5, 10, and 20 K min−1. The effect of the degree of densification on physical characteristics, and kinetic and thermodynamic parameters of d-RDF was investigated. Apparent activation energy (Eα) was estimated employing Friedman (FR), Kissinger-Akahera-Sunnose (KAS), and Flynn-Wall-Ozawa (FWO) methods. Derived Eα values were used to determine the pre-exponential factor (Aα) using the Kissinger method. Experimental results revealed that the durability of d-RDFs increased from 79.26 % to 98.73 % as the densification degree increased from II to IX. Furthermore, the Eα values exhibited a decreasing trend in the first peaks of the DTG profiles, while an opposite trend was observed in the second peaks of DTG curves. However, with an increase in the degree of densification, the mean values of Eα decreased by 5–10 % for all methods. The Aα values, assessed using the FR method, surpassed the critical value of (109 s−1) for all samples. However, with the KAS and FWO methods, these values fell below (109 s−1) within the conversion range of 0.05–0.25. Thermodynamic parameters confirmed the endothermicity of the thermal degradation process.

Green degradation of ofloxacin in electric Fenton based on Fe3+/Fe2+ internal cycling within Fe3O4 under neutral condition

To break the drawbacks of the traditional electro-Fenton (EF) such as narrow pH, low utilization of ·OH, Fe2+ loss, and low Fe3+ reduction rate, a new strategy that the ·OH generation in EF is based on the internal cycling of Fe2+/Fe3+ within Fe3O4 is proposed. A new-type homogeneous EF system (EF-Fe3O4@CF) where the Fe3O4-modified carbon felt box with clinoptilolite addition was used as the cathode, was established. The experimental results indicate that the system has 100 % removal efficiency for ofloxacin (OFL) and 86.4 ± 2.4 % removal efficiency for TOC at 120 min at pH = 7, and in multi-cycle operation the efficiency of OFL and TOC degradation did not decrease. Fe2+ (within Fe3O4) can activate H2O2 to generate ·OH and Fe3+ (within Fe3O4) is simultaneously reduced to Fe2+ on the cathode, so the internal cycling of Fe3+/Fe2+ within Fe3O4 achieve the green regeneration of ·OH. The conversion range of Fe3+/Fe2+ within Fe3O4 crystal is 4.43:1–1.46:1. The EF-Fe3O4@CF with multi-functions of adsorption, catalysis, and green degradation showed good stability and reusability. Our work provides fundamental research for Fe3O4 as a promising heterogeneous EF catalyst in advanced wastewater treatment.

Construction of Nanoflower Cobalt-Based Catalyst for Methane-Free CO Hydrogenation to Hydrocarbon Reaction.

Methane and its oxidation product (i. e., CO2) are both greenhouse gases. In the product chain of CO hydrogenation to hydrocarbon reaction, methane is also an unwanted product due to its poor added value. Herein we investigated the effect of structure-directing agent urotropine on cobalt-based catalyst supported on Al-O-Zn type carrier and achieved an initial and pioneering exploration of methane-free CO hydrogenation to hydrocarbon reaction at mild CO conversion range. The catalyst modified by urotropine has a nanoflower micromorphology and can significantly change the reaction performance, almost completely eliminating the ability of the catalyst to inhibit C-C coupling within a mild CO conversion range, that is, it can produce no or less C1-C4 gaseous hydrocarbons, while rich in condensed hydrocarbons (i. e., C5+ hydrocarbon selectivity can reach as high as 92.8 %-100.0 %).

Meso-Tetrahexyl-7,8-dihydroxychlorin and Its Conversion to ß-Modified Derivatives.

meso-Tetrahexylporphyrin was converted to its corresponding 7,8-dihydroxychlorin using an osmium tetroxide-mediated dihydroxylation strategy. Its diol moiety was shown to be able to undergo a number of subsequent oxidation reactions to form a chlorin dione and porpholactone, the first meso-alkylporphyrin-based porphyrinoid containing a non-pyrrolic building block. Further, the diol chlorin was shown to be susceptible to dehydration, forming the porphyrin enol that is in equilibrium with its keto-chlorin form. The meso-hexylchlorin dione could be reduced and it underwent mono- and bis-methylation reactions using methyl-Grignard reagents, and trifluoromethylation using the Ruppert-Prakash reagent. The optical and spectroscopic properties of the products are discussed and contrasted to their corresponding meso-aryl derivatives (where known). This contribution establishes meso-tetrahexyl-7,8-dihydroxychlorins as a new and versatile class of chlorins that is susceptible to a broad range of conversions to generate functionalized chlorins and a pyrrole-modified chlorin analogue.

Experimental study and modeling of the liquid phase hydrogenation of acetylene

Selective hydrogenation of acetylene is an important process for both ethylene purification and ethylene production from acetylene in the industry. Herein, we proposed liquid phase acetylene hydrogenation for high feed concentrations of C2H2 (8 %) and CO (20 %), which is used to produce ethylene as a subsequent process of partial oxidation of natural gas. The experiments were carried out in a stirred tank reactor using N-methylpyrrolidone (NMP) as solvent and PdAg/SiO2 as catalyst. The liquid phase process obtained a much higher selectivity to ethylene (92 %) with only 8 % selectivity to green oil (GO) and C4, compared to 71 % ethylene selectivity in gas phase hydrogenation. Furthermore, in the liquid phase ethylene selectivity increased with increasing acetylene conversion, especially in the conversion range of 80–100 %. We developed a model incorporating reaction kinetics, mass transfer and reactor model to predict the acetylene conversion and ethylene selectivity in liquid phase hydrogenation. The calculation results indicated that hydrogenation in the liquid phase operated at a lower acetylene concentration and a higher H2/C2H2 ratio, especially under high acetylene conversions. This explains why the liquid phase hydrogenation of acetylene has a much higher selectivity to ethylene than the gas phase process.