Search Results (11)

The optimization of distillation processes is particularly challenging due to the presence of nonlinear equations and integer variables, resulting in complex mixed-integer nonlinear programming (MINLP) problems. This work introduces an enhanced optimization algorithm, the logic-based proximity principle Bender’s decomposition (LB-PBD), to address non-convex MINLP issues in simulator-based distillation optimization. The key innovation, the proximity principle, improves lower bound predictions by prioritizing information from the closest known integer solutions. Additionally, the integration of a multi-start points strategy and a delayed convergence strategy ensures the algorithm achieves global optimality while avoiding premature convergence. The effectiveness if the proposed LB-PBD is validated through three case studies. Numerical experiments demonstrate so-called proximity principle superior ability of original algorithm to navigate local optima, making LB-PBD more versatile than traditional deterministic algorithm (logic-based outer approximation algorithm) and stochastic algorithm (adaptive superstructure-differential evolution algorithm). In a single-column distillation case, LB-PBD achieves high accuracy. In an extractive distillation case, the algorithm successfully optimizes the separation of a near-azeotropic mixture, reducing energy consumption and improving product recovery compared to previous solutions. These results highlight LB-PBD as a robust and effective tool for solving non-convex MINLLP problems, particularly in simulator-based distillation process optimization. Full article

Triple organic Rankine cycle (TORC) is gradually gaining interest, but the maximum thermal efficiencies (around 30%) are restricted by low critical temperatures of common working fluids (<320 °C). This paper proposes a high-temperature (up to 400 °C) TORC system to ramp up efficiency. A near-azeotropic mixture biphenyl/diphenyl oxide (BDO), which has a stellar track record in the high-temperature ORC applications, is innovatively adopted as the top and middle ORC fluid simultaneously. Four conventional organic fluids are chosen for the bottom ORC. A mixing heat exchanger connects the top and middle ORCs to reduce irreversible loss. Thermodynamic analysis hints that the optimal performance is achieved on the use of benzene as the bottom fluid. The maximum thermal and exergy efficiencies are respectively 40.86% and 74.14%. The largest exergy destruction occurs inside the heat exchanger coupling the middle and bottom ORCs, accounting for above 30% of the total entropy generation. The levelized energy cost (LEC) is 0.0368 USD/kWh. Given the same heat source condition, the TORC system can boost the efficiency by 1.02% and drive down LEC by 0.0032 USD/kWh compared with a BDO mixture-based cascade ORC. The proposed system is promising in solar thermal power generation and Carnot battery applications using phase change materials for storage. Full article

Distillation is widely recognized as the preferred method for separation due to its operational and control benefits. Traditional distillation processes, however, cannot successfully separate azeotropic mixtures with near boiling points. Numerous special distillation processes have been developed to address this limitation. Extractive distillation, in particular, has gained significant popularity in the chemical, petrochemical, pharmaceutical, and refining industries. This review examined the state-of-the-art advances in extractive distillation. The importance of the proper selection of a solvent was discussed. Several configurations of extractive distillation processes were presented. Additionally, alternative extractive distillation systems have been elaborated. However, significant research gaps remain, such as the need for an exhaustive investigation of various control variables, the impact of certain entrainers on distillation processes, and cost comparisons across specialized distillation systems. Furthermore, process intensification strategies require additional research to solve complexity and operability issues. The integration of energy-efficient technologies, developments in renewable energy consumption, and the development of cost-effective reactive or split distillation columns will shape the future of distillation operations. These advances will help the chemical process sector achieve improved energy efficiency, lower environmental impact, and increased sustainability. Full article

Methanol-to-gasoline (MTG) and dimethyl ether-to-gasoline (DTG) fuels are rich in heavy aromatics such as 1,2,4,5-tetramethylbenzene, resulting in low volatilities due to a lack of light ends, increased emission tendencies and drivability problems due to crystallization. Approaches addressing these issues mainly focus on single aspects or are optimized for petroleum-based feedstocks. This research article introduces an upgrading strategy for MTG and DTG fuels through hydroprocessing (HP) heavy-ends and applying a sophisticated blending concept. Different product qualities were prepared by HP heavy gasoline (HG) and Fischer-Tropsch wax using commercially available Pt/HZSM-5 and Pt/SAPO-11 catalysts in a fixed-bed reactor. The products were used for blending experiments, focusing on gasoline volatility characteristics. Accordingly, methanol, ethanol, methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE) were evaluated in a second blending experiment. The results were finally considered for preparing blends meeting EN 228. HP of HG was found to improve the amount of light-ends and the vapor pressure of the DTG fuel with increasing reaction temperature without, however, satisfying EN 228. The front-end volatility was further improved by blending methanol due to the formation of near-azeotropic mixtures, while ethyl tert-butyl ether (ETBE) considerably supported the mid-range volatility. A final blend with an alcohol content of less than 3 vol.%, mostly meeting EN 228, could be provided, making it suitable even for older vehicles. Full article

Standard gases are often prepared using high-pressure gas cylinders. However, it is difficult to accurately prepare a known concentration of hydrogen chloride (HCl) gas using this method because HCl is highly corrosive and adsorptive. In this study, a simple method for the continuous generation of HCl gas was developed using a diffusion tube containing hydrochloric acid and a nitrogen carrier gas. The concentration of HCl produced from this system was almost unstable, but constant gas generation was realized for several hours when azeotropic hydrochloric acid (20.6% HCl in water) and a temperature near the azeotropic point (108.5 °C) were used, resulting in the generation of 103.6 ppm (mean, n = 5) of HCl gas with a relative standard deviation (RSD) of 2.34%. In this case, the percentage of HCl present in the entire gas mixture of HCl and water vapor was 22.5%, which is almost equivalent to the HCl content in the azeotropic hydrochloric acid (20.6%). The HCl concentration could also be controlled by changing the flow rate of the carrier gas. This work demonstrates a simple technique based on the diffusion theory that allows for the constant, controllable generation of a known concentration of HCl gas using an azeotropic hydrochloric acid system. Full article

Electricity companies around the world are constantly seeking ways to provide electricity more safely and efficiently while reducing the negative impact on the environment. Mineral oils have been the most popular transformer insulation, having excellent electrical insulating properties, but have many problems such as high flammability, significant cleaning problems, and are toxic to fish and wildlife. This paper presents an alternative approach to mineral oil: a transformer design that is clean and provides better performance and environmental benefits. A 50 kVA, 34.5/0.4 kV gas insulated distribution transformer was designed and evaluated using the COMSOL Multiphysics environment. R410A was used as insulation material. R410A is a near-azeotropic mixture of difluoromethane (CH2F2, called R-32) and pentafluoro ethane (C2HF5, called R-125), which is used as a refrigerant in air conditioning applications. It has excellent properties including environmentally friendly, no-ozone depletion, low greenhouse effect, non-explosive and non-flammable, First, the breakdown voltage of the selected gas was determined. The electrostatic and thermal properties of the R410A gas insulated transformer were investigated in the COMSOL environment. The simulation results for the performance of oil and SF6 gas insulated transformers using the same model were compared. The gas-insulated transformer is believed to have equivalent performance and is an environmentally friendly alternative to current oil-based transformers. Full article

Membrane technology can play a very influential role in the separation of the constituents of HFC refrigerant gas mixtures, which usually exhibit azeotropic or near-azeotropic behavior, with the goal of promoting the reuse of value-added compounds in the manufacture of new low-global warming potential (GWP) refrigerant mixtures that abide by the current F-gases regulations. In this context, the selective recovery of difluorometane (R32, GWP = 677) from the commercial blend R410A (GWP = 1924), an equimass mixture of R32 and pentafluoroethane (R125, GWP = 3170), is sought. To that end, this work explores for the first time the separation performance of novel mixed-matrix membranes (MMMs) functionalized with ioNanofluids (IoNFs) consisting in a stable suspension of exfoliated graphene nanoplatelets (xGnP) into a fluorinated ionic liquid (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate ([C₂C₁py][C₄F₉SO₃]). The results show that the presence of IoNF in the MMMs significantly enhances gas permeation, yet at the expense of slightly decreasing the selectivity of the base polymer. The best results were obtained with the MMM containing 40 wt% IoNF, which led to an improved permeability of the gas of interest (P_R32 = 496 barrer) with respect to that of the neat polymer (P_R32 = 279 barrer) with a mixed-gas separation factor of 3.0 at the highest feed R410A pressure tested. Overall, the newly fabricated IoNF-MMMs allowed the separation of the near-azeotropic R410A mixture to recover the low-GWP R32 gas, which is of great interest for the circular economy of the refrigeration sector. Full article

Adsorption processes are characterized by their kinetics and equilibrium isotherms described by mathematical models. Nowadays, adsorption with molecular sieves is a method used to separate certain elements or molecules from a mixture and produce hydrogen, nitrogen, oxygen, ethanol, or water treatment. This study had two main objectives. The first one was focused on the use of different natural (Clinoptilolite-S.L. Potosi, Clinoptilolite-Puebla, and Heulandite-Sonora) and synthetic (Zeolite Type 3A) adsorbents to separate the mixtures $H_{2}O/H_{2}S{O}_4$ and $H_{2}O/C_2{H}_{5}OH$ . It was determined that both Zeolite Type-3A and Heulandite-Sonora have greater adsorption capacity in a shorter time compared with the Clinoptilolites at different temperatures. The second objective was the simulation of a pressure swing adsorption process to dehydrate ethanol using the parameters obtained from Zeolite Type 3A (with maximum adsorption capacity). Several configurations were considered to calculate the appropriate nominal values for the optimal process. The results illustrate that the purity of ethanol is increased when the following parameters are considered in the adsorption process: a high pressure, a constant temperature between 100 and 120 ${}^{°}$ C, a feed composition near the azeotropic point with lower water content, and a purge pressure near the vacuum. Finally, the results show that it is possible to take advantage of the length of the absorber bed in order to reduce the energy costs by increasing the ethanol production as well as complying with the international purity standards. Full article

This work explores the possibility to adopt in organic Rankine cycle (ORC) plants mixtures of water (acting as solvent) plus an organic compound (acting as solute) as the working fluid. Initially an evaluation of the thermodynamic properties of the mixtures is performed, in order to assess their properties, and to point out the molar fractions which entail a near-azeotropic behaviour. Four species from three different classes of chemical compounds are investigated: 2,2,2-trifluoroethanol and n-butanol for alcohols, where the first is fluorinated, acetonitrile for nitrile class and 2-methylpyrazine as a heterocyclic aromatic compound. Simultaneously, the thermal stability of the pure substances considered as the possible solute for the mixtures is experimentally investigated in order to estimate the temperature applicability range. The ORC plant performance, from a low-enthalpy geothermal heat source (hot water stream from 100 to 200 °C), adopting the selected mixtures as the working fluid is finally evaluated, and the analysis includes a preliminary discussion on the turbine design; results are compared with respect to the reference case of a hypothetical plant adopting water as the working fluid. Full article

It has been well-established that effects such as cracking are observable when wet layers are dried. In particular, the layer thickness, as well as the surface tension of the liquid, is responsible for this behavior. The layer formation of polymer electrolyte fuel cells and electrolyzer electrodes, however, has not yet been analyzed in relation to these issues, even though the effect of cracks on cell performance and durability has been frequently discussed. In this paper, water propanol polymer-containing carbon-black dispersions are analyzed in situ with regard to their composition during drying. We demonstrate that crack behavior can be steered by slight variations in the initial dispersion when the solvent mixture is near the dynamic azeotropic point. This minor adjustment may strongly affect the drying behavior, leading to either propanol or water-enriched liquid phases at the end of the drying process. If the evaporation of the solvent results in propanol enrichment, the critical layer thickness at which cracks occur will be increased by about 30% due to a decrease in the capillary pressure. Microscopic images indicate that the crack area ratio and width depend on the wet layer thickness and initial liquid phase composition. These results are of much value for future electrode fabrication, as cracks affect electrode properties. Full article

In this work we investigate the critical line of binary azeotropic mixtures of acetone-n-pentane. We pinpoint the abnormal behavior of the critical density line as a function of the mole fraction of one of the component and show its influence on other thermodynamic properties such as the volume, the enthalpy and the entropy. Full article