Azeotropic Research Articles

A systematic approach for screening green entrainers combining the environmental-health-safety indexes and separation performance

Here we propose a new approach for extractive distillation (ED) process design, integrating environmental-health-safety (EHS) indexes as early as during the entrainer screening phase. Typically, safety and environmental factors are addressed later in the design process, often during optimization or in a sequential evaluation after cost-based optimization. However, in this study, we propose for the early incorporation of EHS considerations during the entrainer screening phase. This involves assessing the entrainer suitability using traditional metrics alongside additional EHS criteria, such as lethal dose (LD50) and flash point. Two azeotropic mixtures, i.e., tetrahydrofuran (THF)/ethanol (EtOH) and THF/methanol (MeOH), are chosen to exemplify our proposed methodology. Among the 1432 screened entrainers, the top 10 entrainers were identified based on separation index. These candidates were then subjected to further evaluation based on EHS criteria. Ethylenediamine (EDA) emerged as the optimal choice for the separation of THF/MeOH and THF/EtOH mixtures, demonstrating commendable EHS performance. Both separation processes were successfully simulated using Aspen Plus, which confirms the validity and suitability of the screened entrainer.

Novel energy-efficient design of side-stream extractive distillation process with intermediate reboiler for separating multi-azeotropic mixture based on multi-objective optimization

Side-stream extractive distillation is extensively employed to separate azeotropic mixtures since its energy-efficient benefits. Nevertheless, its economic effect is not always obvious due to the introduction of expensive high-pressure steam. In this article, a conventional triple-column extractive distillation process is firstly researched for separating n-hexane/ethyl acetate/acetonitrile mixture. To effectively decrease the requirement for high-pressure steam and achieve a reduction in economic costs of side-stream extractive distillation, three innovative side-stream extractive distillation processes with intermediate reboiler are proposed. A multi-objective genetic method is applied to optimize the four processes with total annual cost (TAC) and entropy production as two objective functions. Additionally, due to the presence of intermediate reboiler, heat integration design is implemented to the three side-stream extractive distillation processes with intermediate reboiler. Compared to the triple-column extractive distillation process, the heat integration of the three side-stream extractive distillation processes with intermediate reboiler exhibit better performance considering economy, energy-efficient, and entropy production. It indicates that the heat integration of the double side-stream extractive distillation process with intermediate reboiler can reduce 20.10% of TAC, 29.65% of energy consumption, and 35.63% of entropy production, respectively.

Covalently assembling multi-dimensional carbon-based nanoclay composites via ionic liquid linkers into PVA membrane for molecular separation

The application of membrane-based separation technology in purifying azeotropic solutions plays a crucial role in minimizing energy consumption during reactive distillation. The strategic integration of multi-dimensional structural composites within mixed matrix membranes (MMMs), characterized by a robust framework and efficient molecular transport channels, poses challenges but demonstrates significant potential for advancing the development of high-performance membrane fabrication. Herein, we proposed a novel strategy to covalently assemble halloysite nanotubes (HNTs) and graphene oxide (GO) using ionic liquids (ILs) as linkers. When incorporated into the polyvinyl alcohol (PVA) matrix, the ILs@HNTs@GO (IHGO) composites exhibit excellent interfacial compatibility, and ILs also enhanced the composite’s selective transfer ability to water molecules. The optimal separation performance for pervaporation dehydration from a ternary solution was respectively 2.57 (selectivity) and 1.74 (permeability) times higher than those of the pristine PVA membrane. The structural stability of the MMMs and their separation mechanism has been comprehensively validated by adjusting the content of GO in IHGO composites and conducting simulations. This study holds significant theoretical and practical implications for organic compounds purification, while simultaneously paving new avenues for the fabrication of structurally robust and high-performance MMMs with optimal filler effectiveness.

Molecular-Sieving Separation of Methanol/Benzene Azeotrope by a Flexible Metal-Organic Framework.

Separation of methanol/benzene azeotrope mixtures is very challenging not only by the conventional distillation technique but also by adsorbents. In this work, we design and synthesize a flexible Ca-based metal-organic framework MAF-58 consisting of cheap raw materials. MAF-58 shows selective methanol-induced pore-opening flexibility. Although the opened pores are large enough to accommodate benzene molecules, MAF-58 shows methanol/benzene molecular sieving with ultrahigh experimental selectivity, giving 5.1 mmol g-1 high-purity (99.99%+) methanol and 2.0 mmol g-1 high-purity (99.97%+) benzene in a single adsorption/desorption cycle. Computational simulations reveal that the preferentially adsorbed, coordinated methanol molecules act as the gating component to selectively block the diffusion of benzene, offering a new gating adsorption mechanism.

Influence of Process Parameters on the Efficiency of Pervaporation Pilot ECO-001 Plant for Raw Ethanol Dehydration.

Pervaporation is a membrane-based process used for the separation of liquid mixtures. As this membrane process is governed by the differences in the sorption and diffusivities of separated components, close boiling mixtures and azeotropic mixtures can effectively be separated. The dehydration of ethanol is the most common application of hydrophilic pervaporation. The pilot scale properties of hydrophilic composite poly(vinyl alcohol) PVA membrane (PERVAPTM 2200) in contact with wet raw bioethanol are presented. The wet raw bioethanol was composed of ethanol (82.4-89.6 wt%), water (5.9-8.5 wt%), methanol (2.3-6.9 wt%), cyclohexane (0.2-2.4 wt%), higher alcohols (0.2-1.3 wt%), and acetaldehyde (0.004-0.030 wt%). All experiments were performed using a SULZER ECO-001 plant equipped with a 1.5 m2 membrane module. The efficiency of the dehydration process (i.e., membrane selectivity, permeate flux, degree of dehydration) was discussed as a function of the following parameters: the feed temperature, the feed composition, and the feed flow rate through the module. It was found that the low feed flow rate influenced the dehydration efficiency as the enthalpy of evaporation caused a high temperature drop in the module (around 25 °C at a feed flow rate equal to 5 kg h-1). The separation coefficient during pervaporation was in the range of 600-1200, depending on the feed composition. The increase in temperature augmented the permeation flux and shortened the time needed to reach the assumed level of dehydration. It was revealed that dehydration by pervaporation using ECO-001 pilot plant is an efficient process, allowing also to investigate the influence of various parameters on the process efficiency.

Development of novel hybrid pre-separation/extractive reactive distillation processes for the separation of methanol/methyl acetate/ethyl acetate

The treatment of waste streams is an important research topic for the sustainable development of chemical process. Recently, reactive distillation-based (RD) processes with ethylene oxide hydrolysis have been developed to separate water-containing azeotropic mixtures. To separate Serafimov’s class 2.0–2b mixtures containing methanol/methyl acetate, a methyl acetate transesterification reaction between propylene glycol monomethyl ether is introduced to convert methyl acetate to methanol and coproduce produce propylene glycol monomethyl ether acetate as advanced solvents. Three-column reactive-extractive distillation (TCRED) and extractive-reactive distillation (TCERD), and double-column pre-separation-reactive distillation (DCPSRD) processes, are proposed. Then, we use a parallel genetic algorithm to optimize processes to maximize total net revenue. The case study is methanol/methyl acetate/ethyl acetate. Though TCRED is not suitable due to the occurrence of ethyl acetate transesterification reactions, to compare economic performances of three RD-based processes, TCRED is regarded as a pseudo process. The total net revenue of three RD-based processes is relatively larger than (∼20 % increase) that of the conventional extractive distillation process. Compared with TCRED process, TCERD and DCPSRD can achieve $582336 and $1045995 increase in TNR, 27.43 % and 49.99 % TAC reduction, respectively. In summary, proposed RD-based processes are promising to separate Serafimov’s class 2.0–2b mixtures containing methanol/methyl acetate, especially TCRED and DCPSRD.

Selective absorption of ionic liquids in separating R-1243zf or R-161 from refrigerant blends

In order to recover and reuse pure refrigerants from the mixtures used in waste refrigeration facility, it is necessary to find a good way for separation. Due to the extremely low vapor pressure and good selectivity, ionic liquids (ILs) are regarded as promising entrainers for the extractive separation process of azeotropic or near-azeotropic mixtures. Phase behavior of refrigerant with ILs is the basic property in the design of selective absorption-separation process. In this work, the solubility of 3,3,3-trifluoropropene (R-1243zf) and ethyl fluoride (R-161) with trihexyltetradecylphosphonium chloride ([P6,6,6,14][Cl]) were measured based on the isochoric saturation method. The experimental temperature range was from 283.15 K to 343.15 K. Five activity coefficient models, including Margules, van Laar, Scatchard-Hamer, Wilson and non-random two-liquid (NRTL) model, were used to correlate the experimental data, and the results were discussed. In addition, based on the literature data, the separation capacities of different ILs for refrigerant blends composed of R-1243zf or R-161 were investigated.

The Impact of Feed Composition on Entrainer Selection in the Extractive Distillation Process

The selection of entrainers primarily focuses on their ability to alter the relative volatility. However, the impact of feed composition on entrainer selection has often been overlooked. In this study, we conducted two case analyses of the minimum azeotropic mixtures in the ethyl acetate–ethanol and acetone–methanol systems to explore how the feed composition influences the entrainer selection when aiming for maximum economic efficiency. Additionally, the impact of the entrainer type (positive or reverse) on the economic benefits was also investigated. The cases revealed that economic benefits will be notably enhanced when the selected entrainer preferentially targets and removes the low-content component as the light key component. For the two cases studied, when the feed composition was 0.2–0.8, compared to preferentially separating the high-content component, preferentially separating the lower-content component resulted in a reduction in energy consumption by more than 24.14% and 22.72%, respectively. The results show that the ideal entrainer should be capable of converting the higher-content component in the feed into the heavy key component.

Separation of Azeotropic Refrigerant Mixtures: R-450A, R-456A, R-515B, and R-516A Using Phosphonium- and Imidazolium-Based Ionic Liquids

Separation of Azeotropic Refrigerant Mixtures: R-450A, R-456A, R-515B, and R-516A Using Phosphonium- and Imidazolium-Based Ionic Liquids

Applicability exploration and sustainable assessment of heat integration and vapor recompression heat pump to side-stream extractive distillation processes for separating ternary azeotropic system

The side-stream extractive distillation (SSED) process is attracting extensive attention due to its high energy efficiency for separating ternary azeotropic mixture. However, the correlation between the bottom temperature level of distillation columns depending on the flowrates and compositions of side streams and the introduction of heat integration (HI) and vapor recompression heat pump (VRHP) technology is ignored. In the work, a range of initialization extractive distillation processes including one conventional extractive distillation (CED) process and five SSED processes considering different flowrates, compositions, and feed locations of side streams are proposed for separating acetonitrile/isopropanol/water ternary azeotropic system. The optimization results with the minimum the total annual costs (TAC) as the optimization objective show that not all SSED schemes are superior to the CED separation process, and the SSED separation schemes can achieve up to a 2.72 % reduction in the TAC. Following that, the HI and VRHP assisted extractive distillation schemes are proposed based on the temperature levels between the top and bottom of different distillation columns and compressor restraints for the initialization extractive distillation schemes mentioned after optimization. Moreover, sustainable evaluations covering economy, energy consumption, environment, and energy utilization are implemented for the extractive distillation schemes proposed. The evaluation results indicate that the CED-HI scheme overcomes all SSED-HI and SSED-VRHP schemes in terms of economic costs, but the optimal SSED-HI processes can reduce 8.77 % of energy consumption and 4.73 % of CO2 emissions, while the energy utilization raised from 1.70 % to 1.78 % compared to the CED-HI process.

Design and energy-saving strategy of sustainable pressure-swing distillation with thermally and electrically coupled intensification for separating ternary mixture with multiple azeotropes

The separation of ternary mixtures that form multiple azeotropes is frequently encountered in industry. Benefiting from the pressure-sensitive nature of the azeotropic mixture, the pressure-swing distillation (PSD) is promising to realise the separation without introducing foreign solvents. However, the wide application of PSD seems challenging from an energetic point of view. This work has developed a sustainable PSD process with thermally and electrically coupled intensification to decrease energy consumption, taking the separation of homogeneous acetonitrile/ethanol/water mixture as a demonstrating example. Two conventional PSD processes with different product sequences are designed through the ternary phase diagram and further optimised using the NSGA-II, considering multiple objectives, including total capital cost, total operating cost, and CO2 emissions. The optimal solution is selected by the TOPSIS analysis for each sequence and is then intensified with thermal heat integration and electricity-driven heat pump techniques. The results show that, in comparison to the non-heat-integrated PSD process, the proposed intensified design can dramatically reduce the total annual cost by up to 48%, simultaneously decreasing CO2 emissions by up to 60% and boosting energy efficiency. The present study can be of reference for designing a sustainable PSD process in ternary azeotropic separation.

Network engineering of organosilica membranes for efficient pervaporation dehydration

In the petroleum industry, the mixing of ethanol (EtOH), isopropanol (IPA), and n-butanol (n-BuOH) with water is a prevalent occurrence in both production and recovery phases. Obtaining the required degree of purity via dehydration poses a significant challenge that needs to be addressed. Pervaporation has emerged as a promising method for separating azeotropic mixtures due to its energy efficiency and independence from vapor-liquid equilibrium constraints. In this study, organosilica precursors, namely 1,2-bis(triethoxysilyl)ethane (BTESE), 1,2-bis(triethoxysilyl)ethylene (BTESEthy), and 1,2-bis(triethoxysilyl)acetylene (BTESA), were utilized for the fabrication of organosilica membranes using the sol–gel method. Subsequently, these membranes were employed for pervaporation dehydration of EtOH, IPA, and n-BuOH. This study investigates the effect of the degree of unsaturation of the bridged group, feed composition, and C atom count of alcohol on membrane dehydration performance. The membranes demonstrated superior separation performance for the n-butanol/water mixtures compared to other alcohol/water systems investigated. In this particular context, BTESE membrane exhibited a significant separation factor, although accompanied by a reduced permeation flux. Conversely, BTESA membrane demonstrated a decreased separation factor but an increased permeation flux. The comparison between gas permeation and pervaporation highlighted that the separation mechanism was primarily governed by molecular sieving through the organosilica membranes.

Pervaporation Separation of Tetrahydrofuran/Water Azeotropic Mixtures using Phosphorylated Blend Membranes

In this study, we developed novel phosphoric acid crosslinked blend membranes for the pervaporation separation of tetrahydrofu-ran/water mixtures. Sodium alginate and chitosan blend membranes were prepared by solution casting and solvent evaporation technique. These blend membranes were crosslinked with phosphoric acid in isopropanol/water baths and used for pervaporation separation of feed mixtures ranging from 6 to 43 wt.% water in tetrahydrofuran (THF)/water mixtures at 30 °C. Crosslinking was confirmed by Fourier transform infrared (FTIR) and Ion Exchange Capacity (IEC) study. Thermal stability and crystallinity of the membranes were determined from thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies respectively. The surface morphology of the membranes was observed using Scanning electron microscopy (SEM). Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the membranes in THF, water and binary mixtures. The effect of experimental parameters such as feed composition, membrane thickness, and permeate pressure on separation performance of the phosphorylated membranes were determined. These membranes were found to have good potential for breaking the azeotrope of 94 wt.% THF with a selectivity of 459 and normalized flux of 0.25 kg m−2 h−1 10 µm. The membrane performance exhibited a reduction in selectivity and an improvement in flux with increasing feed water compositions. Selectivity improved and flux decreased with increasing membrane thickness. Both flux and selectivity decreased with increasing permeate pressure.

The conceptual design and process intensification of the separation of ternary azeotropic mixture with heterogeneous characteristic

A substantial amount of ternary azeotropic mixtures with heterogeneous properties are generated in the production processes of the pharmaceutical and fine chemicals industries. While the presence of heterogeneous features complicates the thermodynamic behavior of such mixtures, it also creates opportunities for separations using heterogeneous distillation. Thus, this study focuses on the conceptual design and process intensification for the separation of heterogeneous ternary azeotrope mixtures integrating decanter, distillation, and heat pump technology. Based on the characteristics of a mixture with a liquid-liquid partial miscibility region, the design procedure including conceptual design, multi-objective optimization, and heat pump-assisted intensification has been proposed. The separation of acetonitrile-cyclohexane-toluene is used to illustrate the capability of the proposed design procedure. The results demonstrated that the heat pump-assisted process including one decanter, one distillation column, and two stripper columns provides the best separation process, excelling in economic, environmental, and thermodynamic performance, whose TAC is 76.15% lower than the conventional heterogeneous distillation.

Isothermal (vapor ＋ liquid) equilibrium measurements and correlation of the binary mixture 3,3,3-trifluoropropene (R1243zf) ＋ isobutane (R600a) at temperatures from [formula omitted] to [formula omitted] K

The restrictions set by the F-gas Regulation and the Kigali Amendment to the Montreal Protocol have pushed an extensive research into alternatives for fluorinated greenhouse gases in air conditioning and refrigeration. Hydrofluoroolefins (HFOs) are emerging as promising substitutes for hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons (HCFCs) in HVAC and refrigeration. Amongst these, R1243zf raised interests as low-GWP substitutes for R134a. The pursuit of low GWP refrigerants has also led to the examination of hydrocarbons (HCs), like propane (R290) and isobutane (R600a), due to their efficiency, low charge, and affordability, despite their flammability. The mixtures of R1243zf and isobutane could be of interest for medium temperature heat pump applications. Moreover, blending HFOs with HCs usually leads to azeotropic mixtures. While HCs benefit of a wide range of data and reliable Equations of State (EoS), HFOs, and in particular their mixtures, lack comprehensive information. This study reports vapor–liquid equilibrium (VLE) measurements for the 3,3,3-trifluoropropene (R1243zf) + isobutane (R600a) binary system in the temperature range between 283.15 K and 323.15 K. The measurements have been carried out by means of a vapor-recirculation apparatus combined with gas-chromatographic analysis. This work reports 53 experimental data with an expanded uncertainty (k=2) of 0.003 mol mol−1. The reported data, along with the data available in the literature, have been used to developed two new mixture models based on the Helmholtz free energy EoS, both leading to a significant improvement in the VLE prediction, with RMSE values lower than 0.005 mol mol−1 for both the liquid and the vapor phase composition.

Ultrasound assisted lycopene extraction from tomato skin waste by volatile natural deep eutectic solvent

In this work, a completely green method was applied for the extraction of lycopene from tomato skins waste. The combination of the ultrasound-assisted technique (UAE) and the use of volatile natural deep eutectic solvent (VNADES) menthol: thymol 1:1 allowed to obtain a green extraction process. Lycopene content was assessed by HPLC-DAD and compared with the lycopene extraction yields obtained using α-pinene and n-hexane as extraction solvents. The evaporation of the DES menthol:thymol was conducted using a Vacuum Vortex Evaporator. The highest concentration of extracted lycopene was obtained with n-hexane (735.9 mg/g of dried extract (DE)) compared to terpene-based solvents; 468.1 mg/g and 358.7-484.2 mg/g DE were recovered from α-pinene and DES menthol/thymol as azeotropic mixture and as such, respectively.

Molecular mechanism of efficient separation of isopropyl alcohol and isooctane by extractive distillation

In this paper, a method of extracting isopropyl alcohol and isooctane system from industrial wastewater of fuel oil by extractive distillation is proposed to realize resource utilization of waste and reduce environmental pollution. Isooctane and isopropyl alcohol are both products obtained from petroleum refining, which are widely used in many fields. In this study, the quantum chemical was used to determine that glycerol (Gl) and N, N-dimethylacetamide (DMAC) were the best extractants to separate Isopropanol and isopropyl alcohol. The intermolecular electrostatic interaction and reaction site between the extractant and the system were determined by electrostatic potential (ESP) analysis. Inter-complex compounds and weak interactions were analyzed by interaction region indicator (IRI). The independent gradient model based on Hirschfeld partition (IGMH) was used to visualize the electron density of the molecule. Meanwhile, the simulation process of azeotropic mixture separation of IPA and ISO by extractive distillation was established, and the process was optimized by a sequential iterative method. The economic and environmental were used to evaluate and analyze the process, and the azeotropic mixture separation was realized. Compared with Gl, the extractive distillation separation of isopropyl alcohol and isooctane by DMAC reduces the total annual cost by 5 %, energy consumption, and reduces the greenhouse gas emissions by 1 %, and has greater environmental protection and economic benefits. This work is guided by quantum chemical calculation and reveals the interaction mechanism of solvent separation azeotropic mixture from the microscopic level, which provides an important reference value for realizing high efficiency, energy saving, and green separation of azeotropic mixture in industry.

Process design and optimization of the reactive-extractive distillation process assisted with reaction heat recovery via side vapor recompression for the separation of water-containing ternary azeotropic mixture

To facilitate the high-energy-consumption separation of water-containing azeotropes, a reactive-extractive coupled distillation (RED) method has been proven as an effective approach. However, the reaction heat has not been fully utilized and the entrainer recovery column can be further improved in thermodynamics. For these purposes, different intensified methods have been developed in this study. Firstly, two published RED processes are conducted in IPA/DIPE/water system. To improve thermodynamic performance, a flash-coupled double-column reactive-extractive distillation (FL-DCRED) process is developed. These three processes are optimized to minimize total annual cost (TAC) via the particle swarm optimization algorithm. To fully utilize the reaction heat, a side-vapor-recompression and heat-integrated DCRED (SVRHI-DCRED) process is further designed by analyzing the temperature-enthalpy (T-H) diagram. Various evaluation methods are employed to assess the economic, environmental, thermodynamic effects, and energy recoverability of each process. The SVRHI-DCRED process is the most superior process across all indexes, which are 29.5%, 56.5%, 206.3% lower with respect to the DCRED process regarding TAC, CO2 emission, and maximum energy recoverability index, respectively. The thermodynamic efficiency is elevated from 38.27% to 43.10% via exergy analysis. The SVRHI configuration could be applicable to other processes with highly exothermic reaction for obtaining a more energy-efficient and economically advantageous process.

Enviro-economic investigation of Novel heat-integrated configurations for pressure swing distillation

Pressure Swing Distillation is a widely adopted solution for the separation of pressure-sensitive azeotropic mixtures in various chemical industries. While this method yields high-purity products, it comes with inherent challenges such as elevated operating costs and energy consumption. However, the temperature differential between the two columns involved presents a compelling opportunity for heat integration. In this study, 18 distinct heat integration scenarios were systematically evaluated using a process simulation software to identify the optimal column configuration for minimizing the Total Annualized Cost. These scenarios span five categories: the Conventional Method, Partial Heat Integration, Full Heat Integration, Internal Heat Integration Distillation Column, and External Heat Integration Distillation Column. The Vapor Recompression Column and Divided Wall Column schemes were applied to each method. Genetic Algorithm served as the optimization tool to determine the best arrangement with TAC as the objective function. Additionally, the environmental impact, assessed through CO2 emissions, was considered. Results indicate that the most economically and environmentally friendly solution is the I-HIDiC with divided wall columns, incorporating VRC systems in both columns. This approach offers a remarkable 66.5% cost savings and a substantial 96.3% reduction in CO2 emissions.

Phase behavior and intermolecular interaction analysis of the ternary system of water + 2-methylpyridine + octanols from 303.2 K to 323.2 K

Wastewater from coking and pharmaceutical processes often contain a significant amount of 2-methylpyridine, which forms an azeotropic mixture with water. Effectively and cleanly separating 2-methylpyridine from wastewater while conserving energy and obtaining high purity products is an urgent challenge. In this study, ternary liquid-liquid equilibrium (LLE) data for the extraction of 2-methylpyridine from wastewater were measured using three distinct solvents at temperatures of 303.2 K, 313.2 K, and 323.2 K. The obtained ternary data were subsequently correlated with thermodynamic models (NRTL and UNIQUAC) to get relevant binary interaction parameters, bridging a gap in Aspen Plus simulations of 2-methylpyridine separation by octanol solvents. Furthermore, the GUI tool was used to validate these parameters and the results confirmed the reliability of the obtained parameters. It was observed that as the temperature increased, the extraction performance of all systems decreased, indicating that elevated temperature are not conducive to the extraction process. Among the various components, iso-octanol showed the highest separation factor indicating better extraction efficiency of 2-methylpyridine. Additionally, this study integrated quantum chemical calculations to reveal the interaction mechanisms between different solvents, 2-methylpyridine, and water at the microscopic level. The computational results indicated that iso-octanol exhibited the most robust binding affinity with 2-methylpyridine, suggesting that iso-octanol has more excellent extraction properties.