Distillation is widely used for separating liquid mixtures, but its high heating demand poses challenges for achieving net-zero emissions. This study presents an innovative approach to electrifying distillation for load adaptability and flexible operation, aligning with dynamic electricity markets driven by renewables. The approach integrates flash vapor circulation and thermal storage into the distillation to optimize power usage and capitalizes on economic opportunities from load-flexible operation in response to fluctuating electricity pricing. A methanol/water distillation case study, using two typical electricity pricing scenarios, demonstrates that the proposed approach is more economically efficient than mechanical vapor recompression distillation, especially in lowering operational costs when the latter operates under fixed electricity pricing. However, compressor capital costs significantly impact overall costs, with sensitivity analysis examining different cost models. This approach can be applied to general distillation, allowing integration with the power sector and demand response programs, while enhancing flexibility, decarbonization, and efficiency.

Gravitation dictates the allowable flow phases and the achievable mass transfer rates in classic distillation columns, which are tall for that exact reason. High-gravity (HiGee) devices use a high centrifugal field to increase the interfacial area through high-speed rotating packing, resulting in a large enhancement of gas–liquid mass transfer and thus smaller equipment volumes. HiGee is an effective process intensification approach to enhance both reaction and separation efficiency. Combining reaction and distillation in a HiGee equipment (R-HiGee) is a topic that attracts significant attention. This paper summarises recent developments in HiGee (reactive) distillation technologies, including process synthesis and design, modelling and analysis of rotating packed bed systems, and equipment design. It also highlights future directions for developments in order to facilitate the systematic evaluation and application of high-gravity (reactive) distillation technologies.

The isobaric vapor–liquid equilibrium (VLE) data of the binary mixture of methylcyclohexane (1) + toluene (2) at 101.3 kPa; the pseudoternary mixture of methylcyclohexane (1) + toluene (2) + gamma-valerolactone (GVL) (3) with the entrainer-to-feed ratio (E/F) = 1 (mass basis) at 50, 80, and 100 kPa, and E/F = 2 and 3 at 100 kPa; and the pseudoternary mixture of methylcyclohexane (1) + toluene (2) + 1-methylpyrrolidin-2-one (NMP) (3) with E/F = 1 at 100 kPa were measured using a Fischer Labodest VLE602 ebulliometer. The reliability of the experimental VLE data was tested and confirmed by Van Ness and Fredenslund thermodynamic consistency tests. The experimental results indicate that the presence of GVL and NMP increases the relative volatility of methylcyclohexane to toluene; therefore, both entrainers remove a close-boiling behavior in the mixture. Non-random two-liquid (NRTL) and universal quasi chemical (UNIQUAC) thermodynamic models were applied in the experimental data correlation to obtain the optimum binary interaction parameters. For the mixture involving GVL, the experimental VLE data were accurately correlated by NRTL and UNIQUAC. However, NRTL has more accurate results compared with UNIQUAC. For the mixture containing NMP, both the UNIQUAC and NRTL models show favorable regression results.

Electrification of distillation processes through discretely heat integrated distillation columns (D-HIDiC) is an effective approach to enhance energy efficiency and lower carbon emissions. For separating systems with high temperature lift, multi-stage compression and inter-stage cooling are necessary to link the high-pressure rectifier and low-pressure stripper. Traditionally, heat recovery employs pumparound loops, but this study introduces liquid injection as a more efficient and innovative alternative. Simulation results using methanol/water separation indicate that liquid injection reduces both reboiler duty and compression power, achieving up to 50% primary energy savings compared with conventional distillation columns. Unlike continuous heat exchange in conventional HIDiC (C-HIDiC), D-HIDiC simplifies heat integration, avoiding complex hardware and energy penalties. Comparative analysis across multiple configurations, including SuperHIDiC, confirms the potential of D-HIDiC with liquid injection to fully electrify distillation, eliminate steam utility, and significantly support sustainable industrial operations.

The butanediols (BDOs), 2,3-, 1,4- and 1,3-butanediol, are platform chemicals that are mainly produced from fossil hydrocarbons but may be obtained through fermentation. However, low product concentration, by-product formation and high boiling temperatures of BDOs hinder downstream processing and increase overall fermentation costs. This study increases the competitiveness of industrial biotechnology by designing a large-scale process (broth processing capacity of 160 ktonne/y) for the final purification of BDOs after fermentation (recovery >99 %). It includes an initial preconcentration step in a vacuum distillation column to remove most water and light impurities. The initial removal of most of the water and the use of a heat pump system allowed significant energy reduction. At the heart of the process is an integrated dividing-wall column that can efficiently purify BDO from the remaining light and heavy impurities. Moreover, a single process design was proven effective in purifying different BDOs to > 99.4 wt%. This was cost-effective (total purification costs of 0.208 – 0.243 $/kgBDO) and energy-efficient (with primary energy requirements of 1.854 – 2.176 kWthh/kgBDO). The proposed purification sequence can be used for each BDO type, which offers flexibility in developing sustainable bioprocesses for BDO production.

The valorisation of green hydrogen and captured CO2 to produce chemicals or energy carriers holds immense potential to reduce GHG emissions. Among them, formic acid (FA) is an essential chemical with diverse applications and a growing market demand. Furthermore, due to liquidity at ambient conditions and its chemical stability, it is a promising hydrogen carrier. However, its direct thermochemical synthesis from CO2 hydrogenation still faces significant challenges due to a high thermodynamic barrier. This study presents a novel and eco-efficient process design for a 50 kta FA production from CO2 and green H2. Initially, CO2 is converted to CO as an intermediate compound that undergoes a carbonylation reaction with methanol to form methyl formate, which is then hydrolysed into FA. The major challenges of this new proposed process lie in the purification of CO and the energy-intensive downstream separation of FA. The former is addressed by using the COPure™ technology, which combines chemical and physical absorption, while the latter requires the use of process intensification techniques to minimize the energy and capital expenses. The newly designed process achieves high molar yields of 95 % for CO2 and 96 % for H2 with a specific energy intensity of 21.8 MJ/kg of FA. Notably, the CO2 emissions can be reduced by almost half as compared to the existing FA synthesis from fossil fuels, coupled with a 64 % reduction in electricity usage and 20 % decrease in steam requirements.

Pass-through distillation (PTD) is a novel separation technology that can effectively overcome challenges related to using vacuum distillation in bio-based processes (defined temperature limit for evaporation that might result in very low condensation temperature). This method allows evaporation and condensation to be performed at different pressures by decoupling them using an absorption-desorption loop with an electrolyte absorption fluid. This original paper presents a process design for large-scale bioethanol recovery from fermentation broth (production capacity ~100 ktonne/y) by PTD. The flexibility of the novel PTD technology is expanded by combining it with heat pumps (PTD-HP) and multi-effect distillation (PTD-MED). Total cost and energy requirements for the recovery of high-purity bioethanol (99.8 wt%) are respectively 0.122 $/kgEtOH and 1.723 kWthh/kgEtOH for PTD-HP, and 0.131 $/kgEtOH and 1.834 kWthh/kgEtOH for PTD-MED, proving the effectiveness of the newly designed recovery processes for concurrent alcohol recovery and fermentation.

Distillation is widely used for fluid separation in chemical industries, but accounts for a half of the operational cost and 40–50 % of the energy usage due to its low energy efficiency. Process intensification could effectively enhance the energy efficiency as well as improve the economic performance of distillation processes by integrating unit operations or functions. However, matching suitable intensified distillation techniques systematically with given separation tasks remains a challenge. This study is the first to generate a conceptual multi-step selection and decision approach by first going through several high level questions with corresponding suggested solutions for a separation task, then identifying the process bottlenecks and intensification targets via a list of evaluation criteria. Each of the technologies goes through a pre-filled process intensification (PI) matrix, and the most promising intensified technologies are recommended, and potential solutions are compared against the task specifications. The PI matrix proposed in this work yields a short list of appropriate solutions to be designed and economically assessed, proposing a screening framework for fluid separations in order to make a rapid selection at an early stage. Several binary, ternary, and multicomponent zeotropic and azeotropic mixture separations are carried out as case studies to illustrate the application of the proposed methodology, being validated using literature data. The proposed methodology can also help reduce the search space before carrying out rigorous optimization for the synthesis and design of the distillation.

Green organic entrainers and natural deep eutectic solvents (NADESs) possessing high boiling points and decomposition temperatures, exhibit considerable potential as advanced materials for green entrainers in extractive distillation. However, there is a wide range of solvents to choose from and their properties are only rarely available for use in process design and simulation. The present study aims to assess the selection parameters and examine the performance of and select green organic entrainers and NADESs for the separation of the close boiling mixture methylcyclohexane-toluene. The evaluation carried out was based on selectivity and relative volatility values obtained by using predictive models. COSMO-RS (a unimolecular quantum chemical calculation) was employed to predict the selectivity at infinite dilution, while group contribution methods such as UNIFAC and modified UNIFAC (Dortmund) were used to predict the relative volatility. According to the calculated results, the selectivity appeared a more important selection parameter than the performance index. The relative volatility prediction using the UNIFAC and UNIFAC Dortmund methods exhibits comparable trends to the selectivity results derived from COSMO-RS. However, the use of UNIFAC and modified UNIFAC (Dortmund) in predicting the relative volatility of NADES containing mixtures is limited due to the absence of functional group parameters. This CAPE study reveals that, based on the calculated selectivity (using COSMO-RS) and relative volatility (using UNIFAC, and modified UNIFAC (Dortmund)), most of the proposed green organic entrainers and NADESs exhibit a higher or comparable selectivity and relative volatility as the benchmark entrainers. This confirms the potential of the evaluated green entrainers with higher selectivity and relative volatility to enhance the design of extractive distillation. Therefore, the cost, energy and water consumption, as well as CO2 emissions in the methylcyclohexane and toluene separation can be reduced.

Distillation remains the leading and most frequently adopted technique for the separation and purification of condensable mixtures in numerous industries. However, the inherently poor thermal efficiency of distillation requires a large amount of thermal energy, making it the chief factor in total process energy usage and a significant emitter of carbon dioxide due to the combustion of fossil fuels. To address this issue, electrification has arisen as a popular approach to reduce carbon emissions in different processes by primarily replacing the energy source with electricity derived from renewable energy resources. This review is designed to thoroughly explore the electrification concept in decarbonizing distillation and present a detailed analysis and summary of the cutting-edge technologies used in various distillation operations. The focus is on creating electrified distillation processes and their associated utility systems, making use of a range of power-to-heat and intensification strategies, to achieve simultaneous carbon reduction and energy savings. With the increasing variety of operating environments that incorporate renewable power, this review additionally encompasses the control and operation aspects to ensure efficient management of electrified distillation processes. To further delve into the advantages of incorporating electrification into distillation, this work proposes future directions from the viewpoints of technological advancement, design optimization, operation, and real-time scheduling of electrified distillation processes. Furthermore, this review highlights the enormous potential of electrification in dramatically lowering carbon emissions and promoting sustainable practices in the distillation industry.

Downstream processing of natural gas liquids (NGL) provides feedstock needed for plastic production, upgraded fuels and heating, but it is one of the largest high-pressure and energy intensive processes. This original study is the first to integrate novel process intensification options from a holistic viewpoint for the full process covering all sections: 1) NGL recovery, 2) NGL fractionation, and 3) isomerization. Intensified fluid separation technologies (e.g. complex columns, thermal coupling, and heat pumps) are explored and integrated into a full NGL process to improve the energy efficiency and mitigate GHG emissions, and to establish the limits of operation, utility usage, and specific product costs. All NGL processes are rigorously simulated in Aspen Plus, and evaluated based on a fair economic and sustainability analysis. The enhanced recycle split vapor process for NGL recovery results in a full heat recovery for the reboiler of the demethanizer (2.9 MW energy savings), while the enhanced gas subcooled process results in 17.9% reduction of the refrigerant duty, 20.2% reduction of the electrical duty, and 19.9% reduction of the total utility cost. For the NGL fractionation section, heat pump assisted double dividing wall process improves energy intensity for a fraction of the utility cost although requiring external incentives (e.g., carbon tax) to become commercially viable. The total utility costs as well as GHG emissions are reduced up to 30% and 49%, respectively, while the specific product cost reduces to $23.45/t or $24.38/t with carbon tax. The heat pump assisted recycled isomerization process for the last section increased AKI from 65.3 to 89.6, with 19.1% reduction of utility usage and 42.4% reduction of carbon emission.

Ethyl acetate is a platform chemical conventionally obtained through fossil fuel routes, but more recently its production by fermentation from carbohydrates has been scaled up to a pilot scale. Yet, the complexity of downstream processing (low product concentrations in liquid broth and in off-gas, azeotrope formation, and the presence of microorganisms) may complicate industrial application. This original theoretical study is the first to develop advanced downstream processing, based on process intensification principles, for large-scale recovery (~10 kton/year) of ethyl acetate after fermentation. To minimize product losses, ethyl acetate is separated from both the liquid broth and off-gas. The final purification is performed in a highly integrated azeotropic dividing-wall column. The economic and sustainability analysis shows that using refrigeration for initial product separation from the gas phase is more cost-effective (~0.61 $/kg) and less energy-intensive (2.20–2.40 kW_thh/kg) than compression combined with high-pressure condensation using chilled water (1.09 $/kg and 9.98 kW_thh/kg).

Process Intensification (PI) is an effective way to enhance process efficiency and sustainability at affordable costs and efforts, attracting particular interest in the European area, as one of the most important chemical production areas in the world. PI primarily contributes by developing and testing new processing technologies that once integrated within a process improve the overall process performance substantially but as a result, it may alter the overall process (flowsheet) structure and its dynamic behavior. As such PI plays a key role in improving energy efficiency, optimizing resource allocation, and reducing environmental impact of industrial processes, and thereby leading to a cost-effective, eco-efficient, low-carbon and sustainable industry. However, along with opportunities, the PI new technologies have challenges related to failures in longer-term performance. In this respect, Process Systems Engineering (PSE) stance is more on integration aspects of new PI technologies into processes by making process (re)designs, doing operability studies, and performance optimizations within a supply chain setting. PSE contributes to overcoming the challenges by providing systematic approaches for the design and optimization of PI technologies. This perspective paper is a lightly referenced scholarly opinion piece about the status and directions of process intensification field from a PSE viewpoint. Primarily, it focuses on PSE perspectives towards sustainable lower energy usage process systems and provides a brief overview of the current situation in Europe. It also emphasizes the key challenges and opportunities for (new) PI technologies considering their integration in a process in terms of process synthesis and design, process flowsheet optimization, process and plantwide control, (green) electrification, sustainability improvements. Potential research directions on these aspects are given from an industrial and academic perspective of the authors.

Isopropanol-butanol-ethanol (IBE) fermentation is a superior biofuel production technology as compared to acetone-butanol-ethanol (ABE) fermentation due to the better fuel properties of the obtained products. However, low product concentrations, thermodynamic constraints and the presence of microorganisms lead to complex downstream processing that limits the competitiveness of this biofuel production method. Thus, this original research proposes a novel thermally self-sufficient and eco-efficient downstream process for industrial-scale recovery after IBE fermentation (74 ktonne/y capacity), from a highly dilute broth (>97 wt% water). Gas stripping and heat pump-assisted vacuum evaporation were implemented to separate valuable products from most of the broth. Furthermore, an advanced highly integrated heat pump-assisted azeotropic dividing-wall column was designed to recover high-purity (99 wt%) butanol biofuel and isopropanol – ethanol fuel supplement (89 wt%). The proposed purification process recovers over 99 % of biofuel products in a cost-effective (0.130 $/kg_IBE) and energy-efficient way (0.673 kW_eh/kg_IBE) while allowing full recycle of biomass and most of the separated water. Besides improving yield by continuously recovering the inhibitory products, fermentation can be further enhanced by avoiding biomass loss and reducing water requirements. Lastly, the implemented energy-saving techniques ensure complete electrification of the proposed IBE recovery process. Therefore, the original results of this research study significantly contribute to the development of sustainable biofuel production processes.

Methanol and DME are highly efficient fuels and relevant building blocks that can be synthesized by CO₂ hydrogenation. While several alternatives for methanol production by CO₂ hydrogenation have already been developed at a commercial scale, DME production is still based on methanol dehydration. In this sense, the development of bifunctional methanol synthesis/dehydration catalysts is a clear opportunity for the simultaneous coproduction of methanol and DME in a single-step process. Although a few alternatives for DME-methanol coproduction have been proposed, either they need external fuels or refrigerants, or part of the CO₂ used as raw material is purged, resulting in a loss of methanol and DME yields. This work presents a novel thermally self-sufficient process that hydrogenates CO₂ into methanol and DME in a single reactor at 100 % yield (only water as a byproduct at 0.94 kg_water/kg_product), that only consumes air, cooling water (0.006 m³ _water/kg_products) and electricity (net CO₂ emissions of −1.20 or 0.64 kg_CO2eq/kg_products when the plant is operated with green or grey electricity, respectively). The innovative design, based on the combination of a top-divided wall column, an integrated heat network, and limited pressure drop in the reaction-separation loop, results in a thermally self-sufficient process that uses only 0.76 kWh per kg products.

Distillation is widely used for separation in chemical industries, but accounts for a half of operational costs and 40% of the energy usage due to its low energy efficiency. Process intensification could effectively enhance the energy efficiency and reduce the energy requirement of the distillation processes by integrating unit operations or functions. However, there is no general methodology that enables to choose the best intensified distillation technologies among all available choices for a given separation task. This study generates a conceptual de-composed selection and decision approach by first identifying the process bottlenecks and intensification targets, and then select the most promising intensified techniques via a selection framework and decision matrix based on the identified bottlenecks and intensification targets. Two separation cases are illustrated to demonstrate the developed methodology, and the outcomes are verified with conceptual designs reported in the literature.

Despite the huge efforts devoted to the development of the electrochemical reduction of CO2 (ECO2R) in the past decade, still many challenges are present, hindering further approaches to industrial applications. This paper gives a perspective on these challenges from a Process Systems Engineering (PSE) standpoint, while at the same time highlighting the opportunities for advancements in the field in the European context. The challenges are connected with: the coupling of these processes with renewable electricity generation; the feedstock (in particular CO2); the processes itself; and the different products that can be obtained. PSE can determine the optimal interactions among the components of such systems, allowing educated decision making in designing the best process configurations under uncertainty and constrains. The opportunities, on the other hand, stem from a stronger collaboration between the PSE and the experimental communities, from the possibility of integrating ECO2R into existing industrial productions and from process-wide optimisation studies, encompassing the whole production cycle of the chemicals to exploit possible synergies.

This chapter focuses on the design and control of reactive distillation (RD) columns, which are seen as an integral part of an intensified chemical process. While most of the published literature presents analyses of the RD columns as standalone process units, this work frames the RD columns within a process where recycle streams (to these columns) are present, as typical to industrial practice. These recycle streams originate from the incomplete conversion of reactants or their conversion to undesired by-products. Therefore, the unreacted reactants need to be recovered and recycled, while the by-products need to be recovered and reconverted into reactants followed by their recycle to the RD columns.

A case study of industrial importance is used to illustrate key aspects of design and control of such reactive distillation systems with recycles. The design is focused on developing the topology of the entire process and solving the mass and energy balance based on which key process performance indicators (e.g. reactant utilization, energy efficiency, material and energy intensity, and carbon dioxide emissions) can be analyzed. The control is focused on developing a plantwide strategy to achieve the material inventory (in other words, balancing the reactions' stoichiometry), along with achieving the desired production rate and product purity. Several key process changes (e.g. flowrate and composition changes) are implemented to test the proposed control structure of the plant. All this work makes use of both steady-state and dynamic, rigorous process simulations.

Propionic acid is a valuable platform chemical that is usually produced via fossil routes. As these are energy-intensive and eco-unfriendly processes, fermentative production of propionic acid is becoming more attractive. However, the complex downstream processing (due to low achievable product concentrations, high water content, presence of by-products and thermodynamic constraints), presents a potential barrier to scale-up this technology. This original research proposes a novel intensified large-scale (production capacity of ∼ 20 ktonne/y) process for the final recovery of propionic acid after the initial biomass and counterion removal. Vacuum distillation steps ensure the recovery of a high-purity succinic acid product (>99.9 wt%) and a water stream that may be recycled to the fermentation to reduce the fresh water requirements. The main unit that follows is a highly integrated heat pump-assisted dividing-wall column (DWC), which allows the effective separation of propionic (>99.9 wt%) and acetic acid (99.4 wt%) products. Alternatively, it can serve as a reactive DWC that performs the esterification and separation of methyl propionate (99.8 wt%), methyl acetate (91.0 wt%) as higher added value products, and water by-product. If needed, extractive distillation can be implemented additionally to recover methyl acetate at higher purity (99.9 wt%). Overall, both options are proven to be economically interesting (recovery costs of 0.399 – 0.469 $/kg considering the product price of 1.349 – 1.802 $/kg) and environmentally attractive (3.206 – 3.678 kWthh/kg).

Valorization of carbon dioxide towards value added chemicals can drastically mitigate the increased CO2 levels in the atmosphere. In this context, formic acid is a versatile bulk chemical with promising market potential. The novel process design proposed in this work involves a sustainable thermochemical synthesis of formic acid from CO2, which is rigorously simulated using Aspen Plus V12 as a CAPE tool. The process relies on the reverse water-gas shift reaction (RWGS) to synthesize CO from green H2 and CO2. The purified CO is used for the synthesis of methyl formate, which is then hydrolyzed to produce formic acid. To address downstream processing energy intensity, a distillation column with a dividing wall (DWC) is employed. The designed process achieves high molar yields of 95% for CO2 and 96% for H2 with a specific energy intensity of 21.8 MJ/kg of formic acid. The new process achieves a substantial reduction of 51% in the CO2 emissions, 64% in electricity consumption and 20% in steam usage as compared to conventional fossil fuel-based FA production plants (reference case).