Integrated adsorbent‐process optimization for carbon capture and concentration using vacuum swing adsorption cycles

A novel approach for integrated adsorbent and process design is proposed. The traditional pressure or vacuum swing adsorption (PSA) / vacuum swing adsorption (VSA) process optimization for chosen objectives, where operating conditions are the decision variables, and CO₂ purity and recovery are constraints, is expanded to include adsorbent isotherm characteristics as additional decision variables. Two VSA cycles, namely a four‐step process¹, currently known to have the lowest energy consumption for CO₂ capture and concentration (CCC), and a six‐step process², recently proven to have a wider operating window for the evacuation pressure, have been investigated in the current study. The integrated optimization results simultaneously provide the lower bound of minimum energy and upper bound of maximum productivity for CCC achievable from the two VSA processes along with the operating conditions and the corresponding isotherm shapes necessary to achieve them. It may be viewed as an enabler for adsorbent design or expedient adsorbent search by process inversion. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2987–2995, 2017     

Cycle synthesis and optimization of a VSA process for postcombustion CO2 capture

A systematic analysis of several vacuum swing adsorption (VSA) cycles with Zeochem zeolite 13X as the adsorbent to capture CO₂ from dry, flue gas containing 15% CO₂ in N₂ is reported. Full optimization of the analyzed VSA cycles using genetic algorithm has been performed to obtain purity‐recovery and energy‐productivity Pareto fronts. These cycles are assessed for their ability to produce high‐purity CO₂ at high recovery. Configurations satisfying 90% purity‐recovery constraints are ranked according to their energy‐productivity Pareto fronts. It is shown that a 4‐step VSA cycle with light product pressurization gives the minimum energy penalty of 131 kWh/tonne CO₂ captured at a productivity of 0.57 mol CO₂/m³ adsorbent/s. The minimum energy consumption required to achieve 95 and 97% purities, both at 90% recoveries, are 154 and 186 kWh/tonne CO₂ captured, respectively. For the proposed cycle, it is shown that significant increase in productivity can be achieved with a marginal increase in energy consumption. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4735–4748, 2013     

Techno-economic assessment of pulverized coal boilers and IGCC power plants with CO<Subscript>2</Subscript> capture

The current studies on power plant technologies suggest that Integrated Gasification Combined Cycle (IGCC) systems are an effective and economic CO₂ capture technology pathway. In addition, the system in conventional configuration has the advantage of being more “CO₂ capture ready” than other technologies. Pulverized coal boilers (PC) have, however, proven high technical performance attributes and are economically often most practical technologies. To highlight the pros and cons of both technologies in connection with an integrated CO₂ capture, a comparative analysis of ultrasupercritical PC and IGCC is carried out in this paper. The technical design, the mass and energy balance and the system optimizations are implemented by using the ECLIPSE chemical plant simulation software package. Built upon these technologies, the CO₂ capture facilities are incorporated within the system. The most appropriate CO₂ capture systems for the PC system selected for this work are the oxy-fuel system and the postcombustion scheme using Monoethanolamine solvent scrubber column (MEA). The IGCC systems are designed in two configurations: Water gas shift reactor and Selexol-based separation. Both options generate CO₂-rich and hydrogen rich-gas streams. Following the comparative analysis of the technical performance attributes of the above cycles, the economic assessment is carried out using the economic toolbox of ECLIPSE is seamlessly connected to the results of the mass and energy balance as well as the utility usages. The total cost assessment is implemented according to the step-count exponential costing method using the dominant factors and/or a combination of parameters. Subsequently, based on a set of assumptions, the net present value estimation is implemented to calculate the breakeven electricity selling prices and the CO₂ avoidance cost.     

Techno-economic assessment of pulverized coal boilers and IGCC power plants with CO2 capture

The current studies on power plant technologies suggest that Integrated Gasification Combined Cycle (IGCC) systems are an effective and economic CO₂ capture technology pathway. In addition, the system in conventional configuration has the advantage of being more “CO₂ capture ready” than other technologies. Pulverized coal boilers (PC) have, however, proven high technical performance attributes and are economically often most practical technologies. To highlight the pros and cons of both technologies in connection with an integrated CO₂ capture, a comparative analysis of ultrasupercritical PC and IGCC is carried out in this paper. The technical design, the mass and energy balance and the system optimizations are implemented by using the ECLIPSE chemical plant simulation software package. Built upon these technologies, the CO₂ capture facilities are incorporated within the system. The most appropriate CO₂ capture systems for the PC system selected for this work are the oxy-fuel system and the postcombustion scheme using Monoethanolamine solvent scrubber column (MEA). The IGCC systems are designed in two configurations: Water gas shift reactor and Selexol-based separation. Both options generate CO₂-rich and hydrogen rich-gas streams. Following the comparative analysis of the technical performance attributes of the above cycles, the economic assessment is carried out using the economic toolbox of ECLIPSE is seamlessly connected to the results of the mass and energy balance as well as the utility usages. The total cost assessment is implemented according to the step-count exponential costing method using the dominant factors and/or a combination of parameters. Subsequently, based on a set of assumptions, the net present value estimation is implemented to calculate the breakeven electricity selling prices and the CO₂ avoidance cost.     

Dynamic real-time optimization for a CO2 capture process

Growing awareness of climate change has led to increased focus on new energy processes that mitigate generation of CO₂, or provide for its efficient capture. To enable the development of these processes, advanced modeling and optimization platforms have been created. New capabilities among platforms include efficient solution strategies for online optimization problems. For real time, dynamic optimization of CO₂ capture processes, we demonstrate the application of the Python-based Pyomo platform to facilitate realization of Moving Horizon Estimation and Nonlinear Model Predictive Control, through novel nonlinear optimization and sensitivity strategies. This capability allows large scale, first principle models to be applied for online optimization. Here, we introduce the Control and Adaptation with Predictive Sensitivity Enhancements (CAPRESE) framework to demonstrate this framework for advanced energy processes. Moreover, we present two case studies: profile tracking with detailed tray-by-tray distillation models and Bubbling Fluidized Bed reactors for CO₂ capture. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16511 2019     

A superstructure‐based optimal synthesis of PSA cycles for post‐combustion CO2 capture

Recent developments have shown pressure/vacuum swing adsorption (PSA/VSA) to be a promising option to effectively capture CO₂ from flue gas streams. In most commercial PSA cycles, the weakly adsorbed component in the mixture is the desired product, and enriching the strongly adsorbed CO₂ is not a concern. On the other hand, it is necessary to concentrate CO₂ to high purity to reduce CO₂ sequestration costs and minimize safety and environmental risks. Thus, it is necessary to develop PSA processes specifically targeted to obtain pure strongly adsorbed component. A multitude of PSA/VSA cycles have been developed in the literature for CO₂ capture from feedstocks low in CO₂ concentration. However, no systematic methodology has been suggested to develop, evaluate, and optimize PSA cycles for high purity CO₂ capture. This study presents a systematic optimization‐based formulation to synthesize novel PSA cycles for a given application. In particular, a novel PSA superstructure is presented to design optimal PSA cycle configurations and evaluate CO₂ capture strategies. The superstructure is rich enough to predict a number of different PSA operating steps. The bed connections in the superstructure are governed by time‐dependent control variables, which can be varied to realize most PSA operating steps. An optimal sequence of operating steps is achieved through the formulation of an optimal control problem with the partial differential and algebraic equations of the PSA system and the cyclic steady state condition. Large‐scale optimization capabilities have enabled us to adopt a complete discretization methodology to solve the optimal control problem as a large‐scale nonlinear program, using the nonlinear optimization solver IPOPT. The superstructure approach is demonstrated for case studies related to post‐combustion CO₂ capture. In particular, optimal PSA cycles were synthesized, which maximize CO₂ recovery for a given purity, and minimize overall power consumption. The results show the potential of the superstructure to predict PSA cycles with up to 98% purity and recovery of CO₂. Moreover, for recovery of around 85% and purity of over 90%, these cycles can recover CO₂ from atmospheric flue gas with a low power consumption of 465 k Wh tonne^?1 CO₂. The approach presented is, therefore, very promising and quite useful for evaluating the suitability of different adsorbents, feedstocks, and operating strategies for PSA, and assessing its usefulness for CO₂ capture. Published 2009 American Institute of Chemical Engineers AIChE J, 2010     

The role of water on postcombustion CO2 capture by vacuum swing adsorption: Bed layering and purge to feed ratio

The influence of water vapor on the adsorption of CO₂ in carbon capture by vacuum swing adsorption (VSA) was described. VSA experiments with single and multilayered columns using alumina and zeolite 13X were conducted to understand the migration of water. The penetration depth of water in the column could be controlled by maintaining the purge‐to‐feed ratio above a critical value. At high water content in the feed (>4%), employment of a water adsorbing prelayer was essential to prevent failure of the carbon capture process. A simple axial working capacity model predicts the penetration depth of water in the column for a given feed temperature and adsorption isotherm, and the layering ratio can be selected accordingly. Although water is detrimental to CO₂ capture with polar adsorbents, long‐term recovery of CO₂ is still possible by appropriate layering and ensuring an adequate purge‐to‐feed ratio. © 2013 American Institute of Chemical Engineers AIChE J 60: 673–689, 2014     

Screening Supported Amine Sorbents in the Context of Post-combustion Carbon Capture by Vacuum Swing Adsorption

The aim of this work was to evaluate the performance of three different supported amine sorbents in a 6-step vacuum swing adsorption (VSA) cycle through process simulation and optimization for a representative post-combustion CO₂ capture system. Detailed process optimization revealed that all the adsorbents were able to achieve the desired purity-recovery targets. The best performing adsorbent in terms of productivity was Lewatit with a productivity of 0.48 mol m⁻³ ads s⁻¹. All the adsorbents exhibited similar minimum specific energy value of around 1 MJ kg⁻¹ on an electric basis.     

Solution‐reprocessable microporous polymeric adsorbents for carbon dioxide capture

Solution‐processable microporous polymers are promising materials for CO₂ capture because of their low synthetic cost and high processability. In this work, we for the first time systematically evaluate the feasibility of two microporous polymers, namely PIM‐1 and its hydrolyzed form hPIM‐1, as adsorbent materials for postcombustion CO₂ capture. By conducting ternary CO₂/N₂/H₂O breakthrough experiments, PIM‐1 demonstrates several promising features: moderate CO₂ working capacity, low water vapor uptake capacity, good moisture resistance, and easy regeneration process. In addition, we have pioneeringly studied the multiple‐cycle CO₂ adsorption–desorption induced relaxation effect on soft PIM‐1 polymers. Through a simple dissolution–precipitation approach, PIM‐1 can restore its BET surface area, CO₂ uptake capacity, and pore‐size distribution. The solution reprocessability of PIM‐1 demonstrated in this study distinguishes it from other rigid adsorbents and thus offers a new insight for the future design of economically‐viable and facilely regenerable adsorbents. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3376–3389, 2018     

Optimization of energy usage for fleet‐wide power generating system under carbon mitigation options

This article presents a fleet‐wide model for energy planning that can be used to determine the optimal structure necessary to meet a given CO₂ reduction target while maintaining or enhancing power to the grid. The model incorporates power generation as well as CO₂ emissions from a fleet of generating stations (hydroelectric, fossil fuel, nuclear, and wind). The model is formulated as a mixed integer program and is used to optimize an existing fleet as well as recommend new additional generating stations, carbon capture and storage, and retrofit actions to meet a CO₂ reduction target and electricity demand at a minimum overall cost. The model was applied to the energy supply system operated by Ontario power generation (OPG) for the province of Ontario, Canada. In 2002, OPG operated 79 electricity generating stations; 5 are fueled with coal (with a total of 23 boilers), 1 by natural gas (4 boilers), 3 nuclear, 69 hydroelectric and 1 wind turbine generating a total of 115.8 TWh. No CO₂ capture process existed at any OPG power plant; about 36.7 million tonnes of CO₂ was emitted in 2002, mainly from fossil fuel power plants. Four electricity demand scenarios were considered over a span of 10 years and for each case the size of new power generation capacity with and without capture was obtained. Six supplemental electricity generating technologies have been allowed for: subcritical pulverized coal‐fired (PC), PC with carbon capture (PC+CCS), integrated gasification combined cycle (IGCC), IGCC with carbon capture (IGCC+CCS), natural gas combined cycle (NGCC), and NGCC with carbon capture (NGCC+CCS). The optimization results showed that fuel balancing alone can contribute to the reduction of CO₂ emissions by only 3% and a slight, 1.6%, reduction in the cost of electricity compared to a calculated base case. It was found that a 20% CO₂ reduction at current electricity demand could be achieved by implementing fuel balancing and switching 8 out of 23 coal‐fired boilers to natural gas. However, as demand increases, more coal‐fired boilers needed to be switched to natural gas as well as the building of new NGCC and NGCC+CCS for replacing the aging coal‐fired power plants. To achieve a 40% CO₂ reduction at 1.0% demand growth rate, four new plants (2 NGCC, 2 NGCC+CCS) as well as carbon capture processes needed to be built. If greater than 60% CO₂ reductions are required, NGCC, NGCC+CCS, and IGCC+CCS power plants needed to be put online in addition to carbon capture processes on coal‐fired power plants. The volatility of natural gas prices was found to have a significant impact on the optimal CO₂ mitigation strategy and on the cost of electricity generation. Increasing the natural gas prices resulted in early aggressive CO₂ mitigation strategies especially at higher growth rate demands. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

CO2 capture from dry flue gas by vacuum swing adsorption: A pilot plant study

The capture and concentration of CO₂ from a dry flue gas by vacuum swing adsorption (VSA) has been experimentally demonstrated in a pilot plant. The pilot plant has the provision for using two coupled columns that are each packed with approximately 41 kg of Zeochem zeolite 13X. Breakthrough experiments were first carried out by perturbing a N₂ saturated bed with 15% CO₂ and 85% N₂ feed, which is representative of a dry flue gas from coal‐fired power plants. The breakthrough results showed long plateaus in temperature profiles confirming a near adiabatic behavior. In the process study, a basic four‐step vacuum swing adsorption (VSA) cycle comprising the following steps: pressurization with feed, adsorption, forward blowdown, and reverse evacuation was investigated first. In the absence of any coupling among the steps, a single bed was used. With this cycle configuration, CO₂ was concentrated to 95.9 ± 1% with a recovery of 86.4 ± 5.6%. To improve the process performance, a four‐step cycle with light product pressurization (LPP) using two beds was investigated. This cycle was able to achieve 94.8 ± 1% purity and 89.7 ± 5.6% recovery. The Department of Energy requirements are 95% purity and 90% recovery. The proposed underlying physics of performance improvement of the four‐step cycle with LPP has also been experimentally validated. The pilot plant results were then used for detailed validation of a one‐dimensional, nonisothermal, and nonisobaric model. Both transient profiles of various measured variables and cyclic steady state performance results were compared with the model predictions, and they were in good agreement. The energy consumptions in the pilot plant experiments were 339–583 ± 36.7 kWh tonne^?1 CO₂ captured and they were significantly different from the theoretical power consumptions obtained from isentropic compression calculations. The productivities were 0.87–1.4 ± 0.07 tonne CO₂ m^?3 adsorbent day^?1. The results from our pilot plant were also compared with available results from other pilot plant studies on CO₂ capture from flue gas. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1830–1842, 2014     

Comparative simulation study of PSA,VSA, and TSA processes for purification of methane from CO2 via SAPO-34 core-shell adsorbent

Cyclic adsorption processes of PSA, VSA, and TSA were modeled and numerically simulated using SAPO-34 core-shell adsorbent. The results were compared with ordinary SAPO-34 to achieve a more efficient process for CO₂–CH₄ separation. OCM coupled with method of lines was used for numerical solution of the mechanistic model. The simulation results revealed higher efficiency of core-shell adsorbent with less usage of SAPO rather than the ordinary adsorbent to achieve the same degree of purification and recovery. VSA and TSA processes against PSA resulted in CH₄ purification capability more than 99% with more than 73% recovery. However, VSA process has revealed higher productivity rather than TSA.     

Aminating modification of viscose fibers and their CO2 adsorption properties

An adsorbent for CO₂ capture was prepared by the grafting of acrylonitrile (AN) onto viscose fibers (VFs); this was followed by amination with triethylene tetramine (TETA). The effects of the reaction conditions, such as the concentrations of the monomer, initiator, and nitric acid, on the grafting degree and grafting efficiency were studied. The adsorption performance of the adsorbent for CO₂ was evaluated by fixed‐bed adsorption. The highest dynamic adsorption capacity of the adsorbent for CO₂ was 4.35 mmol/g when the amine content of the adsorbent VF–AN–TETA reached 13.21 mmol/g. Compared with the polypropylene (PP)‐fiber‐based adsorbent (PP–AN–TETA), VF–AN–TETA with hydroxyl groups on the fibers facilitated the diffusion of CO₂ and water and led to a higher CO₂ adsorption capacity than that of PP–AN–TETA. The VF–AN–TETA adsorbent also showed good regeneration performance: its CO₂ adsorption capacity could still retain almost the same capacity as the fresh adsorbent after 10 adsorption–desorption cycles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42840.     

Techno-economic evaluation of a PVAm CO2-selective membrane in an IGCC power plant with CO2 capture

Published data for an operating power plant, the ELCOGAS 315 MWe Puertollano plant, has been used as a basis for the simulation of an integrated gasification combined cycle process with CO₂ capture. This incorporated a fixed site carrier polyvinylamine membrane to separate the CO₂ from a CO-shifted syngas stream. It appears that the modified process, using a sour shift catalyst prior to sulphur removal, could achieve greater than 85% CO₂ recovery at 95 vol% purity. The efficiency penalty for such a process would be approximately 10% points, including CO₂ compression. A modified plant with CO₂ capture and compression was calculated to cost €2320/kW, producing electricity at a cost of 7.6 € cents/kWh and a CO₂ avoidance cost of about €40/tonne CO₂.     

Application of polyethylenimine‐impregnated solid adsorbents for direct capture of low‐concentration CO2

A systematic study of CO₂ capture on the amine‐impregnated solid adsorbents is carried out at CO₂ concentrations in the range of 400–5000 ppm, relating to the direct CO₂ capture from atmospheric air. The commercially available polymethacrylate‐based HP2MGL and polyethylenimine are screened to be the suitable support and amine, respectively, for preparation of the adsorbent. The adsorbents exhibit an excellent saturation adsorption capacity of 1.96 mmol/g for 400 ppm CO₂ and 2.13 mmol/g for 5000 ppm CO₂. Moisture plays a promoting effect on CO₂ adsorption but depends on the relative humidity. The presence of O₂ would lead to the decrease of adsorption capacity but do not affect the cyclic performance. The diffusion additive is efficient to improve the adsorption capacity and cyclic performance. Moreover, the adsorbents can be easily regenerated under a mild temperature. This study may have a positive impact on the design of high‐performance adsorbents for CO₂ capture from ambient air. © 2014 American Institute of Chemical Engineers AIChE J, 61: 972–980, 2015     

Economical assessment of competitive enhanced limestones for CO2 capture cycles in power plants

CO₂ capture systems based on the carbonation/calcination loop have gained rapid interest due to promising carbonator CO₂ capture efficiency, low sorbent cost and no flue gases treatment is required before entering the system. These features together result in a competitively low cost CO₂ capture system. Among the key variables that influence the performance of these systems and their integration with power plants, the carbonation conversion of the sorbent and the heat requirement at calciner are the most relevant. Both variables are mainly influenced by CaO/CO₂ ratio and make-up flow of solids. New sorbents are under development to reduce the decay of their carbonation conversion with cycles. The aim of this study is to assess the competitiveness of new limestones with enhanced sorption behaviour applied to carbonation/calcination cycle integrated with a power plant, compared to raw limestone. The existence of an upper limit for the maximum average capture capacity of CaO has been considered. Above this limit, improving sorbent capture capacity does not lead to the corresponding increase in capture efficiency and, thus, reduction of CO₂ avoided cost is not observed. Simulations calculate the maximum price for enhanced sorbents to achieve a reduction in CO₂ removal cost under different process conditions (solid circulation and make-up flow). The present study may be used as an assessment tool of new sorbents to understand what prices would be competitive compare with raw limestone in the CO₂ looping capture systems.     

Adsorption behavior and kinetics of CO2 on amine-functionalized hyper-crosslinked polymer

A hyper-crosslinked polymer (XAD-4-pc) was developed by modifying the commercial polystyrene resin (XAD-4) through a Friedel–Crafts reaction, followed by impregnation with polyethyleneimine (PEI) for CO₂ capture. The physicochemical properties of the as-synthesized adsorbents were analyzed by different characterization techniques, and the adsorption behavior of CO₂ on these adsorbents was evaluated in a self-assembled adsorption setup with gas chromatography. Experimental results found that the Brunauer–Emmett–Teller surface area and pore volume of XAD-4-pc were significantly higher than that of XAD-4, which was favorable to the improvement of PEI loading and CO₂ adsorption. The maximum CO₂ uptake for PEI-functionalized XAD-4-pc was 3.24 mmol g⁻¹ at 25 °C. The adsorption isotherm of CO₂ on the adsorbent was well described by the Langmuir equation, and the kinetics data could be accurately described by Avrami model over the entire adsorption range. The diffusion mechanism study showed that the film diffusion and intraparticle diffusion were mainly the rate-limiting steps. Moreover, this adsorbent could be well regenerated at relatively low temperature and exhibited stable regenerability after five adsorption-regeneration cycles, showing its high potential for the capture of CO₂ from flue gases. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48479.     

Using short‐term resource scheduling for assessing effectiveness of CCS within electricity generation subsector

A new methodology for assessing the effectiveness of carbon capture and storage (CCS) that does explicitly consider the detailed operation of the target electricity system is proposed. The electricity system simulation consists of three phases, each one using a modified version of an economic dispatch problem that seeks to maximize the producers’ and consumers’ surplus while satisfying the technical constraints of the system. The economic dispatch is formulated as a dynamic mixed‐integer nonlinear programming problem and implemented in general algebraic modelling system (GAMS). The generating unit with CCS is designed and simulated using Aspen Plus®. In the first case study, the operation of the IEEE RTS ’96 (Institute of Electrical and Electronics Engineers One‐Area Reliability Test System—1996) is simulated with greenhouse gas (GHG) regulation implemented in the form of CO₂ permits that generators need to acquire for every unit of CO₂ that it is emitted. In the second case study, CCS is added at one of the buses and the operation of the modified IEEE RTS ’96 is again simulated with and without GHG regulation. The results suggest that the detailed operation of the target electricity system should be considered in future assessments of CCS and a general procedure for undertaking this for any GHG mitigation option is proposed. Future work will use the novel methodology for assessing the effectiveness of generating units with flexible CO₂ capture. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4210–4234, 2015     

Investigation of CO2 removal by immobilized carbonic anhydrase enzyme in a hollow‐fiber membrane bioreactor

Gas–liquid membrane contactors are compelling candidate bioreactors for implementing CO₂ capture because of large mass transfer rates and liquid–solid interfaces, low pressure drop, low axial dispersion and mixing, modularity, simple scale‐up or scale‐down, and operational suppleness. Binding the carbonic anhydrase (CA) enzyme on the membrane surface adds extra advantages due to the impressive large hydration turnover number and offers an attractive way for CO₂ capture. This novel approach to CO₂ removal by immobilized CA in a hollow‐fiber membrane bioreactor (HFMB) was investigated via a multiscale steady‐state model, under gas‐filled and partially liquid‐filled membrane pores conditions. The impact of CA loading, buffer acid‐base constant and concentration, membrane wetting, uncatalyzed/catalyzed CO₂ hydration in the wetted membrane zone, operating conditions, and cocurrent/countercurrent flow orientation on the HFMB performance was analyzed. The results showed that this low‐cost, green, and environmentally friendly technology could be an appealing alternative to CO₂ capture from stationary emissions sources. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2996–3007, 2017     

Large‐scale optimization strategies for pressure swing adsorption cycle synthesis

Pressure swing adsorption (PSA) is an efficient method for gas separation and is a potential candidate for carbon dioxide (CO₂) capture from power plants. However, few PSA cycles have been designed for this purpose; the optimal design and operation of PSA cycles for CO₂ capture, as well as other systems, remains a very challenging task. In this study, we present a systematic optimization‐based formulation for the synthesis and design of novel PSA cycles for CO₂ capture in IGCC power plants, which can simultaneously produce hydrogen (H₂) and CO₂ at high purity and high recovery. Here, we apply a superstructure‐based approach to simultaneously determine optimal cycle configurations and design parameters for PSA units. This approach combines automatic differentiation, efficient ODE solvers for the state and sensitivity equations of the PSA model, and state of the art nonlinear programming solvers. Three optimization models are proposed, and two PSA case studies are considered. The first case study considers a binary separation of H₂ and CO₂ at high purity, where specific energy is minimized, whereas the second case study considers a larger five component separation. © 2012 American Institute of Chemical Engineers AIChE J, 58: 3777–3791, 2012