Simulation of integrated novel PSA/EHP/C process for high-pressure hydrogen recovery from Coke Oven Gas

This paper introduces a novel Coke Oven Gas (COG) hydrogen purification/compression system based on the technologies of Pressure Swing Adsorption (PSA) and Electrochemical Hydrogen Purification and Compression (EHP/C). As the EHP/C tolerates O₂, N₂ and CH₄ impurities, PSA can be utilized solely for CO and CO₂ removal (other COG impurities were not considered in this work). A relaxation of PSA hydrogen purity could significantly enhance its recovery rate. In this study, the suitability of traditional hydrogen PSA as part of the hybrid PSA/EHP/C approach was investigated. Aspen Adsorption and Matlab were used to model the PSA and EHP/C systems, respectively. The effect of adsorption pressure, purge-to-feed-ratio (P/F-ratio) and adsorption time within cycle on PSA performance is reported. This study found that breakthrough of non-detrimental components is typically accompanied with poisonous CO. Hence, the CO removal with traditional H₂-PSA resulted into high purity product. In a two-bed PSA, 36.3% of hydrogen was recovered at 99.9988% purity and 0.18 ppm CO. Subsequently, as a result, the EHP/C purification capability was merely utilized, but polished this hydrogen to >99.999% purity. Simultaneously, hydrogen was isothermally compressed to 20 MPa, consuming a marginal 2.42 kWh/kg. Compared to mechanical compression, this is 31.6% more energy efficient. Recovering hydrogen from by-product COG was found to save 0.5 kg CO₂/kg H₂ compared to hydrogen produced from natural gas. Conventional hydrogen PSA, utilizing 70% Activated Carbon and 30% Molecular Sieve 5A, was found not to be effective to target the removal of CO specifically. To increase synergy between PSA and EHP/C, the PSA requires adequate design and operation using appropriate adsorbents and cycle steps to target elimination of CO. An increased EHP/C catalyst tolerance for CO also contributes to higher flexibility.     

H2 PSA purifier for CO removal from hydrogen mixtures

A two-bed PSA purifier was developed to produce high purity hydrogen for fuel cell applications. Two types of hydrogen-rich mixtures produced from coal off-gas were used. Feed 1 consisted of a 99% H₂ mixture (H₂:CO:CO₂:N₂ = 99:0.1:0.05:0.85 vol.%) containing 0.1% CO while Feed 2 was a 95% H₂ mixture (H₂:CO:CO₂:CH₄:N₂ = 95:0.3:0.1:0.05:4.55 vol.%) containing 0.3% CO. An increase in the P/F ratio and adsorption pressure led to an almost linear decrease in H₂ recovery with increasing purity. However, a sharp drop in CO concentration occurred at a specific operating range in both feeds. The feed was purified to 1.1 ppm CO with 99.99+% H₂ purity and 80.0% recovery under 6.5 bar and 0.15 P/F ratio while CO in Feed 2 could be reduced to 6.7 ppm with 99.96% H₂ purity and 78.4% recovery. The PVSA process, which combined vacuum and purge steps, could improve recovery by about 10% compared to the PSA process.     

Elevated temperature pressure swing adsorption using LaNi4.3Al0.7 for efficient hydrogen separation

The application of LaNi₅ based alloys as adsorbent for hydrogen separation and purification has been proposed for a long time. However, the actual utilization is limited by the poor CO tolerance of the alloys at atmospheric temperature. In this study, an elevated temperature vacuum pressure swing adsorption (ET-VPSA) method for H₂ separation using hydrogen storage material LaNi_4.3Al_0.7 is proposed and demonstrated to be energy efficient. Elevating the working temperature results in improved CO tolerance of LaNi_4.3Al_0.7, making it possible for the alloy to be used in more situations. An ET-VPSA model was built to explore the correlations between product H₂ purity, recovery rate, feed gas composition, cycle duration and counter-current blow down (CD) pressure. The results show that H₂ recovery rate of ET-VPSA reaches 95% while it is usually 85% or lower for regular pressure swing adsorption (PSA). The energy efficiency of these two separation methods is evaluated by methanol reforming-proton exchange membrane fuel cell system models which contain PSA or ET-VPSA as H₂ purification unit. A larger net power generation amount indicates less energy loss during H₂ purification process. Although the vacuum pump will lead to extra energy consumption, benefiting from higher H₂ recovery rate, the net efficiency of the system with ET-VPSA is 0.475, still higher than that with PSA (0.448).     

Optimization of VPSA-EHP/C process for high-pressure hydrogen recovery from Coke Oven Gas using CO selective adsorbent

The production of hydrogen through conventional pathways and recovery from by-products typically utilize pressure swing adsorption (PSA) technology as final purification step. Dual-layered PSA columns packed with conventional activated carbon and molecular sieve 5A material exhibit relatively low selectivity for O₂, N₂ and CO in particular. Therefore, eliminating CO (and other poisons) using conventional PSA to acceptable concentrations for EHP/C is only achievable with lower recovery rates. To improve recovery rates, there is a need for a highly efficient purification process that is highly selective for these hydrogen contaminants without compromising the product quality. Here we report an optimization study where vacuum PSA (VPSA) and electrochemical hydrogen purification and compression (EHP/C) technology is utilized for purification and compression of hydrogen from Coke Oven Gas (COG). The VPSA columns were packed with activated carbon and CuCl(7.0)-activated carbon to selectively retain poisonous CO₂ and CO, respectively. The optimal operating conditions were determined with surrogate models produced via non-linear regression of known sample input-output data points, by varying the adsorbent layering ratio (0.30–0.84), adsorption pressure (0.38–0.78 MPa), purge to feed ratio (P/F-ratio) (1–10%), adsorption step time (100–1500 s) and the EHP/C stack current per cell (37–52 A) in the original models. The two-bed VPSA system obtained 90.5% recovery and retained CO and CO₂ below their thresholds at 0.84 layering ratio, 0.78 MPa adsorption pressure, 840s adsorption time and 5.3% P/F-ratio, at the expense of H₂ purity (77.1%) by breakthrough of CH₄, N₂ and O₂. Hydrogen purity was upgraded to >99.999% by EHP/C, which recovered 90.0% of hydrogen and simultaneously compressed to 20 MPa, which required 3.2 kWh/kg H₂. The overall VPSA-EHP/C recovery rate in this configuration was 81.5%. By utilizing the EHP/C retentate gas as VPSA purge gas, overall VPSA-EHP/C recovery rates may reach 87.3% and consume less energy due to a decrease in adsorption pressure. We show that adsorption columns designed to function as poisonous component eliminator are an effective strategy to pre-condition hydrogen synthesis gases prior to further processing with EHP/C. Although the EHP/C was exposed to significant concentrations of methane, nitrogen and oxygen by their advancement through VPSA, the performance was only slightly affected. The VPSA-EHP/C method is applicable to a wide range of hydrogen gas mixtures that require further purification and compression. Traditional PSA for purification from primary and by-product (COG, annealing, chlor-alkali and flat/float glass manufacturing) hydrogen sources can be changed to a VPSA-EHP/C systems for hydrogen purification and simultaneous compression.     

Hydrogen quality for fuel cell vehicles – A modeling study of the sensitivity of impurity content in hydrogen to the process variables in the SMR–PSA pathway

As fuel cell vehicles approach wide-scale deployment, the issue of the quality of hydrogen dispensed to the vehicles has become increasingly important. The various factors that must be considered include the effects of different contaminants on fuel cell performance and durability, the production and purification of hydrogen to meet fuel quality guidelines, and the associated costs of providing hydrogen of that quality to the fuel cell vehicles. In this paper, we describe the development of a model to track the formation and removal of several contaminants over the various steps of hydrogen production by steam-methane reforming (SMR) of natural gas, followed by purification by pressure-swing adsorption (PSA). We have used the model to evaluate the effects of setting varying levels of these contaminants in the product hydrogen on the production/purification efficiency, hydrogen recovery, and the cost of the hydrogen. The model can be used to track contaminants such as CO₂, CO, N₂, CH₄, and H₂S in the process. The results indicate that a suggested specification of 0.2 ppm CO would limit the maximum hydrogen recovery from the PSA under typical design and operating conditions. The steam-to-carbon ratio and the process pressure are found to have a significant impact on the process efficiency. Varying the CO specification from 0.1 to 1 ppm is not expected to affect the cost of hydrogen significantly, although the cost of gas analysis to comply with such stringent requirements may add 2–10 cents/kg to the cost of hydrogen.     

Hydrogen purification using compact pressure swing adsorption system for fuel cell

Adsorption of CO and CO₂ in mixtures of H₂/CO/CO₂ was achieved using compact pressure swing adsorption (CPSA) system to produce purified hydrogen for use in fuel cell. A CPSA system was designed by combining four adsorption beds that simultaneously operate at different processes in the pressure swing adsorption (PSA) process cycle. The overall diameter of the cylindrical shell of the CPSA is 35 cm and its height is 40 cm. Several suitable adsorbent materials for CO and CO₂ adsorption in a hydrogen stream were identified and their adsorption properties were tested. Activated carbon from Sigma–Aldrich was the adsorbent chosen. It has a surface area of 695.07 m²/g. CO adsorption capacity (STP) of 0.55 mmol/g and CO₂ at 2.05 mmol/g were obtained. The CPSA system has a rapid process cycle that can supply hydrogen continuously without disruption by the regeneration process of the adsorbent. The process cycle in each column of the CPSA consists of pressurization, adsorption, blowdown and purging processes. CPSA is capable of reducing the CO concentration in a H₂/CO/CO₂ mixture from 4000 ppm to 1.4 ppm and the CO₂ concentration from 5% to 7.0 ppm CO₂ in 60 cycles and 3600 s. Based on the mixture used in the experimental work, the H₂ purity obtained was 99.999%, product throughput of 0.04 kg H₂/kg adsorbent with purge/feed ratio was 0.001 and vent loss/feed ratio was 0.02. It is therefore concluded that the CPSA system met the required specifications of hydrogen purity for fuel cell applications.     

Optimization of pressure swing adsorption for hydrogen purification based on Box-Behnken design method

Pressure swing adsorption (PSA) is an important technology for mixture gas separation and purification. In this work, a dynamic model for a layered adsorption bed packed with activated carbon and zeolite 5A was developed and validated to study the PSA process. The model was validated by calculating breakthrough curves of a five-component gas mixture (H₂/CH₄/CO/N₂/CO₂ = 56.4/26.6/8.4/5.5/3.1 mol%) and comparing the results with available experimental data. The purification performance of six-step layered bed PSA cycle was studied using the model. In order to optimize the cycle, the Box-Behnken design (BBD) method was used, as implemented in Design Expert?. The parametric study showed that, for adsorption step durations ranging from 160 to 200 s, as the adsorption time increased, the purity decreased, whereas the recovery and productivity increased. During the pressure equalization step, the purity increased as the pressure equalization time increased, but the recovery and productivity decreased for step durations ranging from 10 to 30 s. As the P/F ratio (hydrogen used in purge step to hydrogen fed in adsorption step) increased from 0.05 to 0.125, the purity increased, whereas the recovery and productivity decreased. The optimization of the layered bed PSA process by the BBD method was then performed. In addition to the adsorption time, the pressure equalization time and the P/F ratio were considered as independent optimization parameters. Quadratic regression equations were then obtained for three responses of the system, namely purity, recovery, and productivity. When purity is set as the main performance indicator, the following values were obtained for the optimization parameters: an adsorption time of 168 s, a pressure equalization time of 14 s, and a P/F ratio of 0.11. Under those conditions, the system achieved a purity of 99.99%, a recovery of 57.76%, and a productivity of 6.41 mol/(kg·h).     

Simulation of 12-bed vacuum pressure-swing adsorption for hydrogen separation from methanol-steam reforming off-gas

This study focuses on analysis of a 12-bed vacuum pressure-swing adsorption (VPSA) process capable of purifying hydrogen from a ternary mixture (H₂/CO₂/CO 75/24/1 mol%) derived from methanol-steam reforming. The process produces 9 kmol H₂/h with less than 2 ppm and 0.2 ppm of CO2 and CO, respectively, to supply a polymer electrolyte membrane fuel cell. The process model is developed in Aspen Adsorption® using the “uni-bed” approach. A parametric study of H₂ purity and recovery with respect to adsorption pressure, adsorbent height, activated carbon:zeolite ratio, feed composition, and number of beds is performed. Results show 12-bed VPSA can meet the H₂ purity goals, with H₂ recovery as high as 75.75%. Adsorption occurs at 7 bar, the column height is 1.2 m, and the adsorbent ratio is 70%:30%. A 4-bed VPSA can achieve the same purity goals as the 12-bed process, but H₂ recovery decreases to 61.34%.     

Ru–Ni/GA-MMO composites as highly active catalysts for CO selective methanation in H2-rich gases

CO selective methanation (CO-SMET) is as an ideal H₂-rich gases purification measurement for proton exchange membrane fuel cell system. Herein, the graphene aerogel-mixed metal oxide (GA-MMO) supported Ru–Ni bimetallic catalysts are exploited for CO-SMET in H₂-rich gases. The results reveal that a three-dimensional network structure GA-MMO aerogel with higher specific surface area, better thermal stability and more defects or structural disorders is formed when MMO:GO mass ratio is in the range of 1–4. After loading of Ru, more NiO are reduced to metallic Ni by hydrogen spillover effect, and thus obviously enhances the reactivity. The GA-MMO supported Ru–Ni catalyst exhibits more excellent metal dispersion, reducibility, stronger CO adsorption and activation than the MMO supported Ru–Ni catalyst, thereby resulting in better catalytic performance and stability. This work offers new insights into the construction of highly active catalyst for the efficient generation of high-quality H₂ from H₂-rich gases.     

Machine learning–based optimization for hydrogen purification performance of layered bed pressure swing adsorption

An adsorption, heat and mass transfer model for the five-component gas from coal gas (H₂/CO₂/CH₄/CO/N₂ = 38/50/1/1/10 vol%) in a layered bed packed with activated carbon and zeolite was established by Aspen Adsorption software. Compared with published experimental results, the hydrogen purification performance by pressure swing adsorption (PSA) in a layered bed was numerically studied. The results show that there is a contradiction between the hydrogen purity and recovery, so the multi-objective optimization algorithms are needed to optimize the PSA process. Machine learning methods can be used for data analysis and prediction; the polynomial regression (PNR) and artificial neural network (ANN) were used to predict the purification performance of two-bed six-step process. Finally, two ANN models combined with sequence quadratic program (SQP) algorithm were used to achieve multi-objective optimization of hydrogen purification performance. According to the analysis of the optimization results, the ANN models are more suitable for optimizing the purification performance of hydrogen than the PNR model.     

Artificial neural network based optimization for hydrogen purification performance of pressure swing adsorption

A pressure swing adsorption (PSA) cycle model is implemented on Aspen Adsorption platform and is applied for simulating the PSA procedures of ternary-component gas mixture with molar fraction of H₂/CO₂/CO = 0.68/0.27/0.05 on Cu-BTC adsorbent bed. The simulation results of breakthrough curves and PSA cycle performance fit well with the experimental data from literature. The effects of adsorption pressure, product flow rate and adsorption time on the PSA system performance are further studied. Increasing adsorption pressure increases hydrogen purity and decreases hydrogen recovery, while prolonging adsorption time and reducing product flow rate raise hydrogen recovery and lower hydrogen purity. Then an artificial neural network (ANN) model is built for predicting PSA system performance and further optimizing the operation parameters of the PSA cycle. The performance data obtained from the Aspen model is used to train ANN model. The trained ANN model has good capability to predict the hydrogen purification performance of PSA cycle with reasonable accuracy and considerable speed. Based on the ANN model, an optimization is realized for finding optimal parameters of PSA cycle. This research shows that it is feasible to find optimal operation parameters of PSA cycle by the optimization algorithm based on the ANN model which was trained on the data produced from Aspen model.     

The effect of H2S and CO mixtures on PEMFC performance

Proton exchange membrane fuel cells (PEMFCs) most likely will use reformed fuel as the primary source for the anode feed which always contains carbon dioxide (CO) and hydrogen sulfide (H₂S). Trace amount of CO and H₂S can cause considerable cell performance losses. A comparison between the effect of CO and that of H₂S on PEMFC performance was made in this paper. Under the same conditions, the H₂S poisoning rate is much higher than CO because of different adsorption intensity. When the fuel stream contains the gas mixture (25 ppm CO and 25 ppm H₂S), the fuel cell performance deteriorates more quickly than 50 ppm CO but slowly than 50 ppm H₂S and can be only partially recovered by reintroducing neat H₂. The resulting effects of the mixtures can be divided into two parts roughly: during the inception phase, the cell voltage drops quickly and the actual values of anode overvoltage are bigger than the corresponding calculated values; then the deterioration rate of the cell performance decreases gradually.     

Single- and double-bed pressure swing adsorption processes for H2/CO syngas separation

Pressure swing adsorption (PSA) technology is an effective method to extract hydrogen from synthesis gas (syngas) and purify the produced hydrogen. The dynamic adsorption models for syngas (H₂/CO 70/30 mol%) treatment by single- and double-bed PSA systems with zeolite 5A were developed. The breakthrough curves of the single-bed hydrogen purification PSA system were studied. Subsequently, the performance of the single- and double-bed PSA cycles was studied. The models were built and implemented using the Aspen Adsorption platform. After model validation and successful simulation of the breakthrough curves in the single-bed model, the simulation of five- and six-step PSA cycles in the single-bed and double-bed models, respectively, were carried out. A parametric study of both single- and double-bed models was then carried out. The results reveal that the simulated breakthrough curves agree with the experimental curves very well. The parametric study shows that, with certain range of 1.38 × 10⁻⁶ to 2.08 × 10⁻⁶ kmol/s for feed flow rate, the adsorption time of 240–360 s for single-bed and 180–300 s for double-bed, a lower feed flow rate and shorter adsorption time leads to higher purity, lower recovery, and lower productivity. For the double-bed PSA model, the influence of the pressure equalization time, with the range of 5–40 s, on the PSA process was also studied. It can be found that, as the pressure equalization time increased, better purity and recovery but lower productivity were obtained. The results show that, at a feed flow rate of 1.58 × 10⁻⁶ kmol/s, the recovery and productivity of the double bed are higher by 11% and 1 mol/kg/h, respectively, than those of the single bed.     

Two-stage PSA/VSA to produce H2 with CO2 capture via steam methane reforming (SMR)

A two-stage pressure/vacuum swing adsorption (PSA/VSA) process was proposed to produce high purity H₂ from steam methane reforming (SMR) gas and capture CO₂ from the tail gas of the SMR-H₂-PSA unit. Notably, a ten-bed PSA process with activated carbon and 5A zeolite was designed to produce 99.99+% H₂ with over 85% recovery from the SMR gas (CH₄/CO/CO₂/H₂ = 3.5/0.5/20/76 vol%). Moreover, a three-bed VSA system was constructed to recover CO₂ from the tail gas using silica gel as the adsorbent. CO₂ product with 95% purity and over 90% recovery could be attained. Additionally, the effects of various operating parameters on the process performances were investigated in detail.     

Numerical study and field synergy analysis on CO selective methanation packed-bed reactor

Carbon monoxide selective methanation (CO-SMET) is one of the most efficient technologies for hydrogen purification and CO deep removal. This paper applies the field synergy principle for a deep understanding on the chemically reactive flow in a CO-SMET tubular reactor. The variation of CO conversion rate under different operating conditions is interpreted, at the first time, as relevant to the variation of the synergy angle between temperature and gas concentration fields. Sensitive analyses of the bed pressure, CO/CO₂ ratio, heat exchange modes, etc., are studied to obtain the profile of field synergy angle in the inlet gas temperature range of 373 K – 873 K. It is found that the region with synergy angles between 0° and 70° enhances the heat transfer between mass transfer and contributes the main output of CO conversion. This work provides a fundamental basis on the future optimal design of CO–SMET reactors.     

Investigation of a methanol processing system comprising of a steam reformer and two preferential oxidation reactors for fuel cells

Methanol steam reforming is able to produce hydrogen-rich syngas onsite for fuel cells and avoids the problems of hydrogen storage. Nevertheless, CO in the reformate needs to be further removed to ppm level before it can be fed into proton exchange membrane fuel cells. In this study, a methanol processing system consisting of a methanol reformer and two-stage preferential oxidation reactors is developed. The hydrogen production performance and scalability of the reformer are experimentally investigated under various operating conditions. The methanol reformer system shows stable methanol conversion rate and linearly increased H₂ flow rate as the number of repeating unit increases. Methanol conversion rate of 96.8% with CO concentration of 1.78% are achieved in the scaled-up system. CO cleanup ability of the two-stage preferential oxidation reactors is experimentally investigated based on the reformate compositions by varying the operating temperature and O₂ to CO ratios. The results demonstrate that the developed CO cleanup train can decrease the CO concentration from 1.6% to below 10 ppm, which meets the requirement of the fuel cell. Finally, stability of the integrated methanol processing system is tested for 180 h operation.     

Transition metal atom embedded graphene for capturing CO: A first-principles study

The adsorption of CO and H₂ on single-metal-atom (Fe, Co, Ni and Cu) embedded graphene (M-G) has been studied using density functional theory calculations. Fe-G and Co-G can capture up to three CO molecules per metal atom strongly, but tend to weakly or not adsorb H₂ molecules. Under standard conditions (298.15 K and 1 bar), they show a high adsorption selectivity ratio for CO over H₂. The density of states analysis reveals that the strong adsorption between CO and Fe(Co)-G results from the hybridization between d states of Fe (Co) and sp states of CO. Our findings suggest that Fe-G and Co-G can be used as a filter membrane for removing CO efficiently in the feed gas of hydrogen fuel cells.     

Hydrogen from ethanol by steam iron process in fixed bed reactor

This research is devoted to the use of ethanol (i.e. bio-ethanol) in the combined production and purification of hydrogen by redox processes. The process has been studied in a single lab scale fixed bed reactor. Iron oxides, apart from their remarked redox behavior, exert an important catalytic role allowing the complete decomposition of ethanol at temperatures in the range from 625 to 750 °C. The resulting gas stream (mainly H₂ and CO) reduces the solid to metallic iron. During a subsequent oxidation with steam, the solid can be regenerated to magnetite producing high purity hydrogen (suitable to be used in PEM fuel cells). Even though small amounts of coke are deposited during the reduction step, this is barely gasified by steam during the oxidation step (detection of CO_x in concentrations lower than 1 ppm). Influence of parameters like temperature, ethanol partial pressure and alternate cycles' effect has been studied in order to maximize the production of pure hydrogen.     

Energy analysis of an electrolytic-based selective CO oxidation system for on-board pure hydrogen production

Carbon monoxide (CO) in the hydrogen (H₂) stream diminishes the performance of a low temperature polymer electrolyte membrane (PEM) fuel cell significantly. The existing technologies for on-board/site production of pure hydrogen with low CO concentrations operate at high temperatures and pressures and need on-board oxygen or air supply for CO oxidation. This study offers an alternative solution to on-board/site production of hydrogen suitable for low temperature PEM fuel cell applications. A thorough energy analysis and parametric study have been carried out to investigate the effect of different operating parameters on the performance of an electrolytic-based selective CO oxidation system operating at room temperature. Such a system electrochemically removes the CO molecules in a fuel stream where they are adsorbed onto the catalyst surface at the anode side of an electrolyzer, and produces additional hydrogen at the cathode side through an electrochemical water gas shift reaction. This additional hydrogen thus offsets the energy required to drive the electrolysis, making it an attractive solution for on-board/site applications. The breakthrough curves are measured for the adsorber (50 cm² area PEM reactor) fed with different CO concentrations (100, 300 and 500 ppm CO) present in the wet hydrogen stream at different flow rates (40, 80, 120, 160 and 200 ml min⁻¹), under the room temperature and atmospheric pressure. The electrolytic process (regeneration) parameters are optimized with an attempt of completely removing the adsorbed CO molecules. Furthermore, a thermodynamic-electrochemical model is developed to simulate the energy balance of the electrolyzer indicating that this process offsets the actual energy consumption as it produces extra hydrogen. Thermodynamically, removing CO by electricity is more efficient than by heat which leads to high energy efficiencies (>80%). The study has demonstrated that the electrolytic-based selective CO oxidation system is a promising system for on-board/site pure hydrogen production.     

Elevated temperature pressure swing adsorption process for reactive separation of CO/CO2 in H2-rich gas

Purification of CO and CO₂ to the ppm level in H₂-rich gas without losing H₂ is one of the technical difficulties for fuel cell power systems. In this work, a two-column seven-step elevated temperature pressure swing system with high purification performance was proposed. The concept of reactive separation by adding water gas shift catalysts into the columns filled with elevated temperature CO₂ adsorbents was adopted. The H₂ recovery ratio and H₂ purity were greatly improved by the introduction of steam rinse and steam purge, which could be realized due to the increasing operating temperature (200–450 °C). An optimized operating region to both achieve high efficiency and low energy consumption was proposed. The optimized case with 0.09 purge-to-feed ratio and 0.15 rinse-to-feed ratio could achieve 99.6% H₂ recovery ratio and 99.9991% H₂ purity at a stable state for a feed gas containing 1% CO, 1% CO₂, 10% H₂O, and 88% H_2. No performance degradation was observed for at least 1000 cycles. The proposed (ET-PSA) system possessed self-purification ability while the columns were penetrated by CO₂. It is however suggested that periodical heat regeneration should be adopted to accelerate performance recovery during long-term operation.