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Adsorption is a potential technology that is expected to meet NOx ultra-low emission standards and achieve the recovery of NO2. In this study, the adsorption/desorption behavior of NOx with competitive gases (e.g., H2O(g) and CO2) was studied on MFI zeolites with different Si/Al ratios and under different relative humidity (0~90% RH). Sample characterization of self-synthesizing zeolites was conducted by means of X-ray diffraction, Ar adsorption-desorption, and field emission scanning electron microscopy. The results showed that low-silica HZSM-5(35) showed the highest NOx adsorption capacity of 297.8 μmol/g (RH = 0) and 35.4 μmol/g (RH = 90%) compared to that of other adsorbents, and the efficiency loss factor of NOx adsorption capacity at 90%RH ranged from 85.3% to 88.1%. A water-resistance strategy was proposed for NOx multicomponent competitive adsorption combined with dynamic breakthrough tests and static water vapor adsorption. The presence of 14% O2 and lower adsorption temperature (25 °C) favored NOx adsorption, while higher CO2 concentrations (~10.5%) had less effect. The roll-up factor (η) was positively correlated with lower Si/Al ratios and higher H2O(g) concentrations. Unlike Silicalite-1, HZSM-5(35) exhibited an acceptable industrial desorption temperature window of NO2 (255~265 °C). This paper aims to provide a theoretical guideline for the rational selection of NOx adsorbents for practical applications. [ABSTRACT FROM AUTHOR]

A small scale (~270 Nm3·h−1) vacuum pressure swing adsorption (VPSA) air separation system was established in Qinghai Province (in China) with an altitude of 3800 m, which was used to supply oxygen for relieving the hypoxia. The effects of adsorption and desorption time, purge and pressure equalization step and feed temperature on the performance of the process were investigated by performing experiments under plateau special conditions. Results showed that pressure equalization and intermittent purge steps could effectively improve the performance of the VPSA process. The system could produce 270 Nm3·h−1 of 90% O2 with 62.6% oxygen recovery from compressed air. The maximum productivity and minimum energy consumption with pressure ratio of 160:42 for ~90% O2 were 121.7 L·h−1·kg−1 and 0.55 kWh·Nm−3, respectively. [ABSTRACT FROM AUTHOR]

Naphthalene (NAP) is a typical gaseous polycyclic aromatic hydrocarbons (PAHs) pollutant that displays toxicological effects on biosystems. Ordered mesoporous carbon has relatively adequate adsorption capacity; however, the attached hydrophilic functional groups were proven to affect the adsorption performance in the presence of moisture. In this paper, trimethylchlorosilane (TMCS) is used to carry out the hydrophobic modification of ordered mesoporous carbon FDU-15, and the adsorption and desorption properties of FDU-15 were studied. Furthermore, the adsorption isotherms of naphthalene on FDU-15 and modified FDU-15 were fitted by L-F equation, and the kinetic parameters of desorption of naphthalene on modified FDU-15 were analyzed based on the method of temperature programming desorption (TPD). The results showed that the micropore volume and specific surface area of FDU-15 were significantly increased after hydrophobically modified by TMCS, and the polar functional groups of the hydrophobically modified FDU-15 were significantly reduced. Furthermore, the adsorption of naphthalene by FDU-15 before and after modification conformed to the L-F equation (R2 > 99%), and the adsorption of naphthalene by modified FDU-5 at low concentration was significantly improved due to the increase of micropores. Based on desorption kinetic performance study of modified FDU-15, it can be seen that the adsorption kinetic characteristics of naphthalene on the modified FDU-15 conform to the mechanical function of the JMA equation. When the mass ratio of TMCs to FDU-15 is 1:10 in the modification process, the pore structure and surface hydrophobicity of the modified FDU-15 reach an excellent balance. At this time, the adsorbent had the optimum desorption performance under experimental conditions, and the desorption activation energy was decreased from 60.98 kJ/mol of FDU-15 to 50.28 kJ/mol. [ABSTRACT FROM AUTHOR]

[Display omitted] • Comparisons of NO x adsorption and desorption among series of zeolites are conducted. • Effects of zeolite structures, cations, SiO 2 /Al 2 O 3 ratios on NO x sorption are shown. • H-typed 10-membered-ring straight-channel zeolite is selected as preferred sorbent. • Importance of kinetics of NO oxidation-NO 2 physisorption process is revealed. • Accessibility of Brønsted acid sites that drives NO-NO 2 catalytic cycle is discussed. Adsorption is a promising technology for deep purification of nitrogen oxides (NO x) from flue gases and simultaneously recycling NO 2 as an economically valuable chemical. Zeolite as a robust NO x adsorbent provides the key step for success in practical applications, of which the screening remains challenging regarding the NO-NO 2 oxidation and adsorption combined process. In this work, experimental evaluations on practical NO x sorption performances on series of zeolites were conducted. Effects of the zeolite typological structure, compensating cation, and SiO 2 /Al 2 O 3 ratio on deep purification efficacy, water resistance, and regenerability at varying humidity were obtained, revealing the importance of kinetics of the NO oxidation and NO 2 physisorption consecutive process. The H-typed 10-membered-ring straight-channel zeolites (MFI and FER) were demonstrated to be the preferred NO x adsorbents qualified for industrial needs, as compared to other caged-channel, hybrid-channel, larger-sized straight-channel, or Na-typed counterparts. Deeper insights into the key role of Brønsted acid sites (BAS) in driving the NO-NO 2 catalytic cycle and promoting the adsorption competitiveness of NO x over water vapor were revealed based on in-situ diffuse reflectance Fourier transform infrared spectroscopy characterizations. The MFI zeolite with improved performance at the low-silica version could benefit from the efficient utilization of BAS within the highly accessible medium-sized straight channel, while the FAU zeolite (representative caged-channel zeolite) requiring appropriate SiO 2 /Al 2 O 3 ratio for optimal BAS utilization may suffer from the limited site accessibility. The findings clarify the relationships between NO x oxidative adsorption performances and zeolite properties, which provides a fundamental perspective and scientific screening strategy for NO x adsorbents. [ABSTRACT FROM AUTHOR]

Adsorption as an air purification method is widely employed to remove volatile organic compounds with low concentration using zeolites. In this study, ZSM-5 and LSX zeolites modified by alkali metal cations (Li+, Na+ and K+) were used as adsorbents for the abatement of toluene. The adsorption behaviors of toluene onto adsorbents with different pore sizes and cation contents were evaluated systematically based on the experiments of adsorption equilibrium, kinetic diffusion and desorption. Besides, Langmuir and Freundlich model, constant-pattern wave propagation model and Kissinger method were applied to fit with the above experimental data. The adsorption amount followed the sequence of Li-LSX > Na-LSX > K-LSX > Li-ZSM-5 > Na-ZSM-5 > K-ZSM-5 obtained from equilibrium isotherms. LSX zeolites showed twice adsorption capacity on unit volume compared to ZSM-5. The mechanisms of steric hindrances and electrostatic interactions controlling the diffusion rate under high and low concentrations were proposed, respectively. At relatively low loadings of toluene, the diffusion resistances were primarily affected by electrostatic interaction due to preferential adsorption of toluene on cationic sites. While at relatively high loadings, the diffusion resistance was mainly restricted by steric effect because of saturated cationic sites. The strength of adsorbate-adsorbent interactions was assessed by temperature programmed desorption experiments. It showed that both adsorption sites and microporous walls contributed to the desorption energy. [ABSTRACT FROM AUTHOR]

Abstract Adsorption thermodynamics of N 2 and O 2 on two most commonly used zeolites (5A and Li-LSX) under plateau special conditions of wide ranges of temperature (238–298 K) and pressure (0–300 kPa) for pressure swing adsorption (PSA) oxygen production were studied based on molecular simulations and theoretical model fitting. Adsorption isotherms for each adsorbate-adsorbent pair at different temperatures were fitted by Langmuir, Freundlich and Sips models, obtaining equilibrium parameters including adsorption capacity, strength, heterogeneity and N 2 /O 2 selectivity. Thermodynamic parameters such as Gibb's free energy, enthalpy, and entropy changes were numerically derived, and isosteric adsorption heats and distributions of potential energy were simulated. The results suggest that the adsorption capacity and affinity follow the order of N 2 -Li-LSX > N 2 -5A > O 2 -5A > O 2 -Li-LSX, leading to higher N 2 /O 2 selectivity on Li-LSX compared to 5A. For Li-LSX, N 2 /O 2 selectivity increases significantly with temperature above 273 K due to the difference in adsorption thermodynamics of N 2 and O 2 varying with temperature in terms of different adsorption heterogeneities. For 5A, the homogeneous distributions of N 2 and O 2 as well as the wide scopes of affinities from Na+ and Ca2+ exhibit N 2 /O 2 selectivity with negligible temperature dependence, which is beneficial for stable oxygen production with a fixed PSA process under large day-and-night temperature difference. This study provides theoretical basis for obtaining an optimal balance between efficiency and stability of oxygen production by using a proper mixture of Li-LSX and 5A. Highlights • Adsorption equilibrium of N 2 and O 2 on zeolites at plateau conditions are obtained. • N 2 /O 2 selectivity is higher with greater temperature dependence on Li-LSX than on 5A. • Adsorption capacity and affinity follow the order of N 2 -Li-LSX > N 2 -5A > O 2 -5A > O 2 -Li-LSX. • Advantage of thermodynamic stability of 5A over wide temperature range is discussed. [ABSTRACT FROM AUTHOR]

Radial flow is an important type of flow direction for large-scale pressure swing adsorption (PSA) oxygen generation systems. In this study, a numerical simulation of a PSA oxygen generation process based on radial-flow adsorbers was performed with two-dimensional CFD modeling. The gas distribution, the maldistribution factor and the pressure difference were comparatively investigated at each flow type of the radial-flow adsorber. Considering the gas adsorption performance, the results indicated that the centripetal π-flow radial adsorber has the best flow characteristics for the PSA process. The oxygen purity distribution within the adsorption bed was studied to compare centripetal and centrifugal π-flows, and the former was shown to perform better on oxygen enrichment and adsorbent desorption. The steady state was achieved after eight cycles for the centripetal-π adsorber and each of the four steps of the PSA process was explored in detail to show the advantageous properties for oxygen generation in terms of adsorption and desorption. The relationships between the product flow rate and the oxygen purity and recovery were further investigated. [ABSTRACT FROM AUTHOR]

Modelling dynamic adsorption of sulfur dioxide (SO 2 ) on activated carbons (ACs) is significant in guiding practical desulphurization processes and making highly efficient use of adsorbents in terms of the adsorption rate which largely depends on particle size. In this work, models derived from the Vermeulen and an improved linear driving force (LDF) rate equation were studied for the first time on SO 2 adsorption over AC particles with different sizes. For larger particles (≥3 mm), breakthrough curves predicted by the Vermeulen equation showed good agreement with experimental data, demonstrating that intraparticle diffusion resistance varied with particle size, feed concentration, adsorption time and location. For smaller particles (1 mm), a correction on the volume-averaged adsorption capacity as a function of adsorption time and saturation in the rate equation was developed to avoid the underestimation of adsorption rate due to the inappropriate parabolic concentration profile inherent in the conventional LDF model. By providing a concentration gradient and adsorption rate closer to actual values, the improved LDF equation was confirmed to provide excellent prediction results on 1-mm particles. Different modelling characteristics of the two models indicates varying effects of intraparticle diffusion on adsorption rate with particle size regarding the specificity of SO 2 physisorption on ACs. [ABSTRACT FROM AUTHOR]

The kinetics of the thermal desorption of CO2 adsorbed on zeolite 13X were obtained using a differential thermogravimetric analyser under two different carrier gas conditions. The varying heating rates were set as 8, 12, 16, and 20 K min−1, respectively. The desorption activation energy of the physisorption sites for this experiment evaluated by an integral method without prediction of the reaction order ranged from 12.15 to 14.12 kJ mol−1 (CO2 as the carrier gas) and 43.32 to 50.42 kJ mol−1 (Ar as the carrier gas), respectively. The desorption activation energy of the chemisorption sites ranged from 57.95 to 58.53 kJ mol−1 (CO2 as the carrier gas) and 74.02 to 79.92 kJ mol−1 (Ar as the carrier gas), respectively. [ABSTRACT FROM AUTHOR]

Adsorption is a promising technology for simultaneously capturing nitrogen oxides (NO x) from flue gases and recycling NO 2 as a profitable chemical, for which a robust and efficient adsorbent provides the key step for success in practical applications. This work reports the enhancement of NO x adsorption performances with less cost of desorption energy on Cu-ZSM-5 zeolites prepared by a facile and rapid (690 s) modification method, the incipient-wetness impregnation coupled with microwave drying (IM). In comparisons to H-ZSM-5, Na-ZSM-5 and conventionally liquid-phase ion-exchanged counterparts under sub-1000 ppm NO x feed concentrations and room temperature, the IM sample renders a record NO x adsorption capacity (q t,NOx) of 0.878 mmol/g from dry gas stream on zeolites, and an applicable q t,NOx of 0.1 mmol/g from wet gas stream with a proper copper loading (2.1 wt%). The temperature programmed desorption of NO x on the optimal IM sample saturated with NO x from wet gas stream exhibit primary peak temperature lower than reported Cu-ZSM-5 and significant NO 2 proportion (72.6 %) in desorbed NO x. Deeper insights into advantageous NO x oxidative adsorption over the properly-loaded Cu-ZSM-5 in terms of diverse adsorbate states and competitiveness towards H 2 O were gained, showing IM method a promising sorbent improvement strategy for practical use. [Display omitted] • Cu-ZSM-5 is prepared by incipient-wetness impregnation coupled with microwave drying. • A record NO x adsorption capacity at sub-1000 ppm dry gas feed on zeolites is obtained. • Applicable NO x adsorption capacity at wet feed is gained on properly-loaded Cu-ZSM-5. • Lower NO x desorption temperature and higher NO 2 proportion in desorbed gas are shown. • Advantageous NO x oxidative adsorption competing with H 2 O on Cu-ZSM-5 is revealed. [ABSTRACT FROM AUTHOR]

Abstract: In order to solve hypoxic problems in high altitude area and ensure workers life safety, a new cycle named as Low Pressure Swing Adsorption for oxygen concentration was proposed. In this cycle, the high efficiency liking Vacuum Pressure Swing Adsorption was obtained but the vacuum was not used. The relationship between oxygen concentration and oxygen flux was revealed. And the matching air content curve in different altitudes was acquired. Basing on the experiment data, the life safety system with oxygen supplied for workers was suggested. After using this system, the oxygen partial pressure of the tunnel face could be enhanced by 2 – 3kPa and the incidence of AMS in the workers decreased significantly, blood oxygen saturation increased, pulse rate and breaths per minute decreased. [Copyright &y& Elsevier]

A novel adsorbent of CO2 from biogas was prepared by synthesizing and modifying the mesoporous molecular silica of SBA-15 with methyl-diethyl-amine (MDEA) and piperazine (PZ). The adsorbent showed good performance in separating CO2 from biogas. The loaded amines did not change the ordered structure of SBA-15, but enhanced its adsorption of CO2. The adsorbents were characterized by X-ray powder diffraction (XRD) and N2 adsorption/desorption. With the increase in MDEA loading, the surface area, pore size, and pore volume of the MDEA-loaded SBA-15 decreased. The modification of amines enlarged the difference between the equilibrium adsorption of CO2 and CH4. Quantitatively evaluated on the basis of the breakthrough curves, the separation factors between CO2 and CH4, was increased more than seven fold due to the MDEA modification. With mixed-amine (MDEA + PZ) modification, the separation factors between CO2 and CH4 was further improved. In addition, not only the adsorbent was regenerable by purging with the purified gas, but also the adsorption performance is stable in adsorption cycles. Effect of moisture on adsorption of CO2 is investigated and the results show the increase in the adsorption performance. [ABSTRACT FROM AUTHOR]

Capturing and recovering naphthalene as a profitable chemical from hot flue gas are of significance in terms of environmental protection with economic benefits, for which the adsorption technology using high-performance sorbents provides the key step for success in practical applications. Carbonaceous materials with hydrophobic natures have been shown to render high affinities with non-polar naphthalene, but remain challenging due to difficulties in tackling the trade-off between adsorption and desorption. This work reports a systematic investigation with deeper insights into adsorption equilibria, kinetics and regenerabilities of gaseous naphthalene on typical carbonaceous sorbents originated from different texture properties, including ordered mesoporous carbons (CMK-3, CMK-5 and FDU-15), carbon nanotubes (SWCNT and MWCNT) and a coconut-shell-based activated carbon (AC). The adsorption isotherm and breakthrough curves at wide feed concentration ranges and temperature programmed desorption curves for each sorbent were obtained along with series of theoretical model fitting. FDU-15 and CMK-5 were demonstrated as superior sorbents with high maximum adsorption capacities (1.13 and 1.735 mmol/g) and low desorption activation energy (62.66 and 72.68 kJ/mol), respectively exhibiting advantages of the 3-dimensional diffusion-controlled desorption upon a hexagonal pore arrangement and the efficient adsorption upon a reasonable mesopore-micropore hierarchical structure, in contrast to poor kinetics on pure microporosity (AC) and 1-dimensional topologies (CNTs). Deeper insights into the morphology-affinity relationship revealed advantageous naphthalene transport behaviors over 3-dimensional ordered mesoporosities with appropriate coexisting microporosities and narrower primary size (2–5 nm) or diverse forms of mesopore, which contribute toward reaching comprehensive balances of sorption performances. [Display omitted] • Adsorption equilibria of gaseous naphthalene on carbonaceous sorbents are obtained. • Regenerability with desorption kinetic triplet for each sorbent is quantified. • Ordered mesoporous carbons, FDU-15 and CMK-5, are demonstrated as superior sorbents. • 3-dimensional ordered mesoporosities with narrower primary size (2–5 nm) are favored. • Micropore-mesopore hierarchical structure gives high adsorption/desorption kinetics. [ABSTRACT FROM AUTHOR]

Conventional flue gas nitrogen oxides (NO x) abatement technologies commonly convert NO x into harmless compounds, while less effort has been made to recycle NO 2 as a profitable chemical in many industries. Towards this end, adsorption is a promising technology for which an advanced technique for NO 2 desorption and efficient sorbent regeneration provides the key step for success in practical applications. This work reports a novel cyclic adsorption process for NO x removal with recycling of NO 2 from iron-ore sintering flue gas of a steel plant. This process using self-prepared and validated pelletized Na-ZSM-5 zeolites as low-cost sorbents involves NO x catalytic adsorption and reversible desorption using multiple hot gas circulations (GC) within the enclosed fixed bed followed by scavenging and purge at mild conditions. In comparison to conventional cyclic processes, greater amount of recyclable NO 2 was obtained, rendering the NO x recovery of >92% and the mean NO 2 concentration of >2% significantly enriched from original 20 ppm in feed gas. A robust adsorption-desorption performance with appreciable NO x working capacity was achieved for up to 16 cycles. The key role of the segmentation of GC in boosting NO x regenerability was addressed, providing an economical three-tower strategy for continuous NO 2 production for practical use. ga1 • NO x removal and with recycling of NO 2 from flue gas was studied through field tests. • Comparisons among different adsorption cycles in NO x removal and recycling were made. • A novel technique for efficient NO 2 desorption and sorbent regeneration was proposed. • NO x recovery of 92% and recyclable desorbed NO 2 concentration of >2% were obtained. • Robust cyclic performance with NO x working capacity of >0.1 mmol/g was demonstrated. [ABSTRACT FROM AUTHOR]

• Binary adsorption of N 2 and O 2 on FAU zeolites at plateau conditions is obtained. • Water interacting with zeolites via hydrogen bond competes with N 2 and O 2 adsorption. • Effect of water content is greater than that of temperature change on air separation. • Trade-off between N 2 /O 2 selectivity and performance stability is addressed. • X zeolite with Si/Al close to 1.5 is recommended for PSA O 2 production in plateau. Adsorption thermodynamics of N 2 and O 2 on faujasite (FAU) zeolites with different Si/Al molar ratios under plateau conditions of wide ranges of temperature and humidity for pressure swing adsorption (PSA) oxygen production were studied based on validated molecular simulations. Binary adsorption isotherms and N 2 /O 2 selectivity on each adsorbent were obtained. The results suggest that dehydrated feed air with very low dew point of 213 K could still lead to ~10 wt% water adsorption capacity in FAU zeolites. The effect of water content was larger than that of temperature change on N 2 /O 2 separation performance, causing reductions in N 2 /O 2 selectivity of 50.9% and affinities of 15.6% and 10.6% for N 2 and O 2 at 238 K, and those of 45.7%, 13.7% and 11.1% at 298 K on FAU-1.1, respectively. The strong interaction of water with zeolites via hydrogen bond was shown to decrease the pore volume by 25.61%, occupy the cationic sites, and thermodynamically form competitive adsorption over N 2 and O 2. The increase in Si/Al molar ratio suppressed the negative impact of water and temperature change but sacrificed the N 2 /O 2 selectivity. To reach an optimal balance between the air separation performance and the adsorbent robustness, X zeolites with Si/Al molar ratio close to 1.5 would be recommended for PSA O 2 production under the plateau special condition. [ABSTRACT FROM AUTHOR]

[Display omitted] • Development of oxygen generation from air over zeolite by PSA was reviewed in this work. • Mechanisms of O 2 separation from N 2 over zeolite by adsorption were discussed. • Requirements for zeolite adsorbents to improve the O 2 purity were analyzed. • Effect of impurities in air on the nitrogen–oxygen separation was concluded. The adsorptive generation of oxygen from air has become increasingly important in the chemical and medical industries due to the growing demand for O 2 with high purity. Among the commonly used three methods of cryogenic distillation, pressure swing adsorption (PSA) and membrane separation for N 2 /O 2 separation, PSA has received much attention due to the advantages of small volume, low management cost, and short start-up time, etc. Zeolites, with their unique pore structure, highly polarized pore environment, and abundant ion exchange sites, are widely employed as an efficient adsorbent in N 2 /O 2 separation. Hence, in this work, a review about the application of zeolites in O 2 generation via PSA was performed. In detail, the common PSA techniques applied for O 2 generation were summarized and compared from both the characteristics and application scenarios firstly. Then, the main mechanisms of O 2 separated from N 2 in air over zeolite by adsorption were summarized from three aspects of the steric effect, kinetic effect and equilibrium effect. Based on above, the requirements for silica-alumina zeolite adsorbents to improve the O 2 purity clarified from skeleton topology, extra-framework cations as well as physical & chemical properties. Moreover, the operation conditions and impurities having a significant effect on the product O 2 quality were discussed. Finally, both the challenges and prospects of air separation and O 2 generation are proposed based on existing research results. [ABSTRACT FROM AUTHOR]

[Display omitted] • Adsorption of toluene and naphthalene by OMS were investigated by simulation. • The adsorption selectivity of toluene and naphthalene was predicted by IAST. • The mechanism of selective adsorption was elucidated at molecular level. • Adsorbents with the desired pore size were prepared by template synthesis method. • The experimental results are in good agreement with the simulation results. In order to ensure regeneration property of adsorption materials in the air pollution purification system of the airtight cabin, such as submarine and space station, it is necessary to selectively separate semi-volatile organic compounds whose desorption is difficult. For this reason, the effects of pore size on the adsorption capacity and adsorption selectivity of toluene and naphthalene were investigated by both molecular simulation and experimental investigation. The ordered porous silica-based adsorbents with pore sizes ranging from 1.0 nm to 2.8 nm were constructed by simulation and were prepared by template synthesis method in this study. Both simulation and experiment show that the adsorption capacity of toluene and naphthalene firstly increased and then decreased with the increase of the pore size of adsorbents from 1.0 nm to 2.8 nm, and the pore diameter (1.3 nm) corresponding to the maximum adsorption amount of toluene was smaller than that (2.3 nm) of naphthalene. Simulation results show that the adsorption energy and adsorption stability of naphthalene are higher than those of toluene, and binary-component co-adsorption experiments also testified that toluene molecules could be replaced by naphthalene molecules. The optimum pore size for selective adsorption of naphthalene is 2.3 nm. [ABSTRACT FROM AUTHOR]