Adsorption of CO2 on Zeolite 13X and Activated Carbon with Higher Surface Area

In this work, adsorption isotherms and adsorption kinetics of CO₂ on zeolite 13X and activated carbon with high surface area (AC-h) were studied. The adsorption isotherms and kinetic curves of CO₂ on the adsorbents were separately measured at 328 K, 318 K, 308 K, and 298 K and with a pressure range of 0–30 bar by means of the gravimetric adsorption method. The mass transfer constants and adsorption activation energy E_a of CO₂ on the adsorbents were estimated separately. Results showed that at very low pressure the amounts adsorbed of CO₂ on the zeolite 13X was higher than that on the AC-h, while at higher pressure, the amounts adsorbed of CO₂ on the AC-h was higher than that on the zeolite 13X since the AC-h has a larger surface area and a larger total pore volume compared to the zeolite 13X. The adsorption kinetics of CO₂ can be well described by the linear driving force (LDF) model. With the increase of temperature, the mass transfer constants of CO₂ adsorption on both samples increased. The adsorption activation energy E_a for CO₂ on the two adsorbents decreased with the increase of pressure. Furthermore, at low pressure the E_a for CO₂ adsorption on the zeolite 13X was slightly lower than that on the AC-h, while at higher pressure the E_a for CO₂ adsorption on the zeolite 13X was higher than that on the AC-h.     

Adsorption microcalorimetry applied to the characterisation of adsorbents for CO2 capture

The present work presents the design, assembly and experimental validation of a microcalorimetric device coupled to a volumetric adsorption setup applied to the characterisation of adsorbents for carbon dioxide (CO₂) capture. Three adsorbents were evaluated for CO₂ adsorption at 273 K in the pressure range of vacuum to 101 kPa. The data for CO₂ on zeolite 13X agreed well with the available data reported in the literature, thus validating the device, which also provided reproducible results with an activated carbon sample. For the amine‐modified zeolite, the differential enthalpy at lower coverage was increased by a factor of 1.7 as compared to the zeolite matrix. This points out to the potential of such technique to characterise heterogeneities introduced by amine impregnation. However, the adsorption uptake was decreased by factor of 2.7 at 101 kPa. This fact suggests that amino groups may be blocking some physisorption sites, leading to restricted chemisorption on the outer surface. Thus, the main novelty of this study is the simultaneous measurement of adsorption isotherms and respective differential enthalpy curves for amine‐impregnated adsorbents, which may be considered a fingerprint of the modified surface chemistry. This work has been carried out in the framework of a cooperation project between three South American universities and is part of the effort to develop and fully characterise adsorbent materials intended for CO₂ capture. © 2012 Canadian Society for Chemical Engineering     

Adsorption of H2, CO2, CH4, CO,N2 and H2O in Activated Carbon and Zeolite for Hydrogen Production

Abstract

The design of a layered pressure swing adsorption unit to treat a specified off-gas stream is based on the properties of the adsorbent materials. In this work we provide adsorption equilibrium and kinetics of the pure gases in a SMR off-gas: H₂O, CO₂, CH₄, CO, N₂, and H₂ on two different adsorbents: activated carbon and zeolite. Data were measured gravimetrically at 303–343 K and 0–7 bar. Water adsorption was only measured in the activated carbon at 303 K and kinetics was evaluated by measuring a breakthrough curve with high relative humidity.     

Bio‐Regeneration of Desulfurization Adsorbents by Selected P. delafieldii R‐8 Strains

Abstract

Adsorption properties of different adsorbents such as reduced NiY, AgY, alumina, 13X, and activated carbon were studied with dibenzothiophene (DBT) and naphthalene as model compounds. The desorption of DBT was carried on thermo gravimetric–differential thermal analysis (TG‐DTA). The interaction of DBT with different adsorbents follows the sequence: activated carbon > reduced NiY > AgY > activated alumina > 13X. The bio‐regeneration of these adsorbents was studied with P. delafieldii R‐8 as desulfurization strains. Adding P. delafieldii R‐8 cells can improve DBT desorption from adsorbent AgY. The desorption of DBT from adsorbents by bio‐regeneration of adsorbents follows the sequence: 13X > alumina > AgY > reduced NiY>activated carbon. The presence of naphthalene can decrease the desorption of sulfur compounds. The adsorption capacity of AgY decreases for the first time recycling and then changes little. The decrease of the adsorption capacity is due to the loss of Ag⁺ ions.     

Comparative Study of Zn2+, Cd2+, and Pb2+ Removal From Water Solution Using Natural Clinoptilolitic Zeolite and Commercial Granulated Activated Carbon. Equilibrium of Adsorption

Abstract

The aim of this work is to study the effectiveness of regional, low-cost natural clinoptilolitic zeolite tuff in heavy metal ions removal from aqueous solution, through comparative study with commercial granulated activated carbon. The equilibrium of adsorption of Cd²⁺, Pb²⁺, and Zn²⁺ on both adsorbents have been determined at 25, 35, and 45°C in batch mode. The granulated activated carbon has shown around three times higher adsorption capacity for Cd²⁺ and Zn²⁺ than natural zeolite, and almost the same adsorption capacity for Pb²⁺ as the natural zeolite. The metal ion selectivity series Pb²⁺ > Cd²⁺ > Zn²⁺, on a mass basis, has been obtained on both adsorbents. The Langmuir and Freundlich model have been used to describe the adsorption equilibrium. The thermodynamic parameters were calculated from the adsorption isotherm data obtained at different temperatures. The study of the influence of the acidity of the metal ion aqueous solution has shown an increase of metal ion uptake with increase of the pH. The sorption mechanism of Cd²⁺, Pb²⁺, and Zn²⁺ on natural zeolite changes from ion-exchange to ion-exchange and adsorption of metal-hydroxide with increase of the pH from 2 to 6 (and 7 for Zn²⁺). The preliminary cost calculation, based on adsorbents maximum adsorption capacity and their price, have revealed the potential of natural zeolite as an economic alternative to the granulated activated carbon in the treatment of heavy metal polluted wastewater.     

Criteria for Selection of an Adsorbent for a Temperature Swing Process: Applied to Purification of an Aliphatic Solvent Contaminated with Aromatic Solutes

Abstract

Temperature swing adsorption (TSA) is different in several respects from conventional adsorption. This paper explores the distinctions from the standpoint of adsorbent characteristics. In particular, a fixed-bed TSA process is considered for separating dilute aromatics from aliphatics (e.g., toluene and/or xylene in heptane). Relevant adsorbent characteristics include thermal-exchange capacity and properties that affect dissipative effects, e.g., intraparticle diffusivity, bed permeability, axial dispersion coefficient, and thermal diffusivity. Many of the dissipative effects can be manipulated by adjusting particle size, though trade-offs exist that have no clear-cut technical resolution. The adsorbents considered were silica gel, activated alumina, activated carbon, zeolite 13X, and a polymeric adsorbent (XAD-7). Silica gel was selected due to its superior thermal-exchange capacity. The other properties did not vary enough among the other adsorbents to compensate for their lesser capacities.     

Adsorption of Radon and Water Vapor on Commercial Activated Carbons

Abstract

Equilibrium adsorption isotherms are reported for radon and water vapor on two commercial activated carbons: coconut shell Type PCB and hardwood Type BD. The isotherms of the water vapor were measured gravimetrically at 298 K. The isotherms of radon from dry nitrogen were obtained at 293, 298, and 308 K while the data for the mixture of radon and water vapor were measured at 298 K. The concentrations of radon in the gas and solid phases were measured simultaneously, once the adsorption equilibrium and the radioactive equilibrium between the radon and its daughter products were established. The shape of the isotherms was of Type III for the radon and Type V for the water vapor, according to Brunauer's classification. The adsorption mechanism was similar for both the radon and the water vapor, being physical adsorption on the macropore surface area in the low pressure region and micropore filling near saturation pressure. The uptake capacity of radon decreased both with increasing temperature and relative humidity. The heat of adsorption data indicated that the PCB- and the BD-activated carbons provided a heterogeneous surface for radon adsorption. The equilibrium data for radon were correlated with a modified Freundlich equation.     

Adsorption of methylene chloride vapor on activated carbons

A laboratory investigation on the adsorption of hazardous methylene chloride (METH) vapor on the commercial activated carbons BPL and PCB, which were made from bituminous coal and coconut shell, respectively, was conducted at 283, 293, 303, and 313 K. The physical properties and surface functional groups of the two activated carbons were also measured and compared with each other. The experimental results indicate that the adsorption capacity of carbon PCB is slightly higher than that of carbon BPL. It was found that the Langmuir, Freundlich, and Dubinin–Radushkevich adsorption equations were well fitted by the measured adsorption data. The values of the parameters of the adsorption equations were determined for the two adsorbents. The physical properties (e.g. micropore volume) of the adsorbents are consistent with the parameters obtained from the adsorption results.     

Equilibrium and Kinetic Studies of Ni (II) Adsorption using Pineapple and Bamboo Stem Based Adsorbents

This work addresses the preparation and characterization of inexpensive adsorbents for the removal of Ni (II) from aqueous solutions. Activated carbon based adsorbents have been prepared from plant based biomass resources, namely Pineapple stem ( Ananas Comosus ) and Bamboo Stem ( Bambuseae ). Adopting phosphoric acid and heat treatment techniques, it has been observed that the bamboo stem activated charcoal (BSAC) and pineapple stem (PS) adsorbents had a BET surface area of 116 and 11.47 m ² /g, respectively. FTIR analysis indicated that various surface functional groups (such as C ≡ N stretching, stretching vibration of C = O, –CH₃ wagging and C–O stretching vibration) contribute towards Ni (II) adsorption. Batch mode adsorption experiments were conducted for these adsorbents in the range of 50–300 mg/L Ni (II) solution concentration, 2–10 pH, 15–300 min. contact time, and 0.02–0.1 g/50 mL dosage. The BSAC adsorbent has been characterized with a metal uptake and %removal of 121.72 mg/g and 92.47, respectively, which corresponds to 45% higher metal uptake than corresponding bamboo based adsorbents presented in the literature. Further experimentation with BSAC enabled to achieve activated charcoal with surface area values similar to that of the commercial activated carbon adsorbent. The bamboo adsorbent has also been evaluated to perform similar to the commercial activated carbon for the removal and recovery of Pd (II) from synthetic electroless plating solutions. Also, a conceptual cost analysis indicated and affirmed towards the potential of the BSAC adsorbents for waste water treatment applications.     

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     

基于改进型吸附等温线模型的空气预纯化TSA双层床模拟

为了掌握空气中CO2和水蒸气在空分装置双层床变温吸附(TSA)纯化器中的动态吸附特性,通过LDF传质假设及非绝热假设,建立了一维二元稀组分系统的双层床TSA过程数学模型。一种改进型的多组分等温线模型用于描述水蒸气的Ⅱ型吸附等温线以及水蒸气和CO2混合物的吸附平衡关系。通过对比模拟结果与TSA纯化器的现场监控数据发现,基于改进型等温线模型的模拟结果与现场数据吻合良好。最后对多种工况下的TSA纯化器中的温度、浓度及吸附量床层分布和穿透曲线进行了数值模拟和分析。     

The adsorption of dibenzothiophene using activated carbon loaded with cerium

Cerium-loaded activated carbon was prepared by classical soaking impregnation method and tested for dibenzothiophene adsorption from model fuels. The new adsorbents showed much better adsorption capacity and selectivity towards DBT than the virgin carbon. The adsorbents were characterized by N₂ adsorption, Boehm titration and FTIR. The improved performance is mainly due to changes in surface chemistry. The results show that the performance of activated carbon as desulfurization adsorbents can be considerably enhanced by a simple cerium loading method.     

Efficiency of different clay minerals modified with a cationic surfactant in the adsorption of pesticides: Influence of clay type and pesticide hydrophobicity

In the present work we studied the efficiency of a series of clay minerals (montmorillonite, illite, muscovite, sepiolite and palygorskite) modified with the cationic surfactant octadecyltrimetylammonium bromide (ODTMA) in the adsorption of the pesticides penconazole, linuron, alachlor, atrazine and metalaxyl. A study was also carried out on the effect of the structure (expansible and non-expansible layered, and non-layered), the surface area and charge density of the clay minerals, and the hydrophobicity of the pesticides (K_ow) on the adsorption process. Adsorption–desorption isotherms of the pesticides by clay minerals were obtained and the constants of the Freundlich model (K_f and K_fd) (natural clays) and of the linear model (K and K_des) (ODTMA-clays) were determined. Correlation coefficient values (r²) found between K and K_des, and organic matter (OM) content of ODTMA-clays indicate a more effective partitioning of the pesticides in the organic phase of ODTMA after desorption. Furthermore the positive significant correlation found between the K_desom values and the charge density of different ODTMA-clays indicates that a higher density of ODTMA in the clay gives rise to the formation of an organic phase more effective for the partition of the pesticides. This correlation explained that the highest K_desom value obtained was for kaolinite and the lowest K_desom value was for montmorillonite in the adsorption of all pesticides by the different organo clays. Simple correlations between adsorption constants and K_ow values, and multiple correlations between these constants and clay OM contents and K_ow values were also calculated. The results obtained indicate the interest of ODTMA-clays in the adsorption of hydrophobic pesticides. Non-expandible layered and fibrous clay minerals may also be of interest as adsorbents derived from their density charge, and these minerals, when modified with ODTMA, and used in appropriate amounts, higher than that of montmorillonite, or when present in soils with high clay contents, even in the absence of montmorillonite, may be good adsorbents for hydrophobic pesticides. According to the results of the study, ODTMA-clays and ODTMA-soils could be used as barriers to prevent the mobility of certain hydrophobic pesticides from a point source of pollution.     

Removal of Metanil Yellow from its Aqueous Solution by Fly Ash and Activated Carbon Produced from Different Sources

Abstract

The present study has been undertaken to observe the relative efficiency of removal of metanil yellow from its aqueous solution by using different adsorbents like fly ash and activated carbon produced from different sources i.e. coconut shell, mehagani saw dust, and rice husk. It has also been observed that the rate of adsorption is highly dependent on contact time, adsorbent dose, pH, and initial concentration of the dyestuff. Rate of removal has been observed to increase with increasing contact time and adsorbent dose but with decreasing initial concentration. Higher removal has been observed generally in acidic range. Adsorptions by the adsorbents under investigation follow the Freundlich and Langmuir isotherm models where Freundlich and Langmuir constants have also been determined at different temperatures. Isotherms have been used to obtain the thermodynamic parameters like free energy, enthalpy and entropy of adsorption. Kinetic studies showed that all the adsorbents follow first order adsorption rate model with respect to the dye solution concentration. Various kinetic parameters such as first order adsorption rate constant, mass‐transfer co‐efficient, pore‐diffusion constant, and activation energy of adsorption were evaluated to establish the mechanism. Adsorption processes were found to be endothermic, spontaneous, and pore‐diffusion controlled for all the adsorbents. Among the adsorbents used in this study, activated carbon produced from mehagani saw dust has been found to be the most effective, which remove almost 100% metanil yellow from its 1000 ppm aqueous solution.     

A novel double-function porous material: zeolite-activated carbon extrudates from elutrilithe

Zeolite-activated carbon (ZEOAC) extrudates were synthesized from natural elutrilithe through a two-step process consisting of the chemical activation of elutrilithe with K₂CO₃ at 800°C followed the hydrothermal transformation in NaOH solution. During the chemical activation, carbon in elutrilithe was activated, and the kaliophilite crystalline phase with framework structure of linked (Si, Al)O₄ tetrahedra was formed simultaneously, which was then converted into zeolite A in alkaline medium. The as-synthesized samples were characterized by thermal gravimetric and differential thermal analyses (TG/DTA), N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM) and adsorptive capacities for water and hexane. The results show that this new material ZEOAC possesses the typical characteristics of zeolite and activated carbon, micro- and mesoporous structure, hydrophilic and hydrophobic properties.     

Trennen von Gasgemischen durch Adsorption

Separation of gas mixtures by adsorption . Gas mixtures are separated primarily by absorption and rectification. Rectification requires at least (v + 1)-fold of the enthalpy of the distillate as heat energy (v is the reflux ratio). In the case of absorption, the resulting solution is frequently subjected to thermal regeneration with the energy requirement depending inter alia on the boiling point of the solvent. In view of the high energy requirements of these processes and the development of new adsorbents, possibilities of separating by adsorption with subsequent regeneration of the adsorbents, above all by change in pressure, are investigated. The separation of gas mixtures in adsorber beds (e.g. molecular sieves, silica gel, activated charcoal and coke, or alumina) depend upon various separating effects: steric effects, equilibrium effects, kinetic effects. A survey is given of proposed and practical industrial separation processes utilizing adsorption.     

Comparison of different sorbents (inorganic and biological) for the removal of Pb2+ from aqueous solutions

In an attempt to evaluate the suitability of activated sludge for Pb²⁺ removal, a comparative study was carried out using several chemical adsorbents and three types of biomass. The order of Pb²⁺ removal capacities for chemical adsorbents was found to be: ion exchange resin > zeolite > granular activated carbon (GAC) > powdered activated carbon (PAC), while for biomass the order was Aureobasidium pullulans > Saccharomyces cerevisiae > activated sludge. Although Pb²⁺ removal capacity (mg Pb²⁺ g⁻¹) of the activated sludge (30.9) was lower than those of the ion exchange resin (167.7) and other pure cultures of A pullulans (170.4) and S cerevisiae (95.3), it was higher than those of other chemical adsorbents such as GAC (26.0), PAC (2.1), and zeolite (30.2). The initial Pb²⁺ removal rates for the chemical adsorbents were in the order of PAC > GAC > zeolite > ion exchange resin, while for the biomass samples it was A pullulans > activated sludge > S cerevisiae. The initial Pb²⁺ removal rate of activated sludge was higher than those of GAC, zeolite, ion exchange resin and S. cerevisiae cells. Therefore, it was concluded that activated sludge that has been used in a municipal wastewater facility can be effectively used in heavy metal removal processes, in situ. © 2000 Society of Chemical Industry     

Water vapor adsorption and the microporous structures of carbonaceous adsorbents

The principal role in adsorption of almost all vapors organic and inorganic substances on nonporous and microporous carbonaceous adsorbents is played by dispersion interactions. They are characterized by a considerable increase in adsorption potentials as a result of superposition of the fields of the opposite pore walls. This effect determines the entire specifics of adsorption in micropores and, in particular, the substantial increase in adsorbability. A theoretical estimate of the adsorption potentials of benzene and water in adsorption on graphite, and a comparison of the differential heats of adsorption of water vapors on a non-porous carbon black previously heated in a vacuum at 950°C and on an active carbon show that water adsorption is due to the formation of hydrogen bonds both between the oxygen complexes on the surface of carbonaceous adsorbents and between the adsorbed molecules themselves. Dispersion interactions are weak and can be neglected to a first approximation. It has been shown for microporous structures and the slitlike model that one can calculate, from the parameters W₀ and E₀ of the adsorption equation of the theory of volume filling of micropores (determined from the adsorption isotherm of a standard vapor, benzene) the volume of the micropores, their halfwidth, and the specific surface area of the micropore walls. The latter are in good agreement with the specific surface areas of the micropores, as estimated by the independent method of similarity of the adsorption isotherms of water in micropores and on the surface of a nonporous carbonaceous adsorbent. The application of the BET and t-methods to microporous carbonaceous adsorbents is physically unsubstantiated.     

A method of thermal and chemical activation of waste bleaching earth for preparation of a low-cost carbon-mineral adsorbent for chromium(VI) removal

ABSTRACT

In this study, the use of a spent bleaching earth for removal of Cr(VI) ions from aqueous solutions was investigated. The waste material derived from the process of vegetable oil purification was subjected to thermal and chemical activation. The so-prepared carbon-mineral adsorbents were characterised by the uptake of chromium(VI) from synthetic solutions. The highest adsorption capacities were obtained for adsorbents carbonised at 400°C (15.9 mg?g^?1) and activated with H₂SO₄ (15.8 mg?g^?1). Based on the equilibrium and kinetic studies, it was concluded that the adsorption mechanism was based on chemisorption only since no correlation with the porous texture was found.     

Adsorption of Uranium from Dilute Aqueous Solution on Inorganic Adsorbents

Abstract

The adsorption of uranium from a dilute aqueous solution by a large number of inorganic adsorbents has been investigated. A mixture of aluminum hydroxide, ferric hydroxide, and activated carbon in the weight ratio 1:3:4 has shown a high adsorbability for uranium. The separation of uranium from a dilute aqueous solution by this mixed adsorbent under various temperatures and pH values has been studied. The adsorbability was found to exhibit a maximum at pH 4.0 to 5.5 and to decrease with increasing temperature. A number of eluting solutions for the desorption of uranium from the mixed adsorbent were also tested; 1 N (NH₄)₂ CO ₃ was found to be the most suitable eluting solution (93% recovery of uranium).