Adsorption of CO2 on nitrogen-enriched activated carbon and zeolite 13X

Adsorption may be a potentially attractive alternative to capturing CO₂ from stationary sources in the context of Carbon Capture and Sequestration (CCS) technologies. Activated carbon and zeolites are state-of-art adsorbents which may be used for CO₂ adsorption, however physisorption alone tends to be insignificant at high temperatures. In the present work, commercial adsorbents have been impregnated with monoethanolamine (MEA) and triethanolamine (TEA) in order to investigate the effect of the modified surface chemistry on CO₂ adsorption, especially above room temperature. Adsorption isotherms for CO₂, N₂ and CH₄ were measured in a gravimetrically system in the pressure range of UHV to 10 bar, at 298 and 348 K for activated carbon and zeolite 13X supports. The adsorbed concentration of CO₂ was significantly higher than those of CH₄ and N₂ for both adsorbents in the whole pressure range studied, zeolite 13X showing a remarkable affinity for CO₂ at very low pressures. However, at 348 K, the adsorbed concentration of CO₂ decreases significantly. The supports impregnated with concentrated amine solutions and dried in air suffered a detrimental effect on the textural properties, although CO₂ uptake became much less susceptible to temperature increase. Impregnations carried out with dilute solution followed by drying in inert atmosphere yielded materials with very similar textural characteristics as compared to the parent support. CO₂ isotherms in such materials showed a significant change with similar capacities at 348 K as compared to the original support at 298 K in the case of activated carbons. The impregnated zeolite showed a decrease in adsorbed phase concentration in low pressures for a given temperature, but the adsorbed amount also seemed to be less affected by temperature. These results are promising and indicate that CO₂ adsorption may be enhanced despite high process temperatures (e.g. 348 K), if convenient impregnation and drying methods are applied.     

活性炭的孔径分布对CH4和CO2的吸附性能的影响

采用不同炭化温度和活化温度,以椰壳作为前驱体制备了系列结构性能相同,表面吸附基团相似,不同孔结构的活性炭。分别采用密度函数理论(DFT)吸附法和BJH估算了系列活性炭的孔径分布。结果表明,随炭化温度和活化温度的升高系列活性炭中微孔量先增加后减少。当炭化温度为700 ℃,活化温度为800 ℃时,制备的活性炭微孔量达到最大。随炭化温度和活化温度的升高,系列活性炭的中孔依次增加。考查了CH₄,CO₂在系列活性炭上的吸附性能。结果表明该系列活性炭对CO₂有很强的吸附能力,在常温常压下对CO₂的吸附量均高于1.0 mmol·g^-1;系列活性炭对CH₄的吸附能力有较大的差异,在对CO₂具有最大吸附量的活性炭上对CH₄具有最小的吸附量。采用变压吸附法测试了该系列活性炭在25 ℃时对n_CH4∶n_CO2=9∶1的混合气体的分离性能。结果表明炭化温度为700 ℃,活化温度为800 ℃时制备的活性炭对CH₄-CO₂混合气具有最好的分离效果,是变压吸附分离CH₄,CO₂混合气的优异吸附剂。     

Characterization of the pore structure of three-dimensionally ordered mesoporous carbons using high resolution gas sorption

The use of colloidal crystals with various primary particle sizes as templates leads to the formation of three-dimensionally ordered mesoporous (3DOm) carbons containing spherical pores with tailorable pore size and extremely high pore volumes. We present a comprehensive structural characterization of these novel carbons by using nitrogen (77.4 K) and argon (87.3 K) adsorption coupled with the application of novel, dedicated quenched solid density functional theory (QSDFT) methods which assume correctly the underlying spherical pore geometry and also the underlying adsorption mechanism. The observed adsorption isotherms are of Type IV with Type H1-like hysteresis, despite the fact that pore blocking affects the position of the desorption branch. This follows also from detailed, advanced scanning hysteresis experiments which not only allow one to identify the underlying mechanisms of hysteresis, but also provide complementary information about the texture of these unique porous materials. This work addresses the problem of pore size analysis of novel, ordered porous carbons and highlights the importance of hysteresis scanning experiments for textural analysis of the pore network.     

Pilot production of activated carbon from cotton stalks using H3PO4

Cotton stalks, an agricultural waste, were chemically activated in a batch process using H₃PO₄ in a locally designed carbonizer at 420 °C in the absence of any purging gases. Mechanically cut short sticks were soaked in diluted H₃PO₄ for a short duration (Batch 1) and an extended period (Batch 2) prior to thermal treatment. The derived carbons contained both coarse and fine grains with acidic effect. Porosity was characterized by N₂ adsorption at −196 °C and the isotherms analyzed by the α-method to estimate total and microporous surface areas in addition to total and microporous volumes. The produced carbons exhibited well-developed porosity that was essentially microporous in composition. Several key performance parameters were altered considerably as a result of impregnation with H₃PO₄ and the extended chemical activation period (Batch 2). Most of the internal porosity of both carbons was accessible to adsorption of iodine, whereas the uptake of methylene blue dye was proportional to the average size of micropores which were larger for the batch with a longer acid soaking time. SEM and FTIR investigations revealed the presence of a developed honeycomb structure and different oxygen functionalities on surfaces of the activated products which are advantageous in liquid-phase applications. Preliminary laboratory-scale experiments with Pb(II) indicate that adsorption capacity of target heavy metals compares favorably with commercially available activated carbons. The raw material, pre-processing, and activation process prove feasible for the production of activated carbon on a large scale, thereby providing a sustainable strategy for treatment of toxic waste streams.     

A TPD-MS study of the adsorption of ethanol/cyclohexane mixture on activated carbons

The adsorption of ethanol/cyclohexane binary mixtures on different types of activated carbons was studied in this work by temperature programmed desorption coupled with mass spectroscopy (TPD-MS). The texture, morphology and surface chemistry of the carbons were evaluated by N₂ adsorption, scanning electron microscopy (SEM) and TPD-MS techniques. The ethanol and cyclohexane TPD-MS desorption profiles showed that specific interactions between the carbon material and the adsorbate are involved during the adsorption. Most of the activated carbons adsorb strongly ethanol on the surface, leading to desorption temperatures above 100 °C. Only one carbon exhibits an affinity for cyclohexane. These observations were correlated to the different surface chemistry of the materials.     

树脂基球状活性炭的制备及对二氧化碳吸附性能的研究

以四种离子交换树脂（两种强碱性树脂D201和D280、两种弱碱性树脂D301G和D301R）为原料,经过磺化、炭化、活化处理制备了树脂基球状活性炭。采用TG、SEM、N₂吸附等对球状活性炭的收率、表面形貌、比表面积进行了表征,研究了所制球状活性炭对CO₂的吸附性能。结果表明,磺化处理有助提高树脂球的炭化收率;得到的四种球状活性炭对CO₂吸附性能良好,强碱性树脂球原料比弱碱性树脂球更具有优势,其中,由强碱性树脂球D201制得的树脂球状活性炭在30 ℃下对CO₂的吸附量可达2.57 mmol/g;十次循环吸附之后,树脂球仍能保持很好的CO₂吸附性能。     

Dihydrogen adsorption isotherms (77 K) on carbon nanomaterials

Dihydrogen adsorption at 77 K on a number of fine-particle carbon materials, activated carbons, and carbon nanotubes has been investigated. The micropore structure parameters of these materials have been determined using a volumetric comparative method and nonlocal density functional theory (NLDFT). These data processing methods lead to different values of textural parameters. This difference is attributed to the presence of specific sorption sites on the surface of real carbon materials. The pore size range in which the NLDFT method is applicable to the C-H₂ system has been determined. A comparison between the hydrogen sorption properties of different carbon nanotubes is presented.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Synthesis,characterization, and KOH activation of nanoporous carbon for increasing CO2 adsorption capacity

Ordered nanoporous carbons (ONCs) were prepared using a soft-templating method. To improve the CO₂ adsorption efficiency, ONCs were chemically activated to obtain high specific surface area and micro-/mesopore volume with different KOH amounts (i.e., 0, 1, 2, 3, and 4) as an activating agent. The prepared nanoporous carbons (NCs) materials were analyzed by low-angle X-ray diffraction for confirmation of synthesized ONCs structures. The structural properties of the NCs materials were analyzed by high-angle X-ray diffraction. The textural properties of the NCs materials were examined using the N₂/77 K adsorption isotherms according to the Brunauer–Emmett–Teller equation. The CO₂ adsorption capacity was measured by CO₂ isothermal adsorption at 298 K/1 bar. From the results, the NCs activated with KOH showed that the increasing specific surface areas and total pore volumes resulted in the enhancement of CO₂ adsorption capacity.     

Application of density functional theory to analysis of energetic heterogeneity and pore size distribution of activated carbons

A new approach based on the nonlocal density functional theory to determine pore size distribution (PSD) of activated carbons and energetic heterogeneity of the pore wall is proposed. The energetic heterogeneity is modeled with an energy distribution function (EDF), describing the distribution of solid-fluid potential well depth (this distribution is a Dirac delta function for an energetic homogeneous surface). The approach allows simultaneous determining of the PSD (assuming slit shape) and EDF from nitrogen or argon isotherms at their respective boiling points by using a set of local isotherms calculated for a range of pore widths and solid-fluid potential well depths. It is found that the structure of the pore wall surface significantly differs from that ofgraphitized carbon black. This could be attributed to defects in the crystalline structure of the surface, active oxide centers, finite size of the pore walls (in either wall thickness or pore length), and so forth. Those factors depend on the precursor and the process of carbonization and activation and hence provide a fingerprint for each adsorbent. The approach allows very accurate correlation of the experimental adsorption isotherm and leads to PSDs that are simpler and more realistic than those obtained with the original nonlocal density functional theory.     

DFT-based prediction of high-pressure H2 adsorption on porous carbons at ambient temperatures from low-pressure adsorption data measured at 77 K

Hydrogen adsorption isotherms were measured both at cryogenic temperatures below 1 atm and at ambient temperature at high pressures, up to 90 atm, on selected porous carbons with various pore structures. The nonlocal density functional theory (NLDFT) model was used to calculate the pore size distributions (PSDs) of the carbons, from H2 adsorption isotherms measured at 77 K, and then to predict H2 adsorption on these carbons at 87 and 298 K. An excellent agreement between the predicted and measured data was obtained. Prior to analyzing the porous carbons, the solid-fluid interaction parameters used in the NLDFT model were derived from H2 adsorption data measured at 77 K on nonporous carbon black. The results show that the NLDFT model with appropriate parameters may be a useful tool for optimizing carbon pore structures and designing adsorption systems for hydrogen storage applications.     

Adsorption of SO2 by typical carbonaceous material: a comparative study of carbon nanotubes and activated carbons

Applying activated carbons for SO₂ adsorption and conversion to H₂SO₄, as a dry process, has been considered the development direction of desulfurization technology. Coal-based activated carbon, coconut shell activated carbon, single wall carbon nanotube and multi-wall carbon nanotubes were used as typical carbonaceous materials to study the SO₂ adsorption mechanism. SEM, N₂ adsorption, XPS and fixed-bed reaction system were employed to study the morphology, pore structure, surface functional groups and SO₂ adsorption behaviors of the four adsorbents. The fixed-bed experiment was carried out at normal pressure and SO₂ concentration was set 1,000 ppm. According to SEM and N₂ adsorption results, hierarchical pore structure was an important characteristic of activated carbon. Aggregation was an important characteristic of CNTs. Mesopores and macropores took the dominance of pore structure in CNTs. According the SO₂ adsorption data and correlation analysis, it can be concluded that the dominant adsorption type on activated carbons does not alter with adsorption temperature changing. However, the adsorption type of SO₂ adsorption on CNTs changes with adsorption temperature varying. With adsorption temperature increasing, the dominant adsorption type transforms to chemisorption by physisorption. Higher-density π–π* in carbon nanotubes may be the active sites for the SO₂ chemical adsorption. Micropores with the diameter smaller than 0.7 nm were the best SO₂ adsorption place for both activated carbons and carbon nanotubes. The results provided a profound insight into the microstructure and SO₂ adsorption mechanism of the two kinds of carbonaceous materials.     

Carbon slit pore model incorporating surface energetical heterogeneity and geometrical corrugation

In our recent paper (Jagiello and Olivier, Carbon 55:70–80, 2013) we considered introducing energetical heterogeneity (EH) and geometrical corrugation (GC) to the pore walls of the standard carbon slit pore model. We treated these two effects independently and we found that each of them provides significant improvement to the carbon model. The present work is a continuation of the previous one, as we include both effects in one comprehensive model. The existing standard slit pore model widely used for the characterization of activated carbons assumes graphite-like energetically uniform pore walls. As a result of this assumption adsorption isotherms calculated by the non-local density functional theory (NLDFT) do not fit accurately the experimental N₂ data measured for real activated carbons. Assuming a graphene-based structure for activated carbons and using a two-dimensional-NLDFT treatment of the fluid density in the pores we present energetically heterogeneous and geometrically corrugated (EH–GC) surface model for carbon pores. Some parameters of the model were obtained by fitting the model to the reference adsorption data for non-graphitized carbon black. For testing, we applied the new model to the pore size analysis of porous carbons that had given poor results when analyzed using the standard slit pore model. We obtained an excellent fit of the new model to the experimental data and we found that the typical artifacts of the standard model were eliminated.     

Role of surface oxygen groups in incorporation of nitrogen to activated carbons via ethylmethylamine adsorption

Coal origin and wood origin activated carbons were used in this study. To broaden the spectrum of surface features, the surface of the initial samples was modified using oxidation with nitric acid or impregnation with urea followed by heat treatment. Boehm and potentiometric titrations, thermal analysis, and sorption of nitrogen were used to characterize the pore structure and surface chemistry. Then adsorption of ethylmethylamine from aqueous solutions was carried out without controlling the pH of the carbon suspension. The isotherms were measured at 299 K and fitted to the Freundlich equation. The results showed that the amount of ethylmethylamine adsorbed on all carbons at a high concentration is dependent on the total number of surface groups whereas at low concentration it depends on the type of surface groups. The latter was observed exclusively for initial and oxidized carbons where acidic groups are present. The ethylmethylamine adsorption is mainly governed by dipole-dipole, hydrogen bonding, or specific acid-base interactions. Those interactions play a crucial role in incorporation of nitrogen to the carbon matrix at elevated temperatures.     

活性碳纤维的结构修饰及其吸附氙性能的研究

活性炭纤维对氙的吸附容量与其孔结构密切相关，为了提高活性炭纤维对氙气的吸附容量，本文分别用亚甲基蓝、对硝基苯酚等有机物，或氯化钠、碘等无机化合物填充的方法修饰活性炭纤维的孔结构；以及利用高锰酸钾或硝酸等氧化处理修饰活性炭纤维的表面化学性质，同时，利用低温氮等温吸附表征了这些改性活性炭纤维的孔结构，以及通过光电子能谱表征了改性活性炭纤维的表面化学结构，上述化合物充填或氧化改性活性炭纤维对氙的吸附性能的研究结果表明，适量化合物填充，或合适浓度硝酸对活性炭纤维的表面处理，可以有效地修饰活性炭纤维的孔结构或改变活性炭纤维表面对氙的亲和力。因而可有效地提高改性活性炭纤维对氙的吸附容量。     

Adsorption of gases on layered silicates at high pressures

Equilibrium adsorption of nitrogen, carbon dioxide, and argon was examined on the sodium and pyridinium forms of montmorillonite and on the hydrogen form of bentonite. The measurements were carried out at 303, 343, 373, and 400 K over pressure ranges of 0.1–90 MPa (Ar and N₂) and 0.1–6 MPa (CO₂). The amount of nitrogen vapor adsorbed was determined at 77 K and pressures from 0 to 0.1 MPa. The porous structure parameters of the studied samples were determined using adsorption isotherms of nitrogen, argon, and carbon dioxide vapors. At elevated temperatures and pressures >10 MPa, Ar and N₂ adsorption processes on the Na-form of montmorillonite and Ar adsorption on bentonite are activated, since the amounts of the gases adsorbed and adsorption volumes increase with temperature. No activated adsorption is observed for carbon dioxide adsorption on these adsorbents. A comparison of the excess adsorption isotherms of gases on the Py-form of montmorillonite and H-form of bentonite shows that adsorption in micropores predominates for the Py-form of montmorillonite, whereas for the Na-form of bentonite and H-form of bentonite adsorption occurs mainly in meso- and macropores.     

Removal of ionic liquids and ibuprofen by adsorption on a microporous activated carbon: Kinetics,isotherms, and pore sites

Ionic liquids (ILs) are considered as emergent pollutants as their synthesis and further use at a large scale might generate environmental problems. The adsorption on activated carbons represents one of the most effective methods to remove ionic liquids and other micropollutants from wastewater. In this work, the adsorption properties on an activated carbon cloth of two pyridinium ionic liquids (4-tert-butyl-1-propylpyridinium bromide (IL1) and 4-tert-butyl-1-(2-carboxyethyl)pyridinium bromide (IL2)) newly synthesized, were compared with the ones of ibuprofen. The adsorption kinetics and isotherms were studied at pH 3 and 7.5. The adsorption thermodynamic parameters calculated from the isotherms indicate an exothermic process, typical of physisorption. The adsorption kinetics of a mixture of the molecules show a competition between ibuprofen and IL2. The location of each adsorbed ionic liquid and ibuprofen into the porosity of the activated carbon cloth was determined from N₂ (at 77 K) and CO₂ adsorption isotherms (at 273 K). The purification process of an effluent containing the ionic liquids and the ibuprofen in mixture or in single solute could be workable by adsorption on an activated cloth.     

Water vapor adsorption and microporous structure of carbon adsorbents. 18. Effect of surface chemistry of activated carbons on water vapor adsorption

This investigation has been devoted to a study of the chemical composition of the surfaces of activated carbons. A study has been made of the way in which changes in the surface chemistry of a series of carbons, as a result of heat treatment, affects the nature of their adsorption of water vapor. A differentiation has been made between oxygen-containing groups found on the surface of activated carbons before and after their heat treatment. It has been established that the original adsorption centers, which play a determining role in water vapor adsorption by activated carbons, comprise functional groups like strongly acidic free hydrogen ions, carboxylic and phenolic groups, situated on on the pore surface of the activated carbons. The number of these functional groups on the pore surface of the activated carbons has been correlated with the parametera ₀ (the number of original adsorption centers) in the isotherm equation for water vapor adsorption. The relative pressure corresponding to the formation of an adsorption layer on the surface of the activated carbons has been shown to depend on the number of original adsorption centers, the acidic functional groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1991.     

Preparation of highly porous carbon from fir wood by KOH etching and CO2 gasification for adsorption of dyes and phenols from water

Fir wood was first carbonized for 1.5 h at 450 degrees C, then soaked in a KOH solution KOH/char ratio of 1, and last activated for 1 h at 780 degrees C. During the last hour CO2 was poured in for further activation for 0, 15, 30, and 60 min, respectively. Carbonaceous adsorbents with controllable surface area and pore structure were chemically activated from carbonized fir wood (i.e., char) by KOH etching and CO2 gasification. The pore properties, including the BET surface area, pore volume, pore size distribution, and pore diameter, of these activated carbons were first characterized by the t-plot method based on N2 adsorption isotherms. Fir-wood carbon activated with CO2 gasification from 0 to 60 min exhibited a BET surface area ranging from 1371 to 2821 m2 g(-1), with a pore volume significantly increased from 0.81 to 1.73 m2 g(-1). Scanning electron microscopic (SEM) results showed that the surfaces of honeycombed holes in these carbons were significantly different from those of carbons without CO2 gasification. The adsorption of methylene blue, basic brown 1, acid blue 74, p-nitrophenol, p-chlorophenol, p-cresol, and phenol from water on all the carbons studied was examined to check their chemical characteristics. Adsorption kinetics was in agreement with the Elovich equation, and all equilibrium isotherms were in agreement with the Langmuir equation. These results were used to compare the Elovich parameter (1/b) and the adsorption quantity of the unit area (q(mon)/Sp) of activated carbons with different CO2 gasification durations. This work facilitated the preparation of activated carbon by effectively controlling pore structures and the adsorption performance of the activated carbon on adsorbates of different molecular forms.     

Kinetic and equilibrium adsorption of methylene blue and remazol dyes onto steam-activated carbons developed from date pits

Steam-activated carbons DS2 and DS5 were prepared by gasifying 600 °C-date pits carbonization products with steam at 950 °C to burn-off = 20 and 50%, respectively. The textural properties of these carbons were determined from the nitrogen adsorption at ?196 °C. The chemistry of the carbon surface was determined from the surface pH and from neutralization of the surface carbon–oxygen groups of basic and acidic type. The kinetic and equilibrium adsorption of MB and RY on DS2 and DS5 was determined at 27 and 37 °C and at initial sorption solution pH 3–7.DS2 and DS5 have expanded surface area, large total pore volume and contain both micro and mesoporosity. They have on their surface basic and acidic groups of different strength and functionality. This enhanced the sorption of the cationic dye (MB) and of the anionic dye (RY). The adsorption of MB and RY on DS2 and DS5 involves intraparticle diffusion and followed pseudo-second order kinetics. The adsorption isotherms were applicable to the Langmuir isotherm and high monolayer capacities for MB and RY dyes were evaluated indicating the high efficiencies of the carbons for dye adsorption.