Response Surface Modeling and Optimization of Remazol Brilliant Blue Reactive Dye Removal Using Periwinkle Shell-Based Activated Carbon

This work investigates both batch and optimization studies of adsorption of Remazol Brilliant Blue Reactive (RBBR) dye onto activated carbon prepared from periwinkle shells (PSAC). The effects of three preparation variables: CO₂ activation temperature, CO₂ activation time, and KOH: char impregnation ratio (IR) were studied using Response Surface Modeling (RSM). Based on the central composite design (CCD), a quadratic model and two-factor interaction models (2FI) were developed to correlate the three preparation variables to the two responses: RBBR dye removal and PSAC yield. The optimum conditions for preparing PSAC for adsorption of RBBR dye were found as follows: CO₂ activation temperature of 811°C, CO₂ activation time of 1.7 h and IR of 2.95, which resulted in 82.76% of RBBR dye removal and 35.83% of PSAC yield. Experimental results obtained agreed satisfactorily well with the model predictions. The activated carbon prepared under optimum conditions was mesoporous with BET surface area of 1894 m²/g, total pore volume of 1.107 cm³/g and average pore diameter of 2.32 nm. The surface morphology and functional groups of PSAC were respectively determined from the scanning electron microscopy (SEM) and Fourier transform infrared analysis (FTIR).     

Hydrotalcites for adsorption of CO2 at high temperature

Adsorption of carbon dioxide by hydrotalcites was investigated by using a gravimetric method at 450 ‡C. Hydrotalcites possessed higher adsorption capacity of CO₂ than other basic materials such as MgO and Al₂O₃. Two different preparation methods of hydrotalcite with varying Mg/Al ratio were employed to determine their effects on the adsorption capacity of CO₂. In addition, varying amounts of K₂CO₃ were impregnated on the hydrotalcite to further increase its adsorption capacity of CO₂. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 showed the most favorable adsorption-desorption pattern with high adsorption capacity of CO₂. K₂CO₃ impregnation on the hydrotalcite increased the adsorption capacity of CO₂ because it changed both the chemical and the physical properties of the hydrotalcite. The optimum amount of K₂CO₃ impregnation was 20 wt%. The hydrotalcite prepared by the high supersaturation method with Mg/Al=2 and 20 wt% K₂CO₃ impregnation has the highest adsorption capacity of CO₂ with 0.77 mmol CO₂/g at 450 ‡C and 800 mmHg.     

Effect of Preparation Conditions on the Property Cu/AC Adsorbents for Phosphine Adsorption

Copper-based activated carbon adsorbents (Cu/AC) were prepared and used to investigate the effects of various copper precursors, impregnation solution concentration, and calcination temperature on phosphine (PH₃) adsorption removal from yellow phosphorus tail gas. N₂ adsorption isotherm and X-ray Diffraction (XRD) were used for characterizing the Cu/AC adsorbents. It can be seen that the Cu(N)/AC adsorbent prepared from the Cu(NO₃)₂ precursor has higher PH₃ breakthrough adsorption capacity than other three adsorbent because the surface copper status of it is mainly CuO. Fresh activated carbon requires an optimal impregnation solution concentration (0.05 mol/L) to reach this optimal PH₃ breakthrough adsorption capacity (78.62 mg/g). The result shows that the surface chemical characteristics (Cu content) of activated carbon is more important than the physical ones (specific surface or pore volume) for the PH₃ adsorption performance. When the calcination temperature is 350°C, the Cu(N)/AC adsorbent has the biggest PH₃ breakthrough adsorbed amount of 112.38 mg/g. The present study confirmed that the Cu/AC adsorbents would be one of the candidates for PH₃ adsorption removal from yellow phosphorus tail gas.     

Adsorption of CO<Subscript>2</Subscript> by iron-exchanged heteropolyacid Fe<Subscript>1.5</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript> supported on mesoporous cellular foams

Novel low-temperature swing adsorbents that preferably adsorb CO₂ were synthesized by varying loading of heteropolyacid Fe_1.5PMo₁₂O₄₀ (Fe–PMA) supporting on mesoporous cellular foams (MCFs) by wetting impregnation. The synthesized materials were characterized by various physicochemical, thermal and spectral techniques and the CO₂ adsorption capacity of the materials were evaluated. Solid adsorbents showed a significantly high adsorption capacity toward CO₂ due to the chemisorptions of CO₂. The CO₂ adsorption capacities of the materials decreased as the temperature increased. The results showed that the adsorption capacity reached a level of 81.8 mg CO₂/g-adsorbent at 25 °C for the 20 wt% Fe–PMA–MCFs. These results indicated that the iron (Fe²⁺) complexes acted as efficient catalysts for the separation of CO₂. The as-synthesized adsorbents were selective, thermally stable, long-lived, and could be recycled at a temperature of 110 °C.     

Preparation of Activated Carbons from Tobacco Stems by Potassium Hydroxide Activation and Phosphine Adsorption

Activated carbon preparation from tobacco stems by KOH activation at different activation temperatures and KOH/char mass ratios were investigated in this study. The effects of preparation parameters on activated carbon pore structure, morphometrics, microcrystallinities, and surface functional groups were characterized by N₂ adsorption, SEM, XRD, and FTIR technologies, respectively. The optimum preparation condition of activated carbon was activation temperature of 850°C, and KOH/char mass ratio of 2. Under this condition, the BET surface area of 2215 m²/g, and the pore volume of 1.343 cm³/g can be obtained. Prepared activated carbon showed clearly honeycomb holes, and a predominated amorphous structure. With increase of activation temperature and KOH/char mass ratio, decrease of surface oxygen functional group, and aromatization of the carbon structure was found. The activated carbon was subject to PH₃ purification, and the maximum PH₃ adsorption capacity of 253 mg/g can be realized based on well prepared KOH-AC with modification of 2.5% Cu. It seems that the activated carbon produced from chemical activation of tobacco stem would be an effective and alternative adsorbent for PH₃ adsorption because of its high surface area, adsorption capacity, and low cost.     

CO2 adsorption performance of polyethyleneimine-modified ion-exchange resin

A series of solid amine adsorbents were prepared by the template method with ion-exchange resin (D001) as the carrier and polyethyleneimine (PEI) as the modifier. The absorbents were characterized by energy disperse spectroscopy (EDS), scanning electron microscope (SEM), N₂ adsorption–desorption, Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) techniques. The effects of PEI loading, adsorption temperature and influent velocities on CO₂ adsorption capacity in a fixed-bed reactor were investigated. The results show that the solid amine adsorbent prepared by the template method had a better PEI dispersion, stability and CO₂ adsorption capacity. The maximum CO₂ adsorption capacity was 3.98 mmol·g^?1 when PEI loading was 30%, the adsorption temperature was 65°C and the influent velocity was 40 mL·min^?1. The CO₂ adsorption capacity decreased only by 9.50% after 10 cycles of adsorption–desorption tests. The study of kinetics indicates that both chemical adsorption and physical adsorption occurred in the CO₂ adsorption process. The CO₂ adsorption process included fast breakthrough adsorption and gradually approaching equilibrium stage. The particle internal diffusion process was the control step for CO₂ adsorption.     

Bimetallic Zeolite Catalyst for CO2 Reforming of Methane

The catalytic activity of Ni–Rh on the synthesized BEA zeolite in carbon dioxide reforming of methane has been investigated. Catalysts were prepared using the incipient wetness impregnation method, with a total content of metals up to 5 wt%. Catalysts were characterized through XRD, TPR, N₂ adsorption, SEM, AAS, TG/DSC analyses. The prepared Ni–Rh zeolites were tested for their catalytic activity at 700 °C, at atmospheric pressure, and at CH₄/CO₂ ratio of 1. Catalytic results showed that bimetallic based zeolites exhibit high activity (CH₄ and CO₂ conversion equal to 73 and 78, respectively) but monometallic Rh catalysts were the only one stable against coke formation.     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

Diuron Multilayer Adsorption on Activated Carbon from CO2 Activation of Grape Seeds

Granular activated carbons were obtained from grape seeds by pyrolysis at 600°C and subsequent physical activation with CO₂ (750–900°C, 1–3 h, 25–74% burn-off). The carbon and ash content increased during the activation, reaching values of 79.0% and 11.4%, respectively. Essentially microporous materials with BET surface areas between 380 and 714 m²/g were obtained. The performance of the activated carbon in the adsorption of diuron in aqueous phase was studied within the 15–45°C temperature range. Equilibrium data showed that the maximum uptake increased with temperature from 120 to 470 µmol/g, also evidencing some dependence of the adsorption mechanism on temperature. Data were fitted to five isotherm models [Langmuir, Freundlich, Dubinin–Radushkevich, BET, and GAB (Guggenheim, Anderson, and de Boer)]. Kinetic data were analyzed using first- and second-order rate equations and intraparticle diffusion model. The second-order rate constant values obtained (2.8–13.5 × 10^?3 g/µmol min) showed that the hollow core morphology of the material favors the adsorption kinetics.     

CO<Subscript>2</Subscript> adsorption at high pressures in MCM-41 and derived alkali-containing samples: the role of the textural properties and chemical affinity

The adsorption properties of N₂ and CO₂ of MCM-41 and derived alkali-containing samples were analyzed over a wide range of pressures (up to ~4500 kPa) and temperatures (between 30 and 300 °C). The high-pressure and high-temperature experiments were carried out on pure MCM-41 and K- and Na-impregnated derived samples. It was analyzed the influence of pressure and temperature on the CO₂ capture capacity on pure and impregnated samples. The adsorption performance was correlated to the structure and textural properties of the materials using X-ray diffraction and N₂ adsorption–desorption measurements. The addition of an alkaline element changes the textural properties of the material increasing the pore size, which positively affected the CO₂ adsorption capacity of these materials at high pressure. In addition, the isosteric heats of adsorption gave information about the chemical affinity between the impregnated materials and CO₂. The CO₂ adsorption at ~ 4500 kPa for the samples with 5 wt% Na at 100 and 200 °C were 77.98 and 9.79 mmol g^?1, respectively, while the pure MCM-41 adsorbs only 8.92 mmol g^?1.     

Effect of KI and KOH Impregnations over Activated Carbon on H2S Adsorption Performance at Low and High Temperatures

In the present work, commercial-grade activated carbon was modified by steam activation to improve its surface properties for high temperature desulfurization. The modified sample was also further upgraded by impregnating with KOH and KI to promote the chemisorption with of H₂S. The H₂S adsorption performance was tested under the temperature range of 30–550°C using the temperature program adsorption technique to understand the effect of adsorption temperature on the material adsorption characteristic. It was found that at ambient temperature, the impregnation of activated carbon with KOH can promote the H₂S adsorption capacity of activated carbon, whereas the impregnation with KI does not provide a significant beneficial effect. At high adsorption temperature (upto 550°C), both KOH and KI impregnation considerably improve the H₂S adsorption performance of activated carbon in terms of the adsorption capacity and breakthrough time. It was revealed from N₂ adsorption, SEM and EDS measurement that the chemical reactions between H₂S and alkaline compounds (KOH and KI) are promoted at high temperature. Based on all experimental results, the equilibrium adsorption model using the linear isotherm was developed to predict the adsorption behavior of these sorbents in terms of equilibrium isotherm constant and mass transfer coefficient for later scaling-up process.     

CO2 capture of amino functionalized three-dimensional worm-hole mesostructured MSU-J silica

Tetraethylenepentamine (TEPA) was employed to functionalize the large-pore mesoporous silica (denoted MSU-J) with 3D worm-hole framework structures which was prepared through a supramolecular hydrogen-bonding assembly pathway from low-cost H₂NCH(CH₃)CH₂[OCH₂CH(CH₃)]₃₃NH₂ (D2000) as structure-directing porogens and tetraethylorthosilioate as the silica source for capturing CO₂. The resultant adsorbents were characterized by FT-IR, Transmission electron microscopy (TEM), N₂ adsorption/desorption and thermogravimetric analysis. Textural properties, elemental analysis and TEM measurement of the samples showed a severe pore filling of MSU-J as TEPA loading was increased to 70 wt%. CO₂ adsorption isotherms measured at different temperatures revealed the optimal adsorption temperature is 25 °C. The adsorption capacity of MSU-J with different TEPA loading contents was calculated. As a result, 50 wt% of TEPA supported on as-synthesized MSU-J achieved the highest capacity with the value of 164.3 mg/g under the conditions of 99.99 % CO₂ at 25 °C and 0.1 MPa. Repeated adsorption/desorption cycles revealed that amine-impregnated materials was very efficient for less apparent decrease in CO₂ adsorption capacity even after 6 adsorption–regeneration cycles.     

Carbon dioxide capture under postcombustion conditions using amine-functionalized SBA-15: Kinetics and multicyclic performance

ABSTRACT

In this work, ordered mesoporous SBA-15 was synthesized and functionalized by polyethyleneimine (PEI). The morphological properties were characterized by N₂ adsorption/desorption, field–emission scanning electron microscopy (FE-SEM), high–resolution transmission electron microscopy (HR-TEM) and Fourier transform infrared (FTIR) spectroscopy methods. The carbon dioxide (CO₂) uptake on the sorbents, kinetics of CO₂ adsorption/desorption and long-term multicycle stability of PEI-impregnated sorbent were measured. An optimal amine loading of 50 wt.% showed a CO₂ adsorption capacity ~3.09 mmol g^?1 using 10% pre-humidified CO₂ at 75°C. The presence of moisture in flue gas showed a promoting effect in CO₂ sorption capacity. The temperature swing adsorption/desorption cycles showed excellent multicycle stability over 60 cycles during 65 h of operations under humid CO₂.     

Textural and hydrogen sulphide adsorption behaviour of double metal–silica modified with potassium permanganate

A new MgCa–silica material with bimodal pore size is impregnated with KMnO₄ for dynamic adsorption of H₂S. The MgCa–silica was synthesized using sodium silicate and calcium and magnesium salts as precipitating agents. The KMnO₄ impregnation onto MgCa–silica was obtained through either direct addition into MgCa–silica wet coagulum or doping of dried MgCa–silica pellets into KMnO₄ solution. These chemisorbents were characterized by nitrogen physisorption, spectrophotometer, microscopy and dynamic H₂S adsorption test setup similar to ASHRAE standard I45.I. The results show that impregnation route and KMnO₄ wt% cause a reduction of surface area and total pore volume. The decrease in pore volume was slightly more in chemisorbents obtained via post doping compared to direct impregnation. Regardless of pore volume reduction the pore size range, 1–32 nm, was as in the parent MgCa–silica with micro and meso-pore diameter centered at 1.4 and 5.4 nm respectively. Thus obtained chemisorbents have their pore entrances neither blocked nor shifted. The MgCa–silica/KMnO₄ chemisorbents exhibits good H₂S uptake performance. The chemisorbent with 11.4 wt% KMnO₄ and obtained via direct impregnation possesses the highest uptake capacity. The lowest capacity was observed for chemisorbent with 8 wt% KMnO₄ and made by direct impregnation. The variations in uptake capacity are likely due to impregnation route, the KMnO₄ content and its location in the pore system. The results suggest that the MgCa–silica/KMnO₄ chemisorbents can remove H₂S from indoor air at room temperature.     

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.     

Optimized and functionalized paper sludge activated with potassium fluoride for single and binary adsorption of reactive dyes

The yield and adsorption uptake of optimized paper sludge activated carbon (PSAC) prepared using potassium fluoride as alternative chemical activation agent was investigated. The PSAC was functionalized with ethylenediamine (FPSAC) and both adsorbents were used for single and binary adsorption of Reactive orange 16 (RO16) and Reactive blue 19 (RB19). Effect of pH on the adsorption process, equilibrium, kinetics, isotherm and thermodynamic studies were carried out. Optimum PSAC preparation parameters were: activation temperature, X₁ = 810 °C; activation time, X₂ = 105 min; and impregnation ratio, X₃ = 0.95 which gave adsorption uptake of 178 and 158 mg/g for RO16 and RB19, respectively.     

Combined processes of glycerol polymerization/carbonization/activation to produce efficient adsorbents for organic contaminants

BACKGROUND: Glycerol was used to produce efficient adsorbents with a high surface area for organic contaminants by a combined process based on polymerization, carbonization and activation. RESULTS: Glycerol and sulfuric acid catalyst at concentrations of 0, 0.5, 1, 2 and 5 mol% were heated to 150 °C to form polyglycerol, which was then decomposed at 580 °C and activated with CO₂ at 850 °C. The resulting activated carbons had a high specific area (1630 m²g^?1) and high adsorption capacity of methylene blue used as a model organic contaminant. This process was also used to produce a special composite adsorbent based on expanded vermiculite (EV) coated with activated carbon. These composites were produced by impregnation of EV with glycerol followed by polymerization, thermal decomposition and activation with CO₂ to produce up to 25 wt% carbon and a surface area of 835 m²g^?1. CONCLUSIONS: The carbon layer present in the EV composite/activated carbon (GVE4CA2) produces a remarkable increase in the methylene blue adsorption capacity of the expanded vermiculite and strongly decreases undesirable water absorption. Copyright © 2012 Society of Chemical Industry     

Preparation of amine-modified SiO<Subscript>2</Subscript> aerogel from rice husk ash for CO<Subscript>2</Subscript> adsorption

Amine-modified SiO₂ aerogel was prepared using 3-(aminopropyl)triethoxysilane (APTES) as the modification agent and rice husk ash as silicon source, its CO₂ adsorption performance was investigated. The amine-modified SiO₂ aerogel remains porous, the specific surface area is 654.24 m²/g, the pore volume is 2.72 cm³/g and the pore diameter is 12.38 nm. The amine-modified aerogel, whose N content is up to 3.02 mmol/g, can stay stable below the temperature of 300 °C. In the static adsorption experiment, amine-modified SiO₂ aerogel (AMSA) showed the highest CO₂ adsorption capacity of 52.40 cm³/g. A simulation was promoted to distinguish the adsorption between the physical process and chemical process. It is observed that the chemical adsorption mainly occurs at the beginning, while the physical adsorption affects the entire adsorption process. Meanwhile, AMSA also exhibits excellent CO₂ adsorption–desorption performance. The CO₂ adsorption capacity dropped less than 10 % after ten times of adsorption–desorption cycles. As a result, AMSA with rice husk ash as raw material is a promising CO₂ sorbent with high adsorption capacity and stable recycle performance and will have a broad application prospect for exhaust emission in higher temperature.     

The effect of impregnation strategy on structural characters and CO2 methanation properties over MgO modified Ni/SiO2 catalysts

Mg-modified Ni/SiO₂ catalysts with different MgO contents were prepared by two impregnation methods. The catalysts prepared by co-impregnation method could show better activity and stability than those prepared by sequential impregnation method. The modification of MgO acted as a key factor in enhancing the capacity of CO₂ adsorption and accelerating the activation of CO₂. Moreover, modified MgO could also increase Ni species dispersion and suppress the metallic Ni sintering and oxidation.     

Hydrogenation of CO<Subscript>2</Subscript> to methanol over Au–CuO/SBA-15 catalysts

A series of Au–CuO/SBA-15 catalysts with 1–3 wt% Au and 30 wt% CuO were successfully prepared for CO₂ hydrogenation to methanol by chemical reduction and the following impregnation. The influence of Au content on the physicochemical properties of Au–CuO/SBA-15 catalysts was investigated in terms of ICP-AES, N₂ physisorption, XRD, TEM, N₂O titration, XPS and H₂–TPR technique. The results showed that the as-prepared Au–CuO/SBA-15 catalysts exhibited higher catalytic activity than CuO/SBA-15 catalyst. 2 % Au–CuO/SBA-15 catalyst showed the best catalytic activity with 13.5 % methanol selectivity and 24.2 % CO₂ conversion for CO₂ hydrogenation to methanol. The addition of Au NPs played an important role in improving the catalytic activity for CO₂ hydrogenation to methanol, which may be attributed to the interaction between Au and CuO.