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.     

Desulfurization of high-sulfur jet fuel by mesoporous π-complexation adsorbents

Desulfurization of JP-5 jet fuel (1172 ppmw S) was investigated by π-complexation adsorption with AgNO₃ supported on mesoporous silica SBA-15 and MCM-41. The average pore sizes of AgNO₃/SBA-15 and AgNO₃/MCM-41 were 48.8 and 19.1 Å, respectively. The results of JP-5 desulfurization showed that significant sulfur breakthrough occurred at ∼10.0 and ∼15.0 mL/g by AgNO₃/SBA-15 and AgNO₃/MCM-41, respectively, at a space velocity of 1.25 h⁻¹. The spent AgNO₃/MCM-41 was regenerated by a simple process (heating in air at 200 °C) and ∼50% of the sulfur capacity was recovered after the first cycle. Molecular orbital calculations show that Cu⁺ (as that in CuY zeolite) formed stronger π-complexation bonding with the thiophenic compounds than Ag⁺ (in AgNO₃), as evidenced by experimental heats of adsorption. However, pore diffusion limitation of the large sulfur molecules (alkylated benzothiophenes) became an important factor for desulfurization of high sulfur jet fuels such that the AgNO₃-supported mesoporous sorbents yielded substantially better results than Cu(I)Y, although Cu(I)Y was better for a model fuel that contained only small sulfur molecules. Among all sorbents that have been investigated, the AgNO₃/MCM-41 sorbent showed the best desulfurization performance for high sulfur jet fuels.     

Synthesis of mesoporous silica from bottom ash and its application for CO<Subscript>2</Subscript> sorption

A supernatant solution of silicate species extracted from bottom ash in a power plant was used to prepare a mesoporous silica by the synthesis protocol of SBA-15. XRD, N₂ adsorption-desorption, and TEM confirmed a disordered mesopore structure. The pore volume and average pore size of the product were significantly larger than SBA-15 prepared using pure chemicals, and complementary textural mesoporosity was detected. When the mesoporous silica was tested for carbon dioxide sorption after polyethyleneimine (PEI) impregnation, substantially higher CO₂ sorption capacity (169 mg CO₂/g-sorbent) was achieved than that of PEI-impregnated pure SBA-15 under the same test conditions. High CO₂ sorption capacity was maintained when the gas composition was changed to 15% CO₂, and the hybrid material exhibited satisfactory performances during the 10 recycle runs.     

Mesoporous silicas containing carboxylic acid: Preparation,thermal degradation,and catalytic performance

The calcination and thermal degradation behaviors of surfactants in mesoporous silicas SBA-15 and MCM-41 were investigated by FT-IR, ¹³C CP/MAS NMR, TG/DTA, and GPC. It was found that carboxylic acid-containing products were generated as active components in the mesopores of SBA-15 and MCM-41 from the triblock copolymer (PEO)₂₀(PPO)₇₀(PEO)₂₀ and cetyltrimethylammonium bromide (CTAB), respectively; the latter materials were used as templates. The carboxylic acid-containing mesoporous silica obtained showed a catalytic activity for hydrolysis of sucrose. The acidity was evaluated by means of NaOH titration. The acidity sensitively depended on both the calcination temperature and the atmosphere; the maximum appeared at 150 °C in air for SBA-15 where the highest activity was observed. However, the product in MCM-41 showed a lower catalytic activity than that in SBA-15. The SBA-15 product was easily leached from the mesopores of SBA-15 into the solution, but the degree of leaching for MCM-41 was considerably smaller than that for SBA-15.     

Zr (IV)-ninhydrin supported MCM-41 and MCM-48 as novel nanoreactor catalysts for the oxidation of sulfides to sulfoxides and thiols to disulfides

Modification of MCM-41 and MCM-48 mesoporous materials with bonded aminosilane species, Schiff base preparation by ninhydrin and finally complexation with zirconium, has attracted much attention in order to design catalyst with advanced applications in the oxidation of sulfides to sulfoxides and thiols to disulfides in the presence of hydrogen peroxide. In all oxidation of sulfides to sulfoxids 0.4 mL H₂O₂ used as oxidant in the presence of Zr(IV)-ninhydrin supported MCM-41 (0.01 g) or Zr(IV)-ninhydrin supported MCM-48 (0.005 g) at room temperature and solvent-free condition. Also the best conditions for oxidation of thiols to disulfides with 0.4 mL H₂O₂ were 0.005 g Zr(IV)-ninhydrin supported MCM-41 or Zr(IV)-ninhydrin supported MCM-48 at room temperature and in ethanol. These catalysts are characterized by SEM, XRD, TGA, FT-IR, EDS, ICP and BET analysis. Also the Turn over frequency (TOF) and Turn over number (TON) of catalysts are calculated. Obtained results by these heterogeneous catalysts revealed several advantages including short reaction times, simple workup, easy isolation and reusability.     

SBA-15-supported ionic liquid compounds containing silver salts: Novel mesoporous π-complexing sorbents for separating polyunsaturated fatty acid methyl esters

Novel π-complexing sorbents were prepared by covalently immobilizing ionic liquids (ILs) onto mesoporous SBA-15 using a one-pot sol–gel process followed by coating these SBA-15-supported IL compounds with silver salts. The mesoporous π-complexing sorbents were characterized by small angle X-ray scattering (SAXS), FTIR, TEM, SEM, nitrogen adsorption desorption isotherm, NMR, and nitrogen elemental analysis. Two advantages were obtained using these novel mesoporous π-complexing sorbents versus the traditional π-complexing sorbents formed by directly anchoring silver salts onto silica gel. (1) Higher extraction capacities were found. The extraction capacity for the polyunsaturated fatty acid methyl ester (PUFAME), methyl all-cis-5,8,11,14,17-eicosapentaenoate (20:5 or EPA), was 195 mg/g sorbent using the mesoporous AgBF₄/SBA-15 · IL · PF₆ sorbent. The capacity decreased to 121 mg/g sorbent with microporous complexing sorbent AgBF₄/SiO₂ · IL · PF₆. (2) Better reusability was also achieved. The supported IL phase immobilized and retained silver salt on SBA-15 due to the interaction between the ionic liquid’s imidazolium cations and silver ions. Eight successive sorption runs with the AgBF₄/SBA-15 · IL · PF₆ sorbent showed a satisfactory reusability. The traditional π-complexing sorbent has a silver salt directly anchored on silica without the supported ionic liquid phase. Higher silver leaching into organic solution occurred from the AgBF₄/SBA-15 sorbent determined by ICP-AES. The combined percentage (wt%) of the omega-3 PUFAMEs: 20:5 and methyl all-cis-4,7,10,13,16,19-docosahexaenoate (22:6 or DHA) stripped from the AgBF₄/SBA-15 · IL · PF₆ by 1-hexene was significantly enriched from 18% in the original cod liver oil to 90.5%.     

Highly selective oxidation of alcohols catalyzed by Cu(II)-Schiff base-SBA-15 with hydrogen peroxide in water

An efficient catalyst for selective oxidation of alcohols was prepared by grafting the Cu(II) Schiff base complex onto the channels of mesoporous silica material SBA-15. The characterizations illustrated that the functionalized SBA-15 maintained the primary hexagonally ordered mesoporous structure, and the Cu(II) Schiff base complexes were bonded inside the mesoporous channels of SBA-15. The selective oxidation of benzyl alcohol was carried out in water phase with hydrogen peroxide. The C₆H₅CH₂OH conversion could reach 98.5 % with 100 % of the selectivity to C₆H₅CHO under the optimum conditions. The catalyst could also react well on the selective oxidation of other primary alcohols.     

Propane oxidative dehydrogenation over vanadia catalysts supported on mesoporous silicas with varying pore structure and size

The structural characteristics and the performance of vanadia catalysts (0.7–8 wt.% V) supported on mesoporous (MCM-41, HMS, MCF, SBA-15), microporous (silicalite) and non-porous (SiO₂) silicas in oxidative dehydrogenation of propane were investigated. The structure of vanadia species, the redox and the acidic properties of the catalysts were studied using in situ Raman spectroscopy, TPD- NH₃ and H₂-TPR. The only vanadia species detected on the surface of HMS and MCM-41 for V loadings up to 8 wt.% were isolated monovanadates indicating high vanadia dispersion. Additional bands ascribed to V₂O₅ nanoparticles were evidenced in the case of SBA-15 and MCF supported catalysts while these bands were the only ones identified on the surface of the catalysts supported on silicalite and non-porous silica. The catalysts supported on mesoporous HMS and MCM-41 materials showed the best performance achieving high propane conversions (35–40%) with relatively high propene selectivities (35–47%). Lower activity due to the lower degree of vanadia dispersion, caused by the partial destruction of the pore structure was observed for the SBA-15 and MCF supported catalysts. The degree of dispersion of the V species on the catalyst surface and not the pore size and structure of the mesoporous support or the acidity/reducibility characteristics mainly determine the catalytic activity towards propene production. In addition, it was shown that the pore structure and size of the mesoporous supports did not have any significant effect in the turnover rates (TOF values) of propane conversion (and propene formation at low propane conversion, below ca. 10%). However, the highest propene yield (up to 19%) and stable catalytic behavior was attained for catalysts supported on HMS mesoporous silica, and especially for those combining framework mesoporosity and textural porosity (voids between primary nanoparticles).     

Kinetics of CO2 Adsorption/Desorption of Polyethyleneimine‐Mesoporous Silica

The kinetics of adsorption of CO₂ on solid sorbents based on polyethyleneimine/mesoporous silica (PEI/MPS) was studied by following the mass gain during CO₂ flow. Linear (PEI‐423) and branched (PEI‐10k) polymers were studied. The solid sorbents were synthesized by impregnating the PEI into MPS foam. The kinetics of adsorption was fitted with a double‐exponential model. In contrast, the desorption process obeyed first‐order kinetics. The activation energy of desorption of PEI‐423 was lower than that of PEI‐10k, presumably because the branched polymer required more energy to expose its nitrogen to CO₂. To increase the CO₂ sorption capacity, the MPS was treated with nonionic surfactant materials prior to impregnation with PEI. This also lowered the maximum sorption temperature and desorption activation energies.     

Epoxidation of propene on vanadium species supported on silica supports of different structure

Silica supports such as mesoporous materials (SBA-3, SBA-15 and MCM-41), silicalite and amorphous silica were used for accommodation of vanadium species introduced on the support surface by means of impregnation, with vanadium concentration from 1 to 7 wt.%. Catalysts were characterised by means of XRD, low temperature adsorption/desorption of nitrogen, DR UV–vis and Raman spectra and also H₂-TPR measurements. Isolated vanadium species dispersed in the channels of mesoporous SBA-3 with pores diameter related to micropores range, seems to be the most active for propene epoxidation.     

Extraction of Ultra Trace Amounts of Palladium on 9-Acridinylamine Functionalized SBA-15 and MCM-41 Nanoporous Silica Sorbents

The application of the modified MCM-41 and SBA-15 nanporous silicas in extraction of trace amounts of palladium is investigated and developed. Surface of nanoporous silicas, MCM-41 and SBA-15, were modified with 9-acridinylamine ligand and then utilized as solid-phase sorbents for the extraction of palladium. Different experimental conditions such as pH, flow rates of the sample, and eluent solution were studied. The type and the smallest amount of eluent for elution were optimized and the breakthrough volume and the influence of various cationic interferences on the adsorption was investigated. The recovery values in this method are greater than 95% and 98.5%. The obtained limits of detections (LOD) are lower than 0.17 ng mL^?1 and 0.15 ng mL^?1 for SBA-15 and MCM-41, respectively. The pre-concentration factors were calculated to be more than 193 and 187.5 for SBA-15 and MCM-41, respectively. The relative standard deviations (RSD) of the method are lower than 4% and 1.5%, and the adsorption capacities were also obtained to be more than 170 mg g^?1 and 195 mg g^?1 for SBA-15 and MCM-41, respectively. The proposed procedure was applied on real samples and the amount of palladium was successfully derived.     

Low-temperature H2S removal from gas streams with SBA-15 supported ZnO nanoparticles

Mesoporous silica SBA-15 with zinc oxide (ZnO) nanoparticles was prepared via incipient wetness impregnation and ultrasonic method, followed by in situ activation at 523 K. The mesoporous materials obtained were characterized by ICP, XRD, FTIR, nitrogen adsorption, TEM and XPS. The prepared materials showed a superior ability to remove H₂S down to parts per billion (ppb) from gas stream at lower temperature (298 K), and the highest H₂S breakthrough capacity, 436 mg S/g adsorbent, was observed for SBA-15 with 3.04 wt% zinc loading. The enhancement of H₂S removal capacity was attributed to the integration of the high surface area of the mesoporous material and the promising desulphurization properties of ZnO nanoparticles. It was believed that ZnO-modified SBA-15 is a promising adsorbent for H₂S cleaning at ambient conditions, which will extend the application of the mesoporous materials to the environmental protection area.     

Total Oxidation of Naphthalene Using Mesoporous CeO2 Catalysts Synthesized by Nanocasting from Two Dimensional SBA-15 and Three Dimensional KIT-6 and MCM-48 Silica Templates

Ceria catalysts have been prepared by a nanocasting procedure using SBA-15, MCM-48 and KIT-6 silica-based templates, and investigated for the total oxidation of naphthalene. In all cases cubic fluorite CeO₂ was prepared, and the structure of the template was replicated when SBA-15 and MCM-48 were used. The KIT-6 template was not replicated by the nanocasting synthesis, but in all cases mesoporous CeO2 was obtained with high surface areas (91–190 m² g^?1). All of the catalysts demonstrated high activity for naphthalene oxidation to CO₂, and the most active was the catalyst prepared from the KIT-6 template. The high activity was attributed to the small crystallite size of the CeO₂, combined with high surface area and the highly accessible catalyst surface.     

Immobilization of Ru(II)(salen)(PPh3)2 on Mesoporous MCM-41/SBA-15: Characterization and Catalytic Applications

Ru(II)(salen)(PPh₃)₂ immobilized on MCM-41 and SBA-15 modified with aminopropyl groups as linkers has been synthesized and characterized by elemental analysis, TEM, FTIR, BET, and TGA. Elemental analysis shows that the grafted samples contain 0.7–0.8 wt.% Ru. The retaining of long range ordering of the mesoporous MCM-41 and SBA-15 supporting materials after grafting is evident from TEM and N₂ adsorption/desorption measurements. FTIR and TGA spectra show the formation of metal salen complexes with the amino groups acting as connectors to the SiO₂ surface. Both grafted materials were successfully applied as catalysts for the olefination of various aldehydes with very good yields and high E-selectivity. The catalyst materials are recyclable for several catalytic runs.     

Direct Electrochemistry and Electrocatalysis of Hemoglobin on Bimetallic Au–Pt Inorganic–Organic Nanofiber Hybrid Nanocomposite and Mesoporous Molecular Sieve MCM-41

A glassy carbon electrode modified with MCM-41 and bimetallic inorganic–organic nanofiber hybrid nanocomposite was prepared and used for determination of trace levels of hydrogen peroxide (H₂O₂). The direct electron transfer (DET) and electrocatalysis of hemoglobin (Hb) entrapped in the MCM-41 modified Au–Pt inorganic–organic nanofiber hybrid nanocomposite electrode (Au–PtNP/NF/GCE) were investigated by using cyclic voltammetry in 0.1 M pH 7.0 phosphate buffer solution. Due to its uniform pore structure, high surface area and good biocompatibility, the mesoporous silica sieve MCM-41 provided a suitable matrix for immobilization of biomolecules. The MCM-41 modified Au–Pt inorganic–organic nanofiber hybrid nanocomposite electrode showed significant promotion to DET of Hb, which exhibited a pair of well-defined and quasi-reversible peaks for heme Fe(III)/Fe(II) with a formal potential of ?0.535 V (vs. Ag/AgCl). Additionally, the Hb immobilized on the MCM-41 modified electrode showed excellent electrocatalytic activity toward H₂O₂ reduction.     

Modelling electrocatalysis of hydroquinone oxidation by nicotinamide adenine dinucleaotide coenzyme encapsulated within SBA-15 and MCM-41 mesoporous aluminosilicates

The electrochemical response of NADH associated to two mesoporous aluminosilicates, MCM-41 and SBA-15, is described upon attachment of such materials into polymer-film electrodes. The studied materials display a significant electrocatalytic activity towards the oxidation of 1,4-dihydrobenzoquinone, H₂Q. Two models for describing the electrocatalytic process, based on the general theory of mediated electrocatalysis and the Lovric and Scholz formulation of the voltammetry of microparticles are discussed. Voltammetric and chronoamperometric data indicate that the electrocatalytic process involves the formation of a surface-confined NADH-H₂Q adduct in the case of SBA-15, while a surface reaction/regeneration scheme prevails for MCM-41.     

Preparation of mesoporous MCM-41 supported zinc sorbents by microwave in-situ oxidation for H2S removal in coal gas

Zn-based MCM-41 supporter sorbents were prepared using the microwave in-situ oxidation method. Other sorbents were heated using a conventional heating method to contrast the performance for H₂S removal. The sorbents were tested at 500°C in fixed reactor and dried simulated Texaco coal gas was employed for the sulphurized atmosphere. The results show that sorbents prepared by microwave oxidation had a better toleration for the adsorption of H₂S. A 13.2% improvement occurred in the sulphur capacity of the sorbents heated by the microwave method. XRD, SEM with EDS-element mapping, TEM, N₂ adsorption, and XPS were used to characterize the properties of the sorbents. Due to the selective heating of the microwave and the superiority of the in-situ oxidation method, the sorbents heated by microwave exhibited more appropriate structures for sulphurization. Meanwhile, the even heating environment supplied by the microwave resulted in a more uniform distribution of the active component. The microwave also had an effect on the chemical bond and reduced the binding energy of the active component, which enhanced the reactivity between the H₂S and the sorbents. The preferable features generated by microwave in-situ oxidation accelerate the replacement of S to O, and therefore the Zn-based MCM-41 sorbents prepared by the microwave method have an increased capability for H₂S removal in high temperature coal gas.     

Hydroxylation of phenol by iron(II)-phenanthroline(Phen)/MCM-41 zeolite

MCM-41 mesoporous molecular sieve and iron(II)-Phen/MCM-41 have been prepared and characterized by XRD, IR, NH₃-TPD, BET and UV-Vis. The iron(II)-Phen/MCM-41 molecular sieve + 30% H₂O₂ system is capable of performing hydroxylation of phenol.     

Selective removal of sulfur compounds in city-gas by adsorbents

Silver nitrate impregnated on beta zeolite (BEA), mesoporous silica MCM-41 and SBA-15 (AgNO₃/BEA, AgNO₃/MCM-41, AgNO₃/SBA-15) were prepared to remove sulfur compounds selectively in city-gas, which contains tetrahydrothiophene and tert-butylmercaptane. Sulfur adsorption capacity was determined when the sulfur concentration of effluent gas in breakthrough test reached 0.1 ppm, which is acceptable sulfur concentration for hydrogen production in a reformer for fuel cells. As the AgNO₃ concentration in AgNO₃/BEA, AgNO₃/MCM-41, and AgNO₃/SBA-15 increased, their sulfur adsorption capacities also increased. Although microporous zeolite BEA has smaller pore volume and lower surface area than those of mesoporous silica MCM-41 and SBA-15, the sulfur adsorption capacity of AgNO₃/BEA was higher than those of AgNO₃/MCM-41 and AgNO₃/SBA-15. Adsorbed sulfur molecules per impregnated silver nitrate and the shape change of breakthrough curves depending on the adsorption temperature showed that not only chemisorption but also physisorption was involved in sulfur compounds adsorption on AgNO₃ impregnated adsorbent. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Peculiarities of functionalization of mesostructured silicates MCM-41 and SBA-15 by a sulfide modifier

The synthesis and physical-chemical characteristics of sorbents based on mesoporous silicates MCM-41 and SBA-15 with grafted sulfide functional groups are described. Similar experiments were performed on silica gels for the comparison. For the above materials, the X-ray and texture characteristics before and after functionalization, as well as the grafted groups content and the sorption parameters of sorbents, have been determined using physical-chemical methods. The effect of the different conditions of the modification process on the grafting density of sulfide groups has been investigated. The evaluation of the sorption capacity of the obtained materials with respect to Pd(II) ions has been performed: the capacity is around 0.55 mmol/g, the recovery degree is 98–99% and the distribution coefficient is 26000 cm³/g.