Management of methyl mercaptan contained in waste gases - an overview.

Methyl mercaptan is a typical volatile organosulfur pollutant contained in many gases emitted by urban waste treatment, various industries, natural gas handling, refining processes, and energy production. This work is a comprehensive overview of the scientific and practical aspects related to the management of methyl mercaptan pollution. The main techniques, including absorption, adsorption, oxidation, and biological treatments, are examined in detail. For each method, its capability as well as the technical advantages and drawbacks have been highlighted. The emerging methods developed for the removal of methyl mercaptan from natural gas are also reviewed. These methods are based on the catalytic conversion of CH3SH to hydrocarbons and H2S.

Influence of the Mesoporosity of Hierarchical ZSM-5 in Toluene Alkylation by Methanol.

Among the different strategies to design highly shape-selective ZSM-5 to obtain para-xylene through toluene alkylation with methanol, the introduction of mesopores to increase reactant and product diffusion has been proposed but barely studied. In this study, we prepared mesoporous ZSM-5 catalysts, named ZSM5-MT(x), from commercial ZSM-5 (Si/Al = 15), using a two-step micelle-templating procedure with octadecyltrimethylammonium bromide as a surfactant in basic medium (x = NaOH/Si). These materials were used as catalysts for the alkylation of toluene by methanol at a low contact time to avoid thermodynamic equilibrium of the xylene isomers. Compared to the parent ZSM-5, the mesoporous ZSM5-MT(x) catalysts did not improve the para-xylene selectivity, revealing that the strategy of increasing diffusion in the catalyst is not a good strategy to follow. However, ZSM5-MT(0.5) showed less deactivation on stream than the parent ZSM-5. Therefore, introducing mesopores to ZSM-5 could be interesting to explore, combined with another strategy of shape selectivity, such as the passivation of the external surface acidity.

Engineering the Morphostructural Properties and Drug Loading Degree of Organic-Inorganic Fluorouracil-MgAl LDH Nanohybrids by Rational Control of Hydrothermal Treatment.

Layered double hydroxides (LDHs) or hydrotalcite-like compounds have attracted great attention for the delivery of anticancer drugs due to their 2D structure, exhibiting a high surface-to-volume ratio and a high chemical versatility. The drug is protected between the layers from which it is slowly released, thus increasing the therapeutic effect and minimizing the side effects associated to nonspecific targeting. This work aimed to design LDHs with Mg and Al (molar ratio of 2/1) in brucite-like layers, which retained fluorouracil (5-FU; 5-FU/Al = 1, molar ratio) in the interlayer gallery as the layers grow during the co-precipitation step of the synthesis. To rationally control the physicochemical properties, particularly the size of the crystallites, the aging step following the co-precipitation was performed under carefully controlled conditions by changing the time and temperature (i.e., 25 °C for 16 h, 100 °C for 16 h, and 120 °C for 24 h). The results revealed the achievement of the control of the size of the crystals, which are gathered in three different agglomeration systems, from tight to loose, as well as the loading degree of the drug in the final organic-inorganic hybrid nanomaterials. The role played by the factors and parameters affecting the drug-controlled release was highlighted by assessing the release behavior of 5-FU by changing the pH, solid mass/volume ratio, and ionic strength. The results showed a pH-dependent behavior but not necessarily in a direct proportionality. After a certain limit, the mass of the solid diminishes the rate of release, whereas the ionic strength is essential for the payload discharge.

Hydrolytic vs. Nonhydrolytic Sol-Gel in Preparation of Mixed Oxide Silica-Alumina Catalysts for Esterification.

The development of green and sustainable materials for use as heterogeneous catalysts is a growing area of research in chemistry. In this paper, mesoporous SiO2-Al2O3 mixed oxide catalysts with different Si/Al ratios were prepared via hydrolytic (HSG) and nonhydrolytic sol-gel (NHSG) processes. The HSG route was explored in acidic and basic media, while NHSG was investigated in the presence of diisopropylether as an oxygen donor. The obtained materials were characterized using EDX, N2-physisorption, powder XRD, 29Si, 27Al MAS-NMR, and NH3-TPD. This approach offered good control of composition and the Si/Al ratio was found to influence both the texture and the acidity of the mesoporous materials. According to 27Al and 29Si MAS NMR analyses, silicon and aluminum were more regularly distributed in NHSG samples that were also more acidic. Silica-alumina catalysts prepared via NHSG were more active in esterification of acetic acid with n-BuOH.

Modeling biosorption of Cr(VI) onto Ulva compressa L. from aqueous solutions.

The marine biomass Ulva compressa L. (ECL) was used as a low-cost biosorbent for the removal of Cr(VI) from contaminated aqueous solutions. The operating variables were optimized: pH ∼ 2, initial concentration of 25 mg/L, solid/liquid ratio of 6 g/L and a temperature of 50 °C, leading to an uptake elimination of 96%. A full factorial experimental design technique enabled us to obtain a mathematical model describing the Cr(VI) biosorption and to study the main effects and interactions among operational parameters. The equilibrium isotherm was analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models; it has been found that the adsorption process follows well the Langmuir model. Kinetic studies showed that the pseudo-second order model describes suitably the experimental data. The thermodynamic parameters indicated an endothermic heat and a spontaneity of the Cr(VI) biosorption onto ECL.

Conversion of Methyl Mercaptan to Hydrocarbons over H-ZSM-5 Zeolite: DFT/BOMD Study.

Methyl mercaptan-a harmful impurity in natural gas-may be selectively converted into H2S and hydrocarbons [methyl mercaptan to hydrocarbon (M2TH) process], using zeolite catalysts. When M2TH is compared with the well-known MTH (methanol to hydrocarbons) process, significant differences emerge, essentially regarding the formation and distribution of products. Density functional theory (DFT) and Born-Oppenheimer molecular dynamics (BOMD) were employed to reveal possible origins for the experimentally observed differences. We established a close similarity between DFT intrinsic (electronic) reaction profiles in the stepwise mechanism of methanol and mercaptan dehydration, although no variance in reactivity was revealed. BOMD simulations at the experimental temperature of 823 K reveal rapid hydrogen abstraction from the methyl group in mercaptan, adsorbed in the zeolite cavity in the presence of the methoxy intermediate. The formation of •CH2SH radical is 10 times faster than that of •CH2OH at the same temperature. The varied reactivity of methanol and mercaptan in MTH and M2TH processes, respectively, can therefore first be attributed to very rapid hydrogen abstraction in mercaptan, which occurs in the zeolite cavity, following the formation of surface methoxy.

Efficient mesoporous silica-titania catalysts from colloidal self-assembly.

Mesoporous silica-titania materials of tunable composition and texture, which present a high catalytic activity in the mild oxidation of sulfur compounds, have been obtained by combining the spray-drying process with the colloidal self-assembly of α-chitin nanorods (biopolymer acting as a template) and organometallic oligomers.

Distillate-range products from non-oil-based sources by catalytic cascade reactions.

An original two-step process efficiently catalyzed by functionalized mesoporous materials is proposed as a potential route for converting light olefins into long-chain hydrocarbons in the distillate range. In the first step, ethylene can be selectively transformed into C4 -C10 olefins with an even number of carbon atoms, over nickel-exchanged AlMCM-41, at 150 °C. When the nickel-catalyzed oligomerization was assisted by a second acid-catalyzed step over H-MCM-41, olefins with chains longer than 10 carbon atoms were mainly produced with a productivity of 180 g g⁻¹ h⁻¹.

Mesoporous silica functionalized with 1-furoyl thiourea urea for Hg(II) adsorption from aqueous media.

New organic-inorganic hybrid materials were prepared by covalently anchoring 1-furoyl thiourea on mesoporous silica (SBA-15). By means of various characterization techniques (X-ray diffraction, nitrogen adsorption-desorption, thermogravimetric analysis, and FTIR spectroscopy) it has been established that the organic groups were successfully anchored on the SBA-15 surfaces and the ordering of the inorganic support was preserved during the chemical modifications. The hybrid sorbents exhibited good ability to remove Hg(II) from aqueous solution. Thus, at pH 6, the adsorption capacity of mercury ions reached 0.61 mmol g(-1).

Hydrogenation of Unsaturated Carbonyl Compounds on non-Calcined LDHs. I. Synthesis and Characterization of ZnNiCuAl Hydrotalcite-like Materials.

Several Zn/Ni/Cu/Al layered double hydroxides (LDH) with variable Ni/Cu ratios but constant Zn/Al, as well as M2+/M3+ ratios, were synthesized by coprecipitation method with CO32- as compensating anion. The main goal of the study was to investigate the influence of the catalysts composition, especially Ni/Cu ratio, on the physical and catalytic properties of these materials. The XRD results show that all the LDHs samples are well crystallized and contain only pure phases. Moreover, the spectral techniques (FT-IR and DR-UV-VIS) indicated that both Ni and Cu species are present in the brucite-like layers of LDHs. The shape of the nitrogen physisorption isotherms obtained at -196 °C indicates a predominantly mesoporous materials; the surface areas and pore volumes are in the specific ranges between 37-86 m2.g-1 and 0.31-0.75 cm3.g-1, respectively. Three characteristic weight losses between 30 and 400 °C are identified by TG analysis for the hydrotalcite-like materials synthesized in this study. Moreover, an influence of the Ni/Cu ratios on the amount of the physisorbed water was noticed. The preliminary catalytic test revealed unusual catalytic properties of the non-calcined samples in the liquid phase hydrogenation of trans-cinnamaldehyde.

Removal of dimethylsulfoxide from wastewater using mild oxidation with H2O2 over Ti-based catalysts.

The mild catalytic oxidation of dimethylsulfoxide (DMSO) into biodegradable dimethylsulfone is proposed as an efficient pretreatment of wastewaters subjected to biological treatment processes. A SiO(2)-TiO(2) mesoporous xerogel prepared by a non-hydrolytic route, as well as titanium silicalite TS-1 showed very good activity and stability in the catalytic oxidation of DMSO with H(2)O(2) in dilute aqueous solution, at room temperature.

Non-hydrolytic synthesis of mesoporous silica-titania catalysts for the mild oxidation of sulfur compounds with hydrogen peroxide.

A SiO(2)-TiO(2) mesoporous xerogel prepared in one-step by a non-hydrolytic route shows excellent performance in the mild oxidation of sulfides, sulfoxides and thiophenes with aqueous solutions of H(2)O(2).

Modified SBA-15 mesoporous silica for heavy metal ions remediation.

N-Propylsalicylaldimino-functionalized SBA-15 mesoporous silica was prepared, characterized and used as an adsorbent for heavy metal ions. The organic-inorganic hybrid material was obtained using successive grafting procedures of SBA-15 silica with 3-aminopropyl-triethoxysilane and salicylaldehyde, respectively. For comparison an amorphous silica gel was functionalized using the same procedure. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis and FTIR spectroscopy. The organic functional groups were successfully grafted on the SBA-15 surfaces and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids for the adsorption of heavy metals ions from aqueous solutions was investigated. The hybrid materials showed high adsorption capacity and high selectivity for copper ions. Other ions, such as nickel, zinc, and cobalt were adsorbed by the modified SBA-15 material. The adsorbent can be regenerated by acid treatment without altering its properties.

Catalytic oxidation processes for removing dimethylsulfoxide from wastewater.

An effective method for removing dimethylsulfoxide (DMSO) from wastewater, based on the mild selective catalytic sulfoxidation with H(2)O(2), is proposed in this study. The catalysts are W-containing layered double hydroxides (LDH), and they were obtained by ionic exchange of the nitrate anions from MAl-LDH precursors (M=Mg(2+) or Zn(2+)) with both WO(4)(2-) and W(7)O(24)(6-) species. Results of X-ray diffraction (XRD), N(2) adsorption, thermal gravimetric analysis (TGA), diffuse reflectance ultraviolet spectroscopy (DRUV) and Raman spectroscopy confirmed the formation of the W-oxospecies inside the interlayer space and the modification of the textural properties upon the exchange process. All catalysts showed very good activity and stability in the DMSO conversion into dimethylsulfone with dilute H(2)O(2) aqueous solution, at low temperatures (20-50 degrees C). The efficiency of the H(2)O(2) was higher than 95% and the behaviour of the water as solvent was very close to that of the organic solvents (ethanol, acetonitrile, 1,4-dioxane).