Correlation of H<Subscript>2</Subscript>S and COS in the hot coal gas stream and its importance for high temperature desulfurization

Thermodynamic analysis of the correlation of H₂S and COS has been carried out at the temperature range of 400–650 °C at which high temperature desulfurization of coal gas is usually performed. The correlation of the two sulfur species is mainly through the reaction H₂S+CO→COS+H₂. Simulated coal gas with the following composition CO 32.69%, H₂ 39.58%, CO₂ 18.27%, N₂ 8.92% and H₂S 0.47% was used in this study, and the equilibrium concentrations of the two species at different temperatures were calculated. The results of Fe-based sorbents during sulfidation were compared with calculations. It is concluded that the above reaction may reach equilibrium concentration in the presence of the Fe-based sorbents, which means the Fe-based sorbents may effectively catalyze the reaction between H₂S and CO. Because of the correlation of the two sulfur species, both can be effectively removed at high temperatures simultaneously, offering high temperature desulfurization some advantages over low temperature desulfurization processes.     

Spectroscopic observation of H<Subscript>2</Subscript> migration in structure-I clathrate hydrate

We demonstrate the spectroscopic observation of H₂ migration in the binary structure-I (sI) clathrate hydrate. The H₂ molecules captured into sI small cage (sI-S) at lower temperature migrate to sI large cage (sI-L) through shared pentagonal face of 5¹²6² cage. The hexagonal faces of 5¹²6² cage provide the windows essential for creating continuous diffusion paths for H₂ molecules. It is essential to realize that the vacant channels formed by the linkage of specific cages can play an important role in guest diffusion pathways and occupancy occurring in a complex clathrate hydrate matrix.     

Solar light-driven photocatalytic hydrogen evolution over ZnIn<Subscript>2</Subscript>S<Subscript>4</Subscript> loaded with transition-metal sulfides

A series of Pt-loaded MS/ZnIn₂S₄ (MS = transition-metal sulfide: Ag₂S, SnS, CoS, CuS, NiS, and MnS) photocatalysts was investigated to show various photocatalytic activities depending on different transition-metal sulfides. Thereinto, CoS, NiS, or MnS-loading lowered down the photocatalytic activity of ZnIn₂S₄, while Ag₂S, SnS, or CuS loading enhanced the photocatalytic activity. After loading 1.0 wt.% CuS together with 1.0 wt.% Pt on ZnIn₂S₄, the activity for H₂ evolution was increased by up to 1.6 times, compared to the ZnIn₂S₄ only loaded with 1.0 wt.% Pt. Here, transition-metal sulfides such as CuS, together with Pt, acted as the dual co-catalysts for the improved photocatalytic performance. This study indicated that the application of transition-metal sulfides as effective co-catalysts opened up a new way to design and prepare high-efficiency and low-cost photocatalysts for solar-hydrogen conversion.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Electrolytic properties of the MeLn<Subscript>2</Subscript>S<Subscript>4</Subscript>-Ln′<Subscript>2</Subscript> S<Subscript>3</Subscript> phases synthesized using the sol-gel and cryochemical technologies

The possibility of synthesizing sulfide-conducting solid electrolytes based on the ternary sulfides MeLn₂S₄ doped with the binary sulfides Ln′₂S₃ has been approved and the influence of dopants on the electrolytic properties of the basic compounds has been investigated for the first time. The influence of the specific features of the method used for synthesizing complex sulfide phases from nanometer-sized oxide precursors on the important functional properties of the solid electrolytes has been analyzed. The samples have been examined using the X-ray powder diffraction analysis, electron scanning microscopy, and electron microprobe analysis. The region of the existence of the solid solutions has been determined, the total electrical conductivity has been studied, and the activation energy for electrical conduction for samples with different dopant contents has been calculated. The ionic and electronic transfer numbers have been determined using the modified versions of the emf method and the Hebb-Wagner polarization method. A possible mechanism of defect formation has been proposed.     

Selective oxidation of H<Subscript>2</Subscript>S to sulfur over CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> catalyst

The catalytic oxidation of hydrogen sulfide (H₂S) to elemental sulfur was studied over CeO₂-TiO₂ catalysts. The synthesized catalysts were characterized by various techniques such as X-ray diffraction, BET, X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption of ammonia, and scanning electron microscopy (SEM). Catalytic performance studies of the CeO₂-TiO₂ catalysts showed that H₂S was successfully converted to elemental sulfur without considerable emission of sulfur dioxide. CeO₂-TiO₂ catalysts with Ce/Ti=1/5 and 1/3 exhibited the highest H₂S conversion, possibly due to the uniform dispersion of metal oxides, high surface area, and high amount of acid sites.     

The effect of ethane on the performance of commercial polyphenylene oxide and Cardo-type polyimide hollow fiber membranes in CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation applications

Impurities such as hydrogen sulfide, water vapor and heavy hydrocarbons in natural gas have considerable effects on the membrane performance. Small amounts of condensable and polymer soluble components in the feed gas cause swelling or plasticization of glassy membranes, leading to a reduction in membrane selectivity. In the present research the influence of ethane was investigated on the permeance and selectivity of two commercially available hollow fiber membranes, namely Cardo-type polyimide and PPO hollow fibers for CO₂/CH₄ separations. It was concluded that the gas mixture permeation rate was increased in the presence of C₂H₆. However, the CO₂/CH₄ separation factors remained almost the same in the presence and absence of the C₂H₆.     

Phase cooperation of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> in the selective oxidation of H<Subscript>2</Subscript>S containing ammonia and water

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium oxide-based catalysts. The investigation was focused on the role of V₂O₅, and phase cooperation between V₂O₅ and Bi₂O₃ in this reaction. The conversion of H₂S continued to decrease since V₂O₅ was gradually reduced by treatment with H₂S. The activity of V₂O₅ was recovered by contact with oxygen. A strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V₂O₅ and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO) and two bed reaction tests were performed to explain this synergistic effect by the reoxidation ability of Bi₂O₃. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Photo-Induced Electron Transfer Process on Pristine and Sc-Substituted B<Subscript>12</Subscript>N<Subscript>12</Subscript> Nanocage as H<Subscript>2</Subscript>S Chemosensor: A Fully DFT and TD-DFT Study

In this study, B₁₂N₁₂ nanocage sensor function for H₂S absorption was examined theoretically. For this purpose, the interaction between B₁₂N₁₂ nanocage with H₂S gas in both ground and excited states have been investigated by DFT and TD-DFT methods. Interaction between nanocage with H₂S gas in ground state were studied with electron localization function, charge decomposition analysis and natural bond orbitals. TD-DFT calculations for B₁₂N₁₂ cage and Sc-substituted cage suggest that the optical properties of the cage can be improved by Sc-substitution. Survey the absorption uv spectrum of Sc@(BN)₁₂ after gas absorption showed this substituted nanocage is more favorable as an optic sensor. UV–Vis spectra display new absorption peaks confirming sensing ability of Sc-substituted B₁₂N₁₂ for detection of H₂S molecule. Subsequently in viewpoint of absorption, charge transfer mechanism via the photo-induced electron transfer process was investigated. Also desired nanosensor has short recovery time because adsorption energy of H₂S molecule is not too large. So it is expected that Sc-substituted B₁₂N₁₂ nanocage acts as new potential nanosensor to detect toxic H₂S molecule.     

Experimental investigations on combustion characteristics of syngas composed of CH<Subscript>4</Subscript>, CO,and H<Subscript>2</Subscript>

The residual gas and remained raw gas in dual gas resources polygeneration system are quite complex in components (mainly CH₄, CO, and H₂), and these results to the distinguished differences in combustion reaction. Experimental investigations on basic combustion characteristics of syngas referred above are conducted on a laboratory-scale combustor with flame temperature and flue gas composition measured and analyzed. Primary air coefficient (PA), total air coefficient (TA), and components of the syngas (CS) are selected as key factors, and it is found that PA dominates mostly the ignition of syngas and NO _x formation, while TA affects the flue gas temperature after high temperature region and NO _x formation trend to be positive as H₂/CO components increase. The results provide references for industrial utilization.     

Nanoclays as nano adsorbent for oxidation of H<Subscript>2</Subscript>S into elemental sulfur

Modified bentonites were used for the oxidation of H₂S into elemental sulfur. Active phases such as iron and cobalt sulfide were added to supports Cloisite 30B and 15A. The produced nano adsorbents were characterized by X-Ray diffraction, ICP, BET surface area and SEM. Selective oxidation of H₂S was carried out over the nano adsorbent in the experimental setup. The tests were performed at 70 and 180 °C, under atmospheric pressure and in the presence of 5,000 ppm of H₂S in the inlet gas stream. The results confirmed the increase in the distribution of active metals and activity of Cloisite 30B, in comparison with Cloisite 15A. Cobalt-containing support showed significant improvement in the capacity of H₂S removal, and in the outlet stream less than 50 ppm of H₂S was detected.     

Simulation of CO<Subscript>2</Subscript> removal in a split-flow gas sweetening process

Split-flow gas sweetening is known to consume less energy than a conventional gas sweetening process when the inlet sour gas contains a high concentration of acid gases. In this work, a computer simulation of a split-flow natural gas sweetening process based on absorption/stripping process with alkanoamine (MEA and DGA) solutions, using Aspen plus, was performed. The input of parameters such as the concentration of sour gases (CO₂, H₂S) in the feed gas has been examined. Simulation results show that the split-flow gas sweetening process can reduce the reboiler duty of a stripping tower better than the conventional gas sweetening process according to the concentration of CO₂ in the feed gas.     

Sorption studies of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript>, N<Subscript>2</Subscript>, CO,O<Subscript>2</Subscript> and Ar on nanoporous aluminum terephthalate [MIL-53(Al)]

Aluminum terephthalate, MIL-53(Al), metal–organic framework synthesized hydrothermally and purified by solvent extraction method was used as an adsorbent for gas adsorption studies. The synthesized MIL-53(Al) was characterized by powder X-Ray diffraction analysis, surface area measurement using N₂ adsorption–desorption at 77 K, FTIR spectroscopy and thermo gravimetric analysis. Adsorption isotherms of CO₂, CH₄, CO, N₂, O₂ and Ar were measured at 288 and 303 K. The absolute adsorption capacity was found in the order CO₂>CH₄>CO>N₂>Ar>O₂. Henry’s constants, heat of adsorption in the low pressure region and adsorption selectivities for the adsorbate gases were calculated from their adsorption isotherms. The high selectivity and low heat of adsorption for CO₂ suggests that MIL-53(Al) is a potential adsorbent material for the separation of CO₂ from gas mixtures. The high selectivity for CH₄ over O₂ and its low heat of adsorption suggests that MIL-53(Al) could also be a compatible adsorbent for the separation of methane from methane–oxygen gas mixtures.     

Electrical conductivity and structure of glasses in the Na<Subscript>2</Subscript>O-Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>O<Subscript>5</Subscript> and Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>S<Subscript>5</Subscript> systems

The glasses, in which oxygen was partially replaced with sulfur, have been synthesized in the Na₂O-P₂O₅-Na₂S system. The chemical and chromatographic analyses of the glasses synthesized have been performed. The temperature-concentration dependences of electrical conductivity of the glasses have been studied over a wide temperature range; the glass transition temperatures and the nature of charge carriers have been determined. The IR spectra and Raman spectra have been recorded at room temperature; the density and microhardness of the glasses and ultrasound velocity have been measured. A comparison of the electrical conductivities of the investigated glasses with those of the earlier studied glasses in the Na₂O-P₂O₅ system has shown their fair coincidence. The introduction of sodium sulfide into the Na₂O-P₂O₅ system is accompanied by an approximately threefold increase in electrical conductivity, although the concentrations of charge carriers (sodium ions) in the glasses amount to ∼17 and ∼26 mmol/cm³, respectively. The rise in electrical conductivity has been assumed to be caused by the increase in the degree of dissociation of polar structural chemical units including sulfide ions and by the higher mobility of sodium ions in the oxygen-free matrix.     

CeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZSM-5 sorbents for high-temperature H<Subscript>2</Subscript>S removal

Performance of CeO₂-La₂O₃/ZSM-5 sorbents for sulfur removal was examined at temperature ranging from 500 oC to 700 oC. The sulfur capacity of 5Ce5La/ZSM-5 was much bigger than that of CeO₂/ZSM-5. H₂ had a negative impact on the sulfidation; however, CO had little influence on sulfur removal. The characterization results showed that CeO₂ and La₂O₃ were well dispersed on ZSM-5 because of the intimate admixing of La₂O₃ and CeO₂, the major sulfidation products were Ce₂O₂S and La₂O₂S, the XRD and SEM results revealed that ZSM-5 structure could remain intact during preparation and sulfidation process, the H₂-TPR showed that the reducibility of CeO₂ can be remarkably enhanced by addition of La.     

Catalytic formation of carbonyl sulfide during warm gas clean-up of simulated coal-derived fuel gas with Pd/γ-Al2O3 sorbents

Coal gasification processes, such as the Integrated Gasification Combined Cycle (IGCC), will increase in importance due to the expanding concern over CO₂ emissions and global climate change. During the development of a Pd/γ-Al₂O₃ sorbent for warm (200 °C) fuel gas cleanup, the catalytic formation of carbonyl sulfide (COS), was observed. This is attributed to a heterogeneous reaction involving fuel gas components (CO/CO₂/H₂/H₂S/H₂O) and Pd/γ-Al₂O₃. The concentration of COS increases 200-fold when exposed to the Pd/γ-Al₂O₃ sorbent. A Langmuir–Hinshelwood reaction mechanism is proposed and a kinetic model is developed based on experimental results. The effect of γ-Al₂O₃, a common catalyst for hydrolysis of COS, and H₂O on the COS concentration is discussed.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

Regeneration of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> catalyst in the direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas

Methods for regenerating H₃PW₁₂O₄₀ catalyst in the solvent-free direct preparation of dichloropropanol (DCP) from glycerol and hydrochloric acid gas were investigated. Regenerated H₃PW₁₂O₄₀ catalyst was then applied to the solvent-free direct preparation of DCP. In the solvent-free direct preparation of DCP, selectivity for DCP over H₃PW₁₂O₄₀ catalyst regenerated by method I (recovery of solid H₃PW₁₂O₄₀ catalyst by evaporating homogeneous liquidphase product solution) significantly decreased with increasing recycling run, while that over H₃PW₁₂O₄₀ catalyst regenerated by method II (regeneration of H₃PW₁₂O₄₀ catalyst by oxidative calcination of solid product recovered by method I) was slightly decreased with no significant catalyst deactivation with respect to recycling run. On the other hand, selectivity for DCP over H₃PW₁₂O₄₀ catalyst regenerated by method III (regeneration of H₃PW₁₂O₄₀ catalyst by recrystallization and subsequent oxidative calcination of solid product recovered by method II) was the same as that over fresh catalyst without any catalyst deactivation with respect to recycling run. Thus, method III was found to be the most efficient method for the regeneration of H₃PW₁₂O₄₀ catalyst.     

Simultaneous biofiltration of H<Subscript>2</Subscript>S,NH<Subscript>3</Subscript> and toluene using cork as a packing material

Simultaneous removal of ternary gases of NH₃, H₂S and toluene in a contaminated air stream was investigated over 185 days in a biofilter packed with cork as microbial support. Multi-microorganisms including Nitrosomonas and Nitrobactor for nitrogen removal, Thiobacillus thioparus (ATCC 23645) for H2S removal and Pseudomonas aeruginosa (ATCC 15692), Pseudomonas putida (ATCC 17484) and Pseudomonas putida (ATCC 23973) for toluene removal were used simultaneously. The empty bed residence time (EBRT) was 40–120 seconds and the inlet feed concentration was 50-180 ppmv for NH₃, 30–160 ppmv for H₂S and 40–130 ppmv for toluene, respectively. The observed removal efficiency was 45–100% for NH₃, 96–100% for H₂S, and 10–99% for toluene, respectively. Maximum elimination capacity was 5.5 g/m³/hr for NH₃, >20.4 g/m³/hr for H₂S and 4.5 g/m³/hr for toluene, respectively. During long-term operation, the removal efficiency of toluene gradually decreased, mainly due to depositions of elemental sulfur and ammonium sulfate on the cork surface. The results of microbial analysis showed that nearly the same population density was observed on the surfaces of cork chips collected at each sampling point. Kinetic model analyses showed that there were no particular evidences of interactions or inhibitions among the microorganisms.     

Mitigation of N<Subscript>2</Subscript>O and CH<Subscript>4</Subscript> Emission from Rice and Wheat Cropping Systems Using Dicyandiamide and Hydroquinone

Agriculture contributes considerably to the emission of greenhouse gases, such as N₂O and CH₄. Here we summarize results from previous pot experiments assessing the effectiveness of urease and nitrification inhibitors reducing both N₂O and CH₄ emissions from wheat and rice cropping systems fertilized with urea (U). For the wheat cropping system, using a cambisol, we observed that the application of U with hydroquinone (HQ, a urease inhibitor), U with dicyandiamide (DCD, a nitrification inhibitor) and U with HQ plus DCD decreased the N₂O emissions by 11.4, 22.3 and 25.1%, respectively. For the rice copping system, using a luvisol, we found that the application of U with HQ, U with DCD and U with HQ plus DCD decreased N₂O emissions by 10.6, 47.0 and 62.3%, respectively, and CH₄ emissions by 30.1, 53.1 and 58.3%, respectively. In terms of total global warming potential (GWP) a reduction of 61.2% could be realized via the combined addition of HQ and DCD. The addition of wheat straw reduced the activity of HQ and DCD in the rice cropping experiments. In terms of total GWP only a reduction of 30.7% could be achieved. In general, both in upland and flooded conditions, the application of HQ and DCD alone was less effective than HQ in combination with DCD, but not significantly for U plus DCD treatment. Our observations may be further constrained, however, by practical, economic or social problems and should therefore be tested at the scale of a region (e.g. a watershed) and related to an integrated abatement of agricultural N losses.