Simultaneous absorption of CO<Subscript>2</Subscript> and SO<Subscript>2</Subscript> into aqueous AMP/NH<Subscript>3</Subscript> solutions in binary composite absorption system

To enhance the absorption rate for CO₂ and SO₂, aqueous ammonia (NH₃) solution was added to an aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The simultaneous absorption rates of AMP and a blend of AMP+ NH₃ for CO₂ and SO₂ were measured by using a stirred-cell reactor at 303 K. The process operating parameters of interest in this study were the solvent and concentration, and the partial pressures of CO₂ and SO₂. As a result, the addition of NH₃ solution into aqueous AMP solution increased the reaction rate constants of CO₂ and SO₂ by 144 and 109%, respectively, compared to that of AMP solution alone. The simultaneous absorption rate of CO₂/SO₂ on the addition of 1 wt% NH₃ into 10 wt% AMP at a p _A1 of 15 kPa and p _A2 of 1 kPa was 5.50×10⁻⁶ kmol m⁻² s⁻¹, with an increase of 15.5% compared to 10 wt% AMP alone. Consequently, the addition of NH₃ solution into an aqueous AMP solution would be expected to be an excellent absorbent for the simultaneous removal of CO₂/SO₂ from the composition of flue gas emitted from thermoelectric power plants.     

Influence of operating temperature on CO<Subscript>2</Subscript>-NH<Subscript>3</Subscript> reaction in an aqueous solution

Although aqueous ammonia solution has been focused on the removal of CO₂ from flue gas, there have been very few reports regarding the underlying analysis of the reaction between CO₂ and NH₃. In this work, we explored the reaction of CO₂-NH₃-H₂O system at various operating temperatures: 40 °C, 20 °C, and 5 °C. The CO₂ removal efficiency and the loss of ammonia were influenced by the operating temperatures. Also, infrared spectroscopy measurement was used in order to understand the formation mechanism of ion species in absorbent, such as NH₂COO⁻, HCO₃⁻, CO₃²⁻, and NH₄⁺, during CO₂, NH₃, and H₂O reaction. The reactions of CO₂-NH₃-H₂O system at 20 °C and 40 °C have similar reaction routes. However, a different reaction route was observed at 5 °C compared to the other operating temperatures, showing the solid products of ammonium bicarbonates, relatively. The CO₂ removal efficiency and the formation of carbamate and bicarbonate were strongly influenced by the operating temperatures. In particular, the analysis of the formation carbamate and bicarbonate by infrared spectroscopy measurement provides useful information on the reaction mechanism of CO₂ in an aqueous ammonia solution.     

Syndiospecific Polymerization of Styrene Using Half-Titanocene Catalyst Covalently Supported on MgCl<Subscript>2</Subscript>/AlEt<Subscript>n</Subscript>(OEt)<Subscript>3-n</Subscript>

The novel half-titanocene catalyst bearing reactive functional amino group, η⁵-pentamethylcyclopentadienyltri(p-amino-phenoxyl) titanium [Cp^∗Ti(p-OC₆H₄NH₂)₃], was easily synthesized by the reaction of η⁵-pentamethylcyclopentadienyltrichloride titanium (Cp^∗TiCl₃) with p-amino phenol in the presence of triethyl amine (NEt₃). Cp^∗Ti(p-OC₆H₄NH₂)₃ covalently anchored on MgCl₂/AlEt_n(OEt)_3-n support obtained from the reaction of triethylaluminium (AlEt₃) with the adduct of magnesium chloride (MgCl₂) and ethanol (EtOH), has been investigated and used to catalyze syndiospecific polymerization of styrene. Influences of the support structure, cocatalyst, and the molar ratio of Al in methylaluminoxane (MAO) and Ti (Al_MAO/Ti) on catalytic activity, syndiotacticity and molecular weight of the resultant polystyrene were investigated. Compared with the corresponding Cp^∗Ti(p-OC₆H₄NH₂)₃ homogeneous catalyst, a considerable increase in activity and molecular weight of syndiotactic polystyrene (sPS) was observed for the Cp^∗Ti(p-OC₆H₄NH₂)₃-MgCl₂/AlEt_n(OEt)_3-n supported catalyst even at a relatively low Al_MAO/Ti ratio of 50, and the kinetics of polymerization was stable during the reaction process.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

Study on the properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO lead-free glass using in the electronic pastes

The Sb₂O₃ doping lead-free glass in Bi₂O₃-B₂O₃-BaO ternary system were prepared in the composition of several different subsystem, and the glass powder was produced through the process of water quenching. Glass transition temperatures (T _g ), glass soften temperatures(T _s ), the volume resistivity (ρ) in the temperature range of 80–200°C, and linear thermal coefficients of expansion in the temperatures range of 25–300°C (α_25–300) were measured for subsystems along with the different ratio of Bi₂O₃, B₂O₃ and BaO. For these subsystems, T _g ranged from 458 to 481°C, and T _s ranged from 490 to 512°C, both decreasing with the increasing of Bi₂O₃/B₂O₃ ratio, and increasing with the increasing of BaO/B₂O₃ ratio. The measured α_25–300 ranged from 65.3 to 76.3 × 10⁻⁷ K⁻¹, with values increasing with increasing Bi₂O₃/B₂O₃ and BaO/B₂O₃ ratio. The volume resistivity remains at a high standards, which may caused by it’s non-alkali composition, and it fluctuated from 10¹³ to 10¹¹ Ω cm with the temperature varied from 80–200°C. The structure of Bi₂O₃-B₂O₃-BaO ternary leadfree glass system was mearsured by FT-IR. The IR studies indicate that these glasses are made up of [BiO₆], [BO₃], and [BO₄] basic structural units, and it appears that Ba²⁺ acts as a glass-modifier in this ternary system, but the Bi³⁺ has entered the glass network when it is in relative high content so as to change the α_25–300, T _s and T _g .     

Synthesis of monohydric alcohols from CO and H<Subscript>2</Subscript> on Fe/Sibunit catalysts

It was demonstrated that R ₂–R ₄ saturated monohydric alcohols can be synthesized from CO and H₂ in the presence of Fe catalysts containing a carbon support of the Sibunit type with granule sizes of 3–5, 1–2, and 0.05–0.1 mm in a fixed-bed reactor at 3 MPa and 240–300°C. It was found that the activity of Fe/Sibunit catalysts and their selectivity for the formation of liquid synthetic products increased with the size of granules and the amount of iron. The catalysts make it possible to obtain fatty alcohols, in which the fraction of R ₂–R ₄ alcohols is as high as 75%, in yields to 56 g/m³.     

The Effect of Sulfur on ZrO<Subscript>2</Subscript>-Based Biomass Gasification Gas Clean-Up Catalysts

The effect of sulfur on biomass gasification gas clean-up over ZrO₂, Y₂O₃–ZrO₂ and SiO₂–ZrO₂ catalysts was examined. Experiments were carried out at the temperature range of 600–900 °C with sulfur free and 100 ppm H₂S containing simulated gasification gas feeds. A mixture of toluene and naphthalene was used as a tar model compound. Results revealed that the sulfur addition affected positively on the catalyst properties mainly at 600 and 700 °C: over Y₂O₃–ZrO₂ and ZrO₂ sulfur addition improved naphthalene and ammonia conversion. However, over SiO₂–ZrO₂ no clear effect with H₂S addition was observed. The effect of sulfur addition on the catalyst properties was connected to the formation of SO₂ from H₂S when oxygen was available. The intensity of the sulfur effect increased with the Lewis basicity strength of the catalysts. This indicates that the sulfur adsorption has a role in generating new type of active sites and/or plays role in changing the redox properties of the zirconia. Since the biomass gasification gas contains usually significant amounts of H₂S the sulfur tolerance of the zirconia based catalysts is a remarkable benefit.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

The system SiC–W<Subscript>2</Subscript>B<Subscript>5</Subscript>–LaB<Subscript>6</Subscript>

Experiments and calculations have been applied to the structure of the triple eutectic system SiC–W₂B₅–LaB₆(T _eu = 1900 ± 40°C), composition in mol.%: 10 LaB₆, 44 SiC, 46 W₂B₅, error ±2–3%, which opens up prospects for making ceramic materials for various purposes.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.     

Control of H2S waste gas emissions with a biological activated carbon filter

The removal of high concentrations of H₂S from waste gases containing mixtures of H₂S and NH₃ was studied using the pilot‐scale biofilter. Granular activated carbon (GAC), selected as support material in this study, demonstrated its high adsorption capacity for H₂S and good gas distribution. Extensive tests to determine removal characteristics, removal efficiency, and removal capacity of high H₂S levels and coexisting NH₃ in the system were performed. In seeking the appropriate operating conditions, the response surface methodology (RSM) was employed. H₂S removal capacities were evaluated by the inoculated bacteria (biological conversion) and BDST (Bed Depth Service Time) methods (physical adsorption). An average 98% removal efficiency for 0.083–0.167 mg dm^?3 of H₂S and 0.004–0.021 mg dm^?3 of NH₃ gases was achieved during the operational period because of rapid physical adsorption by GAC and subsequently an effective biological regeneration of GAC by inoculated Pseudomonas putida CH11 and Arthrobacter oxydans CH8. The results showed that H₂S removal efficiency for the system was not affected by inlet NH₃ concentrations. In addition, no acidification was observed in the BAC biofilter. High buffer capacity and low moisture demand were also advantages of this system. The maximal inlet loading and critical loading for the system were 18.9 and 7.7 g‐H₂S m^?3 h^?1, respectively. The results of this study could be used as a guide for the further design and operation of industrial‐scale systems. Copyright © 2004 Society of Chemical Industry     

Initiation of combustion of a CH<Subscript>4</Subscript>-O<Subscript>2</Subscript> mixture in a supersonic flow with excitation of O<Subscript>2</Subscript> molecules by an electric discharge

The possibility of intensification of ignition of a methane-oxygen mixture in a supersonic flow behind the front of an oblique shock wave by means of excitation of O₂ molecules to the states a ¹Δ_g and b ¹Σ_g⁺ in an electric discharge is discussed. Through numerical simulations, activation of O₂ molecules by an electric discharge is demonstrated to speed up chain reactions in the CH₄-O₂ mixture and to reduce the induction-zone length. Even a small amount of energy input to O₂ molecules in the discharge (≈3·0⁻² J/cm³) can reduce the ignition-delay length by a factor of hundreds and initiate combustion at distances of ≈1 m from the discharge zone at comparatively low temperatures of the gas behind the front (≈1000 K) and moderate pressures (≈10⁵ Pa). Excitation of O₂ molecules by an electric discharge is much more efficient than simple heating of the mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 3, pp. 3–16, May–June, 2008.     

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.     

Method of estimating absolute concentrations of C<Subscript>2</Subscript>H<Subscript>5</Subscript> and H radicals in hydrocarbon diffusion flames

A method for estimating absolute concentrations of C₂H₅ and H radicals in hydrocarbon diffusion flames is proposed and substantiated. Concentration profiles of C₂H₅ and H on the flame axis are obtained. In the method proposed, the concentration of C₂H₅ is determined from the equality of two quantities — the rate of loss of n-butane by diffusion and the rate of its formation by recombination of two C₂H₅ radicals. The concentration of H radicals is determined from the relation between the ratio C₂H₅/H and experimental profiles of C₂H₄, C₂H₆, and O₂. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 13–20, November–December, 2007.     

Synthetic spinels of the system MgO-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Synthetic spinels of the system MgO-Cr₂O₃-Al₂O₃-Fe₂O₃ are considered and the desirability of organizing their production for the refractory industry is demonstrated. Translated from Novye Ogneupory, No. 6, pp. 32–35, June 2008.     

Pd/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts on cellular supports for VOC vapor neutralization

The results from investigating the influence of temperature, concentration, and flow rate on the catalytic oxidation of vapors of volatile organic compounds (VOCs) in the presence of Pd/γ-Al₂O₃ catalyst on cellular supports are presented. The activity of Pd/γ-Al₂O₃ catalysts on ceramic and metal monolith supports with a cellular structure during the catalytic neutralization of VOC (ethanol, ethyl acetate) vapors under laboratory conditions was determined, and the most stable catalyst for the preliminary study of a large batch was chosen. A pilot unit was created to test a large batch of cellular monolith catalyst in neutralizing VOC vapors under conditions of flexographic production. It was established that a high rate of conversion (> 99 %) was achieved for VOC concentrations of 0.5 g/m³ at space velocities of up to ∼10⁴ h⁻¹, and for VOC concentrations of 5.0 g/m³ at space velocities of up to ∼5 × 10⁵ h⁻¹. The change in the activity of the catalysts on metal (nickel alloyed by aluminum) and ceramic cellular supports in service was investigated. After 300–500 min of operation, virtually complete deactivation of catalyst on a metal support was observed, accompanied by the formation of nickel oxide and acetate. Pilot unit tests with catalyst on cellular supports having a volume of 14.5 l in neutralizing the ventilation exhausts of flexographic production confirmed the possibility of more than 90% conversion at VOC concentrations of ∼0.1 g/m³ and more than 97% at VOC concentrations of over 1 g/m³. A consistently high conversion of VOC was observed during a 100 h test of the pilot unit. A system for recovering the heat released during VOC oxidation lowers the operating costs of the pilot unit.     

NMR Characterization of the Higher Molecular Weight Byproducts Formed During the Synthesis of [PCl<Subscript>2</Subscript>N]<Subscript>3</Subscript>

The by-product chlorophosphazenes obtained from the reaction of PCl₅ and NH₄Cl at ∼ 140°, have been characterized by 2D ³¹P–¹⁵N HMQC and DOSY NMR spectroscopy. These NMR spectra show that the byproducts are a very complex mixture. CAT would like to thank Chris Allen for an being an important role model. By his actions, she learned that wanting to be both a good scientist and a good parent need not be mutually exclusive.     

Experimental study of the structure of a lean premixed indane/CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/Ar flame

In order to better understand the chemistry involved during the combustion of diesel fuel components, the structure of a laminar lean premixed methane flame doped with indane has been investigated. This flame contains 7.1% (molar) of methane, 36.8% of oxygen, and 0.90% of indane, corresponding to an equivalence ratio of 0.74 and a C₉H₁₀/CH₄ ratio of 12.75%, with argon used as a dilutant. The flame has been stabilized on a burner at a pressure of 6.7 kPa, with the gas velocity at the burner exit equal to 49.2 cm/sec at 333 K. Quantified species include usual methane combustion products C₀–C₂, but also eleven C₃–C₅ hydrocarbons and three C₁–C₃ oxygenated compounds, as well as 17 aromatic products, namely benzene, toluene, phenylacetylene, styrene, ethylbenzene, xylenes, trimethylbenzenes, ethyltoluenes, indene, methylindane, methylindene, naphthalene, phenol, benzaldehyde, and benzofuran. The temperature has been measured by a PtRh(6%)-PtRh(30%) thermocouple settled inside the enclosure: from 800 K close to the burner up to 2000 K in the burned gases.     

The effect of poly(vinyl caprolactone-co-vinyl pyridine) and poly(vinyl imidazol-co-vinyl pyridine) on the corrosion of steel in H<Subscript>3</Subscript>PO<Subscript>4</Subscript> media

The inhibiting effect of two organic copolymers namely poly(vinyl caprolactone-co-vinyl pyridine) (PVCVP) and poly(vinyl imidazol-co-vinyl pyridine) (PVIVP) on the corrosion of steel in phosphoric acid was investigated at various temperatures. The study was carried out by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurements. Inhibition efficiency (E %) increased with polymer concentration to attain 85% at 10⁻⁴ M for PVIVP. Adsorption of polymers on the steel surface in 2 M H₃PO₄ followed the Langmuir isotherm model. EIS measurements show that the dissolution of steel occurs under activation control. Polarisation curves indicate that the tested polymers functioned as cathodic inhibitors. E % values obtained from various methods used are in good agreement with each other. The temperature effect on the corrosion behaviour of steel in 2 M H₃PO₄ in the presence and absence of the inhibitor was studied in the temperature range 298–338 K. The adsorption free energy (ΔG ^o _ads) and the activation parameters (E _a, , ΔS ^o _a) for the steel dissolution reaction in the presence of polymer were determined.     

Methanol selective oxidation to dimethoxymethane on H<Subscript>3</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>/SBA-15 supported catalysts

A series of SBA-15 supported H₃PMo₁₂O₄₀ catalysts were prepared for the one-step oxidation of methanol to dimethoxymethane (DMM). The evaluation and characterization revealed that higher DMM selectivity obtained on the incipient wetness impregnation (IM) catalyst was related to the instability of H₃PMo₁₂O₄₀ on it. Raman spectra showed that 12-molybdophosphoric acid was more stable on the direct synthesis (DS) catalyst than on the IM catalyst and the existence of SBA-15 support enhanced the stability of H₃PMo₁₂O₄₀. Moreover, higher H₃PMo₁₂O₄₀ loading resulted in more acid sites and low DMM selectivity, furthermore the thermal pretreatment on H₃PMo₁₂O₄₀ influenced its structure and thus affected DMM selectivity. This paper was presented at the 7 ^th Korea-China Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.