A study on the conversion of trona to sodium bicarbonate

The deactivation model was used to explain kinetics underlying the conversion reaction of trona to NaHCO₃ (sodium bicarbonate). The model showed good agreement with the experimental data obtained from the conversion reaction of trona to NaHCO₃. It gave the value of 0.94 as an average correlation coefficient with the experimental data. However, at lower temperature, the model was in poor agreement with the data. This would be related to the structural variation of trona particles at the lower temperature. A trona particle is initially nonporous and then it begins to crack. This structural variation creates more surface area for the reaction with CO₂ and water vapor. However, at the lower temperature, the fissures on the surface of the particles are not fully developed during the beginning of the reaction. As a consequence, the level of the conversion of trona at the lower temperature is low during the beginning of the reaction and the time to approach the complete conversion is shorter as temperature increases. However, since the deactivation model does not include the term articulating the degree of the structural variation during the reaction, it does not fit well to the experimental data at the lower temperature. The deactivation rate constant, k_d is strongly temperature dependent and the change of the slope suggests the reaction mechanism changes as the reaction temperature increases.     

Flue gas desulfurization by citrate process and optimization of working parameters

In this study, model flue gas was bubbled into 0.25 L tribasic sodium citrate (TSC) solution being in 0.5 L glass absorber to remove its SO₂ content. Size of gas bubbles, absorption temperature, gas flow rate, solution concentration and stirring rate were taken as working parameters to investigate their effect on SO₂ removal from flue gas. The Taguchi's experimental design method was used to obtain optimum values of working parameters for SO₂ saturation time of the TSC solution selected as a quality characteristic. The optimum levels of parameters to maximize the SO₂ saturation time of TSC solution were coarse bubbles for gas delivery, 35 °C for absorption temperature, 1.5 slm for gas flow rate, 0.5 M for TSC solution concentration and 500 rpm for stirring rate. Under these conditions, the SO₂ saturation time of the TSC solution was achieved as 511 min in average. The most effective parameters on the absorption of SO₂ in TSC solutions were ranked to the least as solution concentration, gas flow rate, size of gas bubbles, absorption temperature and stirring rate.     

Determination of the Optimum Conditions for Copper Leaching from Chalcopyrite Concentrate Ore Using Taguchi Method

The optimum conditions for the extraction of copper from chalcopyrite concentrate into SO₂-saturated water were evaluated using the Taguchi optimization method. High level copper recovery was obtained in an environmentally friendly process that avoids sulfur dioxide emission into the atmosphere because SO₂ forming in the roasting is used in the dissolution. Experimental parameters and their ranges were chosen as follows: reaction temperature, 293–333 K; solid-to-liquid ratio, 0.025–0.15 g/mL; roasting time, 30–90 min; roasting temperature, 773–973 K; stirring speed, 400–800 rpm; and reaction time, 10–60 min. The particle size and gas flow rate were 63 µm and 10 cm³/min, respectively. The optimum conditions of the dissolution process were determined to be reaction temperature of 318 K, a solid-to-liquid ratio of 0.025 g mL^?1, a roasting time of 75 min, a roasting temperature of 773 K, a stirring speed of 400 rpm, and a reaction time of 30 min. Under optimum conditions, dissolution yield of copper was 91%.     

Study on the Poisoning Mechanism of Sulfur Dioxide for Perovskite La0.9Sr0.1CoO3 Model Catalysts

The reaction and poisoning mechanism of SO₂ with La_0.9Sr_0.1CoO₃ model catalysts have been investigated. The structure and the chemical states of the model catalysts have been studied by using AES, XPS and XRD techniques. The results indicated that SO₂ diffused into the La_0.9Sr_0.1CoO₃ film during poisoning. La₂(SO₄)₃ species was formed on the surface of the film and La₂(SO₄)₃, La₂(SO₃)₃, La₂O₂SO₄ and CoO species were found in the interior. The perovskite structure of La_0.9Sr_0.1CoO₃ was destroyed by invasion of SO₂. The concentration of sulfur in the film layer was related to the reaction temperature and time. After the sample was poisoned for a fairly long time, the distribution of sulfur in the La_0.9Sr_0.1CoO₃ layer became homogeneous, suggesting that a dynamic equilibrium was achieved between the poisoning reaction and the decomposition of the sulfates. XRD and catalytic activity test results proved that the destruction of perovskite structure and the formation of sulfates were the main causes of deactivation.     

Application of Taguchi method in the optimization of dissolution of ulexite in NH4Cl Solutions

The Taguchi method was used to determine optimum conditions for the dissolution of ulexite in NH₄Cl solutions. The ranges of experimental parameters were between 50–87 ‡C for reaction temperature, 0.05-0.20 gmL^-1 for solid-to-liquid ratio, 1–4 M for NH₄Cl concentration, 5–25 min for reaction time, and (-850+600)-(-90) Μm for particle size. The optimum conditions for these parameters were found to be 87 ‡C, 0.05 gmL^-1, 4M, (-300+212) Μm, and 18 minutes, respectively. Under these conditions, the dissolution percentage of ulexite in NH₄Cl solution was 98.37. Reaction products were found to be boric acid, ammonium tetraborates, sodium tetraborate decahydrate, calcium chloride, and sodium chloride.     

Catalytic Performance and Sulfur Dioxide Resistance of One-Pot Synthesized Fe-MCM-22 in Selective Catalytic Reduction of Nitrogen Oxides with Ammonia (NH3-SCR)—The Effect of Iron Content

The catalytic performance of Fe-catalysts in selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR) strongly depends on the nature of iron sites. Therefore, we aimed to prepare and investigate the catalytic potential of Fe-MCM-22 with various Si/Fe molar ratios in NH₃-SCR. The samples were prepared by the one-pot synthesis method to provide high dispersion of iron and reduce the number of synthesis steps. We have found that the sample with the lowest concentration of Fe exhibited the highest catalytic activity of ca. 100% at 175 °C, due to the abundance of well-dispersed isolated iron species. The decrease of Si/Fe limited the formation of microporous structure and resulted in partial amorphization, formation of iron oxide clusters, and emission of N₂O during the catalytic reaction. However, an optimal concentration of Fe_xO_y oligomers contributed to the decomposition of nitrous oxide within 250–400 °C. Moreover, the acidic character of the catalysts was not a key factor determining the high conversion of NO. Additionally, we conducted NH₃-SCR catalytic tests over the samples after poisoning with sulfur dioxide (SO₂). We observed that SO₂ affected the catalytic performance mainly in the low-temperature region, due to the deposition of thermally unstable ammonium sulfates.     

First-principles DFT study of SO2 and SO3 adsorption on 2PANI: a model for polyaniline response

Interaction of SO_x (x?=?2,3) molecules on active sites of dianiline (as a model for polyaniline, denoted here as 2PANI) was studied using density functional theory at the BLYP-D/6-31+G(d) level of theory. Natural population analysis was used to find out the charge distribution as well as the net transferred charge of SO_x upon adsorption on 2PANI and the result has been compared with Mulliken charge analysis to evaluate the sensing ability of 2PANI. The computed density of states point to the remarkable orbital hybridization between SO_x and 2PANI during the adsorption process. As a consequence, the results of UV–VIS confirm the sensing ability of 2PANI toward SO₂ and SO₃. Based on our results, it can be found that at proper configuration the SO₂ and SO₃ molecules can be adsorbed on 2PANI with adsorption energies (E_ads) of ?18.2 and ?62.9?kJ/mol (BSSE), respectively.     

Optimization of experimental conditions based on Taguchi robust design for the preparation of nano-sized TiO2 particles by solution combustion method

This investigation was aimed at preparing nanocrystalline TiO₂ powder by solution combustion method, and searching the optimum preparing conditions by employing Taguchi robust design method. Taguchi robust design method with L₁₈ orthogonal array was implemented to optimize experimental conditions for preparing nano-sized titania particles. Titanium IV n-butoxide was hydrolyzed to obtain titany1 hydroxide [TiO(OH)₂], and titanyl nitrate [TiO(NO₃)₂] was obtained by reaction of TiO(OH)₂ with nitric acid. Finally, the aqueous solution containing titanyl nitrate [TiO(NO₃)₂] and a fuel, glycine, were mixed and combusted to obtain the nano-sized titania. The optimum conditions obtained by this method are as follows (based on 1 mol of TiO₂ per batch): concentration of HPC, 0.053 mg cm⁻³; mole ratio of Ti:H₂O:IPA, 1:4:10; hydrolysis time, one hr; the amounts of HNO₃ and glycine are 10 ml and 0.5 g, respectively; nitrated temperature, 298 K and nitrated time, 2 h. TiO₂ nanocrystalline (∼15 nm) with high BET surface area (350 m² g⁻¹) and narrow band gap energy (2.7 eV) were thus obtained.     

The preparation and characterization of NaWO3 particles for heat shielding by Taguchi optimization method

The synthesis of sodium tungsten oxides (NaWO₃) particles was accomplished to apply on the heat shielding film. In this preparation, Taguchi method with L₉ orthogonal array was used to optimize experimental conditions for the formation of NaWO₃ particles. Primary mean particle size and the standard deviation of NaWO₃ particles were considered as the characteristics. Concentration of sodium tungstate (Na₂WO₄), concentration of sodium borohydride (NaBH₄), and pH value were selected as main parameters. As the result of Taguchi analysis in this work, the concentration of sodium tungstate was the most influencing parameter on the particle size and the standard deviation. The pH value had also principal effect on particle size and size distribution. The optimal conditions were determined by using Taguchi optimization design method and NaWO₃ particles with primary mean size (∼100 nm) were prepared. By the analyses of X-ray diffraction and UV–vis spectrum, it was found that the annealed NaWO₃ particles were more effective on heat shielding than non-annealed particles.     

Absorption of NO by Aqueous Solutions of KMnO4/H2SO4

The absorption of NO in aqueous solutions of KMnO₄ and H₂SO₄ was carried out in a stirred tank reactor under atmosphere pressure. The results indicated that the absorption process was under a fast pseudo-m th reaction regime. The reaction between NO and aqueous solutions of KMnO₄/H₂SO₄ was found to be first-order with respect both to NO and to KMnO₄. The addition of H₂SO₄ to KMnO₄ solutions increased the absorption rate of NO and increasing reaction temperature was also favorable to the absorption of NO.     

Development of Catalyst-Sorbents for Simultaneous Removal of SO2 From Flue Gas by Low Temperature Ozone Oxidation

One technological process employing ozone and heterogeneous catalyst-sorbents was proposed for removal of SO₂ from flue gas. The catalyst-sorbents were developed and tested especially for adsorption and oxidation of SO₂. Alternative catalyst-supporters including γ-Al₂O₃, permutite, silica gel, activated carbon and diatomite combined with different metal oxides (MnO₂, Cr₂O₃, Fe₂O₃, CuO, CoO and NiO) were evaluated and tested. It was found that γ-Al₂O₃ doped with MnO₂ can be considered as removal-effective sorbent for adsorption and oxidation of SO₂. The synergetic effect between ozone and catalyst was found to be dominated. Effects of catalyst preparation parameters like calcination temperature, metal loaded and reaction temperature, etc. were investigated based on the MnO₂/Al₂O₃ catalyst-sorbents. Results show that γ-Al₂O₃ combined with 8% Mn, calcinated under 573 K and reacted at 413 K are the optimal parameters for removal of SO₂. Extra NO in flue gas can slightly enhance the capture efficiency of SO₂.     

Effect of SO2 on a cordierite honeycomb supported CuO catalyst for NO reduction by NH3

Supporting CuO on a Al₂O₃-coated cordierite honeycomb yields a good catalyst (CuO/HC–Al) for selective catalytic reduction (SCR) of NO with NH₃ at 350–500 °C. SO₂ has complex effects on the catalysts activity. It significantly promotes the SCR activity through conversion of CuO to CuSO₄, however, when a certain amount of CuO is converted, it slightly decreases the SCR activity through competitive adsorption with NH₃. This competitive adsorption reduces the amount of NH₃ adsorbed on the catalyst surface, especially on the sites highly active to the SCR. It also prevents transformation of CuO to CuSO₄ and as a result, the catalysts subjected to pre-sulfation and in situ sulfation show different SCR behaviors.     

XPS evidence for molybdenum nitride formation in ZSM-5

Microwave plasma-assisted catalytic reduction of SO₂ by CO was studied over four catalysts. The activities of the four catalysts under microwave plasma decreased in the order of CoO/γ-Al₂O₃>>SnO₂> copper wires > iron wires, which was consistent with the results under conventional heating. By comparing the activity of CoO/γ-Al₂O₃ catalyst in the microwave plasma mode with that in the conventional mode, it is demonstrated that the temperature at which the full SO₂ conversion was obtained in the microwave plasma mode was about 200 °C lower than that under the conventional heating mode. Moreover, an increase of space velocity had little effect on SO₂ conversion and sulfur selectivity under microwave plasma; while under conventional heating mode, both SO₂ conversion and sulfur selectivity significantly decreased with an increase of space velocity.     

Influence of low concentration of SO2 for selective reduction of NO by C3H8 in lean-exhaust conditions on the activity of Ag/Al2O3 catalyst

The effect of SO₂ for the selective reduction of NO by C₃H₈ on Ag/Al₂O₃ was investigated in the presence of excess oxygen and water vapor. The NO_x conversion decreased permanently even in the presence of a low concentration of SO₂ (0.5–10 ppm) at <773 K. The increase in SO₂ concentration resulted in a large decrease in NO_x conversion at 773 K. However, when the reaction temperature was more than 823 K, the activity of Ag/Al₂O₃ remained constant even in the presence of 10 ppm of SO₂. The sulfate species formed on the used Ag/Al₂O₃ were characterized by a temperature programmed desorption method. The sulfated species formed on silver should mainly decrease the deNO_x activity on the Ag/Al₂O₃. The sulfated Ag/Al₂O₃ was appreciably regenerated by thermal treatment in the deNO_x feed at 873 K. The moderate activity remains at 773 K in the presence of 1 ppm SO₂ for long time by the heat treatment at every 20 h intervals.     

Reduction of lean NOx by ethanol over Ag/Al2O3 catalysts in the presence of H2O and SO2

The reduction of lean NOx using ethanol in simulated diesel engine exhaust was carried out over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. The Ag/Al₂O₃ catalysts are highly active for the reduction of lean NOx by ethanol but the reaction is accompanied by side reactions to form CH₃CHO, CO along with small amounts of hydrocarbons (C₃H₆, C₂H₄, C₂H₂ and CH₄) and nitrogen compounds such as NH₃ and N₂O. The presence of H₂O enhances the NOx reduction while SO₂ suppresses the reduction. The presence of SO₂ along with H₂O suppresses the formation of acetaldehyde and NH₃. By infrared spectroscopy, it was revealed that the reactivity of NCO species formed in the course of the reaction was greatly enhanced in the presence of H₂O. The NCO species readily reacts with NO in the presence of O₂ and H₂O at room temperature, being converted to N₂ and CO₂ (CO). Addition of SO₂ suppresses the formation of NCO species and lowers the reactivity of the NCO species. However, the reduction of NOx is still kept at high conversion levels in the presence of H₂O and SO₂ over the present catalysts. About 80% of NOx in the simulated diesel engine exhaust was removed at 743 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

Use of Raw and Acid-Treated MnO2 as Catalysts for Oxidation of Dyes in Water: A Case Study with Aqueous Methylene Blue

Catalytic wet oxidation has become one of the best options for mineralization of dyes in water. In this work, mineralization of methylene blue in water was tried by using raw and acid-treated (0.50, 0.75, and 1.00 N H₂SO₄) MnO₂ as oxidation catalysts. Fourier transform infrared, scanning electron microscopy, surface area and cation exchange capacity measurements were used to characterize the catalysts. The acid-treated materials showed large increases in surface area while changes in other surface characteristics were moderate in nature. The oxidative destruction of the dye was possible at near room temperature and the process was optimized with respect to interaction time, dye concentration, catalyst loading, pH of the medium, and temperature. The dye (1.0 mg/L) was oxidized to the extents of 88.5%, 96.5%, 96.8%, and 97.7% with corresponding chemical oxygen demand (COD) reduction of 64.7%, 86.4%, 87.2%, and 88.2% by raw MnO₂, 0.50, 0.75, and 1.00 N acid-treated MnO₂(catalyst loading 2.5 g/L), respectively. The reduction in COD indicated oxidation of the dye to simpler organic compounds achieving mineralization to a large extent. The oxidation followed first-order kinetics and the catalysts could be used up to six repeated runs without much change in activity. Analysis of the intermediate products of oxidation helped in proposing the potential pathways for oxidative conversion of methylene blue.     

An experimental study of sulphate transformation during pyrolysis of an Australian lignite

The transformation of sulphate minerals during pyrolysis of an Australian lignite has been studied using pure sulphates (CaSO₄, FeSO₄ and Fe₂(SO₄)₃), a high mineral (HM) lignite sample and a low mineral (LM) lignite sample collected from different locations of the same deposit, and samples of acid-washed LM doped with sulphates (CaSO₄+ LM and FeSO₄+ LM), respectively. Thermogravimetric analysis and fixed-bed reactor techniques were used for the pyrolysis experimentation and the lignite samples and their chars were analysed using FTIR and XRD. The TGA experiments showed that CaSO₄ decomposes between 1400 and 1700 K in nitrogen and a 50/50 N₂/CO₂ mixture, while in air CaSO₄ decomposes between 1500 and 1700 K. Using a TGA-MS it was found that only a small fraction of CaSO₄ in CaSO₄+ LM decomposed at 653 K, releasing SO₂. CaSO₄ was still observed in the char recovered at 1073 K as confirmed by the FTIR and XRD analysis. FeSO₄·7H₂O released the bound water below 543 K and the remaining FeSO₄ decomposed between 813 and 953 K. FeSO₄ in FeSO₄+ LM decomposed at 500 K to release SO₂. The inherent sulphates in HM were dominated by iron sulphates which started to decompose and release SO₂ at around 500 K and all sulphate had been decomposed at 1073 K. It was observed that during the fixed-bed pyrolysis at 1073 K in nitrogen, approximately 36% of the total sulphur in the CaSO₄+ LM decomposed, 88% of the total sulphur in the FeSO₄+ LM decomposed and around 76% of the total sulphur in HM decomposed. It was also confirmed that FeSO₄+ LM produced more volatile sulphur than CaSO₄+ LM during pyrolysis.     

分光光度法快速测定粉煤灰水泥中粉煤灰含量

通过分光光度法,对粉煤灰水泥中Fe2O3和SO3总含量进行检测,后分别检测粉煤灰、熟料、脱硫石膏中的Fe2O3和SO3含量,最后通过混合材掺量计算公式,计算粉煤灰水泥中的粉煤灰含量。该检测方法准确性较高,并且检测快捷方便,检测结果绝对误差范围小于5%。     

Prediction of a highly sensitive molecule sensor for SOx detection based on TiO2/MoS2 nanocomposites: a DFT study

First principles calculations within density functional theory have been carried out to investigate the adsorptions of SO_x (x?=?1, 2) molecules on TiO₂/MoS₂ nanocomposites in order to fully discover the gas sensing capabilities of TiO₂/MoS₂ composite systems. The van der Waals interactions were included to obtain the most stable geometrical structures of TiO₂/MoS₂ nanocomposites with adsorbed SO_x molecules. SO_x molecules preferentially interact with the doped nitrogen and fivefold coordinated titanium sites of the TiO₂ anatase nanoparticles because of their higher activities in comparison with the other sites. The results presented include structural parameters such as bond lengths and bond angles and energetics of the systems such as adsorption energies. The variation of electronic structures are discussed in view of the density of states and molecular orbitals of the SO_x molecules adsorbed on the nanocomposites. The results show that the adsorption of the SO_x molecule on the N-doped TiO₂/MoS₂ nanocomposite is energetically more favorable than the adsorption on the undoped one, implying that the nitrogen doping helps to strengthen the interaction of SO_x molecules with TiO₂/MoS₂ nanocomposites. These calculated results thus provide a theoretical basis for the potential applications of TiO₂/MoS₂ nanocomposites in the removal and sensing of harmful SO_x molecules.     

Activity and characterization of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for the SCR of NO with CO in the presence of SO2 and HCl

SO₂ and HCl are major pollutants emitted from waste incineration processes. Both pollutants are difficult to remove completely and can enter the catalytic reactor. In this work, the effects of SO₂ and HCl on the performance of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for NO removal were investigated in simulated waste incineration conditions. The characterizations of the catalysts were analyzed by BET, SEM/EDS, XRD, and ESCA. Experimental results indicated the 1%Rh/Al₂O₃ catalyst was significantly deactivated for NO and CO conversions when SO₂ and HCl coexisted in the flue gas. The addition of between 2 and 10 wt.% Na promoted the activity of the 1%Rh/Al₂O₃ catalyst for NO removal, but decreased the CO oxidation and BET surface area. The catalytic activity for NO removal was inhibited by HCl as a result of the formation of RhCl₃. Adding Na to the Rh/Al₂O₃ catalyst decreased the inhibition of SO₂ because of the formation of Na₂SO₄, which was observed in the XRD and ESCA analyses. SEM mapping/EDS showed that more S was residual on the surface of the Rh-Na/Al₂O₃ catalyst than Cl.