Application of thermoanalytical methods to the study of limestone sulphation

The role that can be played in the elucidation of the limestone sulphation mechanism by thermal analysis methods with some specific procedures is discussed. Contrasting examples of applications of thermoanalytical techniques using the variable conditions are provided. These examples deal with the programmed thermal analysis using different gas sequences, the influence the calcination and sulphation conditions on the capture of SO₂, the effect of catalysts on limestone sulphation and the thermal stability of CaSO₃. Two proposed mechanisms were supported by the phase identification of the solid products.     

Physico-Chemistry of the Limestone Sulphation Process

Aspects of the mechanism of the overall reaction between CaCO₃/CaO and SO₂/SO₃ under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging. Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO₄ and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO₃ disproportionation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Decarbonization of Natural Lime-containing Materials and Reactivity of Calcined Products Towards SO2 and CO2

The results obtained by studying decarbonization of different samples of Estonian limestone and dolomite and the following sulphation or carbonation of calcined products to estimate their SO2 and CO2 binding ability were presented. Experiments were carried out with thermogravimetric equipment(Q-Derivatograph, MOM and Labsys™, SETARAM) – calcination of the samples in the atmosphere of air with the heating rate 10 K per minute using multiplate crucibles, the following sulphation or carbonation of the calcined products after cooling to the fixed temperature (temperature range 400–900°C) under isothermal conditions in the flow of air-SO₂ or air-CO₂ mixture. Chemical, X-ray, BET nitrogen dynamic desorption, etc. methods for the characterization of the initial samples, intermediate and final products were used. In addition, the possibilities of recurrent use of oil shale ashes taken from different technological points at operating thermal power plants (Estonian and Baltic TTPs, Estonia) as sorbents for SO₂ binding from gaseous phase were studied, as well as the possibilities of activation of these ashes towards SO₂ binding. The results of these studies confirmed the high reactivity of Estonian limestone and dolomite towards SO₂ and CO₂. Dependence of SO₂ binding mechanism on the SO₂ concentration has been established. Modelling of SO₂ capture of dolomite and limestone was carried out to establish the kinetic parameters of these processes. The possibilities of activation of oil shale ashes and their effective recurrent use for binding SO₂ and CO₂ from gaseous phase were confirmed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mechanism and kinetics of inorganic sulphates decomposition

Thermal decomposition of different inorganic sulphates are presented. A number of techniques, but mainly TG and DTA, are used to prove the mechanism and kinetics of CaSO₄, BaSO₄, FeSO₄·xH₂O, Al₂(SO₄)₃·xH₂O under various gas atmospheres. It is shown how the partial pressure of gas components and heating rate may effect the mechanism and kinetic parameters. There are also examples on the effects of some additives and initial treatment on the thermal processes. On the base of the results obtained some recommendations are given concerning the precautions to be taken into account in the thermal decomposition studies and the sulphur recovering.     

The role of doped Fe on the activity of alumina-supported Pt and Pd diesel exhaust catalysts

Supported Pt and Pd are most commonly used for oxidation catalysts. They have similar and different characteristics for deactivation factors. The catalytic activity of Pt and Pd catalysts supported on ??-Al₂O₃ was studied in the presence and absence of H₂O and SO₂ during CO oxidation under simulated conditions of diesel exhaust gas. Without the addition of H₂O and SO₂ to the feed gas, Pd/Al₂O₃ had a superior catalytic activity compared to Pt/Al₂O₃. The addition of H₂O to the feed gas strongly and negligibly affected the activity of Pd and Pt, respectively, while the addition of SO₂ to the feed gas had a strong poisoning effect on the catalytic activity of both Pt and Pd catalysts. Although being the most active, Pd catalysts exhibited a strong sensitivity to water and sulfur-containing compounds. Fe was added to the Pt and Pd catalysts to introduce sulfur resistance. The addition of Fe enhanced the activity of the catalysts by suppressing the phase transition of Al₂O₃ to Al₂(SO₄)₃ and by hindering metal sintering.     

Crystallization and Phase Stability of CaSO<Subscript>4</Subscript> and CaSO<Subscript>4</Subscript> – Based Salts

Summary.  Calcium sulfate occurs in nature in form of three different minerals distinguished by the degree of hydration: gypsum (CaSO₄·2H₂O), hemihydrate (CaSO₄·0.5H₂O) and anhydrite (CaSO₄). On the one hand the conversion of these phases into each other takes place in nature and on the other hand it represents the basis of gypsum-based building materials. The present paper reviews available phase diagram and crystallization kinetics information on the formation of calcium sulfate phases, including CaSO₄-based double salts and solid solutions. Uncertainties in the solubility diagram CaSO₄–H₂O due to slow crystallization kinetics particularly of anhydrite cause uncertainties in the stable branch of crystallization. Despite several attempts to fix the transition temperatures of gypsum–anhydrite and gypsum–hemihydrate by especially designed experiments or thermodynamic data analysis, they still vary within a range from 42–60°C and 80–110°C. Electrolyte solutions decrease the transition temperatures in dependence on water activity. Dry or wet dehydration of gypsum yields hemihydrates (α-, β-) with different thermal and re-hydration behaviour, the reason of which is still unclear. However, crystal morphology has a strong influence. Gypsum forms solid solutions by incorporating the ions HPO₄ ²⁻, HAsO₄ ²⁻, SeO₄ ²⁻, CrO₄ ²⁻, as well as ion combinations Na⁺(H₂PO₄)⁻ and Ln³⁺(PO₄)³⁻. The channel structure of calcium sulfate hemihydrate allows for more flexible ion substitutions. Its ion substituted phases and certain double salts of calcium sulfate seem to play an important role as intermediates in the conversion kinetics of gypsum into anhydrite or other anhydrous double salts in aqueous solutions. The same is true for the opposite process of anhydrite hydration to gypsum. Knowledge about stability ranges (temperature, composition) of double salts with alkaline and alkaline earth sulfates (esp. Na₂SO₄, K₂SO₄, MgSO₄, SrSO₄) under anhydrous and aqueous conditions is still very incomplete, despite some progress made for the systems Na₂SO₄–CaSO₄ and K₂SO₄–CaSO₄–H₂O. Corresponding author. E-mail: daniela.freyer@chemie.tu-freiberg.de Received December 17, 2002; accepted January 10, 2003 Published online April 3, 2003     

Calcium Sulfite Solids Activated by Iron for Enhancing As(III) Oxidation in Water

Desulfurized gypsum (DG) as a soil modifier imparts it with bulk solid sulfite. The Fe(III)–sulfite process in the liquid phase has shown great potential for the rapid removal of As(III), but the performance and mechanism of this process using DG as a sulfite source in aqueous solution remains unclear. In this work, employing solid CaSO₃ as a source of SO₃²⁻, we have studied the effects of different conditions (e.g., pH, Fe dosage, sulfite dosage) on As(III) oxidation in the Fe(III)–CaSO₃ system. The results show that 72.1% of As(III) was removed from solution by centrifugal treatment for 60 min at near-neutral pH. Quenching experiments have indicated that oxidation efficiencies of As(III) are due at 67.5% to HO^•, 17.5% to SO₅^•− and 15% to SO₄^•−. This finding may have promising implications in developing a new cost-effective technology for the treatment of arsenic-containing water using DG.     

The effect of the ammonium paratungstate source on the tungsten crystallite size

In an investigation into the effects of CaCl₂ on the sulfation of limestones in a laboratory furnace simulating fluidized-bed coal combustion conditions, small additions of CaCl₂ (<1 mole%) to the limestone prior to calcination were found to increase the extent of sulfation by changing the limestone pore structure. These changes were effected by trace amounts of liquid in the system in a synthetic SO₂/O₂ flue gas at 850°C. At much higher concentrations of CaCl₂, large amounts of a liquid phase are produced, containing a substantial quantity of dissolved CaO and leading to greatly enhanced sulfation when exposed to SO₂/O₂. The use of CaCl₂ additive in fluidized-bed combustion would reduce the quantity of limestones required to meet air pollution standards for SO₂ and also reduce the quantity of solid waste generated.     

Production of high-purity carbon dioxide and sodium bicarbonate by lime cellar gas cleaning and chemical recycling: Process simulation and techno-economic analysis

The cement industry is responsible for 8% of total global CO₂ emissions, which mainly originate from limestone calcination and fuel combustion. In view of the application potential of using CO₂ to produce chemicals, this paper developed a novel process based on the Aspen Plus process simulation for the co-production of 99.99% CO₂ by means of Methyldiethanolamine (MDEA) absorption/desorption and NaHCO₃ by carbonization of CO₂, NH₃ and Na₂SO₄. The effects of absorption temperature, NH₃ and Na₂SO₄ feeding amount, crystallizer temperature and pressure on CO₂ capture rate and utilization rate were explored. The results showed that the best CO₂ capture rate was achieved when the cellar gas inlet temperature of the absorber tower was 37 °C; Saturated Na₂SO₄ solution was favorable for CO₂ absorption, and the CO₂ utilization rate increased with the increase of Na₂SO₄ dosage; NaHCO₃ yield decreased with the increase of crystallizing temperature, and the best NaHCO₃ yield was achieved when the crystallizer temperature was 35.5 °C; Crystallizing pressure had little impact on the reaction. Economic analysis showed that the project will start to be profitable in 6.48 years with a Net Return Rate (NRR) value of 13.51%. It indicates that the project has economic benefits and provides a new way to reduce CO₂ emissions from lime cellar gas.     

The effect of H2O on the sulfation of Havelock limestone under oxy-fuel conditions in a thermogravimetric analyser

A gas mixture representing oxy-fuel combustion conditions was employed in a thermogravimetric analyser to determine the effect of water vapor and SO₂ concentration on limestone sulfation kinetics over the temperature range of 800 to 920 °C. Here, experiments used small samples of particles (4 mg), with small particle sizes (d_p < 38 µm) and large gas flow rates (120 mL/min@NTP) in order to minimize mass transfer interferences. The gas mixture contained 5000 ppm_v SO₂, 2% O₂, and the H₂O content was changed from 0% to 25% with the balance CO₂. When water vapor was added to the gas mixture at lower temperatures (800–870 °C), the limestone SO₂ capture efficiency increased. However, as the temperature became higher, the enhancement in total conversion values decreased. As expected, Havelock limestone at higher temperatures (890 °C, 920 °C, and 950 °C) experienced indirect sulfation and reacted at a faster rate than for lower temperatures (800–870 °C) for direct sulfation over the first five minutes of reaction time. However, the total conversion of Havelock limestone for direct sulfation was generally greater than for indirect sulfation.     

Zur Darstellung und Charakterisierung von Calciumhydrogensulfaten

Preparation and Characterization of Calcium Hydrogen Sulfate CaSO₄ · H₂SO₄ was identified as calcium hydrogen sulfate whereas CaSO₄ · 3 H₂SO₄ is an adduct of CaSO₄ with H₂SO₄. Depending on the excessive amount of H₂SO₄ both compounds exist side by side up to a temperature of 343 K, whereas above this temperature only Ca(HSO₄)₂ is stable. The DTA curve of Ca(HSO₄)₂ shows two maxima at 488 K and 523 K, according to the separation of H₂O under formation of pyrosulfate and decomposition of this compound under elimination of SO₃. In comparison with other hydrogen sulfates Ca(HSO₄)₂ shows a considerable increased O? H distances. The d-values of Ca(HSO₄)₂ are calculated and represented.     

Flue Gas Desulfurization by Dielectric Barrier Discharge

There are many problems with flue gas desulfurization by traditional gas ionization discharge, including the large size of the plasma source, high energy consumption, and the need for a traditional desulfurization method. This paper introduces oxidization of SO₂ to sulfuric acid (H₂SO₄) in a duct by reactive oxygen species (O₂ ⁺, O₃) produced by strong ionization dielectric barrier discharge. The entire plasma reaction process is completed within the duct without the use of absorbents, catalysts, or large plasma source. The reactive oxygen species O₂ ⁺ reacts with gaseous H₂O in the flue gas to generate ·OH radicals, which can oxidize trace amounts of SO₂ in large volumes of the flue gas to produce H₂SO₄. Sulfuric acid is also produced by O₃ oxidation of SO₂ to SO₃, and SO₃ reacting with gaseous H₂O in the flue gas. Experimental results showed that with a gas temperature of 22 °C and reactive oxygen species injection rate of 0.84 mg/L, the SO₂ removal rate was 81.4 %, and the SO₄ ^2? concentration in the recovered liquid H₂SO₄ reached 53.8 g/L.     

老山汉墓土遗址盐分调查与分布规律探索

老山汉墓土遗址中可溶-微溶盐导致遗址表面酥碱、起甲、泛白和块状脱落等病害较为严重.利用X射线荧光光谱(XRF)、X射线衍射仪(XRD)、X射线光电子能谱(XPS)以及离子色谱(IC)等方法测定了老山汉墓遗址不同取样位置及距遗址表面不同深度处可溶盐的成分及含量,并分析了盐分对遗址破坏的可能机制.结果表明,该遗址的主要有可溶盐有Na2SO4、Na2SO4·10H2O、Na Cl、Na12Mg7(SO4)13·15H2O,微溶盐有Ca SO4、Ca SO4·2H2O,此外还含有少量的Ca Cl2、KNO3、KCl、Mg Cl2、K2SO4、Mg SO4等盐分.随着取样深度增加,各盐分的种类及含量有所减少,此分布规律可能与可溶盐的赋存环境及水分运移有关.试验结果对于老山汉墓土遗址的保护措施具有一定的参考价值.     

Calcium sulphate scaling in membrane distillation process

Formation of precipitates containing CaSO₄ during membrane distillation, applied to the concentration of aqueous salt solutions, is discussed in this paper. It was found that the concentration of SO₄²⁻ ions in such solutions should not exceed 600 mg L⁻¹ when they are subjected to concentration. However, concentration of sulphates at the level of 800 mg L⁻¹ in the feed is permissible provided that the excess of CaSO₄ is removed in a crystallizer. Crystallisation of salts, mainly CaSO₄ · 2H₂O, on the surface and inside the membrane was observed at higher feed concentrations, causing damage of the module. Precipitation of calcium sulphate was also observed during the production of demineralised water when high values of the water recovery coefficient (above 90 %) were used. In this case, the formed precipitate also contained CaCO₃, the co-precipitation of which significantly changed the properties of the scaling layer. The precipitate containing both CaSO₄ and CaCO₃ was formed mainly on the membrane surface and it could easily be removed by rinsing the module with a HCl solution. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatransé Matliare, 26–30 May 2008.     

Dispersed platinum and tin polyaniline film electrodes for the anodes of the direct methanol fuel cell

To develop better and cheaper electrocatalysts for the oxidation of methanol in direct methanol fuel cells, several combinations of a conductive polymer polyaniline (PANI) and dispersed metal particles such as Pt and Sn were examined. The anodic current for the methanol oxidation (i _MeOH) showing the electrocatalytic activity of Pt particles was remarkably enhanced when the particles were dispersed on PANI films that should provide higher surface areas for the dispersed particles. The activity strongly depended on the morphology and the electric conductivity of the PANI films electropolymerized in five different acid solutions: H₂SO₄, HNO₃, HClO₄, HBF₄, and HCl. The highest activity was achieved using the dispersed Pt particle on PANI film electropolymerized from H₂SO₄ polymerizing solution. In order to reduce the dispersed amount of the expensive Pt particles, other metal particles were pre-dispersed on the PANI film prepared from the H₂SO₄ polymerizing solution, and then Pt particles were dispersed on the film. Among the pre-dispersed metal particles attempted here (Sn, Cu, Cr, Ni, In, Co, Sb, Bi, Pb, and Mn), the highest activity was obtained with Sn particles. When the ratio of dispersed Pt to Sn particles ranges from 32:68 to 100:0, i _MeOH is higher than that measured with the dispersed Pt particle on PANI films without the Sn particles. This means that the dispersed amount of the Pt particles could be reduced by utilizing dispersed Sn particles.     

ChemInform Abstract: Structure,Atomistic Simulations,and Phase Transition of Stoichiometric Yeelimite.

Ca₄[Al₆O₁₂]SO₄ (yeelimite) is prepared by solid state reaction of CaCO₃, Al₂O₃, and CaSO₄ (1300 °C, 4 h, slow cooling).     

A DFT study on PtMo resistance to SO2 poisoning

Pt is a catalyst in proton exchange membrane fuel cell (PEMFC), and its activity will be degraded in the air due to the existence of SOx impurities. On strategy is introducing of Mo into the Pt catalyst because it can improve the SOx -tolerance capacity. Based on the aforementioned phenomenon, a density function theory (DFT) study on SO x adsorbed on Pt(111) and PtMo(111) was performed to enhance Pt catalytic activity. The adsorption energy of adsorbed species, the net change, partial density of state (PDOS), and d-band center were calculated and analyzed comparatively. The results show that the presence of Mo-atom weakens the S-Pt bond strength and reduces the adsorption energies for SO2 , S and SO3 on PtMo(111). Moreover, the Mo atom weakens the effects of SO2 on the PtMo(111) electronic structure and makes the catalyst maintains its original electronic structure after SO2 adsorption as compared with Pt(111).     

Polyhalite and its analogous triple salts

Polyhalite (K₂SO₄ · MgSO₄ · 2CaSO₄ · 2H₂O) and analogue triple salts, where Mg²⁺ is substituted by Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺, have been synthesized. The salts were characterized by thermal analysis, Raman spectroscopy and X-ray powder diffraction. Diffraction patterns and Raman spectra resemble those of natural polyhalite, except K₂SO₄ · CuSO₄ · 2CaSO₄ · 2H₂O. The latter corresponds to the mineral leightonite, which is structurally different.     

碳纳米管-氧化铝:高抗硫及再生性能的Pt基催化剂载体及在NO_x还原反应中的应用(英文)

通过乙炔在Al2O3上的分解制备碳纳米管-氧化铝(Al2O3-CNTs)载体.采用浸渍法,分别制备了Pt/Ba/Al2O3-CNTs和Pt/Ba/Al2O3催化剂.利用XRD,SEM,TEM,低温N2物理吸附,XPS和in-situ DRIFTS等手段对催化剂的物化性质进行了表征.结果表明,在SO2存在下的NOx还原反应中,Pt/Ba/Al2O3-CNTs比Pt/Ba/Al2O3具有更高的抗SO2性能和再生性能.In-situ DRIFTS表明SO2的存在对NOx储存还原的途径没有影响.     

High temperature thermogravimetry of chlorides and sulphates : A study of the application to soils

Quantitative volatilization of NaCl and KCI occurs between 900 and 1200°. CaCl₂ and MgCl₂ are converted to the oxides at lower temperatures. CaSO₄, Na₂SO₄ and K₂SO₄ require the admixture of quartz to catalyse their decomposition with a total loss of SO₃ between 1150 and 1335°. MgSO₄ does not require quartz for its decomposition. The catalytic effects of Al₂O₃ and Fe₂O₃ on sulphate decomposition were also examined. The findings were applied to the analysis of saline soils. The thermogravimetric determination of chlorides in soils is subject to several interferences, but the conditions are more favourable for sulphates.