An experimental study into pyrite transformation during pyrolysis of Australian lignite samples

Transformation of pyrite in an Australian lignite during pyrolysis was studied using a thermogravimetric analyser (TGA) and a fixed-bed reactor. Samples of a lignite with high pyrite content, a pyrite-free lignite, acid-washed lignite, a pyrite mineral, and pyrite-free lignite blended with various amounts of the pyrite minerals were employed in the experimentation. It was shown that in nitrogen the pyrite mineral (S/Fe = 2) decomposes to troilite (S/Fe = 1) at ca. 1200 K and above this temperature, some of the troilite further decomposes to form elemental iron (S/Fe < 1). However, when blended with the demineralised lignite, the pyrite mineral can be completely decomposed to troilite at 873 K as confirmed by FTIR, SEM-EDS and XRD analyses on the resulting chars. During the TGA pyrolysis of the pyrite-lignite blends, two DTG peaks were observed, indicating two major decomposition events occurring. The first DTG peak was related to the devolatilisation of the lignite, while the second peak was attributed to the pyrite decomposition. Using a mass spectroscopy coupled with the TGA, it was revealed that hydrogen sulphide and a small quantity of sulphur dioxide were released during the pyrolysis of the pyrite-lignite blends. However, only sulphur dioxide was detected during the pyrolysis of the lignite with high pyrite content. This is attributed to the reactions of the inherent pyrite with oxygenates in the lignite structure. By analysing sulphur retention in the chars, it was shown that inherent inorganic matter in the raw lignite retains part of the sulphur in the solid phase. For the pyrite-lignite blends, pyrite initially decomposes to form FeS, some of which further decomposes to elemental iron at a much slower rate.     

Hot corrosion behaviors of gas tunnel type plasma sprayed La2Zr2O7 thermal barrier coatings

Gas tunnel type plasma sprayed free-standing La₂Zr₂O₇ coating specimens with a thickness of 300-400 μm were prepared under optimized operating conditions and were subjected to hot corrosion test in the presence of corrosive impurities such as V₂O₅, Na₂SO₄, and Na₂SO₄ + V₂O₅ mixtures (60:40 wt%) at two different temperatures for duration of 5 h, i.e. 1000 and 1350 K for V₂O₅ and Na₂SO₄ + V₂O₅ mixtures, 1200 and 1350 K for Na₂SO₄. For temperatures at 1350 K, the reaction mechanism of V₂O₅ and the mixture of Na₂SO₄ + V₂O₅ are similar and LaVO₄ is formed as the corrosive product, which leads to massive phase transformation from pyrochlore to tetragonal and monoclinic phases. Microstructural observations from planar reaction zone (PRZ) and melt infiltrated reaction zone (MIRZ) reveals that the present La₂Zr₂O₇ coating exhibits good hot corrosion resistance in V₂O₅ environment and moderate for the mixture of Na₂SO₄ + V₂O₅, but is worst in Na₂SO₄ environment.     

Synergy in devolatilization characteristics of lignite and hazelnut shell during co-pyrolysis

Coal/biomass blends were prepared in the lignite/biomass ratios of 98:2, 96:4, 94:6, 92:8, 90:10, and 80:20 using a Turkish lignite from Elbistan region and hazelnut shell. Co-pyrolysis characteristics were investigated in a thermogravimetric analyzer (TGA) from ambient to 1173 K with a linear heating rate of 20 K/min under dynamic nitrogen flow of 40 ml/min. Char products from pyrolysis were investigated using XRD and SEM techniques. Devolatilization yields from the blends were evaluated in a synergistic manner and found that the overall yields for all the blends exceeded the expected yields which calculated from the additive behavior. As regards to devolatilization characteristics in given temperature intervals, it was concluded that there was significant synergy between 400 and 600 K, whereas additive behavior took place beyond 600 K. No evidence of synergy was observed in the activation energies. It was also concluded that the addition of hazelnut shell into lignite contributed to the sulfur fixing potential of char in the form of CaS and CaSO₄.     

Comparison of sintering and compressive strength tendencies of a model coal mineral mixture heat-treated in inert and oxidizing atmospheres

The chemical interactions responsible for sintering in a coal mineral mixture were investigated in air and in N₂. A mineral mixture was made up by mixing kaolin, pyrite, quartz, calcite, hydromagnesite, FeCO₃ and anatase in a fixed ratio. The mineral mixture was pelletized and heat-treated up to 1100 °C in order to evaluate sintering by recording the compressive strength values and visual assessment with scanning electron microscopy (SEM). Chemical interactions responsible for the trends in the compressive strength results were investigated with simultaneous thermogravimetric and differential thermal analysis (TG/DTA), as well as X-ray diffraction. The results indicated that the formation of anhydrite (CaSO₄) was responsible for increased mechanical strength in the mineral mixture pellets heated in air at temperatures higher that 400 °C. CaSO₄ formed from the reaction of the decomposition products of pyrite and calcite (SO_x and CaO). The TG/DTA results also indicated that the reaction with pyrite in air caused the decomposition of calcite in the mixture at a lower temperature than was observed for calcite only. The pellets heated in N₂ did not increase in mechanical strength during heat-treatment due to the lack of CaSO₄ formation in the inert atmosphere. However, SEM analysis indicated that sintering did occur at the higher temperatures in N₂. A decrease was observed in the compressive strength values obtained in air at temperatures from 900 °C to 1100 °C. Reasons for the decreased compressive strengths may include increased porosity, decomposition of CaSO₄, and changes in the characteristics of the aluminosilicate phases.     

The effect of BaCO3 addition on the sintering behavior of lignite coal fly ash

The effect of BaCO₃ (witherite) addition on the sintering behavior of lignite coal fly ash taken from the Seyitömer power plant of Kütahya/Turkey was examined at temperatures of 1100, 1150 and 1200 °C in air atmosphere. Bloating of the fly ash samples sintered at 1150 °C was prevented, that is, the decomposition temperature of CaSO₄ in the fly ash is shifted to a higher temperature, and their physico-mechanical properties (porosity, water absorption, bulk density and bending strength) were improved with BaCO₃ addition. Positive effects of BaCO₃, however, were not seen on the fly ash samples sintered at 1100 °C. All the fly ash samples sintered at 1200 °C were bloated due to the gas evolving and also they melted. During the thermal treatment at 1150 °C a phase transformation from CaSO₄ (anhydrite) to BaSO₄ (Barite) occurred in the fly ash with BaCO₃ addition as seen from the X-ray diffraction (XRD) patterns and the bar shaped fly ash samples with BaCO₃ saved their structural integrity up to 1150 °C.     

Biomass pyrolysis experiments in an analytical entrained flow reactor between 1073 K and 1273 K

Experiments are performed in an entrained flow reactor to better understand the kinetic processes involved in biomass pyrolysis under high temperatures (1073-1273 K) and fast heating condition (>500 K s⁻¹). The influence of the particle size (0.4 and 1.1 mm), of the temperature (1073-1273 K), of the presence of steam in the gas atmosphere (0 and 20 vol%) and of the residence time (between 0.7 and 3.5 s for gas) on conversion and selectivity is studied. Under these conditions, the particle size is the most crucial parameter that influences decomposition. For 1.1 mm particles, pyrolysis requires more than 0.5 s and heat transfer processes are limiting. For 0.4 mm particles, pyrolysis seems to be finished before 0.5 s. More than 70 wt% of gas is produced. Forty percent of the initial carbon is found in CO; less than 5% is found in CO₂. The hydrogen content is almost equally distributed among H₂, H₂O and light hydrocarbons (CH₄, C₂H₂, C₂H₄). Under these conditions, the evolution of the produced gas mixture is not very significant during the first few seconds, even if there seems to be some reactions between H₂, the C₂ and tars.     

Processing and performance of solid oxide fuel cell with Gd-doped ceria electrolyte

Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La_0.8Sr_0.2)(Co_0.8Fe_0.2)O₃ cathode using H₂ fuel containing 3 vol% H₂O. A maximum power density, 436 mW/cm², was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N₂ atmosphere of 10⁻¹⁵-10⁰ Pa oxygen partial pressures (Po₂) at 773-1073 K was independent of Po₂, which indicated the diffusion of oxide ions. The conductivity of GDC in H₂O/H₂ atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H₂ → 2H⁺ + 2e⁻). The hole conductivity was observed at 873 K in Po₂ = 10⁰-10⁴ Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H₂ fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.     

Joining of Si3N4 to Si3N4 using a AuPd(Co,Ni)–V filler alloy and the interfacial reactions

Au38.0–Pd28.0–Co18.0–Ni7.0–V9.0 (in wt%) alloy was designed as a filler for joining Si₃N₄. The filler alloy showed a contact angle of 77.2° on Si₃N₄ ceramic at 1473 K. The Si₃N₄/Si₃N₄ joint brazed with the rapidly-solidified filler foils at 1443 K for 10 min exhibits an average three-point bend strength of 320.7 MPa at room temperature and the strength values are 217.9 MPa and 102.9 MPa at 1073 K and 1173 K respectively. The interfacial reaction products were composed of V₂N and Pd₂Si, and the elements Co and Ni in the brazing alloy did not participate in the interfacial reactions. The coarse-network-like distribution of refractory Pd₂Si compound within the Au–Pd–Co–Ni alloy matrix throughout the joint contributes to the stable high-temperature joint strengths.     

Study of the preasphaltenes of coal liquefaction and its hydro-conversion kinetics catalyzed by SO4/ZrO2

The investigation of hydro-conversion behavior of the heavy intermediate products derived from coal direct liquefaction is advantageous to optimize the technological conditions of direct coal liquefaction and improve the oil yield. In this paper, the hydro-conversion of preasphaltenes catalyzed by SO₄²⁻/ZrO₂ solid acid was investigated based on the structural characterization of preasphaltenes and its hydro-conversion products, and the determination of products distribution and the kinetics of preasphaltenes hydro-conversion. The results indicated that the content of condensed aromatic rings increased, and the contents of hydrogen, oxygen and aliphatic side chains of preasphaltenes decreased with the increase of coal liquefaction temperature. The preasphaltenes showed higher hydro-conversion reactivity while SO₄²⁻/ZrO₂ solid acid was used as catalyst. Higher temperature and longer time were in favor of increasing the conversion and the oil + gas yield. The conversion of preasphaltenes hydro-conversion under 425 °C, for 40 min reached 81.3% with 51.2% oil + gas yield. SO₄²⁻/ZrO₂ solid acid was in favor of the catalytic cracking rather than the catalytic hydrogenation in the hydro-conversion of preasphaltenes. The activation energy of preasphaltenes conversion into asphaltenes was 72 kJ/mol. The regressive reactions were only observed at a higher temperature.     

Thermodynamic modeling of CO2 solubility in aqueous solutions of NaCl and Na2SO4

A thermodynamic model based on the electrolyte NRTL activity coefficient equation and PC-SAFT equation-of-state is developed for CO₂ solubility in aqueous solutions of NaCl and Na₂SO₄ with temperature up to 473.15 K, pressure up to 150 MPa, and salt concentrations up to saturation. The Henry's constant parameters of CO₂ in H₂O and the characteristic volume parameters for CO₂ required for pressure correction of Henry's constant are identified from fitting the experimental gas solubility of CO₂ in pure water with temperature up to 473.15 K and pressure up to 150 MPa. The NRTL binary parameters for the CO₂-(Na⁺, Cl⁻) pair and the CO₂-(Na⁺, SO₄²⁻) pair are regressed against the experimental VLE data for the CO₂-NaCl-H₂O ternary system up to 373.15 K and 20 MPa and the CO₂-Na₂SO₄-H₂O ternary system up to 433.15 K and 13 MPa, respectively. Model calculations on solubility and heat of solution of CO₂ in pure water and aqueous solutions of NaCl and Na₂SO₄ are compared to the available experimental data of the CO₂-H₂O binary, CO₂-NaCl-H₂O ternary and CO₂-Na₂SO₄-H₂O ternary systems with excellent results.     

Influence of ionic speciation on electrocatalytic performance of polyaniline coated platinum electrode: Fe(III)/Fe(II) redox reaction

Porous-polyaniline coated Pt electrode (PANI/Pt) was electro-synthesized potentiodynamically in 0.1 M aniline + 0.5 M H₂SO₄ and morphologically characterized by scanning electron microscopy (SEM). Nature of predominant Fe-species in HCl and H₂SO₄ was checked by UV-vis spectrophotometry. Electrocatalysis of Fe(III)/Fe(II) reaction was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for three different solution compositions viz. (i) FeCl₃/FeCl₂ in 1 M HCl, (ii) FeCl₃/FeCl₂ in 0.5 M H₂SO₄ and (iii) Fe₂(SO₄)₃/FeSO₄ in 0.5 M H₂SO₄. For different thicknesses of PANI, the peak current increased irrespective of the nature of the Fe-species, but the polarity of the charge on the Fe-species showed great influence on reversibility of electrocatalysis by PANI/Pt. The Donnan interaction of the polyaniline modified electrode for the three compositions was investigated with respect to [Fe(CN)₆]³⁻/H₂[Fe(CN)₆]²⁻ which are believed to be the predominant species present in K₃[Fe(CN)₆]/K₄[Fe(CN)₆] solution in 0.5 M H₂SO₄. The electrocatalytic performance of PANI/Pt for Fe(III)/Fe(II) redox reaction was found superior in HCl compared to that in H₂SO₄.     

Study on the Anti-Coking Nature of Ni/SrTiO3 Catalysts by the CH4 Pyrolysis

A solid phase crystallization (spc) method was applied for the preparation of SrTiO₃-supported Ni catalysts and compared to the impregnation (imp) method. spc-Ni_0.2/SrTiO₃ has highly dispersed and stable Ni metal particles resulting in higher activity and higher sustainability against coking than imp-Ni_0.2/SrTiO₃ in the partial oxidation of CH₄. Both catalysts were tested for the CH₄ pyrolysis in order to elucidate the catalytic nature against coking of spc-Ni_0.2/SrTiO₃. The amount of carbon and the rate of H₂ formation were similar over both catalysts at both 773 and 1073 K. On both catalysts, CH₄ continuously decomposed at 773 K, while the rate of CH₄ pyrolysis quickly decreased at 1073 K. Fibrous carbons grew up with a Ni metal particle on the tip of the fiber at 773 K, while carbon balls and short carbon fibers with a Ni metal particle encapsulated inside formed and no sufficient growth of the fiber was observed at 1073 K. The carbon species formed at 773 K was hydrogenated completely to CH₄ around 873 K, while the hydrogenation of that formed at 1073 K needed higher temperature around 1073 K. However, the carbon species formed on both the catalysts at either 773 or 1073 K was completely oxidized around 773 K. Thus, judging from the anti-coking nature, the behaviors in the CH₄ pyrolysis are similar over both catalysts, nonetheless spc-Ni_0.2/SrTiO₃ was far superior to imp-Ni_0.2/SrTiO₃ in the CH₄ oxidation. It is likely that the high sustainability against coking of spc-Ni_0.2/SrTiO₃ is not due to its intrinsic nature suppressing the coking but due to its high activity of reforming which can quickly eliminate the carbon formed on the catalyst surface.     

DRIFTS study of the catalytic N2O reduction by SO2 on FeZSM-5

SO₂ has been recognized as an effective reducing agent for N₂O over iron-containing zeolite catalysts, lowering the operation temperature up to 100 K with respect to the direct N₂O decomposition. This unique behavior contrasts with the common poisoning effect of SO₂ over other active de-N₂O metals (e.g. Co, Cu, Rh, and Ru). The formation of surface sulfates has been generally posed as the main cause for catalyst deactivation by SO₂. Through the use of in situ infrared spectroscopy (DRIFTS), we show that steam-activated FeZSM-5 indeed builds up stable sulfate species during the N₂O + SO₂ reaction. Significant amounts of sulfur were detected in the used catalyst by elemental analysis and X-ray photoelectron spectroscopy. However, the enhanced N₂O conversion is remarkably stable, indicating that the reducing action by SO₂ and the sulfation of the surface are decoupled. The resulting sulfate species are thus spectators in the catalytic process and do not block or alter the structure of the active sites for N₂O reduction and decomposition.     

Synthesis and characterization of LiFePO4/(Ag + C) composite cathodes with nano-carbon webs

LiFePO₄/(Ag + C) composite cathodes with a new type of nano-sized carbon webs were synthesized by two methods of an aqueous co-precipitation and a sol-gel process, respectively. Simultaneous thermogravimetric-differential thermal analysis indicates that the crystallization temperature of LiFePO₄ is about 455-466 °C, which is close to the pyrolysis temperature of polypropylene, 460 °C. The silver and carbon co-modifying does not affect the olivine structure of LiFePO₄ but improves its kinetics in terms of discharge capacity and rate capability. Discharge capacities were improved from 153.4 mA h g^− 1 of LiFePO₄/C to 160.5 mA h g^− 1and 162.1 mA h g^− 1 for LiFePO₄/(Ag + C) cathodes synthesized by the co-precipitation and sol-gel methods, respectively. The possible reasons for the small difference in discharge capacity of two LiFePO₄/(Ag + C) cathodes were discussed. AC impedance measurements show that the Ag + C co-modification decreases the charge transfer resistance of LiFePO₄/(Ag + C) cathodes.     

Influence of bath temperature and bath composition on Co-Ag electrodeposition

A study of the best conditions to prepare smooth heterogeneous Co-Ag films with low amounts of S from a thiourea-based electrolytic bath has been performed. Using a 0.01 M AgClO₄ + 0.1 M Co(ClO₄)₂ + 0.1 M thiourea + 0.1 M sodium gluconate + 0.3 M H₃BO₃ + 0.1 M NaClO₄ bath, low temperature (10 °C) allowed obtaining compact and smooth deposits containing 2 wt.% sulphur. Decreasing thiourea content 0.06 M and increasing gluconate concentration up to 0.3 M, better deposits (more compact with lower sulphur content (1.2 wt.%)) were obtained. A clear influence of the species present in the bath on the film quality was observed: while gluconate favoured film cohesion, boric acid hindered hydrogen adsorption. For all films, fcc-Ag, hcp-Co and hcp-CoAg₃ phases were always detected by XRD, TEM and electron diffraction, their proportions varying with the electrodeposition conditions. Magnetic measurements revealed that the increase in the CoAg₃ led to an increase in the film coercivity. GMR values were only measured at cryogenic temperatures, they being higher for the deposits with the lowest sulphur content revealing that sulphur exerts a negative effect on magnetoresistance.     

Phase stability and hot corrosion behavior of ZrO2–Ta2O5 compound in Na2SO4–V2O5 mixtures at elevated temperatures

For thermal barrier coating (TBC) applications, yttria stabilized zirconia (YSZ) is susceptible to hot corrosion. This paper examines the hot corrosion performance of ZrO₂/Ta₂O₅ compounds. Different compositions of ZrO₂–Ta₂O₅ samples in the presence of molten mixture of Na₂SO₄+V₂O₅ at 1100 °C were tested. The compositions were selected to form tetragonal and orthorhombic phases of zirconium-tantalum oxides. Results show that orthorhombic zirconium-tantalum oxide is more stable, both thermally and chemically in Na₂SO₄+V₂O₅ media at 1100 °C, and shows a better hot corrosion resistance than the tetragonal phase.     

Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N₂O. HCl greatly increases CO and CH₄ emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO₂ system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K.     

Influences of carbon structure on the reactivities of lignite char reacting with CO2 and NO

Raw and demineralized lignite samples were pyrolyzed from 773 to 1673 K to generate chars. The chars were characterized with Raman spectroscopy for the structure evolution. The reactivities of the chars reacting with CO₂ and NO were measured with thermogravimetric analysis. The derived reactivity indexes were correlated with the treatment temperature and the Raman structural parameters to demonstrate the applicability of Raman spectroscopy for evaluation of the reactivities of char CO₂ gasification and char-NO reaction. It was found that char microstructure evolution with the treatment temperature could be represented by Raman band area ratios. I_D1/I_G and I_G/I_ALL represented the evolution of the ordered carbon structure while the combination of I_D3/(I_G + I_D2 + I_D3) reflected the evolution of the amorphous carbon structure of the lignite chars with increasing the treatment temperature from 773 to 1673 K. Reactivity indexes of the demineralized chars reacting with both CO₂ and NO were found to increase with increasing the treatment temperature, implying that the structure ordering did result in the losses of the reactivities. Higher reactivities of the non-demineralized chars indicated the catalytic role of inorganic matter in the reactions with both gases. I_D1/I_G and I_G/I_ALL had good linear correlations with the reactivities particularly of the demineralized chars if considering the structure evolution behaviors at lower and higher temperatures, respectively. I_D3/(I_G + I_D2 + I_D3) was found to have fairly good linear correlations with the reactivity indexes of the lignite chars generated over the whole temperature range.     

Effects of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels in acidic chloride solutions

The role of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels was investigated in 0.5 M H₂SO₄, 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions using potentiodynamic polarization, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. The passive film stability was enhanced in 0.5 M H₂SO₄ and the pitting resistance was improved in 3.5% NaCl solution by more nitrogen addition. The influence of nitrogen extended the whole anodic polarization region in 0.5 M H₂SO₄ + 0.5 M NaCl solution, as demonstrated by the enhanced dissolution resistance, promoted adsorption and passivation process, improved film protection and pitting resistance with increasing nitrogen content. Possible mechanisms relating to the role of nitrogen in different potential regions were discussed.     

Decomposition behavior of CaSO4 during potassium extraction from a potash feldspar-CaSO4 binary system by calcination

The extraction of potassium from a tablet mixture of K-feldspar ore and CaSO_4by roasting was studied with a focus on the effects of the decomposition behavior of CaSO_4on the potassium extraction process.The roasted slags were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy,and thermogravimetric(TG)analysis.The XRD analysis revealed that hydrosoluble mischcrystal K_2Ca_2(SO_4)_3was obtained by ion exchange of Ca~(2+)in CaSO_4and K~+in KAlSi_3O_8.Meanwhile,the intermediate product,SiO_2,separated from KAl Si_3O_8and reacted with CaSO_4to decompose CaSO_4.The SEM results showed that some blowholes emerged on the surface of the CaSO_4particles when they reacted with SiO_2at 1200°C,which indicates that SO_2and O_2gases were released from CaSO_4.The TG curves displayed that pure CaSO_4could not be decomposed below 1200°C,while the mixture of K-feldspar ore and CaSO_4began to lose weight at 1000°C.The extraction rate of potassium and decomposition rate of CaSO_4were 62%and 44%,respectively,at a mass ratio of CaSO_4to K-feldspar ore of 3:1,temperature of 1200°C,tablet-forming pressure of6 MPa,and roasting time of 2 h.The decomposition of CaSO_4reduced the potassium extraction rate;therefore,the required amount of CaSO_4was more than the theoretical amount.However,excess CaSO_4was also undesirable for the potassium extraction reaction because a massive amount of SO_2and O_2gas were derived from the decomposition of CaSO_4,which provided poor contact between the reactants.The SO_2released from CaSO_4decomposition can be effectively recycled.