Showing papers on "Inert gas published in 2014"

Effects of pyrolysis parameters on hydrogen formations from biomass: a review

Abstract: This study investigates the effects of different parameters such as biomass composition, moisture content, particle size, heating rate, temperature, inert gas, reactor system, and catalyst on the production of hydrogen gas (HG) and other gases (OGs) such as CO2, CO, CH4, C2H6, and so on. The reformation of OGs into H2 via the shift reaction significantly increases the total HG formation during biomass pyrolysis. Biomass raw material is capable of producing different proportions of HG at different temperatures because the raw material structure varies from one material to another. It is very puzzling that the formation of HG and total gas (TG) could either increase or decrease with moisture and this result varied between researchers. Smaller particles are more suitable than larger ones in terms of HG and TG formation. Additionally, longer residence times and higher temperatures favor good HG yield while the heating rate is a function of heat flux and particle size of biomass fuel is supposed to increase the pyrolytic gases and properties. Moreover, the heating rate would play a smaller role on the process when the system is introduced with inert gas and if the purpose is to maximize the production of TGs, secondary reactions such as thermal cracking, re-polymerization, and re-condensation should be maximized because the inert gas removes the volatiles from the pyrolysis environment. Therefore, the ultimate product of biomass conversion is dependent on the reactor design and type of feedstock in the presence of appropriate catalysts.

Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs).

Abstract: Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300–1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based pre...

Lattice oxygen activity in Pr- and La-Doped CeO2 for low-temperature soot oxidation

Abstract: Effects of Pr- and La-doped CeO2 on desorption of active lattice oxygen to soot oxidation were studied. Thermogravimetric analysis under N2 flow indicated that, despite the decrease in reducible Ce content, the amount of oxygen deficiency increases with increasing La content (x) to 15 mol % in Ce0.80–xPr0.20LaxO2. In inert atmosphere, the introduction of oxygen vacancies by doping La increased the available lattice oxygen for desorption. In the oxygen isotopic exchange, under 18O2 flow, desorption of oxygen molecules containing lattice oxygen atom (16O) was favored because of Pr and La doping in CeO2. These dopants increase the exchange rate constant between gas-phase and lattice oxygen atoms. The apparent activation energy, derived from an Arrhenius plot, for CeO2, Ce0.80Pr0.20O2, and Ce0.65 Pr0.20La0.15O2 were 311, 230, and 135 kJ/mol, respectively. The values indicated that Pr and La doping causes facile oxygen exchange between the gas phase and the solid. The comparison of the rate constants for 16O18...

CuO-Based Oxygen-Carrier Particles for Chemical-Looping with Oxygen Uncoupling - Experiments in Batch Reactor and in Continuous Operation

Abstract: Chemical-looping with oxygen uncoupling (CLOU) is an innovative method to oxidize fuels with inherent CO2 sequestration, which utilizes a solid oxygen-carrier material to provide O-2 for fuel combustion. In this study, a range of CuO-based oxygen-carrier particles have been manufactured and examined. Out of 24 samples prepared, 10 were examined in a batch fluidized-bed reactor, of which three were selected for further examination by continuous operation in a small circulating fluidized-bed reactor system. Composite particles consisting of CuO as active phase and support material such as ZrO2, YSZ, CeO2, and MgAl2O4 were capable of providing full conversion of CH4 at 900 and 925 degrees C, and were also found to release gas phase O-2 into inert atmosphere when fluidized with N-2. Particles using semiactive support such as Fe2O3, Mn2O3, and Al2O3 formed combined spinel phases with CuO. Such materials were still capable of releasing gas phase O-2 but at different concentrations as compared to particles with inert support. Materials with semiactive support had less good reactivity with CH4. No formation of unexpected phases could be detected by X-ray diffractometry, and all chemical reactions were completely reversible. The three materials that were examined in continuous operation were readily capable of providing more or less full conversion of natural gas under the chosen conditions. However, they also suffered from quick attrition and turned into a flour-like substance after a few hours of continuous operation with fuel. Crushing strength analysis showed that particles used in continuous operation were physically much weaker than fresh. In total, 23 h of continuous operation with fuel addition was recorded.

In Situ Preparation of Highly Stable Ni-Based Supported Catalysts by Solution Combustion Synthesis

Abstract: Solution combustion synthesis (SCS) is typically used to produce nanostructured oxides and bulk metallic materials for a variety of application including catalysis. Here, we report in situ, one-step SCS of high surface area (155 m2/g) Ni catalysts supported on fumed silica (SiO2). Time-resolved X-ray diffraction is used to investigate the dynamics of phase formation during combustion of nickel nitrate–glycine–ammonium nitrate reactive gels impregnated onto porous SiO2. It is shown that highly dispersed nickel nanoparticles (5 nm) formed in the reaction front are followed by their rapid oxidation by air oxygen. To prevent the undesired oxidation process, the synthesis was conducted in an inert atmosphere (argon, helium). It is demonstrated that low concentration oxygen impurity (less than 0.001 wt %) in the inert gas passivates the Ni nanoparticles through the formation of a thin amorphous oxide layer. The thus prepared Ni/SiO2 supported catalyst possesses high activity during the ethanol decomposition tow...

Activation of carbon-supported platinum catalysts by sodium for the low-temperature water-gas shift reaction

Abstract: The activation of multi-walled carbon nanotube-supported platinum catalysts for the low-temperature water-gas shift reaction is demonstrated by the addition of sodium. Nitric acid oxidation of the carbon nanotubes allows for the addition of sodium through ion-exchange and creates anchoring sites for platinum. We show that an oxidized platinum state is stabilized by the presence of sodium. Evidence for a sodium-promoted Pt-(OH)x active site is given through XPS analysis of the catalysts before and after reaction and confirmed by CO-TPR. Removal of the oxygen groups and partial removal of sodium by annealing the Na-modified carbon nanotubes to 800 °C in inert atmosphere creates a surface on which Pt is initially very active, but of lower stability due to the absence of a sufficient number of surface sodium anchoring sites.

Production of aromatics by catalytic fast pyrolysis of cellulose in a bubbling fluidized bed reactor

Abstract: Catalytic fast pyrolysis of cellulose was studied at 500°C using a ZSM-5 catalyst in a bubbling fluidized bed reactor constructed from a 4.92-cm ID pipe. Inert gas was fed from below through the distributor plate and from above through a vertical feed tube along with cellulose. Flowing 34% of the total fluidization gas through the feed tube led to the optimal mixing of the pyrolysis vapors into the catalyst bed, which experimentally corresponded to 29.5% carbon aromatic yield. Aromatic yield reached a maximum of 31.6% carbon with increasing gas residence time by changing the catalyst bed height. Increasing the hole-spacing in the distributor plate was shown to have negligible effect on average bubble diameter and hence did not change the product distribution. Aromatic yields of up to 39.5% carbon were obtained when all studied parameters were optimized. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1320–1335, 2014

Experimental Investigation of Mildly Pressurized Torrefaction in Air and Nitrogen

Abstract: Torrefaction, a mild roasting process in inert atmosphere, is an emerging thermo-chemical pretreatment process that can eliminate many of the shortcomings of raw biomass, but the supply of an inert...

Sulfur Tolerance of CaxMn1–yMyO3−δ (M = Mg, Ti) Perovskite-Type Oxygen Carriers in Chemical-Looping with Oxygen Uncoupling (CLOU)

Abstract: Perovskite-structured oxygen carriers of the type CaxMn1–yMyO3−δ (M = Mg, Ti) have been investigated for the CLOU process. The oxygen carrier particles were produced by spray-drying and were calcined at 1300 °C for 4 h. A batch fluidized-bed reactor was used to investigate the chemical-looping characteristics of the materials. The effect of calcium content, dopants (Mg and Ti), and operating temperature (900, 950, 1000, and 1050 °C) on the oxygen uncoupling property and the reactivity with CH4 in the presence and absence of SO2 was evaluated. In addition, the attrition resistance and mechanical integrity of the oxygen carriers were examined in a jet-cup attrition rig. All of the investigated perovskite-type materials were able to release gas phase oxygen in inert atmosphere. Their reactivity with methane was high and increased with temperature and calcium content, approaching complete gas yield at 1000 °C. The reactivity decreased in the presence of SO2 for all of the investigated oxygen carriers. Decreasing the calcium content resulted in a less severe decrease in reactivity in the presence of SO2, with the exception of materials doped with both Mg and Ti, for which a higher resistance to sulfur deactivation could be maintained even at higher calcium contents. The drop in reactivity in the presence of SO2 also decreased at higher temperatures, and at 1050 °C, the decrease in the reactivity of the Mg- and Ti-doped material was minimal. Sulfur balance over the reactor system indicated that the fraction of the introduced SO2 that passed through the reactor increased with temperature. It was shown that it is possible to regenerate the oxygen carriers during reduction in the absence of SO2. Most of the materials also showed relatively low attrition rates. The results indicate that it is possible to modify the operating conditions and properties of perovskite-type oxygen carriers to decrease or avoid their deactivation by sulfur.

Thermolytic Decomposition of Ethane 1,2-Diamineborane Investigated by Thermoanalytical Methods and in Situ Vibrational Spectroscopy

Abstract: Ethane 1,2-diamineborane (BH3NH2CH2CH2NH2BH3, EDAB hereafter) samples have been synthesized by reacting ethylenediamine dihydrochloride with sodium borohydride in tetrahydrofuran solution. Structural and bonding properties of EDAB have been characterized by liquid-state nuclear magnetic resonance, X-ray powder diffraction, and vibrational spectroscopy (infrared and Raman). The thermolytic decomposition of EDAB has been investigated by means of combined thermogravimetry, differential thermal analysis, and mass spectrometry measurements, both under vacuum and inert gas flow conditions. These experiments allow the determination of the enthalpies and activation energies of two hydrogen desorption stages below 520 K as well as the yields and purity of the released gases. These results show that EDAB presents a thermal stability, both under vacuum and under inert gas flow, higher than that of its parent counterparts methylamine borane (BH3NH2CH3) and ammonia borane (BH3NH3). Contrary to those compounds, EDAB re...

Experimental Investigation of Based Oxygen Carriers Used in Continuous Chemical-Looping Combustion

Abstract: Three materials of perovskite structure, (M = Mg or Mg and Ti), have been examined as oxygen carriers in continuous operation of chemical-looping combustion (CLC) in a circulating fluidized bed system with the designed fuel power 300 W. Natural gas was used as fuel. All three materials were capable of completely converting the fuel to carbon dioxide and water at 900°C. All materials also showed the ability to release gas phase oxygen when fluidized by inert gas at elevated temperature (700–950°C); that is, they were suitable for chemical looping with oxygen uncoupling (CLOU). Both fuel conversion and oxygen release improved with temperature. All three materials also showed good mechanical integrity, as the fraction of fines collected during experiments was small. These results indicate that the materials are promising oxygen carriers for chemical-looping combustion.

Warm Spray Forming of Ti-6Al-4V

Abstract: Warm spray (WS) is a modification of high-velocity oxy-fuel spraying, in which the temperature of the supersonic gas flow generated by the combustion of kerosene and oxygen is controlled by diluting the combustion flame with an inert gas such as nitrogen. The inert gas is injected into the mixing chamber placed between the combustion chamber and the powder feed ports, thus the temperature of the propellant gas can be controlled from ~700 to 2,000 K. Since WS allows for higher particle temperatures in comparison to cold spray, warm sprayed particles are more softened upon impact, thus resulting in greater deformation facilitating the formation of shear instability for bonding. Recently, the combustion pressure of WS has been increased from 1 (low-pressure warm spray) to 4 MPa (high-pressure warm spray) in order to increase the velocity of sprayed particles. Effects of spray parameters on microstructure, mechanical properties, and splats formation of Ti-6Al-4V were systematically studied. Obtained coatings were examined by analyzing the coating cross-section images, microhardness as well as oxygen content. In addition, flattening ratio of splats was calculated as a function of nitrogen flow rate. It was found that the increased particle velocity caused by the increased combustion pressure had significant beneficial effects in terms of improving density and controlling the oxygen level in the sprayed Ti-6Al-4V coatings.

Natural iron ore as an oxygen carrier for biomass chemical looping gasification in a fluidized bed reactor

Abstract: Chemical looping gasification (CLG) of biomass was performed in a thermogravimetric analyzer (TG) reactor together with a fluidized reactor with natural iron ore oxygen carrier under inert atmosphere. TG experiments indicated that iron ore can provide oxygen source for biomass conversion in the form of lattice oxygen. In the fluidized bed experiments, the influences of reduction temperature on CLG of biomass were emphatically investigated in terms of gas distribution and solid characters. The gas yield and carbon conversion increased, but the tar content decreased in the temperature range of 1,013–1,213 K. In this temperature range, the conversion of oxygen carrier increased from 24.11 to 53.59 %. X-ray diffraction analysis shows that more FeO was generated with temperature increasing. Scanning electron microscope analysis indicates that sintering was observed at elevated temperature. An optimum mass ratio of biomass/oxygen carrier (B/O) of 0.67 was obtained with aim of achieving maximum gasification efficiency of 76.93 %.

Production and examination of oxygen-carrier materials based on manganese ores and Ca(OH)2 in chemical looping with oxygen uncoupling

Abstract: This study concerns production of oxygen-carrier particles using six different manganese ores. The ores were made to react with Ca(OH)2 at elevated temperature, forming calcium manganite. The method utilized to manufacture particles was extrusion. Methane and syngas conversion and oxygen release of the samples in inert atmosphere were investigated. The oxygen carrier based on South African (B) manganese ore, showed good methane conversion and was able to transfer oxygen corresponding to 1.5% of its mass during reduction with gaseous fuel. All examined oxygen carriers were capable of converting syngas completely. The ability to release gaseous oxygen was examined by adding wood char in a stream of nitrogen for four selected samples sintered at 1300°C/6 h. These samples released an amount of oxygen corresponding to 0.37–0.68% of their mass. The reactivity of all the ores was improved after the proposed treatments. Reactivity results of the oxygen carrier made from South African (B) ore and Ca(OH)2, sintered at 1300°C for 6 h were the most promising. Attrition measurements with a jet cup of the oxygen carriers sintered at 1300°C/6 h showed that all the samples made from ores were at least three times more resistant to mechanical attrition compared to particles made from synthetic Mn2O3. Producing feasible oxygen carriers directly from ores could potentially cut the cost of chemical looping with oxygen uncoupling and have a significant impact on its competitiveness among other carbon capture technologies.