NOx sorption–desorption study: application to diesel and lean-burn exhaust gas (selective NOx recirculation technique)

NO_x adsorption/desorption capacities of barium aluminates and BaSnO₃ were measured under representative exhaust gas mixture at temperatures below 550°C and compared to those of bulk BaO. The capacities are high and the test of sorption–desorption is reproducible on barium aluminate and BaSnO₃, while this is not the case on BaO. The difference is due to the electronic environment of barium oxide. If BaO is not engaged in a chemical bond, progressive formation of high stability carbonates is observed. This is not the case with barium aluminate and BaSnO₃, where carbonation does not take place because the competition between nitrate and carbonate formation is in favour of the nitrate due to its chemical nature. An N-bounded nitrate, with IR frequencies at 1360 and 1415 cm⁻¹, is formed on barium aluminate and BaSnO₃ and not on bulk BaO.     

Removal of NOx: Part I. Sorption/desorption processes on barium aluminate

NO_x adsorption/desorption capacities of barium aluminates were measured under representative exhaust gas mixture at temperatures below 550°C. The solid doped with Pt or not, exhibits good NO₂ sorption capacities with a reversible adsorption to desorption process. With bulk BaO, desorption was observed at high temperature. The different behaviour between the two catalysts is explained by the fact that strongly bonded carbonates are formed on bulk BaO while they do not exist on barium aluminate, therefore allowing the formation of nitrates which can be decomposed by a thermal process. SO₂ poisoning was also studied.     

Storage of NO2 on BaO/TiO2 and the influence of NO

The influence of NO on the adsorption and desorption of NO₂ on BaO/TiO₂ has been studied under lean conditions. The adsorption of NO₂ involves the disproportionation of NO₂ into an adsorbed nitrate species and NO released to the gas phase with a 3:1 ratio,

BaO+3NO₂→NO+Ba(NO₃)₂.

Three different nitrate species form on the catalyst: surface nitrates on the TiO₂ support, surface nitrates on BaO, and bulk barium nitrate. The stability of the three species in different gas feeds was investigated by temperature-programmed desorption (TPD).

The reverse reaction of the NO₂ disproportionation has also been observed. If NO is added to the feed, nitrates previously formed on the sorbent will decompose into NO₂. Therefore, the above chemical equation should be considered as an equilibrium reaction. Applying this finding to the NO_x storage and reduction catalyst means that NO probably reacts with the previously formed nitrates yielding NO₂ as an intermediate product. This NO₂ is subsequently reduced by the reducing agents (hydrocarbons and CO) present during the regeneration period.     

Characterisation by TPR, XRD and NOx Storage Capacity Measurements of the Ageing by Thermal Treatment and SO2 Poisoning of a Pt/Ba/Al NOx-Trap Model Catalyst

The deactivation of a Pt/Ba/Al₂O₃ NO _x -trap model catalyst submitted to SO₂ treatment and/or thermal ageing at 800 °C was studied by H₂ temperature programmed reduction (TPR), X-ray diffraction (XRD) and NO _x storage capacity measurements.The X-ray diffractogram of the fresh sample exhibits peaks characteristic for barium carbonate. Thermal ageing leads to the decomposition of barium carbonate and to the formation of BaAl₂O₄. The TPR profile of the sulphated sample shows the presence of (i) surface aluminium sulphates, (ii) surface barium sulphates, (iii) bulk barium sulphates. The exposure to SO₂ after ageing leads to a small decrease of the surface barium-based sulphates, expected mainly as aluminate barium sulphates. This evolution can be attributed to a sintering of the storage material. TPR experiments also show that thermal treatment at 800 °C after the exposure to SO₂ involves the decomposition of aluminium surface sulphates to give mainly bulk barium sulphates, also pointed out by XRD. Thus, the thermal treatment at 800 °C leads to a stabilization of the sulphates.These results are in accordance with the NO _x storage capacity measurements. On non-sulphated catalysts, the treatment at 800 °C induces to a decrease of the NO _x storage capacity, showing that barium aluminate presents a lower NO _x storage capacity than barium carbonate. Sulphation strongly decreases the NO _x storage capacity of catalysts, whatever the initial thermal treatment, showing that barium sulphates inhibit the NO₂ adsorption. Moreover, the platinum activity for the NO to NO₂ oxidation is lowered by thermal treatments.     

二氧化锡不同掺杂方式对钛酸钡介电性能的影响

研究了二氧化锡不同掺杂方式对钛酸钡介电性能的影响。采用固相法制备出掺杂比例为2mol%SnO2&BaO、2mol%SnO2和4mol%SnO2三组不同方式SnO2掺杂钛酸钡样品。结果表明,两种掺杂方式对钛酸钡的作用效果截然不同,SnO2-BaO共掺杂会以BaSnO3的形式固溶入钛酸钡晶格,从而增大其介电常数,减小居里温度,同时介电损耗不会增大;SnO2单独掺杂则会引入Sn4+杂质离子,造成钛酸钡介电常数的减小以及介电损耗的增大,导致介电性能的劣化。     

Nature of Cation Vacancies Formed to Compensate Donors during Oxidation of Barium Titanate

Oxidative cooling is a critical step in the processing of barrier layer electroceramics based on BaTiO₃. While it has been proposed that barium vacancies are formed at the grain boundaries to compensate donors,^{1, 2} no direct evidence for this mechanism exists. On the other hand, literature data can be found to support the compensation of donors in the bulk by either barium or titanium vacancies. As a result the defect(s) formed at electrically active titanate grain boundaries during oxidation has remained uncertain. We explore this phenomenon by observing changes in the surface composition of donor-doped BaTiO₃ when cation vacancies are introduced during oxidation, using SAES (scanning Auger electron spectroscopy). Direct experimental support for the formation and in-diffusion of barium vacancies during oxidative cooling is obtained in a composition containing 0.7% Nb. It is suggested that barium vacancy compensation constitutes a metastable defect equilibrium in BaTiO₃. In a sample of lower concentration (0.3% Nb), results are inconclusive, perhaps because of slower oxidation limited by surface reaction kinetics.     

Water-induced bulk Ba(NO3)2 formation from NO2 exposed thermally aged BaO/Al2O3

Phase changes in high temperature treated (>900 °C) 8 or 20 wt% BaO supported on γ-Al₂O₃ model lean NO_x trap (LNT) catalysts, induced by NO₂ and/or H₂O adsorption, were investigated with powder X-ray diffraction (XRD), solid state ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and NO₂ temperature programmed desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state ²⁷Al MAS NMR results confirm that stable surface BaO and bulk BaAl₂O₄ phases are formed for 8 and 20 wt% BaO/Al₂O₃, respectively. Following NO₂ adsorption over these thermally treated samples, some evidence for nanosized Ba(NO₃)₂ particles are observed in the XRD results, although this may represent a minority phase. However, when water was added to the thermally aged samples after NO₂ exposure, the formation of bulk crystalline Ba(NO₃)₂ particles was observed in both samples. Solid state ²⁷Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO₂ TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NO_x uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials.     

Comparison of Ba(OH)2, BaO, and Ba as Starting Materials for the Synthesis of Barium Titanate by the Alkoxide Method

A discussion of the relative merits and problems of using Ba(OH)₂, BaO, and Ba as starting materials for the synthesis of barium titanate by the alkoxide method is presented. The Ba(OH)₂ process is promising because it does not involve the synthesis of barium alkoxide, whereas the BaO (93% pure) process suffers from complex chemical reactions; the impurities in BaO cause unknown effects on the composition and properties of the final ceramic. Use of high-purity Ba metal (99.99%) for the synthesis of barium alkoxide is more desirable since it results in high-purity, ultrafine barium titanate powders.     

静电纺丝法制备BaO微/纳米纤维及其表征

以聚乙烯吡咯烷酮(PVP)为络合剂,与醋酸钡[Ba(CH3COO)2]反应制得前驱体溶液;以36%乙酸为钡盐的相容剂,和乙醇组成了混合溶剂体系,用静电纺丝法制备了PVP/Ba(CH3COO)2纤维,经煅烧得到BaO微/纳米纤维。对所制备纳米纤维的结晶度、纯度和表面形貌,分别采用差热-热重分析、红外光谱、X-射线衍射、扫描电镜等进行了表征。结果表明:煅烧前后,纤维的结晶度和形貌有很大变化。     

Forming and Sintering of in Situ Alumina Composite with Hydraulic Inorganic Binder

Two types of barium aluminate binders were prepared by heat treatment of barium aluminate precursors, synthesized by using solution processes, at low temperatures ( T < 500°C). One was barium monoaluminate (BaAl₂O₄), and the other was barium aluminate binder (BAH binder) composed of amorphous phase, barium aluminate monohydrate (BaAl₂O₄·H₂O), and BaAl₂O₄. The setting time of the BAH binder was controlled by adjusting the heat-treatment temperature of the BAH binder precursor. The addition of the synthesized BaAl₂O₄ powders to Al₂O₃ powders improved the bending strength of Al₂O₃ matrix green bodies. The synthesized BaAl₂O₄ powders led to the in situ forming of barium hexaaluminate (BaO· x Al₂O₃, x = 6.9: BA6) platelets in the matrix by reacting with Al₂O₃ during sintering. The formed BA6 platelets inhibited the grain growth of the matrix Al₂O₃ grains.     

A study of the behaviour of Pt supported on CeO2–ZrO2/Al2O3–BaO as NOx storage–reduction catalyst for the treatment of lean burn engine emissions

The behaviour of a Pt(1 wt.%) supported on CeO₂–ZrO₂(20 wt.%)/Al₂O₃(64 wt.%)–BaO(16 wt.%) as a novel NO_x storage–reduction catalyst is studied by reactivity tests and DRIFT experiments and compared with that of Pt(1%)–BaO(15 wt.%) on alumina. The former catalyst, designed as a hydrothermally stable sample, is composed of an alumina modified with Ba ions and an overlayer of ceria-zirconia. The results pointed out that during the calcination barium ions migrates over the surface of the catalyst which thus show a good NO_x storage–reduction behaviour comparable with that of Pt–BaO on alumina, although Ba ions result much better dispersed.     

Effect of Nb2O5 as additive to MgO catalyst on vapor phase hydrogen transfer reaction between methacrolein and ethanol

The effect of Nb₂O₅ as an additive to MgO catalyst for vapor phase hydrogen transfer reaction between methacrolein and ethanol to form methallyl alcohol and acetaldehyde has been studied. Nb₂O₅ itself was not effective for this reaction, but when Nb₂O₅ was added to MgO, the catalytic performance was enhanced. This result suggests that the preferable active sites on catalyst are increased by combination of Nb₂O₅ and MgO and so the catalytic performance is improved. On the other hand, when BaO or alkali metal oxide was added to Nb₂O₅, the catalytic performance became higher than that of Nb₂O₅ alone. This result suggests that the preferable active site is formed newly by combination of Nb₂O₅ and BaO or alkali metal oxide.     

Modelling of NOx adsorption over NOx adsorbers

Modelling of the phenomena involved during the adsorption of NO_x on NO_x trap catalysts was developed. The aim of the model is the prediction of the quantity of stocked barium nitrate as well as the emissions of NO and NO₂, as a function of time and temperature. The mechanism of the process is sounded on the adsorption of gas species (NO, NO₂, O₂) on platinum sites, equilibrium reaction between adsorbed species followed by the formation of Ba(NO₃)₂. This formation of barium nitrate is limited by the thermal decomposition reaction which liberates NO in the gas phase. The kinetic constant of decomposition of barium nitrate was determined by temperature programmed thermogravimetry on pure Ba(NO₃)₂, using the method of Freeman and Carroll. Other kinetic constants bound to the mechanism were estimated by fitting the results of the model to experimental results.The mechanism was validated for various values of the molar fraction of O₂, the molar fraction of NO and various values of the NO/NO₂ ratio in the gas entering the reactor. It was also tested with different catalyst compositions (variation of the platinum and BaO concentrations). The importance of oxygen in the process was clearly demonstrated as well as the promoting role of NO₂.     

Effect of Na2O Additions in the Crystallization of Barium Ferrite from a BaO-B2O3-Fe2O3 Glass

A glass crystallization method was utilized to synthesize nanosized BaO-6Fe₂O₃ platelets from a 0.412BaO-0.258B₂O₃-0.330Fe₂O₃ batch composition. Quenched ribbons were inhomogeneous, showing microclustering and ∼1 μm hematite crystals. Na₂O substitutions for BaO greatly enhanced the glass-forming tendency of quenched ribbons, though quenched-in ∼0.5 μm barium ferrite crystals were infrequently present. The improved homogeneity with Na₂O substitution was attributed to lower vapor pressure of BaO during batch melting, which increased its retention in the as-quenched ribbons. Quantities of BaO equal to or in excess of Fe₂O₃ allowed iron ions to adopt stable network positions in the glass melt. With Na₂O substitution, devitrification of dispersed ∼40 nm barium ferrite particles from phase-separated regions occurred after secondary heat treatment. 5 mol% Na₂O batch substitution showed the lowest crystallinity in the as-quenched ribbons, and the highest crystallinity after secondary heat treatment. After optimum devitrification, the maximum values of saturation magnetization and coercivity were 21.22 emu/g and 2.82 kOe, respectively.     

Phase Equilibrium in a Portion of the Ternary System Ba OA-I2,O3,-SiO2,

Phase-equilibrium relations on the liquidus surface in the system Ba0-A1₂O₃-SiO₂ have been investigated by the quenching method. The compositions investigated within the ternary area were those containing less than 30%, A1₂O₃ and more than 20% SiO₂ by weight. Petrographic and X-ray techniques were employed in the determination of the crystalline phases.
The crystal phases that separate from melts within the area investigated are barium orthosilicate (2BaO. SiO₂,), barium metasilicate (BaO 2SO₂,), solid solutions, sanbornite (BaO 2SiO₂), tridymite and cristobalite (SO₂), mullite (3A1₂O₃ 2SiO₂), and celsian (BaO A1₂O3_.2SiO₂). Diagrams show the isotherms and indices of refraction of the glasses.
Five quintuple points and eleven boundary curves have been determined within = .5yo compositional variations. The liquidus-surface temperatures have been obtained within limits of ± 125°C.     

Performance Improvement of NO x -Storage BaO/Al2O3 by Using Barium Peroxide as the Precursor of BaO

Comparison of barium peroxide, Ba(OH)₂ and Ba(NO₃)₂ as the precursor of BaO for the preparation of NO _x -storage BaO/Al₂O₃ material was carried out. The as prepared materials were calcined at 550 and 800 °C and characterized by N₂ physisorption, XRD, Raman and FT-IR spectroscopy. Measurements of the NO _x storage performances of these BaO/Al₂O₃ materials by NO₂ adsorption and NO _x -TPD experiments showed that the use of barium peroxide as the precursor of BaO inhibited the formation of BaAl₂O₄ and led to remarkable improvements in the thermal stability as well as NO _x storage capacity of the final BaO/Al₂O₃ material calcined at 800 °C.     

Solubility of BaO in BaTiO3

The solubility and mode of incorporation for BaO in BaTiO₃ were studied by X-ray powder diffraction, scanning and transmission electron microscopy, electron probe microanalysis, and equilibrium electrical conductivity measurements. The presence of barium orthotitanate, Ba₂TiO₄, as a second phase for samples containing >0.1 mol% excess BaO was confirmed by direct microscopic examination. There was no evidence to support the incorporation of excess BaO into BaTiO₃ by a Ruddlesden-Popper type of superlattice ordering mechanism. Measurement of the equilibrium electrical conductivity showed no detectable shift in the conductivity profile resulting from excess BaO, thus setting an upper limit of 100 ppm for the solubility of BaO in BaTiO₃.     

Construction of the Quasi-ternary Phase Diagram in the NdO1.5-BaO-CuOx System in an Air Atmosphere: Part I, Equilibrium Tie Lines in the Nd1+xBa2−xCu3O6+δ Solid Solution and Liquid Region

Quasi-ternary phase diagrams of the NdO_1.5-BaO-CuO _x system near the CuO _x corner have been constructed near the peritectic temperature in air of the Nd_{1+ x} Ba_{2− x} Cu₃O_6+delta (Nd123) solid-solution phase. Liquidus curves were determined by measuring the temperature dependences of the neodymium, barium, and copper solubilities in Nd-Ba-Cu-O solutions with different BaO:CuO ratios. Solidus line compositions and equilibrium tie lines were determined by analyzing the compositions of the Nd123 solid solution equilibrated with the melt by quenching samples held isothermally. Based on the tie-line features in the Nd123-and- liquid two-phase field, the Nd123 solid solution with the smaller substitution content was observed to be equilibrated with the solution melt with a higher BaO:CuO ratio, even in an air atmosphere. Nd123 crystal with a substitution content of ∼0.02 could be formed from the solution with the BaO:CuO ratio of greaterthan equal to0.75, which resulted in higher critical superconducting transition temperatures.     

利用苛化沉淀合成铝酸钡实验研究

通过实验研究，探讨了苛化沉淀与Al(OH)3合成铝酸钡的工艺条件选择及铝酸钡的苛化效果。展望了以天然碳酸钡矿为原料加工钡盐添加剂在氧化铝工业中良好的应用前景。     

Properties and Morphology of Barium Germanate Glasses

The density, thermal expansion behavior, and transformation-range viscosity of barium germanate glasses containing 0 to 9 mol% BaO were measured. The addition of BaO to Ge0₂ resulted in phase separation at all BaO concentrations. The results of the property measurements indicate that glasses containing up to 3 mol% BaO consist of a matrix of essentially pure GeO₂ with barium-rich droplets. Glasses containing 6 mol% BaO or more consist of two interconnected vitreous phases. The morphology of glasses containing between approximately 3.5 and 5.5 mol% BaO can be altered from the droplet/matrix form to that of two continuous phases by the appropriate heat treatment.