蒙脱石预处理对制备柱撑蒙脱石的促进作用研究

在制备柱撑蒙脱石的过程中，首次提出了蒙脱石的预处理工艺，并以莱西钙基膨润土为原料，研究了预处理方法、预处理时间、料浆浓度、分散剂种类及用量对蒙脱石分散程度的影响，将钙基蒙脱石颗粒分散达到0.964 μm。经过预处理后，用钙基蒙脱石直接制备柱撑蒙脱石，并用SEM、XRD、DTA-TG和SRF等进行了表征。经300 ℃焙烧2 h后，其层间距为1.262 nm，热稳定性达588 ℃，此法省去了蒙脱石的钠化改性，简化了制备工艺。     

Catalytic decomposition of ammonia gas with metal cations present naturally in low rank coals

A novel hot gas cleanup method to decompose a low concentration of NH₃ to N₂ with metal cations present inherently in low rank coals has been studied with a quartz reactor under the conditions of 750–850 °C, 0.1 MPa and high space velocity of 45,000 h⁻¹. Each coal is pyrolyzed at 900 °C to prepare the char, which is subjected to the decomposition of 2000 ppm NH₃ after pretreatment with H₂. All of five chars examined promote NH₃ decomposition in inert gas, but the promotion effect depends strongly on the kind of char and can correlate more closely with the Fe content than with the Ca content. This result may indicate that the Fe plays a crucial role in the reaction. A commercial activated carbon with a very low Fe content of <0.05 wt% exhibits lower conversion of NH₃ to N₂ than five chars. The TEM pictures reveal the formation of nanoscale particles of Fe and Ca components on a brown coal char that provides the largest catalytic performance. The char maintains the high conversion level of 80% during 25 h reaction at 750 °C and achieves the complete decomposition of NH₃ at 850 °C. The co-feeding of a mixture of H₂, CO, and CO₂ does not change significantly the catalytic activity of the char at a steady state, whereas the coexistence of 2000 ppm H₂S lowers it in the whole range of time on stream. It is proposed by combining the XRD and TPD observations with our previous results that the catalytic decomposition of NH₃ in inert gas with the chars derived from low rank coals proceeds through two cycle mechanisms involving iron metal, iron nitrides, CaO and CaCN₂.     

水溶液中纳米二氧化钛光催化降解甲基橙的影响因素

用沸腾回流直接水解法制备了粒径为25～35 nm纯锐钛矿型纳米二氧化钛(TiO2).用X射线衍射和透射电镜表征材料的结构与形貌.用该催化剂催化降解甲基橙,研究了催化剂用量、甲基橙的起始浓度、溶液pH值、光强度、溶液中添加金属离子的影响.结果表明:在较强紫外光照射下,当甲基橙的起始浓度为0.02 g/L,TiO2用量为1.0g/L,光催化效率最高.酸性条件有利于光催化降解甲基橙.掺加Fe3 或Zn2 的光催化效率显著增加.掺加Mn2 或Ca2对光催化活性没有影响.在紫外光区域(366 nm),样品对催化降解水溶液中甲基橙的活性较高.     

Investigation of LSM/8YSZ cathode within an all-ceramic SOFC,Part II: Optimization of performance and co-sinterability

This paper focuses on the cathode and current collector layers of a co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. Challenges to reach good electrochemical performance have to be overcome, due to more demanding manufacturing conditions, including a relatively high co-sintering temperature. Master sintering curves show that the sintering activity of lanthanum strontium manganite (LSM) is significantly higher than that of 8-mol% yttria stabilized zirconia (8YSZ). By applying a double-layered cathode and a current collector with optimized microstructures the best electrochemical performance of the cathode is 0.26 $\mathrm{\Omega }$cm${}^2$ at 800 $°$C, evaluated from polarization resistances of 8YSZ electrolyte-supported symmetric cells post-sintered at 1150 $°$C $<T<1250$ $°$C. The cathode and current collector materials are adapted to fit the co-sintering process by adjustment of the paste compositions. Half-cells consisting of silicate mechanical support, LSM current collector, LSM mixed with 8YSZ composite cathode and 8YSZ electrolyte are co-sintered porous and defect-free at 1150 $°$C $<T<1250$ $°$C.     

Type-A zeolites with hydroxyapatite surface layers formed by an ion exchange reaction

To enhance adsorption of harmful ions on type-A zeolites (LTA), hydroxyapatite (HAp) thin layers were synthesized on the LTA surface by an ion exchange reaction of Ca²⁺ for NH₄⁺ under hydrothermal treatment. The temperatures and durations in the reactions were varied ranging from 25 to 200 °C and from 1 to 168 h. The samples synthesized were characterized by X-ray diffraction method (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer–Emmet–Teller method (BET). The structure of LTA was not destroyed by the hydrothermal treatments at 25 to 160 °C for 8 h and also at 120 °C for 1 to 72 h. The yield of HAp grown on the LTA surface, synthesized at 120 °C for 8 h, showed a maximum value of 0.82. The morphologies of HAp were dependent mainly on the temperatures. The specific surface area remained unchanged in the treatments at 25 to 40 °C for 8 h, as compared to the specific surface area of Ca-LTA, however up to 80 °C, the value decreased with an increase of exchange temperature.     

Synthesis and swelling properties of poly[acrylamide-co-(crotonic acid)] superabsorbents

Superabsorbent polymers of acrylamide (AAm)/crotonic acid (CA) were synthesized by foamed polymerization in an aqueous solution of AAm with CA as a comonomer, initiated by an initiator couple of ammonium persulfate and N,N,N′N′-tetramethylethylenediamine. A crosslinking agent N,N′-methylenebisacrylamide, a foaming agent sodium bicarbonate, and a foam stabilizer, a triblock copolymer of polyoxyethylene/polyoxypropylene/polyoxyethylene, were used in the polymerization. The influences of the relative contents of CA, crosslinking agent, and initiator, on the swelling properties of the superabsorbent polymer systems were examined. The superabsorbent polymer synthesized with an AAm/CA ratio of 98:2 by mole, 0.5 wt.% of N,N′-methylenebisacrylamide and 1 wt.% of ammonium persulfate at 250 rpm and 50 °C for 30 min of polymerization time produced the highest water absorption of 211 ± 9 times its dried weight and could absorb water up to 162 ± 4 g g⁻¹ of the dry copolymer within 10 min. The electrochemical reaction for acrylamide–crotonic acid polymerization was investigated by cyclic voltammetry. The anodic current indicated that acrylamide acting as an electron donor whereas crotonic acid performed as an electron receiver, then providing the cathodic current. The diffusion of water into the superabsorbent polymer was non-Fickian (case II and anomalous). Acrylamide–crotonic acid superabsorbents containing various crosslinker concentrations had a water swelling in the range of 79–289 g g⁻¹. The diffusion coefficients varied between 6.9 × 10⁻⁹ and 5.1 × 10⁻⁸ cm² s⁻¹. Adsorption of the basic dye by the superabsorbent was a monolayer evaluated by the Langmuir isotherm. The superabsorbents can thus be used to adsorb cationic dyes in textile industry.     

In situ generation of hydrogen peroxide from reaction of O2 with hydroxylamine from hydroxylammonium salt in neutral aqueous or non-aqueous medium using reusable Pd/Al2O3 catalyst

In situ generation of H₂O₂ with high yield can be accomplished by reacting O₂ with NH₂OH from hydroxylammonium salt [NH₂OH · HCl or (NH₂OH)₂ · H₂SO₄] in a neutral aqueous medium using a reusable heterogeneous Pd (1.0 wt%)/Al₂O₃ catalyst, even at low temperature (10 °C), with the formation of harmless by-products (viz. N₂ and water). The presence of KCl or KBr in the medium has beneficial effect. The H₂O₂ generation is strongly influenced by the pH of medium, reaction period and temperature; best results are obtained at the optimum pH and reaction medium.     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

邻溴苯酚在高温碱水中的脱溴和降解动力学研究

利用间歇反应器研究了邻溴苯酚在250℃～350℃高温液态水中的降解行为,探讨了脱溴效率的影响因素和降解反应动力学。结果表明：升高温度和添加碱性物质能显著提高脱溴率;邻溴苯酚在0.1mol/L碳酸钠溶液中的降解符合表观一级反应动力学规律。GC-MS分析结果表明邻溴苯酚在高温碱水中降解的主要产物为苯酚和邻苯二酚,并由此推测出降解途径。