热辅助紫外光催化氧化方法用于总磷检测的实验研究和动力学分析(英文)

A novel thermal-assisted ultra-violet (UV) photocatalysis digestion method for the determination of total phos-phorus (TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion were conducted using a 365 nm wavelength UV light and TiO2 particles as the photocatalyst. Sodium tripolyphosphate and sodium glycerophosphate were used as the typical components of TP and the digested samples were then determined by spectrophotometry after phosphomolybdenum blue reaction. The effects of operational parameters such as reaction time and temperature were studied for the digestion of TP and the kinetic analysis of two typical components was performed in this paper. The pseudo-first-order rate constants k of two phosphorus compounds at different temperatures were obtained and the Arrhenius equation was employed to explain the effect of temperature on rate constant k. Compared with the conventional thermal digestion method for TP detection, it was found that the temperature was decreased from 120 °C to 60 °C with same conversion rate and time in this thermal-assisted UV digestion method, which enabled the digestion process work at normal pressure. Compared with the individual ultra-violet (UV) photocatalysis process, the digestion time was also decreased from several hours to half an hour using the thermal-assisted UV digestion method. This method wil not lead to secondary pol ution since no oxidant was needed in the thermal-assisted UV photocatalysis digestion process, which made it more compatible with electrochemical detection of TP.     

蠕虫形管状镧铝复合介孔材料的合成及表征

The lanthanum aluminum mesoporous materials were synthesized using sodium dodecyl sulfate as a template agent by ultrasonic hydrothermal method.The resulting samples were characterized by low angle X-ray diffraction(XRD),N2 adsorption-desorption studies,transmission electron microscopy(TEM)and surface morphology analysis(SEM),surface acid(NH3-TPD),reducibility properties(TPR),X-ray energy dispersive spectrometer(EDS)and thermogravimetric analysis(TG/DTG).A l/La composite mesoporous material were synthesized with n(Al)︰n(La)=70︰1.0,80°C of reaction temperature,20 h of reaction time,12 h of crystallization time,650°C of calcination temperature.The specific surface area of the sample is 273.90 m 2 ·g ?1 ,with the average diameter 5.642 nm and pore volume 0.2354 cm 3 ·g ?1 .The samples have mesoporous structure and its particles are similar to a worm-shaped tubular structure.The influence of calcination temperature on the surface physical and chemical properties of Al/La composited mesoporous materials was examined,and the results showed that the acid strength was increased but the amount of acidic sites is decreased as the calcination temperature increased.It was found that the sample calcined at 650°C had appropriate acid content,acid strength and better reducibility.     

掺杂的阳离子缺陷型磷灰石 La9.33－2x/3MxSi6O26 (M=Mg,Sr,Ca)的合成及离子导电特性

Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33－2x/3MxSi6O26 (M＝Mg, Ca, Sr) is prepared by the sol-gel method with sintering at 1000°C. The powder is characterized by X-ray diffraction (XRD) and scan-ning electron micrograph (SEM). The apatite can be obtained at relatively low temperature as compared to the con-ventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33－2x/3MxSi6O26 (M＝Ca, Mg, Sr) indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lat-tice distortion arising from cation vacancies.     

混合导体透氢膜SrCe_(0.95-x)Zr_xTm_(0.05)O_(3-δ)(0≤x≤0.40)的制备及其性能研究(英文)

Zr-substituted,Tm-doped SrCeO3(SrCe0.95-xZrxTm0.05O3-δ,0≤x≤0.40)were synthesized via citrate complexing method,and the membranes of SrCe0.95-xZrxTm0.05O3-δwere prepared by pressing followed by sintering. X-ray diffraction(XRD)was used to characterize the phase structure of sintered membrane.The microstructure of the sintered membranes was studied by scanning electron microscopy(SEM).Protonic and electronic conductivities were measured under different circumstance.Hydrogen permeation through the SrCe0.75Zr0.20Tm0.05O3-δmembranes was carried out using gas permeation setup.Hydrogen permeation fluxes( 2H J)of the SrCe0.75Zr0.20Tm0.05O3-δ membrane reach up to 0.042 ml·min -1 ·cm-2 at H 2 partial pressure of 0.4×10 5 Pa at 900°C.The hydrogen permea- tion fluxes( 2H J)obtained in this paper are slightly lower than that of SrCe0.95Tm0.05O3-δon the same orders,and Zr doping can increase chemical stability of the SrCe0.75Zr0.20Tm0.05O3-δmembranes.     

A simple strategy to synthesize and characterization of zirconium modified PCs/γ–Al_2O_3

Crystalline phase is the key factor for catalyst activity. The zirconium modified PCs/γ-Al_2O_3 samples were prepared through a simple step incipient-wetness impregnation method. The raw materials and samples were characterized by thermogravimetric-differential analysis(TG-DTA), X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), temperature-programmed desorption of ammonia and carbon dioxide(NH_3-and CO_2-TPD). The effects of calcination temperature and zirconium content on structure, chemical transformation,and acidity-basicity were investigated. Calcination temperature exhibited the major effect on the crystalline phase of samples. The new phase of Al0.1Zr_(0.9)O_(1.95) was exhibited which was above 650 ℃. In addition, zirconium content was influenced by the acidic and basic properties of the surface. The acidity and basicity of the Zr PCs/γ-Al_2O_3 sample increased with the increasing of zirconium content.     

Application Performance of Microporous Sintered Alumina in Alumina Magnesia Castables for Ladles

In this study, a kind of microporous sintered alumina was analyzed and applied. The microporous sintered alumina has a lot of nano and sub-micron closed pores in the crystals, the average pore size of 140 nm, and the thermal conductivity of 4.864 at 800 ℃, 38% lower than that of common sintered alumina. The microporous sintered alumina was used as the aggregates in alumina magnesia castables for ladles to replace the common sintered alumina. The properties of the microporous alumina castable were measured, and the temperature field of the ladle outer wall was simulated and calculated. The results show that the refractoriness under load(T0.6) and the hot modulus of rupture(1 400 ℃, 0.5 h) of the microporous castable are the same as the common castable; the thermal conductivity at 800 ℃ decreases by 15%; the retention ratio of modulus of rupture increases by about 5% after five thermal shock cycles(1 100 ℃, water quenching); and the temperature of the ladle outer wall is reduced by 5-41 ℃.     

高Al_(13)含量聚合氯化铝制备γ-Al_2O_3及表征(英文)

In this paper a polyaluminum chloride solution with high Al13 content was prepared and used as raw material for preparation ofγ-Al2O3.The texture and crystalline phase of the prepared alumina samples were characterized by energy dispersive X-ray spectroscopy(EDX) ,X-ray diffraction,transmission electron microscope(TEM) and nuclear magnetic resonance(NMR) analyses.The effects of alkaline solution and calcination temperature were investigated.The results showed that alkaline solution including NH3·H2O and NaOH had little effect on the alumina sample formation.The impurities of NH4Cl and NaCl in solution can be removed through repeated washing by EDX analysis.Calcination temperature had a significant effect on alumina crystal phase.The alumina sample can transform completely toγ-Al2O3 in the subsequent heating from 600°C to 800°C.It is very interesting that Al13 can be existed inγ-Al2O3 phase even after calcinations.The results indicate that polyaluminum chloride with high Al13 content is an effective material to prepareγ-Al2O3.     

Evolvement behavior of microstructure and H2O adsorption of lignite pyrolysis☆

The effect of pyrolysis on the microstructure and moisture adsorption of lignite was investigated with low field nuclear magnetic resonance spectroscopy. Changes in oxygen-containing groups were analyzed by Fourier transform infrared spectroscopy(FTIR), and H2 O adsorption mechanism on the surface of lignite pyrolysis was inferred. Two major changes in the pore structure of lignite char were observed as temperature increased in 105–200 °C and500–700 °C. Pyrolysis temperature is a significant factor in removing carboxyl and phenolic hydroxyl from lignite.Variation of ether bond content can be divided into three stages; the content initially increased, then decreased,and finally increased. The equilibrium adsorption ratio, content of oxygen-containing groups, and variation of pore volume below 700° were closely correlated with each other. The amount of adsorbed water on char pyrolyzed at700 °C increased. Moreover, the adsorption capacity of the lignite decreased, and the adsorption state changed.     

Modeling of thermal conductivity and density of alumina/silica in water hybrid nanocolloid by the application of Artificial Neural Networks

In this research work, the thermal conductivity and density of alumina/silica(Al_2O_3/SiO_2) in water hybrid nanofluids at different temperatures and volume concentrations have been modeled using the artificial neural networks(ANN). The nanocolloid involved in the study was synthesized by the two-step method and characterized by XRD, TEM, SEM–EDX and zeta potential analysis. The properties of the synthesized nanofluid were measured at various volume concentrations(0.05%, 0.1% and 0.2%) and temperatures(20 to 60 °C). Established on the observational data and ANN, the optimum neural structure was suggested for predicting the thermal conductivity and density of the hybrid nanofluid as a function of temperature and solid volume concentrations. The results indicate that a neural network with 2 hidden layers and 10 neurons have the lowest error and a highest fitting coefficient o thermal conductivity, whereas in the case of density, the structure with 1 hidden layer consisting of 4 neurons proved to be the optimal structure.     

Infrared thin layer drying of saffron (Crocus sativus L.) stigmas: Mass transfer parameters and quality assessment

Saffron is the most precious and expensive agricultural product. A dehydration treatment is necessary to convert Crocus sativus L. stigmas into saffron spice. To the best of our knowledge, no information on mass transfer parameters of saffron stigmas is available in the literature. This study aimed at investigating the moisture transfer parameters and quality attributes of saffron stigmas under infrared treatment at different temperatures(60,70, …, 110 °C). It was observed that the dehydration process of the samples occurred in a short accelerating rate period at the start followed by a falling rate period. The effective moisture diffusivity and convective mass transfer coefficient were determined by using the Dincer and Dost model. The diffusivity values varied from1.1103 × 10~(-10)m~2·s~(-1)to 4.1397 × 10~(-10)m~2·s~(-1) and mass transfer coefficient varied in the range of 2.6433 × 10~(-7)–8.7203 × 10~(-7)m·s~(-1). The activation energy was obtained to be 27.86 k J·mol~(-1). The quality assessment results showed that the total crocin content increased, when the temperature increased up to90 °C but, in higher temperatures, the amount of crocin decreased slightly. The total safranal content of the samples decreased slightly when drying temperature increased from 60 °C to 70 °C and then continuously increased up to 110 °C. Also, the amount of picrocrocin increased from 83.1 to 93.3 as the drying temperature increased from 60 °C to 100 °C.     

La2O3的添加方式对Al2O3热稳定性的影响

采用3种不同添加方式制备La₂O₃改性的Al₂O₃材料La-Al₂O₃。La-Al₂O₃分别经500 ℃、1 000 ℃和1 200 ℃焙烧,采用物理吸附、X射线衍射和荧光光谱等对高温处理的La-Al₂O₃进行比表面积和结构表征。结果表明,La₂O₃的添加能有效抑制Al₂O₃在高温条件下向热力学稳定态α-Al₂O₃转变,同时提高高温处理后La-Al₂O₃比表面积,使Al₂O₃热稳定性得到明显提高。在3种La₂O₃添加方式中,La(NO₃)₃浸渍法效果最为显著,制得的La-Al₂O₃(N)材料经1 200 ℃焙烧4 h的比表面积为30 m²·g^－1,是未经改性的Al₂O₃样品经同等温度焙烧比表面积的2.2倍。     

Hot isostatic pressing of SiC/Si3N4 composite with rare earth oxide additions

SiC/Si₃N₄ composites with rare earth oxide additions have been prepared by glass encapsulated hot isostatic pressing at 1850 °C and 200 MPa pressure. Mechanical properties and microstructures of the sintered samples have been studied. It is shown that different molar ratios of La₂O₃ to Y₂O₃ and the total amount of La₂O₃ and Y₂O₃ additions can affect the mechanical properties significantly. With 3 wt% La₂O₃ + Y₂O₃ additions, lower La₂O₃/Y₂O₃ molar ratio exhibits higher bending strength and median fracture toughness, but relatively lower Vickers hardness. For addition of 6 wt% La₂O₃ + Y₂O₃, the higher bending strength, Vickers hardness and fracture toughness correspond to a certain La₂O₃/Y₂O₃ molar ratio of 1.5, 1.0 and 0.5, respectively. SEM observation shows that the SiC matrix composite with fine grain size and homogeneous microstructure can be obtained.     

Reduction of LaMnO3. Structural features of phases La8Mn8O23 and La4Mn4O11

Two new phases with ordered anion vacancies, La₈Mn₈O₂₃ and La₄Mn₄O₁₁, both having the general formula A_nB_nO_3n·1, form during the reduction of perovskites of the type LaMnO_3.07. The solid LaMnO_3.07, obtained in air at 1100°C and subsequently reduced in flowing carbon monoxide at 350°C, gives the stoichiometric perovskite LaMnO_3.00, whose reduction starts at 420°C and is completed at 450°C with formation of the phase La₈Mn₈O₂₃. The second reduction stage starts at approximately 500°C and is completed at 520°C with formation of La₄Mn₄O₁₁. The solids in the range of composition LaMnO_3.00-La₈Mn₈O₂₃ and La₈Mn₈O₂₃-La₄Mn₄O₁₁ would seem by X-ray examination to be biphasic but the behaviour during reduction is typical of a monophasic substance, the oxygen pressure of which at constant temperature progressively decreases as the composition tends to the limiting values La₈Mn₈O₂₃ and La₄Mn₄O₁₁. The crystal lattice of La₈Mn₈O₂₃ can be considered as resulting from a sequence of seven octahedral sheets, MnO₆, alternated with tetrahedral sheets, MnO₄, and the crystal lattice of La₄Mn₄O₁₁ from a sequence of three MnO₆ sheets alternating with MnO₄ sheets.     

La2O3/AC催化剂在CO同时还原SO2和NO反应中的性能

以改性活性炭为载体,采用等体积浸渍法制备了La₂O₃/AC催化剂。采用XRD和BET手段对催化剂进行表征,使用微型固定床反应器考察催化剂的脱硫脱硝活性。结果表明,La₂O₃/AC催化剂对CO同时还原SO₂和NO具有良好活性,负载质量分数10%的La₂O₃/AC催化剂活性较好,SO₂和NO转化率达到90%的反应温度最低,分别为335 ℃和325 ℃;载体与活性组分之间存在协同作用,引入活性炭载体能够降低反应温度并提高催化活性。     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

柠檬醛在La2O3/γ-Al2O3催化剂上的等温吸附

对柠檬醛-乙酸乙酯溶液中柠檬醛在La₂O₃/γ-Al₂O₃催化剂上等温吸附行为进行了研究。结果表明,30 ℃柠檬醛在La₂O₃/γ-Al₂O₃催化剂上的吸附动力学符合准二阶吸附动力学模型,吸附动力学方程为：1/q_t=2.350/t+0.063 3(R²=0.998 5)。（30~65） ℃柠檬醛在La₂O₃/γ-Al₂O₃催化剂上的等温吸附符合Langmuir方程,温度升高使柠檬醛的饱和吸附量增加,吸附热为32.19 kJ·mol^-1。     

Synthesis and properties of lanthanum hexaaluminate ceramic La1−xCaxAl11−y−zMgyTizO18

The aim of the present work is to obtain ceramic materials with a hexagonal structure and high density, hardness and mechanical strength at lower synthesis temperature. Ceramic samples with nominal composition La_1−xCa_xAl_11−y−zMg_yTi_zO₁₈ (x=0–1; y=0–3; z=0–3,5) are prepared. The samples are sintered at temperature 1500 °C by one-stage and two-stage ceramic technology. By X-ray diffraction and scanning electron microscopy, predominant phase LaAl₁₁O₁₈ and second phases LaAlO₃ and -Al₂O₃ are identified. Ceramic materials are characterized with high physico-mechanical properties and may be find application for production of mill bodies and materials for immobilization of nuclear waste.     

Characteristics of La2O3 thin films deposited using metal organic chemical vapor deposition with different oxidant gas

La₂O₃ films were deposited using O₃ and the structural and electrical properties were investigated and compared with those of La₂O₃ films deposited using O₂. The deposition temperature of the La₂O₃ films using O₃ was slightly reduced compared to that of the La₂O₃ films generated using O₂. After a post-annealing process at 600 and 900 °C, the crystallinity of the La₂O₃ films using O₃ were smaller than that using O₂. The leakage current density increased after annealing at 600 °C due to densification and then decreased after annealing at 900 °C due to interfacial layer growth. The effective dielectric constant of the La₂O₃ films deposited using O₃ decreased at 900 °C due to interfacial layer growth. The La₂O₃ films deposited using O₃ showed better structural and electrical properties in this study.     

Mechanochemical synthesis and thermal evolution of La–ZrO2 cubic solid solutions

The formation of cubic solid solutions in the system La₂O₃–ZrO₂ by mechanochemical activation of a mixture of the oxides (molar ratio ZrO₂ 82%–La₂O₃ 18%) is studied. After 6 h of activation at room temperature, a poorly crystalline cubic solid solution is formed, with ultimate crystallite sizes in the nanometer range. The mixtures activated during 1–3 h form the solid solution on subsequent heating at 1000 °C, while the non-activated mixture does not react, even after thermal treatment at 1200 °C. The solid solution obtained at room temperature undergoes partial structural ordering at temperatures between 800 and 1000 °C. Long time heating at temperatures of 1000 °C and above results in the formation of La₂Zr₂O₇ and rejection of the excess ZrO₂. Mechanochemical activation offers interesting possibilities for the synthesis of these materials at temperatures lower than those used in conventional processing, and for the control of their physicochemical and microstructural properties.     

Sintering of lime doped with La2O3 and CeO2

The sintering of lime doped with up to 2 mol% La₂O₃ as well as CeO₂ was followed on firing at 1400, 1500 and 1600°C. X-ray diffraction and reflected-light microscopy techniques have been used to investigate the phase composition and texture of the fired samples. The load bearing capacity and the rate of hydration of the obtained dense lime samples have also been determined to assess its quality. It is found that doping lime with 0·5–1·0 mol% of either La₂O₃ or CeO₂ and firing up to 1600°C leads to dense and hydration-resistant lime with uniform texture. At this level of the dopant oxides, normal grain growth occurred with the increase in the degree of direct bonding. Doping with less than 0·5 mol% La₂O₃ or CeO₂ is insufficient for inhibiting the discontinuous grain growth of the lime grains. On the other hand, increase in the dopant content above 1·0 mol% showed finer grain sizes at the expense of the degree of direct bonding.