Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

基于CaO引导的甲烷蒸汽重整化学链燃烧制氢系统

为在重整气中得到高纯H_2和降低尾气CO_2分离成本,建立了基于CaO引导的甲烷蒸汽重整化学链燃烧制氢系统,该系统在重整反应器中加入CaO吸收剂,用以吸收重整器内的CO_2,提高重整气中H_2浓度,形成的CaCO_3固体在煅烧器中受热分解重新生成CaO。利用Aspen Plus进行了过程模拟及热力学分析,并研究主要参数对系统性能的影响,得到优化的操作条件为:CaO循环量/CH_4比为0.5,CH_4(燃料)/CH_4比为0.35,NiO循环量/CH_4比为1.4。CaO循环量/CH_4比从0变化到0.5时,重整气中H_2浓度从0.60增长到0.99;CH_4(燃料)/CH_4比在0.25~0.45区间变化时,重整气中H_2浓度从0.86提高到0.99,产气量增加;NiO循环量/CH_4比在1~1.6区间变化时,重整气中H_2浓度从0.88增长到0.99,系统有效能效率变化较小。     

应用炉膛压力诊断气流床气化炉的火焰状态

气化炉是煤气化技术中的关键设备 .气化炉内火焰燃烧稳定性下降 ,会出现燃烧噪音增加、气化燃烧效率降低及熄火等现象 ,对安全性和经济性产生严重的影响 .对气流床气化炉内不同气化燃烧状态下的火焰压力信号进行了小波分析 .结果表明 ,压力信号在一定频段内的分布与气化炉内火焰燃烧的状态密切相关 ,发现随着火焰燃烧稳定性加强 ,气化炉内压力信号向高频方向移动 ,以此可以建立气流床气化炉燃烧诊断模型 .     

Ignition and Combustion of Dust-Gas Suspensions

The ignition and combustion of dust-gas suspensions are considered. It is shown that the ability of these systems to accumulate heat is determined not only by their kinetic and thermal properties but also by the relation between their reaction surface and the heat-removal surface (f). Experimental information on flame temperatures, ignition delays, and flame propagation over gas suspensions is processed using the parameter f, and the postulate on the stimulating role of the developed reaction surface in activating these processes is validated. It is shown that during overall burning, diffusion combustion of particles occurs only for rather small values of f. The ambiguous effect of the parameter f on the ignition and combustion processes leads to the necessity of optimizing the fuel size distribution and concentration for the effective operation of the power devices. The role of the macroparameters of two-phase flames of refractory metals in the synthesis of combustion nanoproducts is analyzed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 3–14, November–December, 2005.     

Study of the deactivation and regeneration of copper chromite on γ-alumina and magnesium chromite on γ-alumina catalysts for fuel combustion

The causes of the deactivation of catalysts for fuel combustion MeCr₂O₄/ -Al₂O₃ (Me = Cu or Mg) have been investigated using a variety of complex physical-chemical methods: IRS, ESDR, XPS, TPD and a pulse microcatalytic method. It has been concluded that the observed deactivation of catalysts during fuel combustion is due to the combined effect of high temperatures and reduction media.     

Mechanism and laws of combustion of composite solid propellants with a coolant

The model of combustion of a composition consisting of a quasi-homogeneous composite propellant (matrix) and coolant particles is considered. The model is based on the leading role of exothermal decomposition of the matrix and on the cooling effect of the second component by virtue of transverse heat transfer between the components in the condensed and gas phases. Formulas for combustion characteristics (temperature, burning rate, its sensitivity to pressure, and initial temperature) are derived and analyzed. The calculated dependences of these characteristics on pressure, particle size, concentration, and thermal effects of decomposition of the components show that transitional regimes with a stronger dependence of the burning rate on pressure than that of the initial propellant are reached in a certain range of parameters. An algorithm is proposed, and a parametric identification of the model on the basis of experimental data is performed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 6, pp. 51–60, November–December, 2007.     

Toluene oxidation on Pd catalysts supported by CeO2–Y2O3 washcoated cordierite honeycomb

A novel CeO₂–Y₂O₃ (CY) washcoat on cordierite honeycomb was prepared by an impregnation method, which was used as a support to prepare a Pd catalyst. A model reaction of the complete combustion of toluene was conducted to evaluate the performance of the developed Pd/CY catalyst. The CY washcoat support and the Pd/CY catalyst were characterized by XRD, Raman spectroscopy, H₂-TPR and SEM techniques. The results show that compared with conventional washcoat the CY washcoat has better adhesion and higher vibration- and heat-resistance. The CY washcoat can anchor well Pd onto the cordierite honeycomb substrate. The formation of a CeO₂–Y₂O₃ solid solution and the steady present of PdO occur at high calcination temperatures, resulting in a better thermal stability. On a Pd/CY catalyst calcined at 500 °C, a 99% of toluene conversion was obtained at 210 °C, and it was stable for reaction time up to 30 h.     

合成煤中钠对煤燃烧及灰特性影响

准东煤中钠含量高，燃用时锅炉会出现严重结渣问题。通过向准东煤为原料制取的超纯煤中添加灰的模型化合物，得到合成煤。并在此基础上利用热重-差示扫描量热分析法（TG/DTG/DSC）、X射线衍射仪（XRD）和灰熔融温度测定分析手段，研究Na₂O含量对煤燃烧特性和灰熔融性的影响。结果表明：钠主要影响合成煤的着火温度（T_i）与焦炭燃烧阶段，钠含量增加使T_i升高，并且Na₂O在灰中质量分数由5%升高至8%后，钠含量增加使焦炭燃烧速率先减小后加快，并能够改善煤粉燃尽特性。钠能够降低灰熔融温度，并在Na₂O质量分数高于5%后，温度下降更加明显。在三元相图中钠对莫来石的助熔作用是造成灰熔融温度降低的重要原因。XRD分析表明Na₂O含量增加，充当骨架作用的石英在钠的助熔作用下与难熔矿物硅钙石、MgO等生成低熔点长石类矿物，这类矿物在高温下有助熔作用，能够降低灰熔融温度。同时还生成助熔性含钠矿物霞石，加剧了灰熔融。     

定容条件下火药实际燃烧规律的数值模拟

为研究火药的实际燃烧规律,建立了定容条件下火药燃烧的修正数学模型,分析了火药实际弧厚的分布及变化、点火不同步和燃速系数变化等因素对火药实际燃烧规律的影响。在此基础上,用考虑综合因素的修正数学模型对定容条件下火药的实际燃烧过程进行了模拟,计算值与实验结果具有较好的一致性,说明修正模型所建立的假设及处理方案是合理的。     

水煤浆在燃油热水锅炉内的燃烧试验

主要介绍了７ＭＷ燃油热水锅炉改烧水煤浆的改造设计，水煤浆炉前系统的调试，锅炉改造后的调试和水煤浆燃烧试验的结果。