LaDAIY型沸石的裂解活性和抗氮性能

采用脉冲微反技术,以含吡啶的正庚烷为原料,考察了LaDAlY型沸石的裂解和抗氮性能。结果表明,LaDAlY型沸石的裂解与抗氮性能均优于其母体样品DAlY。结合NH_3-TPD的数据,讨论了酸性与裂解和抗氮性能之间的关系,对吡啶中毒的机理进行了探讨。     

正庚烷在β沸石负载碳化钼催化剂上的异构化研究

利用程序升温还原法制备了β沸石负载碳化钼催化剂。XRD表征显示，利用正戊烷作为碳源得到了对异构化具有活性的βMo2C。以正庚烷为模型反应物，在连续流动固定床反应装置上考察了温度、压力、空速和氢烃比对βMo2C/β沸石催化剂临氢异构化反应性能的影响。获得了β沸石负载碳化钼催化剂上正庚烷异构化的最佳反应条件温度270℃～275℃，压力1.0MPa～1.5MPa，体积空速1.0h－1，氢烃体积比200∶1。在最佳条件下反应物转化率为82%，选择性和异构产物收率分别达到71%和58%。     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

3-D simulation of soot formation in a direct-injection diesel engine based on a comprehensive chemical mechanism and method of moments

Here, we propose both a comprehensive chemical mechanism and a reduced mechanism for a three-dimensional combustion simulation, describing the formation of polycyclic aromatic hydrocarbons (PAHs), in a direct-injection diesel engine. A soot model based on the reduced mechanism and a method of moments is also presented. The turbulent diffusion flame and PAH formation in the diesel engine were modelled using the reduced mechanism based on the detailed mechanism using a fixed wall temperature as a boundary condition. The spatial distribution of PAH concentrations and the characteristic parameters for soot formation in the engine cylinder were obtained by coupling a detailed chemical kinetic model with the three-dimensional computational fluid dynamic (CFD) model. Comparison of the simulated results with limited experimental data shows that the chemical mechanisms and soot model are realistic and correctly describe the basic physics of diesel combustion but require further development to improve their accuracy.     

载体的晶化对Ni/WO3-ZrO2催化剂结构及催化正庚烷异构化活性的影响

采用XRD、BET、IR、SEM、NH3-TPD方法对以无定形Zr(OH)4和已晶化的ZrO2为载体制备的Ni-WO3/ZrO2催化剂进行了表征,考察了载体晶化对催化剂结构、酸性及催化性能的影响。结果表明,载体晶化减弱了W与Zr间的相互作用,抑制了四方相ZrO2的生成,减少了催化剂上强酸中心的数目,从而降低了Pt-WO3/ZrO2催化剂上正庚烷异构化反应活性.     

正庚烷化学动力学简化模型的构建及优化

提出了一个新的适用于HCCI发动机燃烧模拟的正庚烷化学反应动力学简化模型(40种组分和62个反应)。由三个子模型组成:低温反应子模型是在Li等人模型的基础上,定义具体的醛类(RCHO)产物和小分子碳氢产物(Rs)而构建;增加了用于链接低温反应向高温反应过渡的大分子直接裂解成小分子反应子模型;高温反应子模型是在Griffiths等人模型的基础上,去除了无关的基元反应,增加两个关于CO和CH3O的氧化反应而构建。另外,采用遗传优化技术对模型动力学参数进行调整。计算表明,新模型能够在当量比0．2-1．2,温度从300-3000 K的范围内精确模拟正庚烷HCCI燃烧时冷焰和热焰反应过程,与详细模型(544种组分和2446个反应)计算结果吻合较好。     

Pt/SAPO-11临氢异构化催化剂反应特性的研究

以正庚烷为模型化合物，在10 mL连续流动固定床反应装置上，考察了温度、压力、空速与氢烃摩尔比对0.4%Pt/SAPO-11催化剂临氢异构化反应性能的影响。结果表明，催化反应以烷烃异构化为主，正庚烷转化率达70%时异构产物选择性保持在90%以上，压力和氢烃摩尔比较小时，产物的选择性较高；压力太高裂解产物生成量增多对异构化选择性不利。获得了正庚烷在Pt/SAPO-11催化剂上临氢异构化的优化反应条件为，360 ℃～380 ℃，0.5 MPa～1.0 MPa，2.1 h-1～4.1 h-1，H2/CH(摩尔比)2～6；烷烃临氢异构化反应的一个条件变化，需要其他条件的改变来达到最佳的匹配。     

SiO2骨架支撑MoOx催化剂用于正庚烷异构化反应

 采用SEM，XRD，EDS及N2吸附－脱附方法研究了骨架型MoOx－SiO2催化剂和负载型MoOx／SiO2催化剂的物理化学结构，并在常压固定床流动反应器上考察了两种催化剂对正庚烷异构化反应的催化性能．结果表明，在MoOx－SiO2催化剂中，44．6％的SiO2即可起到很好的骨架支撑作用；MoOx晶相以足够大的空间区域聚集包裹在SiO2骨架中，形成类似MoOx催化剂的独特的中孔结构．与MoOx催化剂相比，MoOx－SiO2催化剂显著提高了机械强度，并维持了MoOx催化剂较高的活性和选择性．由于钼物种和载体之间的相互作用，负载型MoOx／SiO2催化剂表现出较低的比活性．脉冲注入H2S实验结果表明，MoOx－SiO2催化剂具有较好的抗硫性能．