乙酸丁酯反应精馏过程模拟设计

反应精馏偶合了反应和精馏两种单元操作,通过精馏促进反应,可以提高反应转化率和收率,为可逆反应的化工过程生产提供了新的设计途径。基于严格热力学分析计算,利用计算机模拟和优化手段。提出了乙酸丁酯反应精馏、分离纯化的生产流程。采用UNIQUAC方程表征乙酸-正丁醇-乙酸丁酯-水四元非理想体系的汽液平衡,首先,根据实验数据回归了热力学模型中的交互作用参数,并预测了体系中5个共沸物组成,模型的计算结果与实际数据吻合。基于平衡级模型,提出了由平衡反应器、反应精馏塔、倾析器和纯化塔构成的可行流程,对提出的设计流程进行了模拟、优化,得到了操作工艺参数。模拟结果对工业过程的设计和改造具有一定的指导意义。     

Development of automatic fault point locating and sectional isolating system for power distribution line

This paper describes the development of the Automatic Fault Point Locating and Sectional Isolating System. This system locates a single-line-to-ground fault point at each pole by using ground-current sensors, and isolates the faulted section by controlling pole switches with no outage of unfaulted sections. The ground-current sensor is connected to the line between allied ground terminals of pole devices and grounded conductor. It detects a ground fault current of more than 0.64 amperes that is determined so as to avoid an unexpected operation by stray current, but to detect the fault current accurately, and sends out an emergency signal with time delay of 0.1 s. Sectional isolation starts when both the emergency signal from the sensor and relay operation signals from a substation are received and ends within a feeder circuit-breaker tripping time of 1.5 s.     

Mechanism of formation of C2-oxygenated compounds from CO + H2 reaction over SiO2-supported Rh catalysts

The mechanism of acetaldehyde and ethanol formation from the CO + H₂ reaction below atmospheric pressure has been investigated by combining infrared spectroscopic measurement and ¹³CO and C¹⁸O isotopic tracer studies with reaction kinetics. The rates of acetaldehyde and ethanol formation are markedly dependent on the nature of metal precursors employed. The addition of sodium cations depresses the total catalytic activity, while the selectivity for ethanol is increased by the addition of manganese cations. From the behavior of surface species under reaction conditions, it is concluded that acetaldehyde is formed through the following two steps: (i) CO insertion into C₁ species which are reaction intermediates for not only hydrocarbons but also for the methyl group in acetaldehyde, and (ii) subsequent formation of acetate ions whose one oxygen atom is supplied from the support, finally producing acetaldehyde. Differences in ¹⁸O distribution in acetaldehyde and ethanol during the C¹⁸O + H₂ reaction indicate that ethanol is not produced via direct hydrogenation of acetaldehyde.     

Sintering Behavior of Pt Metal Particles Supported on Silica-Coated Alumina Surface

The sintering behavior of Pt metal particles was studied by supporting them on silica-coated alumina. Silica coating was found to be effective for the retention of a large surface area of alumina even after calcination at elevated temperatures. Before sintering, the size of Pt metal particles on all the silica-coated aluminas, including the uncoated alumina, was identical, while the particle size was larger on silica than on alumina. After sintering the Pt catalyst at 1073 K, the particle size increased on uncoated alumina as well as on alumina coated with thicker silica layers, especially on the supports previously calcined at >1473 K. On the other hand, the size of Pt metal particles did not increase much on alumina coated with monolayer silica. The observed suppression of sintering of Pt metal particles resulted from the retention of a large surface area of alumina with a thinner silica layer. In the case of a thicker silica layer, although a large surface area was maintained after calcination at elevated temperatures, the existence of a bulk silica-like property of the support did not favor the suppression of sintering of Pt metal particles.     

Preparation of High-Performance Co3O4 Catalyst for Hydrocarbon Combustion from Co-Containing Hydrogarnet

Supported Co₃O₄ catalysts were prepared via the calcination of Co-containing hydrogarnet, (Ca_3-x Co _x )Al₂(SiO₄)_{3- y} (OH)_4y , at 400 °C. Such precursors with various extents of substitution were synthesized from the hydrothermal reaction of a stoichiometric mixture of calcium oxide, amorphous silica, alumina sol, and cobalt hydroxide at 200 °C. It was found that the catalyst consisted of Co₃O₄, CaO, and mayenite and exhibited a high activity for the combustion of propylene, benzene, and toluene at temperatures below 300 °C.     

Dynamic behavior of reaction intermediates on catalyst surfaces in the working state: Behavior of formate ion during the decomposition of formic acid on Ni/SiO2 catalyst

The reactivity of the formate ions on Ni/SiO₂ catalyst was examined during the course of the formic acid decomposition. It is of great interest to note that the reactivity was markedly increased by the presence of formic acid in the ambient gas compared to that at the same coverage under vacuum. It is accordingly suggested that the formate ion behaves as reaction intermediate through the interaction between the formic acid molecules in the ambient gas.     

Formation of brownmillerite type calcium ferrite (Ca2Fe2O5) and catalytic properties in propylene combustion

Several types of calcium ferrite base catalysts (Ca/Fe = 0.33–3) for propylene (C₃H₆) combustion were prepared. Calcium ferrite catalyst with brownmillerite crystal structure provided catalytic activity for C₃H₆ combustion in the temperature range of 250–450 °C. The brownmillerite phase (Ca₂Fe₂O₅) was responsible for the formation of oxygen adspecies (O ₂ ⁻ ) in the surface layer below 450 °C.     

A crucial role of O2 and O2 on mayenite structure for biomass tar steam reforming over Ni/Ca12Al14O33

Newly synthesized nickel calcium aluminum catalysts (Ni/Ca₁₂Al₁₄O₃₃) were tested in a fixed bed reactor for biomass tar steam reforming, toluene as tar destruction model compound. Four catalysts (Ni/Ca₁₂Al₁₄O₃₃) were prepared with Ni loading amount from 1, 3, 5 to 7 wt%, even 1% loading catalyst also showed excellent performance. Catalysts aged experiments in the absence (60 h on stream) and presence of H₂S were characterized by BET, X-ray diffraction (XRD), and Raman spectra. It was observed that Ni/Ca₁₂Al₁₄O₃₃ showed excellent sustainability against coke formation due to the “free oxygen” in the catalysts. It also exhibited higher H₂S-poisoning resistance property compared to the commercial catalysts Ni/Al₂O₃ (5%) and Ni/CaO_0.5/MgO_0.5. Raman spectra revealed that “free oxygen O₂⁻ and O₂²⁻” in the structure of the catalysts could be substituted by sulfur then protected Ni poisoning on some degree, but reactivation experiments by O₂ flowing showed that the sulfide Ni/Ca₁₂Al₁₄O₃₃ was difficult to completely restore, incorporation of sulfur in the structure only partly regain by O₂. The kinetic model proposes, as generally accepted, a first-order reaction for toluene with activation energy of 82.06 kJ mol⁻¹ was coincident with the literature data. The Ni/Ca₁₂Al₁₄O₃₃ catalyst was effective and relative cheap, which may be lead to reduction in the cost of hot gas cleaning process.