Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff{\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (2) dehydrogenation of ethanol to acetaldehyde ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{CHO+H}}_{\mathrm{2}}), (3) esterification of acetic acid with ethanol ({\mathrm{C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+CH}}_{\mathrm{3}}\mathrm{COOH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+H}}_{\mathrm{2}}\mathrm{O}), (4) dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}\mathrm{OH}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ({\mathrm{2C}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{OH+O}}_{\mathrm{2}}\iff {\mathrm{CH}}_{\mathrm{3}}{\mathrm{COOC}}_{\mathrm{2}}{\mathrm{H}}_{\mathrm{5}}{\mathrm{+2H}}_{\mathrm{2}}\mathrm{O}). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.     

油页岩矿物质催化半焦燃烧特性及机理

利用微型流化床反应分析仪（MFBRA）研究了油页岩矿物质催化半焦燃烧特性，重点考察了半焦内部矿物质和外部页岩灰床料对半焦燃烧的催化作用，揭示了流化床反应器中半焦燃烧过程和机理。结果表明：内部矿物质和外部床料对半焦燃烧均具有明显催化作用，而两者共同催化效果最为显著。矿物质中CaO和Fe₂O₃对半焦燃烧具有催化活性，CaO催化作用强于Fe₂O₃。油页岩半焦燃烧反应活化能在60.41~78.97 kJ/mol之间，矿物质的催化作用会明显降低反应活化能。流化床反应器中，矿物质对半焦燃烧的催化作用主要表现在四个反应，即：挥发分裂解和燃烧、半焦表面炭燃烧、半焦内部炭燃烧以及一氧化碳燃烧。     

磁流变阻尼器抑制转子系统振动试验

针对大型旋转机械通过临界转速时振动过大及运行中故障频发等问题,搭建转子试验台,模拟启停机过程和碰摩、不对中故障。不改变原有支撑形式,安装自主设计的磁流变阻尼器,在不停机的情况下,试验研究阻尼器抑制转子通过临界转速时振动过大及各类故障振动。试验结果表明,阻尼器可以有效抑制转子系统临界转速附近的振动,降幅在60%以上;转子发生碰摩或不对中故障时,阻尼器可以降低其高倍频振动。     

Modelling of electron energy absorption and backscattering during EBW

A three-dimensional heat flux model for deep-penetrating electron beam welding (EBW) is established to mathematically describe the physical heat generation process during interaction between electrons and the dynamic molten pool free surface. Monte Carlo method is used to determine the electron-target interaction, and random distribution of initial electrons, progressive trajectory tracing and electron backscattering models are used to describe the spatial distribution of electrons absorption. The model is verified in preset keyholes and applied in the simulation on electron beam welding process, and the calculated bead shape shows a good consistency with experimental results.     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry     

-15℃下Na+， K+， Mg2+//Cl-， NO3-， SO42——H2O体系相平衡研究

新疆卤水硝酸盐矿主要含有Na⁺、K⁺、Mg²⁺、Cl^-、NO₃^-、SO₄^2-六种离子，属于高元复杂体系，其合理利用和开发需要不同温度下的相平衡研究作为理论支撑。采用等温溶解平衡法，对Na⁺， K⁺， Mg²⁺//Cl^-， NO₃^-， SO₄^2--H₂O体系在-15℃、NaCl·2H₂O饱和条件下的相平衡进行了研究，并构建了相图。相图中有六个零变量点和八个两盐结晶区，只存在一种复盐KCl·MgCl₂·6H₂O。八个两盐结晶区，分别对应于NaCl·2H₂O+Na₂SO₄·10H₂O、NaCl·2H₂O+NaNO₃、NaCl·2H₂O+KCl、NaCl·2H₂O+KNO₃、NaCl·2H₂O+MgSO₄·7H₂O、NaCl·2H₂O+MgCl₂·8H₂O、NaCl·2H₂O+Mg(NO₃)₂·6H₂O和NaCl·2H₂O+KCl·MgCl₂·6H₂O，其中NaCl·2H₂O+Na₂SO₄·10H₂O共晶区最大，在低温时，硫酸钠的溶解度最小，降温过程中较易结晶析出。与该体系在25℃下的相图相比，复盐种类减少5种，零变量点减少19个，相关系得以极大简化。     

15CrMoG钢棒材表面缺陷机理分析和工艺改进

分析得出,棒材表面细小纵裂纹和表面裂口缺陷产生于铸坯加热之前,且与结晶器弯月面保护渣有关。利用Thermo-Calc热力学软件计算15CrMoG钢凝固相变过程,结合亚包晶钢连铸凝固特点综合分析15CrMoG钢棒材表面缺陷的产生原因和产生机理。结果表明:15CrMoG钢在固相线温度附近发生包晶反应L+δ→γ和包晶转变δ→γ,不仅导致初生坯壳生长不均匀,而且加剧P、S元素在凝固前沿的偏析。而初生坯壳不均匀是导致棒材表面缺陷根本原因。棒材表面细小纵裂纹产生于结晶器内坯壳薄弱处,经过二冷和轧制工序在夹杂物和硫偏聚处扩展长大。棒材表面裂口缺陷是初生坯壳不均匀导致结晶器内液面波动大,造成铸坯夹渣所致。通过控制[C]0.16%～0.17%、[S]≤0.005%、保护渣碱度1.2、熔点≥1200℃、粘度≥1.0Pa·s,260 mm×30mm铸坯水量150 m³/h,拉速0.5 m/min等措施,裂纹合格探伤合格率由原45%提高至98%。     

矿用钻孔深度测量仪的设计

设计了一种以STM32F103微控制器为控制核心,基于24位高精度模数转换器的钻孔深度测量仪器。利用弹性波回波测距原理,通过测量出钻孔中钻杆的长度,实现钻孔深度的快速、无损、准确的测量,主要用于井下瓦斯抽放钻孔、探放水钻孔等煤矿通防工作的施工验收。仪器小巧轻便,操作简单,单人即可完成测量工作,节约下井的人力物力,提高生产效率,最长测量长度可达250米,误差不超过1米。