酶促合成生物柴油反应动力学

以Candidasp.99-125脂肪酶为催化剂,甘油三油酸酯和甲醇为底物,采用有序机制模型对酶促合成生物柴油的酯交换反应动力学进行了研究,并与经典乒乓机制模型进行了比较。研究结果表明,反应初速率的实验值与有序机制模型方程的计算值吻合很好。对于固定化Candidasp.99-125脂肪酶催化合成生物柴油的酯交换反应机理进行研究,采用有序机制模型比经典乒乓机制模型更为精确。反应过程中,醇抑制为竞争性抑制,在甘油三油酸酯浓度较小的范围内,醇抑制作用较为显著,醇浓度越低反应初速率越快。该有序机制模型可用来预测生物柴油的生产批次或连续反应器中酯交换反应的速率,确定最佳底物油脂和醇的浓度。     

Kinetics of methylamine conversion on a Pd catalyst in the presence of H2

The kinetics of disproportionation of methylamine to dimethylamine and ammonia in the presence of hydrogen have been investigated over a silica-supported palladium catalyst. At a fixed partial pressure of methylamine, the reaction rate generally increases with decreasing hydrogen partial pressure, approaching a limiting or maximum value at sufficiently low pressures of hydrogen. The existence of a maximum is supported by the observation that the presence of some hydrogen appears to be necessary for the reaction to proceed at a conveniently measurable rate. At a fixed hydrogen partial pressure, the reaction rate increases with increasing methylamine partial pressure. When the methylamine partial pressure is sufficiently low or the hydrogen partial pressure is sufficiently high, the reaction order with respect to methylamine can be somewhat higher than one. At such conditions, a mechanism involving a bimolecular reaction between two partially dehydrogenated methylamine molecules on the surface appears to make a significant contribution to the overall catalytic reaction.     

ANALYSIS OF OPEN SUN DRYING EXPERIMENTS

Open sun drying has lost its previous importance due to the fact that different factors affect its reliability and the quality of the products obtained.

One of the set-backs for the analysis of solar drying exoeriments is their deoendence on a non-controlled source of energy, i.e. solar radiation depends on climatic conditions and experiments are difficult to compare. It is thus necessary to investigate the advantages of a particular set up as well as the climatic influences. Open sun drying could constitute the natural reference, allowing the comparison of different drying strategies.

A new way of standardizing drying times, based on solar radiation inout, is proposed, to allow better evaluation of the experiments. An equivalent time is defined, allowing comparison of experiments carried out under different circumstances. Carrots and potatoes were used in these experiments.

The use of the average daily solar radiation 15.28 MJ m^-2.d^-1 in Palma de Mallorca (39.33°N, 2.37°E), is proposed for comparison purposes. An improvement of more than 12 % in the explained variance was observed, the unexplained variance being lower than 1 %.     

On the use of the WLF model in polymers and foods.

The validity of the WLF model with fixed "universal" coefficients was tested against that of the model original form with variable coefficients using published coefficients of polymers and amorphous sugars crystallization and viscosity data. The disagreement between the two versions of the model is particularly large at temperature ranges starting about 20 to 30 degrees K above the glass transition or reference temperature, excluding the former from being a model of general applicability. Because the WLF model mathematical structure entails the existence of an almost linear region near the reference temperature, establishment of its validity as a kinetic model and meaningful determination of its constants requires data spread over an extended temperature range, especially when the experimental results have a scatter.     

无机灰分对餐厨沼渣中有机质热解特性的影响

针对餐厨垃圾厌氧处理所产生的沼渣具有产量大、灰分质量分数高的特点,研究沼渣中无机灰分对其热解过程的影响. 通过热重分析和热裂解?气相色谱质谱联用技术（Py-GC/MS）分析沼渣热解动力学特性及其产物. 动力学分析结果表明,沼渣除灰后,失重速率显著提高,热解起始温度由180 ℃降至160 ℃. 除灰沼渣的总表观活化能比沼渣的略高,原因可能是除灰使沼渣内部孔隙增加,在促进挥发分析出的同时,削弱了部分组分在热解过程中的催化裂解作用. 产物分析结果表明,NaCl能够促进油相产物中烃类向酮类的转化,ZnCl₂通过促进酸类的脱羧作用,使烃类质量分数提高至66.8%;Fe₂O₃和Al₂O₃使烃类物质的质量分数分别提高至66.8%和72.7%,CaO和MgO可以促进酸类脱羧生成酮,使产物中酮类的质量分数高达46.5%和39.4%.     

预转变马氏体对GCr15钢贝氏体转变动力学的影响SCIEI

本文利用磁性法和膨胀法研究了GCr15钢M_s点以下贝氏体转变动力学以及不同温度预转变马氏体对240℃等温时贝氏体转变动力学的影响。试验结果表明,过冷奥氏体在M_s点以下等温过程中首先形成变温马氏体,继而转变为下贝氏体。随着等温温度的降低和预淬马氏体数量的增加,应力促发作用有助于贝氏体转变的加速,200℃左右其孕育期最短。但是,当温度继续下降、预淬马氏体超过一定数量之后,贝氏体转变却愈趋困难,此外,M_s点以下不同温度的预转变马氏体对随后240℃等温时贝氏体转变动力学影响的研究结果,也具有相同的特性。     

Reactivity study and kinetic evaluation of CuO-based oxygen carriers modified by three different ores in chemical looping with oxygen uncoupling (CLOU) process

In the chemical looping with oxygen uncoupling (CLOU) process,CuO is a promising material due to the high oxygen carrier capacity and exothermic reaction in fuel reactor but limited by the low melting point.The combustion rate of carbon is faster than the decoupling rate of oxygen carrier (OC).Hence,high tem-perature tolerance and rapid oxygen release rate of CuO modified by three different ores were investi-gated in this study.The kinetics analysis of oxygen decoupling with Cu-based oxygen carriers was also evaluated.Results showed that CuO modified by chrysolite had faster oxygen release rate than that of CuO.Limestone showed obvious positive effect on the oxidization process.The selected OCs could keep stable in at least 20 cycles,for about 1200 min.Shrinking core model (SCM) fitted well for the decoupling process in the temperature range of 1123-1223 K.Reduction rate kinetic information may aid in the development of chemical looping with oxygen uncoupling (CLOU) technologies during reactor design and process modeling.Ternary doped copper oxide with chrysolite and limestone could improve the reactivity of CuO in decoupling and coupling process and also improve the high temperature tolerance.     

丁腈橡胶硫化反应动力学研究

设计了促进剂A 4种不同用量的丁腈橡胶配方;基于配方,先利用密炼机将丁腈橡胶、硬脂酸和ZnO混炼,再利用开炼机加入硫黄、促进剂和防老剂,再利用无转子硫化仪分别测试了160℃、170℃和180℃下胶料硫化曲线;基于硫化曲线计算出了每组配方胶料硫化反应速率常数K和活化能Ea。结果表明,在焦烧期时,NBR硫化反应为非一级反应,真正的一级反应开始于硫化速率达到最大时,即tdis;焦烧期后的反应可分为2个阶段且遵循一级动力学反应规律。     

20CrMnTi连铸瞬态与平均冷速条件下凝固原位观察

 宽淬透性带和大尺寸TiN析出物严重危害20CrMnTi齿轮钢的产品质量,其控制的关键基础是掌握连铸过程中凝固组织演变行为机理。传统高温激光共聚焦扫描显微镜(HT-CSLM)原位观察研究通常将糊状区冷却速率设定为固定值,这不能有效反映连铸凝固过程中冷却速率的变化。为此,以国内某钢厂20CrMnTi 160 mm×160 mm小方坯为研究对象,首先通过二维切片凝固传热计算,确定内弧表面下方20、40、60 mm位置处糊状区的热历程、瞬态与平均冷却速率,进而设计HT-CSLM试验升温与降温方案。然后,开展这些位置处糊状区瞬态与平均冷却速率条件下HT-CSLM试验,研究揭示不同冷却条件下20CrMnTi的凝固过程、δ晶粒生长动力学和包晶相变机制。最后,通过电子探针分析(EPMA),考察冷却条件对凝固组织尺寸的影响规律。结果表明,由于凝固潜热的补偿,内弧皮下20、40、60 mm位置处初始凝固阶段冷却速率较小,凝固中后期逐渐增大,且越深入方坯内部越显著。这些位置处的平均冷却速率分别为102.81、44.63和34.93 ℃/min。δ晶粒率先从钢液中析出,其平均生长速率随着冷却速率的提升而增大。在瞬态冷却速率条件下,随着凝固的进行,瞬时生长速率呈增大的趋势,但是在平均冷却速率条件下瞬时生长速率则略微降低。这是因为在瞬态冷却速率条件下,糊状区冷却速率由慢至快,不断补偿了凝固潜热,同时初始形核数量少,生长空间大,溶质过冷度的影响相对较弱。当熔体温度降低至包晶相变临界温度时,δ晶粒快速转变为γ晶粒,即发生块状转变,导致固相率迅速增加,且伴随有部分γ晶粒快速聚合。整体上讲,包晶相变临界温度随着冷却速率的增大而降低,但是也受溶质初始含量的影响。此后,剩余液相向γ相转变,直至完全凝固。晶粒半径随着冷却速率的提升而减小,且在平均冷却速率条件下比瞬态冷却速率条件更小,这取决于初始凝固阶段的形核数量。     

基于相变产物构建DP1180相变动力学方程研究

摘要：DP1180钢相变动力学方程的构建,有利于其力学性能的精准调控。利用Gleeble 3500对DP1180钢进行相变点测定,结合切线法、金相 硬度法研究了DP1180钢在冷却过程中的显微组织演变规律,绘制连续冷却转变曲线(CCT),并基于相变产物对相变动力学方程（JMAK方程）进行了修正。结果表明：冷速为0.5~1℃/s时,组织为铁素体(F)和贝氏体(B);冷速为2℃/s时,有马氏体(M)出现;冷速为10℃/s时,组织为贝氏体(B)和马氏体(M);冷速大于20℃/s时,组织以马氏体(M)为主;显微硬度随冷速的增加而升高;基于不同相变产物对n值的影响规律,对传统JMAK方程进行修正,构建了基于相变产物的相变动力学方程,预测精度得到提升。