Phase Diagram of the Quaternary System KCl–MgCl<Subscript>2</Subscript>–NH<Subscript>4</Subscript>Cl–H<Subscript>2</Subscript>O at <Emphasis Type="Italic">t</Emphasis> = 60.00 °C and Their Application

Based on the requirement for the comprehensive exploitation and utilization of the salt lake resources magnesium chloride and potassium chloride, a new technology to produce KCl and ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) by using NH₄Cl as salting-out agent to separate carnallite is proposed. The solubilities of quaternary system KCl–MgCl₂–NH₄Cl–H₂O were measured by the isothermal method at t = 60.00 °C and the corresponding phase diagram was plotted and analyzed. The analysis of this phase diagram shows that there are seven saturation points and eight regions of crystallization. These eight regions of crystallization represent salts corresponding to KCl, NH₄Cl, MgCl₂·6H₂O, (K_1?n (NH₄) _n )Cl, ((NH₄) _n K_1?n )Cl, (K_1?n (NH₄) _n )Cl·MgCl₂·6H₂O, KCl·MgCl₂·6H₂O and NH₄Cl·MgCl₂·6H₂O. According to the phase diagram analysis and calculations, ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) and KCl can be obtained using carnallite as raw materials and ammonium chloride as salting-out agent at t = 60.00 °C. The new technology shows the advantages of being easy to operate and having low energy consumption. The research on this quaternary phase diagram is the foundation for reasonable development of carnallite resources and comprehensive utilization of the salt lake brines.     

SO_2和H_2O(g)对新疆高钠煤中钠挥发和形态迁移的研究

在水平管式炉上进行了400-1 100℃新疆高钠煤恒温燃烧实验,并利用逐级提取的方法分析煤及煤灰中钠的赋存形态,研究煤中钠的释放和形态迁移特性。重点考察700和1100℃下H_2O(g)和SO_2(g)单因素及双因素对煤中无机钠挥发和形态迁移的影响。结果表明,随着温度的升高,煤中钠的释放比例逐渐增大,其中,有机态钠最先析出,其次是水溶态无机钠,硅铝酸盐形式的无机钠则由于高热稳定性不易分解或挥发。低温下(700℃)H_2O(g)的存在降低了钠的挥发,而较高温度下(1 100℃)焦炭与水蒸气反应生成的局部还原性气氛促进煤中钠的挥发,但当入口气氛中H_2O(g)浓度高于20%时,促进作用减小。SO_2的存在抑制了煤中钠的挥发,随着燃烧温度升高,SO_2对钠的抑制作用减弱。H_2O和SO_2双因素作用下,低温下(700℃)抑制了煤中钠的挥发,而较高温度下(1 100℃)钠的挥发特性取决于两者在入口气氛中的浓度。对于选取的高钠煤,20%H2O和2.0×10-3SO_2入口气氛下,1 100℃煤燃烧钠的挥发比例由86%提高到了87.1%。     

不同等级煤与油共炼的转化率差异及残渣分析

选取安徽褐煤、辽宁褐煤和贵州烟煤三种煤为原料,以油溶性环烷酸钼为催化剂,分别与马瑞常渣(MRAR)、克炼常渣(KAR)以及催化裂化油浆(FCCS)在高压釜内模拟悬浮床加氢共炼反应。结果表明,不同的油体系下,两种褐煤都能达到83%以上的转化率,而对于贵州烟煤,转化率最高的FCCS体系与最低的KAR体系分别为67.75%和50.31%,相差很大。采用FT-IR和SEM分析反应后固体残渣,计算了固体残渣中脂肪族和芳香族中各个基团的相对含量,并对比了不同体系反应后固体残渣的微观形貌。结果表明,KAR体系的固体残渣脂肪链较长,支链化程度高,取代度较低。转化率较高的褐煤反应后固体残渣结构松散,分散度高;转化率较低的烟煤固体残渣随着转化率降低,残渣颗粒逐渐变大,表面更加光滑,板结程度加深。     

Progress in fluorene-based wide-bandgap steric semiconductors

Molecular bulks are favorable for the thermal and morphological stability in organic wide-bandgap semiconducting polymers with potential applications in both information and energy electronics. In this review, we present our progress in the design of fluorene-based bulky semiconductors with a fractal four-element pattern. Firstly, we established one-pot methods to spirofluorenes, especially spiro[fluorene-9,9′-xanthene](SFX) serving as the next-generation spiro-based semiconductors. Secondly, we observed the supramolecular forces at the bulky groups and discovered the supramolecular steric hindrance(SSH) effect on polymorphisms, nanocrystals as well as device performance. Thus, a synergistically molecular attractor-repulsor theory(SMART) was proposed for the control of nanocrystal morphology, thin film phase and morphology. Thirdly, the third possible type of defects has been identified to generate green band(g-band) emission in widebandgap semiconductors by the introduction of molecular strain design of cyclofluorene. Finally, the first bulky polydiarylfluorene with highly crystalline and β conformation was achieved by an attractor-repulsor design of tadpole-shape monomer, which offered an effective platform to fabricate stable wide-bandgap semiconducting devices. All the discoveries offer the solid basis to break through bottlenecks of organic/polymer wide-bandgap semiconductors by the improvements of overall performances.     

偶联剂改性对γ-Al2O3催化氧化偏三甲苯性能的影响

研究了偶联剂改性的廉价填料级γ-Al_2O_3直接催化偏三甲苯(TMB)氧化为2,3,5-三甲基苯醌(TMBQ)性能的影响。结果表明,γ-(2,3-环氧丙基)丙基三甲氧基硅烷(KH560)改性后的填料γ-Al_2O_3催化氧化活性较高。考察了KH560用量、水解时间、吸附时间及吸附温度对催化效果的影响。在优化条件下(2mL KH560/Et OH溶液(体积比1∶25),水解1h,吸附4h,吸附温度50℃),偶联剂对填料γ-Al_2O_3表面产生一定的包覆,在催化氧化TMB时较温和,副反应较少,TMB转化率和TMBQ选择性分别为14.3%和72.4%。     

VERIFICATION OF SMOM AND QMOM POPULATION BALANCE MODELING IN CFD CODE USING ANALYTICAL SOLUTIONS FOR BATCH PARTICULATE PROCESSES

For many processes of industrial significance, due to the strong coupling between particle interactions and fluid dynamics, the population balance must be solved as part of a computational fluid dynamics （CFD） simulation. In this work, a CFD based population balance model is tested using a batch crystallization reactor. In this CFD model, the population balance is solved by the standard method of moments （SMOM） and the quadrature method of moments （QMOM）. The results of these simulations are compared to analytical solutions for the population balance in a batch tank where 1） nucleation, 2） growth, 3） aggregation, and 4） breakage are taking place separately. The results of these comparisons show that the first 6 moments of the population balance are accurately predicted for nucleation, growth, aggregation and breakage at all times.     

平面叶栅跨音流场气动特性的数值研究

通过对模型方程的分析，给出了一种新的隐格式构造思想。将它运用到关通量分裂格式中，可得到无近似因子分解、无矩阵运算的高效二阶精度隐式矢通量分裂差分格式，并用来直接求解时间平均Ｎａｖｉｅｒ－Ｓｔｏｋｅｓ方程组。数值计算标明：该方法具有精度高、稳定性好、计算量少、收敛快等优点，在平面叶栅跨音流场的计算中，较好地捕获了激波，与实验比较，结果令人满意。     

稳恒扩展裂纹尖端的弹粘塑性场

采用弹粘塑性力学模型代替通常的弹塑性模型，对于I型和Ⅱ型问题，分别求得了不可压缩材料中平面应变动态扩展裂纹尖端的指数奇异性场和对数奇异性场，消除了弹塑性解中存在的塑性激波。通过数值计算，分别求得了两种奇异属性的分界线，建立起统一的裂纹尖端奇异性场。     

增韧环氧树脂的动态裂纹扩展研究

本文主要进行了环氧及增韧环氧树脂的断裂韧性及裂纹快速扩展的试验研究。试验过程中采用了ＧＬＣ－１型高速裂纹扩展测试仪来测试裂纹的扩展速度,得到在裂纹扩展过程中裂纹扩展速度曲线。本文结合不同的计算公式及有限元分析方法,讨论了各个确定断裂韧性公式的准确程度,发现传统的静态断裂韧性的分析方法所得到的结果偏大,有一定的危险性,建议使用试验与数值计算相结合的方法;同时还发现增韧不仅可以提高材料的静态和动态断裂性能,而且在裂纹扩展过程中可以起到减缓裂纹扩展的作用     

Synthesis of Novel Spiro Pyrrolidine and Pyrrolizine Derivatives by 1,3-Dipolar Cycloaddition

The 1,3‐dipolar cycloaddition of azomethine ylides derived from isatin and amino acids viz. sarcosine and proline to 2‐arylmethylidene‐5,6‐dihydroimidazo[2,1‐b]thiazol‐3(2H)‐ones afforded novel spiro pyrrolidines and pyrrolizidines regio‐ and stereoselectively in moderate yields. The products were characterized thoroughly by IR, MS, NMR together with elementary analysis.