单级闪蒸问题的新算法——部分双向校正法

本文提出了定焓定嫡闪蒸问题的一个新算法——部分双向校正法。该法选择两个合适的误差函数,依它们下降的方向,分别同时校正两个变量。通过考核并与双层迭代法、牛顿-拉甫逊法进行比较,结果表明,该法具有适用物系范围宽,收敛速度较快、对初值要求不高等优点。     

低温液氮洗涤塔模拟计算

本文提出了由PR状态方程计算低温液氮洗体系的汽液平衡时氢的有效偏心因子计算式ωH2=-0.1015/(1～25.2474/MT),通过对低温液氮洗体系的露点、等焓闪蒸计算,证明了该校正方法的可靠性。并用全变量牛顿-拉甫逊法对低温液氮洗涤塔进行了模拟计算,收敛稳定,收敛速度较快。计算结果与国外提供的数据吻合较好。本工作是在M68000型微机上完成的。     

水-丙酸二元体系汽液平衡的热力学性质

用新型泵式沸点仪测定了在101.325kPa下水-丙酸二元系在不同液相组成时的沸点,用过量自由焓函数Q,采用间接法由Tpx推算了水-丙酸二元系的汽相平衡组成y。汽相的非理想性用截至第二项的维里系数的状态方程求出汽相混合物中组分逸度系数。二元体系活度系数的关联分别用Wilson模型、NRTL模型、Margules模型和vanLaar模型进行关联,用最小二乘法求出了它们的液相活度系数模型参数。用所得的液相活度系数来计算三个二元体系的过量吉布斯自由焓函数GE/RT。计算的泡点温度与实验测得的沸点温度吻合良好,由面积积分法检验这些模型参数计算的二元体系相平衡数据,得到很好的热力学一致性。     

水-乙酸-乙酸丁酯体系汽液平衡研究

用改进Rose釜测定了乙酸-乙酸丁酯、水-乙酸-乙酸丁酯(完全互溶区)体系在101.33 kPa下的汽液平衡数据。考虑乙酸的缔合效应,利用维里方程和Hayden-O'Connell(HOC)模型计算各组分的汽相逸度系数,校正汽相的非理想性,液相的非理想性全部归结到液相活度系数中予以校正。用NRTL,UNIQUAC模型对乙酸-乙酸丁酯的汽液平衡数据进行关联,并得到相应的模型参数、温度偏差和汽相组成偏差。比较二元体系的关联结果,用NRTL模型参数预测了三元汽液平衡数据,计算值与实验值吻合良好,预测精度较好,说明采用的模型参数是可靠的,能够为精馏的设计和模拟计算提供基础热力学数据。     

二甲基硫醚-二硫化碳-甲醇体系等压汽液平衡

用泵式沸点仪测定了100 kPa下二甲基硫醚-二硫化碳、二甲基硫醚-甲醇2个二元系以及二甲基硫醚-二硫化碳-甲醇三元系在不同液相组成时的汽液平衡数据,用Wilson、NRTL、Margules和van Laar模型分别对2个二元系活度系数进行关联,用最小二乘法求出其液相活度系数模型参数,用这些模型参数来计算其汽相组成y,根据过量Gibbs自由能函数Q(GE/RT),采用间接法由Tpx推算了2个二元系的汽相平衡组成。用所得的液相活度系数计算2个二元系的过量吉布斯自由能函数GE/RT,并由2个二元系与三元系回归出二硫化碳-甲醇二元系的NRTL模型参数。用3个二元系NRTL模型参数对所测的三元系数据进行关联,建立三元系汽液平衡的热力学模型并计算平衡时的汽相组成y和泡点温度。分别由Herington法和McDermott-Ellis法对2个二元系和三元系进行热力学一致性检验,结果表明这些相平衡数据满足热力学一致性。     

水-乙酸二元体系汽液平衡的热力学性质分析

用新型泵式沸点仪测定了在101.325kPa下水-乙酸二元系在不同液相组成时的沸点,用过量自由能函数Q,采用间接法由Tpx推算了水-乙酸二元系的汽相平衡组成y。汽相的非理想性用截至第二项的维里系数的状态方程求出汽相混合物中组分逸度系数。二元体系活度系数的关联分别用Wilson模型、NRTL模型、Margules模型和vanLaar模型进行关联,用最小二乘法求出了它们的液相活度系数模型参数。所得的液相活度系数来计算三个二元体系的过量吉布斯自由能函数GE/RT。计算的泡点温度与实验的所测得的沸点温度吻合良好,由面积积分法检验这些模型参数计算的二元体系相平衡数据得到很好的热力学一致性。     

甲乙酮-水-醋酸体系等压汽液平衡研究

用改进Rose釜测定了甲乙酮-醋酸、甲乙酮-水-醋酸体系在101.33kPa下的汽液平衡数据,其中二元体系汽液平衡数据均通过了热力学一致性检验.考虑醋酸的缔合效应,利用化学理论模型和Hayden-O'Connell(HOC)模型计算各组分的汽相逸度系数,校正汽相的非理想性,液相的非理想性全部归结到液相活度系数中予以校正.用NRTL、UNIQUAC模型对甲乙酮-醋酸的汽液平衡数据进行关联,并得到相应的模型参数、温度偏差和汽相组成偏差.用2组甲乙酮-水体系模型参数、5组水-醋酸体系模型参数结合本研究关联得到的甲乙酮-醋酸体系模型参数对甲乙酮-水-醋酸体系的汽液平衡数据进行了预测,通过比较预测偏差的大小筛选出了最优模型参数组合,用最优模型参数组合进行预测的结果为:温度的平均绝对偏差为0.51℃,甲乙酮、水、醋酸的汽相组成平均绝对偏差分别为0.0047、0.0065、0.0067.预测精度较好,说明采用的模型参数是可靠的,能够为精馏的设计和模拟计算提供基础热力学数据.     

甲醇-乙酸-丙酸多元体系汽液平衡

用新型泵式沸点仪测定了在100kPa下甲醇-乙酸、甲醇-丙酸、乙酸-丙酸3个二元体系以及甲醇-乙酸-丙酸三元系在不同液相组成时的沸点,并用间接法T-p-x(温度、压力和液相摩尔分数)推算了3个二元体系的汽相平衡组成。3个二元体系活度系数分别用Wilson模型、NRTL模型、Margules模型和van Laar模型进行关联,用最小二乘法求出了它们的液相活度系数模型参数,同时,用这些模型参数来计算它们的汽相摩尔分数。所得的液相活度系数来计算3个二元体系的过量吉布斯自由能函数,且所研究的所有体系中各组分之间不存在共沸点。用3个二元体系Wilson模型参数对所测的三元体系数据进行关联,建立该系统汽液平衡的热力学模型并计算平衡时的汽相摩尔分数和泡点温度。由面积积分法检验这些模型参数计算的3个二元体系相平衡数据,得到很好的热力学一致性。     

醋酸—甲酸—醋酸甲酯三元体系汽液平衡的研究

本文测定了醋-甲酸-醋酸甲酯三元体系和醋酸-甲酸、醋酸-醋酸甲酯、甲酸-醋酸甲酯三组二元系在760mmHg下的汽液平衡数据。采用Tamir等提出的考虑汽相分子缔合反应及非理想性给予校正的热力学摸型计算汽相逸度系数,液相活度糸数用Wilson方程进行热力学关联。     

α-蒎烯+β-蒎烯+对伞花烃常压汽液平衡测定与关联

采用改进的Ellis平衡釜测定了在常压(100.7 kPa)下三个二元物系α-蒎烯＋β-蒎烯(428.82 K ~ 438.13 K)，α-蒎烯＋对伞花烃(429.05 K ~ 447.15 K)，β-蒎烯＋对伞花烃(439.20 K ~ 448.66 K)和一个三元物系α-蒎烯＋β-蒎烯＋对伞花烃(432.17 K ~ 448.11 K)的汽液相平衡数据,并利用Herington规则，以积分检验法对实验数据进行了热力学一致性检验。选用Wilson、NRTL、UNIQUAC和UNIFAC活度系数方程进行关联和估算，用最小二乘法求出二元物系的最佳配偶液相活度系数模型的能量参数，并比较了汽相组成的计算值与实验值，其平均相对偏差均小于0.40 %。将得到的最佳Wilson二元模型参数直接用于该体系三元体系汽液相平衡数据的预测，计算的平衡温度与实验测得的平衡温度平均偏差为0.16 K。     

CALCULATION METHODS FOR DISTILLATION SYSTEMS WITH REACTION

A calculation procedure is presented for the solution of the equations describing a distillation process in which reaction is taking place. A mathematical model based on matrix notation is used to formulate the system equations. It is assumed that the distillation process can be represented by a system of interconnected stages, each of which is well mixed with the vapor and liquid phases in equilibrium. Reaction may take place in the vapor phase, liquid phase, or both. The equations describing this system are first presented. Then a calculation sequence and a correction algorithm are derived for the case in which the liquid and vapor solutions are ideal—that is, the equilibrium ratios are functions only of temperature and pressure and not of composition. The calculation sequence uses as variables of iteration the vectors of vapor flow rate, temperature, and reaction extents. A derivative correction method is used, and equations for the calculation of the Jacobian matrix are derived. The application of the method is illustrated by solution of two sample problems. The special case in which the heat of reaction is small, and constant molal overflow can be assumed, and the case in which the reaction rate is very fast and chemical equilibrium exists in each stage are considered.     

CALCULATION METHODS FOR DISTILLATION SYSTEMS WITH REACTION

A calculation procedure is presented for the solution of the equations describing a distillation process in which reaction is taking place. A mathematical model based on matrix notation is used to formulate the system equations. It is assumed that the distillation process can be represented by a system of interconnected stages, each of which is well mixed with the vapor and liquid phases in equilibrium. Reaction may take place in the vapor phase, liquid phase, or both. The equations describing this system are first presented. Then a calculation sequence and a correction algorithm are derived for the case in which the liquid and vapor solutions are ideal—that is, the equilibrium ratios are functions only of temperature and pressure and not of composition. The calculation sequence uses as variables of iteration the vectors of vapor flow rate, temperature, and reaction extents. A derivative correction method is used, and equations for the calculation of the Jacobian matrix are derived. The application of the method is illustrated by solution of two sample problems. The special case in which the heat of reaction is small, and constant molal overflow can be assumed, and the case in which the reaction rate is very fast and chemical equilibrium exists in each stage are considered.     

金属有机化学气相沉积法制备Al掺杂ZnO透明导电膜

采用自行开发的金属有机化学气相沉积(metal organic chemical vapor deposition,MOCVD)法,以乙酰丙酮锌和乙酰丙酮铝分别为锌源和铝源,以氮气为载气,在玻璃衬底上制备Al掺杂ZnO(Al-doped ZnO,ZAO)薄膜。通过改造MOCVD设备提高制备薄膜的稳定性和均匀性,研究了基片温度、载气流量、水蒸气等沉积条件对薄膜结构,沉积速率及其光、电性能的影响。用扫描电子显微镜、X射线衍射、紫外-可见分光光度计和四探针双电测电阻仪分别观察薄膜形貌结构,并测试其光、电性能。结果表明:薄膜为均匀、致密的纳米多晶薄膜,具有六角纤锌矿结构,且呈c轴择优取向生长;薄膜的(002)衍射峰与纯ZnO相比向低角度方向偏移,表明Al进入了ZnO晶格,并导致晶格膨胀;薄膜的紫外-可见光谱透过率在85%以上;电阻率最小可达10-4??cm。     

信号奇异性的边缘检测小波对CHF和最小膜态沸腾起始点的检测

汽液两相流动的CHF(临界热流密度)和T_min(最小膜态沸腾起始点)等特性点附近曲线存在转折,即在此点附近曲线的梯度要发生变化,从数学角度看这些点必然具备一定的奇异性.目前对于函数(信号)奇异性的检测方法主要是用小波变换实现的,由于小波分解具有良好的空间域和频率域的局部化特性,小波变换可以刻画出信号的变化规律以及对信号内奇异点的各种奇异性质进行检测和分析.对汽液两相流动中各传热特性点也可以用边缘检测小波变换去进行分析,并实现对它们的检测、定位和定量分析.通过对具体试验数据的边缘算子的检测证明了边缘检测小波完全可以用于对汽液两相流动的CHF和T_min等特性点进行检测,并开创了一类新的汽液两相流动的试验研究方法.     

载料气体对化学气相沉积合成石英玻璃沉积速率的影响

采用化学气相沉积工艺合成了石英玻璃,研究了沉积速率与载料气体之间的关系.利用扫描电子显微镜观察火焰中SiO2粒子微观形态和尺寸.通过对SiCl4水解、氧化反应速率的计算表明:在一定温度下,当同时存在充足的H2O和O2时,SiCl4氧化反应速率远高于水解反应速率.当载料气体为H2,Sicl4流量为25g/min时,观察火焰中SiO2粒子的微观形态发现存在大量非球状无定形聚集体,表明SiCl4未反应完全,沉积速率较低,约为220～240 g/h.同样SiCl4流量下.采用O2作为载料气体时火焰中颗粒均为球状,SiCl4全部反应,沉积速率较高,达到300～350 g/h.当SiCl4流量为15 g/min时,载料气体的改变对SiO2粒子形态和尺寸没有影响,SiCl4可以全部反应,沉积速率基本相同.当SiCl4流量较高(25 g/min)时,载料气体对反应机理和沉积速率有显著影响,若要SiCl4在极短时间内完全反应生成球状SiO2粒子,需选择O2作为载料气体,充足的O2保证SiCl4可以通过氧化反应全部反应完毕,沉积速率相应提高.     

OPTIMIZATION OF PARAMETERS FOR THE SYNTHESIS OF SILVER IODATE SUBMICRON BELTS BY TAGUCHI ROBUST DESIGN METHOD

A statistical experimental design method was implemented to optimize experimental conditions for the preparation of silver iodate fine belts using precipitation method. Ultrafine silver iodate belts were synthesized by addition of silver ion solution to the iodate reagent. The optimal conditions were determined using the Taguchi method. The effect of reaction conditions such as silver and iodate concentrations, flow rate of reagent addition, and temperature on the diameter of synthesized silver iodate belts were investigated. The results for analysis of variance (ANOVA) showed that silver iodate submicron belts can be synthesized by controlling silver concentration, flow rate, and temperature. Finally, the optimum conditions for synthesis of silver iodate submicron belts by this simple and fast method were proposed. The results of ANOVA showed that 0.001 mol/L silver ion concentration, 10 mL/min flow rate for addition of iodate reagent to the solution, and 0°C temperature are optimum conditions for producing silver iodate submicron belts with 228 ± 32 nm width.     

垂直管内R124-DMAC鼓泡吸收过程流型演化可视化实验

通过搭建一套垂直管管内鼓泡吸收热、质耦合传递特性可视化实验平台,对以R124-DMAC(一氯四氟乙烷-二甲基乙酰胺)为工质的鼓泡吸收过程的流型特征与分布规律进行研究。结果表明,制冷剂气体流率、吸收溶液流率和进口温度对鼓泡吸收过程的流型及其分布规律均产生一定的影响。在制冷剂气体流率和溶液入口温度较高的情况下,鼓泡吸收过程存在搅拌流、弹状流、泡状流3种流型。制冷剂气体在吸收管内被完全吸收的条件下,搅拌流流型高度不超过总吸收高度(喷嘴出口到气泡消失的垂直距离)的1/2;弹状流流型所占总吸收高度的比例不超过2/5;其余的吸收高度为泡状流流型。     

EXPERIENCE WITH ADOPTING ONE-PARAMETER IMBEDDING METHODS TOWARD CALCULATION OF COUNTERCURRENT SEPARATION PROCESSES

The one-parameter imbedding method (also called homotopy or continuation) was adopted toward solution of large sets of nonlinear algebraical equations describing counter-current separation processes. Different imbedding functions were tested on a spectrum of difficult distillation problems ranging from distillation of hydrocarbons to strongly nonideal distillation problems. For the one-parameter imbedding functions studied in this report the classical Newton-Raphson Formula can be easily generated after an appropriate selection of the control parameters. Two different approaches were used to solve the homotopy equations: i) marching integration, ii) sequential use of the Newton-Raphson method. The one-parameter imbedding technique represents a trade-off between robustness and computation time. The algorithm is more robust than the Newton-Raphson technique, however, the computational time is usually higher. A combination of the one-parameter imbedding and the Newton-Raphson approach seems to be a very efficient method, the solution is approached by the one-parameter imbedding technique and the Newton-Raphson method is used to finish the iteration process. Geometrical interpretation of convergence is presented.     

复杂反应体系的化学平衡分析

本文提出了一种新的通用化学平衡计算方法.该方法以反应程度和组分摩尔数同为迭代变量,用松弛法估计初值,Newton-Raphson法加速收敛,具有良好的收敛稳定性.同时用新算法分析了甲烷蒸汽转化中的结焦和Ti(C.N)的化学气相沉积,并对NH_3-CO_2-SO_2-H_2S-H_2O-CH_4-C_2H_6体系进行了热力学计算.所有考证的实例从零初值都得到了正确的结果.     

蒸馏塔板上汽液传质系数的确定——非平衡池法(Ⅰ)模型的建立及求解

本文提出一种确定蒸馏塔板上汽液传质系数的新方法——非平衡池法.该法将塔板沿液流方向分为适当数目的串联非平衡池,通过联立求解每一池各相的物料衡算、能量衡算、相平衡和传质传热速率方程,可从塔板入口组成得到出口组成.调整汽液传质系数使计算的出口组成与实测值相等,从而可确定出两相传质系数.方程组用混合牛顿法求解.