STAGE SEPARATION WITH CHEMICAL REACTION STEADY STATE COUNTERCURRENT EQUILIBRIUM STAGE SEPARATION WITH CHEMICAL REACTION BY RELAXATION METHOD

The relaxation method is used to calculate mole fractions and temperature profiles in a rectification column where a chemical reaction takes place. The method is general and the non-ideal vapor-liquid equilibria can be easily incorporated. The computer time is very low and the danger of divergence can be alleviated by an appropriate guess of relaxation factor. Calculated problems involving esterification reactions are presented.     

COUNTERCURRENT GAS ABSORPTION WITH CHEMICAL REACTION IN A LAMINAR FALLING FILM

An analytical solution for absorption of a gas with an accompanying first order reaction in a laminar falling film is developed. The gas flow is countercurrent to that of the liquid film. Change in the gas phase concentration because of the reaction, as it happens in practical situations, has been taken into account. Some computed results are presented to show the effects of the system parameters—namely, the reaction rate parameter, the Biot number, and the absorption factor— on the mass transfer enhancement factor and on the fractional removal of the feed gas over a given non-dimensional film length.     

化学气相反应法制备Zr-Si-C涂层

为了提高Zr-Si-C涂层与基体的结合强度,基于粉末埋入反应辅助涂覆工艺,采用新型化学气相反应法在SiC陶瓷表面制备Zr-Si-C涂层.SiC陶瓷基片被包埋于Zr-1%(质量分数)I2混合粉体中,在850～1 100 ℃进行化学气相反应.碘促进Zr原子向SiC陶瓷表面的传输,Zr与SiC之间的扩散反应导致在SiC表面生成连续的Zr-Si-C复合涂层.采用X射线衍射、扫描电镜结合X射线能谱分析以及相图分析确定了涂层微结构及相组成.结果表明:复合涂层内层为ZrC、中间层为Zr2Si-ZrC1-x复相区、外层为ZrC1-x.通过测量涂层厚度研究了涂层的生长动力学,在850～1 100 ℃范围内,涂层生长符合抛物线规律,活化能为(210±20)kJ/mol.     

GAS ABSORPTION WITH INSTANTANEOUS CHEMICAL REACTION IN A FALLING FILM FOR PARALLEL AND COUNTERCURRENT FLOWS

A theoretical analysis is presented for the absorption of a gas accompanied by instantaneous chemical reaction with a dissolved reagent in a falling liquid film of liquid. The reaction occurs on a moving front inside the liquid film separating the zones containing either of the reactants. The governing equations are solved by using a coordinate transformation to immobilize the reaction front. The effects of the different system parameters on the reaction front profile, absorption rate and enhancement factor are presented for both cocurrent and countercurrent flow of the gas. In the former case the reaction front profile shows a maximum, but in the later case it is monotonic in the axial distance along the film. The enhancement factor plots exhibit maxima in both the cases.     

SIMULATION OF STEADY DISTILLATION PROCESS ACCOMPANIED WITH MULTIPLE CHEMICAL EQUILIBRIUM REACTIONS BASING ON TRANSFORMED VARIABLES

The equations describing the steady state operation of distillation column with simultaneous equilibrium chemical reactions have been transformed into a new set or MESH equations by introducing transrormed composition, flow rate and enthalpy variables. The new set of equations are similar to equations describing traditional non-reactive distillation, and it is general when one or several reactions occur and inert components are present.

An algorithm combining relaxation method and modified Newton-Raphson method is proposed to solve the new equations, the relaxation method is used to estimate initial values, while the modified Newton-Raphson method is used to set solution. The reactive distillation processes of MTBE synthesis with n-butane and the separation of meta- and para-xylene are simulated as numerical examples     

高频等离子体化学气相沉积法制氮化硅的化学平衡计算

基于Ｇｉｂｂｓ自由能最小原理，开发了热力学通用程序，分析了以Ａｒ为载气、ＳｉＣｌ４和ＮＨ３为原料、在高频等离子体化学气相沉积反应器中制备Ｓｉ３Ｎ４超细粉的化学热力学过程得到了在典型条件下系统的主要组成，分析了温度、反应物浓度对平衡组成的影响通过热力学模拟，发现当ＳｉＣｌ４进料口在前，ＮＨ３进料口在后，且两个进料口均在高频等离子体尾焰处时，经脱ＮＨ４Ｃｌ的产物中氮含量较高，而反应物ＮＨ３与ＳｉＣｌ４的比例以（６～８）：１为好     

ENHANCEMENT OF STEADY STATE REACTION RATES THROUGH COOPERATIVE ADSORPTION†

The Elovich model for single component adsorption is extended to treat two components, especially when surface heterogeneity and interactions are present. When only surface heterogeneity is present, the resulting unique steady state is stable; also the steady state rate is decreased in comparison to the Langmuir model. When attractive forces are acting in opposition to surface heterogeneity, the resulting unique steady state displays enhanced rates. When surface heterogeneity has negligible influence, the system can exhibit triple (two stable and one unstable) steady stales. In the present case attractive interactions are present between all types of molecular pairs. However oscillations are not observed for the choice of realistic interaction parameters. In addition the stable steady slates display lower rates in comparison to the single steady state.     

含反应节点过程数据校正的扩展独立物流法

Among the techniques developed for bilinear data reconciliation problems, the method based on independent flows is well known in terms of both accuracy and efficiency. However, the independent flow method is not effective when reactor units are present in the process. In this paper, an extended independent flow method is proposed for the data reconciliation of the process with chemical reaction. By the new method, the independent flows finding algorithm is adjusted to avoid the difficulties caused by the reactors in the process, and the reaction constraints are introduced into the objective function of data reconciliation. As a result, the new method can be applied to the process with chemical reaction while retaining high solution accuracy. To test the performance, the new method and the most typical Crowe‘s projection method are used in the data reconciliation of a typical industrial process. The results show that the new method can effectively accomplish the data reconciliation of the muhicomponent process with chemical reaction and gives more accurate estimates than the Crowe‘s method.     

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.     

ON THE CONCEPT OF THE STEADY STATE IN CHEMICAL REACTOR ANALYSIS

The inlet and outlet streams of a chemical reactor may reach a steady state before the internal distributions of concentration, etc. have come to the steady state. Such a steady state, in which the reactor is viewed only as a system with certain inputs and outputs, may be called the black-box steady state (BBSS). The existence of a BBSS does not always imply that of a true SS, and the BBSS may be attained in a finite time even though the SS is only attained asymptotically. Indeed under some circumstances the BBSS can be achieved immediately upon start-up. Provided that the internal transients are not catastrophic, the practical, or operator's, concept of a steady state is really that of a BBSS.     

新松弛法与流量加和法结合模拟吸收过程

对传统的流量加和法进行了讨论和改进,并与新松弛法结合用于多级多组分吸收过程的模拟计算。实际考核结果表明,本文提出的算法具有初值要求不高,收敛稳定性好和计算速度快的特点。     

内校正2N牛顿-拉甫逊法与新松弛法结合用于多级多组分分离过程的计算

提出了将“内校正”观点引入2N牛顿-拉甫逊法的新算法,其主要特点是:①在雅可毕(Jacobian)矩阵的计算中同时考虑了温度、汽相流率和液相组成对目标函数的影响,在校正温度、汽相流率的同时,也隐含着对液相组成的校正。②ME方程系由非稳态的物料衡算式导出。③允许有多种设计变量指定方案。计算结果表明:该法兼具松弛法稳定性好和牛顿-拉甫逊法收敛速度快的优点,能同时适用于烃类物系和非理想物系的分离计算。     

在铂催化剂上-氧化碳氧化反应的多定态特性

对铂催化剂上一氧化碳氧化反应的多定态特性进行了实验研究,借助于奇异理论和突变理论,对实验结果进行了分析,找出了系统可能存在的定态数目,并预测出在定态数目不同的操作参数区域内,描述系统状态变量与操作参数的分岔图型式,最后,尝试利用系统的多定态特性识别反应的动力学模型,取得了满意的效果.     

MODEL OF CHEMICAL REACTION EQUILIBRIUM OF SULFURIC ACID SALTS OF TRIOCTYLAMINE

The chemical reaction of trioctylamine (TOA) and sulfuric acid in organic solvent/aqueous solution was carried out. TOA salt products of various kinds were obtained based on different conditions of operation and organic solvents. An equilibrium model, based on the chemical reaction of sulfuric acid and trioctylamine, is proposed. The equilibrium constants of various reactions of trioctylamine and sulfuric acid were searched by means of the modified LETAGROP-DISTR computer program, from which the sum of the least-square error of the extraction of sulfuric acid per unit concentration of TOA salts was minimized. The corresponding concentration profiles of the various main products as a function of the activity of sulfuric acid in the aqueous solution were also obtained. The activity coefficient of the sulfuric acid in the aqueous phase and the density of the aqueous solution of sulfuric acid were considered in order to evaluate the activity of the sulfuric acid in the aqueous solution more accurately. The results obtained from the proposed model are consistent with that of Wilson's published model.     

在铂催化剂上-氧化碳氧化反应的多定态特性

对铂催化剂上一氧化碳氧化反应的多定态特性进行了实验研究,借助于奇异理论和突变理论,对实验结果进行了分析,找出了系统可能存在的定态数目,并预测出在定态数目不同的操作参数区域内,描述系统状态变量与操作参数的分岔图型式,最后,尝试利用系统的多定态特性识别反应的动力学模型,取得了满意的效果.     

DESORPTION WITH CHEMICAL REACTION IN CONTACTING DEVICES

Chemical processes where a gas is absorbed into a liquid and reacts to give a product that desorbs back into the gas are quite common in the industry. In this study, the reaction between the absorbed gaseous reactant and a nonvolatile reactant is considered to be slow, fast or instantaneous, while the volatile product may react further in a slow reaction. Effects of various operating parameters such as the liquid and gas flow rates, the gas-liquid interfacial area and the coefficients for mass transfer are examined. Situations can arise where the absorbing gas reacts but the product diffuses completely to the bulk of the liquid, and the rate of desorption is null. The expressions presented here define conditions to avoid this situation and allow the calculation of the optimal design and operation of the gas-liquid contacting device     

化学气相反应法制备SiC涂层

采用化学气相反应法,以3种不同工艺在C／C复合材料表面制备了SiC涂层,并检测了其抗氧化性能．以工业用Si和辅助剂SiO2为原料,在高温、惰性环境中反应产生SiO蒸气,将其引入反应室与C／C复合材料在不同温度下进行气相反应,在试样表面生成一层致密的SiC涂层。X射线衍射分析表明：涂层是由β-SiC组成。从试样截面的扫描电镜可知：不同工艺制得的SiC涂层界面过渡带颗粒的微观形貌各异。经最优工艺制备的涂层过渡带很窄,有β-SiC纳米晶须生成,且其抗氧化性能最佳。     

固相法制备高光学质量氧化镧钇透明陶瓷

以国产商业纳米粉为原料,采用传统固相法制备直线透过率大于80%的高光学质量的氧化镧钇和掺钕氧化镧钇透明陶瓷。氧化镧钇透明陶瓷透光范围在0.3～8.5μm,可用于高温红外窗口;掺钕氧化镧钇透明陶瓷具有掺钕氧化钇透明陶瓷几乎一致的激光光谱性能,但其吸收带宽更大,在激光泵浦源806nm波段,吸收带宽达到7nm,有利于激光器件的小型化。Nd0.03Y1.77La0.2O3透明陶瓷实现连续激光输出,在1080nm波长最大激光输出功率为63mW。