多相多组分体系相平衡计算的改进τ因子法

提出了一种多相平衡计算的改进τ因子法,该方法基于一种修正各相摩尔分数和的概念,研究模型的建立和用遗传算法计算多组分复杂体系的相平衡问题。首先通过建立数学模型,将相平衡计算问题转化为带线性约束的非线性规划(NLP)问题;其次用遗传算法对模型进行求解,并通过对优化变量采取动态边界的可行域编码方法保证了算法的有效实施;最后对2个体系的计算表明,结果与文献值相吻合,且此方法不仅可以求解不含化学反应体系的相平衡问题,也同样适用于含化学反应体系的相平衡计算,是一种比较可靠和通用的方法。     

一种计算含盐有机溶液气液相平衡的方法

提出了一种计算含盐混合溶剂气液相平衡的新模型,即把活度系数表示为盐的质量摩尔浓度ms和溶剂组成摩尔分数xi的函数,其中盐质量摩尔浓度项表示为盐质量摩尔浓度的二次函数,溶剂组成项由UNIQUAC模型计算。以文献中水-醇-盐和醇-醇-盐的11个体系为例,将新模型用于其气液平衡的计算,关联得到了各体系的模型参数。结果表明:将活度系数表示为ms和xi的函数是合适的;每种溶剂组分气相分压的计算值与实验值吻合良好,最大误差为0.928 k Pa。因此,新模型是一种可广泛用于含盐有机溶液体系气液相平衡计算的方法。     

Matlab在二元完全理想系相平衡关系计算中的应用

为了探索Matlab在二元完全理想系相平衡关系计算中的应用,以苯-甲苯体系为例,采用直接计算法得出其气液相平衡数据,随后以图解法、三次样条插值法、系数向量法和相对挥发度法计算该体系的泡、露点温度和饱和气、液相中轻组分苯的摩尔分数。当苯的摩尔分数为0.5时,上述四种方法所得体系的泡点温度分别为92.11、92.11、92.08、91.94℃,露点温度分别为98.77、98.77、98.77、98.90℃;当系统温度为95℃时,饱和气相中苯的摩尔分数依次为0.6264、0.6264、0.6267、0.6216,饱和液相中苯的摩尔分数依次为0.4045、0.4045、0.4037、0.4015。相对偏差分析发现,以图解法为基准时,其他方法的计算精度由高到低依次是：三次样条插值法、系数向量法和相对挥发度法;最大相对偏差低于1%,均可用于后续的精馏计算中。     

多相平衡的状态方程一步算法研究

介绍一种多相平衡的状态方程一步算法 ,即一种通过修正摩尔分数和的解方程法———τ因子法。该法只需要求解一次最小化问题 ,就可以同时给出多相平衡时存在的相数、各相的量及组成。文中对正十六烷 水 氢气和甲苯 水 氢气等两个体系进行了闪蒸计算。     

含R1234yf混合工质汽液相平衡的混合规则评估与预测研究

含R1234yf混合工质具有系统性能优良且对环境友好的特点,在当前制冷剂迭代中受到了广泛关注。汽液相平衡性质是混合工质的基础热物理性质,其理论计算至关重要。为提高含R1234yf混合工质汽液相平衡数据的计算精度,选取PR状态方程结合vdW、WS、MHV1三种混合规则和NRTL活度系数模型评估了16种含R1234yf二元混合工质的汽液相平衡性质。结果表明,WS混合规则和MHV1混合规则计算性能优于vdW混合规则;vdW混合规则对大多数混合工质计算性能较好。最后提出一种预测模型预测含R1234yf混合工质汽液相平衡性质,预测的相对压力偏差值为0.49%,气相摩尔分数绝对偏差值为0.0031,预测偏差满足工程应用。     

双流化床生物质气化的三维全循环数值模拟

基于多相质点网格方法 (multi-phase particle-in-cell,MP-PIC)对工业尺度的双流化床生物质气化过程进行了三维全循环数值模拟。其中,在拉格朗日框架下求解颗粒团运动,采用大涡模拟法(large-eddy simulation, LES)求解气相湍流,同时考虑复杂的气固耦合以及生物质的热解、气化、均相/异相反应。首先,通过独立性检验确定了计算所需的最佳网格数与计算颗粒数,且模拟结果和实验结果对比良好。其次,揭示了流化床内生物质气化过程中的气固流动特性及气体组分分布规律,研究了床内温度、生物质粒径、曳力模型等因素对产物气体组分分布的影响。结果表明:温度升高,出口处的CO摩尔分数增加,而其余组分都减小;较小生物质粒径的气化效果要优于较大的生物质颗粒粒径;曳力模型对各产物气体组分的摩尔分数几乎无影响。     

浅谈独立组分数

本文详细分析了相平衡系统中物种数和独立组分数的概念,指出在应用时独立组分数比物种数更方便,在涉及盐类的水合物问题时,运用组分数便于学生理解,因此相律的表达式中用独立组分数而没有用物种数。     

R32+R1234yf+R1234ze（E）混合制冷剂气液相平衡实验研究

基于液相循环法搭建的气液相平衡实验装置,在263.15~323.15 K温度范围内,实验测量了R32+R1234yf和R1234yf+R1234ze（E）二元混合物以及R32+R1234yf+R1234ze（E）三元混合物的气液相平衡数据,利用PRSV状态方程结合WS混合法则和NRTL活度系数模型进行关联拟合,获得二元混合工质的交互参数,并在其基础上预测了三元混合工质气液相平衡性质。计算结果与实验数据对比表明,二元体系R32+R1234yf和R1234yf+R1234ze（E）的压力平均绝对偏差分别为0.71%和0.20%,气相摩尔分数平均绝对偏差均约为0.0016,三元体系R32+R1234yf+R1234ze（E）的压力平均绝对偏差为0.82%,系统组分R32和R1234yf的气相摩尔分数平均绝对偏差均约为0.007。     

非理想多相共存体系的平衡计算

对于给定温度和压力的系统，平衡状态时其吉布斯自由能最小。根据热力学基本关系式，在多组分体系中元素和电荷守恒的限制条件下，最小化吉布斯函数，通过SQP方法来求解此有约束的优化问题，通过迭代法求解反应后的温度。该方法可用于复杂的非理想、多相流体、电解液或非电解液混合物的相平衡计算，平衡计算结果包括温度、密度、组分浓度等。对于某新型热动力系统中使用的一种含铝火药，应用本文方法，获得了化学平衡计算结果。     

苯和二甲苯体系固液相平衡的数据预测与相图

针对对二甲苯装置结晶单元中由苯和二甲苯组成的相关体系,选取了固液相平衡计算模型—Van′t Hoff方程简式,利用与苯和二甲苯有关的二元和三元体系固液相平衡文献数据对该模型进行考察,利用该模型预测由苯和二甲苯组成的二元和三元体系的固液相平衡数据,并绘制三元体系的固液相平衡相图。结果表明：采用Van′t Hoff方程简式计算,苯和二甲苯有关体系的液相摩尔分数的平均相对偏差为2.69%,低共熔点温度的偏差最高为0.59℃,最低为0.01℃,表明所选模型适用于由苯和二甲苯组成的体系固液相平衡计算;利用该模型预测苯-间二甲苯、苯-邻二甲苯二元体系及对二甲苯-间二甲苯-苯、对二甲苯-邻二甲苯-苯、间二甲苯-邻二甲苯-苯三元体系的固液相平衡数据,绘制了对二甲苯-间二甲苯-苯三元体系的固液相平衡相图,这些新的相平衡数据和相图均未见有文献报道,可为对二甲苯结晶相关体系的固液相平衡研究提供理论指导和依据。     

Computation of phase and chemical equilibria

A new method is proposed for the computation of simultaneous phase and chemical equilibria by minimization of the Gibbs energy. A non-linear programming approach is used which enables one to determine the number and identity of phases at equilibrium, as well as the compositions of each component in each phase. Any thermodynamic model which predicts fugacities can be incorporated easily in this method. Numerical results of various systems that involve gases, liquids and solids are presented.     

伴有平衡反应的分离过程的数学模拟(Ⅰ)板式反应精馏塔的模拟计算

本文提出了相平衡和化学平衡同时存在的多相复杂可逆反应的反应精馏计算方法。模型方程由物料衡算方程,化学平衡方程,相平衡方程,归一方程,焓衡算方程组成。模型分三层迭代求解。该算法可适用于非理想系统、反应动力学未知的快速可逆反应过程。并且对不同操作条件下的计算均能稳定收敛,可以进行操作条件的调优。应用该算法模拟计算未达到平衡的反应过程,可以预测各板上的最大转化率和各板组成。     

混合整数非线性规划法求解多组分复杂体系相平衡问题

基于Gibbs自由能最小化原理,提出一种求解多组分复杂体系相平衡问题的混合整数非线性规划(MlNLP)方法.通过建立MlNLP模型,将相平衡计算问题转化为有约束的双层最优化问题,内层用来计算给定相组合结构下的平衡组成,外层则是搜索最优的相组合结构,整个求解过程通过遗传算法来实现.所建立的方法只需要求解最小化问题,就可以同时给出多相平衡时存在的相数、相态及各相组成.以苯-乙氰-水和甲醇合成两个体系的相平衡计算为例,结果表明该方法是可行和有效的.     

复杂体系化学平衡组成计算方法

The chaos-Monte Carlo algorithm (CMCA) was proposed for solving chemical equilibrium of complex system. By introducing random well-distributed points into the Monte Carlo algorithm, this new approach showed good convergent probability and high-speed. Equilibrium composition of some complex systems, such as methanol synthesis, ammonia oxidation, and Claus process were calculated. The results showed good agreement with Liu Xiaodi‘s and Xu Jinhuo‘s calculations. Compared with the gradient method, the genetic algorithm and the modified genetic algorithm, the CMCA is simple, general and insensitive to initial value. It is an efficient algorithm based on the theory of minimization of Gibbs free energy to solve chemical equilibrium of complex system.     

伴有平衡反应的分离过程的数学模拟——(Ⅱ)催化精馏塔的模拟计算

提出了平衡反应的非均相催化反应精馏过程的微分数学模型。应用多目标打靶法和 Newtor-Raphson 迭代对模型方程进行了求解。本算法应用于非理想系统,反应动力学未知的快速可逆反应过程。可求得沿塔最大转化率和平衡浓度分布。应用本算法对 MTBE 的催化反应过程进行了模拟计算,能快速稳定收敛。计算结果与文献数据进行比较,表现出良好的一致性。     

An improved algorithm for the three‐fluid‐phase VLLE flash calculation

The VLLE flash is important in water and hydrocarbons mixtures, hydrocarbon and CO₂ rich mixtures, and hydrocarbon methane rich mixtures that are encountered in reservoir performance and recovery studies. A robust VLLE flash algorithm is proposed. The equilibrium and mass balance equations are solved as a constrained minimization problem. An inverse barrier function is used to handle the inequality constrains to solve for the phase fractions. It warrants always arriving to the solution. The challenging cases analyzed showed that the initialization procedure proposed, together with successive substitution iteration in the outer loop, is a good method for a stable VLLE flash algorithm, even near critical points. Whenever the result is in the region outside the three‐phase physical domain, the solution suggests that the system has fewer phases. In one of the cases analyzed, a region with three liquid phases was encountered and the algorithm found two different solutions with positive phase fractions. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3081–3093, 2015     

A QUASI-NEWTON ALGORITHM FOR SOLVING MULTIPHASE EQUILIBRIUM FLASH PROBLEMS

A new algorithm has been developed for solving the multicomponent vapor-liquid-liquid equilibrium Mash problem. The algorithm is an extension of the “inside-out” approach proposed by Boston and Britt for the vapor-liquid equilibrium flash problem.

Conventional flash algorithms use temperature, pressure, composition, and phase fraction as the problem independent variables, In the inside-out approach a new set of independent variables is introduced in place of the conventional variables. The new variables are chosen to be as independent as possible of the conventional variables and as free as possible of mutual interaction. Complex phase equilibrium models are used only to generate parameters for a simple equilibrium ratio model. These parameters become the problem independent variables. The Quasi-Newton method of Broyden is employed to promote convergence of these variables.

The algorithm first obtains a solution for the vapor-liquid equilibrium flash. By examining the liquid phase, a heuristic algorithm is employed which quickly locates a two liquid phase composition region of reduced total system free energy when the original liquid is unstable. The solution of the vapor-liquid-liquid equilibrium flash is initiated only when this occurs.

The performance of the algorithm is demonstrated by a number of problems which exhibit varying degrees of nonideality.     

A QUASI-NEWTON ALGORITHM FOR SOLVING MULTIPHASE EQUILIBRIUM FLASH PROBLEMS

A new algorithm has been developed for solving the multicomponent vapor-liquid-liquid equilibrium Mash problem. The algorithm is an extension of the “inside-out” approach proposed by Boston and Britt for the vapor-liquid equilibrium flash problem.

Conventional flash algorithms use temperature, pressure, composition, and phase fraction as the problem independent variables, In the inside-out approach a new set of independent variables is introduced in place of the conventional variables. The new variables are chosen to be as independent as possible of the conventional variables and as free as possible of mutual interaction. Complex phase equilibrium models are used only to generate parameters for a simple equilibrium ratio model. These parameters become the problem independent variables. The Quasi-Newton method of Broyden is employed to promote convergence of these variables.

The algorithm first obtains a solution for the vapor-liquid equilibrium flash. By examining the liquid phase, a heuristic algorithm is employed which quickly locates a two liquid phase composition region of reduced total system free energy when the original liquid is unstable. The solution of the vapor-liquid-liquid equilibrium flash is initiated only when this occurs.

The performance of the algorithm is demonstrated by a number of problems which exhibit varying degrees of nonideality.     

Constrained chemical equilibrium and incompletely specified elemental abundance data

A general method for the computation of equilibrium composition in the presence of linear equilibrium constraints on chemical potentials is described for use in a standard general-purpose algorithm. The existence of constraints, implied by product specifications or measured product distribution, is related to incomplete specification of elemental abundances and has implications for feed composition. The method is illustrated by two examples: SO₂ removal from stack gas and catalytic reforming. The distinction between equilibrium subject to equilibrium constraints on chemical potentials and that subject to stoichiometric restrictions is emphasized.