Effect of Feed Location on the Performance of Single-Stage Membrane Permeators

Abstract

The effect of feed location on the performance of single-stage membrane permeators was determined based on the minimum unit compressor load (recycle ratio). Since certain feed locations correspond to several well-known permeator configurations (e.g., simple recycle permeator, continous membrane column), it is possible to characterize the relative performance of these configurations for separating binary gas mixtures. For separations involving oxygen, nitrogen, and carbon dioxide, it was found that the location of feed introduction was related to the apparent difficulty of separation. For binary seprations of low to moderate difficulty, the optimum feed location was at a dimensionless axial distance of 0.6 to 0.75 from the top of the column. This feed location corresponded to the continuous membrane column configuration. For difficult separations, the optimum feed location was at the top of the column which corresponded to the simple recycle permeator. Based on this study, the simple recycle permeator configuration outperforms the continuous membrane column for the most difficult separations such as in the separation of oxygen from air. However, the continuous membrane column configuration can be used effectively for less difficult gas separations which cannot be accomplished by a membrane permeator without recycle, but do not require high recycle ratios to achieve the desired separation.     

Asymmetric Permeators—A Conceptual Study

Abstract

The asymmetric permeator concept of Ohno et. al. utilizing two different membranes for rare gas separation has been explored in general. Various geometrical arrangements and possible applications to gas separations other than rare gas-nitrogen mixtures have been discussed. The utility of an asymmetric permeator for multicomponent gas separations has been investigated. The separation factor of a ternary system in a perfectly mixed asymmetric permeator has been obtained. The amount of separation obtained with a ternary feed in a perfect crossflow stage having no axial mixing has been analytically determined for some limiting cases with an asymmetric permeator. The asymmetric permeator concept has been extended also to a high separation factor liquid solution separation process like reverse osmosis desalination. Preliminary calculations have been carried out to show that an asymmetric desalinator with reverse osmosis (RO) and piezodialysis (PD) membranes has a lower increase in brine concentration along the module length for a given water recovery resulting in a lower operating pressure. With hollow fiber asymmetric desalinators having RO and PD membranes, the concentration polarization, if any, may be significantly reduced. Practical applications of asymmetric permeator's for phenol-water separation etc. have been discussed.     

Modelling of multicomponent gas separation with asymmetric hollow fibre membranes—methane enrichment from biogas

A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fibre membranes was developed considering the permeate pressure build‐up inside the fibre bore and cross flow pattern with respect to the membrane skin. The solution technique provides reliable examination of pressure and concentration profiles along the permeator length (both residue/permeate streams) with minimal effort. The proposed simulation model and scheme were validated with experimental data of gas separation from literature. The model and solution technique were applied to investigate dynamic performance of several membrane module configurations for methane recovery from biogas (landfill gas or digester gas), considering biogas as a mixture of CO₂, N₂ and CH₄. Recycle ratio plays a crucial role, and optimum recycle ratio vital for the retentate recycle to permeate and permeate recycle to feed operation was found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane‐selective or nitrogen‐selective membranes was calculated. © 2012 Canadian Society for Chemical Engineering     

双膜分离器的数学模型

建立了适用于双膜分离器的数学模型,并用实验数据验证了数学模型的可行性和合理性;对非对称膜渗透过程的数学计算模型作了进一步的探讨,指出在本实验范围内非对称膜的渗透行为与对称膜的渗透行为相近。     

REACTOR-MEMBRANE PERMEATOR CASCADE FOR ENHANCED PRODUCTION AND RECOVERY OF H2 AND CO2 FROM THE CATALYTIC METHANE-STEAM REFORMING REACTION

The catalytic reforming of methane by steam is an important industrial process that produces H₂, CO and CO₂, thus chemically transforming natural gas, coal gas and light hydrocarbon feedstocks to synthesis gas or hydrogen fuel. Methane-steam reforming may consist of a number of reactions depending on the reforming catalyst, operating conditions and feedstock composition, The typical industrially desirable reactions are the reverse of methanation (CH₄ + H₂O = CO + 3H₂) and the water-gas shift (CO + H₂O = CO₂ + H₂). Both reactions are equilibrium limited and the composition of the mixture that exits the reformer is in accordance with the one calculated thermodynarmically. Removal of reaction products at the reactor exit by means of selective membrane permeation can offer improved CH₄ conversions and CO₂ and H₂ yields, assuming the subsequent utilization of the reject streams by a second methane-steam reformer. We numerically investigated the feasibility of a system of two tubular methane-steam reformers, in series with an intermediate permselective polyimide membrane permeator, as means of improving the overall CH₄ conversion and the H₂, CO₂ yields over conventional methane-steam reforming equilibrium reaction-separation schemes that are currently in industrial practice. The unique feature of the permselective polyimide separator is the simultaneous removal of H₂ and CO₂ versus CH₄ and CO from the reformed streams. The utilized 6FDA-3,3', 5,5'-TMB aromatic polyimide was reportedly characterized [10] and found to exhibit superior permselective properties compared with other polyimides of the same or different dianhydride sequence. Conversion and yield of the designed reactor-membrane permeator reforming system can be maximized by optimizing the permselective properties of the membrane material and the design variables of the reactors and the permeator. Product recovery and purity in the permeate stream need to be compromised to overall enhance methane conversion and product yield. The operating variables that were varied to investigate their effect on the magnitude of conversion and yield included the inlet pressure of the first reformer, the temperature of both reformers, and the permeator dimensionless Pe' number (variation of the first two variables results to a drastic change in the composition of the reformed stream that enters into the permeator). The numerical results show that the new reformer-membrane permeator cascade process can be more effective (it can offer increased CH₄ conversions and H₂, CO₂ yields) than conventional equilibrium methane-steam reforming reaction-separation processes currently in practice.     

A pressure swing membrane separation process

A new pressure swing membrane permeation process that can achieve significant improvement in the selectivity of a membrane possessing opposite diffusivity and solubility characteristics toward a gas pair is proposed. By operating a membrane permeator under an unsteady state, the opposite mobility and solubility selectivities of the membrane can work synergistically to accomplish a degree of separation beyond the steady-state membrane permselectivity in the following manner: along the flow direction in the feed channel, the gas mixture is separated by the selective absorption of gases into the membrane; and simultaneously across the membrane, the gas mixture is separated by the diffusivity selectivity of the membrane. The viability of the new process is supported by the results of a theoretical and experimental study on the transient responses of a membrane permeator with a silicone rubber membrane separating a helium-methane mixture. Two different operating schemes are identified in carrying out the proposed process, depending on the mobilities and solubilities of the gas species to be separated.     

Optimization of membrane gas separation systems using genetic algorithm

Genetic algorithm is applied for the optimization of the membrane gas separation systems. Air separation for enriched oxygen production is the selected system for investigation. Optimizations for single and triple objective functions are studied. The optimization problem involves the selection of the optimal system configurations from three alternatives, including continuous membrane column (CMC), single stripper permeator (SSP), and two stripper in series permeator (TSSP), as well as the optimal operating conditions. Models of the three configurations and the genetic algorithm procedure are computerized. The objective functions discussed are the Rony separation index, power consumption per unit equivalent pure oxygen, and the membrane area. Both high-pressure and low-pressure (vacuum) operation modes are optimized and the effects of different oxygen product purity and feed rate are analyzed. For single objective function optimization, the solutions obtained using genetic algorithm are slightly inferior in one case but superior in other cases compared to those by pure mathematical optimization methods. For triple objective function optimization, the Pareto plots presenting multiple trade-off solutions are generated. In general, compared to high-pressure operation mode, the product recovery and power consumption for low-pressure operation mode are lower. For almost all the cases studied, CMC configuration with its high flexibility appears in the optimal solutions.     

Design and synthesis of multicomponent thermally coupled distillation flowsheets

The design and synthesis of thermally coupled distillation flowsheets for separations of five-component mixtures are studied. Four types of possible configurations are identified when simple and complex columns are both considered in a flowsheet. A universal design procedure is developed for design of any types of the identified configurations based on the abstraction of the three basic units in the flowsheets. Two examples demonstrated that this shortcut design method can be used in design of any types of the identified multicomponent thermally coupled distillation flowsheets, as well as give very good initializations for rigorous simulation of such configurations. Moreover, with a proposed computer representation of all the types of the feasible configurations, a synthesis algorithm is developed for synthesizing of multicomponent complex distillation flowsheets with both simple and complex columns. It is practical by the proposed methods for optimal design of multicomponent distillation systems in an extended search space to include the complex distillation flowsheets for industrial problems.     

膜分离捕集燃煤电厂烟气CO2过程优化设计

全球CO₂的排放量不断升高,导致气候问题频发。“双碳”目标下,如何高效、低成本地捕集燃煤电厂烟气CO₂已经成为迫在眉睫的问题。传统的化学吸收法由于能耗高、成本高、溶剂易挥发等问题严重制约了其发展,而膜法碳捕集因为其操作简单、能耗低、环境污染小等优势被认为是最有前景的捕集方式。本文以PI中空纤维膜为分离膜,建立和求解了气体分离膜模型。并以燃煤电厂烟气CO₂为捕集目标,利用多岛遗传算法求解了膜分离捕集CO₂工艺的不同配置,并优化了分离过程中的关键参数(膜面积、操作压力)。结果显示：在二级膜分离工艺中,二级一段膜分离工艺的第一级膜和第二级膜操作压力分别为5.8 bar和7.1 bar,第一级膜和第二级膜的面积分别为448000 m²和180000 m²时,单位捕集成本为27.36 USD/t CO₂。与二级二段膜分离以及其他几种传统的CO₂捕集方法(MEA法、相变吸收法)相比,二级一段膜分离捕集CO₂的捕集成本和能耗均最小。本研究将为CO₂捕集实现低能耗和低成本化提供依据。     

Separation of methane from different gas mixtures using modified silicon carbide nanosheet: Micro and macro scale numerical studies

This research discusses the separation of methane gas from three different gas mixtures, CH₄/H₂S, CH₄/N₂ and CH₄/CO₂, using a modified silicon carbide nanosheet (SiCNS) membrane using both molecular dynamics (MD) and computational fluid dynamics (CFD) methods. The research examines the effects of different structures of the SiCNSs on the separation of these gas mixtures. Various parameters including the potential of the mean force, separation factor, permeation rate, selectivity and diffusivity are discussed in detail. Our MD simulations showed that the separation of CH₄/H₂S, and CH₄/CO₂ mixtures was successful, while simulation demonstrated a poor result for the CH₄/N₂ mixture. The effect of temperature on the diffusivity of gas is also discussed, and a correlation is introduced for diffusivity as a function of temperature. The evaluated value for diffusivity is then used in the CFD method to investigate the permeation rate of gas mixtures.     

Modeling CO2-facilitated transport across a diethanolamine liquid membrane

We compared experimental and model data for the facilitated transport of CO₂ from a CO₂–air mixture across an aqueous solution of diethanolamine (DEA) via a hollow fiber, contained liquid membrane (HFCLM) permeator. A two-step carbamate formation model was devised to analyze the data instead of the one-step mechanism used by previous investigators. The effects of DEA concentration, liquid membrane thickness and feed CO₂ concentration were also studied. With a 20% (wt) DEA liquid membrane and feed of 15% CO₂ in CO₂–air mixture at atmosphere pressure, the permeance reached 1.51E−8 mol/m² s Pa with a CO₂/N₂ selectivity of 115. Model predictions compared well with the experimental results at CO₂ concentrations of industrial importance. Short-term stability of the HFCLM permeator performance was examined. The system was stable during 5-days of testing.     

面向不同工业二氧化碳分离体系的膜材料研究进展

膜法二氧化碳分离具有无相变、低能耗等优势，在碳捕集和气体净化等领域具有极大的潜力。膜分离是一种基于组分渗透速率差异的分离过程，其中，气体组分的物化性质差异是实现分离的前提，而膜材料有效识别组分的差异则是高效分离的关键。烟道气、天然气、合成气是最典型的三种二氧化碳分离体系，组成以及操作条件都存在显著的不同。膜材料的设计，既要充分利用组分的性质差异，进行功能基团和聚集结构的针对性设计，实现高分离性能，又要充分考虑操作条件的特殊性，保证良好的分离效率、耐受性和操作稳定性。以二氧化碳分离膜的渗透传质机理为基础，结合不同体系的组成差异和操作条件差异，综述近年来二氧化碳分离膜材料的研究进展，并对未来的研究方向以及瓶颈问题进行展望。     

The separation of multicomponent mixtures by gas permeation

Two types of modules are most common in gas permeation: the hollow fibre module and the spiral wound module. With some simplifying assumptions regarding the flow pattern, the separation characteristics of such modules can be calculated for binary and ternary mixtures.More important in practice, however, is the separation of multicomponent mixtures. This paper discusses the design of multicomponent systems including cases where non-permeating components or carrier gases at the permeate side are present.The results of some calculations are discussed and compared with the usual short-cut method based on the assumption of a pseudo-binary mixture. The results demonstrate that the reduction of a multicomponent mixture to a pseudo-binary mixture is only reasonable when components of similar permeability are lumped together. Serious deviations with respect to membrane area or product composition must be expected for larger differences in permeabilities.     

The separation of multicomponent mixtures by gas permeationDie trennung von vielkomponenten-gemischen durch gaspermeation

Two types of modules are most common in gas permeation: the hollow fibre module and the spiral wound module. With some simplifying assumptions regarding the flow pattern, the separation characteristics of such modules can be calculated for binary and ternary mixtures.More important in practice, however, is the separation of multicomponent mixtures. This paper discusses the design of multicomponent systems including cases where non-permeating components or carrier gases at the permeate side are present.The results of some calculations are discussed and compared with the usual short-cut method based on the assumption of a pseudo-binary mixture. The results demonstrate that the reduction of a multicomponent mixture to a pseudo-binary mixture is only reasonable when components of similar permeability are lumped together. Serious deviations with respect to membrane area or product composition must be expected for larger differences in permeabilities.     

CHARACTERIZATION OF MIXED GAS PERMEATION THROUGH HOLLOW FIBERS

We have studied the mixed gas permeation in hollow fiber membrane modules using two approaches: namely, the co- current plug flow model and the complete mixing model with the combination of experimental data. Elucidation was made to determine the permeance of CO2 and CH4 and the selectivity of CO2/CH4 in a polyimide hollow fiber membrane permeator It is found that the intrinsic gas separation properties of hollow fibers for mixed gases can be accurately determined based on (1) the cocurrent plug now model, and (2) the complete mixing model with the assumption of averaged retentate concentration of the feed and the retentate outlet.     

Characterization of hollow fiber membranes in a permeator using binary gas mixtures

We have studied the CO₂/CH₄ mixed gas permeation through hollow fiber membranes in a permeator. An approach to characterize the true separation performance of hollow fiber membranes for binary gas mixtures was provided based on experiments and simulations. Experiments were carried out to measure the retentate and permeate flow rates and compositions at each outlet. The influences of pressure drop within the hollow fibers, non-ideal gas behavior in the mixture and concentration polarization were taken into consideration in the mathematics model. The calculation results indicate that the net influence of the non-ideal gas behavior, competitive sorption and plasticization yields the calculated CO₂ permeance in a mixed gas permeator close to that obtained in pure gas tests. Whereas the CH₄ permeance is higher in the mixed gas tests than that in the pure gas tests, as the plasticization caused by CO₂ dominates the permeation process. As a result, the CO₂/CH₄ mixed gas selectivity is smaller than those obtained in pure gas tests at equivalent pressures.The calculated membrane performance shows little changes with stage cut if the effect of concentration polarization is accounted for in the calculation. The integration method developed in this study could provide more accurate characterizations of mixed gas permeance of hollow membranes than other estimation methods, as our model considers the roles of non-ideal gas behavior and concentration polarization properly.     

From graphical to model-based distillation column design: A McCabe-Thiele-inspired mathematical programming approach

We propose a mixed-integer nonlinear programming (MINLP) model for simple and complex distillation column design and optimization. The model is based upon the concepts and equations underpinning the McCabe-Thiele method. Generalizing this method, we introduce material balances at various locations of the column and employ binary variables to determine the optimal number of trays and optimal feed locations. We model the vapor–liquid equilibrium using continuous piecewise linear approximating functions. The model is extended to account for multicomponent mixtures and non-constant-molar overflow. We also discuss how to estimate the minimum number of trays and the minimum reflux ratio.     

MINLP optimization of a heterogeneous azeotropic distillation process: Separation of ethanol and water with cyclohexane as an entrainer

Heterogeneous distillation processes are widely used in industry for the separation of azeotropic and close-boiling mixtures. This paper addresses the optimization of a heterogeneous distillation process for the separation of an azeotropic ethanol/water mixture using cyclohexane as an entrainer. Starting from a given process superstructure a MINLP problem is set up to consider continuous as well as discrete decision variables such as the feed locations and the number of stages of the distillation columns. A modified Generalized Benders Decomposition algorithm to account for non-convexities of the model equations solves the MINLP problem. The algorithm can be attached via Visual Basic for Applications (VBA) to any commercial process simulator with NLP and VBA capabilities. Various optimization runs show that the algorithm is easily applicable and returns solutions independent of the initial values.     

Membrane gas separation with permeate purging

The effect of purging with an impermeable gas on the permeate side of a flat sheet permeator has been investigated. A three component gas mixture was used in the separation. It has been shown that a small stream of purge can improve the degree of separation achieved and reduce the need to maintain a high pressure ratio across the membrane. Excellent agreement has been obtained between the experimental and the predicted data from a perfect mixing model.     

A New Numerical Approach for a Detailed Multicomponent Gas Separation Membrane Model and AspenPlus Simulation

A new numerical solution approach for a widely accepted model developed earlier by Pan [1] for multicomponent gas separation by high‐flux asymmetric membranes is presented. The advantage of the new technique is that it can easily be incorporated into commercial process simulators such as AspenPlus^TM [2] as a user‐model for an overall membrane process study and for the design and simulation of hybrid processes (i.e., membrane plus chemical absorption or membrane plus physical absorption). The proposed technique does not require initial estimates of the pressure, flow and concentration profiles inside the fiber as does in Pan's original approach, thus allowing faster execution of the model equations. The numerical solution was formulated as an initial value problem (IVP). Either Adams‐Moulton's or Gear's backward differentiation formulas (BDF) method was used for solving the non‐linear differential equations, and a modified Powell hybrid algorithm with a finite‐difference approximation of the Jacobian was used to solve the non‐linear algebraic equations. The model predictions were validated with experimental data reported in the literature for different types of membrane gas separation systems with or without purge streams. The robustness of the new numerical technique was also tested by simulating the stiff type of problems such as air dehydration. This demonstrates the potential of the new solution technique to handle different membrane systems conveniently. As an illustration, a multi‐stage membrane plant with recycle and purge streams has been designed and simulated for CO₂ capture from a 500 MW power plant flue gas as a first step to build hybrid processes and also to make an economic comparison among different existing separation technologies available for CO₂ separation from flue gas.