Separation of Methane and Carbon Dioxide Gas Mixtures by Pressure Swing Adsorption

Abstract

Two pressure swing adsorption processes for separation of methane and carbon dioxide gas mixtures are described. One process simultaneously produces a high purity CH₄ and a high purity CO₂ product with high recoveries of both components from the feed gas. The other process only produces a high purity CH₄ product with high recovery. Test data for these processes are reported and their relative advantages are discussed.     

Separation of Binary Gas Mixture into Two High-Purity Products by a New Pressure Swing Adsorption Cycle

Abstract

Binary mixtures can be separated into two high-purity products by a new pressure swing adsorption (PSA) cycle. The product purity depends on the purge/feed ratio of the respective gases in the PSA cycle. The process characteristics of the new PSA cycle, using activated carbon as the sorbent, can be adequately predicted by an equilibrium model.     

炼厂气回收过程中分离技术的能效分析

针对炼厂气多目标回收工艺设计时缺乏理论指导的问题,本文系统阐述了分离过程能效比的概念,将气体分离过程中压力和温度变化导致系统与外界交换的能量统一用电功表示,得到了分离过程能耗与产品回收量间关系的定量表示方法;以某厂炼厂气回收过程为例,比较了不同分离技术和不同分离过程的能效比。当产品氢纯度要求不高（≥97%）时,采用变压吸附（PSA）工艺的能效比较高（0.86）,与膜分离工艺相比,提高了28%;当产品氢纯度要求较高（≥99.9%）时,采用膜分离-PSA工艺可以获得更高的能效比（0.54）,与PSA-膜分离工艺相比,能效比提高了40%。研究结果表明：分离过程的能效比可以用于评价不同分离技术或不同分离过程的能量效率,可用于指导不同分离技术的适用范围和多技术耦合工艺过程的设计,能够为炼厂气回收工艺设计提供一定的理论指导。     

Simultaneous Production of Hydrogen and Carbon Dioxide from Steam Reformer Off-Gas by Pressure Swing Adsorption

Abstract

Pressure swing adsorption (PSA) processes are used for the production of ultrapure hydrogen from a crude hydrogen stream containing H₂O, CO₂, CO, CH₄, and N₂ impurities which is produced by steam reformation of natural gas or naphtha. Two commercial PSA processes designed for this purpose are reviewed and a new commercial PSA process which simultaneously produces ultrapure hydrogen and high purity carbon dioxide products from the crude hydrogen with high recoveries of both components is described. Performance data for the new process are reported.     

Gas Mixture Fractionation to Produce Two High Purity Products by Pressure Swing Adsorption

Abstract

Pressure swing adsorption processes have been traditionally used to produce one high purity gas stream from a gas mixture. One of the most common uses of this technology is in the production of ultrahigh purity hydrogen from various gas streams such as steam methane reformer (SMR) off-gas. However, many of these gas streams contain a second gas in sufficiently high concentrations, e.g., carbon dioxide in SMR off-gas, that the recovery of this secondary gas stream along with the primary product is extremely desirable. A new pressure swing adsorption (PSA) process, GEMINI-8, has been developed at Air Products and Chemicals, Inc., to achieve this goal. Process cycle steps for the GEMINI-8 PSA process are illustrated by SMR off-gas fractionation for the production of hydrogen and carbon dioxide. Capital and power savings of this process as well as other advantages compared with the previous technology are discussed.     

Pressure swing adsorption/membrane hybrid processes for hydrogen purification with a high recovery

Hydrogen was recovered and purified from coal gasification-produced syngas using two kinds of hybrid processes: a pressure swing adsorption (PSA)-membrane system (a PSA unit followed by a membrane separation unit) and a membrane-PSA system (a membrane separation unit followed by a PSA unit). The PSA operational parameters were adjusted to control the product purity and the membrane operational parameters were adjusted to control the hydrogen recovery so that both a pure hydrogen product (>99.9%) and a high recovery (>90%) were obtained simultaneously. The hybrid hydrogen purification processes were simulated using HYSYS and the processes were evaluated in terms of hydrogen product purity and hydrogen recovery. For comparison, a PSA process and a membrane separation process were also used individually for hydrogen purification. Neither process alone produced high purity hydrogen with a high recovery. The PSA-membrane hybrid process produced hydrogen that was 99.98% pure with a recovery of 91.71%, whereas the membrane-PSA hybrid process produced hydrogen that was 99.99% pure with a recovery of 91.71%. The PSA-membrane hybrid process achieved higher total H₂ recoveries than the membrane-PSA hybrid process under the same H₂ recovery of membrane separation unit. Meanwhile, the membrane-PSA hybrid process achieved a higher total H₂ recovery (97.06%) than PSA-membrane hybrid process (94.35%) at the same H₂ concentration of PSA feed gas (62.57%).

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Performance Comparison of Different Separation Systems for H2 Recovery from Catalytic Reforming Unit Off‐Gas Streams

The performance of pressure swing adsorption (PSA), membrane separation, and gas absorption systems for H₂ recovery from refinery off‐gas stream was studied by simulation‐based data. The PSA process was simulated using adsorbents of silica gel and activated carbon for removing heavy and light hydrocarbons. The mole fraction profiles of all components and the relationship between hydrogen purity and recovery as a function of feed pressure were examined. The solution‐diffusion model was applied for modeling and simulation of a one‐stage membrane process. The gas absorption process with a tower tray was simulated at sub‐zero temperature and the correlation between hydrogen purity and recovery as a function of tower pressure and temperature was evaluated at different solvent flow rates.     

真空变压吸附分离氮气甲烷流程灵敏度分析与优化

首先采用实验室自制椰壳活性炭为吸附剂,进行了氮气/甲烷(65%/35%)原料气的真空变压吸附工艺(VPSA)分离实验。通过对比实验和gPROMS 动态模拟软件的分离效果,对变压吸附数学模型进行了验证,证明了所采用数学模型的准确性。在此基础上,对影响产品气甲烷纯度、回收率的关键决策变量进行了灵敏度分析。分析结果表明:产品气纯度主要由原料气流量和置换气流量来进行调控,产品气回收率则需要关键变量共同的作用才能实现最大化。依据灵敏度分析结果,对两塔分离氮气甲烷混合气的变压吸附工艺进行了动态优化。在最优的工况下,可以将进料组成为35%的甲烷富集到75%,回收率达到97.08%;从而达到对于废混合气的高效回收利用。     

Modelling and evaluation of dual-reflux pressure swing adsorption cycles: Part I. Mathematical models

Dual-reflux pressure swing adsorption (DR-PSA) systems represent new options for producing two pure products from binary gas mixtures using adsorption. Within the constraint of DR-PSA, there are several options: feed to the low- or high-pressure bed and equalize, repressurize and blowdown with either the weakly or strongly adsorbed gas (opposite ends of the adsorption column). Each of these options leads to different flow sheets and results in different system performance, in particular productivity and work consumption tradeoff. In part I of this two part study we formulate method-of-characteristics models for all of the dual-reflux (DR) cases—in several cases new DR models are developed which are yet to be reported. In part II, we apply our models to show how the DR-PSA system can be assessed for a variety of gas mixtures and adsorbent type.     

Concentration-Thermal Swing Adsorption Process for Separation of Bulk Liquid Mixtures

Abstract

A novel concentration-thermal swing adsorption process is described for separation of bulk binary liquid mixtures. The process is designed to produce essentially two pure products with high recoveries of both components. It is particularly suited for separation of azeotropic or close-boiling liquid mixtures which are difficult to separate by distillation. An example of the performance of the new process for separation of an azeotropic water-methyl acetate mixture is given. Experimental binary surface excess equilibrium isotherms, adsorptive mass transfer coefficients, and column dynamics for adsorption of water-methyl acetate mixtures on NaX zeolite are reported.     

Pressure swing adsorption processes to purify oxygen using a carbon molecular sieve

Four different pressure swing adsorption (PSA) cycles using CMS for oxygen purification were developed to produce high-purity oxygen of over 99% with a high level of productivity. The cyclic performances such as purity, recovery, and productivity of the four different PSA cycles were experimentally and theoretically compared under non-isothermal conditions. In addition, one binary (O₂/Ar; 95:5 vol%) and two ternary (O₂/Ar/N₂; 95:4:1 and 90:4:6 vol%) mixtures were used to study the effects of feed composition. The PSA cycles with two consecutive blowdown steps produced oxygen with 98.0-99.9% purity and 56-66% recovery. The PSA cycle with oxygen generation in the second blowdown step produced oxygen with a higher level of purity and productivity. Also, the cycle introducing a pressure equalization step instead of a pure step produced oxygen with about 99.8% purity and 78% recovery. The period for the cyclic steady state of the ternary feed with 1% N₂ was slightly longer than that of the binary feed, while the PSA performance of the ternary feed was similar to that of the binary feed without nitrogen. However, in the ternary feed with 6% N₂, the purity of the O₂ in the purification cycles decreased by up to 97.3%. Therefore, nitrogen played a key role in producing high-purity oxygen in the CMS PSA instead of argon.     

基于双回流变压吸附工艺的空气分离模拟及分析

双回流变压吸附是一种在吸附塔中间位置进料,塔顶和塔底分别采用轻、重组分回流的变压吸附过程,能够同时生产两种高纯度、高回收率的产品气。以实验室自主合成的LiLSX分子筛为吸附剂,利用Aspen Adsorption模拟软件,对进料组成为78%N₂/21%O₂/1%Ar的实际空气进行了两塔双回流变压吸附的模拟研究。模拟结果表明：当原料气为78%N₂/21%O₂/1%Ar,吸附压力为2 bar(1 bar=10⁵ Pa),解吸压力为0.3 bar,进料量为0.4 m³/h,轻组分回流流量为0.095 L/min,重组分回流流量为5.22 L/min时,能够得到体积分数为95.67%的O₂和体积分数为98.25%的N₂,回收率分别为94.60%和99.91%。并且进一步探究了进料位置、吸附时间、轻组分回流流量、重组分产品气流量等因素对O₂和N₂两种产品气纯度和回收率的影响。     

Air Fractionation by Adsorption

Abstract

Pressure swing adsorption (PSA) processes for air separation differ by the modes and conditions of operation of the adsorption, the desorption, and the complementary steps, as well as by the types of adsorbents used. Three commercial PSA processes for air separation are reviewed and compared. The first process uses a zeolitic adsorbent and produces only an oxygen-enriched product gas. The second process uses a carbon molecular sieve and produces only a nitrogen-enriched product gas. The third process uses a zeolite and simultaneously produces both oxygen-and nitrogen-enriched product gases. The performance and separation efficiency of the last process, called the ‘vacuum swing adsorption (VSA) process’, are reported to be superior to the others.     

基于Aspen Adsorption的氦气/甲烷吸附分离过程模拟优化

工业氦气主要通过深冷、膜分离和变压吸附（PSA）耦合从天然气提取,其中PSA是获得高纯He的关键。吸附过程模拟可以克服实验局限,有效指导工程设计、优化工艺条件。以体积分数90%的粗He为原料,利用Aspen Adsorption软件建立He/CH₄ 单塔PSA模型,获得穿透曲线。以此为基础,建立双塔分离流程,分析吸附、顺放、逆放、冲洗、升压步骤中吸附塔内气相组成的变化,五步最佳操作时间分别为 60、180、30、60和180 s。在三塔流程中,一个循环周期的最佳吸附时间和均压时间分别为135 s和90 s,产品纯度可达98.42%,回收率达60.45%。在五塔流程中,考虑到各步骤时间的匹配及生产的连续性,需要对一个周期内的循环时间进行优化。循环时间为300~340 s时,产品纯度达到99.07%以上。     

Separation of Ternary Mixtures by Pseudo‐Simulated Moving‐Bed Chromatography: Separation Region Analysis

The application of the pseudo‐simulated moving bed process, known as JO process of Japan Organo Co., to the separation of ternary mixtures was studied. In order to perform a desired separation, the choice of the different operation parameters such as the duration of each step and its respective flow rates requires the use of a methodology that could provide the best process performance. This issue is addressed by proposing an innovative method to determine the JO operation region, which establishes the operation limits of the process. In addition, a methodology is presented to determine the separation region where a minimum purity requirement is guaranteed. This methodology was applied to a ternary mixture considering linear adsorption isotherms. It was possible to construct a separation region for minimum purity of 99.9 % in all the outlet streams and identify the best operation point in terms of the process performance.     

Production of argon free oxygen by adsorptive air separation on Ag‐ETS‐10

The purification of different components of air, such as oxygen, nitrogen, and argon, is an important industrial process. Pressure swing adsorption (PSA) is surpassing the traditional cryogenic distillation for many air separation applications, because of its lower energy consumption. Unfortunately, the oxygen product purity in an industrial PSA process is typically limited to 95% due to the presence of argon which always shows the same adsorption equilibrium properties as oxygen on most molecular sieves. Recent work investigating the adsorption of nitrogen, oxygen and argon on the surface of silver‐exchanged Engelhard Titanosilicate‐10 (ETS‐10), indicates that this molecular sieve is promising as an adsorbent capable of producing high‐purity oxygen. High‐purity oxygen (99.7+%) was generated using a bed of Ag‐ETS‐10 granules to separate air (78% N₂, 21% O₂, 1% Ar) at 25°C and 100 kPa, with an O₂ recovery rate greater than 30%. © 2012 American Institute of Chemical Engineers AIChE J, 59: 982–987, 2013     

煤层气在活性炭和炭分子筛上变压吸附分离

变压吸附分离是有效的气体分离提纯方法,采用合适的吸附剂可对煤层气(CH4/N2混合气体)进行高效分离,节约能耗。在单床吸附装置上测量了CH4/N2混合气体在3种活性炭和4种炭分子筛吸附柱上的穿透曲线,并进行实验研究再生条件对吸附剂分离性能的影响。实验结果表明,7种吸附剂均对CH4/N2混合气具有一定程度的分离能力,且高温真空再生后吸附效果更好;但仍需开发出更有效的吸附剂。     

Hydrogen recovery from Tehran refinery off-gas using pressure swing adsorption, gas absorption and membrane separation technologies: Simulation and economic evaluation

Hydrogen recovery from Tehran refinery off-gas was studied using simulation of PSA (pressure swing adsorption), gas absorption processes and modeling as well as simulation of polymeric membrane process. Simulation of PSA process resulted in a product with purity of 0.994 and recovery of 0.789. In this process, mole fraction profiles of all components along the adsorption bed were investigated. Furthermore, the effect of adsorption pressure on hydrogen recovery and purity was examined. By simulation of one-stage membrane process using co-current model, a hydrogen purity of 0.983 and recovery of 0.95 were obtained for stage cut of 0.7. Also, flow rates and mole fractions were investigated both in permeate and retentate. Then, effects of pressure ratio and membrane area on product purity and recovery were studied. In the simulation of the gas absorption process, gasoline was used as a solvent and product with hydrogen purity of 0.95 and recovery of 0.942 was obtained. Also, the effects of solvent flow rate, absorption temperature, and pressure on product purity and recovery were studied. Finally, these three processes were compared economically. The results showed that the PSA process with total cost of US$ 1.29 per 1 kg recovered H₂ is more economical than the other two processes (feed flow rate of 115.99 kmol/h with H₂ purity of 72.4 mol%).     

A COMPARISON OF GAS SEPARATION PERFORMANCE BY DIFFERENT PRESSURE SWING ADSORPTION CYCLES

By simulations using an equilibrium model, a quantative comparison is made for different pressure swing adsorption (PSA) processes for gas separation. The comparison is based on the performance curve, which is defined as the relationship between product purity and product recovery at a fixed feed throughput.

For bed repressurization in the PSA cycle, the use of the light product yields superior separations compared to that using the feed mixture. For the pressure reduction step, it is found that the separation results are better when the heavy-product purge step is used, as compared to that using cocurrent depressurization. For an ultrahigh-purity light product, however, the PSA process using cocurrent depressurization is superior.

A new PSA process is suggested in which the heavy-product purge step is accomplished by using (or pressure-equalizing with) the effluent from another bed which undergoes the countercurrent blowdown step.     

Separation of a Five-Component Gas Mixture by Pressure Swing Adsorption

Abstract

Bulk separation of a five-component mixture simulating coal gasification products was performed by pressure swing adsorption (PSA) using activated carbon. The PSA cycle consisted of four commercially used steps: (I) pressurization with H₂, (II) adsorption, (III) blowdown, and (IV) evacuation. Using this cycle, four products were obtained with a single PSA unit: H₂ (over 99.7% purity), CO, CH₄, and acid gas (CO₂ + H₂S). The first three products contained less than 0.001% H₂S, and the acid gas was suitable for sulfur recovery. A mathematical model incorporating equilibrium adsorption of mixture and mass transfer resistance (of CO₂) was found capable of simulating all steps of the PSA cycle. The model simulation results were in fair agreement with the experimental data. A fundamental understanding of the dynamics of the cyclic process was gained through the model.