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%).     

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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丙烷脱氢反应气分离提纯丙烯和氢气过程严格模拟与能效评估

丙烷脱氢(PDH)是生产丙烯产品的重要方式之一,丙烷脱氢反应气组分复杂,为获得聚合级丙烯和纯度不小于99.90 mol/mol的氢气产品,在Aspen软件中对丙烷脱氢反应气分离和富氢尾气回收氢气的过程进行建模和模拟,分离过程包括醇胺脱碳、压缩深冷、脱乙烷、丙烯精馏和变压吸附单元。为了合理利用丙烯精馏塔的能量,对丙烯精馏塔进行能量集成,采用变压吸附工艺回收氢气并对分离过程工艺参数进行灵敏度分析及优化工艺参数,以提高经济性和能效。模拟结果可得到符合要求的丙烯和氢气产品,单位产品能耗分别为267.46 kg标准油/t丙烯产品,474.44 kg标准油/t氢气产品。     

A parametric study of layered bed PSA for hydrogen purification

The production of high purity hydrogen (99.99+%) at reduced cost is an important and sought target. This work is focused on the separation of hydrogen from a five component mixture (H₂/CO₂/CH₄/CO/N₂) by pressure swing adsorption. A complete mathematical model that describes the dynamic behaviour of a PSA unit is presented. This model is applied in the study of the behaviour of both single column and four columns PSA processes with layered activated carbon/zeolite beds and with an eight steps cycle. In the single column simulation, a 99.9994% purity hydrogen stream is attained at the end of the feed step for a process hydrogen recovery of 51.84% and a productivity of . The multicolumn simulation predicts a hydrogen recovery and purity, respectively, of 52.11% and 99.9958%. The influence of feed flow rate, purge to feed ratio and lengths of both adsorbent layers on the system performance is assessed. It is shown that the introduction of the zeolite layer improves both the purity and recovery of the process. Reduced models are formulated based on the sequential identification of controlling resistances in the complete model. The predictions of the reduced models are evaluated by comparing their results with those obtained from the complete model. It is shown that the model that merely takes into account the micropore resistance (described by the LDF model) and assumes thermal equilibrium only between the gas and solid phases satisfactorily predicts the behaviour of the pressure swing adsorption unit.     

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 COCO2N2 gas mixture for high-purity CO by pressure swing adsorption

A pressure swing adsorption (PSA) process for separating CO from a COCO₂N₂ mixture is proposed. The adsorbent used in this process is active carbon supported copper, which has been developed by this laboratory. By cycling the pressure of a bed of this adsorbent between ambient pressure and 20–30 Torr at room temperature, high purity CO can be obtained from the COCO₂N₂ gas mixture with a high recovery. The CO product purity depends crucially on the step of CO cocurrent purge after adsorption in the cycle and the regeneration of sorbent.     

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。     

非耦联吸附塔新变压吸附工艺的实验研究

通过提氢实验研究一种新的变压吸附工艺.变压吸附流程的主要特征是通过中间均压罐打开吸附塔之间由均压步骤形成的耦联,从而实现了各塔操作的独立性,并提供了降低吸附压力的可能性.以H₂/N₂/CH₄（60/10/30）混合气模拟石油炼厂干气,进行低吸附压力（≤1 MPa）条件下的提氢操作.针对已有变压吸附工艺的不足和新流程特征,确定了新流程的变压吸附循环时序.分别采用普通活性炭（OAC）和高比表面活性炭（SAC）与5A沸石分子筛（ZMS-5A）的组合吸附剂,研究了不同吸附压力下的变压吸附分离效果,证明此种变压吸附新工艺在1 MPa以下、甚至0.4 MPa的低吸附压力下运行,亦可在较高的回收率下达到99.99%的高氢气纯度,并且显示出更强的对偶然性故障的应变能力.     

Layered two- and four-bed PSA processes for H2 recovery from coal gas

Huge amounts of global warming gas emissions have prompted interest in the recovery of H₂ from off-gases in the iron and steel industries. Pressure swing adsorption (PSA) processes with layered beds packed with zeolite 5A and activated carbon were applied for H₂ recovery from coal gas with relatively low H₂ concentrations (H₂/CO₂/CH₄/CO/N₂; 38/50/1/1/10 vol.%). Breakthrough curves in the layered bed showed behavior results between the zeolite 5A bed and the activated carbon bed. The bed with the higher zeolite ratio produced H₂ of higher purity in the PSA operation, but recovery loss became more significant with its increasing ratio. The variation of purity and recovery by operating variables were more significant in the two-bed PSA process than they were in the four-bed PSA process. The purity in the two-bed PSA varied asymptotically according to P/F ratio in the range of 0.1–0.3, while purity variation in the four-bed PSA process was almost linear. The zeolite layer in the two-bed PSA process worked as a separator of N₂, while that in the four-bed PSA process worked as a purifier of N₂. The four-bed PSA process could produce H₂ with a purity of 96–99.5% and a recovery of 71–85% with N₂ as the major impurity. The dynamics of the breakthrough and H₂ PSA processes were studied using a non-isothermal dynamic model.     

Application of high‐pressure swing adsorption process for improvement of CO2 recovery system from flue gas

Although the super cold separator applied to the system for CO₂ recovery from flue gas can produce pure CO₂ liquid, the CO₂ recovery efficiency is low. Therefore, the addition of a PSA plant was considered for the secondary CO₂ recovery from the noncon‐densing gas to improve the efficiency. The PSA plant was operated for adsorption at the same pressure as that of the super cold separator and for desorption at the atmospheric pressure. From both the simulation and the experimental data, it was confirmed that CO₂ could be concentrated from 50% in the noncondensing gas to 70% in the recovery gas by the PSA plant and the CO₂ recovery efficiency of the plant was about 90%.     

The effect of number of pressure equalization steps on the performance of pressure swing adsorption process

Cycle sequence has an important effect on the performance of pressure swing adsorption (PSA) processes. Pressure equalization steps influence significantly the purity and recovery of product, and therefore, may be properly designed to improve the performance of PSA processes. Open literature lacks of a systematic study on the effect of cycle sequence design on the performance of a specific PSA process as a controlling parameter. In this work, the results of recent studies on different cycle schedule design strategies have been used as a basis for comparing various cycle schedules (proposed by the authors of this work) on the performance of a six-bed PSA process for hydrogen purification. Three different cycle sequences have been designed, the pressure equalization and idle steps consisting the main controlling parameters. Simulation results showed that designs with more pressure equalization steps result in higher product recovery and those with less pressure equalization steps result in higher product purity. The proper performance of a PSA process is a tradeoff between product recovery and product purity. In this view, a target function has been developed that enables us to lump the latter performance parameters into one function for comparing the performance of the different cycles employed.     

净化吸收塔并联PSA技术改造

中国石油辽河石化分公司10000 m3/h常规焦化干气蒸汽转化制氢装置在生产中仅能达到85%负荷,原因是净化吸收塔达不到设计,成为生产瓶颈.通过对原闲置的催化干气PSA提纯装置进行改造后与净化系统吸收塔并联,分流部分低变气,从而在保证吸收塔正常运行的情况下实现制氢装置提高生产负荷30%以上.     

氯苯废液中苯和氯苯的回收模拟研究

利用ChemCAD流程模拟软件,在1 atm下,对苯-氯苯-邻二氯苯三元体系间歇精馏回收苯和氯苯的过程进行模拟计算,并进行了实验验证。模拟结果表明：全塔理论级数为10,间歇精馏过程采用变回流比,分三步进行,回流比分别为：15：1、5：1和15：1,热力学性质采用PR模型计算,精馏时间约4.4 h,得到纯度为100%的苯,回收率为5.11%,纯度为99.99%氯苯,回收率为34.68%。模拟了间歇精馏塔各步操作的温度分布,塔顶最低温度为80.2℃,塔底最高温度为152.5℃,模拟值与实验值吻合良好。     

制氢驰放气优化利用方案的研究

制氢装置PSA单元产生的驰放气中含有高浓度的甲烷、氢气、一氧化碳、二氧化碳。比较了变压吸附法、溶剂吸收法和膜分离法分离驰放气中的二氧化碳,从净化气指标、总能耗、运行费用和装置投资方面进行比较,得出变压吸附法分离优于其它两种方案。另外,变压吸附法分离没有涉及化学过程,相比操作运行更简单方便,可实现在线切换吸附器,有利于装置长周期运行。     

VPSA技术在干气回收氢气的应用

回收氢气装置是利用经过脱硫处理后的芳烃厂富氢干气,采用国内成熟的变压吸附专利技术回收干干气气中氢气。利用高压吸附,低压抽真空解吸的原理,从含粗氢的干气中提纯出99.9%(v)的产品氢,提供芳烃装置用氢。同时变压吸附的尾气通过尾气压缩机增压后供芳烃装置做加热炉燃料,从而达到厂内富氢干气综合利用的目的,提高装置综合经济效益。     

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.     

Modelling and simulation of two-bed PSA process for separating H_2 from methane steam reforming

Methane steam reforming is the main hydrogen production method in the industry. The product of methane steam reforming contains H_2, CH_4, CO and CO_2 and is then purified by pressure swing adsorption(PSA) technology. In this study, a layered two-bed PSA process was designed theoretically to purify H_2 from methane steam reforming off gas. The effects of adsorption pressure, adsorption time and purgeto-feed ratio(P/F ratio) on process performance were investigated to design a PSA process with more than99.95% purity and 80% recovery. Since the feed composition of the PSA process changes with the upstream process, the effect of the feed composition on the process performance was discussed as well.The result showed that the increase of CH_4 concentration, which was the weakest adsorbate, would have a negative impact on product purity.     

酒精尾气回收工艺模拟与优化

研究从中药厂酒精尾气中回收酒精的吸收 解吸工艺。采用UNIFAC模型和Wilson模型分别预测吸收塔和解吸塔内的平衡关系,并对吸收塔和解吸塔内的工艺参数进行优化。结果表明：当吸收塔理论板数为25,液气比为0.24 L/m³,常温常压下操作时塔顶排气乙醇质量分数为28×10^-6,塔釜乙醇回收率接近1;解吸塔为简单精馏塔,采用20块理论板,回流比为3,第10块板进料,塔顶可得91.7%的乙醇,塔釜得到几乎纯净的水,经冷却后作为吸收塔的吸收剂,循环套用。模拟结果对工业过程设计和设备改造具有一定指导意义。     

Understanding the performance of membrane for direct air capture of CO2

Direct air capture (DAC) of CO₂ is becoming increasingly important for reducing greenhouse gas concentrations in the atmosphere. However, the cost and energy requirements associated with DAC make it less economically feasible than carbon capture from flue gases. While various methods like solid sorbents and gas–liquid absorption have been explored for DAC, membrane processes have only recently been investigated. The objective of this study is to examine the separation performance of a membrane unit for capturing CO₂ from ambient air. The performance of a membrane depends on several factors, including the composition of the feed gas, pressure ratio, material selectivity, and membrane area. The single-stage separation process with the co-current flow and constant permeability flux model is evaluated using a commercial module integrated with a process simulator to separate a binary mixture of carbon dioxide and nitrogen to assess the sensitivity of selectivity on purity and recovery of CO₂ in permeate, and power requirement. Additionally, three levels of CO₂ reduction from the feed stream to the retentate stream (25%, 50%, and 75%) are studied. A trade-off between purity and recovery factor is observed, and achieving high purity in permeate requires high concentration in the retentate.     

Mass transfer investigation and operational sensitivity analysis of amine-based industrial CO2 capture plant

In this article, the industrial process of CO₂ capture using monoethanolamine as an aqueous solvent was probed carefully from the mass transfer viewpoint. The simulation of this process was done using Rate-Base model, based on two-film theory. The results were validated against real plant data. Compared to the operational unit, the error of calculating absorption percentage and CO₂ loading was estimated around 2%. The liquid temperature profiles calculated by the model agree well with the real temperature along the absorption tower, emphasizing the accuracy of this model. Operational sensitivity analysis of absorption tower was also done with the aim of determining sensitive parameters for the optimized design of absorption tower and optimized operational conditions. Hence, the sensitivity analysis was done for the flow rate of gas, the flow rate of solvent, flue gas temperature, inlet solvent temperature, CO₂ concentration in the flue gas, loading of inlet solvent, and MEA concentration in the solvent. CO₂ absorption percentage, the profile of loading, liquid temperature profile and finally profile of CO₂ mole fraction in gas phase along the absorption tower were studied. To elaborate mass transfer phenomena, enhancement factor, interfacial area, molar flux and liquid hold up were probed. The results show that regarding the CO₂ absorption, the most important parameter was the gas flow rate. Comparing liquid temperature profiles showed that the most important parameter affecting the temperature of the rich solvent was MEA concentration.