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.     

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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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.     

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.     

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。     

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 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.     

Efficient pressure swing adsorption for improving H<Subscript>2</Subscript> recovery in precombustion CO<Subscript>2</Subscript> capture

An efficient design for pressure swing adsorption (PSA) operations is introduced for CO₂ capture in the pre-combustion process to improve H₂ recovery and CO₂ purity at a low energy consumption. The proposed PSA sequence increases the H₂ recovery by introducing a purge step which uses a recycle of CO₂-rich stream and a pressure equalizing step. The H₂ recovery from the syngas can be increased over 98% by providing a sufficient purge flow of 48.8% of the initial syngas feeding rate. The bed size (375m³/(kmol CO₂/s)) and the energy consumption for the compression of recycled CO₂-rich gas (6 kW/(mol CO₂/s)) are much smaller than those of other PSA processes that have a CO₂ compression system to increase the product purity and recovery.     

π型向心径向流吸附器变质量流动特性研究

对径向流吸附器内变压吸附(PSA)制氧的变质量流动规律进行研究,有助于准确掌握吸附过程及床层内的变量因素对制氧性能的影响。对π型向心径向流吸附器建立气固耦合的两相吸附模型,并对其PSA制氧过程进行了数值模拟研究,得到了床层内氧气浓度分布、温度分布以及产品气浓度的变化规律。结果表明：首次循环结束时床层内氧气最高摩尔分数可达66.02%,回收率29.2%。非稳定循环期间,氧气摩尔分数从66.02%升高至 97.5%,回收率从29.2%提高至38.5%。循环达到稳定后,床层内氧气摩尔分数最高可达98.6%,回收率38.9%左右,且达到稳定状态后床层内气固两相温差减小,逐渐达到热平衡。获得了吸附器内部气体与吸附剂两相间的传质、传热过程,为π型向心径向流吸附器用于PSA制氧提供技术支持。     

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.     

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.     

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。     

快速变压吸附制氢工艺的模拟与分析

目前工业上主要通过变压吸附技术从蒸汽甲烷重整气中制取氢产品气。然而,能源需求量的快速增加使得传统变压吸附技术在产量方面的不足越发明显。为此,进行了快速变压吸附从蒸汽甲烷重整气中制取氢气的模拟研究。采用活性炭和5A分子筛作为吸附剂,并以测得的原料气中各组分在两种吸附剂上的吸附数据为基础,进行了六塔快速变压吸附工艺的数值模拟与分析。在分析了塔内温度、压力和固相的浓度分布后,探究了进料流量、双层吸附剂高度比以及冲洗进料比三个操作参数对于快速变压吸附工艺性能的影响,结果表明：原料气组成为H₂/CH₄/CO/CO₂=76%/3.5%/0.5%/20%,吸附压力为22 bar（1 bar=10⁵ Pa）,解吸吹扫压力为1.0 bar,处理量为0.8875 mol·s^-1,吸附剂床层高度比为0.5∶0.5,冲洗进料比为22.37%时,可获得H₂纯度99.90%,回收率69.88%,此时H₂产量为0.4713 mol·s^-1。相比之下,氢气纯度为99.90%时,尽管PSA工艺回收率为83.40%,但处理量只有0.39 mol·s^-1,因此H₂产量仅为0.2472 mol·s^-1。     

吸附法产品氢纯度和收率的研究

本文探讨了中国神马集团尼龙66盐公司制氢装置的变压吸附气体分离的机理,通过试验,找出了运行方式与回收率的关系以及吸附压力、真空度、吸附时间对产品氢纯度的影响,确定了对产品氢的纯度和收率起主要作用的工艺参数,并选定了合适的操作条件,使得产品氢纯度达到了99.9%以上,产品氢的收率增至85%以上。     

CO2 recovery from flue gas by PSA process using activated carbon

An experimental study was performed for the recovery of CO₂ from flue gas of the electric power plant by pressure swing adsorption process. Activated carbon was used as an adsorbent. The equilibrium adsorption isotherms of pure component and breakthrough curves of their mixture (CO₂ : N₂ : O₂=17 : 79 : 4 vol%) were measured. Pressure equalization step and product purge step were added to basic 4-step PSA for the recovery of strong adsorbates. Through investigation of the effects of each step and total feed rate, highly concentrated CO₂ could be obtained by increasing the adsorption time, product purge time, and evacuation time simultaneously with full pressure-equalization. Based on the basic results, the 3-bed, 8-step PSA cycle with the pressure equalization and product purge step was organized. Maximum product purity of CO₂ was 99.8% and recovery was 34%.     

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。     

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。     

Removal of CO from process gas with Sn–activated carbon in pressure swing adsorption

A pressure swing adsorption (PSA) system using activated carbon impregnated with SnCl ₂·2H ₂ O and pure activated carbon was used to remove CO from a model H ₂/CO mixture representing the steam reformer process gas. On comparing PSA results for both carbons, the CO adsorptive capacity of impregnated carbon was found to be superior to that of the pure carbon. This was confirmed by the fact that the concentration of CO, initially at 1000 ppm, was successfully reduced to 4.02% and 1.04% of its initial concentration by the pure and the impregnated activated carbons respectively in the PSA system. The species in the impregnated carbon responsible for the improved gas phase CO adsorption was found to be SnO ₂. Simulation results at a cyclic time of 600 s in the PSA operating at 10 atmospheres gave a product recovery and purity of 99.99% and 57.48%, respectively. At 6 atmospheres, the product recovery and purity were 92.17% and 77.12%, respectively. © 2000 Society of Chemical Industry     

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.     

Separation of Hydrogen-Lean Mixtures for a High-Purity Hydrogen by Vacuum Swing Adsorption

Abstract

High-purity hydrogen is commercially produced by pressure swing adsorption from hydrogen-rich mixtures. In this work, a vacuum pressure swing adsorption cycle is used to produce high purity hydrogen from a hydrogen-lean binary mixture (20/80 H₂/CO) using zeolite 5A as the sorbent. The effects of different process variables on separation performance have been studied. The purity of hydrogen product increases at low throughput, high feed pressure, high end pressure of cocurrent depressurization, low end pressure of countercurrent evacuation, and short cycle time. Also, it was found that for a H₂-lean mixture, the separation is improved at higher ambient temperature. In addition, a new “vacuum purge” step was found to improve the separation and is therefore a promising step for commercial application.