Adsorption of natural gas and biogas components on activated carbon

Experimental results are presented for the adsorption equilibria of methane, ethane, propane, butane, carbon dioxide, and nitrogen, as well as natural gas odorants tert-butyl mercaptan and tetrahydrothiophene, on an activated carbon with the desirable characteristics for use in a guard bed for adsorbed natural gas storage, but that can also be applied for separation of biogas components, such as carbon dioxide and nitrogen. The adsorption experiments were performed using both open- and closed-loop gravimetry over the pressure and temperature ranges of 0–9 MPa and 273–325 K, respectively. The two odorants were analyzed at the very low concentrations usually found in natural gas (0–25 mg/(N m³)). The experimental data were successfully correlated by the adsorption potential theory and collapsed into a single temperature-independent characteristic curve. This analysis allows for extrapolation of the adsorption data to higher alkanes, for which no experimental data are available, in order to span the global composition of a typical natural gas stream. The adsorption equilibrium data for methane, carbon dioxide and nitrogen were fitted to the Toth and Sips isotherm models and their isosteric heats of adsorption were determined. The preferential adsorption capacity for carbon dioxide indicates that the carbon can be used for methane purification from natural gas, carbon dioxide sequestration from flue gas, or biogas purification.     

Adsorption of carbon dioxide, ethane, and methane on titanosilicate type molecular sieves

The separation of carbon dioxide from light hydrocarbons is a vital step in multiple industrial processes that could be achieved by pressure swing adsorption (PSA), if appropriate adsorbents could be identified. To compare candidate PSA adsorbents, carbon dioxide, methane, and ethane adsorption isotherms were measured for cation exchanged forms of the titanosilicate molecular sieves ETS-10, ETS-4, and RPZ. Mixed cation forms, such as Ba/H-ETS-10, may offer appropriate stability, selectivity, and swing capacity to be utilized as adsorbents in CO₂/CH₄ PSA processes. Certain cation exchanged forms of ETS-4 were found to partially or completely exclude ethane by size, and equivalent RPZ materials were observed to exclude both methane and ethane, while allowing carbon dioxide to be substantially adsorbed. Adsorbents such as Ca/H-ETS-4 and Ca/H-RPZ are strong candidates for use in PSA separation processes for both CO₂/C₂H₆ and CO₂/CH₄, potentially replacing current amine scrubber systems.     

Separation of He/N2/CH4 ternary mixtures by a triple-reflux pressure swing adsorption process

Conventional pressure swing adsorption (PSA) processes can only produce one high purity product in a single stage, whereas the state-of-art dual-reflux PSA (DR-PSA) can produce two high purity products simultaneously. However, multicomponent gas separation is often required in the industry, targeting at recovering several valued products at the same time. In this study, we propose a novel adsorption process, namely triple-reflux PSA (TR-PSA), to separate three components simultaneously. A middle product outlet and a middle reflux stream were introduced to the adsorption columns of a conventional DR-PSA process to separate ternary mixtures of nitrogen, methane, and helium. Nonisothermal dynamic models were built to investigate the impacts of operating parameters particularly the location of the middle reflux/product stream and the middle reflux flow rates. Results showed that the TR-PSA process successfully separated ternary mixtures obtaining three enriched products simultaneously in a single stage, yielding a separation performance comparable to that of the double-stage DR-PSA with significantly lower capital and energy cost.     

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。     

炭分子筛CH4/N2吸附分离

煤层气(CBM)是一种非常规天然气。在中国,煤层气在抽采出来时常混有空气。考虑到安全因素,氧气首先应该被去除。之后,煤层气利用的最重要步骤则是甲烷-氮气混合气体的甲烷高效提浓。本文搭建了双床变压吸附(PSA)装置,选择特定的炭分子筛(CMS)进行CH₄/N₂混合物分离实验研究。由于CMS的动力学吸附特性,氮被吸附在CMS上,带有一定压力的甲烷则连续输出。研究了吸附压力、进气速度和循环周期等因素对吸附过程整体性能的影响。从50% CH₄/50% N₂的原料气可以获得95.45%纯度的甲烷产品,而从30% CH₄/70% N₂的原料气可以获得94.89%纯度的甲烷产品。研究表明,以上3个参数都对分离性能有影响,其中后两者的影响更大。在较低吸附压力和较低进气速度时更容易获得纯度90%以上的甲烷产品。另外,循环周期越短,获得的甲烷纯度越高。     

Vacuum pressure swing adsorption process for coalbed methane enrichment

The enrichment of low concentration coalbed methane using adsorption process with activated carbon adsorbent was studied in this work.Adsorption isotherms of methane,nitrogen and carbon dioxide on activated carbon were measured by volumetric method,meanwhile a series of breakthrough tests with single component,binary components and three components feed mixture has been performed for exploring dynamic adsorption behaviors.Moreover,a rigorous mathematical model of adsorption bed containing mass,energy,and momentum conservation equation as well as dual-site Langmuir model with the Linear driving force model for gas-solid phase mass transfer has been proposed for numerical modeling and simulation of fixed bed breakthrough process and vacuum pressure swing adsorption process.Furthermore,the lumped mass transfer coefficient of methane,nitrogen and carbon dioxide on activated carbon adsorbent has been determined to be 0.3 s~(-1),1.0 s~(-1) and 0.06 s~(-1) by fitting the breakthrough curves using numerical calculation.Additionally,a six bed VPSA process with twelve step cycle sequence has been proposed and investigated for low concentration coalbed methane enrichment.Results demonstrated that the methane molar fraction in feed mixture ranged from 10% to 50% could be enriched to 32.15% to 88.75% methane in heavy product gas with a methane recovery higher than 83%under the adsorption pressure of 3 bar(1 bar=10~5 Pa) and desorption pressure of 0.1 bar.Energy consumption of this VPSA process was varied from 0.165 kW·h·m~(-3) CH_4 to 0.649 kW·h·m~(-3) CH_4.Finally,a dual-stage VPSA process has been successfully developed to upgrade a low concentration coalbed methane containing 20% methane to a target product gas with methane purity higher than 90%,meanwhile the total methane recovery was up to 98.71% with a total energy consumption of 0.504 kW·h·m~(-3) CH_4.     

Basics and industrial applications of pressure swing adsorption (PSA), the modern way to separate gas

Pressure swing adsorption (PSA) technology is increasingly applied for purification of gases and for bulk separation of most various gas mixtures. Typical product gases are hydrogen, carbon monoxide, ethylene, nitrogen, oxygen and methane. This paper presents an introduction to the technique of PSA plants and gives a survey of current practical applications of adsorption technology in modern process plant complexes.     

锆基MOF次级结构单元调控及轻烃吸附分离性能增强

从天然气中回收C₂/C₃轻烃组分具有重要的工业价值,吸附分离技术可在常温常压下实现轻烃的回收。对MOF材料进行次级结构单元（SBU）调控,可在继承其晶体结构和发达孔道的同时,优化孔道化学微环境并引入新的吸附位点。使用三嗪（TZ）取代Zr-TBAPy(NU-1000)SBU中的配位水分子,在其孔道内构筑对轻烃吸附质具有更强限域作用的碱性表面化学微环境,得到了高选择性的新型TZ@Zr-TBAPy吸附剂。TZ的引入在分子尺度上提高了孔道的表面粗糙度,同时强化对轻烃吸附质的限域作用,提高材料对烷烃的吸附容量和选择性。常温常压下,TZ@Zr-TBAPy对丙烷和乙烷的吸附容量分别为10.08和4.19 mmol?g^-1,比Zr-TBAPy提高了27%和9%,是目前国际上已报道的丙烷吸附容量最高的吸附剂之一。此外,丙烷/甲烷的IAST选择性为1518,是原材料的6.27倍;乙烷/甲烷的IAST选择性为11.7,比原材料提高了22%。更为重要的是,以TZ@Zr-TBAPy吸附剂为核心的固定床吸附过程可实现在常温常压天然气中乙烷和丙烷的一步分离回收。     

变压吸附分离工业废气二氧化碳的研究进展

概述了未来人类对过量二氧化碳排放的处理办法,即碳的捕获和存储(CCS).简介了4种二氧化碳的分离工艺及特点和工业中二氧化碳的捕获系统.阐述了变压吸附工艺的基本原理和其在捕获工业废气中二氧化碳上的应用,以及变压吸附分离二氧化碳的工艺在循环结构设计、吸附剂材料和数值模拟等方面的研究进展和国内外的工业化应用.分析了目前该工艺仍存在的问题,指出该技术具有广阔的应用前景.     

Equilibrium isotherms and adsorption heats analysis for ternary mixture of methane,ethane, and propane on 4A zeolite

Equilibrium isotherms were obtained experimentally and theoretically for adsorption of methane, ethane, and propane mixtures on 4A zeolite at 301 K. The experimental data were measured using constant volume method and analyzed by extended Langmuir, modified extended Langmuir, and extended Freundlich isotherm models. The best correlation was achieved with the extended Freundlich isotherm equation and the negative values for heats of adsorption indicate exothermic adsorption nature for these gases on 4A zeolite. The selectivity of 4A zeolite to adsorb gases was also studied with the observation that ethane was more selectively adsorbed than methane on 4A zeolite, while propane was less selectively adsorbed on this zeolite at the studied temperature. Also, it was found that an increase in initial partial pressure of ethane decreases the adsorbed amount of methane, while the increase in partial pressure of methane had no effect on adsorbed amount of ethane.     

天然气常规组份分析方法的研究

着重研究了利用多柱与多阀协同完成对天然气中烃类与永久性气体的分离,并利用TCD检测器进行分析测试。本方法对天然气中甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷、异戊烷、己烷、二氧化碳、氩(氧)和氮各组份进行分离检测,并对定量方法进行了研究。本方法精密度、准确度均能满足天然气常规组份的检测要求;并且操作简单、快捷。     

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.     

Phase equilibria of hydrates from ternary mixtures of methane + ethane + propane and methane + propane + carbon dioxide

Hydrate–liquid–vapour (HLV) equilibrium of aqueous clathrates formed from gas mixtures can be complex compared to hydrates formed with single guests. Typically, pressure and temperature are controlled to obtain these data, but for multicomponent systems, it is necessary to control/report more intensive variables, namely, composition. Metastability, manifested as impractically long experimental times, has been reported to be a challenge with some multicomponent systems. We present HLV equilibrium conditions of two ternary gas mixtures: methane + ethane + propane (90:7:3 molar ratio) and methane + propane + carbon dioxide (55:5:40 molar ratio). Conditions varied in the temperature range of 275–285 K and the pressure range of 1.24–4.75 MPa. Experimental standard uncertainties were on average 0.10 K and 0.005 MPa for methane + ethane + propane and 0.19 K and 0.005 MPa for methane + propane + carbon dioxide. Our technique allowed us to bypass the limitations reported in the literature and provided fast, reproducible HLV equilibria for gas-dominated systems.     

Methane and carbon dioxide in dual-porosity organic matter: Molecular simulations of adsorption and diffusion

Shale gas, which predominantly consists of methane, is an important unconventional energy resource that has had a potential game-changing effect on natural gas supplies worldwide in recent years. Shale is comprised of two distinct components: organic material and clay minerals, the former providing storage for hydrocarbons and the latter minimizing hydrocarbon transport. The injection of carbon dioxide in the exchange of methane within shale formations improves the shale gas recovery, and simultaneously sequesters carbon dioxide to reduce greenhouse gas emissions. Understanding the properties of fluids such as methane and methane/carbon dioxide mixtures in narrow pores found within shale formations is critical for identifying ways to deploy shale gas technology with reduced environmental impact. In this work, we apply molecular-level simulations to explore adsorption and diffusion behavior of methane, as a proxy of shale gas, and methane/carbon dioxide mixtures in realistic models of organic materials. We first use molecular dynamics simulations to generate the porous structures of mature and overmature type-II organic matter with both micro- and mesoporosity, and systematically characterize the resulting dual-porosity organic-matter structures. We then employ the grand canonical Monte Carlo technique to study the adsorption of methane and the competing adsorption of methane/carbon dioxide mixtures in the organic-matter porous structures. We complement the adsorption studies by simulating the diffusion of adsorbed methane, and adsorbed methane/carbon dioxide mixtures in the organic-matter structures using molecular dynamics.     

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.     

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.     

Adsorption of Methane,Ethane, Ethylene,and Carbon Dioxide on High Silica Pentasil Zeolites and Zeolite-like Materials Using Gas Chromatography Pulse Technique

Abstract

Adsorption of methane, ethane, ethylene, and carbon dioxide in H-ZSM-5, Na-ZSM-5, H-ZSM-8, Na-ZSM-8, Silicalite, and ALPO-5 at 303–473 K has been investigated using a gas chromatography pulse technique. The zeolites have been compared for the heat of adsorption of the adsorbates at near zero adsorbate loading and also for the specific retention volume (or thermodynamic adsorption equilibrium constant) of ethane, ethylene, and carbon dioxide relative to that of methane. Among the zeolites, ALPO-5 has a high potential for the separation of methane, ethane, ethylene, and carbon dioxide from their mixture.     

Hydrothermal gasification of olive mill wastewater as a biomass source in supercritical water

In this study, the hydrothermal gasification of biomass in supercritical water is investigated. The work is of peculiar value since a real biomass, olive mill wastewater (OMW), is used instead of model biomass compounds. OMW is a by-product obtained during olive oil production, which has a complex nature characterized by a high content of organic compounds and polyphenols. The high content of organics makes OMW a desirable biomass candidate as an energy source. The hydrothermal gasification experiments for OMW were conducted with five different reaction temperatures (400, 450, 500, 550 and 600 °C) and five different reaction times (30, 60, 90, 120 and 150 s), under a pressure of 25 MPa. The gaseous products are mainly composed of hydrogen, carbon dioxide, carbon monoxide and C₁-C₄ hydrocarbons, such as methane, ethane, propane and propylene. Maximum amount of the gas product obtained is 7.71 mL per mL OMW at a reaction temperature of 550 °C, with a reaction time of 30 s. The gas product composition is 9.23% for hydrogen, 34.84% for methane, 4.04% for ethane, 0.84% for propane, 0.83% for propylene, 49.34% for carbon dioxide, and 0.88% for minor components such as n-butane, i-butane, 1-butene, i-butene, t-2-butene, 1,3-butadiene and nitrogen at this reaction conditions.     

Simple group contribution theory for adsorption of alkanes in nanoporous carbons

This paper develops a simplified form of the group-contribution theory of Russell and LeVan (Chem. Eng. Sci. 51 (1996) 4025) for the prediction of adsorption equilibria of n-alkanes on activated carbon. Molecules are separated into elements or groups, and adsorbate group-adsorbent interactions are the determining factor for adsorption equilibrium. The adsorbent surface is considered to be heterogeneous with a single dimensionless energy distribution. Model parameters are determined for pure-component adsorption of methane, ethane, n-butane, and n-hexane on BPL activated carbon at multiple temperatures. The resulting parameters are then used to predict adsorption equilibrium of propane and n-octane at multiple temperatures and mixtures of methane and n-hexane and ethane and n-hexane. The model gives a more accurate prediction of mixture adsorption than the ideal adsorbed solution theory. The model is also used to describe methane, propane, and n-pentane adsorption on BAX activated carbon (Ind. Eng. Chem. Res. 40 (2001) 338) and methane, ethane, and propane on Columbia Grade L carbon (Ind. Eng. Chem. 42 (1950) 1315) at multiple temperatures. The model is shown to describe adsorption equilibria of alkanes on all three activated carbons with good accuracy and can also be used as a predictive tool for components on which no experimental data are available.     

我国变压吸附技术的工业应用现状及展望

介绍了我国变压吸附技术近十多年发展状况及变压吸附技术在各应用领域的最新发展,并对今后的应用和发展作了展望。