Parametric Study of a Pressure Swing Adsorption Process

The performance of a pressure swing adsorption (PSA) process for production of high purity hydrogen from a binary methane-hydrogen mixture is simulated using a detailed, adiabatic PSA model. An activated carbon is used for selective adsorption of methane over hydrogen. The effects of various independent process variables (feed gas pressure and composition, purge gas pressure and quantity, configuration of process steps) on the key dependent process variables (hydrogen recovery at high purity, hydrogen production capacity) are evaluated. It is demonstrated that many different combinations of PSA process steps, their operating conditions, and the feed gas conditions can be chosen to produce an identical product gas with different hydrogen recovery and productivity.     

变压吸附技术的应用研究进展1

变压吸附(PSA)技术是近几十年来在工业上新崛起的气体分离技术,是物理化学渗流理论在工业上的具体应用。自上世纪70年代以来,变压吸附技术因其优势明显,在化工分离中占有重要地位,受到关注和发展。文章简要综述了变压吸附技术的发展里程、理论基础及其研究进展、分离过程的计算机模拟和在国内外工业领域中的应用情况,并对其应用前景进行了展望。     

Simulation of a Combined Isomerization Reactor & Pressure Swing Adsorption Unit

The Total Isomerization Process developed by Union Carbide in 1970 (Gary, 1987) for the conversion of normal paraffin's to their isomers consists of a reactor followed by a PSA unit each operating at similar pressures and temperatures. The combination of these two operations in one unit in a Pressure Swing Adsorption Reactor (PSAR) process may provide an increased throughput and a significant cost saving in ancillary equipment.The simulation of a mathematical model linking the catalyst packed-bed and the adsorbent packed-bed is reported. The catalyst is a Pd/Y-zeolite and the adsorbent is 5A zeolite. The simulated feed consists of 17% each of n- and isopentane with the remainder being hydrogen. The mathematical model assumes dispersed plug-flow in both sections, constant velocity in the reactor section but varying in the adsorber, with mass transfer in the adsorber section due to external fluid film resistance and macropore diffusion in series. The fraction of the total column length occupied by the catalyst (denoted by ) is accounted for in the model by solving numerically using orthogonal collocation on finite elements. Parameters varied are the ratio of catalyst/column length (), temperature range (506–533 K), high pressure (15–20 bars), with the low pressure held constant at 2 bars. The catalyst/column ratio has a strong effect at low temperatures. The optimum catalyst/column length ratio appears to be controlled by the low pressure step and occurs at = 0.7 for the assumptions used in this work.     

Study on Pressure Swing Adsorption Removing C2^＋ from Natural Gas as Raw Material for Thermal Chlorination

The experimental investigation demonstrates that a setisfactory can be expected for pressure swing adsorption (PSA) purification of natural gas as raw material for thermal chlorination process.Using hh-4 molecular sieve as adsorbent for removing C2^ components,the suitable adsorption pressure is 0.4-0.45 MPa,desorption vacuum is 0.08-0.09 MPa and circulation time is 20-21 min.     

Study on Pressure Swing Adsorption Removing C+2 from Natural Gas as Raw Material for Thermal Chlorination

The experimental investigation demonstrates that a satisfactory result can be expected for pressure swing adsorption (PSA) purification of natural gas as raw material for thermal chlorination process. Using hh-4 molecular sieve as adsorbent for removing C2 components, the suitable adsorption pressure is 0.4-0.45 MPa, desorption vacuum is 0.08-0.09 MPa and circulation time is 20-21 min.     

Comparison of Finite Difference Techniques for Simulating Pressure Swing Adsorption

Three different finite-difference routines were compared for solving the nonlinear, coupled, partial differential and algebraic equations that describe pressure swing adsorption processes. A successive substitution method (SS), a block LU decomposition procedure (BLUD), and the method of lines approach with adaptive time stepping (DASSL) were used to simulate and compare the computation times required to reach the periodic state for two different PSA systems: PSA-air drying and PSA-solvent vapor recovery. For both systems, the results showed that DASSL was nearly twice as fast as BLUD, whereas SS was nearly an order of magnitude slower than BLUD. DASSL and BLUD were also very robust and accurate, as nearly identical bed profiles were obtained from both methods under both transient and periodic state conditions.     

吸附分离技术在现代工业中的应用

概括介绍了吸附分离技术的发展,详细评述了吸附分离技术的最新进展和在现代工业中的应用,并预测了吸附分离技术未来的发展方向。     

Mathematical Modeling of Multicomponent Nonisothermal Adsorption in Sorbent Particles Under Pressure Swing Conditions

A detailed model for nonisothermal sorption of multicomponent mixtures in a single sorbent particle (monodisperse or bidisperse with negligible intracrystalline mass transport limitations) under pressure swing conditions is developed in this study. The dusty-gas model is used to describe the coupling of the molar fluxes, the temperature, the partial pressures and the partial pressure gradients of the components in the pore space of the particle. The variations of the temperature are described by an energy equation in which both convective and conductive modes of heat transport are accounted for. No limitations are imposed on the number of the components in the mixture and on the type of the adsorption isotherm. The model is applied in the investigation of the industrially important air-zeolite 5A system. Two cases with respect to the surrounding gas phase are examined: infinite environment, which is representative for single particle experiments, and finite environment, which is representative for the situation in packed bed adsorbers. It is found that in an infinite environment the external and internal temperature gradients are equally important while in a finite environment the external heat transport limitations are negligible. It is concluded that in modeling the nonisothermal operation of adsorption processes occurring in packed beds it is not necessary to allow for the temperature differences between the gas phase and the surface of the adsorbing particles. Furthermore, if the temperature gradients within the particles can be neglected, only a single temperature equation is needed to describe the energy transport in the bed.     

捕集高湿烟气中CO2的变压吸附技术

变压吸附法在捕集烟气中的CO₂这一领域中显示出强大的优越性,但实际电厂烟气含有少量的水蒸气,这对利用常规吸附剂捕集CO₂造成很大挑战。为解决上述瓶颈问题,改进变压吸附工艺以及开发对湿度不敏感、高效的吸附剂成为最主要的途径。本文详细介绍了两种常用的变压吸附工艺,即多层变压吸附及微波辅助真空再生法分离高湿烟气的研究进展,综述了近年来研发的适于捕集高湿烟气的高效吸附剂,系统阐述了各种吸附剂的物理化学特性及其吸附CO₂、H₂O的机制,并在此基础上讨论了变压吸附技术捕集高湿烟气时存在的问题,提出了研究展望。相信随着人们对变压吸附工艺的改进以及对新型高效吸附剂的进一步研发,必将显著降低捕集高湿烟气中CO₂的成本,这将对燃煤电厂等高湿CO₂排放源的温室气体减排具有重要意义。     

Pressure Swing Adsorption Technologies for Carbon Dioxide Capture

The principles of pressure swing adsorption (PSA) for carbon dioxide capture are reviewed. Previous work on PSA, relevant modeling and experimental investigation for specifically carbon dioxide separation are also presented and significant findings highlighted. Simple rules for PSA process design based on analysis of the inherent properties of adsorbate-adsorbent systems encompassing equilibrium isotherm, adsorption kinetics, shape of breakthrough curves, screening and selection of adsorbent, bed porosity, adsorption time, purge to feed ratio, residence time, pressure equalization and rinse steps are provided to promote better understanding of the technology so that it gains wider acceptance in the future to address the global environmental concern, particularly in the removal of carbon dioxide as a greenhouse gas.     

基于地方特色开发的化工过程模拟实验——以变压精馏为例

基于六盘水地区海拔高、气压低的特点,开设了具有地方特色的变压精馏过程模拟实验,低压塔设定为六盘水地区大气压值。以变压精馏分离乙酸甲酯-甲醇共沸物为例,通过相图确定精馏序列及工艺流程,讨论了进料位置、回流比和塔板数等变量对年度总费用TAC的影响,对于学生掌握化工技术和经济分析具有良好的教学效果。同时,对于培养人才的工程实践能力和服务地方产业提供了有效的保障。     

R and D Note: Separation of a Nitrogen-Carbon Dioxide Mixture by Rapid Pressure Swing Adsorption

A N₂-CO₂ mixture is separated in a rapid pressure swing adsorption apparatus, which consists of single or double adsorbent beds filled with silica gel and operates in the sequence of adsorption, backflow and desorption. Nitrogen-rich gas is produced at the top of the bed, and carbon dioxide-rich gas at the bottom. Carbon dioxide purity of 89.5% and recovery of 70% were obtained in the single-bed apparatus, while purity of 93.5% and recovery of 72.3% were obtained in the double-bed apparatus. The feed in both cases consisted of 81% N₂ and 19% CO₂.     

Performance of a Two-Bed Pressure Swing Adsorption Process with Incomplete Pressure Equalization

Incomplete pressure equalization (PE) is practiced in a commercial oxygen concentrator for medical use by adopting simultaneous PE and feed-pressurization for pressurizing an adsorption bed. In such a cycle configuration, extent of equalization during PE affects process performance. In order to assess the effect, performance of pressure swing adsorption (PSA) process with incomplete PE was determined by both simulations and experiments. In simulations, an equilibrium model was used with the assumptions of multicomponent Langmuir isotherms, isothermal operation, and no pressure drop through a bed. The required parameters for simulations were measured in separate experiments. PSA experiments were performed for a two-bed cycle with PE. Two kinds of pressurization, feed and product, were examined. Effects of purge amount and extent of equalization on process performance were assessed in view of productivity and light-component recovery. From the obtained results performance contours were constructed. 95 oxygen mole percent production from air with zeolite 13× was considered as a case study. In both pressurizations, an optimal specific purge and an extent of equalization for the productivity and recovery were observed, but with a different level of equalization. For a maximum productivity feed-pressurization favored incomplete PE, while a maximum recovery occurred at complete PE for both pressurizations. The simulations depicted well existence of optimum conditions, though they showed quantitative disagreement with experiments.     

Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer

Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents.     

Effect of variable feed concentration on the performance of a pressure swing adsorption process

Effects of variable feed composition on the performance of a pressure swing adsorption process are analyzed by simulation. Two scenarios are considered. The first, increasing impurity, case considers low impurity concentration in the feed followed by high impurity concentration in the feed. The second, decreasing impurity, case considers high impurity concentration in the feed followed by low impurity concentration in the feed. These results are compared against a case which has an impurity concentration in the feed at an average of the high and the low impurity concentrations. Simulations show that the increasing impurity scenario is expected to perform better, and the decreasing impurity scenario is expected to perform worse than the average feed concentration case.     

Supercapacitive Swing Adsorption of Carbon Dioxide

An electrical effect, the supercapacitive swing adsorption (SSA) effect is reported, which allows for reversible adsorption and desorption of carbon dioxide by capacitive charge and discharge of electrically conducting porous carbon materials. The SSA effect can be observed when an electrically conducting, nanoporous carbon material is brought into contact with carbon dioxide gas and an aqueous electrolyte. Charging the supercapacitor electrodes initiates the spontaneous organization of electrolyte ions into an electric double layer at the surface of each porous electrode. The presence of this double layer leads to reversible, selective uptake and release of the CO₂ as the supercapacitor is charged and discharged.     

An Equilibrium Relation for Gas Adsorption Applications

A new multicomponent equilibrium relation is proposed for engineering applications. This relation is based on a lattice model for mixtures of unequally sized molecules. An approximation is introduced for loading-dependent enthalies of adsorption that simplifies the energy balance in fixed-bed models and allows efficient solution of the equation set in process simulations. Comparisons are made with nonideal binary data in the literature.     

Piston-driven ultra rapid pressure swing adsorption

The piston-driven ultra rapid pressure swing adsorption (URPSA) equipment was developed and oxygen enrichment from air was examined as an example. The adsorbent bed is directly connected to the cylinder where a piston moves at high frequency. Thus pressurization and depressurization in the bed are driven by mechanical piston motion, which can achieve far more rapid cycles compared with the conventional pressure swing operation using valves. The cycle time is usually on the order of seconds or sub seconds. Oxygen enrichment from air up to about 60% or higher of oxygen concentration was achieved by small-scale equipment using zeolite 5A with a oxygen production capacity of 100 Nm³-product gas/m³-zeolite/hr, which is about ten times larger than those of commercialized PSAs for this purpose.A simplified numerical model describing the mass transfer taking place in URPSA was developed. The model could simulate fairly well the air separation characteristics in terms of oxygen concentration, oxygen production capacity and oxygen yield. The proposed model helps in the understanding of the basic nature of URPSA and possible applications. This novel PSA is promising as a compact yet high-capacity PSA to be utilized in a wide variety of applications.     

Tuning of Pressure Swing Adsorption Systems Based on Differential Pressure Profile

A method for tuning a Pressure Swing Adsorption (PSA) system aimed to achieve symmetrical operating conditions based on pressure differential in the adsorption vessels is developed in this study. Simulation of an oxygen Pressure-Vacuum Swing Adsorption (PVSA) process indicates that the pressure drop inside the adsorption vessel is closely related to the nitrogen concentration and gas velocity. The technique is applied to the tuning of an oxygen PVSA process. Adsorbent vessels of the PSA system are monitored and tuned by making corrective adjustments in each of the steps in a PSA cycle in response to imbalances in the differential pressure profiles in each of the adsorbent vessels. The method developed in this study provides a faster, easier, and more effective way to bring a PSA plant to its symmetrical, optimal state than those based on other parameters such as concentration, temperature, and pressure profile. This paper is dedicated to the memory of Professor Wolfgang Schirmer.     

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne-Functionalized Nickel(II)-Pyrazolate-Based MOFs

C₂H₂/CO₂ separation is a highly challenging process as a consequence of their similar physicochemical properties. In this work we have explored, by static and dynamic gas sorption techniques and computational modelling, the suitability of a series of two isoreticular robust Ni(II)pyrazolate-based MOFs, bearing alkyne moieties on the ligand backbones, for C₂H₂/CO₂ separation. The results are consistent with high adsorption capacity and selectivity of the essayed systems towards C₂H₂ molecules. Furthermore, a post-synthetic treatment with KOH ethanolic solution gives rise to linker vacancy defects and incorporation of extraframework potassium ions. Creation of defects is responsible for increased adsorption capacity for both gases, however, strong interactions of the cluster basic sites and extraframework potassium cations with CO₂ molecules are responsible for a lowering of C₂H₂ over CO₂ selectivity.