Carbon-based oxygen selective desiccants for use in nitrogen PSA

Techniques for the production of composite oxygen selective adsorbents are disclosed. These adsorbents are comprised of a carbon molecular sieve (CMS) which is kinetically selective for the adsorption of oxygen over nitrogen and an agent for the sorption of water such as LiCl or SiO₂. The adsorption properties of the composite adsorbents and results obtained from pressure swing adsorption (PSA) process testing are presented. The composite adsorbents improve the nitrogen PSA process performance (recovery and productivity) over the use of conventional desiccants which do not exhibit oxygen selectivity. Using a standard nitrogen PSA process cycle, replacement of conventional inorganic desiccants like alumina with the current CMS-based desiccants improved air recovery 2 to 4 percentage points and increased nitrogen productivity 15 to 20% at 70°F and a nitrogen purity of 99.5%.     

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。     

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     

变压吸附空分制氮过程的研究

建立了一套中试装置 ,对以商业炭分子筛为吸附剂的变压吸附 (PSA)空分制氮循环过程进行了系统研究 .用所建立的数学模型对相应实验进行模拟并将模型预测与实验数据进行比较 ,结果表明模型是可靠的 .     

Equilibrium Analysis of Cyclic Adsorption Processes: CO2 Working Capacities with NaY

Abstract

The most common application of adsorption is via pressure swing adsorption. In this type of design, the feed and regeneration temperatures are kept approximately equal, whereas the feed pressure is higher than the regeneration pressure. By exploiting the difference in the amount adsorbed at a higher pressure to the amount adsorbed at a lower pressure, a working capacity is realized. Therefore, by examining the expected (ideal) working capacity of an adsorbent, a performance characteristic can be analyzed for a pressure swing adsorption process (PSA). For this work, feed pressures up to 2.0 atm CO₂ and feed temperatures from 20°C to 200°C were investigated. These limits were chosen due to the nature of the target process: CO₂ removal from flue gas.

Carbon dioxide adsorption isotherms were determined in a constant volume system at 23°C, 45°C, 65°C, 104°C, 146°C, and 198°C, for pressures between 0.001 and 2.5 atm CO₂ with NaY zeolite. These data were fit with the temperature dependent form of the Toth isotherm. Henry's Law constants and the heat of adsorption at the limit of zero coverage were also determined using the concentration pulse method. Comparison of the Henry's Law constants derived from the Toth isotherm, and those obtained with the concentration pulse method provided excellent agreement.

By using the Toth isotherm, expected working capacity contour plots were constructed for PSA (Pressure Swing Adsorption), TSA (Temperature Swing Adsorption), and PTSA (Pressure Temperature Swing Adsorption) cycles. The largest expected working capacities were obtained when the bed was operated under a high‐pressure gradient PSA cycle, or a high thermal and pressure gradient PTSA cycle. The results also showed that certain TSA and PSA cycle conditions would result with higher expected working capacities as the feed temperature increases.     

Fractionated Vacuum Swing Adsorption Process for Air Separation

Abstract

A novel adsorptive process for air separation using a zeolitic adsorbent is described. The process essentially consists of three simple cyclic steps, and it can be used for simultaneous production of an 80—90% oxygen-enriched gas and a 98 + % nitrogen-enriched gas from ambient air. Successful operation of the process requires the use of a zeolite which exhibits high nitrogen adsorption capacity and selectivity from air. The role of nitrogen adsorption selectivity of the zeolite in the vacuum desorption process is examined, and experimental performance data for the air separation process are reported.     

Solvent Vapor Recovery by Pressure Swing Adsorption. III. Comparison of Simulation with Experiment for the Butane—Activated Carbon System

Abstract

A fully predictive (no adjustable parameters), nonisothermal, multicomponent mathematical model was developed and used to simulate a pressure swing adsorption (PSA) process designed for the separation and recovery of concentrated butane vapor from nitrogen using BAX activated carbon. Nearly quantitative agreement with experiment was realized with this model over a wide range of process conditions, and for both the transient and periodic state process dynamics and the periodic state process performance. The model also verified some unique characteristics of this PSA process, and it revealed some of the subtleties associated with accurately simulating a PSA-solvent vapor recovery (SVR) process. These subtleties included the need to account for the adsorbate heat capacity and the temperature dependence of the gas-phase physical properties. No PSA models in the literature have included both of these features, which were critical to the accurate prediction of the heat effects in this PSA-SVR process.     

Surface properties of carbons from poly(vinyl chloride)

Non-activated carbons were prepared by the thermal degradation of poly(vinyl chloride) (PVC) in air or nitrogen atmosphere in the temperature range 600-1000°C. Carbon dioxide-activated carbons from PVC were also obtained by gasification of non-activated carbon from PVC at 900°C burn-off (4-50%). Thermal degradation in air atmosphere gave high carbon yield because the oxygen of air increased crosslinking at lower temperature and chemisorbed on the carbon surface at high temperatures. Thermal degradation in air and gasification with carbon dioxide created carbon-oxygen surface groups which increased the hydrophilicity of the carbon surface and consequently increased water adsorption capacity. Gasification with carbon dioxide to high burn-off created new pores and widened already existing pores.     

Adsorption and Desorption of Carbon Dioxide and Nitrogen on Zeolite 5A

The adsorption equilibrium data of CO₂ and N₂ at (303, 333, 363, 393, 423) K ranging 0-1 bar on zeolite 5A is reported. The pressure and temperature range covers the operating pressure in adsorption units for CO₂ capture from power plants. Experimental data were fitted by the multi-site Langmuir model. The adsorbent is much more selective to CO₂: loading at 303 K and 100 kPa is 3.38 mol/kg while loading of N₂ at the same pressure is 0.22 mol/kg. The Clausius-Clapeyron equation was employed to calculate the isosteric enthalpy of adsorption. The fixed-bed adsorption and desorption of carbon dioxide and nitrogen on zeolite 5A pellets has been studied. A model based on the bi-LDF approximation for the mass transfer, taking into account the energy and momentum balances, had been used to describe the adsorption kinetics of carbon dioxide and nitrogen. The model predicted satisfactorily the breakthrough curves obtained with carbon dioxide–nitrogen mixtures. Desorption process (consisting of depressurization, blowdown, and purge) was also performed. Following the feasibility of concentration and capture of carbon dioxide from flue gases by Pressure Swing Adsorption (PSA) process was simulated. A CO₂ recovery of 91.0% with 53.9% purity was obtained using a five-step Skarstrom-type PSA cycle.     

用高性能制氧分子筛变压吸附

对沸石分子筛进行离子交换改性 ,同时严格控制成型活化条件 ,开发出变压吸附空分用系列高性能制氧分子筛。测试其氮、氧静态吸附等温线以及吸附热数据 ,并对数据结果进行分析。这为进一步开发和优化变压吸附制氧过程提供了良好的基础     

A Pressure Swing Adsorption Process for Production of 23–50% Oxygen-Enriched Air

Abstract

A simple pressure swing adsorption process for direct production of low to medium purity (23–50%) O₂-enriched gas from ambient air is described. The process provides a high O₂ production capacity per unit amount of the adsorbent and a high O₂ recovery combined with a very low energy requirement for the separation. The performance of the process using three different air separation adsorbents is described.     

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     

Combination of Sorption-Enhanced Steam Methane Reforming and Electricity Generation by MCFC: Concept and Numerical Simulation Analysis

Abstract

Reformed gas made by the steam methane reforming(SMR) process is used as fuel feed to MCFC, but it is not as good as pure hydrogen due to the presence of CO₂ and CO. The sorption-enhanced steam methane reforming(SE-SMR) process can reduce CO₂ and CO to a low level and produce high purity hydrogen. Considering the merits of similar operating temperatures (about 500°C) and carbon dioxide recycle, a novel concept of a six-step sorption-enhanced steam methane reforming (SE-SMR) combined with electricity generation by molten carbonate fuel cell (MCFC) is proposed. In the present paper, a cycle of the SE-SMR process, which include the steps of reaction/adsorption, depressurization, gas purges (nitrogen and reformed gas, respectively), and pressurization with reformed gas, is modeled and analyzed. The process stream in the SE-SMR process is used as anode feed in MCFC. According to the result of numerical simulation, a fuel cell grade hydrogen product (above 80% purity) at the SE-SMR temperature of 450°C can be obtained. A carbon dioxide recycle mechanism is developed for cathode feed of MCFC from flue gas by burning with excess air to achieve a proper CO₂/air ratio (about 30:70). The novel electricity generation system, which can operate at lower energy consumption and high purity hydrogen feed is helpful for the MCFC'S performance and life time.     

Effect of Drying Method on Gas Adsorption Characteristics of Carbon Gel Microspheres

Abstract

The effect of drying method used in the preparation of carbon gel microspheres was studied by comparing the porous properties of carbon cryogel microspheres (CCM) and carbon xerogel microspheres (CXM), which were respectively obtained using freeze drying and hot air drying. CCM were found to possess higher mesoporosity than CXM because freeze drying was effective to suppress the shrinkage of the mesopores during drying. On the other hand, the microporosity of the carbon gel microspheres was hardly influenced by not only the drying method but also the synthesis condition. Although the amounts of nitrogen and oxygen adsorbed were almost the same, the adsorption rate of nitrogen on both CCM and CXM possessing ultramicroporous surfaces was much larger than that of oxygen, which indicated the applicability of the carbon gel microspheres to adsorbents for pressure swing adsorption (PSA) of air. The relations between the temperature and the amount of oxygen adsorbed showed the adsorption characteristics of CCM and CXM as adsorbents for temperature swing adsorption (TSA) were almost the same.     

Preparation of activated carbon from olive mill solid residue

A process was developed for producing high quality activated carbon from Algerian mill waste. The solid olive mill residue was carbonized at 800 °C and physically activated with CO₂, air or steam. An optimum activation temperature of about 850 °C was determined for all the activation agents used. Steam appeared to be the most efficient activator as compared with air and CO₂. An optimal activation time of about 2 h was then determined with steam as the optimum activation agent. The porous structure of the activated carbon was characterized by nitrogen adsorption at −196 °C, and in all cases the surface areas, calculated by DR and BET methods, confirmed the production of a material with good microstructural characteristics and specific surfaces exceeding 1500 m² g⁻¹ for the carbon prepared by steam activation. Phenol adsorption isotherms gave the adsorption properties and the adsorption capacity of about 11.24 mg of phenol per gram of the activated carbon produced. The kinetics of the phenol adsorption onto the porous material was evaluated by means of two models: the external resistance model and the linear model. The second model appeared to constitute a more appropriate fit for the experimental data. © 2000 Society of Chemical Industry     

Adsorption and Thermal Desorption of Volatile Organic Compounds in a Fixed Bed – Experimental and Modeling

Adsorption and thermal desorption dynamics of acetone in fixed-bed silica gel were studied experimentally and theoretically. The effect of process factors on adsorption and desorption performances was established. Acetone adsorption from air stream was performed by the dynamic (flowing gas) method in a laboratory setup at two levels of air superficial velocity (0.7 and 1.7 cm s^?1), temperature (30 and 40°C), and adsorbent particle diameter (0.21 and 0.54 cm). The values of saturation adsorption capacity (0.147–0.270 g g^?1) increased up to 78% and 36%, respectively, with a decrease in air velocity and adsorption temperature. Acetone thermal desorption from spent silica gel was studied in a thermobalance at three levels of process temperature (60, 70, and 80°C) and two values of particle size (0.21 and 0.54 cm). Equilibrium desorption efficiency (63–81%) was up to 14% larger for finer particles and increased with the desorption temperature. Kinetic models with relevant parameters adjusted based on experimental data were adopted to predict the dynamics of acetone adsorption and thermal desorption. The models simulated well the real conditions and could be applied to scale up and operate the adsorption columns used for air remediation.     

Oxygen enrichment from air through multilayer thin low‐density polyethylene films

Several multilayer thin low‐density polyethylene (LDPE) films were fabricated by blown thin film having a thickness of 7 μm and an area of 130 cm². They were characterized for their oxygen‐enrichment performance from air by a constant pressure–variable volume method in a round permeate cell with an effective area of 73.9 cm². The relationship between oxygen‐enrichment properties, including oxygen‐enriched air (OEA) flux, oxygen concentration, permeability coefficients of OEA, oxygen, nitrogen, as well as separation factor through the multilayer LDPE films, and operating parameters, including transfilm pressure difference, retentate/permeate flux ratio, temperature, as well as layer number, are all discussed in detail. It is found that all of the preceding oxygen‐enrichment parameters increase continuously with an increase of transfilm pressure difference from 0.1 to 0.65 MPa, especially for the trilayer and tetralayer LDPE films. The oxygen concentration and separation factor appear to rapidly increase within the retentate/permeate flux ratio below 200, and then become unchangeable beyond that, whereas the OEA flux and the permeability coefficients of OEA, oxygen, and nitrogen seem to remain nearly constant within the whole retentate/permeate flux ratio investigated, especially for the monolayer and bilayer LDPE films. The selectivity becomes inferior, whereas the permeability becomes superior, as the operating temperature increases from 23 to 31°C. The highest oxygen concentration was found to be 44.8% for monolayer LDPE film in a single step with air containing oxygen of 20.9% as a feed gas and operating pressure of 0.5 MPa at a retentate/permeate flux ratio of 340 and 23°C. The results demonstrate a possibility to prepare an oxygen‐enriching membrane directly from air, based on the easily obtained thin LDPE films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3013–3021, 2002; DOI 10.1002/app.2331     

空分富氧沸石分子筛吸附剂的研究

介绍了国内外目前以PSA技术进行空气分离制备氧气所用沸石分子筛吸附剂的研究状况。从研究结果来看，N2吸附容量和N2／O2分离选择性的提高主要通过对沸石分子筛4A和13X进行离子交换，以对其表面进行改性，从而调整对N2、O2的吸附性能。另外，沸石分子筛制备过程中的硅铝比和成型条件等对N2和O2的吸附也有一定的影响。     

Interaction of Hyaluronic Acid (HA) with Organosilicon (Si‐QAC) Modified Magnetite for HA Recovery

Abstract

Cetylpyridinium chloride (CPC) is commonly used to precipitate hyaluronic acid (HA) from crude extract in a HA purification process. 3‐(Trimethoxysilyl)‐propyldimethyl octadecyl ammonium chloride (Si‐QAC) has a structure very similar to CPC when it is bonded to surfaces through its silane base. By taking advantage of its easy surface bonding property, Si‐QAC was bonded to the silica‐coated magnetite to facilitate HA recovery. The effects of pH, salt concentration, and the temperature on HA adsorption to Si‐QAC‐magnetite were studied. Not only the positively charged nitrogen but also hydrophobic long tail of Si‐QAC contributed to the strong interaction between HA and Si‐QAC‐magnetite. The maximum HA adsorption capacity was 38 mg/g‐dry magnetite and the equilibrium dissociation constant was 0.016 g/l at pH 4 under 37°C. The adsorbed HA could be effectively desorbed by 1 N NaCl supplemented with 0.1% Triton X100.