Development of new carbon honeycomb structures from cellulose and pitch

In this paper the development of a new, low-cost method for the preparation of carbon honeycomb structures for gas adsorption applications is described. The method comprises the impregnation of a petroleum pitch into a cellulose-based corrugated paper. The resultant material has a high carbon content and retains the original structure of the paper, making it suitable for usage in gas flow applications. TEM and SAD studies on the carbonised material suggest the presence of two different types of carbon structures, a disorganised structure and a more organised one. The porosity of the samples was characterised by CO₂ and N₂ adsorption. The results indicated an appreciable narrow microporosity with a high structural stability to high temperatures (presence of the porosity at high temperatures). Finally, the molecular sieve properties of the materials were studied by CH₄ and CO₂ adsorption kinetics and compared favourably with those of a commercial carbon molecular sieve (CMS), indicating their promise for high temperature applications, such as catalyst supports or for gas separations.     

Adsorption separation of N2, O2, CO2 and CH4 gases by β-zeolite

In the present study, adsorption equilibrium and kinetic separation potential of β-zeolite is investigated for N₂, O₂, CO₂ and CH₄ gases by using concentration pulse chromatography. Adsorption equilibrium and kinetic parameters have been studied. Henry’s Law constants, heat of adsorption values, micro-pore diffusion coefficients and adsorption activation energies are determined experimentally. The three different mass transfer mechanisms, that have to take place for adsorption to occur, are discussed. From the equilibrium and kinetic data, the equilibrium and kinetic selectivities are determined for the separation of the gases studied.With β-zeolite, carbon dioxide has the highest adsorption Henry’s Law constant at all the temperatures studied, followed by methane, nitrogen and oxygen. Carbon dioxide separation from oxygen, nitrogen and methane has good equilibrium separation factors. This factor is not very high for methane/nitrogen and methane/oxygen systems and is the lowest for nitrogen/oxygen system. Micro-pore diffusion is the dominant mass transfer mechanism for all the systems studied, except CH₄, with β-zeolite. The kinetic separation factors are very small at high temperatures for all the systems studied. Nitrogen/carbon dioxide and oxygen/carbon dioxide can be separated in kinetic processes with reasonable separation factors at low temperatures. Both equilibrium and kinetic separation factors decrease as column temperature increases. Considering all the observations from this study, it was concluded that β-zeolite is a good candidate for applications in flue gas separations, as well as natural gas and landfill gas purifications.     

铁离子改性碳分子筛对氮气/甲烷分离性能的研究

针对碳分子筛对氮气/甲烷分离体系分离比低的问题,采用浸渍法以市售空分碳分子筛（CMS）为基体,制备了分离氮气/甲烷的铁离子改性碳分子筛。通过静态吸附量、分离比、吸附动力学及热力学性质考察了铁离子负载量对碳分子筛吸附分离氮气/甲烷性能的影响。结果表明：铁（Ⅲ）的负载减小了CMS的比表面积、微孔体积和孔径,使CMS超微孔的孔径分布呈现更集中的趋势。这种集中性以动力学性能下降为代价,明显提高了碳分子筛对氮气/甲烷的吸附分离比。在303 K、0.7 MPa条件下,综合性能优异的0.3%铁改性CMS具有6.03的氮气/甲烷吸附分离比。     

氧和氮在炭分子筛上的吸附与扩散

用重量法研究了氧、氮在两种空分用炭分子筛上的吸附与扩散。结果表明,氧和氮在炭分子筛中的扩散是活化扩散,该过程可用双孔模型进行描述。求得了氧、氮的扩散系数。     

Investigation of the mechanism for the separation of nitrogen—oxygen mixtures on carbon molecular sieves

Sorption separation of nitrogen-oxygen mixtures by carbon molecular sieves, e.g. to produce nitrogen using the pressure swing adsorption principle, proceeds under the condition of non-equilibrium. Experimental data based upon measurements of sorption equilibria and kinetics for nitrogen and oxygen on several samples of carbon molecular sieve particles in the temperature range 0–50°C suggest the existence of a surface barrier in the pore mouths of slit-like micropores for these particular samples. The conclusion on this phenomenon is supported by the results of canonical and grand canonical Monte Carlo simulations. Both types of analysis give a deeper insight into the complex non-equilibrium separation process.     

Kinetics of removal of impurities from gases by high pressure adsorption

Among other processes, adsorption is used for the removal of hydrogen sulphide from natural gases. Hereby, competitive adsorption of the different gas components plays an important role, e.g., that of carbon dioxide. Data of equilibrium loading and adsorption kinetics are required for the design of adsorbers, filled with molecular sieve. In order to obtain these data under the prevailing operating conditions, hydrogen sulphide was removed from gas mixtures H₂S/CH₄ and H₂S/CO₂/CH₄, in a pilot plant, by adsorption on molecular sieve 5A. The equilibrium loading, the height of transfer zone, and the length of unused bed were determined from the measured breakthrough curves of H₂S. With these data, the breakthrough time and the optimum process conditions were calculated for a practical example.     

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     

Molecular sieve properties obtained by cracking of methane on activated carbon fibers

Molecular sieve properties of activated carbon fibers modified by cracking treatment with methane are studied herein. The effect of methane treatment on the porous texture of the samples has been studied while varying temperature and time. These materials have been evaluated for their selectivity during CO₂ and CH₄ separation; their uptakes have been compared with non-treated activated carbon fibers (studied previously), which were considered suitable to be used as molecular sieves. Kinetics of CO₂ and CH₄ uptake have also been investigated in this research. The treatment produced materials exhibiting fast kinetics and high selectivity during CO₂ and CH₄ separation; at the same time however, the CO₂ uptake capacity was diminished.     

Kinetische Untersuchungen der adsorptiven Luftzerlegung an Kohlenstoffmolekularsieben

In recent years, the adsorptive air separation was established as one of the most important thermal separation processes for the generation of nitrogen and oxygen from air. Both the effects of equilibrium and kinetics can be applied for the separation of nitrogen and oxygen. Nitrogen can be enriched by an equilibrium effect in the adsorbed phase of zeolites, whereas oxygen remains in the gas phase. In contrast to zeolites, oxygen can diffuse much faster into the pores of carbon molecular sieves resulting in a gas phase enriched with nitrogen. In order to exploit this kinetic separation effect in industrial applications, the properties of carbon molecular sieves, e.g., pore aperture, overall pore volume, or release of heat of adsorption are important. Furthermore, research activities are focused on theoretical approaches to describe the kinetic behavior.     

Adsorption properties of carbon molecular sieves prepared from an activated carbon by pitch pyrolysis

In this study a heat-treatment process using an activated carbon and coal-tar pitch was developed to prepare carbon molecular sieves (CMSs) for CH₄/CO₂ separation. This process results in a partial blockage of the pores of the activated carbon precursor, so that a reduction in the pore size takes place. Equilibrium CO₂ adsorption measurements at different temperatures, and CO₂ and CH₄ kinetic measurements at different temperatures and feed pressures were carried out using the TEOM technique for a carbon molecular sieve (CMS) prepared by this process (sample CB3) and a commercial CMS (Takeda 3A, sampleT3A). The overall diffusion for CO₂ in sample CB3 was faster than that in T3A and a slightly higher CO₂ adsorption capacity of CB3 was obtained. The transient uptake profiles in both samples at different temperatures and different CO₂ partial pressures were described in some cases by a micropore diffusion model, and in other cases by a dual resistance model. Both equilibrium and kinetic results demonstrate a better CO₂/CH₄ separation performance for the CMS prepared in the present study (CB3) than for the commercial CMS (Takeda 3A), due to the existence of slightly wider pore-mouth openings in sample CB3. This study demonstrates that the process used in this work is an interesting and reproducible approach to prepare CMS for CO₂/CH₄ separation.     

甲烷沉积法对甲烷/氮气分离炭分子筛性能的研究

高性能甲烷/氮气分离用炭分子筛是保证低浓度煤层气变压吸附分离的前提.以椰壳炭化料为原料在一定条件下活化制备了炭前驱体,以甲烷为沉积剂通过气相炭沉积调孔制备炭分子筛,考察沉积时间、沉积温度、沉积剂浓度和沉积剂量对变压吸附分离甲烷/氮气效果的影响,采用N2吸附法分析了炭前驱体的比表面积和孔径分布.结果表明:炭化时间40 m...     

Novel carbon molecular sieve honeycomb membrane module: configuration and membrane characterization

A new production concept of carbon molecular sieve membranes modules is described. The supported membrane synthesis process allows for industrial production with uniform and reproducible properties, using flat membranes as a starting precursor. The corresponding membrane modules are made in a honeycomb configuration, leading to high packing density and thermochemical stability. Some of the carbon membranes produced for use in these modules are characterized. Species H₂, O₂, N₂, CO₂ and SF₆ were used in monocomponent adsorption and permeation experiments to obtain adsorption equilibrium and permeation data. High permeabilities were attained in combination with high selectivities. The pore size distribution of the membrane was determined. A number of complementary morphological and structural characterizations were also performed.     

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%.     

Predictive Dynamic Model of Air Separation by Pressure Swing Adsorption

A general dynamic model is developed for separation of air over a carbon molecular sieve and a zeolite adsorbent for production of nitrogen and oxygen. The proposed model is validated using experimental data from working laboratory scale N₂–PSA and laboratory scale O₂–PSA systems. Simulations studies are performed to investigate the effect of changing various process variables, such as the duration of PSA steps, bed length and feed inlet velocity.     

炭分子筛上氧、氮吸附特性的实验测定

针对BF型炭分子筛孔结构的特点,利用双分散孔结构吸附模型,采用色谱扰动-应答方法,对微孔扩散控制传质机理进行了实验认定,测定了O2的吸附平衡常数K、扩散时间常数Dc/rc2以及O2、N2两组分常温下的吸附等温线.     

Modelling of the pressure swing air seperation process

A theoretical analysis is given of the separation of oxygen and nitrogen in air by a single column pressure swing gas separation process. The problem treated includes changes in mass flow due to adsorption. The findings are compared with data obtained using molecular sieve adsorbent.     

Modified activated carbon with an enhanced nitrobenzene adsorption capacity

To enhance nitrobenzene removal from aqueous solution, commercial activated carbon (AC) was modified by oxidation with HNO₃ followed by heat treatment in a nitrogen atmosphere. The modification process introduced oxygen-containing functional groups and changed the charge properties of the AC surface. The effects of surface chemical properties and pore structure on the adsorption of nitrobenzene by the AC were investigated through kinetics and equilibrium isotherms. HNO₃ oxidation modified the surface chemical properties and increased the number of acidic oxygen-containing surface groups, but had an almost negligible effect on the pore structure. Subsequent heat treatment caused decomposition of oxygen-containing functional groups on the AC surface, increased the pH point of zero charge (pH_PZC) and increased the number of mesopores. The maximum adsorption capacity achieved by the modified AC was 1,443.53 mg g^?1, 3.33 times of that unmodified AC. HNO₃ oxidation combined with heat treatment was an effective method for the preparation of AC with high nitrobenzene adsorption capacity and fast adsorption kinetics. An appropriate pH_PZC, amount of surface oxygen groups and the presence of well-developed mesopores together with micropores were the main reasons for the high nitrobenzene adsorption capacity of the modified AC.     

Production of carbon molecular sieves from palm shell based activated carbon by pore sizes modification with benzene for methane selective separation

Palm shell based activated carbon prepared by K₂CO₃ activation is used as precursor in the production of carbon molecular sieve by chemical vapor deposition (CVD) method using benzene as depositing agent. The influences of deposition temperature, time, and flow rate of benzene on pore development of carbon molecular sieve (CMS) and methane (CH₄) adsorption capacity were investigated. The parameters that varied are the deposition temperature range of 600 to 1000 °C, time from 5.0 to 60 min, and benzene flow rate from 3.0 to 15 mL/min. The results show that in all cases, increasing the deposition temperature, time, and flow rate of benzene result in a decrease in adsorption capacity of N₂, pore volume and pore diameter of CMS. The BET surface area of CMS (approximately 1065 m²/g) and the adsorption capacity of CH₄ were at a maximum value at a deposition temperature of 800 °C, time of 20 min and benzene flow rate of 6 mL/min. The product has a good selectivity for separating CH₄ from carbon dioxide (CO₂), nitrogen (N₂), and oxygen (O₂).     

Oxygen and Nitrogen Enrichment in Air by Cycling Zone Adsorption

Abstract

Enrichment of N₂ and O₂ in air has been obtained by cycling zone adsorption in the double zone standing wave mode. The solid adsorbent is molecular sieve type 5 A. The maximum separation factor obtained in these experiments is 10.6 for oxygen.