High resolution,quasi-equilibrium sorption studies of molecular sieves

Argon, nitrogen, and neopentane adsorption isotherms from molecular sieves are recorded at 87 K, 77 K, and 273 K, respectively, by a quasi-equilibrium, high resolution gas sorption technique. The molecular sieves used in this study are alkali exchanged zeolite X, AlPO₄-11, AlPO₄-5, VPI-5, KL, CaA, ZSM-5, and ZSM-11. Little relation is observed between the transition pressure for microporous nitrogen adsorption and pore size. Small changes in the effective pore size resulting from variations in cation size are detected in the transition pressure for argon adsorption. Large shifts in the transition pressure for argon adsorption are found for the 10-, 12-, and 18-membered ring pores of AlPO₄-11, AlPO₄-5, and VPI-5, respectively. Argon adsorption combined with neopentane adsorption on microporous materials provides additional information regarding transitions in the isotherm that result from dual pore systems and effects that may be due to adsorbate packing. The step in the nitrogen isotherm atP/P ₀> 0.1 from ZSM-5 is not observed in the nitrogen isotherm from ZSM-11.     

Characterization and fluorine-free microwave hydrothermal synthesis of AlPO<Subscript>4</Subscript>-5 molecular sieves as adsorbents

With a characteristic of S-shaped water sorption isotherms, AlPO₄-5 molecular sieves have been considered as up-and-coming adsorbents for the utilization in adsorptive cooling and heating systems. In order to avoid toxicity and corrosion of fluoride, this paper introduced a fluorine-free microwave hydrothermal synthesis strategy of pure AlPO₄-5 crystals. The effects of hydrothermal conditions including template agent, crystallization temperature and time on the performances of AlPO₄-5 adsorbents were systematically investigated. Fourier transform infrared spectroscopy, X-ray diffraction (XRD), ²⁷Al and ³¹P solid state magic angle spinning nuclear magnetic resonance (MAS NMR), pore size analyzer and Scanning electron microscopy (SEM) were used to determine the chemical structure, crystalloid phase, framework, pore structure and the morphology. Adsorption and desorption performances were measured by static adsorption, thermogravimetry and temperature programmed desorption. XRD results indicated that both triethylamine and tetraethylammonium hydroxide as templates, AlPO₄-5 crystals could quickly be synthesized within 30–45 min under fluorine-free microwave irradiation. By comparison, the adsorption and desorption performance of the former (recorded as AlPO₄-5A) was superior to that of the latter (recorded as AlPO₄-5H). FT-IR, MAS NMR and SEM results revealed that AlPO₄-5 crystals have the frameworks of alternating AlO₄ and PO₄ units and typical hexagonal rod-like morphologies.     

Temperature-programmed desorption study of molecular oxygen adsorbed on MFI-type zeolites

The adsorption of molecular oxygen at room temperature on the proton form of MFI zeolites with different Si/Al ratios has been investigated by temperature-programmed desorption (TPD). The internal Si-OH defects (silanol groups) in these zeolites are found to serve as O₂ adsorption sites. The apparent activation energies (17.5–21.8 kcal-mol^-1) of desorption determined from O₂ TPD measurements reveal that the extent of interactions between the Si-OH defects and the adsorbed O₂ molecules becomes weaker with decreasing Al content in the zeolite.     

Small pore VPI-5: Pore blockage due to thermally induced stacking disorders

The transformation of VPI-5 to AIPO₄-8 generates stacking disorders with the crystal which severely restricts its function as a molecular sieve. Evidence of these stacking disorders is established with adsorption measurements and high resolution transmission electron microscopy (HRTEM). Even partial transformation (less than 10% conversion) results in an 80% loss in adsorption capacity. These stacking disorders originate from the symmetry of the VPI-5 structure.     

稀土改性分子筛的表征与性能

以酸性稀钕土盐、镧盐为改性剂,13X分子筛经浸渍、过滤、干燥并焙烧得稀土改性分子筛.对改性分子筛进行傅里叶红外(FTIR),X射线衍射(XRD)及光电子能谱(XPS)表征;采用程序升温脱附(TPD)和热失重(TG)来评价稀土改性分子筛脱附性能,静态法吸附来测试其吸附性能.FTIR及XRD谱表明稀土掺杂没有改变分子筛的根...     

Effect of framework distortion on xylene adsorption in AlPO4-11 predicted from Monte Carlo simulations

In this short communication we present a study of xylene adsorption equilibria in distorted and non-distorted AlPO₄-11 (AEL) materials using grand canonical Monte Carlo (GCMC) simulations. A previous energy minimization study showed that the AlPO₄-11 crystal distorts upon xylene adsorption, but the effect of this distortion on the adsorption loadings was not known. In this work, we compare predictions from GCMC simulations in the distorted and non-distorted frameworks with experiments. The simulations show that the distorted structure adsorbs smaller amounts of xylenes than the non-distorted structure, and simulations in both structures predict ortho-selectivity, as seen in experiment. The lower adsorption capacity of the distorted structure can be related to changes in the adsorption sites. The results indicate that, besides pore blocking, structural deformations can be an important cause of lower adsorption capacity in molecular sieves.     

Zn-MCM-41介孔分子筛的合成及结构表征

以十六烷基三甲基溴化铵（CTAB）为模板剂,正硅酸乙酯（TEOS）为硅源,乙二胺为碱性介质,当n（TEOS）：n（Zn（NO3）2）：n（CTAB）：n（H2NCH2CH2NH2）：n（H2O）=1：0．01：0．13：2．2：120合成Zn-MCM-41介孔分子筛,通过XRD、IR、N2吸附脱附、NH3-TPD等方法对分子筛的晶体结构和表面物性进行了研究,结果表明,合成的分子筛具有典型的六方介孔结构特征,孔径分布较窄,具有较大的比表面积和较强的酸性。     

One-Dimensional Molecular Sieves for Hydrocarbon Cold Start Emission Control

One-dimensional channel molecular sieves were synthesized and tested as hydrocarbon traps using toluene and ethylene as heavy and light HC probe molecules, respectively. Binary TPD traces of these two gases allow a systematic comparison of the adsorption/desorption behavior of molecular sieves. These results show a drastic difference between molecular sieves with 10 oxygen ring apertures (10R) and 12R. Ammonia TPD traces of the series of 12R molecular sieves allow to rationalize the different ethylene/toluene TPD traces.     

沼气变压吸附剂吸附性能比较

研究了工程上常用的3种吸附剂CO2吸附剂硅胶、13X分子筛和碳分子筛在高压(0.1~1 MPa)下对CO2和CH4的吸附容量、稳定性和选择性,以确定其在沼气变压吸附分离中应用的可行性. 结果表明,硅胶的吸附稳定性非常好,0.1 MPa时吸附选择性系数为8~10,能有效分离CH4?CO2;13X分子筛对CH4和CO2吸附容量最高、吸附选择性最好,重复使用5次CO2的吸附容量略有下降;以CH4的损失率作为评价标准时,13X分子筛吸附CH4的损失率最低. 降压不能使被碳分子筛吸附的CH4完全解吸,吸附位不能充分释放,不适用于CH4与CO2的分离.     

Characterization of AlPO4-based molecular sieves and methanol conversion to light olefins

Of the AlPO₄-based molecular sieves, A1PO₄, SAPOs, and MeAPOs of different pore sizes were prepared at 100-200°C by a hydrothermal crystallization method. This study was purposed to maximize the yield of light olefins through methanol conversion. Crystal structure was confirmed by means of XRD and SEM, and acidity was examined by TPD and IR of adsorbed ammonia on the catalysts. It was found that SAPO-34 exhibited more than 90% selectivity for light olefins such as ethylene, propylene, and butylene due to shape selectivity through small pores, although it had a strong acidity. MeAPO-34 exhibited slightly lower selectivity for light olefins than SAPO-34 and different product distribution, depending on the electronegativity of the metal in its framework. SAPO17 and SAPO-44, which have the same pore size with SAPO-34 but different pore structure from SAPO-34, showed less selectivity for light olefins than SAPO-34.     

Basic catalytic behavior of MgO directly dispersed on zeolites by microwave irradiation

MgO could be directly dispersed onto zeolites-L, ZSM-5, β and AlPO₄-11 and hexagonal mesoporous silica (HMS) molecular sieve by microwave irradiation. New solid bases were formed being active in the dehydrogenation of isopropanol or the isomerization of cis-2-butene.     

Amorphous TiO2-Derived Large-Capacity Lithium Ion Sieve for Lithium Recovery

The lithium titanium oxide ion sieve with good structural stability and high adsorption capacity is generally considered to be a promising adsorbent for lithium recovery. Herein, the lithium ion sieve precursor Li₂TiO₃ was prepared based on amorphous TiO₂, and then Li⁺ was acid-eluted to obtain the lithium adsorbent H₂TiO₃, denoted as HTO-Am. The structure and adsorption properties of HTO-Am were investigated, and the results demonstrated that the HTO-Am prepared at the optimum temperature had excellent adsorption properties for Li⁺. The adsorption process follows pseudo-second-order kinetic and Langmuir isotherm equations, indicating that lithium is adsorbed chemically and monolayer on HTO-Am. HTO-Am ion sieves were prepared successfully for the first time and exhibited high selectivity, favorable adsorption rate, and cycle performance for Li⁺.     

Adsorption and reduction of NO2 over activated carbon at low temperature

The reactive adsorption of NO₂ over activated carbon (AC) was investigated at 50 °C. Both the NO₂ adsorption and its reduction to NO were observed during the exposure of AC to NO₂. Temperature programmed desorption (TPD) was then performed to evaluate the nature and thermal stability of the adsorbed species. Adsorption and desorption processes have been proposed based on the nitrogen and oxygen balance data. The micropores in AC act as a nano-reactor for the formation of -C(ONO₂) complexes, which is composed by NO₂ adsorption on existing -C(O) complexes and the disproportionation of adsorbed NO₂. The generated -C(ONO₂) complexes are decomposed to NO and NO₂ in the desorption step. The remaining oxygen complexes can be desorbed as CO and CO₂ to recover the adsorptive and reductive capacity of AC.     

Modification of pore size in activated carbon by polymer deposition and its effects on molecular sieve selectivity

The separation of air for nitrogen production can be carried out by pressure-swing-adsorption over a carbon molecular sieve. The separation is kinetically controlled, since the equilibrium adsorption of both oxygen and nitrogen is very similar, but the adsorption kinetics for oxygen is faster than for nitrogen. Several methods to prepare carbon molecular sieves are reported. In this work, we synthesized a carbon molecular sieve from a commercial activated carbon. After deposition of polyfurfuryl alcohol, these materials were subjected to carbonization at 800°C under an inert atmosphere. All the microporous materials were characterized by analysis of kinetics and equilibrium adsorption data. The molecular sieve performance was assessed by the O₂/N₂ uptake ratio. The material prepared by two depositions has characteristics similar to those of commercial CMS.     

Characterization and hydroisomerization performance of SAPO-11 molecular sieves synthesized by dry gel conversion

SAPO-11 molecular sieves were synthesized by two types of dry gel conversion (DGC) methods, namely, steam-assisted conversion (SAC) and vapor phase transport (VPT), and by conventional hydrothermal (CHT) method. The properties of these samples were characterized by XRD, XRF, SEM, N₂-adsorption, Pyridine-IR and ²⁹Si MAS NMR methods. The results show that di-n-propylamine (DPA) is a suitable structure-directing agent (SDA) for the preparation of impurity-free SAPO-11. SAPO-11 molecular sieves synthesized by SAC and VPT exhibit higher crystallinity, higher Si content and more strongly acidic sites than that synthesized by CHT. ²⁹Si MAS NMR results demonstrated that the two samples obtained by the DGC methods contain more Si(nAl)(0 < n < 4) species than that obtained by CHT. These facts suggest that the SAC and VPT methods contribute either to better Si incorporation into the AlPO₄ framework or to better Si dispersal, thus decreasing the size of Si islands and increasing the number and strength of acidic sites. The results from the hydroisomerization of n-dodecane indicate that the Pt/SAPO-11 synthesized by SAC possesses the highest hydroconversion activity and isomer yield among those three catalysts, due to the high acidity of the molecular sieve supporter.     

Proportion Pressure Swing Adsorption for Low Concentration Coal Mine Methane Enrichment

Using traditional Pressure Swing Adsorption (PSA) with a single adsorbent for low concentration coal mine methane (LCCMM) at a concentration of 30% or less can result in a final CH₄ concentration very close to the explosion limit, increasing the risk of explosion. Proportion Pressure Swing Adsorption (PPSA) is a new and safer enrichment method suggested for LCCMM enrichment that uses a mixture of active carbon (AC) and carbon molecular sieves (CMS) as adsorbents. With this method, CH₄ and O₂ in LCCMM can be adsorbed simultaneously because CH₄ is mostly adsorbed by active carbon and O₂ is mostly adsorbed by the CMS. Therefore, the concentration of CH₄ and O₂ is well controlled and does not exceed the explosive limit during the adsorption and desorption processes. We have demonstrated the safety and feasibility of PPSA for obtaining 30% CH₄ from LCCMM, with 20% CH₄ in air as a feed stock. Our results show that the O₂ concentration can be controlled well and does not exceed the explosive limit in both adsorption and desorption, and the CH₄ concentration in the desorption gas can be increased to more than 30% by adjusting the bed length and mass ratio of the AC and CMS. Taking these results together, it appears that PPSA is a safe method for LCCMM enrichment.     

Molecular engineering of microporous crystals: (III) The influence of water content on the crystallization of microporous aluminophosphate AlPO4-11

The influence of water content on the crystallization of the microporous aluminophosphate AlPO₄-11 was investigated by a combination of in situ UV Raman and ex situ XRD and NMR characterizations. Under high water content conditions (Al₂O₃:H₂O = 1:20-69), an AlPO₄-5 intermediated formed first and later co-existed with AlPO₄-11. In the last stage of crystallization, the crystalline AlPO₄-5 completely disappeared and well-crystallized AlPO₄-11 was obtained. The position of the three signals observed in the ³¹P MAS NMR spectra of the isolated solid samples did not change during the hydrothermal treatment, suggesting that the fragments containing the P site in the junction of 6- and 4-membered rings of both AlPO₄-5 and AlPO₄-11 formed first and that the environments of the P sites were very similar to those in the final structure. A significant increase of Al concentration in liquid media was observed before the appearance of XRD detectable AlPO₄-11. Under low water content conditions (Al₂O₃:H₂O = 1:15), the AlPO₄-11 was directly crystallized from the initial mixture. In situ Raman spectra showed that the 10-membered rings were complete by the time the transformation of octahedral Al to tetrahedral Al was finished and that the conformation of the protonated di-(i-propyl)amine changed little during the crystallization. The present study showed that the composition of the liquid phase is critical to the formation of a specific structure.     

分子筛结构和酸性对正丁烯异构化反应的影响

利用XRD、SEM、NH3-PTD和吡啶吸附红外光谱等手段对ZSM-35和SAPO-11分子筛的结构和酸性质进行表征和对比,考察两种分子筛对正丁烯异构化制备异丁烯反应的催化性能。结果表明,对于硅铝型ZSM-35分子筛,由于存在较强的B酸中心,在异构化反应过程中,丁烯二聚及裂解等副反应发生多,异丁烯选择性低。而SAPO-11分子筛主要以中等偏弱的B酸中心为主,加上一维十元环孔道结构,在异构化反应中更有利于异丁烯的生成,表现出更高的异丁烯选择性及收率。     

Temperature-programmed desorption vs. N2 desorption in determining pore-size distribution of mesoporous silica molecular sieves

Two mesoporous silica molecular sieves, one synthesized by cationic template method and another by neutral template route, were characterized for their pore-size distribution by a novel Temperature-Programmed Desorption (TPD) method and the widely used N₂ desorption method. The pore-size distributions determined by the two methods agree quite well and are within experimental errors. For example, TPD method gave a pore size distribution (radius) centered at 14 Å while N₂ desorption method showed a peak centered at 13.3 Å. for the mesoporous silica prepared by cationic template route. The new TPD method based on thermogravimetric analysis is a viable option for mesopore characterization of silica-based materials.