Synthesis, characterization and adsorption capacities of microporous titanosilicate EMS-3

A titanosilicate, named EMS-3, has been synthesized using the organic base TMAOH (tetramethylammonium hydroxide) and Na ion, as structure directing agents, under hydrothermal conditions. The XRD pattern of EMS-3 contains sharp and broad reflections typical of a partially disordered structure. EMS-3 has low thermal stability, indeed XRD pattern shows a decreased resolution after thermal treatment at 300 °C. An amorphous phase is observed at 500 °C. EMS-3 has a high cationic exchange capacity. A small amount of TMA cation has been detected in all the exchanged forms of EMS-3, as showed by IR spectroscopy and thermogravimetric analyses. Cation exchanged EMS-3’s show higher thermal stability than as-synthesized EMS-3. In particular, the typical features of EMS-3 are maintained, although Sr-EMS-3 exhibits poorly resolved XRD pattern after thermal treatment at 500 °C. Divalent cation exchanged EMS-3’s have higher specific surface area than as-synthesized EMS-3, due to a lower amount of extra-framework atoms inside the porous structure. CO₂ adsorption capacity is higher than both CH₄ and N₂. Both the charge and the ionic radius of the exchanged cations affect the adsorption properties. Ca-EMS-3 has the highest adsorption capacity for all the adsorbates.     

Thermal and cation influence on ir vibrations of modified natural clinoptilolite

The study of IR spectra in the range of 400 to 1700 cm⁻¹ of cation exchanged natural clinoptilolite-heulandite samples has shown the influence of the characteristics of cations and their content in the frequency and transmittance of vibration modes of zeolite. The 450 cm⁻¹ band assigned to T-O internal bending, 1205 cm⁻¹ band of T-O internal asymmetric stretching, and 1640 cm⁻¹ band of OH bending, were most affected by the cation exchange and thermal history of the sample.     

Influence of monovalent cations and CuO nanoparticles on X-nanozeolite in uranium anionic species separation from contaminated drinking water

The main purpose of this work was the modification of NaX nanozeolite using copper oxide nanoparticles and various monovalent cations such as K~+, Cs~+, and Ag~+in order to make the negatively charged zeolite surface accessible for anionic forms of uranium which are the most dominant species of uranium in the contaminated radioactive waters at natural p H. Various methods such as the X-ray fluorescence(XRF), X-ray powder diffraction(XRD), field emission scanning electron microscopy(FE-SEM), transmission electron microscopy(TEM), Fourier transform infrared spectroscopy(FT-IR), and atomic absorption spectroscopy(AAS) were used to characterize the final synthesized absorbents. Batch technique was used to study the adsorption behavior of uranium ions from polluted drinking water by Na X nanozeolite and its modified forms. In order to better understand the performance of them, the results were compared with those that were obtained for synthesizing bulk NaX zeolite and Na-form of clinoptilolite natural zeolite. Preliminary results indicated that uranium sorption increased as the loading level of CuO nanoparticles on NaX nanozeolite increased from 2.1 wt% to 11.2 wt%. In addition,from the obtained data, an increase in uranium removal efficiency resulted as charge/ionic radius ratio of exchanged cation decreased. Also, the effect of contact time, solid–liquid ratio, initial concentration and temperature on the adsorption process was studied. It is worth mentioning that, in this study, the sorption of uranium was performed under natural conditions of pH and the presence of competing cations and anions which are available in drinking waters.     

Effects of exchanged ammonium cations on structure characteristics and CO2 adsorption capacities of bentonite clay

Different alkali and alkaline earth cation forms of bentonite clay were exchanged with protonated mono-, di- and triethanolamine compounds, to study the effect of the exchanged ammonium cations on the structure characteristics, thermal behavior, surface properties and CO₂ adsorption capacities of bentonite clay. The revolution of the interlayer structure characteristics, thermal properties, the specific surface area and elemental analysis were characterized by XRD, FTIR, TGA, BET and CHNS techniques respectively, while the CO₂ adsorption capacities were gravimetrically measured by using magnetic suspension balance (MSB) equipment. It was found that the intercalation of ammonium cations into the interlayer space of bentonite clay induced a step change in its basal spacing, depending on their molar mass and the interlayer molecular arrangement. The presence of the characteristic IR peaks of amine compounds in the spectra of bentonite clay adsorbents modified by amines was qualitatively supported by the incorporation of ammonium cations in the interlayer space of bentonite, while the presence of C, H and N elements using CHNS technique was quantitatively confirmed by the intercalation process of amine compounds. It was also found that the molar mass of amines has an inverse effect on the amount of the adsorbed water (intensity), its desorption temperature (position) and the specific surface area of the synthesized materials. The CO₂ adsorption capacities on all the studied bentonite clay adsorbents modified by amines were found to increase between 2.68 and 3.15 mmol/g, compared to 0.93 mmol/g for untreated bentonite at the studied temperature and pressure. As expected, bentonite clay modified with di- and triethanolammonium cations showed lower CO₂ adsorption capacities than that treated with monoethanolammonium cations, due to their low specific surface area.     

Influence of the exchanged cation in coke deposition during n-hexane reactions on Pt/Mβ zeolite catalysts

The performances of platinum β zeolite exchanged with alkali (Na, K, Cs) and alkali-earth (Mg, Ba) cations have been examined for n-hexane reactions. The nature of coke deposited on the catalysts is slightly influenced by alkali cations because coke is deposited on metallic sites. In Pt/alkali-earth catalysts the coke depends on the support acidity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of Na‐P1‐Type Zeolite and its Composite Material with Nanosized Magnetite

The Na‐P1‐type zeolite having a high cation‐exchange capacity (CEC) was obtained using the waste coal fly ash from thermal power stations and a 2M NaOH solution at 100°C. The Na‐P1‐type zeolite was formed with the reaction time of 6 h at 100°C, and its CEC value increased with an increase in the reaction time. The addition of a suitable amount of NaAlO₂ to the fly ash was also effective for improving the CEC value. A new composite material consisting of the Na‐P1‐type zeolite and magnetite was synthesized from the fly ash and iron chlorides because the magnetic collection was possible using this composite material after radioactive Cs⁺ ion adsorption. The existence of nanosized magnetites in the polycrystalline zeolite (several micrometers) was confirmed by TEM observations. The CEC and magnetic property of these composite materials were characterized.     

Synthesis of layered MCM-22(P) in the presence of hexamethonium cations and its transformation into EUO- and MWW-type zeolites

Layered MCM-22(P) was synthesized in the presence of hexamethonium (HM) cations. Compared to zeolite EU-1 (EUO-type structure), which crystallizes in similar conditions, its formation is favored at high HM concentrations (HM/SiO₂ ≥ 0.3) and in the absence of Na₂O. HM-containing MCM-22(P) was used as starting material for zeolite formation. Upon hydrothermal treatment, HM-MCM-22(P) transforms into zeolite EU-1 and upon calcination into a MWW-type zeolite. Transformation mechanisms were studied by standard characterization techniques such as XRD, SEM and TEM. Catalytic properties of the MWW-type zeolite obtained from this precursor were evaluated in a m-xylene isomerization reaction. Compared to zeolite MCM-22 prepared with hexamethyleneimine, a higher catalytic activity and an increased isomerization selectivity were observed and discussed.     

Effects of steaming-made changes in physicochemical properties of Y-zeolite on cracking of bulky 1,3,5-triisopropylbenzene and coke formation

The effects of acidic properties and structural changes of Y zeolite, produced by steaming, on the zeolite cracking activity, coking tendency and distribution of various products during catalytic conversion of bulky 1,3,5-triisopropylbenzene (TIPB) are reported. NaY zeolite with framework Si/Al ratio of 2.4 was synthesized by a hydrothermal method and ammonium exchanged. The zeolite was dealuminated by a temperature-programmed steaming to form USY1 and USY2 zeolites with framework Si/Al ratio of 8.1 and 12.3 respectively. The catalysts were characterized by XRD, XRF, SEM, AAS, NH₃–TPD and N₂ adsorption–desorption techniques. The samples were in-situ activated at 748 K and evaluated by TIPB cracking at 623 K. The coke content of the catalyst beds was estimated by TPO using an FT-IR gas cell. The results of activity measurements reveal that the dealuminated zeolites lead to lower cracking activity initially; while, they exhibit higher activity at longer times. In addition, a slight modification of the window diameter of Y zeolite, as revealed by pore size distribution analyses, alters the diffusion limitation of the reactant and products through the pores of the zeolite and significantly affects the adsorbent–adsorbate interactions. TPO experiments show that compared to the precursor zeolite, lower amount of coke is formed on the dealuminated catalysts possessing lower density of acid sites. However, the coke formed on USY samples is heavier than that formed on its precursor Y zeolite. This may be attributed to the larger pores shaped in the dealuminated catalysts which in turn provide suitable places for coke formation and growth.     

Synthesis and adsorption property of zeolite FAU/LTA from lithium slag with utilization of mother liquid☆

Co-crystalline zeolite FAU/LTA-0 was synthesized by hydrothermal method from lithium slag. To make the most of excess silicon and alkali sources in mother liquid derived from FAU/LTA-0, zeolite FAU/LTA-1b was synthesized in the same method with the use of mother liquid by adding a certain amount of aluminum source. Influences of different adding ways of aluminum source and recycling dosages of mother liquid on synthesis of zeolites FAU/LTA with mother liquid were investigated. The phase, microstructure and thermostability of FAU/LTA-0 and FAU/LTA-1b were characterized by XRD, SEM and TG-DTA. The calcium and magnesium cation exchange capacities (CECs) of the zeolites were determined. The results have shown that co-crystalline zeolite can be synthesized with the use of mother liquid by adding aluminum source after 2 h of reaction. Compared with FAU/LTA-0, the crystal twinning structure of FAU/LTA-1b became weaker, the grain size was smaller, and the thermostability was better. With a lower dosage of mother liquid, the content of P-type impurity in product decreased significantly, and the content of LTA phase increased. The reuse rate of mother liquid can reach 48%. The CECs of FAU/LTA-1b-150 can reach 343 mg CaCO3·g?1 and 180 mg MgCO3·g?1, showing more excellent adsorption capacities than FAU/LTA-0 and commercial zeolite 4A. The full recycling use of mother liquid to synthesize zeolite FAU/LTA which can be applied for detergent not only improves resource utilization but also reduces production cost.     

Surface-Modified Carbons for the Drying of Gas Streams

Abstract

As-received commercial activated carbons do not adsorb noticeable amounts of water vapor at lower relative vapor pressures (r.v.p.). Following surface oxidation with nitric acid, moisture sorption capacity at lower r.v.p. increases 100-fold. Exchange of surface H⁺ ions of oxidized carbons by metal cations (Li, Na, K, Ca) brings about a further substantial increase in moisture sorption capacity. At lower r.v.p., water uptake on some of the cation exchanged samples is comparable to that on commercial zeolite molecular sieves. Following an adsorption run, moisture sorption capacity of ion-exchanged carbons can be fully restored upon outgassing at 140°C. This is in sharp contrast to the zeolite sieves which need to be heated to above 350°C to be completely regenerated.     

The effect of cation content of some raw and ion-exchanged Victorian lignites on their equilibrium moisture content and surface area

Six Victorian lignites of known inorganic content have been water and acid-washed. The acid-washed form of one of these lignites (LYLA(R)) was subsequently exchanged with Na, Mg, Ca and Al salts. The equilibrium moisture contents (EMC) of all samples have been determined across a range of relative vapour pressures (RVP) extending previous observations in the case of a single lignite exchanged with a series of cations. Previous measurements for a single lignite exchanged with a series of cations have only been made at a single RVP. The effects of the different metal cations on the EMC values varied depending on the RVP. The surface areas determined by CO₂ adsorption also showed an effect of cation content.     

Supercritical fluid CO2 processing and counter ion substitution of nafion® membranes

Nafion®‐117 was exposed to supercritical fluid (SCF) CO₂ and a cation solution using two different approaches: first was processed with SCF CO_2, and then exchanged using six different cations: K⁺¹, Ca⁺², Ba⁺², Cu⁺², Fe⁺³, and Al⁺³. The second method performed the cation substitution first, followed by the SCF CO₂ processing. The resulting composite membranes were characterized using several techniques: thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transforms infrared spectroscopy (FT‐IR), small angle X‐ray scattering (SAXS), and X‐ray diffraction (XRD). These techniques were used to identify the changes in the chemical and thermal properties of the membranes, as well as to evaluate changes in the resulting morphologies and crystallinities. Proton conductivity and methanol permeability were measured to understand how the different approaches promoted or inhibited the transport of certain substances through the membrane. Significant differences in their thermal, physical and transport properties were observed when Nafion® was processed with SCF CO₂ and exchanged with cations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and catalytic performance of a bi-phase core-shell zeolite composite

A zeolite composite Y/Beta with core-shell structure was synthesized by adding tetraethylammonium bromide (TEABr) exchanged NaY zeolite into the pre-reacted mixture used to prepare Beta zeolite. The composite was characterized by XRD, N₂ adsorption, SEM, and FTIR spectra of pyridine. The results show that the composite is composed of a core zeolite Y and a shell of intergrown zeolite Beta crystals, representing dual microporous structures of both Y and Beta zeolites and a new mesoporous structure. The composite has a high activity in n-octane catalytic cracking because of the formation of intergrowths and the change of acidity due to the distorted interface and surface defects.     

Cooperative Effect of Sodium and Potassium Cations on Synthesis of Ferrierite

Ferrierite type zeolite can be synthesized without using any organic structure-directing agent from Na- or (Na, K)- or K-aluminosilicate system. (Na, K)-ferrierite is synthesized from wide range of OH/SiO₂ region of the reactant mixture compared with Na- and K-ferrierite. The crystallization process of ferrierite in each system is investigated in detail by X-ray diffraction and Raman spectroscopy. The role of potassium and sodium cations and cooperative effect of two cations in the formation of the framework of ferrierite are elucidated.     

Influence of the exchanged cation in Pd/BEA and Pd/FAU zeolites for catalytic oxidation of VOCs

0.5 wt% palladium supported on exchanged BEA and FAU zeolites were prepared, characterized and tested in the total oxidation of volatile organic compounds (VOCs). The BEA and FAU zeolites were exchanged with different cations to study the influence of alkali metal cations (Na⁺, Cs⁺) and H⁺ in Pd-based catalysts on propene and toluene total oxidation. The exchange with different cations (Na⁺, Cs⁺) and H⁺ led to a decrease of the surface area and the micropore volume. All Pd/BEA and Pd/FAU zeolites were found to be powerful catalysts for the total oxidation of VOCs. They were active at low temperature and totally selective for CO₂ and H₂O. However, their activity depends significantly on the type of zeolite and on the nature of the charge-compensating cation. The activity order for propene and toluene oxidation on FAU catalysts, Pd/CsFAU > Pd/NaFAU > Pd/HFAU, is the reverse of the activity order on BEA catalysts: Pd/HBEA > Pd/NaBEA > Pd/CsBEA. The catalytic activities can be rationalized in terms of the influence of the electronegativity of the charge-compensating cation on the Pd particles, the Pd dispersion, the PdO reducibility and the adsorption energies for VOCs.     

徐州地区煤系高岭土合成4A沸石分子筛

研究以徐州地区煤系高岭土为原料、NaOH溶液为浸取液,先于550℃煅烧2 h得到偏高岭土,再在全密封反应釜中通过偏高岭土和NaOH溶液（固液质量比1∶20）之间的水热反应制备4A沸石分子筛[Na12(Al12Si12O48)·27H2O]。并采用X射线衍射仪（XRD）、傅里叶转换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）和N2吸附脱附等测试手段对4A沸石分子筛进行表征。结果表明,煤系高岭土经550 ℃煅烧2 h后转变成无定形态的偏高岭土,碱浸取后变成4A沸石分子筛;合成4A沸石分子筛过程中NaOH溶液的最佳浓度是2 mol/L;4A沸石分子筛具有狭缝状孔道,但孔的形状和分布不均匀。     

几种不同产地粉煤灰水热法合成沸石性能探究

利用粉煤灰合成沸石的方法很多,其中水热法合成沸石因操作简单、能耗低被认为是将粉煤灰基沸石商业化最可行的手段。采用水热法将国内外不同产地的几种粉煤灰合成沸石,并通过X射线衍射（XRD）、X射线荧光光谱（XRF）、热重分析（TG-DTA）、扫描电镜（SEM）等手段对合成的沸石产品进行表征,并在同一水热合成参数下考察不同粉煤灰合成沸石在品质上的差异。XRD谱图表明,原料中有80%~90%的成分转化为沸石,且沸石主要结晶类型为Na-P1型,也有少量的A型;XRF分析表明,3种粉煤灰基沸石硅铝物质的量比分别为1.61、1.35、1.45,符合XRD谱图的分析结论;TG-DTA表明,合成沸石在500 ℃以上几乎没有质量损失,具有良好的热稳定性;由SEM照片可见,合成的沸石为非球形,表面的纹理可增加沸石比表面积,结晶状态好。整个实验过程简单、成本低、合成沸石样品品质较高,由此可见通过水热法将粉煤灰合成沸石产品具有巨大的商业化潜力。     

加入碱金属盐合成超微沸石

采用水热合成法,用工业水玻璃作硅源,考察了各种碱金属盐、晶化时间、晶化温度和搅拌速度对合成超微低硅沸石的影响,经X射线衍射、红外光谱、扫描电镜、激光粒度分析和吸附量的测定证实,合成配比取Na2O∶Al2O3∶SiO2∶H2O=3∶1∶2∶185,在晶化温度90℃、晶化时间5 h、搅拌速度3 000 r/min(成胶)和1 500 r/min(成核)的合成条件下,加入0.1 mol NaF,沸石粒度由常规法合成沸石的2μm减小为180 nm;吸附总量由普通沸石的0.25 mg/L增加为0.26~0.272 mg/L;5 min吸附量由0.13 mg/L增加为0.2~0.22 mg/L。     

NU-87分子筛的合成与表征

考察了n(Na_2O)∶n(SiO_2)、n(H_2O)∶n(SiO_2)、n(SiO_2)∶n(Al_2O_3)及晶化时间对NU-87分子筛合成的影响,优化了合成条件,以EU-1分子筛为异质晶种,合成出NU-87分子筛,缩短了晶化时间。利用XRD、FT-IR、SEM及N_2等温吸附-脱附等方法对NU-87分子筛进行表征。结果表明,高n(H_2O)∶n(SiO_2)和低n(Na_2O)∶n(SiO_2)有助于NU-87分子筛的生成,优选的n(Na_2O)∶n(SiO_2)=0.14～0.15、n(H_2O)∶n(SiO_2)=48～55、n(SiO_2)∶n(Al_2O_3)=50、55和60时均合成出NU-87分子筛。晶化时间对NU-87分子筛的合成影响较大,最优晶化时间为8天。采用非晶种法合成NU-87分子筛时,随投料n(SiO_2)∶n(Al_2O_3)增大,合成NU-87分子筛的n(SiO_2)∶n(Al_2O_3)增大,比表面积逐渐减小,孔容与平均孔径大小基本未发生变化,B酸、L酸及总酸量逐渐减少。采用异质晶种法合成NU-87分子筛时,所得分子筛的n(SiO_2)∶n(Al_2O_3)最小,但其比表面积、孔容、平均孔径及B酸、L酸和总酸量均显著增大。NU-87分子筛为矩形条板状。     

Preparation of metallic cobalt inside NaY zeolite with high catalytic activity in Fischer–Tropsch synthesis

Metallic cobalt clusters are synthesized inside the cages of NaY zeolite by a method including four steps, i.e.: (1) ion exchange, (2) precipitation of exchanged cobalt cations, (3) calcination and (4) reduction of the calcined oxide nano-particles inside the zeolite. As compared with that prepared by the ion exchange followed directly by calcination and reduction and that by the conventional impregnation method, the sample by this four-step method exhibits higher CO conversion and higher selectivity to n-C₁₀–C₂₀ paraffins in Fischer–Tropsch (FT) synthesis. The small metallic cobalt clusters inside the supercages of NaY zeolite probably account for the high catalytic performances.