Synthesis of zeolite A and zeolite X from electrolytic manganese residue,its characterization and performance for the removal of Cd^(2+)from wastewater

Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.

Study of the Temperature-Programmed Desorption of Carbon Dioxide (CO2) on Zeolites X Modified with Bivalent Cations

Study of physisorbed and chemisorbed carbon dioxide (CO2) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca2+ and Ba2+) by temperature-programmed desorption of CO2 (CO2-TPD). Others results were obtained by infrared to complete the study. The results of this research showed, in the physisorption region (213 - 473 K), that the cationic exchanges on NaX zeolite with bivalent cations increase slightly the interactions of CO2 molecule with adsorbents and/or cationic site. Indeed, the desorption energies of physisorbed CO2 obtained on the reference zeolite NaX (13.5 kJ·mol-1) are lower than that of exchanged zeolites E-CaX and E-BaX (15.77 and 15.17 kJ·mol-1 respectively). In the chemisorbed CO2 region (573 - 873 K), the desorption energies related to desorbed species (bidentate carbonates: CO32-) on the exchanged zeolites E-CaX and E-BaX are about 81 kJ·mol-1, higher than the desorbed species (bicarbonates: HCO32-) on the reference R-NaX (62 kJ·mol-1). In addition, the exchanged E-BaX zeolite develops the secondary adsorption sites corresponding to bicarbonates species with desorption energies of 35 kJ·mol-1 lower to desorption energies of bicarbonates noted on the reference zeolite NaX.

Cu离子分子筛催化材料在去除NO_(x)方面应用的研究进展

控制大气中氮氧化物的排放对环境和人体健康有着至关重要的作用,应用于NO_(x)去除的技术有很多,其中选择性催化还原(NH3-SCR)技术是去除NO_(x)极有效的技术之一,利用CO去除NO_(x)为烟气脱硝(CO-SCR)提供了一种简单且低成本的技术,直接催化分解NO_(x)被认为是去除NO_(x)最理想、最环保的技术。Cu离子分子筛作为去除NO_(x)的高效催化剂,具有宽温度窗口和良好的水热稳定性。本文综述了Cu交换分子筛在去除NO领域的研究进展,讨论了Cu离子分子筛在NH3-SCR、CO-SCR以及直接催化分解NO中的应用,着重总结了Cu离子参与去除NO的反应机理,归纳了分子筛中Cu活性位点对脱硝性能的影响,还讨论了铜离子分子筛的抗H_(2)O和SO_(2)中毒性能,展望了Cu离子分子筛未来可能的发展方向。

Stellerite-seeded facile synthesis of zeolite X with excellent aqueous Cd^(2+)and Ni^(2+)adsorption performance

Zeolite X was synthesized by a two-step hydrothermal method using natural stellerite zeolite as the silicon seed,and its adsorption performance for Cd^(2+)and Ni^(2+)ions was experimentally and comprehensively investigated.The effects of p H,zeolite X dosage,contact time,and temperature on adsorption performance for Cd^(2+)and Ni^(2+)ions over were studied.The adsorption process was endothermic and spontaneous,and followed the pseudo-second-order kinetic and the Langmuir isotherm models.The maximum adsorption capacitiesfor Cd^(2+)and Ni^(2+)ions at 298 K were 173.553 and 75.897 mg.g-1,respectively.Ion exchange and precipitation were the principal mechanisms for the removal of Cd^(2+)ions from aqueous solutions by zeolite X,followed by electrostatic adsorption.Ion exchange was the principal mechanisms for the removal of Ni^(2+)ions from aqueous solutions by zeolite X,followed by electrostatic adsorption and precipitation.The zeolite X converted from stellerite zeolite has a low n(Si/Al),abundant hydroxyl groups,and high crystallinity and purity,imparting a good adsorption performance for Cd^(2+)and Ni^(2+)ions.This study suggests that zeolite X converted from stellerite zeolite could be a useful environmentally-friendly and effective tool for the removal of Cd^(2+)and Ni^(2+)ions from aqueous solutions.

Antibacterial Activity of Cu^(2+)-ZnO-modified 13X Zeolite against E.coli and S.aureus

A new type of zeolite composite antibacterial agents was prepared by introducing zinc oxide and copper ions into 13 X zeolite through the coprecipitation and ion-exchange methods. The structural properties of the tested antibacterial material were characterized and the antibacterial activity was evaluated. In Cu^(2+)/ZnO-13 X(CZ-13), zinc oxide and copper ions were either embedded in the interlayer space or dispersed on surface of 13 X zeolite. Excellent antimicrobial activity of CZ-13 was observed on Escherichia coli(E. coli) and Staphylococcus aureus(S.aureus). In the case of Cu^(2+)/ZnO-13 X, both MIC and MBC against E.coli were 0.2 mg/mL and 0.8 mg/mL. For S.aureus, CZ-13 also showed similar antibacterial properties. The bacterial cells turned from normal rod-shape into irregular shapes after treatment with the tested CZ-13. An increase of the intracellular enzyme activity after CZ-13 addition suggested that the permeability of the cell membrane increased and bacteria were damaged.

油页岩灰渣制备Na-X型沸石及其吸附性能研究

水体中的亚甲基蓝分子对生态环境造成了严重的危害,也在一定程度上威胁着人类的健康。本文以油页岩加工的副产物油页岩灰渣为原料,采用碱熔融-水热合成法合成了Na-X型沸石,并探讨导向剂的使用量、NaOH的用量、水热温度、水热时间和酸浸浓度对沸石结晶度的影响,最终得到合成沸石的最佳条件。用合成的Na-X型沸石处理水溶液中亚甲基蓝分子,得到吸附平衡数据采用吸附等温线和吸附动力学模型进行拟合。结果表明,朗格缪尔等温线模型和伪二阶动力学模型与亚甲基蓝的吸附数据相吻合,表明Na-X型沸石对亚甲基蓝的吸附过程属于单层的化学吸附过程。综上所述,由油页岩灰渣制备的Na-X型沸石材料可作为吸附水溶液中亚甲基蓝分子的吸附剂。

Synthesis of Zeolite X from Locally Sourced Kaolin Clay from Kono-Boue and Chokocho, Rivers State, Nigeria

This work describes the development of a process to produce zeolite X from mined kaolin clay from Kono-Boue and Chokocho, Rivers State, Nigeria. The procedures involved the beneficiation of the raw kaolin and calcinations at 850°C, to transform the kaolin to a more reactive metakaolin. Afterwards, the extremely reactive metakaolin was purge with sulphuric acid to obtain the much needed silica-alumina ratio for zeolite X synthesis. An alkaline fusion stage was then carried out to transform the metakaolin into zeolite by mixing with aqueous NaOH to form gel then allowed to stay for a duration of seven days at room temperature. The samples were then charged into a propylene container and placed in an oven at a temperature of 100°C for the reaction to take place for 6 h. Identification of the crystalline phases by X-ray Diffraction (XRD), chemical/elemental compositions by X-ray Fluorescence (XRF)/Energy Dispersive Spectroscopic analyses (EDS), surface morphology by Scanning Electron Microscopy (SEM) and molecular vibration of units by Fourier Transform Infrared Spectrophotometry (FT-IR) were done. The results showed that the zeolite synthesized from Chokocho kaolin (CK) was more crystalline/larger with sharper peaks on both XRD and FTIR than that from Kono-Boue. This was also supported by slightly rougher surface morphology of CK over KK on SEM. XRF Si:Al ratios of 10.73 and 14.36 were obtained for KK and CK respectively. EDS results supported the XRF ratios. Sharper zeolitic characteristic O-H stretching bands at 3488 and 3755 cm-1 were recorded for CK than KK. However, both results showed that zeolite X have been produced from both Kono-Boue and Chokocho kaolin clays respectively.

Nanocrystalline low-silica X zeolite as an efficient ion-exchanger enabling fast radioactive strontium capture

NaA zeolite(Si/Al=1.00)has been commercially applied for capturing radioactive 90Sr^(2+)because of its high surface charge density,effectively stabilizing the multivalent cation.However,owing to its narrow micropore opening(4.0Å),large micron-sized crystallites,and bulkiness of hydrated Sr^(2+),the Sr^(2+)exchange over NaA has been limited by very slow kinetics.In this study,we synthesized nanocrystalline low-silica X by minimizing a water content in a synthesis gel and utilizing a methyl cellulose hydrogel as a crystal growth inhibitor.The resulting zeolite exhibited high crystallinity and Al-rich framework(Si/Al of approximately 1.00)with the sole presence of tetrahedral Al sites,which are capable of high Sr^(2+)uptake and ion selectivity.Meanwhile,the zeolite with a FAU topology has a much larger micropore opening size(7.4Å)and a much smaller crystallite size(~340 nm)than NaA,which enable significantly enhanced ion-exchange kinetics.Compared to conventional NaA,the nanocrystalline low-silica X exhibited remarkably increased Sr^(2+)-exchange kinetics(>18-fold larger rate constant)in batch experiments.Although both the nanocrystalline low-silica X and NaA exhibited comparable Sr^(2+)capacities under equilibrated conditions,the former demonstrated a 5.5-fold larger breakthrough volume than NaA under dynamic conditions,attributed to its significantly faster Sr^(2+)-exchange kinetics.

低硅铝比X型分子筛的金属阳离子改性

采用液相离子交换法制备了系列金属阳离子改性低硅铝比X型分子筛(LSX)吸附剂,利用ICP,XRD,SEM等方法对改性吸附剂进行了表征,优化了离子交换条件及干燥工艺,并分析了改性吸附剂的吸附性能。实验结果表明,Ca-LSX和Sr-LSX有较高的氮气吸附容量,Sr-LSX的氮氧分离效果最好,Ce-LSX更适合用于吸附氧气。在25℃下对LSX进行离子交换和干燥能有效避免分子筛结构破坏,可获得最佳吸附性能和效果。Ca-LSX引入适量Sr后,产品氮气吸附容量略微降低,但氮氧分离系数显著提高,由3.96提升至4.35。

CaLi-LSX分子筛的制备及其母液循环利用

通过对Ca-LSX分子筛进行Li^(+)交换制备了不同锂交换度的CaLi-LSX分子筛,对分子筛的离子交换工艺进行了改进,通过母液回用法降低了离子交换过程中的锂盐用量,并采用XRD,ICP,FTIR等表征手段及吸附热、静态竞争吸附、Rietveld精修等模拟计算对分子筛进行分析。实验结果表明,随锂交换度的提高,CaLi-LSX分子筛的吸附容量整体呈下降趋势,氮氧分离系数先升高后降低,在锂交换度43.7%时达到最高值5.23,此时氮气吸附容量为28.94 cm^(3)/g;Rietveld精修结果显示,单个晶胞中有10.357个Li^(+)位于SⅢ位点;母液回用法制备的分子筛吸附性能无显著下降,重复性好,产品锂交换度和常温氮氧吸附容量均相差较小,可使锂盐用量降低约90.6%。

Preparation of Single Phase Na-X Zeolite from Oil Shale Ash by Melting Hydrothermal Method

A single phrase Na - X zeolite was synthesized from pretreated oil shale ash by alkaline fusion and hydrotherreal treatment. Eff3cts of the NaOH concentration, crystallization time ant temperature on the formation of Na-X zeolite were studied in detail. The single phase Na- X zeolite powders can. be prepared by alkaline fusion o.f pretreated oil shale ash at 600 ℃ .for 1 h, and crystalli-zation at 80 - 100 ℃ .for 8 - 10 h with NaOH concentration of 3 -3. 5 tool · L-1. Na - A zeolite appears when decreasing NaOH concentration, crystallization time or temperature, ant an unnamed zeolite emerges when prolonging crystallization time or raising crystalli-zation, temperature. SEM micrographs suggest that the aggregates of Na-X zeolite particles have perfect dispersity and uniform granular with about 1.5 μm in size, and most of the Na-X zeolite crystals display a regular octahedral structure with the size of about 500 nm. The specific surface area of the powders with single Na-X zeolite phase reaches the maximum value of 488. 163 2 m2· g -1, larger than that of multiple zeolite powders.

不同Cu含量的Cu(X)/SSZ-13分子筛催化剂同时消除炭烟和NO_(x)的性能研究

柴油机由于其较强的动力性与耐久性等优势,已经广泛应用于运输、农业、建筑等重工业领域。然而,柴油机排放的尾气污染物,如炭烟颗粒和氮氧化物(NO_(x)),严重危害人们的健康和生活环境。因此,消除柴油机尾气中的炭烟颗粒和氮氧化物已成为一项重要的研究课题。通过控制原料中CuSO_(4)的添加量,采用一锅法合成了含有不同Cu含量的Cu(X)/SSZ-13分子筛催化剂。通过XRD、N_(2)吸附-脱附、SEM、H_(2)-TPR、NO-TPO、NH_(3)-TPD、Soot-TPR等表征手段,研究了制备的Cu(X)/SSZ-13分子筛催化剂的形貌和物理化学性质,并测试了所合成的催化剂在同时消除炭烟和NO_(x)方面的活性。结果表明,不同Cu含量的Cu(X)/SSZ-13分子筛在同时消除炭烟和NO_(x)方面的活性存在明显差异,Cu含量还会影响Cu(X)/SSZ-13分子筛的形貌、比表面积和氧化还原性能。当Cu含量为1.25时,制备的Cu(1.25)/SSZ-13催化剂表现出最佳的催化性能,其在153~427℃温度范围的NO转化率超过90%,炭烟燃烧的峰值温度(T_(m))为504℃。

低水体系合成X型分子筛及其硅/铝比与碱度的定量关系

采用不同含水量(n(H_(2)O)/n(SiO_(2)))和碱度(n(M_(2)O)/n(H_(2)O),M为K和Na)的钾-钠体系水热合成X型分子筛,采用X射线荧光光谱、X射线衍射、扫描电镜、^(29)Si魔角旋转固体核磁和^(27)Al魔角旋转固体核磁等手段对X型分子筛进行表征,并对Ba^(2+)交换X型分子筛进行混合碳八芳烃静态吸附评价。结果表明:当合成体系n(SiO_(2))/n(Al_(2)O_(3))为2.8时,随着n(H_(2)O)/n(SiO_(2))从21增加到60,获得纯相X型分子筛的n(M_(2)O)/n(SiO_(2))范围从1.3逐渐增大至3.1。保持合成体系n(SiO_(2))/n(Al_(2)O_(3))不变,X型分子筛n(SiO_(2))/n(Al_(2)O_(3))与单一影响因素n(M_(2)O)/n(H_(2)O)线性相关,相关性系数R2为0.90。当合成体系n(SiO_(2))/n(Al_(2)O_(3))和n(M_(2)O)/n(H_(2)O)相同时,n(H_(2)O)/n(SiO_(2))分别为40和60制备的X型分子筛的粒径、非骨架铝物种、孔体积无明显差别。相比而言,低水体系所得X型分子筛的晶体结构中Si(4Al)物种占比更高,对二甲苯相对于乙苯吸附选择性更高,为3.19;对二甲苯相对于邻二甲苯和间二甲苯吸附选择性稍低,分别为3.25和6.84。

多晶X射线衍射Rietveld方法在石油炼制与化工催化剂研究中的应用

在石油化工领域,多晶X射线衍射Rietveld方法(简称Rietveld方法)是一种有效且应用广泛地研究催化剂晶体结构的分析方法。简要介绍了Rietveld方法的基本原理、判据及常用的软件,并结合实例重点从催化剂定量相分析和分子筛骨架外阳离子的定位2方面综述了近年来Rietveld方法在石油炼制与化工催化剂研究领域中的应用,总结了利用Rietveld方法进行定量相分析和测定晶体结构的步骤、注意事项及适用范围,最后对Rietveld方法在与电子衍射、计算化学和原位表征相结合以及软硬件技术升级等方面的发展前景进行了展望。

Cs/MgAl-LDO@X催化剂制备及甲苯侧链烷基化反应性能研究

以X分子筛为载体,在其表面上生长MgAl-LDH层状氢氧化物,浸渍Cs后焙烧,制备一系列Cs/MgAl-LDO@X催化剂。采用XRD、SEM、TPD等对催化剂的结构进行表征,并对甲苯侧链烷基化反应性能进行评价。表征发现,MgAl-LDO呈层状生长在X分子筛表面,随着生长量增多,层厚度逐渐增大,浸渍Cs后酸量和酸强度降低,碱强度增加。通过性能测试确定最佳Mg与Al比和MgAl-LDO生长量,此条件下甲苯转化率为4.33%,苯乙烯选择性为60.07%。

红辉沸石两步水热制备高品质X型分子筛及其高效吸附Cd^(2+)、Ni^(2+)性能研究

本研究以红辉沸石为原料,经两步水热法制备高品质的X型分子筛,探究了n(H_(2)O/SiO_(2))、n(Na_(2)O/SiO_(2))、n(Al_(2)O_(3)/SiO_(2))、陈化时间、晶化温度、晶化时间等因素对红辉沸石转化为X型分子筛的影响,以及考察了X型分子筛对Cd^(2+)、Ni^(2+)的吸附性能。研究表明,X型分子筛的最优转化条件为:n(H_(2)O/SiO_(2))=55、n(Na_(2)O/SiO_(2))=1.1、n(Al_(2)O_(3)/SiO_(2))=0.33、陈化时间48 h、晶化温度82℃、晶化时间4 h。红辉沸石溶解后解聚为低聚态Si物种且在体系中保留参与分子筛的生长,使得所合成的X型分子筛相对结晶度达100%、n(Si/Al)值为1.14,并缩短了晶化时间和降低了晶化温度,其中所合成的X型分子筛对Cd^(2+)和Ni^(2+)的吸附容量分别达到173.553 mg/g和75.897 mg/g。因此,本研究将为天然矿物快速转化为高品质的X型分子筛设计与制备提供理论基础和技术支持。

Guidelines for rational design of high-performance absorbents:A case study of zeolite adsorbents for emerging pollutants in water

Rational design is important to achieve high-performance sorbents used to remove the contaminants of emerging concern(CECs) from water.However, it is hard to propose effective design guidelines due to the lack of a clear understanding of the interaction mechanisms. By means of systematic quantum chemical computations, as a case study, we investigated the interactions between zeolite X/M^(n+)-zeolite X(Si/Al=1,M^(n+)=Cu^(2+) and Ni^(2+)) and three commonly used CECs(namely salicylic acid, carbamazepine and ciprofloxacin) in water to clarify the adsorption mechanisms. Our computations found that anionic salicylic acid cannot be adsorbed by neither zeolite X nor M^(n+)-zeolite X in neutral water due to the high electrostatic repulsion. In comparison, carbamazepine and ciprofloxacin have favorable binding energies with both zeolite X and M^(n+)-zeolite X, and their interactions with M^(n+)-zeolite X are stronger due to the joint effects of H-bond, metal complexation and electrostatic interaction. The adsorption loading of ciprofloxacin, which has a large molecular size, on M^(n+)-zeolite X is limited due to the steric hindrance. In general, steric hindrance, electrostatic interaction, H-bond and metal complexation are dominant factors for the examined systems in this study. Thus, for the design of high-performance absorbing materials, we should fully consider the molecular properties of pollutants(molecular size, surface electrostatic potential and atomic type, etc.), and properly enhance the favorable effects and avoid the unfavorable factors as much as possible under the guidance of the interaction mechanisms.

Cs/CuAl-LDO@X催化剂制备及甲苯侧链烷基化反应性能

以X分子筛为载体,在其表面生长CuAl-LDH层状氢氧化物,浸渍Cs后焙烧,制备了一系列不同CuAl-LDO含量的Cs/CuAl-LDO@X催化剂。采用XRD、SEM、NH 3-TPD和CO 2-TPD手段对催化剂结构进行了表征,并在固定床微反应器上评价了催化剂的甲苯侧链烷基化一步制苯乙烯的反应性能。结果表明,在Cs/CuAl-LDO@X催化剂中,X分子筛表面的CuAl-LDO呈现花簇状二维层状结构;随着CuAl-LDO含量的增加,催化剂的酸、碱活性中心有一定量的增加;不同CuAl-LDO含量的催化剂对甲苯侧链烷基化反应都具有良好的催化性能,其中CuAl-LDO含量为16.6%(质量分数)的Cs/CuAl-LDO-3@X催化剂具有最好的催化性能,在甲苯转化率为4.78%时,苯乙烯选择性为46.91%.

微波辐射法合成NaX分子筛

NaX是低硅铝比的八面沸石,一般在低温水热条件下合成.因反应混合物配比不同,以及采用的反应温度不同,晶化时间为数小时至数十小时不等. 近年来,微波辐射方法被应用于无机及有机化合物的合成中.Chu Pochen等在专利文献中报道了微波辐射法在沸石分子筛合成中的应用,其中提到了NaX分子筛。

在多孔陶瓷载体上X型分子筛生长成膜的研究

研究X型分子筛在多孔陶瓷载体上的生长条件 ,合成膜的晶化液组成n(SiO2 ) /n(Al2 O3) =3 .0～ 5 .0 ,n(Na2 O) /n(SiO2 ) =1.3～ 9.8,n(H2 O) /n(SiO2 ) =12 0～ 80 0 ;晶化温度 85～ 10 5℃ ;晶化时间 2 4～ 96h。SEM显示多孔陶瓷载体上负载生长分子筛膜要经过 6～ 7次涂膜操作 ,才能获得较理想的均匀连续的顶膜 ,膜厚 10～ 2 5 μm。考察了晶化液的配方、合成条件及晶化次数对分子筛负载量的影响 ,多孔载体的表面形貌及规格对表面膜均匀连续性的影响等。结果表明 ,成膜的渗透通量下降为载体的 7%～ 9% ,分子筛膜选透率用 (C4H9) 3N和 (C4F9) 3N的纯蒸汽表征 ,在 3 5 0℃下 (C4H9) 3N对 (C4F9) 3N的选透率达到 69。