Chemical,Physical, and Catalytic Properties of Large Pore Acidic Zeolites

Abstract

catalysts corminins acid zeolitea a m more active, more selective to gasoline production, aad more stable in thermal and hydrothermal environmcnu [1–3]. It was esdznaud in 1973 that the selecdvky characmrisdcs of zeolite cmcklag araiysts were respoasible for a savings of aver 200 million bvrals of cmda oil per year oa the North Amartcan coadaent [4]. Acftpttp aa be madoat; zta Since purzeolita catalysts a n be forrnrrktad whtch are many orden of magnitude more acde than the older amorphous catalysts. Typid relative actidties of some zeoffte catalysts Uons are presented in Table 1. Considerafforu other than intrinsic-vie, for example. heat and mass tzuufer Umi Molu and/or equipment design factors, may set limits on the maximum aczivly. Today rkrtudly all commerchl cracktnq aulysts conraia zeolites.     

Chemical, Physical, and Catalytic Properties of Large Pore Acidic Zeolites

catalysts corminins acid zeolitea a m more active, more selective to gasoline production, aad more stable in thermal and hydrothermal environmcnu [1-3]. It was esdznaud in 1973 that the selecdvky characmrisdcs of zeolite cmcklag araiysts were respoasible for a savings of aver 200 million bvrals of cmda oil per year oa the North Amartcan coadaent [4]. Acftpttp aa be madoat; zta Since purzeolita catalysts a n be forrnrrktad whtch are many orden of magnitude more acde than the older amorphous catalysts. Typid relative actidties of some zeoffte catalysts Uons are presented in Table 1. Considerafforu other than intrinsic-vie, for example. heat and mass tzuufer Umi Molu and/or equipment design factors, may set limits on the maximum aczivly. Today rkrtudly all commerchl cracktnq aulysts conraia zeolites.     

Methane Combustion over Pd Catalysts Loaded on Medium and Large Pore Zeolites

Methane combustion was conducted over Pd catalysts supported on medium (ZSM-5, ferrierite, TNU-9, TNU-10) and large (USY, mordenite, beta) pore zeolites. Among the catalysts studied here, Pd/H-TNU-10 exhibited the highest combustion activity, together with excellent durability in the presence of water vapor. A combination of TEM and Pd K-edge XAFS measurements reveals the formation of highly dispersed PdO particles within the TNU-10 pores. This is also the case of Pd/H-ferrierite, while frequently there are large particles (60–100 Å) on its outer surface. In contrast, most of PdO on zeolites other than these two medium pore materials were found to exist as aggregated particles (>50 Å) on their outer crystallite surface. It appears that zeolite structures with intersecting 10- and 8-ring pores may be better supports for stabilizing nanometric PdO particles than those with the uniform 10-ring size or with the 12-ring pore system.     

Xylene Isomerization in the Liquid Phase Using Large‐Pore Zeolites

Three large‐pore zeolites, Beta with Si/Al ratios of 25 and 35 and Mordenite with an Si/Al ratio of 30, were studied in the conversion of o‐xylene at 493 K. Maximum conversion was achieved by the catalyst with the highest Si/Al ratio due to faster diffusion of the isomer inside the zeolite channels because of the lower acidity of the solid even with larger crystal size. A kinetic study was then carried out over this catalyst between 473 and 513 K in a batch reactor in the liquid phase. The activation energies obtained do not indicate the presence of diffusional constraints towards any isomer. Finally, the kinetic model obtained was simulated in a fixed‐bed reactor and compared to ZSM‐5 in the temperature range from 493 to 533 K. An increment in p‐xylene production of 20 % on average was obtained.     

大孔容孔径氧化铝的合成研究

采用中和成胶法,以偏铝酸钠、硫酸铝等为原料,考察了成胶温度、成胶p H值、助剂等条件对合成氧化铝产品性能的影响。结果表明:升高成胶温度,氧化铝产品的结晶度随之增高,比表面积呈先增大后减小的趋势,孔容、孔径增大,在成胶温度为70℃时产品的最可几孔径最大。随成胶pH的升高,氧化铝产品的比表面积逐渐减小,pH=7时以小孔为主,pH=8时孔容增至最大,孔分布向大孔方向偏移,继续增高p H值孔容和大孔比例均减小。在成胶体系中引入2%的P、F、Si作为助剂均可有效提高氧化铝的孔径,助剂F和Si会使氧化铝的比表面积和孔容有所减少,而P会显著提高氧化铝的比表面积和孔容。加入0.2%~1%的B_2O_3作为助剂后,产品的孔径分布向大孔方向显著偏移。     

Synthesis and Characterization of Titanium-Substituted Large Pore SSZ-42 Zeolite

Titanium-substituted large pore SSZ-42 zeolite was synthesized for the first time using the corresponding borosilicate as starting material. Substitution of boron by titanium took place via either high temperature treatment with TiCl₄ vapor or by treatment with Ti(OiPr)₄ in dry toluene at 120°C. Both deboronated and boron-containing samples were found to be suitable for post-synthesis incorporation of titanium in the zeolite framework. The obtained materials were characterized by FTIR, UV-visible and XPS. Titanium-modified SSZ-42 was found to be active for phenol hydroxylation and cyclohexene epoxidation.     

The Synthesis of Novel Hierarchical Zeolites and Their Performances in Cracking Large Molecules

Novel hierarchical zeolites with continuous micrometer-scale macropores and mesopores other than popular nanometer-scale mesopores and micropores were synthesized by transforming the skeletons of the silica monolith into zeolites through both the steam-assisted conversion and nanocasting methods. Results showed the novel hierarchical zeolites exhibited high catalytic activity for catalytic cracking large molecules.     

纳米ZSM-5分子筛的合成研究

相比于微米ZSM-5分子筛,纳米ZSM-5分子筛具有孔道短,酸量多,外表面积大,抗积炭失活等优势。通过添加分散介质、分散剂、矿化剂及晶种导向剂等手段抑或通过不同的合成方法,可以得到纳米ZSM-5分子筛。文章综述了纳米ZSM-5分子筛的合成影响因素及合成方法。     

Generation of Large Pore Channels for Bone Tissue Engineering Using Camphene-Based Freeze Casting

The present study reports an innovative way to produce large pore channels with a size >100 μm for applications in bone tissue engineering using the camphene-based freeze casting method, and using an unusually high freezing temperature, which is close to the solidification temperature of the slurry, in order to allow the formation of excessively overgrown camphene dendrites due to the extremely low solidification velocity. To accomplish this, hydroxyapatite (HA)/slurries with various solid loadings (10, 15, and 20 vol%) were frozen at 35°C for 20 h. The frozen samples were freeze dried and sintered at 1250°C for 3 h. All of the fabricated samples showed highly porous structures with large pore channels >100 μm in size and dense HA walls without any noticeable defects, such as cracks or pores. As the initial solid loading was increased from 10 to 20 vol%, the porosity of the sample decreased linearly from 76% to 55%, while the pore channels became narrower. However, the compressive strength was remarkably improved from 2.5 to 16.7 MPa.     

Methanol-to-Olefins Reaction over Large-Pore Zeolites: Impact of Pore Structure on Catalytic Performance

In the methanol-to-olefins (MTO) reaction, product flexibility is important for meeting the fluctuating chemicals demands. In this paper, the catalytic performance of recently reported zeolites having 12-ring pores, such as boroaluminosilicate CON-type zeolite ([Al,B]-CON), MCM-68, and YNU-5 zeolites, in the MTO reaction was compared to understand the relationship between zeolite framework and product selectivity. The catalytic performance of the synthesized zeolites was compared with that of Beta, mordenite, and ZSM-5. The highest selectivities for propylene and butylenes were achieved over MCM-68. The highest propylene-to-ethylene ratio in the products was obtained over [Al,B]-CON. ZSM-5 and [Al,B]-CON exhibited a superior ability to suppress coke formation compared to Beta, mordenite, MCM-68, and YNU-5.     

以哌啶为模板剂静态合成MCM-22和MCM-36分子筛

以来源易得的哌啶(PI)取代六亚甲基亚胺(HMI)为模板剂,采用静态合成的方法制备MCM-22分子筛,并进一步以十六烷基三甲基氯化铵(CTMACL)、四丙基氢氧化铵(TPAOH)作为溶胀剂,以正硅酸乙酯(TEOS)为柱撑剂合成MCM-36分子筛,以探索MCM-22和MCM-36的新合成途径。通过XRD、IR、SEM、N2吸附-脱附、NH3-TPD、正丁胺回滴法对MCM-22和MCM-36结构形貌、比表面积、孔径、表面酸量进行表征。结果表明,采用静态法以哌啶为模板剂是合成MCM-22和MCM-36的有效途径,MCM-22结晶度达到98.5%。合成的MCM-22比表面积为382 m2?g-1,孔容为0.25 cm3?g-1,外表面酸量为0.78 mmol?g-1;合成的MCM-36比表面积为468 m2?g-1,孔容为0.39 cm3?g-1,外表面酸量为0.94 mmol?g-1,介孔孔径达2.7 nm。     

粉煤灰合成分子筛的研究

在中国,粉煤灰合成分子筛是处理粉煤灰的一个重要方法,粉煤灰正成为沸石合成的一个重要原料.比较了水浴合成和微波合成制备分子筛的特点.XRD和SEM分析表明,微波晶化合成的沸石外观形状更加规则,均为圆形或者椭圆形的小球,且微波晶化合成的沸石分布均匀,结构致密.微波晶化可以快速晶化产生沸石,但随着晶化时间的推移,由于微波晶化的晶化反应太过剧烈,不利于核的增长.     

Removal of Metal Cations from Water Using Zeolites

Abstract

Zeolites from abundant natural deposits were investigated by the Bureau of Mines for efficiently cleaning up mining industry wastewaters. Twenty-four zeolite samples were analyzed by x-ray diffraction and inductively coupled plasma. These included clinoptilolite, mordenite, chabazite, erionite, and phillipsite. Bulk densities of a sized fraction (-40, +65 mesh) varied from 0.48 to 0.93 g/mL. Attrition losses ranged from 1 to 18% during an hour-long shake test. The 24 zeolites and an ion-exchange resin were tested for the uptake of Cd, Cu, and Zn. Of the natural zeolites, phillipsite proved to be the most efficient, while the mordenites had the lowest uptakes. Sodium was the most effective exchangeable ion for exchange of heavy metals. Wastewater from an abandoned copper mine in Nevada was used to test the effectiveness of clinoptilolite for treating a multi-ion wastewater. The metal ions Fe³⁺, Cu²⁺, and Zn²⁺ in the copper mine wastewater were removed to below drinking water standards, but Mn²⁺ and Ni²⁺ were not. Calcium and NH₄ ⁺ interfered with the uptake of heavy metals. Adsorbed heavy metals were eluted from zeolites with a 3% NaCl solution. Heavy metals were concentrated in the eluates up to 30-fold relative to the waste solution. Anions were not adsorbed by the zeolites.     

纳米级ZSM-12分子筛的合成及表征

采用双季铵盐模板剂溴代1,4-二氮甲基哌啶基-丁烷,通过动态水热晶化法成功制备了纳米级ZSM-12分子筛。采用X射线衍射、扫描电镜、透射电镜、红外光谱分析及N2吸附-脱附技术等测试方法对所得颗粒进行了研究。所合成的颗粒呈长条形状,长约150 nm,宽约30 nm。所得的ZSM-12沸石结晶体结构完整,无明显骨架缺陷,富含微孔和介孔孔隙。介孔孔隙来源于ZSM-12纳米晶粒之间的堆积孔隙。在酸分布上,所得的HZSM-12分子筛的中强酸及B酸比例较多,使得该沸石在催化反应中具备优良的反应活性。     

动态条件下ZSM-12分子筛的合成

采用动态晶化法,系统考察了硅源、硅铝比、模板剂含量以及水含量对ZSM-12分子筛合成的影响,得到合成纯相ZSM-12分子筛的最佳条件为:硅溶胶为硅源,n(Si)/n(Al)=45~70,n(四乙基氢氧化铵,TEAOH)/n(SiO_2)=0.14,n(H2O)/n(SiO_2)=13。通过XRD、SEM、BET、NH3-TPD对所合成的产物进行了表征。体系中的硅铝比对所合成产物的晶相和晶化动力学有显著影响:当硅铝比(Si/Al摩尔比,下同)过低时,容易导致MFI和BEA结构的杂晶相的生成;硅铝比较高时,动态晶化比静态晶化更有利于提高分子筛的合成效率;体系中的n(TEAOH)/n(SiO_2)和n(H_2O)/n(SiO_2)会在很大程度上影响所合成产物的晶相和形貌。     

以稻壳为硅源和成孔剂合成多孔堇青石陶瓷的研究

以稻壳中的硅质组分和碳质组分分别作为多孔菫青石合成所需的硅源和成孔剂,并以La<,2>O<,3>为外加剂,烧结制备了多孔菫青石陶瓷,研究了试样的物相组成随烧结温度的变化,观察与分析了烧结试样的显微形貌,并测定了烧结试样的主要物理性能.结果显示:在1350℃、保温5 h条件下,所得多孔菫青石陶瓷的抗弯强度为11.38 MPa,气孔率45.02%,热膨胀系数3.03×10<,-6℃-1>.分析显示La<,2>O<,3>能够促进酶青石的形成,使堇青石的开始形成温度降低至1100℃,并能在不降低菫青石孔隙率的情况下,大幅度提高其抗弯强度,它在烧结过程中产生的液相起"点焊"的作用.     

以杨木为模板制备高度有序的多级复合孔材料

以天然植物杨木作为大孔硬模板,以嵌段共聚物P123作为介孔相软模板成功制备出一种具有连续的骨架和相互贯通的大孔孔道,其大孔孔径约为10μm,其孔壁为介孔相的高度有序多级复合孔材料。并用扫描电子显微镜（SEM）、粉末X射线衍射仪（X R D）、高分辨率透射电镜（H R TEM）、N2吸附-脱附等测试手段对样品进行了系统的...     

Kinetic Studies on Diacetyl Synthesis over V-Containing Zeolites

The gas-phase oxidation of methyl ethyl ketone (MEK) was studied on V-ZSM-5 zeolite in the presence of molecular oxygen. Two types of competitive partial oxidations, i.e., diacetyl formation and oxidative scission reaction leading to acetaldehyde and acetic acid, took place at 200–350°C. A detailed kinetic study was realized for the oxidation reaction, a linear relationship was observed between the conversion and partial pressure of oxygen, and an activation energy of 16 kcal/mol was encountered. The content of vanadium in the catalyst was also analyzed.     

The Synthesis and Properties of Two Catalytically Important Zeolites

With his discovery of stilbite in 1756, Cronstedt [1] recognized the existence of a new group of minerals consisting of hydrated “aluminosilicates” of the alkali and alkaline earth cations. While several members of the group may have similar or nearly identical compositions, each possesses its own, unique crystal structure. At present there are 35 known naturally occurring zeolites. The crystal structures have been determined for 27 and all but about 10 have been prepared synthetically. This paper will present the definition of zeolites and focus on the synthesis and physicochemical properties of two catalytically and commercially important synthetic zeolites, zeolite Y and zeolite ZSM-5.