ZSM－35分子筛的合成及模板效应的研究

以1,6-己二胺为模板剂合成了ZSM-35分子筛,通过对比ZSM-35、ZSM-5和丝光沸石的合成条件,采用化学组成分析、热重分析及¹³CNMR等技术研究了1,6-己二胺和乙二胺的模板效应。结果表明,二者均对ZSM-35有较好的模板作用,而1,6-己二胺对ZMS-5的模板效应更佳。     

利用ＳＢＡ-１５介孔内纳米碳合成含介孔的ＺＳＭ-５分子筛

SBA-15介孔分子筛内填充蔗糖并炭化后, 分别在碱性和弱酸性条件下, 用含铝源及TPABr的溶液浸渍,将SBA-15分子筛孔壁的无定形结构转化成ZSM-5分子筛的晶体结构, 除碳后得到含介孔的ZSM-5分子筛. 用X射线衍射、 N_2吸附-脱附、 ~(27)Al MAS NMR、 NH_3-TPD、 TEM、 SEM等对样品进行了表征, 考察了晶化时间等参数对样品的影响. 结果表明, 碱性条件下合成的ZSM-5分子筛晶体中含有少量孔径约3.2～4.2 nm的介孔孔道, 其酸强度接近与常规ZSM-5分子筛的酸强度;弱酸性条件下合成的ZSM-5分子筛晶体中含有大量孔径约1.4～1.6 nm的孔道, 其酸强度明显低于常规ZSM-5分子筛的酸强度.     

硼和氟掺杂ZSM-5分子筛的制备及其甲醇制丙烯反应性能

采用两步水热晶化法,通过在合成体系中加入硼酸、氟化铵、氟硼酸铵,合成出了硼和氟改性的ZSM-5分子筛。利用X射线衍射、氮气吸附-脱附、29Si固体核磁共振波谱、傅里叶变换红外光谱、扫描电子显微镜以及NH₃程序升温脱附等测试手段对样品进行了表征。结果表明：硼和氟掺杂条件下可以合成具有较高结晶度的ZSM-5分子筛,杂原子掺杂提高了分子筛的硅铝比;硼和氟掺杂可以显著降低ZSM-5分子筛的Lewis酸量,但提高了Brønsted酸量;硼和氟共同作用可以降低ZSM-5分子筛的颗粒尺寸。甲醇制丙烯评价结果显示：较低的Lewis酸量和适宜的Brønsted酸性有利于提高丙烯选择性和催化剂寿命;NH₄BF₄改性的ZSM-5分子筛（Z5-BF2）表现出较高的丙烯选择性和较长的催化剂寿命。     

Study on Methylation of Naphthalene with Methanol over ZSM-5 (core)/SAPO-11(shell) Composite Molecular Sieve

ZSM-5 (core)/SAPO-11 (shell) composite molecular sieve was synthesized by the hydrothermal method in order to combine the advantages of ZSM-5 and SAPO-11 for the methylation of naphthalene with methanol. For comparison, the mechanical mixture was prepared through the blending of ZSM-5 and SAPO-11. The characterization results indicated that ZSM-5/SAPO-11 composite molecular sieve exhibited a core–shell structure, with the ZSM-5 phase as the core and the SAPO-11 phase as the shell. The pore size of the composite was between that of ZSM-5 and SAPO-11. The composite had fewer acid sites than ZSM-5 and mechanical mixture while more acid sites than SAPO-11. The experimental results indicated that the composite exhibited high catalytic performances for the methylation of naphthalene with methanol.     

以十六烷基三甲基溴化铵为模板剂合成MCM-41/ZSM-5复合分子筛的研究

采用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂、以ZSM-5为晶种,在水热晶化条件下合成了同时具有微孔和介孔的MCM-41/ZSM-5复合分子筛;并考察了陈化温度、陈化时间、晶化时间及模板剂用量等条件对合成复合分子筛的影响.通过X射线衍射、扫描电镜、高分辨率透射电镜、红外光谱及N2静态吸附法等手段对合成样...     

SAPO-34分子筛催化丁烯转化制丙烯的研究

通过水热法合成SAPO-34分子筛,将其制成催化剂用于催化丁烯转化制取丙烯,考察了反应温度、空速和铝磷比等对催化性能的影响;还比较了SAPO-34分子筛与ZSM-5分子筛催化该反应的差异.结果表明,在实验范围内,反应温度升高会使得丁烯的转化率明显增高,且丙烯选择性提高;而空速增加,则丁烯的转化率和丙烯选择性降低;铝磷比越大,对丙烯的选择性越差.在有效的反应时间内,SAPO-34分子筛催化效果好于ZSM-5分子筛,但单程寿命较ZSM-5分子筛短.     

改性ZSM-5-SBA-15及甲苯甲醇烷基化性能研究

通过浸渍法对ZSM-5进行金属M(M为Mg、Ni、Sr)改性,合成法制备了M-ZSM-5-SBA-15复合分子筛,采用XRD、N2吸附-脱附、FT-IR、NH3-TPD和Py-FTIR等技术对样品进行表征,考察了HZSM-5的硅铝比、不同金属对ZSM-5-SBA-15复合分子筛烷基化性能的影响。结果表明,HZSM-5的硅铝比为80时,ZSM-5-SBA-15复合分子筛的烷基化性能较好,Sr的引入钝化了ZSM-5-SBA-15(80)的强B酸中心,降低了B酸与L酸的比值,Sr-ZSM-5-SBA-15(80)的甲苯甲醇烷基化性能明显提高,甲苯转化率为30.15%,对二甲苯选择性为77.41%。     

Study of One Step Synthesis of Rare Earth Zeolite (Ln–ZSM-5) and Application for Low Temperature CO Catalytic Oxidation

A series of rare earth zeolites Ln–ZSM-5 (Ln = La, Ce, Pr, Nd) were synthesized directly via a one-step hydrothermal method. The obtained zeolites were used as support and applied in low-temperature CO oxidation. The influence of various factors such as rare earth types, rare earth contents, particle sizes of molecular sieve, and silica alumina ratios, etc., on the catalytic activity of CO oxidation were investigated in detail. The results showed that low silica small size Ce–ZSM-5 (1 % Ce content) had the highest activity. The results also showed that Ce–ZSM-5 zeolite prepared by one-step direct synthesis was more suitable as catalytic support than ZSM-5 or Ce/ZSM-5 zeolite, prepared by impregnation of ZSM-5 with Ce.     

Synthesis and catalytic performance of ZSM-5/MCM-41 composite molecular sieve from palygorskite

ZSM-5/MCM-41 composite molecular sieve has been hydrothermally synthesized through a two-step crystallization process using palygorskite (PAL) as silicon and aluminum source. The products were characterized by various means and their catalytic properties for acetalization of cyclohexanone and esterification of acetic acid and n-butanol were also investigated. In the first step ZSM-5 zeolite could be formed from the acid-treated PAL after hydrothermal treatment using tetrapropylammonium bromide as template. XRD patterns, N₂ adsorption and desorption data, and TEM images show that the composite obtained in the secondary step had a well-ordered mesoporous MCM-41 phase and a microporous ZSM-5 zeolite phase. Compared with ZSM-5, ZSM-5/MCM-41 composite possessed more total acid amount, weak acid sites and large pore structure due to the formation of MCM-41 and exhibited higher catalytic activity for the acetalization and esterification reaction.     

A highly efficient oxidation of cyclohexane over Au/ZSM-5 molecular sieve catalyst with oxygen as oxidant

A highly efficient oxidation of cyclohexane to cyclohexanol and cyclohexanone is accomplished over calcined Au/ZSM-5 molecular sieve catalyst with oxygen as oxidant.     

Synthesis of hollow polypyrrole-platinum complex spheres and their successful application as a catalyst for decomposition of hydrogen peroxide

Hollow pyrrole-platinumpoly (PPy-Pt) complex spheres effectively catalyze the decomposition of hydrogen peroxide to form oxygen. The method used to synthesize the catalysts employs chemical polymerization of pyrrole with potassium hexachloroplatinate(IV) as oxidant and ZSM-5 molecular sieve as a hard template removable by dissolution. ZSM-5 molecular sieve used as template has the following merits: it can be easily removed, it is inexpensive and owing to micrometer size it shows a minimal aggregation. In addition, the use of the zeolite avoids the need for non-volatile surfactants which may be adsorbed onto the synthesized PPy-Pt complex spheres and interfere with their possible applications in catalysis. The new micron-sized hollow PPy-Pt complex spheres are produced simply and cost-effectively, and they can be expected to play an important role in wastewater treatment technologies. The synthetic method may represent a novel route to prepare hollow conductive polymer spheres doped by various metals for specific applications.     

Determination of transport coefficients in microporous solids

Macroscopic transient methods are reviewed with respect to their applicability to the investigation of molecular transport in microporous sorption systems. Various levels of sophistication of data evaluation for nonequilibrium sorption results obtained by means of batch methods are identified and characterised. Special attention is paid to the characterisation ofFickian (intracrystalline) diffusion as well as to the identification and quantification of additional rate mechanisms that, in general, may simultaneously occur in molecular sieve systems. A state-of-art determination of transport coefficients is exemplified for the systems benzene/microporous gallosilicate of MFI-type, n-hexane/silicalite-I and p-ethyltoluene/ZSM-5. Their sorption rate behaviour can be understood either byFickian diffusion or byFickian diffusion and intracrystalline molecular immobilisation/mobilisation and surface barrier penetration, respectively. To analyse complex sorption rate patterns in microporous systems, the method oftotal curve fitting with full parameter region consideration becomes mandatory.     

Effects of the Operating Conditions on Coke Deactivation of 5A Molecular Sieve in N-Decane Adsorption/Desorption

The influence of operating conditions (time-on-stream, temperature, pressure and paraffin feed concentration) on the deactivation of a 5A molecular sieve during the adsorption/desorption of n-decane has been studied using a cyclic operating procedure. After 10 adsorption/desorption cycles, the 5A molecular sieve used in this study showed the same deactivation level as an used industrial molecular sieve provided that the deactivation of the zeolite was due to coke deposition by site coverage and pore blockage. The temperature effect was studied in the range of 373–523 K, obtaining a minimum deactivation at 448 K. The pressure does not influence adsorption parameters in the range of 1–3 MPa, but it does affect the nature of the coke deposited on the zeolite. The influence of paraffin concentration can be considered negligible.     

液晶模板合成多级孔ZSM-5分子筛及其催化应用

以哌嗪基丙基甲基二甲氧基硅烷偶联剂(PZPMS)和阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为复合液晶模板,在水热条件下合成多级孔ZSM-5分子筛.采用XRD、 SEM、 BET、 XRF、 FT-IR和NH_3-TPD对催化剂的性能进行了表征.结果表明, PZPMS/CTAB复合液晶模板的加入可以减小颗粒尺寸,增加外表面积,有利于合成多级孔ZSM-5分子筛.加入液晶模板可以有效调整催化剂表面B酸与L酸量比例,改善催化剂表面酸性.对合成的催化剂样品在MTA反应中进行了催化性能测试,样品在反应中对芳烃表现出较高的选择性,催化寿命有不同程度的提高.     

Aromatization ofn-butane over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica, fiber

The reaction ofn-butane aromatization was carried out over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica fiber during the process of ZSM-5 zeolite synthesis. The catalysts prepared were characterized by X-ray powder diffraction, nitrogen adsorption and X-ray fluorescency. The acidic properties of the catalysts were investigated by temperature-programmed desorption of ammonia using a mass spectrometer equipped with a QTMD detector. The effect of catalyst pretreatment, reaction temperature, and time on stream on the reaction ofn-butane to aromatic hydrocarbons were investigated. The modification of ZSM-5 by Ni and Cu increased the selectivity to aromatic hydrocarbons. The state of Ni and Cu and their stabilization in the ZSM-5 structure was highly influenced by the mode of catalyst pretreatments.     

分子筛担载金催化剂催化烯烃环氧化制环氧化合物

烯烃的环氧化是工业上的重要反应之一，在众多的烯烃中，端烯尤其是直链端烯是相对较难氧化的一类。     

Hetero-Atom Zeolite (Ⅱ)——Studies on the Crystal Structures of B-Si Pentasil zeolite Molecular Sieves

The crystal structure of B-Si pentasil zeolite molecular sieve was determined by means of the x-ray diffraction for polycrystalline samples and refined by Rietveld method.The parameters of the unit cell are e=19.983(1)A;b=19.773(1)A;c=13.303(1)A.Its space group is D2h1G-Pnma The framework topology found agrees with reported Si-Al ZSM-5zeolite molecular sieves.It is concluded from the structural determination that B is introduced into the framework of this sample.     

气相转移法合成ZSM-5/SAPO-5复合分子筛

以磷酸、拟薄水铝石和硅溶胶为原料, 三乙胺为模板剂, 采用气相转移法合成了一系列ZSM-5/SAPO-5复合分子筛. 产物经X射线衍射、扫描电镜、X射线能量散射谱、红外光谱及N2 静态吸附法等手段对其进行了表征, 证明合成材料是以ZSM-5为核、SAPO-5为壳的双结构分子筛. 实验结果表明, 干胶制备条件及液相组成都影响复合分子筛的结晶. 晶化温度的提高和晶化时间的延长有利于分子筛结晶度的提高. VPT法可以减小SAPO-5和复合分子筛颗粒的直径, 改善SAPO-5在ZSM-5分子筛表面的分布. 重油裂化结果表明, 核壳结构复合分子筛对生成低碳烯烃的性能优于机械混合的样品.     

Ag(x)/ZSM-5催化剂的CH4-SCR脱硝性能

采用浸渍法制备Ag(x)/ZSM-5(x=3、6、9)催化剂。采用XRD、SEM、NH_3-TPD、Py-FTIR、XPS和NO-TPD等手段对催化剂的理化性质进行表征,在常压固定床微型反应器中评价催化剂甲烷选择性催化还原(CH_4-SCR) NO催化性能,考察Ag负载量对Ag(x)/ZSM-5催化剂CH_4-SCR脱硝性能的影响。结果表明,ZSM-5分子筛负载Ag,催化剂的酸性和酸量发生变化,改善了催化剂对NO的吸附脱附性能。随着Ag负载量增加,形成较大的Ag晶粒,有利于甲烷活化,Ag(x)/ZSM-5催化剂CH_4-SCR脱硝活性提高。Ag(9)/ZSM-5催化剂CH_4-SCR脱硝性能较好,在350℃时NO转化率为41.87%。     

高岭土原位无溶剂法合成小粒径ZSM-5分子筛

结合原位水热法和无溶剂法的优点,在不添加有机模板剂和溶剂的基础上,以高岭土为原料通过晶种诱导绿色高效地合成出ZSM-5分子筛。运用X射线衍射、N2吸附-脱附、扫描电镜、透射电镜和NH3程序升温脱附(TPD-NH3)等技术对ZSM-5分子筛进行表征。表征结果与原位水热法合成的ZSM-5分子筛相比,原位无溶剂法合成ZSM-5分子筛的结晶度较高、晶体粒径较小、酸强度略高、孔结构相似。