水热脱铝ZSM-5/Y复合分子筛的表征和催化裂化性能

ZSM-5/Y是一种通过原位合成方法制备的新型复合分子筛材料,用XRD、IR光谱、N2吸附／脱附等手段,研究了水热处理对ZSM-5/Y物化性质的影响,并以正己烷为原料考察了样品的催化裂化性能.结果表明,与机械混合样品相比,在550 ℃和700 ℃水热处理条件下,复合分子筛中的Y型沸石相具有更好的结晶保留度.复合分子筛的中孔孔径分布范围大于机械混合分子筛,但复合分子筛样品所表现出的中、大孔体积小于相应的机械混合分子筛.吡啶吸附定量IR研究表明,550 ℃水热处理使复合分子筛的B酸量和L酸量减少;而机械混合样品则是B酸量和L酸量变化很小.进一步700 ℃水热处理则使B和L酸量都大量减少.与氢型样品相比,550 ℃脱铝样品的正己烷裂化活性显著增加,700 ℃脱铝后活性明显降低.产物分布的分析表明活性的提高与反应机理的改变有关.     

Adsorption of hydrocarbons and water on ZSM 5 and on ZSM 5 converted by dealumination into silicalite

Adsorption measurements of hydrocarbons and water have been performed on ZSM 5 (Si/Al=30) and on two samples prepared from this by dealumination. The properties of the highly dealuminated sample agree essentially with those of silicalite obtained by direct synthesis.The pecularities in the adsorption of benzene at more than one molecule per 1/4 unit cell are discussed.     

Structural and acidic characteristics of Cu-Ni-modified acid-leached mordenites

Two series of dealuminated Na-mordenite zeolites (DML and DMH) were impregnated, in comparison with the parent nondealuminated NaMSP, in aqueous nitrate solutions of Cu and Ni to achieve varying loadings for both of the cations. These samples were characterized by N(2) adsorption, XRD, DSC of ammonia desorption, ammonia volumetric sorption, IR of ammonia adsorption, and FTIR-photoacoustic (FTIR-PAS) techniques. The FTIR-PAS spectrum of CuNi-loaded NaMSP shows a band at 935 cm(-1) ascribed to O(3)Siz.sbnd;Oz.sbnd;SiO(3) linkages produced as a result of dealumination caused by the synergistic effect of Cu and Ni cations under the preparation conditions. As a confirmation, this band was intensified upon acid dealumination (DML) where, at the extent of dealumination (DMH), collapsing of the zeolite structure was obtained subsequent to cation modification. In addition, the dealumination effect was markedly enhanced upon increasing the load of Cu in proportion to Ni. A total erosion of OH group characteristics of Siz.sbnd;(OH)z.sbnd;Al at 3610 cm(-1) was depicted when the Ni content exceed that of Cu where it did not show any change when the Cu content surpasses that of Ni. The amount of adsorbed ammonia measured volumetrically was enlarged after dealumination as well as after increasing the contents of the modificating cations. The IR study of ammonia adsorption revealed a band at 1428 cm(-1), in either nondealuminated or dealuminated-modified samples, assigned to stronger Bronsted acid sites than those at 1455 cm(-1). The band at 1428 cm(-1) was markedly enhanced in the latter samples than in the former. This was due in part to the replacement of the protons by cations, producing sufficiently mobile protons. In conformity, DeltaH values obtained for DSC effects via ammonia desorption were enhanced after dealumination. Other correlations with XRD and surface texturing on one hand and the structural variations following cations incorporation on the other hand are evaluated and discussed.     

脱铝MCM-49分子筛的结构、酸性及苯与丙烯液相烷基化催化性能研究

采用硝酸回流和水蒸气两种处理方法对用动态水热法合成的纳米MCM-49分子筛进行脱铝改性. 用XRD、氮气吸附-脱附、NH3-TPD、FTIR和NMR等技术进行了表征, 并考察了脱铝前后MCM-49分子筛在苯与丙烯液相烷基化反应中的催化性能. 27Al核磁共振谱表明, 硝酸回流和水蒸气处理能有效地脱除MCM-49分子筛的部分骨架铝和非骨架铝. NH3-TPD和FTIR表征结果表明, 脱铝降低了MCM-49分子筛的Brönsted酸和Lewis酸的酸量. 硝酸脱铝未改变分子筛的酸强度分布, 而在600 ℃水蒸气脱铝则造成酸强度的降低. 实验条件下, MCM-49分子筛的丙烯转化率为99.5%, 异丙苯的选择性为73.6%. 脱铝改性降低了烷基化反应活性和异丙苯的选择性, 提高了收率. 与脱铝前MCM-49分子筛相比, 常温下经硝酸处理5 h的脱铝MCM-49分子筛在保持催化活性相当的情况下, 异丙苯收率提高了5.3%.     

Effect of mordenite dealumination on the structure of encapsulated molybdenum catalysts

A series of dealuminated mordenites treated under various conditions of acid leaching was impregnated in an aqueous solution of ammonium heptamolybdate to achieve a loading of 12 wt% Mo. These samples were characterized by XRD, UV-DRS, N(2) adsorption, TGA, and FTIR techniques. Special attention was given to the far-IR measurements and IR study of surface hydroxyl groups before and after dealumination. A polymolybdate species was recognized by the appearance of bands at 344, 319, and 236 (229) cm(-1) due to the vibrational modes of delta(Mo-O) and delta(Mo-O-Mo), respectively. The disappearance of the 236 cm(-1) band as well as that at 344 cm(-1) in favor of the 319 cm(-1) band, with the dealumination, was related to the high dispersion of Mo species in the produced mesopore surface assessed by the N(2) adsorption at 77 K. No bands due to bulk MoO(3) were detected from the IR and XRD results. A strong interaction between Mo species and dealuminated mordenite surfaces (OH groups) was recognized by a decrease in intensity and a marked shift of the band at 3745 to 3727 cm(-1) as well as the appearance of a new band at 3668 cm(-1). The latter band was produced by the interaction of the framework Al-OH with Mo species. The BET surface areas of Mo-dealuminated mordenite samples were higher than the corresponding Mo-free ones. The diffuse reflectance measurements suggested that Mo cations are predominantly present as an octahedrally coordinated Mo(6+), along with some tetrahedral Mo(6+). New spectral features as a consequence of dealumination events in the far-IR range were evaluated and discussed.     

Catalytic performance of imidazole modified HZSM-5 for methanol to aromatics reaction

A facile approach was developed for the preparation of nano-sized HZSM-5 with a hierarchical mesoporous structure by adding imidazole into conventional zeolite synthesis precursor solution. The physicochemical properties of modified HZSM-5 were characterized by X-ray diffraction(XRD), N_2 adsorption–desorption isotherms, scanning electron microscopy(SEM), NH_3-temperature-programmed desorption(NH_3-TPD) and pyridine adsorption infrared spectroscopy(Py-IR). The coke in spent catalysts was characterized by thermogravimetry(TG). The results showed that hierarchical HZSM-5 zeolites with excellent textural properties, such as abundant porous structure, uniform particle size and suitable acidity, could be synthesized by the recipe of one-pot synthesis routes. Moreover, the obtained HZSM-5 exhibited higher selectivity of total aromatics as well as longer lifetime in the catalytic conversion of methanol to aromatics, comparing with conventional HZSM-5. It is expected that the synthesis approach demonstrated here will be applicable to other zeolites with particular textural properties and controllable particle sizes, facilitating the emergence of new-type porous materials and their related applications in catalysis and separation.     

Microparticle HZSM-5 zeolite as highly active catalyst for the hydration of cyclohexene to cyclohexanol

Microparticle HZSM-5 zeolite (MPZ) has been prepared without employing any organic templates, and used as a catalyst for the hydration of cyclohexene to synthesize cyclohexanol. MPZ exhibits better catalytic performance and superior settlement separation property than those of commercial HZSM-5 prepared by the traditional method using an organic template. The stability of MPZ has been investigated for a 1200-h test, and the regenerated performance of MPZ has also been investigated. The results show that although MPZ was reused for five recycles, the high cyclohexene conversion of 9.6 % and the high cyclohexanol selectivity of 96.8 % are still attained after the fifth regeneration. FT-IR, XRD and N₂ adsorption–desorption characterizations show that coke deposit on the surface and in the channels of MPZ is the main reason for the deactivation. ICP-AES, SEM–EDS and NH₃-TPD characterizations indicate that hydrothermal dealumination reduces the strong acidity and accelerates the catalyst deactivation. The spent catalyst by regeneration with H₂O₂ could be recovered to its initial high catalytic activity, due to the restored appropriate channels and exposed active sites.

     

四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能

采用四丙基氢氧化铵(TPAOH)溶液对纳米ZSM-5分子筛进行改性, 运用X射线衍射、扫描电镜、²⁷Al和²⁹Si固体核磁、X射线光电子能谱、N₂物理吸附脱附法和NH₃程序升温脱附等手段对所制样品进行了表征, 并评价了其催化甲醇制汽油反应性能. 结果表明, 改性后的HZSM-5相对结晶度增加, 晶体形貌更加规整, 表面硅铝比增加, 比表面积和微孔表面积增大, 强酸位酸量增多. 同时, TPAOH改性不仅可以使分子筛脱硅脱铝, 而且伴有二次晶化补硅补铝, 改变了分子筛的硅铝分布. 改性的HZSM-5在甲醇制汽油反应中的稳定性大幅度提高, 其寿命由70h增至170h以上, 随着TPAOH处理时间的增加, 催化剂寿命增加, 氢转移反应加快, 导致油相产品中异构烷烃增多, 烯烃减少.     

磷酸三乙酯改性HZSM-5沸石的活性及理论研究

采用XRD表征了水蒸气和磷联合改性的HZSM-5沸石分子筛的结构．通过NH3-TPD和N2吸附脱附研究了样品的酸性和比表面．采用正庚烷的裂化反应研究了样品的裂化活性，研究结果表明，磷改性样品与母体样品相比，经过水蒸气处理后显示出较高的酸量和正庚烷裂化活性．上述结果首次用模型簇和计算量子化学方法进行了解释．采用Gaussian94软件包和PM3半经验量子化学方法对模型簇进行了全优化和频率分析．计算结果显示磷改性后样品的脱铝补硅反应热大于母体样品脱铝补硅反应热，从而显示出磷对骨架的稳定化作用．     

F-Nb摩尔比对F-Nb/HZSM-5催化剂催化乙醇脱水性能的影响

利用BET、NH3-TPD、FT-IR、MAS-NMR和SEM等方法研究了经不同F/Nb负载的F-Nb/HZSM-5催化剂的结构和表面酸性,并与乙醇催化脱水制乙烯的反应催化性能进行了关联.结果表明,F-Nb改性后的HZSM-5分子筛发生了明显的脱铝现象,且随着F离子添加量的增加,脱铝越发严重.经 27Al MAS NM...     

不同方法制备的脱铝Y沸石的孔结构

Y沸石脱铝有多种方法。由于在脱铝过程中发生水解、聚合、重排等反应,分子筛的孔结构将发生很大的变化,如形成空穴,甚至可导致骨架结构单元的崩塌,形成二次孔。由于不同的脱铝方法的脱铝机理不同,即使它们的脱铝程度一致,产生的孔结构也将不同,这必将导致它们的酸性质和催化性能的差异。目前关于Y沸石孔结构的研究报导还很少,尤其对SSY,US-SSY沸石孔结构的报导更为鲜见。本文用低温N_2吸附-脱附等温线和层厚t等方法,对四种不同方法制备的脱铝Y沸石(USY,DAY,SSY和US-SSY)的微孔、二次孔及其孔径分布(2.0～60.0nm)进行了初步研究,得到了一些有用的信息,为进一步研究其酸性质和催化性能打下了基础。     

烃在HZSM-5沸石上的程序升温脱附

本文研究了烃在HZSM-5沸石上的程序升温脱附(TPD).正己烷、环己烷和苯的TPD谱只有一个陡峰,对和间二甲苯的TPD谱均呈现出双峰.实验测得脱附活化能的次序为:正己烷>对二甲苯>苯>环己烷.水汽处理对正己烷的TPD影响不大;但对二甲苯的TPD影响较大.随着吸附量的增大,二甲苯逐渐占据孔道深处的强活性位置.     

Cu-HZSM-5上氯苯气相羟化反应及催化剂失活

研究了Cu-HZSM-5催化剂上的氯苯气相羟化合成苯酚反应及催化剂的失活情况.发现在773 K和水/氯苯体积比为3的反应条件下,1.6%Cu-HZSM-5催化剂上氯苯转化率高达82.4%,苯酚选择性为98.2%,但催化性能随着反应的进行有逐渐下降的趋势.采用X射线衍射、氮气静态吸附、X射线能谱和吡啶吸附红外光谱等手段对反应前后的催化剂进行了表征.结果表明,铜的流失、HZSM-5分子筛骨架脱铝、晶格塌陷和积炭是导致催化剂失活的主要原因.     

Acidity adjustment of HZSM-5 zeolites by dealumination and realumination with steaming and citric acid treatments

This article describes a novel method for acidity adjustment of HZSM-5 zeolites with steaming and citric acid treatments and demonstrates the realumination effect of citric acid on HZSM-5 zeolites dealuminated by steaming. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), (27)Al MAS NMR spectroscopy, hydroxyl infrared spectroscopy (OH-IR), pyridine-adsorbed infrared spectroscopy, and N(2) adsorption in the present investigation. The results showed that compared with single HCl or citric acid treatment, steaming treatment, and steaming/HCl treatments, citric acid treatment after steaming exclusively increased the amount of framework Al due to reinsertion of extraframework Al into the defective sites of the steamed HZSM-5 framework. This realumination effect of the citric acid treatment on the steamed HZSM-5 zeolite, which is reported here for the first time to the best of our knowledge, could nearly recover the pore structure of the steamed zeolite to that of the parent HZSM-5 zeolite and appropriately tailor the amount and strength of different acid sites, which sheds light on optimizing the physicochemical properties of HZSM-5 zeolites. It was also found that the steaming treatment prior to the citric acid treatment was the precondition of the realumination of HZSM-5 zeolites, suggesting that the lattice defect sites generated during steaming were necessary for citric acid to work.     

渣油FCC改性Y沸石研究

研究了不同方法和不同程度脱铝对Y型沸石浸镧老化后的结构性质和催化裂化性能的影响。结果表明，氟硅酸铵脱铝补硅和水热处理两个步骤联合，所得样品骨架铝分布均匀，通过控制脱铝程度可更有效地抑制结焦并保持催化裂化高活性；草酸脱铝和水热处理联合，所得样品二次孔结构发达，具有更好的渣油裂化生成液态低碳烃选择性。     

新型多级微/介孔固态胺吸附剂的制备及其CO2吸附性能研究

将HZSM-5与MCM-41按不同质量比混合得到复合分子筛载体,以四乙烯五胺(TEPA)为改性剂,采用浸渍法将其负载到复合分子筛上,制备了一系列新型的具有多级微/介孔结构的固态胺吸附剂。采用N₂吸脱附、傅里叶变换红外光谱(FT-IR)、热重分析(TGA)等手段对吸附剂进行表征。在固定床反应器中考察了HZSM-5和MCM-41的质量比、TEPA负载量、吸附温度、进气流量和CO₂分压等因素对CO₂吸附性能的影响。结果表明,当HZSM-5与MCM-41的质量比为1:1、TEPA负载量为30%、吸附温度为55℃、进气流量为30 mL/min时,平衡吸附量高达3.57 mmol/g,且经10次吸脱附循环后,吸附量仅下降8.1%。HZSM-5/MCM-41-30%TEPA对CO₂的吸附过程包括快速的穿透吸附和相对缓慢的逐渐平衡阶段,且穿透吸附量接近于平衡吸附量的80%。HZSM-5/MCM-41-30%TEPA对CO₂的吸附过程符合Avrami动力学模型,表明CO₂吸附是物理吸附和化学吸附的结果。     

Influence of V content on the nature and strength of acidic sites in VSibeta zeolite evidenced by IR spectroscopy

VSibeta zeolites prepared by a two-step postsynthesis method have been characterized by physical techniques. A significant reduction of intensity of the IR band near 3515 cm(-1) after impregnation of dealuminated beta zeolite with aqueous NH4VO3 indicates that V ions specifically react with hydrogen-bonded SiO-H groups of vacant T sites. IR bands at 3618 and 3645 cm(-1) are assigned to SiO-H groups interacting with V and to VO-H groups, respectively. In VSibeta, diffuse reflectance UV-visible data show that below 1.9 wt % V is present as lattice tetrahedral species and at higher content as extra-lattice octahedral species (mononuclear and polynuclear). VSibeta samples are EPR-silent at 298 or 77 K suggesting that there are no paramagnetic VIV ions. IR studies show that V-OH groups are less acidic than Si-OH-Al groups of parent HAlbeta zeolite. IR results of CO adsorption evidence three kinds of Lewis acidic sites, related to lattice mononuclear and extra-lattice mononuclear and polynuclear V species. Quantitative IR studies of ammonia and pyridine adsorption reveal that only about half of V introduced into zeolite is able to form either Br?nsted or Lewis acidic sites.     

Temperature-programmed desorption of aromatic hydrocarbons from ZSM-5 type zeolites

Temperature-programmed desorption of C₆–C₁₂ aromatic hydrocarbons from HZSM-5 and NaZSM-5 in helium stream has been studied. The role of the length, branching and number of alkyl groups was analyzed. It was shown that adsorption of aromatic ring occurs on Na-cations.     

沸石骨架脱羟与脱铝数量之间关系的NMR研究

本文讨论了用小板例角脉冲技术测试具有半整数自旋四极核＾２７Ａｌ和ＮＭＲ谱。通过ＮａＣｌ反交换测量不同温度焙烧的ＨＺＳＭ－５，ＨＭ，ＨＦＵ－９和Ｈ－镁碱沸石Ｂ酸位的变化以及用ＥＰＲ测试Ｌ酸位变化，发现在５００～７００℃温域四种沸石各自有一个脱羟的空变温区。用小板倒角脉冲＾２７ＡｌＮＭＲ技术观察到这些样品仅有少量非骨架铝，从而确定了四种分子筛脱羟与脱铝是不同步的。