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过刊目录

    催化学报
    Chinese Journal of Catalysis

    2015, Vol. 36, No. 6
    Online: 2015-05-21

    封面介绍:

    樊卫斌等采用离子交换法和物理混合法制备了 Zn/HZSM-5 催化剂, 将该催化剂用于乙烯芳构化反应. 发现催化剂中 Zn 物种以 ZnO 晶粒、ZnO 团簇和 Zn(OH)+ 三种状态存在, ZnO 物种促进低碳烷烃脱氢, Zn(OH)+ 促进烯烃芳构化. 见本期第 880–888 页.

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    目录
    第36卷第6期目次
    2015, 36 (6):  0-0. 
    摘要 ( 124 )   PDF(1837KB) ( 730 )  
    编者语
    Preface to Special Issue on Zeolite Materials and Catalysis
    Jihong Yu, Feng-Shou Xiao, Avelino Corma
    2015, 36 (6):  787-788.  DOI: 10.1016/S1872-2067(15)60876-2
    摘要 ( 217 )   [Full Text(HTML)] () PDF(222KB) ( 607 )  
    综述
    固体核磁共振研究分子筛的新进展
    李申慧, 周雷, 郑安民, 邓风
    2015, 36 (6):  789-796.  DOI: 10.1016/S1872-2067(14)60290-4
    摘要 ( 339 )   [Full Text(HTML)] () PDF(1137KB) ( 914 )  

    分子筛由于具有独特的孔道及可调控酸碱性等特征, 被作为离子交换剂、吸附剂及催化剂而广泛应用于石油化工的各种催化过程中. 固体核磁共振是研究分子筛结构、酸性及主客体相互作用的强有力谱学手段之一. 简单概述了固体核磁共振研究分子筛的最近进展.

    快讯
    无溶剂合成SAPO-5沸石中表面活性剂对其片状形貌的控制
    陈鲜, 孟祥举, 肖丰收
    2015, 36 (6):  797-800.  DOI: 10.1016/S1872-2067(14)60285-0
    摘要 ( 230 )   [Full Text(HTML)] () PDF(1114KB) ( 692 )  

    在表面活性剂如十六烷基三甲基溴化铵(CTAB)的存在下, 采用无溶剂法合成出具有片状形貌的SAPO-5沸石晶体. X射线衍射和扫描电镜结果表明, 所合成的样品具有很好的结晶度和可控的片状形貌, 在合成过程中, CTAB的添加量对其片状形貌特别是片状的厚度的影响很大. 考虑到一维的微孔AFI结构独特, 具有特殊片状形貌的SAPO-5晶体有望应用于催化方面.

    Ce-Beta分子筛的制备及其催化性能
    唐波, 戴卫理, 孙晓明, 武光军, 李兰冬, 关乃佳, Michael Hunger
    2015, 36 (6):  801-805.  DOI: 10.1016/S1872-2067(14)60277-1
    摘要 ( 383 )   [Full Text(HTML)] () PDF(599KB) ( 821 )  

    采用简单、易重现的两步后合成法成功制备了Ce-Beta分子筛. 制备过程中, H-Beta分子筛首先经过脱铝处理得到Si-Beta分子筛, 然后再以异丙醇铈为前驱体, 通过干法浸渍的途径向Si-Beta分子筛引入Ce (IV). 利用XRD, FT-IR, UV-Vis和1H MAS NMR等对其结构进行了表征, 结果表明, Ce(IV)物种以四配位的形式成功引入Beta分子筛的骨架, Ce原子进入分子筛骨架的机理通过DRIFT光谱得以证实. 通过环氧化合物水合制备1,2-二醇反应对所制的Ce-Beta催化剂进行了催化性能评价.

    论文
    不同硅铝比ZSM-5分子筛作为助催化剂在渣油裂化中的应用
    刘璞生, 张忠东, 贾明君, 高雄厚, 于吉红
    2015, 36 (6):  806-812.  DOI: 10.1016/S1872-2067(14)60311-9
    摘要 ( 422 )   [Full Text(HTML)] () PDF(900KB) ( 1202 )  

    采用不同方法表征了硅铝比(SiO2/Al2O3)为33、266和487的质子型ZSM-5分子筛, 并研究了ZSM-5分子筛作为助催化剂在渣油裂解中的应用. 与USY分子筛基催化剂混合后, 在固定流化床上, 评价了ZSM-5分子筛助催化剂的催化裂化性能. 研究发现, 提高ZSM-5分子筛硅铝比, 可以有效抑制混合催化剂对汽油烯烃的裂解, 从而避免了汽油烷烃的大量损失. 加入ZSM-5助催化剂后, 伴随着液化气(LPG)产率的增加, 异丁烷和异戊烷产率增加, 这可能是由USY基催化剂和ZSM-5助催化剂的综合效应引起的. 汽油烷烃和芳烃含量的变化, 引起了汽油辛烷值的增加. 高硅铝比ZSM-5分子筛(硅铝比为266和487)不仅可以显著改善汽油的辛烷值, 而且有效避免了汽油的大量损失. 催化汽油辛烷值的改善主要是由于高硅铝比ZSM-5分子筛具有适宜的芳构化和异构化活性, 这些变化主要源于高硅铝比ZSM-5分子筛小的孔道直径和适宜的酸性.

    Synthesis and characterization of Si/Ga Eni Carbon Silicates
    Giuseppe Bellussi, Angela Carati, Stefania Guidetti, Caterina Rizzo, Roberto Millini, Stefano Zanardi, Erica Montanari, Wallace O'Neil Parker Jr., Michela Bellettato
    2015, 36 (6):  813-819.  DOI: 10.1016/S1872-2067(14)60296-5
    摘要 ( 197 )   [Full Text(HTML)] () PDF(734KB) ( 607 )  

    Phenylene-gallosilicates were prepared with the same crystalline structure as their aluminum analogues. The new Ga-Eni Carbon Silicates (Ga-ECS) phases were investigated by X-ray diffraction, scanning electron microscopy, nuclear magnetic resonance and thermogravimetric analysis, which demonstrated that gallium isomorphously replaced aluminum in the framework of the organic-inorganic hybrids similar to the case of classical zeolites. Hybrid ECS materials were obtained with different types of bridged silsesquioxane precursors that maintained the aluminum-silicate nature of the inorganic moiety. This work confirms a new level of crystal chemistry versatility for this class of materials, and demonstrates the possibility to tailor also the inorganic part of the framework by changing the nature of the trivalent heteroatom.

    双功能[Sn,Al]-Beta分子筛一步催化葡萄糖生成5-羟甲基糠醛
    李良, 丁姜宏, 蒋金刚, 朱治国, 吴鹏
    2015, 36 (6):  820-828.  DOI: 10.1016/S1872-2067(14)60287-4
    摘要 ( 389 )   [Full Text(HTML)] () PDF(529KB) ( 835 )  

    以部分脱铝的Beta分子筛为母体, 采用同晶置换法将Sn植入骨架制备双功能[Sn,Al]-Beta分子筛, 并应用于葡萄糖一步催化生成5-羟甲基糠醛(5-HMF)反应中. 样品中Sn与Al的含量通过酸洗的浓度和酸洗的时间以及SnCl4处理的时间来控制. 由于骨架中有与Al相关为B酸位, 和Sn相关的L酸位, [Sn,Al]-Beta可作为一种双功能的固体酸催化剂. 优化了[Sn,Al]-Beta催化葡萄糖一步催化生成5-HMF的反应参数, 在最优Sn/Al比条件下, 葡萄糖转化率为60.0%, 5-HMF选择性为62.1%.

    Activation of Mo/HZSM-5 for methane aromatization
    Christiaan H. L. Tempelman, Xiaochun Zhu, Emiel J. M. Hensen
    2015, 36 (6):  829-837.  DOI: 10.1016/S1872-2067(14)60301-6
    摘要 ( 382 )   [Full Text(HTML)] () PDF(1022KB) ( 995 )  

    The effect of Mo/HZSM-5 pretreatment at 973 K in inert (He), oxidizing (artificial air), and carburizing (CH4/He mixture) atmospheres on its performance in non-oxidative methane dehydroaromatization (MDA) was investigated. The effect of post-synthesis silylation on deactivation of external acid sites was also studied. Precarburization resulted in increased aromatic selectivity and improved catalyst stability. The benzene selectivity was the highest for the silylated Mo/HZSM-5 catalyst (benzene + naphthalene selectivity after 1 h on stream was close to 100%). The deactivation of precarburized zeolites was less pronounced than that of zeolites heated in air or He. During heating in air or He, larger fractions of the molybdenum oxide species diffused into the micropores than during heating in methane. Carburization of the molybdenum oxide species in the micropores during MDA resulted in the formation of molybdenum carbide particles, and these contributed to pore blocking, making the Brønsted acid sites inaccessible. The formation of molybdenum carbides during heating in methane resulted in a less mobile Mo phase. It is argued that the presence of molybdenum carbide particles in the micropores contributes to rapid catalyst deactivation, in addition to the formation of hard coke on the external surface.

    由纳米晶前驱体组装有序介孔silicalite-1分子筛
    魏方方, 宋卫国, 魏芳, 曹昌燕
    2015, 36 (6):  838-844.  DOI: 10.1016/S1872-2067(14)60255-2
    摘要 ( 291 )   [Full Text(HTML)] () PDF(1431KB) ( 722 )  

    采用两步法将不同尺寸的silicalite-1分子筛纳米晶种通过自组装合成了一系列有序介孔silicalite-1分子筛. 首先将强碱性的silicalite-1前驱体分别加热不同时间得到纳米晶种, 然后在类似合成SBA-15的强酸性条件下组装成有序的介孔材料. 合成条件的剧烈变化阻止了分子筛晶种的继续长大, 并在三嵌段共聚物模板的诱导下组装成有序介孔材料. 这种"自下而上"的方法制备有序介孔分子筛同时包含微孔和介孔. 氮气吸脱附结果表明所制备的介孔分子筛材料均表现了很大的比表面积(730 m2/g以上).

    Heterogeneous oxidation of cyclohexanone catalyzed by TS-1: Combined experimental and DFT studies
    Changjiu Xia, Long Ju, Yi Zhao, Hongyi Xu, Bin Zhu, Feifei Gao, Min Lin, Zhenyu Dai, Xiaodong Zou, Xingtian Shu
    2015, 36 (6):  845-854.  DOI: 10.1016/S1872-2067(15)60859-2
    摘要 ( 239 )   [Full Text(HTML)] () PDF(809KB) ( 773 )  

    The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite TS-1 using aqueous H2O2 as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H2O2 was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H2O2 was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H2O2 catalyzed by a hollow TS-1 zeolite were ε-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite.

    离子热法合成沸石咪唑骨架材料及其溶解-结晶机理研究
    王亚松, 徐云鹏, 李大伟, 刘浩, 厉晓蕾, 陶硕, 田志坚
    2015, 36 (6):  855-865.  DOI: 10.1016/S1872-2067(14)60278-3
    摘要 ( 265 )   [Full Text(HTML)] () PDF(1284KB) ( 733 )  

    基于沸石咪唑骨架材料在离子液体和低共熔溶剂中冷却结晶的析出方式, 开发了一种离子热法合成沸石咪唑骨架材料的新途径, 采用X射线衍射、扫描电镜、核磁共振光谱、红外光谱以及热重分析等方法对制备的产物进行了表征, 研究了合成条件对产物结晶度、尺寸和形貌的影响, 探讨了沸石咪唑骨架材料在离子热合成体系中的溶解-结晶析出机理. 研究发现, 冷却速率能够影响产物形貌, 急速冷却时, sod (RCSR代码)型产物的形貌为球形, zni (RCSR代码)型产物为棒状或平板状; 程序控制冷却时, sod型产物的形貌为多面体, zni型产物呈团簇状.

    单一微孔模板剂一锅法制备多级结构ZSM-5沸石
    葛同广, 华子乐, 贺晓耘, 朱颜, 任文超, 陈立松, 张玲霞, 陈航榕, 林初城, 姚鹤良, 施剑林
    2015, 36 (6):  866-873.  DOI: 10.1016/S1872-2067(14)60263-1
    摘要 ( 537 )   [Full Text(HTML)] () PDF(1534KB) ( 906 )  

    以微孔模板剂四丙基氢氧化铵为单一模板剂, 采用一种温和的低温水热一锅法工艺, 成功制备出多级结构ZSM-5沸石(HSZs). 与传统的双模板法和后处理法相比, 这种结合了沸石生长与后刻蚀于一体的新方法, 不仅减少了模板剂的用量及二次酸/碱刻蚀、煅烧造成的环境污染, 同时也极大地简化了合成工艺. 利用XRD, N2吸附, SEM, TEM, XRF, 27Al NMR与NH3-TPD等测试手段对合成的HSZs进行了全面表征, 并提出了一种"成核/生长-刻蚀/再晶化"的形成机理. 与传统ZSM-5沸石相比, 这种具有均一梭型形貌的HSZs具有高的水热稳定性, 并在三异丙苯催化裂解的探针反应中表现出优异催化性能和较长使用寿命.

    Location and orientation of the N,N-diisopropylethylamine template molecule in the AlPO4-18 framework by X-ray synchrotron diffraction and molecular modelling
    Christiana Zenonos, Dewi W. Lewis, Gopinathan Sankar
    2015, 36 (6):  874-879.  DOI: 10.1016/S1872-2067(14)60306-5
    摘要 ( 164 )   [Full Text(HTML)] () PDF(912KB) ( 666 )  

    Phase pure AlPO4 with the AlPO4-18 (AEI) structure was synthesised using N,N- diisopropylethylamine as a template. Using a combination of X-ray powder diffraction and computational methods, the location and orientation of the N,N-diisopropylethylamine molecules inside the cages of the AEI structure were determined. Thermogravimetric analysis confirmed that the number of template molecules per unit cell was consistent with the diffraction study. We unequivocally show that only one template molecule is present in each cage of the crystalline AEI material. Our work demonstrates that a combined approach enables accurate structure resolution of such complex materials.

    Zn物种对乙烯芳构化反应过程的影响
    陈绪川, 董梅, 牛宪军, 王凯, 陈刚, 樊卫斌, 王建国, 秦张峰
    2015, 36 (6):  880-888.  DOI: 10.1016/S1872-2067(14)60289-8
    摘要 ( 314 )   [Full Text(HTML)] () PDF(1128KB) ( 977 )  

    分别采用离子交换法和物理混合法制备了不同Zn含量的ZSM-5分子筛催化剂, 采用X射线衍射、扫描电子显微镜、N2物理吸附、氨程序升温脱附、吡啶红外吸附光谱、紫外-可见光谱和X射线光电子能谱等技术研究了催化剂的结构、表面性质及Zn物种种类, 探讨了Zn物种存在状态对乙烯芳构化反应的影响. 结果表明, 引入到HZSM-5中的Zn物种包括三种状态, 即ZnO晶体、存在于分子筛孔道中的ZnO团簇以及Zn和分子筛质子酸中心通过固相反应生成的Zn(OH)+物种; 不同的制备方法显著影响Zn物种的分布. 比较了制备方法和Zn含量对ZSM-5分子筛催化剂在乙烯芳构化反应中性能的影响, 发现Zn(OH)+物种是芳构化的主要活性中心, 同时ZnO物种的存在有助于乙烯制芳烃反应的发生.

    铝离子在beta沸石晶化过程中对多形体A富集的影响
    鲁婷婷, 高攀, 徐君, 王永睿, 闫文付, 于吉红, 邓风, 慕旭宏, 徐如人
    2015, 36 (6):  889-896.  DOI: 10.1016/S1872-2067(14)60300-4
    摘要 ( 321 )   [Full Text(HTML)] () PDF(1238KB) ( 703 )  

    以四乙基氢氧化铵为有机结构导向剂, 采用超浓水热方法, 从氟离子体系合成出手性多形体A(简称A形体)富集的全硅beta沸石. 在同样的初始混合物中引入铝源后, 所合成的beta沸石中A形体含量明显降低, 产物为普通的硅铝beta沸石. 用粉末X射线衍射、元素分析、热重-差热分析、氮气吸附、扫描电子显微镜和固体魔角自旋核磁共振等表征手段对全硅beta沸石和硅铝beta沸石进行了详细的表征, 并研究了其晶化过程. 结果表明, 铝源的引入可以加速beta沸石的晶化, 得到的硅铝beta沸石晶体粒径明显减小. 在硅铝beta沸石的晶化过程中生成了五配位铝物种, 五配位铝物种可能是导致产物中A形体含量降低的原因.

    Co-ETS-10 and Co-AM-6 as active catalysts for the oxidation of styrene to styrene oxide and benzaldehyde using molecular oxygen
    Shuvo Jit Datta, Kyung Byung Yoon
    2015, 36 (6):  897-905.  DOI: 10.1016/S1872-2067(15)60864-6
    摘要 ( 244 )   [Full Text(HTML)] () PDF(980KB) ( 657 )  

    Pristine ETS-10 and AM-6 and their Co2+-exchanged forms were prepared, and their catalytic activities toward the oxidation of styrene in oxygen atmosphere were studied in dimethylformamide. The catalysts were denoted as Co-E10-n (n = 0, 9, 26, 68, 81) and Co-A6-m (m = 0, 8, 23, 63, 79), where n and m denote the degree of Co2+ exchange. The products of the oxidation process were identified as styrene epoxide (E) and benzaldehyde (B). Both the pristine forms, ETS-10 (Co-E10-0) and AM-6 (Co-A6-0), and Co2+-exchanged forms displayed catalytic activities. With increasing n or m, the conversion, and hence the rate, increased. Specifically, the rates varied from 6.1 to 12.5 mmol·g-1·h-1 with increasing n (Co-E10-n catalysts) and from 5.4 to 12.4 mmol·g-1·h-1 with increasing m (Co-A6-m catalysts). In contrast, the E/B ratio decreased with increasing n or m. More specifically, the E/B ratio decreased from 2.1 to 0.1 with increasing n from 0 to 81 (Co-E10-n catalysts) and from 1.3 to 0.1 with increasing m from 0 to 79 (Co-A6-m catalysts). Co-E10-9 displayed the highest E yield and Co-A6-79 generated the highest B yield. The highest turnover frequency obtained was 36.3 Co-1·h-1, which was the highest one obtained among those obtained for the Co2+-exchanged zeolites and mesoporous silica reference materials studied in this work.

    后处理工艺制备多级孔Ti-BEA沸石及其环氧化催化性能
    任文超, 华子乐, 葛同广, 周晓霞, 陈立松, 朱颜, 施剑林
    2015, 36 (6):  906-912.  DOI: 10.1016/S1872-2067(14)60267-9
    摘要 ( 231 )   [Full Text(HTML)] () PDF(1146KB) ( 751 )  

    基于脱铝多级孔BEA沸石与二氯二茂钛的固相反应, 开展了钛掺杂量可调的多级孔Ti-beta后处理工艺制备研究. 对制备的多级孔Ti-beta样品的理化性质进行了表征, 包括X射线衍射、氮气吸附脱附测试、扫描电镜、透射电镜、紫外可见吸收光谱和紫外拉曼光谱等. 结果表明, 多级孔BEA沸石具有较好的化学稳定性, 脱铝-钛化的后处理过程未对样品多级孔结构产生明显影响. 以环己烯和十二烯的烯烃环氧化为探针反应表征了合成多级孔Ti-beta与纯相微孔Ti-beta沸石的催化性能. 结果表明, 在小分子环己烯的环氧化反应中, 多级孔Ti-beta沸石的催化活性(转化率59.4%)与微孔Ti-beta相当(转化率57.9%); 但是在较大分子十二烯的催化反应中, 多级孔结构Ti-beta材料的催化性能(转化率11.1%)明显优于纯相微孔材料(转化率6.8%), 且产物中环氧化物选择性更高(分别为60.3%和37.8%).