ZSM-5 改性与碱处理报告人：邱园指导教师：刘国柱 2012-06-09

课题组学术报告之一 ZSM-5改性与碱处理报告人：邱园指导教师：刘国柱 2012-06-09

ZSM-5 四面体 MFI 交叉孔道 Al不能直接和Al相连

形貌

结构和酸性质 红外表现硅的存在形式 B酸：Si-(OH)-Al Al-OH L酸：非骨架Al或者平衡电荷的金属阳离子测试手段：红外吡啶 NH3-TPD B酸高温脱羟基可形成L酸，三配体Al不可转化成B酸核磁可以看出Al和Si的存在形式和红外共同研究可以确定分子筛结构

为什么要改性？WHY Pérez-Ramírez, J et al. 2008 Chem. Soc. Rev.37(11): 2530. Johan Groen Delft University of Technology 2007

怎么改性？HOW

孔的形成 微孔：水热合成和直接合成围绕单个模板剂介孔：围绕有机模板剂聚集成的胶束生长 MCM (Mobil Composition of Matters)系列 MCM-41：六方介孔管道 MCM-48：三维联通 MCM-50：复合材料层之间由高分子等连接 ITQ-2：对层状前驱体MCM-22（p）插层膨胀，超声剥离得到 ITQ-21 ITQ-15

Johan Groen Delft University of Technology 2007

Čejka, J. and S. Mintova (2007). Catalysis Reviews49(4): 457-509.

分子筛Al含量多时可进行脱铝，易形成空穴，易造成酸性下降分子筛Al含量多时可进行脱铝，易形成空穴，易造成酸性下降使铝进入骨架的的方法： 1、碱溶液处理脱铝的分子筛使硅重新进入骨架 2、高硅铝比的分子筛暴露在AlCl3或AlBr3蒸汽中等 Johan Groen Delft University of Technology 2007

碱处理 优点：孔道酸性加强离子交换能力等影响因素 Si/Al 温度处理时间碱种类阳离子搅拌碱溶液浓度配比放大效应。。。。 Verboekend, D. and J. Perez-Ramirez (2011). Catalysis Science & Technology1(6): 879-890.

与核磁相比？ Holm, M. S., S. Svelle, et al. (2009). Applied Catalysis A: General356(1): 23-30. Johan Groen Delft University of Technology 2007

BET Tensile Strength Effect (TSE) p/p0 = 0.45 突降对MCM-41进行研究 Johan Groen Delft University of Technology 2007

BET Adsorbate phase trasitions in MFI zeolites Johan Groen Delft University of Technology 2007

BET monolayer ormation Johan Groen Delft University of Technology 2007

介孔比表面积可达到约250m2/g 孔径：约10nm 只能在硅铝比为25-50时有明显介孔 0.2 M NaOH at 338 K for 30min 优化 Johan Groen Delft University of Technology 2007

实验 A flaskmade of polyethylene was used to treat ZSM-5. First, 300 mLof the NaOH solution in the flask was heated to 353 K with areflux condenser in a water bath, and then 10 g of as-receivedzeolite was added there while stirring. After 300 min, the slurrywas cooled down immediately in an ice bath and filtered. Thefiltered cake was dried in an air oven at 383 K overnight. Afterdrying, alkali-treated ZSM-5 was rinsed with distilled water at 353 K for 2 h to eliminate silicate materials which could be precipitated during the alkali treatment.

Versatile Controllable Scalable

硅铝比的影响 铝碎片对其影响 Pérez-Ramírez, J., C. H. Christensen, et al. (2008). " Chem. Soc. Rev.37(11): 2530-2542.

铝分布的影响 Pérez-Ramírez, J., C. H. Christensen, et al. (2008). Chem. Soc. Rev.37(11): 2530-2542.

机理 PH高时溶解，PH低时铝沉积 situ pH and ATR-IR measurements Johan Groen Delft University of Technology 2007

引入PDA，增强可控性

PDA pore-directing agent 干浸渍 Perez-Ramirez, J., D. Verboekend, et al. (2009). Advanced Functional Materials19(24): 3972-3979.

PDA pore-directing agent 通过对silicate-1研究效果和正常碱处理差不多 Al(OH)-部分进入骨架增强酸性 Perez-Ramirez et al (2011). Chemistry-A European Journal 17(4): 1137-1147.

除了PDAs的浓度、位置、和分子筛的亲和作用也很重要除了PDAs的浓度、位置、和分子筛的亲和作用也很重要 Perez-Ramirez et al (2011). Chemistry-A European Journal 17(4): 1137-1147.

加入PDAs的好处： 1、保护微孔，酸性 2、加入量不同量形成的孔径不同增强了可控性 J. Perez-Ramirez et al (2011). Chemistry-A European Journal17(4): 1137-1147.

Verboekend, D., A. M. Chabaneix, et al. (2011). CrystEngComm13(10): 3408-3416.

用酸洗去沉积Al 提高结晶度、孔道、酸性使硅铝比可用范围达到10-1000 Perez-Ramirez,et al (2011). Catalysis Science & Technology1(6): 879-890.

Descriptors HF=( Vmicro/Vpore) * (Smeso/SBET) Hierarchy Factor 修正后 IHF = ((Vmicro/Vmaxmicro) *(Smeso/Smaxmeso)). Indexed Hierarchy Factor Desilication Efficiency=slope (dSmeso/d(weight loss) ) ACI Accessibility index Determined by relating the amount of acid sites probed by alkylpyridines of different sizes to the total amount of acid sites in the zeolite. pyridine (0.57 nm) lutidine (0.67 nm) collidine (0.74 nm) micro-pore (0.56 nm)

性能表征 1、反应性能测试 2、扩散性能测试 TEOM DRIFTS

HF：孔道的影响 L/B酸：酸性质 Zheng, J., Q. Zeng, et al. (2011). " Catalysis Today168(1): 124-132.

ZSM-5 改性与碱处理报告人：邱园指导教师：刘国柱 2012-06-09