Brönsted方程动力学模型研究ZSM-5催化乙烯齐聚及芳构化活性和酸强度分布之间的定量关系

乙烯催化齐聚和芳构化是烯烃高值化和合成液体燃料的关键过程，采用NH₃-TPD谱图分析计算方法得到的探针分子脱附活化能作为催化剂的酸位点强度分布的参数，结合线性自由能理论在Br?nsted方程中引入酸强度对反应的影响因子γ作为动力学方程参数关联探针分子脱附活化能与反应活化能，明确固体酸酸强度的基准在催化动力学方程中的物理意义。建立同为MFI拓扑结构 Si /Al摩尔比为12.5、19、25、60、70的ZSM-5分子筛催化剂上不同酸强度位和乙烯齐聚及芳构化中氢转移、齐聚、芳构化各单元步骤以及对应的烷烃、低碳烯烃和芳烃产物分布的定量关系。根据拟合得到动力学参数γ可以发现不同强度的酸位点对乙烯齐聚及芳构化具有不同的作用系数。氨脱附活化能(DAE)为90 kJ·mol^-1的酸位点是氢转移反应的主要活性位点，而对于乙烯齐聚反应中主要的活性酸位点为DAE 90 kJ·mol^-1和124 kJ·mol^-1，DAE为150 kJ·mol^-1的酸位点是芳构化反应的主要活性位点。     

Synthesis and characterization of MCM-41-supported nano zirconia catalysts

Series of MCM-41 supported sulfated Zirconia (SZ) catalysts with different loadings (2.5–7.5% wt.) were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.     

Mineralization of Para-Chlorobenzoic Acid in Water by Cobalt-Incorporated MCM-41 Catalyzed Ozonation

Cobalt-incorporated MCM-41(Co-MCM-41) was used as a heterogeneous catalyst for the ozonation of para-chlorobenzoic acid (p-CBA) in aqueous solution. Cobalt oxide supported on MCM-41(Co/MCM-41) was synthesized for comparison. Their textural properties were elucidated by various characterization techniques to understand the relationship between surface texture and catalytic activity. TOC removal at 60 min reached 91% with Co-MCM-41, 83% with Co/MCM-41 and only 52% with ozone alone, respectively. Observations from diffuse reflection spectroscopy demonstrated that different metal phases were formed in these cobalt-modified molecular sieves samples. Radical scavenger experiments indicated the formation of hydroxyl radicals that were responsible for the effective degradation of p-CBA. An integrated approach to the catalytic mechanism was proposed by considering the variation of pH in the course of ozonation as well as its subsequent influence on the dissociation of targeted compounds and surface charge of the catalyst. In the reusability experiments, the reused Co-MCM-41 was able to regain the same catalytic capability as the fresh one within 5 cycles. X-ray photoelectron spectroscopy results indicated that a part of Co²⁺ was oxidized to Co³⁺ after oxidation reaction.     

Novel core-shell-like Ni-supported hierarchical beta zeolite catalysts on bioethanol steam reforming

Hierarchical-Beta zeolites have been hydrothermally synthesized by adding a new gemini organic surfactant. The used gemini surfactant play the role of a “pore-forming agents” on the mesoscale, on the same time, providing alkaline environment for the system. With this hierarchical Beta zeolite as the core support, we successfully prepared a shell layer of Ni-containing (22 wt%) petal-like core-shell-like catalyst and applied it to bioethanol steam reforming. At the reaction temperature of 350 °C–550 °C, the conversion rate of ethanol and the selectivity of hydrogen were always above 85% and 70%. After reaction of 100 h on stream at 400 °C, there were not obvious inactivation could be observed on NiNPs/OH-MBeta catalyst.     

ZSM-5沸石膜用于生物油的脱水分离及其再生过程研究

在水热条件下通过无模板剂法合成了连续的ZSM-5沸石膜，并将其用于生物油的渗透汽化以进行高效脱水分离。ZSM-5沸石膜在强酸性、多组分的生物油体系中保持了很好的化学稳定性和优异的分离选择性，但在分离过程中面临着较强的膜污染问题，导致了膜通量的大幅下降。ZSM-5沸石膜的再生研究表明，膜的渗透通量随着再生温度的升高而逐渐提高。当再生温度为220℃时，ZSM-5沸石膜的渗透通量可以恢复至初始的88%。再生的机理研究表明，ZSM-5沸石膜中大量的晶内孔在生物油体系中极易被污染，从而导致渗透通量迅速下降；而相对较大的晶间孔却难以被完全堵塞，水分子在被污染的ZSM-5沸石膜中主要通过晶间孔进行渗透。上述结果表明，通过合理调控ZSM-5沸石膜的晶间孔的数量和尺寸大小可有效提升ZSM-5沸石膜在生物油中的渗透汽化脱水分离性能。     

Ru/MCM-41催化剂上苯的液相加氢反应

 以Si-MCM-41、Al-MCM-41(1) (n(Si)/n(Al)=15)、Al-MCM-41(2) (n(Si)/n(Al)=10)以及用NH4NO3或HAc的醇溶液分别与Si-MCM-41离子交换所得的H-MCM-41(N)和H-MCM-41(H)为载体制备了系列Ru/MCM-41催化剂。采用N2吸附、XRD和H2-TPR表征了负载Ru前后催化剂的结构及Ru在各种载体表面上的分散状态。以0.5%（质量分数）苯的环己烷溶液为模型化合物，在298K、3.0MPa反应条件下，考察了上述催化剂的苯液相加氢反应性能，并与Ru/HY、Ru/H和Pt/MCM-41催化剂进行了比较。结果表明，载体MCM-41的n(Si)/n(Al)和表面化学组成等性质对Ru在其表面上的分散状态、还原性及催化性能均有影响。对苯的转化率与反应时间的关系曲线进行拟合，发现其遵循一级动力学方程，加氢反应速率常数按照Ru/Al-MCM-41(2)相似文献   

Na+、K+离子交换对Co-Mo/MCM-41加氢脱硫催化剂的影响

 用偏硅酸钠和正硅酸乙酯作硅源制备了MCM-41（分别记作MCM-41(S)和MCM-41(T)）分子筛，并用Na₂C₂O₄和K₂C₂O₄对MCM-41(S)进行了碱金属离子交换改性。以质量分数0.8 %的二苯并噻吩（DBT）的十氢萘溶液为模型化合物，考察了不同MCM-41担载的Co-Mo硫化物催化剂对DBT的加氢脱硫反应性能。结果表明，MCM-41担载的Co-Mo催化剂加氢活性较低，DBT主要通过直接脱硫反应路径脱硫。其活性顺序为：Co-Mo/MCM-41(T)>Co-Mo/MCM-41(S)>Co-Mo/MCM-41(K)>Co-Mo/MCM-41(Na)。UV-Vis结果表明，部分Co与MCM-41(S)中少量Al发生相互作用，生成了CoAl₂O₄，是造成Co-Mo/MCM-41(S)活性降低的重要因素。而在Co-Mo/MCM-41(K)和Co-Mo/MCM-41(Na)中，除CoAl₂O₄物种之外，碱金属的引入还促进了Co₃O₄物种的形成，使其活性进一步降低。     

Cd-ZSM-5沸石催化剂的制备、表征和芳构化催化性能

采用离子交换、浸渍和混合三种方法制备镉改性ZSM-5沸石催化剂,考察了改性方法和镉含量对催化剂的表面酸性和Cd状态以及芳构化性能的影响。结果表明,加入镉降低了B酸性,Cd~(2+)与沸石结合形成了L_(1612)酸中心,其生成量取决于改性方法和Cd含量,并与芳构化活性提高有直接关系。