Preparation of magnetic zeolite/chitosan composite using silane as modifier for adsorption of Cr(VI) from aqueous solutions

This study aimed to prepare an efficient, cost-effective, and separable magnetic zeolite/chitosan composite (MZFA/CS) adsorbent from solid waste to deal with the water pollution of Cr(VI). The MZFA/CS was characterized by X-ray fluorescence (XRF), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and vibrating sample magnetometer (VSM) techniques. Then, the effect of pH, temperature, initial concentration of Cr(VI) ions, and contact time was considered in the study. For a sorbent dose of 0.1 g in 50 mL of a Cr(VI) solution, at a contact time of 30 min, temperature of 30°C, and a pH of 3, an adsorption capacity (q_e) of 16.96 mg g⁻¹ was achieved. Adsorption kinetics and isotherm data obtained for all adsorption systems were well-fitted by pseudo-second-order and Langmuir models, respectively. The thermodynamic study suggested that the adsorption process is spontaneous and endothermic in nature. In summary, the adsorbent with better separability (Ms = 16.83 emu g⁻¹) and adsorbability was successfully fabricated.     

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。     

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.     

SBA-15固载磷钨酸催化剂的制备及催化合成叔丁基苯酚

以不同硅烷偶联剂改性的介孔分子筛SBA-15为载体、PW_(12)为催化剂,通过对SBA-15表面共价及非共价修饰制备磷钨酸@介孔分子筛/硅烷偶联剂复合催化剂PW_(12)@SBA-15/YSiX_3(YSiX_3=Apts、Atapts、Papts);并利用FT-IR、XRD、TEM、N_2吸附-脱附对其组成、结构及形貌进行表征。以改性SBA-15分子筛固载磷钨酸催化剂催化合成叔丁基苯酚为研究对象,考察不同硅烷偶联剂、反应温度、苯酚与叔丁醇物质的量比对催化合成叔丁基苯酚的影响,并获得合成叔丁基苯酚的最佳工艺条件,即反应温度145℃、n(苯酚)∶n(叔丁醇)=1∶2.5、重时空速2.2 h~(-1),该最佳反应条件下,PW_(12)@SBA-15/Apts催化剂催化合成叔丁基苯酚的催化活性最高,苯酚转化率为98.3%,2,4-二叔丁基苯酚选择性为57.3%.     

Enhanced compactness of oriented MFI zeolite films by heat treatment of seed layer

The achievement of compact and defect-free film structure is crucial for the application of b-oriented MFI zeolite film. In this work, a novel heat treatment technique was used to treat zeolite seeded substrates prior to secondary growth. The influence of the heat treatment parameters such as treat temperature and time on the final film morphology were systematically investigated. The relationship between film compactness and the parameters was established. Under the optimized treat temperature of 120?°C and treat time of 1?h, compact and uniform b-oriented MFI zeolite film was achieved. The applicability of the optimum heat treatment condition was validated by employing various film substrates.     

Structure,stability and permeation properties of NaA zeolite membranes for H2O/H2 and CH3OH/H2 separations

NaA zeolite membranes were synthesised in the secondary growth hydrothermal method based on the seeding of the inner surface of a ceramic α-alumina tube. The impacts of crystallisation time and zeolite precursor concentration (in H₂O) were investigated. The structure and stability of the prepared NaA zeolite membranes were also investigated with operating temperatures, times and pressures. The results indicate that the optimal synthesis gel molar composition was 3Na₂O: 2SiO₂: Al₂O₃: 200H₂O. This led to cubic-shaped NaA zeolite which showed good stability. The optimal NaA zeolite membrane had H₂O and CH₃OH fluxes of 2.77 and 0.19 kg/m²h, with H₂O/H₂ and CH₃OH/H₂ separation factors of ∞ and 0.09 at a temperature of 30 °C. The NaA zeolite membrane had high thermal stability, but poor separation performance at high temperature (240 °C). The results suggested that the H₂ permeation flux is significantly influenced by preferential adsorption of vapour in the NaA zeolite membrane.     

多级孔HZSM-5分子筛催化快速热解生物质制芳烃

采用酸和/或碱处理法制备了一系列多级孔HZSM-5分子筛，采用XRD、N₂吸附、XRF、TEM、²⁷Al MAS NMR和NH₃-TPD等表征手段对其孔道结构和酸性进行表征。表征结果表明，采用碱处理方法，可获得孔径集中于3~6 nm的介孔结构，通过改变酸、碱处理次序，可调变酸中心数量和强酸/总酸中心比例。在Py-GC/MS装置上，以纤维素和水稻秸秆为原料，研究多级孔分子筛结构对催化快速热解（CFP）制芳烃反应的影响。反应评价结果表明，同商品级HZSM-5相比，采用先碱后酸处理获得的多级孔HZSM-5分子筛（HZ-OH/H），可将纤维素CFP芳烃碳产率由32.3%提高至43.6%，可将水稻秸秆CFP芳烃碳产率由23.0%提高至30.8%。多级孔HZ-OH/H分子筛的孔道结构和酸中心分布特征，对开发应用于生物质制芳烃的高效工业催化剂具有借鉴意义。     

不同催化剂催化裂化愈创木酚的性能

以分子筛为活性组分、高岭土为载体制备HZSM-5/K,HZSM-5/MK,HY/K,5A/K 4种催化剂,采用FTIR技术对催化剂的表面酸性进行表征。以愈创木酚为模型化合物,在480~560℃、WHSV=3~6 h-1条件下的固定床反应器中考察4种催化剂的催化裂化性能。实验结果表明,催化剂表面酸量大小的顺序为:HY/KHZSM-5/K≈HZSM-5/MK5A/K;愈创木酚裂化过程中主要生成苯酚、甲基苯酚、乙基苯酚等单环芳烃和多环芳烃,在540℃、WHSV=4 h-1条件下单环芳烃产率较高,焦炭产率较低;HZSM-5/MK,HZSM-5/K,HY/K,5A/K 4种催化剂作用下得到的单环芳烃产率依次为57.14%,51.65%,36.74%,30.00%,焦炭产率大小的顺序为:5A/KHY/KHZSM-5/K≈HZSM-5/M K。     

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。     

分子筛协同有机磷酸盐改性聚丙烯性能的研究

采用直接混合法制得等规聚丙烯(iPP)/分子筛体系和iPP/有机磷酸盐成核剂(NA11)/分子筛体系,研究不同种类分子筛在不同含量下对iPP结晶温度及力学性能的影响,进而研究不同分子筛在低含量下协同有机磷酸盐对iPP体系成核性能的影响,从动力学角度解释了提升原因。结果表明,单独添加分子筛制得的iPP体系,随着分子筛含量的增加,结晶性能和力学性能得到显著提升,不同分子筛对iPP性能的影响不同,ZSM-5型分子筛在含量为5%(质量分数,下同)以上具有促进iPPβ晶型生成的效果;采用直接混合法制得的不同分子筛复配有机磷酸酯钠盐NA11成核剂可提升iPP的力学性能;特别是当0.1%NA11和0.1%4A型分子筛一起添加到iPP中时,可在保证iPP具有较好刚性的同时兼具有良好的韧性,使iPP的弯曲模量提高35.2%、冲击强度提高14.4%,从而达到促进iPP材料刚韧平衡的效果。