Small pore VPI-5: Pore blockage due to thermally induced stacking disorders

The transformation of VPI-5 to AIPO₄-8 generates stacking disorders with the crystal which severely restricts its function as a molecular sieve. Evidence of these stacking disorders is established with adsorption measurements and high resolution transmission electron microscopy (HRTEM). Even partial transformation (less than 10% conversion) results in an 80% loss in adsorption capacity. These stacking disorders originate from the symmetry of the VPI-5 structure.     

Organic-free VPI-5: Synthesis and characterization of AlPO4-H1

The aluminophosphate H1 first reported by D'Yvoire in 1961 has been prepared in highly crystalline pure form from a reactive gel system without aging in the absence of an organic additive. Potential seeding in this system was avoided by using new crystallization vessels. Its physical and thermal properties are identical to that of VPI-5. These results indicate that VPI-5 does not represent a new microporous phase but rather H1 prepared in the presence of organic additives.     

Influence of thermal treatments on the structure and stability of gelatin gels

The influence of thermal history on the structure of gelatin gels has been investigated by measuring the specific optical rotation [α]_λ at λ = 436 nm. The helix content χ in the gels was derived by reference to the native collagen. Two types of thermal treatments have been applied: (a) cooling and heating at constant rates, and (b) quenching and annealing for long periods. Our results support the idea that the gels are non-equilibrium systems and exhibit thermal hysteresis. The kinetics of helix formation were analysed by the Avrami theory and compared to other techniques. The stability of the structures formed suggests the existence of several mechanisms of hydrogen bonding of the helices: disordered aggregation or partial collagen renaturation.     

晶化条件对HZSM-5分子筛合成收率和性能的影响

考察了SiO2-Al2O3-TPABr-NH3·H20—H2O体系晶化时间、晶化温度和原料用量等对合成HZSM-5性能的影响。当n（SiO2）：n（Al2O3）=100、n（TPABr）：n（SiO2）=0．1、n（NH3）：n（SiO2）=1．5、n（H2O）：n（SiO2）=22和晶种添加质量分数为4％时,180℃静态晶化72h,合成收率与相对结晶度分别为10．1％和99．8％,对应理论收率为11．4％,合成收率与理论收率比为0．89。当投料n（SiO2）：n（A1203）从50增加到400,合成收率与结晶度分别超过8．9％和82．8％,合成收率与理论收率比为0．76—0．89;样品酸量随着n（SiO：）：n（Al2O3）的增加逐渐减小,比表面积为405m2·g-1,合成样品HZSM-5对甲醇制烯烃反应具有良好的酸催化活性。设定反应条件,采用投料n（SiO2）：n（AlO3）=250的样品,甲醇转化率、丙烯选择性和C=2～C=4选择性分别为100％、39．27％和62．01％。     

硅源对高岭土合成ZSM-5分子筛的影响

以煤系高岭土为原料,分别以水玻璃、气相Si O_2、正硅酸四乙酯和硅酸为硅源,氢氧化钠为矿化剂,四丙基氢氧化铵为模板剂,合成了ZSM-5分子筛。随后,在氯化铵氛围下离子交换合成HZSM-5分子筛。利用XRD、SEM、FTIR、NH_3-TPD、BET对HZSM-5进行了表征。最后,利用甲醇制汽油(MTG)反应测试HZSM-5的催化性能。结果表明:以硅酸合成的HZSM-5分子筛催化效果优异,在MTG反应43 h后开始失活,高碳烃(C_(5+))类产物的选择性为41.75%。     

Time and thermal stability improvement of polyethylene ferroelectrets

Ferroelectrets with good piezoelectric coefficients have been produced based on cellular polyethylene (PE) via extrusion film blowing. The quasi-static piezoelectric coefficient (d₃₃) value obtained (935 pC/N) was well above typical values for cellular polypropylene (PP) considered as the workhorse of piezoelectric polymers. Here, a focus was made on increasing the time and thermal stability of cellular PE piezoelectric activity. To do so, specific thermal treatments were applied on the films to improve their microstructure. First, films crystallinity was increased via thermal annealing at 80 °C for 5 min leading to a 32% increase of the initial d₃₃ value as well as its time stability. However, thermal treatment did not give a significant thermal stability improvement because the treated films almost completely lost their piezoelectric activity (96%) at 80 °C. Therefore, the films were treated with orthophosphoric acid resulting in substantial charge stability improvements, especially at higher temperature. Overall, it was possible to increase the continuous service temperature (CST) of PE ferroelectrets from 40 to 80 °C, which is similar to the typical CST of PP. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47646.     

表面活性剂性能对MCM-41中孔分子筛稳定性的影响

通过对各种表面活性剂、不同环境的表面活性剂以及几种表面活性剂混合使用对提高MCM-41中孔材料水热稳定性影响的介绍，提出了表面活性剂的性能直接影响MCM-41分子筛的稳定性和特性，新的表面活性剂的开发和应用是改善MCM-41性能的重要途径之一；MCM-41无定型孔壁的晶化是解决目前中孔材料的根本措施之一；表面活性剂周边环境的调常和改性以及不同性能的表面活性剂同时利用，对提高MCM-41的水热稳定性有明显的作用。一种新的具有相当水热稳定性的中微孔材料也在文中报道。     

HZSM-5催化剂上甲醇制丙烯反应条件的研究

以HZSM-5分子筛为催化剂,在固定床反应器中考察了反应温度和原料空速对甲醇制丙烯性能的影响。结果表明,随着反应温度的升高,乙烯和丙烯选择性均增加,但温度过高容易引起催化剂的失活;而随原料空速的增大,甲醇转化率、乙烯和丙烯的选择性均呈下降趋势。最佳的反应条件为反应温度为460°C,原料液时空速为1.4 kg(Methanol)/kg(cat.).h。对添加粘结剂与未添加粘结剂成型后的催化剂性能比较,表明添加粘结剂成型后,甲醇转化率和丙烯选择性有所下降。     

晶粒尺寸对ZSM-5丙烯选择性的影响

ZSM-5分子筛由于其独特的骨架结构和酸性等特性,广泛用于石油化工领域。在催化裂化过程中,ZSM-5分子筛及其改性产品经常被加入以提高产品性能和选择性,特别是提升汽油辛烷值,增产丙烯等高附加值化工原料。通过严格控制化学合成与制备条件,制备具有相同晶体形貌、硅铝物质的量比约100和晶粒尺寸2.5μm至100 nm系列分子筛。研究分子筛的酸性、晶粒尺寸和比表面积对分子筛热稳定性、水热稳定性、活性和孔道等的影响。制成FCC助剂后,利用ACE和炼油厂原料考察FCC助剂在催化裂化反应中的性能,结果表明,硅铝物质的量比为80~100和晶粒尺寸为2.5μm的ZSM-5分子筛,可以获得最佳的丙烯选择性。     

含Co介孔分子筛的合成与稳定性研究

两步法进行含Co介孔分子筛的合成,采用XRD,FT-IR,TPR,TEM,N2吸附-脱附等方法对样品的物化性能进行表征结果表明:合成出了具有介孔结构的CoMCM-41,550℃焙烧可以将模板剂有效去除并不影响介孔结构,CoMCM-41的比表面积大于700m2/g,孔径分布在3.4～4.5 nm范围内.650℃热处理3 h或100℃水热处理5 d后CoMCM-41的比表面、孔径和孔体积变化较小,表明CoMCM-41的热稳定性和水热稳定性较好.     

ZSM-5/SAPO-34复合分子筛的制备与甲醇芳构化性能研究

采用Na OH溶液处理法制备了介孔ZSM-5分子筛。采用包埋法合成了ZSM-5/SAPO-34复合介孔分子筛,并采用X射线衍射图谱(XRD)、电子扫描电镜(SEM)、氮吸附进行分析,在固定床反应器中进行了甲醇芳构化反应。研究结果表明,ZSM-5/SAPO-34复合分子筛孔径呈微孔和介孔多级孔分布,孔径和孔容均高于ZSM-5分子筛。当ZSM-5与SAPO-34分子筛的质量比为1∶2时,ZSM-5/SAPO-34复合分子筛具有较好的芳构化活性。在反应温度为475℃、反应压力0.5 MPa、空速(LHSV)1.2 h-1条件下,BTX(苯、甲苯和二甲苯)的收率可达30.8%。     

Influence of the reaction conditions on the thermal stability of mesoporous MCM-48 silica obtained at room temperature

The thermal stability of MCM-48 silicas synthesized at room temperature under basic conditions using cetyltrimethylammonium bromide (CTAB) as template was evaluated as a function of the reaction time, CTAB/TEOS and H₂O/ethanol molar ratios and ammonium hydroxide (NH₄OH) concentration in the initial gel composition. Samples were characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption analyses, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that synthesis conditions affect the structural and thermal properties of the MCM-48 silicas. These silicas exhibited a size from 200 to 500 nm with spherical morphology.     

5A分子筛的改性制备及其对汞的吸附研究

以5A分子筛为原料,Ce(NO3)3.6H2O为改性试剂,通过一步浸渍法并结合干燥、焙烧与研磨过程,制备CeO2/5A分子筛吸附剂,研究了5A分子筛在改性前后及不同温度下对汞的吸附性能,由表征和吸附热力学分析的结果可知:改性后的5A分子筛与改性前相比,吸附能力提高将近一倍,穿透时间延长;CeO2/5A分子筛对汞的最佳去除温度是175℃,去除率为90％,吸附量是6.25 μg/g;改性后的5A分子筛孔径增大,比表面积减小,有利于对汞的吸附;TG结果表明CeO2成功的负载到5A分子筛上,使5A分子筛对汞的吸附能力增强;热力学研究发现Langmuir吸附模型的拟合结果比Freundlich模型要好;CeO2/5A分子筛对汞的吸附过程是一个多层吸附过程.     

CoAPO-5分子筛的水热合成研究

以拟薄水铝石、质量分数85%的正磷酸、四水合醋酸钴为原料,N,N-二乙基乙醇胺为模板剂,水热法合成了CoAPO-5分子筛。考察了模板剂用量、晶化温度和晶化时间对水热法合成CoAPO-5的影响以及焙烧条件对CoAPO-5分子筛性状的影响。结果表明,模板剂用量对产物纯度有较大影响,R/Al₂O₃为 1.25时,可在较宽的温度范围内（150～200 ℃）合成出CoAPO-5纯相。较高温度下晶化得到的晶体晶粒度较大,但过高的晶化温度又会导致杂质相的生成,同时晶化时间过长也将导致致密相杂质的生成,在200 ℃下晶化48 h,能得到晶粒度达24.244 nm的分子筛纯相。焙烧温度和时间决定CoAPO-5分子筛最终的物化性能,焙烧温度低于500 ℃不能有效去除模板剂,而高于600 ℃将导致分子筛骨架的破坏,Co^2+向Co^3+转化是一个逐渐转化的过程,550 ℃下焙烧10 h,能较好地去除模板剂和结合水及实现Co²⁺的转化。     

以异丙胺为结构导向剂合成ZSM-5纳米棒

以异丙胺为结构导向剂既可以合成ZSM-23分子筛,也可以合成ZSM-5分子筛。在水玻璃-硫酸铝-浓硫酸-水-异丙胺体系中,存在ZSM-23与ZSM-5两种分子筛的晶相竞争,可以通过调变体系中异丙胺和碱量实现对最终产品晶相的控制,在低硅铝比和高碱量条件下成功制备了ZSM-5分子筛。XRD、SEM及N_2吸脱附测试结果表明,所得样品为棒状纳米ZSM-5分子筛,具有高结晶度和大的外表面积。     

影响SAPO-5分子筛合成的因素研究

以三乙胺为模板剂合成了SAPO-5分子筛，并系统地研究了各种合成条件对SAPO-5分子筛合成的影响。结果表明，晶化液原料配比、硅铝比、模板剂用量、加料顺序及水含量对SAPO-5分子筛的结晶度和稳定性都有重要影响，n（SiO2）／n（Al203）=1．5和／n（H2O）／n（Al2O3）=40为SAPO-5合成的适宜条件，此时晶化产物的结晶度高，稳定性好。     

杂质对DTBP热稳定性影响的研究

为研究杂质对二叔丁基过氧化物(DTBP)热稳定性的影响,利用C600微量热仪对DTBP与杂质的混合物进行热分解动力学试验研究,测定了纯DTBP在不同升温速率下及其与杂质的混合物在0.5K·min-1升温速率下的起始放热温度和分解热,并计算得到DTBP热分解反应的动力学参数。依据Arrhenius定律和化学反应理论确定了其与水、混合酸、NaOH、NaCl、铁和橡胶等杂质混合后活化能以及指前因子,研究表明,水、混合酸、NaOH、NaCl的加入使DTBP的活化能有增加的趋势,而铁和橡胶则在一定程度上降低了活化能,结合自加速分解温度(SADT)值进一步证明,水、混合酸、NaOH、NaCl对DTBP的稳定性没有影响,铁和橡胶对DTBP热稳定性影响最大。     

Hydrothermal Post-synthesis of HZSM-5 Zeolite to Enhance the Coke-resistance of Mo/HZSM-5 Catalyst for Methane Dehydroaromatization

Hydrothermal post-synthesis was used to modify the micropores and acidity of commercially available HZSM-5 zeolites. The recrystallization and the dynamic incorporation and extraction of the framework Al not only stabilized the framework with high crystallinity, but also inhibited the creation of extra-pores during the post-synthesis in NaOH aqueous solution. The resulted Mo/HZSM-5 catalyst showed rather high catalytic stability and greatly enhanced selectivity towards aromatics for methane dehydroaromatization reaction by effectively inhibiting the coke formation.     

Breakthrough Analysis for Adsorption of Phosphine on 5A Molecular Sieve

Adsorption experiments were carried out under dynamic conditions for the removal of phosphine (PH₃) in nitrogen on a fixed bed of 5A molecular sieve. The experiments were conducted to characterize the breakthrough characteristics of PH₃ in the fixed bed under different operating conditions, including bed temperature, bed mass, and initial PH₃ concentration. A mathematical model was developed to predict the breakthrough profiles of PH₃ during adsorption on the 5A molecular sieve. The model was successfully validated with the observed experimental breakthrough data, showing that the adsorption capacity increases with decreasing temperature and with rising phosphine concentration in the gas mixture. The study showed the potential application of 5A molecular sieve in controlling PH₃ emission.     

粘结助剂对ZSM-5甲醇制烯烃催化活性的影响

采用机械混合法在H-ZSM-5分子筛中添加不同氧化物粘结剂,考察其对甲醇制烯烃(MTO)催化反应性能的影响,并采用x射线衍射(XRD)、氨气-程序升温脱附(NH3-TPD)实验、傅立叶红外光谱(FT-IR)和热重(TG)分析表征催化剂结构.结果表明:在H-ZSM-5中分别添加不同的氧化物粘结剂SiO2,γ-Al2O3和Kaolin(H-ZSM-5和氧化物质量比2∶1),在催化剂1 g,CH3OH与N2物质的量之比1∶4,催化剂质量与原料流速之比(W/F)为10(g·h)/mol,反应压力0.1 MPa和反应温度723 K的条件下,反应3 h,甲醇转化率为100%;与H-ZSM-5相比,烯烃产物分布发生了变化,添加SiO2使C3=选择性下降,添加γ-Al2O3使C1选择性增加,添加Kaolin使C3=选择性增加,同时添加Kaolin与SiO2(Kaolin和siO2质量比2∶1)的H-ZsM-5具有最高的C2=～C4=选择性,其中C3=选择性为38%.添加氧化物降低了催化剂的总酸量,反应11 h前后催化剂的物相没有发生明显变化,积炭不明显.