高岭土原位合成高硅铝比小晶粒NaY分子筛

以不同温度焙烧的苏州高岭土为原料,采用原位晶化法合成高硅铝比小晶粒NaY分子筛,考察晶种胶添加量、陈化温度、晶化温度和m(高土)∶m(偏土)对晶化过程和产物性质的影响。结果表明,m(高土)∶m(偏土)=1时,在晶种胶添加质量分数15%、陈化温度90℃和晶化温度100℃条件下,以普通高岭土为原料原位合成NaY样品的相对结晶度约为80%,骨架硅铝比(SiO2与Al2O3物质的量比)为6.4,平均粒径约500nm。调整原料中m(高土)∶m(偏土)可以控制原位晶化样品中的分子筛含量。以细化高岭土为原料合成的NaY分子筛(平均约445nm)粒径小于普通高岭土合成的样品。骨架硅铝比高于6.0的原位晶化样品的骨架坍塌温度高于950℃,具有很高的结构稳定性。     

改性Hβ沸石的物化性能表征

用相同物质的量浓度的硝酸铵、柠檬酸以及柠檬酸铵溶液对Naβ沸石进行改性处理得到Hβ沸石;采用XRD、XRF、FT-IR、27Al MAS NMR和29Si MAS NMR等表征手段进行分析.结果表明,采用含羟基的柠檬酸或柠檬酸铵对Naβ沸石进行改性处理,不但可以提高样品结晶度还可以有效限制骨架铝的脱除;经柠檬酸或柠檬酸铵改性可以使Naβ中的Al(S4R,SiteA)转化成Al(S6R,SiteB),而硝酸铵改性的Naβ沸石中只发现一种骨架四面体;还发现硝酸铵和柠檬酸铵改性Naβ沸石后,少量的骨架铝转化为非骨架铝并存在于孔道内,而经过柠檬酸改性后,这部分非骨架铝被带出孔道.     

后处理法制备多级孔Y型分子筛及其加氢裂化性能研究

以柠檬酸和乙二酸四乙酸二钠(EDTA-2Na)为复合改性剂,通过后处理法制备出具有多级孔结构的Y分子筛。在保证分子筛结晶度的同时,柠檬酸和EDTA-2Na可有效脱除骨架铝和六配位非骨架铝物种。改性后Y分子筛的骨架硅铝摩尔比[n(SiO₂)/n(Al2O₃)]提高1倍,结晶度仅降低1. 3%;分子筛的比表面积得到有效提高,介孔含量明显增加,并且连通性更好。以其作为酸性组分制备的加氢裂化催化剂,馏分油总收率比商业USY分子筛提高6. 5%。     

有机酸改性对USY分子筛晶体结构的影响

采用有机酸作为脱铝改性剂,对工业水热超稳Y型分子筛USY进行了化学改性.考察了酸的加入量、反应温度和反应时间对分子筛晶体结构的影响.结果表明,该有机酸可以起到脱除USY非骨架铝的作用,改性后分子筛的结晶度明显提升.     

柠檬酸复合改性对多环芳烃选择性开环铂/Beta催化剂性能的影响

通过水热处理、柠檬酸处理及其复合处理对Beta分子筛进行后改性,并以改性后的载体制得铂/Beta催化剂。采用X射线衍射（XRD）、X射线荧光光谱仪（XRF）、程序升温脱附（NH₃-TPD）、红外吡啶吸附（Py-IR）、骨架铝核磁共振技术（²⁷Al MAS NMR）及骨架硅核磁共振技术（²⁹Si MAS NMR）等表征了改性前后Beta分子筛的物化性质,并考察了改性前后铂/Beta的多环芳烃选择性开环性能。结果表明,Beta分子筛在柠檬酸处理过程中可同时发生络合脱铝与骨架补铝,实现骨架铝的再分布;Beta分子筛在水热处理过程中优先脱除稳定性相对较低的Si（2 Al）处骨架铝,产生骨架缺陷的同时生成一定比例的二次介孔结构;水热-柠檬酸复合处理影响Beta分子筛骨架补铝及骨架铝再分布的效果,水热处理后Beta分子筛中存在更多的骨架缺陷,促进活性Al（OH）₂⁺物种的骨架补铝作用。当Beta分子筛采用水热-柠檬酸复合处理顺序时,骨架补铝及骨架铝再分布效果显著,样品以中强酸为主,且具有较高的B酸量与L酸量的比值,所制备催化剂的多环芳烃选择性开环活性及稳定性最优。     

改性Hβ沸石的物化性能表征

用相同摩尔浓度的硝酸铵,柠檬酸以及柠檬酸铵溶液对Naβ沸石进行改性处理得到Hβ沸石;采用XRD、XRF 、FT-IR、27Al MAS NMR和29Si MAS NMR等表征手段进行分析.结果表明,采用含羟基的柠檬酸或柠檬酸铵对Naβ沸石进行改性处理,不但可以提高样品结晶度还可以有效限制骨架铝的脱除;经柠檬酸或柠檬酸铵改性可以使Naβ中的Al(S4R,SiteA)转化成Al(S6R,SiteB),而硝酸铵改性的Naβ沸石中只发现一种骨架四面体;还发现硝酸铵和柠檬酸铵改性Naβ沸石后,少量的骨架铝转化为非骨架铝并存在于孔道内,而经过柠檬酸改性后,这部分非骨架铝被带出孔道.     

USY分子筛表面酸性的调变及其在催化脱除芳烃中烯烃的应用

详细论述了柠檬酸对USY分子筛的改性作用,以脱除高溴指数芳烃中烯烃的反应为例对其催化活性进行了评价。实验结果表明:0.2mol/L柠檬酸溶液酸性适宜,对分子筛的骨架铝以及非骨架铝进行了有效的脱除,脱除的铝在分子筛中以无定形的非骨架铝形式存在。柠檬酸改性过程可使分子筛的介孔面积以及介孔孔容增大,这十分有利于减缓分子筛的失活速率。柠檬酸改性过程使分子筛表面的强B酸减少,强L酸增多,这有助于减缓分子筛上积炭的生成速率。经过柠檬酸改性的USY分子筛对脱除芳烃中微量烯烃的催化效果明显高于目前工业中在用的普通白土和改性白土。再生实验说明,经3次焙烧再生后,改性分子筛的活性依然在90%以上,具有很好的可再生性。     

Y型分子筛结晶度和晶胞常数随温度变化规律

选取1种NaY分子筛和3种Si Cl4气相超稳法制得的DY分子筛作为研究对象,通过X荧光光谱(XRF)、N2吸附-脱附、热重(TG-DSC)和场发射扫描电镜(SEM),考察4种Y型分子筛物化性质的差异,利用原位升温粉末X射线衍射(in-situ XRD)考察相对结晶度(室温升至1 000℃)和晶胞常数(室温升至600℃)随温度变化的规律。结果表明,升温过程中4种Y型分子筛相对结晶度均表现为先升后降,NaY型分子筛在900℃时晶体结构完全消失,硅铝比较高的DY分子筛在1 000℃时,相对结晶度仅15%~35%;随着温度升高,NaY分子筛晶胞常数先减后增,而DY-1和DY-2分子筛晶胞常数先增后减,DY-3分子筛晶胞常数一直减少。(555)晶面衍射峰的偏移也随温度和骨架硅铝比变化呈规律性改变。     

以低温固相碱熔活化高岭土为原料合成ZSM-5分子筛

以天然矿物高岭土为主要硅铝原料,经低温固相碱熔活化后,在常规水热条件下合成ZSM-5分子筛,考察m(高岭土)∶m(氢氧化钠)、碱熔温度及碱熔时间等因素对高岭土活化效果的影响。采用XRF、XRD、FT-IR和N2-吸脱附等对不同样品进行表征。结果表明,在m(高岭土)∶m(氢氧化钠)=1∶1.5、碱熔温度250℃和碱熔时间30 min条件下,可以实现高岭土完全活化。该活化方式不仅降低了活化温度,且能在极短时间内提高高岭土活性。以最适宜低温固相碱熔活化条件下所得活性硅铝物质为主要原料,硅溶胶为外加硅源,采用水热法合成高相对结晶度的纯相ZSM-5分子筛。与工业ZSM-5分子筛相比,合成ZSM-5分子筛具有更大的比表面积和孔容。     

高硅铝比B-NaY分子筛合成及催化二乙苯烷基转移性能

为了得到性能良好的B-NaY分子筛,采用直接水热合成法合成杂原子B-NaY分子筛,研究了未处理硅源以及分别用草酸、硫酸、硫酸铝预处理硅源方法所合成B-NaY分子筛物化性能。结果表明,当采用草酸对硅源进行预处理时,可以得到相对结晶度为97%,骨架硅铝比为6.3的高硅B-NaY分子筛,且晶化速率较快。采用草酸对硅源进行预处理,不仅可以增大硅源中硅酸根离子的聚合度,而且在晶化过程中草酸作为一种络合剂能通过与OH-一起和Al3+配位形成四配位活性铝物种,促进凝胶溶解,使得溶液中活性铝物种含量增加,有利于加速晶化。考察了所合成分子筛在二乙苯与苯烷基转移制备乙苯的反应中的催化性能,在反应温度175℃、反应压力3 MPa、苯与二乙苯质量比2、质量空速为3.3 h-1条件下,二乙苯转化率达50%以上,乙苯选择性达99.3%。草酸预处理硅源合成B-NaY分子筛的方法操作简单、快捷,所合成B-NaY分子筛性能优异,有良好的工业应用前景。     

L型沸石的离子交换与脱铝改性研究

为了改善L型沸石的催化性能,优化其在FCC中的应用,对L沸石进行离子交换和脱铝的改性研究。考察离子交换时间和离子交换方式对降低L沸石中氧化钾含量的影响及水热焙烧和化学脱铝对提高L沸石硅铝物质的量比的影响。结果表明,L型沸石离子交换时间不易过长,较适宜的时间为3 h。离子交换和水蒸汽处理相结合对降低L型沸石的钾含量更有效,离子交换和水蒸汽处理交替进行3次的样品氧化钾质量分数可降至0.82%。水热焙烧和化学脱铝能使L型沸石显著脱铝,其中,经过700 ℃水蒸汽处理1 h,再进行盐酸处理而制得改性L型沸石样品的硅铝物质的量比可达21.91,相对结晶度高于80％。     

假白榴正长岩提钾滤渣硅铝分离的研究

假白榴正长岩提钾滤渣中的主要物相为沸石Na6[AlSiO4]6.4H2O,富含氧化铝和氧化硅。采用高压水化学法,按CaO/SiO2=1.0(摩尔比)加入Ca(OH)2进行碱热浸取可实现滤渣中的硅铝分离。实验得出的优化条件为:反应温度280℃,反应时间30 min,碱的加入量为每处理100 g提钾滤渣需NaOH200 g。氧化铝的溶出率大于88%,碱浸滤液为高苛性比铝酸钠溶液,可用于制取氢氧化铝和氧化铝产品。该工艺在综合利用非水溶性钾矿的同时,为铝业生产提供了新资源。     

H-MCM-22 zeolitic catalysts modified by chemical liquid deposition for shape-selective disproportionation of toluene

Catalysts were prepared by dealumination of H-MCM-22 zeolite with oxalic acid leaching, followed by shaping and liquid phase modification with siloxane. The catalytic performance was measured with selective disproportionation of toluene in a fixed-bed reactor. The unmodified H-MCM-22 zeolite exhibited much higher initial activity than H-ZSM-5 with a thermodynamic equilibrium distribution of xylene products. The oxalic acid treatment of H-MCM-22 improved the selectivity for para-xylene by 10–18%. The modification by siloxane of the oxalic acid treated H-MCM-22 turned out to be highly selective for para-xylene, however, with the expense of the conversion. It is proposed that the high para-selectivity was closely associated with the contraction of micropore windows and the elimination of acid sites at the external surface by the deposited silica. Therefore, the modified H-MCM-22 is a potential catalyst for the selective disproportionation of toluene with a high para-selectivity.     

H-MCM-22 zeolitic catalysts modified by chemical liquid deposition for shape-selective disproportionation of toluene

Catalysts were prepared by dealumination of H-MCM-22 zeolite with oxalic acid leaching, followed by shaping and liquid phase modification with siloxane. The catalytic performance was measured with selective disproportionation of toluene in a fixed-bed reactor. The unmodified H-MCM-22 zeolite exhibited much higher initial activity than H-ZSM-5 with a thermodynamic equilibrium distribution of xylene products. The oxalic acid treatment of H-MCM-22 improved the selectivity for para-xylene by 10–18%. The modification by siloxane of the oxalic acid treated H-MCM-22 turned out to be highly selective for para-xylene, however, with the expense of the conversion. It is proposed that the high para-selectivity was closely associated with the contraction of micropore windows and the elimination of acid sites at the external surface by the deposited silica. Therefore, the modified H-MCM-22 is a potential catalyst for the selective disproportionation of toluene with a high para-selectivity.     

Synthesis of pure zeolite Y using soluble silicate, a two-level factorial experimental design

Four methods were used for the synthesis of pure zeolite Y using soluble silicate as a silica source: (1) the gelling of soluble silicate to silica–alumina gel, by aluminate (or aluminium sulphate), (2) the precipitation of soluble silicate to precipitated silica–alumina gel, by aluminate (or aluminium sulphate), (3) the gelling of soluble silicate by sulphuric acid plus alumina impregnation, and (4) the precipitation of soluble silicate by sulphuric acid plus alumina impregnation. A 2⁴ two-level factorial design was used to study the influence of four different variables on the purity of zeolite Y (expressed in terms of degree of crystallinity). The ageing time turned out to be the most significant variable. Synthesis time, alkalinity and mixing rate were also found to be statistically significant. X-ray diffraction patterns were used to characterize the samples, which ranged from well-crystallized faujasite structures to amorphous materials. The highest purity achieved in method (1) was 38%. The best synthesis condition derived from method (1) was applied to the other three methods. Only method (4) yielded the pure zeolite Y. Therefore, the effect of silica–alumina precursor preparation on producing the pure zeolite Y is extremely important.     

Dealumination of Zeolite Beta Catalyst Under Controlled Conditions for Enhancing its Activity in Acylation and Esterification

This work deals with the dealumination of zeolite beta under different conditions to optimize its catalytic performance. The dealumination was carried out either using oxalic or tartaric acid solution of different pH values or steaming up to 500 °C. The dealuminated zeolite samples were characterized using X-ray diffraction, N₂-physisorption, ICP, ²⁷Al NMR and NH₃-TPD. Their catalytic activities were studied for acylation reaction of 2-methoxy naphthalene or naphthalene with acetic anhydride and esterification of benzyl alcohol with hexanoic acid. Among the dealuminated samples examined, those treated with oxalic acid or tartaric acid at pH 2 showed high activity. The high activity can be correlated with the relative increase in the amount of strong acid sites and with the enhanced accessibility of the reactants to the active sites, which are caused by removal of extra-framework Al species on the acid treatments.     

体型化NaA分子筛的制备研究

以粉煤灰一步酸溶法提取氧化铝剩余的酸溶渣为原料制备具有一定强度的地质聚合物,经过水热反应原位转化NaA分子筛。通过研究合成过程中的硅铝比、碱量、液固比等因素对制备体型化分子筛的影响,得到了制备酸溶渣基地质聚合物原位转化NaA型分子筛的最佳条件：在二氧化硅与三氧化二铝物质的量比为1.8、氧化钠与三氧化二铝物质的量比为1.0、水与酸溶渣质量比为1.2条件下制备出地质聚合物,之后在0.5 mol/L的75 mL氢氧化钠溶液中晶化,在晶化温度为100 ℃、晶化时间为8 h条件下可以制备出晶相单一、结晶度高的NaA体型化分子筛。制备的NaA体型化分子筛具有明显的立方体形貌,颗粒分布均匀,孔径为0.685 nm,比表面积为86.75 m²/g,抗压强度为4.5 MPa。     

晶种导向剂法制备纳米ZSM-5沸石

在水热合成体系中添加自制晶种导向剂成功制备了纳米ZSM-5沸石,考察了晶种导向剂、晶化温度和合成体系硅铝物质的量比对合成纳米ZSM-5沸石的影响。制备的晶种导向剂是全硅的Silicalite-1沸石纳米颗粒、沸石初级或次级结构单元的SiO₂以及模板剂TPAOH的混合胶体溶液,结果表明,在ZSM-5沸石制备体系中添加晶种导向剂可有效降低有机模板剂的使用量,缩短晶化时间,并能得到纳米尺寸的ZSM-5沸石,降低晶化温度和合成体系硅铝比有利于减小纳米ZSM-5沸石晶体尺寸。     

水热法合成β沸石结晶度的研究

以四乙基氢氧化铵为模板剂 ,采用水热法合成 β沸石。考察水热法合成 β沸石时体系中有机模板剂用量、水硅比、钠硅比及晶化时间等对合成的 β沸石相对结晶度的作用。样品的相对结晶度用X射线衍射仪分析。得出各种因素对合成 β沸石相对结晶度的影响     

Realumination of dealuminated HZSM-5 zeolite by citric acid treatment and its application in preparing FCC gasoline hydro-upgrading catalyst

This article describes a novel citric acid treatment method for realuminating dealuminated HZSM-5 zeolite and its application in enhancing the performance of the zeolite derived FCC gasoline hydro-upgrading catalysts. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and the influences of the different modification methods on the acidity, pore structure and catalytic performance of the modified HZSM-5 zeolite supported catalysts were compared in the present investigation. The results showed that compared with the single HCl or citric acid treatment, the steaming treatment, and the steaming/HCl treatments, the citric acid treatment after steaming exclusively increased the amount of framework Al species due to its realumination effect on the steamed HZSM-5 zeolite. This realumination effect of the citric acid treatment could optimize the ratio of framework Al to extra-framework Al in the steamed HZSM-5 zeolite and thus greatly improve the acidity distribution and pore structure of the corresponding catalyst. The catalytic performance assessments of the different zeolite supported catalysts for FCC gasoline hydro-upgrading revealed that the catalyst supported on the steaming/citric acid treated HZSM-5 zeolite had balanced initial and long-term activities in hydrodesulfurization, hydroisomerization and aromatization, high liquid yield and improved gasoline road octane number. The superior catalytic performance of the catalyst could be closely related to its suitable ratio of framework Al to extra-framework Al achieved by the combinational use of the steaming dealumination and the citric acid realumination, fully demonstrating the effectiveness of the steaming and citric acid treatments in optimizing the physicochemical properties and catalytic performance of HZSM-5 zeolite supported catalysts.