无定形硅铝催化生物质热裂解气齐聚合成汽油的特性

选取无定形硅铝(ASA)作为生物质热裂解气齐聚反应催化剂,分析了齐聚反应前后ASA的织构性质、酸性和积碳行为的变化规律,并在固定床反应器中评价了ASA在不同反应条件(100~320℃,2.0~4.0MPa)下的齐聚反应性能.结果表明,在不同齐聚反应条件下ASA均有不同程度的酸性损失和积碳,L酸位量损失随着温度升高呈现先降低后增加的趋势,在280℃达到最低;压力的升高则有利于降低L酸位量的损失.催化剂积碳量变化与L酸位量变化趋势一致.在反应过程中,低碳烯烃转化率和汽油段产物收率随着温度和压力的升高逐渐增大,在4.0 MPa,280℃反应条件下达到最优,其乙烯、丙烯和丁烯的反应转化率分别为19.2%,37.3%和58.7%,汽油段产物收率(摩尔分数)为22.9%,C_5~+的烯烃类选择性可达73.5%.     

Phase transition in niobium pentoxide supported on silica-alumina

Nb₂O₅ supported on SiO₂-Al₂O₃ were prepared with a wide loading range (2, 5, 10, 15, 20 and 25 mass%) and analyzed by simultaneous thermogravimetric (TG) and differential thermal analysis (DTA). The materials presented a phase transition close to 1364°C. This phase transition was studied by XRD, FTIR and Raman spectroscopy. Amixture of orthorhombic (T) andmonoclinic (H andM) crystalline phases was evidenced in the supported samples, which is coverage dependent, in contrast to the formation of only the monoclinic phase (H and M) when pure Nb₂O₅ is heated under the same conditions. These results indicate the stabilization of Nb₂O₅ on silica-alumina surface.     

无定形硅铝载体的酸性对费托蜡加氢裂化反应中柴油选择性的影响

利用逐梯度铵交换处理的方法合成了三个织构性质相似、酸性不同的无定形硅铝载体,并通过XRD、N₂吸附-脱附、NH₃-TPD、Py-FTIR和NMR等手段对载体的物化性质进行了研究。经等体积浸渍负载贵金属Pt,制成加氢裂化催化剂,以费托蜡加氢裂化生产柴油为探针反应,研究了无定形硅铝载体的酸性与柴油选择性之间的构效关系。结果表明,柴油选择性主要与载体的B酸性质有关,受L酸的影响很小;催化剂载体的强B酸含量与柴油选择性成相反关系,载体强B酸的含量越低,柴油选择性越高;催化剂Pt/B-1具有相对最高的柴油选择性,在反应压力7.0 MPa,H₂/wax（volume ratio）=1 000：1,LHSV=1.0 h^-1,温度为370℃的条件下,C₂₂₊转化率为62.52%时,对柴油的选择性达87.12%,具有比文献报道及商业化无定形硅铝载体ASA制备的催化剂Pt/ASA相对更高的活性和柴油选择性。     

Differential Scanning Calorimetry Evaluates Relative Proportions and Strength of Acid-Sites in Catalytic Materials and Adsorbents Alumina and Amorphous Silica-Alumina

Abstract

Differential scanning calorimetry (DSC) is employed to evaluate the relative proportions and strength of acid-sites in gammaalumina and amorphous silica-alumina through presorption of tri-ethylamine (TEA) followed by its thermal desorption in the DSC equipment. From the data obtained, total acid-sites in silica-alumina is found to be 2.3 times as large as those present in gamma-alumina, and 5–5% of total acidity in alumina is of Bronsted type whereas in silica-alumina this type comprises 28.9%' The Bronsted acidity strength in alumina and silica-alumina is identical although greatly different in quantity. Lewis acidity in silica-alumina is significantly stronger than that in alumina.     

Texture modifications of silica-alumina gels by microwave drying

The porous texture of silica-alumina hydrogel can be taylored by controlling the operating parameters of the preparation process. As the drying drastically modifies the texture it is important to minimize pore volume and radius decreases. Owing to a low drying temperature microwave heating coupled with convective drying could be a way to preserve the hydrogel texture. Its effects have been studied and it appears that the characteristics of the air flow are the main parameters of this drying mode which does not present decisive advantages as compared with other drying modes.     

Insertion of zeolite in sol-gel made catalytic material: an EPR study

Incorporation of zeolite to catalyst base-supports generally endows them with improved catalytic properties; especially those related to selectivity and activity. These effects are due to the stronger than normal acidity of zeolites and their molecular sieve effect. Such properties alter notoriously the way in which metals incorporate into a crystalline sol-gel catalytic matrix. Most noticeable effects on the surface as per EPR analysis occur upon incorporation of copper as metal catalyst when ZSM-5 zeolite is added, then when adding β-zeolite and finally when using Y-zeolite. This revised version was published online in June 2006 with corrections to the Cover Date.     

Textural Characterization of Silica and Silica-Alumina Gels: Comparison of Different Techniques

The porous texture of silica and silica-alumina hydrogels has been studied by means of thermoporometry measurements. The texture of the xerogels resulting from spray-drying of silica-alumina hydrogels is then evaluated by different methods: BET, Hg-porosimetry and thermoporometry. As each method is based on different physical principles and assumptions, differences are observed between the results. However, these results are complementary and their comparison leads to a better knowledge of the texture of the catalyst particles. A good agreement is observed between thermoporometry and nitrogen adsorption-desorption measurements, whereas mercury porosimetry results are very different. Silica-alumina gels appear as mainly mesoporous materials.     

低结焦渣油催化裂化催化剂的制备及其性能

 采用联合脱铝法制备了一系列高硅铝比Y型沸石FSY,并对其加La老化的LaFSY催化裂化性能进行了研究. 结果表明, (NH4)2SiF6处理和水热处理两个步骤联合可有效调节FSY沸石的酸密度,所得LaFSY沸石具有适量强酸位和较少弱酸位,在保持高微反活性的同时有效地降低了重油结焦率. 以大庆常压渣油为裂化原料,与另一种广泛使用的工业催化剂相比,该LaFSY沸石为活性组分的微球催化剂可使轻质产品收率由85.4%提高到88.9%, 而结焦率由9.0%下降到7.5%.     

Preparation of mesoporous silica-alumina derived from FSM-16 and its catalytic activity for cumene cracking

Mesoporous silica-alumina catalysts with different alumina contents were prepared by impregnation of a mesoporous silica (FSM-16) with an alcohol solution of aluminium isopropoxide. The resulting mesoporous silica-alumina catalysts possess protonic acid sites, and exhibit activities for cumene cracking, though the activities are lower than that of an amorphous silica-alumina catalyst. The maximum activity as well as the maximum amount of protonic acid sites were observed for the sample with a Si/Al ratio of 4.1.     

Crystallization in the SiO2-Al2O3 System from Amorphous Powders

The crystallization of amorphous chemically homogeneous powders in the SiO₂.Al₂O₃ system has been studied by differential scanning calorimetry and X-ray diffraction. Up to 1300°C only one exotherm has been observed. Only mullite crystallizes for compositions ≤69 mol% Al₂O₃ and spinel for those ≤80%. The crystallizations into mullite and spinel are sharp and exothermic, with an enthalpy of 250–300 J/g. The chemical composition of the crystallized mullite regularly increases from 68 to 76 mol% Al₂O₃ with increasing bulk composition from 60 to 75 mol% Al₂O₃.