脱铝八面沸石的研究(Ⅳ)——异丙苯催化裂化

以脉冲微型反应技术研究了脱铝八面沸石对异丙苯的催化裂化行为,并与反应条件下表面酸性进行了关联。样品裂化活性随骨架Si/Al比增加呈山峰形变化,Si/Al=5.38时最大;反应条件下酸中心数随脱铝深度增加却单调降低。动力学数据表明,样品裂化反应速度常数与强质子酸中心数随骨架Si/Al比增加具有平行的山峰形变化规律,Si/Al比为8.87附近的样品最高。     

Organic-Free Interzeolite Transformation in the Absence of Common Building Units

Zeolite crystals can be used as seeds or aluminosilicate sources in syntheses to control polymorphs and/or reduce the quantity of organics used as structure-directing agents. A frequently invoked hypothesis for interzeolite transformations is that zeolites share some underlying similarity in structure, most notably in cases pertaining to organic-free syntheses. Herein, we show for the first time that ZSM-5 (MFI) can be directly obtained from USY (FAU) through an interzeolite transformation between parent–daughter structures lacking common building units in the absence of a structure-directing agent and seeds. We show that interzeolite transformation leads to a crystalline product with fewer defects. Our findings also reveal that ZSM-5 is a metastable intermediate that undergoes further transformation to mordenite (MOR) and quartz. The MFI-to-MOR transition is counter to reported trends for which transformations lead to structures with reduced molar volume. Herein, we propose mechanistic arguments that suggest the driving force for interzeolite transformation is more complex than guidelines posited in the literature.     

富硅超稳八面沸石研究：制备,表征,稳定性,羟基酸性及催化活性

用(NH_4)_2SiF_6二次合成法制备了Si/Al=4.2～7.1、结晶度大于94％的系列八面沸石(FSY样品),再于500℃水热处理得到相应的US-SY样品。XRD、DTA及IR研究发现US-SY样品较FSY样品有更高的热稳定性、骨架稳定性和酸强度,其裂解、歧化活性也优于FSY样品。     

CoPc在八面沸石笼中的原位合成及性能研究

采用苯酐－尿素路线，对CoPc金属配合物在八面沸石超笼中原位合成进行了考察，并采用多种物化手段和催化反应对所制备的CoPcY进行了详细的表征。结果表明，该制备路线是一简便有效的合成路线，采用该路线可在八面沸石超笼中原位合成CoPc金属配合物并将之固定于八面沸石中。在该制备方法中合成温度、离子交换所采用的盐类型及催化剂对CoPc金属配合物在八面沸石超笼中的合成及所制备的CoPcY在环己烷氧化反应中的催化性能有很大的影响，其中180 ℃为最佳合成温度，氯化钴较适合作为交换的盐类。在八面沸石超笼中原位合成的CoPc金属配合物在温和的反应条件下对环己烷氧化具有良好催化活性，转化数TON最高可达5 000以上。     

Conversion of nitrogen(I,II) oxides on nanodispersed [Pt(Pd)-Au]/HY zeolite catalysts

We have shown that conversion of nitrogen(I,II) oxides in reduction by carbon monoxide and light C₁, C₃–C₄ alkanes in the presence of nanodispersed [Pt(Pd)-Au]/HY catalysts is determined by the reagent activation routes in an oxidizing/reducing atmosphere. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 156–161, May–June, 2006.     

On the structures of X- and Y-type zeolites. Structural changes within the cavities of Na-Y during dehydration and contrasts with Na-X systems

Samples of dehydrated and partially dehydrated Na-Y were examined by X-ray diffraction methods revealing the progressive structural changes which occur as water is removed and the different behaviour compared with Na-X. The differences between Na-Y and Na-X reflect the reduced Al content of Na-Y and the consequential lower average capability of each framework oxygen atom for balancing cation charges. In the small-pore region of Na-Y, the total number of Na atoms remains relatively constant during dehydration (ca. 15 per unit cell compared withca. 18 in Na-X); unlike Na-X, Na-Y, has no site I atoms. Significant dehydration of the small-pore region, and the change from low to high site II occupancy, do not occur until the total water content of the sample is less than that which pertains under atmospheric conditions. In the 12-ring regionn of Na-Y, [Na(H₂O)₂]⁺ units are observed at an intermediate level of dehydration, possibly linked by water molecules astride the site III region to networks in adjacent 12-rings. There is no build-up, as in Na-X, of Na at site III, and site IIB (=III) is (at least partially) occupied by H₂O rather than Na. Further dehydration progressively removes H₂O but there is little rearrangement of Na atom positions, except the build-up in site II which accounts for much of the loss of Na from the mobile phase.     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

Evaluation of the Secondary Pore Structure of Hydrothermally- and Acid-treated Faujasite Type Zeolites

With regard to H-Y type zeolites dealuminated by hydrothermal and acid treatments, their physical properties were characterized by measurements of 29Si- and 27Al-MAS-NMR, IR, and X-ray diffraction. The secondary pores were quantitatively analyzed by the t-plot method for nitrogen adsorption isotherm at liquid nitrogen temperature and were then compared with the results of samples dealuminated by SiCl4 treatment.The plateau region of the nitrogen adsorption isotherm diminished as hydrothermal and acid treatments proceeded, with the result that the shape of the t-plot changed to that of three straight sections. This t-plot shape suggested that the secondary pores with relatively consistent sizes could develop with the progress of the treatment. On the other hand, SiCl4 treatment was found to produce less secondary pores than hydrothermal and acid treatments. The surface area of micropores calculated from the t-plots gave a considerably higher value than values obtained from the BET equation and from that calculated geometrically. This is attributable to the micropore filling effect.     

On the Role of Protonic Acid Sites in Cu Loaded FAU31 Zeolite as a Catalyst for the Catalytic Transformation of Furfural to Furan

The aim of the present paper is to study the speciation and the role of different active site types (copper species and Brønsted acid sites) in the direct synthesis of furan from furfural catalyzed by copper-exchanged FAU31 zeolite. Four series of samples were prepared by using different conditions of post-synthesis treatment, which exhibit none, one or two types of active sites. The catalysts were characterized by XRD, low-temperature sorption of nitrogen, SEM, H₂-TPR, NMR and by means of IR spectroscopy with ammonia and CO sorption as probe molecules to assess the types of active sites. All catalyst underwent catalytic tests. The performed experiments allowed to propose the relation between the kind of active centers (Cu or Brønsted acid sites) and the type of detected products (2-metylfuran and furan) obtained in the studied reaction. It was found that the production of 2-methylfuran (in trace amounts) is determined by the presence of the redox-type centers, while the protonic acid sites are mainly responsible for the furan production and catalytic activity in the whole temperature range. All studied catalysts revealed very high susceptibility to coking due to polymerization of furfural.     

甲苯甲醇侧链烷基化反应中甲酸盐的形成及其作用

将碱金属碳酸盐修饰的KX和NaY沸石用于催化甲苯甲醇侧链烷基化反应,并结合甲醇吸附的红外光谱以及异丙醇和甲醇催化分解反应结果,剖析了甲酸盐的形成及其作用.结果表明,碱金属碳酸盐的负载能提高碱金属离子交换八面沸石的催化活性.在反应过程中催化剂表面形成了不同数量的甲酸盐,尤其是K2CO3修饰的KX上;甲酸盐主要来源于碳酸盐与甲醇分解产物甲醛的反应,它的形成对催化剂甲苯甲醇侧链烷基化活性的影响较大,类似于碱金属硼酸盐的修饰,改善了催化剂的表面酸碱性,形成了更为有效的活性中心.