Sn-modified Pt/SAPO-11 catalysts for selective hydroisomerization of n-paraffins

The hydroconversion of n-paraffins is a key reaction in hydrodewaxing of lubricating base oil. In this paper, we investigate the performance of Pt/SAPO-11 catalysts for isomerization of n-paraffins by the model compound of n-dodecane. Under this experimental condition, yields of feed isomers as well as cracking products are a function of the total n-dodecane conversion. Primary products are methylundecane while multi-brancheds and cracking products are formed in successive reactions. The result shows that the addition of Sn increases the selectivity for isomerization reaction. The most ideal experimental data for hydroconversion of n-dodecane is that the selectivity of isomerized products gets 90% when conversion of n-dodecane is 90% for the Sn-promoted Pt/SAPO-11 catalyst.

Mn-containing AlPO-11 and SAPO-11 catalysts for simultaneous isomerization and dehydrogenation of n-butane

MnAPO-11 and MnAPSO-11 were synthesized hydrothermally, and supported Mn-AlPO-11 and Mn-SAPO-11 were also prepared for comparison. Characterization results showed that there were differences in acidity and reducibility caused by the different incorporation methods of manganese. The manganese species in the samples also weakened the metallic properties of the palladium particles when the latter was added into the catalysts. Catalytic testing results for dehydroisomerization of n-butane indicated that incorporation of manganese increased the selectivity toward isomerization products. The highest isobutene selectivity (34.86%) could be obtained over a Pd/MnAPO-11 catalyst. When a combined catalyst system containing Pd/SAPO-11 and MnAPSO-11 was used in a single bed of two layers, the isobutene selectivity could be greatly improved, as compared to the single catalyst alone.

Crystallization and Si incorporation mechanisms of SAPO-34

In this study of the synthesis of SAPO-34 molecular sieves, XRD, SEM, XRF, IR and NMR techniques were applied to monitor the crystalloid, structure and composition changes of the samples in the whole crystallization process in order to get evidence for the crystallization as well as Si incorporation mechanism of SATO-34. XRD results revealed that the crystallization contained two stages. In the first 2.5 h (the earlier stage), high up to similar to80% of relative crystallinity could be achieved and the crystal size of SAPO-34 was almost the same as that of any longer time, indicating a fast crystallization feature of the synthesis. In this stage, IR revealed that the formation of SAPO-34 framework structure was accompanied by the diminution of hydroxyls, suggesting that crystal nuclei of SAPO-34 may arise from the structure rearrangement of the initial gel and the condensation of the hydroxyls. NMR results reveal that the template and the ageing period are crucial for the later crystallization of SAPO-34. Preliminary structure units similar to the framework of SAPO-34 have already formed before the crystallization began (0 h and low temperature). Evidence from IR, NMR, and XRF shows that the formation of the SAPO-34 may be a type of gel conversion mechanism, the solution support and the appropriate solution circumstance are two important parameters of the crystallization of SAPO-34. Meanwhile, NMR measurements demonstrated that about 80% of total Si atoms directly take part in the formation of the crystal nuclei as well as in the growth of the crystal grains in the earlier stage (<2.5 h). Evidence tends to support that Si incorporation is by direct participation mechanism rather than by the Si substitution mechanism for P in this stage (<2.5 h). In the later stage (>2.5 h), the relative content of Si increased slightly with a little decrease of Al and P. The increase of Si(4Al) and the appearance of the Si(3Al), Si(2Al), Si(1Al) and Si(OAl) in this stage suggest that substitution of the Si atoms for the phosphorus and for the phosphorus and aluminum pair takes place in the crystallization. The relationship among structure, acidity and crystallization process is established, which suggests a possibility to improve the acidity and catalytic properties by choosing a optimum crystallization time, thus controlling the number and distribution of Si in the framework of SAPO-34. (C) 2002 Elsevier Science Inc. All rights reserved.