Synthesis of titanium silicalites in different template systems and their catalytic performance

Titanium silicalites have been synthesized in the TPABr+ammonia, TPABr+hexanediamine, TPABr+ethylenediamine, TPABr+diethylamine, TPABr+TEAOH, TPABr+n-butylamine, TPABr+TBAOH and TBAOH+n-butylamine systems. As-synthesized titanium silicalites were characterized by XRD, IR and C-13 CP MAS NMR. Catalytic performance in epoxidation of propylene and template effect was investigated. It has been shown that both TPABr and TBAOH serve as templating agent in TPABr+TBAOH system. But in other systems, when there is enough TPABr, organic amines or ammoniums only act as the bases. TEAOH or n-butylamine can take the role of template when less TPABr is added. It indicates that the ability of organic amines or ammoniums to direct the Pentasil structure decreases as follows: TPA(+)>TBA(+)>TEA(+)>n-butylamine. Catalysts exhibiting good performance in epoxidation of propylene can be attained using TPABr as the template and ammonia, n-butylamine, diethylamine, hexanediamine or TBAOH as bases. (C) 1999 Elsevier Science B.V. All rights reserved.

Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Identifying framework titanium in TS-1 zeolite by UV resonance Raman spectroscopy

Framework titanium in Ti-silicalite-1 (TS-1) zeolite was selectively identified by its resonance Raman bands using ultraviolet (W) Raman spectroscopy. Raman spectra of the TS-1 and silicalite-1 zeolites were obtained and compared using continuous wave laser lines at 244, 325, and 488 nm as the excitation sources. It was only with the excitation at 244 nm that resonance enhanced Raman bands at 490, 530, and 1125 cm(-1) appeared exclusively for the TS-1 zeolite. Furthermore, these bands increased in intensity with the crystallization time of the TS-1 zeolite. The Raman bands at 490, 530, and 1125 cm(-1) are identified as the framework titanium species because they only appeared when the laser excites the charge-transfer transition of the framework titanium species in the TS-1. No resonance Raman enhancement was detected for the bands of silicalite-1 zeolite and for the band at 960 cm(-1) of TS-1 with any of the excitation sources ranging from the visible tb UV regions. This approach can be applicable for the identification of other transition metal ions substituted in the framework of a zeolite or any other molecular sieve.

Post-grafting preparation of large-pore mesoporous materials with localized high content titanium doping

A new post-grafting process, consisting of two steps of substrate preparation and sol - gel post-grafting, has been developed to prepare titanium-doped mesoporous SBA-15 material with a double-layered structure and locally concentrated titanium content at the inner pore surface. With this novel technique, the single phased and originally ordered mesostructures can be well conserved; in the conventional direct synthesis they can be partially damaged when the frameworks are doped with high content heteroatoms. Titanium species exist in an isolated, tetrahedral structure and are localized at the pore surface; this is beneficial to both reactant access and product release. Characterization with XRD, N-2 adsorption/desorption isotherms, HREM/ EDS, ICP, UV - Vis, and the newly developed UV - Raman spectroscopy confirm these results. Preliminary catalytic tests with the selective epoxidation of cyclohexene show good catalytic activity. Among them, sample TiSBA-15-10 with a Si : Ti molar ratio of 10 shows a TON value of 75 and a highest product ( epoxide) yield of 55%.

Titanium: An allergen of growing significance

info:eu-repo/semantics/published

The tilt casting of titanium aluminides

TiAl castings are prone to various defects including bubbles entrained during the turbulent filling of moulds. The present research has exploited the principles of the Durville tilt casting technique to develop a novel process in which the Induction Skull Melting (ISM) of TiAl alloys in a vacuum chamber has been combined with controlled tilt pouring to achieve the tranquil transfer of the metal into a hot ceramic shell mould. Practical casting equipment has been developed to evaluate the feasibility of this process in parallel with the development of novel software to simulate and optimize it. The PHYSICA CFD code was used to simulate the filling, heat transfer and solidification during tilt pouring using a number of free surface modelling techniques, including the novel Counter Diffusion Method (CDM). In view of the limited superheat, particular attention was paid to the mould design to minimize heat loss and gas entrainment caused by interaction between the counter-flowing metal and gas streams. The model has been validated against real-time X-ray movies of the tilt casting of aluminium and against TiAl blade castings. Modelling has contributed to designing a mould to promote progressive filling of the casting and has led to the use of a parabolic tilting cycle to balance the competing requirements for rapid filling to minimize the loss of superheat and slow filling minimize the turbulence-induced defects.

Modelling the tilt-casting process for the tranquil filling of titanium alloy turbine blades

The tilt-casting method is used to achieve tranquil filling of gamma-TiAl turbine blades. The reactive alloy is melted in a cold crucible using an induction coil and then the complete crucible-mould- running system assembly is rotated through 180degrees to transfer the metal into the mould. The induction current is ramped down gradually as the rotation starts and the mould is preheated to maintain superheat. The liquid metal then enters the mould and the gas within it (argon) escapes through the inlet aperture and through auxiliary vents. Solidification starts as soon the metal enters the mould and it is important to account for this effect to predict and prevent misruns. The rotation rate has to be controlled carefully to allow sufficient time for gas evacuation, but at the same time preserve superheat. This 3-phase system is modelled using the FV method, with a fast implicit numerical scheme used to capture the transient liquid free surface. The enthalpy method is used to model solidification and predict defects such as trapped bubbles, macro-porosity or surface connected porosity. Modeling is used to support an experimental program for the development of a production method for gamma-TiAl blades, with a target length of 40cm. The experiments provide validation for the model and the model in turn optimizes the tilt-casting process. The work is part of the EU project IMPRESS.