Silica hydrothermal treatment

The silicalite-alumina membrane was prepared after adding a solution containing the silicalite precursor (i e silica + template) to the above-mentioned porous tube (hereafter called support) and a specific hydrothermal treatment performed [8], under the chosen conditions no material is formed in the absence of the porous support. The tube is then calcined at 673 K for removing the template. 

The binders are silica, lime, slag, or cement. The balls are somewhat dried, if necessary, and then cured in steam autoclaves. During the hydrothermal treatment lime and silica react to form hydrosilicate gels, which act as binders. 

A preformed chitosan-silica composite with 60% weight inorganic part [7] is used as the source of silica for the zeolite synthesis. An alkaline solution of sodium aluminate (Na 2.1 M, Al 1 M) was used in three methods of preparation (A) beads of the chitosan-silica composite were stirred overnight in the aluminate solution, extracted and submitted to a hydrothermal treatment at 80 °C during 48h (B) beads of the chitosan-silica composite were immersed in the aluminate solution and the system underwent a hydrothermal treatment at 80 °C for 48h (C) beads of the chitosan-silica composite were stirred overnight in the aluminate solution, extracted, dried at 80 °C and exposed to water vapour at 80°C during 48h. 

In the X-ray powder diffraction patterns of the composites, the disappearance of the broad band centered at 22 °20, typical of amorphous silica, indicates that the zeolitisation of the mineral fraction of the parent composite was complete. In no diffraction pattern any sign of crystallised chitosan could be found. The two methods in which the silica-polymer beads were extracted from the aluminate solution after impregnation (methods A and C) allowed the formation of the expected zeolite X, with traces of gismondine in the case of the method C. The method B, in which excess aluminate solution was present during the hydrothermal treatment, resulted in the formation of zeolite A. 

Membranes with extremely small pores ( < 2.5 nm diameter) can be made by pyrolysis of polymeric precursors or by modification methods listed above. Molecular sieve carbon or silica membranes with pore diameters of 1 nm have been made by controlled pyrolysis of certain thermoset polymers (e.g. Koresh, Jacob and Soffer 1983) or silicone rubbers (Lee and Khang 1986), respectively. There is, however, very little information in the published literature. Molecular sieve dimensions can also be obtained by modifying the pore system of an already formed membrane structure. It has been claimed that zeolitic membranes can be prepared by reaction of alumina membranes with silica and alkali followed by hydrothermal treatment (Suzuki 1987). Very small pores are also obtained by hydrolysis of organometallic silicium compounds in alumina membranes followed by heat treatment (Uhlhom, Keizer and Burggraaf 1989). Finally, oxides or metals can be precipitated or adsorbed from solutions or by gas phase deposition within the pores of an already formed membrane to modify the chemical nature of the membrane or to decrease the effective pore size. In the last case a high concentration of the precipitated material in the pore system is necessary. The above-mentioned methods have been reported very recently (1987-1989) and the results are not yet substantiated very well. 

Synthesis of uniform and stable millimeter-sized mesoporous silica ropes by the addition of polymer and ammonia hydrothermal treatment... 

The addition of water-soluble polymers such as polyethylene oxide (PEO) or polyvinyl alcohol (PVA) into the synthetic mixture of the C TMAX-HN03-TE0S-H20 system (n = 16 or 18 X = Br or Cl) under shear flow is found to promote uniformity and elongation of rope-like mesoporous silica. The millimeter-scaled mesoporous silica ropes are found to possess a three-level hierarchical structure. The addition of water-soluble polymer does not affect the physical properties of the silica ropes. Moreover, further hydrothermal treatment of the acid-made material under basic ammonia conditions effectively promotes reconstruction of the silica nanochannels while maintaining the rope-like morphology. As a result, a notable enhancement in both thermal and hydrothermal stability is found. 

As indicated by XRD patterns, there exist just 2-3 broad peaks in the calcined acid-made materials (Fig. 3A). Moreover, the N2 adsorption/desorption isotherm shown in Fig. 3B, the calcined acid-made mesoporous silica indeed possesses a broad capillary condensation at the partial pressure p/p0 of ca. 0.2-0.4, indicating a broad pore size distribution with a FWHM ca. 1.0 nm calculated from the BJH method. This is attributed to the occurrence of partial collapse of the mesostructure during the high temperature calcination. The hexagonal structure completely collapsed when subjected to further hydrothermal treatment in water at 100 °C for 3 h. Mesoporous silica materials synthesized from the acid route are commonly believed to be less stable than those from the alkaline route [6,7]. 

To improve the meso-structural order and stability of the mesoporous silica ropes, a postsynthesis ammonia hydrothermal treatment (at 100 °C) was invoked. As indicated by the XRD profile in Fig. 3A, 4-5, sharp features are readily observed in ammonia hydrothermal treated samples. Moreover, after the post-synthesis ammonia treatment, the sample also possesses a sharp capillary condensation at p/po 0.35(Fig. 3B) corresponding to a much narrower BJH pore size distribution of ca. 0.12 nm (at FWHM). In other words, the mesostructures are not only more uniform but also more stable when subjected to the post-synthesis treatment. The morphology of the silica ropes remained unchanged during the ammonia hydrothermal process. The mesostructures remain intact under hydrothermal at 100 °C in water even for extended reaction time (> 12 h). 

To further characterize the effect of the ammonia hydrothermal treatment, we compared elemental analysis data and 1R spectra before and after ammonia hydrothermal treatment to quantitatively disclose the role of counterion between the silica framework and surfactants. In Table 2, the N/C molar ratio of the mesoporous materials prior to the ammonia hydrothermal treatment is nearly twice of that after the treatment. Moreover, the IR band at 1383 cm 1, which arises from the N03 stretch bending mode, completely disappears after ammonia hydrothermal treatment [20], These results verify that the existence of nitrate counterion (the nitrate/surfactant 1) between surfactant molecules and silica framework in the acid-made mesoporous materials. The bridging counterion N03 was completely removed after ammonia hydrothermal treatment. 

The elemental analysis data and IR adsorption band at 1383 cm 1 of the mesoporous silica ropes synthesized from the C TMAX-TEOS-HNO3-PEO-6000-H2O system before and after the ammonia hydrothermal treatment. ... 

A possible mechanism of the ammonia hydrothermal treatment for the acid-made sample is shown below. The predominant interaction between the silica wall and the surfactant of the acid-made products is the weak hydrogen bond interaction through an intermediate counterion (i.e. N03). Such weaker interaction eases the removals of organic template by hot water or organic solvent [6], Thus, when the acid-made materials are subjected to the ammonia hydrothermal treatment, the interactions between the surfactant and silicate framework would be transformed as ... 

Such ammonia hydrothermal treatment is also applicable to mesoporous silica materials synthesized under different conditions, e.g., different acid source or temperature. This and other interesting issues will be reported later. 

The reaction of pure silica MCM-48 with dimethyldichlorosilane and subsequent hydrolysis results in hydrophobic materials with still a high number of anchoring sites for subsequent deposition of vanadium oxide structures. The Molecular Designed Dispersion of VO(acac)2 on these silylated samples results in a V-loading of 1.2 mmol/g. Spectroscopic studies evidence that all V is present as tetrahedral Vv oxide structures, and that the larger fraction of these species is present as isolated species. These final catalysts are extremely stable in hydrothermal conditions. They can withstand easily hydrothermal treatments at 160°C and 6.1 atm pressure without significant loss in crystallinity or porosity. Also, the leaching of the V in aqueous conditions is reduced with at least a factor 4. 

In the first place, we learned more about the formation of nickel hydrosilicates under certain circumstances from an investigation of Van Eijk van Voorthuysen and Franzen (2). These investigators made a number of preparations by combining boiling dilute solutions of nickel nitrate and alkali silicate in various proportions. In order to find out to what extent co-precipitation is required for the formation of hydrosilicate structures, acid was added to a nickel hydroxide suspension in a silicate solution by which silica is precipitated, or conversely, alkali was added to a suspension of silica gel in a nickel nitrate solution. Some of the preparations were subjected to a hydrothermal treatment at 250° C. for 50 hrs. with a sufficient quantity of water for developing the best possible structure. 

AI2O3 were prepared by precipitating alumina onto silica gel, followed by hydrothermal treatment. These materials were characterized by 27A1NMR and ESCA and evaluated in gas oil cracking. NMR revealed the presence of tetrahedral, pentacoordinated and octahedral A1 species in the steamed Si02 - AI2O3 samples with 27 and 13% AI2O3. 

However, they found that the more completely the surface was dehydroxylated, the longer the time required for rehydroxylation. A surface dehydroxylated at 1173 K for 10 h required several years in water at ambient temperature to become fully rehydroxylated. When the same silica sample was hydrothermally treated in boiling water, 60 h sufficed to obtain full rehydroxylation. Caution is necessary however in using hydrothermal treatment, since some silicas tend to undergo drastic changes in structure and reduction in surface area under these conditions. 

Additionally, the liquid phase produced by the hydrothermal treatment can be employed as a silica source for the preparation of aluminosilicate gels for the posterior synthesis of zeolites [24,120-122],... 

V. M. Gun ko, J. Skubiszewska-Zieba, R. Leboda, and V. V. Turov, Impact of Thermal and Hydrothermal Treatments on Structural Characteristics of Silica Gel Si-40 and Carbon/Silica Gel Adsorbents, Colloids Surf. A 235 (2004) 101-111. 

It is known13,14 that both thermal (T) and hydrothermal treatments (HTT) of silica gels change their pore structure. The specific surface area diminishes and the pore size increases depending on treatment temperature. This occurs due to hydrolysis of Si-O-Si bonds, transferring of Si(OH)4 and larger complexes with... 

Table 1 presents the structural characteristics of adsorbents prepared with Si-40 and acenaphthene.15 Larger changes in the Si-40 structure are caused by hydrothermal treatment, despite a relatively low temperature (150°C), than by heating at 500°C. However in the case of carbon-silica adsorbents, both hydrothermal modification and high-temperature pyrolysis changes the pore structure to a large extent. 

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