Microporous structures

Micropore structure parameters and S of the active carbon AG. (Standard... 

Table 2. Micropore structure data for large CFCMS monoliths activated via the O2 chcmisorption/activation route [7,27]...

Pretreating the feedstocks with hydrogen is not always effective in reducing heavy metals, and it is expensive. Other means that proved successful are modifying the composition and the microporous structure of the catalyst or adding metals like Sb, Bi or Sn, or Sb-Sn combination. Antimony organics have been shown to reduce by 50% gas formation due to metal contaminants, especially nickel. ... 

Microporous insulation materials consist mainly of highly dispersed silica with a particle size of only 5-30 nm. The highly dispersed silica powder is pressed to plates, which receive heat treatment up to 800 °C, after which the plates are self-supporting and possess a micropore structure with pore diameter of 0.1pm. The addition of opacifiers to the highly dispersed silica starting material reduces the loss of heat by radiation. The dates for such insulation boards are shown in Table 18. 

Fig. 16.4 Microporous structures of CU-4 (a) and CU-2 (b) showing the framework variation upon exchanging the content of sait at high temperature, see text. The frameworks...

Shape selective catalysis as typically demonstrated by zeolites is of great interest from scientific as well as industrial viewpoint [17], However, the application of zeolites to organic reactions in a liquid-solid system is very limited, because of insufficient acid strength and slow diffusion of reactant molecules in small pores. We reported preliminarily that the microporous Cs salts of H3PW12O40 exhibit shape selectivity in a liquid-solid system [18]. Here we studied in more detail the acidity, micropore structure and catal3rtic activity of the Cs salts and wish to report that the acidic Cs salts exhibit efficient shape selective catalysis toward decomposition of esters, dehydration of alcohol, and alkylation of aromatic compound in liquid-solid system. The results were discussed in relation to the shape selective adsorption and the acidic properties. 

Industrial applications of zeolites cover a broad range of technological processes from oil upgrading, via petrochemical transformations up to synthesis of fine chemicals [1,2]. These processes clearly benefit from zeolite well-defined microporous structures providing a possibility of reaction control via shape selectivity [3,4] and acidity [5]. Catalytic reactions, namely transformations of aromatic hydrocarbons via alkylation, isomerization, disproportionation and transalkylation [2], are not only of industrial importance but can also be used to assess the structural features of zeolites [6] especially when combined with the investigation of their acidic properties [7]. A high diversity of zeolitic structures provides us with the opportunity to correlate the acidity, activity and selectivity of different structural types of zeolites. 

Table 1. Micropore structure development during steam activation for CFCMS monoliths manufactured from P-200 carbon fibers.

The micropore volume varied from -0.15 to -0.35 cm3/g. No clear trend was observed with respect to the spatial variation. Data for the BET surface area are shown in Fig. 14. The surface area varied from -300 to -900 m2/g, again with no clear dependence upon spatial location within the monolith. The surface area and pore volume varied by a factor -3 within the monolith, which had a volume of -1900 cm3. In contrast, the steam activated monolith exhibited similar micropore structure variability, but in a sample with less than one fiftieth of the volume. Pore size, pore volume and surface area data are given in Table 2 for four large monoliths activated via 02 chemisorption. The data in Table 2 are mean values from samples cored from each end of the monolith. A comparison of the data in Table 1 and 2 indicates that at bum-offs -10% comparable pore volumes and surface areas are developed for both steam activation and 02 chemisorption/activation, although the process time is substantially longer in the latter case. 

B is a function of the micropore structure, decreasing as microporosity increases. 

Beyer and Belenykaia (27) have investigated the sorption properties of DAY zeolites prepared from Y zeolite and SiCl vapors. They reported a very low adsorption capacity for water and ammonia, similar to that of the almost aluminum-free silicalite (49). The low adsorption capacity for water is indicative of a hydrophobic zeolite surface. The adsorption isotherms for n-butane, benzene and n-hexane obtained on the aluminum-deficient zeolite have a shape similar to those obtained on NaY zeolite and are characteristic for micropore structures. They show the absence of secondary pores in this DAY zeolite. 

Micromeritics) or Autosorb-1 (Quantachrome) allow measurements of AIs starting from P/P0 10 7, and comparative plots in this range discover new opportunities for more detailed studies of micropore structure and surface heterogeneity evaluation [84-87],... 

Microporous structures form on cast film from rod-coil block copolymer micelles... 

Fig. 10 Schematic representation of the nanoreplication processes from block copolymers, a Growth of high-density nanowires from a nanoporous block copolymer thin film. An asymmetric PS-fc-PMMA diblock copolymer was aligned to form vertical PMMA cylinders under an electric field. After removal of the PMMA minor component, a nanoporous film is formed. By electrodeposition, an array of nanowires can be replicated in the porous template (adapted from [43]). b Hexagonally packed array of aluminum caps generated from rod-coil microporous structures. Deposition of aluminum was achieved on the photooxidized area of the rod-coil honeycomb structure (Taken from [35])...

Membranes can also be used as a reactor where catalysts are used frequently. The membrane may physically segregate the catalyst in the reactor, or have the catalyst immobilized in the porous/microporous structure or on the membrane surface. The membrane having the catalyst immobilized in/on it acts almost in the same way as a catalyst particle in a reactor does, except that separation of the product(s) takes place, in addition, through the membrane to the permeate side. All such configurations involve the bulk flow of the reaction mixture along the reactor length while diffusion of the reactants/products takes place generally in a perpendicular direction to/from the porous/microporous catalyst. 

Improvement of some properties (such as dimensional stabilization) requires that, in some cases, the modifying agent resides within the cell wall micropore structure. 

The silicoaluminophosphate (SAPO) family [30] includes over 16 microporous structures, eight of which were never before observed in zeolites. The SAPO family includes a silicon analog of the 18-ring VPI-5, Si-VPI-5 [31], a number of large-pore 12-ring structures including the important SAPO-37 (FAU), medium-pore structures with pore sizes of 0.6-0.65 nm and small-pore structures with pore sizes of 0.4-0.43 nm, including SAPO-34 (CHA). The SAPOs exhibit both structural and compositional diversity. 

In the metal aluminophosphate (MeAPO) family the framework composition contains metal, aluminum and phosphorus [27]. The metal (Me) species include the divalent forms of Co, Fe, Mg, Mn and Zn and trivalent Fe. As in the case of SAPO, the MeAPOs exhibit both structural diversity and even more extensive composihonal variation. Seventeen microporous structures have been reported, 11 of these never before observed in zeoUtes. Structure types crystallized in the MeAPO family include framework topologies related to the zeolites, for example, -34 (CHA) and -35 (LEV), and to the AIPO4S, e.g., -5 and -11, as well as novel structures, e.g., -36 (O.Snm pore) and -39 (0.4nm pore). The MeAPOs represent the first demonstrated incorporation of divalent elements into microporous frameworks. 

Synthetic zeolites and other molecular sieves are important products to a number of companies in the catalysis and adsorption areas and numerous applications, both emerging and well-established, are encouraging the industrial synthesis of the materials. There are currently no more than a few dozen crystalline microporous structures that are widely manufactured for commercial use, in comparison to the hundreds of structures that have been made in the laboratory. See Chapter 2 for details on zeolite structures. The highest volume zeolites manufactured are two of the earliest-discovered materials zeolite A (used extensively as ion exchangers in powdered laundry detergents) and zeolite Y (used in catalytic cracking of gas oil). 

The catalysts are predominantly modified ZSM-5 zeolite. In general, the modifications are intended to restrict pore mouth size to promote the shape selective production of para-xylene within the microporous structure. The same modifications also serve to remove external acid sites and eliminate the consecutive isomerization of para-xylene. Methods used to modify the zeolite pore openings have included silation [50], incorporation of metal oxides such as MgO, ZnO and P2O5 [51, 52], steaming and the combination of steaming and chemical modification [53]. 

The catalyst consists of basic and acid sites in a microporous structure provided by zeolite and microporous materials [58-62]. Basic sites are provided by framework oxygen and/or occluded CsO. Acid sites are provided by the Cs cation and, possibly, additives such as boric and phosphoric acids. The addition of Cu and Ag increased the activity [63, 64]. Incorporation of li, Ce, Cr and Ag also has been shown to increase the styrene to ethylbenzene product ratio [65]. The reactivity of catalysts is sensitive to the presence of occluded CsO, which is in turn influenced by the preparative technique as shown by Lacroix and co-authors [64] and pointed out by Lercher [61]. 

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