Solid catalysts industrial applications

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

K. Tanabe and WF. Holderich, Industrial Applications of Solid Acid-Base Catalysts , Applied Catalysis A, General, 1999, 181, 399. 

Improved characterization of the morphological/microstructural properties of porous solids, and the associated transport properties of fluids imbibed into these materials, is crucial to the development of new porous materials, such as ceramics. Of particular interest is the fabrication of so-called functionalized ceramics, which contain a pore structure tailored to a specific biomedical or industrial application (e.g., molecular filters, catalysts, gas storage cells, drug delivery devices, tissue scaffolds) [1-3]. Functionalization of ceramics can involve the use of graded or layered pore microstructure, morphology or chemical composition. 

Zeolite catalysts play a vital role in modern industrial catalysis. The varied acidity and microporosity properties of this class of inorganic oxides allow them to be applied to a wide variety of commercially important industrial processes. The acid sites of zeolites and other acidic molecular sieves are easier to manipulate than those of other solid acid catalysts by controlling material properties, such as the framework Si/Al ratio or level of cation exchange. The uniform pore size of the crystalline framework provides a consistent environment that improves the selectivity of the acid-catalyzed transformations that form C-C bonds. The zeoHte structure can also inhibit the formation of heavy coke molecules (such as medium-pore MFl in the Cyclar process or MTG process) or the desorption of undesired large by-products (such as small-pore SAPO-34 in MTO). While faujasite, morden-ite, beta and MFl remain the most widely used zeolite structures for industrial applications, the past decade has seen new structures, such as SAPO-34 and MWW, provide improved performance in specific applications. It is clear that the continued search for more active, selective and stable catalysts for industrially important chemical reactions will include the synthesis and application of new zeolite materials. 

It appears to us that the way forward to further industrial application of solid base catalysts may emerge from the discovery of unusual selectivity effects or new reactions that require well-balanced base and acid-base pair sites with relatively inexpensive solid catalysts that last long enough to process large quantities of reactants per unit mass of catalyst. 

The most spectacular solid catalyst reported in the literature is probably the sulfonated carbon. Indeed, in contrast to all other solid catalysts, sulfonated carbon was able to hydrolyze, in water, cellulose to soluble 1,4-p-glucan with high yield. The presence of hydroxyl groups on the carbon surface was found to be crucial and allows a better adsorption of cellulose on the catalyst surface. However, the amount of catalyst used is unacceptable for an industrial application and much effort is stiU needed. 

Oxidation of carbohydrates can be achieved by either chemical or biochemical processes [98, 99]. Owing to their cation sequestering properties, the resulting carboxylic derivatives find potential applications in the detergent industries [100, 101]. Although homogeneous catalysts are often used in oxidation processes, utilization of solid catalysts has proved to be a feasible alternative [102]. 

The transformation of alcohols to the corresponding carbonyl compounds or carboxylic acids is one of the few examples in which a heterogeneous (solid) catalyst is used in a selective, liquid phase oxidation (7,2). The process, which is usually carried out in an aqueous slurry, with supported platinum or palladium catalysts and with dioxygen as oxidant, has limited industrial application due to deactivation problems. 

The tungstophosphoric acid shows high activity, close to H2SO4 used as a benchmark. Regrettably, this acid is soluble in water and hence not usable as a solid catalyst. However, the corresponding cesium salt (Cs2.5) is also super acidic and its mesoporous structure has no limitations on the diffusion of the reactants. Cs2.5 exhibits low activity per weight, hence it is not suitable for industrial applications. 

In addition to large-scale industrial applications, solid acids, such as amorphous silica-alumina, zeolites, heteropoly acids, and sulfated zirconia, are also versatile catalysts in various hydrocarbon transformations. Zeolites are useful catalysts in fine-chemical production (Friedel-Crafts reactions, heterosubstitution).165-168 Heteropoly compounds have already found industrial application in Japan, for example, in the manufacture of butanols through the hydration of butenes.169 These are water tolerant, versatile solid-phase catalysts and may be used in both acidic and oxidation processes, and operate as bifunctional catalysts in combination with noble metals.158,170-174 Sulfated zirconia and its modified versions are promising candidates for industrial processes if the problem of deactivation/reactivation is solved.175-178... 

Since the mid-fifties sulfonated resins based on styrene/divinylbenzene copolymers, initially developed as ion exchangers mainly for water treatment, nave also been used as strongly acidic solid catalysts. Witn few exceptions, industrial application in continuous processes is limited to the manufacture of bulk chemicals, sucn as Disphenol A, (meth)acrylates, metnyl ethers of branched olefins (MTBE, TAME) and secondary alcohols (IPA, SBA). 

Despite the high specific surface areas, the amount of accessible catalyst remains low due to the limited thickness of the porous catalytic layer dictated by considerations such as the adhesion to the substrate. The susceptibility of the fine channels to blockage with solid impurities or deposits formed in the reaction, together with the problems of integrating connections with the external macroenvironments and ensuring uniform gas distribution between the individual channels, a prerequisite for numbering up, represent further questions that have to be resolved for the industrial application of microreactors to become practicable. 

In most applications, the reaction occurs between a dissolved gas and a liquid-phase reactant in the presence of a solid catalyst. In some cases, the liquid is an inert medium and the reaction takes place between the dissolved gases at the solid surface. These reactors have many diverse applications in catalytic processes and are used extensively in the chemical industry. Trickle-bed reactors have been developed by the petroleum industry for hydrodesulfurization, hydrocracking, and hydrotreating of various petroleum fractions of relatively high boiling point. Under reaction conditions, the hydrocarbon feed is frequently a vapor-liquid mixture that reacts at liquid hourly space velocities (LHSV in volume of fresh feed, as liquid/volume of bed, hr) in the... 

Silver-impregnated solids may also serve as catalysts in [4+2] cycloadditions. Thus, Mayoral reported that silver ion-exchanged montmorillite K10 functioned as a catalyst for the reaction of methyl 2-cyanocinnamate and cyclopentadiene 185 (Scheme 2.49). The use of such heterogeneous catalysts may enhance catalyst recovery, an important consideration for industrial applications. 

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