Fouling, of catalysts

EE Petersen. The Fouling of Catalysts Experimental Observations and Modeling in Catalyst Deactivation, edited by E E Petersen and J B Butt, Marcel Dekker, Inc., New York, 1987... 

One disadvantage of fluidized heds is that attrition of the catalyst can cause the generation of catalyst flnes, which are then carried over from the hed and lost from the system. This carryover of catalyst flnes sometimes necessitates cooling the reactor effluent through direct-contact heat transfer hy mixing with a cold fluid, since the fines tend to foul conventional heat exchangers. 

Because soHd acid catalyst systems offer advantages with respect to their handling and noncorrosive nature, research on the development of a commercially practical soHd acid system to replace the Hquid acids will continue. A major hurdle for soHd systems is the relatively rapid catalyst deactivation caused by fouling of the acid sites by heavy reaction intermediates and by-products. 

There are situations where thermal oxidation may be preferred over catalytic oxidation for exhaust streams that contain significant amounts of catalyst poisons and/or fouling agents, thermal oxidation may be the only technically feasible control where extremely high VOC destmction efficiencies of difficult to control VOC species are required, thermal oxidation may attain higher performance and for relatively rich VOC waste gas streams, ie, having >20 25% lower explosive limit (LEL), the gas stream s explosive properties and the potential for catalyst overheating may require the addition of dilution air to the waste gas stream (12). 

These various reactions should be minimized to avoid plugging the catalyst and to prevent fouling of the downstream air preheaters, when these components condense from the gas at the lower temperatures. 

Over the next four years, Houdry, working closely with Sun s engineering team headed by Clarence Thayer, worked to build a commercial plant. The limitations imposed by a static catalyst bed design imposed a major obstacle, particularly in the formation of carbon deposits that fouled the catalyst mass and impeded a continuous system of production. 

For the catalyst activity factor (aj), several models have been proposed, depending on the origin of catalyst deactivation, that is, sintering, fouling, or poisoning. The following differential equation can semiempiricaUy represent different kinds of... 

For some processes, though they would not be classified as batch processes, the period of continuous production will be limited by gradual changes in process conditions such as, the deactivation of catalysts or the fouling of heat-exchange surfaces. Production will be lost during the periods when the plant is shut down for catalyst renewal or equipment clean-up, and, as with batch process, there will be an optimum cycle time to give the minimum production cost. 

The same types of catalyst have been employed in 1-octene hydroformylation, but with the substrates and products being transported to and from the reaction zone dissolved in a supercritical fluid (carbon dioxide) [9], The activity of the catalyst is increased compared with liquid phase operation, probably because of the better mass transport properties of scC02 than of the liquid. This type of approach may well reduce heavies formation because of the low concentration of aldehyde in the system, but the heavies that do form are likely to be insoluble in scC02, so may precipitate on and foul the catalyst. The main problem with this process, however, is likely to be the use of high pressure, which is common to all processes where supercritical fluids are used (see Section 9.8). 

Cross-flow filtration systems utilize high liquid axial velocities to generate shear at the liquid-membrane interface. Shear is necessary to maintain acceptable permeate fluxes, especially with concentrated catalyst slurries. The degree of catalyst deposition on the filter membrane or membrane fouling is a function of the shear stress at the surface and particle convection with the permeate flow.16 Membrane surface fouling also depends on many application-specific variables, such as particle size in the retentate, viscosity of the permeate, axial velocity, and the transmembrane pressure. All of these variables can influence the degree of deposition of particles within the filter membrane, and thus decrease the effective pore size of the membrane. 

As already noted (Chapter 3), petroleum oil often contains water, inorganic salts, snspended solids, and water-soluble trace metals. As a first step in the refining process, to reduce corrosion, plugging, and fouling of equipment and to prevent poisoning the catalysts in processing units, these contaminants must be removed by desalting (dehydration). 

Unfortunately for Houdry, the lead in gasoline used at the time fouled the catalyst. After operating for a short period, the catalyst lost its ability to filter out noxious gases. Houdry s company failed. Two decades later, however, after lead had been banned in gasoline, his idea was reinvented and became the basis of nearly all modern catalytic converters. 

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