Cracking coke formation

Yen eta/ [1988] Fluid catalytic cracking Coke formation is kinetics control with fourth order reaction None considered (1) Complex - many parameters (2) Tested against actual coke data from both pilot and commercial fluid catalytic cracking units... 

In single-stage units which do not produce kerosene or other critical stocks, flash zone temperatures may be as high as 750 - 775 F. The principal limitation is the point at which cracking of distillates to less valuable gas or the rate of coke formation in the furnace tubes becomes excessive. 

In a cat cracker, a portion of the feed, mostly from secondary cracking and polymerization reactions, is deposited on the catalyst as coke. Coke formation is a necessary byproduct of the FCC operation the heat released from burning coke in the regenerator supplies the heat for the reaction. 

In a series of investigations of the cracking of alkanes and alkenes on Y zeolites (74,75), the effect of coke formation on the conversion was examined. The coke that formed was found to exhibit considerable hydride transfer activity. For some time, this activity can compensate for the deactivating effect of the coke. On the basis of dimerization and cracking experiments with labeled 1-butene on zeolite Y (76), it is known that substantial amounts of alkanes are formed, which are saturated by hydride transfer from surface polymers. In both liquid and solid acid catalysts, hydride transfer from isoalkanes larger than... 

Zeolite Y, 2 345t, 5 238-239, 11 678, 679 coke formation on, 5 270 for liquid separation adsorption, 1 674 manufacture, 2 359 structure, 1 675 Zeolite ZSM-5, 11 678 Zeolitic cracking catalysts, 16 835 Zeolitic deposits, 16 813 Zeonex, 10 180 Zeotypes... 

We expect wide site separation (2-3 Al/U.C.) to increase cracking versus hydrogen transfer if hydrogen transfer is a two-center reaction like coke formation... 

The first reaction is the isomerization from a zero-octane molecule to an alkane with 100 octane the second is the dehydrocyclization of heptane to toluene with 120 octane, while the third is the rmdesired formation of coke. To reduce the rate of cracking and coke formation, the reactor is run with a high partial pressure of H2 that promotes the reverse reactions, especially the coke removal reaction. Modem catalytic reforming reactors operate at 500 to 550°C in typically a 20 1 mole excess of H2 at pressures of 20-50 atm. These reactions are fairly endothermic, and interstage heating between fixed-bed reactors or periodic withdrawal and heating of feed are used to maintain the desired temperatures as reaction proceeds. These reactors are sketched in Figure 2-16. 

Modem steam cracking reactors use 4-in. steel tubes 100 ft long in a tube furnace heated to -850°C. Pressures are approximately 2 atm (sufficiently above 1 atm to force reactants through the reactor), and residence times are typically 1 sec. Water (steam) interacts very httle with the hydrocarbons by homogeneoirs reactions, but more water than alkane is typically added to reduce coke formation. 

In present catalytic cracking processes the production of gasoline is accompanied by the formation of substantial amounts of coke, as well as the production of hydrogen and light hydrocarbons. As the control of the combustion of coke was the main problem facing the commercial development, the effects of variables are conveniently expressed in terms of coke formation in the following discussion. 

The major industrial source of ethylene and propylene is the pyrolysis (thermal cracking) of hydrocarbons.137-139 Since there is an increase in the number of moles during cracking, low partial pressure favors alkene formation. Pyrolysis, therefore, is carried out in the presence of steam (steam cracking), which also reduces coke formation. Cracking temperature and residence time are used to control product distribution. 

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