Cracking reaction rates

Whereas the cracking reaction rate becomes significant above 700 dehydrogenations only take place substantially above 800 to 850. Moreover, the processes of the formation of polyaromatic hydrocarbons and coke only occur rapidly at temperatures above 900 to 100(y C The adoption of long residence times or the elevation of the reaction temperatures hence favor the reaction yielding heavy aromatic derivatives at the expense of the production of light olehns by cracking. 

Higher temperatures will enhance both isomerization as well as cracking reaction rates. However, at higher operating temperatures, the ability of the solvent to extract the precursor compounds will suffer because of decrease in solvent density and hence in solvent power. The inability to extract coke precursor compounds will lead to eventual deactivation of the catalyst. Furthermore, the overall rate of reaction may be limited by... 

Cracking reactions result in a net yield loss because methane and ethane are unreactive at Cyclar process conditions. The presence of the promoter in the catalyst greatly increases the dehydrogenation reaction rate relative to the cracking reaction rates, and thus the net aromatics yield is increased. The result of the nearly complete conversion of the oligomer is an aromatic product with virtually no impurities. 

Cracking reaction Rate coefficient (at 850 K), m " mol "" kgcat s" Activation energy, kJ mol ... 

Pa Pr = partial pressures of butane and butene Ps = partial pressure of hydrogen k = cracking reaction rate constant... 

The algebraic form of the expression (9.24) for the enhancement factor is specific to the particular reaction rate expression we have considered, and corresponding results can easily be obtained for other reactions in binary mixtures, for example the irreversible cracking A—2B. ... 

The similarity of oxidation rates of different hydrocarbons in the higher temperature regions is probably related to the predominance of alkyl radical cracking reactions under these conditions (reaction 28). The products of such reactions would be similar for most common hydrocarbons (96). 

Pyrolysis. Pyrolysis of 1,2-dichloroethane in the temperature range of 340—515°C gives vinyl chloride, hydrogen chloride, and traces of acetylene (1,18) and 2-chlorobutadiene. Reaction rate is accelerated by chlorine (19), bromine, bromotrichloromethane, carbon tetrachloride (20), and other free-radical generators. Catalytic dehydrochlorination of 1,2-dichloroethane on activated alumina (3), metal carbonate, and sulfate salts (5) has been reported, and lasers have been used to initiate the cracking reaction, although not at a low enough temperature to show economic benefits. 

Cracking temperatures are somewhat less than those observed with thermal pyrolysis. Most of these catalysts affect the initiation of pyrolysis reactions and increase the overall reaction rate of feed decomposition (85). AppHcabiUty of this process to ethane cracking is questionable since equiUbrium of ethane to ethylene and hydrogen is not altered by a catalyst, and hence selectivity to olefins at lower catalyst temperatures may be inferior to that of conventional thermal cracking. SuitabiUty of this process for heavy feeds like condensates and gas oils has yet to be demonstrated. 

It is appropriate to emphasize again that mechanisms formulated on the basis of kinetic observations should, whenever possible, be supported by independent evidence, including, for example, (where appropriate) X-ray diffraction data (to recognize phases present and any topotactic relationships [1257]), reactivity studies of any possible (or postulated) intermediates, conductivity measurements (to determine the nature and mobilities of surface species and defects which may participate in reaction), influence on reaction rate of gaseous additives including products which may be adsorbed on active surfaces, microscopic examination (directions of interface advance, particle cracking, etc.), surface area determinations and any other relevant measurements. 

A hydrocarbon is cracked using a silica-alumina catalyst in the form of spherical pellets of mean diameter 2.0 mm. When the reactant concentration is 0.011 kmol/m3, the reaction rate is 8.2 x 10"2 kmol/(m3 catalyst) s. If the reaction is of first-order and the effective diffusivity De is 7.5 x 10 s m2/s, calculate the value of the effectiveness factor r). It may be assumed that the effect of mass transfer resistance in the. fluid external Lo the particles may be neglected. 

Consider the gas-phase decomposition A B -b C in an isothermal tubular reactor. The tube i.d. is 1 in. There is no packing. The pressure drop is 1 psi with the outlet at atmospheric pressure. The gas flow rate is O.OSSCF/s. The molecular weights of B and C are 48 and 52, respectively. The entering gas contains 50% A and 50% inerts by volume. The operating temperature is 700°C. The cracking reaction is first order with a rate constant of 0.93 s . How long is the tube and what... 

Example 5.6 Hydrocarbon cracking reactions are endothermic, and many different techniques are used to supply heat to the system. The maximum inlet temperature is limited by problems of materials of construction or by undesirable side reactions such as coking. Consider an adiabatic reactor with inlet temperature Tm. Then T z) < T, and the temperature will gradually decline as the reaction proceeds. This decrease, with the consequent reduction in reaction rate, can be minimized by using a high proportion of inerts in the feed stream. 

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