Thermal and catalytic processes in petroleum refining by S D Raeev

By S D Raeev

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CÀC¼CÀCÀ þ CH3 j j C C  130  C6 H5 CH2 CH2 ! 5 Kinetic Constants for the Decomposition of Selected Radicals A (sÀ1 ) E (kJ/mole) Ref. 5 33 1 À C3 H7 ! 5 33 1 À C3 H7 ! 8 33 2 À C3 H7 ! 8 27 34 1 À C4 H9 ! 4 35 1 À C4 H9 ! 3 35 2 À C4 H9 ! 1 35 2 À C4 H9 ! 6 35 i À C4 H9 ! 7 27 i À C4 H9 ! 3 35 i À C4 H9 ! 2 27 C5 H11 ! 2 33 C5 H11 ! 9 27 C5 H11 ! 2 33 1 À C6 H13 ! 6 35 2 À C6 H13 ! 8 35 3 À C6 H13 ! 8 35 3 À C6 H13 ! 1 35 C2 H3 ! 9 27 C3 H5 ! 6 27 C4 H7 ! 4 33 C4 H7 ! 9 27 Methyl À allyl ! 5 27 Methyl À allyl !

9 27 Methyl À allyl ! 5 27 Methyl À allyl ! 2 27 Reaction   C2 H5 ! C2 H4 þ H        13          14 14      13  13                     14 14 10 14   12 The above information on the reactions generated by the radicals formed in the initial breaking of the C – C bonds, make it possible to analyze the succession of transformations that take place during the thermal decomposition of hydrocarbons. These transformations consist of successive breaking of C – C bonds in position to the odd electron, of the radicals produced following the initial cleavage (reactions of the type b1 ).

The available data do not allow the formulation of even hypothetical cracking mechanisms. It is known that the cyclic compounds are much more stable than the acyclic ones. The presence of elementary sulfur in the heavy products resulting from pyrolysis may be explained as result of the decomposition of disulfides. Thus, it may be assumed that the interaction of the disulfides with the radicals, followed by the cleavage in position, may lead, among others, to the formation of two types of radicals:   RÀ S and RÀSÀ S The first one, may produce a mercaptan:   RÀ S þR1 H !

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