An improved selective hydrogenation process for removing acetylenic impurities
such as vinyl acetylene, ethyl acetylene, propyl acetylene and acetylene in a steam
cracked crude butadiene stream by selective hydrogenation is carried out in two
steps. In the first step, the partial selective hydrogenation is carried out in
a fixed bed with a copper based catalyst to have the ratio of vinyl acetylene to
ethyl acetylene in a range of from 0 to about 1, preferably from about 0.01 to
0.6, in the product stream. In the second step, the selective hydrogenation of
the remaining C4 acetylenic impurities is carried out to completion
in the catalytic distillation mode using a palladium promoted copper catalyst,
an improved palladium catalyst or a combination of these two. The product stream
from the first step partial hydrogenation is introduced to the catalytic distillation
column at a position within the catalytic reaction zone and hydrogen feed gas is
introduced below the catalyst bed to maximize the recovery of 1,3-butadiene. The
feed position to the catalytic distillation column may vary along the catalyst
loading zone depending on the feed composition from the first step selective hydrogenation
reactor. Optionally, to prolong the catalyst service and cycle time, a solvent
is added to the reactor with the hydrocarbon bed stream in the first step or the
second step or both steps.