Unit-IV

C4 & C5 Compounds
 Introduction
C4 Olefins and their derivatives offer many potential
applications for manufacture of a large number of
intermediates which are being used in synthetic,
plastics, stabilizers, plasticizers, solvents, gasoline
additives, antioxidants, herbicides, etc.,
C5 hydrocarbons are used as feedstock for a wide
variety of end products such as chemical
intermediates, thermoplastics, elastomers,
insecticides, pharmaceuticals, solvents, etc.,
According to chem. systems, global demand for
butadiene, isobutylene and butene will climb 11.2,
18.8 and 1.7 million tonnes, respectively by 2010.
Product profile of C4 Olefins
Product profile of C5 Chemicals
 Butadiene
Butadiene is produced commercially by three
processes:
Steam Cracking of Paraffinic Hydrocarbons:
In this process, butadiene is a co-product in
the manufacture of ethylene (the ethylene
co-product process).
Catalytic Dehydrogenation of n-Butane and
n-Butene (the Houdry process).
Oxidative Dehydrogenation of n-Butene
(the Oxo-D or O-X-D process).
1. Steam Cracking of Paraffinic Hydrocarbons
Catalyst: Chromia-alumina 2. Catalytic Dehydrogenation of Butanes
Temp: 600-6700c
Pressure: 15-70 kPa
Space velocity: 1-3 hr-1
chromium/alumina : catalysts 2. Catalytic Dehydrogenation of
Butanes
Catalyst: Chromia-Iron
Temp: 620-6800c 3. Catalytic Dehydrogenation of Butenes
Pressure: 0.15-0.18MPa
Steam to Butane : 8-10:1
Space velocity: 1-3 hr-1
 In the Houdry process, n-butane is dehydrogenated over
chromium/alumina catalysts.
The reactors normally operate at 12-15 centimeters Hg absolute
pressure and approximately 1100-1260 F (600-680 C).
Three or more reactors can be used to simulate continuous
operation: while the first reactor is on-line, the second is being
regenerated, and the third is being purged prior to regeneration.
Residence time for feed in the reactor is approximately 5-15 minutes.
As the endothermic reaction proceeds, the temperature of the
catalyst bed decreases and a small amount of coke is deposited.
In the regeneration cycle, this coke is burned with preheated air,
which can supply essentially all of the heat required to bring the
reactor up to the desired reaction temperature.
The reactor effluent goes directly to a quench tower, where it is
cooled. This stream is compressed before feeding an
absorber/stripper system, where a C4 concentrate is produced to be
fed to a butadiene extraction system for the recovery of high purity
butadiene.
gen/butene molar ratio of approximately 0.55

3. Catalytic dehydrogenation of Butenes

 In general, in an oxydehydrogenation process, a mixture of
n-butenes, air and steam is passed over a catalyst bed
generally at low pressure and approximately 930-1110 F
(500-600 C).
The heat from the exothermic reaction can be removed by
circulating molten heat transfer salt, or by using the stream
externally for steam generation. An alternate method is to
add steam to the feed to act as a heat sink. The heat can
then be recovered from the reactor effluent.
Reaction yields and selectives can range from 70-90%,
making it unnecessary to recover and recycle feedstock.
(Yield losses can produce the CO2.)
a mixture of air, steam, and n-butenes is passed over the
dehydrogenation catalyst in a continuous process.
The air feed rate is such that an oxygen/butene molar ratio
of approximately 0.55 is maintained, and the oxygen is
totally consumed. A steam to butene ratio of 10:1 has been
reported as necessary to absorb the heat of reaction and to
limit the temperature rise.
The reactor effluent is cooled and the C4 components are