B00233659

Catalytic Processs for

the
Production of Propylene

Contents
Introduction............................................................................................................... 2
Chemical Properties and Reactions.................................................................................. 2
Manufacturing propylene.............................................................................................. 2
Mechanism of reaction................................................................................................. 3
Safety and environmental impacts................................................................................... 5

Introduction
Propylene, also knowing as propene is a gas at room temperature and pressure
that is colourless. Propylene has the same formula as cyclopropane but the
atoms are connected in a different way together making them structural isomers.
Propylene is heavily used in the plastics industry as the raw basic starting base
material for the manufacture of plastics. Propylene is also used to make variety
of chemicals such as acetic acid, butyraldehyde and acrylonitrile. In the year
2013 about 58 million tons of propylene were manufactured and processed
worldwide and that number is steadily increasing year by year as the demand
grows.

Chemical Properties and Reactions

Chemical formula
Mass (g/m)
Density
Meting point
Boiling point
Solubility in water
Viscosity
Flash point
Std. enthalpy of formation fH298
Std. molar entropy S298
Std. enthalpy of combustion cH298
Upper flammability limit in air
Lower flammability limit in air

C3H6
42.08
1.81 kg/m3
-185.2C
-47.6C
0.61 g/m3
8.34 Pas at 16.7 C
-108C
20.41 kj mol-1
81.73 kj-1 mol-1 K
-2057.8 kj mol-1
11%
2.1%

Due to Propylenes weak double bond it tends to react with substances that achieve
addition reactions fairy quickly. Like most alkenes, propylene undergoes the following
reactions:

Oxidation
Polymerisation
Halogenation
Hydration
Alkylation

During the combustion of propylene, in the presence of sufficient oxygen propylene burns
to produce water and carbon dioxide.

Manufacturing propylene
Propylene is produced from natural oil, gas and even coal and is usually a by-product of
oil refining and natural gas processing. During oil refining propylene as well as ethylene
and other hydrocarbons are produced as a result of cracking larger hydrocarbon
molecules to produce the smaller more commercially viable hydrocarbons. The main
source of propylene is naptha cracking as a side product with the main product produced
being ethylene. Propylene can be separated from other hydrocarbons by distillation.
Other commonly used ways to produce propylene are:
Olfin metathesis: a reversible reaction between ethylene and butane where double bonds
are broken then reformed to form propylene. This is a very successful process in areas
where there is an abundance of ethylene and butane and gives propylene yields of
around 90%.
Propane dehydrogenation: this process converts propane into propene by the removal of
hydrogen which forms a double bond between the carbons turning it into propene. He
reaction yield is around 80%. Propane is converted to propylene in a rector with a
temperature ranging between 500C and 700C and a Nobel metal catalyst.
High severity fluid catalytic cracking: This particular process converts heavier le desired
hydrocarbons down to smaller much more desired hydrocarbons. This process uses
higher than normal catalyst to oil ratios, stream injection ratios, temperatures and pressures in
order to maximise production yields. The FCC unit is usually fed with gas oil and residues.
Modern fluid catalytic cracking usually use a fine powders catalyst with a bulk density of
0.8 to 0.96 g/cm3 and having a particle size distribution ranging from 10 to 150 m and
an average particle size ranging between 60 to 100 m. The desirable properties of an
FCC catalyst are:
Good stability at high temperature
High activity
Good resistance to attrition
Low coke production
A modern fluid catalytic cracking catalyst has four major components:
1. Crystalline zeolite
2. Matrix
3. Binder
4. Filler

Mechanism of reaction
Cracking reactions that occur such as in the fluid catalytic cracking unit involve a carbon
carbon rupturing catalysed by the acid solid such as SiO2Al2O3 or zeolites with a
carbonium ion intermediate briefly occurring.
Initiation step:
H abstraction
R1-CH2-CH2- R2 + L
R1-CH2-CH+- R2 + HL
Alkane
Lewis site
Carbrnium ion
Cracking step ( -scisson):
R3-CH2-CH+- R4
R 3+
+ CH2=CH- R4
Carbrnium ion
Carbrnium ion
Alkene

Figure 1: Generalised catalytic cycle for cracking of an alkane- (Farrauto, 2006)

Figure 2: Decrease I alkene and increase in alkane selectivity for a given carbon number(Farrauto, 2006)

Cracking catalysts are solid acids principally made up of amorphous silica-aluminas and
rare earth exchanged Y-zeolites. A typical commercial cracking catalyst is a mixture of yzeolite and SiO2-Al2O3 which is prepared by mixing silica solution and then the resultant
slurry is spray dried to produce spherical particles. The result particles are between 10
and 40% y-zeolites usually with ion exchanged rare earth metal ions to give better
thermal stability. The resultant mixture is a large balance of SiO 2-Al2O3 matrix. The matrix
structure also functions as a protector for the zeolites from poisons and offer attrition
resistance. Additives are usually added as well to the catalyst. Attrition resistance is
usually a really important property as it determines rate of addition of catalyst into the
reactor which effects the process economics as well and influences the particle size
distribution within the bed and hence the fluidity. Typically attrition increases with zeolite
content and therefore zeolite content is usually limited to 35-40%.
Additives to the process make up no more than 5% of the solid catalyst and usually have
a great effect on improving the yield, the catalyst life and the particle distribution.
Regeneration of the catalyst involves the use of baffles as the heavier more dense
catalyst molecules will move by gravity towards the bottom of the reactor where they are
then stripped of any residual oil by steam when taken to the steam stripper and the
resultant catalyst that is removed is fed back into the rector. The regenerated catalyst
usually contains about 0.05% coke and is separated further by the use of cyclones.
Accumulation of coke will greatly affect the catalysts ability to function and may lead to
deactivation of the catalyst.

Figure 3: Typical simplified catalytic Cracking flow sheet- (Farrauto, 2006)a

Safety and environmental impacts

Propylene has low inhalation toxicity but can cause anaesthetic effects and maybe even
unconsciousness at high concentrations. Propylene is very volatile and flammable so

precautions must always be taken to avoid exposure to sources of ignition (including

static charge). Care must be taken that any propylene that has been accidently realised
does not gather to for explosive pockets, if such a thing occurs all ignition sources must
be eliminated and ventilation must be established to disburse the cloud. Propylene is
usually stored as a liquid under pressure for ease of transport.

Bibliography
Farrauto, H. a. (2006). Fundementals of industrial processes.
http://www.icis.com/resources/news/2007/11/06/9076456/propylene-productionand-manufacturing-process/
http://www.essentialchemicalindustry.org/chemicals/propene.html
http://www.freepatentsonline.com/4435282.html
Coulson and Richardson handbook of chemical engineering