Optimization of Dehydrogenation to produce Propylene from Propane

Propylene is a major industrial chemical intermediate that serves as one of the

building blocks for an array of chemical and plastic products. Historically propylene
is produced as a by-product of petroleum refining and of ethylene production by
steam cracking of hydrocarbon feedstock. US natural gas supplies have significantly
increased due to the rising exploitation of shale gas. Ethylene producers are shifting
to lighter feedstocks (more ethane, less naphtha), which is decreasing yields of
propylene in cracking operations.
The increasing demand for propylene and the availability of low-cost feedstock
make propane dehydrogenation an economically attractive chemical route. Propane
is recovered from propane-rich liquefied petroleum gas (LPG) streams from natural
gas processing plants. Propane maybe obtained in smaller amounts as a by-product
of petroleum refinery operations, such as hydrocracking and fluidized catalytic
cracking (FCC).
Dehydrogenation of propane involves the breaking of two carbon-hydrogen bonds
with the simultaneous formation of a hydrogen molecule. The double bond is a
highly reactive and facilitates the use of molecules as an intermediate for the
production of typical petrochemical products such as polymers.

C H C H +H
3 8
3 6
2
The Propane Dehydrogenation Process (PDH) is used to supply polymer-grade
propylene from propane to meet the growing propylene market needs, independent
of a steam cracker or FCC unit. PDH process provides a dedicated, reliable source of
propylene with control over feedstock costs for downstream chemical operations.
Reaction system for the dehydrogenation of propane must supply a large amount of
reaction heat at a temperature and maintain strict control of the temperature, to
minimize the formation of by-products. The reaction paths lead to the depositing of
carbon (coke) on the surface of the catalyst. Even with a highly selective catalyst,
the depositing of coke gradually makes the catalyst less active. The maximum level
of coke accumulation and consequent time needed for each phase in the reaction
cycle and regeneration depend on the nature of the particular catalyst used.

To purge the coke accumulated on the catalyst surface during the reaction either a
continuous catalyst regenerator (CCR) or a fixed-bed reactor is required. In the CCR
unit the catalyst circulates in moving beds through the reactors, before being fed for
regeneration. The CCR operates independently of the reaction, burning off the coke
and returning the catalyst to its reduced state. In the fixed-bed reactor process at
least two (or more) reactors must be used so that the catalyst in one reactor can be
regenerated without stopping the process. The advantage with a moving bed or a
fluidized bed is that the catalyst can be continuously removed from the reactor and
be regenerated. The disadvantage is that a separate regeneration unit is needed.

Steam
Propane

Dehydrogenrati
on Reaction

Gas Compresion
& Separation

Heat Recovery

Fractionation

Propylene
Product
Fuel Gas

Fixed Bed Reactor 1

These processing conditions, together with the thermodynamic and kinetic

requirements, have pushed researchers to develop optimal reactor design solutions
for the industrial exploitation of dehydrogenation reactions. The available
commercial technologies offer different choices as regards the reaction system,
tending to simultaneously optimize the reaction conditions and the supply of energy
to the reaction.
Real-time measurement of process gases and impurities is critical to optimize
product conversion, product purity and catalyst regeneration cycles. Process Mass
Spectrometry is the premier technology for process gas analysis being able to
measure these compounds regardless of the catalyst regeneration process.
2

Some

of the primary advantages of Mass Spectrometry are;

Primary Analytical Method
High Sensitivity and Selectivity
Analysis time is less than 10 seconds per stream
Measure of multiple reactor on a single analyzer
Measure multiple components simultaneously
Low Life Cycle Cost of Ownership
Web/Server based operating system to interface with DCS

Stream Analysis Table:

Name

HYDROGEN
N-BUTANE
ETHYLENE
ETHANE
PROPANE
PROPYLENE
ISOBUTANE
1-BUTENE
OXYGEN
METHANE
o-Xylene
TOLUENE
BENZENE
N-PENTANE

Estimate
Concentrat
ion

Sensitiv
ity

Detect
ed
Mass

RIF

RSD(F)

28.50%
0.04%
0.70%
0.90%
39.90%
26.40%
0.16%
0.56%
0.10%
1.79%
30ppm
30ppm
0.04%
0.03%

0.175
2
1
1
1
1
2
1
0.98
0.698
2
2
2
2

2
58
26
30
29
41
43
56
32
16
106
92
78
72

<0.01
0.73
16.22
3.41
<0.01
0.21
32.01
<0.01
<0.01
0.05
<0.01
0.11
<0.01
0.06

%
0.13
4.03
1.89
1.30
0.05
0.06
3.05
0.63
0.96
0.27
6.14
4.87
1.06
5.63

RSD(M
)
%
0.54

STD(F)
vol.
pm
383
16
132
117
190
170
49
36
10
49

0.82
0.65
0.75

STD(
M)
vol.
ppm
2.15

0.25
0.19
4
17

0.23

Definition of terms appearing in the evaluation tables.

RIF:
Relative Interference Factor, (intensity of all interfering ions/intensity of
the ion of interest)
RSD(F):
Relative Standard Deviation (one sigma) as a % of the reported
concentration with the use of Faraday Cup detector
RSD(M):
Relative Standard Deviation (one sigma) as a % of the reported
concentration with the use of Electron Multiplier detector
STD(F):
Standard Deviation (one sigma) in absolute units of concentration with
the use of Faraday Cup detector
STD(M):
Standard Deviation (one sigma) in absolute units of concentration with
the use of Electron Multiplier detector