157
2.2.1 Propane Dehydrogenation (PDH)
Gradually, PDH has become a preferred route for the on-purpose production of
chemical grade propylene. Propane, the feedstock for PDH process, comes as byproduct while processing of natural gas or from refinery liquefied petroleum gas
(LPG). The recent discovery of shale gas in the North America and the vast reserve
of natural gas in the Middle East have boosted the commercial prospect of PDH
technology [25]. There are five major proven PDH technologies available in a commercial scale, these include: (a) CATOFIN process by ABB Lummus Global, (b)
OLEFLEX process by UOP (c) steam active reforming (STAR) by Krupp Udhe, (d)
PDH by Linde-BASF-Statoil, and (e) fluidized bed dehydrogenation (FBD) by
Snamprogetti. Each technology has its own merits and demerits. Major difference
among all the PDH technologies comes from reactor technology, catalyst type,
operating conditions, and performance of the catalyst (Table 2).
STAR process is based on fixed-bed reactor and Pt-Sn catalyst supported on
zinc-aluminate and with calcium/magnesium aluminate as binder is used. The reaction is operated at 500–600 °C at 5–6 bar pressure. Steam is co-fed with feed/propane for coke reduction and thus it is called steam-activated reforming (STAR) [27,
28]. Snamprogetti and Yarsintez commercialized fluidized bed dehydrogenation
Table 2 Commercial process for propane dehydrogenation (PDH) and process conditions [26]
S.
no. Technology Licensor
Type of
reactor
Catalyst
formulation
Process
condition
Performance of
the catalyst
1
CB&I Lummus
(Catofin)
Multiple
parallel
fixed-bed
reactors
18–20 wt%
CrO x on Al 2 O 3
support, promoted
by Na or K
(1–2 wt%)
575 °C,
0.2–
0.5 bar
Conversion >15%,
C3 = selectivity:
98%
2
UOP (Honeywell)
Oleflex
Fluidized
catalytic
reactor
<1 wt% Pt and
1–2 wt% Sn on
Al 2 O 3 support,
promoted by Na or
K (0–1 wt%)
525–
705 °C,
0.2–
0.5 bar
Conversion >20%,
C3 = selectivity:
98%
3
Uhde (STAR:
steam-activated
reforming)
Fixed-bed
reactor
Pt-Sn on zinc−
aluminate support
and calcium/
magnesium–
aluminate binder
500–
600 °C,
5–9 bar
Conversion >20%,
C3 = selectivity:
98%
4
Linde/BASF
Fixed-bed
reactor
(similar like
STAR
process)
Pt-Sn supported on
ZrO 2
590 °C,
5–9 bar
Conversion >20%,
C3 = selectivity:
98%
5
Snamrogetti/
Yarsintez (FBD:
fluidized bed
dehydrogenation)
Fluidized
catalytic
reactor
CrO x /Al 2 O 3
catalyst, with alkali
metal promoter
550–
600 °C,
1.1–
1.5 bar
Conversion >15%,
C3 = selectivity:
98%
C3-Based Petrochemicals: Recent Advances in Processes and Catalysts
2.2.1 Propane Dehydrogenation (PDH)
Gradually, PDH has become a preferred route for the on-purpose production of
chemical grade propylene. Propane, the feedstock for PDH process, comes as byproduct while processing of natural gas or from refinery liquefied petroleum gas
(LPG). The recent discovery of shale gas in the North America and the vast reserve
of natural gas in the Middle East have boosted the commercial prospect of PDH
technology [25]. There are five major proven PDH technologies available in a commercial scale, these include: (a) CATOFIN process by ABB Lummus Global, (b)
OLEFLEX process by UOP (c) steam active reforming (STAR) by Krupp Udhe, (d)
PDH by Linde-BASF-Statoil, and (e) fluidized bed dehydrogenation (FBD) by
Snamprogetti. Each technology has its own merits and demerits. Major difference
among all the PDH technologies comes from reactor technology, catalyst type,
operating conditions, and performance of the catalyst (Table 2).
STAR process is based on fixed-bed reactor and Pt-Sn catalyst supported on
zinc-aluminate and with calcium/magnesium aluminate as binder is used. The reaction is operated at 500–600 °C at 5–6 bar pressure. Steam is co-fed with feed/propane for coke reduction and thus it is called steam-activated reforming (STAR) [27,
28]. Snamprogetti and Yarsintez commercialized fluidized bed dehydrogenation
Table 2 Commercial process for propane dehydrogenation (PDH) and process conditions [26]
S.
no. Technology Licensor
Type of
reactor
Catalyst
formulation
Process
condition
Performance of
the catalyst
1
CB&I Lummus
(Catofin)
Multiple
parallel
fixed-bed
reactors
18–20 wt%
CrO x on Al 2 O 3
support, promoted
by Na or K
(1–2 wt%)
575 °C,
0.2–
0.5 bar
Conversion >15%,
C3 = selectivity:
98%
2
UOP (Honeywell)
Oleflex
Fluidized
catalytic
reactor
<1 wt% Pt and
1–2 wt% Sn on
Al 2 O 3 support,
promoted by Na or
K (0–1 wt%)
525–
705 °C,
0.2–
0.5 bar
Conversion >20%,
C3 = selectivity:
98%
3
Uhde (STAR:
steam-activated
reforming)
Fixed-bed
reactor
Pt-Sn on zinc−
aluminate support
and calcium/
magnesium–
aluminate binder
500–
600 °C,
5–9 bar
Conversion >20%,
C3 = selectivity:
98%
4
Linde/BASF
Fixed-bed
reactor
(similar like
STAR
process)
Pt-Sn supported on
ZrO 2
590 °C,
5–9 bar
Conversion >20%,
C3 = selectivity:
98%
5
Snamrogetti/
Yarsintez (FBD:
fluidized bed
dehydrogenation)
Fluidized
catalytic
reactor
CrO x /Al 2 O 3
catalyst, with alkali
metal promoter
550–
600 °C,
1.1–
1.5 bar
Conversion >15%,
C3 = selectivity:
98%
C3-Based Petrochemicals: Recent Advances in Processes and Catalysts