Naphtha catalytic cracking for

propylene production
Investment in on-purpose propylene production technology based on
naphtha-based feedstock is taking on various process configurations
CHRISTOPHER DEAN
High Olefins FCC Technology Services

thylene
is
produced
through steam cracking of
hydrocarbon feedstock (for
example, ethane, naphtha and
gas oils) derived during
conventional and unconventional natural gas production
and from refinery crude oil
processing. Ethane and natural
gas liquids (NGLs) are derived
from natural gas and heavy
liquid feedstocks of naphtha,
and gas oils from crude.
Naphtha is the predominant
feedstock on a global basis,
including straight-run naphthas (SRN) from refinery crude
units and naphtha derived
from condensates during natural gas production. While
ethylene is the worlds primary
petrochemical building block,
propylene is second in importance only to ethylene as a raw
material
building
block.
Traditionally, propylene has
been obtained as a byproduct
from steam cracking naphtha
and gas oils to produce
ethylene, and from gasoline-producing refinery fluid
catalytic
cracking
(FCC)
processes.
Global ethylene and propylene demand has recovered

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Other
10%

China
34%

Southeast Asia
8%

North America
10%

Middle East
21%
Indian subcontinent
14%
Northeast Asia
excl. China
3%

Figure 1 2012-2016 ethylene

capacity additions

from the 2008-2009 recession,

and longer term demand
expansion
is
expected.
Propylene
demand
was
increasing faster than ethylene
demand before the recession,
which is not the case today. Up
to 2007, global propylene
demand was increasing annually at 6.0%, while today it is
expected to increase by 3.6%
on average for the next several
years, according to analysis
from Nexant ChemSystems.
Even at these lower demand
predictions, there is expected
to be shortages in propylene
supply.
Nonetheless, future global
ethylene demand still determines steam cracking capacity
and is expected to be met in

each region, as shown in the

graphic developed by CMAI in
Figure 1.
Figure 1 reflects ethylene
capacity additions according to
CMAIs research. Asia is the
fastest-growing light olefin
market and uses naphtha as its
feedstock.
Existing
Middle
Eastern steam crackers as well
as those being built use primarily ethane-based feedstock for
producing ethylene. The North
American units are emerging
due to access to cheap shalebased ethane feedstock (less
than 22.50 cents per gallon as of
mid-January 2013), and several
will come on line after 2016.1
These
bargain
prices
for
US-based ethane and natural
gas feedstock are expected to be
sustained beyond 2016 relative
to similar feedstocks in Asia
and elsewhere. However, in
spite of these competitive
prices, it is well known that
ethane-based steam crackers
produce very little propylene
relative to naphtha and gas
oil-based steam crackers, which
is why the onus is on investing
in
on-purpose
propylene
production (OPP) technology.
Steam
cracking
heavy

Processing Shale Feedstocks 2013 1

Typical light olefin yields for steam cracking

Feedstock
Ethylene, wt%
Propylene, wt%
Ethane
80
3
Propane
44
15
Naphtha
30
16
Gas oil
23
15

P/E
0.04 (0.0375)
0.34
0.53
0.65

Table 1

feedstocks of naphtha and gas

oils produces about 60% of the
global
propylene
demand,
while 30% comes from traditional FCC units that produce
gasoline.
High
propylene
yields from steam cracking are
ultimately produced through
various recycling and operating severities of these heavy
feeds
or
non-ethane-based
feedstocks. Steam cracking
produces more pounds of
ethylene to pounds of propylene on a weight basis. Table 1
is based on general industry
knowledge and shows the typical ethylene and propylene
yield in weight percentage for
a pound of feed as it varies for
a particular feedstock. The
propylene/ethylene (P/E) ratio
indicates the selectivity of the
cracking conditions to produce
propylene.
The P/E ratio is one way of
tracking
global
propylene
demand in relationship to
ethylene demand. This ratio
also indicates which production propylene processes are
needed to meet this demand.

feedstocks being diverted to

meet higher product demand
for diesel and other fuels.
In the pre-recession period
up to 2007, it was estimated
that the global propylene
demand required a P/E ratio
of greater than 0.85. Today, this
demand is still expected to be
higher than those P/E ratios
produced by cracking naphtha
and even gas oil feedstocks.
Therefore, in order for OPP
proposals to materialise, they
have to be better than the P/E
ratios of 0.53 to 0.65 for naphtha and gas oil steam cracking,
respectively. Existing FCC and
the new high olefin FCC
(HOFCC) process will produce
P/E ratios from 1.0 to greater
than 2.0 to meet this propylene
demand.
The well-documented shift in
ethane production from multiple shale plays in North
America has placed steam
crackers utilising heavy feeds of
naphtha and gas oil at a
competitive disadvantage in
spite of their high propylene
production
capacity
(P/E
between 0.53 to 0.65) relative to
ethane-based steam crackers
(P/E only 0.04). Since steam
cracking is determined by ethylene demand and the shift to gas
feedstocks from liquids, global
propylene demand cannot be
met from the expected increase
in steam cracking production.
This is particularly the case

Increasing P/E ratios beyond 1.0

The P/E ratios of 0.65 and 0.53

for gas oil and naphtha, respectively, indicate that heavier
feeds produce a higher ratio of
propylene to ethylene. It is
important to note that globally
gas oil steam cracking is being
reduced due to these heavier

2 Processing Shale Feedstocks 2013

with the North American

propylene market should all the
announced ethane-based steam
crackers (approximately seven)
go online by 2017.
As ethane cracking capacity
increases, propylene production
decreases significantly and is
reflected in the increased pricing ratio of propylene to
ethylene.
Besides,
CMAI,
Nexant and others predict that
propylene pricing will remain
higher than ethylene pricing.
This is especially true in the US,
where there was historically an
abundant propylene supply due
to significant refining capacity.
However, refining capacity is
decreasing and what remains is
shifting from gasoline to more
diesel
production,
which
reduces propylene production.
Since ethylene demand is
expanding proportionally faster
to propylene, naphtha steam
crackers cannot meet the
expected incremental demand
for propylene. Other OPP technology
will
therefore
be
developed.
High-severity FCC processing (HS-FCC) produces high
yields of light olefins and
reduces liquid fuels. Existing
FCC units can operate at more
severe conditions that will
increase light olefin yields but
still
produce
significant
amounts of fuels (gasoline).
The HS-FCC term is somewhat
confusing due to licensing
issues and for processes that
specifically produce petrochemical feedstocks. These
FCC processes produce light
olefins and highly aromatic
content liquid products that are
used for petrochemical unit
feedstocks. To clarify, the term
HOFCC will be used to differentiate those FCC processes

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that are only petrochemical

product based. In this instance,
HS-FCC refers to HOFCC-type
processes.
CMAI research indicates OPP
capacity will increase from 13%
to 20% over the next several
years and future demand for
non-steam cracking propylene
sources will continue. Propane
dehydrogenation
(PDH)
processes currently show the
largest increase for meeting
this propylene demand. Most
of these processes besides the
HOFCC are being installed by
chemical companies and not
refiners to meet their propylene
feedstock requirements.
Other OPP technology for
propylene production, including metathesis of ethylene and
butylenes, and olefinic naphtha
cracking, require integration
with a steam cracker or other
processes that produce olefins
as byproducts. In addition,
these processes cannot produce
significant propylene yields at
cost advantages compared to
HOFCC
processes.
These
processes also cannot produce
the additional byproduct petrochemical
feedstocks
of
butylenes and aromatics as
those from the HOFCCs.
As mentioned previously, the
second significant source of
propylene production is in the
form of a byproduct from existing FCC processes primarily
designed for producing gasoline
and other fuels. These processes
have been modified by operating at higher severities and
different catalysts to produce
high levels of propylene and
other light olefins and aromatics
at the expense of gasoline and
other liquid fuels. In the US,
there is a current and expected
future slump in gasoline

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demand with an increase in

diesel demand, which reduces
the FCC units effectiveness for
maximising propylene production. As a result, significant
propylene production increases
from these modified FCC units
will not meet the expected
propylene demand.

Catalytically cracking naphtha

The HOFCC processes and

related technologies will be the
future OPP drivers for petrochemicals. Future incremental
propylene supply will come
from these enhanced FCC
processes that target light
olefin production and heavier
petrochemical feedstocks, such
as aromatics, instead of the
traditional gasoline product.
These future processes will not
just be heavy oil feedstock, but
will also include FCC processes
to catalytically crack naphtha.
As
previously
inferred,
HOFCC is a group of proprietary FCC processes targeting
light olefin production instead
of gasoline product from traditional FCC process technology.
These HOFCC processes utilise
traditional FCC technology
with
some
modifications.
Operating severities and different catalysts are used for
producing and maximising
propylene and other light
olefin products. These HOFCC
processes use heavier treated
feedstocks from crude oil, gas
oils or resids, similar to gasoline FCC feedstocks. These
units produce more light products and will minimise gasoline
produced for the gasoline fuel
blending pool, which is why
HOFCC units are essentially
petrochemical feedstock units.
They are also being integrated
into refining and petrochemical

complexes, resulting in configurations on a world-class scale.

Traditional FCC units were
designed to meet gasoline
demand by cracking heavy gas
oils or resids that generally
produce propylene yields from
8.0 wt% to 12 wt%, which is
why the major FCC licensors
have focused on HOFCC technology to increase propylene
yields by 15 wt% to 25 wt%
(and higher). However, existing gasoline FCC units cannot
be easily or cost-effectively
modified or revamped to
produce and recover significantly
higher
propylene
quantities
above
original
design.
Several significant modifications to FCC units have been
designed and commercialised.
These
modifications
or
enhancements include adding
a second reactor in the form of
a riser reactor or a downflow
reactor for recycle of a cracked
product; or as a separate feedstock reactor to generate more
propylene and lighter products. In addition, significant
changes to the gas and lighter
product recovery sections are
necessary. Modifying existing
units in certain marketing
regions may increase propylene
yields,
but
not
significantly enough to meet
the
expected
propylene
demand. These designs have
been mentioned in numerous
articles and are fairly well
known in the industry. The
engineering companies are the
primary HOFCC third-party
licensors, including Technip
Stone & Webster, Honeywell
UOP, Lummus Technology,
KBR and Axens.
These HOFCC processes will
provide significant OPP capac-

Processing Shale Feedstocks 2013 3

ity. However, feedstock to

these units is derived from
crude oil feedstock. Hence, not
enough of these units may
become available due to feedstock
competition
and
economics
favouring
fuel
production (primarily diesel).
The increasing naphtha and
lighter liquid hydrocarbons
developed from crude and gas
production are becoming more
attractive
for
producing
propylene. Therefore, next-generation HOFCCs are being
designed to crack naphtha as
the primary feedstock for
propylene production.

Naphtha supply

Naphtha supply is increasing

globally. Naphtha availability
from crude oil refining of
lighter crudes, and naphtha
derived as byproduct condensate (and some NGLs) in
natural gas production, are the
sources of this increasing
global supply. Increased global
condensate
production,
reduced gasoline demand in
the US and other developed
countries, switching to diesel,
cleaner and more efficient
fuels, and declining naphtha
steam cracker capacity all
impact the naphtha balance,
producing
higher
naphtha
inventories.
These factors will continue to
exert pressure on naphtha
balances, driving lower naphtha prices and a larger
differential between crude oil
and naphtha pricing. A final
conclusion on future naphtha
pricing is somewhat decoupling of naphtha from crude
pricing.
Higher propylene prices are
expected to continue, with
propylene pricing spiking due

4 Processing Shale Feedstocks 2013

Proprietary KBR FCC

reactor features
Propylene/ethylene
(P/E) product ratio 1
Proprietary catalyst
from SK Corporation
All proven hardware
and processes
Robust and flexible,
compared to other
processes

Recycle C4-C6
non aromatics
Straight run
naphtha

Figure 2 Advanced Catalytic Olefins

to lower supply. With expected

lower naphtha pricing and
more ethane being used in
ethylene
production,
the
expected worldwide propylene
demand will be met by catalytically
cracking
paraffinic
naphtha from a refinery or
naphtha derived from natural
gas production. Naphtha will
be the feedstock of choice for
future HOFCCs.
There
are
commercially
viable catalytic cracking naphtha processes available for

Figures 3a and b Two Axens and

Stone & Webster process technology
concepts of using the downflow
reactor as an enhancement to an
existing resid feedstock-based FCC
and as a standalone unit

propylene production, while

others are in the final stages of
development. One that is
licensed by KBR is Advanced
Catalytic Olefins (ACO), as
shown in Figure 2.
This process is a dual riser
system
utilising
refinery
straight-run naphtha and recycle material as feedstock. The
ACO
produces
ethylene,
propylene and high BTX
content in the gasoline product.
The process produces a P/E
ratio of approximately 1.0 that
is significantly better than the
P/E ratio of 0.55 from naphtha
steam cracking.
Another naphtha cracking
process is based on the HS-FCC
process technology that is in
semi-commercial operation in
Japan and licensed by Axens
and Technip Stone & Webster.
This naphtha cracking process
is in the final development
stages and can be used as an
enhancement (modification) to
existing FCC units, utilising a
downflow reactor or downer as
a second reaction zone for
cracking refinery light straightrun
or
other
paraffinic
naphthas. This downflow reactor
process
has
shown
propylene yields of 16.8 wt%,
with ethylene yields of 7.1 wt%
for a P/E ratio of 2.4.
The standalone unit in Figure
3b shows the downflow reactor
system and indicates the locations for feed injection, the
downflow reactor section and
the important rapid product
separator that separates the
reaction products from the
catalyst. The catalyst from the
bottom of the product separator empties into a catalyst
stripper,
where
additional
products are steam stripped
to remove any remaining

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www.digitalrefining.com/article/1000787

100

Catalytic
cracking
downer

Steam
cracking
furnace
14.5%

16.5%

1.8%
7.1%

80

Yield, %

hydrocarbon products before

the catalyst is regenerated. The
downflow reactor enhancement
can be utilised by any existing
FCC process technology, as
shown in Figure 3a. This shows
that the reaction system and
catalyst stripper are located at
similar elevations.
The downflow reactor allows
for higher operating severities
with
higher
catalyst-to-oil
ratios and higher reactor
temperatures than in riser or
up-flow reactor FCC unit
designs. To prevent undesirable
side
reactions
from
occurring, short contact time in
the reactor cracking zone or
low residence time at these
high reactor conditions is
provided.
Figure 4 shows the expected
yields from catalytic cracking
full-range naphtha from crude
oil with the yields from steam
cracking light and full-range
naphtha. From catalytic cracking, there is a significant
advantage in P/E ratio over
steam cracking of 2.4 to 0.55,
respectively. There are fewer
byproducts of gas and more
aromatic gasoline than in
steam cracking.
Clearly, there are viable
processes available that can
utilise naphtha to produce
propylene from standalone
units such as the ACO process,
and one using a downflow
reactor. In addition, adding a
second riser or downflow reactor
as
an
enhancement
to existing FCC units to

16.8%

60

28.1%

31.1%

8.6%

48.5%

20

17.1%

4.8%
7.4%

5.3%
5.6%

24.2%
0

C1
C2=
C3=
C4=
C4==
Gasoline

15.5%

40

17.4%

Full range

Full range

Light

P/E = 2.4

P/E = 0.55

P/E = 0.55

Figure 4 Downflow vs steamcracking yield summary

produce additional propylene

from
naphtha
is
being
commercialised.

Conclusion

The HOFCC process technology will utilise naphtha

derived from natural gas
production and any excess
from crude oil refining to meet
global
propylene
demand.
With the increase in naphtha
and NGL supply from US shale
gas production, utilising catalytic naphtha cracking has
significant merit to meet future
propylene demand. In the US,
areas within close proximity to
existing refineries near shale oil
and gas plays, and in other
areas with high concentrations
of integrated refinery and
petrochemical complexes, catalytic naphtha cracking has
significant potential to meet
propylene
demand
and

increase profitability. Refineries

can produce significant propylene and aromatics as well as
maintain fuel production to
address the needs of both the
petrochemical
and
fuels
markets for increased profitability and operating flexibility.
References
1 www.icis.com/about/price-reports
Christopher F Dean is an independent
consultant with over 35 years
experience. He is the founder of High
Olefins FCC Technology Services
LLC (www.higholefinsfcc.com).

LINKS
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categories:
Fluid Catalytic Cracking
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Processing Shale Feedstocks 2013 5