Beruflich Dokumente
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KBR Internal Reference Paper 2235
Abstract: With the number of new ethane-based crackers coming on line in the next few
years, it is anticipated that the traditional source of nearly two-thirds of the worlds propylene,
steam crackers, will fall short of demand. Thus, there is great interest in new propylene-onpurpose technologies. One such technology is the Advanced Catalytic Olefins (ACOTM)
process, an FCC-type process which cracks straight run feeds such as naphtha (already the
feed source for approximately half of the worlds ethylene production) to large quantities of
propylene and ethylene. Compared to a traditional steam cracker, ACO produces significantly
more propylene (typical P/E production ratio is approximately 1:1) and more total olefins at
lower energy consumption and CO2 footprint. A description of the ACO process is provided,
along with an economic comparison to steam cracking when processing a typical naphtha
feed. A description of the ACO Demonstration Unit constructed by SK Global Chemical
(formerly SK Energy) at its site in Ulsan, Korea, the first commercial demonstration of ACO
technology, is also provided, including a summary of early operations which began in 4Q10.
regions of the world, naphtha cracking represents a significantly higher percentage of ethylene
production:
Figure 1
Ethylene Production from Naphtha
90
80
70
60
50
Percent
40
30
20
10
0
South
America
W. Europe
Central
Europe
Baltic / CIS
India
NE Asia
(incl.
China)
SE Asia
Source: CMAI
Steam cracking, or pyrolysis, the standard process for ethylene production used in the
petrochemical industry since its inception more than sixty years ago, has many drawbacks,
however, as follows:
Cracking reactions occur at very high temperatures, typically greater than 850oC and
approaching 900oC for high conversion gas cracking
Propylene production is limited to 0.4-0.6 parts by weight per part of ethylene
Furnaces must be periodically removed from service to remove the coke which forms in
the furnace coils as a result of the high process temperatures
Pyrolysis is an energy-intensive process, and greenhouse gas emissions are high
The ACO process is an alternative process which catalytically cracks naphtha feed rather
than thermally, and as such it addresses all of these drawbacks while also producing increased
total light olefins yields at much higher propylene-to-ethylene ratios.
While many of the new propylene-on-purpose technologies which have come into the
market in recent years use costly, niche, or less-prevalent feeds, the ACO process has been
developed specifically to use the most common feed currently used for olefins production:
naphtha.
ACO
TM
Figure 2
Reactor System
To Flue
Gas System
Catalyst
Fines
ACO
Orthoflow
Reactor /
Regenerator
Fresh Feed
Reactor
Effluent
To Recovery
Steam
Fuel
Oil
BFW
Oil Wash
Tower
Catalyst Storage
And Handling
Recycle
Regeneration
Air
Similar to any refinery FCC, the ACO reactor (converter) is comprised of four sections:
riser/reactor, disengager, stripper and regenerator. The feed is introduced at the bottom of
the riser and mixed with hot regenerated catalyst. The feed is vaporized and the reactions
take place as the feed gas and catalyst flow upward in the riser. At the end of the riser the
product gas and catalyst are separated in cyclones, housed in the disengager. The catalyst is
then routed to the stripper, where product gases still entrained in the catalyst pores are
stripped with steam or nitrogen and routed with the reactor effluent. Stripped catalyst then
flows to the regenerator, where air is introduced and coke which has formed on the catalyst
during the cracking operation is burned, regenerating the catalyst for re-use in the riser.
Accessory systems for the unit include air supply, flue gas handling and heat recovery and
catalyst storage. Reactor overheads are typically routed to the primary fractionator and
subsequent product separation and recovery.
As can be seen in Figure 2 KBRs FCC design uses a configuration known as
OrthoflowTM, in which the Disengager is stacked directly above the Regenerator. The
advantages of the Orthoflow configuration are several: first of all, the plot space required is
much smaller for this configuration compared to the side-by-side type of unit. Foundation and
structural costs are also reduced. The Orthoflow configuration allows the unit to be fabricated
and dressed off-site and set into place with one lift, saving on construction costs and with less
welding required in the field. The stripper is submerged within the regenerator which reduces
the vertical height of the unit and thus the cost.
One significant advantage of the ACO converter is economy of scale regarding olefins
capacity. The maximum commercially demonstrated capacity in a single cell, liquid-feed
pyrolysis furnace, is nearly 200 kta ethylene, or approximately 300 kta of total olefins. By
contrast, if sized similarly to existing large commercial FCC units the ACO reactor can be
designed to make about 5-6 times more olefins, or up to 1,700 kta ethylene + propylene
within a single reactor.
Relative to the refinery FCC, ACO employs some unique and innovative design aspects
which address the fact that the light straight run feeds used in ACO are so much lighter than
refinery FCCs:
Heat Balance similar to refinery FCC the ACO (and the SUPERFLEX) process is
endothermic. A typical refinery FCC uses coke formed on the catalyst as the heat
source to maintain the units heat balance. In ACO, however, the feed is substantially
lighter and far less coke is formed. As such, to maintain heat balance, fuel must be
imported into the reaction system. KBRs patented (US#7,153,479) catalyst well design
with continuous fuel firing has now been commercially proven at the Sasol
SUPERFLEXTM unit and is applicable to both ACO and SUPERFLEX technology.
very efficient, invariably some catalyst fines will carry over with the reactor effluent
cracked gas. In refinery FCC these catalyst fines concentrate into the fuel oil byproduct stream (slurry oil). However, with ACO the quantity of fuel oil produced is
much smaller, and thus an alternative means of dealing with catalyst fines is necessary.
KBRs patented (US#7,011,740) catalyst fines removal system has now been
commercially demonstrated and applicable to both ACO and SUPERFLEX technology.
Recycle to Reactor
Cold
box
Mix C4/C5
C3
Ref
Light gas
C2
Ref
Ethylene
Drying 3
1-2
C3
C2
Splitter Splitter
Treating
Quenched
Gas
Propylene
Dehexanizer
Depropanizer
Demeth- Deethanizer anizer
Non-aromatic
C6+
Depentanizer
BTX
+
Ethane/
Propane
ACO Performance
Figures 4 and 5 below compare the yields obtained from steam cracking and from ACO
for two grades of naphtha:
Figure 4
Comparison of LSR Naphtha Cracking Yields
100
Wt%
75
Other
Gasoline
Propylene
Ethylene
50
25
0
Steam
Cracker
ACO
Figure 5
Comparison of FRN Cracking Yields
100
Wt%
75
Other
Gasoline
Propylene
Ethylene
50
25
0
Steam
Cracker
ACO
The ACO process makes about 10-25% more ethylene plus propylene on a relative
basis, depending on the operating conditions and feed quality. In the examples above, the
total ethylene plus propylene product yields are about 25% and 11% higher than the steam
cracker for LSR and FRN, respectively. However, as clearly illustrated from the red portions of
the graphs above the propylene yield is much higher, with a resultant P/E ratio of
approximately 0.9. Further, the ACO process has a higher concentration of BTX in the
gasoline fraction, resulting in about 50% higher absolute aromatics yield from the ACO
process.
The ACO process is also advantageous over the steam cracker from an energy
consumption, and thus greenhouse gas emissions, perspective. This is an important
consideration given the current increased focus on CO2 emissions. The primary benchmark for
energy consumption in the industry is specific energy, or the overall energy consumed in the
plant per unit of product made. Specifically for olefins plants, the major ISBL utilities including
fuel, steam import / export and electrical power are converted to a fuel equivalent (based on
typical boiler and power generation efficiencies) and divided by the production rate. On this
basis, the specific energy per unit of olefins produced for ACO is about 10% and 7% lower
than steam cracking for the LSR and FRN cases above, respectively.
All of this leads to an improvement in the overall economics for naphtha cracking.
Based on current values for naphtha and the various products, an ACO unit cracking the same
quantity of naphtha as a new steam cracker designed to produce 700 kta of ethylene at a 0.5
P/E production ratio has a gross margin improvement of $115MM/yr and $111MM/yr for the
LSR and FRN cases above, respectively. This results in much improved IRR and profitability of
the plant.
ACO Commercialization
SK Global Chemical is a division of SK, a Korean-based conglomerate with 2009 sales
over US$29 billion. SK Global Chemical owns and operates two naphtha crackers in Ulsan with
a total ethylene capacity of about 800,000 MTY and its sister company, SK Energy, also
operates several refinery units in Ulsan including two FCCs.
SK Global Chemical has recently begun commercial operations in a new demonstrationsized ACO converter system integrated with SKs existing facilities in Ulsan. This unit began
operations in 4Q10 and thus SK Energy has become the first commercial adopter of the ACO
process.
KBR completed basic engineering for this demonstration unit in 2008. The unit has a
capacity of 40 kta of olefins (ethylene plus propylene); thus, the unit is of sufficient capacity to
demonstrate the anticipated conversion and yields of the ACO reactor system. During 2009
and 2010, SK Global Chemical completed the detailed engineering for the project and procured
the equipment on a world-wide basis. The ACO reactor system was fabricated at a shop in
Ulsan, Korea and arrived on site and lifted into place 2Q2010, with mechanical completion of
the unit in 3Q2010.
The ACO demonstration unit includes the installation of the ACO converter system,
fresh / spent catalyst handling facilities and reactor effluent heat recovery facilities. The
effluent from the reactor is sent directly to the existing #2 RFCC Main Column section and the
flue gas from the ACO regenerator is sent to the existing #2 RFCC CO Boiler system. The
combustion air needed in the ACO regenerator is also supplied from the existing #2 RFCC
Main Air Blower. A recent photograph of the unit is shown below:
ACO Commercial Demonstration Unit
To date, operations of the Demonstration Unit have met expectations. Various grades of
naphtha are being fed to the ACO unit during its early operations, and process variables are
being varied to determine the impact. The effluent is processed in the existing refinery. Early
yield data is promising, with performance of the Demonstration unit cracking LSR consistent
with pilot plant results, as shown in the figure below (in which the actual yields obtained in the
commercial unit are added to those shown from the earlier comparison in Figure 4).
Figure 6
LSR Naphtha Cracking Yields
100
75
Other
Gasoline
50
Propylene
Ethylene
25
Steam ACO
Cracker
Demo
Unit
Ethylene yield is slightly less than the pilot plant tests but propylene yield is slightly better,
with overall olefins yield comparable to expectations per the pilot plant tests.
FRN is now being fed to the unit, and while full analysis of the yields for FRN is underway and
not yet complete the expectation is that performance will be similar to that shown for LSR
naphtha.
Summary
Steam cracking and refinery sources will not keep pace with future propylene demand
and so on-purpose technologies are becoming more prevalent. KBR offers several such
technologies, with the use dependent on the type of feed available. The ACO process uses
commonly available, straight run paraffinic feeds and cracks them to produce more total
olefins than conventional pyrolysis, with P/E ratios near 1/1 and at lower energy consumption.
SK Global Chemical successfully began operating the worlds first commercial ACO unit in
Ulsan, Korea, which came into operation in 4Q2010, with all performance expectations met to
date.