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hydrotreater revamp
Primary revamp of reactors, exchangers and other FCC pretreater components
provided return on investment for a complex refining facility
A
s part of the Marathon Ashland Petroleum sulphur to less than 50ppm sulphur and in some
LLC (MAP) clean fuels programme at the locations in the EU will actually start to require
Catlettsburg, Kentucky, refinery, the exist- zero sulphur gasoline with less than 10ppm
ing fluid catalytic cracker (FCC) feed sulphur. By 2009, zero sulphur gasoline will be
hydrotreating unit was revamped to allow required throughout the EU. Gasoline sulphur
increased capacity, processing of tougher feeds, specifications are also being reduced in the Far
and production of lower sulphur product. The East.
design rate increased from 40000 to 60000 To meet these specifications, refiners with an
bpsd and the blended feed to the unit will FCC will have two choices. One option is the
contain 15% deasphalted oil (DAO). The hydrot- post-treat option that requires treating the FCC
reated product sulphur specification is set at gasoline. The second option is the pretreat
750ppm to produce FCC gasoline that can be option, which requires reducing the sulphur in
blended directly into the gasoline pool and still the feed to the FCC. One problem with post-
meet the future low sulphur gasoline treatment is the potential loss of octane. This
specifications. can be addressed through advanced technology.
The primary revamp included addition of four The more fundamental problem of post-treat-
new reactors, additional exchangers, a new ment is that there is little chance for ROI. The
membrane unit for purifying hydrogen, and post-treat processes will meet the product
upgrading of the wash water system. The unit sulphur spec but will produce a product that is
modifications described here are part of an over- at best equal to the feed value while incurring
all restructuring of the Catlettsburg refinery and capital and operating costs.
will not only enable MAP to meets the require- The fundamental problem with pretreatment is
ments of the clean fuels project, but also provide the high capital cost. However, due to the
a return on the investment (ROI) with improved improvements in the feed, the yield structure
FCC operation. will be more favourable from the FCC and an
Gasoline sulphur specifications are tightening ROI is possible. This is especially true if costs
throughout the world. In the USA, a company can be minimised in a revamp of an existing
pool average gasoline sulphur specification of unit. In general, enhancing FCC feed hydrotreat-
120ppm was begun in January this year. In ing is economical when the combination of
January 2005, this is to be reduced to 90ppm improved FCC yields, heavier feedstocks, and
and an additional refinery specification of 30ppm environmental credits are available.
will also begin. In January 2006, a per-gallon MAP faced the challenges of meeting future
limit of 80ppm will be required in the USA gasoline sulphur specifications and turned this
generally, with an even more stringent standard adversity to an advantage. MAP chose to revamp
in California. their FCC feed pretreater as well as to restruc-
In 2005, the European Union will cut gasoline ture the refinery operations.
Objectives Pre-revamp
The Catlettsburg refinery has operated since Based on an alliance between MAP and Haldor
1917, and was the origination of Ashland Oil and Topsoe, the technology requirements for all of
Refining Company. Two additional refineries the FCC feed pretreaters in the MAP refining
have been integrated into the facility since that system are provided by Haldor Topsoe. To date,
time and petrochemical facilities were added that designs have been completed for four units, in
make it a very complex refinery. This FCC project addition to three revamps and one grassroots
originally began to increase the severity of an unit. Two of the four units have successfully
existing catalytic feed hydrotreater and was started up, including the Catlettsburg refinery
combined with other projects for refinery stream- HPVGO hydro-treater. In addition, reactor inter-
lining and simplification, as well as gasoline nals have been provided for other hydrotreating
desulphurisation. units.
The overall refinery objectives were to meet At the Catlettsburg refinery, two hydrotreating
existing and future gasoline sulphur require- units were revamped for FCC feed hydrotreating
ments while improving refinery economics. service. The existing unit had a name-plate
Specifically, the objectives were: capacity of 40000bpsd using two reactor trains
• Improve FCC economics by hydrotreating all with two, single-bed reactors in each train. The
of the FCC feed, including all DAO production. unit was typically operated at 1050psi, which
• Avoid post-treating cost/investment by reduc- was significantly less than the 1500psi original
ing FCC gasoline sulphur to a level allowing design due to hydraulic and equipment limita-
direct blending to the gasoline pool while meet- tions. The unit contained an amine scrubber to
ing 2006 requirements. remove the H2S from the recycle gas. Product
• Reduce fixed and operating costs, and improve from the high-pressure loop was sent to the
overall refinery reliability, by reducing refinery stripper before being sent out to the FCC unit.
complexity and multiplicity of equipment. The feed was straight run gas oil with some
• Avoid major turnaround (TAR)/ revamp costs DAO. However, the quantity of DAO that was
on existing FCC unit. added was limited due to high deactivation rates.
• Expand distillate hydrotreater, and reduce The feedstock typically averaged 1.7% sulphur
2006 ultra low sulphur diesel (ULSD) revamp and product sulphur averaged 0.4 wt% for a little
costs by reducing the quantity and sulphur less than 80% desulphurisation. At these rela-
content of light cycle oil (LCO). tively low sulphur conversions, the nitrogen
An FCC gasoline sulphur content of 45ppm, conversion was also low at less than 30%. The
when blended with the existing gasoline compo- gravity improvement averaged on the order of
nents, was determined to produce the targeted two API numbers with about 24 API in the feed
Temperature, °F
TC 3
were accomplished in the time 670 TC 4
normally required for a catalyst TC 5
660 TC 6
change. Sulphiding and startup took TC 7
Bed 3
place in June 2003. Startup and 650 TC 8
normal operation were attained with Bed 2 TC 9
640 Bed 1 TC 10
few problems other than plugged TC 11
strainers. A test run at the design 630 Reactor 1 Reactor 2
TC 12
TC 13
conditions was performed in 620
September 2003. 0 20 40 60 80 100
Catalyst, %
45
Gasoline yield, vol%
70 Design
40
68
35
66
64 Design 30
62 25
60 20
74 76 78 80 82 84 79 79.5 80 80.5 81 81.5 82
Conversion, wt% Conversion, wt%
Figure 5 Pilot FCC gasoline yields at the “knee” Figure 6 High severity hydrotreating produces gasoline
exceeding 67 vol% and gasoline selectivities well above well below 40ppm sulphur, even at high conversion
80% levels
Composition, wt%
50
10 40
Benzo
thiophene 30
5
Thiophene 20
0 10
RSH Sulphide Methyl Mt Bz
thiophene thiophene 0
Saturates 1 Ring 2 Ring 3 Ring 4 Ring Polars
Figure 7 Sulphur speciation values for the pilot plant Figure 8 Aromatics conversion data
test at the gasoline knee
is relatively flat, as shown in Figure 5, which of the test run were to validate hydraulic capa-
should provide good operability for the FCC in bility of the unit at the 60000bpd revamp rate
this region with limited sensitivity to minor and to verify that 750ppm sulphur product
changes in operating variables. would be produced at design conditions.
FCC gasoline sulphur design for the project Overall results are shown in the right-hand
was slightly over 40 ppm. All of the pilot gaso- column of Table 2, under Test Run, compared to
line data were below 40 ppm, even though the the earlier design and pilot plant information.
feedstock had more sulphur than design (700 vs Feed sulphur was lower than desired due to a
660ppm). As shown in Figure 6, this is a strong larger proportion of sweet crude in the crude
confirmation that FCC gasoline sulphur can slate, but high rates of DAO were processed. A
confidently be prepared at these levels with high full 60000bpd feed rate was attained, resulting
severity hydrotreating. in product sulphur of 640ppm at a relatively low
To further confirm the sulphur values, sulphur 671°F weighted average bed temperature
speciation was performed by GC–AED in the (WABT). The test run showed the normalised
Catlettsburg laboratories. Figure 7 shows the desulphurisation and denitrogenation activity of
sulphur speciation values for the pilot plant test the catalyst was higher than the design.
at the gasoline knee. Few mercaptans, sulphides, The maximum capacity of the unit was tested
and/or thiophenes were present. These materi- and the bottleneck was found to be the feed
als may, at least in part, be recombinant products pump motors at a rate of 61000bpsd. This issue
that are a function of H2S partial pressure, resi- is under evaluation. It is believed that kinetically
dence time and reactor effluent cooling curves. the revamped unit will be able to process signifi-
The data demonstrate that for a unit with low cantly more than the 60000 bpd design rate.
residence time and H2S partial pressures, these Aromatics conversion data are good indica-
values should be low. tions of FCC performance improvement. As
Benzothiophenes are also remarkably low and shown in Figure 8, multi-ring aromatics are
significant levels of sulphur compounds only converted roughly at a 50% conversion rate, with
begin to occur with methyl benzothiophenes and the saturation products resulting in increases in
heavier compounds. This provides the refiner one-ring aromatics and saturates. A total
with yet another control point in case of hydrot- aromatics saturation rate (increase in paraffins)
reater upsets. Even with high severity of 9% is excellent, as most one-ring species are
hydrotreating, EP control can be used for prod- difficult to saturate with a base metal catalyst.
uct sulphur adjustment if needed. Not all of the refinery projects have been
completed in time to provide commercial results
Test run at 60000bpd on the new units at the design conditions.
An acceptance test run was performed on 30 However, interim operations on the HPVGO
September 2003. A post-refinery revamp feed- when providing about 90 percent of the feed to
stock was not available since all of the overall the old FCC resulted in:
project changes had not been accomplished, so a • Dramatic shift in yields with a 2.5 vol%
simulated feed was used. The primary objectives increase in gasoline, 4.2 vol% increase in