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Catalyst solutions
With the first UOP fixed bed Platforming unit starting up in 1949, and well over
200 modern UOP CCR Platforming units started up since 1971, UOP has been
the leader in reforming technology development. In step with numerous
process, equipment, and control innovations, UOP has also developed many
catalysts needed to push production limits further and maximise profitability.
UOP catalysts have been designed to provide both high activity and high yields
of reformate, hydrogen, and aromatics for motor fuel and aromatic applications.
Specifically formulated high yield catalysts offer an extra boost to higher yields
R-234 average
performance
Non-UOP catalyst
R-234 performance
estimated at previous
conditions
98 - 102
99.53
87.32
87.76
H2 yield, wt%
4.1
4.6
H2 production, wt%
74.5
76.2
RON
103.6
103.6
3.99
4.16
73.38
76.69
RONC
105
>105**
while higher density catalysts offer the highest activity and the ability to
overcome catalyst pinning constraints. The latter properties are ideal for
increasing aromatic and/or C5+ production by processing more naphtha
feed in the unit.
The UOP R-230 series CCR Platforming catalysts were
commercialised in the year 2000 with specific objectives of providing
good activity, increased yields and significantly lower coke make than the
industry standard UOP R-134 and R-132 CCR Platforming catalysts at that
time. A lower coke catalyst offers the ability to debottleneck CCR
Platforming units operating at a coke burning limit, thus allowing higher
octane operation, increased feed rate, options to process heavier or
cracked naphtha feedstocks, or a reduction in the H2/HC ratio.
The development of the R-230 series catalysts involved improving
the catalyst alumina base and the metal-to-acid ratio. The alumina base
was modified through new manufacturing techniques and the acid
function was modified to match the new base. As a result, compared to
the R-130 series catalysts, the coke production was reduced by 20 - 25%,
while the C5+ yield was increased by 0.5 - 0.6 wt%. The R-234 catalyst
and higher Pt version R-232 catalyst have now been applied in over
100CCR Platforming units worldwide and continue to provide higher
yields and lower coke for a wide range of customers and applications.
Catalyst life
An important factor in catalyst selection is how long the catalyst can
operate in the unit before a changeout is required. A study was conducted
to identify the number of commercial UOP CCR Platforming units that had
10+ years of catalyst life. Figure 2 shows that approximately 50 units
have achieved catalyst life of 10 or more years. There have been two units
that achieved over 20 year catalyst life. The long catalyst life is attributed
to the stability of UOPs alumina base, chloride retention properties,
catalysts but the R-254 catalyst was 4 C more active than R-274. The
results also demonstrate the effect of the promoter in reducing the C3+C4
yields (reduced acid cracking) and lowering the C1+C2 yields (reduced
metal cracking).
A second new high yield catalyst has been formulated using UOP's
high density alumina base. The new R-284 catalyst has the same density,
metals and chloride levels as the R-264 catalyst but with the addition of
the same promoter as used in the R-254 and R-274 catalysts. The activity
of the R-284 catalyst is 3 F (2 C) more active with higher yields as
compared to the R-254 catalyst. For current reformers, the higher density
of R-284 can aid in processing high throughputs if constrained by catalyst
pinning. For new CCR Platforming units, the performance and properties
of the R-284 catalyst make it an ideal candidate to produce maximum
aromatic and xylene yields for petrochemical production.
Years in unit
% promoter on catalyst
2.8
98%
6.5
97%
Table 4. Pilot plant delta temperature and coke for R-254 and R-274
versus R-234 catalyst
R-234 reference catalyst
Delta WAIT
DELTA COKE, %
R-254
R-274
+6 F (+3.3 C)
+13 F (+7 C)
-15%
-13%
Figure 3. Pilot plant delta yields for R-254 and R-274 catalysts versus
R-234 catalyst.
Conclusion
The recent economic climate, impact of government regulations, and
new market trends have impacted the role of the reformer in
different regions to varying degrees. Some refiners are reducing the
severity of the reformer while others are pushing their units for more
production of C5+, H2 and aromatics. A variety of catalysts including
UOPs R-234, R-264 and the new high yield R-254 and R-284
catalysts are available for providing the best yield, activity and coke
performance based upon unit objectives. Local manufacture and
supply of UOP catalysts such as FR-234 bring value to emerging
regions such as China as demonstrated by the PLPC refinery case
study.