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Factors Influencing ULSD Product Color

roduct color is a common con- the product color exceeded 2.5


Greg Rosinski
Technical Services Engineer P cern for refiners with a number
of petroleum products includ-
ing kerosene, jet fuel, diesel fuel and
ASTM, the pipeline color specifica-
tion for diesel, at a reactor outlet
temperature above 730°F. The feed
Brian Watkins lube base oils. With the introduction of to this unit contained 30% LCO and
Technical Services Engineer ultra low sulfur diesel (ULSD) the issue it was operated at 1.0 LHSV and
of diesel product color has become 850 psig inlet pressure.
Charles Olsen more of an issue as the typical ULSD
Worldwide Technical Services unit cycle length may now be limited It is well known that the color of distil-
Manager by color degradation of the product. late products is affected by the reac-
Refiners have been uncertain about tion conditions in the hydrotreater,
end of run (EOR) reactor outlet tem- especially temperature and hydrogen
Advanced Refining Technologies peratures with expectations in the partial pressure. As (outlet) tempera-
Chicago, IL USA range of 710-760°F. The typical ULSD ture increases and/or hydrogen par-
unit has a deactivation rate in the tial pressure decreases, the product
range of 2-3°F/month so an increase color degrades. It is also generally
in EOR temperature of 10-20°F has a accepted that the species responsi-
significant impact on a refiner’s plan- ble for color formation in distillates are
ning and economics. polynuclear aromatic (PNA) mole-
cules. Some of these PNA’s are
Figure 1 summarizes data from a com- green/blue and fluorescent in color
mercial ULSD unit using ART cata- which is apparent even at very low
lysts. The data shows that in this case concentrations of these species.
Certain nitrogen (and other polar)
34 www.e-catalysts.com
Figure 1 uct color over a wide range of oper-
ULSD Product Color Using a SmART Catalyst SystemTM ating conditions. The study utilized
spent ART CDXi, a premium high
3.5 activity CoMo catalyst for ULSD.
The sample of spent catalyst had
3.0 been in commercial diesel service
for well over a year and had a car-
2.5
bon content of 10.9 wt.%. The test-
ing program included straight run
Product Color (ASTM)

(SR) diesels, a 30 vol.% LCO blend


2.0 and a 30 vol.% light coker gas oil
(LCGO) blend. The properties of
1.5 all the feeds are listed in Table I.
The test was designed to examine
1.0
the effects of H2 partial pressure,
H2/Oil ratio and temperature on
ULSD product color. H2 partial
0.5
pressure varied from 300-1150 psi
and the H2/Oil ratio covered the
0.0
580 600 620 640 660 680 700 720 740 760 780 range of 700-2100 scfb.

Average Bed Temperature ˚F Figure 3 shows how the diesel prod-


uct color changes with temperature
and pressure for the straight run
compounds have also been impli- ies responsible for diesel product feed (SR #1). Not surprisingly, pres-
cated as problems for distillate color degradation were concentrated sure clearly has a significant
product color and product instabili- in the higher boiling points in the impact. At the lowest operating
ty. These species can polymerize to diesel (>480°F). This suggests that pressure, which corresponds to
form condensed aromatic struc- color can be improved by adjusting 300-350 psi H2 pressure, the prod-
tures which tend to be green to yel- the diesel endpoint. They also sug- uct color exceeds 2.5 ASTM at a
low/brown in color and can also gest that the color bodies responsible temperature greater than 740-750°F.
form sediment via oxidation and for color formation in desulfurized Doubling the unit pressure to 800
free radical reactions.(1) Work con- diesel are newly formed PNA struc- psig allows the temperature to
ducted by Ma et.al.(2) concluded that tures from desulfurized aromatic com- increase to 780°F before the prod-
the specific species responsible for pounds. uct color reaches 2.5 ASTM, and at
color degradation are anthracene, even higher pressures the product
fluoranthene and their alkylated To learn more about color degradation color is well below 2.5 ASTM for all
derivatives. These are both three in ULSD, ART completed a pilot plant practical temperatures encountered
ringed aromatic structures and are study which investigated diesel prod- in ULSD processing. At these con-
shown in Figure 2.

PNA’s such as these are readily sat- Figure 2


urated to one and two ringed aro- Primary Fluorescence Species in
matics under typical diesel Hydrotreated Diesel (Ref 2)
hydrotreating conditions at start of
run (SOR), but as the temperature
of the reactor increases towards
EOR, an equilibrium constraint may
be reached whereby the reverse
dehydrogenation reaction becomes
more favorable. At some combina-
tion of low hydrogen partial pres-
sure and high temperature the
dehydrogenation reaction predomi-
nates and PNA’s begin to form anthracene fluoranthene
resulting in a degradation of the
color of the diesel product. Other
work completed by Takatsuka
et.al.(3,4) showed that the color bod-

Catalagram 105 Spring 2009 35


Table I
Feedstock Properties

SR #1 SR #1/LCO SR #2 SR #2/LCGO
˚API 33.27 27.73 34.44 33.63
Sulfur, wt.% 0.68 0.93 1.12 1.34
Nitrogen, wppm 120 293 127 249
Total Aromatics, vol.% 31.5 40.0 27.3 30.1
PNA’s (2-ring+), vol.% 10.7 21.9 9.5 10.8
ASTM Color L3.5 L6.5 L2.0 L5.5
Distillation (D2887), ˚F
IBP 275 265 222 238
10% 454 439 477 437
50% 580 565 613 579
90% 600 703 681 667
FBP 837 841 740 754

Figure 3 ditions the H2 partial pressure


Product Color Improves with Pressure increases by a factor of about 3.4
going from 400 psig up to 1200 psig
3.5
Straight Run total pressure for temperatures
around 750°F.
3.0
The data in Figure 3 were generated
400 Psig
2.5 at the low end of H2/Oil ratios inves-
800 Psig
ASTM Color

tigated. Figure 4 shows the effect of


2.0 1200 Psig
increasing the H2/Oil ratio at 400
psig on the SR #1 feed. At this low
1.5 pressure, the H2/Oil ratio has a sig-
nificant impact on product color.
1.0 The data show that the temperature
can be increased from 745°F to well
0.5 above 760°F before product color
exceeds 2.5 ASTM. AT 400 psig
0.0 total pressure and 760°F, changing
680 700 720 740 760 780 800 the H2/Oil ratio from 700 to 2100
Temperature, ˚F scfb results in a 10% increase in H2
partial pressure which appears to
Figure 4 be enough to keep the reaction
Product Color Improvement with Increased H2/Oil Ratio environment on the favorable side of
the hydrogenation-dehydrogenation
3.5
Straight Run equilibrium curve. At higher operat-
ing pressures the impact of increas-
3.0 700 scfb H2 ing the H2/Oil ratio is reduced when
2100 scfb H2
processing the SR feed, but still has
2.5
a positive effect on suppressing
ASTM Color

product color.
2.0
As might be expected, adding LCO
1.5 to the ULSD unit feed makes the
product color situation worse.
1.0 Figure 5 compares the product
color for the SR feed and the 30%
0.5
LCO feed at 2100 scfb H2/Oil ratio
and two pressures. The SR feed
0.0
results in acceptable color over the
680 690 700 710 720 730 740 750 760 770 wide range of temperatures for both
pressures shown. This compares
Temperature, ˚F
36 www.e-catalysts.com
with the 30% LCO feed which goes Figure 5
off color at about 730-740°F at 800 Comparison of Product Color for SR and 30% LCO
psig; and at 1200 psig the tempera-
ture can exceed 760°F before 4.0
reaching 2.5 ASTM color. This data 800 psig
3.5
demonstrates the significant impact SR
that pressure has on diesel product 3.0 LCO
color when processing feeds that

ASTM Color
contain LCO. 2.5 1200 psig
800 psig

Figure 6 demonstrates the effects of 2.0


the H2/Oil ratio on product color
1.5 1200 psig
when processing the 30% LCO
feed. It shows the temperature at 1.0
which the color reaches 2.5 ASTM
as a function of H2/Oil ratio for both 0.5
800 and 1200 psig total pressure.
0.0
The temperature increases by about 640 660 680 700 720 740 760 780 800
25°F when the H2/Oil ratio is Temperature, ˚F
increased from 700 to 2100 scfb.
That range of H2 rates corresponds
Figure 6
to an increase in hydrogen partial Effects of H2/Oil Ratio on Product Color for 30% LCO
pressure of 5-10% 780
Temperature for 2.5 ASTM Color, ˚F

770 1200 Psig


The pilot plant program also investi-
gated the effects of a coker derived 760
800 Psig

material on ULSD product color.


Figure 7 compares the product 750
color for the second SR feed and a
30% LCGO/70% SR #2 blend at 800 740
psig. The data indicates that the
feed containing LCGO behaves sim- 730

ilarly to the SR feed. In both cases


720
the outlet temperature can exceed
780°F before product color 710
approaches the ASTM 2.5 level.
This is not surprising when compar- 700
ing the properties of the two feeds. 500 1000 1500 2000 2500
The aromatics level, and in particu- H2/Oil Ratio, scfb
lar the PNA concentrations, are
essentially the same for the SR and Figure 7
the coker blend. Compare this with Product Color Comparison for LCGO and SR
the LCO blend shown in Table I 2.0
where the PNA’s are twice that of
SR #2
the SR or LCGO feeds.
LCGO

1.5
As mentioned previously, it is gen-
erally accepted that product color
ASTM Color

is related to PNA’s, and earlier work


has concluded that specific three-
1.0
ringed aromatics are responsible
for color degradation in diesel.
Figure 8 shows a comparison of
the product PNA’s (three-ring aro- 0.5
matics) and diesel product color
for all the feeds and conditions of
the study. It is readily apparent that
the PNA’s correlate reasonably well 0.0
640 660 680 700 720 740 760 780 800
with product color..
Temperature, ˚F

Catalagram 105 Spring 2009 37


From these data it is clear that Figure 8
hydrogenation of PNA’s is key to 3+ Ring Aromatics Correlate with Diesel Product Color
maintaining acceptable product
color in ULSD. This suggests a cou- 4.0
ple of approaches that allow an
3.5 SR
increase in EOR outlet temperatures
LCO
and thereby increase the ULSD unit
3.0 LCGO
cycle length.
2.5

ASTM Color
One approach which has been put
to commercial practice is to 2.0
increase quench to the bottom bed
of the hydrotreater. This accom- 1.5
plishes two things which are impor-
tant to maintaining a good environ- 1.0
ment for hydrogenation of PNA’s. It
reduces the outlet temperature and 0.5
helps to increase the outlet hydro-
0.0
gen partial pressure relative to no or 0.0 1.0 2.0 3.0 4.0 5.0
lower amounts of quench.
Product PNAs (3 rings+), vol.%

This, of course, requires that the


upper beds of the hydrotreater be
has on diesel product color. Reducing References
run at higher WABT’s in order to
(or eliminating) the amount of LCO in
maintain the required HDS conver-
the feed will help to suppress product 1. J. Pedley et.al, ACS Division of Fuel
sion. This means that the furnace Chemistry, 35 (4), 1100-1107 (1990).
color degradation as the unit
must have sufficient capacity to
approaches EOR. There is also data 2. X. Ma et. al., Energy and Fuels, 10, pp
achieve the higher inlet tempera-
showing that the color bodies that 91-96 (1996).
tures. Operating in this manner
cause problems for ULSD tend to be
offers the potential to add an addi- 3. T. Takatsuka et.al., 1991 NPRA Annual
concentrated at the higher boiling
tional 10-20°F on to the cycle length Meeting, Paper AM-91-39.
points of the distillation on the
depending on the unit capabilities
feed/product. Reducing the endpoint 4. T. Takatsuka et.al., Journal of the Japan
(furnace, quench capacity).
of the LCO reduces the concentration Petroleum Institute, Vol. 23, No. 2, pp 179-
of these species which will help main- 184, 1992.
Another approach, which may be
tain acceptable product color as the
implemented with the one just dis-
unit moves towards EOR.
cussed, involves adjusting the feed
to the unit. The data from this work
shows the significant impact LCO

38 www.e-catalysts.com