686 Energy & Fuels 1999, 13, 686-693

Color Degradation of Hydrocracked Diesel Fuel

Isabelle Bergeron,† Jean-Pierre Charland, and Marten Ternan*,‡
Energy Research Laboratories, CANMET, Natural Resources Canada,
Ottawa, Ontario, K1A 0G1, Canada, and Department of Chemical Engineering, University of
Ottawa, Ottawa, Ontario, K1N 6N6, Canada

Received October 5, 1998

A combination of two first-order reactions that had different rate constants was found to describe
the rate of color development in the 288-343 °C diesel fraction from hydrocracked Llyodminster
atmospheric bottoms. These two reactions were the conversion of color precursors which were
either (a) unsaturated compounds or (b) heteroatom compounds. The color precursors were
correlated with the composition of the diesel fraction. The heteroatom color precursors were
correlated with the combination of sulfur and nitrogen content of the diesel fraction. The
unsaturated color precursors were correlated with its density, since density can be related to the
aromatic content. The rate constants were related to catalyst composition. The fact that all of
the parameters in the correlation were related to physical phenomena supported the hypothesis
that color development is related to these two types of color precursors. The hydrocracking
conditions were 17.3 MPa, 415 °C, 0.59 LHSV, and 570 L (H2 at STP)/L of feed [2400 scf/bbl].
Eleven different hydrocracking catalysts were examined, most of which contained two components,
a conventional CoMo:γAl2O3 component and a zeolite component (sodalite containing nickel, SOD-
Ni). The same two rate expressions were found to describe the results obtained from all of the
catalysts. The conversion of the heteroatom compounds that were color precursors was associated
with the CoMo:γAl2O3 component of the catalyst component. The conversion of the unsaturated
compounds that were color precursors was associated with the SOD-Ni catalyst component.

Introduction peroxides) was necessary. Many of the studies per-

formed since that time are consistent with his views.
The production of distillate fractions by hydrocracking
Brooks noted that the organic peroxides, which are
heavy oil residue has been the subject of several studies
necessary for color formation, could be formed by the
performed in our laboratory. Under some conditions, the
autoxidation of olefins, including some that are formed
diesel fraction from hydrocracking has been observed
from cracking processes. Subsequent work on the au-
to change color, from a clear transparent hue when it
toxidation of olefins at low temperature and other
is first produced to a dark brown or black after several
autoxidation mechanisms has been reviewed by Wal-
days of storage. This degradation in color is not gener-
lace.2 However, Brooks proposed that the organic per-
ally accompanied by any apparent change in the other
oxides have a different role in color formation than in
measurable physical or chemical properties. While the
gum formation. Organic peroxides induce polymeriza-
dark color does not affect diesel fuel performance, it is
tion of unsaturates to form gum.
undesirable because consumers tend to associate dark
The compounds in fuels, which contribute to the
colors with poor fuel grades.
development of color, have been identified by Bhan et
Discoloration and gum formation were discussed in
al.3 Ion-exchange liquid chromatography was used to
an early paper by Brooks.1 On the basis of his experi-
separate six different diesel fuel samples into acidic,
ments with cracked gasoline, Brooks concluded that
basic, and neutral fractions. The acid fraction of each
color is formed by adding acid (HCl or SO2 which
diesel fuel was much more deeply colored than the other
becomes H2SO4, or sulfonic acids formed by oxidation
two fractions. This is consistent with the observations
of thiols or disulfides) to fuels containing organic
by Brooks. A gas chromatography mass spectrometry
peroxides. He reported that air alone did not cause color,
(GCMS) analysis of the entire acid fraction identified
since pure hydrocarbons could be oxidized sufficiently
three homologous series, indoles, cycloalkylindoles, and
to form gum but still had a light color. Similarly, only
benzoindoles (predominantly carbazoles). Subsequently,
slight decoloration occurred when sulfur dioxide was
the acid fraction was separated into subfractions by
added to samples that were not permitted to contact air.
performing high-performance liquid chromatoraphy
The presence of both acid and air (required to form
(HPLC) using a strong basic mobile phase so that the
* To whom correspondence should be addressed.
fractionation would occur according to acidity. Several
† Current Address: Pan Canadian Petroleum, Calgary, Alberta, T2P

2S5, Canada. E-mail: Isabelle•bergeron@pcp.ca. (2) Wallace, T. J. In Advances in Petroleum Chemical Refining;
‡ Current Address: 147 Banning Road, Kanata, Ontario, K2L 1C5, Wiley-Interscience: New York, 1964; pp 353-407.
Canada. E-mail: ternan@ncf.ca. (3) Bhan, O. K.; Brinkman, D. W.; Green, J. B.; Carley, B. Fuel 1987,
(1) Brooks, B. T. Ind. Eng. Chem. 1926, 18, 1198-1203. 66, 1200-1214.

10.1021/ef980214q CCC: $18.00 © 1999 American Chemical Society

Published on Web 04/17/1999
Color Degradation of Hydrocracked Diesel Fuel
of the fractions were analyzed by GCMS. Fraction 2
contained hydroperoxides and the bulk of the pyrrolic
benzologues (indole, carbazole). Fractions 3 and 4
contained hydroxyaromatics and carboxylic acids, re-
spectively. Oxygenated hydrocarbons were found in all
of the fractions.
Color can develop from autoxidation reactions be-
tween the fuel and air. Hydroperoxide formation was
orders of magnitude greater in bottles of jet fuel that
were loosely covered compared to bottles that were
tightly capped.4 This was a clear demonstration that
oxygen from the air does react with the fuel. Unsatur-
ated hydrocarbons react particularly rapidly. Early
studies by Thompson et al.5 and Offenhauer et al.6
associated much more fuel instability with catalytically
cracked distillates (which have large concentrations of
alkenes) than with straight run distillates (which are
generally 100% alkanes). A more recent example7
showed that after 16 months there was no change in
the color of a straight run diesel fuel, while a blend of
90% straight run and 10% catalytically cracked stock
became substantially darker. Dorbon et al.8 also showed
that much darker colors developed in light cycle oils
than in straight run distillates. Although saturated
hydrocarbons autoxidize more slowly than either olefins
or molecules with benzyl C-H structures,9 some nitro-
gen-containing and oxygen containing molecules au-
toxidize readily to hydroperoxides.
Three different mechanisms explaining fuel instabil-
ity were mentioned in a recent review by Mushrush and
Speight:10 free-radical hydroperoxide initiated oxidation,
electron-transfer initiated oxidation, and soluble mac-
romolecular oxidation. The free-radical hydroperoxide
initiated oxidation mechanism has been discussed in the
greatest detail. Its initiation step has been described2
as follows:
RH + O2 f R• + HO2• (1)
It could occur in the presence of metal catalysts such
as copper.11 Different oxidation states for the metal
during redox catalysis have been suggested.2,9 Alterna-
tively, it has been indicated that the metal could be an
electron acceptor.12 Balster, Balster, and Jones13 have
pointed out that the fuel species RH, in eq 1, needs to
have weakly bound H atoms and that aromatics can
function as initiators.
A simplified mechanism for the propagation steps has
been outlined:13
(4) Black, B. H.; Hardy, D. R.; Beal, E. J. Energy Fuels 1991, 5, 281-
282.
(5) Thompson, R. B.; Druge, L. W.; Chenicek, J. A. Ind. Eng. Chem.
1949, 41, 2715-2721.
(6) Offenhauer, R. D.; Brennan, J. A.; Miller, R. C. Ind. Eng. Chem.
1957, 49, 1265-1266.
(7) Pedley, J. F.; Hiley, R. W.; Hancock, R. A. Fuel 1987, 66, 1646-
1651.
(8) Dorbon, M.; Bigeard, P. H.; Denis, J.; Bernasconi, C. Fuel Sci.
Technol. Int. 1992, 10, 1313-1341
(9) Walling, C. In Free Radicals in Solution; Wiley: New York, 1957;
pp 411-416.
(10) Mushrush, G. W.; Speight, J. G. Rev. Proc. Chem. Eng. 1998,
1, 5-28.
(11) Finseth, D. H.; Schmidt, C. E.; Link, T. A. Prepr.sAm. Chem.
Soc., Div. Pet. Chem. 1984, 29, 980-982.
(12) Mushrush, G. W. Fuel Sci. Technol. Int. 1992, 10, 1523-1560.
(13) Balster, L. M.; Balster, W. J.; Jones, E. G. Energy Fuels 1996,
10, 1176-1189.
Energy & Fuels, Vol. 13, No. 3, 1999 687
R• + O2 f ROO• (2)
ROO• + RH f ROOH + R• (3)
Free-radical concentrations (R•) in diesel fuels have been
measured by Wright et al.14 The ROOH hydroperoxide
product from eq 3 provides an additional initiation
reaction
ROOH f RO• + HO• (4)
The compounds, RH, that are susceptible to oxidation
were identified by Bahn et al.3 as partially hydrogenated
aromatic hydrocarbons, hydroxyaromatics, pyrroles, in-
doles, and polycylic aromatics, as well as olefins from
catalytic cracking. Alkyl indoles have received attention
in many studies.7,8,15-18 Oxidation is the initial step in
fuel degradation. Subsequently, the products of oxida-
tion can combine with either polar compounds or neutral
compounds in the fuel via chemical bonding (including
hydrogen bonding) to form sediment. Mushrush12 has
stated that nitrogen, sulfur, and oxygen heteroatoms
contribute to fuel instability. An example is the reaction
of polycyclic aromatics (phenalene) that react with
oxygen to form polycyclic aromatics with a carbonyl
group (phenalenone). This is followed by acid-catalyzed
condensation of phenalenone and indole to form in-
dolyphenalenes,15,19 which are soluble in the fuel and
sediment precursors. These precursors combine with
acids (p-thiocresol) to form highly colored salts15,19 which
precipitated as sediment. Mushrush and Speight10
concluded that acid-catalyzed condensation reactions
are involved to a significant extent. These observations
can be generalized to suggest that (1) oxidized com-
pounds can condense with heteroatom compounds to
form fuel-soluble oligomers and (2) the fuel-soluble
oligomers combine with organic acids to form colored
species.
The electron-transfer initiated oxidation mechanism
for fuel instability was proposed by Beaver et al.20,21
Various molecular types (alkyl derivatives of pyrroles,
indoles, phenols, and polycyclic aromatics) could be
oxidized by this mechanism. The role of alkyl indoles
has also been interpreted in terms of this mechanism.22
The soluble macromolecule oxidation mechanism was
proposed by Hardy and Wechter.23,24 It proposes that
reactive fuel monomers combine via oxidation and
condensation to form species with molecular weights in
the 650-1000 range and that these soluble species are
sediment precursors. One study that could be grouped
in this classification is the study of visbroken short
(14) Wright, B. W.; Kalkwarf, D. R.; Smith, R. D.; Hardy, R. D.;
Hazlett, R. N. Fuel 1985, 64, 591-594.
(15) Pedley, J. F.; Hiley, R. W.; Hancock, R. A. Fuel 1989, 68, 27-
31.
(16) Dorbon, M.; Bernasconi, Fuel 1989, 68, 1067-1074.
(17) Ali, M. F.; Nizami, A.; Hamdan, A. J. Fuel Sci. Technol. Int.
1995, 13, 655-678.
(18) Hughes, J. M.; Beal, E. J.; Mushrush, G. W. Fuel Sci. Technol.
Int. 1995, 13, 413-429.
(19) Pedley, J. F.; Hiley, R. W.; Hancock, R. A. Fuel 1988, 67, 1124-
1130.
(20) Beaver, B. D.; Hazlett, R. N.; Cooney, J. V.; Watkins, J. M. Fuel
Sci. Technol. Int. 1988, 6, 131-150.
(21) Beaver, B. D. Fuel Sci. Technol. Int. 1991, 9, 1287-1335
(22) Beaver, B.; Gilmore, C.; Veloski, G.; Sharief, V. Energy Fuels
1991, 5, 274-280.
(23) Hardy, D. R.; Wechter, M. A. Energy Fuels 1990, 4, 270-274.
(24) Hardy, D. R.; Wechter, M. A. Energy Fuels 1994, 8, 782-787.
688 Energy & Fuels, Vol. 13, No. 3, 1999
residues by Singh et al.25 They suggested that oxidized
aromatics play a role in fuel stability.
Color degradation is not the only fuel instability phe-
nomenon. Several reviews on fuel instability emphasiz-
ing sediment formation have been published.2,21,26-28
Deposits on heat-exchange surfaces29 and the formation
of both soluble and insoluble gums30 are other types of
fuel instability. Because storage sediment has been
studied more extensively than other instabilities, more
of those studies are available to compare with color
degradation.
An equilibrium relationship between the colored
species remaining in the fuel (liquid phase) and the
sediment that precipitates (solid phase) might be ex-
pected. In one study,8 data for real fuel distillates with
no additives showed a linear relationship between color
and the logarithm of the total insolubles. In contrast,
another study3 found no relationship between the two
quantities. This apparent contradiction can be explained
in terms of data presented in tables by Ali, Nizami, and
Hamdan.17 Their color data for pure compound additives
was plotted as a function of the sediment that was
produced by those compounds. Two observations were
apparent. (1) Initially, the color increased markedly
while little sediment was formed. Subsequently, the
color remained at a constant value while progressively
larger amounts of sediment were formed. (2) For each
additive (pure compound) there was a different maxi-
mum color. The color did not become darker than this
value, even though more and more sediment was
formed. This suggests a relationship between color in
the liquid phase and the amount of sediment if the
liquid is not saturated with color bodies. In contrast, if
the liquid is saturated with color bodies, all quantities
of sediment greater than a particular value will cor-
respond to the same color and there will be no relation-
ship between color and sediment. Thus, the explanation
arising from the data of Ali et al.17 can also provide a
consistent explanation for the earlier data.3,8 Further-
more, it indicates that color develops prior to extensive
sediment formation.
The distillates produced in our catalytic hydrocrack-
ing experiments with heavy oil will contain some of the
compound types described in the above studies. Both
cracking and hydrogenation reactions occur when heavy
oil is hydrocracked. It is the cracking reactions that can
produce compounds that are susceptible to oxidation.
These are the compounds that must either be treated
or removed to avoid color formation.
Petroleum refiners31 have suggested the following
strategies to minimize color formation in hydrocracked
diesel. (1) Hydrocracking reactors should be operated
at low temperatures, low space velocities, and large
hydrogen partial pressures. (2) A catalyst with a large
hydrogenation activity should be used. (3) The final
boiling point of the diesel fraction should be decreased
(25) Singh, I. D.; Kapoor, M. P.; Ramaswamy, V. Fuel 1991, 70, 195-
199.
(26) Batts, B. D.; Fathoni, A. Z. Energy Fuels 1991, 5, 2-21.
(27) Mushrush, G. W. Energy Fuels 1991, 5, 258-262.
(28) Mushrush, G. W. Energy Fuels 1991, 5, 749-753.
(29) Jones, E. G.; Balster, L. M.; Balster, W. J. Energy Fuels 1995,
9, 906-912.
(30) Power, A. J. Fuel 1986, 65, 133-137.
(31) Anon, National Petroleum Refiners Association Question and
Answer Session. Oil Gas J. 1993, 88-91.
Bergeron et al.
to eliminate the components with the greatest molecular
weights. The first two suggestions would increase the
removal of unsaturated compounds (partially hydroge-
nated aromatics, polycyclic aromatics, and olefins) and
heteroatom compounds (hydroxy aromatics, pyrroles,
and indoles) which were identified above as being
responsible for color formation. Such strategies, which
emphasize hydrogenation, can be successful. For ex-
ample, an unstable thermally cracked coker distillate
derived from oil sands bitumen was hydrogenated to
produce a stable product.18
Recently, there have been reports of the effect of
hydrocracking on fuel stability.32 Takatusuka et al.33
stated that a large hydrogen pressure would hydroge-
nate radicals and suppress color. In contrast, greater
temperatures (increased hydroprocessing severity) re-
tarded hydrogenation and facilitated color. They re-
ported that by increasing the hydrodesulfurization rate,
a yellow diesel fuel could become colorless. However, if
the rate of hydrodesulfurization exceeded a certain
value, the diesel oil product would become fluorescent
yellow-green. Polycyclic aromatic molecules were re-
ported to be the source of the fluorescent color. In an
earlier study, Takatusuka34 suggested that color is
caused by the changing energy state of π electrons in
aromatic compounds. A study on the effect of hy-
drotreating severity on diesel fuel stability35 indicated
that the color became lighter with increasing severity,
except that at the greatest severity the color became
darker.
In this work, alterations in the composition of the
catalysts used to hydrocrack the heavy oils were made.
The objective was to determine whether changes in
catalyst composition could influence the color stability
of the diesel fraction.
Experimental Section
Hydrocracking experiments were performed using a fixed-
bed continuous flow reactor operating in the up flow mode.
Lloydminster atmospheric residue and hydrogen gas were
mixed, flowed through a preheater, and then flowed through
a fixed bed of catalyst contained in a 316 stainless steel tubular
reactor (length 0.305 m, inside diameter 0.025 m, volume 155
mL). The reactor furnace consisted of three separate heating
zones, which were controlled to maintain the catalyst bed at
a constant temperature of 415 °C. The other operating
variables were 17.3 MPa, pressure; 0.59, liquid hourly space
velocity (LHSV); and 570 L (H2 at STP)/L of feed, hydrogen
gas rate. The reactor product flowed into pressurized receiver
vessels where the liquid was accumulated after being sepa-
rated from the gas. Vapor-phase products were vented con-
tinuously and not analyzed. The temperature of the receiver
vessels was maintained at 150 °C to eliminate the condensa-
tion of water vapor in the liquid product. The feedstock used
for all experiments was obtained from Consumer’s Cooperative
Refineries Ltd. (CCRL), Regina, Saskatchewan. Feedstock
properties are listed in Table 1.
The diesel fraction (288-343 °C) was obtained from each of
the reactor liquid samples by distillation, using a manual
(32) Rahimi, P.; Fairbridge, C. L.; Oballa, M.; Wong, C.; Somogyvari,
A. Prepr.sAm. Chem. Soc., Div. Fuel Chem. 1998, 43, 13-15.
(33) Takatsuka, T.; Inoue, S.; Wada, Y. Catal. Today 1997, 39, 69-
75.
(34) Takatsuka, T.; Wada, Y.; Suzuki, H.; Komatsu, S. Proc. Nat.
Petrol. Refin. Assoc., Washington, 1991; Paper AM-91-39.
(35) Waynick, J. A. Prepr.sAm. Chem. Soc., Div. Fuel Chem. 1998,
43, 8-12.
Color Degradation of Hydrocracked Diesel Fuel Energy & Fuels, Vol. 13, No. 3, 1999 689

Table 1. Properties of Lloydminster Atmospheric suspension consisting of 16.4 g of NaOH in 100 mL of H2O
Residuum (4.1 M), 8.2 g of Al2O3 (Catapal SB Alumina), and 7 g of SiO2
density 15 °C (kg/m3) 999.2 (Cab-O-Sil) was placed in a sealed autoclave and heated at
API gravity 10.11 160 °C for 120 h. After quenching, the resulting crystalline
ibp - 343 °C (wt %) 4.04 powder was filtered and rinsed with 3-4 L of deionized water.
343-525 °C (wt %) 42.76 The solids were dried for 10 h at 105 °C and calcined at 350
+525 °C residue (wt %) 52.9 °C for 4 h. The sodalite crystal structure was identified by
carbon (wt %) 84.4 X-ray diffraction measurements.
hydrogen (wt %) 11.4
The resulting sodalite was subjected to several processes:
sulfur (wt %) 3.74
nitrogen (wt %) 0.45 ion exchange of the sodium ions for nickel ions, impregnated
vanadium (ppm) 123 with nickel nitrate and its conversion to form nickel oxide,
nickel (ppm) 56.7 reduction of the nickel oxide to nickel metal, and ion exchange
ash (wt %) 0.04 of unreduced nickel ions with potassium ions. The objective
microcarbon residue (wt %) 13.4 was to prepare catalysts that contained reduced nickel metal
pentane insolubles (wt %) 14.6 inside catalyst cages. Incorporating large potassium ions would
toluene insolubles (wt %) 0.08 decrease the dimensions of the cage openings so that the access
of hydrogen sulfide to the nickel metal would be decreased.
Table 2. Chemical Properties of Fresh Catalysts
Cage openings that allowed hydrogen, but not hydrogen
catalyst wt % wt % Al2O3 MoO3 CoO sulfide, to reach the nickel metal might have been an interest-
no. Ni-SOD Ni in SOD (wt %) (wt %) (wt %) ing hydrogenation catalyst for hydrocracking sulfur containing
1 10.2 0 73.3 13.8 2.7 feedstocks.
2 10.2 13.1 73.3 13.8 2.7 The nickel exchange was performed by placing 40 g of
3 9.6 25.5 73.8 13.9 2.7 sodalite in 80 g of deionized water in a 1 L boiling flask. Each
4 10.2 34.1 73.3 13.8 2.7 exchange solution was prepared by dissolving 2.48 g of Ni-
5 10.2 38.5 73.3 13.8 2.7
(NO3)2 in 800 g of deionized water (2 wt % Ni). Approximately
6 10.2 44.8 72.0 15.0 3.0
7 0 0 83.1 14.1 2.8 150 mL of the exchange solution was added to the flask per
8 5.1 38.5 78.2 13.9 2.7 hour, and then the slurry was stirred for 20 h. It was
9 20.0 38.5 63.9 13.5 2.7 subsequently filtered and washed, until the wash water had
10 25.9 38.5 56.7 14.5 2.9 a concentration of less than 5 × 10-4 mol Ni2+/L, as measured
ref cat. 0 0 80.1 16.4 3.5 by a conductance meter. The powder was then dried at 120
°C for 400 min and heated to a calcination temperature of 550
Table 3. Composition of the Product Diesel Fraction °C at a rate of 1 °C/min and then maintained at 550 °C for 4
catalyst diesel fraction (288-343 °C) h.
wt % Ni wt % nitrogen sulfur density final color The exchanged powders were impregnated with Ni(NO3)2
in sodalite Ni-sodalite (ppm) (wt %) g/mL C ) Cuns + Chet solutions of varying concentration. The solution concentrations
were chosen to produce various nickel concentrations in the
0 10 673 0.1 0.886 4.25
sodalite. A volume of solution was added that was sufficient
13 10 672 0.094 0.887 4.75
26 10 597 0.16 0.8879 5.25 to fill the pore volume of the sodalite but insufficient to permit
34 10 529 0.14 0.8887 5.25 excess liquid to be present. After standing at 40 °C for 24 h,
39 10 544 0.076 0.8881 4.25 the solids were dried at 105 °C for 10 h and calcined at 350 °C
45 10 602 0.1 0.8799 3.75 for 4 h.
0 0 226 0.113 0.8844 4.75 The reduction was performed by loading the solid powder
39 5 379 0.12 0.8815 3.75 into fine mesh containers and placing them inside a 155 mL
39 20 667 0.14 0.881 3.75 autoclave having a gas inlet and gas outlet. The conditions
39 26 834 0.18 0.8814 4.25
used to attempt reduction were 435 °C in a stream of flowing
ref cat. 468 0.051 0.8848 3.25
no cat. 509 2.55 0.9006 8 hydrogen at 3.4 L H2(STP)/min at 17.3 MPa for 4 h. Subse-
quent hydrogen chemisorption measurements did not indicate
ASTM D-1160 procedure. The color of each diesel fraction was that the nickel had been reduced, and no additional reduction
measured using the ASTM D-1500 method. Measurements steps were performed. Feeley and Sachtler37 made similar
were made daily for the first week following hydrocracking observations of the nonreducibility of metals that are within
and then weekly for a period of 8-16 weeks. The color of the zeolites.
diesel fraction was compared visually with the colored disk of A KNO3 solution equivalent to 4 wt % K+ ions was used to
the ASTM scale, which varies from 0 (colorless) to 8 (dark red), exchange the unreduced nickel ions with potassium ions. The
by 0.5 increments. In accordance with ASTM 1500, when an reduced sodalite powder was slurried in twice its weight of
exact match cannot be found, the next higher ASTM color deionized water in a 1 L boiling flask equipped with a magnetic
value is to be used, preceded by the letter L. For the purpose stirrer and a heating jacket. A slurry of 0.101 g of KNO3/g of
of this study, the letter L was interpreted as being one-half reduced sodalite in 300-400 times its weight of deionized
an increment (0.25) lower than the color value chosen. For water was added to the agitated slurry during a period of 4 h,
instance, a color value of 3.75 would be assigned to an ASTM using five different additions. The resulting nickel sodalite
color of L4.0. powders (SOD-Ni) were dried at 105 °C for 10 h. Subsequently,
In this work, the composition of the catalyst used in the the temperature was increased at 5 °C/min, and the powders
hydrocracking reactor was varied to determine its influence were calcined at 350 °C for 4 h.
on color development in the diesel fraction of the hydrocracked The Co-Mo-γAl2O3 catalyst component was prepared by
product. Ten different catalysts were prepared having the mixing 180 g of pseudoboehmite alumina (Versal 250 from
compositions shown in Table 2. The catalysts were composed Laroche Chemicals) with three aqueous solutions. A solution
of two different principal components. One was a sodalite of ammonium paramolybdate (APM), (NH4)6Mo7O24‚4H2O, was
zeolite to which nickel had been added (SOD-Ni). The other prepared from 33.2 g of APM, 74 g of deionized water, and
was Co-Mo-γAl2O3, which is one of the common catalyst
compositions used for hydrotreating petroleum fractions. (36) Carr, R. M.; Larking, P. W.; Lyon, G. L. Aust. J. Chem. 1985,
The sodalite component (hydrosodalite, 6[NaAlSiO4]‚8H2O) 21, 2555-2559.
was synthesized using the method of Carr et al.36 A colloidal (37) Feeley, J. S.; Sachtler, W. M. H. J. Catal. 1991, 131, 573-581.
690 Energy & Fuels, Vol. 13, No. 3, 1999
Figure 1. ASTM color verus storage time (days). Diesel
fractions prepared using catalysts containing Co-Mo-γ-Al2O3
as the major catalyst component plus 0%, 13%, and 26% of
the SOD-10Ni (10% nickel in sodalite) as the minor catalyst
component. These data are represented by open circles (0%),
solid circles (13%), and open inverted triangles (26%), respec-
tively. Data obtained without a catalyst (solid triangles) and
with the reference catalyst (solid squares) are also shown.
18.9 g of 30% NH4OH. A solution of cobalt nitrate (CN), Co-
(NO3)2‚6H2O, was prepared from 20.7 g of CN and 24.7 g of
deionized water. They were placed in an oven a 125 °C for 10
min to speed dissolution. Finally, 74.7 g of a third solution
composed of 25 volumes of deionized water to 1 volume of 70%
HNO3 was added. The three solutions were mixed with the
alumina to form an aqueous paste.
The above water-based alumina paste was added to a
hydrocarbon-based SOD-Ni paste made from 1 part Ni-SOD
and 1 part Zerice oil (Imperial Oil, 0.899 specific gravity, 245-
535 °C bp range, H/C ) 1.85). Surrounding the SOD-Ni with
oil would inhibit water penetration of the sodalite pores and
subsequent pore blocking of the SOD-Ni by alumina. The
combined paste was extruded and then dried at 110 °C for 18
h. Calcination was performed at a series of sequential tem-
perature plateaus, 190 °C for 10 h, 200 °C for 10 h, 220 °C for
20 h, 285 °C for 7.5 h, 365 °C for 7.5 h, and finally 450 °C for
4 h.
Two different sets of laboratory prepared catalysts were
studied. Their properties are shown in Table 2. Each set was
composed of two components, a sodalite component that
contained nickel x(SOD-yNi) with the balance of the catalyst
being a CoMo:γ-Al2O3 component. The value x is the percent
of SOD-Ni in the catalyst, and y is the percent Ni in the SOD-
yNi. The quantity of nickel in Table 2 is the weight percent
nickel expressed as nickel atoms. One set of catalysts contained
10% Ni-sodalite in which the amount of nickel, y, in the
sodalite was varied 10(SOD-yNi). In the other set, the amount
of sodalite component in the catalyst was varied but the
amount of nickel in the sodalite x was maintained constant at
39%, x(SOD-39Ni). The results obtained using the laboratory
prepared catalysts were compared with those obtained using
a reference catalyst, 1442-B, obtained from American Cyana-
mid.
Results and Discussion
The colors of several diesel fractions are shown in
Figure 1 as a function of the time that had elapsed since
they were removed from the hydrocracking reactor. In
each case there was a rapid initial increase in the color
intensity. Thereafter it increased more slowly until it
had attained its maximum color. The maximum color
Bergeron et al.
varied with the catalyst composition used in the reactor.
The diesel fraction with the darkest color was obtained
when hydrocracking occurred in the absence of a
catalyst. The lightest colored product was obtained
when using the standard reference catalyst. The various
laboratory prepared catalysts produced final colors
which had intermediate values. The reference catalyst
had a similar CoMo:γ-Al2O3 composition to the labora-
tory prepared catalyst that did not contain any nickel
sodalite 0(SOD-0Ni). The difference in the performances
of these catalysts is probably related to different prepa-
ration methods. For example, in a study38 unrelated to
this one, a CoMo:γ-Al2O3 catalyst prepared in the
laboratory by a two-step method (Co added after the Mo
had been calcined on the alumina) produced more
desirable results than the reference catalyst that was
used in this study. In this study, the Co and Mo
components were added during the same catalyst prepa-
ration step.
To explain the color effects shown in Figure 1, it was
postulated that the CoMo:γ-Al2O3 catalyst component
removed heteroatom (het) compounds (sulfur and ni-
trogen) and that the SOD-Ni catalyst component re-
moved unsaturate (uns) compounds (olefins, aromatics,
free radicals). Each of these two families of compounds
correspond to two different groups of color precursors
(colorless species present in concentrations of nuns and
nhet) which could be converted into colored species. After
conversion, each of the species in the two color precursor
groups would probably contribute a different color
intensity, e.g., cuns and chet. The color of a particular
diesel fraction would be derived from each of these two
components, Cuns ) cunsnuns (potential component of color
from the unsaturates) and Chet ) chetnhet (potential
component of color from the heteroatoms). At any time
their respective conversions would be Xuns and Xhet.
Therefore, C(t), the color of the diesel fraction (the color
resulting from both converted color precursors), could
be represented at any time t as
C(t) ) CunsXuns(t) + ChetXhet(t) (5)
where Cuns and Chet are precursor color components that
exist in the fuel and become colored when converted.
For a first-order reaction, conversion to colored species
can be represented as
X(t) ) 1 - exp(-kt) (6)
where k is the first-order rate constant and t is the time
that elapsed after hydrocracking the diesel fraction.
Conversions using eq 6 for both species can be substi-
tuted into eq 5 to obtain:
C(t) ) Cuns[1 - exp(-kunst)] + Chet[1 - exp(-khett)]
(7)
Each of the lines in Figure 1 was obtained by fitting
eq 7 to the color data points. Curve fitting of color data
was performed for each catalyst used in this study,
thereby obtaining the parameters Cuns, Chet, kuns, and
khet. The plots for each of the catalysts not shown in
Figure 1 matched their data just as well as the correla-
(38) Ternan, M.; Rahimi, P. M.; Clugston, D. M.; Dettman, H. D.
Energy Fuels 1994, 8, 518-530.
Color Degradation of Hydrocracked Diesel Fuel
Figure 2. Component of the color derived from unsaturated
compounds that are color precursors, Cuns, and from com-
pounds containing heteroatoms that are color precursors, Chet,
versus the percent of Co-Mo-γ-Al2O3 component in the
catalyst.
tion lines that are shown in Figure 1. When only one
exponential term was used rather than both of the
exponential terms that are in eq 7, the resulting lines
did not match with the data very closely. The agreement
between the correlation in eq 7 and the data in Figure
1 supports the suggestion that color is produced by the
conversion of two different groups of color precursors,
each of which may represent a different class of mol-
ecules in the diesel fraction.
The diesel fuel fraction will contain many different
compounds that could contribute to color. Each com-
pound will have a different rate constant, kuns or khet,
and different precursor color component, Cuns or Chet.
For example, in this work the rate constants reported
will be some type of an average that represents the
compounds that have been converted. Since different
catalysts will convert different combinations of com-
pounds, these rate constants will not be invariant.
The precursor color components, Cuns or Chet, are
shown in Figure 2 as a function of the Co:Mo:γ-Al2O3
content in the catalyst. The other catalyst component
was SOD-39Ni. Chet decreased (from 3.6 at 74% Co:Mo:
γ-Al2O3 to 2.5 at 100% Co:Mo:γ-Al2O3) and Cuns in-
creased (from 0.8 at 74% Co:Mo:γ-Al2O3 to 2.0 at 100%
Co:Mo:γ-Al2O3). There is some physical significance to
these parameters. As the CoMo:γ-Al2O3 component of
the catalyst increased, heteroatom removal would be
expected to increase and therefore the color precursors
remaining in the diesel fraction that are attributed to
heteroatoms, Chet, would be expected to decrease. The
decrease in Chet, shown in Figure 2, is consistent with
these expectations. Correspondingly, the catalyst so-
dalite content decreased when the CoMo:γ-Al2O3 cata-
lyst content increased. As the Co:Mo:γ-Al2O3 content of
the catalyst increased, there would be less sodalite
(SOD-39Ni) component in the catalyst and therefore
Cuns, the color precursors remaining in the diesel
fraction that are attributed to unsaturates, would be
expected to increase. This was observed in Figure 2.
The association of color with heteroatoms has been
suggested frequently in the literature on fuel stability.
Energy & Fuels, Vol. 13, No. 3, 1999 691
Figure 3. Component of the color derived from compounds
containing heteroatoms that are color precursors, Chet, versus
f(S,N), the correlation with sulfur and nitrogen content of the
diesel fraction (eq 8).
As shown in eq 8, Chet was found to correlate with the
sulfur and nitrogen contents of the diesel fractions
produced by the various catalysts
Chet ) 1.4 + (8.9 × 10-4)S + (1.8 × 10-4)N (8)
where S is the sulfur content (ppm) and N is the
nitrogen content (ppm). The resulting correlation, shown
in Figure 3, is also consistent with the postulate that
the color precursor parameters have a real physical
significance.
The above empirical relationship, eq 8, is consistent
with the free-radical hydroperoxide initiated oxidation
mechanism used to explain fuel instability. That mech-
anism requires three steps. First, air reacts with certain
compound classes (partially hydrogenated aromatics
and olefins present in these diesel fractions are ex-
amples) to form hydroperoxide compounds, via free-
radical autoxidation. Second, the hydroperoxide com-
pounds react via acid catalysis with polar or neutral
compounds to form oligomers or polymers. The type of
compound that reacts with the hydroperoxide deter-
mines whether the condensation product is colored.
Compounds containing S and N heteroatoms are polar.
They can also form color bodies. Therefore, the empirical
correlation in eq 8 is consistent with one of the estab-
lished mechanisms used to describe fuel instability.
The other parameter, the precursor color component
Cuns, was attributed to unsaturates (olefins, aromatics,
and free radicals). Since, no direct measurement of these
quantities was made, an indirect measurement (density)
was used to develop a correlation. For equivalent boiling
point, aromatic molecules have greater densities than
aliphatic molecules. Since all the diesel fractions in this
study had the same boiling-point range, changes in
density may be one indication of changes in unsaturates
(aromatics). On this basis, Cuns was correlated with the
measured density of the diesel fraction, as shown in
Figure 4. The greater the value of Cuns, the greater the
quantity of unsaturates (as measured by greater density
or aromatics). Thus, the correlation in Figure 4 is
consistent with Cuns being representative of a physical
692 Energy & Fuels, Vol. 13, No. 3, 1999
Figure 4. Component of the color derived from unsaturated
compounds that are color precursors, Cuns, versus the density
of the diesel fraction (g/mL).
Figure 5. Rate constants kuns (O) and khet (0) (s-1) versus
percent nickel in the sodalite catalyst component 10(SOD-yNi).
The solid symbols represent a laboratory prepared catalyst
that contained only the Co-Mo-alumina component.
quantity and not just a mathematical parameter that
arises from a correlation.
The increase in Cuns in Figure 2 as the SOD-39Ni
component of the catalyst decreases (Co:Mo:γ-Al2O3
component increases) is also consistent with more
unsaturates remaining unaltered. That would be ex-
pected if the SOD-39Ni component of the catalyst caused
the saturation. Again, this suggests that the precursor
color parameters have physical meaning.
The rate constants for the series of catalysts in which
the percent nickel y in the SOD was varied while the
Co-Mo-alumina content and the SOD-yNi content of
the catalysts remained constant are shown in Figure 5
(open symbols). The rate constant for heteroatom re-
moval, khet (open squares), remained virtually constant.
A constant value would be expected because the catalyst
component for heteroatom removal, Co-Mo-alumina,
was constant.
In contrast, in Figure 5 the rate constant for removal
of unsaturates, kuns, was not invariant. It goes through
a maximum as the percent nickel y in the SOD-yNi
Bergeron et al.
component increases. A discussion of these results must
account for the fact that the diesel fractions are a
mixture of compounds and that each compound in the
mixture has its own particular rate constant. The value
of kuns in Figure 5 is a combination of rate constants
for all of the compounds in the mixture that are
converted. Compounds that are converted easily will
have fast rates and large rate constants. The compounds
that are not converted will not contribute to kuns. Thus,
a small value of kuns indicates that compounds which
react slowly have been converted, while a large value
indicates that only the faster reacting compounds have
been converted.
When there was no nickel in the sodalite, the kuns
value was quite small (open circle in Figure 5). It can
be compared to a laboratory prepared catalyst that
contained only the Co-Mo-alumina component (solid
circle). Adding 10% sodalite (with no nickel) to the
catalyst decreased the kuns value substantially while
causing a comparatively smaller increase in the khet
value. This suggests that adding a SOD-Ni component
to the catalyst caused some of the slower reacting
unsaturated species to be converted.
The effect of adding sodalite without nickel to the
catalyst can be explained in terms of hydrogen-transfer
reactions. Acid catalysts are known to facilitate hydrogen-
transfer reactions, and zeolites such as the hydrogen-
sodalite used in this study are acid catalysts. For
example, previous work in our laboratory39 demon-
strated that when mordenite (a zeolite) was added to
catalysts, the hydrodemetallization reactivity increased.
Hydrogen addition is known to be the first step in
hydrodemetallization.40 A plausible explanation for that
observation is that the mordenite zeolite facilitated
hydrogen transfer. Similarly, the sodalite in these
catalysts might aid the transfer of hydrogen from a
hydrogen-rich compound in the diesel fraction to a color
precursor compound. In catalytic cracking reactions, it
is known that acidic sites in zeolites can transfer
hydrogen from olefins and naphthenes to aromatics and
paraffins.41 Since 200 ppm of a compound can cause
color,17 even a small amount of hydrogen transfer could
have a beneficial effect. The observation that increasing
the amount of SOD-39Ni component (and decreasing the
CoMo:γ-Al2O3 component) in the catalyst caused a
lighter color, and a decrease in the Cuns parameter
(Figure 2) is consistent with this hypothesis.
Initially, as nickel is added to the sodalite, the nickel
will become incorporated into the sodalite structure,
thereby blocking some of the hydrogen transfer sites.
As the hydrogen transfer sites are blocked, fewer
unsaturates will be altered and the value of kuns would
be expected to increase, indicating that only the faster
reacting species were converted. This is indicated in
Figure 5 at the smaller % Ni values. Eventually no more
nickel can be accommodated within the sodalite struc-
ture. The nickel content of the catalyst that exceeds this
value will be comparatively easy to reduce to metallic
nickel and then to sulfide to nickel sulfide in the
hydrogen/hydrogen sulfide environment of the hydro-
(39) Minja, R. J. A.; Ternan, M. Energy Fuels 1991, 5, 117-122.
(40) Quann, R. J.; Ware, R. A.; Hung, C. W.; Wei, J. Adv. Chem.
Eng. 1988, 4, 95-259.
(41) Bhatia., S. Zeolite Catalysis: Principles and Applications; CRC
Press: Boca Raton, FL, 1988; p 83.
Color Degradation of Hydrocracked Diesel Fuel
Figure 6. Rate constants kuns (O) and khet (0) (s-1) versus
percent of the sodalite component x(SOD-39Ni) in the catalyst.
The solid symbols represent the Co-Mo-alumina reference
catalyst.
processing reactor. NiS (p-type) can be a weak catalyst
for the dissociation of hydrogen molecules into hydrogen
atoms. Additional hydrogen dissociation would alter
more unsaturated molecules. With large amounts of
nickel in the sodalite, more hydrogen dissociation will
occur and kuns will decrease since the slower reacting
species are being converted when the additional hydro-
gen is available. This is observed in Figure 5 when there
are large amounts of nickel in the SOD-yNi component
of the catalyst.
For the other series of catalysts, the amount of nickel
in the sodalite was maintained constant at 39% while
the fraction of the SOD-39Ni component in the catalyst
increased. The rate constants for this series are shown
in Figure 6. The rate constant for unsaturates, kuns,
decreased as the amount of the SOD-39Ni component
in the catalyst increased. This indicates that more of
the unsaturated molecules are being altered as the
catalyst component causing hydrogen transfer and
hydrogen dissociation increased. This is also consistent
with the value of kuns having a physical significance.
The rate constant for heteroatom removal, khet, in-
creased as the amount of SOD-39Ni component in the
catalyst increased (CoMo:γ-Al2O3 component in the
catalyst decreased). The increase in khet indicates that
faster reacting compounds are being converted. Again,
this provides evidence that the rate constant has a
physical significance (even if it is not invariant) and it
Energy & Fuels, Vol. 13, No. 3, 1999 693
is not just an arbitrary parameter from a mathematical
correlation. The solid symbols in Figure 6 are data
obtained using the commercial reference catalyst. Since
the reference catalyst did not include a sodalite com-
ponent, it can be compared to the laboratory prepared
catalyst that did not contain any of sodalite component.
The smaller values for kuns obtained with the com-
mercial catalyst indicate superior performance than the
laboratory prepared catalyst. As suggested previously,
this difference was probably related to differences in
catalyst preparation procedures rather than differences
in catalyst composition.
In summary, an overview of the color formation
phenomena can be suggested. The final color that forms
in hydrocracked diesel fractions can be attributed to the
amounts of two separate types of color precursors. One
type is the unsaturated compounds (Cuns), and the other
type is the compounds containing heteroatoms (Chet).
These color precursors were correlated with properties
of the diesel fraction. Chet was correlated with the sulfur
and nitrogen contents of the diesel fraction, while Cuns
was correlated with its density, since density can be an
indication of aromatic content.
Both rate constants were related to catalyst composi-
tion. The amount of the CoMo:γ-Al2O3 catalyst compo-
nent that influences heteroatom removal was related
to khet. The amount of the SOD-Ni catalyst component
was related to kuns. The SOD-Ni component influences
either hydrogen transfer (the number of SOD sites that
are not blocked by Ni) or hydrogenation (the number of
Ni atoms that exceed the number of nickel atoms that
can interact with the sodalite). The color at any time
after the diesel fraction had been obtained from the
processing unit was described in terms of four param-
eters. Each of the four parameters, Cuns, Chet, kuns, khet,
were correlated with the following measurable quanti-
ties (density, sulfur and nitrogen content, SOD catalyst
sites, and CoMo:γ-Al2O3 catalyst sites). These correla-
tions are consistent with the hypothesis that color in
diesel fractions is caused the presence of two different
groups of color precursors.
Acknowledgment. The authors are grateful to Bill
Smith for sending the feedstock sample and for his
encouragement. Funding from the Program for Energy
Research and Development (PERD) and from the Natu-
ral Sciences and Engineering Research Council was
greatly appreciated.
EF980214Q