324

Ind. Eng. C h e m Res 1990,29, 324-329

were calculated and are shown in Table IV. The distribution coefficient of dibenzothiophene in the unoxidized
oil extraction was the highest (5.1). After oxidation, hexyl
sulfide was not present in the oxidized oil. The distribution coefficients of dibenzothiophene and phenyl disulfide
in the extraction of oxidized oil were increased: from 5.1
to 11.2 for dibenzothiophene and from 1.8 to 4.5 for phenyl
disulfide. As for the phenyl sulfide, the distribution
coefficient in both extractions was relatively low. These
results are consistent with the results described previously.
Conclusions
Oxidation of the Arabian AGO by nitrogen dioxide has
converted the sulfur compounds of the oil to forms that
are more polar in nature. These sulfur compounds are
more readily extracted by polar solvents, such as lactone,
that have been demonstrated to be aromatic/olefinic
dissolving, thus resulting in higher sulfur removal, lower
solvent-to-oil requirement, and hence, higher extraction
oil yield for the same sulfur removal. Oxidized oils from
other petroleum stocks which have higher contents of
olefins and aromatics do not show an oil yield increase in
the extraction by lactone. The distribution coefficients

of dibenzothiophene and phenyl disulfide in lactone extraction of AGO are greatly increased for the oxidized oil
as compared to the untreated oil.
Registry No. NOz, 7697-37-2; nitrogen dioxide, 10102-44-0;
ybutyrolactone, 96-48-0; hexyl disulfide, 10496-15-8;phenyl
sulfide, 139-66-2; dibenzothiophene, 132-65-0;phenyl disulfide,
882-33-7.

Literature Cited
Deal, C. H.; Derr, E. L., Selectivity and Solvency in Aromatic Recovery. Prep--Am. Chem. Soc., Diu.Pet. Chem. 1962, 7 (4), 214.
Gerster, J. A.; Gorton, J. A,; Eklund, R. B. Selective Solvents for
Separation of n-Pentane from 1-Penteneby extractive Distillation. J . Chem. Eng. Data 1960, 5, 423.
Guth, E. D.; Diaz, A. F. Method of Removing Sulfur and Nitrogen
in Petroleum Oils. US.Patent 3,847,800, 1974.
Guth, E. D.; Helgeson, N. L.; Arledge, K. W.; Brienza, A. R. Petroleum Oil Desulfurization Process. US.Patent 3,919,402, 1975.
Tam, P. S.; Kittrell, J. R. Process for Purifying Hydrocarbonaceous
Oils. U.S. Patent 4,485,007, 1984.
Thompson, R. B.; Druge, L. W.; Chenicek, J. A. Stability of Fuel Oils
in Storage--Effect of Sulfur Compounds. Ind. Eng. Chem. 1949,
;I

121, 2713.

Received for review July 18, 1989

Accepted November 8, 1989

Desulfurization of Fuel Oil by Oxidation and Extraction. 2. Kinetic

Modeling of Oxidation Reaction
Patrick S. Tam,tJil J a m e s R. Kittrell,' and John W. Eldridge*J
Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003, and KSE,
Inc., P.O. Box 368, Amherst, Massachusetts 01004

T h e oxidation of Arabian atmospheric gas oil (AGO) with nitric acid t o remove sulfur from the oil
is similar to the gradual processes involved in the storage instability of petroleum distillates and
synfuels, except that in this process the instability process is accelerated by adding a strong oxidizing
agent, nitric acid. The elemental composition of these sediments is compared. A mathematical kinetic
model is presented to describe the kinetics of sulfur removal in the oxidation of AGO using a CSTR.
This model employs lumping of the sulfur compounds in the oil into four groups, S1, S2, and S3,
according t o their retention times (hence, boiling points) in the gas chromatograph, and residue (R)
containing some of the other three sulfur groups. The first group (Sl) had a very fast reaction rate.
T h e second group (Sa) reacts with second-order kinetics with a rate constant of 17 g of oil/(g of
S2.min) at 25 "C. The third group (S3)was not present in the unoxidized oil, and as it was formed,
it equilibrated between the oil and the residue phases.
The principle of desulfurizing Arabian atmospheric gas
oil (AGO) by oxidative desulfurization (ODS) is to form
a coproduct (residue) that has high sulfur content and can
be separated from the oxidized oil. It has long been recognized that petroleum distillates and synfuels (both crude
and refined) are unstable upon long-term storage in the
presence of air at ambient conditions, with the formation
of sediment (deposit, residue, sludge, and insoluble gum).
The sediment formation from the oil is due to the gradual
oxidation and polymerization of the reactive compounds
present. The ODS process is, in many ways, very similar
to the instability process of fuel oil, except that the oxidation rate in ODS is greatly accelerated by using a strong
oxidizing agent, nitric acid or nitrogen oxides in this case.
The gum formation from jet turbine and diesel fuel is
clearly associated with oxidation and cooxidation of hyKSE, Inc.
University of Massachusetts.
Present address: The Pritchard Corp.. Overland Park, KS
8

66210.

0888-5885/90/2629-0324$02.50/0

drocarbon mixtures (Mayo and Lan, 1983). Walters et al.

(1949) studied the gum formation in cracked gasoline and
found that the gum and peroxide formation is autocatalytic
in nature. It was proportional to the amount of air
available for reaction, indicating that oxidation played the
major role in this process. Not all fuel oils show the same
rate of sediment formation. For thermally cracked gasoline, heavier fractions are less stable than light fractions
(Walters et al., 1949). In general, paraffins, aromatics,
monoolefins, and diolefins are increasingly unstable toward
oxidation in the order named. Offenhauer et al. (1957) also
found the same trend. Straight run distillates which
normally contain mostly paraffinic compounds are more
stable, whereas catalytically cracked distillate fuels containing more unsaturated hydrocarbons are unstable
(Brooks, 1926; Cassar, 1931; Flood et al., 1933). For shale
oil and shale-derived fuels, the instability is even more
pronounced (Inneen and Bickel, 1951; Cooney et al., 1984;
Frankenfeld et al., 1982). Certain heterocyclic sulfur and
nitrogen compounds in addition to those responsible for
the gum in cracked petroleum distillates are involved in
0 1990 American Chemical Society

Ind. Eng. Chem. Res., Vol. 29, No. 3, 1990 325

Table I. High Acid-to-Oil Ratio (0.10) Oxidation of AGO by 90% HNO, (Acetic Acid/Feed Oil = 0.03)
wt of reactants (W)
in CSTR," g
wt of oil ( WOiJ in CSTR, g

oil feed rate (Ff),g/min

space time (01, min
oxidized oil
yield, wt %
sulfur content, 70

s1

52
s3
residue
yield, wt %
sulfur content, 70
aqueous phase
yield, wt %
sulfur content, 70
sulfur balance closure, 70

530
476
135
3.5

483
410
48.2
8.5

479
410
45.7
9.0

578
506
24
21.1

556
479
18.1
26.5

458
376
8.9
42.2

474
383
8.5
45.1

100.2
0.75
0.045
0.576
0.129

98.7
0.63
0.008
0.452
0.171

98.4
0.64
0.033
0.460
0.147

98.9
0.54
0.050
0.358
0.132

97.7
0.50
0.037
0.328
0.135

96.1
0.46
0
0.309
0.151

96.1
0.45
0.009
0.278
0.163

6.1
3.10

10.3
3.36

10.0
3.44

9.5
3.21

11.3
3.20

12.7
3.32

11.9
3.27

7.00
0.64
92.2

5.6
0.48
92.9

6.0
0.48
92.9

5.6
0.46
81.0

5.1
0.38
81.3

7.3
0.50
99.6

6.2
0.39
79.0

"Oil plus residue and acids. Yields were based on oil feed. Oxidized oil had about 2% acetic acid.

the formation of sediment in shale oil naphtha.

Nitrogen compounds are also known to be deleterious
to the stability of hydrocarbon fuels (Nixon, 1962;
Thompson et al., 1951). Pyrrole-type compounds are
found to be significant sediment precursors in fuel oil.
Dominant compounds are alkyl-substituted pyrroles, especially 2,5-dimethylpyrrole (DMP). Indoles also play an
important role in promoting sediment formation, but not
as significant as the pyrroles.
Mathematical models are widely used for the description
of the kinetics of petroleum reactions. For such complex
reactions, lumping the components into pseudospecies is
commonly necessary. Blanding (1953) treated the kinetics
of catalytic cracking by using a one-lump conversion model
and found first-order kinetics. Weekman (1979) used a
three-lump model for the kinetics of cracking of gas oil.
Smith (1959) described catalytic reforming reactions with
a four-lump model.
In the present effort, the kinetics of sulfur removal in
oxidative-desulfurization (ODS) reactions of Arabian atmospheric gas oil (AGO) are modeled by lumping the
sulfur compounds into four groups. The predicted sulfur
removal compares favorably with the measured values.
The yield of sediment formation can also be estimated.

Experimental Section
A continuous stirred tank reactor (CSTR) was used for
the oxidation of a middle distillate (Arabian atmospheric
gas oil) with a mixture of 90% nitric acid and glacial acetic
acid. Use of acetic acid was to disperse the residue coproduct uniformly in the reactor. The extent of oxidation
was controlled by the acid-to-oil (A/O) ratio and the spacc
time. The A/O ratio is defined as the ratio of the flow rate
of HNO, (calculated based on 100% acid) to the flow rate
of feed oil, by weight. The space time used was also based
on weight.
The CSTR was a two-piece, 1-L, cylindrical vessel constructed of Klimax glass with the top and bottom halves
held together by clamps. Oil was pumped into the reactor
from the top, and mixed acids were added to the reactor
from the top by a fine stopcock buret. Reaction temperature was measured by a thermocouple connected to a
digital temperature controller. The oxidation is exothermic. Reaction thermperature was maintained at 25 "C by
immersing the bottom half of the reactor into a water bath.
Agitation of the reaction mixture at 300 rpm provided
uniform mixing of reactants. Products emerged from the
exit tube of the reactor by overflow.
The total sulfur content of the oil was determined by
using a Gamma-Tech Model 100 chemical analyzer. A

Table 11. T h r e e Groups

sulfur group
elution time, min
column temp, "C
bp, "C

of S u l f u r Compounds

s1

0-10
80-170
180-290

s2

10-15
170-220
290-380

s3
15-18
220-250
380+

Table 111. Comparison of Residue from Oxidation of AGO

w i t h Sediment Formed in Cycle Oil
deposit
original oil
(residue)
S, % N, m m S, % N, %
AGO, 0.07 A/O HNO, oxidation 1.19
60
3.82
3.46
AGO, 0.11 A/O HNO, oxidation
1.19
60
3.39
3.97
catalytic cycle stock la
1.28
100
3.38
3.58
1.72 0.80
catalytic cycle stock 2"
0.96
200
nSource: Thompson et al. (1951).

Perkin-Elmer Sigma 2000 gas chromatograph with flame

photometric detector (FPD) was used to analyze for specific sulfur compounds, using the conditions summarized
in Table I of part 1 of this series.

Oxidation of AGO
Atmospheric gas oil with an initial sulfur content of
1.07% was treated with 90% HNO, in a CSTR at 25 "C
and 1 atm, at 0.10 A/O ratio. The weight ratio of acetic
acid to feed oil was 0.03. The results are shown in Table
I. The sulfur removal increased with increasing space time
until at around 45 min it leveled off. Figure 1 shows the
yields of oxidized oil and residue as a function of sulfur
removal. As the sulfur removal was increased, the oil yield
decreased and the residue yield increased. Specific sulfur
chromatograms of the oxidized oil are shown in Figure 2.
A certain group of lower boiling sulfur compounds was
completely removed, even at 3-min space time. These
lower boiling sulfur compounds eluted a t a maximum retention time of 10 min. Formation of higher molecular
weight product sulfur compounds with retention times
greater than 15 min was also observed. These compounds
were not present initially in the feed oil and they constitute
one group of product sulfur compounds believed to have
been produced during oxidation. The elution times, column temperatures, and boiling points corresponding to the
three sulfur groups are listed in Table 11.
Mechanism of Oxidation
Sulfur removal by oxidation is due to the formation of
high-sulfur-containing residue, which results from the
accelerated sedimentation of the oil from instability induced by nitric acid. Table I11 shows the comparison of

326 Ind. Eng. Chem. Res., Vol. 29, No. 3, 1990

Table IV. Comparison of Elemental Compositions of Residue a n d Deposits from Unstable Fuels
elemental compositions of
deposits, %
oil description
C
H
N
O
S
empirical formula
HNO, oxidation of AGO: 0.07 A / O
60.5
3.7
14.9
3.8
6.3
HNO, oxidation of AGO: 0.11 A i 0
64.5
3.8
12.9
3.4
6.6
fuel oil blends with cat. cracked components from
West Texas
76.9
6.7
1.8
8.7
1.9
California
78.5
6.9
3.1
8.5
1.3
6.9
2.1
8.5
4.1
Middle East
77.5
cracked components-Middle East
76.1
6.3
3.4
7.7
2.6
5.0
diesel fuel marine (DFM)
62.0
3.0
25.0
2.0
crude shale oil
74.8
5.8
10.5
0.9
8.0
7.4
6.4
9.6
1.0
mildly hydrotreated shale-derived middle distillates
76.6
61.3
11.3 21.5
NA"
5.7
diesel fuel with 2,5-DMP as dopant
shale-derived fuel with dopants
DMP
62.1
5.7
11.4
20.4
0.1
5.7
DMP plus thiophenol
67.7
4.9
12.1
9.1

OXIDIZED OIL

reference

Offenhauer et al., 1957

Offenhauer et al., 1957

Jones et al., 1984b
Frankenfeld et al., 1982
Frankenfeld et al., 1982
Frankenfeld et al., 1982
Jones et al., 1984a

FEED OIL

< 07 % s
ATTENUATION = 256

A/O=0.10

A/O:0.03
3 5 MIN SPACE TIME

0 75 %

ATTENUATION

RESIDUE

:64

9 0 MIN SPACE TIME

0 64 % S
ATTENUATION = 32

SULFUR REMOVAL (%)

Figure 1. Relation between sulfur removal and yields of oxidation
with 90% HN03.

residue in this process with the sediments formed in cycle

oils due to storage. Although different compounds can be
present in different feedstock, this does show the similarity
of the residue obtained from AGO oxidation and the
precipitate from unstable cycle oils of similar sulfur content.
These similarities are further illustrated in Table IV,
which shows the elemental compositions (C/H/N/O/S).
Various feedstocks-diesel, shale-derived distillate, and
cracked distillates-with and without dopants are reported.
The empirical formulas for the deposits were also determined. Adding dopants (dimethylpyrrole (DMP) or
thiophenol) to the fuel also resulted in deposits of similar
elemental composition. They are based on one atom of
nitrogen. Residue from the oxidation of AGO has a formula of C20H24N04S0.4.
Deposits from unstable fuels have
carbon atoms ranging from 14 to 50, depending on the
properties of the oil. However, the H/C ratio of the deposits from unstable fuels was from l to 1.3, which was

45 1 MIN SPACE TIME

045% S
ATTENUATION = 8

80

4
(10

1
140

<5

20

170

220

270

RETENTION TIME (mini

COLUMN TEMPERATURE ('C)

Figure 2. Sulfur chromatograms from 0.10 A/O ratio CSTR oxidation (0.5-pL volume).

similar to that from the oxidation of AGO (1.2). The ratio

of O / N for all these deposits ranged from 1.3 to 7.3 and
was usually around 2 to 4. The residue of the oxidation
of AGO had a O/N ratio of 3 to 3.5, which was very similar
to the values Offenhauer et al. (1957) obtained from var-

Ind. Eng. Chem. Res., Vol. 29, No. 3, 1990 327

Table V. Consistency of Distribution Coefficient of (Cs& to ( C & with Different Feedstocks
samples
feed AGO
oxidized AGO
feed hydrotreated AGO
oxidized hydrotreated AGO
'K3R

is defined as (Cs3)J(C&

K3R

cs, %
0.73
0.31
0.39
0.12

CSl,

%7

0.321
0.005
0.142
0

csz, %
0.374
0.202
0.248
0.036

cs31

0.036
0.113
0
0.084

(CS)R,

0
2.30
0
1.82

K3R0

0.049
0.046

for the AGO used for modeling studies was 0.045.

RETENTION TIME h i d
COLUMN TEMPERATURE I'C)

Figure 4. Sulfur chromatogram of S1 oil from 0.10 A/O ratio oxidation (0.5-pL volume, attenuation = 256).
Figure 3. Sulfur chromatogram of the residue (0.1-pL volume, attenuation = 64).

ious fuel oil blends with catalytically cracked components.

These fuel oil blends had properties more similar to those
of the AGO used here than did diesel fuel derived from
shale oil. The high percentage of oxygen in these sediments suggests a cooxidation of reactive sulfur, nitrogen,
and olefinic compounds.
All these observations showed that the mechanism of
ODS was actually sedimentation of AGO accelerated by
adding nitric acid or nitrogen oxides. That this is the case
is also supported by Sonnet (19801, who oxidized in situ
shale oil with nitrogen dioxide. The nitrogen compounds
present in the shale oil before and after oxidation were
analyzed by gas chromatography with a nitrogen-phosphorus detector (NPD). The pyrrole and indole compounds were identified in the shale oil. After oxidation,
the relative concentrations of the pyrrole and indole compounds in the shale oil were reduced, even though the total
nitrogen content was higher than before. These compounds were presumably oxidized and condensed in the
residue phase, resulting in sulfur removal in the shale oil.

Reaction Structure
The proposed reaction structure for the oxidation reaction by lumped species is

where S1, S2, and S3 denote the individual lumped sulfur

groups with retention times of 0-10,10-15, and 15-18 min,
respectively, and R designates the residue.
This reaction structure was developed based on the
following observations.
1. The sulfur chromatogram of a residue sample (Figure
3) showed the presence of sulfur compounds within the
boiling ranges (or retention times) of the S1, S2, and S3
groups.
2. The sulfur contents of the S3 group and the residue
were approximately constant at different space times
(Table I). Mutual saturation or phase equilibrium occurred between the S3 in the oil and the total sulfur in the
residue. The equilibrium distribution coefficient, K3R,

between the concentrations of S3 in the effluent oil and

sulfur in the residue was determined to be 0.45 at 25 "C.
Table V compares this coefficient with those determined
from two other feedstocks; they are very similar.
3. Fast disappearance of the S1 group was seen in Figure
2. Oxidation using only the S1 group (distilled from the
AGO stock) as the feed oil showed the creation of the S2
group and formation of residue (Figure 4). About 20%
of the sulfur in the S1 group was converted to the S2 group.

Modeling of the Kinetics

Because of the fast rate of disappearance of the S1 sulfur
group and the almost constant concentration of the S3
product sulfur compounds, the reaction kinetics of oxidation were studied with respect to the S2 sulfur group
only.
The following mass balance applies to a CSTR system:
in by flow - out by flow =
net rate of disappearance by reaction
The sulfur in the S1 group in the feed oil (0.35 w t % )
was divided into two parts: (1)that which would be rapidly
converted to S2 sulfur compounds (0.07 w t %), designated
as (C&, and (2) that which would disappear from the oil
phase quickly by becoming part of the residue, either
directly or via a rapid sequence of forming S2 compounds
first, which then go directly to residue. The general
equation for the S2 sulfur balance in the oil phase is
(1)
Fd(Cs1)n + (CsJfI - Fe(Cs2)e = rs2Woil
Assuming nth order lumped reaction kinetics on the S2
sulfur, its net rate of disapperance, including its going
either to S3 or directly to residue, is
rs2 =

+ k2d(Cs2)en

(2)

One can find n and It, + Ituc by plotting In rsz vs In (CS2),,

as shown by
In rs2 = In ( I t , +
+ n In (CS.Je
(3)
and the rate of S2 disappearance is given by eq 1 to be

A plot of In rs2 vs In (Cs2)e is shown in Figure 5. A

straight line with a slope of 2 fits the data quite well. This
second-order reaction is reasonable and in agreement with
the instability of fuel oil by oxidation; sulfur compounds
polymerize to form heavier molecular weight compounds

328 Ind. Eng. Chem. Res., Vol. 29, No. 3, 1990

"I
6o

--

OBSERVED
PREDICTED

s?

D
-B
1

0 OBSERVED

is-

-pREDlc/

4!
10W

iij

5-

[L

SLLFLR 7OhTEN'

2UE TC 52 SROUP, iCs$,

'9S Z / q

01 J

Figure 5. Evaluation of the reaction kinetics of the S2 sulfur group.

that form sediments of high sulfur and nitrogen content.

The value of the combined reaction rate constants, k 2 +
k2R, was found to be 17 g of oil/(g of S-min).
According to the reaction structure, the following
equations are applicable to the sulfur balance of the S3
group and the residue:
for the S3 sulfur group

The rate constants from eq 5 and 6 were determined to

be 13.5 g of oil/(g of S-min) for k z and 3.5 g of oil/(g of
Ssmin) for k2R.
From the kinetic model of the S2 sulfur group, the space
time can be evaluated by

For a given space time, the sulfur content in the effluent

oil (product) due to the S2 group can be calculated from
eq 7. The residue content was known from experimental
results. From the equilibrium relation between (Cs3)eand
(C&, (CS3)ecan be calculated and then the total sulfur
removed. Figure 6 shows the sulfur removal, % , vs space
time for both predicted values and observed values from
Table I. The solid line represents the predicted values,
which describe the data quite well.
The yield of residue can also be estimated from the total
sulfur balance:
Fd(Cs1)f + ( C S Z )-~ J'e[(Csz)e
+ (c~3)eI
FR =

(8)

(CS)R

Conclusions
A model has been developed to describe the kinetics of
sulfur removal in the oxidation of an atmospheric gas oil
(AGO) using 90% HN03 with an A/O ratio of 0.10 in a
CSTR. The kinetic model was derived by lumping the
sulfur compounds of the oil into four groups of sulfur
compounds: S1, S2, and S3, according to their chromatographic retention times (or boiling ranges), and the
residue. The S1 sulfur group has a very fast reaction rate.
The S2 sulfur group reacts with second-order kinetics and
has a lumped rate constant of 17 g of oil/(g of SZ-min) at
25 "C. The sulfur contents of the oil attributable to the
S3 group and the sulfur content of the residue are constant
for all space times (3-45 min) and are related as follows:
(cS3)e

= 0*045(Cs)R

(9)

The derived kinetic model can also predict the sulfur

removal and residue yields from oxidation for a given space
time.
Nomenclature
Cs = total sulfur content, g of S/g of oil
Csl = sulfur content due to S1, g of S / g of oil

I n d . Eng. Chem. Res. 1990, 29, 329-333

Cs2 = sulfur content due to S2, g of S/g of oil

Cs3 = sulfur content due to S3, g of S/g of oil
(Cs)R = sulfur content of the residue, g of S/g of residue
Ff = weight flow rate of feed oil, g of oil/min
F, = weight flow rate of effluent oil, g of oil/min
F R = weight flow rate of residue in effluent, g of R/min
k , = lumped reaction rate constant of the S1- S2 reaction
k 2 = lumped reaction rate constant of the S2 S3 reaction
k l R = lumped reaction rate constant of the S1- R reaction
k 2 R = lumped reaction rate constant of the S2
R reaction
k 3 R = lumped reaction rate constant of the S3
R reaction
K3R = distribution coefficient between
and (C&, dimensionless
n = reaction order, dimensionless
rs2 = net rate of disappearance of S2 sulfur, g of S/(g of
oilamin)
R = residue
W,,, = weight of oil in reactor, g
6 = space time of the CSTR, min
Registry No. HNO,, 7697-37-2.

--

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Brooks, B. T. The Chemistry of Gasoline. Ind. Eng. Chem. 1926,18
(ll),1198.
Cassar, H. A. Gumming Tendencies of Pure Olefins in Gasoline. Jnd.
Eng. Chem. 1931,23 (lo), 1132.
Cooney, J. V.; Beal, E. J.;Wechter, M. A.; Mushrush, G. W.; Hazlett,
R. N. Nitrogen Compound Induced Storage Instability in Shale
Derived Diesel Fuel Marine. Prepr.-Am. Chem. SOC.,Diu. Pet.
Chem. 1984,29(4), 1003.

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Dinneen, G. U.; Bickel, W. D. Gum Formation in Shale-Oil Naphtha.

Ind. Eng. Chem. 1951,43(7), 1604.
Flood, D. T.; Hladky, J. W.; Edgar, G. Chemical Nature of GumForming Constituents in Gasoline. Ind. Eng. Chem. 1933,25(ll),
1234.
Frankenfeld, J. W.; Taylor, W. F.; Brinkman, D. W. Final Report
DOE/BC/10045-23, 1982; US. DOE: Washington, DC.
Jones, L.; Hazlett, R. N.; Li, N. C.; Ge, J. Storage Stability Studies
of Fuels Derived from Shale and Petroleum. Fuels 1984a,63,
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Jones, L.; Hardy, D. R.; Hazlett, R. N. Storage Stability Studies of
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Mayo, F. R.; Lan, B. Y. Gum and Deposit Formation from Jet
Turbine and Diesel Fuels. Prepr.-Am. Chem. SOC.,Diu. Pet.
Chem. 1983,28( 5 ) , 1209.
Nixon, A. C. Auto-oxidation and Antioxidants; Lundberg, W. O.,
Ed.; Interscience: New York, 1962.
Offenhausr, R. D.; Brennan, J. A.; Millers, R. C. Sediment Formation
in Catalytically Cracked Distillate Oils. Ind. Eng. Chem. 1957,49
(81, 12265.
Smith, R. B. Kinetic Analysis of Naphtha Reforming with Platinum
Catalyst. Ind. Eng. Chem. 1959,55 (6), 76.
Sonnet, J. M. Oxidation and Extraction Removal of Sulfur and
Nitrogen compounds from In-Situ Shale Oil. M.S. Thesis, University of Massachusetts a t Amherst, 1980.
Thompson, R. B.; Chenicek, J. A.; Druge, L. W.; Symon, T. Stability
of Fuel Oils in Storage-Effect of Some Nitrogen Compounds.
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Received for review September 7, 1989

Accepted November 8, 1989

Arrhenius Parameters for the Autoxidation of Solid Organic

Compounds
Hua Liang and Tatsuo Tanaka*
Department of Chemical Process Engineering, Hokkaido University, Sapporo 060, Japan

By use of thermogravimetric analysis, the activation energy and the frequency factor are determined
for the autoxidation of solid organic compounds. It is found that the activation energies are almost
the same so long as the compounds have the same molecular structure around the hydrogen to be
abstracted. As a result, direct or indirect evaluation of the activation energy becomes possible for
the combustible compound in question from its molecular structure, leading t o the quantitative
prediction of self-heating. Further, in the reaction kinetics, it has been said that there is a tendency
called compensatory effect; i.e., the larger the activation energy, the larger the frequency factor.
By use of the reported experimental data of combustible materials, a compensatory effect is roughly
found between the activation energy and the product of the frequency factor and the heat of reaction,
suggesting that the cause of self-ignition is in terms of the molecular structure.
In order to predict the possible self-ignition of combustible powder (Liang and Tanaka, 1987), we found it
particularly necessary to evaluate the activation energy and
the frequency factor of the given material. In our previous
paper (Liang and Tanaka, 1988), it was verified by use of
available experimental data that the Polanyi equation
between the activation energy and the weakest C-H bond
strength held for the chain propagation reaction in the
autoxidation of organic compounds in solution. As for the
solid organic compounds, however, there have been few
experimental works done, and thus, the basic evaluation
methods of the reactivity of autoxidation have not been
found. For this reason, measurement is made in this paper
0888-5885J 90126 29-0329$0 2.50/0

of the reaction rate of autoxidation for solid organic compounds, whose structure is known, in order to investigate
the relation between the Arrhenius parameters and the
molecular structure. Furthermore, mention is given of an
interrelationship between the Arrhenius parameters of
some common combustible materials, using the experimental data reported in the literature.
Experimental Equipment and Procedure
A thermogravimetric analyzer (TGA-31) of the Shimadzu Corporation was used as the measurement instrument of the reaction rate of autoxidation. The sample
holder is a wire mesh cylindr made from platinum, 10 mm
0 1990 American Chemical Society