(4) Dutton, H. J ., Mounts, T. L., J .

Catalysis 3, KO. 4, 363 (1964).

( , 5 ) Faryuhar, J . W., Insull, W., Rosen,
P., Stoffel, TI'., Ahrens, E. H., Sut r .
Abat ~. Rev. 17, No. 8, Part 11, 1 (1959).
(6) Hall, W. K., NacI ver, 1). S., Weber,
H. P., l ad. Eng. Chem. 52, 421 (1960).
(7) Hoelscher, H. E., Poyner, W. G.,
Weger, E., Chem. Revs. 54, 575 (1953).
(8) Homing, E. C., Ahrens, E. H., J r.,
Lipsky, S. R., Rlattson, F. H., Mead,
J . F., Turner, D. A., Goldwater, U'. H.,
J . Lipid Research 5, 20 (1964).
(9) Humko Products, Sterick Bldg., Mem-
phis, Tenn., Humko Tech. Bull., 1963.
(10) J ames, A. T., Wheatley, 5'. R.,
(11) Klenk, E., Eberhagen, D.. Hovve-
Biochem. J . 63, 269 (1956).
Seylers Z. Physiol. Cheh. 328, KO. 3-6,
180 (1962).
112) Kokes. R. J .. Tobin. H.. J r.. Emmett.
P. H. , J. Am. Chem. SOC.'~~, 5860
(1955).
(13) Korn, E. D., J . Biol. Chem. 238,
3584 (1963).
(14) Lindeman, L. P., Chem. Eng. .Vetus
40, No. 38, 61 (1962).
(15) Luddy, F. E., Barford, 11. A.,
Riemanschneider, R. W., J . .4m. Oil
Chemists' SOC. 37, 447 (1960).
(16) Woodford, F. P., \.anGent, C. Rl , ,
RECEIVED for review September 21, 1964.
Accepted Rlarch 4, 1965. Pittsburgh
Conference on Analytical Chemistry and
Applied Spectroscopy, Pittsburgh, Pa.,
March 2 to 6, 1964. Article not copy-
righted. The Northern Laboratory is
part of the Korthern Utilization Research
and Development Division, Agricultural
Research Service, U. S. Department of
Agriculture. hlention of firm names or
trade products does not imply that they
are endorsed or recommended by the
Department over comparable products of
other manufacturers.
J . Lipid Res. 1, 188 (1960).
Determination of Sulfur-Compound Distributions
in Petroleum Samples by Gas Chromatography
with a Coulometric Detector
RONALD L. MARTIN and J OHN A. GRANT
Research and Development Department, American Oil Co., Whiting, Ind.
b The distributions of sulfur compounds
in a variety of petroleum' samples
were determined by a combination of
gas chromatography and microcoulo-
metric sulfur detection. The detection
system responds to sulfur compounds
but not to hydrocarbons. Under op-
timum operating conditions, it quan-
titatively determines individual sulfur
compounds at sulfur levels down to
about 5 p.p.m. Gas chromatographic
separations are made on a silicone-
rubber column, from which sulfur
compounds are eluted nearly in order
of boiling point. Sulfur-compound dis-
tributions by boiling point are shown
for gasoline, coke-still naphtha, light
catalytic cycle oil, virgin naphtha,
kerosene, and gas-oil, Only in the
lower-boiling samples can individual
sulfur compounds be determined. For
a crude oil, gas chromatography-in
conjunction with other analytical tech-
niques-has been used to determine
the distribution of the five principal
sulfur-compound types as a function
of carbon number to C20. These data
illustrate a typical sulfur distribution
for virgin petroleums.
KCRI SASEI ) KNOWLEDGE of the types
I and distributions of sulfur com-
1)ounds is needed in many phases of
~~etrol eum processing. As a ineans for
acquiring such knowledge, gas chro-
niatogt,aIihj. with selective niicrocoulo-
metric sulfur detection was investigated.
'I'he coulometric detector reslmnds to
comllounds containing sulfur but not to
hj.di.oc~arbonh, and thei ~fore can deter-
minp tracc amounts of sulfur com-
1)ounds. even if hydrocarbons are eluted
with t hcni.
hficrocoulometric sulfur detectors for
gas chromatography were developed
independently by Coulson and
Cavanagh ( 7 ) , and Klaas (IS). The
detector of Coulson and Cavanagh,
which followed the design of an earlier
halide detector (6), has been used
extensively in the analysis of pesticides
( 4 , 5 , 7 ) and was suggested for petroleum
analysis ( 7) . Klaas ( I S ) developed a
similar detector and successfully
applied it to petroleum samples; selec-
tive gas chromatography columns were
used in clever fashion to determine
sulfur-compound types- in .naphthas.
Fredericks and Harlow (9) also used a
coulometric detector for sulfur com-
pounds; they modified the "halide"
detector (6) to accurately and selectively
determine thiols in natural gas. This
type of detector was not used in our
study because it does not respond to
other types of sulfur compounds.
I n this work, microcoulometric sulfur
detection was tested for quantitative
performance, interferences, and ap-
plicability to all types of petroleum
samples. Sulfur distributions by boiling
point for seven types of petroleum
samples were determined by the
combination of gas chromatography
and coulometric detection. The gas
chromatographic separations were ob-
tained with conventional nonselective
columns. Analyses for sulfur-com-
pound types were obtained by other
techniques to supplement the gas chro-
matographic data. For a Middle-East
crude, results from gas chromatography,
mass spectrometry, and liquid-solid
chromatography were combined to
obtain distributions of the five principal
sulfur types as a function of carbon
number to Cz0.
MI CROCOULOMETRI C SULFUR DETECTOR
The microcoulometric detection
system is manufactured by Dohrmann
I nstrument Co. (Model C-100) ac-
cording to the design of Coulson and
Cavanagh (6, 7 ) . I t has two main
components-combustion tube and
titration cell. The combustion tube is
located between the column and titra-
tion cell, and serves to osidize the
column effluent; sulfur compounds form
sulfur dioxide, which subsequently is
titrated automatically with coulo-
metrically generated iodine. Hydro-
carbons are converted to carbon dioxide
and water and generally do not affect
the titration. The current used for
iodine generation is recorded to give an
ordinary differential chromatogram for
sulfur compounds. The combustion
tube, which is maint,ained at 750" C., is
10 inches by 5/ 16 inch and packed with
quartz chips. Xitrogen sweep and
oxygen flows of 150 ml. per minute each
are brought in at the head of the tube
along with the column effluent.
The detector is sensitive as well as
selective; the minimum detectable
amount is about gram of sulfur
(between t'hat for thermal-conductivity
and flame-ionization detectors), and
samples with sulfur contents in the parts-
per-million range can be analyzed. The
detector time constant is larger than
that of conventional detectors because of
the time needed for combustion and
titration; this limits the effectiveness
for closely-spaced 1)eaks eluted in the
first several minutes, but otherwise
causes no problems. The detector is
easy to operate and maintain.
Quantitative Performance of De-
tector. For quantitative analyses,
644 ANALYTICAL CHEMISTRY
sulfur dioxide production from all
types of sulfur compounds must be
reproducible and directly proportional
to sulfur content. Sulfur compounds
are converted mainly to sulfur dioxide,
but conversion never reaches 100~o and
depends on operation of the combustion
tube. For example, the conversion to
sulfur dioxide at several combustion-
tube temperatures is shown in Table I
for thiophene.
The conversion to sulfur dioxide was
calculated from the number of coulombs
used for iodine generation. I t is at a
maximum in the 650-7500 C. range,
and drops rather sharply as temperature
is increased to 950'. The drop in con-
version probably is due either to greater
production of sulfur trioxide (which is
kinetically possible even though op-
posite to the direction of equilibrium),
or to less-complete decomposition of the
sulfur compound because of a decrease
in catalytic activity.
The age of t,he quartz packing also
affects sulfur dioxide production.
Freshly packed tubes produced less
sulfur dioxide, especially in the 500"-
700' C. range, than did ones used for a
month or more.
When alumina or 10% platinum on
asbestos was used instead of quartz
chips, sulfur dioxide production was
only a few per cent of theory at all
temperatures.
The flow rate of oxygen, sweep, and
column-eluting gases have little effect
on sulfur-dioxide production. For
example, with quartz chips at 750' C.,
varying oxygen from 20 to 300 and
nitrogen sweep from 0 to 300 ml. per
minute had essentially no effect, nor
did the use of helium instead of nitrogen
as eluting and sweep gases.
Even though conversion to sulfur
dioxide is not complete, quantitative
analyses are possible with the coulo-
metric detection system. This is
indicated by the analysis of a synthetic
mixture (Table 11), for which chromato-
graphic peak areas were assumed pro-
portional to sulfur content and were
normalized to the value for total sulfur;
combustion was performed at 750' C.
The difference between added and
found values averaged only 3%, which
is quite acceptable. The per cent con-
version to sulfur dioxide is nearly the
same, apparently, for compounds of all
types and boiling points.
Linearity of response for the coulo-
metric detection system extends from
the minimum detectable amount
(about 10-8 gram of sulfur) upward for
about three orders of magnitude.
Larger amounts were not tested because
the 1)eaks became broad and flat-toplied
as a result of insufficient speed of iodine
generation.
Detector I nterferences. I nterfer-
ence has been encountered from large
samples of hydrocarbons, and from
compounds that produce strong ox-
idizing agents during combustion-
e.g., compounds containing bromine,
chlorine, or nitrogen.
Interference from hydrocarbons varies
with the size and composition of the
samples. I t is not noticeable in the
usual-sized sample (0.1 to 5 p1, of an
individual hydrocarbon or up to about
100 p l . of a mixture of ai de boiling
range). However, larger samples often
give an interfering response that
generally is positive, but is sometimes
negative or alternately both positive
and negative. The interference from
hydrocarbons apparently arises because
large samples are incompletely oxidized,
and some of the intermediate products
are either oxidized by iodine or reduced
by iodide in the titration cell.
Hydrocarbon response tends to di-
minish, but is not eliminated, as the
oxygen and particularly the sweep flow
rates are increased. However, detector
noise also increases with flow rate, and
becomes excessive when the flows exceed
about 300 ml. per minute. Limiting
the sample size has been the only
successful means of eliminating hydro-
carbon response. This usually limits
the minimum detectable amount for
individual sulfur compounds to about 5
p.p.m.
Compounds containing chlorine, bro-
mine, or nitrogen interfere because their
combustion produces strong oxidizing
agents, which in turn oxidize iodide ion
in the titration cell to give a negative
response. Bromine compounds inter-
fere seriously even in trace amounts.
Interference from chlorine compounds
is less severe, and it can be reduced and
sometimes eliminated if the oxygen is
bubbled through water before combus-
tion (Y), in which case the combustion
product is mostly hydrochloric acid
rather than chlorine. Kitrogen com-
pounds interfere less severely than the
halogens, and their concentrations in
petroleum samples generally are too
low to be troublesome.
GAS CHROMATOGRAPHIC SEPARATIONS
The gas chromatographic separations
were made with a stainless steel column,
20 feet by inch i.d., packed with
15% by weight of silicone rubber
(General Electric SE-30) on acid and
caustic washed 30-60 mesh Chromosorb-
W. Column temperature was pro-
grammed at 4" per minute from 60" C.
to as high as 400". The flow of eluting
gas was maintained at 100 ml. per
minute.
The silicone column was chosen
because it elutes sulfur compounds,
regardless of type, nearly in order of
boiling point. I n the naphtha and
kerosene ranges, boiling points could be
predicted from elution time within 5' C.;
Tabl e 1. Conversion to Sulfur Di oxi de
at Di fferent Temperatures
Combustion-tube % Conversion
temperature, C. to sulfur dioxide
550
enn
650
700
750
850
950
70
80
91
93
89
74
63
Tabl e II. Determination of Sulfur Com-
pounds in Synthetic Mi xt ure
Sulfur, To
Added Found
Thiophene 0 0081 0 0085
Methylpropylsulfide 0 0052 0 0050
3-Methylthiophene 0 0059 0 0058
1-Pentanethiol 0 0092 0 0090
2,5-l>imethylthiophene 0 0057 0 0060
1-Hep tanethiol 0 0068 0 0066
n-Butylsulfide 0 0035 0 0037
Benzolblthiophene 0 0145 0 0144
2-Methvlhenzo Iblthio-
Ethyldisulfide 0 0101 0 0095
, i
pheni 0 0232 0 0236
n-Amyldisulfide 0 0058 0 0057
Dibenzothiophene 0 0107 0 0109
errors in the gas-oil range would be
somewhat higher. I n this work, it was
important that elution time could be
related to boiling point, because in-
dividual compounds generally could not
be identified, and identification by
boiling point had to suffice.
The silicone column occasionally was
used to 400' C.; column bleed begins
earlier (at about 300" C.) but does not
lead to significant response from the
coulometric detector. The relatively
high percentage of silicone rubber
(150j0) is used to avoid adsorption of
thiols on the Chromosorb-W support.
After several months operation, thiol
adsorption increases, and the column
must be replaced.
APPLICATIONS
Characteristic sulfur distributions are
illustrated by determinations on gaso-
line, coke-still naphtha, catalytic cycle
oil, whole crude, and the heavy naphtha,
kerosene, and gas oil fractions from the
crude (Figures 1 through 7) . The
figures are plots of sulfur concentration
us. boiling point of the sulfur com-
pounds, where boiling point has been
estimated from the elution times of pure
compounds with known boiling points.
I3ecause all sulfur tyl m often are pres-
ent in virgin samldes, identification of
individual mpmbers is difficult, and
distributions by boiling 1)oint often
must suffice. In the refined samples,
however, sulfur distributions usually
are less complex, and some individual
VOL. 37, NO. 6, MAY 1965 645
DISULFIDES 2
SULFIDES I I
THI OLS I
THIOPHENES 61
BENZOTHIOPHENES 25
100%
cg '
BrThs
1 250 350 4 50 5
BOILING POlN T, O F
Figure 1 . Sulfur compounds by boiling point in gasoline
I - R I NG THI OP HENES I
2- RI NG THI OP HENES 79
3- RI NG THI OP HE NE S 14
CI O
BzThs
' CI I
2MTh
I ,ISH
HYDROGEN SULFIDE 5
THI OLS 15
DISULFIDES 3
SULFI DES 20
THIOPHENES 52
BENZOTHIOPHENES 5
II
I00 200 300 400 500 I
BOILING POINT, O F
Figure 2. Sulfur compounds by boiling point in coke-still naphtha
components or groups of components
can be determined or at least estimated.
Gasoline. The distribution of sul-
fur compounds in gasoline is relatively
simple, as shown in Figure 1 for a reg-
ular-grade sample containing 0.090%
sulfur. Most of the compounds are
thiophenes, a few of which-thio-
phene, 2- and 3-methylthiophenej benzo-
[blthiophene, and 2- and S-methyl-
benzothiophene-were identified by
emergence times and are labeled on the
chromatogram. The others are identi-
fied only by carbon number because
individual reference compounds were
not available.
The breakdown of sulfur types in the
gasoline, as determined by specific tests
(S, 10, 11, 14, 15, I T ) , is shown at the
upper left of the chromatogram. The
sulfides, thiols, and disulfides are dis-
tributed throughout the boiling range.
About one third of the sulfur is in
com1)ounds boiling above the normal
gasoline end 1)oint of about 415' F.,
most of which are benzothiophenes.
This I)rol)ortion is higher than might be
suspected, but is characteristic of most
gasolines.
About 20 gasolines and catalytically
cracked naphthas (which provide the
bulk of sulfur in most gasolines) have
been surveyed by gas chromatography.
Interestingly, similar sulfur profiles
were obtained in each case, even though
the samples were produced by different
companies from different crudes and
with different catalytic cracking proc-
esses.
Coke-Still Naphtha. I n coke-still
naphtha, which is formed from re-
siduum by thermal cracking, the
distribution of sulfur compounds is
more complex, as shown in Figure 2
for a typical sample containing 0.7201,
sulfur. Thiophenes still predominate,
but significant amounts of hydrogen
sulfide, thiols, and sulfides also are
present.
Most of the thiols could be identified.
They are concentrated in the lower-
boiling part of the sample and decrease
in concentration from ethyl to amyl.
Most of them are straight chained;
isopropyl is the main exception.
Two peaks (thiacyclopentane and
methylthiacyclopentane) were tenta-
tively identified as sulfides by emergence
times. Most of the other sulfides form
a background under the thiophenes;
they are probably cyclic, because the
unidentified peaks, like those in gasoline,
do not match the retention times of
chain sulfides. Chain sulfides probably
are not sufficiently stable to survive the
cracking reactions.
I n light
catalytic cycle oil, which come5 from
catalytic cracking of gas oil, the
distribution of sulfur compounds also
is relatively uncomplicated, as shown
in Figure 3 for a typical sample con-
taining 1,42y0 sulfur. Although this
chromatogram has many unresolved
peaks, the sulfur distribution is less
complicated than those of virgin stocks
of the same boiling range.
Most of the sulfur is thiophenic;
the analyses for sulfur types ( 14) ,
which are included on the chromato-
gram, show that two- and three-ring
thiophenes account for 79% and 14%,
respectively, of the total sulfur.
Only a few individual compounds
could be identified with certainty-
benzothiophene, 2- and 3-methylbenzo-
thiophene (In the peak labeled CS
BaThs), and dibenzothiophene. How-
ever, many of the peak groupings were
tentatively identified by carbon number.
Such identifications were achieved by
comparing mass spectrometric and gas
Light Catalytic Cycle Oil.
0
646 ANALYTICAL CHEMISTRY
BOILING POINT,OF
Figure 4. Sulfur compounds by boi l i ng point in crude oi l
chromatographic data on two- and
three-ring aromatic concentrates ob-
tained by liquid-solid chromatography.
With gas chromatography, compounds
were found, as a first approximation, to
group together by carbon number.
An analysis by carbon number for
benzothiophenes and dibenzothio-
phenes, as calculated from the Figure 3
chromatogram, is given in Table 111.
These values were obtained by inte-
grating the areas of peaks attributed to
each carbon number, and normalizing
the areas to the value for total sulfur
less that determined as nonthiophenic
sulfur ( 14) . Although such analyses are
only qualitatively valid, they have been
very useful in following the progress and
patterns of desulfurization reactions.
Crude Oil. Figure 4 shows the
distribution of sulfur compounds boil-
ing to 1000" F. i n the Middle-East
whole crude (containing 2.72y0 sul-
fur), and illustrates the complexity
of sulfur distributions in -virgin
samples. Only a few components
can be identified with much certainty,
and essentially none can be determined.
Qualitative information, however, can
be deduced. Sulfur in the naphtha
range is low. The big rise begins in t'he
kerosene range with the two-ring
thiophenes, most of which are benzo-
thiophenes and are visible over the
background of other peaks. A second
and steeper rise start's in the light gas-
oil range wit,h the three-ring thiophenes,
which are mostly dibenzothiophenes
and naphthothiophenes. The sulfur
compounds boiling through 1000 F., as
determined by the chart area and also
by analyzing distillation fractions, ac-
count for 40% of the total sulfur.
.i better look at
the naphtha-range sulfur compounds
is provided by Figure 5, which shows
the heavy naphtha (containing 0.090~o
sulfur) from the Middle-East crude be-
fore and after removal of thiols and
disulfides (after reduction) with silver
nitrate.
Virgin Naphtha.
The lower-boiling portion of the total
naphtha contains mainly thiols, most of
which are identified in Figure 5. Un-
like the thiols in coke-still naphtha,
these are mainly branched, which is
consistent with the findings of others on
virgin naphthas ( 3) . Some of these
thiols were not originally present in the
crude oil, but rather were formed during
distillation.
The sulfur compounds in the thiol-
free naphtha are mainly sulfides, since
the thiophene analysis (14) represented
only 1% of the total sulfur. A few of
the major peaks are definitely identified
as straight-chain sulfides. Most of the
Tabl e 111. Thiophenic Compounds by
Carbon Number in Light Cat al yt i c
Cycle Oi l
Sulfur, c/ L
BENZOTHI OPHENES
C* 0 014
C9 0 15
ClO 0 27
cu 0 25
c12 0 18
e13 0 12
Ci4and higher 0 14
ClZ 0 017
Cl? 0 08
DI BENZOTHI OPHENES~
e;;
Clb and higher
0.07
0 05
One-ring thiophenes and non-
thiophenic sulfur* 0.10
__
1. 42
a Includes naphthothiophenes.
Determined by catalytic-decomposi-
tion method (14).
peaks between the straight-chain
members probably are branched-chain
sulfides. Cyclic sulfides apparently are
present in smaller amounts than chain
sulfides, which is reverse to the usual
situation ( 1, 2, 18). Cycloparaffins in
this naphtha also are present only in
small amounts, which suggests that
proportions of cyclic and chain sulfides
in crude oils may follow the proportions
of cyclic and chain paraffins.
I I , I I I I 1
n
THI OL -FREE NAPHTHA
II
TOTAL NAPHTHA
DI S UL F I DE S 6
S U L F I DE S 5 7
I THI OP HE NE S
100%
-
100 200 300 4 00 5 00
BOI LI NG P OI NT , O F
Figure 5. Sulfur compounds by boiling point in heavy naphtha
VOL. 37, NO. 6, MA Y 1965 0 647
THI OL S 6
DI SULF l DES 3
SULFI DES 4 2 EzThs
I - RI NG THI OP HENES 2
2- RI NG THI OP HENES 45
3-RI NG THI OP HENES 2
CI O CI I
I I I I I 1 I I I
1 350 450 550 650 i
cI3
D i 8 I T hs
1 THI OLS
SULFI DES 22
I-RING THI OP HENES I
BOI L I NG P OI NT , OF
Figure 6. Sulfur compounds by boiling point in kerosene
' DiBzThs
A nearly complete resolution of
naphtha-range sulfur compounds might
be obtained with selective liquid phases,
such as those suggested by Karchmer
( l a) and Klaas ( I S ) . Long, wide-bore
capillary columns might be particularly
effective for such work.
Kerosene. The distribution of sul-
fur compounds in the kerosene (con-
taining 0.50% sulfur) from the Mid-
dle-East crude is shown in Figure 6.
The major peaks extending above the
background represent chiefly the 9-,
lo-, 1 I -, and 12-carbon benzothiophenes;
benzothiophene itself is too small to be
positively identified. The higher-boiling
portion contains some dibenzothio-
phenes, and dibenzothiophene itself is
identified. The background consists
mostly of sulfides, which account for
about 42Q/, of the total sulfur. Again,
one-ring thiophenes are present only in
small amounts. Thiols account for
only 6% of the total sulfur, which is a
lower percentage than in the naphtha
range, but a similar absolute amount.
Quantitative use of this chromato-
gram is limited to determining sulfur
distribution by boiling point. In-
dividual compounds or compounds by
carbon number cannot be determined
with certainty. An estimate of the pro-
portion of thiophenic sulfur can, how-
ever, be made.
Gas Oil. The distribution of sulfur
compounds in the light vacuum
virgin gas oil (containing 2.60%
sulfur) from the Middle-East crude is
shown in Figure 7 . Again, thiophenic
compounds extend above the back-
ground of other peaks. The first series
of peaks (between 450" and 600" F.)
consists mostly of benzothiophenes.
The second series (from about 630' to
750" F.) consists mostly of dibenzothio-
phenes, nhich project above an intense
ound that includes benzothio-
lthenes as well as sulfides. I n contrast
to cycle oil, two- and three-ring thio-
phenes cannot be determined, because
the background of other sulfur com-
pounds is too great. The distribution of
thio1)henic types must be obtained by
another method (14).
2-RI NG THIOPHENES 35
3-RI NG THIOPHENES 37 DiBzTh
4-RI NG THI OP HENES 4 4
SULFUR TYPES BY CARBON NUMBER IN CRUDE
OIL
I 0 0 %
E
Gas Chromatography can be more
effective when used in combination with
other analytical techniques than by it-
self. The effectiveness of combining
gas chromatography, mass spectrom-
etry, liquid-solid chromatography, and
specific tests is illustrated by Figure 8,
which shows distributions by carbon
number of the five principal sulfur types
in the Middle-East crude oil. Data for
thiophenic types came from analysis of
liquid-solid chromatographic fractions
by gas chromatography and/or low-
voltage mass spectrometry, and analysis
of distillation fractions by the catalytic
decomposition method ( 14) . Sulfide
and thiol values came from specific tests
on distillation fractions (8, 10, I Y ) , and
were verified by values for nonthio-
phenic sulfur obtained by catalytic de-
composition ( 14, 15) ; carbon numbers
were estimated from the boiling ranges
of the fractions. One-ring thiophenes
are not included in Figure S because
their levels are insignificantly low.
Disulfides are not included because
they mere not found in freshly distilled
fractions. Because some assumptions
had to be made to prepare the plots,
the data should be considered only as
semiquantitative. The data for four-
ring thiophenes probably are the least
accurate.
Two- and three-ring thiophenes are
the principal compound types in the
crude oil. Mass spectrometric analysis
of chromatographic fractions indicates
BOI L I NG P Ol NT pF
Figure 7. Sulfur compounds by boiling point in gas oil
. 06
. o s
01
0:
Figure 8. Sulfur
types by Carbon ,03
Number in Middle- g
East crude
.02
,01
I I I I I I I I I
I\
\
2- RI NG 4 I \ \ /
...-..--
' I / - -\
THIOPHENE^
d B 11 16 20 1 4
CARBON NUMBER
648 ANALYTICAL CHEMISTRY
that 80 to 90% of these thiophenes are
tully aromatic. Two-ring thiophenes
are at a mauimum at CI1 (three carbons
above the first member of the series),
and then decrease gradually with in-
creasing carbon number. Three-ring
thiophenes are at a maximum at CI 4
(two carbon numbers above the first
member of the series) and then decrease
rather sharply with increasing carbon
number. Benzothiophene itself is pres-
ent in very small proportion (0.0002~o) ;
dibenzothiophene, however, is about
0.009%.
Sulfides increase in amount to about
CQ0 and then level off; they are the
principal type in the heavy naphtha
(C,-C,) range. Thiols are at a maxi-
mum at about Cs; they then decrease
and are negligible in the gas-oil range.
The sulfur compounds through Cz0
plotted in Figure 8 account for 0.67%
sulfur, which is only 25y0 of the total
sulfur in the crude. Hydrocarbons
through C?, account for 607, of the
total crude.
Figure 8 illubtrates a typical distribu-
tion of sulfur compounds in petroleum.
Crude oils contain different absolute
amounts of sulfur and slightly different
proportions of the various sulfur types
(f4), but their distributions by carbon
number, in our euperience, usually are
similar. Two- and three-ring thio-
phenes, for example, generally possess
the same maxima and similar rates of
decline as those shown in Figure 8.
This crude has a slightly smaller pro-
portion of sulfides than most crudes
(f4), but the sulfides show the char-
acteristic steady rise in amounts into
the gas-oil range. The crude also shows
a fairly typical distribution of thiols; of
all the compound types, thiols probably
are the most variable among crude oils.
CONCLUSION
Gas chromatography with coulo-
metric detection has proved to be an
effective means for characterizing sulfur
distributions, even though individual
compounds generally cannot be deter-
mined. I n future work, gas chroniatog-
raphy should be used more in combina-
tion with other analytical techniques.
Two excellent techniques would be
linear elution adsorption chromatog-
raphy ( I C ) , and mass spectrometry;
fractions separated by linear chromatog-
raphy would be analyzed by both gas
chromatography and mass spectrom-
etry. Such a combination should
yield much more information than the
techniques could produce individually,
and should be amenable to routine
application.
LITERATURE CITED
( 1 ) Birch, 8. F., Cullum, T. V., Dean,
R. A,, Ilenyer, R. L., I n d . Eng. Chem.
47, 240 (1955).
( 2) Brown, R., Meyerson, S., Ibzd., 44,
2620 (1952).
( 3) Coleman, H. J ., Thompson, C. J .,
Hopkins, R. L., Rall, H. T., J . Chem.
Eng. Data 10, 80 (1965).
( 4) Challacombe, J . A,, AIcNulty, J . A.,
Resi due Rev. 5, 57 (1964).
( 5) Coulson, D. M., in Gas Chroma-
tography, L. Fowler, ed., p. 213,
Academic Press, New York, 1963.
( 6) Coulson, I >. Al ., Cavanagh, L. A,,
AI VAL. CHEM. 32, 1245 (1960).
( 7) Coulson, D. AI. , Cavanagh, L. A.,
Mcrocorilometric Detection in Gas
Chromatography, Pittsbur: h Confer-
ence on Analytical Chemistry and
Applied Spectroscopy, J I arch 1961.
( 8) Ilrushel, H. \., \[iller. J . F.. ANAL.
CHEM. 27. 495 i 1955).
( 9) Fredericks, E. AI ., Harlow, G. A.,
(10) Hastingr, S. H., I bi d. , 25,420 (1953).
( 1 1 ) Hubbard, R. L., Haines, W. E.,
(12) Karchmer, J . H., I bi d. , 31, 1377
(13) Klaaq, P. J ., I bi d. , 33, 1851 (1961).
(14) Martin, R. L., Grant, J . A., I bi d. ,
(15) lI cCoy, R. N., Weiss, F. T., Ibid. ,
(16) Snyder, L. R., Ibi d. , 33, 1527, 1538
Ibid. , 35, 263 (1964).
Ball, J. S., I bi d. , 30, 91 (1958).
(1959).
37, 649 (1965).
26, 1928 (1954).
f 1961).
RuFeau of Mi n e s Rept. I nvest . 6252
(1963).
RECEIVED for review December 14, 1964.
Accepted J anuary 28, 1965. Division of
Petroleum Chemistry, 149th LIeeting,
ACS, Detroit, Nich., April 1965.
Determination of Thiophenic Compounds by
Types i n petroleum Samples
RONALD L. MARTIN and JOHN A. GRANT
Research and Development Department, American Oil Co., Whiting, Ind.
A method f or determining thiophenic-
compound types in petrol eum samples
of al l types and boiling ranges has
been devel oped. Nonthiophenic sul-
fur compounds ar e decomposed over
alumina at 500 C. to form hydrogen
sulfide and aromatic thiols, which ar e
collected and t i t rat ed to determi ne
t ot al nonthiophenic sulfur. Thiophenic
compounds, extensively deal kyl at ed
i n the decomposition reaction, ar e
separ at ed b y gas chromatography
according to number of rings and
det ect ed by microcoulometric titration;
thiophenic types with one, two, three,
four, and fi ve or more rings ar e
determi ned. Accuracy of the method
i s good as j udged by analyses on test
samples and by comparison with other
anal yt i cal techniques. Distillation frac-
tions and residua from seven crude
oils wer e anal yzed to provi de sulfur-
t ype characterizations heret of ore un-
at t ai nabl e. Differences among crudes
in the distribution of sulfur-compound
types usually ar e not l ar ge. Thiophenic
compounds t ypi cal l y account for 50 to
7070 of the sulfur; except i n residua,
most of these compounds have either
two or three rings.
ri THE REFINING of high-sulfur crude
I oils, the determination of sulfur-
compound types often is important.
The need for such analyses is partic-
ularly great in the gas oil and residuum
ranges, where available methods have
not been completely satisfactory. One
particular use is to follow the Iirogress
of desulfurization processes, which pro-
ceed at different rates for each of the
sulfur types.
I n the first relatively complete
delineation of the sulfur types in gas
oils, Lumpkin and J ohnson (1 3) showed
that compounds containing condensed
thiophene and aromatic rings accounted
for iiiost of the sulfur. Their work
provided the basis for the first method
for thiophenic types-the mass-sl)ectro-
metric method of Hastings, J ohnson,
and Lumpkin (10)-which gives semi-
quantitative determinations of benzo-,
dibenzo-, and naphthobenzothiophenes.
Although this method has been very
valuable in following composition trends
and reaction behavior, its accuracy and
alq)licability leave something to be
desired. I n our experience, values for
thiophenic sulfur frequently are high,
paiticularly for samples with limited
boiling ranges. Mass sl)ectronietry
also has been used to determine one-
ring thiophenes ( 9) , but only in naphtha-
range samples.
Liquid-solid chromatography on
VOL. 37, NO. 6, MA Y 1965 649