COMPOSITION OF PARAFFINIC AND NAPHTHENIC

HYDROCARBONS IN PETROLEUM ASPHALTS

A. M. Botvin'evaj N. A. Shkredova, UDC 665.45.035~05

and R. V. Dubkova

The hydrocarbon composition of asphalts is complex and difficult to study. With the
development of effective methods of chromatography and molecular spectroscopy, it has been
possible to investigate this matter by determining the hydrocarbon composition of individual
fractions [i, 2]. We have made an attempt to determine the composition of the paraffinic and
naphthenic hydrocarbons recovered from asphalts by means of a combination of chromatographic,
chemical, and spectroscopic methods.
The asphalt samples (Table I) were first treated with hexane to remove the hard asphalts.
The malthenes that were obtained (5 g) were separated into fractions by means of preparative
liquid-adsorption chromatography with gradient elution of the $-amplewith amixtureof solvents
[3]. The completeness of separation of the paraffinic/naphthenic (saturated) hydrocarbons
from the aromatics was monitored on the basis of UV spectra [4]. The saturated hydrocarbon
fraction was separated by treatment with urea into hydrocarbons forming an adduct and those
not forming an adduct [5]. The content of adduct-forming hydrocarbons in the saturated frac-
tions of these asphalts ranged from 5.3% to 19.8%, or 0.9% to 3.6% on the original asphalt.
It should be noted that high contents of adduct-forming hydrocarbons may be reflected in
poor service properties of the asphalts [5, 6].
Mass spectrometric analysis [7] showed that in the mixture of adduct-forming hydrocar-
bons, along with the n-paraffins there were admixtures of isoparaffins and long-chain aikyi-
naphthenes. This should be expected in view of the high molecular weights of the hydrocar-
bons (600-700) and the large contents of isomeric compounds in the fractions that are used
to form the adduct. With increasing boiling point of the hydrocarbons, i.e., with increasing
molecular weight, the adduct contains increasing amounts of isoparaffins and cycloparaffins
with long alkyi chains. In particular, according to [8], the adduct-forming hydrocarbons
may contain, in addition to the n-paraffins, certain isoparaffins and cycloparaffins (methyl-~
dimethyl-, cyclopentyl-, and cyclohexylalkanes). As was shown in [9], the adduct contains
an average of 92.5 • 5% n-paraffins.

TABLE i
Hydrocarbon group composition, wt. %
a,o---~atio---7 - - ~sins
Asphalt
Asphalt from indicated crude production
method ,~ -~ ,r ,t~ ~ I II r
O0
~ o

. Kamenolozhsk (paving) 39,5 In reactor 38,1 3,1 5"2 5,8 10,1 12,3 1117 15,6
Shaim (construction) 90,0 18,2 3,6 7,0 2,8 17,4 4,5 17,8 32,4
West Siberian (paving) 47,5 In column 14,5 1,5 9,5 4,7 27,4 6,1 19,3 18,4
Dolina Ceonstruction) 74,0 In still 27,1 2,7 19,8 2,1 2,0 20,9
Romashkino (paving) 50,0 In column 17,6 0,9 24,4 10,8 6,4 2o;4 20,a 10,3
East Ukrainian and Mangyshlak ~800 Ill reactor 19,6 2,7 6,6 2,6 t4,0 27,8 , 29,6
(construction) *
Blend of Romashkino vacuum residue
and vacuum distillate (construe-
don)"
95,0 In column 21,4 1,1 10,2 6,8 14,1 9,7 I 9,2

* Samples taken for investigation at the Bashkir Scientific-Research Institute for Petroleum Processin$. Ufa.
i28,6

A. N. Sevchenko Scientific-Research Institute of Applied Physics Problems at the V. i.

Lenin Belorussian State University. Translated from Khimiya i Tekhnologiya Topliv i Masel,
No. 4, pp. 32-34, April 1982.

0009-3092/82/0304-0183507.50 9 1982 PlenumPublishing Corporation 183

 I,5.~

~, !"~

200 2;0 280 Jr0 .1800 1800 lz+O0 1200 '1000.

.k,nm 9 9, c m - I

Fig. i Fig. 2
Fig. i. UV spectra of isoparaffins and cycloparaffins from asphalts
(D is the optical density; k is the wavelength). Spectra i, 2, and 3
are for the asphalts from Kamenolozhsk, Shaim, and Dolina crudes, re-
spectively.
Fig. 2. IR spectra of paraffinic hydrocarbons from asphalts (~ is the
wavenumber; T is the transmission). Spectra i, 2, and 3 are for the
isoparaffin and cycloparaffin fraction of the asphalts from Kamenolozhsk,
Shaim, and Romashkino crudes, respectively; spectrum 4 is for the n-
paraffins of the asphalt from Shaim crude.

The n-paraffins, which make up a major part of the adduct-forming hydrocarbons, were
analyzed by means of gas chromatography. For all of the asphalt samples, the n-paraffins
found in greatest quantities were in the C2o-Cso range. In the asphalt from West Siberian
crude, C,~-C~o n-paraffins were found in the greatest amounts; these included considerable
amounts of a hydrocarbon of the isoprenoid class, pristane (iso-C,,). According to [5], n-
paraffins with higher molecular weights m a y b e present in asphalts; these could not be deter-
mined under our particular conditions of gas chromatographic analysis.
Gas chromatography of the isoparaffins and cycloparaffins showed that they contained
traces of n-paraffins. For the isoparaffins and cycloparaffins that did not form a urea ad-
duct, we determined the refractive index, density (drop pycnometric method), and elemental
composition. A densimetric calculation [i0] based on these data gave a preliminary determina-
tion of their structural-group composition, i.e., the number of carbon atoms in paraffinic
chains and in naphthenic rings, the number of naphthenic rings in the average molecule, and
the average empirical formula.
The naphthenic hydrocarbons from these asphalts, judging by their overall formulas, dif-
fer among themselves in the degree of hydrogen unsaturation; this is explained by differences
in the degree of condensation of the naphthenic rings, the number of which in the number of
molecules ranges from 3 to 5. The increase in the number of rings is confirmed by the increases
in density and refractive indexes with very similar values of the molecular weight. Thus, for
the hydrocarbons in the asphalts from the Kamenolozhsk and Romashkino crudes, the amounts of
the carbon in paraffinic chains are 40.1% and 48.5%, respectively.
The UV spectra of the paraffinic hydrocarbons were recorded in a VSU-2P spectrophoto-
meter (East Germany) with a lightpath of i cm, in hexane solutions (0.001 g/ml). In Fig. i
we show the spectra of the isoparaffins and cycloparaffins from three of the asphalt samples.
The most intense absorption at 205 and 215 nm that is found for the isoparaffins and the
cycloparaffins in the asphalts from Shaim and Kamenolozhsk crudes is explained by the pres-
ence of small smounts of aromatic hydrocarbons as impurities. The similarity of the spectra
can probably be attributed to the presence of monotypical structures in these fractions, these
structures giving more intense absorption in comparison with the other components of the mix-
ture.
The absorption maxima for the benzenoid hydrocarbons are shifted in the long-wave direc-
tion (bathochromic shift) because of the presence of alkyl substituen~s [ii]. Among the
alkylbenzenes, the most intense absorption in this wavelength range is given by the isomers

184