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LITERATURE CITED
i. S. V. Adel'son and V. G, Sokolovskaya, Ref. Zh. Khim., 19 P 150Dep (1976).
2. G. Bakh, Z. Novak, and R. V. Kalinenko, Kinet. Katal., 15, No. 5, 1103-1109 (197~).
3. R. A. Kalinenko, S. G. Shvedova, and N. S. Nametkin, Neftekhimiya, 19, No. 3, 415-424
(1979).
4. Ya. M. Paushkin, S. V. Adel'son, A. P. Smirnov, et al., Neftepererab. Neftekhim.~ No. 7,
24 (1970).

RESID DEASPHALTING WITH LIQUEFIED GAS

A. V. Vishnew~kii, A. G. Martynenko, UDC 66.061:661.91:665.637.86

G. L. Potashnikov, and R. A. Martirosov

Butanes and pentanes have come into use recently as effective solvents in deasphalting
processes [i]. The main advantage of these solvents in comparison with propane is the pos-
sibility of adjusting their extraction properties over a broad range of temperatures. This
makes it possible to obtain deasphalted oils that are suitable as feedstocks for catalytic
cracking and hydrocracking, these oils being obtained in high yields and with low contents
o f ~ul~ur, metals, and aspha!tenes.

The work re~orted here has been aimed at establishing the basic relationship governing
the deasphalting precess in heavy liquefied petroleum has (LPG) in the example of isobutane.
The experiments were performed in a single-stage batch extractor. The starting material was
a straight-run resid from West Siberian crude with a carbon residue of 10.2% by weight, den-
sity (20~ 999 kg/m a, and initial boiling point 458~ The solvent dilution ratio and the
deasphalting temperature were varied over broad limits~ In all of the experiments, the pres-
sure corresponded to the vapor pressure of isobutane at the deasphalting temperature. The
deasphalting results are presented in Fig. i. The plots of the carbon residue, density, and
viscosity of the deasphalted oils vs the solvent dilution ratio were found to be analogous
in all cases, and hence the plots of density and viscosity are not shown in Fig. !.
As the dilution ratio is increased up to a certain level, the deasphalted oil yield drops
off, along with an improvement of its quality. We will term this level the optimal dilution
ratio [2]. Further dilution leads to higher yields of deasphalted oil and poorer quality.
The existence of an optimal dilution ratio and the shapes of the curves are consistent with
data obtained in investigating propane deasphalting, indicating an identical nature of the
dissolution in the two cases, due to the presence of low-molecular-weight hydrocarbons from
the resid in the solvent.
The results shown in Fig. 1 do not reflect the influence of solvent dilution ratio and
deasphalting temperature on the selectivity of separation. In order to determine these rela-
tionships, the deasphalting process was investigated from the standpoint of liquid extraction.
The solvency of the isobutane was expressed in terms of the ratio of the quantity of hydro-
carbons passing into the solvent phase to the total quantity taken for extraction; i.e., the
numerical value of the solvency coincides with the deasphaited oil yield. The selectivity
of the isobutane was determined on the basis of the separation factor [3], which, in applica-
tion to the deasphalting process, can be expressed by the formula

a (lO0--b)
= b O00--a)

where a and b are the respective contents of undesirable components in the solvent-free
asphalt and in the deasphalted oil.

Groznyi Petroleum Scientific-Research Institute (GrozNiI). Translated from Khimiya i

Tekhnologiya Topliv i Masel, No. 3, pp. 12-13, March, 1983.

0009-3092/83/0304-0119507.50 9 1983 Plenum Publishing Corporation 119

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98 9

[ 76
9~

~'~/'1 / g / ~""--

ca
g \ 10 tl

?l

0 g
3 ~ 5 6 7 8
J 6 5 6 7 8 Bobut~e:residweight
Bobumne:rosiclwelghtratlo ratio

Fig o i Fig. 2
Fig. i. Carbon residue (continuous curves) and deasphalted oil yield
(dashed curves) as functions of ratio of resid dilution with isobutane.
Curves i, 2, 3, 4, and 5 are for respective temperatures of 50 ~ 70 ~
90 ~ ii0 ~ and 130~
Fig. 2. Selectivity (continuous curves) and solvency (dashed curves)
of isobutane as functions of dilution ratio. Curve numbering same as
in Fig. i.

The contents of undesirable components in the two phases were determined as follows.
First, a sample of the resid was separated chromatographically into narrow fractions. The
dry residue of asphaltenes and resins insoluble in dichloroethane/benzene mixture was com-
Bined with the heavy aromatics (refractive index n~ ~ > 1.560); this mixture is considered
as the undesirable component. The other hydrocarbon fractions were also combined, represent-
ing the desired component. For each component, the density was determined, :The contents of
the components in the deasphalted oil and asphalt phases were found by the additivity rule.
With this approach, it was possible to establish the relationship between the isobutane
selectivity and its solvency (Fig. 2).
An increase in the deasphalting temperature is accompanied by a drop in selectivity and
solvency of the isobutane. As the dilution ratio is increased, the isobutane selectivity
increases as a result of a decrease in the content of low-molecular-welght components of the
feed in the pure solvent [2]. Here, the solvency first drops to a minimum and then increases.
Consequently, with a high dilution ratio, we observe a symbatic dissolution effect [4],
which is rarely encountered in liquid extraction processes and which is favorable. This
means that the greatest separation effect can be achieved with a dilution ratio above the
optimal. For confirmation, we investigated the influence of temperature and dilution ratio
on the recovery of deasphalted oil relative tO its potential content in the resid, and on the
carbon residue of the deasphalted oil. These relationships are shown in Fig. 3 for tempera-
tures of 86-95~ the same relationships are observed qualitatively for all of the tempera-
tures investigated.
With the optimal dilution ratio, the recoveries of deasphalted oil relative to potential
content in the resid are the lowest. However, without taking the deasphalted oil quality "~
into account, it is impossible to make a judgement as to the worst selectivity of separation.
It is necessary to consider cases in which the quality of the deasphalted oil at points a,
b, c, d, and e (see Fig. 3) are identical, but the conditions of the experiments are dif-
ferent. The recoveries of deasphalted oil of identical quality (relative to the potential
content in the resid) are designated for the respective cases as A, B, C, D, and E. The dot-
and-dash curve passing through these points describes the change in selectivity of separation
of the resid in relation to the temperature and the dilution ratio. An analysis of this curve
shows that the lowest selectivity of separation (point C) is observed at the optimal dilution

120
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- i "L/

i:
J
Isobutane :resid weight
ratio

Fig. 3. Carbon residue (continuous curves)

and recovery of deasphalted oil relative to
potential content in resid (dashed curves)
as functions of resid dilution ratio with
isobutane. Curves i, 2, and 3 are for re-
spective temperatures of 86 ~ , 90 ~ and 95~
Letter designations are explained in text.

ratio. In this connection, the dilution ratio, for a constant temperature, at which the
lowest yield and best quality of the deasphalted oil are obtained will not be termed the
optimal ratio, but rather the extremal ratio.
From the results of these studies, we can draw the following practical conclusions. If
the deasphalting is performed with a dilution ratio below the extremal (curve section ABC),
then, with any change in temperature, an increase in the solvent ratio will lead to a decrease
i n selectivity of separation of the resid. The quality of the deasphalted oil giving the
greatest recovery of the oil relative to its potential content in the resid can be achieved
if the process is carried out at a dilution ratio above the extremal (curve section CDE) and
at the highest possible temperature. These process conditions must be technically and
economically justified.

LITERATURE CITED
i. Neft' Gas Neftekhim., No. 9, 128-130 (1980).
2. L. P. Kazakova and S. E. Krein, Physicochemica! Principles of Petroleum Oil Production
[in Russian], Khimiya, Moscow (1978), pp. 78-79.
. A. Francis, Liquid--Liquid Equilibriums, Interscience, New York (1963).
4. B. V. Klimenok, Khim. Tekhnol. Topl. Masel, No. 3, 3-5 (1969).

121