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was raised from 225 tO 275~ the physicochemical characteristics of the hydrotreated oil
showed progressive changes in comparison with the feed.
The service life of the D-60 catalyst is more than three years without any additional
regeneration. The regeneration is performed by oxidative burnoff of coke from the catalyst
surface with a mixture of gas and air at temperatures no higher than 525~ and a pressure of
4 MPa. An inert gas (nitrogen) is used as the heat carrier. The regeneration cycle re-
quires 4-5 days,
The data that we have obtained demonstrate the feasibility, in principle, of obtaining
industrial oils from West Siberian crudes with satisfactory values of the viscosity index,
solid point, and color, by the use of D-60 catalyst in a G-24/I unit in place of AKM commer-
cial catalyst. During the course of the process, aromatic hydrocarbons and resinous sub-
stances are hydrogenated, and paraffinic--naphthenic hydrocarbons are hydroisomerized.

LITERATURE CITED
i. V. S. Fedorov, Khim. Tekhnol. Topl. Masel, No. 2, 3-7 (1981).
2. A. V. Agafonov, I. Ya. Perezhigina, E. D. Radchenko, et al., Tr. Vses. Nauchno-Issled.
Inst. Pererab. Neftl, No. 28, 13-29 (1978).
3. N. V. Shavolina, A. A. Zlotnikov, T. A. Voitekhov, et al., Tr. Vses. Nauchno-Iss!ed.
Inst. Pererab. Nefti, No. 30, 53-65 (1978).
4. U.S. Pat. 3,660,570.
5. A. K. Khasanov, G. Nurmatov, M. Murusmanova, et al., Material from 3rd Republic Scien-
tific-Technical Conference of Young Scientists on Petroleum Refining and Petrochemicals
[in Russian], Part I, Tashkent (1976), pp. 37-39.

PROCEDURE FOR DEVELOPMENT OF MATHEMATICAL MODEL OF PROPANE

DEASPHALTING PROCESS

P. A. Zolotarev UDC 665.637

In the separation of heavy petroleum resids in propane solution, complex interactions

take place between llke and unlike molecules and supramolecular structures, as well as inter-
actions related to coagulation of asphaltenes and changes in the interfacial energy [i-3].
Solutions of macromolecular organic components in nonpolar solvents are usually classed
as athermal. For such solutions, there is no heat of mixing, but the entropy increment is
significant [4, 5].
No reliable method is currently available for calculating the redistribution of compo-
nents between phases in extraction processes and other oll exchange processes in the separa-
tion of multlcomponent mixtures. The procedure that is proposed in this article for the
development of a mathematical model of the deasphalting process offers a means for calculat-
ing the phase equilibrium on the basis of physicochemlcal constants of the components or
combined fractions, both in single-stage and multistage deasphalting.
For an approximate evaluation of the dissolving power of solvents, Hildebrand intro-
duced the concept of the solubility parameter

where ~ is the solubility parameter; AL is the heat of vaporization; RTb is the excess
energy of the transition to the gas phase; R is the universal gas constant; Tb is the boil-
ing point of the solvent; V is the molecular volume.
The Hildebrand solubility parameter evaluates only the relative dissolving power of
solvents, without regard for their interaction with the component being dissolved. The na-
ture of this component may vary widely and may have a substantial influence on the solubility
parameter.
Ufa Petroleum Institute. Translated from Khlmlya i Teknologiya Topliv i Masel, No. i0,
pp. 16-19, October, 1984.

0009-3092/84/0910-0491508.50
9 1985 Plenum Publishing Corporation 491
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O,ZSol~ntO,~ qe t,o - - ~ ' a~olvent

e . e* o,e g8 t~o-
: ~ e a s p h a l t e d oil _ ]Seasphalte.d oil

Fig. 1. Influence of temperature with various

solvent/feed dilution ratios (a) and influence
of solvent/feed ratio at various temperatures
(b) on deasphalting results.

Calculational studies of extraction regimes have shown that the solubility parameters
for a solvent (or) and a solute (o2) depend on the enthalpy and entropy:
[ AL1 -- RTbt i,M, + AS, T ]1/2
oI= [ vl ('-4 WJ (i)
AL s - R T ~ izg 1 ASIT ]112
(i- = ) + -6U] (2)
where a and i -- a are the molar volume concentrations of the solvent and solute, respec-
tively; iM/V and AS/V are the molar enthalpy and the entropy increment referred to unit
volume; M is the molecular weight; T is the solution temperature; the subscript i denotes
values pertaining to the solvent and the subscript 2 denotes values pertaining to the solute.
For the case of partial dissolution, we can use an improved Hildebrand equation
RT= V m ~ o , - - o , ) ~ (3)
where Vmx is the volume of the mixture; (v~--at)a is the internal pressure in the solution.
Introducing into Eq. (3) the concentrations for the solvent phase, and expressing the
volume of the mixture in terms of the sum of volumes, we obtain

RT=[V,~+~(I_X)](62_o,)2 (4)
where X and i -- X are the respective concentrations of the solvent and solute in the pro,
pane-oll phase.
Solving Eqs. (i), (2), and (4) simultaneously, we find the distribution of solute be-
tween the propane-oil phase and the precipitated heavy oil phase.
For the solvent and solute, the entropy increment determines the difference between
the molar volumes of the interacting components:
AS=R(ln~--lnVt)

The proposed method can be used to calculate not only binary but also multieomponent
solutions, including calculations of the separation of a heavy straight-run resid (vacuum
resld) by propane. One such calculation is described below.
For the calculation of the relationships governing the phase transitions in multicompo-
nent systems, we selected a deasphalted oll with the following properties: density 912.3
kg/m s at 20~ viscosity 21.63 mm2/sec at 100~ refractive index 1.5025 at 50~ Conradson
carbon 1.22% by weight; molecular weight 525; average boiling point 5207C.
Transfer of components of the deasphalted oil to the propane phase was studied at tem-
peratures of 50 ~ 60 ~ 70 ~ 80 ~ and 85~ covering the entire range of working temperatures
in an extraction tower. The weight ratld of solvent to feed was selected from conditions of
coexistence of two equilibrium phases, within the limits from i:I to 4:1.
The influence of the temperature and the dilution ratio on the results obtained in sep-
arating the deasphalted oll are presented in Fig. I. With increasing temperature, the dif-
ference between the solubility parameters gradually increases, indicating a decrease in the
mutual solubility of the deasphalted oil and the propane. By the time the temperature has
reached 85~ the dissolving power of the propane has reached such a low level that the
ratio of propane to deasphalted oll no longer has any influence.

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TABLE 1

Arorna~es i *

Index
me- h~ V. I ,~
dium . . . . YI~ o

Potentialcontent, 13,74 12,44 19,01 28,97 25,84

Mwt.%
olecular weight 470 572 675 815 1500
bensity at 20"C, 883 951 985 1021 1085
kglm'
Relative index ,4832 ,535( 1,5670 1,571~
at 20"C
Sulfur content, 0,39 2,55 2,701 3,23 2,95
wt. %
Carbon. residue, wt. qo 0,17 0,91 2,73 4,12 18,7
Viscosity at lO0*C, 13,29 27,38 48,95 71,20
mmZ/see

*Concentrate of asphaltic/resinous sub-

stances precipitated in treatment of resid
with propane.

Fig. 2. Pseudocountercurrent scheme of Nash:

I) heavy straight-run resid; II) propane;
III) deasphalted oil solution; IV) asphalt
phase.

The decrease in the dissolving power of the propane is related not only to the increase
in the molar volume of the solvent, but also to the decrease in the heat of vaporization of
the propane. The energy of intermolecular interaction is influenced considerably by the
entropy increment. At higher temperatures, AST/V of the solvent is much smaller.
As shown by calculations, the improved method gives a correct description of the rela-
tionships involved in the dissolution process in propane. On the basis of this method, a
model has been developed for multistage deasphalting in the separation of fractions from a
vacuum resid. From narrow chromatographic fractions of the resid, five broader fractions
were made up. The material balance of the separation and the quality characteristics of the
blended fractions are given in Table i.

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TABLE 2
Fractionsof vacuumresid(calc.data) Deasphalted oil
Index ~c, commerical
data data

Capacityof unit,metrict o m / h 27,08 25--29

Deasphalted oliyield, wt. % 30,40 27--31
Carbon residue,~t.90 0,17 0,91 2,73 4,12 t ,t96 I,!--1,32
Refzactive index atg0"C 1,4835 1,5350 1,5670 1,5713 1,5208 1,5090--I ,5250
Sulfur content, wt. 90 0,39 2,55 2,70 3,23 1,66 1,8--2,2
r~stty at 20"C~kg/m s 883 951 985 1021 930,2 910--925
~eomcmar weight 470 572 675 815 548 500--570
ViScosityat IO0*C,mrgS/sec 13,29 27,38 48,95 71,20 23,92 19--23
Yieldof fraction,wt.9o 99,96 67,26 29,14 9,41
of potential

According to data obtained in investigations, the separation capacity of commercial

extraction towers in the deasphalting process is rated as three theoretical stages. The
flow scheme in the tower is organized as countercurrent flow only in the middle section
(extraction zone) of the column; in the upper section, because of the shift in the phase
equilibrium, a single-stage separation process is accomplished, and the heavy oil phase is
separated from the propane--oil phase.
If an extraction tower is arbitrarily divided into three stages, the fresh solvent is
fed to the first stage, where it encounters the asphalt phase of the second stage. The
feed to the second stage of extraction comes into contact with the propane-oil phase of the
first stage and with a solution of heavy oil leaving the third stage. By the use of closed
steam coils in the upper section of the extraction tower, the dissolving power of the pro-
pane is reduced, and the undesirable components of the deasphalted oil leave the propane--
oil phase -- the solution of deasphalted oil. This latter solution is withdrawn from the
third separation stage; and the asphalt phase, depleted in oil components, is withdrawn from
the first extraction stage.
The sequence of contacts in an extraction tower can be readily described by the opera-
tional pseudocounterflow scheme of Nash (Fig. 2). This scheme provides for a gradual ap~
proach to the equilibrium state. In the first rows of the three-stage scheme, the feed and
part of the solvent introduced into the system are consumed in the formation of intermediate
flows. In this section, the quantity of off-product from the system is considerably smaller
than the quantity of products introduced into the system. In the succeeding rows of the op-
erational scheme, the quantity of products withdrawn increases gradually, even thou@h the
quantity of intermediate products in the system continues to increase. Equilibrium is
reached in the final rows of the counterflow scheme, when the quantity of products intro-
duced into the system is compared with the quantity withdrawn. As can be seen from the
scheme, each extraction stage is a section of contacting of counterflows with tower bottom,
middle, and top temperatures 60 ~ 70 ~ and 82~ respectively. The stage temperatures in
the extraction were selected from commercial data.
The calculation is performed from stage to stage. With a selected ratio of solvent to
feed, the indexes of each fraction are introduced successively into the solubility para-
meter~ and the concentration of components in the propane-oil phase is determined. In the
overall balance, the redistribution of components between phases is summed. Using the new
compositions of the propane-oil and asphalt phases, the next separation stage is calculated.
The calculation is continued until stable equilibrium is reached in the system.
The calculation is correct if the weight of solvent to feed for each individual frac-
tion remains unchanged. The mole and mole-volume relationships will change in this case,
since the fractions differ in molecular weight and molar volume.
Any manual calculation from stage to stage is extremely unwieldy; therefore, we con-
structed a mathematical model for calculation of the process in a Mir-i computer, in accord-
ance with the operating conditions of commercial extraction towers. This calculation was
performed by the relaxation method, down to a certain discrepancy in the material balance
of the tower. The results from this calculation give exhaustive information on the extrac-
tion tower operation.

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On the basis of additivity of properties of the narrow fractions that are withdrawn,
we can determine the qualitative characteristics of the deasphalted oil and the asphalt.
The computerissues information on the yield of each narrow fraction and on the carbon resi-
due, sulfur content, density, molecular weight, viscosity (not completely accurate), refrac-
tive index, and other characteristics of the deasphalted oil (and also on the asphalt), if
required); information is also issued on the redistribution of each fraction between phases
with a yield relative to the potential. These data tan be used to calculate the liquid load
in each extraction stage and the internal circulation ratio of the intermediate streams, and
to construct an exact heat balance of the tower.
In Table 2, the calculated data are compared with commercial operating data. Satis-
factory agreement is observed between the results obtained in commercial separation of a
vacuum resid and the values calculated on the basis of the solubility parameter. High
accuracy of the calculation is contingent on the sharpmess of chromatographic separation
and the accuracy of analysis of the fractions in determining all of the physicochemical pro-
perry indexes. The highest accuracy is obtained for the carbon residue and the yield of
deasphalted oil(the property indexes used to control the deasphalting process).
A study was made of the influence of the number of stages (from 2 to 5) on the results
obtained in the separation of multicomponent systems. Variants of the countercurrent schemes
that were investigated are illustrated in Fig. 3.
The extraction temperature gradient in the calculative schemes was 22~ (from 60 ~ to
82~ only the temperature drops from stage to stage in the middle part of the countercur-
rent scheme were varied. The results from these studies are presented in Fig. 4 .

/F
c f

iF

Fig. 3. Countercurrent schemes of extraction:

a) two-stage; b) three-stage; c) four-stage;
d) five-stage. Other notation same as in Fig. 2o

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" ~ " gS~ "

35"g~,c 5~
,y,,
30 9~6 1,5~
5~ " 2,~

25 "g20
5~

6~ q, y2 -1,e 1,6

F3 ~,7 ~,~
zB
i? 7,:
26
~,5 ~

I H~TEg ~ ~g ~ ~ 5
Number of stages
Fig. 4. Influence of number of extraction stages
on quality of deasphalted oil: I) yield, wt. %;
II) density, kg/m3; III) molecular weight; IV) re-
fractive index at 20~ V) sulfur content, wt. %;
VI) carbon residue, wt. %; VII) viscosity of
100~ mma/sec.
According to extensive literature data, the number of separation stages is related to
the input of fresh solvent to the extraction operation. As the solvent input is increased,
the consumption of solvent in maintaining the assumed sharpness of component redistribution
may decrease. The characteristic bend in the curves in Fig. 4 indicates excess consumption
of solvent in five-stage deasphalting of the vacuum resid.
The satisfactory agreement between the commercial and calculated data indicates that
the simplified method, although it does not reflect all the complexities of interactions in
the separation of vacuum resid fractions by the propane solvent, does account for the most
important factors.

LITERATURE CITED
i. Z. I. Syunyaev, Petroleum Carbon [in Russian], Khimiya, Moscow (1980).
2. Z. I. Syunyaev, Phase Transitions and Their Influence on Processes of Petroleum Carbon
Manufacture [in Russian], TsNllTEneftekhim, Moscow (1977).
3. Z. I. Syunyaev, Khim. Tekhnol. Top1. Masel, No. 7, 53-57 (1981).
4. Ya. I. Gerasimov and V. A. Geiderikh, Thermodynamics of Solutions [in Russian], MGU,
Moscow (1980).
5. Yu. Ya. Fialkov, A. M. Zhitomirskii, and Yu. A. Tarasenko, Physical Chemistry of Non-
aqueous Solutions [in Russian], Khimiya, Leningrad (1973).

496