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Chemistry and Technology of Fuels and Oils, Vol. 45, No. 3, 2009

IMPROVEMENT IN PROCEDURE FOR PROPANE AND PROPANE-BUTANE

DEASPHALTING OF PETROLEUM RESIDS

F. M. Sultanov

The total number of installations that provide for propane deasphalting of hydrone at Russian oil refineries
is 23, of which 18 are active, and the remainder are in a conversion stage. A valuable product of the process is hard
petroleum asphalt, which is used for the production of motor oils. The yield of the by-product – asphalt – ranges
from 64-85% of the feedstock. The greater part of the asphalt is utilized extremely ineffectively.
Domestic installations employed for the propane deasphalting of hydrone are inferior to foreign analogies
with respect to specific energy expenditures. Research in the domain of improvement of the procedure employed
for this process, which is directed toward a reduction in the consumption of energy resources, expansion of the
assortment of products derived from the process, and development of new trends for their qualified application, is
therefore urgently needed.

Potential for Deepening Refinement of Crude and New Product Line Based
on Propane-Butane Deasphalting
Investigations of the deasphalting of petroleum resids by various solvents has been on-going for
some time at the GUP INKhP RB. The Bashkirtostan Scientific Research Institute for Petroleum
processing (BashSRIPP) was developing a process for the deasphalting of petroleum resids by light
gasoline (Doben process) as early as the 1960s. The hard gasoline-solvent asphalt (asphaltite) obtained in this
process, however, is characterized by a high softening point (120°C and higher), which complicates its utilization.
In this connection, the GUP INKhP RB initiated development of a procedure for the deasphalting
of petroleum resids using solvents lighter than gasoline, for example, propane-butane, at the outset of
the 1990s [1, 2]. Mingaraev et al. have indicated [1] that propane-butane asphalt can be used in heavy-tonnage
production of highway asphalts, or as a binder for the briquetting of coals; no problems arise, therefore when it is
utilized in this alternate scheme employed for deasphalting at existing installations.
On the other hand, propane-butane deasphalting differs appreciably from gasoline deasphalting by a
lower carbon residue and a content of heavy tar components; this permits its use not only as feedstock for
catalytic cracking, but also as feedstock in lube-oil production to obtain high-viscosity lube stocks by refining
them at solvent-treatment installations [2].
Table 1 presents results of the deasphalting of the hydrone of western-Siberian crude by a

____________________________________________________________________________________________________
GUP Institute Neftekhimpererabotki, Republic of Bashkortostan. Translated from Khimiya i Tekhnologiya
Topliv i Masel, No.3, pp. 14 – 18, May – June, 2009.

0009-3092/09/4503–0157 © 2009 Springer Science+Business Media, Inc. 157

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propane-butane mixture with various process regimes, which make it possible to evaluate the quality of the products.
As is apparent, it is possible, by varying the temperature and composition of the solvent, to obtain highly treated
deasphaltizate with a carbon residue of 3.6-3.8% and a yield of 40-45% with respect to the hydrone. Here, their
content of heavy metals is retained at the minimum level (10-12 ppm).
The GUP INKhP RB proposes to construct new installations for propane-butane deasphalting, which will
make use of new technical solutions that permit a substantial reduction in energy expenditures for the process.
Construction of the installations would be particularly effective at petroleum refineries possessing modern
heavy-duty cat-cracking complexes. The latter are experiencing a scarcity of hydrocarbon feedstock in connection
with the overall reduction in volumes of crude refinement.
Another, more realistic alternate scheme of introducing propane-butane deasphalting to production in the
situation that is building in domestic petroleum refining is the reprofiling of existing, but idle plants intended for
the propane deasphalting of hydrone. The technical feasibility and economic expediency of such a reprofiling was
first demonstrated during the course of a test run at one of the 36-1 type of installations operated by the publicly
owned joint-stock company Ufaneftekhim in 1993 [1, 3].
Finalizing of the procedure for propane-butane deasphalting at the installations intended for propane
deasphalting, and verification of its effectiveness were continued by the publicly owned joint-stock
company NOVOIL in 1998 [2, 3]. Solvent-treatment regimes of propane-butane deasphalting at
installations 37/1 and 39/2 were also worked-out during the course of the runs with the recovery of
high-viscosity PS-28 and P-40 lube stocks, and compounding of the hard propane-butane petroleum asphalts with
hydrone with the recovery of unoxidized highway asphalts satisfying requirements of the Technical Specifications
for Grades BNN 50/80 and BNN 80/120.
Based on our recommendations, two type 36-1 deasphalting installations and one type 36-3 installation
were converted for operation in a propane-butane deasphalting regime by the Ufaneftekhim Co., and also one
type 36-1 deasphalting installation by the NOVOIL Co.

Table 1
Deasphalting with solvent:hydrone ratio of 3:1 and solvent composition of
38% C3H8 + 62% C 4H10 at temperature of, 46% C 3H8 + 54% C4H10 at temperature of,
Indexes
°C °C
120 105 85 110 105 90
Pressure, MPa 3,3 3,3 3,6 3,3 3,3 3,6
Deasphaltizate
Yield, wt. % 41,2 45,1 52,4 39,2 40,7 48,8
Density at 20°C, kg/m3 945 949 956 942 944 953
Carbon reside, % 3,6 3,8 5,1 3,0 3,6 4,6
Content
sulfur, % 1,8 1,8 1,9 1,8 1,8 1,9
vanadium and nickel, ppm 11,0 12,6 17,6 10,0 12,3 16,5
Asphalt
Yield, wt. % 58,8 54,9 47,6 60,8 59,3 51,2
Density at 20°C, kg/m3 1031 1042 1047 1034 1038 1043
Carbon reside, % 23,8 25,7 26,1 22,7 23,7 24,8
Softening point, °C 52 60 63 49 51 59

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New Developments Concerning Energy Conservation for Deasphalting of Hydrone

Deasphalting of petroleum resids by light hydrocarbon solvents is energy-intensive. At all existing
hydrone-deasphalting installations operating at Russian refineries, the solvent is reclaimed from the deasphaltizate
solution by regeneration in evaporators by means of repeated heating and lowering of the pressure with subsequent
cooling and condensation of solvent vapors. This method requires heavy power consumption (water vapor and
circulating water) and is unwieldy with respect to production layout [4].
In 1972, the Norwegian Company Kerr McGee proposed a procedure for the deasphalting of petroleum
resids with solvent regeneration under supercritical conditions. This processed has been named “ROSE.” According
to calculations of the developers, the cost of energy outlays is reduced by 20-40%, and consumption of water
vapor by 20 times, and electric power is conserved with this regeneration, but the fuel consumption is increased
by a factor of 1.5.
Since 1989, the GUP INKhP RB has been developing a procedure for regeneration of solvent from the
deasphaltizate solution under supercritical conditions using an injector system [4-9], which makes it possible to
lower overall consumptions of energy resources for the process by 35-40%. The proposed procedure is original,
and is distinguished from the procedure employed in the “ROSE” process known abroad by regime parameters of
phase separation in the separator (temperature, pressure, temperature gradient), the process-flow diagram, and
new equipment layout for the stage of solvent regeneration. This permits suitable use not only of the excess
thermal energy of the super-critical flow of solvent, but also its high mechanical energy.
Depending on the specific conditions for which various refineries have been built, we are proposing
several alternate schemes for reconstruction of the solvent-regeneration unit at installations for the propane and
propane-butane deasphalting of hydrones.

Conversion of High-Pressure Solvent-Regeneration Unit to Supercritical Operating Regime [4, 6].

In this basic alternate scheme, only the system for regeneration of high-pressure propane from the
deasphaltizate solution is subject to rebuilding. The low-pressure regeneration system for regeneration of propane
from the asphalt solution remains unchanged.
According to this procedure, the deasphaltizate solution, which can be tapped from the extraction tower
using a booster pump, is brought to the supercritical pressure, and then heated to the supercritical temperature in
heat exchangers, after which it is delivered to a separator. Under the supercritical conditions, the solubility of the
deasphaltizate is reduced to virtually zero; gravitational separation of the solvent and deasphaltizate will therefore
occur in the separator. The flow of solvent is tapped from the top of the separator. Its excess heat is used to heat
the deasphaltizate solution prior to its being fed into the separator, and the asphalt solution prior to its delivery
into the furnace. The flow of deasphaltizate, which is directed into stripping towers for separation of solvent
residues, is tapped from the bottom of the separator.
Thus, the solvent is regenerated under supercritical conditions without its phase transitions, owing to
which energy-intensive evaporation and condensation of the solvent are eliminated, and energy expenditures
reduced substantially as a result.
Regeneration of the propane from the asphalt solution is accomplished by the usual method of evaporation
and stripping.
A block diagram of the treatment and compression in the alternate rebuilding scheme under consideration
does not differ from the typical block diagram for regeneration of low-pressure propane. It includes a mixing
condenser for the condensation and separation of water vapor from the propane, a tower for caustic treatment of
the propane, a debutanizer, and a two-stage piston compressor.

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Use of Injector System for Compression of Flows of Gaseous Solvent

at Hydrone-Deasphalting Installations.
This alternate rebuilding scheme for the solvent-regeneration unit opens broad possibilities for
improvement of the deasphalting of petroleum resid [5, 7]. This complex rebuilding encompasses both the
high- and low-pressure solvent-regeneration system; it will result in a more substantial lowering of the demand for
energy resources, a reduction in the number of basic vessels, simplification of the process, and qualified solution
of the problem of lowering the corrosion rate of equipment by incorporating an additional unit for amine treating
of the circulating solvent as a component part of the installation.
Experimental investigations of injectors [8], during the course of which a number of characteristic geometric
relationships were determined for the circulating run of prototypes, and the feasibility of ensuring the required
ejection factors under a given pressure at the outlet from the vessels was confirmed, were conducted on pilot
installations by the GUP INKhP RB. A computer program has been developed for analysis of characteristics of
gas-jet compressors on which the familiar analytical method of E. Ya. Sokolov and N. M. Zinger is based, with
consideration of the operating characteristics of the jet device in the solvent-regeneration system of
hydrone-deasphalting installations [5].
Analyses show that the most optimal alternate scheme for application of the jet devices is a two-stage
scheme, whereby solvent gases of the low-pressure system are injected. In this version, a flow of moderate-
pressure solvent vapors from the evaporators of the deasphaltizate and asphalt solutions is used as the effective
body in the first stage of compression, and the flow of high-pressure solvent proceeding from the super-critical
separator in the second stage.
In this scheme, not only the thermal energy of the flow of solvent from the supercritical separator, which
operates in an evaporation-free regime, but also its potential energy of compression in the jet compressor used to
compress the low-head flow of solvent tapped from the stripping towers are successfully utilized. Moreover, three
solvent evaporators, a piston compressor with its accompanying equipment, and a mixing condenser are omitted
from the regeneration circuit as compared with the traditional circuit.
The first-stage jet compressor is a gas-gas ejector in which no phase transitions take place. For these jet
devices, procedures had been developed for analyzing basic geometric characteristics with respect to assigned
flow parameters; their construction does not therefore present difficulties.
The working fluid delivered in the second stage of compression has supercritical parameters. Phase
transitions take place as it passes through the intake channels and is mixed with the injected medium. As we know,
rigorous analyses of the characteristics of jet devices have yet to be performed when phase transitions are
present in the intake section of the ejectors. The geometric dimensions of the nozzle and mixing chamber,
as well as their configuration were therefore selected by experimental means on test bases operated by
the GUP INKhP RB and the FGUP NPP Motor.
Realization of the proposed methods will require fundamental reconstruction of the solvent-regeneration
unit on the existing type installations for propane deasphalting with inclusion of elevated-pressure vessels in the
system (4.5-5 MPa). A simplified version of the method mentioned above in which the gaseous low-pressure
solvent is also compressed by a jet compressor is therefore proposed. Either a portion of the flow of the liquid
solvent [10] delivered from the liquid-solvent tank to the extraction tower, or water [11] is used as the working
body of the jet compressor, however, in the simplified version of the ejector system for compression of this
solvent. In the latter case, an additional pump is introduced for circulation of the water through the jet pump, and
a tank for separation of liquid propane from the water. Here, the solvent is regenerated from the deasphaltizate
solution by the usual evaporation in three sequentially installed evaporators. To implement this proposal, therefore,

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rebuilding is required only of the unit for compression of the gaseous solvent with low capital expenditures.
Alternate schemes for implementation of the proposed method with use of various solvents are discussed
below.

Redistribution of Power Supply During Hydrone Deasphalting

A distinguishing characteristic of the deasphalting process is the consumption of a substantial amount of
water vapor for the evaporation of propane from the deasphaltizate solution. In a hydrone-deasphalting installation
operated by the NOVOIL Co., for example, the annual consumption of water vapor amounts to 261.9 TJ; this is
associated with the need to evaporate a large amount of solvent from the deasphaltizate solution.
Considering the high cost of water vapor, and the relatively low cost of process fuel, it is suitable under
the latest market conditions to change the structure of the demand for energy-carrying media, transferring the
accent from consumption of water vapor for use as fuel to establishments conducting the deasphalting of hydrone.
In this connection, it is proposed to replace the water vapor by a high-temperature organic heat-transfer
medium – aromatized AMT-300 lube oil [12], and for this purpose, incorporate into the circuit of the hydrone-
deasphalting installation a circulation system for the heat-transfer medium, which consists of a tank, tube furnace,
and pump. The possibility of heating the heat-transfer medium circulating within the system to 250-280°C will
ensure a substantial increase in the effectiveness of heat conduction along the heating coils of the extraction
tower and heating bundles of the evaporators of the deasphaltizate solution.
Technico-economic analyses of the effectiveness of this rebuilding of the propane-deasphalting installation
by the NOVOIL Co. indicate that expenditures for energy resources (fuel, electric power, water, and water vapor for
steam satellites and hot pumps) are reduced by more than three times as a result of the replacement of water vapor
by a circulating organic heat-transfer medium (as calculated per 1 m 3 of hydrone) [12].

Prevention of Equipment Corrosion at Hydrone-Deasphalting Installations

At many active deasphalting installations, major criticality is attached to problems associated with
equipment corrosion. This is dictated, on the one hand, by the stepped charging of crudes, and, on the other,
by AVT performed on the installations to increase the yield of light petroleum products, and measures that have
led to substantial charging of feedstock in the deasphalting installations. Where the conditional viscosity
of 80°C hydrone delivered into the deasphalting installation was regulated between 20 and 40 cP in the 1990s,
hydrones with a viscosity of 100 cP and more are currently being delivered to the deasphalting installation. At
deasphalting plants operated by the Ufaneftekhim and NOVOIL Cos., which refine mixtures of high-sulfur Bashkir
and Tatar crudes, for example, the conditional viscosity of the hydrones reaches 600-800 cP, and their sulfur
content 4%. This has led to a substantial increase in the rate of decomposition of the deasphalting asphalt when
heated in a furnace with the formation of hydrogen sulfide.
Traditional caustic treating of the solvent, with is prevalent in all type deasphalting installations, does
not provide for complete removal from the solvent of the amount of hydrogen sulfide that has been built-up
appreciably in the latter. Hydrogen sulfide gradually accumulates in the circulating solvent (its content may
reach 2-2.5%); this gives rise to an increase in the corrosion rate of the equipment. The procedure that we are
proposing for regeneration of solvent from the deasphaltizate solution using a two-stage injector system to
compress the low-pressure flow of gaseous solvent will make it possible to organize absorption removal of hydrogen
sulfide from the solvent [13].
Figure 1 shows the two-stage circuit for compression of the gas flows using jet compressors and a tower
for the amine removal of hydrogen sulfide from the solvent. Flow I of low-pressure gaseous solvent containing up

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Fig. 1. Diagram showing treating and compression of gas flows using jet compressors:
JC-1, JC-2) jet compressors of first and second compression stages, respectively;
T-1) absorption tower; AC-1) air cooler; I, II, III) low-, moderate-, and high-pressure
flows of solvent; IV) flow of solvent after second compression stage; V) fresh solution
of absorbent; VI) spent solution of absorbent.

to 0.5% of hydrogen sulfide is compressed by jet compressor JC-1 of the first stage, in which flow II of
moderate-pressure gaseous solvent containing up to 0.9% of hydrogen sulfide serves as the working body. Beyond
jet compressor JC-1, the total flow of solvent, which is under pressure of 0.55-0.6 MPa, is cooled by air
cooler AC-1 and directed into absorption tower T-1 for treating. Monoethanolamine or methyldiethanolamine can
be used as the absorbent in the tower. From the top of tower T-1, the treated gas is fed into the receiving chamber
of jet compressor JC-2 for second-stage compression, where flow III of high-pressure solvent is used as the
working body.
After jet compressor JC-2, the total flow of treated solvent, which is under a pressure of 1.7-1.9 MPa, is
coooled, conmdensed, and directed into the extractor for secondary utilization. T h e c o n t e n t o f h y d r o g e n
sulfide in the flow of solvent after JC-2 does not exceed the allowable level of 0.001%.

Industrial Mastering of Procedure for Regeneration of Solvent from Deasphaltizate Solution

under Supercritical Conditions
In 2006-2007, the Ufaneftekhim Co. Redesigned and rebuilt a type 36-1 hydrone-deasphalting installation
based on initial data acquired by the GUP INKhP RB. The following measures were taken by the client for the
rebuilding [9]:
• regular IMPA packings were used in the extraction tower;
• a propane-butane mixture was employed as the solvent;
• regeneration of solvent from the deasphaltizate solution under supercritical conditions was implemented;
• piston compressors for compression of the solvent were replaced by jet devices developed by
the FGUP NPP Motor for liquefaction of the solvent tapped from the low-pressure system;
• an additional unit was incorporated within the circuit of the installation for heating and circulation of the
organic AMT-300 heat transfer-medium in lieu of water vapor; and,

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• an additional unit was incorporated within the circuit for the amine removal of hydrogen sulfide from the
solvent.
Final start-up of the installation after completion of starting-adjustment measures occurred in
September 2007. The installation is operating at an elevated output – 41 m 3/h (the design output is 38 m 3 /h).
As a result of the installations’s rebuilding, the demand for water vapor has been reduced by a factor
of 5.7, and circulating water by a factor of 1.4, but the consumption electric power has increased by 1.9 times, and
fuel by 3.2 times. The saving of energy resources has amounted to 39.4%, or 28.7 million rubles per year.
Noting the advances made in recent years, therefore, it is possible to isolate the following basic trends in
the development of the deasphalting process:
• energy conservation and simplification of equipment layout;
• expansion of the assortment of products produced on the basis of the deasphaltizate and asphalt (owing
to replacement of the solvent);
• production of high-quality asphalt products without use of an oxidation process; and,
• waste-free refinement of hydrones, i.e., deepening of crude refinement.

REFERENCES
1. S. S. Mingaraev, I. R. Khairudinov, F. M. Sultanov et al., Bash. Khim. Zh., 3, No. 3, 33-35 (1996).
2. I. R. Khairudinov, N. R. Saifullin, R. G. Nigmatullin et al., Khim. Tekhnol. Topl. Masel, No. 3, 14-15 (1999).
3. F. M. Sultanov and I. R. Khairudinov, Materials Presented at the Scientific-Practical Conference
“Petroleum Refining and Petroleum Chemistry” [in Russian], GUP INKhP RB, Ufa (2002), pp. 75-82.
4. I. R. Khairudinov, S. S. Mingaraev, F. M. Sultanov et al., Neftepererab. Neftekhim., No. 10, 14-17 (1994).
5. F. M. Sultanov, I. R. Khairudinov, and E. V. Kushneruk, Materials Presented in Section D III at the Congress
of Petroleum and Gas Producers of Russia “Petroleum Refining and Petroleum Chemistry. Problems and
Prospects,” 23 May 2001 [in Russian], GUP IPNKhP AN RB, Ufa (2001), pp. 313-319.
6. Russian Federation Patent No. 2136720.
7. Russian Federation Patent No. 2232792.
8. V. Yu. Kuznetsov, F. M. Sultanov, I. R. Khairudinov et al., International Scientific-Practical Conference
“Petroleum Refining and Petroleum Chemistry– 2005” [in Russian], GUP INKhP RB, Ufa (2005),
pp. 64-67.
9. F. M. Sultanov, I. R. Khairudinov, É. G. Telyashev et al., Neftepererab. Neftekhim., No. 6, 25-28 (2008).
10. Russian Federation Patent No. 2176659.
11. Russian Federation Patent No. 2167344.
12. V. A. Gantsev, R. G. Nigmatullin, F. M. Sultanov et al., Materials Presented at the Second
Scientific-Practical Republican Conference “Energy-Resource Conservation in the Republic of
Bashkortostan [in Russian], Part 2, UGATU, Ufa (1999), pp. 51-55.
13. Russian Federation Patent No. 2279465.

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