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NEW M E T H O D OF D E A S P H A L T I N G PETROLEUM RESIDUE

T. P. Z h u z e UDC 668.54

The present paI)er describes a method for deasphalting petroleum residue, based on selective properties of
compressed hydrocarbon gases.

It has long been known that, beginning at a certain pressure, many gases can readily dissolve liquid and solid
substances with formation of solutions which are also gaseous [1-6]. The solvent properties of compressed gases d i f -
fer markedly in several respects from those of liquid solvents. It is known, for example, that the c a p a c i t y of a l i -
quid to dissolve a given substance at constant temperature is a constant value. But at supereritical temperatures the
dissolving capacity of a gas at constant temperature m a y change arbitrarily, for example it m a y increase, thereby
increasing the compression of the gas, or decrease, so decreasing its pressure. The selective properties of a gas
change with the degree of compression. To recover a liquid solvent from a solution, heat must be expended on rais-
ing the solution's temperature to the boiling point or evaporation temperature of the solvent. To recover a gas from
a gaseous solution, it is sufficient to reduce the pressure in the system at constant temperature to a value at which
the gas can no longer dissolve the given substance. The solute of the gaseous solution is thereby deposited and the
gas recovered. This operation requires little time and a small quantity of heat to m a i n t a i n the gaseous solution at
constant temperature.

The authors of [7-11] studied the solubility of mazuts, tars and cracking residues in different hydrocarbon
gases at temperatures 5-10 ~ C above their critical temperatures, at pressures in the range 40-500 aim. The solu-
bility was determined as follows. The product was placed in a thermostated vessel and gas introduced until the re-
quired pressure was reached. The system was mixed and a sample of the gaseous phase taken after equilibrium b e -
tween the liquid and gaseous phases had been reached. The sample was passed through a throttle valve to a trap (at
atmospheric pressure) connected to a gas meter. The content of the substance in 1 m a of gas, reduced to N.T.P.,
was calculated from the weight of the product deposited in the trap and from the volume of gas passing through the
meter. This content is then called the solubility. A sample of the liquid phase (residue) was taken from the vessel
after all the gaseous phase had been driven out. After removal of dissolved gas, the product in the trap and the
sample of the liquid phase were subjected to physicochemical analysis.

Table 1 gives the characteristics of the products, and Figs. 1-5 their solubility isotherms in different gases,
together with the densities and molecular weights of the dissolved gases. T a b l e 2 gives data on the solubilities of
Romashki tar in n-butane and n-butyIene.

t,2

tO

0,8

.'~ 0,4

=~ 0,2
0
6~

50 tCC, I~ ' 250 ~90 350 z,O0 450 500

Pressure, aim

Fig. 1. Solubility isotherms of T u i m a z i m a z u t

in different gases at 105 ~ C: 1) Propane; 2)
propylene; 3) ethylene.

IG and RGI. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 9, pp.25-31, September, 1966.

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TABLE 1. Characteristics of the Petroleum Residue

Product

Cracking residue
Mazut of T u i m a z i Tar of Romashki
Index from the Moscow
petroleum petroleum
refinery

Density p~o . . . . . . . 0.961 0.999 1.045

Content, %:
asphaltenes . . . . . . 5.2 16.8
sulfur . . . . . . . . . 2.42 3.22 2.79
Cokability, ~ . . . . . 10.8 17.0 26.2
Viscosity at 100 ~C, cs 54.5 123
Fractional c o m p o s i -
tion:
ibp, ~ C ........ 540 310
amount boiling, wt.
%:
below 500 ~ C ..... 31.2 39.7
" 550 ~ C ..... 46.4 50.5
" 625 ~ C ..... 63.3 38.1 64.0

500

~,5g

,..,,.i

~ ,+o6 O
0
N

856 , . ~

50 sO0 250 300 350 o00 450 500

Pressure, atm

Fig. 2. Molecular weights of m a z u t fractions dissolved in d i f -

erent gases at 105 ~ C: 1) Propane; 2) propylene; 3) ethylene.

r
c~ a,35
o,93

o,91 S
i I i~ r I I
0,3> 5O lO0 150 300 350 400 450 500
Pressure, aim

Fig. 3. Densities of m a z u t fractions dissolved in different

gases: i) Propane; 2) propylene; 3) ethylene.

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TABLE 2. Solubilities of Romashki Tar at 160 ~ C in n-Butane and n-But zlene

Characteristics of the dissolved

Gaseous Expt, pres- Solubility, Density of S content in
fractions
solvent sure, atm kg/m 3 residue residue, %
density S content,
mol. wt.
d~ 9
45 insoluble
52 0.200 0.925 540 1.78 p

naButane 55 0.340 0.933 563 I. 89 1.001 3.20

60 0.650 O.948 574 2.18 1.020 3.35
70 1.630

45 0.030 485 m

50 0.600 0.950 638 2.07

n-Butylene 53 0.850 0.954 9 3.59
55 0.900 n
1.025
60 1.360 0.975 700 2.40 1.070

r
~0

48 ~
/s
2

a
DO

>, 44
4~
.,--I

0
Go
0~8

0,6

0,2

0 5fl 100
P
150
II i
250 300
i J
350
. i
400
i
450
/
500
0 Pressure, a i m
50 t00 f50 300 d50 400 450 500
Pressure, atm Fig. 5. Solubility isotherms of cracking residue in differ-
ent gases: 1) Propylene; 2) propane-propylene; 3) pro-
Fig. 4. Solubility isotherms of T u i m a z i tar in differ- pane; 4) ethylene.
ent gases at 105 ~ C: 1) Propane-propylene; 2) pro-
pylene; 3) propane; 4) ethylene. It was found that at the same temperatures and
pressures the capacities of the gases to dissolve the same
product increase in the following order: m e t h a n e - * e t h a n e - , e t h y l e n e ~ p r o p a n e - * p r o p y l e n e - * n - b u t a n e - - , n - b u t y l e n e .

It will be seen that at constant temperature the dissolving c a p a c i t y of a gas is not constant and increases reg-
ularly with pressure. With increasing solubility there is a p a r a l l e l increase in the densities and molecular weights
of the dissolved fractions and their sulfur contents, owing to the increase in gas density with increasing pressure.
This is the distinguishing feature of compressed gases as solvents, enabling us to control their dissolving and s e l e c -
tive capacities at constant temperature by changing the degree of compression.

Comparison of the solubilities of different residues in the same gas shows that mazut dissolves in all the gases
more readily than tar, cracking residue occupying an i n t e r m e d i a t e position throughout virtually the whole pressure
range. The differences in their solubilities are due to the different fractional and group hydrocarbon compositions
of these products. Mazut contains more than 30% of fractions boiling below 500 ~ C, while the ibp of tar is > 500~
The hydrocarbon composition of cracking residue is markedly different to that of m a z u t or tar.

Chromatographic analysis of the dissolved products showed that in comparison with the i n i t i a l products they
had higher contents of methano-naphthenic hydrocarbons and lower contents of p o l y c y c l i c aromatics, sulfur c o m -
pounds, and tars. Asphaltenes were either absent or present as traces. It was therefore established that compressed
gases have selective properties which may be used for separating heavy petroleum residue into hydrocarbon and
asphalt-tar fractions. The most suitable gaseous solvents for use in industrial plants are propane, propylene, and
mixtures of these. The critical temperatures of these gases are low (96.8 and 91.7~ respectively), and they r e a d -
ily dissolve petroleum residue, even at 100-120 aim. The critical temperatures of butanes and butylenes are much
higher (152-147 ~C). These gases dissolve hydrocarbon crude very readily, so their selective properties are not very
marked.

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 TABLE 3. Deasphaltization of Tars by the P r o p a n e - P r o p y l e n e Fraction at i00-ii0 = C

Expt. conditions Characteristics of products from vessels 1, 2, and 3

Cokability Products from
composition of pressure in m e l t i n g point,
Density gas/crude vessels 1, 2,
Crude of crude, propane-propy- vessels 1, cokability,
of crude ratio (by viscosity at, ~ C (according
% and 3, % density %
lene fraction, 2, and 3, 100~ C, cs to KiSh)
wt.) in terms of
vol. % atm
crude*
Tar from mixture of 1.008 20.1 EC 2- i0.7 I01 62.0 1. 048
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28.0 12.535
Tatar petroleums C3H6 -- 5.5 3:1 94 2.1
C3H 8- 80.8 27 32.0 0.919 1.08 15.7
z c 4 - 3.0
Tar from Romashki 0.999 17.0 EC2--3.4 105 68.0 1.037 24.8 5558 56.8
petroleum C3H ~ -- 26. i 1.9:1 105 0.5
C3H8--68.0 39 28.5 0.919 1.56 19.2
z%-2.5
Tar from mixture of 0.997 15.9 EC 2 - 5 . 5 105 45.0 1.061 69.3
T u i m a z i and Bavli C3H~--0.8 2.3:1 68 17.0 0.966 125.1
petroleums C3Hs-85.4 37 36.6 0.924 1.8 25.06
~c4-8.3
Ditto Ditto 2.6:1 105 59.2
72 ii.0 0.9606 82.2
35 28.6 0.9200 i. 04 20.8
Concentrate from O. 940 8.1 EC2--7.4 103 37.6 N
0.999
mixture of Turk- C3H6--2.8 5.5:1 102 2.2 0.914 m D

men petroleums C3H 8 - 86.9 20 60.2 0.908 1.57

C4-2.8
Concentrate from 0.939 7.4 2 Ditto 5.3:1 105 26.0 1.018 75
Zhirnovskii p e - 103 3.5 0.915
troleum 20 70.0 0.914 2.24
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* Losses by difference from 100 %o

ba
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TABLE 4, Deasphaltization of Mazut by the Propane-Propylene Fraction at IO0-110~

Den- Coka- Products I Characteristics of products from

Expt. conditions from I
Islty vessels 1,1 vessels 1, 2, and 3
~ 3fbility
Crude comp, of gas/ pressure 2, and 3,/,@n- coka- silica~
o42~ crude, propane- crude in vessels % ia l atY bility, asphai- get | costtv
vls7
% Dropylene raUo 1, 2, and terms of I O~~ % tenes tars, | at lifo ~
trac. vol.% (by wt.) 3, atm crude* ] 9 / C, cs

Tuimazi mazut 0,960 10,8 E C~--7,6 I00 31,6 1,067 m

C3H0--23, i 8,1:1 I00 0,5 m

C3Hs--59, 1 37 66,2 O,920' 1,5 Traces 9,4 12,74

E C~--6,4
Romashki mazut 0,988 14,7 E C2--I0,7 122 30,0 1,074 28,8 45,4 m

CAH6--28,0 2,9:1 70 28,2 3,950 2,70 37,4

C3H6--58,2 32 36,1 3,922 1,55 Traces 15,5
E C4--3, 1
Ditto 0,988 14,7 E C2--4,4 I00 28,8 1,070 8,3 m m

C3H6--8,9 6,3:1 75 18,9 3,945 3,6 m

15,3 37,00
C3Hs--83,6 25 50,5 3,910 0,5 Traces 5,6 9,83

* Losses by difference from 100%.

TABLE 5. Deasphaltization of Cracking Residue from the Moscow Refinery by the Propane-Propylene Fraction at
105-110 ~ C (cracking residue: density 042~1.054; cokability 26.1%; asphaltenes 19.7%; silica-gel tars 139)

Expt. tditions Removal of Characteristics of products from vessels I , 2, a n d 3

Experi- C o m p o s i t i o n of ~products from
ments the propane-pro- g~ :rude Pressure in vessels 1,2 density silica-gel a sphaltene s,
v e s s e l s 1,2, l a n d 3,% in: ..20 cokability,
pylene fraction, ratio y wt.)
a n d 3, a t m t e r m s of crude P4 % tars, % %
I vol. %

2C2-- 10,6 100 40,0 46,2

C3H6 - 28,0 100 1,1
CAH8_58,2 9,7'I 44 57,0 0,958 1,8 7,4 Traces
XC4--3,2
Ditto 9,0 : 1 100 41,8 1,16
100 0,5
25 54,3 0,961 2,7 7,5 Traces
VCe--4,4 125 42,0 1,16 49,8 15,6 55,5
C.~H6--8,9 125 1,0
C3Hs--83,6 1,8" 1 28 55,6 0,959 3,2 9,1 Traces
EC4--3,1
Ditto 1,9 : 1 125 40,4 l, 164 55,3 m

79 25,2 0,986 6,8 0,4

37 31,1 0,936 0,6 Traces

* Losses by difference from 100%.

As a result of this research, the authors of [12] proposed the following method for deasphalting petroleum resi-
due by compressed gases. Propane or a propane-propylene mixture is mixed with the crude at 105-110 ~ C and 100-
120 atm and passed to the first vessel, in which the temperature and pressure are the same as the mixture. The hy-
drocarbon fraction of the crude dissolves in the gas, forming a gaseous solution of the deasphalted product. The
asphalt-tar components of the crude, which do not dissolve under these conditions, form the residue. When the gas-
eous solution is fed to the next vessel, where the pressure is reduced to 40 atm, the deasphalted product is deposited,
because at 40 atm the gas is no longer a solvent. This deposition is accompanied by recovery of the gas, which is
then passed to the compressor, compressed to 100-120 atm and then recycled to dissolve fresh protions of crude. If
intermediate vessels in which the pressures are 100-120 and 40 atm are interposed between the first and second ves-
sels, the deasphalted products deposited in these vessels will have distinctive compositions and properties.
On this basis the IG and RGI institutes constructed an enlarged laboratory apparatus of the continuous-flow
type, consisting of a crude pump, a backing-up compressor with capacity 25-80 mS/h, a mixer, and three series-
connected 5-liter vessels. The gas lines between the vessels had throttle valves enabling different pressures to be
maintained in the vessels. Liquid-product receivers were connected to the vessels. The prescribed temperature in
the vessels was maintained by external electric furnaces.

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TABLE 6. Group Hydrocarbon Compositions of Deasphaltizates Separated from Petroleum Residue by means of the
Propane-Propylene Fraction (wt. %)

Paraffin- Aromatic coinpounds

naphthe- ~-1.51 Interme-
1.51-1.53
Initial crude Deasphaltizate nic h y - diate Tars
drocar- fraction
boris

40% Romashki First deasphaltizate, obtained

mazut at 75 atm 29.2 18.3 43.0 1.1 7.6
(p~o 0.988, coke Second deasphaltizate, o b -
70 14.7) tained at 25 atm 5O.9 16.3 27.7 1.9 2.6
Tar from mixture Initial tar 12.8 18.4 13.3 11.7 8.5
of Tatar p e t r o l - D e a s p h a l t i z a t e - 4 8 % in
eums (p~O 1.003, terms of tar 34.5 21.6 37.6 2.1 4.2
coke, fro20.1)

Cracking residue Initial cracking residue 18.3 7.6 10.8 15.5" 19.4 I"
(d ~ 1.oo4) D e a s p h a l t i z a t e - 58 % in
terms of cracking residue 34.4 8.7 16.3 12.2" 0.6J"

D e a s p h a l t i z a t e - 31. i % in
terms of cracking residue 46.2 9.7 17.3 4.1 * tracesJ"
* I n t e r m e d i a t e fraction together with tars,
1" Asphaltenes.

TABLE 7. Conditions and Results of Experiments on Extract Solubility in

Compressed Propane at 150 ~ C

Expt. pressure, aim

11 115 150 I 200 300

Propane/extract ratio (by wt.) 3.1 2.25:1 2.25:11 2.25:] 2.25:1

Solubility;
kg/m a ................ 0. i 0.160 0.262 0.500 0.862
~ in terms of extract
charge . . . . . . . . . . . . . . . . 17.4 17.3 28.2 3.8 92.8
Characteristics of the dissolved
fractions
Density p~O.............. 0.9 0.9670 0.9770 0.9901 1.0088
Refractive index n ~ . . . . . . . . 1.5 1.5450 0.5516 1.5620 F 1.5767
Viscosity, cs:
at 50 ~ C . . . . . . . . . . . . . . lC
"i00 ~ C .............. ~3.6 45.69 76.31 M

"150 ~ C .............. - 19.06 54.38

Content of s i l i c a - g e l resins, % . 14.1 18.7 28.8
Group hydrocarbon c o m p o s i -
tion, * ~
paraffin-naphthenic . . . . . . 54.5 50.4
aromatic . . . . . . . . . . . . . 45.5 ~9.6
* Data of chromatographic analysis after r e m o v a l of s i l i c a - g e l resins.

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Crude and gas were fed continuously in the required ratio to the gas-filled system, heated to 100-110 ~ C. A
pressure equal to that for the solution of crude in the gas (100-120 atm) was established in the mixer and the first
vessel, while in the third vessel the pressure established was the maximum value at which the gas has no dissolving
capacity (40 atm); the pressure in the second vessel was varied in accordance with the purposes of the experiment.
The residue was removed from the receiver of the first vessel, and the first and second deasphaltizates removed from
the second and third vessels respectively.

In this apparatus we performed the major part of the research on deasphaltization of petroleum residue by
compressed gases, and determined the technological indices of the process, forming the basis for the planning of a
pilot plant at the Grozny Petroleum and Oil Refinery. Tables 3-6 give the conditions and results of deasphaItization
of mazut, tar, and cracking residue in the enlarged laboratory apparatus. In the deasphaltization of tars we obtained
28.5-53.6 % deasphaltizate, depending on the initial characteristics and experimental conditions, this product being
suitable for further processing to oils; the residue (45-68%) was suitable for the manufacture of bitumen or coke for
electrometailurgical plants.

Deasphaltization of cracking residue gave 54-57 % of a broad deasphalted fraction, and 42-45 ~ residue. The
deasphaltizates could be used wholly or partially as catalytic cracking or hydrocracking crude or as gas turbine fueL
Judging from the density and cokability, the residues are excellent coking crudes, particularly for coking in ceramic
ovens. As regards the use of the deasphaltizates, further studies must be made owing to lack of information on their
hydrocarbon compositions and metal (V, Ni, Cu, Fe) contents.

In the deasphakization of mazuts the overall yield of a broad deasphalted fraction was 64.3-69.4%, that of
the residues 28.8-31.6 %. Mazut deasphaltizates can be further processed to obtain oils (distillate and residual oils)
or used for the same purposes as cracking-residue deasphaltizates. Mazut deasphaltization residues are satisfactory
crudes for coking by the methods employed in the refining industry.

If deasphaltization by compressed gases is performed at successively decreasing pressures in the separating

stages, many deasphaltizates with different properties can be obtained, instead of merely one product. Furthermore,
by increasing or decreasing the mixing pressure of the crude and gas deasphaltization of the initial crude can be in-
tensified or reduced, thereby controlling the yield and quality (density, cokability, melting point, etc.) of the deas-
phaltization residue.
With decreasing pressure the deasphaltizatesobtained from a gaseous solution gradually acquire lighter frac-
tional compositions but sharp boiling ranges are not observed. All the deasphaltizates boil within wide ranges.
However, these fractions have markedly different group hydrocarbon compositions, as will be seen, for example,
from Table 6. Deasphaltizates obtained at lower pressures (seconddeasphaltizates) have higher contents of paraffin-
naphthenic hydrocarbons and lower contents of bicyclic and polycyclic aromatic compounds than the initial crude
or the deasphaltizatesobtained at higher pressures. The differences between the group hydrocarbons and fractional
compositions of the deasphaltizates are due to the fact that deasphaltizates obtained from the same crude but at dif-
ferent pressures differ markedly as regards such important indices as density, viscosity, etc.

As a further iliustration of the method's potentialities, Table 7 gives the results of experiments* on c o m -
pressed-propane extraction of highly viscous components of oil from the extract (density 1.023) obtained in the
manufacture of residual oil at the Grozny Petroleum and Oil Refinery. It will be seen that at 150 ~ C and 115-117 aim
12~ of highly viscous o i l w i ~ a high content of aromatic compounds (45-50%) can be obtained from the extract.
This oil could be a useful source for making highly viscous special oils and lubricants such as transmission oil, cyl-
inder oil, "Vapor oil" (for steam-engine cylinders), etc.

LITERATURE CITED
1. P. Villard, J. Phys., _5 (1896) p. 453.
2. M. S. Robin, J. de phys., t. 14, No. 5 (1953), p. 330.
3. D. Yu. Gamburg, Neft. Khoz.,No. 9 (1947).
4. I. P. Krichevskii, Phase Equilibria in Solutions at High Pressures, Gostoptekhizdat (1952).
5. V. A. Kirillin and A. E. Sheindlin, Thermodynamics of Solutions, Gosenrgoizdat (1956).
6. D. B. Todd and J. C. Elgin, A. I. Ch.E., 1 (1955), p. 20.
7. T. P. Zhuze, Achievements of Science, 2, AN SSSR (1958), p. 450.
8. T . P . Zhuze, Vesmik AN SSSR, No. 11(1959).

'* The experiments were performed in the stationary apparatus of IG and RGL

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9. T . P . Zhuze and G. N. Yushkevich, TrudyInstituta Nefti AN SSSR, No. 1 (1954),

10. T . P . Zhuze and G. N. Yushkevich, Izv. AN SSSR, OTN, No. 11, 12 (1957).
11. T . P . Zhuze and G. N. Yushkevich, Trudy Instftuta NeftiAN SSSR, 13(1959).
12. T . P . Zhuze and M. A. Kapelyushnikov, A u t h o r s ' c e r t i f f c a t e N o . 113, 325, Byull. izobr, No. 6 (1958).

All abbreviations of periodicals in the above bibliography are letter-by-letter translitera-

tions of the abbreviations as given in the original Russian journal. S o m e or al l o f t h i s p e r i -
o d i c a l l i t e r a t u r e m a y w e l l be a v a i l a b l e in E n g l i s h t r a n s l a t i o n . A complete list of the cover-to-
cover English translations appears at the back of the first issue of this year.

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