Chemistry and Technology of Fuels and Oils, Ibl. 35. No.

1, 1999

TECHNOLOGY

VISBREAK[NG VACUUM RESIDS

V. E. Somov, D. A. Rozentai', A. M. Syroezhko,

D. V. Neronov, and A. V. Passet UDC 665.642

Visbreaking heavy resids is one of the processes that are used to cut deeper into the barrel of crude [ 1 - 3]. Four
basic process variations have been developed for visbreaking heavy vacuum resids from high-sulfur crudes [4]. Three of
these are aimed at obtaining boiler fuel or boiler fuel components, the other at increasing the yield of distillates and the
carbon residue of the cracked tar. When visbreaking is aimed at increasing the distillate yield, the process is performed at
a temperature of 455- 480~ and a pressure of approximately 2 MPa.
Two versions of the visbreaking process have been developed, in which an intermediate coking chamber is used to
calcine the thermolyzed products, with either a one-furnace or a two-furnace flow plan. Process conditions are selected
depending on the feedstock quality. With increasing severity of cracking the vacuum resid, the viscosity of the cracked tar
passes through an extremum [5]. Changes in the ratio of breakdown and recombination process rates, and hence changes
in the coke yield in visbreaking, can be accomplished not only by adjusting the temperature, pressure, and contact time,
but also by the use of turbulizers and anticoking additives [6].
In Russia and other countries [7, 8], various types of donor-solvent visbreaking have been carried out; here we
refer to processes developed by the Ufa Petroleum Institute, the Lurgi company, and process HDDV. Of the processes
developed in other countries for vacuum resid thermal cracking, the most attractive are those of Eureka and HSC, which
are steam cracking processes [4, 8].
Distinctive features of the Surgut crude processed at Kinef Ltd. are its high content of paraffins in the free state and
the presence of hybrid molecules with long-chain alkyl substituents on polycyclic naphthenoaromatic structures of the
resins and asphaltenes. These features of the crude suggest that the visbreaking process may be performed under milder
conditions than those required for resids from other crudes.
The quality of the vacuum resid (Table 1) used as feed to the Kinef asphalt unit depends on the type of crude
processed in the refinery. In June 1996, for example, vacuum resid taken from the AVT-2 atmospheric-vacuum distillation

TABLE 1
Feed E l e m e n t a l c o m position~ wt. % G r o u p c o m p o s i t i o n , wt. %

p r oand
duc t C I I H N I S I O PN
Vacuum resid
t AI'AI
......H H TR i ATR, I H

I 85.2 11.6 0.62 2.02 0.50 13.8 22.0 19.7 10.0 30.0 4.5
6 0
II 85.1 11.6 0.46 2.32 0.37 18.8 13.2 10.9 19.2 30.4 7.5
7 8
Residue from visbreaking vacuum resid
86.8 10.5 0.82 1.59 0.17 2.3 36.5 15.5 10.2 28.0 7.5
9 3
II - - - 12.2 29.7 15.2 8.6 28.7 5.6
Notes: PN = paraffins + naphthenes; MAH = monocyclic aromatic hydrocarbons; BAH = bicyclic aromatic
hydrocarbons; TR = toluene-soluble resins: ATR = alcohol/toluene-soluble resins; ASPH = asphaltenes:

KinefLtd. St. Petersburg Technological Institute. Translated fromKhim(va i Tekhnologiya Topliv i Masel, No.
1, pp. 9 - 10, January - February, 1999.

0009-3092/99/3501-0001 $22.00 9 1999 Kluwer Academic/Plenum Publishers 1

 TABLE 2
Yields, wt. % Temperature, ~
Visbreaking
Vacuum end point of softening
temperature, gas vacuum
resid residue vacuum point of
~ gas gasoil
gasoil cracked tar
In distff__! _ationof product from AVT-2 in ARN-2 unit
- 16.0 84.0 445 34.0
In vacuum ~flstillation o f product from visbreaidng
I 415 - 4 2 0 2.2 28.6 69.15 450 33.0
I 400 - 4 0 5 0.85 19.6 79.5 450 32.5
II 400-405 0.9 25.8 73.7 445 33.5

TABLE 3
Content in gas from visbreaking vacuum resid II, %
Hydrocarbon I

at 4 0 0 0 C [ at 420oc
B

cI-h 35.8 34.0

C2H6 0.7 1.0
C2H4 3.0 3.6
C3H8 2.8 5.8
C3H6 26.5 15.5
C4HIo 18.2 23.3
, C4H8 13.0 16.8
Notes. 1) Feed residence time in working temperature zone 9 min.
2) Gas yields 0.9 % at 400~ 1.9 % a t 420~

unit had a softening point of 34~ and a penetration greater than 400 (Batch I); in November 1996, therespective values
were 36~ and 380 (Batch II). The two vacuum resids were practically identical in elemental composition but differed
substantially in group composition and hence in structure. This difference is bound to have some sort of effect on the rate
of thermal cracking and the depth of feed conversion; BAH = bicyclic aromatic hydrocarbons; TR = toluene-soluble
resins; ATR = alcohol/toluene-soluble resins; ASPH = asphaltenes.
The work reported here was aimed at determining the influence of the process temperature on the yields and
properties of the products obtained in the visbreaking operation. The experiments were performed in a flow-type laboratory
unit with a feed residence time of either 9 or 15 min in the working-temperature zone. The process temperature was varied
from 480 ~ to 400~
We also performed control experiments with a longer residence time. At the highest temperature (480~ the
reactor became completely coked in 30 min of operation. When the process temperature was lowered to 4 4 0 - 460~ the
coke formation was reduced to 1%, but the heavy residue from vacuum distillation of the visbreaking liquid products
proved to be unstable with respect to sediment formation and hence unsuitable for use as a commercial product.
A further lowering of the temperature to 4 1 5 - 420~ reduced the coke formation to 0.04%, and the product
obtained by vacuum distillation of the total product of visbreaking (residue above 440~ proved to be stable. Paving-
grade petroleum asphalts containing this residue have good adhesion to mineral aggregate but are lower in ductility than
asphalts obtained by oxidation of straight-run vacuum resids.
Finally, at 400~ we obtained a heavy product of visbreaking that gave a 73.7% yield of residue from vacuum
distillation (when using Batch II vacuum resid) and 79.5% (when using Batch I vacuum resid); these are little different
from the yield of residue obtained directly from the Batch I straight-run vacuum resid after taking off distillates up to
450~ by distillation in an ARN-2 unit (Table 2).
Even though the vacuum resid II contains smaller amounts ofoil components, the distillate yields were higher, thus
indicating that this stock is easier to crack. Data on the product yields at the indicated temperatures, with an optimal
contact time (9 min), are presented in Table 2.
When the visbreaking temperature for vacuum resid I is increased by 10 - 15~ the yield of vacuum gasoil with an
end point of 4 4 5 - 450~ increases by 9%, with a corresponding decrease in the yield of residue. Thus, in visbreaking
 TABLE 4
Content (%) in residue from visbreaking vacuum
Component I [ II
PN 2.3 12.2
MAIl 36.5 29.7
BAIl 15.5 15.2
TR 10.2 8.6
ATR 28.0 28.7
ASPH 7.5 5.6

vacuum resid under mild conditions (atmospheric pressure, temperature 400 - 420~ contact time 9 min), the yield of
vacuum gasoil is 3.6 - 12.6% greater than can be obtained by direct distillation of the original vacuum resid (see Table 2).
In Table 3 we compare the visbreaking gas compositions obtained at 400 ~ and 420~ The ratio of C,_- C4unsaturates
and Ct- C 4 saturates was found to be 0.73 at 400~ and 0.62 at 4200C. Thus we see that methane and butane predominate
among the gaseous products, and propylene and butenes among the unsaturated products.
In the distillation of the total liquid product from visbreaking vacuum resid I at 400- 405 ~ for 9 min, we recovered
1.2% gasoline fraction (87.5 - 205~ with the following physicochemical characteristics: density 821.1 kg/n~ at 20~
iodine number 66 g 12/100 g; sulfur content 0.96%; octane number 72.
We also obtained light gasoil (205 - 350~ and heavy gasoil (350- 450~ with respective yields of 4.9% and
13.5%, with the following physicochemical characteristics: density 855.2 and 918.5 kg/n~ at 20~ iodine number 52 and
34.7 g I_,/100 g; sulfur content 1.62% and 1.92%. Thus we see that with increasing boiling point of the gasoil, the density
and sulfur content increase, while the iodine number decreases.
From a comparison of the group compositions of the feed and the heavy residue from visbreaking (Tables 1 and 4),
it follows that with either type of feed, the visbreaking residue has lower contents of PN and ATR and higher contents of
MAH in comparison with the original vacuum resid; we could not find any general relationships for the other components.
We are currently investigating the possibility of using the total products from low-temperature visbreaking (at 4 0 0 -
405~ without removing the distillates, as a medium-sulfur boiler fuel.

REFERENCES

. M. Akbar and Kh. Gelen, Visbreaking with Coking Chambers Included in the Flow Plan [in Russian], Nedra,
Moscow (1980), pp. 95 - 100.
2. M. A. Tanatarov and A. V. Akhmetov, Production of Unleaded Gasoline [in Russian], TsNIITEneftekhim, Moscow
(1981).
3. D. F. Varfolomeev, Coker Feed and the Efficiency of Its Utilization [in Russian], TsNIITEneftekhim, Moscow
(1987), pp. 124 - 126.
4. I. R. Khairudinov, A. F. Ishkil'din, and M. M. Maksimenko, Thermal Cracking and New Reserves for Increasing
the Depth of Crude Oil Processing [in Russian], UGNTU, Ufa (1995).
5. N. D. Voloshin, Thermal Cracking of Petroleum Resids and Distillates [in Russian], UGNTU, Ufa (1995).
6. M. E. Levinter and S. A. Akhmetov, Exhaustive Processing of Crude Oil [in Russian], Khimiya, Moscow (1992),
pp. 75 - 82.
7. B. Schuetze and H. Hofmann, Neft'GazNeftekhim. Rubezh., Khimiya, Moscow, pp. 104 - 119 (1984).
8. I. P. Fisher, Oil GasJ., 80, No. 11, 111 - 116 (1982).