Chemistry and Technology of Fuels and Oils, Vol. 41, No.

5, 2005

CURRENT PROBLEMS. Refining Residues: Visbreaking

VISBREAKING: THEORY AND PRACTICE

R. G. Gareev UDC 665.642.2:665.637.568

The causes and consequences of development of thermal decomposition of petroleum residues are
examined. The results of theoretical, laboratory, and industrial tests of different process schemes are
investigated. As a function of the problem solved, thermal cracking and visbreaking prevailed in different
stages. The results of using these processes are reported.

There is currently a tendency for hydrocarbon feedstock to have a higher end point due to predominance
of a high-boiling part, 500°C and higher [1, 2].
Improvement and implementation of vacuum distillation of atmospheric resid (equipping vacuum towers
with high-efficiency and high-output packing, liquid injector vacuum systems [3]) allows refining high-end-point
(with density of up to 1100 kg/m 3 ) vacuum resids [4]. Thermal degradation processes that result in a mixture of
hydrocarbons of lower molecular weight and viscosity are most suitable for further refining of such residues.
There are two directions in refining of heavy residues:
• exhaustive thermal decomposition with the maximum yield of gases and distillate and minimum yield of
cracking residue; in the limiting case, delayed coking of vacuum resid, which makes refining of crude oil maximally
exhaustive, is such a process;
• nonexhaustive decomposition to decrease the viscosity to the level of the requirements for boiler fuel to
eliminate an additional operation – addition of diluents; this process only partially makes crude refining exhaustive.
The basic drawback of destructive processes in refining of petroleum residues consists of the difficulty of
regulating the rate of decomposition of the heavy components of the feedstock in industrial conditions. Limiting
the degree of feedstock conversion to prevent overshooting the temperature threshold decreases the yield of
products of decomposition, including naphtha cuts.
Decomposition reactions take place with absorption of thermal energy, which is basically delivered to the
reaction zone by heating the reaction mixture in the furnace coils. When a certain temperature threshold is
attained (as a function of the composition and residence time of the feedstock mixture in the reaction zone under
a certain pressure), the reaction mixture begins to decompose into coke spontaneously and intensively, which is
only acceptable for the delayed coking process.

____________________________________________________________________________________________________
Vostokneftezavodmontazh Planning Institute LLC. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 5, pp. 3 – 7, September – October, 2005.

0009-3092/05/4105–0329 © 2005 Springer Science+Business Media, Inc. 329

 V. G. Shukhov was the first to attempt to regulate the course of the decomposition reactions in developing
equipment for cracking under pressure. He proposed conducting artificial recirculation to avoid coking for
improving heat transfer mechanisms in increasing delivery of heat to the reaction zone. This proposal was
implemented in the mid-1920s [5].
M. F. Nagiev continued research on use of recirculation to make the decomposition conditions more
severe [6]. Considering light cracking of atmospheric resid, cracking of heavy gasoil, and exhaustive cracking of
light gasoil as a unified system, he determined the ratios between the streams entering the reaction chamber from
the furnace coils. The optimum quantitative ratios of recirculation product and initial fresh feedstock – vacuum
resid – were found [7].
The industrial type 15/2 thermal cracking units built at the beginning of the 1950s operated with a
recirculation factor of 3. This ratio of recirculation and feedstock streams (through the light cracking furnace and
through the exhaustive cracking furnace) allowed maintaining a high temperature in the reaction zone at the
optimum pressure and obtaining the maximum amount of naphtha cuts and gases. However, the continuous work

Fig. 1. Implementation of the visbreaking process: 1) basic fractional distillation tower;

2, 3) light and exhaustive cracking furnaces; 4) reaction chamber; 5, 7) high- and
low-pressure evaporators; 6) vacuum tower; 8) separator; 9) condenser-cooler; 10) heat
exchanger; I) vacuum resid; II) gases; III) unstable naphtha cut; IV) thermal reflux;
V) steam; VI) vacuum residue; VII, VIII) heavy and light vacuum gasoils; IX) steam and
gas mixture to vacuum system.

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cycle of the thermal cracking units was limited by accumulation of coke deposits in the equipment and lines and
was from 15 to 30 days.
With the development of technologies for production of high-quality and high-octane gasolines, the need
for the naphtha components of thermal processes decreased, which was reflected in the conditions of conducting
these processes. Some of the thermal cracking units came to be used for “breaking down the viscosity” of oil
refining residues, i.e., for the visbreaking process. This led to the development of a second direction in refining
of heavy petroleum residues.
Many studies of the visbreaking process were conducted in laboratory conditions in different years. In
particular, visbreaking of Arlan crude vacuum resid (yield of 47 wt. % in crude) was investigated in a periodically
operating laboratory setup [8]. The process was conducted at a temperature of 410°C, atmospheric pressure, and
for different times. The minimum viscosity of the visbreaking residue was attained after 12-13 min residence of the

Table 1

West Vacuum resid visbreaking product

Siberian
Indexes crude heavy light
thermal naphtha
vacuum residue vacuum vacuum
reflux cut
resid gasoil gasoil
Density at 20°C, kg/m3 981.8 1013.8 940 920 880 770
Sulfur content, wt. % 2.15 2.14 1.9 1.2 0.96 0.82
Refractive index – – 1.605 1.500 1.440 1.430
Carbon residue (Conradson), wt. % 12.1 20 1.15 0.11 – –
Viscosity
kinematic, mm2/sec
at 20° C – – – 14.9 – –
at 50° C – – 39.4 6.1 – –
nominal (Engler), deg
at 80° C 137.8 42 – – – –
at 100° C 27.8 14.9 – – – –
Solid point, ° C +9 +12 -2 -6 -28 –
Group chemical composition, wt. %
hydrocarbons
olefins – – – – 27.2 26.4
paraffins and naphthene 23 15 38 47 40.3 48.4
aromatics 50.8 55 50 44.6 32.5 25.2
light 9.3 7.5 11 8.9 – –
middle 11.8 10.8 15.6 22.6 – –
heavy 29.7 36.7 23.4 13.1 – –
resins 22.1 22.5 12 8.4 – –
benzene 6 7.1 2.8 0.9 – –
alcohol- benzene 16.1 15.4 9.2 7.5 – –
asphaltenes 4.1 7.5 – – – –

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mixture in the “reaction” chamber and was 19E. A longer residence time increased the viscosity as a result of
intensified thickening and formation of carbenes – the basic viscosity carrier components of visbreaking residue.
Visbreaking residue that satisfies the requirements for grade 100 boiler fuel can be obtained in using
comparatively light Arlan crude residues as feedstock (yield of up to 60 wt. % in crude). In visbreaking of heavier
residues (yield of less than 50 wt. % in crude), the minimum viscosity of the residue obtained attains 25°E [9].
Visbreaking of West Siberian commercial crude cuts is examined in [10]: 400-490, 490-540, >400, >410,
>430, >490, and >540°C. The changes in the viscosity of the products obtained at 450-510°C after distillation of
the cuts under 200°C were determined. The reduction ratio of the viscosity of the feedstock is: light
gasoil (400-490°C cut), 1.2-1.6; heavy gasoil (490-540°C cut), 11-20; >400C cut, 3.5; >410°C cut, 10; >430°C cut, 14;
vacuum resid (>490°C cut), 5; heavy vacuum resid (>540°C cut), 8.
The light distillates in the feedstock reduce the efficiency of heat treatment. However, because of the low
initial viscosity of the heavy distillates (400-490 and 490-540°C) and light vacuum resids (>400, >410, and >430°C)
– from 2.57 to 88°E at 80°C – caused by the light distillate content, boiler fuel with a viscosity of
under 14.5°E at 80°C is obtained from this feedstock.
Thermal conversion of heavy resids (95 wt. % content of cuts >500°C) was investigated in a pilot unit
simulating the industrial visbreaking process with a soaker section in the following conditions: pressure
of 1.5 MPa; residue residence time in reaction zone of 400-500 sec; temperature at furnace outlet of 410-460°C. The
products of conversion were separated in laboratory conditions into gas, naphtha cut, and residue. The quality
of the visbreaking residue was assessed with the viscosity (°E), sulfur content, and distillation (simulated distillation
method).
It was found that at 410-430°C, the yield of >500°C residue increases and the yield of the gasoil
part (195-500°C cut) decreases. At 430-460°C, the yield of products begins to stabilize, with a slight decrease in
these indexes, accompanied by an insignificant increase in the yield of gas and naphtha cut. The observed
increase in the viscosity of the stripped visbreaking residue is not due to a decrease in the distillate content in it
but to accumulation of secondary asphaltenes because of increasing formation of polycondensation products.

Table 2

Feedstock and products wt. % tons/day thousand tons/year

Taken
West Siberian crude vacuum resid 100.0 3000 1050.0
Obtained
Wet gas 5.0 150 52.5
Stabilization head (reflux) 3.0 90 31.5
IBP-170°C stable naphtha cut 10.4 312 109.2
Thermal reflux (170-350°C cut) 8.6 258 90.3
Vacuum gasoil
light (350-420°C cut) 8.0 240 84.0
heavy (420-500°C cut) 14.8 444 155.4
Vacuum residue 49.6 1488 520.8
Losses 0.6 18 6.3
Total 100.0 3000 1050.0
Note. *The unit operated 350 days a year.

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 The results of the studies using pure residues – with no impurities (recirculation products) – are in
agreement with the theoretical assumptions. Like cracking, visbreaking is a set of decomposition and condensation
reactions. As a function of the process temperature and feedstock composition, certain reactions predominate: at
moderate temperatures, polymerization reactions, at high temperatures, decomposition reactions [12].
With an increase in the temperature, the rate of both types of reactions increases, but the decomposition
reactions take place more rapidly than the condensation reactions. The difference between the rates of these
reactions is higher the higher the temperature is.
Moderate (380-430°C) visbreaking temperatures cause condensation reactions, since the activation energy
of these reactions is much lower than for decomposition reactions. The degree of conversion at such temperatures
is lower, since the basic components of heavy residues – native asphaltenes – decompose by separation of
substituents of linear structure from aromatic nuclei, which is confirmed by studies of the light products of
decomposition of residues [13].
An analysis of the published data shows that implementation of the process of thermal decomposition of
heavy petroleum residues should be of two types as a function of the requirements for the final result of the
process – ensuring the maximum yield of gases and distillates and the minimum yield of residue or on the contrary,
the minimum yield of gases and distillates and the maximum yield of residue corresponding to the requirements for
boiler fuel.
The first type of implementation of the visbreaking process essentially retains the scheme (see Fig. 1) and
equipment of thermal cracking units, of type 15/2, for example. Conversion of these units to the visbreaking
process is accompanied by a decrease in the recirculation factor of kerosene–gasoil cuts to 1.8 and the process
temperature at the furnace outlet to ~470°C. Exhaustive cracking furnace 3 is converted from the regime for
cracking the reflux entering from fractional distillation tower tanks 1 to the regime of parallel operation with light
cracking furnace 2.
These changes increase the output in fresh vacuum resid by 40 wt. % [14]. The yield of gas, reflux, and
naphtha cut decreases slightly, but is compensated by takeoff of additional thermal reflux (170-350°C cut) and
vacuum thermal gasoil (350-500°C cut).
After revamping, the visbreaking unit was run to prepare delayed coking feedstock and the yield of
residue decreased less than to 50 wt. % in vacuum resid [15].
The physicochemical properties of West Siberian crude vacuum resid (yield – less than 30 wt. % in crude)
and visbreaking products (with recirculation) are reported in Table 1. According to the material balance (Table 2)
of this process, takeoff of gases and distillates reaches 50 wt. %.
These results were obtained in the visbreaking regime reported in Table 3. For comparison, the thermal
cracking regime with maximum yield of gas, naphtha cuts, thermal reflux, and vacuum gasoil and the minimum yield
of residue is also reported. In visbreaking, the pressure decreases markedly in the furnace coils and reaction
chamber. This is due to elimination of the reduction valve at the reaction chamber outlet, used to make the
conditions of conversion of the feedstock mixture more severe (pressure of up to 2 MPa) together with maintaining
the necessary temperature at the outlet.
It is stated in [14, 15] that the visbreaking scheme with recirculation of kerosene–gasoil cuts has some
drawbacks. The basic ones are: low output for fresh feedstock – vacuum resid – and high power consumption for
heating and conducting the decomposition reactions. For these reasons, preference is increasingly being given
to the use of thermal cracking units under the visbreaking process without recirculation of secondary gasoils. In
this case, it becomes possible to replace some of the secondary gasoils with vacuum resid, which increases output
and decreases power consumption.

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Table 3

Regime for the reaction-fractional distillation

Indexes subsystem of the visbreaking unit (with recirculation)
before updating after updating
Recirculation factor 3 1.8
Furnace pumps
Pressure in feedstock injection line, MPa
heavy 4.5 2.8
light 5 2.8
Temperature, °C
at feed input into furnace
heavy 390 377
light 300 377
at feed exit from furnace
heavy 490 473
light 530 473
Reaction chamber
Pressure, MPa 2 1.5
Temperature of reaction products at reaction chamber outlet, °C 465 465
High-pressure evaporator
Pressure, MPa 1.7 1.2
Temperature of products after one evaporation, °C 440 440
Basic fractional distillation tower
Pressure, MPa 1.1 1
Temperature, °C
at top of tower 190 175
in tank 320 285
at bottom of tower 390 376
Low-pressure evaporator
Pressure, MPa 0.2 0.08
Temperature, °C
at top of tower 186 170
in tank 316 300
at bottom of tower 390 405
Vacuum tower
Pressure, MPa – 0.0068
Temperature, °C
at top of tower – 90
in tank – 290
at bottom of tower – 355

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 However, the fact that effective heating of vacuum resid is eliminated in the fractional distillation tower
and low-pressure evaporator as a result of mixing it with secondary gasoil cuts in the vapor phase is overlooked.
In the new revamping plans for thermal cracking units under the visbreaking process, it is usually provided that
the temperature of the vacuum resid entering the furnace is no higher than 300°C.
This temperature is attained in “vacuum resid–visbreaking residue’ heat exchangers. The temperature of
the feed mixture formed in visbreaking units with recirculation at the bottom of the basic fractional distillation
tower is 390±10°C. For this reason, in modern visbreaking units without recirculation, the vacuum resid is heated
to 390±10°C in an auxiliary furnace after the heat exchangers and collected in an intermediate (buffer) tank [16, 17].
In this way, heating part of the vacuum resid in the fractional distillation tower by the steam and gas
stream from the high-pressure evaporator and part of the vacuum resid in the low-pressure evaporator with the
steam formed is replaced by heating in the auxiliary furnace or heating in the visbreaking furnace reaction cols. As
a consequence, saving power in operating the unit in the regime of one passage of the vacuum resid through the
reaction unit is not confirmed.
Another important aspect of the visbreaking process is the elimination of coked furnace coils and
consequently the increase in the duration of the operating cycle of the units without shutdown for steam burnout
and maintenance. The scheduled run of the visbreaking unit with recirculation of secondary gasoils is 180 days.
The operating cycle without recirculation, as without steam burnout of the furnace coils, is no longer
than 1-2 months.
The lack of a sufficient amount of secondary gasoil cuts in the feedstock mixture decreases the run time.
Their presence in the feed mixture inhibits reactions of spontaneous decomposition of resins and asphaltenes into
coke and light hydrocarbons.
The inhibited composition of the feedstock mixture allows conducting visbreaking at a temperature under
485°C at the furnace outlet if the flow rate at the inlet into the coils is ³3 m/sec. In a reaction chamber with a
descending stream, where the pressure is maintained at 1.5±0.1 MPa, the residence time of the reaction mixture
attains 8-10 min.
As reported in [12, 13], the pressure in the “coil–reaction chamber” subsystem does not affect the
visbreaking process if it is conducted in the liquid phase. However, at a process temperature above 440°C, the
light part of the reaction products has a temperature above the critical temperature and is consequently in the
vapor phase. Increasing the pressure only decreases the volume of the vapor phase, which increases the residence
time of the reaction mixture and reaction products in the reaction chamber and consequently increases the degree
of conversion and yield of reaction products.
The goal of utilizing visbreaking units is “breakdown of the viscosity” of the residues and production of
boiler fuel with viscosity of £16°E. Since at process temperatures of 440-465°C the conversion required for
attaining this goal is not guaranteed, after the unit is started up, the temperature regime in the furnace coils is
boosted and the temperature at the outlet is increased to 485°C.
However, in this case, coking begins on the coils. To prevent this, the flow rate of the streams at the inlet
into the coils is increased with a so-called “turbulizer”, usually highly aromatized 160-400°C distillate. The amount
in different units is from 4 to 10 wt. % in fresh vacuum resid.
Due to low flow, the “turbulizer” has little effect on the flow rate in the furnace coils but inhibits the
mixture with respect to coking. In the final analysis, it almost totally passes into the visbreaking residue, playing
the role of both diluent and stabilizer.
The stream of kerosene–gasoil cuts for reducing the temperature to 415±5°C to stop the decomposition
reaction is added to the reaction products after they come out of the reaction coil. At a product temperature

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of 485°C, the amount of product used to stop the reaction reaches 20 wt. % in vacuum resid. With respect to
distillation, this product is similar to the product fed for turbulization: 160-400°C.
They can be a natural thermal reflux if separated in a sufficient quantity during decomposition of the
residues. However, due to the low degree of conversion, an insufficient amount is usually formed. Then products
close to it in distillation – basically the 200-360°C cut from straight-run distillation of crude – are obligatorily
involved.
Since the use of this cut is equivalent to the use of a diluent in the visbreaking residue, it is replaced by
unused product, for example, slop oil, with 150-400°C distillation. Refining of slop oil in thermal cracking
processes [18] shows that 60-70% of the amount also passes into visbreaking residue and is a diluent.
Both the turbulizer and the product fed in to stop the decomposition reaction in the final analysis are thus
contained in boiler fuel, diluting it to the required viscosity level: £16°E.

REFERENCES
1. S. N. Pavlova, Z. V. Driatskaya, M. A. Mkhchiyan, et al., Crude Oils from Eastern Regions of the USSR. A
Handbook [in Russian], Gostoptekhizdat, Moscow (1962).
2. E. G. Ivchenko and G. V. Sevast’yanova, Medium- and High-Sulfur Crudes from Bashkir ASSR. A
Handbook [in Russian], Part 2, Khimiya, Moscow (1967).
3. K. B. Rudyak, G. G. Musienko, Yu. Yu. Ratovskii, et al., Khim. Tekhnol. Topl. Masel, No. 5, 40-43 (2000).
4. N. R. Saifullin and R. G. Gareev, Ibid., No. 6, 8-10 (1999).
5. V. G. Shukhov, Neftyan. Slants. Khozyaistvo, No. 10, 481 (1923).
6. M. F. Nagiev, Candidate Dissertation, Azerbaidzhan Scientific-Research Institute, Baku (1940).
7. M. F. Nagiev, Chemical Recirculation [in Russian], Nauka, Moscow (1978).
8. M. E. Levinter, M. I. Medvedeva, R. K. Galikeev, et al., in: Proceedings of the Conference of Volga Region
Institutions of Higher Education “Oil Refining and Petrochemistry”, Ufa, December 1965 [in
Russian], Ufa (1968), pp. 77-83.
9. P. M. Alekseev, Z. I. Syunyaev, A. V. Tsin’ko, et al., Trudy BashNII NP, No. 10, 60-68 (1972).
10. D. F. Varfolomeev, V. V. Fryazinov, S. G. Prokopyuk, et al., in: Proceedings of the Republic Scientific and
Practical Conference “Reserves for Increasing the Efficiency and Quality of Operation of Equipment in
the Oil Refining and Petrochemical Industry”, Ufa, September 1982 [in Russian], Mars, Ufa (1982),
pp. 171-177.
11. A. R. Davletshina, S. A. Obukhova, G. S. Degtyarev, et al., in: Proceedings of Section B of the II Congress
of Russian Oil and Gas Industrialists “Oil Refining and Petrochemistry – with Domestic Technologies
into the XXI Century”, Ufa, April 26, 2000 [in Russian], IP NKhP AN RB, Ufa (2000), pp. 63-64.
12. E. V. Smidovich, Oil Refining and Gas Processing Technology [in Russian], Part 2, Khimiya, Moscow
(1966).
13. R. Z. Magaril, Doctoral Dissertation, All-Union Scientific-Research Institute of the Petroleum Industry,
Moscow (1975).
14. G. G. Telyashev, R. N. Gimaev, A. F. Makhov, et al., Khim. Tekhnol. Topl. Masel, No. 4, 8-10 (1987).
15. R. G. Gareev, F. A. Arslanov, G. G. Telyashev, et al., Neftepererab. Neftekhim., No. 5, 10-14 (1997).
16. S. L. Aleksandrova, V. V. Taushev, G. G. Valyavin, et al., Ibid., 14-18.
17. G. G. Musienko, V. P. Ermakov, and V. G. Solovkin, Khim. Tekhnol. Topl. Masel, No. 5, 38-39 (2000).
18. D. F. Varfolomeev, F. Kh. Urazaev, and M. N. Stekol’shchikov, Ibid., No. 5, 7-8 (1970).

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