Chemistry and Technology of Fuels and Oils, Vol. 43, No.

6, 2007

THE POSSIBILITY OF CRACKING HYDROCARBONS WITH CAVITATION.

A Quantitative Energy Assessment

A. I. Nesterenko and Yu. S. Berlizov UDC 66.023:532:528

It was shown that the energy released in collapse of cavitation bubbles can break hydrocarbon bonds
in the molecules of compounds contained in petroleum feedstock. A quantitative energy assessment was
conducted and demonstrated the possibility of using cavitation for cracking the hydrocarbons in crude
oil.

The increase in the prices for crude oil and petroleum products and stiffening of the requirements for the
quality of commercial products have made it necessary to constantly improve existing and develop new oil refining
technologies. The basic effects of researchers are directed toward increasing the exhaustiveness of oil refining,
decreasing the power requirements of existing technologies, guaranteeing quality, and expanding the line of
products manufactured to satisfy the current consumer market.
The use of different physical methods of acting on chemical engineering processes is a promising trend in
creating nontraditional and enhancing existing technologies. Physical and chemical processes which are difficult
or impossible to conduct in ordinary conditions can be implemented as a result of such an action.
Cavitation is one of these methods; for many decades, it was fought against as a negative event that
destroys different working surfaces [1, 2]. However, it is evident that the colossal energy released in cavitation as
a result of bubbles bursting and the large number of methods of creating the conditions for cavitation can be
effectively utilized for enhancing many manufacturing processes [3-6].
The paper presented in 1960 at the All-Union Scientific and Technical Conference on Use of Ultrasound in
Industry was probably one of the first communications concerning the possibility of using cavitation for enhancing
cracking of petroleum feedstock [3]. The results of studies of the effect of ultrasonic vibrations on light cracking
of heavy petroleum residues at high pressure were reported in the paper. Thermal cracking was conducted on a

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ProektStroiProm Ltd. Ukraine State Chemical Engineering University, Dnepropetrovsk. Translated from
Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 43 44, November December, 2007.

0009-3092/07/43060515 2007 Springer Science+Business Media, Inc. 515

continuous laboratory setup at a temperature of 430-470C and pressure of 20-60 MPa. Magnetostrictive oscillators
were installed in the inlet into a tube furnace to create ultrasonic vibrations. The resonant frequency of the
vibrations was 27 kHz.
The conditions of the most effective action of ultrasound were determined as a result of the
studies: temperature of 450C, pressure of 50 MPa. In these conditions, in comparison to the conditions of
ordinary thermal decomposition, the yield of reaction products increased: by 1.3 times for gas, by 1.6 times for the
naphtha cut, and by 1.6 times for the cuts up to 350C. However, the causes of the increase in the yield of light
petroleum products were not elucidated as a result of the experiments. We can only hypothesize that cavitation,
which arises in the liquid stream under the effect of ultrasonic vibrations, is one cause of these results.
In the general case, cavitation is related to the appearance of many cavitation bubbles in a liquid in certain
conditions, these bubbles pulsate, oscillate, enlarge, diminish, collapse, and are moved together with the liquid
stream.
The presence of bubble nuclei in the liquid and a static pressure below the saturated vapor pressure of
this liquid at the given temperature are necessary and sufficient conditions for the appearance of cavitation
bubbles, since the density of supercritical nuclei is relatively high in a real liquid. The method of reducing the
static pressure is not very important.
It is possible to attain a static pressure below the saturated vapor pressure by increasing the velocity of
the liquid as a result of decreasing the area of the cross section of the stream (Venturi tube, centrifugal vortex
chambers, etc.). The experiments on creating hydrodynamic cavitation in a centrifugal vortex chamber to act on a
stream of atmospheric resid showed [7]:
the existence of cavitation in the vicinity of the vortex;
the existence of the bubble collapse stage;
a decrease in the atmospheric resid cracking process temperature.
According to [2], cavitation can arbitrarily be divided into three stages: generation (formation of
supercritical bubbles); development, and disappearance (collapse of bubbles). The stages of the appearance and
development of cavitation are a function of the physicochemical properties of the liquid, the presence of solid or
gaseous contaminants (nuclei) in it, the temperature and pressure in the cavitation zone, and a number of other
factors.

Table 1
Bond type Compound type Energy of bond breaking Eb, kJ/mole
Acids 230
Car Phenols 293
Paraffins 332
N Amines 334
Ethers 376
Car Calk 65 3 384
Naphthenes 385
Paraffins 413
Car Aromatics 434
= Olefins 588
Aromatics 610
Acetylenes 823

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 If the static pressure in the liquid suddenly increases to above the pressure of its saturated vapors that
fill the cavitation bubbles in any way after the first two stages, condensation of these vapors on the walls of the
bubble and collapse of the bubble are almost instantaneous.
According to the data in [2, 5], cumulative stream lines arise when a bubble collapses as a result of
nonspherical compression, and energy is released in the vicinity of the site where the bubble disappears. The
temperature can attain 10 4 K and the pressure can reach 200-400 MPa at the point of collapse of the bubble.
The appearance of cumulative stream lines and extremely high values of these parameters are probably
also the cause of local perturbations of propeller shaft blades, turbine blades, etc. [1, 2].
We performed a quantitative energy assessment of the possibility of using cavitation for cracking the
hydrocarbons in petroleum feedstock.
According to [2], when a cavitation bubble collapses, energy is released

4
(
E c = R03 R 3 p
3
) (1)

where R 0, R are the initial and current radii of the bubble, m; p is the pressure of the liquid far from the cavern, Pa.
Since the radius of the bubble R returns to zero when the bubble collapses, Eq. (1) becomes:

4
E c = R03 p (2)
3

For a quantitative estimation of the energy released when a cavitation bubble collapses, we set R 0 = 1 mm,
p = 106 Pa. Then according to Eq. (2), we will have:

E c = 4 10 3 J

The energy (E b) of breaking some chemical bonds [8] for one mole of several types of compounds is
reported in Table 1. As we see, for breaking a bond of the C C type in one molecule, for example, of paraffins, it
is necessary to expend:

Eb 332000
Em b = = = 5.5 10 19 J
N A 6.022 10 23

where N A is Avogadros number.

The number N of molecules in which a bond can be broken when one cavitation bubble collapses is thus:

Ec 4 10 3
N= = 1016
E m b 5.5 10 19

That is, when one bubble with a radius of R 0 = 1 mm collapses, sufficient energy is released for
cracking 10 16 molecules of hydrocarbons.

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 Collapse of N bubbles is required to break bonds of the C C type in each of the molecules in 1 mole of
hydrocarbons:

N A 6.022 10 23
N = = 10 7
N 1016

Such a number of bubbles will occupy the volume:

4
Vbub = R03 N 4 10 2 m 3 40 l
3

Let the volume fraction of cavitation bubbles in the stream of a petroleum product be 10% of the total
volume. Then for cracking 1 mole of hydrocarbons, it will be necessary to pump 360 liters of petroleum product
through the cavitation apparatus. If we assume that the molecular weight of the hydrocarbons is = 100-300 and
their density is = 700-900 kg/m 3, then after 360 liters of petroleum product has been pumped through the cavitator,
approximately 0.1-0.3 kg of hydrocarbons can be cracked.
The possibility of cracking petroleum hydrocarbons by hydrodynamic cavitation was thus demonstrated.
To increase the yield of cracking products it will be necessary for the design of the cavitation apparatus to ensure
a multicyclic cavitation process and create cavitation bubbles of the maximum density in the petroleum product
stream.

REFERENCES
1. A. I. Pernik, Problems in Cavitation [in Russian], Sudostroenie, Leningrad (1966).
2. R. T. Knapp, J. W. Daley, and R. G. Hammitt, Cavitation, McGraw-Hill, New York (1970).
3. E. S. Padalka, Ultrasound in the Petroleum Industry [in Russian], Gosudarstvennoe Izd. Tekhn. Lit., Kiev
(1962).
4. D. A. Gershgal and V. M. Fridman, Ultrasound Equipment [in Russian], Energiya, Moscow (1976).
5. I. M. Fedotkin and A. F. Nemchin, Use of Cavitation in Manufacturing Processes [in Russian], Vishcha
Shkola, Kiev (1984).
6. A. F. Nemchin, G. I. Sergeev, and A. S. Machinskii, Supercavitation Equipment [in Russian],
TsNIITEneftekhim, Moscow (1988).
7. Yu. S. Berlizov, in: Proceedings of the International Scientific and Technical Conference Progress in
Fuel Technology and Chemmotology of Fuels and Lubricants, Dnepropetrovsk, September 12-15, 2005
[in Ukrainian], UDKhTU, Dnepropetrovsk (2005), pp. 147-148.
8. R. Z. Magaril, Mechanism and Kinetics of Homogeneous Thermal Transformations of Hydrocarbons [in
Russian], Khimiya, Moscow (1970).

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