Chemical and Petroleum Engineering, Vol. 41, Nos.

3–4, 2005

ANALYSIS AND MATHEMATICAL DESCRIPTION

OF THE THERMAL-OXIDATIVE CRACKING
OF NAPHTHA

D. V. Goncharov and M. Yu. Belyaevskii

A mathematical model is developed for the process. A system of differential equations, which permits
design analysis, is cited. The model has been approved for analysis of the thermal-oxidative cracking of
naphtha A-76.

Decomposition of hydrocarbon molecules into individual fragments and simple radicals with their subsequent
regrouping into new molecules occurs at high temperatures (350–600°C) during thermal-oxidative cracking (TOC) of a liq-
uid hydrocarbon fuel, which is proceeding in the presence of atmospheric oxygen and under atmospheric pressure [1, 2]. The
process occurs without interruption: vapors of the initial raw material (liquid fuel – naphtha), which are preheated to the tem-
perature required for the reaction, and air delivered in the form of a mixture comprised of strictly defined proportions to the
reaction zone where a constant reaction temperature is maintained.
The TOC process takes place in the vapor phase, and the amount of heat required for the reaction is transferred by
internal heat due to the introduction of the amount of air required to create the reaction temperature. Here, two processes
occur simultaneously: liberation of reaction heat during oxidation (exothermic reaction) and intensified evaporation of rar-
efied naphtha vapors due to the presence of a neutral gas – atmospheric nitrogen.
The chain mechanism of chemical transformations in the TOC process has three stages: origin of the chain (forma-
tion of free radicals or atoms); continuation of the chain (formation reaction products); and breaking of the chain (disap-
pearance of free radicals).
The stage of chain origin occurs differently: free radicals may be formed from molecules of the initial substances as
a result of monomolecular decomposition and also during bimolecular interaction of particles.
Thus, the chain reaction of the TOC, for example, pentane, begins with its monomolecular decomposition with
respect to the C–C bond in the β-position toward the radical center:

CH3 – CH2 – CH2 – CH2 – CH3 → CH3 – CH2• + CH3 – CH2 – CH2•

However, the feature distinguishing TOC from thermal cracking is that atmospheric oxygen exists in the system.
According to the Bach–Engler theory, an oxygen molecule is attached to an oxidizable substance without dissociating and
forming an oxide molecule:
CH3 – CH2 – CH2• + •O – O• → CH3 – CH2 – CH2OO•

CH3 – CH2• + •O – O• → CH3 – CH2OO•

Under ordinary conditions, a molecule of oxygen is inactive, and its activation takes place by the breaking of only
one bond with formation of the biradical: O = O → •O – O•.

Moscow State University of Engineering Ecology (MGUIÉ). Translated from Khimicheskoe i Neftegazovoe
Mashinostroenie, No. 4, pp. 17–20, April, 2005.

0009-2355/05/0304-0193 ©2005 Springer Science+Business Media, Inc. 193

 It is precisely this activation that occurs during the TOC of hydrocarbons, and the oxygen biradical is an initiator of
bimolecular interaction between particles.
In the stage of chain continuation, free peroxide radicals are subject to isomerization and splitting:

CH3 – CH2OO• → •CH2 – CH2OOH

•CH2 – CH2OOH → CH3 – CHO + •OH

By-products (aldehydes, ketones) and new free radicals are formed as a result of monomolecular decomposition of
the peroxide radicals. With more complete thermal oxidation, molecules of the products obtained enter into reaction with the
original radicals [3–5]:
CH3 – CHO + CH3 – CH2• → CH3 – CH3 + CH3 – CO•

The carbonyl compounds that have been formed decompose into a free radical and end product – carbon monoxide:

CH3 – CH2 – CO• → CH3 – CH2• + CO

In addition to the basic reaction chain, secondary chains also evolve with the formation of hydroperoxide, which is
transformed into an alcohol molecule as a result of a chain reaction. The TOC process occurs, however, at high temperatures
and atmospheric pressures; the alcohol molecule is therefore broken-down into hydrocarbon, carbon monoxide, and hydro-
gen molecules [4, 5].
In the stage of chain breaking, the reactive radicals begin to limit the process, and chain breaking occurs as a result
of interaction between the two free radicals (disproportionation):

CH3 – CH2 – CH2• + CH3• → CH3 – CH2 – CH2 – CH3

CH3 – CH2• + CH3• → CH3 – CH2 – CH3

It must be noted that the longer the chain of hydrocarbon molecules, the more the possible directions taken by the
TOC reactions, and the greater the amount of compounds that are formed here.
Low-molecular alkanes, alkenes, and alkynes, hydrogen, carbon monoxide, and carbon dioxide are reaction prod-
ucts of the TOC of hydrocarbons. Under pressure at low temperatures, however, the TOC process can be used to produce oxy-
gen-containing compounds (alcohols, aldehydes, ketones, acids, phenols, etc.) [4, 5].
Thus, the temperature of the process, the pressure in the reaction volume, and the concentration of initial substances
in the system (hydrocarbon:oxygen ratio) are basic factors affecting the TOC reactions of hydrocarbons with the resultant
required products.
The optimal ratio of initial substances (naphtha:air) was selected experimentally with consideration of the explosive
risk of the mixture in question at high-temperatures. The excess-air coefficient of a naphtha-air mixture α ≤ 0.4 was deter-
mined as a result of experimentation.
In the TOC process, the formation of the following lighter hydrocarbons increases smoothly in the interval
T = 350–500°C: methane (CH4), ethane (C2H6), propane (C3H8), and propylene (C3H6); here, the concentration of n-butane
(n-C4H10) and isobutane (i-C4H10) is reduced. It must be pointed out that the C = ƒ(T) curves for ethane and propane pass
through a maximum [C2H6 ≈ 11.99% (by volume), and C3H8 ≈ 5.44% (by volume)] at a temperature of approximately 500°C.
It may be suggested that secondary reactions begin to occur at this temperature with decomposition of the indicated products
into lighter methane and hydrogen, whereupon a sharp increase is observed in the amount of hydrogen and methane.
The concentration of heavier hydrocarbons (n-butane and isobutane) in the gaseous mixture that is formed decreas-
es with increasing temperature over the entire range investigated: n-C4H10 – from 6.03 to 0.81% (by volume), and i-C4H10 –
from 3.44 to 0.55% (by volume).

194
 TABLE 1

Thermal processes
Reaction
Pyrolysis Catalytic cracking Cracking under pressure Thermal-oxidative cracking
product
Yield of products, % (by weight)

H2 0.8 1.2 0.4 1.3

CH4 10.1 18.7 4.0 18.5
C2H6 2.9 4.6 1.8 3.4
C2H4 28.5 34.1 0.3 18.4
C2H2 – 0.7 – 20.5
C3H8 0.4 0.5 1.5 3.6
C3H6 10.9 12.9 0.8 12.9
∑C4 3.5 5.6 0.5 3.5
Extent of transformation, % (by weight)
Initial product – naphtha 57.1 78.3 9.3 82.1

The yield of hydrogen, methane, ethylene, and acetylene increases with increasing temperature: H2 – from 0 to
14.42% (by volume), CH4 – from 3.51 to 25.20% (by volume), C2H4 – from 6.43 to 14.31% (by volume), and C2H2 – from
5.49 to 17.12% (by volume). The yield of such targeted products as methane, ethylene, ethane, propylene, and acetylene in
the TOC of liquid hydrocarbons is higher than in hydrolysis, catalytic cracking, hydrocracking, and other processes [1, 6, 7].
In the temperature interval investigated, carbon monoxide and carbon dioxide form simultaneously in the products of
thermal decomposition. The concentration of carbon dioxide decreases, while that of carbon monoxide increases with increas-
ing temperature: CO2 – from 4.12 to 1.04% (by volume), and CO – from 0.63 to 7.55% (by volume). This enables us to sug-
gest that carbon black [8], which interacts with carbon dioxide, will form carbon monoxide in the reaction chamber [1, 3].
The extent to which the naphtha is transformed (converted) increases smoothly in the 350–500°C interval, but tends
toward 100% (by weight) from 500°C and above. The extent to which the naphtha is transformed in the TOC process at
600°C is greater than that realized during pyrolysis, catalytic cracking, and thermal cracking under pressure at the same tem-
perature [3], i.e., for the same expenditures of energy resources and raw material, the TOC process is more economically
suitable than other thermal processes employed for the conversion of naphtha. It should be pointed out that the yield of
hydrogen and light hydrocarbons is also higher in the TOC process (see Table 1).
Advantages of TOC Process
• high degree of naphtha transformation;
• high yield of gaseous products and targeted products (methane, acetylene, ethylene, propylene) with no coke for-
mation;
• no expensive catalysts; and
• the process proceeds under atmospheric pressure.
Mathematical models of the kinetics of the thermal process can be conditionally divided into three types; empirical,
semi-empirical, and models based on the actual (free-radical with allowance for elementary reactions) kinetic mechanism of
the process [4, 5].
Semi-empirical models have come into the most widespread use in describing the kinetics of thermal processes [2].
For a raw hydrocarbon material, they include the set of reactions which correspond to the chemistry of the process with some
degree of accuracy. The number of reactions is determined by the number of products considered and by the prescribed degree
of accuracy in determining their yield.
A system of differential equations describing the change in the concentrations of all components participating in
the reaction can be written in conformity with the set of reactions entering into the kinetic model. When it is impossible to

195
ignore the change in volume of a reaction mixture, the system should be supplemented by an equation that accounts for this
change due to the chemical reaction and temperature, and constants of the reaction rates should be represented by Arrhe-
nius’ equation [9].
To compute the concentrations by solving the system of differential equations, it is necessary to know the values of
the constants of the reaction rates, which are calculated by processing experimental data; moreover, one must use precisely
this model, since the addition or deletion of some reactions will change the values of the constants.
In analyzing, describing, and calculating the progress of a reaction, the kinetic laws are usually considered to be
already assigned, and the process is described in the language of formal kinetics [9] the basic concept of which is the reac-
tion rate. The conditional concept of a formally simple reaction is also adopted in formal kinetics.
In the case under consideration, nine concurrently proceeding formally simple reactions can be formulated to sim-
plify analysis of the kinetic laws governing the TOC process (isooctane is accepted as a model of naphtha):
k
i-C 8 H18 + 4O2 
1
→ 4CH 4 + 4CO2 + H2

k
i-C 8 H18 + 4O2 
2
→ 4C 2 H6 + 2CO2 + 3H2

k
i-C 8 H18 + 2O2 
3
→ 3C 2 H 4 + 2CO2 + 3H2

k
i-C8 H18 + 2O 2 
4
→ 3C 2 H 2 + 2CO 2 + 6H 2

k
i-C 8 H18 + 2O2 
5
→ 2C 3 H8 + 2CO2 + H2

k
i-C 8 H18 + 2O2 
6
→ 2C 3 H6 + 2CO2 + 3H2

k
i-C 8 H18 + 4O2 
7
→ n-C 4 H10 + 4CO2 + 4 H2

k
i-C 8 H18 + 4O2 
8
→ i-C 4 H10 + 4CO2 + 4 H2

k
i-C8 H18 + 4O 2 
9
→ 8CO + 9H 2

Here, ki is a constant of the corresponding reaction rate (i = 1–9).

In these equations, the concentrations are inexplicitly temperature-independent. The constant of the reaction rate is
related most closely to temperature; this relationship is usually described by the Arrhenius equation

Ei
−
ki = Ai e RT ,

where Ei is the activation energy in kJ/mole, Ai is a factor before the exponent, R is the universal gas constant, which is equal
to 8.314 J/(K⋅mole), and T is the temperature of the process in K.
The constant ki is determined by a combination of Ei and Ai values; here, the higher the energy Ei, the greater the
extent to which the rate of the reaction will be temperature-dependent [9–11].
To describe the kinetic model, let us assume that the flow of an enriched fuel–air mixture proceeds through an
ideal-substitution apparatus (small-scale reactor). If the chemical reaction proceeds with a constant volume, its progress is,
as a rule, described by a system of differential equation [4, 5, 9, 11].
Experimental data were used in calculating the constants ki. The activation energy and the factor before the expo-
nent were determined graphically from the ln k = ƒ(1/T) relationship for each rate constant.

196
 Using the kinetic parameters Ei and Ai and the rate constants ki determined, the system of differential kinetic equa-
tions for the TOC process will assume the form
34700 14100 16000 26200
dCC 16.4 − 13.8 − 13.6 − 15.4 −
8H18
= − CC CO ( e RT +e RT +e RT +e RT +
dt 8H18 2

13300 4500 30400 24900 50400

12.8 − 11.8 − 6.2 + 6.3 + 17.0 −
+e RT +e RT +e RT +e RT +e RT ) ;

34700 14100 16000 26200

dCO 16.4 − 13.8 − 13.6 − 15.4 −
2
= –C C CO ( 4 e RT + 4e RT + 2e RT + 2e RT +
dt 8H18 2

13300 4500 30400 24900 50400

12.8 − 11.8 − 6.2 + 6.3+ 17.0 −
+ 2e RT + 2e RT + 4e RT + 4e RT + 4e RT );

34700 14100
dCCH 16.4 − dCC 13.8 −
2 H6
4
= 4e RT C
C8H18 CO2 ; = 2e RT C
C8H18 CO2 ;
dt dt

16000 26200
dCC 13.6 − dCC 15.4 −
2H 4 2 H2
= 3e RT C
C8H18 CO2 ; = 3e RT C
C8H18 CO2 ;
dt dt

13300 4500
dCC 12.8 − dCC 11.8 −
3H 8 3H 6
= 2e RT C
C8H18 CO ; = 2e RT C
C8H18 CO2 ;
dt 2 dt

30400 24900
dCnC 6.2 + dCiC 6.3 +
4H10 4H10
=e RT C
C8H18 CO2 ; =e RT C
C8H18 CO 2 ;
dt dt

50400
dCCO 17.0 −
= 8e RT C
C8H18 CO2 ;
dt

34700 14100 16000 26200

dCCO 16.4 − 13.8 − 13.6 − 15.4 −
2
= CC CO ( 4 e RT + 4e RT + 2e RT + 2e RT +
dt 8H18 2

13300 4500 30400 24900

12.8 − 11.8 − 6.2 + 6.3+
+ 2e RT + 2e RT + 4e RT + 4e RT );

34700 14100 16000 26200

dCH 16.4 − 13.8 − 13.6 − 15.4 −
2
= CC CO ( e RT + 3e RT + 3e RT + 6e RT +
dt 8H18 2

13300 4500 30400 24900 50400

12.8 − 11.8 − 6.2 + 6.3+ 17.0 −
+e RT + 3e RT + 4e RT + 4e RT + 9e RT ).

The system of differential equations obtained for the TOC process makes it possible to perform a design analysis,
i.e., required values of reagent concentrations are substituted in the equations of the system, the average dwell time (t = τk)
is found, and the volume of the reaction zone in the reactor Vre = vτk is determined from formula (3), where v is the bulk flow
rate of reagents in m3/sec, and τk is the average dwell time of the reagents in the reaction zone in sec.

197
 The mathematical model developed has been verified for accuracy on the basis of Fisher’s variance ratio. The num-
ber of reactions in the model is determined by the number of products considered. The kinetic model in question assumes
physical significance, and is a part of the method employed for analyzing the design of a small-scale reactor; it may become
suitable for use, however, even for small quantitative changes in the composition of the raw material being converted.
The model obtained has been approved for analysis of the TOC of naphtha A-76. Hereinafter, it is planned to devel-
op a general kinetic model of the TOC process which would be suitable for any form of raw material.

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