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High-selective pyrolysis of naphtha in the fast-mixing reactor

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DOI: 10.1016/j.fuproc.2012.06.017

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Fuel Processing Technology 106 (2013) 48–54

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Fuel Processing Technology

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High-selective pyrolysis of naphtha in the fast-mixing reactor

M.G. Ktalkherman a,⁎, I.G. Namyatov b, V.A. Emel'kim a, K.A. Lomanovich a
a
Khristianovich Institute of Theoretical and Applied Mechanics, Russian Academy of Science, Siberian Branch, Novosibirsk 630090, Russia
b
Institute of Chemical Kinetics and Combustion, Russian Academy of Science, Siberian Branch, Novosibirsk 630090, Russia

a r t i c l e i n f o a b s t r a c t

Article history: The process of naphtha pyrolysis in the heat-carrier at ultra-short time of feedstock / heat carrier mixing is
Received 28 April 2012 studied. The experiments are carried out within the temperature range at the reactor inlet of 1240–1400 K.
Received in revised form 15 June 2012 Detailed data on the temperature and product composition distribution along the reactor axis are obtained.
Accepted 15 June 2012
Experimental results are compared with the calculation. Significant enhance of ethylene yield in our experiments
Available online 4 July 2012
with relation to furnace pyrolysis method is found.
Keywords:
© 2012 Elsevier B.V. All rights reserved.
Naphtha
Pyrolysis
Olefins
Fast-mixing reactor

1. Introduction The other way of process intensification, predominantly purposed

Thermal decomposition of hydrocarbons for the production of basic
petrochemicals (ethylene, propylene) is carried out in steam-cracking
process. Liquid (naphtha, gas oil) and gaseous (ethane, propane, butane)
hydrocarbons are the feedstock for pyrolysis. The feedstock is heated in
the convection section of the furnace; it mixes with the superheated
steam and then enters a fired tubular reactor (radiant coil), where the
endothermic decomposition of feedstock takes places within the
controlled residence time, resulting in light olefins and by-products
formation. Then the mixture enters the transfer-line exchanger from
which the cooled mixture passes through compression, and gas separa-
tion units.
The yield of the most valuable petrochemical – ethylene – is the
determining factor in the total effectiveness of the process. Ethylene
content in pyrolysis products and other mixture components is presented
in [1–4], where the authors also consider the operation conditions of
modern ethylene plants.
Along with the conventional method of furnace pyrolysis, alternative
methods were studied. The results of early investigations are presented
in [5–9], recent results can be found in [10,11].
Among non-traditional methods of pyrolysis, the catalytic method
and feedstock pyrolysis in the heat-carrier flow is the most interesting.
Comparing to modern steam-cracking units, the catalytic pyrolysis pro-
cess in large-scale plants [12,13] is realized at lower temperatures, with
approximately the same ethylene yield, whereas the propylene yield is
much higher.
⁎ Corresponding author.
E-mail address: ktalkherman@itam.nsc.ru (M.G. Ktalkherman).
for ethylene yield gain, is associated with the temperature increase in
the reaction zone. It has been known for a long time that the ethylene
concentration increases in the pyrolysis products as the temperature
in the reaction zone rises [14], but existing technology is constrained
by temperature limitations of coil tube material. This limitation can be
overcome if the heat is supplied to feedstock not through the tube
wall, but is directly transferred via mixing with the high-enthalpy carrier
gas with the heat storage sufficient to realize the pyrolysis at high tem-
peratures. All experiments in the heat-carrier flow show the ethylene
yield higher than in the conventional method.
Since the heat-carrier temperature is much higher than its optimum
value in the reaction zone, the key problem in this case is the feedstock /
heat carrier mixing time. Taking into account that the feedstock
residence time in the reaction zone is much shorter than in the conven-
tional method, the mixing time must be minimal in order to reduce the
duration of feedstock residence in the high-temperature zone of the
mixing region, because it results in uncontrolled reactions prior to the
reactor inlet. In different works, this problem was solved by different
methods. In VNIIOS experiments [6,7], the liquid feedstock was injected
along the reactor axis into the heat-carrier flow moving with the speed
of 300–400 m/s. Hence the processes of feedstock evaporation, mixing,
and reaction were not spatially separated. In the ACR reactor [8,9]
of the Laval nozzle shape, the liquid feedstock was sprayed from the con-
vergent duct walls, upstream the nozzle throat. Droplets evaporation,
mixing with the heat carrier, as well as partial decomposition of the feed-
stock occurs in the supersonic flow as the temperature decreased down-
stream. In a certain cross section of the divergent part of the channel, the
flow quickly transits to the subsonic one in the shock-wave system, its
temperature increases, and the pyrolysis process continues at the high
temperature. In the experiments [11], the mixing and reaction zones

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.06.017
 Author's personal copy
M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54
are completely separated. Gaseous feedstock (ethane) and heat carrier
(superheated steam) are accelerated separately up to supersonic speeds;
they mix at low temperatures due to the interaction between parallel
flows of different density. As the mixing process is over, the flow tran-
sits quickly into the subsonic mode in the shock-wave system in the
same way as in [8,9], and the reactions start up at the prescribed initial
temperature.
Method of hydrocarbon pyrolysis in high-temperature heat carrier
differing from the above mentioned ones is proposed in [15]. This
method is based on the possibility to realize the ultra-short time of
feedstock/heat carrier mixing. The mixer geometry satisfying these
conditions was estimated experimentally in [16] on a gas-dynamic
setup. Study of liquified petroleum gases pyrolysis in the lab-scale
fast-mixing model reactor demonstrated the viability of this method
[17]. The combination of the increased temperature and short mixing
time raises significantly both the ethylene and total ethylene-propylene
yields in comparison with the furnace pyrolysis.
The objective of this study is to examine the process of liquid
feedstock pyrolysis in the fast-mixing reactor. Two tasks were under
consideration:
• Investigation of naphta pyrolysis in the fast-mixing reactor into
wide range of residence time at high feedstock heating rates and
high temperatures in reacting zone,
• Development of a numerical model for prediction of products yield
and its testing by experiment.
2. Method of high-temperature pyrolysis in the fast-mixing reactor
The method of high-temperature pyrolysis investigated is conceptu-
ally similar to those studied before. The difference lies in the manner
of feedstock and heat carrier mixing.
The flow sheet of the process is shown in Fig. 1. Main components
of the unit are: the combustion chamber, mixing device, and reactor
itself. The combustion products of stoichiometric fuel-oxygen mixture
diluted by superheated steam are used as the heat carrier. The feedstock
is injected into the heat-carrier stream by radial jets, mixes quickly and
then enters the reactor channel. At the outlet, the products quenches
quickly. The liquid feedstock is preliminary evaporated. Superheated
steam may also be added to the feedstock.
The realization of the proposed model strongly depends on the
feedstock/heat carrier mixing rate. The set of experiments [16] was
performed in order to develop effective mixing chambers; the charac-
teristics of radial jets mixing with the transverse flow were studied in
these experiments. The results (with inert flows) were then used to
choose the mixer geometry in the tests with liquefied petroleum
gases. This approach turned out to be successful. It permitted to
study the pyrolysis at the high initial mixture temperature [17]. We
used the similar method in the naphta pyrolysis device.
Fig. 1. Block flow diagram.
49
3. Experiment
3.1. Model device
Fig. 2 shows a setup in the configuration used in these tests. Oppo-
site to previous experiments [17], the unit of feedstock evaporation is
added. Main parts consist of the burner, combustion chamber, mixer,
and reactor. The reactor consists of two sections of 40 and 80 mm in
diameter, 1.15 m and 1.52 m in length, respectively. The combustion
chamber is water-cooled; the reactor walls are covered with a mullite
wool layer (10 mm). All device parts are made of stainless steel like
Steel 321. The mixer geometry was chosen in accordance with the
results of experiments [16] with inert flows. The quantity of injecting
nozzles remained the same as in the tests of [17] (n=8), their diameter
d was increased to 1mm in order to realize under these tests conditions
the optimum value of the jet penetration, corresponding the jets collision
in central area of mixer chamber. The mixer diameter D is 15 mm. In
general, the mixer geometry approximated to one version analyzed
in [17].
Prior to the start of the main experiments, the mixing quality was
monitored at the distance of L/D=1 from the injection cross section. In
these model tests nitrogen was used as injected gas and jet penetration
parameter corresponded to the main experiments conditions. The
area-averaged root-mean-square deviation of the injected gas concen-
tration from the average value not exceeded 4 – 5%.
The vaporizer unit is a cylindrical vessel, in which naphta was filled
up prior to the test; it also includes an electrical nitrogen heater and
evaporator wherein the naphta was sprayed in the hot nitrogen stream.
Naphta was driven out from the vessel by nitrogen from a bottle. The
heater presents a spiral stainless-steel tube. Its length is 4.5 m, outer
diameter 8mm, wall thickness 1mm. The tube is all around covered
with a thermal-insulation layer. The naphta-nitrogen hot mixture enters
the receiver connected with the reactor mixer by eight tubes. In order to
provide the uniform distribution of the mass flow rate between injecting
nozzles, a sonic orifice was installed in each line.
3.2. Measurement technique and experimental conditions
The hydrogen-air combustion products (with small hydrogen excess
over stoichiometry) were used as the heat-carrier. Hydrogen excess
was needed to prevent possible incomplete utilization of the air oxygen.
During the experiment, the flow rates of naphta, nitrogen, air, hydrogen
were measured as well as the pressure in the combustion chamber and
mixer receiver, cooling water flow rate and it heating in the cooling
contour, the temperature of the naphta-nitrogen mixture, and tempera-
ture distribution along the reactor axis. The temperature was detected
by K-type thermocouples (junction diameter of 0.7mm), regarding the
correction for emission. The gas samples were collected into 150 ml
syringes. The sampler is a copper tube of 6 mm in diameter, with a
stainless-steel capillary of 1 mm in diameter inside. The 90-degree
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50 M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54

Fig. 2. Experimental fast-mixing reactor.

angled capillary nose was entered into the tube mouth and flush-sealed
on the wall. The capillary intake was oriented toward the flow. The
sampler's tube passed through the reactor walls. Pyrolysis products
quenching occurred directly in the capillary cooled by the water flowing
in the tube.
Samples from each station were collected with two syringes, and the
mixture composition was analyzed with two gas chromatographs:
Crystallux-4000 M (TCD detector) and Agilent 6850 (FID detector).
Aside from hydrocarbons, the content of hydrogen, carbon oxide, and
nitrogen in the mixture was defined. Total amount of the detected
hydrocarbons reached 42.
Fig. 3 shows the typical temperature history of experiment to
illustrate the sequence of operation. First, nitrogen flow rate was
adjusted; then the electric heater was switched on, and walls of the
heater-evaporator-receiver system were heated. A dashed line in
Fig. 3 shows the temperature in the receiver. At the moment t=6 min,
the combustion chamber was initiated, the heating of the combustion
chamber, mixer, and reactor started. Solid lines in Fig. 3 mean the
indications of the thermocouples located on the reactor axis. At t=
18min (an arrow), the naphta supply started. Three minutes later the
sampling started, within the sampling process all operating parameters
were almost unchanged. Then the supply of hydrogen and naphta was
stopped, the current source was off, and for a certain period of time
the device was cooled by air and nitrogen.
The main parameters characterizing the operation conditions are
presented in the Table 1.
The following parameters characterize the feedstock used in the
experiments: density is 714.1 kg/m 3 (15 °С), initial boiling point is
35 °С, and final boiling point is 167 °С. 110 components were detected
in the naphta composition. Group composition is: normal hydrocarbons,
34.03%, aromatics, 4.83%, iso+cycles, 54.81%, fraction С1–С4, 6.13%,
olefins, 0.2%.
4. Pyrolysis modeling
The calculations were carried out on the one-dimensional model.
The point of calculation origin was located at the distance of L/D=1
from the point of jets injection. The flow in this cross section was con-
sidered as uniform, the process of feedstock/heat carrier mixing was
assumed to be so fast that the feedstock decomposition in the mixing

Table 1
Operation conditions.

Parameter Test No

1 2 3

Adiabatic temperature of combustion products (К) 2400 2400 2400

Temperature at mixer inlet (K) 1800 1750 1750
Temperature of naphta/nitrogen mixture (K) 505 500 560
a
Flow temperature after mixing (K) 1240 1320 1400
Pressure in combustion chamber (МPа) 0.156 0.152 0.152
Pressure in reactor (МPа) 0.1 0.1 0.1
Heat carrier/naphta ratiob 6.3 7.3 10.8
Mixing time (ms) ≈0.05 ≈0.05 ≈0.05
c
Residence time (ms) 36 34 33
a
Calculated on the assumption of inert mixing.
b
Heat-carrier composition involves injected nitrogen.
c
Fig. 3. Temperature temporal history in experiment. Calculated for the last sampling point.
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M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54 51

area can be neglected. Temperature distribution along the reactor axis

was assigned experimentally.
The temperature in the initial point was determined from the heat
balance equation for the mixed flow.
The package CHEMKIN-ll and a kinetic model including 764 reactions
with 197 particles were used. The kinetic model was combined from
three parts. The model of butane pyrolysis [18] approved before [17]
was used as a basis for the kinetics. Additive reactions included saturated
and unsaturated hydrocarbons with carbon atoms quantity up to 11 [19]
and cyclic hydrocarbons — cyclohexane, methylcyclohexane [20], etc. The
particles containing oxygen and respective reactions were excluded. In
order to simplify the scheme, paraffins with the atoms number of 7 and
above were joined in groups. For example, the group “nC7H16” contained
all normal and isomers of non-cyclic hydrocarbons with the carbon atoms
number 7. Non-aromatic cyclic hydrocarbons were divided into two
groups — the “cyclohexane” and the “methylcyclohexane” group. The “cy-
clohexane group” contained the cyclic hydrocarbons without associated
methyl, ethyle, and other admixtures, the “methylcyclohexane group”
included all the other cycles. Respectively, in the initial conditions the
mass concentrations of the particles in one group were summed.
The naphtha composition used in simulation is presented in
Table 2.

5. Experimental results and discussion

Three experiments were carried out; the air and hydrogen flow
rates were almost constant, and the temperature of the flow after
mixing, calculated on the assumption of inert feedstock/heat carrier
mixing (Тinert), varied due to the variation of naphta and nitrogen
flow rates. In every case, the naphta temperature before the injection
was higher than the final boiling temperature.
Figs. 4–6 show the varying temperature and principal pyrolysis
products along the reactor axis. Coordinate х=0 corresponds to the
distance of 15 mm from the injection cross section (L/D=1), where,
as was expected, the feedstock and heat carrier mixing should finish
for the greater part, and the reaction should begin. Fig. 4. Temperature and product yields vs. residence time and distance from reactor
Let us consider the results of the experiment 2 in detail. In this inlet at Tinert =1320 K.
test, the volume concentration of naphta in the heat-carrier composition
is 0.03. The remaining experimental parameters are presented in the 1320 К, calculated on the assumption of the inert mixing. In the further
Table 1. points, however (х=30 and 48mm), the temperature varies insignifi-
The upper horizontal axis shows the distance from reactor inlet cantly (1300 and 1335K, respectively) instead of the expected drop. It
corresponding to the residence time. The products mass fraction pres- begins to decrease only upon this point (1304 К at х=78mm, t=
ented in Fig. 5 is approximately 95% of the all pyrolysis products, and 0.33ms). Such a temperature behavior can result from the incomplete
total amount of the chromatographically detected substances exceeded mixing process within the distance L/D=1. The temperature on the
30. axis here evidently differs from the average value, and on a certain dis-
The data in Fig. 5 show the extremely high reaction rate at the initial tance L/D>1, the endothermic decomposition process passes in the
stage of naphta thermal decomposition. Measurements make possible
to analyze the process details. The first thermocouple was located at
15mm from the injection cross section (х=0), the first sampler was
within 24mm from this cross section (х=9 mm). The temperature in
the first point (1340 К) was close to the design temperature Тinert =

Table 2
Reduced naphtha composition.

Particle Mass fraction, %

Xylene 3.2
Isopentane 4.16
Decane 2.12
Cyclohexane 2.83
Methylcyclohexane 24.4
Hexane 8.76
Heptane 16.2
Octane 15.9
Nonane 8.25
Pentane 5.95
Isohexane 5.11
3-Methylpentane 3.12
Fig. 5. Temperature and product yields vs. residence time at Tinert =1240 K.
 Author's personal copy
52 M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54
Fig. 6. Temperature and product yields vs. residence time at Tinert =1400 K.
conditions of slightly varying temperature due to the heat supply to the
axis area from neighboring areas with the higher temperature. When
analyzing the dependence T(t), it can be concluded that the mixing
time tmix ≈0.05ms is some insufficient for the complete feedstock/
heat carrier mixing. Moreover, since the inert mixing condition in this
experiment (Т0 =1750 К, Тinert =1320 К) does not realize completely,
the reactions partially begin in the mixing region. In particular, this is
vindicated by the fact that in the first sampling point the ethylene con-
centration reaches 35%, whereas the propylene concentration is maxi-
mum (15%). As the value Тinert reduced to 1240 К (Fig. 4), the effect of
above factors weakens, and the ethylene concentration is 25% in the
first sampling point, but the maximum values in both cases differ
insignificantly.
As was already mentioned, the characteristic feature of the con-
centration profiles in Figs. 4–6 is the fast gain in the concentrations
at the initial stage of the process. Then, at t≥25 ms, the dependencies
Ci (t) smoothen. Almost permanent level of the concentrations within
great distances from the inlet is maintained by the relative low flow
temperature (Тb1100 K). Figs. 4–6 does not reflect any influence of
the secondary reactions which would result in the ethylene concen-
tration reduction.
Fig. 7 illustrates the temperature influence on the pyrolysis products
composition. The gas analysis data are presented in the points of maxi-
mum ethylene concentration. In various tests, these points correspond
to the residence time t=24–34ms. High ethylene yield has been found
in all experiments. As the temperature grows, the maximum ethylene
concentration in the pyrolysis products rises to 49.4% at Тinert =1400K.
Fig. 7. Effect of temperature on the product yields.
The propylene yield decreases along the reactor (as was mentioned
above, the maximum propylene yield is observed near the reactor
inlet). The butadiene yield also decreases with the temperature increase.
The low level of high-molecule compounds C5+ should also be noted. But
this is typical only for the late stage of naphta decomposition. In the early
stage, the content of fraction C5+ in the pyrolysis products is much
higher. More than 20 components of fraction C5+ with the total concen-
tration of 40, 10, and 5% were identified in the first sampling point at
Тinert =1240, 1320, and 1400 K, respectively. As the residence time
increases, fraction С5+ decreases significantly.
6. Calculation results
Simulation model testing is illustrated in Fig. 4–6, wherein the calcu-
lation results are compared with the measurements. Under the assump-
tions made, the comparison can be correct if the reactions in the mixing
zone do not take place. In our experiments, this assumption was satisfied
approximately. As is seen from Figs. 4–6, the calculation results describe
quite well the behavior of the concentration profiles of the major compo-
nents of the reacting mixture even near the reaction area beginning. For
the other components, their total concentration is 10–15%, the calcula-
tion results are in worse agreement with the experiment (Fig. 4b). A
number of factors influence the correctness of the used model: kinetic
scheme and kinetic constants chosen, hydrocarbon composition admit-
ted for the calculations.
Taking the sufficient accuracy of the used model into account, we
decided to determinate the influence of mentioned above temperature
non-uniformity at the reactor inlet (depended by mixing incompletion
and heat transport to reactor wall) on the pyrolysis process. For this we
performed simulation of naphtha pyrolysis in adiabatic reactor at as-
sumption of instantaneous feedstock/heat carrier mixing. The effects
of these factors on pyrolysis process can be established comparing the
results of that simulation with calculation using experimental profile
T(x), influenced by the mixing process and heat boundary layer. As be-
fore, the starting temperature was equal to Tinert The parameters of ex-
periment 2 were used as an example. Note that in the case of adiabatic
reactor with instantaneous mixing, no experimental information is
used, the simulation results describe directly the kinetic process with
the chosen model.
The comparison results are presented in Fig. 8. Here, the experi-
mental and simulated temperature profiles are shown, as well as
the simulated profiles of ethylene and propylene concentrations.
Under the experimental conditions, the temperature in the reaction
area, as was already mentioned, depends on both heat absorption
due to feedstock decomposition and the feedstock/heat carrier
mixing continuing behind the mixer, and heat transfer to the wall.
Fig. 8. Comparison of simulations for adiabatic (dashed lines) and experimental (solid
lines) reactors. Symbols — experimental results.
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M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54 53

The influence of endothermicity alone reflects the profile T(t) in the

adiabatic reactor, more sharp than it is in the experiment. Approxi-
mately in 5 ms, the simulated temperature approaches to the experi-
mental one, which further becomes lower than it is in the adiabatic
reactor. Such a situation results from the heat transfer through the re-
actor wall. Experimental values of the ethylene concentration in the
reaction area beginning exceed the corresponding values in the adia-
batic reactor, since the flow temperature in the experiment is higher,
and, outward from the inlet, the experiment is in good agreement
with both numerical calculations. As follows from Fig. 8, the simula-
tion at assumptions of instantaneous feedstock/heat carrier mixing
(ideal case) is in general in good agreement with the calculation
based on experimental profile T(t).

7. Influence of heat carrier composition on pyrolysis process

As will readily be observed from Figs. 1 and 2, the heat carrier com-
position in our model experiments is not consistent with the block flow
diagram. The combustion products of stoichiometric H2–air mixture
(namely, N2+H2O) are used for simplicity of the performance of the
experiments instead of CO2+H2O, according to Fig. 1. Since these
mixes differ in heat capacities, temperature history in the reactor and
concentration profiles must be different, too.
Effects of the heat carrier composition on the pyrolysis process have
been studied by numerical simulation. A reasonable good consistence
between calculations and experiments with the model heat carrier,
indicating on the sufficient accuracy of the kinetic model used, was
taken into account.
Parameters of test no. 2, used as a base for simulation of the naphtha
pyrolysis in the heat carrier, are the combustion products of the CH4/
O2-stoichiometric mixture diluted by superheated steam. Steam tem-
perature is 500K. Heat carrier temperature is 1800K. Nitrogen in injected
stream is replaced by the steam. Jet temperature (naphtha+steam) is Fig. 9. Effects of heat carrier composition on product (a) and temperature (b) distribu-
tions. Solid lines, simulation with actual heat carrier (CO2+H2O), dashed lines, simu-
500K. Pressure in reactor is 0.1MPa. Temperature at reactor inlet is
lation with model heat carrier (N2+H2O), symbols, experiment.
1340K. For these conditions, the ratio of heat carrier / naphtha is 7.1
(steam in jets was considered as the heat carrier, too). This value corre-
sponds to the experimental conditions. The reactor walls were assumed The theoretical model used for the analysis of naphtha pyrolysis,
to be heat- insulated. Naphtha/heat carrier mixing is considered to be agrees quite well with the experiment, taking the flow model simplicity
instantaneous. into account. Predicted ethylene yield for the case of practicable heat
The simulation results (temperature distribution and ethylene and carrier is close to the experimental value.
propylene yields versus residence time) are shown in Fig. 9 along
with similar ones for the adiabatic reactor with model heat carrier Nomenclature
(Fig. 8). The data of test no. 2 are plotted, too. x distance from the injection nozzles
As expected, the temperature level in the reaction zone is higher d injection nozzle diameter
in the case of actual heat carrier due to the higher heat capacity, but D mixer diameter
this distinction is comparatively inconsiderable in these conditions. In L mixing length
accordance to that, ethylene and propylene profiles are not far different t time
from each other. Hence, the calculation predicts only slight effects of tmix mixing time
distinction in actual composition of heat carrier from model (experi- T temperature
mental) one on the yields of more valuable pyrolysis products. Tinert inert mixing temperature

8. Conclusion
References
The detailed measurements of the composition of the naphta pyroly-
sis products in the model fast-mixing reactor demonstrated the possibil-
ity to realize the pyrolysis process in the heat-carrier with the
temperature much higher than it is in the conventional method. The
flow parameters at the reactor inlet are close to those in the case of in-
stantaneous feedstock/heat carrier mixing. Under the conditions of the
temperature drop downstream, the kinetic process provides the prod-
ucts composition featuring the high ethylene selectivity. In the tests per-
formed with model heat carrier composition, the ethylene yield reached
almost 50% per pass at the initial process temperature of 1320K. This
value is much higher than it is in conventional naphtha pyrolysis
method.
[1] T. Ren, M. Patel, K. Blok, Olefins from conventional and heavy feedstock: energy
use in steam cracking and alternative processes, Energy 31 (2006) 425–451.
[2] C.P. Bowen, Stone & Webster ethylene technology In: R.A. Meyers (Ed.), Handbook of
petrochemicals production processes, McGraw-ill, 2005, pp. 6.21–6.49.
[3] S. Borsos, S. Ronczy, KBR Score™ ethylene technology, In: R.A. Meyers (Ed.),
Handbook of Petrochemicals Production Processes, McGraw-ill, 2005, pp. 6.51–
6.63.
[4] H. Zimmermann, R. Walzle, Ethylene, http://media.wiley.com/product_data/excerpt/
55/35273038/3527303855.pdf.
[5] L.F. Albright, B.L. Crynes, W.H. Corcoran, Pyrolysis: Theory and Industrial Practice,
Academic, New York, 1983.
[6] T.N. Mukhina, N.L. Barabanov, S.B. Babash, V.A. Men'shikov, G.L. Avrekh, Pyrolysis
of Hydrocarbon Feedstock, Khimiya, Moscow, 1987. (in Russian).
[7] S.P. Chernykh, New processes of organic synthesis, Khimiya, Moscow, 1989. (in
Russian).
 Author's personal copy
54 M.G. Ktalkherman et al. / Fuel Processing Technology 106 (2013) 48–54
[8] G.R. Kamm, D. Milks, J.D. Kearns, H.I. Britt, C.R. Khavarian, US Patent 4 136 015,
1977.
[9] R.L. Baldwin, G.R. Kamm, Make ethylene by ACR process, Hydrocarbon Processing
61 (11) (1982) 127–130.
[10] Hertzberg, A. Mattick, D.A. Russel, US Patent 5 300 216, 1993.
[11] A.T. Mattick, C. Knowlen, D.A. Russel, A. Hertzberg, Pyrolysis of hydrocarbons
using a shock wave reactor, In: 21st International symposium of shock waves,
Great Keppel Island, Australia, 1997, paper 3800.
[12] VNIIOS, Catalytic pyrolysis of petroleum fractions to produce ethylene and propylene,
http://www.vniios.ru/english/1.htm 2003.
[13] M. Tallman, ACO™, The Advanced Catalytic Olefin processes, http://
technologyconference.kbr.com/2009/Dubai/conference.
[14] H.S. Glick Hertzberg, Studies of kinetics in a single-pulse shock tube In: A. Ferri (Ed.),
Fundamental data obtained from shock-ube experiments, Pergamon Press, 1961,
pp. 180–202.
[15] M.G. Ktalkherman, I.G. Namyatov, Pyrolysis of hydrocarbons in a heat-carrier
flow with fast mixing of the components, Combustion, Explosion & Shock
Waves 44 (2008) 529–534.
View publication stats
[16] M.G. Ktalkherman, V.A. Emel'kim, B.A. Pozdnyakov, Influence of the geometrical
and gas-dynamic parameters of a mixer on the mixing with of radial jets colliding,
Journal of Engineering Physics and Thermophysics 83 (2010) 539–548.
[17] M.G. Ktalkherman, I.G. Namyatov, V.A. Emel'kim, High-temperature pyrolysis of
liquefied petroleum gases in fast-mixing reactor, International Journal of Chemical
Reactor Engineering 9 (A69) (2011) 1–23.
[18] N.M. Marinov, W.J. Pitz, C.K. Westbrook, A.M. Vincitore, M.J. Castaldi, S.M. Senkan,
Aromatic and Polycyclic Aromatic Hydrocarbon Formation in a Laminar Premixed
n-Butane Flame, Combustion and Flame 114 (1998) 192–213.
[19] C.K. Westbrook, W.J. Pitz, O. Herbinet, H.J. Curran, E.J. Silke, A Detailed Chemical
Kinetic Reaction Mechanism for n-Alkane Hydrocarbons from n-Octane to
n-Hexadecane, Combustion and Flame 156 (2009) 181–199.
[20] W.J. Pitz, C.V. Naik, T.N. Mhaolduin, C.K. Westbrook, H.J. Curran, J.P. Orme, J.M.
Simmie, Modeling and experimental investigation of methylcyclohexane ignition
in a rapid compression machine, Proceedings of the Combustion Institute 31 (1)
(2007) 267–275.