chemical engineering research and design 9 0 ( 2 0 1 2 ) 19181922

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Physicochemical processes in a ow reactor using laser

radiation energy for heating reactants

V.N. Snytnikov a , T.I. Mischenko a , Vl.N. Snytnikov a , I.G. Chernykh b,

a Boreskov Institute of Catalysis SB RAS, Lavrentjeva ave. 5, Novosibirsk 630090, Russia
b Institute of Computational Mathematics and Mathematical Geophysics SB RAS, Lavrentjeva ave. 6, Novosibirsk 630090, Russia

a b s t r a c t

The use of argon as a buffer gas for isolating of the reaction zone from chemical reactor walls for ethane conversion
process was studied experimentally. Gas-phase conditions are ensured for realization of chemical processes in such
reactors. Reagents are heated by radiation from a continuous CO2 laser. The value of ethane conversion changes
upon variation in the ow rate of argon. Changing the laser generation wavelength in the range of 938972 cm1 was
shown to affect the degree of ethane conversion at close values of laser radiation power. It was found that ethane
can be used instead of argon to form the reaction zone.
2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Ethane pyrolysis; Ethylene production; Natural gas production; CFD modeling

1. Introduction to have the autocatalytic nature with respect to ethylene

It is well known that the pyrolysis of light hydrocarbons is a
gas-phase process. In actually hot walls of pyrolytic furnaces
tubes have an effect on chemical processes. As it is gener-
ally known, reactions of a radical initiation are facilitated on a
surface. At the same time hot surfaces stimulate a synthesis
of longer hydrocarbons including soot. A creation of homoge-
neous conditions is possible with using laser energy.
In our earlier work (Snytnikov et al., 2009) pyrolysis of
ethane to ethylene was performed in a ow reactor with
energy supplied by laser radiation, which is absorbed directly
by the gas. Formation of the reaction zone in the center of reac-
tor was demonstrated. A good agreement of experimental and
calculated data for gas ow mixing was obtained. The high-
temperature reaction zone in the reactor was insulated via
argon supercharging as a buffer gas at the sites of laser radia-
tion input. The other walls were insulated by a relatively cold
mixture of reactants. The transformation of laser energy into
thermal power occurred due to ethylene. Ethylene absorbed
laser radiation energy and heated the gas medium at colli-
sional relaxation. Under such mode of energetic catalysis, an
increase of energy absorption in the reaction volume is related
with increasing content of ethylene as the reaction prod-
uct. The mechanism of ethane dehydrogenation was shown
(Snytnikov et al., 2010, 2011). Three-dimensional calculation
of the gas-dynamic reactants ows and their mixing in reac-
tor with a specied geometry was made using the FLUENT
software package.
Nevertheless, some factors that may affect the ethane con-
version remained unexplored, among them are gas ow rates,
laser radiation wavelength, and replacement of argon by other
gas. To answer these questions, we constructed a ow reactor.
Its geometry implies mainly a rectilinear ow of reactants with
the possibility to form a compact reaction zone. The work was
aimed at studying the operation of the ow laser reactor in
different modes of physicochemical parameters affecting the
degree of ethane conversion in a mixture with ethylene under
the gas-phase conditions.
2. Experimental
2.1. A reactor with laser input of energy for ethane
pyrolysis
A scheme of experimental setup for studying the pyrolysis of
light hydrocarbons is presented in Snytnikov et al. (2009). The
setup includes a continuous CO2 laser, a gas ow former, an
infrared Fourier spectrometer Infralum FT-801 for control of

Corresponding author. Tel.: +7 383 3309665; fax: +7 383 3308783.
E-mail addresses: snyt@catalysis.ru (V.N. Snytnikov), chernykh@ssd.sscc.ru (I.G. Chernykh).
Received 7 April 2011; Received in revised form 3 February 2012; Accepted 1 March 2012
0263-8762/$ see front matter 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2012.03.001
 chemical engineering research and design 9 0 ( 2 0 1 2 ) 19181922
Fig. 1 Scheme of a ow reactor for studying the
transformations of light parafn hydrocarbons to alkenes
with a source of CO2 laser radiation. (1) Inlet for
ethaneethylene mixture. (2) Inlet for the gas not absorbing
CO2 radiation. (3) Transmission optics made of ZnSe. (4)
Aluminum mirror with 98% reectance. (5) Channel B. (6)
Inlet for syringe sampling for chromatographic analysis. (7)
Outlet for the reaction products. (8) Channel A. (9) Radiation
of continuous-wave CO2 laser.
the laser radiation spectrum, and gas chromatographs. In the
present work, we constructed a ow reactor as a cruciform
chamber made of quartz glass (Fig. 1). The reactor has gas feed-
ing elements and optical windows for laser radiation input.
The reactor design provides mutually perpendicular input of
hydrocarbons ow and laser radiation. Inlet (1) is used to feed
the ethaneethylene mixture passing via the main channel A
(8), which is 16 mm in diameter and 120 mm in length. Then
the mixture goes to exhaust pipe or is evacuated by a back-
ing pump (7). CO2 laser radiation is supplied to channel B (5),
which is 18 mm in diameter and 90 mm in length. Diameter of
a laser beam at the reactor inlet is 12 mm. One face of channel
B has a hermetically sealed ZnSe window (3), while the other
face has an Al window with ca. 98% reectance (4). Near the
optical windows in channel B, there are four pairwise inlets
(2) for a gas that does not absorb CO2 radiation. A ow of this
gas shields the optical windows and prevents the occurrence
of chemical reactions in the channel. Reactions were carried
out at atmospheric pressure.
2.2. The mathematical model
The mixing of gas ows in the 3D reactor geometry was cal-
culated with the FLUENT software package by solving a set
of NavierStokes equations, which includes the conservation
equations for mass, energy and momentum. The equations
are presented in Snytnikov et al. (2009). Chemical reactions
didnt take into account at this point of mathematical model.
A convection-diffusive transfer of substances has an effect
on gases distribution in the reactor volume at warming-up
or standard (room temperature) condition of gas ows. The
1919
Fig. 2 IR spectrum of ethylene and laser generation
frequencies in the experiments.
ideal gas approach has been used for gas ow modeling. Also
transfer of radiation energy was taken into account:
(I (r, s)s) + ( + s )I (r, s)
 4
s
=  n2 Ib + I (r, s )(s, s )d (1)
4 0
where  is the wavelength,  is the spectral absorptivity,
and Ib is the intensity of black-body radiation specied by
the Planks function. In the calculations, dispersion coefcient
 s , function of phase dispersion , and index of refraction n
were wavelength independent. Mass ow rates of gases at the
inlets were specied as boundary conditions, with the initial
pressure in the reactor taken equal to 1 atm. The mathemati-
cal model is described more thoroughly in Schmalfeld (1963),
Batchelor (1967).
3. Results of experiments and calculation
3.1. Absorption of radiation in the working mixture
and the range of CO2 laser generation
The spectrum of ethylene absorption near the main maxi-
mum (http://www.nist.gov) and the recorded frequencies of
lasing lines transitions are presented in Fig. 2. The spectrum
of CO2 laser was measured simultaneously with the process
of ethane pyrolysis. We recorded the lines that corresponded
to the wings of ethylene absorption band near the frequen-
cies 938 and 972 cm1 , and in the range of 948950 cm1 .
In the latter case, they corresponded to a maximum in the
ethylene absorption spectrum. At 938 cm1 and 942 cm1 tran-
sitions, laser generated a single frequency. Absorptivity of
ethylene (Snytnikov et al., 2010) in the reactor was equal to
3.6 103 cm1 Torr1 (or 1019 cm2 at T 300 K). We
measured this value at 20 W in ethylene and its mixtures
with methane at the gas pressure p 10/760 Torr. The obtained
value agrees with the known spectral characteristics of ethyl-
ene.
3.2. Gas ows formation; measurement and
calculation
In the numerical model, geometrical dimensions of the reac-
tor corresponded to those of the pilot sample. For calculation
1920 chemical engineering research and design 9 0 ( 2 0 1 2 ) 19181922

Fig. 3 The calculated distribution of ethylene mass fractions in the argonethaneethylene mixture (left image with
radiation taken into account; right image without regard to radiation). Channel A: the total ethaneethylene ow rate 1 L/h,
C2 H6 68 vol.%, C2 H4 32 vol.%. Channel B: argon 2.5 L/h, its fraction in the total ow is 72 vol.%. Laser radiation power
40 W.

we used the laminar ow model with diffusion taken into
account. Energy transfer was calculated using the Discrete
Ordinates model embedded in FLUENT, which is recom-
mended by the package developers for a broad spectrum of
problems including heating of a gas. The gas mixture absorp-
tivity for laser radiation with the wavelength 10.6 m was
set by the custom function depending on ethylene concen-
tration. The mixing of gas ows of ethaneethylene mixture
with 1 L/h ow rate and argon with 2.5 L/h was calculated for
heating by laser radiation with 40 W power. Relation between
C2 H6 and C2 H4 concentrations in base gas mixture was widely
changed in experiments and numerical modeling. The results
of numerical modeling with 68 vol.% of C2 H6 and 32 vol.% of
C2 H4 is presented in this article. These concentrations give
a necessary ethylene concentration in reaction zone for high
ethane conversion conditions. Fig. 3 shows the distribution of
mass fractions of ethylene in the reactor volume upon mixing
of cold gas ows (on the right) and upon heating by laser radia-
tion with the reactor wall temperature set at 400 K (on the left).
The gas-dynamic calculation of gas ow mixing for the heating
mode showed that at the cross-point of reactor, i.e. in its cen-
tral part, the fraction of ethylene ranged from 10 to 25 vol.%.
This value decreased to 2 vol.% at 7-10 mm from the center in
both directions over channel B. The distribution of ethylene in
the reactor volume for the room temperature gas ows gave
the fraction of ethylene near the optical windows lower than
5 vol.%. Experiments in a static reactor with homogeneous
composition of initial gas mixture over the entire volume
revealed a limit of 6% for ethylene content in the reaction mix-
ture before pyrolysis (Snytnikov et al., 2010). At lower ethylene
contents, heating of gases to the temperatures of pyrolysis did
not occur. The region where ethylene concentration exceeds
this value was taken as the reaction zone. Numerical estima-
tions of temperature eld distribution displayed that heating
of a reaction zone was in the range 10001700 K, gradually
growing up from a periphery to a central part. A cross size
of the reaction zone (along channel B) does not exceed 25 mm.
Ethane pyrolysis is a highly endothermic process. It is possible
to decrease the temperature of reaction zone with inclusion
of chemical reactions. However chemical reactions did not
take into account at this stage of modeling. Therefore the
reaction zone temperature was dependent on ethylene con-
centration in a gas mixture and from the heat loss through
reactor walls.
 chemical engineering research and design 9 0 ( 2 0 1 2 ) 19181922
Table 1 Conversion of C2 H6 and yield of main products of ethane pyrolysis versus the absorbed power with argon used
as a buffer gas. Channel A: the total ethaneethylene ow rate 1 L/h, C2 H6 68 vol.%, C2 H4 32 vol.%. Channel B: argon
2.5 L/h, its fraction in the total ow is 72 vol.%.
Absorbed power, W C2 H6 conversion, % YCH4 , %
32 2.4 0.13
33 10.1 0.35
40 51.2 4.78
46.4 66.9 12
56 75.2 17.63
3.3. Pyrolysis of ethane at atmospheric pressure and
temperatures below 1000 C
Fig. 4 shows the ethane conversion at pyrolysis of initial
C2 H6 C2 H4 mixture with ethylene content 32 vol.% versus the
absorbed power. Flow rates of argon, ethane and ethylene
corresponded to the values used for numerical calculation.
Ethane conversion continuously increased to 73% in the range
of absorbed power 3258 W. C2 H4 , CH4 and H2 were the main
products of pyrolysis, C3 H6 and C2 H2 also being detected.
Table 1 shows the weight yields of methane, ethane, ethylene,
acetylene, propylene and hydrogen related to the absorbed
power of laser radiation. The yield of C2 H4 increased from
31.9% to 56%. For methane, the yield ranged from 0.13% to
17.6%. For acetylene and propylene, the yield did not exceed
2.2% and 1%, respectively. The dependence of ethane con-
version on the argon ow rate at 40 W power is presented
in Fig. 5. The argon ow rate decreased from 5.6 to 2.7 L/h
at the ethaneethylene ow rate of 1 L/h. Ethane conversion
increased from 46% to 63% and then decreased to 42%, its
Fig. 4 Ethane conversion versus the absorbed power.
Channel A: the total ethaneethylene ow rate 1 L/h, C2 H6
68 vol.%, C2 H4 32 vol.%. Channel B: argon 2.5 L/h, its
fraction in the total ow is 72 vol.%.
Fig. 5 Ethane conversion versus argon amount in the total
ow. Ethaneethylene mixture ow rate 1 L/h, C2 H6
68 vol.%, C2 H4 32 vol.%. Absorbed power 40 W.
1921
YC2 H4 , % YC2 H6 , % YC2 H2 , % YC3 H6 , % YH2 , %
31.87 67.95 0.05
36.03 63.17 0.01 0.44
55.77 35.58 0.81 0.49 2.57
56.22 25.84 1.32 0.73 3.88
55.33 19.88 2.14 0.68 4.35
maximum corresponding to the argon ow rate of 3.6 L/h.
Ethane does not absorb the radiation of CO2 laser and can
be used for the formation of reaction zone. Ethane ow rate
over channel B was 2.5 L/h; 0.5 L/h of ethylene in a mixture
with 1 L/h of C2 H6 was fed to the inlet of channel A during
the experiment. Ethane conversion increased from 1% to 29%,
Fig. 6. Table 2 shows changes for ethane conversion and weight
yields of reaction products with the increment of the laser
radiation power at the reactor inlet from 53 to 72 W. The weight
yield of ethylene increased from 14.3% to 30.4%. The effect of
laser frequency on ethane conversion and products yield are
presented in Table 3. As the lasing line goes from 938 cm1
to ca. 950 cm1 at a constant power 40 W, ethane conversion
increases from 60% to 81%. The yield of ethylene decreases
from 59.4% to 56%. The yield of methane increases from 8% to
18%. The yield of acetylene increases from 1.8% to 5.4%.
4. Discussion
No provision was made in the reactor for thermal insulation
of the walls, so heat losses through the walls attained 50%
(Snytnikov et al., 2010). The numerical modeling revealed that
content of C2 hydrocarbons near the optical windows was
minor upon heating the reaction mixture by laser radiation.
The absence of C2 H4 and the room-temperature ow of buffer
gas maintained the working temperatures of the optical win-
dows and prevented their destruction. Temperature of the
outer surface of the chamber measured in the experiments
did not exceed 380 K. Such temperature excludes the occur-
rence of chemical reactions in the near-wall region. According
to the calculation, a region with 47 vol.% content of hydrocar-
bons formed in the central part of reactor, the initial content
of ethylene being 1020%. Such value of C2 H4 content provides
heating of reactants up to 1000 C and higher under the action
of laser radiation. The use of argon as a buffer gas allowed
us to obtain data on the location of reaction region in the
Fig. 6 Ethane conversion versus power at the reactor inlet.
Channel A: C2 H6 1 L/h, C2 H4 0.5 L/h; channel B: C2 H6
2.5 L/h.
1922 chemical engineering research and design 9 0 ( 2 0 1 2 ) 19181922

Table 2 Conversion of C2 H6 and yield of main products of ethane pyrolysis versus laser radiation power at the reactor
inlet with ethane used as a buffer gas. Channel A: C2 H6 1 L/h, C2 H4 0.5 L/h. Channel B: C2 H6 2.5 L/h.
Power of laser C2 H6 conversion, % YCH4 , % YC2 H4 , % YC2 H6 , % YC2 H2 , % YC3 H6 , % YC4 H10 , % YH2 , %
radiation at
the reactor
inlet, W

56.3 1.3 0.02 14.31 85.61 0.05 0.01

66 7.7 0.12 18.6 81.04 0.06 0.11 0.61
69.5 12.9 0.63 21.57 76.67 0.01 0.13 0.11 0.89
73.5 24.1 1.97 28.34 67.4 0.21 0.37 0.15 1.55
77.5 28.4 2.7 30.41 64.13 0.28 0.46 0.19 1.83

Table 3 Conversion of C2 H6 and yield of main products of ethane pyrolysis versus changes in the laser generation
region. Channel A: the total ethaneethylene ow rate 1 L/h, C2 H6 68 vol.%, C2 H4 32 vol.%. Channel B: argon - 2.5 L/h,
its fraction in the total ow is 72 vol.%. Absorbed power 40 W.
Wavelength, cm1 C2 H6 conversion, % YCH4 , % YC2 H4 , % YC2 H6 , % YC2 H2 , % YC3 H6 , % YH2 , %

938 61.7 7.99 59.35 27.76 1.8 0.43 2.68

950 80.9 17.54 55.96 15.35 5.44 0.5 5.21

reactor volume. An increased consumption of the buffer gas
(5.6 L/h) compressed the mixture of hydrocarbons, thus dimin-
ishing the residence time of reactants in the reaction zone and
characteristic length of radiation absorption. This decreased
the ethane conversion. As argon ow decreased to 2.7 L/h,
the reaction zone extended over channel B with preferential
absorption of radiation in the gas layers most close to the site
of radiation input. Breakthrough of a part of ethaneethylene
mixture outside the laser beam zone affects the degree of
ethane conversion.
Computational modeling and experiments with Ar as the
buffer gas gives us the possibility of the reaction zone forma-
tion at the central part of the reactor. Also the use of Ar allows
visual determination of dynamics of initial gas mixture ows
and their mixing.
The replacement of argon by ethane provided the ethane
conversion of 29%. This corresponds to conversion of 1 L/h
C2 H6 at the total ethane ow rate of 3.5 L/h over channels A
and B. In the experiments with argon, 0.68 L/h of ethane was
fed over channel A with maximum conversion 73%. 0.5 L/h of
ethane was reacted. Using of argon and ethane as buffer gas
was shown a differences there inuence to ethane pyrolysis.
Inert argon stimulates a concentration decreasing of radicals
in reactions of their termination. The dilution of the reac-
tion mixture with argon reduces the radicals concentration,
it decreases the rate of chain termination reactions. Using of
ethane instead of argon allows radicals generation from the
volume of buffer gas, involving ethane in pyrolysis reactions.
Lasing in the region located at the wings of main peak in the
absorption spectrum of ethylene created conditions for heat-
ing the gas components to the temperatures providing high
conversion of ethane. However, transition to the lasing line
close to the maximum absorption of ethylene at 950 cm1
sharply increased ethane conversion at the same power of
laser radiation, ow rates and composition of initial gas ows.
5. Conclusions
Synthesis of ethylene by ethane pyrolysis was carried out in
a ow reactor with laser input of energy. Three-dimensional
modeling of gas ows and their mixing upon heating the
reaction mixture by laser radiation energy was made with
the FLUENT program package. The calculation revealed the
possibility of forming the reaction zone in the center of reactor.
It was found that a relatively cold gas mixture can insulate the
reaction zone from reactor walls. The fraction of argon in the
total gas ow was shown to affect the degree of ethane con-
version, which is related with the formation of reaction zone
and with the residence time of hydrocarbons in this zone. We
demonstrated that ethane can be used instead of argon, with
C2 H6 being involved in the chemical process. Ethane conver-
sion was found to depend on the lasing line transition in the
range of 938972 cm1 . Ethane conversion increases by 25%,
other parameters being equal, which indicates a considerable
effect of laser generation range on the level of absorbed power.
Ethylene was shown as an efcient converter of laser energy
to heat power for ethane pyrolysis.
Acknowledgements
This work was partially supported by the Federal Program
Scientic and scientic-pedagogical cadres innovation Rus-
sia for 20092013 of the Federal Agency for Science and
Innovation, Federal Program Research and development in
priority directions of scientic-technological complex of Rus-
sia in 20072013, Russian Federation President Grant for the
Leading Scientic Schools for funding (NSh524.2012.3), SB RAS
interdisciplinary integration project No. 130.
References
Batchelor, G.K., 1967. An Introduction to Fluid Dynamics.
Cambridge Univ. Press, Cambridge, England.
FLUENT. http://www.uent.com.
Snytnikov, V.N., Mischenko, T.I., Snytnikov, Vl.N., Chernykh, I.G.,
2009. A reactor for the study of homogeneous processes using
laser radiation energy. Chem. Eng. J. 150, 231236.
Snytnikov, V.N., Mischenko, T.I., Snytnikov, Vl.N., Stoyanovskaya,
O.P., Parmon, V.N., 2010. Autocatalytic gas-phase ethane
dehydrogenation in a wall-less reactor. Kinet. Catal. 51 (1),
1017.
Snytnikov, V.N., Mischenko, T.I., Snytnikov, Vl.N., Malykhin, S.E.,
Avdeev, V.I., Parmon, V.N., 2011. Autocatalytic gas-phase
dehydrogenation of ethane. Res. Chem. Intermediates,
http://dx.doi.org/10.1007/s11164-011-0449-x.
Schmalfeld, P., 1963. Hydroc. Proc. 42 (7), 145148.