Applied Thermal Engineering 125 (2017) 20–28

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Applied Thermal Engineering

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

Research Paper

Development of a non-equilibrium turbulent reaction model of HFC-

134a in a tubular reactor
Misoo Shin a, Dongsoon Jang a,⇑, Jongwook Ha b, S. Acharya c
a
Department of Environmental Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, South Korea
b
Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yusunggu, Daejeon 305-600, South Korea
c
Department of Mechanical Engineering, Louisiana State University, Baton Rouge, LA 70803, USA

h i g h l i g h t s

A hybrid-type EBU model is developed for HFC-134a incineration.

Experiment and numerical prediction data are well compared each other.

The hybrid EBU model shows big difference with the conventional model.

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

Article history: Detailed review and discussions are made for the modeling and non-equilibrium effect in the incineration
Received 18 October 2016 process of various halogenated hydrocarbons using a couple of modified versions of eddy breakup (EBU)
Revised 23 May 2017 model developed from the original EBU model by Magnussen and Hjertager. Further experimental and
Accepted 20 June 2017
numerical studies are made for the development of a hybrid-type EBU model in order to evaluate the
Available online 22 June 2017
non-equilibrium effect of HFC-134a reaction in a tubular reactor. For the numerical calculation using
the hybrid-type EBU model, especially, the relative rate of the turbulent mixing and chemical reaction
Keywords:
should be incorporated in a harmonic mean expression. Thus the overall reaction rate expression of
Halogen compound incineration
HFC-134a
HFC-134a reaction is determined by the fitting the empirical constants with experimental data obtained
Non-equilibrium turbulent reaction model in the tubular reactor via trial and error method. Thereby, the empirical constants in the equation of the
Arrehenius type reaction rate, that is, x
E
Hybrid-type eddy breakup model _ ¼ kC C2 H2 F4 C H2 O C O2 ¼ AT B eRTa C C2 H2 F4 C H2 O C O2 was determined,
where A = 1.0, B = 0.38, Ea = 8.8  107 J/kmol, respectively. Employing this non-equilibrium model, the
calculated overall destruction rate of HFC-134a was in good agreement with the experimental data
obtained for the same reactor. Further, the comparison of HFC-134a concentration profiles between
the fast chemistry and non-equilibrium EBU models show a significant difference even if the calculated
destruction rates of HFC-134a appear similar at the exit. In near future, numerical calculation will be
made for the practical incinerator of HFC-134a in a practical incinerator using the model developed in
this study.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
These days, reclaim and recovery services of used refrigerants
such as HFCs are one of major concern in order to minimize the
environmental impact of waste refrigerants especially in the aspect
of the release of the material of high global warming potential.
However, a significant part of recovered refrigerants have to be
destroyed inevitably in a practical incinerator in an environmen-
tally friendly manner when their compositions or purity are
inferior than specified condition for reclamation [1]. As a matter
⇑ Corresponding author.
E-mail address: p_dsjang@cnu.ac.kr (D. Jang).
of fact, the incineration has been known over several decades as
a preferred method for hazardous waste disposal compared to
other conventional methods because of its potential for immediate
detoxification and the potential for energy recovery. A proper
incineration method for the waste HFCs (hydroflurocarbons) has
become a viable method not only for the reduction of the release
of the greenhouse gases but also for the recovery of the valuable
material such as CaF2 (calcium fluoride) [2]. However, it is gener-
ally known the practical incineration process of most refrigerants
containing halogen species such as F and Cl could not be properly
modeled by typical fast chemistry turbulent reaction model due to
not only its flame inhibition effect but also the low heating value of
halogen containing species. Thus a proper non-equilibrium

http://dx.doi.org/10.1016/j.applthermaleng.2017.06.105
1359-4311/Ó 2017 Elsevier Ltd. All rights reserved.
 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28
turbulent reaction model is quite required for a practical incinera-
tor to develop a reliable predictive model in order to obtain proper
design and operational conditions for the practical HFCs incinera-
tion in turbulent reacting flows. To this end, in this study detailed
review and discussions are made first for the modeling and non-
equilibrium effect in the incineration process of various halo-
genated hydrocarbons. And a numerical and experimental study
has been made in a tubular reactor for the development of proper
non-equilibrium turbulent reaction model of HFC-134a.
2. Review of halogenated compound incineration and
numerical modeling
Research on the combustion of various halogenated hydrocar-
bons has been done mainly in incineration area of hazardous
waste, for chlorinated hydrocarbons, generated from chemical
industries since 1970. Since incineration is known as a preferred
tool for hazardous waste disposal compared to other conventional
methods, this technology is also certified by United Nations Frame-
work Convention on Climate Change (UNFCC) for the thermal
destruction of halogenated hydrocarbons. However, as well known,
only general guideline is given to accomplish 99.99% thermal
destruction efficiency (DRE), based on the empiricism, suggesting
that it requires flame temperature higher than 1200 °C and the res-
idence time more than 2 s [3]. Since halogenated hydrocarbons not
only serve as fire extinguishing agents, but also some of those can-
not produce self-sustaining flame. One of the typical ways for
proper incineration, therefore, is to co-burning of this compound
with auxiliary fuels of containing many hydrogen atoms such as
CH4 and H2. Halogenated hydrocarbons with the aid of this kind
of fuel can be effectively decomposed by the reaction with hydro-
gen and oxygen; hydrogen combines with halogen to form HCl or
HF. In this process, it is noted that the halogen atom originated
from halogenated hydrocarbon plays not only the role of oxidizer
but also inhibition action through the combination of the hydrogen
containing in auxiliary fuel. In this process, the conventional strat-
egy of introducing excess air to ensure complete combustion of the
waste stream in practical incinerators is not quite desirable to the
incineration of CHCs (Chlorinated Hydrocarbons) because of the
following Deacon reaction [4].
1
2HCl þ O2 ! Cl2 þ H2 O ð1Þ
2 and then fuel molecule will react with oxygen molecule for chem-
Excess oxygen can lead to pure chlorine gas, Cl2, which is more
toxic and difficult to scrub out of stack gases than HCl [5]. This
reaction together with the inhibition effect makes incineration of
CHCs difficult to accomplish the goal of DRE 99.99%. Similar argu-
ment can be applied to the HFCs refrigerants containing fluorine.
In general, the fundamental studies have shown that the incin-
eration process of halogenated hydrocarbons is usually inhibited
by the reaction of halogen molecule (X2) with hydrogen H
especially in preheating region since the activation energy of inhi-
bition reaction is much lower than that of the chain branching
reaction [6].
Garner et al. [7] and Valeiras [8] showed that the order of effec-
tiveness of in inhibition for chloromethane by decreasing flame
velocity is CCl4, CHCl3, CH2Cl2 and CH3Cl with the increase of the
chlorine molecule. The flame velocities of the mixture are, of
course, lower than methane and decrease with the increase of
the molar fraction of chlorine compound to the auxiliary fuel (R),
for example R = mole of CHCs/mole of CH4 as in Eq. (2).
CH4 þ RCCl4 þ 2O2 þ 7:25N2 ! ð1 þ RÞCO2 þ 2ð1  RÞH2 O
þ 4RHCl þ 7:25N2 ð2Þ
21
Further as the chlorine content increases by R or by the change
compound, the flammability range decreases and the maximum
flame velocity shifts from fuel rich to fuel lean condition [9]. The
net effect of the halogen inhibition on flame is to increase the
length of the preheat zone over that of the uninhibited flame but
the higher temperature in the reaction zone increases exponen-
tially the chain branching reaction rate enough to overcome the
rates of the inhibition reaction [7]. Further, iodine and bromine
compounds are found to be more strong inhibitors than chlorine
and fluorine compounds [6]. Even if HFCs have been developed
as essential substitute for the ozone depleting refrigerants or
sprays such as CFCs and HCFCs containing chlorine compounds,
some of the alternative HFCs show unexpectedly high flammabil-
ity. Therefore, in order to ensure fire safety application of these
substances, there has been a lot of fundamental combustion study
about fluorinated hydrocarbons [8–14]. A detailed reviews about
this have been made elsewhere [15]. A series of detailed chemistry
data of HFC-134a appear only in the research area of degradation
pathways into trifluoroacetic acid (TFA) in the atmosphere instead
of combustion field like waste incineration. In detail, the OH radical
is expected to be the most important oxidation of HFCs degrada-
tion in daytime troposphere. Extensive experimental studies have
been taken on the kinetics of the hydrogen abstraction of HFC-
134a by hydroxyl radical since this reaction plays an important
role in the gas-phase reaction of HFC-134a in the atmosphere
[16]. The rate constants determined are presented but unfortu-
nately the temperature ranges are below than 500 K, which is far
below the flame temperature.
Along with the fundamental combustion study, even though a
lot of research efforts [17–19] have been made about thermal
destruction of halogenated compound both in large scale incinera-
tors and also model developments have been made to predict the
performance of incineration processes, these studies do not pro-
vide a predictive tool for resolution of the detailed distributions
of the turbulent flow field. Even though Yang et al. [20] made a
detailed numerical calculation for a practical rotary kiln incinera-
tor, they did not include any halogenated compounds as principal
organic hazardous constituents. In general, there are two funda-
mental steps for the process of turbulent combustion; the first step
is turbulent mixing between fuel and air, and the next chemical
reaction by the molecular collision between fuel and oxidizer. In
order to make complete combustion successfully, therefore, it is
necessary to mix efficiently fuel with air by eddy breakup action
ical reaction. The overall reaction rate occurring in a series of com-
petitive process can be typically expressed empirically in a
harmonic form such as
1
Ov erall reaction rate  ð3Þ
1
turbulent mixing rate
þ chemistry
1
rate
The basic problem of the gaseous turbulent combustion lies in
the proper modeling of the well-known turbulent correlation term,
which arises in the non-linear chemical reaction source term like
Reynolds stress in momentum equation. Most turbulent combus-
tion models, however, detour the difficulty by ignoring the chem-
ical kinetic aspects of the problem as shown in the harmonic mean
expression of overall reaction rate in Eq. (3). In detail, the chem-
istry rate is fast and thereby very large compared to turbulent mix-
ing rate. Therefore the term can be neglected. Using the
assumption of fast chemistry, the turbulent mixing will be gov-
erned only by the limit of the mixing rate in Eq. (3). Although mix-
ing limited turbulence only models have been shown to be
successful tools in predicting the overall profiles of main species,
serious drawback exist, since the conventional fast chemistry tur-
bulent reaction models such as the conserved scalar method of Bil-
22 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28
ger [21], the eddy breakup models of Spalding [22] and Magnussen
and Hjertager [23] do not describe the non-equilibrium character-
istics of halogen compounds. Since the effect of inhibitive chem-
istry reaction is as important as that of turbulent mixing an
appropriate turbulent combustion model had to be used, where
chemical kinetics as well as turbulence mixing plays an important
role. In the past, considerable progress has been made in the mod-
eling of chemical kinetic processes in turbulent flows for various
areas such as flame extinction in strong shear flows, NOx genera-
tion in pollutant formation and chlorination process in chemical
reactor [24–28]. However, general non-equilibrium turbulent reac-
tion model is not yet available especially for the halogenated incin-
eration processes. For the numerical modeling efforts of CHCs, CCl4
destruction has been done mainly since CCl4 was one of the major
hazardous waste to be incinerated. Therefore a number of investi-
gators have focused on the modeling of the turbulent reaction in a
premixed CCl4-CH4-air flame. As emphasized above, the reaction
rate of this mixture is believed to be determined not only by turbu-
lence mixing but also by chemical kinetics. This is particularly, true
since CCl4 is incapable of a self-sustaining flame due to inhibition
feature as well as the low enthalpy of combustion. In order to
resolve the non-equilibrium effects in CCl4-CH4-air flames, detailed
chemical kinetic data is required. And a number of research efforts
have been directed on this end [17], but there was no well-
established chemical kinetic data available. Thus an empirical
modeling approach was suggested in the CCl4 incineration process.
The first reduced reaction model for CCl4 destruction [29] is pre-
sented briefly in the following for the discussion of the modified
version of EBU model. The reaction rate of CH4 (RRCH4 ) in a CCl4-
CH4-air mixture is given by the phenomenological eddy breakup
model proposed by Magnussen and Hjertager [23], i.e.


 
m  pr  
m
RRCH4 ¼ minimum of  q  fu =k; q
 Am  A0 OX ð=kÞ; qA0  
s ð1 þ sÞ k 
ð4Þ
where s is the stoichiometric oxidizer mass per unit mass of fuel
and A0 and A are empirical constants given by Lockwood et al.
[30]. The basic idea of this model is based on premise that only
the reaction of CH4 in a CCl4-CH4-air mixture is governed by the fast
chemistry concept and the destruction of CCl4 can be described by
the stoichiometric reaction Eq. (2) according to the destruction of
CH4. It is generally expected that the CH4 reaction rate given by
Eq. (4) will be smaller compared to that in a pure CH4-air-
mixture, (i.e. R = 0.0) because of the decreased mass fractions due
the presence of CCl4 and HCl compound. In order to account for
the CH4 reaction rate in CCl4-CH4-air mixture, the following expres-
sions arc used for the mass fractions appearing in Eq. (4)
mfu ¼ mCH4 ; mOX ¼ mO2 and mpr ¼ mCO2 þ mH2 O þ mHCl ð5Þ
Once the CH4 reaction rate is obtained, the CCl4 destruction rate,
RRCCl4 , can be determined by the following stoichiometric reaction
expression in Eq. (2). Thus, RRCCl4 is given by:
M CCl4
RRCCl4 ¼ RRCH4  R  ð6Þ
MCH4
where M denotes the molecular weight. Further, s can be expressed
as
2MO2
s¼ ð7Þ
M CH4
In Eq. (2), as the R value increases the species mass fraction mCH4
and mO2 decreases, which results in a reduced reaction rate and
finally the reaction will be quenched for large R values. However,
the chemical kinetic aspects have not been directly considered in
this turbulent reaction model. Shin et al. [31] employs a similar
eddy breakup model for the reaction of the mixture of CH4-CCl4.
But they consider the mixture of CH4-CH3Cl behaves together as fast
chemistry reaction, while Jang and Acharya [29] assume that only
CH4 reaction is governed by fast chemistry. The reason why Shin
et al. employ the fast chemistry model for the total mixture of
CH4-CCl4 was in that the small amount of CCl4 would not play ant
significant inhibition action most over strong turbulent reaction
region. This model is reasonable only for the case of the small
amount of CCl4 presence. Further, Jang and Acharya [32] propose
a non-equilibrium turbulent reaction model using burning velocity
data given by Valeiras [8] for CH4-CCl4-air mixture e in 2-D hypo-
thetical kiln. That is, a modified fast chemistry turbulent reaction
model was developed to describe the flame inhibition due to the
presence of CCl4, considering the corresponding burning velocity
data of these mixtures. This modified EBU model was employed
with reasonably good prediction for numerical calculation of prac-
tical incinerators for a rotary kiln and dump combustor [33–35].
The experimental burning velocity data of premixed CCl4-CH4-air
mixture as a function of R and equivalence ratio in a laboratory Bun-
sen flame study [6] is utilized to obtain a more realistic reaction rate
expression. In the aspect to review the modified eddy breakup
model for non-equilibrium turbulent combustion of halogenated
hydrocarbons, let us briefly summarize this model. Based on the
thermal theory of flame propagation [36], the reaction rate (RR)
can be related to the flame burning velocity (Su ) by
1=2
Su ¼ ðaRRÞ ð8Þ
where a denotes the thermal diffusivity. Utilizing Eq. (8) and the
relationship between Su vs R, the reaction rate expression of CCl4-
CH4-air mixture can be obtained as a function of R and / as
 2
Su
a R; / 
 
RRCH4CCl4 at R;/ ¼ 2   RRCH4 R¼0;/ ð9Þ
Su
a R ¼ 0; /

In Eq. (9), RRCH4 R¼0;/ represent the reaction rate of CH4 in a pure
CH4-air reaction. To calculate this term, the same fast chemistry
eddy breakup expression given by Eq. (9) is employed, but the role
of CCl4 as both fuel and oxidizer is accounted for by using the fol-
lowing definition.
MC
mfu ¼ mCH4 þ mCCl4  ;
M CCl4
M Cl4 ð10Þ
mOX ¼ mO2 þ mCCl4  ;
M CCl4
and mpr ¼ mCO2 þ mH2 O þ mHCl
In the above expression, the carbon element of CCl4 is assigned in
the fuel mass fraction and the total fuel mass fraction is assumed
to burn just like fast chemistry reaction as CH4. A similar explana-
tion could be made to the inclusion of Cl in CCl4. Once the CH4 reac-
tion rate is obtained, the individual species reaction rates can be
calculated by using the stoichiometric reaction expression given
by Eq. (2). For example, CH4 and CCl4 reaction rate (RRCCl4 ) can be
expressed as
MCH4
RRCH4 ¼ RRCH4 CCl4  ð11Þ
M CH4 þ R  M CCl4
R  MCH4
RRCCl4 ¼ RRCH4 CCl4 
MCH4 þ R  MCCl4
Further, s can be expressed as appeared in Eq. (11), that is
2M O2 þ 2RMCl2
S¼ ð12Þ
MCH4 þ RMc
 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28
In general, predictions by this model for the experimental data
of the rotary kiln by Ohm [33] and dump combustor [34,35] are
well agreement with the CCl4 destruction rate.
In the incineration of HFCs, as mentioned earlier, the reaction
rate of this mixture is believed to be determined not only by turbu-
lence mixing but also by chemical kinetics. This is particularly true
in the fuel rich and hydrogen deficient condition. However, in an
incinerator operation, the excess air condition is employed in
HFCs-CH4-air flames for the complete destruction of HCFs and it
is possible to circumvent the effort of non-equilibrium effects in
incineration process HCFs-CH4-air flames [15,16]. In Shin et al.
[15], a comprehensive model and numerical calculation are made
for the general and proper thermal destruction of the general
waste HFCs refrigerant. In this study, HFC-23 is selected as the
incineration material of HFCs material and CH4-air flame is used
in an incinerator designed for CDM (Clean Development Mecha-
nism) project. Considering the strong flame promotion effect of flu-
orinated hydrocarbon, however, especially in hydrogen rich and
fuel lean condition, a conventional eddy breakup turbulent reac-
tion model is employed in this excess-air incineration process. This
will be briefly summarized below for the discussion of the model
development of HFC incineration. The stoichiometric reaction
equation of CHF3 with CH4 with auxiliary fuel is given as following;
CHF3 þ CH4 þ 2:5O2 þ 9:4N2 ! 2CO2 þ 3HF þ H2 O þ 9:4N2 þ Hfu
where Hfu is 1074.6 kJ, the heating value of 2 mol of the fuel mix-
ture of CHF3-CH4. In order to account for the fuel reaction rate of
two species such as CHF3 and CH4, wfu in Eq. (4), the following
expressions are used for the mass fractions of Eq. (4) using the reac-
tion coefficients appearing in combustion Eq. (13).
mfu ¼ mCH4 þ mCHF3 ; mox ¼ mO2 ; mpr ¼ mCO2 þ mHF
In Eq. (13), the component of fluorine (F) in CHF3 is assigned into
the fuel part and only oxygen is considered as oxidizer fraction
since HFCs shows fast chemistry behavior compared to chlorinated
hydrocarbons particularly in excess air and hydrogen rich condition.
Once the overall CHF3 and CH4 reaction rate is obtained, the individ-
ual CHF3 and CH4 reaction rates can be determined by the following
stoichioimetric reaction expression in Eq. (13)
_ CH4 ¼ w
w _ fu  M CH4 =ðMCH4 þ MCHF3 Þ
_ CHF3 ¼ w
w _ fu  MCHF3 =ðM CH4 þ M CHF3 Þ
_ O2 ¼ w
w _ fu  2:5  MO2 =ðMCH4 þ MCHF3 Þ
_ _
wHF ¼ wfu  3  M HF =ðM CH4 þ M CHF3 Þ
_ CO2 ¼ w
w _ fu  2  MCO2 =ðM CH4 þ M CHF3 Þ
where M denotes the molecular weight. Further, s is defined as the
stoichiometric mass of oxidizer per unit mass of fuel and can be
expressed as
s ¼ 2:5M O2 =ðM CH4 þ M CHF3 Þ
Employing this kind of fast chemistry EBU model, Shin et al.
[15] evaluate the operational data obtained from the CDM inciner-
ator with the capacity of 70 kg/h with CH4-air flame. Numerical
calculation of CHF3-CH4-air flame has been performed and evalu-
ated successfully with the operation data of a CDM incinerator
such as temperature, CHF3 destruction rate, and other species con-
centrations such as CO and NO at the exit of incinerator. However,
not shown in this paper, the peak flame temperature occurs near
exit region even 20% excess air with relatively high temperature
than measurement. It is believed that the delay of the peak flame
temperature toward the exit region is attributed to the improper
evaluation of the fuel and oxidizer mass fraction as in Eq. (14). In
summary the oxygen mass fraction is underestimated while the
23
fuel mass fraction is overestimated. Since the reaction rate in
EBU model is limited by the deficient mass fraction, the underesti-
mation of oxidizer mass fraction will cause a reduced reaction and
delayed peak flame temperature with the shift of high flame
temperature toward the exit. The corrected expressions of mass
fraction are given in Eq. (17)
mfu ¼ mCH4 þ ðM CHF3  M CH4 Þ=M CHF3 ;
mox ¼ mO2 þ ðM CHF3  MF3 Þ=MCHF3 ð17Þ
mpr ¼ mCO2 þ mHF
In Shin et al. [16], a similar exercise has been made successfully
for the prediction of HFC-134a thermal destruction using the fast
chemistry eddy breakup model employed in Shin et al. [15]. Even
if a series of research efforts of non-equilibrium turbulent model-
ing have been made for the halogenated hydrocarbons, in general,
there is no general predictive model available to deal with halo-
genated hydrocarbon. Therefore, suitable modeling procedure
should be continuously made specifically for each compound
according to characteristics of the Damkohler number each com-
pound in turbulent reacting flows. In this study, therefore, numer-
ical and experimental study has been made in a tubular reactor for
the development of a non-equilibrium turbulent reaction model of
HFC-134a refrigerant.
As mentioned in previous work [16], for the basic empiricism of
ð13Þ incineration strategy, it is usually known that a minimum calorific
value for self-sustaining flame by itself. However, in the incinera-
tion process of the halogenated compound such as HFCs, the neces-
sity of auxiliary fuel comes from another reason in order to supply
hydrogen element in order to make complete reaction by the for-
mation of HF in Eq. (13). If we just supply only air as oxidizer with-
out hydrogen species by the use of auxiliary fuel such as CH4, then
the reaction produces fluorine molecule, F2 instead of HF, as in
ð14Þ
Eq. (13). Even if it is generally known that Freon HFC-134a can
be thermally decomposed effectively only at very high tempera-
ture over 3000 °C [10,11], however, empirical findings occurring
in practical calcination kiln or cokes oven have reported that if
the sufficient amount of vapor exists in an high temperature
environment then the refrigerant HFC-134a can be successfully
decomposed as follows [16,37].
C2 H2 F4 þ 4H2 O þ 1:5O2 ! 4HF þ 3H2 O þ 2CO2 ð18Þ
The empirical work in Eq. (18) presents that for the successful
conversion of C2 H2 F4 into final reaction products of HF, H2O and
ð15Þ CO2 the supply of H and O species are required together with the
necessary energy for the decomposition of C2H2F4. Therefore in this
study a similar exercise has been made with the supply of O2 and
water vapor in a tubular reactor to evaluate the thermal destruc-
tion of HFC-134a as a function of reactor wall temperature together
with the amount of the oxidizer. For the prediction of the non-
equilibrium thermal destruction of HFC-134a, a hybrid type eddy
breakup model is developed by the consideration of the relative
ð16Þ rate of the turbulent mixing and chemical reaction together.
In specific, the turbulent mixing rate in Eq. (3) is obtained by
eddy breakup model from Eq. (4) and the chemical reaction rate
of HFC-134a is obtained from the experimental data in the tubular
reactor. However, in this calculation the mass fraction of fuel,
oxidizer and product are defined as following;
3
C2 H2 F4 þ O2 þ H2 O þ 3:76N2 ! 4HF þ 2CO2 þ 3:76N2 ð19Þ
2
MC2 H2 M H2
mfu ¼ mC2 H2 F4  þ mH2 O  ;
M C2 H2 F4 M H2 O
M F4 MO
mox ¼ mO2 þ mC2 H2 F4  þ mH2 O 
M C2 H2 F4 MH 2 O
mpr ¼ mCO2 þ mHF
24 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28

The empirical reaction rate is assumed as x_ ¼ dtd ðmfu Þ ¼ to satisfy the stoichiometric condition as shown above in Eq. (19).
AT e B ðERTa Þ
mfu mox , where mfu and mox are defined above. The pre- The stoichiometric amount of mass flow rates of O2 and H2O are
47.1 g/h and 17.7 g/h respectively for 100 g/h of C2H2F4. The details
exponential factor A and activation energy Ea are determined by
of experiment for the facility and measuring procedures with cali-
trial and error method via numerical calculation to fit the experi-
bration and accuracy together with other parametric study like the
mental data obtained in a tubular reactor.
change of total flow rate study are presented elsewhere [16,38].

3. Research method
3.1. Experimental facility
In order to figure out the feature of the thermal decomposition
of R-134a as a function of reactor wall temperature and oxygen
flow rate, a series of experiments have been made using tubular
reactor made of Hastelloy material as shown in Fig. 1. In order to
supply the activation energy of R-134a reaction, the tubular reactor
wall temperature is heated to a desired temperature. In specific,
the furnace diameter and the length of reactor are 22 mm and
600 mm respectively and only 500 mm length was heated from
100 to 900 °C with 100 °C interval, while the flow rate of R-134,
water vapor and N2 are fixed with 100 g/h, 17.7 g/h and 100 g/h
respectively. The flow rate of oxygen and water vapor are supplied
3.2. Numerical model and solution procedures
Numerical calculation has been made by a commercial code,
STAR-CCM+(Ver.9.06), which can deal with the pre-process, solver
and post-process using the integrated package CAE (computer
aided engineering) software in one working environment, and
can solve the physical phenomenon in various fluid flow and heat
transfer problems associated with chemical reaction. The same
input condition was employed with the experimental condition
with the flow rate of R-134a 100 g/h together with the O2 47.1 g/
h, H2O 17.7 g/h and carrier gas, N2 100 g/h via the gas mixing
chamber. For completeness, the basic gas phase conservation equa-
tions for mass, momentum, energy, turbulent quantities and spe-
cies concentration can be expressed as in an Eulerian framework,

Fig. 1. Detailed specification of tube reactor and boundary condition.

Table 1
General dependent variable / and diffusion coefficient C/ expression for axi-symmetric cylindrical coordinate system for the general governing Eq.
(22). C2 H2 F4 þ 32 O2 þ H2 O þ 3:76N2 ! 4HF þ 2CO2 þ 3:76N2 ð22Þ.

Variables / C/ S/
   
Axial momentum u leff leff @u @v
@x þ r @r leff r @x  @x
@ 1 @ @p
@x
   
leff leff @u @v v qw
@r þ r @r leff r @r  2leff r2 þ x  @r
Radial momentum v @ 1 @
2
@p
@x
l 
Tangential momentum w leff  eff
þ qrv þ 1 @ leff
w
r2 r @r
Kinetic energy k leff Gk1  qe
rk
leff e
Kinetic energy dissipation rate e rs j ðC 1 C k1  C 2 qeÞ
Specific enthalpy h leff _ fu  Hfu
w
rh
Fuel mass fraction mfu Cfu _ fu
w
Oxygen mass fraction mO2 CO2 _
w
1:5  Mfufu M O2
HF mass fraction mHF CHF 4
_ fu
w
MHF
M fu
CO2 mass fraction mCO2 CCO2 _
w
2  Mfufu MCO2
H2O mass fraction mH2 O CH2 O _
w
 Mfufu MH2O
h  @ v 2  2 i h   @ w2 @u @ v 2 i
Gk1 ¼ 2leff @u 2
þ vr þ leff @w
2
@x þ @r @x þ r @r r þ @r þ @x

C1 = 1.44, C2 = 1.92, Cl = 0.92, rk = 0.9, re = 1.22

 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28 25

where / represents the general dependent variable, and q and u
are density and velocity vector, respectively. Further, C/ and S/
are the effective diffusion coefficients and the source term respec-
tively for /.
@ðq/Þ !
þ r  ðq u /Þ ¼ r  ðC/ r/Þ þ S/
@t
The popular approach is the use of the two equation (k–e) model by
Launder and Spalding, where a Prandtl-Kolmogorov relationship is
used to correlate the turbulence viscosity, lt to the turbulent kinetic
energy (k) and its dissipation rate (e) [39].
lt ¼ Cl qk2 =e
As mentioned above, for the prediction of the non-equilibrium ther-
mal destruction of HFC-134a, a hybrid type eddy breakup model is
developed by the consideration of the relative rate of the turbulent
mixing and chemical reaction together. To this end, empirical con-
stants in the chemical reaction rate are determined by the trial and
error method based on the experimental data in this tubular
!
reactor. Further the hybrid type EBU model is employed for the pre-
diction of the non-equilibrium turbulent reaction in this tubular
reactor. The diffusion coefficient C/ and source term S/ in Eq. (20)
are presented for axi-symmetric cylindrical coordinate system in
Table 1 for the dependent variables such as u, v, k, e, h,
ð20Þ mfu ; mO2 ; mHF ; mCO2 ; mH2 O respectively. The dependent variable u,
v, h, mfu ; mO2 , mHF ; mCO2 , mH2 O are denoted axial and radial veloci-
ties, enthalpy, mass fractions of fuel, oxygen, hydrogen fluoride, car-
bon dioxide and water, respectively. In this calculation, a suitable
radiation model was tested but no visible change was observed,
as expected, probably due to the low emissivity by the small mean
beam length caused by the small tube diameter. Fig. 2 represents a
ð21Þ boundary condition of tube reactor for numerical calculation.
4. Results and discussion
Experimental data of thermal decomposition at reactor exit as a
function of temperature and oxygen concentration are presented in
Tables 2 and 3, respectively. In Table 2, the fraction of the

Fig. 2. Comparison of thermal decomposition of R-134a at the reactor exit between Fig. 3. Comparison of thermal decomposition of R-134a between numerical
numerical calculation and experiment as a function of wall temperature. calculations by two EBU models and experiment as a function of oxygen mole
flow rate.

Table 2
Experimental data of thermal decomposition of R-134a as a function of temperature with fixed amounts of O2 and H2O. (*Carrier gas N2 100 g/h).

Expt no. Reactor wall C2H2F4 (g/h) O2 (g/h) H2O (g/h) Mole ratio Decomposition Decomposition
temperature (°C) (C2H2F4:O2:H2O) percent (%) (experiment) percent (%) (calculation)
1 100 100 47.1 17.7 1:1.5:1 0 0
2 300 100 47.1 17.7 1:1.5:1 0 0
3 500 100 47.1 17.7 1:1.5:1 0 0
4 600 100 47.1 17.7 1:1.5:1 1.1 5.2
5 700 100 47.1 17.7 1:1.5:1 17.7 20.7
6 800 100 47.1 17.7 1:1.5:1 79.6 80.4
7 850 100 47.1 17.7 1:1.5:1 100 100
8 900 100 47.1 17.7 1:1.5:1 100 100

Table 3
Experimental and numerical data of the thermal decomposition of R-134a as a function of oxygen flow using two EBU models (*Carrier gas N2 100 g/h and 900 °C wall
temperature and the stoichiometric amount of H2O.)

Expt Reactor wall C2H2F4 (g/h) O2 (g/h) H2O (g/h) Mole ratio Experimental Numerical decomposition Numerical Decomposition
no. temperature (C2H2F4:O2:H2O) decomposition percent (%) by fast percent (%) by hybrid model
(°C) percent (%) chemistry EBU model
8 900 100 47.1 17.7 1:1.5:1 100 100 100
9 900 100 0 17.7 1:0.0:1 25 31.8 22.7
10 900 100 9.4 17.7 1:0.3:1 50.8 53.4 57.1
11 900 100 15.7 17.7 1:0.5:1 – 67.4 75.7
12 900 100 21.9 17.7 1:0.7:1 – 77.6 86.2
13 900 100 28.3 17.7 1:0.9:1 94 86.8 94.7
14 900 100 37.7 17.7 1:1.2:1 100 94.6 100
26 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28

HFC-134a thermal decomposition is presented with the wall tem- decomposition data at the reactor exit, empirical constants of
perature increase from 100 °C to 900 °C for the fixed value of the pre-exponential factor (A), empirical constant B and activation
stoichiometric amount of oxygen and water vapor. In Table 3, the energy (Ea) in the chemical reaction rate, that is, k ¼ AT B eðRT Þ
Ea

thermal decomposition data are presented as a function of oxygen
concentration with the fixed value of wall temperature and 900 °C
and stoichiometric amount of H2O concentration. As shown in
Table 2, no thermal decomposition of HFC 134a occurs up to the
wall temperature of 500 °C and only very small amount of decom-
position, that is, 1.1% occurs at temperature 600 °C even if there
exist stoichiometric amount of oxygen and water vapor. But the
fraction of thermal decomposition increases 17.7, 79.6 and 100%
as wall temperature increases 700, 800, and 850 °C, respectively.
This data suggests that at least more than 600 °C is necessary in
order to react HFC-134a with O2 and water vapor. Using this
was determined by trial and error method in order to fit the
destruction fraction of HFC-134a in Table 2 using the hybrid type
EBU model for the development of the non-equilibrium turbulent
reaction model of HFC-134a incineration. The value of A, b and
Ea obtained are A = 1.0, B = 0.38, Ea = 8.8  107 J/kmol, respec-
tively. The calculated thermal decomposition data are well com-
pared with experimental data and presented in Fig. 2 and
Table 2, respectively.
Further, using the hybrid EBU model with empirical constants
determined above, the thermal destruction data as in Table 3 are
predicted as a function of oxygen concentration with fixed wall

(a) Velocity vector( inlet velocity,0.126 m/s)

(b) Temperature distribution

(c) Mass fraction of HFC-134a

Fig. 4. Calculation results for the wall temperature of 900 °C and stoichiometric condition of oxygen and water vapor by conventional EBU model for the Exp. No. 8 in
Table 2 or 3.

(a) Velocity vector( inlet velocity,0.126 m/s)

(b) Temperature distribution

(c) Mass fraction of HFC-134a

Fig. 5. Calculation results for the wall temperature of 900 °C and stoichiometric condition of oxygen and water vapor by the non-equilibrium EBU model for the Exp. No. 8 in
Table 2 or 3.
 M. Shin et al. / Applied Thermal Engineering 125 (2017) 20–28
Fig. 6. Comparison of numerical calculations by two EBU models along the axial distance of tube reactor.
temperature 900 °C. In this calculation, the fast chemistry EBU
model used in Shin et al. [16] is also employed for the comparison
purpose. Comparison between calculations by two EBU models and
experiment has been made and presented at Table 3 and in Fig. 3
for the thermal decomposition of R-134a as a function of O2 con-
centration. In general, the prediction by hybrid-type EBU model
agrees better than the conventional fast chemistry model without
any non-equilibrium incorporation. Since the comparison has been
made only for the concentration of HFC-134a at the exit, the calcu-
lated profiles are presented in detail in order to see the difference
of two models. In Figs. 4 and 5, the detailed profiles of HFC-134a
concentration, temperature and velocity field are presented
respectively. Even if the overall thermal decomposition fraction
by two models look similar at the exit, the profiles of temperature
and HFC-134a concentration differ significantly. As shown in Fig. 5,
the reaction of HFC-134a occurs very slowly at low temperature
entrance region due the non-equilibrium effect. Further, detailed
profile comparisons of temperature and HFC-134a have been made
along the reactor centerline axis using two models as shown in
Fig. 6. This clearly shows the non-equilibrium effect of turbulence
reaction model plays a significant role especially in the significant
region of the non-equilibrium chemistry effect especially in low
flame temperature region.
5. Conclusion
Considering the global warming potential of HFC-134a (C2H2F4)
with the substantial generation of this refrigerant as waste mate-
rial in various industrial sectors, the development of proper ther-
mal destruction method of HFC-134a is of great practical
significance especially in the generation of fluorine material like
HF and CaF2. Experiment and numerical calculation have made
for a tubular type in order to figure out the important feature of
the thermal decomposition of HFC-134a as a function of tempera-
ture and reactants such as oxygen and water vapor. Detailed
review and discussions are made for the modeling and non-
equilibrium effect in the incineration process of various halo-
genated hydrocarbons using a couple of modified versions of eddy
breakup (EBU) model developed from the original EBU model.
Employing this non-equilibrium hybrid EBU model, the calculated
overall destruction rate of HFC-134a was in good agreement with
the experimental data obtained for the same reactor. But the
detailed HFC-134a concentration profiles between the fast chem-
istry and non-equilibrium EBU models show a significant differ-
ence even if the calculated destruction rates of HFC-134a appear
similar at the exit. In near future, numerical calculation will be
27
made for the practical incinerator of HFC-134a in a practical incin-
erator using the model developed in this study.
Acknowledgement
This project is supported by the ‘‘R&D Center for reduction of
Non-CO2 Greenhouse gases (2013001690006)” funded by Korea
Ministry of Environment (MOE) as ‘‘Global Top Environment R&D
Program”.
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