Thermochimica Acta 652 (2017) 85–96

Contents lists available at ScienceDirect

Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Review

Thermal reactivity of ethylene oxide in contact with contaminants: A

review
Jingru Liu ∗ , Fan Zhang, Wei Xu, Ning Shi, Shanjun Mu ∗
State Key Laboratory of Safety and Control for Chemicals, SINOPEC Research Institute of Safety Engineering, No. 218, Yananshan Road, Qingdao 266061, PR
China

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

Article history: A review on the experimental studies of the reactivity of ethylene oxide (EO) with various contaminants
Received 4 September 2016 including water, different kinds of iron oxides and alkalis are presented. It is shown that: (1) Pure EO is
Received in revised form 7 March 2017 not prone to initiate a runaway reaction under 200 ◦ C under adiabatic conditions. (2) The possibility of
Accepted 9 March 2017
EO aqueous solution to experience an exothermic reaction depends strongly on the EO concentration,
Available online 18 March 2017
and the onset temperatures could be predicted well by a fourth order reaction rate model. (3) EO exhibits
different sensitivities to various kinds of iron oxides. Although ␥-Fe2 O3 is the most active iron oxide to
Keywords:
EO, its runaway reaction consequence is less severe. The reactivity for EO with iron oxides could be: ␥-
Ethylene oxide
Thermal stability
Fe2 O3 > ␣-Fe3 O4 > hydrated ␣-Fe2 O3 > ␣-Fe2 O3 . (4) Alkalis could reduce the initial reaction temperature of
Calorimetry EO to room temperature with sufficient concentrations, and the proposed hazard potentiality for alkalis
Reactivity is NH4 OH > KOH > NaOH.
Contaminant © 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
2. Basic properties of EO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.1. Physical properties of EO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2.2. Chemical properties of EO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3. The thermal reactivity of pure EO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4. The thermal reactivity of EO with water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.1. Onset temperatures of EO aqueous solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.2. Kinetics for EO reaction with water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5. The thermal reactivity of EO with iron oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.1. Reaction of EO with glass beads or ␣-FeO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2. Reaction of EO with iron oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2.1. Temperature for EO reaction with iron oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2.2. Self-heat rate for EO reaction with iron oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.2.3. Pressure for EO reaction with iron oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .91
6. The thermal reactivity of EO with alkalis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
6.1. Reaction of EO with KOH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6.2. Reaction of EO with NaOH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
6.3. Reaction of EO with NH4 OH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
6.4. Onset temperature comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

∗ Corresponding authors.
E-mail addresses: liujr.qday@sinopec.com (J. Liu), msj.qday@sinopec.com
(S. Mu).

http://dx.doi.org/10.1016/j.tca.2017.03.008
0040-6031/© 2017 Elsevier B.V. All rights reserved.
86 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96
Nomenclature
Notation
A Pre-exponential factor, [(m3 )3 kmol−3 s−1 ]
Cb Specific heat of the bomb, [J (kg ◦ C)−1 ]
Cs Specific heat of the sample, [J (kg ◦ C)−1 ]
dT/dtmax Maximum temperature rise rate, [◦ C min−1 ]
dP/dtmax Maximum pressurization rate, [kPa min−1 ]
E Activation energy, [J/mol−1 ]
H Heat of polymerization, [kJ mol−1 ]
k Rate constant, [(m3 )2 kmol−2 s−1 ]
K Equilibrium constant
Mb Mass of testing cell, [g]
MEO Mass of EO, [g]
MS Mass sample, [g]
Mtotal Total mass of sample and cell, [g]
Pmax Maximum pressure, [kPa]
r1 Rate constant of EO with water, [kmol m−3 s−1 ]
r2 Rate constant of EO with glycols, [kmol m−3 s−1 ]
rEG The formation rate of EG, [kmol m−3 s−1 ]
rDEG The formation rate of DEG, [kmol m−3 s−1 ]
t Time, [s]
Tf Final temperature, [◦ C]
Tmax Maximum temperature, [◦ C]
Tmp Temperature at maximum pressure, [◦ C]
TMR Time to maximum reaction rate, [min]
Ton Onset temperature, [◦ C]
W Mass fraction of EO aqueous solution, [%]
Greek letters
Tc Adiabatic temperature rise, [◦ C]
 Thermal inertia factor
1. Introduction
Ethylene oxide (EO) is one of the most versatile chemical inter-
mediates because its highly strained ring can be opened easily
to produce varieties of fine chemicals [1,2]. Besides its direct use
as disinfectant, sterilizing agent, and fumigant, EO is frequently
applied in the production of many important surfactants, sol-
vents, polyesters, and antifreezes such as ethylene glycol (EG),
ethanolamine, ethylene glycol ethers etc. Important as EO is in
the chemical industry, it is an extremely hazardous material due
to the high reaction sensitivity—it is susceptible to contaminants
such as alkalis, iron oxides and water, which could lead to runaway
reactions or even spontaneous decomposition [3].
Traditionally, EO is produced by the direct oxidation of ethy-
lene with oxygen by metallic silver [4,5]. Due to the deflagration
and explosion risk of the process, some other inherent safer pro-
cesses have been proposed to reduce risk, such as silver-catalyzed
oxidation of ethylene to EO in micro-reactor, or homogeneous liq-
uid phase oxidation with catalyst (methyltriox-orhenium), oxidant
(H2 O2 ) and reaction medium (methanol/water) [6,7]. Also, some
researchers conducted optimization of the reaction concept and
design parameters of EO process in order to save energy and reduce
emission [8–10]. The industrial production technologies for EO
based on direct oxidation process over silver catalyst are mainly
patented and licensed by Shell, Scientific Design (SD) and DOW
Chemical. As shown in Fig. 1, the direct oxidation process consists
of oxidation reaction unit, carbon dioxide removal unit, EO purifi-
cation unit, EO storage/transportation unit and possible ethylene
glycol production unit. A recycle gas stream containing ethylene
and oxygen is first circulated through the fixed bed reactor, partially
oxidizing ethylene into EO over sphere or ring shaped silver cata-
lyst at about 200 ◦ C and 2.0 MPa. The process parameters of direct
oxidation technology has been summarized in Table 1, depending
on catalysts performance and production technology. The recycle
gas containing EO and byproduct such as carbon dioxide, water
and acetaldehyde is then transported into scrubbers to absorb EO
and to remove carbon dioxide. The residual recycle gas is reloaded
with oxygen and ethylene through oxygen mixer and returned to
the reactor. In the liquid phase, the resulting aqueous EO solution
is passed to the EO purification unit to collect pure EO product
through a series of stripping towers and distillation towers, where
low-boiling components are stripped of at the same time. Depend-
ing on the design of the EO plant, the EO product can be refrigerated
and transported to the storage tank or subsequently reacted with
water to produce ethylene glycol.
The process hazards of EO production lie mainly in the oxi-
dation reaction and EO purification process [13] (Fig. 1). In the
oxidation reaction unit, a significant amount of flammable gases
including ethylene and methane mixes and reacts with oxygen. The
flammable gases concentration has to pass through the flammable
region when diluted down by oxygen to the operating level, requir-
ing a fairly complicated control scheme to assure safety therefore.
The oxidation reaction of ethylene is extremely exothermic espe-
cially when the complete oxidation of EO to carbon dioxide takes
place. As a result, the heat removal system must be sufficiently reli-
able to cope with the heat release in the reactor, otherwise runaway
reactions may be induced and the accumulated heat could result in
damage to assets, human health or the environment [14]. Typical
incidents in the oxidation reaction are pre-ignition, temperature
runaway and explosion of flammable cyclic gases. In the EO purifi-
cation unit, high purity EO is combustible and sensitive to various
impurities, prone to cause fires and deflagrations [15–17]. The con-
sequence of incidents in the EO purification unit is often much more
severe than that in other units in the EO production process because
of the strong exothermic effect. The disastrous explosion was usu-
ally initiated by the exothermic reaction of EO with inobservant
impurities. Looking through the history of EO industry, it is not dif-
ficult to name a few incidents caused by the existing impurities in
the EO purification unit.
On July 3rd, 1987, a purification distillation column of BP Chem-
icals’ EO plant in Antwerp exploded. It was concluded after accident
investigation that EO leaked from the manhole flange and was
trapped inside the insulation where it started to react in the pres-
ence of rust, water and the insulation. The temperature gradually
increased because of heat released in the exothermic reactions until
it reached a critical level, where there was an acceleration in the
rate of the exothermic reactions, resulting in a rapid release of heat.
The temperature of the resultant hot metal surface was sufficient to
ignite the EO vapor internally [18]. An EO plant of BASF licensed by
Shell in Antwerp also experienced severe fire and explosion damage
in the EO distillation section on March 7th, 1989. It is believed that
polyethylene glycols (PEG) were formed by escaped EO and accu-
Table 1
Process parameters in the oxygen-based production of EO [11,12].
Parameters Value range
C2 H4 concentration, vol% 15–40
O2 concentration, vol% 5–9
CO2 concentration, vol% 5–15
C2 H6 concentration, vol% 0–2
CH4 concentration, vol% 1–60
Inlet gas temperature, ◦ C 30–40
Reaction temperature, ◦ C 220–275
Pressure, MPa 1–2.2
space velocity, h−1 2000–4000
C2 H4 conversion, % 7–15
Selectivity, % 80–90
 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96
Fig. 1. Typical process flow diagram of EO process (green) and main process hazards (yellow): deflagration and explosion at oxygen mixer; pre-ignition/temperature runaway
at EO reactor; EO runaway reaction/decomposition at EO purification section. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
mulated in the insulation material. During the repair of the level
indicator, air was introduced into the insulation material soaked
with PEG, initiating auto-oxidation of the PEG. This caused the insu-
lation to ignite and to heat the metal wall of the piping to such a
degree that auto-decomposition of EO within the piping took place
[19]. EO decomposition propagated into the column and resulted
in the explosion. Lately (April 21th, 2015), an EO plant of SINOPEC
licensed by SD (Scientific Design) company also experienced a sim-
ilar EO distillation column explosion. The pressure transmitter pipe
at reflux tank was blocked by polymers-polyformaldehyde, leading
to a lower pressure read of the EO column. A faulty operation was
performed to increase the amount of vapor and resulted in the over-
pressure of the column and discharge of the relief valve eventually.
At the same time, EO leaked into the insulation in which obvious
rust was found. It was inferred that EO first began to react with
water and rust, followed by the heat accumulation in the insula-
tion and a runaway reaction eventually. The hot spot in the column
may initiate the decomposition explosion of EO vapor when local
temperature went too high [20].
It could be concluded from the incidents causes listed above that
the onset of EO exothermic reaction could be induced by impurities
such as water, rust, and insulation material. Other contaminants, for
example, aqueous alkali, carbonate aqueous solution, and metal ion
[21] could also be in direct contact with EO/EG during production
and storage/transportation. In order to guarantee the safe operation
of EO plant and to improve the process safety technology of EO, it is
essential to understand systematically the thermal reactivity of EO
in contact with various contaminants. This paper has summarized
available experimental studies of the thermodynamics character-
istics of EO with water, iron oxide and alkali in literatures, which
provides the foundation for further study of EO reaction dynamics.
2. Basic properties of EO
2.1. Physical properties of EO
The structural parameters of ethylene oxide determined by
microwave spectroscopy are shown in Fig. 2 [22]. Ethylene oxide is
a colorless gas at room temperature and it is miscible with water,
alcohol, ether, and most organic solvents in all proportions. It is
highly flammable and poses a dangerous fire and explosion risk—its
explosion limits ranging from 2.6 vol% to 100 vol% in air at 101.3 kPa.
The upper flammable limit (UFL) for EO is 100%, since pure EO
87
Fig. 2. Molecule structure of ethylene oxide [22].
could decompose if ignited at about 500 ◦ C [23]. In the presence
of oxygen (air), combustion and decomposition take place simulta-
neously and the ignition temperature (or energy) is reduced. Some
physical properties of EO are summarized in Table 2 [24]. A sta-
ble clathrate forms when mixing EO with water, which consists
of organic molecules enclosed in a cage structure. In this case, the
cage is an ice lattice composed of unit cells containing 46 water
molecules and two types of cavities: six larger ones and two smaller
ones [25]. As shown in Table 3 [11], the maximum melting point of
EO aqueous solution is 11.1 ◦ C at EO concentration of 30 wt%. This
indicates that the clathrate may block the pipeline or equipment at
low temperature. Due to the low boiling point of EO aqueous solu-
tions (approximately 50 ◦ C), it could evaporate into EO vapor cloud
easily and is considered to be prone to combustion and explosion
[26].
2.2. Chemical properties of EO
The reactions of EO proceed mainly via ring opening and are
highly exothermic. Under appropriate conditions, EO is known to
undergo a variety of reactions, namely isomerization, polymer-
ization, hydrolysis, combustion, and decomposition. Hydroxyethyl
compounds could be produced when EO reacts with compounds
containing a labile hydrogen atom, such as HOH, H2 NH, HRNH,
R2 NH, RCOOH, RCONH2 , HSH, RSH, ROH, etc. (R = alkyl, aryl).
Hydrolysis is the most important hydroxyethylation reaction of EO
since about 60% of the total EO produced is converted into ethy-
lene glycol [27,28]. The reaction of EO with water in the absence
of catalysts at room temperature is relatively slow. Depending
88 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96

Table 2 absence of contaminants. The reactivity of pure EO was investi-

Physical properties of EO [24].
gated by several researchers using adiabatic calorimeters such as
Melting point at 101.3 kPa −112.5 ◦ C the automatic pressure tracking adiabatic calorimeter (APTAC) or
boiling point at 101.3 kPa 10.8 ◦ C accelerating rate calorimeter (ARC). For the calorimeters, adiabatic-
Critical temperature 195.8 ◦ C
ity is achieved by matching the temperature of the surroundings to
Critical pressure 7.3 MPa
Critical density 314 kg m−3
that of the sample. Stepwise heating is suspended when exother-
Refractive index, n7D 1.3597 micity is detected and an adiabatic environment is maintained. At
Explosive limits in air at 101.3 kPa the same time, the temperature and pressure are recorded during
Lower 2.6 vol% the exothermic process. Since EO is vapor state at room tem-
Upper 100.0 vol%
perature and sensitive to any impurities, thorough cleaning and
Electrical conductivity 4 × 10−6 S m−1
Dielectric constant purging of the test cell and transfer line must be conducted at first,
at −1 ◦ C (liquid) 13.9 then the liquid EO could be loaded into the cell at low tempera-
at 15 ◦ C (vapor) 1.01 ture using ice bath. The APTAC applied a heat-wait-search mode
Heat of combustion at 25 ◦ C, 101.3 kPa 29.648 kJ kg−1
(HWS) with a temperature search range of 25–300 ◦ C and the max-
Entropy of the vapor at 101.3 kPa
10.5 ◦ C 5.439 kJ kg−1 K−1
imum tolerance pressure about 14 MPa. An exothermic activity was
25.0 ◦ C 5.495 kJ kg−1 K−1 detected when a threshold of self-heating rate of 0.04–0.1 ◦ C/min
Ignition temperature in air at 101.3 kPa 439 ◦ C was exceeded. For ARC, the exothermic activity was detected if the
Ignition energy in air at 101.3 kPa, 25 ◦ C 0.087 mJ rate of temperature rise exceeds the preset value 0.02–0.04 ◦ C/min,
Minimum ignition energy of the gas at
so the ARC is more sensitive to exothermic activity than APTAC.
220 kPa, 100 ◦ C 64 mJ
Decomposition temperature of the vapor The phi-factor for ARC and APTAC varies generally from 1.05 to 5.0,
at 101.3 kPa 571 ◦ C depending on the cell materials and operational conditions. Usu-
Heat of polymerization 2091 kJ kg−1 ally the APTAC has a lower phi-factor and greater loading amount
Heat of fusion 117.86 kJ kg−1
over ARC. The high phi-factor can potentially mask exotherm that
Heat of decomposition of the vapor 1901 kJ kg−1
Coefficient of cubic expansion
can occur at higher temperatures. Therefore, the temperature and
at 22 ◦ C 0.00161 pressure of a test should be corrected by established techniques to
at 55 ◦ C 0.00170 the low phi-factor conditions.
Heat of solution in water at 25 ◦ C 142.57 kJ kg−1 According to the study of Dinh et al. [31], considerable exother-
mic activity of pure EO was exhibited in the temperature and
Table 3 pressure curves as shown in Fig. 3. The pure EO reached an onset
Physical properties of aqueous solutions of EO [11]. temperature of around 200 ◦ C and the exothermic peak tempera-
EO concentration Specific gravity Melting point Boiling point
ture could exceed 600 ◦ C and the corresponding maximum pressure
[wt%] [103 kg m−3 ] at 10 ◦ C [◦ C] [◦ C] approximate 12 MPa. The time from exothermicity detected to
maximum reaction rate was about 800 min. So without impuri-
0 1.000 0.0 100
2.5 0.9986 −0.9 70 ties, EO is relative stable under 200 ◦ C, but it should be handled
5 0.9977 −1.6 (eutectic) 58 at much lower temperature considering the severe consequence of
10 0.9944 5.6 42.5 EO runaway reactions.
15 0.9888 8.9 38 The experimental calorimetry data of pure EO was obtained both
20 0.9816 10.4 32
30 0.9658 11.1 (max) 27
by ARC and APTAC in Melhem et al.’s study [32]. The onset temper-
40 0.9500 10.4 21 ature was detected when the self-heating rate exceeds 0.02 ◦ C/min
50 0.9356 9.3 19 for ARC and 0.04 ◦ C/min for APTAC. The measured onset tempera-
60 0.9227 7.8 16 ture of pure EO by Melhem et al. is greater than that of Dinh et al.
70 0.9111 6.0 15
mentioned above, this may relate to the adiabaticity, sensitivity of
80 0.9005 3.7 13
90 0.8910 0.0 12 instrument and thermal inertia effects. Thus, the experimental data
100 0.8828 −111.7 10.4 must be used with an appreciation of the limits of the measuring
instruments and methods.
The study of thermal stability of pure EO by Britton [33] shown
on the ratio of water to EO, diethylene glycol, triethylene glycol, that the use of tantalum bombs could minimize the surface effects
and higher molecular mass polyethylene glycol can be produced. because of the inertness, so a high EO loading must be used to
Acidic medium or basic medium favors hydrolysis reaction, while ensure that the reactions are tracked in supercritical material. The
in the neutral medium (5 < pH < 11) the reaction is moderate. EO thick walled HASTELLOY bomb was used in the testing of EO as
could be isomerized into acetaldehyde at 170–300 ◦ C catalyzed Melhem et al. All of the runs indicate that under adiabatic condi-
by Aluminum oxide (Al2 O3 ), phosphoric acid, phosphates and sil- tions a temperature of about 200 ◦ C is required to attain a heat
ver at certain conditions. The spontaneous ignition temperature of rate of 0.02 ◦ C/min in pure EO, which is a little lower than the
acetaldehyde is much lower than that of EO, thus the isomeriza- results of Melhem et al. and agree well with that of Dinh et al.
tion reaction enlarges the probability of combustion and explosion The pressure initially falls due to consumption by polymerization,
of EO. The isomerization of EO may induce the decomposition of but a rapid increase of pressure to about 40 Mpa was observed
gaseous EO when temperature exceeds 400 ◦ C [29,30], and the due to decomposition of the polymer. The reaction products com-
decomposition products are mainly carbon monoxide, methane, prised gas, brown liquid, brown solid, and hard carbon. The inferred
ethane, ethylene, hydrogen and carbon (Table 4). reaction route may be that isomerization to acetaldehyde takes
place initially, then it condenses to acetaldol, later it cracks to
3. The thermal reactivity of pure EO crotonaldehyde and water, then further condensation to croton
oils and solid polymer, and evidently the decomposition occurs
In order to understand the reactivity of EO with the contam- [34,35].
inants, it is necessary to know the properties of pure EO in the
 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96 89

Fig. 3. Variation of temperature and pressure of pure EO in the APTAC [31]: (a) temperature history; (b) pressure history.

4. The thermal reactivity of EO with water
4.1. Onset temperatures of EO aqueous solution
In the process of EO production, the yielded EO is absorbed by
water, therefore it is necessary to understand the thermal proper-
ties of EO aqueous solution. EO could react with water and further
with ethylene glycols to form higher ethylene glycols, determined
by the concentration ratio between water and EO. The reaction of
EO with water can be catalyzed by acids and bases, and can be
started alternatively from glycol in the absence of water. The EO-
water calorimetric tests were conducted by Melhem et al. over a
wide range of phi-factors and EO weight fractions from 10% to 99%
using APTAC. These tests were conducted using three different cell
materials including titanium, Hastelloy-C, and glass. The detected
onset temperatures measured in glass were higher than those
measured in titanium or Hastelloy-C, especially for higher concen-
trations. The reactivity at the cell wall and the thermal inertia of
different cell material may affect the thermal parameters of the
reaction such as onset temperature [36]. The maximum exothermic
temperature detected was about 340 ◦ C for 60% mass fraction. EO-
water solution at this composition has sufficient energy to reach the
glycol decomposition temperature, approximately 300 ◦ C. The gly-
col decomposition reactions require special consideration because
they are very energetic and can produce large amounts of gas.
90 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96

E
= 9525 K or E = 4512 J/gmol (5)
R
CROH was total molar concentration of independent hydroxyl
groups in solution and calculated as:

CROH = CH2 O + 2CEG + 2CDEG + 2CTEG + 2CT4EG + etc. (6)

The glycol concentration terms in Eq. (6) are multiplied by two to

account for the presence of two hydroxyl groups on each glycol
molecule.
EO reacts with glycols to produce higher order glycols or polyg-
lycols. The reactions of EO with glycols occur based on the following
equation:

C2 H4 O + C2i-2 H4i-2 Oi → C2i H4i+2 Oi+1 , i = 2, 3, 4, 5, 6 (7)

The reactions rate of EO and the glycols proceed according to

the following expression:
  
2
r2 = 2kCEO CC CROH , i = 1, 2, 3, 4, 5, 6 (8)
Fig. 4. Comparison of onset temperatures between Melhem et al. [32] and Britton 2i−2 H4i−2 O
et al. [33].
These kinetics are based on the reaction mechanism that EO is
assumed to rapidly associate with two moles of hydroxyl to form
Fig. 4 illustrates the impact of EO mass fraction on the detected an intermediate:
exothermic onset temperatures obtained from the data of Melhem
et al. [32] The detected minimum onset temperature is around EO + 2ROH → I (9)
60 ◦ C at mass fraction 33%, and the onset temperature keeps almost This reaction is presumed to be so fast that chemical equilibrium
constant when the mass fraction below 50%, then it increase with is attained as follow:
mass fraction and tends towards the value of neat ethylene oxide at
CI
100%. The reduction of reaction threshold temperature for EO with K=   (10)
water is also observed by Britton using ARC [33], and the onset CEO CROH
temperature is in accordance with the result of Melhem et al. as where K is the equilibrium constant for this reaction.
shown in Fig. 4. The self-heat rate of EO reaction with water gen- This intermediate is presumed to react slowly with water to
erally increase with temperature, and the maximum self-heat rate form EG, with EG to form DEG, with DEG to form TEG, etc., regen-
could reach 100 ◦ C/min at about 240 ◦ C [26]. The variation trend of erating the two moles of ROH:
self-heat rate for different mass fractions of EO solutions is almost
the same, but the increase of self-heat rate for 98–99% EO-water is I + H2 O → EG + 2ROH (11)
much quicker than other concentrations. 
rEG = k0 CI CH2 O (12)

4.2. Kinetics for EO reaction with water If EG is being converted to DEG, either of the two hydroxyls on
the ethylene glycol can undergo the following reaction and reaction
Reaction orders of one, two and three could be served as candi- rate:
dates for EO and water reaction. These previous models performed
I + EG → DEG + 2ROH (13)
reasonably well in the low concentration range, but misestimated

the detected onset temperatures at high EO concentrations. The rDEG = 2k0 CI CEG (14)
overall fourth-order reaction rate expression was proposed by Mel-
hem et al. [32], which considers all species containing hydroxyl According to Eq. (10), the expression of CI could be substituted
groups and takes into account the impact of the reactions of the into Eqs. (12) and (14), which yields the reactions form described
ethylene glycols on the overall kinetics. herein:
  
According to Melhem et al. [32] EO reacts with water in the liquid 2
rEG = k0 KCEO CH2 O CROH (15)
phase to produce monoethylene glycol according to the following
2   
chemical equation: rDEG = 2k0 KCEO CEG CROH (16)
C2 H4 O + H2 OC2 H6 O2 (1) It is convenient by defining k0 K as k’, and the final rate expression
is given by the following fourth order equations:
The rate of reaction is given by the following expression:
 2  
rEG = k CEO CH2 O CROH (17)
r1 = kCEO CH2 O C2ROH (2)
2    
rDEG = 2k CEO CEG CROH (18)
where r1 is reaction rate, kmol/m3 /s, k is rate constant, and defined
as: The fourth-order reaction model accurately predicts the exper-
 E
 imental onset temperatures, especially at high EO concentration
k = Aexp − (3) compared to the third-order reaction model [32,37]. This model is
RT
useful for the prediction of EO-water contamination incident. The
where pre-exponential factor A and activation energy E were product of EO and water reaction are ethylene glycol, diethylene
determined by fitting the kinetics with obtained ARC/APTAC tests glycol, triethylene glycol and tetraethylene glycol, and the distri-
including the heat-wait-search steps: bution of the above products depends mainly on the initial relative
 3 mass fraction of EO water [38]. Both EO and EG could decompose
A = 338 m3 > kmol−3 s−1 (4)
by exothermic, autocatalytic reactions to produce volatiles and
 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96
non-condensable gases when heated to high temperature approx-
imately 300 ◦ C, which leads to the overpressure or even damage to
the equipment [39,40]. However, the pressure variation during EO
and water reaction is not provided by the previous studies, which
is important for the design of emergency relief systems containing
EO or its aqueous solutions.
5. The thermal reactivity of EO with iron oxides
Iron oxides were believed to be a sensitive contaminant to
induce runaway reactions of EO, which may exists in the pipelines,
end sockets of flanges and tubes of heat exchangers. Iron oxides
have drawn special attention in the production of EO because rust
was responsible for several EO distillation explosion incidents.
The reactivity of EO with iron oxide fines was studied by Levin
[41] using adiabatic calorimetry APTAC. Liquid EO was collected by
attaching the lecture bottle to a dry ice/acetone-cooled condenser
and then was placed in a glove bag, while roughly 0.5 g of fines
(or glass beads) were charged into a stainless-steel basket and also
placed into the glove bag. The basket was then fitted around the
sample and wall thermocouples, inserted into the sample cell, and
the sample cell was then attached to the vessel head. So a variety of
commercially-available iron oxides were suspended in the stainless
steel basket above the EO. Finally the heat-wait-search (H-W-S)
mode was operated to examine the reactivity of EO with solid fines.
5.1. Reaction of EO with glass beads or ˛-FeO
The mild exothermic activity was observed for EO with empty
basket ranging from 60 ◦ C to 165 ◦ C, but it could not be asserted
that the onset temperature of pure EO was about 60 ◦ C. Accord-
ing to the self-heat rate, the case of EO with empty basket shows
only marginal self-heating behavior, so the observed behavior for
the empty basket is not actually an exotherm but just experimental
drift. The starting temperature for the reaction of pure EO was iden-
tified to be around 200 ◦ C as the result of Dinh et al. and Melhem
et al. [31,32] While for EO with glass beads or ␣-FeO, no discernable
exothermic activity was detected and only the typical stair-step
behavior of the heat-wait-search (H-W-S) mode was recorded. The
maximum search temperature was above 250 ◦ C in the case of the
␣-FeO but no exothermic behavior appeared. The pressure history
show parallel trends with temperature.
5.2. Reaction of EO with iron oxides
5.2.1. Temperature for EO reaction with iron oxides
In contrast to glass beads and ␣-FeO, the mixture of EO with
various iron oxide including ␣-Fe3 O4 , ␣-Fe2 O3 , hydrated ␣-Fe2 O3
and ␥-Fe2 O3 display evident exothermic behavior as shown in the
temperature history in Fig. 5. For ␥-Fe2 O3 , the exothermic reaction
took place at room temperature and the maximum temperature
reached 600 ◦ C, so it is dangerous for EO to be contacted with ␥-
Fe2 O3 which could induce the explosive decomposition of EO vapor.
For hydrated ␣-Fe2 O3 , the onset temperature is about 50 ◦ C and
the maximum exothermic temperature is much lower than other
iron oxides. For ␣-Fe2 O3 , though the onset temperature increases
to about 100 ◦ C, the maximum temperature also exceeds 750 ◦ C.
The maximum temperature for ␣-Fe3 O4 was even higher, which
appears to have encountered a programmed instrument shutdown
at 900 ◦ C. The shapes of the curves have more than one peaks sug-
gesting occurrence of multiple reactions. The variation of pressure
for EO with iron oxide is in accordance with temperature [34].
The maximum reaction pressure for EO with ␥-Fe2 O3 is less than
1.4 Mpa though the peak temperature could reach 600 ◦ C. The run-
away reaction pressure for EO with ␣-Fe2 O3 was about 18 Mpa,
91
which is much greater than other iron oxides and the great pres-
sure could result in equipment damage in practical plant. Also, the
multiple peak behavior is apparent in pressure curves, particularly
for ␣-Fe3 O4 and ␣-Fe2 O3 .
5.2.2. Self-heat rate for EO reaction with iron oxides
The self-heat rate for EO with ␥-Fe2 O3 was roughly 1 ◦ C/min
at room temperature and then accelerated to over 1000 ◦ C/min,
which is the highest in the three types of iron oxides [34] (Fig. 6). A
decrease in the rate was seen when the temperature exceed 300 ◦ C,
which may result from the diminishing of the reactant. The next
most active iron oxide material appears to be the ␣-Fe3 O4 fines,
and the self-heat rate exhibits relatively complex trends. A lower
self-heat rate with fluctuation for temperature ranging from room
temperature to about 140 ◦ C was observed, and then the reaction
seems to vanish shortly thereafter. Sustained reaction appeared
again when the temperature was over 260 ◦ C, and the self-heat
rate reached as high as 10,000 ◦ C/min in one case. For ␣-Fe2 O3
and hydrated ␣-Fe2 O3 , the self-heat rate generally increase from
0.1 ◦ C/min to 200 ◦ C/min with temperature, except that there is a
dropping off trend at 140–175 ◦ C for ␣-Fe2 O3 . The complicated vari-
ation of self-heat rate indicates there might be multiple reactions.
5.2.3. Pressure for EO reaction with iron oxides
The pressure generated in the system was characterized and
compared with the pressure of EO vapor + nitrogen pad gas as
shown in the pressure versus temperature plots (Fig. 7). For EO
with ␣-Fe3 O4 /␣-Fe2 O3 /hydrated ␣-Fe2 O3 , the pressure of the sys-
tem follows the curve of EO vapor and nitrogen pad gas pressure
until 170 ◦ C, after which the pressure falls away from the projected
pressure due to consumption of EO and the increasing difference
between solids and gas temperature in the cell. For EO with ␣-
Fe2 O3 , sharp increases in pressurization rate and pressure were
observed at about 380 ◦ C, indicating that the ignition of EO vapor
might take place. During the cool-down period, the pressure for the
system of EO with ␣-Fe3 O4 /␣-Fe2 O3 was below 140 kPa because
the titanium cell ruptured and the rupture disk burst. For EO
with ␥-Fe2 O3 , a deviation of system pressure from the projected
vapor pressure + gas pad line was observed for temperature below
30 ◦ C, then the pressure kept almost constant until 350 ◦ C. Dur-
ing the cool-down period, the pressure remained higher than the
corresponding pressures during heat-up, suggesting generation of
non-condensable gases. The rapid exothermic reactivity of EO in
the presence of iron oxide could be illustrated by the time-to-
maximum rate. The time to maximum rate generally increase with
initial temperature for all the iron oxides. For EO with ␥-Fe2 O3 , it
takes less than 10 min for the rate to reach its maximum from room
temperature, while for ␣-Fe2 O3 /hydrated ␣-Fe2 O3 the time is about
several hours. For EO with ␣-Fe3 O4 , the time-to-maximum rate also
indicate the possibility of multiple reactions as demonstrated in the
profiles of temperature, pressure and self-heat rate.
The calorimetric study suggest the following relative reactive
sensitivity of different iron oxides with EO:
␥-Fe2 O3 > ␣-Fe3 O4 > hydrated␣-Fe2 O3 > ␣-Fe2 O3 >> ␣-FeO ≈ glass
EO in combination with all of the above iron oxide fines except
FeO displays exothermic activity as low as room temperature. The
peak temperature of the fines with EO in many cases ultimately
exceeded 600 ◦ C. The self-heat rates approach 2000 ◦ C/min for ␥-
Fe2 O3 fines while the rates are in excess of 100 ◦ C/min for the other
fines. The pressurization rates approach about 7 Mpa/min for ␣-
Fe3 O4 and ␣-Fe2 O3 . It should be noted that the rust in the practical
device may contain not only one forms of iron oxides, and the sur-
face area of the iron oxide is also an important factor to determine
the reactivity with EO.
92 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96

Fig. 5. Temperature history of EO in contact with iron oxide [41].

Fig. 6. Self-heat rate profiles of EO in contact with iron oxide [41].

6. The thermal reactivity of EO with alkalis
Alkali metal hydroxide such as potassium hydroxide or sodium
hydroxide can be used as a basic catalyst for many ethoxylation
reactions. So alkalis have relatively high possibility to reduce the
thermal stability of EO and cause runaway reactions. There were
many incidents in history in which the alkali presented as an
impurity initiated exothermic polymerization of EO, and the local
temperature was increased to the decomposition temperature of
EO. The reactivity of EO with alkali contaminants including potas-
sium hydroxide (KOH), sodium hydroxide (NaOH), and ammonium
 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96 93

Fig. 7. Pressure-temperature profiles of EO in contact with iron oxide [41].

hydroxide (NH4 OH) was systematically studied by Dinh et al. using
the APTAC [31].
6.1. Reaction of EO with KOH
For EO with KOH, the onset temperature decrease with the
increase amount of KOH, and the exothermic activities appeared at
around 30–60 ◦ C compared to 200 ◦ C for pure EO. While the maxi-
mum temperature or pressure decrease inversely with the increase
weight of KOH. The measured heat rates with respect to tempera-
tures also indicated that the heat release of the sample starts earlier
for higher amount of KOH. Although the self-heat rate attained by
each run was different, no significant difference was observed for
the pressurization rates in the investigated range of contaminant
concentrations. As shown in Fig. 8 the pressure variation versus
temperature of EO/KOH samples, the pressure of the mixture fol-
lows the vapor pressure of pure EO at heat up stage, and then
become flat due to consumption of EO. During the cool-down stage
the slopes were lower than the heating curve slopes indicating that
EO was converted into less volatile components, while this trend is
inverse to the above mentioned EO with iron oxide case. The time
for EO with KOH to reach maximum reaction rate decrease as the
increase of initial temperature, and the amount of KOH is also favor-
able to reduce the time to maximum rate. For EO with 1.0 g KOH,
the time-to-maximum rate from ambient temperature is about 1 h.
6.2. Reaction of EO with NaOH
For EO with NaOH, the main parameters such as the onset
temperature, maximum temperature, maximum heat release rate
and maximum pressurization rate generally shown similar trends
with that of KOH. However, the effect of NaOH concentration on
the onset temperature was not obvious. The self-heat rates for
EO/NaOH was much higher than the ones observed for the KOH,
especially for the 0.1 g NaOH case. For the 0.5 g and 1.0 g NaOH
tests, the cool-down pressure exceeds the heat up pressure indi-
cating there might be non-condensable product, which is different
to the product of EO/KOH. So far, the products of EO with different
contaminants have not been determined and need to be further
studied.
The results of ARC analysis on the various EO-NaOH mixtures
are provided by Freeder et al. [42] as shown in Table 4. The onset
temperature decreases with the increase of NaOH concenrations
and it is as low as room temperature for 1.0 M NaOH molarity. The
adiabatic temperature rise produced by the polymerization of EO
in the presence of NaOH is calculated as follow:
Tc = ˚ · (Tf − Ton ) (19)
where Ton is onset temperature, Tf is final temperature, and  is
the thermal inertia factor defined as:
Ms Cs + Mb Cb
˚= (20)
Ms Cs

Table 4
Experimental results of ARC analysis for EO/NaOH mixtures [42].

NaOH molarity [mol L−1 ] Onset Final Corrected adiabatic Heat of Maximum Temperature at
temperature Ton temperature Tf remperature rise Tc polymerization H pressure Pmax maximum
[◦ C] [◦ C] [◦ C] [kJ mol−1 ] [kPa] pressure Tmp [◦ C]

1.0 22.5 222 415.5 44.2 4465 147.0

0.5 35.5 178 296.5 31.6 3608 152.0
0.25 39.0 250 456.5 48.6 3876 151.8
0.125 55.0 263 439.5 46.7 4055 188.0
94 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96
Fig. 8. Pressure-temperature profiles of EO/KOH mixtures [31].
where Ms is the sample mass, Mb is the cell mass, Cs is the specific
heat of sample, and Cb is the specific heat of cell.
The adiabatic temperature rise appears to be independent of
the concentration of alkali apart from the mixture containing 0.5 M
NaOH. The average value of the polymerization heat calculated
from ARC data is about 42.8 kJ mol−1 . The maximum pressures
are achieved at a temperature below the maximum temperature
because the reduction in the average vapor pressure of the react-
ing mixture as polymerization takes place. According to the plots of
self-heat rate versus temperature, the initial parts of the plots are
approximately linear and the initial gradients have been found to
be independent of the concentration of alkali. This is in reasonable
agreement with the results of Dinh et al. [31].
6.3. Reaction of EO with NH4 OH
For the reactivity of EO with 30% ammonium hydroxide aque-
ous solution, both the effect of NH3 and water were investigated.
The amount of NH4 OH has significant effect on the onset tem-
perature compared to other two alkalis. Compared to the lowest
onset temperature for EO aqueous solution (about 50 ◦ C), the onset
temperature for EO with 1.0 g NH4 OH was decreased to 21 ◦ C, indi-
cating that NH4 OH also reduce the temperature besides water.
However, the onset temperature for EO with 0.1 g NH4 OH could
reach 160 ◦ C, indicating that the mixture with small amount was
relatively stable near ambient temperature. The self-heat rate for
EO with 1.0 g NH4 OH accelerated from 0.1 ◦ C/min at room temper-
ature to 600 ◦ C/min within a short time thereafter (Fig. 9). For EO
with 0.1 g and 0.5 g NH4 OH, multistage self-heating processes were
observed. EO could react with water to produce ethylene glycol, and
then polymerization to diethylene glycol and triethylene glycol.
Similarly, ethanolamine, diethyleneamine and triethyleneamine
could also be produced by EO and ammonia. This two types of
polymerization reactions may compete with each other resulting
in different self-heating rate. Also, the accumulated energy in the
adiabatic environment will probably cause the ultimate decompo-
sition of EO vapor. Thus, the final rate of heat over 1000 ◦ C/min
was observed. The time to maximum rate for EO with 1.0 g NH4 OH
is much lower than the 0.1 g and 0.5 g case, indicating that dif-
ferent reactions might take place for EO with diverse amounts of
ammonium hydroxide aqueous solutions.
6.4. Onset temperature comparison
The onset temperature is an important parameter for evaluation
of the contamination effects on EO thermal reactivity. The initial
reaction temperature is much lower when EO is in contact with
alkalis (Fig. 10). The exothermic onset temperatures decrease with
the increase of contamination mass. The effect of contamination
mass on the onset temperature of EO is more significant for NH4 OH
than for KOH and NaOH. Obviously, the onset temperature for EO
with NaOH is higher than that of EO with KOH in the contaminant
concentration range studied. The presence of NH4 OH with a suffi-
cient concentration has the highest impact to decrease the onset
temperature of contaminated EO, so the following relative reactiv-
ity of contamination is suggested: NH4 OH > KOH > NaOH. However,
the thermokinetics of the reactions of EO with KOH, NaOH, and
NH4 OH should be further determined.
7. Conclusions
In this paper, multiple experimental studies of EO’s thermal
reactivity in the presence of contaminants such as water, iron
oxides, and alkalis have been summarized systematically, provid-
ing basic understanding of the thermokinetic mechanism of the
runaway reactions. The basic thermodynamic and kinetics param-
eters for EO reaction with containments are foundation for further
process safety optimization and emergency relief system design,
since safe process design requires knowledge of the chemical reac-
tivity on the worst scenario of desired as well as undesired chemical
reactions due to upset conditions.
A few conclusions could be drawn from the analysis. For pure
EO, it requires about 200 ◦ C to initiate runaway reaction under adia-
batic conditions, and the maximum reaction pressure could exceed
10 Mpa. For EO with water, a minimum onset temperature around
60 ◦ C was observed for EO concentrations from 20 wt%–40 wt%, and
the onset temperature increases with EO concentration. The fourth-
order reaction rate model proposed by Melhem et al. could predict
the onset temperatures especially at high EO concentrations very
well. When EO was in contact with iron oxides such as ␣-Fe3 O4 ,
␣-Fe2 O3 , hydrated ␣-Fe2 O3 and ␥-Fe2 O3 , exothermic activity was
detected below 100 ◦ C, while for FeO no discernable exothermic
activity was observed. Self-heat rates approaching 2000 ◦ C/min
were observed for the ␥-Fe2 O3 fines, which is considered to be
the most effective iron oxide to catalyze EO polymerization reac-
 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96 95

Fig. 9. Self-heat rate profiles of EO/NH4 OH mixtures [31].

Fig. 10. Comparison of onset temperatures for EO with alkalis [25].

tion. For EO with alkalis, three industrial contaminants, KOH, NaOH,
and NH4 OH were investigated to find that NH4 OH with a suffi-
cient concentration has the highest impact on the thermokinetics
parameters namely onset temperature, pressurization rate and
maximum reaction pressure etc. The mass of alkalis has a pos-
itive effect to reduce the initial reaction temperature especially
for NH4 OH. The relative reactivity of alkali contaminations is sug-
gested: NH4 OH > KOH > NaOH.
Some suggestions could be proposed for inherently safer design
and operation of EO facility. It is better to keep EO away from incom-
patible containments and materials in main equipment, pumps,
valves, pipelines, gasket, hoses, insulation, etc. Temperature is the
best parameter for the detection and analysis of the evolution of
the situation in case of runaway reaction of EO. For this reason, it
is recommended to measure permanently this parameter, to set
adequate alarm and interlock to monitor and control the evolution
of the temperature in case of detected deviation. For EO aqueous
solution in EO purification unit, a moderate concentration should
be selected based on the relationship between onset temperature
and EO concentration, and the local concentration and temperature
need to be detected and controlled.
It should be noted firstly that the thermo-kinetics parameters
obtained from different apparatus under specific operational con-
ditions could vary a lot, which could be attributed to the thermal
inertia or sensitivity of the instruments. Since the thermal inertia of
the laboratory instrument is higher than the plant-scale equipment,
the measured data may underestimate the runway reaction haz-
ards. Besides, it is not explicit what kind of reactions take place and
what the product distribution is for EO with various contaminants.
The reaction kinetics have not been established yet apart from EO
with water. For example, the onset temperature for EO/KOH and
EO/NaOH differs by 60–70 ◦ C though the properties and molecu-
lar structure for KOH and NaOH are similar. Finally, the important
calorimetric data-exothermic heat for EO with various contami-
nants are not provided by previous study, which is an essential
parameter for safety control and equipment design.
Acknowledgments
The authors gratefully acknowledge the financial support pro-
vided by the Ministry of Science and Technology of SINOPEC (No.
414085). The support of professor Mannan from Mary Kay O’Connor
96 J. Liu et al. / Thermochimica Acta 652 (2017) 85–96
Process Safety Center, Artie McFerrin Department of Chemical Engi-
neering, Texas A&M University is acknowledged.
References
[1] M. Ghanta, T. Ruddy, D. Fahey, D. Busch, B. Subramaniam, Is the liquid-phase
H2O2-based ethylene oxide process more economical and greener than the
gas-phase O2-based silver-catalyzed process? Ind. Eng. Chem. Res. 52 (1)
(2013) 18–29.
[2] J.R.H. Carucci, V. Halonen, K. Eränen, J. Wärnå, S. Ojala, M. Huuhtanen, R.
Keiski, T. Salmi, Ethylene oxide formation in a microreactor: from qualitative
kinetics to detailed modeling, Ind. Eng. Chem. Res. 49 (21) (2010)
10897–10907.
[3] J.-L. Gustin, Influence of trace impurities on chemical reaction hazards, J. Loss
Prev. Process Ind. 15 (1) (2002) 37–48.
[4] R.A. Kemp, Ethylene oxide catalyst and process. US5545603. In US, 1996.
[5] F. Tamura, M. Saotome, Silver catalyst for production of ethylene oxide and
method for manufacture thereof. EP, US4645754. In EP, 1987.
[6] H. Kestenbaum, A. Lange de Oliveira, W. Schmidt, F. Schüth, W. Ehrfeld, K.
Gebauer, H. Löwe, T. Richter, D. Lebiedz, I. Untiedt, H. Züchner,
Silver-catalyzed oxidation of ethylene to ethylene oxide in a microreaction
system, Ind. Eng. Chem. Res. 41 (4) (2002) 710–719.
[7] H.J. Lee, M. Ghanta, D.H. Busch, B. Subramaniam, Toward a CO2—free ethylene
oxide process: homogeneous ethylene oxide in gas-expanded liquids, Chem.
Eng. Sci. 65 (1) (2010) 128–134.
[8] M.R. Rahimpour, M. Shayanmehr, M. Nazari, Modeling and simulation of an
industrial ethylene oxide (EO) reactor using artificial neural networks (ANN),
Ind. Eng. Chem. Res. 50 (10) (2011) 6044–6052.
[9] X. Yang, Q. Xu, K. Li, C.D. Sagar, Dynamic simulation and optimization for the
start-up operation of an ethylene oxide plant, Ind. Eng. Chem. Res. 49 (9)
(2010) 4360–4371.
[10] A. Peschel, A. Jörke, K. Sundmacher, H. Freund, Optimal reaction concept and
plant wide optimization of the ethylene oxide process, Chem. Eng. J. 207
(2012) 656–674.
[11] S. Rebsdat, D. Mayer, Ethylene oxide, in: Ullmann’s Encyclopedia of Industrial
Chemistry, Wiley-VCH, Weinheim, 2001.
[12] B. Fabiano, F. Pistritto, A. Reverberi, E. Palazzi, Ethylene–air mixtures under
flowing conditions: a model-based approach to explosion conditions, Clean
Technol. Environ. Policy 5 (2015) 1261–1270.
[13] F. Wang, Y. Zhao, O. Yang, J. Cai, M. Deng, Process safety data management
program based on HAZOP analysis and its application to an ethylene
oxide/ethylene glycol plant, J. Loss Prev. Process Ind. 26 (6) (2013) 1399–1406.
[14] F.I. Khan, M.R. Haddara, Risk-based maintenance of ethylene oxide
production facilities, J. Hazard. Mater. 108 (3) (2004) 147–159.
[15] T.A. Kletz, Fires and explosions of hydrocarbon oxidation plants, Plant Oper.
Prog. 7 (4) (1988) 226–230.
[16] J.L. Woodward, J.W. Wesevich, T.J. Kelly, Q.A. Baker, Analysis of ethylene oxide
gas house explosion, Process Saf. Prog. 26 (2) (2007) 150–154.
[17] R.G. Vanderwater, Case history of an ethylene tank car explosion, Chem. Eng.
Prog. (USA) 85 (1989) 12.
[18] L.G. Britton, Spontaneous fires in insulation, Plant Oper. Prog. 10 (1) (1991)
27–44.
[19] Ameya Joshi, Xiaoqing You, T.A.B. Barckholtz, H. Wang, Thermal
decomposition of ethylene oxide: potential energy surface, master equation
analysis, and detailed kinetic modeling, J. Phys. Chem. A 109 (35) (2005)
8016–8027.
[20] P. Thibault, L.G. Britton, F. Zhang, Deflagration and detonation of ethylene
oxide vapor in pipelines, Process Saf. Prog. 19 (3) (2000) 125–139.
[21] R. Bubbico, G. Dore, B. Mazzarotta, Risk analysis study of road transport of
ethylene oxide, J. Loss Prev. Process Ind. 11 (1) (1998) 49–54.
[22] C. Hirose, The microwave spectra and r0 , rs , and rm structures of ethylene
oxide, Bull. Chem. Soc. Jpn. 47 (6) (1974) 1311–1318.
[23] R. June, R. Dye, Explosive decomposition of ethylene oxide, Plant Oper. Prog. 9
(2) (1990) 67–74.
[24] J.P. Dever, K.F. George, W.C. Hoffman, H. Soo, Ethylene Oxide: Kirk Othmer
Encyclopedia of Chemical Technology, vol. 10, 5th edition, John Wiley & Sons,
Hoboken, NJ, 2005, pp. 632–673.
[25] R.K. Mcmullan, G.A. Jeffrey, Polyhedral clathrate hydrates. IX. Structure of
ethylene oxide hydrate, J. Chem. Phys. 42 (42) (2004) 2725–2732.
[26] Y.L. Huang, T. Merker, M. Heilig, H. Hasse, J. Vrabec, Molecular modeling and
simulation of vapor-liquid equilibria of ethylene oxide, ethylene glycol, and
water as well as their binary mixtures, Ind. Eng. Chem. Res. 51 (21) (2012)
7428–7440.
[27] M. Herskowitz, M. Gottlieb, Vapor-liquid equilibrium in aqueous solutions of
various glycols and poly(ethylene glycols). 2: tetraethylene glycol and
estimation of UNIFAC parameters, J. Chem. Eng. Data 2 (2002) 233–234.
[28] M.R. Altiokka, S. Akyalçin, Kinetics of the hydration of ethylene oxide in the
presence of heterogeneous catalyst, Ind. Eng. Chem. Res. 48 (24) (2009)
10840–10841.
[29] L.D. Chen, G.M. Faeth, Initiation and properties of decomposition waves in
liquid ethylene oxide, Combust. Flame 40 (1) (1981) 13–28.
[30] G.A. Viera, L.L. Simpson, B.C. Ream, Lessons learned from the ethylene oxide
explosion at Seadrift, Texas, Chem. Eng. Prog. 89 (1993) 66–75.
[31] L.T.T. Dinh, W.J. Rogers, M.S. Mannan, Reactivity of ethylene oxide in contact
with basic contaminants, Thermochim. Acta 480 (1) (2008) 53–60.
[32] G.A. Melhem, A. Gianetto, M.E. Levin, H.G. Fisher, S. Chippett, S.K. Singh, P.I.
Chipman, Kinetics of the reactions of ethylene oxide with water and ethylene
glycols, Process Saf. Prog. 20 (4) (2001) 231–246.
[33] L.G. Britton, Thermal stability and deflagration of ethylene oxide, Plant Oper.
Prog. 9 (2) (1990) 75–86.
[34] K.H. Mueller, W.D. Walters, The thermal decomposition of ethylene oxide1,2,
J. Am. Chem. Soc. 76 (2) (2002) 1458–1461.
[35] A.A. Pekalski, J.F. Zevenbergen, M. Braithwaite, S.M. Lemkowitz, H.J. Pasman,
Explosive decomposition of ethylene oxide at elevated condition: effect of
ignition energy, nitrogen dilution, and turbulence, J. Hazard. Mater. 118 (1–3)
(2005) 19–34.
[36] E. Wilcock, R.L. Rogers, A review of the phi factor during runaway conditions,
J. Loss Prev. Process Ind. 10 (5–6) (1997) 289–302.
[37] P. Virtanen, Kinetics of the hydrolysis reactions of ethylene oxide, Ann. Acad.
Sci. Fenticae (1963) 9–89.
[38] T. Tsuji, T. Hiaki, M. Hongo, Vapor-liquid equilibria of the three binary
systems: water plus tetraethylene glycol (TEG), ethanol plus TEG, and
2-propanol plus TEG, Ind. Eng. Chem. Res. 37 (5) (1998) 1685–1691.
[39] L.G. Britton, D.A. Taylor, D.C. Wobser, Thermal stability of ethylene at elevated
pressures, Plant Oper. Prog. 5 (4) (1986) 238–251.
[40] M.A. Villamanan, C. Gonzalez, H.C.V. Ness, Excess thermodynamic properties
for water/ethylene glycol, J. Chem. Eng. Data 29 (4) (1984).
[41] M.E. Levin, The reactivity of ethylene oxide in contact with iron oxide fines as
measured by adiabatic calorimetry, J. Hazard. Mater. 104 (1–3) (2003)
227–245.
[42] B.G. Freeder, T.J. Snee, Alkali-catalysed polymerization of ethylene oxide and
propylene oxide—hazard evaluation using accelerating rate calorimetry, J.
Loss Prev. Process Ind. 1 (3) (1988) 164–168.