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Effects of Temperature and Pressure on the Thermolysis of

Morpholine, Ethanolamine, Cyclohexylamine, Dimethylamine, and
3‑Methoxypropylamine in Superheated Steam
David H. Moed,*,† Arne R. D. Verliefde,‡ and Luuk C. Rietveld†
†
Faculty of Civil Engineering and Geosciences, Delft University of Technology, Stevinweg 1, 2628 CN Delft, The Netherlands
‡
Particle and Interfacial Technology Group, Ghent University, Coupure Links 653, 9000 Gent, Belgium
*
S Supporting Information

ABSTRACT: Alkalizing amines such as cyclohexylamine and dimethylamine have great potential for protecting steam−water
cycles against corrosion, but their thermal stability is limited and anionic decomposition products are a concern because of
increased corrosion risk. In this study, morpholine, ethanolamine, cyclohexylamine, dimethylamine, and 3-methoxypropylamine
were exposed to temperatures of 500, 530, and 560 °C at pressures of 9.5, 13.5, and 17.5 MPa to investigate the effects of
temperature and pressure on amine thermolysis kinetics. The surface/volume ratio of the reactor tube was 0.4 mm−1, close to the
value for superheater tubes in steam−water cycles. All amines thermolyzed by first-order kinetics, with the exception of
dimethylamine. The Arrhenius constants Ea, ln(A), and Va were obtained from the experimental data for all investigated amines.
The effect of pressure on the thermolysis kinetics was less pronounced than in previous studies and was different for each amine.
Dimethylamine did not degrade below 20% and 10% at 500 and 530 °C, respectively, despite the application of longer retention
times, suggesting the synthesis might occur. Limited practical data showed some promise for the applicability of the model to
steam−water cycles. More plant data are needed to fully validate the model. In all cases, thermolysis of the amines led to the
formation of between 150 and 600 ppb organic acid anions. In most cases, the concentrations increased linearly with increasing
degradation percentage. Acetate and formate were found to be major degradation products, with some propionate and traces of
glycolate. Cationic degradation products were ammonia and some amines, meaning that the complete thermolysis of an amine
does not necessarily lead to acidic conditions.

1. INTRODUCTION Some experimental data on the thermal degradation of

The demineralized water used in steam−water cycles is
chemically conditioned to raise the pH of the water and
reduce failures due to corrosion. One of the applied chemical
treatment methods is all-volatile treatment (AVT), which uses
ammonia to raise the pH of both the boiler (feed) water and
the steam or condensate. Although AVT is commonly applied
for steam−water cycles (SWCs), AVT requires high water
purity1 and still enhances the corrosion of any copper that
might be present in an SWC. Also, because ammonia is more
volatile than water, it offers limited protection to corrosion in
areas where flashing occurs or the first droplets of condensate
are formed.2,3 Alkalizing amines such as morpholine (MOR)
and ethanolamine (ETA) offer a less volatile alternative to
ammonia,4 making the SWC more resilient to corrosion.5−7
Because ammonia corrodes copper, amines can also be a good
chemical water treatment solution for systems with mixed
metallurgy. Amines have been applied in nuclear power plants
for decades, and some guidelines are available.3 However, the
use of amines in fossil-fired plants is under debate, because of
the higher operating temperatures and pressures employed.
Because amines are known to have limited thermal stability,
they can decompose to form organic acid anions, lowering pH
and thereby increasing corrosion risks.2,8 Potential formation of
organic acid anions during amine thermolysis is currently
preventing the general acceptance of amines for application in
steam−water cycles.
amines are available, but most such data focus only on
conditions found in nuclear plants,9−12 with data applicable to
fossil-fired plants being more limited. Mori et al.13 tried to
simulate the thermolysis of six amines under fossil-fired plant
conditions at higher temperatures with a boiler−superheater
test loop. They considered the effect of the superheater on
thermolysis by varying the superheater exhaust temperature.
They concluded that MOR breakdown in the boiler was
undetectable and started only from 500 °C onward in the steam
phase, whereas ETA started degrading already at steam exhaust
temperatures of 450 °C. The retention time was not
mentioned, making any calculation of kinetics impossible.
The importance of the superheater in the applicability of
alkalizing amines in fossil-fired plants was also pointed out by
Bull14 in a report detailing the results from a fossil-fired plant
survey on the use of amines.
In another study, MOR was dosed (9 ppm) to investigate the
effects of pressure, temperature, and retention time on amine
degradation kinetics in a flow reactor, mimicking a super-
heater.15 MOR degradation kinetics were found to be first-
order, increasing with temperature and decreasing with
Received: December 12, 2014
Revised: February 13, 2015
Accepted: February 18, 2015
Published: February 18, 2015

© 2015 American Chemical Society 2606 DOI: 10.1021/ie504849v

Ind. Eng. Chem. Res. 2015, 54, 2606−2612
Industrial & Engineering Chemistry Research Article

Figure 1. Schematic of the flow reactor used during the experiments (from left to right): argon, bottle containing the solution of interest, HPLC
pump, fluidized sand bed (FSB), metal tube in the FSB, cooling spiral, and back-pressure regulator (BPR).

pressure. The tubes used in the flow reactor, however, were Table 1. The Investigated Amines, Temperatures, Pressures,
only 1.5 mm in diameter, making the surface/volume (S/V) and Retention Timesa
ratio (4.65 mm−1) much higher than in full-scale fossil-fired
amineb T (°C) P (MPa) t (s)
plants, where the tube diameters are typically at least 10 times
larger. The metal oxide layer on the surface of the tubes MOR 500 9.5 0−5
appeared to also influence the thermolysis kinetics. In a ETA 530 13.5 5−10
previous publication, we provided a relation between the S/V DMA 560 17.5 10−20
ratio and thermolysis kinetics and made a distinction between CHA 20−30
homogeneous (in the bulk steam) and heterogeneous (on the MOPA
a
metal surface) thermolysis.16 Although heterogeneous thermol- T, temperature; P, pressure; t, retention time of the steam inside the
ysis accounted for 82−92% of the value of the degradation rate tube. bEach amine has been tested at every temperature, pressure, and
constant k for tubing with an S/V ratio of 4.65 mm−1, the retention time listed.
contribution was only 6−17% at an S/V ratio of 0.4 mm−1. This
led to the conclusion that an amine thermolysis study is best argon, and 0.1 ppm carbohydrazide was dosed to eliminate any
conducted with larger metal tubes, preferably with S/V ratios of remaining traces of oxygen. A more detailed description of the
0.4 mm−1 or less, to approximate superheater tube sizes. setup and procedure was already published by Moed et al.16
In this study, the effects of temperature and pressure on the 2.2. Analyses. Analysis of organic acid anions was
thermolysis of five amines that are being applied in steam− performed using a Metrohm (Schiedam, The Netherlands)
water cycles [MOR, ETA, dimethylamine (DMA), cyclohexyl- 881 ion chromatography system. A Metrohm A Supp 16 4.0/
amine (CHA), and 3-methoxypropylamine (MOPA)] were 250 anion column was operated at 67 °C with eluent
studied in a flow reactor equipped with a Hastelloy C-276 tube containing 7.5 mM Na2CO3 + 0.75 mM NaOH in ultrapure
with an S/V ratio of 0.4 mm−1. The data were used to construct water. The suppressor was regenerated with 50 mM H2SO4,
a predictive model to assess the applicability of amines in high- and the limit of detection was 1 ppb. For cation analysis, a
temperature and -pressure steam−water cycles. The organic Metrohm C5 cation column was used, with 3 mM HNO3 as the
acid anions and ammonia that are produced during amine eluent, for which the limit of detection for MOR, ETA, MOPA,
thermolysis are discussed, and an explanation is given as to why and DMA was 5 ppb and that for CHA was 50 ppb. The
DMA does not degrade according to first-order kinetics. detection limit for ammonia was 1 ppb.
2.3. Temperature and Pressure Relations. First-order
isobaric degradation kinetics as a function of absolute
2. MATERIALS AND METHODS
temperature were modeled according to the equations17
2.1. Setup and Conditions. A schematic of the
experimental setup is provided in Figure 1. A high-performance r = k(T )C (1)
liquid chromatography (HPLC) pump sends the solution of
k(T ) = A e−Ea / RT (2)
interest through Hastelloy C-276 tubing inside a fluidized sand
bath at a fixed flow rate. The tube inside the fluidized sand bed where r is the degradation rate, k(T) is the degradation rate
was a 12.5-mm Hastelloy C-276 tube with a volume of 6.2 mL constant as a function of temperature, C is the concentration of
and an internal diameter of 10 mm, thus having an S/V ratio of the degrading compound, A is the pre-exponential factor, Ea is
0.4 mm−1. the activation energy, T is the absolute temperature, and R is
The amine solutions of interest were tested under the the universal gas constant.
conditions listed in Table 1, and the experiments were executed The latter equation can be written in logarithmic form as
in duplicate. Retention times were varied by adjusting the Ea 1
HPLC pump flow rate to 0.75, 1.0, 1.5, or 2.5 mL/min, and the ln(k) = ln(A) −
RT (3)
flow rate was checked for accuracy before every run. Because
water and steam increase in volume at higher temperatures, the Therefore, in an Arrhenius plot of ln(k) versus 1/T, the slope
retention time in the tubing is a function of flow rate, of the regression line through the data points gives the
temperature, and pressure inside the tube. Therefore, applied experimental value of Ea/R, and the y intercept corresponds to
retention times are listed in ranges. Oxygen was removed with ln(A).
2607 DOI: 10.1021/ie504849v
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In a previous study, Moed et al.15 showed the independency steam. The linear regression lines given for each pressure
of the activation energy (Ea) and activation volume (Va) on enabled the calculation of the activation energy Ea (by using the
both temperature and pressure. When the natural logarithm of slope) and the prefactor A (by using the y intercept). The
the degradation rate constant (k) is plotted as a function of averages of the resulting three Ea and ln(A) values were used in
pressure (at a constant temperature), the activation volume can the model. The same data were used to plot ln(k) against P for
be derived from the slope each temperature (see Figure 3), from which Va was calculated
Va
ln(k) = ln(k ref ) − (P − Pref )
RTref (4)
where kref is the degradation rate constant corresponding to the
reference temperature (Tref) and reference pressure (Pref). The
calculated values for Va should be independent of the chosen
values for Tref and Pref. Combining eq 3 and 4, the reaction rate
as a function of temperature and pressure can be written as
⎡ E V ⎤
r = k(T , P)C = exp⎢ln(A) − a − a (P − Pref )⎥C
⎣ RT RT ⎦
(5)
To determine the experimental values for k, an integrated
first-order rate law was fitted to the experimentally determined
Figure 3. Arrhenius plot of the relation between ln(k) and P for the
decrease in concentration of the amines upon degradation. First thermolysis of ETA in dry steam at 9.5, 13.5, and 17.5 MPa.
order was assumed because it was found to be the case for
amine degradation in most previous studies.9,10,12,15,16,18,19
using the slope of the linear regression lines at each
C = C0e−kt (6) temperature. The average for the three temperatures was the
The reaction rate constant k can be found by plotting C/C0 value of Va used in the proposed model.
against time and calculating the exponential regression function The Arrhenius plots for the other four amines can be found
y = e−kx. The threshold for a good fit was chosen at R2 = 0.95, in the Supporting Information. Figures S5, S8, and S11 show
and when the results that did not meet this requirement, the the pressure relation of ln(k) for MOR, MOPA, and CHA and
corresponding experiments were repeated. Subsequently, A, Ea, have almost horizontal regression lines. Figures S4, S7, and S10
and Va can be determined from eqs 3 and 4 as described above. (Supporting Information) show their temperature relation of
ln(k), where the regression lines are close together. MOR,
3. RESULTS AND DISCUSSION MOPA, and CHA therefore show no clear pressure depend-
ency. All values found for Ea, A, and Va are summarized in Table
3.1. Temperature and Pressure Relations. Degradation 2, including the errors. The activation volumes of MOR,
curves were constructed from the obtained data. The MOPA, and CHA have been highlighted in italics, because of
thermolysis of all amines led to first-order regression curves, their apparent lack of pressure dependency.
with the exception of DMA, which will be discussed in more It must be noted that a higher activation energy does not
detail later. First-order kinetics applied to degradation necessarily imply higher thermal stability of a compound, as
percentages over 90% as well, showing concentration thermal stability also depends on the prefactor A. The
independency in the range of 1−9 ppm. This range could be activation energy indicates the amount of energy that is
larger, but the data cannot validate such a claim. The values for
k resulting from the degradation curves were used to create Table 2. Summary of Ea, ln(A), and Va Values Found for
Arrhenius plots for the temperature relation. An example of Each Amine, Including Standard Deviations (SDs) and
such a plot is given in Figure 2, which shows the relation Relative Standard Deviations (RSDs)
between ln(k) and 1/T for the thermolysis of ETA in dry
amine constant mean SD RSD (%) units
ETA Ea 189 1 1 kJ mol−1
ln(A) 25.5 0.4 2 s−1
Va 369 59 16 cm3 mol−1
MOR Ea 295 15 5 kJ mol−1
ln(A) 40.2 2.2 5 s−1
Va 137 134 98 cm3 mol−1
MOPA Ea 254 16 6 kJ mol−1
ln(A) 35.6 2.4 7 s−1
Va 6 151 2343 cm3 mol−1
CHA Ea 409 12 3 kJ mol−1
ln(A) 56.9 1.7 3 s−1
Va 272 112 41 cm3 mol−1
DMA Ea 100 3 3 kJ mol−1
Figure 2. Arrhenius plot of the relation between ln(k) and 1/T for the ln(A) 13.6 0.4 3 s−1
thermolysis of ETA in dry steam at 500, 530, and 560 °C. Va 346 19 6 cm3 mol−1

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Industrial & Engineering Chemistry Research
required to start the degradation reaction, but the prefactor A
determines how quickly the amine degrades as a function of
temperature. For example, the thermolysis of CHA in dry steam
has a high activation energy at 500 °C, resulting in a higher
value for k than for MOR, making CHA more stable than MOR
at that temperature. However, the high prefactor determines
that the k values of CHA and MOR are almost the same at 560
°C and 13.5 MPa (0.074 and 0.072 s−1, respectively).
A previous study showed much lower MOR stability than
observed here.15 That study was executed with a smaller
stainless steel tube (S/V = 4.65 mm−1), resulting in a large
contribution of catalytic wall effects to the thermolysis. This
emphasizes the importance of the S/V ratio when studying
thermal degradation under conditions resembling those in full-
scale plants, as was shown in ref 16. In the previous study, a
much greater effect of pressure for MOR was found as well.
This suggests that metal surface catalysis enhances the pressure
dependency effect.
Another report discussed the thermal stability of MOR,
CHA, ETA, and DMA in an experimental setup similar to that
used in this work but with an S/V ratio of 4.65 mm−1.18 MOR,
CHA, and ETA showed lower thermal stability in the smaller
tubing. ETA, for instance, underwent 90% degradation in 12 s
at only 490° and 17.5 MPa. DMA was an exception, showing
higher stability in the small tubing. DMA thermolysis, however,
did not always follow first-order kinetics, thus making modeling
difficult, as discussed in the next section.
To compare the experimentally obtained values of k with
those calculated using eq 5 and the results in Table 2, the
experimental k values were plotted against the calculated k
values. The coefficient of determination R2 was used as a
measure for the goodness of fit. As an example, the relation
between the measured and calculated values of k for ETA is
shown in Figure 4. The figures for all other amines are provided
Figure 4. Calculated values of k plotted against the experimentally
obtained values of k for all experiments conducted with ETA.
in the Supporting Information. The coefficients of determi-
nation of the modeled compared to the experimental data for
ETA, MOR, MOPA, CHA, and DMA were found to be 0.99,
0.97, 0.97, 0.92, and 0.99, respectively.
3.2. Dimethylamine. DMA requires special attention
among the studied amines because it was the only compound
that did not degrade by first-order kinetics in all situations. The
previously discussed Arrhenius plots and model calculations for
DMA were made with k values derived from the shortest
retention times (Figure 5A), but when DMA was exposed to
longer retention times, first-order kinetics no longer applied. At
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500 °C, thermal degradation stopped when DMA was at
around 20%, as shown in Figure 5B. At 530 °C, the DMA
concentration did not drop below 10%. At 560 °C, the DMA
concentration went down to less than 2% within a few seconds,
but the compound never fully degraded. In some cases, DMA
concentrations measured for longer retention times were even
higher than those measured for shorter retention times, and a
clear increasing trend was observed. For instance, at 500 °C and
17.5 MPa, 15% DMA remained after 14 s in the reactor. After
43 s under the same conditions, 23% DMA was left. This
increase cannot be explained through the error of detection of
the ion chromatography system.
Longer retention times do not allow degradation of DMA
below 20% at 500 °C, suggesting that the DMA thermolysis
reaction is reversible. This can happen only if DMA is
synthesized from its breakdown products. Mochida et al.20
investigated the synthesis of DMA and methylamine (MET)
from ammonia and methanol over metal oxides at 300−450 °C,
which could yield up to 50%. A patent by Ashina et al.21
describes almost the same process, but claims that higher
selectivity for DMA can be obtained by exposing methanol and
ammonia to steam at 250−700 °C. During the experiments,
ammonia was a degradation product, and the presence of
methanol was plausible. MET was also found as a degradation
product in all DMA experiments, and its concentration
remained constant at higher retention times. Although this
reasoning is speculative, the synthesis of DMA in a superheater,
or perhaps in the condensing stages, is plausible.
As mentioned before, DMA was much more stable in a 1.6-
mm tube at 490 °C18 than in a 12.5-mm tube at 500 °C. This
indicates that the synthesis of DMA benefits from a high S/V
ratio. Having relatively more metal oxide surface area would
benefit the synthesis of DMA, thereby increasing the apparent
DMA stability as the S/V ratio increases.
3.3. Organic Acid Anion Formation. Potential formation
of organic acid anions during amine thermolysis is currently
preventing the general acceptance of amines for application in
steam−water cycles. In a previous amine thermolysis study,16
formate and acetate were found to be the major anionic
degradation products of MOR and ETA. In addition, glycolate
was measured as a degradation product of MOR and ETA. In
the current study, however, propionate was also found in
samples from MOR degradation. All organic acid data from
MOR thermolysis experiments conducted in the current study
are summarized in Figure 6. Formate was the major
degradation product, which does not correspond to the
findings in the previous study with a higher S/V ratio. This
difference indicates that the surface of the tubes has an affect
not only on the degradation kinetics, but also on what
degradation product is preferably formed. Formate, acetate, and
propionate all increased with increasing degradation (despite
the increasing temperature), whereas glycolate was found at
only trace levels throughout all MOR thermolysis experiments.
The other organic acid plots for all of the investigated amines
can be found in the Supporting Information. It can be seen that
formate and acetate from ETA degradation were found at
similar concentrations (by mass) and their concentrations
increased linearly to 290 ppb for 100% amine degradation. The
glycolate concentration after ETA degradation seemed to
decrease with increasing ETA degradation, but also decreased
with increasing temperature, which indicates the low thermal
stability of glycolate. For MOPA, the highest concentrations
found for the degradation products were those of formate (up
DOI: 10.1021/ie504849v
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Figure 5. Degradation percentage vs retention time for the thermolysis of DMA at 500 °C for (A) shorter and (B) longer retention times. First-order
degradation does not apply to longer retention times.
Figure 6. Acetate, formate, glycolate, and propionate formation vs
degradation percentage during thermolysis of MOR at 500, 530, and
560 °C and 9.5, 13.5, and 17.5 MPa.
to 242 ppb) and acetate (up to 120 ppb). The propionate
concentration increased slightly with increasing MOPA
degradation, but did not exceed 17 ppb.
CHA produced only a low amount of organic acids, with the
highest total organic acid anion concentration being less than
200 ppb. The acetate concentrations from CHA were slightly
higher than the formate concentrations, which were slightly
higher than the propionate concentrations. All three organic
acid anions increased proportional to CHA degradation. An
offset of 5 ppb formate and 10 ppb acetate can be seen for low
degradation percentages. This is caused by organic carbon
contamination (from, e.g., the air or the interior of the plastic
pump), which is hard to prevent, even in full-scale plants. This
is also the reason that DMA thermolysis seemed to produce
small amounts of acetate, which was not the case.
DMA produced almost exclusively formate, which can be
attributed to its small molecule structure, making the formation
of other organic acid anions improbable, unless synthesis
occurred. Formate was also observed to be the only anionic
degradation product by Bull14 when using DMA as an ammonia
replacement for a secondary circuit.
Although the acetate and propionate concentrations did not
fluctuate, the formate concentrations went up and down for all
amines, even under similar conditions and degradation
percentages. This can be seen mostly for ETA, MOPA, and
DMA, where the formic acid concentrations for high
degradation percentages varued in the ranges 159−271, 51−
242, and 62−299 ppb, respectively. What causes the formate
concentrations to be so unpredictable remains unclear. Over
the entire study, 1−15% (by mass) of the carbon released by
degraded amines could be traced back as organic acid anions,
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meaning that a large proportion of the amines degraded to
neutral compounds.
In all cases, thermolysis of the amines led to the formation of
organic acid anions. In most cases, the concentrations increased
linearly with increasing degradation percentage. Organic acid
anions are a concern in power-plant regions with two-phase
flow, because organic acids are more soluble than ammonia.
This means that, when amines are used, there might be a point
at which the acidity of the degradation products has enough
effect on the water phase that the solubility of magnetite (the
protective oxide layer found under power-plant conditions)
increases. In practice, not all amines would be dosed at the
same concentration, as their dosages will depend on their
basicities. An amine that requires a lower dose to maintain
sufficiently high pH in a steam−water cycle will also form fewer
organic acid anions. It also has to be noted that amines and
organic acid anions in a power plant will cycle through the
system, so the thermal stability of organic acids in superheated
steam matters as well. Regardless, the protection an amine
offers is a combination of its thermal stability and its tendency
to produce organic acid anions.
3.4. Nitrogen Balance. As an amine breaks down, the
cationic degradation products could still offer some protection.
Ammonia and other cationic degradation products were
measured in this study to determine the percentage of nitrogen
that can be found as cations providing alkalinity. This quantity
is expressed as a percentage of the total organic nitrogen in the
influent. For MOR, which degraded into ammonia and small
traces of ETA (up to 229 ppb), the results for the cationic
degradation products are shown in Figure 7. Not all nitrogen
Figure 7. Percentage of total nitrogen measured as cationic
degradation products (theoretical and measured) for MOR at 500,
530, and 560 °C and 9.5, 13.5, and 17.5 MPa.
DOI: 10.1021/ie504849v
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could be traced back as ammonia or other cationic degradation
products. This is probably due to the degradation of the amines
and/or ammonia to inorganic nitrogen or to the loss of
ammonia (because of its volatility) during grab sampling. A
blank run with only 0.1 ppm carbohydrazide revealed that 33
(±15) ppb ammonia came from the carbohydrazide. The
results were corrected for this contribution.
For other amines, a higher degree of scattering can be seen in
the nitrogen recovery plots, which are shown in the Supporting
Information. In some cases, 100% of the nitrogen can be
accounted for, usually at lower temperatures or lower
degradation percentages. In all cases, the dominant cationic
degradation product was ammonia. For DMA, traces of MET
(up to 236 ppb) were found as a decomposition products as
well, whereas MOPA also degraded to some hydroxyl
propylamine (up to 204 ppb).
With most nitrogen always being converted into ammonia or
another amine, the thermolysis of an amine in a power plant
does not necessarily have to lead to a hazardous pH drop, as the
pH effect of the formation of organic acids will mainly be
countered by the alkalizing effect of the ammonia. As stated in
the previous section, this could still imply a lower degree of
protection in two-phase flow, as some organic acids are less
volatile than ammonia and prefer the liquid film that covers the
metal surface.
3.5. Comparison with Practical Data. Practical data in
the literature that can be used to verify the model are almost
nonexistent, mostly because of the lack of information on
retention times in superheaters and reheaters. Some general
comparisons can be made, however. Layton and Daniels22
reported a power-plant survey on amine usage that included
detailed data for ETA degradation in several parts of two plants
(A and B), and in plant B, CHA was also dosed. The third plant
(C) ran (partially) on MOPA dosing. The superheat (SH) and
reheat (RH) temperatures of plants A−C were 540, 566, and
538 °C, respectively, with pressures of 17.9, 13.1, and 13.1
MPa, respectively.
Retention times could not be calculated from the reported
data, so degradation percentages can be compared only relative
to each other. Similarities were found between their study and
this study in the stability of CHA relative to ETA. Layton and
Daniels22 showed a loss of CHA and ETA over the SH and RH,
but also showed that CHA is more stable than ETA at 551 °C.
The average loss percentages of CHA and ETA were (47 ±
7)% and (60 ± 11)%, respectively, at a 551 °C RH steam
temperature. According to the model presented in this article, a
47% decrease in CHA at 551 °C and a pressure of 13.1 MPa
corresponds to a 70% loss of ETA under similar conditions. As
such, the findings corroborate the practical data (within the
degree of accuracy of the plant data). When applying the same
retention time to the conditions found in plant C (a heat
recovery steam generator similar to plant B), the model data
predict a 70% loss of MOPA, which is close to the highest
degradation percentage of MOPA found in that specific plant of
66%.
It should be kept in mind that comparisons between model
data based on laboratory-scale experiments and full-scale data
need to be handled with care. Amines in a plant do not stay at a
fixed temperature for a few seconds, but follow a profile of
temperatures. Determining retention times and temperature
profiles in superheaters and reheaters is a challenge. However,
making these kinds of comparisons is important for assessing
the applicability of amine thermal stability modeling.
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A difference in model and plant data was found in the
formation of organic acids in plant A, where ETA was dosed.
Almost no formate was measured at this location, which is
different from what was measured in plant B and the
observations during the ETA degradation in this study. Plant
B had a formate/acetate ratio close to what was experimentally
obtained in this laboratory-scale study. In plant C, the organic
acid concentrations were very low, but MOPA was dosed at
only 20 ppb in this case.
4. CONCLUSIONS
This study has led to the following conclusions:
(1) All amines thermolyzed by first-order kinetics, with the
exception of dimethylamine.
(2) The obtained Arrhenius constants are summarized in
Table 3.
Table 3. Summary of Obtained Arrhenius Constants
Ea (kJ mol−1) ln(A) (s−1) Va (cm3 mol−1)
ETA 189 25.5 369
MOR 295 40.2 137
MOPA 254 35.6 6
CHA 409 56.9 272
DMA 100 13.6 346
(3) The effect of pressure on the thermolysis kinetics was
much less pronounced than in previous studies, which can
probably be attributed to the low S/V ratio in this study, which
was applied to come closer to superheater conditions.
(4) Dimethylamine did not degrade below 20% and 10% of
the initial concentration at 500 and 530 °C, respectively,
despite the application of longer retention times. This suggests
that synthesis might occur, either at high temperature or in the
condensing stages. Further studies are needed to clarify this
phenomenon.
(5) In all cases, thermolysis of the amines led to the
formation of organic acid anions. In most cases, the
concentrations increased linearly with increasing degradation
percentage. Acetate and formate were found to be the major
degradation products, with some propionate and traces of
glycolate.
(6) Cationic degradation products consisted of mostly
ammonia and some amines, meaning that the complete
thermolysis of an amine does not necessarily lead to acidic
conditions. Not all nitrogen could be traced back to these
cationic degradation products, suggesting that some other
inorganic nitrogen species were formed or that ammonia was
lost during sampling.
(7) Comparison of the model to some limited practical
measurements of amines in power plants shows some promise
in the applicability of the model. A larger data set and more
information on superheater retention times are necessary to
validate the model proposed in this article, which should try to
focus on retention times in the hottest sections of power plants.
■
*
ASSOCIATED CONTENT
S Supporting Information
Arrhenius, organic acid anion, and nitrogen recovery plots are
provided to support the findings described in this article. This
material is available free of charge via the Internet at http://
pubs.acs.org.
DOI: 10.1021/ie504849v
Ind. Eng. Chem. Res. 2015, 54, 2606−2612
Industrial & Engineering Chemistry Research Article

■ AUTHOR INFORMATION
Corresponding Author
International Conference on the Properties of Water and Steam, London,
U.K., Sep 1−5, 2013.
(19) Moed, D. H.; Verliefde, A. R. D.; Rietveld, L. C.; Heijman, S. G.
*E-mail: D.H.Moed@tudelft.nl. Tel.: +31-0-152786588. J. Organic acid formation in steam-water cycles: Influence of
Notes temperature, retention time, heating rate and O2. Appl. Therm. Eng.
The authors declare no competing financial interest. 2014, 65, 194−200.

■
(20) Mochida, I.; Yasutake, A.; Fujitsu, H.; Takeshita, K. Selective
ACKNOWLEDGMENTS synthesis of dimethylamine (DMA) from methanol and ammonia over
zeolites. J. Catal. 1983, 82, 313−321.
The authors thank EPRI and Evides Industriewater for financial (21) Ashina, Y.; Fujita, T.; Fukatsu, M.; Yagi, J. Process for producing
and technical support. Specific gratitude goes to Michael dimethylamine in preference to mono- and trimethylamines by gas
Caravaggio and James Mathews from EPRI for useful input and phase catalytic reaction of ammonia with methanol. U.S. Patent
discussions. 4,582,936, 1986.

■
(22) Layton, K. F.; Daniels, D. G. Interim GuidanceAmine
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2612 DOI: 10.1021/ie504849v

Ind. Eng. Chem. Res. 2015, 54, 2606−2612