Synthesis, Optimization, and Thermal Risk Analysis of One-Pot N-Nitrodiethanolamine Dinitrate Synthesis

Article abstract of DOI:10.1021/acs.oprd.9b00300

N-Nitrodiethanolamine dinitrate (DINA) is a nitramine explosive containing both O-nitro and N-nitro groups. In this work, the synthesis of DINA by nitration of diethanolamine hydrochloride (DEAHC) with the fuming nitric acid/acetic anhydride (HNO₃/Ac₂O) system was developed and optimized. It was found that large amounts of acetic anhydride and low reaction temperature are favorable to the yield of DINA. When the DEAHC:HNO₃:Ac₂O molar ratio was 1:4.5:6 and the initial reaction temperature was decreased to 5 °C, the yield of DINA reached a?92%. The thermal risk of this synthesis route was also analyzed. The value of T_D24 for the final reaction mixture was calculated to be 61.9 °C, which is significantly higher than the MTSR for the synthesis process. This indicates that as long as the addition immediately stops in case of the cooling failure scenario, decomposition of the formed DINA will not occur. The above analysis shows that the DINA synthesis approach reported here is favorable in terms of both productivity and safety.

Full text of DOI:10.1021/acs.oprd.9b00300

Article
Cite This: Org. Process Res. Dev. XXXX, XXX, XXX−XXX
pubs.acs.org/OPRD
Synthesis, Optimization, and Thermal Risk Analysis of One-Pot
N‑Nitrodiethanolamine Dinitrate Synthesis
†
‡
§
,†
†
†
Wei Li, Wei Feng, Jie Hao, Zichao Guo,* Liping Chen, and Wanghua Chen
†Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing,
Jiangsu 210094, China
‡
Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
§
Wuhuan Engineering Co. Ltd., Wuhan 430000, China
*
S Supporting Information
ABSTRACT: N-Nitrodiethanolamine dinitrate (DINA) is a nitramine explosive containing both O-nitro and N-nitro groups.
In this work, the synthesis of DINA by nitration of diethanolamine hydrochloride (DEAHC) with the fuming nitric acid/acetic
anhydride (HNO /Ac O) system was developed and optimized. It was found that large amounts of acetic anhydride and low
3
2
reaction temperature are favorable to the yield of DINA. When the DEAHC:HNO :Ac O molar ratio was 1:4.5:6 and the initial
3
2
reaction temperature was decreased to 5 °C, the yield of DINA reached ∼92%. The thermal risk of this synthesis route was also
analyzed. The value of T for the final reaction mixture was calculated to be 61.9 °C, which is significantly higher than the
D24
MTSR for the synthesis process. This indicates that as long as the addition immediately stops in case of the cooling failure
scenario, decomposition of the formed DINA will not occur. The above analysis shows that the DINA synthesis approach
reported here is favorable in terms of both productivity and safety.
KEYWORDS: N-nitrodiethanolamine dinitrate, exothermic reaction, thermal risk, optimization, nitramine explosive
1
. INTRODUCTION
Europe and the U.S.. However, in Russia and China, the
HNO /MgO system with NaCl as the catalyst is more
N-Nitrodiethanolamine dinitrate (DINA) is an energetic
material containing one nitramine (N-nitro) group and two
nitrate ester (O-nitro) groups. DINA has been widely used as a
raw material to produce propellants. The study of applications
3
9
popular.
6
The disadvantage of the synthesis route in Scheme 1 is the
separation of the O-nitration and N-nitration processes, which
results in the formation of large amounts of the dangerous
1
of DINA can be tracked back to the Second World War.
10
intermediate DIA. It has been experimentally determined by
Zhou that the thermal stability of DIA is lower than that of
The most popular route to synthesize DINA is nitration of
diethanolamine (DEA) with fuming nitric acid as the nitrating
agent. For this synthesis route, it has been widely considered
that O-nitration is followed by N-nitration,
Scheme 1. There are two classical approaches for the synthesis
6
DINA. From the inherent safety point of view, the
2
−5
as shown in
accumulation of DIA should be avoided. In addition, for the
HNO /MgO nitration system, the formation of Mg(OH) in
3
2
the O-nitration liquid system may make the reaction mixture
Scheme 1. Traditional Synthesis Route for DINA by
Nitration of DEA
sticky, which is unfavorable to the heat removal efficiency. This
is a dangerous situation in the reaction course.
9
To deal with the disadvantages of the synthesis route in
Scheme 1, a one-pot synthesis of DINA by nitration of
diethanolamine hydrochloride (DEAHC) was developed in
this work. The synthesis route is illustrated in Scheme 2. Ac O
2
is used as both the solvent and the dehydrating agent. The
synthesized DINA was characterized by Fourier transform
Scheme 2. Synthesis Route for DINA by Nitration of
DEAHC
of DINA by nitration of DEA: the nitric acid/acetic anhydride
6
(
HNO /Ac O) approach and the nitric acid/magnesium
oxide (HNO /MgO) approach. For these two approaches, a
3
2
6
3
chloride catalyst is required to promote N-nitration of
7
diethanolamine dinitrate (DIA), which is formed by O-
nitration of DEA. Ac O and MgO in these two approaches are
2
used as the dehydrating agent. The most classical synthetic
approach for DINA was the nitration of DEA by the HNO /
3
8
Ac O system with zinc chloride as the catalyst. The HNO /
Received: July 1, 2019
2
3
Ac O system for the production of DINA is widely used in
2
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.oprd.9b00300
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1
infrared spectrometry (FTIR), H nuclear magnetic resonance
after the temperature rising process presented significant
oscillation. The heat released within and after the temperature
rising process is close to zero and consequently can be
neglected. After the reactions, the reaction mixtures were
poured onto ice to crystallize the desirable DINA. The
crystallized DINA was washed with deionized water and then
filtered in vacuum. Finally, the DINA obtained was dried at 40
1
spectroscopy ( H NMR), and high-performance liquid
chromatography (HPLC). Combined with thermal risk
analysis, the results experimentally prove that this synthesis
route can synthesize DINA both safely and productively.
2
. EXPERIMENTAL SECTION
.1. Materials. Diethanolamine hydrochloride with a purity
of 95% was purchased from Nanjing Juyou Scientific
Equipment Co., Ltd. Fuming nitric acid with a purity of
97.2% was purchased from Sinopharm Chemical Reagent
Company. Acetic anhydride with a purity of ∼98.0% was
purchased from Shanghai LingFeng Chemical Reagent Co.,
Ltd. All of the chemicals were used without further
purification.
°
C for 8 h.
2
To optimize the DINA synthesis conditions from both the
safety and productivity points of view, three RC1e tests were
conducted. The specific operating conditions of the three
RC1e tests are listed in Table 1. For runs 2 and 3, the masses
∼
Table 1. Reaction Conditions for the Three RC1e
Experiments
2
.2. Apparatus. 2.2.1. Reaction Calorimetry. The reaction
run
DEAHC:HNO :Ac O molar ratio
reaction temperature (°C)
3
2
calorimeter (RC1e) used was manufactured by Mettler Toledo
and equipped with a 1 L glass medium-pressure reactor and
automatic feeding device. The RC1e was used to study the
synthesis rate and exothermic feature of the reaction. All of the
RC1e experiments were carried out in the isothermal mode.
1
2
3
1:4.5:4.8
1:4.5:6
1:4.5:6
10
10
5
11
of initially added acetic anhydride and fuming nitric acid were
50 and 50 g, respectively. During the dosing period, 80 g of
diethanolamine hydrochloride and 160 g of fuming nitric acid
were simultaneously added into the reactors.
2
.2.2. Differential Scanning Calorimetry. Differential
3
scanning calorimetry (DSC) is a widely used thermal analysis
tool to study the thermal stability of hazardous chemicals.
12−14
In this work, the thermal stability of the final reaction mixture
was quantitatively tested by DSC in the dynamic mode. The
differential scanning calorimeter used was manufactured by
Mettler Toledo. The samples were sealed in gold high-pressure
crucibles (30 μL) with gold-plated pads. The sample masses
were about 1.2 mg. All of the DSC tests were conducted under
The DINA yield was calculated using the following formula:
n(DINA)
DINA yield =
× 100%
n(DEAHC)
where n is the molar amount.
3. RESULTS AND DISCUSSION
.1. Synthesis and Characterization. 3.1.1. Optimiza-
(1)
a N atmosphere.
2
1
2
.2.3. Fourier Transform Infrared Spectrometry and H
1
Nuclear Magnetic Resonance Spectroscopy. FTIR and H
NMR were employed to check whether the desirable DINA
was formed. The IR spectra were recorded in KBr using a
3
tion of the Acetic Anhydride Content. Since acetic anhydride
acts as both the solvent and dehydrating agent in the synthesis
of DINA, the mole fraction of acetic anhydride in the reaction
mixture should play an important role. To study the effect of
acetic anhydride, runs 1 and 2 were carried out. The heat flow
profiles obtained from these RC1e experiments are shown in
Figures 1 and 2, respectively. The heat production rates within
the dosing period for both runs 1 and 2 are relatively stable.
Once the addition of DEAHC stops, the heat production rates
rapidly decrease to zero. These results indicate that the
1
Nicolet iS10 FTIR spectrometer. H NMR spectra were
obtained using a Bruker Avance III 500 MHz spectrometer.
The chemical shifts (δ) are reported in parts per million
downfield from tetramethylsilane as an internal standard. To
conduct the H NMR analyses, the products obtained from
RC1e experiments were dissolved in dimethyl sulfoxide
1
(
DMSO) as the solvent.
.2.4. High-Performance Liquid Chromatography. HPLC
2
was used to quantitatively determine the yields of the products
from RC1e experiments. The HPLC apparatus was manufac-
tured by Waters. The solvent system was acetonitrile/water
(
2
70:30) at a flow rate of 0.8 mL/min with UV detection at
10−400 nm. The HPLC result for the standard sample of
DINA is shown in Figure S1.
.3. Synthesis of DINA. All of the DINA synthesis
2
reactions were carried out in the RC1e. All of the experiment
runs were carried out in the isothermal mode. The typical
synthesis procedure for DINA is as follows: first, acetic
anhydride with a small amount of fuming nitric acid (mass
ratio of acetic anhydride to fuming nitric acid ≈ 7:1) was
added into the reactor; then diethanolamine hydrochloride and
fuming nitric acid were simultaneously dosed into the reactor
from two different streams after the reaction mixtures had
reached the set temperature. After the dosing process, the
temperature of the reaction system was slowly raised to 40 °C
at constant rise rate of about 1 °C/min. The whole heat flow
profiles for runs 2 and 3 are shown in Figures S2 and S3. It was
experimentally found that the heat generation rate within and
Figure 1. Heat flow and dosing profiles for run 1.
B
DOI: 10.1021/acs.oprd.9b00300
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Organic Process Research & Development
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Figure 2. Heat flow and dosing profiles for run 2.
Figure 3. Heat flow and dosing profiles for run 3.
can see that the heat production rate was also stable over the
whole reaction. Though the heat flow curve after the addition
of DEAHC for run 3 does not decrease to zero as fast as that
for run 2, the thermal accumulation for run 3 is still lower than
reaction rates for both runs 1 and 2 are high and dosing-
controlled, which means that the reaction can rapidly stop
once the additions of both fuming nitric acid and DEAHC
stop, which is desirable from the thermal safety point of view.
It is worthwhile to note that the heat flow profile for run 1
shows a sharp exothermic peak just after the dosing period,
which is attributed to the crystallization phenomenon in the
reactor. The crystallization phenomenon is evidenced by the
picture in Figure 1, which illustrates the mass mixture in the
reactor. The RC1e test was manually stopped after the
4
%. This value of thermal accumulation will not lead to a
thermal accident even if the cooling system fails to work, which
will be explained in detail in the next section.
In addition, over the whole reaction for run 3, no
crystallization phenomenon occurred, which means that the
produced DINA was totally dissolved in the reaction mixture.
1
13
1
The FTIR, H NMR, HPLC, and C NMR results for the
product of run 3 are shown in Figures 4, 5, 6, and S8,
appearance of crystallization. HPLC and H NMR analyses, as
shown in Figures S4 and S5, proved that the white precipitate
in the reactor is mainly composed of DINA. The crystallization
phenomenon indicates that DINA is supersaturated in the
reaction mixture of run 1. From the thermal safety point of
view, the crystallization phenomenon is undesirable because
hot spots may occur in the reactor. According to eq 1, the yield
of DINA for run 1 was calculated to be about 75%.
To restrain the crystallization phenomenon, a greater
amount of acetic anhydride was used for the RC1e test. We
found that when the Ac O:DEAHC molar ratio was increased
2
from 4.8:1 to 6:1, the crystallization phenomenon did not
occur at all. This was evidenced by the fact that no exothermic
peak appeared after the dosing period in Figure 2. The reaction
mixture of run 2 in the reactor remained clear over the whole
reaction. Moreover, the product obtained from run 2 was
1
analyzed by HPLC and H NMR, as shown in Figures S6 and
S7. The chemical shifts at δ 4.15 and δ 4.74 correspond to
hydrogen atoms on the methylene groups of DINA. The
HPLC result indicated that the purity of DINA obtained from
run 2 was higher than 99%. The DINA yield for run 2 was
calculated to be 82%, which is higher than that for run 1.
From the above results, one can conclude that increasing the
Figure 4. IR spectrum of the product of run 3.
respectively. The wavenumbers at 1675−1621 and 1515 cm−
in Figure 4 correspond to the characteristic peaks of O-NO
1
Ac O:DEAHC molar ratio of from 4.8:1 to 6:1 can
2
significantly improve the synthesis of DINA from both the
safety and productivity points of view. However, as shown in
Table S1, the yield of DINA increased just by about 1% when
2
and N-NO . The chemical shifts at δ 4.2 and δ 4.8 correspond
2
to the hydrogen atoms of the two types of methylene groups in
1
13
the Ac O:DEAHC molar ratio was further increased to 8:1.
DINA. The FTIR, H NMR, and C NMR results indicate
that DINA was formed. The HPLC result in Figure 6 indicates
that the purity of the formed DINA was >99%. The yield of
DINA for run 3 was determined to be about 92%, which is
significantly higher than that for run 2. The increase in the
yield of DINA indicates that decreasing the reaction temper-
ature is favorable for the formation of DINA.
2
Hence, increasing the amount of acetic anhydride further is not
necessary.
3.1.2. Optimization of the Reaction Temperature. To
study the effect of the reaction temperature on the synthesis of
DINA, the reaction temperature was decreased from 10 to 5
°C. The heat flow profile for run 3 is shown in Figure 3. One
C
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3
.2.2. Thermal Risk of the Second Decomposition
Reaction. For the synthesis of DINA, the accumulation of
the unstable intermediate (i.e., DIA) is an important risk
source. Combining the RC1e and HPLC results for run 3, one
can reasonably expect that the DIA formed by O-nitration is
rapidly converted to the final product DINA, indicating that
the accumulation of DIA during the DINA synthesis process
can be neglected. The thermal stability of the final reaction
mixture of run 3 was tested by dynamic DSC experiments and
characterized by the concept of time to maximum rate under
18−20
adiabatic situation (TMRad).
Figure 7 shows the heat flow
1
Figure 5. H NMR spectrum of the product of run 3.
Figure 7. DSC test results for the final reaction mixture of run 3 at
different heating rates.
profiles from the DSC tests. The operating conditions and
results of the DSC tests are listed in Table 2. It can be seen
that with an increase in the heating rate, the onset
decomposition temperature (Tonset) of the final reaction
mixture gradually increases.
Figure 6. HPLC result of the product of run 3.
3.2. Thermal Risk Analysis. Since the yield of DINA for
run 3 was the highest, thermal risk analysis was conducted only
for run 3. The cooling failure scenario is generally considered
as the most extreme situation for exothermic reactions that are
carried out in semibatch reactors. To guarantee the thermally
safe operation of the synthesis of DINA, the second
decomposition reactions should be avoided in the case of
cooling failure.
Table 2. Operating Conditions and Results of DSC Tests for
the Final Reaction Mixture of Run 3
test
no.
heating rate
(°C/min)
sample mass
(mg)
T
−ΔH
d
−1
onset
(°C)
(J/g )
1
2
3
4
6
8
1.27
1.1
1.2
123.1
135.7
145.4
934.3
812.0
867.8
3.2.1. Maximum Temperature of the Synthesis Reaction.
It is generally accepted that the maximum temperature of the
synthesis reaction (MTSR) can be used to characterize the
AKTS software was employed to calculate TMR . The
ad
15−17
cooling failure scenario.
The MTSR can be calculated as
kinetic analysis was carried out using the Friedman approach,
which is an isoconversional method. The basis of the
isoconversional method is to determine the correspondence
between the temperature and a certain reaction process value.
The comparison between the experimental and simulated
reaction progress profiles are shown in Figure 8. The
correlation coefficient in Figure 8 is higher than 0.99, which
proves the validation of the simulated results. The average
MTSR = T + Xac,maxΔT
p
ad
(2)
where T is the process temperatue, X
is the maximum
p
ac,max
accumulation of the unreacted reactant, and ΔT is the
ad
adiabatic temperature rise of the exothermic reaction.
Through integration of the heat flow profile in Figure 3, the
total heat generated in run 3 was found to be about 208.15 kJ.
Accordingly, the reaction enthalpy (−ΔH ) with respect to
decomposition heat (−ΔH ) was determined to be 871.4 J/g.
r
d
DEAHC was calculated to be about 368.9 kJ/mol. The
Figure 9 shows the dependence of TMR on the
ad
corresponding value of ΔT for run 3 was calculated to be
temperature as calculated using the AKTS software. One can
see that when the value of TMRad is equal to 24 h, the
corresponding temperature is 61.9 °C, that is, TD24 = 61.9 °C.
3.2.3. Risk Assessment. From the above results, one can see
that the MTSR (9.74 °C) is significantly lower than TD24 (61.9
ad
1
52.84 K. In addition, the thermal conversion at the dosing
end point was about 96.9%. Accordingly, the thermal
accumulation for run 3 was equal to 3.1%. From these values,
the MTSR for run 3 was determined to be 9.74 °C.
D
DOI: 10.1021/acs.oprd.9b00300
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Organic Process Research & Development
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Figure 8. Comparison between the experimental and simulated reaction progress profiles.
4. CONCLUSION
The synthesis of DINA by nitration of DEAHC with the
fuming nitric acid/acetic anhydride (HNO /Ac O) system has
3
2
been reported in this article. The optimized reaction
conditions are a DEAHC:HNO :Ac O molar ratio of 1:4.5:6
3
2
and a reaction temperature of 5 °C. The yield of DINA can
reach ∼92% under these optimized operating conditions.
In addition, a thermal risk analysis has been carried out for
the optimal operating conditions. The value of TD24 for the
final reaction mixture was calculated to be 61.9 °C, which is
significantly higher than the value of the MTSR (9.74 °C).
This result indicates that as long as the addition immediately
stops in the case of the cooling failure scenario, decomposition
of the formed DINA will not occur.
Figure 9. TMRad vs temperature profile for the final reaction mixture
of run 3.
ASSOCIATED CONTENT
■
*
S
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.oprd.9b00300.
°
C). This implies that as the addition immediately stops in the
case of a cooling failure, the decomposition of the formed
DINA will not occur. This is desirable from the thermal safety
point of view.
RC1e experiment results; HPLC, H NMR, and 13C
NMR results; reaction conditions for the laboratory-
scale experiments (PDF)
1
Since the synthesis of DINA is strongly exothermic, the
temperature of the reaction mixture may deviate from the
allowable range if the dosing rates of fuming nitric acid and
DEAHC are accidently higher than the designed values. One
can reasonably expect that if about 40% of the dosed reactants
are accidently added into the reactor in a short time, the
temperature will increase up to 66.1 °C, which is higher than
TD24, and consequently, the second decomposition reaction
will be triggered. Therefore, the dosing rate of fuming nitric
acid and DEAHC must be limited by reliable technical
treatment.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: gzc319@njust.edu.cn. Tel: +86 025 84315526. Fax:
+86 025 84315526.
ORCID
Zichao Guo: 0000-0002-2288-1174
Wanghua Chen: 0000-0002-2716-7674
With respect to the HNO /MgO nitration system, the
3
Notes
reaction mixture becomes sticky during the reaction process as
The authors declare no competing financial interest.
6
a result of the formation of suspended Mg(OH)2. This
phenomenon is undesirable because hot spots may appear in
the sticky reaction mixture. Since the reaction mixture for the
synthesis route reported in this work is homogeneous and clear
over the whole reaction process, hot spots are less possible to
ACKNOWLEDGMENTS
■
This work was financially supported by the National Key R&D
Program of China (2017YFC0804701-4) and the Fundamental
Research Funds for the Central Universities (30917011312).
generate compared with the HNO /MgO nitration system.
3
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DOI: 10.1021/acs.oprd.9b00300
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