Catalysis Communications 28 (2012) 174–178

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Catalysis Communications
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Short Communication

Highly selective co-production of nitrocyclohexane and adipic acid from vapor phase
catalytic nitration–oxidation of cyclohexane with NO2
Kuiyi You, Jian Jian, Haijun Xiao, Pingle Liu, Qiuhong Ai, He'an Luo ⁎
School of Chemical Engineering, Xiangtan University, Xiangtan 411105, PR China

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

Article history: A simple and efficient approach for highly selectivity co-production of nitrocyclohexane and adipic acid from
Received 7 July 2012 vapor phase nitration–oxidation of cyclohexane with NO2 at atmospheric pressure has been successfully devel-
Received in revised form 24 August 2012 oped in this work. This finding provides a novel strategy for co-production of nitroalkanes and dicarboxylic acids
Accepted 3 September 2012
from vapor phase nitration–oxidation of low-carbon cycloalkanes. This method may be very significant to estab-
Available online 8 September 2012
lish such a synthesis process for aliphatic nitro-compounds and dicarboxylic acids in organic fields.
Keywords:
© 2012 Elsevier B.V. All rights reserved.
Catalytic nitration–oxidation
Vapor phase
Co-production
Nitrocyclohexane
Adipic acid

1. Introduction
The nitration of alkanes to nitro-alkanes is an important process
since nitro-alkanes are not only chemical commodities but also very im-
portant precursors for synthesis of a wide variety of chemicals such as
pharmaceuticals and agrochemicals [1]. The nitro group on alkanes
can be easily replaced selectively with maintenance of other functional
groups and reduced to afford various nitrogen-containing compounds
[2]. For example, nitrocyclohexane can be partly hydrogenated into
cyclohexanone oxime, a raw material of ε-caprolactam, which in turn
leads to nylon-6 [3].
Despite their significant importance, there are only a few efficient
methods for nitration of alkanes. In contrast to nitration of aromatic
hydrocarbons, the selective nitration of aliphatic hydrocarbons is very
difficult because of their exceedingly low reactivity [4]. Traditionally,
nitration has been performed by a mixture of nitric and sulfuric acid
(mixed acid method, as shown in Scheme 1). However this method suf-
fers a number of disadvantages, such as generation of large amounts of
waste acids, low selectivity towards the desired product and consump-
tion of a large quantity of mineral or Lewis acid as activators [5]. In turn
those acids are environmentally unfriendly and costly to treat. Further-
more, it's hard to improve the conversion and selectivity of the desired
product by adding additives such as oxygen, ozone, or halogen. These
additives also promote the generation of alkyl radicals and oxygenated
or halogenated byproducts in fact.
In order to overcome the above-mentioned drawbacks, many
research groups have extensively studied on the efficient nitration of
⁎ Corresponding author. Tel.: +86 731 58293545; fax: +86 731 58298267.
E-mail address: heanluo@126.com (H. Luo).
alkanes. Ishii et al. [6–9] developed a novel catalytic method for the ni-
tration of aliphatic hydrocarbons with nitric acid or nitrogen dioxide
using N-hydroxyphthalimide (NHPI) or [VO(H2O)5]H[PMo12O40] as a
key catalyst under mild conditions. However, the control of selectivity
to nitro-alkanes is still difficult issues. Furthermore, most of the NHPI
was decomposed to phthalic acid and other related byproducts, and
the polyoxometalate catalyst is difficult to be prepared and recycled,
which limits its application in industrial production.
Hence, a new general strategy for the nitration of alkanes with NO2
into nitro-alkanes has been desired for a long time in the chemical
industry.
Adipic acid is an important industrial intermediate for the manufac-
tures of nylon-6, 6, which is a polymeric material used in carpet fibers,
tire reinforcement, clothing and many other everyday life applications
[10,11]. Processes for synthesis of adipic acid usually need a number
of steps as shown in Scheme 2, while the oxidation of a cyclohexanol–
cyclohexanone mixture with nitric acid is currently still the most im-
portantly industrial process [12,13]. However, the use of nitric acid
causes some severe environmental problems. The emission of NOx or
N2O during the synthesis can contribute to global warming and ozone
depletion [14,15].
Various methods including biosynthesis [16,17], supercritical meth-
od [18] and ozonolysis [19] have been elaborated for the clean synthesis
of adipic acid. However, they were too expensive or too complicated to
be used as a commercial process.
Therefore, it is highly desirable to develop a more environmentally
benign method to manufacture nitrocyclohexane and adipic acid.
Vanadium phosphorus oxide (VPO) catalyst is well known in the
vapor phase oxidation of n-butane to maleic anhydride (MA) [20,21].
And the VPO catalysts have also been widely investigated for the partial

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http://dx.doi.org/10.1016/j.catcom.2012.09.003
 K. You et al. / Catalysis Communications 28 (2012) 174–178 175

Scheme 1. The routes for the manufacture of nitro-cyclohexane.

Scheme 2. The routes for the manufacture of adipic acid.

oxidation and oxidative dehydrogenation of other lower hydrocarbons
[22,23].
Herein, we report a simple and efficient approach for highly se-
lective co-production of nitrocyclohexane and adipic acid via vapor
phase nitration–oxidation of cyclohexane and NO2, as is shown in
Scheme 3 [24]. A series of VPO composites were successfully employed
to catalyze the nitration–oxidation of cyclohexane with NO2 to nitro-
cyclohexane and adipic acid in vapor phase. The effects of different
VPO catalysts on nitration–oxidation reaction were investigated in our
present work. This is an environmentally friendly co-production meth-
od with advantages of less waste production, simple process and equip-
ment and low cost. And the reduction product NO can be effectively
recovered for reuse by adding dioxygen.
2. Experimental
2.1. Reagents and instrument
Cyclohexane (AR) was purchased from Shanghai Chemical Co., Ltd.,
China. NO2 (purity >99.9%) was purchased from Beijing Chemical Co.,
Ltd., China. Except where specified, all chemicals were of analytical
grade and used as received. Gas chromatography was performed on
an Agilent 7890 equipped with a DB-5 (30 m × 0.25 mm× 0.25 μm)
column for quantitative analysis by using chlorobenzene as internal
standard. Mass spectra were run on an America Varian Saturn 2100T
GC–MS instrument for qualitative analysis.
2.2. Preparation and characterization of VPO composite catalysts
The preparation and characterization processes of a series of VPO
composite catalysts were performed according to our previous work
[25].
2.3. Typical experimental procedure
The vapor phase nitration–oxidation reaction was performed in
a fixed-bed system at atmospheric pressure (see Fig. 1). A vertical
glass pipe of 60 cm length with 10 mm inner diameter was used
as fixed-bed reactor. Cyclohexane was injected to a preheater (the
preheating temperature is 100 °C) by using a pulsation-free recipro-
cating pump with constant flow rate calibrated, and the flow of NO2
is measured by mass flow controller. The mixed gas of cyclohexane
and NO2 was directly introduced to the reactor and their total flow
rate was determined by mass flow controller. The amount of catalyst
was 1 g. The resulting gas flowing from the outlet of reactor was con-
densed with a low-temperature cooling liquid of 6–8 °C to collect the
products. The collected liquid phase products were analyzed by gas
chromatography with FID detector (quantitative analysis by internal

Scheme 3. The novel co-production route of nitrocyclohexane and adipic acid from vapor phase nitration–oxidation of cyclohexane with NO2.
176 K. You et al. / Catalysis Communications 28 (2012) 174–178

Cyclohexane

Tubular gasifier Insulation cotton

Thermocouple

Reciprocating pump

Reactor

Cooling water

Condenser
P

P T
Mass flowmeter Collection bottle

NO2

Fig. 1. The experimental equipment for vapor phase nitration–oxidation.

standard methods). The components of gas phase were analyzed by The conversion of cyclohexane increased rapidly from 2.8% to 19.2%
gas chromatography with TCD detector. The white precipitate in the when the reaction temperature was elevated from 170 °C to 350 °C.
collected products was separated by filtration, washed with cyclohex- The selectivity of nitrocyclohexane also increased slowly with elevat-
ane, dried in a vacuum and characterized by comparison of its spec- ed temperatures. However, the selectivity of adipic acid showed the
tral and physical data with the authentic sample of adipic acid. The decline trend when temperature was over 200 °C. There are several
conversion of cyclohexane and selectivity of products were calculated possible reasons for this phenomenon. The vapor phase nitration
using the following formulas (Eqs. (1), (2) and (3)). All raw material and oxidation reaction of cyclohexane with NO2 happened simulta-
and products are established mass balances (including carbon mass neously and were competitive reaction in this process. Maybe the re-
balance and nitrogen mass balance). action rate of nitration reaction to form nitrocyclohexane was faster
    than that to form adipic acid when temperature was raised. Thus,
the amount ðmolÞ of the amount ðmolÞ of the selectivity of nitrocyclohexane was higher than that of adipic
−
Conversion of ¼ starting cyclohexane cyclohexane recovered
 100% acid. It seems that the decomposition rate of adipic acid becomes
cyclohexane ð%Þ the amount ðmolÞ of much greater than its formation rate when reaction temperature
starting cyclohexane
was over 350 °C. Therefore, elevating temperature was beneficial to
ð1Þ
the selectivity of nitrocyclohexane. And a range of favorable reaction
temperature was about 225–250 °C from the points of total selectiv-
the amount ðmolÞ
Selectivity of of nitrocyclohexane ities of nitrocyclohexane and adipic acid.
¼   
nitrocyclohexane ð%Þ the amount ðmolÞ of the amount ðmolÞ of Moreover, the products of gas and liquid phase were qualitative anal-
−
starting cyclohexane cyclohexane recovered ysis when the reaction temperature was below 300 °C. The results indi-
100% ð2Þ cated that the liquid phase products were mainly nitrocyclohexane and
adipic acid with small amounts of cyclohexanol and cyclohexanone.
the amount ðmolÞ
Selectivity of  of adipic acid Table 1
¼     100%
adipic acid ð%Þ the amount ðmolÞ of − the amount ðmolÞ of Effect of reaction temperature on vapor phase nitration–oxidation of cyclohexane.a
starting cyclohexane cyclohexane recovered
Temperature Conversion Selectivity (%)
ð3Þ (°C) (%)
Nitrocyclohexane Adipic acid Totalb

170 2.8 52.9 30.5 83.4

200 4.1 54.0 33.2 87.2
3. Results and discussion 225 6.4 68.0 31.1 99.1
250 9.9 75.6 24.1 99.7
3.1. Effects of reaction temperature on vapor phase nitration–oxidation 275 14.7 80.8 15.7 96.5
reaction of cyclohexane with NO2 300c 17.3 81.0 5.2 86.2
350d 19.2 81.5 0 81.5
a
Effects of reaction temperature on the conversion of cyclohexane Reaction conditions: molar ratio of cyclohexane with NO2 is 1:1, residence time is
and total selectivity of nitrocyclohexane and adipic acid in the vapor 60 s.
b
Total selectivity stands for the sum of selectivity for nitrocyclohexane and adipic
phase nitration–oxidation reaction were examined, and the results acid, the other products are mainly cyclohexanol and cyclohexanone.
are summarized in Table 1. It is clearly found that there is significant c,d
The residual products are mainly some deep oxidation products and extremely
influence of reaction temperature on the conversion and selectivity. small amount of cyclohexanol, cyclohexanone, and nitrocyclohexene.
 K. You et al. / Catalysis Communications 28 (2012) 174–178 177

The gas phase components were only NO2 and NO while other reduced Table 2
products such as N2, N2O, and CO2 were not formed. Some deep oxida- Effect of molar ratio of cyclohexane with NO2 on vapor phase nitration–oxidation
reaction.a
tion products such as CO2 and CO were detected in the gas phase when
reaction temperature was over 300 °C. These results indicated that the Molar ratio Conversion Selectivity (%)
reaction temperature was a significant factor to regulate the product (cyclohexane:NO2) (%) b
Nitrocyclohexane Adipic acid Total
ratio of nitrocyclohexane to adipic acid from the vapor phase nitration–
2.0:1 5.8 72.7 22.4 95.1
oxidation of cyclohexane and NO2. 1.5:1 7.6 75.0 20.6 95.6
1.0:1 9.9 75.6 24.1 99.7
0.8:1 11.9 75.8 22.9 98.7
3.2. Effects of residence time on vapor phase nitration–oxidation reaction 0.4:1 14.3 79.9 18.9 98.8
0.2:1 17.4 83.2 15.4 98.6
Fig. 2 depicts the representative results of the vapor phase nitration– a
Reaction conditions: the residence time is 60 s; reaction temperature: 250 °C;
oxidation reaction in different residence times at 250 °C. It can be seen b
Total selectivity stands for the sum of the selectivity for nitrocyclohexane and
that conversion of cyclohexane and selectivity of nitrocyclohexane grad- adipic acid; the other products are mainly cyclohexanol and cyclohexanone.
ually increase with prolonged residence time, while the selectivity of
adipic acid decreases gradually. A possible reason is that the decomposi-
tion rate of adipic acid becomes dominant compared with its formation
to NO2 was 1:1 in vapor phase nitration–oxidation of cyclohexane
rate under these reaction conditions. Therefore, the residence time is
with NO2.
also an important factor to affect the selectivities in the vapor phase
nitration–oxidation reaction of cyclohexane with NO2. From the points
of selectivities of total and adipic acid, obviously, a favorable residence
3.4. The vapor phase nitration–oxidation reaction of cyclohexane with
time should not be beyond 60 s at 250 °C from Fig. 2.
NO2 catalyzed by VPO composites

3.3. The effects of molar ratio of cyclohexane to NO2 on vapor phase
nitration–oxidation reaction
Table 2 shows the effects of molar ratio of cyclohexane to NO2 on
the vapor phase nitration–oxidation reaction under the residence
time of 60 s and the reaction temperature of 250 °C. It can be seen
that the conversion of cyclohexane increases with reducing the
molar ratio or raising the concentration of NO2. The selectivity of
nitrocyclohexane seems to increase slightly with the molar ratio
from 2.0 to 0.2, while the selectivity of adipic acid decreases roughly
in the range of molar ratio. That means increasing the concentration
of NO2 may be helpful to generate nitrocyclohexane. However, the
total selectivity for nitrocyclohexane and adipic acid varies little and
keeps a higher value (over 95%). These results show that the molar
ratio only have a little effect on the total selectivity. From the points
of the total selectivity, it is clearly found that the favorable molar
ratio of cyclohexane with nitrogen dioxide is about 1:1 under the res-
idence time of 60 s and the reaction temperature of 250 °C.
Therefore, from the single factor experiment results, the optimal
reaction conditions were obtained that the residence time was 60 s,
reaction temperature was 250 °C, and the molar ratio of cyclohexane
Table 3 summarizes representative results for the nitrosation reac-
tion of cyclohexane over the VPO and AlVPO composite catalysts. In
this catalytic system, the catalytic performances of the present cata-
lysts were different. Nitrocyclohexane and adipic acid could be
formed from cyclohexane and NO2 in the absence of any catalysts,
however, the selectivity to adipic acid was only 24.1%. The selectivity
to adipic acid was obviously improved when transition metal was in-
troduced to VPO composite catalysts. Especially, the transition metal
modified AlVPO composite catalysts could further enhance the selec-
tivity to adipic acid to some extent. Among these composite catalysts,
the Ni–AlVPO composite gave the best results. Under the optimal con-
ditions, a conversion of 11.6% with 52.4% selectivity for adipic acid
was obtained, and the total selectivity for nitrocyclohexane and
adipic acid was over 99%. Therefore, the promoting effect of the tran-
sition metal may be connected with the generation of V 5+ sites close
to the abundant V 4+ center of the pyrophosphate structure. It cannot
be discarded, however, that the presence of trace amounts of either
element at the surface level may contribute to the C\H bond break-
ing of the starting paraffin. These results illustrate that the transition
metals introduced to VPO and AlVPO precursor improve the catalytic
performance of catalysts.

100 Table 3
Effect of various VPO and AlVPO composite catalysts on the nitration–oxidation reac-
90 tion of cyclohexane with NO2.a
Conversion or selectivity (%)

80 VPO composite Conversion Selectivity (%)

catalysts (%) b
70 Nitrocyclohexane Adipic acid Total

Conversion of cyclohexane VPO 8.9 73.3 25.7 99.0

60
Cr-VPO 9.2 66.5 30.5 97.0
Selectivity to nitrocyclohexane
50 Mn-VPO 11.2 64.2 34.1 98.3
Selectivity to adipic acid Co-VPO 8.8 63.5 34.8 98.3
40 Total selectivity of both Ni-VPO 10.4 58.7 38.4 97.1
Cu-VPO 9.8 60.6 37.0 97.6
30 AlVPO 8.1 68.7 30.5 99.2
Cr–AlVPO 10.6 63.4 34.9 98.4
20 Mn–AlVPO 10.4 61.2 37.7 98.9
Co–AlVPO 10.9 59.4 39.6 99.0
10
Ni–AlVPO 11.6 47.0 52.4 99.4
20 40 60 80 100 120 Cu–AlVPO 12.5 60.4 38.3 98.7
Residence time (s) a
Reaction conditions: the residence time is 60 s; reaction temperature: 250 °C; the
molar ratio of cyclohexane to NO2 is 1:1; the mass of catalyst is 1 g.
b
Fig. 2. Effects of residence time on the nitration–oxidation reaction. Reaction conditions: Total selectivity stands for the sum of the selectivity for nitrocyclohexane and
the molar ratio of cyclohexane to NO2 is 1:1; reaction temperature 250 °C. adipic acid; the other products are mainly cyclohexanol and cyclohexanone.
178 K. You et al. / Catalysis Communications 28 (2012) 174–178
Scheme 4. The possible formation pathway of nitrocyclohexane and adipic acid in the vapor phase catalytic nitration–oxidation of cyclohexane with NO2.
3.5. The possible mechanism of catalytic nitration–oxidation reaction
On the basis of these results in this work, the possible formation
pathway of nitrocyclohexane and adipic acid from vapor phase catalytic
nitration–oxidation of cyclohexane with NO2 is proposed in Scheme 4.
Obviously, the vapor phase nitration and oxidation reaction of cyclo-
hexane with NO2 happens simultaneously. Nitrocyclohexane was
obtained from the nitration reaction and adipic acid was afforded
from the oxidation reaction. In the present system, a small amount of
other oxygenated adducts such as cyclohexanol and cyclohexanone
were formed as main by-products in all cases. In this process, V 5+ spe-
cies maybe play an important role in abstracting H-atom from alkanes
[26,27] in our present nitration–oxidation system. Moreover, the
rearrangement change process between V4+ and V5+ is also explained
from the color of reaction mixture where the initial green color of
the reaction mixture (V4+) slowly changed to greenish yellow and
then to brown (V5+), which further changed to green (V4+). In other
words, it appears that dispersed V5+ species in combination with
(VO)2P2O7 (V4+) is important for the oxidation of cyclohexane whereas
the V5+ species act as a dynamic oxidizing center [28,29]. Calcination of
the catalyst at high temperature results in more VOPO4 (V5+) phase,
which is detrimental to the catalytic activity.
4. Conclusions
In conclusion, we have developed a novel approach for highly se-
lective co-production of nitrocyclohexane and adipic acid via vapor
phase nitration–oxidation of cyclohexane with NO2 under atmo-
spheric pressure. The results indicated that highly total selectivity
(over 95%) for nitrocyclohexane and adipic acid with good conversion
was obtained. Further studies for the optimization of the vapor phase
catalytic nitration–oxidation reaction conditions are now in progress.
Assuming that the better catalysts can be developed, the method pro-
vides a novel strategy for highly selective synthesis of nitroalkanes
and dicarboxylic acids.
Acknowledgments
The authors are grateful for the financial support for this work
by the National Natural Science Foundation of China (21006081,
21276216), Program for New Century Excellent Talents in University
(NCET-10-0168), the Scientific Research Fund of the Hunan Provincial
Education Department (11B122, 08B087 and 09K035), and the Natu-
ral Science Foundation of Hunan Province (11JJ3024).
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