Synthesis of N-methylaniline over molecular sieve catalysts

Article abstract of DOI:10.1134/S0965544116030038

The preparation of N-methylaniline in two various processes: alkylation of aniline with methanol and hydroalkylation of nitrobenzene with methanol has been studied. Bifunctional molecular sieves containing metal copper as the hydrogenating component and zeolites BEA, MOR, MFI, FAU (Y) and mesoporous material MCM-41 as an alkylating component were used as catalysts. It has been shown that the modification of samples with copper nitrate increases the number of Lewis acid sites and decreases the number of Br?nsted acid sites as copper embeds into cation exchange positions. It has been determined that the catalyst modification with copper increases the activity and enhances the selectivity towards N-alkylated products.

Full text of DOI:10.1134/S0965544116030038

ISSN 0965ꢀ5441, Petroleum Chemistry, 2016, Vol. 56, No. 3, pp. 205–210. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © M.V. Belova, O.A. Ponomareva, I.I. Ivanova, 2016, published in Neftekhimiya, 2016, Vol. 56, No. 3, pp. 222–227.
Synthesis of NꢀMethylaniline over Molecular Sieve Catalysts
M. V. Belovaa, O. A. Ponomarevaa, b, and I. I. Ivanovaa, b
a Moscow State University, Moscow, Russia
b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
eꢀmail: belova.msu@gmail.com
Received November 16, 2015
Abstract—The preparation of Nꢀmethylaniline in two various processes: alkylation of aniline with methanol
and hydroalkylation of nitrobenzene with methanol has been studied. Bifunctional molecular sieves containꢀ
ing metal copper as the hydrogenating component and zeolites BEA, MOR, MFI, FAU (Y) and mesoporous
material MCMꢀ41 as an alkylating component were used as catalysts. It has been shown that the modification
of samples with copper nitrate increases the number of Lewis acid sites and decreases the number of Brønsted
acid sites as copper embeds into cation exchange positions. It has been determined that the catalyst modifiꢀ
cation with copper increases the activity and enhances the selectivity towards
N
ꢀalkylated products.
Keywords: aniline, nitrobenzene, methanol,
Nꢀmethylaniline, alkylation, hydroalkylation, zeolites, molecuꢀ
lar sieves
DOI: 10.1134/S0965544116030038
Zeolites and mesoporous molecular sieves are aniline, but also in one step via hydroalkylation of
promising heterogeneous catalysts that combine high nitrobenzene with methanol [18] since both processes
environmental friendliness, unique porous structure can be carried out on similar catalytic systems and
and ability to be modified to give catalysts with acidic, under close conditions. The catalyst for the oneꢀstep
basic or redox properties. On the basis of zeolites, the
Nꢀmethylaniline synthesis should be bifunctional and
multifunctional systems capable of catalyzing multiꢀ combine both hydrogenating and alkylating functions.
step reactions may be synthesized by introducing metꢀ Metals are used as a hydrogenating component and
als using ion exchange or impregnation techniques [1]. molecular sieves can be used as an alkylating compoꢀ
As a result of numerous advantages over homogeneous nent. Metallic copper supported on SiO2 is known to
catalysts, molecular sieve catalysts are widely used in
various petrochemical and petroleum refining proꢀ
cesses. In particular, high activity parameters are
achieved in the processes of alkylation of aromatic
compounds, such as benzene alkylation with the forꢀ
mation of ethylbenzene and cumene [2, 3], alkylation
of phenol with various alcohols and alkenes [4–6], and
aniline alkylation with methanol [7, 8].
be an industrial catalyst for nitrobenzene hydrogenaꢀ
tion [19]; besides, copperꢀcontaining catalysts based
on various metal oxides exhibit high activity in aniline
alkylation with methanol [10]. Therefore it can be
assumed that the modification of molecular sieves
with copper could increase their activity in both
aniline alkylation and nitrobenzene hydroalkylation
with methanol. In this paper, these two processes were
investigated in the presence of copperꢀmodified
molecular sieves. For comparative analysis were examꢀ
ined the catalytic activity of the Hꢀforms of these
molecular sieves and the influence of their acidic charꢀ
acteristics and modification with copper on their
physicochemical and catalytic properties.
The alkylation of aniline with methanol is an
industrially important reaction due to a wide range of
applications of substituted anilines:
(NMA), N,Nꢀdimethylaniline (NNDMA), and toluꢀ
idines (T). ꢀalkylated products are valuable raw
Nꢀmethylaniline
N
materials for the synthesis of organic compounds and
are used as additives in the production of dyes, synꢀ
thetic rubbers, herbicides, and explosives [8, 9]. The
reaction of aniline methylation has been studied over
oxide catalysts [10]; spinels CrxMnyFe2O4 [11] and
EXPERIMENTAL
The commercially available zeolites MFI
CuCr2– FexO4 [12]; aluminophosphates AlPO4 [13];
(
(
SiO2/Al2O3 = 80), BEA (SiO2/Al2O3 = 75), MOR
SiO2/Al2O3 = 97), and FAU(Y) (SiO2/Al2O3 = 60)
x
zeolites of various structural types such as MFI [8, 14,
15], Y [14, 15], and BEA [16]; and mesoporous mateꢀ
rials MCMꢀ41 [9] and SBAꢀ15 [17].
(Zeolyst) were used as the zeolite component of the
catalyst. The mesoporous material MCMꢀ41 with the
ratio of SiO2/Al2O3 = 50 was synthesized according to
Moreover, it has been shown that Nꢀmethylaniline
can be obtained not only via direct alkylation of a published procedure [20] and then subjected to the
205

206
BELOVA et al.
triple ion exchange with ammonium nitrate solution. room temperature under argon, after which a mixture
In order to obtain the Hꢀforms of zeolites and MCMꢀ containing 3.5% hydrogen in argon was passed
41, the NH4ꢀforms of the samples were calcined in a through the reactor at a rate of 10 mL/min. The temꢀ
perature was raised to 800°С at a rate of 8°C/min. The
flow of dry air at 550°С for 6 h. The modification of
change in the thermal conductivity of the gas flow durꢀ
ing the uptake of hydrogen by the sample was recorded
using a thermal conductivity detector.
the catalysts with copper was conducted using incipiꢀ
ent wetness impregnation of the parent zeolite with an
aqueous copper nitrate solution taken in amount to
obtain 7.5 wt % metal loading. The prepared samples
Catalytic experiments on the alkylation of aniline
and hydroalkylation of nitrobenzene with methanol
were conducted in a downꢀflow reactor under atmoꢀ
spheric pressure. Prior to the experiment the catalyst
were dried at 100
400 for 6 h, and reduced in situ prior to the experiꢀ
ment at 300 in a hydrogen stream for 30 min.
°С, calcined in a flow of dry air at
°С
°С
Lowꢀtemperature nitrogen adsorption/desorption
isotherms were measured using a Micromeritics
ASAP2000 automated porosimeter. All the samples
was activated in a hydrogen stream at 300
30 min. The catalytic reaction was studied in the gas–
liquid phase mode in a hydrogen stream at 300 at
°С for
°С
were preliminarily evacuated at 350°С
to 10–3 Pa. The
reactants molar ratio aniline (or nitrobenzene) : methꢀ
anol : hydrogen = 1 : 3 : 4.5 in a wide range of feedꢀ
stock weight hourly space velocities of 5–100 h–1.
total adsorption pore volume was calculated from the
amount of nitrogen adsorbed at a relative pressure
p/p0 = 0.945. The surface area was calculated using a
Reaction products were determined using a gas–
liquid chromatography technique on a Kristall 2000M
chromatograph equipped with a flame ionization
detector and a fused silica capillary column (30 m)
coated with the SEꢀ30 stationary phase and coupled
gas chromatography–mass spectrometry on a Thermo
DSQꢀII instrument integrated with a Trace GC gas
chromatograph equipped with an OVꢀ101 coated
fused silica capillary column (50 m). Chromatograms
were recorded and processed using a HewlettꢀPackard
hardware–software complex. The catalytic properties
of the samples were evaluated by aniline and nitrobenꢀ
zene conversions and initial rates of product formation
in the conversion range of 0–20%.
Brunauer–Emmett–Teller (BET) method. The
micropore volume was determined using the de Boer–
Lippens tꢀplot method. The mesopore volume was
determined by the Barrett–Joyner–Halenda (BJH)
method in pores with a size of 10–100 Å.
The acidic properties of the samples were studied
using temperatureꢀprogrammed desorption of ammoꢀ
nia (TPD NH3) on a sorption analyzer USGAꢀ101
(Unisit). The sample was calcined in a flow of dry
helium at 550
ture. The adsorption of ammonia was conducted for
30 min at 60 , ammonia was diluted with nitrogen in
a 1 : 1 ratio. Physically sorbed ammonia was removed
in a flow of dry helium at 100 for 1 h. The experiꢀ
ments on the TPD NH3 were conducted in the temꢀ
perature range of 60–800 in a flow of dry helium
(flow rate of 30 mL/min). The heating rate was
°С and then cooled to room temperaꢀ
°C
°С
°С
RESULTS AND DISCUSSION
Physicochemical Properties of Catalysts
8°C/min.
IR spectra were recorded on a Nicolet Protege 380
The physicochemical characteristics of the samꢀ
ples: Hꢀforms of various molecular sieves and copperꢀ
containing molecular sieves prepared via incipient
wetness impregnation are given in Table 1. According
to this data the introduction of copper in an amount of
7.5 wt % leads to a decrease in the pore volume by less
than 20%.
Fourier transform spectrometer. The spectrometer was
equipped with an MCT detector, the recording in the
region of structural vibrations was conducted within
the range of 1700–400 cm–1 with the resolution of
4 cm–1. The adsorption of pyridine (Py) was carried
out on a vacuum unit that operated at a vacuum of 5 ×
10–4 Pa and was equipped with absolute pressure senꢀ
Zeolites of four various structural types with the
close Si / Al ratios, namely MOR, BEA, FAU (Y) and
MFI were used in the study. The first three zeolites are
molecular sieves with wide pores and channel diameꢀ
ters of 7.0 (MOR), 7.7 (BEA), and 7.4 (FAU) Å. Zeoꢀ
lite MOR has a pseudoꢀoneꢀdimensional channel sysꢀ
tem with windows of main channels formed by 12ꢀ
membered rings. Zeolites BEA and FAU (Y) have a
threeꢀdimensional channel system; the windows are
formed by 12ꢀmembered rings along each of the three
dimensions; there are also “supercages” of a 12 Å size
in faujasite. Zeolite MFI possesses a threeꢀdimenꢀ
sors. Before the experiment catalyst samples were
evacuated, heated to 450
and calcined at that temperature until a vacuum of
10–3 Pa was reached. The adsorption of pyridine
was performed at 150 and a Py pressure of 3 Torr
followed by the evacuation at 150 for 1 h. The
°С at a rate of 0.5°C/min,
≤
1 ×
°С
°C
obtained IR spectra were processed using the OMNIC
ESP 7.3 software package.
The redox properties of the catalysts were studied
using temperatureꢀprogrammed reduction by hydroꢀ
gen (TPR H2) on Unisit USGAꢀ101 sorption analyzer.
A sample weight was placed in a fusedꢀsilica reactor sional channel system with 10ꢀmembered rings up to
and subjected to pretreatment, the samples were held 5.5 Å in diameter and is related to mesoporous zeolites
at 375°С
for 1 h in an argon stream and then cooled to with mediumꢀsized pores [21].
PETROLEUM CHEMISTRY Vol. 56
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SYNTHESIS OF
N
ꢀMETHYLANILINE OVER MOLECULAR SIEVE CATALYSTS
207
Table 1. Physicochemical characteristics of the catalysts
Amount of desorbed NH3,
Sample
HFAU (Y)
SiO2/Al2O3 (mol)
V
pore, cm3/g
V
micropore*, cm3/g
µ
mol NH3/g
60
97
80
75
50
60
97
80
75
50
0.45
0.25
0.23
0.68
0.88
0.40
0.20
0.19
0.55
0.75
0.24
0.16
0.14
0.45
1.32
0.21
0.13
0.10
0.15
1.03
357
404
564
704
417
664
826
893
871
936
HMOR
HMFI
HBEA
HMCMꢀ41
Cu/FAU (Y)
Cu/MOR
Cu/MFI
Cu/BEA
Cu/MCMꢀ41
* For HMCMꢀ41 and Cu/MCMꢀ41 samples is the mesopore volume calculated by the BJH method is presented.
All zeolites are characterized by the presence of two copper leads to the increase in the total amount of desꢀ
peaks on TPD NH3 curves (Fig. 1): the lowꢀtemperaꢀ
ture and the highꢀtemperature peaks corresponding to
weak acid sites and physisorbed NH3 and strong acid
sites, respectively. For all zeolite samples there is a
prevalence of strong acid sites, they make more than
orbed ammonia in the TPD NH3 experiments for all
the samples, with the strength distribution of acid sites
altering as compared to the initial Hꢀforms. The conꢀ
tribution of the lowꢀtemperature peak significantly
increases, indicating an increase in the amount of
weak and mediumꢀstrength acid sites, while the highꢀ
50% of total amount of acid sites.
temperature peak for zeolites is in the region of 350–
460 ; by its value the initial zeolites can be arranged
Tmax of the highꢀ
temperature peak observed at 450°С has a low intenꢀ
°С
sity for all the samples. The decrease in the number of
strong acid sites for zeolitic catalysts can be explained
by the fact that ion exchange of zeolite protons for
copper cations occurs during the impregnation. The
appearance of an additional ammonia desorption peak
in the following row according to the strength of acid
sites: FAU (Y) < BEA < MFI < MOR. The TPD NH3
curve for MCMꢀ41 is characterized by the presence of
only one broad peak corresponding to weak acid sites
and mediumꢀstrength acid sites with Tmax in the temꢀ
at 320–350°С on the TPD NH3 curves of copperꢀconꢀ
perature range of 170–250°С.
taining samples was also noticed. This peak correꢀ
sponds to the decomposition of copper ammine comꢀ
plexes according to the authors of [22].
The modification of molecular sieve catalysts with
copper nitrate leads to a change in the acidic characꢀ
teristics of the samples. Figure 2 displays TPD NH3
curves for the HFAU (Y) and Cu/FAU (Y) samples;
the other catalysts reveal a similar dependence after
modification with copper nitrate. The introduction of
0.5
0.4
HFAU
(Y)
0.5
1—HBEA
2—HMFI
1
0.3
0.4
2
3—HMOR
3
1
4—HMCMꢀ41
5—HFAU(Y)
0.3
0.2
0.1
0
0.2
0.1
0
2
4
5
3
5
50
250
450
650
50
150
250
350
, °C
450
550
650
T
, °C
T
Fig. 1. TPD NH curves for zeolites of various structural
Fig. 2. TPD NH curves for the HFAU (Y) and Cu/FAU
3
3
types and mesoporous material MCMꢀ41.
(Y) samples.
PETROLEUM CHEMISTRY Vol. 56
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208
BELOVA et al.
(a)
(b)
1452
1451
1611
1611
1547
Cu/BEAꢀox
1547
1637
Cu/BEAꢀred
HBEA
Cu/MOR
HMOR
1622
1637
1622
1454
1700 1650 1600 1550 1500 1450 1400 1350
Wavenumber, cm–1
1700
1600
1500
1400
1300
Wavenumber, cm–1
Fig. 3. IR spectra of pyridine adsorbed at 150°C on (a) HMOR and Cu/MOR and (b) HBEA and Cu/BEA.
The nature of the acid sites was studied using FTIR tion in the range of aniline conversion of 0–20%. The
spectroscopy of adsorbed pyridine (Py). Figure 3 disꢀ relative measurement error did not exceed 15%. Only
plays the IR spectra of Py adsorbed at 150
samples of the initial and the copperꢀmodified zeolites (NNDMA), and
°
С
on the
N
ꢀmethylaniline (NMA), N,Nꢀdimethylaniline
pꢀtoluidine (T) were obtained as the
BEA and MOR; the spectra for other zeolites have a products at low conversions. The Hꢀforms of molecuꢀ
similar pattern. According to the FTIR data, part of lar sieves demonstrated rather low activity in alkylaꢀ
zeolite protons is exchanged by Cu+ cations after the
impregnation with copper nitrate, this assumption is
confirmed by an almost complete disappearance of the
bands of pyridine fixed to Brønsted acid sites (1637
and 1547 cm–1). While the intensity of the characterꢀ
istic bands of pyridine adsorbed on Lewis acid sites
(1622 and 1454 cm–1) increases in case of Cuꢀcontainꢀ
ing samples and the band shifts to lower frequencies
[23]. Thus a part of copper introduced by incipient
wetness impregnation is embedded in the cation
exchange positions, and the other part remains in the
form of copper oxide, which is reduced to metallic
tion at 300°C; the initial rates of product formation on
the zeolite catalysts were close (Table 2). The initial
formation rate of the desired product was two times
higher over the mesoporous material MCMꢀ41, but
the selectivity towards
Nꢀmethylaniline was noticeꢀ
ably lower; the predominant product was N,Nꢀdimeꢀ
thylaniline. The formation of a large amount of the
dialkylated product over MCMꢀ41 can be explained
by a larger pore size of this material.
The modification of the molecular sieve catalysts
by introducing 7.5 wt % copper resulted in an increase
in the alkylating activity by one to two orders of magꢀ
nitude. This result can be associated with the increase
in total acidity of the samples as well as with the
copper during the treatment with hydrogen at 300
°С,
that is confirmed by TPR H2 data (not presented in
this paper). On the other hand, the exchanged Cu+ change of the type of the acid sites, i.e., the increase in
ions are not reduced to Cu0 during the in situ treatꢀ
the contribution of mediumꢀstrength Lewis acid sites.
It should be noted that the yield of ꢀtoluidine as a
p
ment with hydrogen at 300°С, and the band at
1547 cm–1 does not appear on the spectra of the
reduced Cu/BEA sample (Fig. 3b).
product of Cꢀalkylation on Cuꢀcontaining catalysts
decreases, which may be due to a decrease in the quanꢀ
tity of strong Brønsted acid sites. These conclusions
are in good agreement with the results of TPD NH3
data and IR spectra of adsorbed pyridine. The catalyst
Cu/MCMꢀ41 demonstrated the highest activity; the
Alkylation of Aniline with Methanol
The reaction of aniline alkylation with methanol initial rate of Nꢀmethylaniline formation over this catꢀ
was studied over various molecular sieves: zeolites alyst was an order of magnitude higher than on Cuꢀ
BEA, FAU (Y), MOR and MFI and the mesoporous containing zeolite catalysts. The zeolite catalysts can
material MCMꢀ41 as well as on the samples modified be arranged in accordance with alkylating activity as
with 7.5 wt % copper. The catalytic properties were follows: Cu/MOR < Cu/BEA < Cu/FAU (Y) <
compared in terms of initial rates of products formaꢀ Cu/MFI. The samples of Cu/MFI and Cu/MOR are
PETROLEUM CHEMISTRY Vol. 56
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2016

SYNTHESIS OF
N
ꢀMETHYLANILINE OVER MOLECULAR SIEVE CATALYSTS
209
Table 2. Initial rates of products formation in aniline alkyꢀ
lation with methanol at 300
C, 5–100 h–1, aniline :
CH3OH = 1 : 3 (mol)
agreement with the amount of active sites. The paramꢀ
eters of the nitrobenzene hydroalkylation with methaꢀ
nol over Cu/MFI and Cu/MOR were quite close, the
catalysts exhibited similar activity in hydroalkylation.
°
Initial rate, mol
10–9/(g s)
×
However, the highest selectivity for
Nꢀmethylaniline
Catalyst
(97%) among the alkylation products was demonꢀ
strated by the Cu/MOR sample. Cu/AlꢀMCMꢀ41
showed rather high contribution of N,Nꢀdimethylaꢀ
niline (25%), most probably, due to the bigger pore
size.
Also, the catalytic properties of Cu/MFI,
Cu/MOR, and Cu/MCMꢀ41 were compared under
NMA
NNDMA
T
HFAU (Y)
HMOR
4.8
4.2
2.1
1.5
0.9
0.3
0.7
0.2
0.2
7.0
0.2
0.0
7.8
8.6
HMFI
5.2
2.3
HBEA
4.5
1.8
HMCMꢀ41
Cu/FAU (Y)
Cu/MOR
Cu/MFI
8.8
10.9
5.7
identical conditions: a temperature of 300°С and a
feedstock weight hourly space velocity of 5.8 h–1. The
conversion of nitrobenzene was 74.1–99.9% over all
the samples with aniline being the main product of the
hydroalkylation of nitrobenzene, whereas the selectivꢀ
47.3
20.6
99.0
37.3
317.4
0.9
11.2
7.3
ity towards the desired product
Nꢀmethylaniline
Cu/BEA
reached only 7.4–13.4 mol %. The least amount of
alkylation byproducts was obtained in case of
Cu/MOR catalyst. The results of the experiments
demonstrate that Cuꢀcontaining molecular sieves
Cu/MCMꢀ41
137.9
characterized by higher selectivity towards
laniline.
Nꢀmethyꢀ
are promising catalysts for the oneꢀstep synthesis of
methylaniline.
Nꢀ
Hydroalkylation of Nitrobenzene with Methanol
CONCLUSIONS
The aniline alkylation and nitrobenzene
hydroalkylation reactions with methanol over copperꢀ
containing molecular sieves have been studied. In the
investigation of the aniline alkylation process, it has
been found that the modification with copper leads to
enhancement of the alkylating ability of the catalysts
based on molecular sieves; the initial rates of formaꢀ
For catalytic experiments on the hydroalkylation of
nitrobenzene with methanol were chosen three copꢀ
perꢀmodified molecular sieve catalysts that demonꢀ
strated the highest activity and/or selectivity in the
aniline alkylation process. The data on the initial rates
of formation of the main products: aniline, Nꢀmethyꢀ
laniline and N,Nꢀdimethylaniline are presented in
Fig. 4. The best catalytic performance was demonꢀ
strated by the Cu/MCMꢀ41 sample, which is in good
tion of the desired product
Nꢀmethylaniline have
increased by one to two orders of magnitude. It has
been demonstrated that Cuꢀcontaining molecular
sieves are effective catalysts for both aniline alkylation
with methanol and the oneꢀstep synthesis of Nꢀmethꢀ
700
ylaniline from nitrobenzene and methanol. The cataꢀ
lyst Cu/MCMꢀ41 exhibited the highest activity in the
hydroalkylation of nitrobenzene, whereas the highest
selectivity towards the desired product (97 mol %)
among alkylation products was achieved over the
Cu/MOR sample.
600
Aniline
NMA
500
400
300
200
100
0
NNDMA
ACKNOWLEDGMENTS
The authors thank the Russian Science Foundation
for the financial support (Grant no. 14ꢀ23ꢀ00094).
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