Applied Clay Science 44 (2009) 255–258

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Selective N-alkylation of aniline with methanol over a heteropolyacid on

montmorillonite K10
Manoj Nehate, Vijay V. Bokade ⁎
Catalysis Division, National Chemical Laboratory (CSIR), Pune-411008, India

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

Article history: N-methylaniline is an industrially important product in the manufacture of paper, textile dyes, drugs,
Received 1 July 2008 perfumes and explosives. The vapour phase alkylation of aniline with methanol forming N-methylaniline is
Received in revised form 20 February 2009 advantageous over liquid phase alkylation. In present study, vapour phase methylation of aniline over
Accepted 27 February 2009
dodecatungestophosphoric acid supported on K10 montmorillonite was systematically studied and
Available online 16 March 2009
optimization of process parameters was carried out. The 20% m/m DTPA/K10 was found to be optimum
Keywords:
with 79% aniline conversion and 99% N-methylaniline selectivity. The reaction required milder operating
Aniline conditions than reported for commercial catalysts. We also studied the feasibility of 20% m/m DTPA/K10 as a
Alkylation catalyst for the alkylation of aniline with other alcohols like ethanol, n-propanol, iso-propanol and n-butanol.
Heteropolyacid The activity of 20% m/m DTPA/K10 decreased with increasing carbon number.
Montmorillonite K10 © 2009 Elsevier B.V. All rights reserved.
N-methylaniline

1. Introduction (OT). However, there is a selectivity issue between mono-N and N,N-
dimethylated products of the existing catalysts, based on zeolite or
Alkylation belongs to the most important reactions in organic alumina are successful in stopping or controlling the conversion of
chemistry. Aniline alkylation is an industrially important reaction due mono-N-methylated to N,N-dimethylated aniline products. Such
to the fact that alkyl-anilines are basic raw materials for synthesis of conversion is mainly controlled by the process parameters (Luque
organic chemicals, chemical intermediates and/or additives in dyes, et al., 2007).
synthetic rubbers, explosives, herbicides and pharmaceuticals Demand for the selective synthesis of N-methylanilines has recently
(Negwer, 1994; Kim et al., 2002; Stauffer and Hartwig, 2003; grown due to a variety of applications in agrochemical industries, as
Sunwanprasop et al., 2004). Vapour phase aniline alkylation over antioxidants in rubber industries and as dye-stuffs in textile industries
environmentally safe solid catalysts is the answer to the conventional (Baustista et al., 1997; Baustista et al., 1998; Ullmann, 1999; Narayanan
method of liquid phase alkylation using mineral acids and Friedel– and Deshpande, 2000; Ivanova et al., 2001; Garces et al., 2003). The
Crafts type catalysts (Bhattacharya and Nandi, 1975). Although it selective N-alkylation of aniline with dialkyl carbonates in liquid phase
provides higher yields (Doraiswamy et al., 1981) than vapor phase on zeolites with high yields was reported (Selva et al., 2005). However, a
alkylation, this process is restricted due to disadvantages such as high very large molar ratio of dialkyl carbonate to aniline (up to 70:1)
capital cost, corrosion problems and formation of byproducts that employed in this study prevents the process from being commercially
cannot be recycled. With the increasing awareness of environmental viable. The products are complex (Scheme 1) and the selectivity
issues, a wide variety of solid acid catalysts and alkylating reagents depends strongly on the experimental conditions and on the nature of
have been employed in this process. Recently, progress in the the catalyst. In particular, it is more difficult to control the reaction for
application of acid catalysts for aniline alkylation has been reviewed obtaining NMA with a high selectivity.
(Narayanan and Deshpande, 2000). Several solid acids have been The aim of this study was to develop a new catalyst and to chose
reported for aniline alkylation with methanol, including zeolites the process parameters for selective synthesis of N-methylaniline
(Narayanan and Sultana, 1998; Ivanova et al., 2001; Anand et al., from aniline and methanol. A heteropolyacid supported on K10
2003), modified clay minerals (Narayanan and Deshpande, 1996; montmorillonite fulfills this condition.
Sreekumar and Sugunan, 2002; Yadav and Doshi, 2003), vanadium
(Narayanan and Deshpande, 1995; Narayanan and Prasad, 1995) and
iron oxides (Sreekumar et al., 2000; Nishamol et al., 2004), leading to 2. Experimental
N-methylaniline (NMA), N,N-dimethylaniline (DMA) and o-toluidine
2.1. Chemicals

⁎ Corresponding author. Tel.: +91 20 2590 2458; fax: +91 20 2590 2634. Dodecatungstophosphoric acid [H3W12O40 xH2O] (DTPA), metha-
E-mail address: [email protected] (V.V. Bokade). nol (99%), montmorillonite K10 and aniline (99%) were obtained from

0169-1317/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.02.011
256 M. Nehate, V.V. Bokade / Applied Clay Science 44 (2009) 255–258

Scheme 1. Reaction scheme.

M/s S.D. Fine Chemicals, Mumbai. All reagents were of analytical samples until no more NH3 was uptaken. NH3 was desorbed in the
grade and used without further purification. helium flow by increasing the temperature to 813 K with a heating
rate of 10 °C/min NH3 desorption with a TCD detector (Table 2).
2.2. Catalyst preparation
2.4. Catalyst formulation
DTPA/montmorillonite was prepared by impregnation. An amount
of 2 g DTPA was dissolved in methanol and was added slowly to 20 g All catalysts were formulated as pellets by applying 10 ton
K10 with stirring. The paste was dried on a water bath, then at 90 °C to pressure. The pellets were cut into small pieces of 10–20 mesh
remove methanol completely. Prior to use, the sample was dried at (3 mm irregular size).
100 °C to remove moisture. The composition of the catalysts was 5–
30% m/m DTPA/K10. 2.5. Reaction procedure

2.3. Catalyst characterization The vapor phase reaction was carried out in a SS316 (20 ml
volume) continuous downflow reactor (Fig. 2). The catalyst (10 g) was
2.3.1. Powder X-ray diffraction activated at 250 °C, under nitrogen (50 ml/min) for 2 h, prior to the
The crystallinity and the phase purity of the samples were experiment. Typically, a mixture of aniline: methanol at a molar ratio
determined by powder X-ray diffraction (XRD) (Rigaku Miniflex, of 1:6, at 260 °C at a weight hourly space velocity (WHSV) of 1.1 h− 1
Japan, Cu-Ka) (Fig. 1). and atmospheric pressure was used. Each reaction was performed for
a period of 6 h during the steady state. The products were cooled in a
trap and collected at regular intervals for analysis.
2.3.2. Nitrogen adsorption
The specific surface area was obtained from nitrogen adsorption–
2.6. Analysis
desorption isotherms at 787 K measured in an SA 3100, USA analyzer.
The surface area was calculated by the BET method (Table 1).
The liquid reaction products were analyzed by gas chromatography
(GC-1000) (packed column, liquid phase 5% SE-30, solid support
2.3.3. Temperature programmed ammonia desorption (TPAD) CHW-HP, 1/8' diameter × 8' length) with nitrogen as a carrier gas and
The total amount of acidic sites present in the catalyst was programmable temperature between 40 and 200 °C. The reaction
estimated by using temperature-programmed desorption (TPD) of
NH3 on a Micromeritics AutoChem 2910 instrument. 0.1 g of the
catalyst was dehydrated at 773 K in dry air for 1 h and then purged
with helium for 0.5 h. The temperature was decreased to 398 K under
Table 1
the flow of helium, and then 0.5 ml NH3 pulses were supplied to the
Nitrogen adsorption by BET method.

No. Catalyst Specific BET surface area (m2/g)

1 K10 montmorillonite 223
2 5% m/m DTPA/K10 217
3 10% m/m DTPA/K10 195
4 15% m/m DTPA/K10 156
5 20% m/m DTPA/K10 135
6 30% m/m DTPA/K10 104

Table 2
Total acidity measured by TPAD.

No. Catalyst Total acidity Increase of acid site concentration

(mmol g− 1) after DTPA loading (%)
1 K10 montmorillonite 0.139 –
2 5% m/m DTPA/K10 0.189 5.00
3 10% m/m DTPA/K10 0.242 10.3
4 15% m/m DTPA/K10 0.328 18.9
5 20% m/m DTPA/K10 0.423 28.4
Fig. 1. Powder X-ray diffraction for different percent loading of DTPA on K10
6 30% m/m DTPA/K10 0.426 28.7
montmorillonite.
 M. Nehate, V.V. Bokade / Applied Clay Science 44 (2009) 255–258 257

Table 4
Effect of reaction temperature.

Reaction temperature(°C) 200 240 260 280

% Conv.Aniline 84 75 79 62
%Sel.NMA 85 68 99 99
%Sel.DMA 15 32 1 1

Reaction conditions: – Catalyst: 20% m/m DTPA/K10; Catalyst: 10 g, Reaction pressure:

1 atm, WHSV: 1.1 h− 1, Molar ratio (aniline:methanol): 1:6, Conv.: Conversion, Sel.:
Selectivity. Time on stream: 5 h. 4th h.

conversion did not increase and selectivity decreased from 89% (1:6)
to 77% (1:8). The optimum ratio was therefore 1:6.

3.4. Effect of weight hourly space velocity

Aniline conversion decreased with increasing WHSV from 1.1 to

4 h− 1 (Table 6). This may be due to reduced contact time with
increasing WHSV. The selectivity of N-methylaniline decreased from
Fig. 2. Experimental set up. 1: Feed pump; 2: Fixed bed reactor (20 cc); 3: Catalyst bed; 99% to 79% and N,N-dimethylaniline formation increased from 1% to
4: Electrical furnace; 5: Condenser; 6: High pressure product receiver; 7: Back pressure
21%, with WHSV from 1.1 to 4 h− 1. This may be due to a higher rate of
valve; 8: Atmospheric product receiver.
N-methylaniline alkylation at 260 °C.

products were also studied by GC-MS (Shimadzu-QP5000). The 3.5. Effect of different alcohols
gaseous products were analyzed in FID using a GS-Q Plot Column.
Aniline conversion decreased from 79% to 4%, by alkylation with
3. Result and discussion ethanol, n-propanol, iso-propanol, n-butanol instead of methanol
(Table 7). The reaction is believed to be consecutive or sequential and
3.1. Catalyst selection follows the order: aniline → N-methylaniline → N,N-dimethylanili-
ne → Others. Moderate reaction conditions favored the selective
K10 montmorillonite and DTPA/ K10 samples were tested at formation of N-methylaniline. Thus, N-alkylated products can be
240 °C, 1.1 h− 1 and a molar ratio aniline: methanol = 1:2 at 1-atm.
Each reaction was conducted for the reaction period of 6 h (Table 3).
Table 5
All DTPA loaded samples has shown higher activity compared to K10
Effect of molar ratio of aniline:methanol.
montmorillonite. DTPA contents increasing upto 30% m/m increased
aniline conversion from 14% to 78% and selectivity of N-methylaniline Aniline:methanol 1:2 1:3 1:4 1:6 1:8
from 17% to 68%. The optimum loading of DTPA was 20% m/m, above % Conv.Aniline 70 64 72 79 81
%Sel.NMA 70 83 84 99 77
which aniline conversion increased, but not selectivity. This may be
%Sel.DMA 9 5 – 1 23
due to the increased in acidity and multilayer formation of DTPA. %Sel.Other 20 11 16 – –

Reaction conditions: – Catalyst: 20% m/m DTPA/K10, Catalyst: 10 g, Reaction pressure:

3.2. Effect of reaction temperature 1 atm, Reaction temperature: 260 °C WHSV: 1.1 h− 1, Conv.: Conversion, Sel.: Selectivity.
Time on stream: 5 h. 4th h.
Increasing the reaction temperature from 200 to 280 °C reduced
aniline conversion from 84% to 62% but increased selectivity from 85%
to 99% (Table 4). The reason is that methanol in the feed decomposes Table 6
due to reforming reactions as confirmed by hydrogen and methane in Effect of weight hourly space velocity (WHSV, h− 1).
the gaseous products. WHSV, h− 1 1.1 1.5 2 3 4
% Conv.Aniline 79 48 11 6 4
3.3. Effect of molar ratio of aniline:methanol %Sel.NMA 99 92 97 89 79
%Sel.DMA 1 8 3 11 21

Aniline conversion was 70% (Table 5) up to aniline:methanol molar Reaction conditions: – Catalyst: 20% m/m DTPA/K10; Catalyst: 10 g, Reaction pressure:
1 atm, Reaction temperature: 260 °C, Mole ratio: 1:6, Conv.: Conversion, Sel.: Selectivity.
ratio of 1:6 and selectivity increased to 89%. Above 1:6, aniline
Time on stream: 5 h. 4th h.

Table 3
Selectivity of N-methylaniline formation.
Table 7
Catalyst K10 5% m/m 10% m/m 15% m/m 20% m/m 30% m/m Effect of different alcohols.
DTPA/K10 DTPA/K10 DTPA/K10 DTPA/K10 DTPA/K10
% Conv.Aniline 14 50 57 60 75 78 Alcohols Methanol Ethanol n-Propanol iso-Propanol n-Butanol
%Sel.NMA 17 25 36 67 68 68 % Conv.Aniline 79 21 20 8 4
%Sel.DMA 34 43 49 33 32 18 %Sel.NAA 99 91 74 98 33
%Sel.Other 49 40 15 – – 13 %Sel.DAA 1 9 26 2 67

Reaction conditions: – Catalyst: 10 g, Reaction temperature: 240 °C, Reaction pressure: Reaction conditions: – Catalyst: 20% m/m DTPA/K10; Catalyst: 10 g, Reaction Pressure:
1 atm, WHSV: 1.1 h− 1, Molar ratio (aniline:methanol): 1:6, Conv.: Conversion, Sel.: 1 atm, Reaction temperature: 260 °C WHSV: 1.1 h− 1, Molar ratio: aniline:alcohol 1:6,
Selectivity. Time on stream: 5 h. 4th h. Conv.: Conversion, Sel.: Selectivity. Time on stream: 5 h. 4th h.
258 M. Nehate, V.V. Bokade / Applied Clay Science 44 (2009) 255–258

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