ELSEVIER

Applied Catalysis A: General 11 I (1994) LlOl-L108

Letter

Synthesis of 2-picoline from acetone over modified

ZSM-5 catalysts* *
A.V. Rama Rao, S.J. Kulkarni, R. Ramachandra Rao,
M. Subrahmanyam
Indian Institute of Chemical Technology, Hyde&ad
(Received

16 March 1993, revised manuscript

500 007, India

received 10 November

1993)

Abstract
In the reaction of acetone, formaldehyde and methanol with ammonia over modified ZSMJ
catalysts, 2-picoline and 2,6-lutidine are synthesized selectively. The catalysts studied were H-ZSM5 with Si/Al ratios, 30, 150 and 280, Pb-ZSM-5, W-ZSMJ and modified silica-alumina. The yields
of 2-picoline obtained were 30-47 wt.-% at 50-60 wt.-% conversions of acetone. The unconverted
acetone and methanol can be recycled to increase the over-all yield. Pb-ZSMJ was identified as the
best catalyst.
Key work

acetone; Pb-ZSM-5; picoline; W-ZSMJ;

zeolites; ZSM-5

1. Introduction
Pyridine and substituted pyridines are useful intermediates in pharmaceuticals, herbicides
agents [ 11. The reaction of acetaldehyde, formaldehyde and ammonia
over acidic catalysts leads to pyridine and 3-picoline [ 1.21. On the other hand, the reaction
of acetaldehyde and ammonia gives 2-picoline and 4-picoline. The catalysts used in the
preparation of substituted pyridines are Pd-A&O, promoted by PbO, CuO or Si02-A1,03
promoted by ThOz, ZnO and Cd0 with 40-60% yield. We have reported [ 21 the reactions
of propylene oxide, propylene glycol; ethylene glycol or acetaldehyde with ammonia over
H-ZSM-5 catalyst leading to substituted pyridines and aliphatic amines. Pyridine was also
synthesized from ethanol and ammonia over ZSM-5 catalyst in the presence of oxygen with
low yields [ 3].2-Picoline
was observed as a major side-product in the amination of phenol

and surface-active

*Corresponding author.
* *IICT Communication

No. 3 1.51.

0926-860X/94/$07.00
0 1994 Elsevier Science B.V. All rights reserved
SSDIO926-860X
(94)00025-M

LlO2

A.V. Ratna Rao et al. /Applied

Catalysis A: General Ill

(1994) LIOI-L108

over ZSM-5 at higher temperature (5 10C) [ 41. Picolines were synthesized over various
modified Si02-A&O3 and pentasil catalysts [5-l 11.
In this paper, we report the selective synthesis of 2-picoline from acetone, formaldehyde,
methanol and ammonia over modified ZSM-5 catalysts, with 2,6-lutidine as a major side
product.

2. Experimental
H-ZSM-5 catalysts used in this study were supplied by Conteka, Sweden. The catalyst
was modified with a known weight of lead nitrate (20% PbO) and ammonium metatungstate ( 12 wt.-% W). Silica-alumina
used in this study was supplied by Akzo Chemie,
Netherlands with 84: 16 wt.-% of silica-alumina.
Modification of the catalysts was carried
out by the impregnation technique. The ice-cooled mixture of acetone and 40 wt.-% aqueous
formaldehyde was used in the feed. Ammonia gas was introduced separately.
The reactions were carried out using a tubular, down-flow Pyrex reactor with 20 mm
internal diameter. The reaction mixture was fed from the top using a Sage syringe pump.
The product was cooled using ice-cooled water and collected at the bottom. A sufficient
number of ice-cooled traps were used at the outlet end to collect the total amount of products.
The products were analyzed by SE-30 (5%) and [ chromosorb (5%) ] columns. The analysis
was confirmed by mass spectra and gas chromatography-mass
spectrometry (CC-MS).

3. Results and discussion

The reaction of acetone, formaldehyde and methanol with ammonia was carried out over
various ZSM-5 catalysts. The results are tabulated in Table 1. The reaction was carried out
Table 1
The synthesis of 2-picoline
Reaction

from acetone over modified ZSM-5 catalysts

temperature=420C,

WHSV =0.5

hh,

feed: CH,COCHr:

HCHO:CH?OH:

NH? = ( I : 1.3:0.9: 1.3)

molar

S. No. Catalyst

2Picoline
Time-on-stream
(h)

I.
2.
3.
4.
5.
6.
1.

H-ZSM-5 (30)
H-ZSM-5 ( 150)
H-ZSM-5 (280)
Pb-ZSMJ
W-ZSM-5
PbSA(1)
PbSA (2)

2
4
3
2
(2+3)
2
2

Based on acetone.
2,6-Lutidine is > 90% among lutidines.

Conversion (wt.-%)
with respect to

Yield (wt.-%)

Acetone

Formaldehyde

2-Picoline

4-Picoline

Lutidine

40.8
58.7
41.1
69.0
51.2
59.5
22.6

100
100
100
100
100
100
100

21.0
33.5
28.0
35.0
29.0
16.0
6.8

3.0
4.0
8.0
2.0
2.0

10.8
21.2
13.1
26.0
22.2
41.5
13.8

4Picoline

9.0
8.4
4.4
8.0
3.4

A.V. Rama Rao et al. /Applied Catalysis A: General lll(1994)

LlOl-L108

I.103

at 420C with a 0.5 h- weight hourly space velocity for 4 hour on stream. Three H-ZSM5 catalysts with (Si/Al) = 30, 150 and 280 were tested. H-ZSMJ (30), H-ZSM-5 (150)
and H-ZSM-5 (280) showed 40.8, 58.7 and 41.1% conversion of acetone, respectively.
The yields of 2-picoline for H-ZSM-5 (30), H-ZSM-5 ( 150) and H-ZSM-5 (280) were
27.0,33.5 and 28.0 wt.-% based on acetone and (2-/4-picoline)
ratios were 9.0, 8.4% and
very high, respectively. H-ZSM-5 ( 150) showed the highest activity for the formation of
2-picoline. 4-Picoline was not observed in the case of H-ZSM-5 (280). To get a high
activity in the dehydrocyclization
reaction, an optimum number of active centres are
required. With the increase of the (Si/Al) ratio there was an increase in the (2-/bpicoline)
ratio. The yield of total lutidines obtained was lo-40 wt.-% and 2,6-lutidine was > 90%
among the lutidines. Bipyridine ( < 10%) compound was also obtained at lower (350C)
temperature confirmed by GC-MS.
In the case of Pb-ZSM-5 and W-ZSM-$, the conversions of acetone were 69.0 and 5 1.2
wt.-% while the yields of 2-picoline were 35.0 and 29.0 wt.-%, respectively. The yield of
4-picoline observed was low (2 wt.-%). Thus lead and tungsten have a promoting effect in
increasing the yield of 2-picoline. The lead promoted silica-alumina
PbSA ( 1) and
PbSA( 2) showed 16.0 and 6.8 wt.-% 2-picoline formation. In the case of Pb-ZSM-5 and
W-ZSM-5, the yield of lutidines was 18-25 wt.-%.
To understand the stoichiometry, the following different reactions were carried out over
Pb-ZSM-5 ( 150) at 420C and 0.5 h-i WHSV, ( 1) acetone, formaldehyde, methanol and
ammonia, (2) acetone, formaldehyde ( 1: 1.05 molar) and ammonia, ( 3) acetone, formaldehyde (4 : 1) and ammonia, (4) acetone, methanol and ammonia and (5) acetone and
ammonia. The experimental data are given in Table 2. The selectivity among the picolines
and yield of 2-picoline were enhanced predominantly after addition of formaldehyde to the
feed. The molar ratios of acetone to formaldehyde were varied widely, including a ratio of
1: 3, but formaldehyde polymerized, forming a solid and coke in the pre-heater zone; so the
addition of methanol is essential to enhance the yield. The stoichiometry may be suggested
as follows for the formation of picoline.
acetone + 3 formaldehyde

+ ammonia + picoline + 4 water

(1)

As lutidines are also observed in the products, the mechanism and stoichiometry may also
be represented as given in Scheme 1.
The influence of the WHSV is depicted in Table 3. The WHSV .was varied from 0.25 to
1 h- . The reaction of acetone, formaldehyde, methanol with ammonia was carried out over
Pb-ZSM-5 at 420C. The conversions of acetone for 1,0.75,0.50,0.37
and 0.25 h - WHSV
were 59.3, 72.6, 69.0, 68.2 and 69.4 wt.-% and yields for 2-picoline were 15.6, 31.5, 35,
47.5 and 45 wt.-%, respectively. With the increase of WHSV, the yield increased upto 0.37
h- . The ratio of 2-picoline/4-picoline
increased with the decrease of WHSV. The experimental data in Table 4 indicate that 2-picoline in the product increases, as the amount of
lutidines decreases. The reaction of lutidine and water (1:2.5 mol) over Pb-ZSM-5 at
420C and 0.5 h- WHSV leads to > 5.6 wt.-% 2-picoline and 3.6% pyridine at > 90%
conversionof
lutidine. The reaction of 2,6-lutidine, water and ammonia also leads to the
formation of > 10% 2-picoline and pyridine. The reaction of methanol over Pb-ZSM-5 and
W-ZSM-5 at 420C and 0.5 h- WHSV leads to the formation of 79.1,36.4% formaldehyde

 (CH,COCH, + HCHO +
CH,OH + NH3)
( CH@CHJ + HCHO + NH?)
(CH3COCH9+ HCHO + NHS)
( CHSCOCHJ+ CHSOH + NH?)
(CHDCH3 + NH3)

Feed

Based on acetone.
b2,6-Lutidine is > 90%.

2.
3.
4.
5.

I.

S. No.

1:1.05:1.3
4: I: 1.3
112: 1.3
1: 1.3

l:O.i:O.9: 1.3

Molar ratio

2
3
3
3

Time-on-stream
(h)

Catalyst = Pb-ZSMJ ( 150). reaction temperature = 420C. WHSV = 0.5 h-

Table 2
The synthesis of 2-picoline from acetone: the variation of feed

64.4
28.5
25.6
15.0

69.0
100
100
-

100

40.0
20.0
20.6
5.0

35.0

7.0
-

8.0

4-Picoline

2-Picoline

Acetone

Formaldehyde

Yield (wt.-%)

Conversion (wt.-%)

17.4
8.5
5.0
10.0

26.0

Lutidines*

5.7
-

4.4

Z-Picoline
4-Picoline

A.V.

Rama Rao

etal.

/Applied Catalysis A:

C3

General 11111994)

LlO5

LlOl-L108

Cn, COCH3
I

("3

0=

'

CH3COCH=CICH312

CH3

Scheme I.

at 80.4,37.6% conversion of methanol respectively. Under our experimental conditions, 2picoline and 2,6-lutidine were the major products.
The weight percent conversion of acetone, yield of 2,6-lutidine based on acetone and
selectivity with respect to the variation of the weight hourly space velocity in the reaction
of acetone, formaldehyde, methanol and ammonia over Pb-ZSM-5 at 420C is shown in
Fig. 1. Thus Scheme 1 is plausible to account for the formation of 2,6-lutidine and other
products. We have varied the acetone to formaldehyde ratio from 1: 3 to 4 : 1 with or without
Table 3
The synthesis of 2-picoline from acetone: the effect of WHSV
Reaction temperature = 420C. catalyst = Pb-ZSM-5 (150), Feed: CH&OCHs : HCHO : CH30H : NH3 =
(1:1.3:0.9:1.3)molar
2-Picoline
Yield (wt.-%)
S. No. Weight hourly Time-on-stream Conversion (wt.-%)
4-Picoline
space velocity (h )
with respect to
(h-l)
Acetone Formaldehyde 2Picoline 4-Picoline Lutidinesh
1.
2.
3.
4.
5.

I.00
0.75
0.50
0.37
0.25

4
1
2
(3+4)
2

Based on acetone.
2,6-Lutidine is > 90%.

59.3
72.6
69.0
68.2
69.4

I00
100
I00
I00
I00

15.6
31.5
35.0
47.5
-45.0

4.5
6.0
8.0
8.0
6.0

39.2
35.1
26.0
12.7
18.4

3.5
5.3
4.4
6.0
7.5

A. V. Rama Rao et al. /Applied Catalysis A: General Ii l(1994)

L106

LIOI-L108

0 : Conversion of ucetone
A :

Yield of 2.6

- lutidine

0.25
hourly

space

1.0

0.75

0.5

Weight

velocity

(hr-)

btg. t . Acetone conversion, yield and selectivity of 2.6~lutidine as a function of weight hourly space velocity.

methanol. The experiments in which polymerized formaldehyde was not observed in the
pre-heater zone are reported. The experimental data in Table 2 indicate that the increase of
formaldehyde in the feed increases the amount of 2-picoline in the product. This may be
explained by the stoichiometric J$. ( 1) . The reaction of acetone over H-ZSM-5 and the
various parallel reactions involved in such intermolecular cyclization to heterocycles are
also reported and discussed in refs. [ 111 and [ 121.
The experimental data regarding the effect of the reaction temperature on the synthesis
of 2-picoline are given in Table 4. The reaction of acetone, formaldehyde, methanol with
ammonia was carried out over 4 g Pb-ZSMJ catalyst at 0.5 hh WHSV, in the temperature
range of 300 to 420C. At reaction temperatures 300,350,380,400 and 42OC,the conversions of acetone were 26.0, 50.5, 53.8,44.0 and 69.0 wt.-%, and yields of 2-picoline were
Table 4
The synthesis of 2-picoline from acetone: the effect of temperature
Catalyst=

Pb-ZSM-5

(4 g), WHSV=0.5

h-,

feed: CHSCOCHS: HCHO:CH20H:

NH,=

(I : 1.3:0.9:

1.3)

molar
SNo.

2-Picoline

Reaction

Time-on-

temperature

stream

(0

(h)

I.

420

2.

400

3.

380

4,
5.

350
300

Yield (wt.-%)

Acetone

Formaldehyde

2-Picoline

4Picoline

4-Picoline

Lutidinesb

69.0

100

35.0

8.0

26.0

4.4

44.0

100

32.0

7.0

5.0

3.6

53.8

100

43.0

10.0

0.8

4.3

50.5

100

32.0

7.0

11.5

4.6

26.0

100

14.5

4.0

7.5

3.6

2
(2+3)
2

Based on acetone.
2,6-Lutidine

Conversion (wt.-%)

is > 90%.

A.V. Rama Rao et al. /Applied Catalysis A: General lll(l994)

Table 5
The synthesis of 2-picoline

from acetone: the time-on-stream

Catalyst = Pb-ZSM-5 ( 150). reaction temperature.

= (1:1.3:0.9:1.3)
molar
S. No.

Time-on-stream

LIOI-L108

effect

= 420C. feed = (CHFGCH3

: HCHO : CHIOH : NH,)

2-Picoline

Conversion

(wt.-%)

Yield (wt.-%)

Acetone

Formaldehyde

2-Picoline

4-Picoline

Lutidines

50.5
69.0
50.9
51.5
50.3

100
100
100
100
100

31.0
35.0
31.0
31.0
35.0

6.5
8.0
5.0
4.0
6.5

13.0
26.0
14.9
16.5
8.8

4-Picoline

(h)

1.
2.
3.
4.
5.

1
2
(3+4)
(5+6)
7

L107

4.8
4.4
6.2
5.2
5.4

Based on acetone.
2,6-Lutidine is > 90%.

14.5,32,43,32.0
and 35 wt.-% respectively. The (2-picoline/4-picoline)
ratio was between
3.4 and 4.6. There is not much effect of the reaction temperature on the selectivity ratio. On
the other hand, promoters like lead or tungsten affect the selectivity considerably.
The reaction of acetone, formaldehyde, methanol and ammonia was carried out at 420C
over Pb-ZSM-5 ( 150) for 7 h and time-on-stream effect is given in Table 5. There was no
notable deactivation. For 1, 2, (3 + 4)) (5 + 6) and 7 hour on stream, the conversions of
acetone were 50.5, 69.0, 50.9, 51.5 and 50.3 wt.-% while yields for 2-picoline were 31 .O,
35.0, 31.0 and 35.0 wt.-%, respectively. The (2-picoline/4-picoline)
ratio varied from 3.7
to 6. Pb-ZSMJ
showed the best activity for the synthesis of 2-picoline and 2,6-lutidine
from acetone.

Acknowledgement
We are thankful to the referee for suggesting
emphasizing the discussion regarding it.

the stoichiometry

of the reaction

and

References
[ 1]
[2]
[ 31
[4]

[5]
[6]
[7]
[8]
[9]

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L108

A.V. Rama Rao et al. /Applied Catalysis A: General lll(l994)

LIOI-L108

[lo] C.W. Ha@, US Patent 3 829 428 (1974).

[ 111 R. Ramachandra Rao, S.J. Kulkami, M. Subrahmanyam and A.V. Rama Rao, presented at 1Ith National
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[ 121 S.J. Kulkami, M. Subrahmanyam and A.V. Rama Rao, Ind. J. Chem., 32A ( 1993) 28.