THE OF

QUESTION PYRIDINE
A. V.

OF ON

THE

LIQUID-PHASE CATALYSTS

HYDROGENATION

RUTHENIUM

S. C h e g o l y a , G. D . M i k h a i l o v , A. M a l y k h , R . A. K a r a k h a n o v ,

UDC
and N. I . S h u i k i n

542.941.7+547.821

It is known that on a whole s e r i e s of c a t a l y s t s (nickel, c o p p e r - c h r o m i u m , platinum), pyridine h y d r o genates with e x t r e m e difficulty. Thus, on nickel c a t a l y s t s the reaction is c a r r i e d out at the high t e m p e r a t u r e of 200~ and a p r e s s u r e of 100 atm [1-3]. Hydrogenation is g e n e r a l l y a c c o m p a n i e d by side--reactions [4-5]. Even on platinum, the p r o c e s s r e q u i r e s severe conditions and the c a t a l y s t rapidly l o s e s its activity [6-7]. The n e c e s s i t y for using s e v e r e conditions in hydrogenation is connected with the f a c t that pyridine is a ~H~,liter cumulative nucleus which r e v e r s i b l y poisons the c a t a l y s t s . One of the p r e s ent authors [8-9] has p r e v i o u s l y r e p o r t e d the c o n s i d e r a b l e activity of ruthenium c a t a l y s t s in the liquid-phase hydrogenation of pyridine.
/ ~, liter/rain

9
'

O
'

''
60
"C min

YHz'li~er
80 100

tO, O

gO

z~O

In the p r e s e n t communication we give the r e s u l t s of the hydrogenation of pyridine on v a r i o u s types of ruthenium c a t a l y s t s together with data on the kinetics of the liquid-phase hydrogenation of the pyridine ring in the p r e s ence of ruthenium 9 T h e r e is p r a c t i c a l l y no i n f o r m a t i o n in the l i t e r a t u r e on the kinetics of the hydrogenation of pyridine. Table 1 gives f i g u r e s on the hydrogenation of pyridine in a p p a r a t u s of the discontinuous type. The m o s t active c a t a l y s t s w e r e those containing ruthenium on alumina. A study of the kinetics of the hydrogenation of the pyridine ring in the p r e s e n c e of 10% Hu/A120 3 showed that up to the a b s o r p t i o n of 65-75% of the t h e o r e t i c a l l y n e c e s s a r y amount of hydrogen the o r d e r of the r e a c t i o n with r e s p e c t to the organic component is z e r o . Then the r a t e falls, but the r e a c tion p r a c t i c a l l y c o m e s to an end (Fig. 1). An investigation of the r a t e of the p r o c e s s at v a r i o u s constant p r e s s u r e s of hydrogen (Fig. 2) showed that the o r d e r of the r e a c t i o n with r e s p e c t to hydrogen is one up to 70-75 at-m, and above this p r e s s u r e the total o r d e r of the r e a c t i o n b e c o m e s zero. To calculate the activation e n e r g y of the hydrogenation of pyridine in the region w h e r e the total o r d e r of the r e a c t i o n is zero, the t e m p e r a t u r e dependence of the r a t e of the r e a c t i o n was found (Table 2). In the range of t e m p e r a t u r e s studied, f r o m 80 to 140~ no side r e a c t i o n s take place and the only p r o d u c t of the r e a c t i o n is piperidine. This conclusion was drawn on the b a s i s of a l a r g e amount of c h r o m a t o g r a p h i c data (Fig. 3).

Fig. 1. Kinetic c u r v e s of the hydrogenation of p y r i dine on 10%Ru/A1203 (weight of c a t a l y s t 0.3 g; weight of pyridine 0.16 mole; 120~ at constant p r e s s u r e s of hydrogen: 1) 90 atm; 2) 45 a t m . tu ml/min 000 JOt 205 100
o 30 60 #oP.i atm

TABLE I. Hydrogenation of Pyridine on Ruthenium Catalysts (100~ PH 2 = 80 atm).

Time of Yield of Catalyst Amt,, g ]hydroge- piperidine, ;nation, h o/o

Fig. 2. Rate of h y d r o genation of pyridine as a function of the p r e s s u r e of hydrogen on 10% Ru/A12Oa (weight of c a t a l y s t 0.3 g; weight of pyridine 0.16 mole).

TABLE 2. Hydrogenation (ml/min) of Pyridine at V a r i ous T e m p e r a t u r e s (Catalyst 10% Ru/A1203, Weight of

Catalyst o.3 g; Weight of

P y r i d i n e 0.16 mole; PH 2 = 90 atm).
Temperature, ~
kcal~ole

Ru/A12Oa I 55 au/C Ru/SiO2 10

4.5
17.5

100 100 I00

48. 0

I-~ 118.0 t 380.0 630.0 1

15--16

N 9 D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 682-684, March, 1988. Original article submitted August 30, 1967.

669

,.a

A[

EXPERIMENTAL The catalysts were prepared by depositing Ru(OH)CI 3 from aqueous ethanolic solution on the appropriate support and subjecting it to reduction with hydrogen. The trial of the catalysts was carried out in rotating laboratory autoclaves and Vishnevskii glandless reactors. The kinetic experiments were carried out in a special apparatus forming a modification of the static system and permitting working at any constant pressure from 1 to 150 atm. The principle of the apparatus will be clear from the sketch given (Fig. 4). Before hydrogenation, the pyridine was rectified in a column with an efficiency of 20 theoretical plates. The catalyzates were analyzed on a LKhM-7A chromatograph (with Chromosorb W as the solid phase and polyethyleneglycol 2000 as the liquid phase).
CONCLUSIONS

1~ I} rain

Fig. 3. Characteristic chromatogram of the composition of the catalyzate from the incomplete hydrogenation of pyridine: 1) piperidine; 2) pyridine

1. The behavior of ruthenium catalysts during the hydrogenation of pyridine has been investigated. 2. The kinetics of the hydrogenation of pyridine on ruthenium has been studied. Fig. 4. Sketch of the apparatus for studying the kinetics of liquid-phase hydrogenation processes under a pressure of up to 150 atm: 1) high-pressure catalytic vessel; 2) rocking device; 3) thermostat; 4) highpressure burette; 5) highpressure levelling vessel; 6) cylinder containing hydrogen; 7) buffer volume; 8) pressure gauge; 9) fine-adjustment valve.
8, 9.

LITERATURE

CITED

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

M. I. Ushakov and A. I. Bronevskii, Zh. Obshch. Khim., 7, 450 (1937). J. J. Jones, J. Chem. Soc., 1950, 1392. N. C. Haneox, Austral. J. Chem., 6, 143 (1956). N. I. Shuikin and V. A. Tulupov, Vestn. Mosk. Univ., No. 3, 73 (1956). N. I. Shuikin and V. M. Brusnikina, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1959, 1288. C. H. Tflford and M. G. Van Campen, J. Am. Chem. Soc., 7__9_9, 472 (1957).

7. A. P, Gray, J. Org. Chem., 2 _ . 3 _ 3 , 1453 (1958). A. A. Ponomarev and A. S. Chegolya, Heterocycles in Organic Synthesis [in Russian], Kiev (1964). A. S. Chegolya, V. N. Dyukareva, and A. A. Ponomarev, Khim. Geterotsikl. Soedin., 2, 239 (1966).

670