React.

Kinet.

Catal.

Lett.,

Vol.

51, No.

i, 177-181

(1993)

RKCL2153

SELECTIVE

CYCLODEHYDRAT!ON Bezouhanova of Sofia, Ave,

OF DIOLS ON ZEOLITES Jabur

C.P. University

and F.A.

F a c u l t y of C h e m i s t r y Sofia 1126, Bulgaria

i, J. B o u r c h i e r

Received October 8, 1992 A c c e p t e d May 6, 1993

1,4-Butanediol, were selectively

2,5-hexanediol converted

and 1 , 5 - p e n t a n e d i o l and

to t e t r a h y d r o f u r a n of LaHY, of these

tetrahydropyran H-ZSM-6

in the p r e s e n c e The advantage

CaHY and zeolites

zeolites.

is in their high s t a b i l i t y

and faster regeneration.

The use of zeolites

as acid c a t a l y s t s interest

for organic

reacof

tions has found c o n s i d e r a b l e the c a t a l y s t parative appeared

[11. The s e l e c t i v i t y importance

to be of great Earlier

for its pre-

application.

investigations

on the dehydrashowed and

tion of 1 , 4 - b u t a n e d i o l that t e t r a h y d r o f u r a n

on synthetic A and X zeolites

can be o b t a i n e d with high s e l e c t i v i t y as catalyst

very good y i e l d using HNaX zeolite of t e t r a h y d r o f u r a n diminished after

[23. The y i e l d

14 hours on stream and it could be regenerated. for 2,5-hexanewas higher

has not been shown how long the catalyst In another investigation

[3J N a H Y was applied conversion.

diol and 1 , 5 - p e n t a n e d i o l

The t e m p e r a t u r e

than hhat in E43, where A l ( I I I ) - m o n t m o r i l l o n i t e lyst and data on catalyst deactivation

was the cata-

have not been presented. are easily deaccations ac-

It is well known that HNaX and HNaY zeolites tivated by coking stabilizes tivity. [51. The i n t r o d u c t i o n structure

of m u l t i v a l e n t

the zeolite

and improves structure

the c a t a l y t i c

The s t a b i l i t y of the zeolite

as well as deKiad6, Budapest

Akad4miai

BEZOUHANOVA,

JABUR:

CYCLODEHYDRATION

OF DIOLS

activation

by coking depends zeolites

also on the ratio Si/AI. of the pentasil structures type

In this have

respect h i g h - s i l i c a been

(ZSM-5)

found to possess very stable because

and low rate of w h i c h do not Taking into ac-

deactivation

of the channel dimensions,

allow the formation of the bulky coke deposits. count the improved v a l e n t cations stability of faujasites

containing multizeolites,

and the low coking ability of H-ZSM-5 and s e l e c t i v i t y of LaHY,

we checked the activity H-ZSM-5 zeolites

CaHY and 2,5-

in c y c l o d e h y d r a t i o n

of 1,4-butanediol,

hexanediol

and 1,5-pentanediol.

EXPERIMENTAL Catalysts LaHY and CaHY were p r e p a r e d by ion exchange w i t h NH4CI and the c o r r e s p o n d i n g scribed in [5]. H-ZSM-5 of NaY zeolite de-

salts under conditions

(Si/AI=40)

was o b t a i n e d by H C l - s o l u t i o n Na-ZSM-5 zeolite. The ac-

t r e a t m e n t of C z e c h o s l o v a k tivation and r e g e n e r a t i o n at 773 K in air flow. Reagents

commercial

of the used catalysts was p e r f o r m e d

The diols were c o m m e r c i a l 1,5-pentanediol ture) were

products.

1,4-Butanediol

and

from Fluka;

2,5-hexanediol

(isomer mix-

from M e r c k - S c h u c h a r d t .

Apparatus The c a t a l y t i c experiments were p e r f o r m e d in a fixed bed (0.05-1 g), nm size.

flow reactor w i t h d i f f e r e n t pressed,

catalyst

quantities

crushed and sieved to p a r t i c l e s the catalysts were

of 1.25-2.5

Before the e x p e r i m e n t s gen. The diols were

flushed w i t h nitrosyringe.

introduced

using a c a l i b r a t e d

Analysis GC analysis 2 m column w i t h at 453 K. of the reaction products were p e r f o r m e d 15% R e o p l e x - 4 0 0 on C h r o m o s o r b P/NAW on a 30-60 m e s h

178

BEZOUHANOVA,

JABUR:

CYCLODEHYDRATION

OF DIOLS

RESULTS AND D I S C U S S I O N The e x p e r i m e n t a l selective conditions have been d e t e r m i n e d for the

cyclodehydration

o f 1,4- and 1,5-diols.

It has been conThe

established

that at 523 K 1 , 4 - b u t a n e d i o l (Fig. zeolite

was c o m p l e t e l y

v e r t e d to t e t r a h y d r o f u r a n selectivity of the three

i) in the presence catalysts used was

of LaHY. 100%.

This

fact has been v e r i f i e d by GC analysis products. times The catalyst activity

and IR spectra of the at smaller contact

diminished

(greater WHSV).

100-

80> C 0 U

60-

1.2

2.4
WHSV h -1

6.1

12.2

Fig.

I.

1,4-Butanediol and H-ZSM-5

conversion

on LaHY at 523 K,

(A), CaHY

(e)

(o) zeolites

1 h on stream

Similar rillonite lysts

results

have been o b t a i n e d using A l ( I I I ) - m o n t m o [43. The a d v a n t a g e of the zeolite cata-

as catalyst

is in the simple a p p a r a t u s

(not in autoclave)

and the

better r e p r o d u c i b i l i t y

of zeolite preparation. conversion [6], LaHY showed of CaHY

As in the case of p i n a c o l e the best performance, and H-ZSM-5 ble. zeolites

followed by CaHY. in 1 , 4 - b u t a n e d i o l with

The a c t i v i t i e s conversion

were comparaa mixture of

From 2,5-hexanediol,

zeolite catalysts,

cis- and t r a n s - i s o m e r s

of 2 , 5 - d i m e t h y l t e t r a h y d r o f u r a n

[7] has

179

BEZOHHANOVA,

JABUR:

CYCLODEHYDRATION

OF D I O L S

100

8O
c

50 40

o o

20
i [ I i i

075

15

3.4

~5

15

WHSV h - I

Fig.

2.

2,5-Hexanediol

conversion i)

on z e o l i t e s

at 503 K

( n o t a t i o n as in Fig.

been obtained tact times

(Fig.

2). The c o n v e r s i o n was of L a H Y or CaHY, times

100% at g r e a t e r

con-

in the p r e s e n c e At shorter

while H-ZSM-5 was dropped

less active. rather

contact

the c o n v e r s i o n

sharply. was selectively on LaHY, CaHY obtained by the d e h y d r a zeolites se-

Tetrahydropyran t i o n of (Fig.

1,5-pentanediol

and H - Z S M - 5

3). The r e s u l t s w e r e

similar

to t h o s e zeolite

in E43. A h i g h catalysts

lectivity

in c y c l o d e h y d r a t i o n

of the

studied

has b e e n a c h i e v e d

at t e m p e r a t u r e s [43, b u t

slightly higher

than with [3]. Our

Al(III)-montmorillonite experiments

lower than with NaHY of L a H Y r e m a i n e d

s h o w e d t h a t the a c t i v i t y t h a t of C a H Y observed. LaHY, CaHY

constant

for 12 h, w h i l e

for 8 h on stream.

No d e a c t i v a -

t i o n of H - Z S M - 5 was In c o n c l u s i o n tive c a t a l y s t s hydrofuran

and H - Z S M - 5

zeolites

are

selec-

for the c y c l o d e h y d r a t i o n and of 1,5-diols

of 1 , 4 - d i o l s

to t e t r a -

derivatives of t h e s e

to t e t r a h y d r o p y r a n s . lower deactiva-

The a d v a n t a g e

catalysts

is in t h e i r

180

BEZOUHANOVA,

JABUR:

CYCLODEHYDRATION

OF DIOLS

I00 BO 60
o
tO

40 20

\
I I t

0.75

I'50 3.00 7150 15.00

WHSV h - I

Fig.

3.

1,5-Pentanediol

conversion i)

on zeolites

at 533 K

(notation as in Fig.

tion and better

regeneration.

REFERENCES i. W. Hoelderich, Engl., 2. Kh.I. 195 3. 27, 226 M. Hesse, (1988). G.O. Chivadze: Khim. Geterotsikl. Soed., F. Naumann: Angew. Chem. Int. Ed.

Areshidze,

(1969). I. Bucsi, M. Bart6k: in Proc. May Int. 13-16. Symp. 1985, on p.571. 650

A. Moln~r, Zeolite

Catalysis, P.K.

Si6fok,

Hungary, Soc.

4.

D. Kotkar, (1986).

Ghosh:

J. Chem.

Chem.

Commun.,

5.

C.P.

Bezouhanova, Katal., 19,

P. Kovacheva, 760 (1978),

Kh. Dimitrov,

Y. Kurteva:

Kinet. 6. 7.

and refs therein.

C. Bezouhanova, G. Kyryacos, 222 (1959).

F.A.

Jabur:

in p r e p a r a t i o n C.E. Boord: Anal. Chem., 31,

H.R. Menapace,

181