Download pdf - Process for the synthesis of ortho-cresol, 2,6-xylenol and 2,3,6

OS)

Europaisches Patentamt

European Patent Office

Office europeen des brevets © Publication number: 0 0 3 8 3 7 7

A 1

EUROPEAN PATENT APPLICATION

© Application number: 80106224.1

© Date of filing: 13.10.80

© Int. CI.3: C 07 C 3 7 / 1 6 C 07 C 39/07, B 01 J 21 /10 B 01 J 23/12, B 01 J 23 /26

© Priority: 28.01.80 US 116061 © Applicant: CONOCO INC. 1000 South Pine Street P.O. Box 1267 Ponca City Oklahoma 74601 (US)

3) Date of publication of application: 28.10.81 Bulletin 81/43 © Inventor: Leach, Bruce Eugen

„ 1628 Dover (84) Designated Contracting States: Ponca City, Oklahoma 74601 (US) BE CH DE FR GB LI

© Representative: Patentanwalte Dipl.-lng. A. Grunecker, Dr.-lng. H. Kinkeldey, Dr.-lng. W. Stockmair, Dr. rer. nat. K. Schumann, Dipl.-lng. P.H. Jakob, Dr. rer. nat. G. Bezold Maximilianstrasse 43 D-8000 Munchen 22(DE)

(55) Process for the synthesis of ortho-cresol, 2,6-xylenol and 2,3,6-trimethyl phenol. Phenol is methylated over an alumina catalyst using

methanol, and the reaction product therefrom is combined with additional methanol over a promoted magnesium oxide catalyst. Major reaction products are ortho-cresol, 2,6-xylenol and 2,3,6-trimethylphenol. The promoted magnesium oxide catalyst contains metal promoters selected from the group consisting of titanium, chromium, and uranium together with sulfate ions.

T h i s i n v e n t i o n r e l a t e s to t h e m e t h y l a t i o n o f

p h e n o l . More s p e c i f i c a l l y , t h i s i n v e n t i o n r e l a t e s to a

t w o - s t e p m e t h y l a t i o n of p h e n o l to p r o d u c e p r e d o m i n a n t l y

o r t h o - c r e s o l , 2 , 6 - x y l e n o l and 2 , 3 , 6 - t r i m e t h y l p h e n o l .

2 , 6 - x y l e n o l i s u s e f u l as a p r e c u r s o r to 2 , 3 , 6 -

t r i m e t h y l p h e n o l and o t h e r u s e f u l p r o d u c t s . 2 , 6 - x y l e n o l

a l s o f i n d s u s e s in p o l y m e r and p l a s t i c s a p p l i c a t i o n s s u c h

as t h o s e d e s c r i b e d in U .S . P a t e n t 3 , 4 4 6 , 8 5 6 . 2 , 3 , 6 - t r i -

m e t h y l p h e n o l i s u s e f u l as an i n t e r m e d i a t e in V i t a m i n E

s y n t h e s i s . O r t h o - C r e s o l i s u s e f u l in c h e m i c a l a p p l i c a t i o n s

as an i n t e r m e d i a t e , f o r e x a m p l e , as a p r e c u r s o r to 6 - c h l o r o -

2 - m e t h y l p h e n o l w h i c h i s u s e d in t h e s y n t h e s i s of h e r b i c i d e s .

O t h e r u s e s a r e w e l l known to t h o s e s k i l l e d in t h e a r t .

Many a l u m i n u m o x i d e c a t a l y s t s ( a l u m i n a s ) a r e

known in t h e a r t . Of t h e s e , gamma a l u m i n a s a r e p r e f e r r e d

f o r many r e a c t i o n s i n v o l v i n g p h e n o l s , w h e t h e r c a r r i e d o u t

in e i t h e r t h e v a p o r or l i q u i d p h a s e . T h e s e r e a c t i o n s

a r e c a r r i e d ou t b y r e a c t i n g p h e n o l and o l e f i n s or a l c o h o l s

to i n t r o d u c e h y d r o c a r b o n g r o u p s o n t o t h e a r o m a t i c r i n g o f

a p h e n o l . R e p r e s e n t a t i v e e x a m p l e s of s u c h p r o c e s s e s a r e

U .S . P a t e n t s 3 , 2 9 0 , 3 8 9 , 3 , 3 6 9 , 9 8 1 , 3 , 5 4 2 , 7 5 0 , 2 , 4 5 0 , 7 6 6 ,

3 , 6 7 0 , 0 3 0 , and B r i t i s h P a t e n t 1 , 1 0 2 , 3 0 9 . T h e s e p r o c e s s e s

t o g e t h e r or s i n g l y t e a c h r e a c t i n g p h e n o l s w i t h o l e f i n s i n

t h e p r e s e n c e of a gamma a l u m i n a f o r p u r p o s e s s u c h a s

p o l y m e r i z i n g c y c l i c a l k y l e n e o x i d e s , i n t r o d u c i n g h y d r o c a r b o n

g r o u p s o n t o r i n g s of a p h e n o l , and p r o d u c t i o n of p h e n o l s

a l k y l a t e d in t h e o r t h o p o s i t i o n .

In a d d i t i o n , a l o n g c a t a l y s t l i f e , h i g h a c t i v i t y

l i q u i d p h a s e p r o c e s s i s shown in U.S . 3 , 9 9 4 , 9 8 2 , h e r e b y

i n c o r p o r a t e d in i t s e n t i r e t y i n t o t h e i n s t a n t s p e c i f i c a t i o n

by r e f e r e n c e .

V a p o r p h a s e m e t h y l a t i o n of p h e n o l s o v e r m a g n e s i u m

o x i d e i s t a u g h t in U .S . 3 , 4 7 9 , 4 1 0 w h i c h a l s o r e q u i r e s t h e

p r e s e n c e of 2 , 4 , 6 - t r i m e t h y l p h e n o l as an i n g r e d i e n t in t h e

f e e d s t r e a m . C a t a l y s t s c o n t a i n i n g m a g n e s i u m o x i d e a n d

t u n g s t e n o x i d e a r e known f o r t h e d i s p r o p o r t i o n a t i o n o f

o l e f i n s s u c h as U .S . 3 , 4 9 1 , 1 6 3 . U.S . 4 , 1 1 0 , 2 5 3 s h o w s

t h e m e t h o d of p r o m o t i n g m a g n e s i u m o x i d e w i t h t u n g s t e n

o x i d e s to p r o v i d e a l o n g - l i v e d e a s i l y r e g e n e r a b l e c a t a l y s t

s u i t a b l e f o r t h e d i s p r o p o r t i o n a t i o n of h i g h l y a l k y l a t e d

p h e n o l s w i t h p h e n o l . T h e s e c a t a l y s t s l i k e w i s e h a v e e x c e l l e n t

c r u s h r e s i s t a n c e .

H o w e v e r , p u r i f i c a t i o n of t h e m a j o r p r o d u c t s o f

t h e s e and s i m i l a r r e a c t i o n s h a s b e e n a p r o b l e m . T h i s i s

e s p e c i a l l y t r u e when 2 , 6 - x y l e n o l i s p r o d u c e d a l o n g w i t h

m e t a - and p a r a - c r e s o l s ( m , p - c r e s o l s ) . Due to t h e g r e a t

s i m i l a r i t y in t h e b o i l i n g p o i n t s in t h e s e c o m p o u n d s , i t

w o u l d be g r e a t l y d e s i r a b l e t o h a v e d i r e c t m e t h y l a t i o n o f

p h e n o l u n d e r c o n d i t i o n s w h i c h m i n i m i z e - f o r m a t i o n of u n d e s i r a b l e

b y - p r o d u c t s w h i l e f o r m i n g d e s i r a b l e p r o d u c t s s u c h as o r t h o -

c r e s o l , 2 , 6 - x y l e n o l , and 2 , 3 , 6 - t r i m e t h y l p h e n o l .

I t i s t h e r e f o r e an o b j e c t of t h e p r e s e n t i n v e n -

t i o n t o p r o v i d e an i m p r o v e d , t w o - s t e p p r o c e s s f o r t h e

d i r e c t m e t h y l a t i o n of p h e n o l to p r o d u c e 2 , 6 - x y l e n o l ,

o r t h o - c r e s o l and 2 , 3 , 6 - t r i m e t h y l p h e n o l in h i g h p r o p o r t i o n .

O t h e r o b j e c t s w i l l b e c o m e a p p a r e n t to t h o s e s k i l l e d i n

t h i s a r t as t h e d e s c r i p t i o n p r o c e e d s .

In a c c o r d a n c e w i t h t h e p r e s e n t i n v e n t i o n ,

we h a v e d i s c o v e r e d an i m p r o v e d p r o c e s s f o r s e l e c t i v e l y

p r o d u c i n g 2 , 6 - x y l e n o l , 2 , 3 , 6 - t r i m e t h y l p h e n o l , and o r t h o -

c r e s o l in h i g h p r o p o r t i o n s by c a r r y i n g o u t a d i r e c t

m e t h y l a t i o n of p h e n o l i n t h e p r e s e n c e of a gamma a l u m i n a ,

t h e n u s i n g t h e p r o d u c t s t r e a m f r o m t h i s r e a c t i o n a s a d i r e c t

f e e d t o a s e c o n d s t e p , w h i c h d i r e c t l y m e t h y l a t e s t h e f e e d -

s t r e a m w i t h a d d i t i o n a l m e t h a n o l in t h e p r e s e n c e of a m a g n e s i u m

o x i d e c a t a l y s t p r o m o t e d w i t h a m o r p h o u s m e t a l i o n s of t i t a n i u m ,

u r a n i u m , and c h r o m i u m t o g e t h e r w i t h s u l f a t e i o n s . T h i s

p r o c e s s i s an i m p r o v e m e n t o v e r t h e h e r e t o f o r e known p r o c e s s e s in many r e g a r d s , g i v i n g e x c e p t i o n a l l y h i g h p r o p o r t i o n s o f

d e s i r e d p r o d u c t s . The l i n k i n g of two d i s t i n c t a l k y l a t i o n

p r o c e s s e s w i t h o u t any s e p a r a t i o n of t h e f e e d s t r e a m of t h e

f i r s t p r o c e s s b e f o r e c a r r y i n g o u t t h e s e c o n d a l k y l a t i o n i n

t h e p r e s e n c e of a p r o m o t e d m a g n e s i u m o x i d e c a t a l y s t a l l o w s

f o r e x t r e m e l y h i g h c o n v e r s i o n of p h e n o l d u r i n g a s i n g l e p a s s

of t h e t w o - s t a g e p r o c e s s .

In t h e f i r s t s t a g e of t h e p r o c e s s , p h e n o l can b e

a l k y l a t e d u s i n g any of t h e p r i o r a r t p r o c e s s e s i n v o l v i n g

gamma a l u m i n a c a t a l y s t s , b o t h l i q u i d and v a p o r p h a s e . F o r

mos t p u r p o s e s , a v a p o r p h a s e p r o c e s s w i l l be e m p l o y e d , s i n c e

i t i s e a s i e r to r e d u c e p r e s s u r e to t h e p r e s s u r e of t h e

s e c o n d s t e p of t h e p r o c e s s , as o p p o s e d to a h i g h - p r e s s u r e

l i q u i d p h a s e p r o c e s s . The a d v a n t a g e s of s e l e c t i v i t y of t h e

l i q u i d p h a s e p r o c e s s a r e d e s i r e a b l e , b u t a r e no t n e c e s s a r y in t h e p r o c e s s of t h e i n s t a n t i n v e n t i o n , s i n c e an e x c e l l e n t

c o n v e r s i o n to t h e t h r e e d e s i r e d ma in c o m p o n e n t s i s o b t a i n e d .

N o r m a l l y , in c a r r y i n g o u t t h e f i r s t s t e p in t h e

p r o c e s s of t h e p r e s e n t i n v e n t i o n f rom a b o u t 0 .2 mole to a b o u t

1 .0 mole of m e t h a n o l or any o t h e r s u i t a b l e m e t h y l a t i n g

a g e n t s s u c h as i s o - b u t y l e n e a r e u s e d p e r mole of p h e n o l , b u t

f rom a b o u t 0 .4 mole to a b o u t 0 .8 mole i s p r e f e r r e d . M e t h a n o l

i s p r e f e r r e d as a m e t h y l a t i n g a g e n t . T e m p e r a t u r e s of f r o m

300°C to 400°C a r e p r e f e r r e d f o r t h i s r e a c t i o n . In c o n t i n u o u s

r e a c t i o n s , l i q u i d h o u r l y s p a c e v e l o c i t i e s (LHSV) of f r o m

a b o u t 1 to 10 can be u s e d and f rom a b o u t 2 to 8 a r e p r e f e r r e d .

The p r e s s u r e s u s e d w i l l d e p e n d on w h e t h e r t h e p r o c e s s i s

b e i n g c a r r i e d ou t in l i q u i d or v a p o r p h a s e , b u t n o r m a l l y

p r e s s u r e s of f rom a b o u t a t m o s p h e r i c to a b o u t 1000 p e r s q u a r e i n c h g a u g e a r e p r e f e r r e d .

In t h e s e c o n d s t a g e of t h e i n s t a n t i n v e n t i o n , t h e

p r o d u c t s s t r e a m f r o m t h e f i r s t s t a g e c o n t a i n i n g a m i x t u r e o f

a l k y l a t e d p h e n o l s _ a n d a d d i t i o n a l a l k y l a t i n g a g e n t i s p a s s e d

d i r e c t l y i n t o c o n t a c t w i t h t h e p r o m o t e d m a g n e s i u m o x i d e

c a t a l y s t s a t a new mole r a t i o of f rom a b o u t 1 to a b o u t 10, a

t e m p e r a t u r e r a n g i n g f rom a b o u t 400° to a b o u t 5 0 0 ° C and a

p r e s s u r e r a n g i n g f r o m a b o u t a t m o s p h e r i c to a b o u t 5 a t m o s p h e r e s .

When c a r r i e d o u t c o n t i n u o u s l y , an LHSV of f rom a b o u t 1 .0 t o

a b o u t 1 0 . 0 i s u s e d .

The m a g n e s i u m o x i d e c a t a l y s t of t h e s e c o n d s t a g e is p r o m o t e d w i t h f r o m a b o u t 2 to a b o u t 10 w e i g h t p e r c e n t s u l f a t e i o n and f r o m a b o u t 2 to a b o u t 10 w e i g h t p e r c e n t

m e t a l i o n s s e l e c t e d f rom t h e g r o u p c o n s i s t i n g of a m o r p h o u s

t i t a n i u m , c h r o m i u m , and u r a n i u m . For c r u s h s t r e n g t h a n d

a d d i t i o n a l s u r f a c e a r e a , o p t i o n a l l y f r o m 1 t o 5 w e i g h t

p e r c e n t s i l i c a can be u s e d , and f rom 1 to 3 w e i g h t p e r c e n t

g r a p h i t e can be i n s e r t e d as a l u b r i c a n t . W h i l e s i l i c a t e n d s

to f u r t h e r p r o m o t e t h e c a t a l y s t , i t s p r i m a r y p u r p o s e i s f o r

c r u s h r e s i s t a n c e and s u r f a c e a r e a of t h e c a t a l y s t p e l l e t s .

. The p r o c e s s of t h e p r e s e n t i n v e n t i o n c an be c a r r i e d

o u t e f f i c i e n t l y in e i t h e r b a t c h or c o n t i n u o u s f l o w r e a c t o r s .

Of t h e s e , t h e c o n t i n u o u s f l o w r e a c t o r s a r e p r e f e r r e d . F l o w

f r o m t h e f i r s t s t a g e to t h e s e c o n d s t a g e can be c a r r i e d o u t

q u i t e e a s i l y . In t h e c o n t i n u o u s f l o w r e a c t o r s c h e m e , t h e

a l u m i n a c a t a l y s t and t h e m a g n e s i u m o x i d e c a t a l y s t s a r e b o t h

s u i t a b l y d i v i d e d and p l a c e d in p o s i t i o n t o c a t a l y z e t h e

r e a c t i o n b e t w e e n t h e p h e n o l and t h e m e t h y l a t i n g a g e n t i n t h e

f i r s t s t a g e , and t h e p r o d u c t s t r e a m f r o m t h e f i r s t r e a c t i o n

and a d d i t i o n a l m e t h y l a t i n g a g e n t in t h e s e c o n d s t a g e .

R e a c t o r f l o w in b o t h c a s e s can be e i t h e r u p w a r d o r by g r a v i t y ;

h o w e v e r , g r a v i t y f l o w i s p r e f e r r e d .

The t w o - s t a g e p r o c e s s of t h e p r e s e n t i n v e n t i o n

g r e a t l y r e d u c e s u n w a n t e d b y - p r o d u c t s i n t h e r e a c t i o n . In a r e a c t i o n c a r r i e d o u t u s i n g b o t h s t a g e s , o r t h o - c r e s o l can b e

o b t a i n e d in a m o u n t s r a n g i n g f r o m 5 - 40 p e r c e n t , 2 , 6 - x y l e n o l

in a m o u n t s of 1 0 - 40 p e r c e n t , and 2 , 3 , 6 - t r i m e t h y l p h e n o l i n

a m o u n t s of 1 0 - 40 p e r c e n t . Mos t o t h e r b y - p r o d u c t s , w i t h

t h e e x c e p t i o n of 2 , 4 , 6 - t r i m e t h y l p h e n o l , a r e p r e s e n t i n

s u b s t a n t i a l l y l e s s t h a n 1 p e r c e n t a m o u n t . B y - p r o d u c t s

w h i c h a r e e s p e c i a l l y u n d e s i r a b l e , s u c h as m e t a - p a r a -

c r e s o l , l i k e w i s e f a l l b e l o w 1 p e r c e n t of t h e f i n a l p r o d u c t ,

t h u s b e i n g p r o d u c e d in a l o w e r b y - p r o d u c t s / t o p r o d u c t r a t i o .

The i n v e n t i o n i s more c o m p l e t e l y d e s c r i b e d w i t h

r e f e r e n c e to t h e e x a m p l e s b e l o w w h e r e i n a l l p a r t s a n d

p e r c e n t a g e s a r e by w e i g h t u n l e s s o t h e r w i s e s p e c i f i e d . T h e

e x a m p l e s a r e p r o v i d e d to i l l u s t r a t e t h e i n s t a n t i n v e n t i o n

and n o t to l i m i t i t .

The d a t a d i s c l o s e d h e r e i n was g e n e r a t e d u s i n g a

1 / 2 - i n c h s t a i n l e s s s t e e l r e a c t o r c o n t a i n i n g 1 / 1 6 - i n c h

c a t a l y s t p e l l e t s . F low in t h e r e a c t o r c o u l d be v a r i e d

e i t h e r u p w a r d or by g r a v i t y .

EXAMPLE 1 '

A s a m p l e was c o l l e c t e d f rom a c o m m e r c i a l

o p e r a t i n g p l a n t u s i n g p h e n o l m e t h y l a t e d w i t h m e t h a n o l .

The r e a c t i o n was a v a p o r p h a s e r e a c t i o n c a r r i e d o u t w i t h

a t e m p e r a t u r e of f rom a b o u t 370 to a b o u t 420°C , a

p r e s s u r e f rom ATM to 3 ATM, an LHSV of a b o u t 3 . 5 , a

m e t h a n o l - t o - p h e n o l mole r a t i o of a b o u t 0 . 7 .

A s a m p l e of t h e p r o d u c t s t r e a m f rom t h i s

r e a c t i o n was o b t a i n e d and a n a l y z e d p r i o r to b e i n g i n s e r t e d

t h r o u g h t h e s e c o n d m a g n e s i u m o x i d e r e a c t i o n . The c o m -

p o s i t i o n of t h i s p r o d u c t s t r e a m ( f e e d to t h e s e c o n d

s t a g e ) i s s e t f o r t h in T a b l e 1 .

EXAMPLE 2

A 1 / 2 - i n c h d i a m e t e r s t a i n l e s s s t e e l r e a c t o r

was l o a d e d w i t h 20 c u b i c c e n t i m e t e r s (cc) of c a t a l y s t .

C a t a l y s t was p r e p a r e d by a d d i n g 6 g r a m s of t i t a n i u m

i s o p r o p o x i d e to 90 g r ams of m a g n e s i u m o x i d e (MERCK

MAGLITE-D, t r a d e m a r k of and s o l d by Merck C h e m i c a l C o m p a n y )

f o l l o w e d by t h e a d d i t i o n of 2 g r a m s o f a m m o n i u m s u l f a t e

in a q u e o u s s o l u t i o n and 10 g r a m s of 30 p e r c e n t c o l l o i d i a l

s i l i c a in w a t e r . The m i x t u r e was a i r - d r i e d and t a b l e t e d .

The t a b l e t s w e r e d r i e d a t 150°C f o r 2 h o u r s , t h e n c a l c i n e d

in a i r a t 500°C f o r two h o u r s .

The f e e d m i x t u r e was p a s s e d o v e r t h e c a t a l y s t

a t a r e a c t i o n t e m p e r a t u r e of a b o u t 4 6 0 ° C . R e a c t i o n w a s

c a r r i e d o u t c o n t i n u o u s l y u s i n g a l i q u i d h o u r l y s p a c e

v e l o c i t y of 3 . 0 . The m e t h a n o l m o l e r a t i o was 100 p a r t s

f e e d m a t e r i a l to 1 3 7 . 5 p a r t s of m e t h a n o l by w e i g h t . T h e

r e s u l t s a r e s e t f o r t h in T a b l e 1 b e l o w .

A m a t e r i a l s b a l a n c e was made and t h e r e s u l t s a r e

s e t - f o r t h i n T a b l e 1. P h e n o l c o n v e r s i o n was 97 p e r c e n t

t o t a l f o r b o t h s t e p s and s e l e c t i v i t y t o o r t h o - c r e s o l , 2 , 6 -

x y l e n o l and 2 , 3 , 6 - t r i m e t h y l p h e n o l was 89 p e r c e n t f o r t h e

c o m b i n e d r e a c t i o n s e q u e n c e . M e t h a n o l u s a g e was much m o r e

s e l e c t i v e t h a n f o r t y p i c a l m a g n e s i u m o x i d e c a t a l y s t s .

S e l e c t i v i t y b a s e d on m e t h a n o l was 93 p e r c e n t , c o m p a r e d t o a

t y p i c a l v a l u e of 70 p e r c e n t f o r p r i o r a r t m a g n e s i u m o x i d e

r e a c t i o n s w i t h o u t a p r i o r a l k y l a t i o n o v e r a l u m i n a . M a j o r

a d v a n t a g e s a p p e a r t o be o b t a i n e d b e c a u s e t h e m e t a - c o n t a i n i n g

s u b s t i t u t i o n p r o d u c t s of t h e a l u m i n a - c a t a l y z e d r e a c t i o n a r e

c o u p l e d w i t h t h e h i g h p e r p a s s p h e n o l c o n v e r s i o n o v e r t h e

m a g n e s i u m o x i d e c a t a l y s t s of t h e p r e s e n t i n v e n t i o n w h i c h

h a v e h i g h o r t h o s u b s t i t u i o n s e l e c t i v i t y .

EXAMPLE 3

The p r o c e d u r e s e t f o r t h in E x a m p l e s 1 and 2 w a s

r e p e a t e d , a n d a r e a c t i o n was c a r r i e d o u t f o r 24 h o u r s .

M e t h a n o l l o s s was d e t e r m i n e d by t h e w e i g h t of f e e d / w e i g h t

of p r o d u c t in t h e r u n . M e t h a n o l r e c o v e r y was made b y

d i s t i l l a t i o n . W a t e r was a l s o d e t e r m i n e d by d i s t i l l a t i o n

f o l l o w e d by e x t r a c t i o n w i t h CH2C12 to r e m o v e p h e n o l i c s .

The p h e n o l i c s r e m o v e d were a n a l y z e d by gas c h r o m a t o g r a p h y .

T a b l e 1 shows t h e c o m b i n e d a n a l y s i s of a l l f r a c t i o n s i s o -

l a t e d .

EXAMPLE 4

A s i l i c a - f r e e c a t a l y s t was p r e p a r e d by a d d i n g 15

g r a m s of t i t a n i u m i s o p r o p o x i d e to 180 g r ams of m a g n e s i u m

o x i d e (Merck M a g l i t e D), f o l l o w e d by t h e a d d i t i o n of 6 . 2 5 g of m a g n e s i u m s u l f a t e and 4 g of g r a p h i t e . The m i x t u r e w a s

t a b l e t e d and c a l c i n e d as d e s c r i b e d in E x a m p l e 2. A r e a c t i o n

was c a r r i e d o u t u s i n g t h e same f e e d d e s c r i b e d in E x a m p l e 1 .

The r e a c t i o n was c a r r i e d o u t a t a t e m p e r a t u r e of 4 6 8 ° C ,

p r e s s u r e of 40 p s i g and LHSV of 1 .4 and 3 . 0 . The c a t a l y s t

had a l o w e r c r u s h s t r e n g t h t h a n s i l i c a - c o n t a i n i n g c a t a l y s t s

and was s l i g h t l y l e s s a c t i v e . The r e s u l t s a r e s e t f o r t h

in T a b l e 2. E x a m p l e 2 p r o d u c t c o l u m n i s on a 100 p e r c e n t

p h e n o l i c s b a s i s , w i t h o u t w a t e r and m e t h a n o l and i s e q u i v a -

l e n t to t h e E x a m p l e 2 p r o d u c t c o l u m n in T a b l e 1 .

T h u s , i t can be s e e n t h a t t h e p r e s e n t i n v e n t i o n

g i v e s e x t r e m e l y h i g h s e l e c t i v i t y to t h e d e s i r e d p r o d u c t s

w i t h o u t i n c r e a s i n g t h e s e v e r i t y o f r e a c t i o n c o n d i t i o n s a n d

w i t h o u t i n c r e a s i n g a m o u n t s of b y - p r o d u c t s , e s p e c i a l l y u n - d e s i r a b l e b y - p r o d u c t s s u c h as m e t a - p a r a - c r e s o l . I t i s

r e a d i l y a p p a r e n t t h a t t h i s i m p r o v e d t w o - s t e p p r o c e s s i s

much s u p e r i o r to t h o s e p r o v i d e d i n t h e p r i o r a r t as s i n g l e -

s t e p p r o c e s s e s . W h i l e c e r t a i n e m b o d i m e n t s and d e t a i l s h a v e b e e n

shown f o r t h e p u r p o s e of i l l u s t r a t i n g t h i s i n v e n t i o n , i t

w i l l be a p p a r e n t to t h o s e s k i l l e d in t h i s a r t t h a t v a r i o u s

c h a n g e s and m o d i f i c a t i o n s may be made h e r e i n w i t h o u t d e p a r t -

i ng f rom t h e s p i r i t or s c o p e of t h e i n v e n t i o n .

C l a i m 1. An i m p r o v e d m e t h o d f o r t h e d i r e c t

m e t h y l a t i o n of p h e n o l to p r o d u c e p r e d o m i n a t e l y o r t h o - c r e s o l ,

2 , 6 - x y l e n o l , and 2 , 3 , 6 - t r i m e t h y l p h e n o l , w h e r e i n p h e n o l i s

m e t h y l a t e d ' o v e r a l u m i n a c a t a l y s t to p r o d u c e a p r o d u c t

s t r e a m , t h e i m p r o v e m e n t c o m p r i s i n g p a s s i n g t h e p r o d u c t

s t r e a m t h r o u g h a s e c o n d m e t h y l a t i o n o v e r a c a t a l y s t in t h e

p r e s e n c e of f rom a b o u t 1 to a b o u t 10 mole r a t i o of m e t h a n o l

a t a t e m p e r a t u r e o f f r o m 400°C to a b o u t 5 0 0 ° C , and a p r e s s u r e of f rom a b o u t a t m o s p h e r i c to a b o u t 5 a t m o s p h e r e s , w h e r e i n

t h e c a t a l y s t i s m a g n e s i u m o x i d e p r o m o t e d w i t h a m o r p h o u s

m e t a l i o n s s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g of t i t a n i u m ,

u r a n i u m , and c h r o m i u m and s u l f a t e i o n s .

C l a i m 2. A m e t h o d as d e s c r i b e d in C l a i m 1

w h e r e i n t h e m e t a l i o n s a r e t i t a n i u m i o n s .


w h e r e i n t h e p r o c e s s i s c a r r i e d ou t c o n t i n u o u s l y .


w h e r e i n t h e c a t a l y s t c o n t a i n s f rom a b o u t 2 to 10 w e i g h t

p e r c e n t m e t a l , and f r o m a b o u t 2 to 10 w e i g h t p e r c e n t

s u l f a t e i o n s .


w h e r e i n in a d d i t i o n , t h e c a t a l y s t c o n t a i n s f r o m 1 to 5

w e i g h t p e r c e n t s i l i c a . - C l a i m 6. A m e t h o d as d e s c r i b e d in C l a i m 5

w h e r e i n t h e c a t a l y s t c o n t a i n s f rom 1 to 3 w e i g h t p e r c e n t

g r a p h i t e as l u b r i c a n t .


w h e r e i n t h e p r o c e s s i s c a r r i e d ou t c o n t i n u o u s l y .


w h e r e i n t h e l i q u i d h o u r l y s p a c e v e l o c i t y i s f r o m a b o u t

1 to a b o u t 1 0 .


w h e r e i n t h e r e a c t i o n i s c a r r e d o u t a t a t e m p e r a t u r e o f

f r o m a b o u t 440° t o a b o u t 4 8 0 ° C , a p r e s s u r e of f r o m a b o u t

a t m o s p h e r i c to a b o u t 2 a t m o s p h e r e s , mole r a t i o of m e t h a n o l

to f i r s t s t a g e r e a c t a n t p r o d u c t of f rom a b o u t 1 .0 to 5 a n d

w h e r e i n t h e l i q u i d h o u r l y s p a c e v e l o c i t y i s f r o m a b o u t 1 .0 to 5 .


w h e r e i n t h e f i r s t s t a g e m e t h y l a t i o n i s c a r r i e d o u t in t h e

v a p o r p h a s e .


w h e r e i n t h e f i r s t s t a g e m e t h y l a t i o n i s c a r r i e d o u t i n

l i q u i d p h a s e .