Catalysts supports and cracking catalysts incorporating them

J E u r o p a i s c h e s

Patentamt

European Patent Office © Publication number: 0 0 3 2 2 9 8

Office europeen des brevets A 2

© EUROPEAN PATENT APPLICATION

© Application number: 80304509.5 ©Int. CI.3: B 01 J 29 /06

© Date of filing: 15.12.80

© Priority. 17.12.79 US 104522 © Applicant: MOBIL OIL CORPORATION 150 East 42nd Street New York New York 10017(US)

© Date of publication of application: 22.07.81 Bulletin 8129 © Inventor: Chester, Arthur Warren

517 Country Club Drive © Designated Contracting States: Cherry Hill New Jersey 08003IUS)

DE GB NL @ Inventor: Stover, William Albert

38 North Columbia Street Woodbury, New Jersey 08096(US)

© Representative: Cooper, John Anthony et al, Mobil Court 3 Clements Inn London WC2A2EBIGB)

Catalysts supports and cracking catalysts incorporating them. A catalyst support is prepared by mixing colloidal

alumina and colloidal silica to obtain a composite having a defined pore-size distribution. The support suitably includes also a particulate weighting agent. Catalyst compositions having excellent resistance to metal poisoning and useful in both cracking and non-cracking processes, are obtained by incorporating various hydrocarbon cracking components into the support.

T h i s i n v e n t i o n r e l a t e s to c a t a l y s t s u p p o r t s a n d

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

c o l l o i d a l d i s p e r s i o n s , such c a t a l y s t s p o s s e s s i n g e x c e l l e n t

c a t a l y t i c and p h y s i c a l p r o p e r t i e s and a l s o h a v i n g

e x c e l l e n t r e s i s t a n c e to m e t a l p o i s o n i n g .

U n i t e d S t a t e s P a t e n t 3 , 9 1 2 , 6 1 9 , d e s c r i b e s t h e

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

n e u t r a l i z i n g s i l i c a t e w i t h 30-90% of t he r e q u i r e d a l u m i n a ,

a g i n g the h y d r o g e l , a d d i n g f a r t h e r a l u m i n a and d r y i n g .

The c a t a l y s t has a p o r e s t r u c t u r e such t h a t a m a j o r i t y o f

p o r e s a re b e t w e e n 45 and 125AO. In U n i t e d S t a t e s P a t e n t

3 , 9 3 3 , 6 2 1 , h i g h a l u m i n a , s i l i c a - a l u m i n a c a t a l y s t s a r e

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

a d d i t i o n of a b a s e . The a l u m i n a c o n t e n t is 5 6 - 9 0 % ,

p r e p f e r a b l y 65%. T h i s p a t e n t a l s o s u m m a r i z e s p r e v i o u s

p r i o r a r t for p r e p a r i n g h i g h a l u m i n a c a t a l y s t s . In U n i t e d

S t a t e s P a t e n t 4 , 0 1 0 , 1 1 6 , c r a c k i n g c a t a l y s t s a re p r e p a r e d

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

s y n t h e t i c m i c a m o n t m o r i l l o n i t e , z e o l i t e and a c l a y m a t r i x

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

the use of " s i l i c a s o l s " in c r a c k i n g c a t a l y s t s : In U n i t e d

S t a t e s P a t e n t 3 , 8 6 7 , 3 0 8 , c r a c k i n g c a t a l y s t s a re p r e p a r e d

by i n c o r p o r a t i n g c l a y and z e o l i t e in a s i l i c a so l p r e p a r e d

by r a p i d n e u t r a l i z a t i o n of s o d i u m s i l i c a t e w i t h a c i d . An

i m p r o v e m e n t i s shown in U n i t e d S t a t e s P a t e n t 3 , 9 5 7 , 6 8 9 i n

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

of s u l f u r i c a c i d and a l u m i n u m s u l f a t e . In U n i t e d S t a t e s

P a t e n t 3 , 9 7 2 , 8 3 5 , the s i l i c a s o l is p r e p a r e d by i o n

e x c h a n g e of s o d i u m s i l i c a t e w i t h an a c i d i c ion e x c h a n g e

r e s i n .

The e f f e c t s of m e t a l p o i s o n i n g on the c r a c k i n g

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

i n v e s t i g a t e d ( U n i t e d S t a t e s P a t e n t 3 , 2 3 4 , 1 1 9 ) ; h o w e v e r ,

o n l y r e c e n t l y have the e f f e c t s been d e t a i l e d f o r z e o l i t i c

c r a c k i n g c a t a l y s t s . As a r e s u l t of s u c h s t u d i e s , i t i s

now known t h a t c o n t a m i n a n t coke and h y d r o g e n y i e l d s ( c o k e

and h y d r o g e n p r o d u c e d by t h e m e t a l p o i s o n i n g ) a r e l o w e r on

z e o l i t i c t h a n a m o r p h o u s c a t a l y s t s , b u t t h a t m e t a l a c t i v i t y

is d e a c t i v a t e d more r a p i d l y on a m o r p h o u s c a t a l y s t s

( C i m b a l o et a l . , Oi l & Gas J o u r n a l , May 15, 1972 , p .

1 1 2 ) . T h e r e f o r e , a number of m e t h o d s have been p r o p o s e d

to o v e r c o m e t he p r o b l e m s a s s o c i a t e d w i t h t he c r a c k i n g o f

m e t a l - c o n t a m i n a t e d f e e d s t o c k s . For i n s t a n c e , U n i t e d

S t a t e s P a t e n t 3 , 9 4 4 , 4 8 2 p r o p o s e s t he c r a c k i n g of h i g h

m e t a l s - c o n t e n t f e e d s t o c k in t he p r e s e n c e of a c a t a l y s t

c o m p r i s i n g 1 to 40 w e i g h t % of a z e o l i t e h a v i n g c r a c k i n g

c h a r a c t e r i s t i c s , d i s p e r s e d in a r e f r a c t o r y m e t a l o x i d e

m a t r i x h a v i n g a l a r g e p o r e s i z e d i s t r i b u t i o n ( a b o u t

5 0 - 1 0 0 A ° ) . A l so U n i t e d S t a t e s P a t e n t 3 , 7 1 1 , 4 2 2 p r o p o s e s

t h a t m e t a l - p o i s o n e d c r a c k i n g c a t a l y s t s can be p a r t i a l l y

r e s t o r e d w i t h a n t i m o n y c o m p o u n d s and U n i t e d S t a t e s P a t e n t

3 , 9 7 7 , 9 6 3 p r o p o s e s t h a t the e f f e c t s of m e t a l p o i s o n i n g c a n

be n e g a t e d w i t h b i s m u t h or m a n g a n e s e c o m p o u n d s .

H o w e v e r , none of the a b o v e p r i o r a r t f e a t u r e s t h e

u n i q u e c o m b i n a t i o n of t he mixed c o l l o i d a l s o l and t h e

- c a t a l y s t p o r e s t r u c t u r e of t he c a t a l y s t c o m p o s i t i o n s o f

t h e p r e s e n t i n v e n t i o n .

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

is p r o v i d e d a c a t a l y s t s u p p o r t c o m p o s i t i o n p r e p a r e d b y

m i x i n g from 1 to 99 w e i g h t % of a c o l l o i d a l d i s p e r s i o n o f

a l u m i n a p a r t i c l e s and f rom 1 to 99 w e i g h t % of a c o l l o i d a l

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

p a r t i c l e s e a c h h a v i n g d i a m e t e r s of f rom 10 to 1 0 , 0 0 0 A ° ,

and d r y i n g the r e s u l t i n g c o m p o s i t e , t he c o m p o s i t e h a v i n g

a t l e a s t 40% of i t s p o r e vo lume w i t h i n t he 30 to 3 0 0 A °

d i a m e t e r r a n g e c o m p r i s i n g p o r e s of from 60 to 80A°

d i a m e t e r , and a t l e a s t 25% of i t s p o r e v o l u m e in e x c e s s o f

30A° d i a m e t e r c o m p r i s i n g p o r e s of f rom 60 to 80A° d i a m e t e r .

The c o m p o s i t i o n is s u i t a b l y p r e p a r e d by m i x i n g

from 5 to 95 w e i g h t % of a c o l l o i d a l a l u m i n a p a r t i c l e s a n d

from 5 to 95 w e i g h t % of a c o l l o i d a l s i l i c a p a r t i c l e s , a n d

more p r e f e r a b l y by m i x i n g f rom 20 to 90 w e i g h t % o f

c o l l o i d a l a l u m i n a p a r t i c l e s and from 10 to 80 w e i g h t % o f

c o l l o i d a l s i l i c a p a r t i c l e s .

The c o m p o s i t i o n may a l s o i n c l u d e from 1 to 75

w e i g h t %, b a s e d on t he t o t a l c o m p o s i t e , of a w e i g h t i n g

a g e n t , and may f u r t h e r i n c l u d e from 1 to 75 w e i g h t % of a n

a c t i v e h y d r o c a r b o n c o n v e r s i o n c o m p o n e n t ( c r a c k i n g

c o m p o n e n t ) mixed t h e r e w i t h .

C a t a l y s t s u p p o r t s and n o n - z e o l i t i c ( a m o r p h o u s )

c r a c k i n g c a t a l y s t s fo r a p p l i c a t i o n in h y d r o t r e a t i n g ,

r e f o r m i n g and o t h e r c a t a l y t i c p r o c e s s e s a re c o n v e n i e n t l y

p r e p a r e d f rom (1) c o l l o i d a l a l u m i n a , (2) c o l l o i d a l s i l i c a ,

and (3) a p a r t i c u l a t e w e i g h t i n g a g e n t i f d e s i r e d .

C r a c k i n g and h y d r o c r a c k i n g c a t a l y s t s a r e s i m i l a r l y

p r e p a r e d from c o m p o n e n t s ( 1 ) , ( 2 ) , (3) and (4) a c r a c k i n g

c o m p o n e n t i f d e s i r e d .

C a t a l y s t s w i t h e x c e l l e n t c a t a l y t i c and p h y s i c a l

p r o p e r t i e s may be p r e p a r e d o v e r a wide r a n g e of a l u m i n a

c o n t e n t s , f o r e x a m p l e 5-95% A1203 in t he s y n t h e t i c

p o r t i o n of the m a t r i x (sum of c o m p o n e n t s (1) and ( 2 ) ) .

C r a c k i n g c a t a l y s t s p r e p a r e d by the m e t h o d of t h i s

i n v e n t i o n have e x c e l l e n t c a t a l y t i c p r o p e r t i e s

( s e l e c t i v i t y , a c t i v i t y and s t a b i l i t y ) and p h y s i c a l

p r o p e r t i e s ( h i g h d e n s i t y and m o d e r a t e po re v o l u m e ) a n d

show e x c e l l e n t r e s i s t a n c e to the e f f e c t s of m e t a l

p o i s o n i n g . In a d d i t i o n , s i n c e c o l l o i d a l d i s p e r s i o n s o f

s i l i c a and a l u m i n a g e n e r a l l y have o n l y low l e v e l s of i o n i c

c o n t a m i n a n t s , fo r e x a m p l e s o d i u m and s u l f a t e , t he c a t a l y s t

can be m a n u f a c t u r e d by a h i g h l y s i m p l i f i e d p r o c e s s

i n v o l v i n g o n l y m i x i n g t he c o m p o n e n t s and d r y i n g t h e

c o m p o s i t e ; no f u r t h e r c h e m i c a l p r o c e s s is n e c e s s a r y .

F u r t h e r , c o n t r o l of c h e m i c a l c o m p o s i t i o n and s i z e of t h e

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

b o t h c a t a l y t i c and p h y s i c a l p r o p e r t i e s .

The c o m p o n e n t s of t he c a t a l y s t m a t e r i a l a r e

d e s c r i b e d be low in more d e t a i l . " C o l l o i d a l " r e f e r s t o

p a r t i c l e s in t h e s i z e r a n g e 1 0 - 1 0 , 0 0 0 A ° ( 1 - 1 0 0 0 m µ ) ; i n

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

2 0 - 1 0 0 0 A ° a r e p r e f e r r e d .

(1) A l u m i n a - c o l l o i d a l a l u m i n a i s a v a i l a b l e

c o m m e r c i a l l y . D i s p e r s i o n s a r e g e n e r a l l y p r e p a r e d

by t he a d d i t i o n of s o l i d a l u m i n a to d i l u t e a c i d

s o l u t i o n ( n i t r i c , h y d r o c h l o r i c , a c e t i c ) .

A l t e r n a t i v e l y , a l u m i n a d i s p e r s i o n s may b e

p r e p a r e d f rom s o l u b l e a l u m i n u m s a l t s ( e . g . , s e e

J o u r n a l of I n o r g a n i c and N u c l e a r C h e m i s t r y , V o l .

35, p a g e s 3 6 9 1 - 3 7 0 5 , 1 9 7 3 ) .

(2) S i l i c a - c o l l o i d a l d i s p e r s i o n s of s i l i c a a r e

r e a d i l y a v a i l a b l e c o m m e r c i a l l y in many c o n c e n t r a t i o n s and p a r t i c l e s i z e s ( f o r e x a m p l e ,

L u d o x , N a l c o a g p r o d u c t s ) . A l t e r n a t i v e l y , s i l i c a

d i s p e r s i o n s may be p r e p a r e d f rom s o l u b l e

s i l i c a t e s ( e . g . , see " C o l l o i d a l S i l i c a " by R. E .

I l e r in E. M a t i j e v i c , E d . , " S u r f a c e and C o l l o i d

S c i e n c e " , Vo l . 6, J. W i l e y , N . Y . , 1 9 7 3 ) .

(3) W e i g h t i n g a g e n t - many t y p e s of w e i g h t i n g a g e n t s

a re a v a i l a b l e such as c l a y , a l p h a - a l u m i n a ,

z i r c o n , m u l l i t e , a l u m i n a m o n o - o r t r i h y d r a t e ,

h a l l o y s i t e , s a n d , t i t a n i a or o t h e r r e l a t i v e l y

i n e r t m a t e r i a l s .

(4) C r a c k i n g c o m p o n e n t s - t he most u s e f u l a re r a r e

e a r t h - e x c h a n g e d fo rms of z e o l i t e s X and Y, o r

a m m o n i u m - e x c h a n g e d z e o l i t e s X or Y.

o t h e r z e o l i t e c a t a l y t i c m a t e r i a l s u s e f u l in t h e

c a t a l y s t s i n c l u d e ZSM-4, ZSM-5, ZSM-11, ZSM-12, Z S M - 3 5 ,

ZSM-38 and o t h e r s i m i l a r m a t e r i a l s , s u c h as e r i o n i t e ,

m o r d e n i t e and f a u j a s i t e .

T h i s i n v e n t i o n a l s o c o n c e r n s c a t a l y s t s h a v i n g

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

Such c a t a l y s t s may a l s o be p r o m o t e d w i t h fo r e x a m p l e t h e

a d d i t i o n of s m a l l a m o u n t s ( a b o u t 0 . 1 - 1 0 0 ppm) of a

p l a t i n u m g r o u p m e t a l , i . e . , p l a t i n u m , p a l l a d i u m , r h e n i u m ,

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

p l a t i n u m . T h i s a s p e c t of t he i n v e n t i o n is more f u l l y

d e s c r i b e d b e l o w .

C l a y s a re the p r e f e r r e d w e i g h t i n g a g e n t s . C l a y s

of t he a t t a p u l g i t e , m o n t m o r i l l o n i t e and k a o l i n f a m i l i e s ,

i n c l u d i n g t h o s e f a m i l i e s w h i c h i n c l u d e the s u b - b e n t o n i t e s

and the k a o l i n s commonly known as D i x i e , M c N a m m e - G e o r g i a

and F l o r i d a c l a y s or o t h e r s in w h i c h the main m i n e r a l

c o n s t i t u e n t i s h a l l o y s i t e , k a o l i n i t e , d i c k i t e , i l l i t e ,

n a c r i t e or a n a u x i t e and a c t i v a t e d c a r b o n s , a re e s p e c i a l l y

u s e f u l . B a u x i t e , a t t a p u l g i t e and f u l l e r ' s e a r t h a r e

p r e f e r r e d . Such c l a y s can be u s e d in the raw s t a t e a s

o r i g i n a l l y mined or i n i t i a l l y s u b j e c t e d to c a l c i n a t i o n ,

a c i d t r e a t m e n t or c h e m i c a l m o d i f i c a t i o n . C l a y s h a v i n g a

p a r t i c l e s i z e from a b o u t 0 . 5 to 5 m i c r o n s a re g e n e r a l l y

u s e d .

___ The c a t a l y s t s or s u p p o r t s a re g e n e r a l l y p r e p a r e d

by m i x i n g t he c o l l o i d a l s i l i c a and a l u m i n a c o m p o n e n t s a n d

the w e i g h t i n g a g e n t a n d / o r z e o l i t e c o m p o n e n t s i n

a p p r o p r i a t e p r o p o r t i o n s , t h e n d r y i n g the c o m p o s i t e by

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

c a t a l y s t s may be p r e p a r e d by a d d i t i o n of the c o l l o i d a l

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

a d d i n g the z e o l i t e c o m p o n e n t and s p r a y - d r y i n g t h e

c o m p o s i t e to form m i c r o s p h e r o i d a l p a r t i c l e s of s u i t a b l e

s i z e . A l t e r n a t i v e l y , t he m i x t u r e may be o v e n - o r

f l a s h - d r i e d , t h e n f o r m e d i n t o s u i t a b l e p a r t i c l e s ( p e l l e t s

or e x t r u d a t e ) . F u r t h e r , the m i x t u r e may be a d j u s t e d t o

s u i t a b l e c o n c e n t r a t i o n and t e m p e r a t u r e to form b e a d - t y p e

c a t a l y s t p a r t i c l e s . H y d r o c r a c k i n g c a t a l y s t s can b e

p r e p a r e d s i m i l a r l y . C a t a l y s t s u p p o r t s and a m o r p h o u s

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

z e o l i t e c o m p o n e n t in any of t he a b o v e f o r m s .

The s i l i c a and a l u m i n a d i s p e r s i o n s a r e e a c h

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

s i z e ) bu t m i x t u r e s of m o n o d i s p e r s e d p a r t i c l e s may be u s e d

to a l t e r t h e m a t r i x s t r u c t u r e . The s i l i c a and a l u m i n a

p a r t i c l e s i z e s a re in g e n e r a l d i f f e r e n t .

The m i x i n g of t h e c o m p o n e n t s may be p e r f o r m e d i n

a n y . o r d e r , a l t h o u g h t h e o r d e r of a d d i t i o n of the c o l l o i d a l

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

A l t e r n a t i v e l y , a l l t he c o m p o n e n t s or s u i t a b l e m i x t u r e s c a n

be m i x e d s i m u l t a n e o u s l y in a s u i t a b l e m i x i n g d e v i c e , t h u s

e l i m i n a t i n g t he need fo r l a r g e m i x i n g v e s s e l s in t h e

m a n u f a c t u r i n g p r o c e s s . The c a t a l y s t c o m p o s i t i o n s may b e

s p e c i f i e d as f o l l o w s :

(1) The s y n t h e t i c m a t r i x p o r t i o n i s s u b s t a n t i a l l y

f o r m e d by m i x i n g c o l l o i d a l s i l i c a and a l u m i n a

s u c h t h a t t he a l u m i n a or s i l i c a c o n t e n t is 1 - 9 9

w e i g h t %, and p r e f e r a b l y 1 0 - 8 0 w e i g h t % s i l i c a

and 2 0 - 9 0 w e i g h t % a l u m i n a .

(2) The p a r t i c u l a t e w e i g h t i n g a g e n t , f o r e x a m p l e ,

c l a y , can c o n s t i t u t e from 1 to 75 w e i g h t % of t h e

d r i e d c a t a l y s t c o m p o s i t e .

(3) The z e o l i t e c o m p o n e n t can c o n s t i t u t e 1 to 75

w e i g h t % of t he d r i e d c a t a l y s t c o m p o s i t e , a n d

p r e f e r a b l y w i l l be in the r a n g e 5-35% w h e n

i n c l u d e d .

An i m p o r t a n t use of t he c a t a l y s t s p r e p a r e d i n

t h i s m a n n e r i s in the c a t a l y t i c c r a c k i n g of h i g h b o i l i n g

h y d r o c a r b o n f e e d s t o c k s to v a l u a b l e l o w e r b o i l i n g l i q u i d

p r o d u c t s . Such c h a r g e s t o c k s i n c l u d e gas o i l s , vacuum o r

a t m o s p h e r i c r e s i d u a , or even w h o l e or r e d u c e d c r u d e s . T h e

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

p r o d u c t s . The c r a c k i n g p r o c e s s , w h i c h i n c l u d e s a

h y d r o c a r b o n c o n v e r s i o n ( c r a c k i n g ) p h a s e and a r e g e n e r a t i o n

p h a s e , to r e m o v e coke f o rmed on t h e c a t a l y s t d u r i n g

c r a c k i n g and p r o v i d e p r o c e s s h e a t , may be of t he m o v i n g

bed t y p e (TCC, H o u d r i f l o w ) or more i m p o r t a n t l y , one of t h e

many a v a i l a b l e f l u i d c r a c k i n g p r o c e s s e s . In a p p l y i n g

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

o p e r a t i o n s , t he i m p o r t a n t c a t a l y s t p r o p e r t i e s a r e a s

f o l l o w s :

C a t a l y s t A c t i v i t y and S t a b i l i t y : C r a c k i n g

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

h y d r o t h e r m a l d e a c t i v a t i o n is r e q u i r e d to m a i n t a i n a c t i v i t y

d u r i n g r e g e n e r a t i o n . In a d d i t i o n , a c a t a l y s t c o m p o s i t i o n

t h a t g i v e s h i g h a c t i v i t y and s t a b i l i t y at a g i v e n z e o l i t e

c o n t e n t can m i n i m i z e c a t a l y s t c o s t by r e d u c i n g t h e

r e q u i r e d z e o l i t e c o n t e n t f o r a g i v e n c a t a l y s t a c t i v i t y .

C a t a l y s t S e l e c t i v i t y : C a t a l y s t s t h a t m a x i m i z e

t he y i e l d of l i q u i d p r o d u c t s ( g a s o l i n e , f u e l o i l , b u t a n e s )

and m i n i m i z e c a t a l y t i c coke y i e l d s and l i g h t g a s e s p r o v i d e

t h e most p r o f i t a b l e o p e r a t i o n s .

A t t r i t i o n R e s i s t a n c e : C a t a l y s t s c i r c u l a t i n g i n

FCC u n i t s b r e a k up ( a t t r i t ) by many m e c h a n i s m s and a r e

l o s t from the u n i t ; t h u s h i g h a t t r i t i o n r e s i s t a n c e i s

d e s i r a b l e .

The m e t h o d used for a t t r i t i o n m e a s u r e m e n t

i n v o l v e s c o n t a c t i n g 7 cc. of c a t a l y s t in a 1 i n . ( 2 5 . 4 mm)

i n t e r n a l d i a m e t e r "U" t ube w i t h an a i r j e t f o r m e d by

p a s s i n g h u m i d i f i e d (60%) a i r at 21 l i t e r s / m i n u t e t h r o u g h a

0 . 0 7 i n . ( 1 .78mm) d i a m e t e r n o z z l e . The t e s t is p e r f o r m e d

in the R o l l e r a p p a r a t u s . F i n e s in t h e 0 -14 µ r a n g e a r e

r e m o v e d as f o r m e d and c a u g h t in a p a p e r c o l l e c t i o n

t h i m b l e . At the c o n c l u s i o n of the a t t r i t i o n p h a s e , t h e

p a r t i c l e s i z e of t he r e s i d u e is d e t e r m i n e d ; t h e

i n c r e m e n t a l w e i g h t of t he c o l l e c t i o n t h i m b l e i s added t o

t h e 0 - 2 0 µ f r i c t i o n .

The a t t r i t i o n i n d e x is d e f i n e d as t he i n c r e a s e i n

t he f i n e s f r a c t i o n ( 0 - 2 0 µ ) c a u s e d by t h e a t t r i t i o n p h a s e :

A t t r i t i o n i n d e x = x p a c k e d d e n s i t y

w h e r e WA = w e i g h t % in 0 - 2 0 P f r a c t i o n a f t e r a t t r i t i o n .

WB = w e i g h t % in 0 - 2 0 µ f r a c t i o n b e f o r e a t t r i t i o n .

The p a c k e d d e n s i t y is i n c l u d e d s i n c e a c o n s t a n t

v o l u m e of c a t a l y s t i s u s e d .

P h y s i c a l P r o p e r t i e s : Both ( p a c k e d ) d e n s i t y a n d

p o r e vo lume a r e i m p o r t a n t p a r a m e t e r s . C a t a l y s t s of h i g h

d e n s i t y a re more e a s i l y r e t a i n e d in FCC u n i t s , s i n c e t h e y

a r e l e s s s u b j e c t to l o s s by e l u t r i a t i o n . In g e n e r a l , f o r

a g i v e n t y p e of c a t a l y s t , a t t r i t i o n r e s i s t a n c e i n c r e a s e s

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

low po re v o l u m e s a r e d e s i r a b l e , too low a p o r e v o l u m e c a n

l e a d to s e l e c t i v i t y l o s s e s due to d i f f u s i o n a l

r e s t r i c t i o n s . D e s i r a b l e v a l u e s a r e t h e r e f o r e a c o m p r o m i s e :

P a c k e d D e n s i t y :

Pore v o l u m e :

M e t a l R e s i s t a n c e : The a b i l i t y to r e s i s t a c t i v i t y

and s e l e c t i v i t y l o s s e s c a u s e d by m e t a l p o i s o n s (Ni , V, C u ,

Fe) d e p o s i t e d from the c h a r g e s t o c k is a l s o i m p o r t a n t ,

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

m e t a l s t o c k s such as r e s i d u a , h y d r o t r e a t e d r e s i d u a a n d

w h o l e or r e d u c e d c r u d e s . In g e n e r a l , m e t a l p o i s o n s c a u s e

i n c r e a s e d " c o n t a m i n a n t " y i e l d s of coke and h y d r o g e n ,

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

Po re S i z e D i s t r i b u t i o n : The p o r e s i z e

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

o t h e r t y p e s of c r a c k i n g c a t a l y s t s . The p o r e s i z e

d i s t r i b u t i o n s p r e s e n t e d h e r e i n a f t e r a r e n o r m a l i z e d to a

3 0 - 3 0 0 A ° b a s i s . A c o n s i d e r a b l e f r a c t i o n of the p o r e vo lume o c c u r s in p o r e s g r e a t e r t h a n 3 0 0 A ° . Mos t , i f n o t

a l l , of t h e s e l a r g e r p o r e s a c t u a l l y r e p r e s e n t

i n t e r p a r t i c l e v o i d s c r e a t e d by the l o o s e p a c k i n g of t h e

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

c a t a l y s t f u n c t i o n s in a f l u i d i z e d bed . Po re s i z e

d i s t r i b u t i o n is d e t e r m i n e d by m e a s u r i n g the amoun t of a

f l u i d ( i n t h i s c a s e , m e r c u r y in c c / g r a m ) f o r c e d i n t o t h e

p o r e s t r u c t u r e as a f u n c t i o n of p r e s s u r e . As p r e s s u r e

i n c r e a s e s , t he m e r c u r y i s f o r c e d i n t o s m a l l e r and s m a l l e r

p o r e s . The s p e c i f i c po re s i z e s a r e d e t e r m i n e d by a

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

d e t e r m i n a t i o n i s l i m i t e d to p o r e s i z e s of 30A° and a b o v e .

The f o l l o w i n g e x a m p l e s i l l u s t r a t e the i n v e n t i o n ,

and r e l a t e to b o t h z e o l i t i c and a m o r p h o u s c r a c k i n g

c a t a l y s t s , w i t h s p e c i f i c r e f e r e n c e to t he p r o p e r t i e s

d e s c r i b e d a b o v e .

DESCRIPTION OF SPECIFIC EMBODIMENTS

E x a m p l e 1 - Rare E a r t h Y and Low Sod ium Rare E a r t h Y

A r a r e e a r t h - e x c h a n g e d z e o l i t e Y, w h i c h had b e e n

c a l c i n e d f o r a b o u t 10 m i n u t e s at 1 2 0 0 ° F ( 6 4 9 ° C ) and h a d

the c o m p o s i t i o n 3.17% Na, 61 .4% S i 0 2 , 21.7% A 1 2 0 3 and 15.9% RE203 ( E x a m p l e lA) was t r e a t e d w i t h 5%

ammonium s u l f a t e s o l u t i o n at 1 8 0 ° F ( 8 2 ° C ) . A f t e r

f i l t r a t i o n , t he t r e a t e d z e o l i t e was f u r t h e r t r e a t e d t w i c e

w i t h 12.5% r a r e e a r t h c h l o r i d e s o l u t i o n at 180°F ( 8 2 ° C ) ,

t h e n f i l t e r e d , w a s h e d and d r i e d a t 2 5 0 ° F ( 1 2 1 ° C ) . T h e

p r o d u c t , low s o d i u m ( 0 . 6 5 % Na) REY ( E x a m p l e 1B), w a s

i n c o r p o r a t e d in t h e c a t a l y s t s of E x a m p l e s 2 - 6 .

E x a m p l e s 2 - 6 - Mixed S i l i c a - A l u m i n a vs P u r e S i l i c a o r

A l u m i n a

A s e r i e s of c a t a l y s t s was p r e p a r e d by m i x i n g

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

a d d i n g c l a y as a w e i g h t i n g a g e n t and the REY of E x a m p l e 1B

as t he a c t i v e c o m p o n e n t .

The c o l l o i d a l s i l i c a was o b t a i n e d as a c o m m e r c i a l

p r e p a r a t i o n w i t h 30% S i 0 2 , 0.1% Na20 and a p a r t i c l e

d i a m e t e r of 17 m i l l i m i c r o n s .

The c o l l o i d a l a l u m i n a was p r e p a r e d by d i s p e r s i n g

a c o m m e r c i a l s p r a y - d r i e d a l u m i n a , w h i c h c o n t a i n e d 90%

a l u m i n a m o n o h y d r a t e (77% A1203) w i t h a p a r t i c l e

d i a m e t e r of 4 . 8 m i l l i m i c r o n s , in an a q u e o u s s o l u t i o n

c o n t a i n i n g 0.6% c o n c e n t r a t e d (70%) n i t r i c a c i d .

The c a t a l y s t s were p r e p a r e d by m i x i n g the c l a y

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

u s e d ) , t h e n m i x i n g a p p r o p r i a t e q u a n t i t i e s of the c o l l o i d a l

d i s p e r s i o n s of s i l i c a and a l u m i n a ( e x c e p t whe re p u r e s i l i c a or a l u m i n a was u s e d ) , t h e n m i x i n g in the low s o d i u m

REY of Example 1B. The c o m p o s i t e s we re t h e n s p r a y d r i e d

w i t h an a i r i n l e t t e m p e r a t u r e of 7 0 0 ° F ( 3 7 1 ° C ) and a n

o u t l e t t e m p e r a t u r e of 350°F ( 1 7 7 ° C ) to o b t a i n the f i n i s h e d

d r i e d c a t a l y s t s .

The c a t a l y s t s were e a c h g i v e n a t h e r m a l t r e a t m e n t

c o n s i s t i n g of a d d i n g t he c a t a l y s t s l o w l y to a f low o f

s t e a m at 1 2 0 0 ° F ( 6 4 9 ° C ) , t h e n c a l c i n i n g in n i t r o g e n ( o r

a i : ) at 1 2 0 0 ° F ( 6 4 9 ° C ) in a f l u i d i z e d bed fo r a n

a d d i t i o n a l 30 m i n u t e s . The t h e r m a l t r e a t m e n t s i m u l a t e s

t h e c o n d i t i o n of f r e s h c a t a l y s t i m m e d i a t e l y a f t e r a d d i t i o n

to t he r e g e n e r a t o r of a c o m m e r c i a l f l u i d c r a c k i n g u n i t .

The t h e r m a l l y - t r e a t e d c a t a l y s t s were t e s t e d fo r c r a c k i n g

a c t i v i t y and s e l e c t i v i t y by c r a c k i n g a w i d e - c u t

M i d - c o n t i n e n t gas o i l (WCMCGO) at 915°F ( 4 9 1 ° C ) , 2 C / 0 ,

1 2 . 5 WHSV in a f i x e d f l u i d i z e d bed . The p r o p e r t i e s of t h e

gas o i l a re g i v e n in T a b l e 1 .

In a d d i t i o n , e a c h c a t a l y s t was m i l d l y s t e a m e d by

t r e a t i n g the c a t a l y s t f o r 4 h o u r s at 1 4 0 0 ° F ( 7 6 0 ° C ) and 0

p s i g (101 kPa) w i t h 100% s t e a m in a f l u i d i z e d b e d ,

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

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

c a t a l y s t s were t r e a t e d u n d e r t he same c o n d i t i o n s as t h e

t h e r m a l l y t r e a t e d c a t a l y s t s ( 9 1 5 ° F ( 4 9 1 ° C ) , 2 C /0 , 1 2 . 5

WHSV, WCMCGO) as w e l l as at a h i g h e r s e v e r i t y , 9 2 0 ° F

( 4 9 3 ° C ) , 3 C /0 , 8 . 3 3 WHSV, WCMCGO.

The c a t a l y s t c o m p o s i t i o n s , p h y s i c a l , c h e m i c a l a n d

c a t a l y t i c p r o p e r t i e s a r e l i s t e d in T a b l e 2. For t he m i x e d

s i l i c a - a l u m i n a c a t a l y s t s , t he o r d e r of m i x i n g t h e

c o l l o i d a l d i s p e r s i o n s a r e a l s o s p e c i f i e d .

The d a t e in T a b l e 2 d e m o n s t r a t e s t h a t , i n

c o m p a r i s o n to t he c a t a l y s t s in w h i c h o n l y s i l i c a o r

a l u m i n a is p r e s e n t in t he s y n t h e t i c p o r t i o n of the m a t r i x ,

t he mixed s i l i c a - a l u m i n a c a t a l y s t s ( E x a m p l e s 3, 4, 5) a r e

h i g h e r in d e n s i t y , more a t t r i t i o n r e s i s t a n t , more a c t i v e

fo r c r a c k i n g , more s e l e c t i v e ( l o w e r coke y i e l d at c o n s t a n t

c o n v e r s i o n ) and more s t a b l e in t h a t l e s s a c t i v i t y is l o s t

by h y d r o t h e r m a l d e a c t i v a t i o n .

E x a m p l e s 7 - 1 2 - V a r i a t i o n of C o m p o s i t i o n

The c a l c i n e d r a r e e a r t h z e o l i t e Y (REY) o f

E x a m p l e 1A was i n c o r p o r a t e d in a s e r i e s of c a t a l y s t s i n

w h i c h the c o l l o i d a l s i l i c a , c o l l o i d a l a l u m i n a and c l a y

c o n t e n t s were v a r i e d . The m e t h o d of p r e p a r a t i o n was t h e

same as the p r e v i o u s e x a m p l e s . In E x a m p l e 12, on ly t h e

REY was s l u r r i e d w i t h h a l f of t he c o l l o i d a l s i l i c a , t h e

c o l l o i d a l a l u m i n a t h e n a d d e d , f o l l o w e d by a d d i t i o n of t h e

r e m a i n i n g s i l i c a .

Each c a t a l y s t was g i v e n a t h e r m a l t r e a t m e n t a s

w e l l as a m i l d s t e a m i n g as d e s c r i b e d in p r e v i o u s

e x a m p l e s . In a d d i t i o n , e a c h c a t a l y s t was s e v e r e l y s t e a m e d

by t r e a t i n g t h e c a t a l y s t f o r 4 h o u r s at 1 4 7 5 ° F ( 8 0 2 ° C ) , 0

p s i g (101 kPa) w i t h 100% s t e a m in a f l u i d i z e d b e d . T h e

s e v e r e s t e a m i n g s i m u l a t e s t h e e f f e c t of s e v e r e

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

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

t e s t e d f o r c r a c k i n g a c t i v i t y at t h e c o n d i t i o n s d e s c r i b e d

a b o v e .

The c a t a l y s t c o m p o s i t i o n s , p h y s i c a l , c h e m i c a l a n d

c a t a l y t i c p r o p e r t i e s a r e l i s t e d in T a b l e 3. The d a t a i n

T a b l e 3 d e m o n s t r a t e t h a t o v e r a wide r a n g e of a l u m i n a

c o n t e n t s , c l a y c o n t e n t s and a l u m i n a to s i l i c a r a t i o s , t h e

c a t a l y s t s of t h i s i n v e n t i o n show e x c e l l e n t c r a c k i n g

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

e x c e l l e n t a t t r i t i o n r e s i s t a n c e . The z e o l i t e c a t a l y s t s

d e s c r i b e d in E x a m p l e s 1 - 1 2 , as w e l l as o t h e r s of t h i s

n a t u r e , may, by t h e i n c o r p o r a t i o n of s u i t a b l e

h y d r o g e n a t i o n c o m p o n e n t s , be u s e d fo r h y d r o c r a c k i n g . S u c h

c o m p o n e n t s i n c l u d e , f o r e x a m p l e , c o b a l t and m o l y b d e n u m

o x i d e s , n i c k e l and t u n g s t e n o x i d e s , as w e l l as n o b l e

m e t a l s , fo r e x a m p l e p a l l a d i u m . Such c o m p o n e n t s may b e

i n c o r p o r a t e d by s t a n d a r d m e t h o d s , such as i m p r e g n a t i o n o r

ion e x c h a n g e .

E x a m p l e s 1 3 - 1 4 - N o n - Z e o l i t e C a t a l y s t s

Two c a t a l y s t s were p r e p a r e d by t h e m e t h o d s

d e s c r i b e d a b o v e , bu t no z e o l i t e c o m p o n e n t was a d d e d . T h e

c a t a l y s t s were m i l d l y s t e a m e d and t e s t e d fo r c r a c k i n g

a c t i v i t y w i t h WCMCGO a t a more s e v e r e c o n d i t i o n t h a n f o r

z e o l i t i c c a t a l y s t s : 925°F ( 4 9 6 ° C ) , 5 C /0 , 5 WHSV. T h e

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

in T a b l e 4, and c o m p a r e d w i t h a c o m m e r c i a l s i l i c a - a l u m i n a

c r a c k i n g c a t a l y s t . The c a t a l y s t s of t h i s i n v e n t i o n h a v e

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

and a re more s e l e c t i v e . These c a t a l y s t s a l s o may be u s e d

as s u p p o r t s f o r o t h e r a p p l i c a t i o n s , fo r e x a m p l e

h y a r o t r e a t i n g , h y d r o c r a c k i n g and r e f o r m i n g , w h e r e i n t h e

a p p r o p r i a t e a c t i v e c o m p o n e n t s a r e i n c o r p o r a t e d on t h e

c a t a l y s t by s u i t a b l e m e t h o d s s u c h as i m p r e g n a t i o n . S u c h

a c t i v e c o m p o n e n t s i n c l u d e , fo r e x a m p l e , c o b a l t a n d / o r

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

a n d / o r o t h e r n o b l e m e t a l s fo r r e f o r m i n g and o t h e r s w e l l

known to t h o s e s k i l l e d in the a r t .

E x a m p l e 1 5 - M e t a l R e s i s t a n c e

The c a t a l y s t s of E x a m p l e s 2, 3, 5 and 6 w e r e

t e s t e d for r e s i s t a n c e to p o i s o n i n g by m e t a l s as f o l l o w s :

t he m i l d l y s t e a m e d c a t a l y s t s were i m p r e g n a t e d at a m b i e n t

t e m p e r a t u r e w i t h a WCMCGO c h a r g e s t o c k c o n t a i n i n g a b o u t

1700 ppm each Ni and V as n a p h t h e n a t e s d i l u t e d w i t h x y l e n e

to a t o t a l v o l u m e s u f f i c i e n t to j u s t f i l l the c a t a l y s t

p o r e s . The r a t i o of c a t a l y s t - t o - c h a r g e s t o c k was 5 w t / w t . ,

so t h a t t he i m p r e g n a t e d c a t a l y s t s c o n t a i n e d a b o u t 340 ppm

e a c h Ni and V. A f t e r e v a p o r a t i o n of t he x y l e n e at 2 5 0 ° F

( 1 2 1 ° C ) , t he i m p r e g n a t e d s a m p l e s were h e a t e d to 9 8 0 ° F

( 5 2 7 ° C ) in a s t r e a m of n i t r o g e n in a f i x e d f l u i d i z e d b e d ,

t h e n h e l d at 9 8 0 ° F ( 5 2 7 ° C ) fo r 10 m i n u t e s , a l l o w i n g t h e

i m p r e g n a t e d c h a r g e s t o c k to c r a c k and d e p o s i t t he m e t a l s

and coke on the c a t a l y s t . The coke was r e m o v e d by

o x i d a t i o n in a i r at 1 2 0 0 ° F ( 6 4 9 ° C ) and the c a t a l y s t s

t e s t e d at 920°F ( 4 9 3 ° C ) , 3 C /0 , 8 . 3 3 WHSV, WCMCGO. S i n c e

a c t i v i t i e s d i f f e r e d , e s t i m a t e s of coke and h y d r o g e n y i e l d s

were made at a c o n s t a n t (75% v o l . ) c o n v e r s i o n to a l l o w

d i r e c t c o m p a r i s o n . The r e s u l t s were shown in T a b l e 5 a n d

d e m o n s t r a t e t h a t t he mixed s i l i c a - a l u m i n a c a t a l y s t s

p r o d u c e r e l a t i v e l y low c o n t a m i n a n t y i e l d s ; the pu re s i l i c a

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

E x a m p l e 1 6 - Po re S i z e D i s t r i b u t i o n

The p o r e s i z e d i s t r i b u t i o n of t he c a t a l y s t s o f

e x a m p l e s 3, 5, 7 -12 a f t e r the m i l d s t e a m i n g a re l i s t e d i n

T a b l e 6 .

The s t e a m e d c a t a l y s t s a r e c h a r a c t e r i z e d by h a v i n g

at l e a s t 40% of t h e i r p o r e v o l u m e w i t h i n t h e 3 0 - 3 0 0 A °

d i a m e t e r r a n g e b e t w e e n 60 and 80A° and at l e a s t 25% of t h e

t o t a l p o r e v o l u m e in t he same ( 6 0 - 8 0 A ° ) r a n g e .

Pore s i z e d i s t r i b u t i o n s fo r t he t h e r m a l l y t r e a t e d

c a t a l y s t s of E x a m p l e s 3 and 5 a r e l i s t e d in T a b l e 7; a

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

c o l l o i d a l s i l i c a o n l y ( E x a m p l e 2 ) . The e f f e c t of s t e a m i n g

on the p o r e s t r u c t u r e is a l s o shown in T a b l e 7; t he p o r e

s i z e d i s t r i b u t i o n is s h i f t e d by s t e a m i n g , bu t r e m a i n s

s h a r p . The p o r e s i z e d i s t r i b u t i o n of some t y p i c a l

c o m m e r c i a l c a t a l y s t s a f t e r t h e r m a l and s t e a m t r e a t m e n t a r e

l i s t e d in T a b l e 8. The c a t a l y s t c l a s s i f i c a t i o n i s

a c c o r d i n g to t h a t g i v e n by J. S. Magee and J. J. B l a z e k i n

a p a p e r a p p e a r i n g on page 615 of " Z e o l i t e C h e m i s t r y a n d

C a t a l y s i s , " e d i t e d by J. A. Rabo , p u b l i s h e d as ACS

M o n o g r a p h 171 by t h e A m e r i c a n C h e m i c a l S o c i e t y i n

W a s h i n g t o n , D.C. in 1 9 7 6 . None of t h e s e c a t a l y s t s s h o w s

d i s t r i b u t i o n s s i m i l a r to t h e mixed s o l c a t a l y s t s and s h o w

c o n s i d e r a b l e b r o a d e n i n g upon s t e a m i n g .

The d a t a i l l u s t r a t e d in T a b l e 6, 7 and 8

e s t a b l i s h e s t h e f a c t t h a t t he c a t a l y s t s p r e p a r e d f r o m

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

a c c o r d a n c e w i t h t he i n v e n t i o n e m b o d i e d h e r e i n p o s s e s s e s

u n i q u e and n o v e l c h a r a c t e r i s t i c s h e r e t o f o r e unknown in t h e

a r t .

E x a m p l e 1 7

A c a t a l y s t c o n t a i n i n g 15% wt . REY i n c o r p o r a t e d i n

a s i l i c a - a l u m i n a - c l a y m a t r i x d e r i v e d f rom c o l l o i d a l

d i s p e r s i o n s of s i l i c a and a l u m i n a and from G e o r g i a K a o l i n

c l a y was p r e p a r e d as f o l l o w s :

The m a t r i x was f o r m e d by f i r s t p r e p a r i n g a

d i s p e r s e d a l u m i n a s l u r r y by s l o w l y a d d i n g 1 5 5 5 . 6 gms ( 90%

A1203) to a s o l u t i o n c o n t a i n i n g 9 3 . 3 gms o f

c o n c e n t r a t e d n i t r i c a c i d (70% w t . ) and 14093 gms of H20 and t h e n a d j u s t i n g t h e pH to 4 . 0 w i t h c o n c e n t r a t e d NH40H ( 2 9 . 9 % w t . ) . T h i s a l u m i n a d i s p e r s i o n was s l o w l y a d d e d t o

a . s i l i c a - c l a y d i s p e r s i o n f o r m e d by s l u r r y i n g 1200 gms

G e o r g i a k a o l i n c l a y and 4 6 6 6 . 7 gms c o l l o i d a l s i l i c a ( 3 0 . 0 %

wt. S i 0 2 ) in 11522 gms H20. The a p p r o p r i a t e a m o u n t o f

REY, d e s c r i b e d in E x a m p l e lA, was a d d e d to g i v e 15% w t .

REY in t h e t o t a l a d m i x t u r e . The m i x t u r e was t h e n

h o m o g e n i z e d and s p r a y d r i e d a t 7 0 0 ° F ( 3 7 1 ° C ) i n l e t

t e m p e r a t u r e and 3 5 0 ° F ( 1 7 7 ° C ) o u t l e t t e m p e r a t u r e .

E x a m p l e 1 8

A c a t a l y s t was p r e p a r e d as in E x a m p l e 17 e x c e p t t h a t ,

p r i o r to t he a d d i t i o n of z e o l i t e REY, s u f f i c i e n t s o l i d

c h l o r o p l a t i n i c a c i d was a d d e d to d e p o s i t 10 ppm Pt on t h e

c a t a l y s t . The c a t a l y s t was t h e n f u r t h e r p r o c e s s e d a s

d e s c r i b e d in E x a m p l e 1 7 .

E x a m p l e 19

A p o r t i o n of t h e c a t a l y s t d e s c r i b e d in E x a m p l e 17

was c o n t a c t e d w i t h a s o l u t i o n c o n t a i n i n g s u f f i c i e n t

p l a t i n u m a c e t y l - a c e t o n a t e d i s s o l v e d in mixed x y l e n e s t o

d e p o s i t 5 ppm Pt on t h e c a t a l y s t . The c a t a l y s t was t h e n

d r i e d at 250°F ( 1 2 1 0 C ) f o r a b o u t 18 h o u r s . A f t e r d r y i n g

the c a t a l y s t was h e a t e d to 980°F ( 5 2 7 ° C ) and the x y l e n e

s o l u t i o n a d s o r b e d in t he p o r e s of t h e c a t a l y s t a l l o w e d t o

u n d e r g o a c r a c k i n g r e a c t i o n on the c a t a l y s t . The c a t a l y s t

was t h e n r e g e n e r a t e d at 980°F ( 5 2 7 ° C ) w i t h o x y g e n .

E x a m p l e s 2 0 - 2 2

The f r e s h l y p r e p a r e d c a t a l y s t s in E x a m p l e s 1 7 - 1 9

were each s t e a m e d fo r 4 h o u r s at 1 4 0 0 ° F ( 7 6 0 ° C ) at 0 p s i g

(101 kPa) in 100% s t e a m in a f i x e d f l u i d i z e d bed . In e a c h

i n s t a n c e , t he c a t a l y s t s were p r e h e a t e d to 1 3 5 0 ° F ( 7 3 2 ° C )

in s t e a m , t h e n to 1 4 0 0 ° F ( 7 6 0 ° C ) in n i t r o g e n b e f o r e

b e g i n n i n g 4 h o u r s s t e a m i n g . The s t e a m e d c a t a l y s t s w e r e

t h e n t e s t e d f o r c r a c k i n g a c t i v i t y and s e l e c t i v i t y by

c r a c k i n g a Sour Heavy Gas Oil (SHGO), h a v i n g t h e

p r o p e r t i e s h e r e i n a f t e r s e t f o r t h in T a b l e 9 at 9 6 0 ° F

( 5 1 6 ° C ) , 3 C / 0 , 1 .0 m i n u t e s on s t r e a m , in a f i x e d

f l u i d i z e d bed t e s t u n i t .

T h e s e c o k e d c a t a l y s t s were t e s t e d for CO

o x i d a t i o n a c t i v i t y by r e g e n e r a t i n g 4 g rams t o t a l of c o k e d

ano c l e a n b u r n e d b l e n d e d to 0 .65% wt. c a r b o n at 1 2 1 5 ° F

( 6 5 7 ° C ) w i t h a i r . The C02 and CO c o n t e n t of t h e

r e g e n e r a t i o n gas i s c o n t i n u o u s l y d e t e r m i n e d and an o v e r a l l

C02/CO mole r a t i o i s c a l c u l a t e d . CO c o n v e r s i o n i s

d e t e r m i n e d by p a s s i n g 215 c c / min. of a gas c o n t a i n i n g

8 . 3 1 mol % CO2, 4 . 0 1 mol % CO and 4 . 0 2 mol % 02 o v e r

the r e g e n e r a t e d c a t a l y s t at 1215°F ( 6 5 7 ° C ) . The o v e r a l l

C02/CO r a t i o and t h e CO c o n v e r s i o n fo r t h e s e c a t a l y s t

s a m p l e s a re g i v e n in T a b l e 10 a l o n g w i t h c r a c k i n g a c t i v i t y

and s e l e c t i v i t y .

E x a m p l e s 20 and 21 a r e REY c o n t a i n i n g c a t a l y s t s

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

w i t h a d d e d c l a y . E x a m p l e 17 i s u n p r o m o t e d and E x a m p l e 1 8

was p r o m o t e d by a d d i t i o n of c h l o r o p l a t i n i c a c i d to t h e

s i l i c a - a l u m i n a - c l a y m i x t u r e b e f o r e z e o l i t e a d d i t i o n a n d

s p r a y d r y i n g . From t h e d a t a in T a b l e 10 i t can be s e e n

t h a t t h e c a t a l y s t in w h i c h p r o m o t o r a l o n e was a d d e d to a

p r e c u r s o r of t he f i n a l c a t a l y s t m a t r i x ( E x a m p l e 1 8 )

p o s s e s s e s CO o x i d a t i o n a c t i v i t y .

E x a m p l e 22 d e p i c t s a s e m i - s y n t h e t i c

R E Y - c o n t a i n i n g c a t a l y s t p r o m o t e d by i m p r e g n a t i o n w i t h a

m e t a l - c o n t a i n i n g c o m p o u n d ( p l a t i n u m a c e t y l a c e t o n a t e )

d i s s o l v e d in a n o n - a q u e o u s medium ( x y l e n e ) . C o m p a r i s o n o f

t h e C O - o x i d a t i o n a c t i v i t y of t h i s c a t a l y s t w i t h i t s b a s e

( E x a m p l e 20) in T a b l e 10 shows t h a t t h i s m e t h o d o f

p r o m o t i o n i s v e r y e f f e c t i v e .

The d a t a d i s c l o s e d a b o v e d r a m a t i c a l l y i l l u s t r a t e s

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

t h i s i n v e n t i o n . The m i x e d c o l l o i d a l d i s p e r s i o n s h e r e i n

a r e f o r m e d by t he n o v e l p r o c e d u r e of m i x i n g p r e f o r m e d ,

m o n o d i s p e r s e c o l l o i d a l d i s p e r s i o n s of s i l i c a and a l u m i n a .

C o n s e q u e n t l y ge l f o r m a t i o n d o e s no t o c c u r to a n

a p p r e c i a b l e e x t e n t . A d d i t i o n a l l y c l a y i s no t an i n t e g r a l

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

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

of f o r e i g n c a t i o n s and a n i o n s , f o r e x a m p l e Na and S 0 4 ,

so t h a t f u r t h e r p r o c e s s i n g ( e x c h a n g e and w a s h i n g ) i s

u n n e c e s s a r y . The p o r e s t r u c t u r e i s u n u s u a l and v e r y

s t a b l e to h y d r o t h e r m a l d e a c t i v a t i o n , so t h a t a c t i v i t y l o s s

i s m i n i m i z e d o v e r a w ide t e m p e r a t u r e r a n g e . The c a t a l y s t s

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

r e s i s t a n c e and o t h e r p r o p e r t i e s r e l e v a n t f o r c r a c k i n g

c a t a l y s t s - - s e l e c t i v i t y , m e t a l r e s i s t a n c e - - a r e

e x c e l l e n t , as d i s c u s s e d a b o v e .

1. A c a t a l y s t s u p p o r t c o m p o s i t i o n p r e p a r e d by

m i x i n g from 1 to 99 w e i g h t % of a c o l l o i d a l d i s p e r s i o n o r

a l u m i n a p a r t i c l e s and from 1 to 99 w e i g h t % of a c o l l o i d a l

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

p a r t i c l e s e a c h h a v i n g d i a m e t e r s of from 10 to 1 0 , 0 0 0 AO,

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

at l e a s t 40% of i t s p o r e vo lume w i t h i n the 30 to 300 A°

d i a m e t e r r a n g e c o m p r i s i n g p o r e s of f rom 60 to 80 A°

d i a m e t e r , and at l e a s t 25% of i t s p o r e vo lume in e x c e s s o f

30 AO d i a m e t e r c o m p r i s i n g p o r e s of f rom 60 to 80 A°

d i a m e t e r .

2. A c o m p o s i t i o n a c c o r d i n g to c l a i m 1, p r e p a r e d

by m i x i n g from 20 to 90 w e i g h t % o f ' c o l l o i d a l a l u m i n a

p a r t i c l e s and f rom 10 to 80 w e i g h t % of c o l l o i d a l s i l i c a

p a r t i c l e s .

3. A c o m p o s i t i o n a c c o r d i n g to c l a i m 1 or c l a i m

2, c o n t a i n i n g f rom 1 to 75 w e i g h t %, b a s e d on the t o t a l

w e i g h t of t he f i n a l c o m p o s i t e , of a w e i g h t i n g a g e n t .

4. A c o m p o s i t i o n a c c o r d i n g to c l a i m 3, w h i c h

c o n t a i n s from 5 to 35 w e i g h t % of a w e i g h t i n g a g e n t .

5. A c o m p o s i t i o n a c c o r d i n g to c l a i m 3 or c l a i m

4, w h e r e i n t he w e i g h t i n g a g e n t is a p a r t i c u l a t e c l a y .

6. A c o m p o s i t i o n a c c o r d i n g to c l a i m 5, w h e r e i n

the c l a y is a t t a p u l g i t e , b a u x i t e , m o n t m o r i l l o n i t e , k a o l i n

or f u l l e r ' s e a r t h .

7. A c a t a l y s t c o m p r i s i n g a c o m p o s i t i o n

a c c o r d i n g to a n y o n e of c l a i m s 1 to 6, and from 1 to 75

w e i g h t % of an a c t i v e h y d r o c a r b o n c o n v e r s i o n c o m p o n e n t ,

b a s e d on the t o t a l c a t a l y s t c o m p o s i t i o n .

8. A c a t a l y s t a c c o r d i n g to c l a i m 7, w h e r e i n t h e

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


z e o l i t e is X or Y z e o l i t e , ZSM-4, ZSM-5, ZSM-11, Z S M - 1 2 ,

ZSM-35, ZSM-38, e r i o n i t e , m o r d e n i t e or f a u j a s i t e .


z e o l i t e is a r a r e e a r t h - e x c h a n g e d form of z e o l i t e X or Y

or an a m m o n i u m - e x c h a n g e d form of z e o l i t e X or Y.

11. A c a t a l y s t a c c o r d i n g to a n y o n e of c l a i m s 8

to 10, w h i c h c o n t a i n s f rom 5 to 35 w e i g h t % b a s e d on t h e

t o t a l c a t a l y s t c o m p o s i t i o n of z e o l i t e .


to 11, w h i c h c o n t a i n s a h y d r o g e n a t i n g c o m p o n e n t c o m p r i s i n g

a m e t a l of Group VI B or V I I I of t h e P e r i o d i c T a b l e .


to 12, w h i c h c o n t a i n s f rom 0 . 0 1 - 1 0 0 ppm of a p l a t i n u m

g r o u p m e t a l .

1 4 . A c a t a l y s t a c c o r d i n g to c l a i m 13, w h e r e i n

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

Catalysts supports and cracking catalysts incorporating them

Documents