Characterization of Catalyst Materials as ... - ACS Publications

Chapter 39

Characterization of Catalyst Materials as Reference Standards

Downloaded by UNIV OF PITTSBURGH on February 11, 2015 | http://pubs.acs.org Publication Date: October 3, 1989 | doi: 10.1021/bk-1989-0411.ch039

Ruth A. Haines National Institute of Standards and Technology, Gaithersburg, M D 20899

Through a series of round robin tests conducted by participating laboratories, ASTM Committee D-32 on Catalysts has characterized a variety of catalyst materials using standard test methods. Materials include fluid cracking catalysts, zeolites, silicas, aluminas, supported metals, and a gas oil feedstock. Properties characterized include surface area, crush strength, catalytic microactivity, particle size, unit cell dimensions and metal content. These materials are available from the National Institute of Standards and Technology as reference materials. ASTM Committee D-32 on C a t a l y s t s was o r g a n i z e d i n the mids e v e n t i e s i n response t o a r e c o g n i z e d need on the p a r t o f the c a t a l y s t p r o d u c e r s and u s e r s f o r t e s t methods and s t a n d a r d s . The Committee i s s t r u c t u r e d to b r i n g t o g e t h e r i n t e r e s t s i n measuring p h y s i c a l - c h e m i c a l and p h y s i c a l - m e c h a n i c a l p r o p e r t i e s , c a t a l y t i c p r o p e r t i e s and c o m p o s i t i o n . Working groups are o r g a n i z e d t o d e v e l o p s p e c i f i c s t a n d a r d t e s t methods o f i n t e r e s t t o t h e membership u s i n g commercial c a t a l y s t s o r c a t a l y s t s u p p o r t s . Key t o the s u c c e s s o f these w o r k i n g groups i n e s t a b l i s h i n g t e s t methods i s the a v a i l a b i l i t y o f c a t a l y s t m a t e r i a l s i n l a r g e enough q u a n t i t i e s t o a l l o w f o r e x t e n s i v e round r o b i n t e s t i n g o f the methods w i t h i n the Committee. I n f a c t , adequate q u a n t i t i e s e x i s t t o make t h e s e w e l l c h a r a c t e r i z e d m a t e r i a l s a v a i l a b l e f o r use as s t a n d a r d s . F e a r i n g l o s s o f t h e s e m a t e r i a l s i n the warehouses o f the many donor companies, the Committee has asked the N a t i o n a l I n s t i t u t e o f Standards and Technology ( f o r m e r l y the N a t i o n a l Bureau o f S t a n d a r d s ) t o d i s t r i b u t e the samples. A t the p r e s e n t time s e v e r a l c a t a l y s t m a t e r i a l s are a v a i l a b l e from the N a t i o n a l I n s t i t u t e o f Standards and Technology and more w i l l be made a v a i l a b l e i n the near f u t u r e . (1) U s i n g commercial m a t e r i a l s donated by i n t e r e s t e d companies t h e members o f D-32 have been a b l e t o t e s t f o r a wide range o f i m p o r t a n t p r o p e r t i e s o f c a t a l y s t s o r c a t a l y s t s u p p o r t s . I n most This chapter not subject to U.S. copyright Published 1989 American Chemical Society

In Characterization and Catalyst Development; Bradley, S., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1989.


39.

HAINES

Catalyst Materials as Reference Standards

431

c a s e s a w o r k i n g group agrees on a t e n t a t i v e measurement p r o c e d u r e , asks p a r t i c i p a t i n g l a b o r a t o r i e s t o f o l l o w the p r o c e d u r e to c h a r a c t e r i z e one or more m a t e r i a l s , s t u d i e s the f i n d i n g s , r e f i n e s the p r o c e d u r e and f r e q u e n t l y asks f o r a n o t h e r s e t o f l a b o r a t o r y measurements. The r e s u l t s o f the t e s t s are t r e a t e d s t a t i s t i c a l l y and r e p o r t e d i n d e t a i l i n r e s e a r c h r e p o r t s f i l e d w i t h the ASTM. The t e s t methods appear i n Volume 05.03 o f the A n n u a l Book o f ASTM S t a n d a r d s (2) o r i n the s p e c i a l p u b l i c a t i o n ASTM Standards on C a t a l y s t s . (3) T a b l e I l i s t s the c a t a l y s t m a t e r i a l s c h a r a c t e r i z e d and a v a i l a b l e f o r use as r e f e r e n c e m a t e r i a l s . For each p r o p e r t y measured, the number o f the ASTM S t a n d a r d T e s t Method used i n the d e t e r m i n a t i o n i s i d e n t i f i e d ; the m a t e r i a l i s s p e c i f i e d ; the consensus mean v a l u e d e t e r m i n e d i s l i s t e d ; the i n t e r l a b o r a t o r y r e p r o d u c i b i l i t y and the i n t r a l a b o r a t o r y r e p e a t a b i l i t y from round r o b i n t e s t s are p r e s e n t e d ; and the number o f the ASTM r e s e a r c h r e p o r t d e s c r i b i n g the round r o b i n d a t a i s l i s t e d . These round r o b i n s were conducted i n accordance w i t h ASTM E-691 -- S t a n d a r d P r a c t i c e f o r C o n d u c t i n g an I n t e r l a b o r a t o r y Study t o Determine the P r e c i s i o n o f a T e s t Method. T a b l e I I summarizes the t e s t methods used f o r the c h a r a c t e r i z a t i o n o f the c a t a l y s t samples. These methods have been s u b j e c t t o the b a l l o t i n g p r o c e d u r e s o f the ASTM a f t e r e x t e n s i v e r e v i e w by t a s k f o r c e members. The p r o c e d u r e s s p e c i f y equipment parameters when n e c e s s a r y . L i m i t s i n the a p p l i c a t i o n o f the methods are o u t l i n e d . I n a l l cases the t e s t method must be f o l l o w e d i n o r d e r t o a s s u r e c o m p a r a b i l i t y o f the r e s u l t s t o the values assigned. I t s h o u l d be n o t e d t h a t the o f f i c i a l ASTM t e s t method numbers have two more d i g i t s w h i c h r e p r e s e n t the y e a r o f i s s u e o r r e v i s i o n o f the s t a n d a r d .

S u r f a c e A r e a and P a r t i c l e S i z e R e f e r e n c e M a t e r i a l s Among the p h y s i c a l - c h e m i c a l p r o p e r t i e s o f most w i d e s p r e a d use i n the c a t a l y s t i n d u s t r y are s u r f a c e a r e a and p a r t i c l e s i z e distribution. Three m a t e r i a l s , a low s u r f a c e a r e a k a o l i n , a moderate s u r f a c e a r e a a l u m i n a and a h i g h s u r f a c e a r e a s i l i c a a l u m i n a , have been c h a r a c t e r i z e d f o r s u r f a c e a r e a u s i n g n i t r o g e n gas o r a n i t r o g e n - h e l i u m f l o w i n g gas m i x t u r e . Several e x t e n s i v e round r o b i n t e s t s have been conducted u s i n g s t a n d a r d s t a t i c and c o n t i n u o u s f l o w t e s t methods a p p r o p r i a t e t o c a t a l y s t s or c a t a l y s t s u p p o r t s t h a t have Type I I o r IV n i t r o g e n a d s o r p t i o n isotherms. As a r e s u l t these m a t e r i a l s are recommended as r e f e r e n c e m a t e r i a l s by an i n d u s t r y funded ASTM Committee (S-21) r e s p o n s i b l e f o r standards f o r p a r t i c l e m e t r o l o g y . Because s e v e r a l t e c h n i q u e s are f r e q u e n t l y used i n the i n d u s t r y t o c h a r a c t e r i z e p a r t i c l e s i z e d i s t r i b u t i o n , an FCC c a t a l y s t has been c h a r a c t e r i z e d u s i n g l a s e r l i g h t s c a t t e r i n g , e l e c t r o n i c c o u n t i n g , and s i e v i n g i n the 20 t o 150-/zm e q u i v a l e n t s p h e r i c a l d i a m e t e r range. V a l u e s f o r the consensus mean found w i t h each type o f t e s t method are l i s t e d i n T a b l e I . Comparison o f the v a r i o u s c u m u l a t i v e p e r c e n t d a t a from the t h r e e methods u s i n g the same m a t e r i a l s has been r e p o r t e d by F l a n k . (4)



Platinum, Wt % Palladium, Wt% Zeolite Area

D-4438(b)

Median Diameter

Pd/Silica-Alumina Molecular Sieve FCC C a t a l y s t AGZ-200

D-4782

D-4365

Pt/Alumina

fj>m

fim

87.3 g/cm

0.539%

0.578%

64.3

3

lbs-force

64.4 /zm

56.7

20.19

10.3 sq m/g 1535 sq m/g 278 sq m/g

10.9 sq m/g 158 sq m/g 291 sq m/g

( 2 , 3,)

D32-1011

3.2 1.9 1.7

6.4 5.7 8.2

36.5

4.54

5.4

0.78

0.93

D32-1004

6.0

8.7

2.31

D32-1019 1.7 1.7 1.6

17.6 14.5 16.8

D32-1009

D32-1015

D32-1013

D32-1006

12.2 4.3 2.8

17.6 7.5 6.1

ASTM 2.77S(a). P e r c e n t o f Consensus Mean Research Interlaboratory Intralaboratory Report Reproducibility Repeatability

CATALYST MATERIALS CHARACTERIZED

Consensus Mean

D-4642

D-4513

D-4464(b)

Alumina EAS-480 Spheres

D-4179(b)

Crush Strength

E q u i l i b r i u m FCC C a t a l y s t CC-408 E q u i l i b r i u m FCC C a t a l y s t CC-408 E q u i l i b r i u m FCC C a t a l y s t CC-408

K a o l i n M136384 Alumina N10131 S i l i c a Alumina R50475

D-4567

Test M a t e r i a l

K a o l i n M136384 Alumina N10131 S i l i c a Alumina R50475

T e s t Method

D-3663(b)

Surface Area

Property

Table I .


w

S

a) H

I

• o

8

H

2

In Characterization and Catalyst Development; Bradley, S., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1989. 9.J 8,.9 10, .4

76. ,06 76. ,16 80, ,87 70. ,07

Catalyst/ Catalyst/ Catalyst/ Catalyst/

Standard d e v i a t i o n not using weighted data

T h i s method employs a NaY z e o l i t e s t a n d a r d r e f e r e n c e m a t e r i a l a v a i l a b l e from NIST.

(b)

(c)

reduction.

2.77S i s t h e 95% p r o b a b i l i t y i n t e r v a l l i m i t on t h e d i f f e r e n c e between two t e s t r e s u l t s , and S i s t h e appropriate estimate o f standard d e v i a t i o n .

1.,7

3.,4

3.,6

3,.5

4,.3

D32-1016

D32-1010

D32-1002

(a)

11, .4

12, .5

64. .94

4,.3

8,.7

Catalyst/

8,.6

34, .5

12. .8%

59. ,39 wt%

7..3

0 .2

71 .2

0 .4

12. .3%

24, .723A

Catalyst/

D- 3907

Percent Conversion

FCC Oil FCC Oil FCC Oil FCC Oil FCC Oil FCC Oil

FCC C a t a l y s t AGZ-200 FCC C a t a l y s t Bobcat 2

D- 3906(b,c)

Relative Diffraction

RR-1 Gas RR-2 Gas RR-3 Gas RR-4 Gas RR-5 Gas RR-6 Gas

FCC C a t a l y s t AGZ-200

Unit C e l l Dimension

D-•3942


6

3-

I

I

So

8

f


Title

Surface Area o f Catalysts

Single-point Determination of the S p e c i f i c Surface Area of C a t a l y s t s Using N i t r o g e n A d s o r p t i o n by t h e Continuous Flow Method

S i n g l e P e l l e t Crush S t r e n g t h o f Formed C a t a l y s t Shapes

P a r t i c l e Size D i s t r i b u t i o n o f C a t a l y s t M a t e r i a l by E l e c t r o n i c Counting

P a r t i c l e Size D i s t r i b u t i o n of C a t a l y t i c M a t e r i a l by L a s e r Light Scattering

P a r t i c l e Size D i s t r i b u t i o n o f C a t a l y t i c M a t e r i a l by S i e v i n g

D-3363

D-4567

D-4179

D-4438

D-4464

D-4513

v o l u m e t r i c (BET) s u r f a c e a r e a by n i t r o g e n

P a r t i c l e s i z e d i s t r i b u t i o n o f c a t a l y s t p a r t i c l e s (20 t o 420/jm) as measured w e i g h t o f sample p a s s i n g through c a l i b r a t e d sieves

P a r t i c l e s i z e d i s t r i b u t i o n o f c a t a l y s t p a r t i c l e s (20 t o 150/xm e q u i v a l e n t s p h e r i c a l d i a m e t e r ) as a s c e r t a i n e d by l a s e r l i g h t scattering

P a r t i c l e s i z e d i s t r i b u t i o n o f c a t a l y s t p a r t i c l e s (20 t o 150/xm e q u i v a l e n t s p h e r i c a l d i a m e t e r ) as d e t e r m i n e d by an e l e c t r o c o n d u c t i v e s e n s i n g method

S t r e n g t h o f s p h e r i c a l o r t a b l e t shaped p a r t i c l e s i n d i v i d u a l l y c r u s h e d between two f l a t s u r f a c e s

S i n g l e - p o i n t surface area u s i n g continuous flowing n i t r o g e n - h e l i u m gas m i x t u r e

Multi-point adsorption

Summary o f the Method

I I . SUMMARY OF METHODS FOR CATALYST CHARACTERIZATION

ASTM Method Number

Table


In Characterization and Catalyst Development; Bradley, S., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1989. R e l a t i v e f r a c t i o n o f z e o l i t e as determined by x - r a y d i f f r a c t i o n peak i n t e n s i t i e s

Relative Zeolite Intensities

Method f o r T e s t i n g F l u i d C a t a l y t i c Cracking Catalysts by M i c r o a c t i v i t y T e s t

A c t i v i t y o f FCC c a t a l y s t s as e v a l u a t e d by p e r c e n t c o n v e r s i o n o f gas o i l u s i n g a f i x e d bed r e a c t o r

comparing

U n i t c e l l d i m e n s i o n o f s y n t h e t i c f a u j a s i t e type z e o l i t e by x - r a y d i f f r a c t i o n

Determination o f the U n i t C e l l Dimension o f a F a u j a s i t e - t y p e

Diffraction

T-plot a n a l y s i s o f p o r t i o n of t o t a l area a t t r i b u t e d to zeolite fraction

Determining Z e o l i t e Area of a Catalyst

Assay f o r p l a t i n u m i n a n o n - z e o l i t i c r e f o r m i n g c a t a l y s t by d i s s o l u t i o n o f the c a t a l y s t and s p e c t r o p h o t o m e t r y absorbance for platinum P o t e n t i o m e t r i c t e c h n i q u e f o r d e t e r m i n i n g about 0.5 w e i g h t percent palladium i n molecular sieve c o n t a i n i n g f r e s h catalyst.

Catalysts

Paladium i n M o l e c u l a r S i e v e Catalyst

P l a t i n u m i n Reforming


436

CHARACTERIZATION AND CATALYST DEVELOPMENT


Catalyst Activity Of p a r t i c u l a r mention and o f w i d e s p r e a d i n t e r e s t throughout the p e t r o c h e m i c a l i n d u s t r y has been t h e Committee's s u c c e s s i n o b t a i n i n g round r o b i n r e s u l t s on t e s t i n g f l u i d c r a c k i n g c a t a l y s t s . Overcoming a n a t u r a l d e s i r e n o t t o share d a t a o r methods, i n d u s t r y r e p r e s e n t a t i v e s d e v e l o p e d a s t a n d a r d method t o determine the w e i g h t p e r c e n t c o n v e r s i o n o f gas o i l i n a f i x e d bed m i c r o a c t i v i t y u n i t . The t e s t r e q u i r e s t h e use o f a s t a n d a r d b a t c h o f gas o i l as a f e e d s t o c k and a s e t o f e q u i l i b r i u m f l u i d c r a c k i n g c a t a l y s t s w i t h consensus mean c o n v e r s i o n v a l u e s a s s i g n e d i n a r e a c t o r o f s p e c i f i e d design. The gas o i l and the s e t o f e q u i l i b r i u m c r a c k i n g c a t a l y s t s are u s e f u l r e f e r e n c e m a t e r i a l s . C o n v e r s i o n f o r any e q u i l i b r i u m o r l a b o r a t o r y - d e a c t i v a t e d f l u i d c r a c k i n g c a t a l y s t c a n be measured and compared t o a c o n v e r s i o n c a l i b r a t i o n curve. C o n v e r s i o n i s measured by t h e d i f f e r e n c e between the amount o f f e e d used and t h e amount o f u n c o n v e r t e d m a t e r i a l . The u n c o n v e r t e d m a t e r i a l i s d e f i n e d as a l l l i q u i d p r o d u c t w i t h a b o i l i n g p o i n t above 216°C. Other P h y s i c a l and Chemical P r o p e r t i e s A l t h o u g h s e v e r a l s t a n d a r d t e s t methods have been d e v e l o p e d f o r the c h e m i c a l a n a l y s i s o f c a t a l y s t s o n l y s m a l l samples o f s u p p o r t e d p l a t i n u m and p a l l a d i u m r e f e r e n c e m a t e r i a l s a r e a v a i l a b l e . Z e o l i t e s have been c h a r a c t e r i z e d f o r z e o l i t e a r e a , u n i t c e l l d i m e n s i o n s , and r e l a t i v e x - r a y d i f f r a c t i o n i n t e n s i t y . The c r u s h s t r e n g t h o f a l u m i n a p e l l e t s has a l s o been determined. As t h e needs o f c a t a l y s t u s e r s and p r o d u c e r s change so w i l l t h e m a t e r i a l s c h a r a c t e r i z e d . To the e x t e n t t h a t adequate amounts o f m a t e r i a l can be donated, s t a n d a r d t e s t methods developed, and round r o b i n t e s t s p e r f o r m e d Committee D-32 on c a t a l y s t s w i l l c o n t i n u e t o make them a v a i l a b l e t h r o u g h NIST as r e f e r e n c e m a t e r i a l s . S p e c i a l acknowledgment goes t o Steve B r a d l e y and the many D-32 members who worked on the c h a r a c t e r i z a t i o n o f t h e m a t e r i a l s d e s c r i b e d i n t h i s paper. Literature Cited 1. 2. 3. 4.

NBS Standard Reference Materials Catalog; Seward, R. W., Ed.; 1988-89, NBS Special Publication 260. Annual Book of ASTM Standards: ASTM: Philadelphia, PA, 1988; Vol. 05.03, p 569-654. ASTM Standards on Catalysts: ASTM: Philadelphia, PA, (3rd Edition, 1988). Flank, W. H.; Ind. Eng. Chem. Res. 1987, 26, 1750.

RECEIVED

April 27, 1989


Characterization of Catalyst Materials as ... - ACS Publications

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