THERMAL HYDROCRACKING O F ATHABASCA BITUMEN: COMPARISON OF COMPUTER-SIMULATED FEED AND PRODUCT VAPORIZATION VALUES WITH PILOT PLANT DATA

D.J.

Patmore and B.B.

Pruden

Energy Research L a b o r a t o r i e s Canada C e n t r e f o r Mineral and Energy Technology Department of Energy, Mines and Resources 555 Booth S t r e e t , O t t a w a , O n t a r i o , Canada, K l A O G 1

INTRODUCTION

The Energy Research L a b o r a t o r i e s of t h e Canada C e n t r e f o r M i n e r a l and Energy Technology (CANMET) are engaged i n a c o n t i n u i n g upgrading p r o j e c t i n v o l v i n g t h e hydrocracking o f Canadian o i l sand bitumen and heavy o i l . Such upgrading i s n e c e s s a r y t o remove s u l p h u r and t o r e d u c e t h e v i s c o s i t y of t h e bitumen t o f a c i l i t a t e t r a n s p o r t by p i p e l i n e t o t h e r e f i n e r y . C u r r e n t l y upgrading i s accomplished on a commercial s c a l e by Great Canadian O i l Sands Limited u s i n g a c o k i n g p r o c e s s which c o n v e r t s u p t o 20% of t h e bitumen t o c h a r . One aim of t h e CANMET work i s t o dev e l o p a n economical p r o c e s s which would c o n v e r t a l l of t h e bitumen t o u s a b l e p r o d u c t s , and t h u s r e d u c e t h e waste of a v a l u a b l e r e s o u r c e . For t h i s purpose a one-barrel-per-day p i l o t p l a n t was b u i l t and h a s been o p e r a t e d s u c c e s s f u l l y w i t h a v a r i e t y of f e e d s t o c k s . T h i s work h a s c o n c e n t r a t e d o n b o t h p l a n t o p e r a b i l i t y , i n p a r t i c u l a r t h e p r e v e n t i o n of r e a c t o r c o k i n g ( l ) , and on t h e e f f e c t of o p e r a t i n g c o n d i t i o n s on y i e l d s and p r o d u c t q u a l i t i e s ( 2 ) . E f f i c i e n t and economical scale-up of t h i s p r o c e s s t o a commercial-size p l a n t r e q u i r e s q u a n t i t a t i v e knowledge o f b o t h t h e d e g r e e of v a p o r i z a t i o n of f e e d and p r o d u c t and t h e f r a c t i o n of t h e reactor o c c u p i e d by g a s under r e a c t o r c o n d i t i o n s . The l a t t e r , u s u a l l y r e f e r r e d t o as v o i d a g e , h a s a l r e a d y b e e n i n v e s t i g a t e d i n det a i l ( 3 ) . Such knowledge i s needed t o c a l c u l a t e hydrogen p a r t i a l p r e s s u r e s and t r u e l i q u i d and vapour r e s i d e n c e t i m e s . These i n t u r n a r e n e c e s s a r y t o a c c u r a t e l y estimate t h e s i z e of v a r i o u s p l a n t components as w e l l as t o f o r m u l a t e a k i n e t i c model f o r t h e t h e r m a l h y d r o c r a c k i n g r e a c t i o n . Because i t is n o t f e a s i b l e t o measure l i q u i d and vapour c o m p o s i t i o n s i n t h e r e a c t o r d i r e c t l y , r e c o u r s e must be made t o c o m p u t a t i o n a l methods. These inv o l v e e s t i m a t i n g t h e e q u i l i b r i u m v a p o r i z a t i o n c o n s t a n t , K, f o r v a r i o u s components of t h e system u s i n g known o r e s t i m a t e d v a l u e s o f t h e i r thermodynamic p r o p e r t i e s . Computations f o r t h e p r e s e n t s t u d y were c a r r i e d o u t u s i n g t h e GraysonS t r e e d m o d i f i c a t i o n of t h e Chao-Seader c o r r e l a t i o n employing t h e p r i n c i p l e of c o r responding s t a t e s ( 4 , 5 ) . A package program was employed. Vapour-liquid e q u i l i b r i u m d a t a were o b t a i n e d from measurements i n a h o t s e p a r a t o r downstream of t h e p i l o t p l a n t r e a c t o r . T h i s well-mixed s e p a r a t o r , which was t e m p e r a t u r e c o n t r o l l e d , w a s assumed t o behave a s a s i n g l e s t a g e c o n t a c t o r , and measurements of l i q u i d and vapour f l o w s and c o n c e n t r a t i o n s w e r e t a k e n a t s t e a d y State conditions.

63

EXPERIMENTAL The p i l o t p l a n t i s shown s c h e m a t i c a l l y i n F i g . 1. Bitumen and hydrogen are f e d a t t h e bottom of a l o n g unpacked h e a t e d t u b u l a r column (3.81 c m diam. x 3.95 m l o n g ) . The hydrocracked p r o d u c t s are l e d from t h e t o p of t h e r e a c t o r t o a h o t s e p a r a t o r kept a t a t e m p e r a t u r e below t h a t of t h e r e a c t o r . The heavy o i l p r o d u c t i s withdrawn and t h e vapour passed i n t o a c o l d r e c e i v e r and condensed. The l i g h t o i l product i s a g a i n withdrawn and c o l l e c t e d . The h o t s e p a r a t o r was w e l l mixed a s t h e r e a c t o r p r o d u c t s e n t e r e d below t h e l i q u i d l e v e l , and t h e r e w a s a h i g h r a t i o of gas t o l i q u i d . I t f o l l o w s t h a t t h e f r a c t i o n of l i q u i d v a p o r i z e d , f , w a s t h e weight of l i g h t o i l p r o d u c t d i v i d e d by t h e t o t a l l i q u i d p r o d u c t . The h o t sepa r a t o r was t e m p e r a t u r e c o n t r o l l e d so t h a t t h e above r a t i o c o u l d b e o b t a i n e d as a f u n c t i o n of t e m p e r a t u r e . The g a s f l o w was metered u s i n g t h e o r i f i c e , and t h e g a s composition a t t h e r e a c t o r i n l e t c o n t r o l l e d by s c r u b b i n g . Accordingly t h e a c t u a l g a s composition and flow i n t h e h o t s e p a r a t o r c o u l d b e computed by u s i n g t h e s e d a t a a l o n g w i t h d i s s o l v e d g a s f l o w s and c o m p o s i t i o n s , r e a c t i o n hydrogen r e q u i r e m e n t s and hydrocarbon g a s make. Athabasca bitumen c o n t a i n i n g 51% p i t c h ( m a t e r i a l b o i l i n g above 524OC e q u i v a l e n t a t m o s p h e r i c b o i l i n g t e m p e r a t u r e ) w a s f e d i n a l l c a s e s . P r o d u c t s are i d e n t i f i e d by t h e amount o f p i t c h c o n v e r s i o n based on f e e d . F u r t h e r d e t a i l s a r e given i n Reference 6.
T h e computer s i m u l a t i o n w a s c a r r i e d o u t f o r CANMET by S a t u r n Engineering, C a l g a r y , A l b e r t a , u s i n g t h e DISTILL program l i c e n s e d by t h e Chem S h a r e C o r p o r a t i o n , Houston, Texas. S i m u l a t i o n s were c a r r i e d o u t f o r Athabasca bitumen and f o u r t y p i c a l hydrocracked p r o d u c t s c o v e r i n g t h e r a n g e 49 t o 93% p i t c h c o n v e r s i o n . I n p u t t o t h e program c o n s i s t e d o f l i q u i d and g a s r a t e s , c o m p o s i t i o n s and p r o p e r t i e s . The c o m p o s i t i o n and p r o p e r t i e s of l i q u i d f e e d and p r o d u c t were approximated by t e n f r a c t i o n s w i t h mean a v e r a g e b o i l i n g p o i n t s r a n g i n g from 65.5OC (150OF) t o 648.9OC (1200OF). These f r a c t i o n s were d e r i v e d from Hempel d i s t i l l a t i o n s and g r a v i t i e s of e a c h c u t , using s t a n d a r d c o r r e l a t i o n p r o c e d u r e s f o r petroleum f r a c t i o n s .

For e a c h s p e c i f i e d t e m p e r a t u r e and p r e s s u r e combination t h e program c a l c u l a t e d f , t h e weight f r a c t i o n of l i q u i d t h a t v a p o r i z e s under t h e s p e c i f i e d c o n d i t i o n s , as a f u n c t i o n of s p e c i f i e d v a l u e s of G/L, t h e r a t i o of g a s r a t e a t STP ( i n g mol/h) t o l i q u i d r a t e a t STP ( i n k g / h ) . G a s c o m p o s i t i o n was a l s o e n t e r e d and t r e a t e d a s a parameter.

RESULTS AND DISCUSSION C a l c u l a t e d v a l u e s of t h e d e g r e e of v a p o r i z a t i o n w e r e p l o t t e d a s f u n c t i o n s o f G/L and t e m p e r a t u r e ( F i g s . 2 t o 5 ) . From t h e s e g r a p h s i n t e r p o l a t i o n s c a n be made t o o b t a i n f v a l u e s a t c o n d i t i o n s o t h e r t h a n t h o s e s p e c i f i e d . F i g u r e s 2 and 3 i l l u s t r a t e t h e e f f e c t of G/L on f f o r d i f f e r e n t p r e s s u r e s and t e m p e r a t u r e s f o r b i t u men and f o r a hydrocracked p r o d u c t w i t h 93% p i t c h c o n v e r s i o n . The t r e n d i s a n i n i t i a l r a p i d i n c r e a s e i n f f o l l o w e d by a g e n e r a l f l a t t e n i n g o u t of t h e c u r v e , a t r e n d which becomes more pronounced a t h i g h e r t e m p e r a t u r e s and p r e s s u r e s . T h i s r e f l e c t s t h e presence of a v e r y h i g h b o i l i n g f r a c t i o n ( p i t c h ) which i s v a p o r i z e d t o o n l y a s m a l l e x t e n t . A similar t r e n d i s s e e n when f i s p l o t t e d a g a i n s t t e m p e r a t u r e as shown i n F i g s . 4 and 5 f o r bitumen and 3 hydrocracked p r o d u c t s (49, 76 and 93% p i t c h c o n v e r s i o n ) a t 1 0 . 4 4 MPa and v a r i o u s G/L v a l u e s . The d e g r e e of v a p o r i z a t i o n i n t h e high conversion c a s e reached very high values. The e f f e c t of p r e s s u r e on f i s a l s o i l l u s t r a t e d i n F i g s . 2 and 3 . For t y p i c a l c o n d i t i o n s of 45OoC and G/L = 4 0 g mollkg, i n c r e a s i n g p r e s s u r e from 10.44 t o P a d e c r e a s e s f by 50% from 0.37 t o 0.185 f o r Athabasca bitumen, and by 20%, 17.34 M 64

from 0.86 t o 0.69 f o r product hydrocracked t o 93% c o n v e r s i o n ; w h i l e f o r G/L = 1 0 , f i s d e c r e a s e d by 54% and 44% r e s p e c t i v e l y . Another f a c t o r which i n f l u e n c e s t h e d e g r e e of v a p o r i z a t i o n i s t h e g a s c o m p o s i t i o n ; i n c r e a s i n g t h e c o n c e n t r a t i o n of hydrogen c a u s e s a d e c r e a s e i n f . T h i s i s i l l u s t r a t e d i n F i g . 6 f o r 35OoC and 13.89 MPa f o r a p r o d u c t hydrocracked t o 83% c o n v e r s i o n . In t h e r a n g e 50 t o 90 mol % H2, f i s l i n e a r l y p r o p o r t i o n a l t o hydrogen concentration. For a l l hydrocracked p r o d u c t s , f w a s c a l c u l a t e d f o r b o t h 6 0 and 80 mol %; f o r most c a s e s s t u d i e d a n i n c r e a s e of 33% from 60 t o 80 mol % H 2 caused a n approximate 10% d e c r e a s e i n f . Average l i q u i d r e s i d e n c e t i m e s ( t ) c a n be c a l c u l a t e d from t h e s e v a p o r i z a t i o n f i g u r e s by t a k i n g a v e r a g e v a l u e s f o r bitumen and hydrocracked p r o d u c t , a f t e r making allowance f o r t h e f r a c t i o n of r e a c t o r volume occupied by g a s ( v o i d a g e ) , a s follows : t = [ ( r e a c t o r vol)x(l-voidage)]/[ ( v o l of l i q u i d f e d p e r h ) x ( l - a v e . f r a c t i o n vaporized)

Such c a l c u l a t i o n s were c a r r i e d o u t f o r a s e r i e s of p i l o t p l a n t r u n s a s shown i n F i g . 7 , where t h e p r o d u c t of a v e r a g e r e s i d e n c e time and l i q u i d h o u r l y spac v e l o c i t y (LHSV) were p l o t t e d a g a i n s t t h e t e m p e r a t u r e a t which e a c h hydrocracked product w a s o b t a i n e d . The a v e r a g e f r a c t i o n v a p o r i z e d was t a k e n a s t h e a v e r a g e o f f f o r bitumen and f o r p r o d u c t . A s e a c h p r o d u c t r e p r e s e n t e d a d i f f e r e n t p i t c h conv e r s i o n , and a s t h e computer s i m u l a t i o n gave v a p o r i z a t i o n v a l u e s o n l y f o r a l i m i t e d number of p r o d u c t s a t f i x e d c o n v e r s i o n s , a l i n e a r i n t e r p o l a t i o n was used t o c a l c u l a t e values f o r t h e s e intermediate conversions. A similar i n t e r p o l a t i o n w a s a l s o used t o c o r r e c t f o r d i f f e r e n t hydrogen c o n c e n t r a t i o n s . F i g u r e 7 shows t h a t t h e c a l c u l a t e d r e s i d e n c e t i m e s a r e v e r y s e n s i t i v e t o r e a c t i o n t e m p e r a t u r e , and become i n c r e a s i n g l y h i g h e r t h a n t h e nominal s p a c e t i m e a s t e m p e r a t u r e and s p a c e v e l o c i t y increase. Although e x p e r i m e n t a l v a p o r i z a t i o n d a t a f o r t h e r e a c t o r were n o t a v a i l a b l e , i t w a s p o s s i b l e t o t e s t t h e computer s i m u l a t i o n by comparing t h e c a l c u l a t e d v a l u e s of f w i t h e x p e r i m e n t a l d a t a o b t a i n e d a t lower t e m p e r a t u r e s f o r t h e h o t s e p a r a t o r where v a p o u r / l i q u i d r a t i o s are r o u t i n e l y measured. Again t h e f v a l u e s c a l c u l a t e d by computer were i n t e r p o l a t e d t o c o r r e c t f o r p i t c h c o n v e r s i o n and hydrogen c o n c e n t r a t i o n f o r e a c h r u n c o n s i d e r e d . To t e s t t h e d a t a f o r bitumen i t s e l f a s e r i e s o f r u n s were c a r r i e d o u t w i t h b o t h r e a c t o r and hot s e p a r a t o r a t 35OoC and 37OoC a t which t e m p e r a t u r e s h d r o c r a c k i n g r e a c t i o n s o c c u r t o o n l y a l i m i t e d e x t e n t ( 2 3% p i t c h c o n v e r s i o n a t 370 C ) . C a l c u l a t e d v a l u e s were p l o t t e d a g a i n s t e x p e r i mental d a t a ( F i g . 8 ) . The b e s t l i n e f i t t e d t h e e q u a t i o n :

FE = ( 3 . 3

0.9)

(0.85 ? 0.07)FC

where FE and F a r e e x p e r i m e n t a l and c a l c u l a t e d v a l u e s of t h e p e r c e n t of C l i q u i d v a p o r i z e d . The agreement i s r e a s o n a b l e c o n s i d e r i n g a l l t h e p o s s i b l e s o u r c e s of e x p e r i m e n t a l e r r o r , and i n f a c t FE and FC a r e i n c l o s e agreement above a b o u t 1 5 % . The r e s u l t s f o r hydrocracked p r o d u c t s are shown i n F i g . 9 , i n which 75 from p i l o t p l a n t r u n s c a r r i e d o u t under a v a r i e t y of c o n d i t i o n s a r e compared c a l c u l a t e d v a l u e s . P r e s s u r e ranged from 10.44 t o 17.34 MPa, and t e m p e r a t u r e 300 t o 43OoC. Although t h e r e i s c o n s i d e r a b l e s p r e a d i n t h e d a t a , t h e b e s t l i e s c l o s e t o t h e d i a g o n a l and is g i v e n by t h e e q u a t i o n :

data with from line

FE

(1.8 f 1 . 2 )

(0.95 f 0.04)F

I t i s b e l i e v e d t h a t much of t h e s p r e a d is caused by e x p e r i m e n t a l e r r o r , p a r t i c u l a r l y i n measurements of g a s r a t e and c o m p o s i t i o n where e r r o r s of ? 5% o r 65

4OO0C
Bitumen 193% Prod.

G / L = 20 g m ~ i / k g

G / L = 40 g mollkg 4OOOC 0.205 0.672

6, %a 450C
0.241 0.712

6 , Xa
8.3 3.2

A, Zb
105.1 29.1

6, %a 45OoC
10.0 4.2 0.378 0.860

6, %"
4.2 1.7

A, %b
84.4 28.0

0.1175 8 . 5 0.505 1 4 . 6

P e r c e n t a g e i n c r e a s e i n f f o r a 12.5% i n c r e a s e i n G / L . P e r c e n t a g e i n c r e a s e i n f f o r a 12.5% i n c r e a s e i n T.

It i s s e e n t h a t f o r a 1 2 . 5 % i n c r e a s e , t e m p e r a t u r e h a s a g r e a t e r e f f e c t t h a n G/L. However, a s t h e a c c u r a c y o f t e m p e r a t u r e measurements i s much g r e a t e r t h a n t h o s e of G / L d e t e r m i n a t i o n s , t h e e r r o r s a r e p r o b a b l y of s i m i l a r magnitude. E r r o r s can a l s o be i n t r o d u c e d by t h e a p p r o x i m a t i o n s used i n t h e interp o l a t i o n s f o r p i t c h c o n v e r s i o n and hydrogen c o n c e n t r a t i o n s , a s w e l l from d i s c r e p a n c i e s between s i m u l a t e d and a c t u a l l i q u i d and g a s p r o p e r t i e s .

CONCLUSIONS Comparison of c a l c u l a t e d v a l u e s of l i q u i d v a p o r i z a t i o n u s i n g a computer s i m u l a t i o n w i t h e x p e r i m e n t a l d a t a i n d i c a t e d t h a t such c o m p u t a t i o n a l methods w i l l g i v e r e a s o n a b l y a c c u r a t e v a l u e s f o r t h e d e g r e e of v a p o r i z a t i o n , c o n s i d e r i n g t h e approximation and e x p e r i m e n t a l e r r o r s i n v o l v e d , f o r a v e r y heavy o i l s u c h as tar sand bitumen and i t s hydrocracked p r o d u c t s . REFERENCES 1.

Merrill, W.H., Logie, R.B. and Denis, J . M . "A p i l o t s c a l e i n v e s t i g a t i o n of t h e r m a l h y d r o c r a c k i n g of Athabasca bitumen"; CANMET (Canada C e n t r e f o r Mineral and Energy Technology, f o r m e r l y Mines Branch, Department o f Energy, Mines and Resources) R e s e a r c h R e p o r t R-281; Dec. 1973.
Pruden, B.B., L o g i e , R . B . and Denis, J . M . "Thermal hydrocracking of Athabasca bitumen: R e d u c t i o n o f r e a c t o r f o u l i n g " ; CANMET Report 76-33; Aug. 1976. "Thermal h y d r o c r a c k i n g of Athabasca Shah, A.M., Pruden, B.B. and Denis, J . M . bitumen: C o r r e l a t i o n of r e a c t o r v o i d a g e i n v e r t i c a l two-phase flow"; C A N M E T Report 77-48; Dec. 1976. Chao, K . C . and S e a d e r , J . D . "A g e n e r a l c o r r e l a t i o n o f v a p o u r - l i q u i d e q u i l i b r i a i n hydrocarbon m i x t u r e s " ; Am. I n s t . Chem. Eng. J o u r n . ; v . 7, no. 4, p 598; D e c . 1961. Grayson, H.G. and S t r e e d , C.W. "Vapour l i q u i d e q u i l i b r i a f o r h i g h t e m p e r a t u r e , h i g h p r e s s u r e hydrogen-hydrocarbon systems"; P r o c . V I t h World P e t r o l . Congr., F r a n k f u r t f M a i n ; Sect. V I I , paper 20, P07, p 233; J u n e 1963. Pruden, B.B. and D e n i s , J . M . "Heat o f r e a c t i o n and v a p o r i z a t i o n of f e e d and p r o d u c t i n t h e t h e r m a l hydrocracking o f Athabasca bitumen"; CANMET Report 76-30; Apr. 1976.

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