LIQUID CHROMATOGRAPHIC CHEMICAL CLASS ANALYSIS OF BITUMEN

AND HEAVY PETROLEUM CRUDES

C. R e i c h e r t and L. Grant
O i l Sands Research Centre
A l b e r t a Research Council
Edmonton, A l b e r t a T6G 2C2

INTRODUCTION

The importance o f bitumen and heavy crudes i s s t e a d i l y i n c r e a s i n g

as reserves o f c o n v e n t i o n a l crudes d i m i n i s h around t h e w o r l d p r o d u c i n g an
increased emphasis upon t h e development o f methods o f recovery f o r bitumens
and heavy crudes. Because o f t h e e x t r e m e l y h i g h v i s c o s i t i e s encountered, a
v a r i e t y o f n o v e l i n - s i t u r e c o v e r y methods u s i n g combinations o f steam, s o l v e n t s ,
s u r f a c t a n t s , and combustion a r e b e i n g i n v e s t i g a t e d .

Conventional and heavy p e t r o l e u m crudes c o n s i s t o f a l a r g e v a r i e t y

o f o r g a n i c molecules g e n e r a l l y c l a s s i f i e d i n t o f o u r major groups i d e n t i f i e d
as s a t u r a t e s , a r o m a t i c s , r e s i n s and asphaltenes. Each o f these c l a s s e s have
i n d i v i d u a l uses and t h e i r r e l a t i v e r a t i o s determine t h e upgrading processes
employed. Bitumen and heavy crudes t e n d t o have l a r g e r p r o p o r t i o n s o f r e s i n s
and asphaltenes t h a t a r e l e s s e c o n o m i c a l l y c o n v e r t e d t o u s a b l e p r o d u c t s .
P r e c i p i t a t i o n o f a s p h a l t e n e s i n t h e f o r m a t i o n o r p r o d u c t i o n o f asphaltenes
from o t h e r compounds can o c c u r d u r i n g t h e r e c o v e r y process n e c e s s i t a t i n g
some m o n i t o r i n g o f p r o c e s s streams for changes i n t h e r e l a t i v e r a t i o s o f
these c l a s s e s o f compounds.

Numerous methods a r e used t o separate p e t r o l e u m hydrocarbons i n t o

t h e i r t y p e and c l a s s e s . The most common method u t i l i z e s pentane p r e c i p i t a t i o n
o f t h e asphaltenes i n a procedure s i m i l a r t o ASTM D 893-69. A variety of
procedures (1-6) a r e employed f o r t h e subsequent f r a c t i o n a t i o n o f t h e r e m a i n i n g
o i l . Many o f t h e procedures f o r t h e s e p a r a t i o n o f t h e a r o m a t i c s and s a t u r a t e s
u s i n g s i l i c a and/or a l u m i n a columns a r e m o d i f i c a t i o n s o f ASTM D 2549-75. Some
o f t h e methods a c h i e v e s e p a r a t i o n s i n t o subgroupings such as monoaromatics,
d i a r o m a t i c s , p o l y a r o m a t i c s and p o l a r compounds.

Each o f t h e procedures however has t h e disadvantage t h a t a t o t a l

c l a s s a n a l y s i s r e q u i r e s s e v e r a l s t e p s and t o o b t a i n t h e d a t a r e g a r d i n g t h e
d i s t r i b u t i o n o f t h e f r a c t i o n s r e q u i r e s s e v e r a l days.

The p r o c e d u r e discussed here enables t h e s e p a r a t i o n o f t h e bitumen

o r heavy p e t r o l e u m c r u d e i n t o t h r e e g r o u p i n g s namely asphaltenes, r e s i n s and
a m i x t u r e of a r o m a t i c s and s a t u r a t e s w i t h no p r i o r s e p a r a t i o n o f t h e p o l a r
c o n s t i t u e n t s o r of b a c k f l u s h i n g o f t h e columns. U s i n g a 254 nm UV d e t e c t o r
i t i s p o s s i b l e t o q u a n t i f y each o f t h e f r a c t i o n s i n t h e bitumen.

EXPER IMENTAL

The l i q u i d chromatograph used i n t h i s s t u d y was a V a r i a n Model 8500

d u a l s y r i n g e pump i n s t r u m e n t equipped w i t h a V a r i a n Aerograph 254 nm UV
d e t e c t o r connected t o a V a r i a n CDS I l l Data System. The columns used were a
25 cm V a r i a n Aerograph Micropak CH-10 connected i n s e r i e s w i t h a 25 cm V a r i a n
Aerograph H i c r o p a k CN-IO.
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 Two m o b i l e phase systems can be used t o a c h i e v e t h e s e p a r a t i o n .
One system employed 99% methanol-I% isopropanol f o r 4 minutes, 40% o f t h e 99%
methanol-1% i s o p r o p a n o l mixture-60% t e t r a h y d r o f u r a n f o r 10 minutes and
f i n a l l y 100% THF f o r 10 minutes. The second system used 90% a c e t o n i t r i l e - l O %
water f o r 5 minutes f o l l o w e d by 50% a c e t o n i t r i l e mixture-50% methylene c h l o r i d e
f o r 10 minutes f o l l o w e d f i n a l l y by 100% methylene c h l o r i d e f o r 10 minutes.
Separation achieved by t h e two methods i s comparable and i s accomplished i n
25-30 minutes u s i n g a f l o w r a t e o f 60 cc/hr.

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

a t a c o n c e n t r a t i o n of 10-20 mg/ml w i t h 2-5 V I o f sample being i n j e c t e d on t h e
c o l umns .

D I S C U S S I O N AND RESULTS

F i g u r e 1 shows a t y p i c a l chromatogram o f t h e s e p a r a t i o n o f s a t u r a t e s
and aromatics, r e s i n s , and asphaltenes i n samples o f Athabasca Bitumen.
Superimposed on t h e chromatogram i s a p l o t o f t h e change i n t h e s o l v e n t
gradient during the analysis.

Chromatograms o f a r o m a t i c s and r e s i n s m a t e r i a l o b t a i n e d by s e p a r a t i o n
on passage through a t t a p u l g u s c l a y and s i l i c a - a l u m i n a columns s u c c e s s i v e l y
a r e g i v e n i n F i g u r e s 2 and 3 r e s p e c t i v e l y . The chromatograms show t h a t t h e
aromatics produced by column chromatography c o n t a i n m a t e r i a l t h a t we c l a s s i f i e d
as r e s i n s by t h i s procedure w h i l e t h e r e s i n samples c o n t a i n some a r o m a t i c
m a t e r i a l and a l s o some asphaltene m a t e r i a l . A chromatogram o f an a s p h a l t e n e
sample o b t a i n e d by pentane p r e c i p i t a t i o n i s g i v e n i n F i g u r e 4 w h i c h shows t h e
presence o f a r e s i n s peak. I t i s e v i d e n t f r o m these chromatograms t h a t a
v e r y s i m i l a r f r a c t i o n a t i o n o f t h e bitumen I s o b t a i n e d i n our HPLC method as
compared t o t h e c o n v e n t i o n a l column s e p a r a t i o n . S a t u r a t e s m a t e r i a l i n t h e
bitumen i s e l u t e d w i t h t h e a r o m a t i c s f r a c t i o n however s i n c e s a t u r a t e s
a b s o r p t i o n a t 254 nm i s n e g l i g i b l e they a r e n o t detected. By e v a l u a t i o n o f
t h e amount o f a r o m a t i c s , r e s i n s and asphaltenes t h e percentage o f each o f t h e
f o u r f r a c t i o n s i n a bitumen sample can be determined.

CONCLUSIONS

The HPLC method discussed i n t h i s paper achieves a s e p a r a t i o n o f

bitumen i n t o i t s c l a s s components i . e . , asphaltenes, r e s i n s and m i x t u r e o f
aromatics and s a t u r a t e s , i n p r o p o r t i o n s comparable t o t h a t o b t a i n e d i n c l a s s i c a l
s e p a r a t i o n by asphaltene p r e c i p i t a t i o n w i t h pentane and subsequent successive
passage through a t t a p u l g u s c l a y and s i l i c a alumina columns.

ACKNOWLEDGMENT

T h i s s t u d y was funded by t h e A l b e r t a O i l Sands Technology and .

Research A u t h o r i t y .

LITERATURE CITED

G.L. Brown and A.L. Jones, Hydrocarbon Processing P e t r o l R e f i n e r , 2,

(I) 156 (1960).
(2) J. Coleman, J.E. Oooly, D.E. H i r s c h and C.J. Thompson, A n a l y t i c a l
Chemistry, 45,
1724 (1973).

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16 (1976).
George, G.T. Smiley and D . S . Montgomery, F u e l , I
(4) G.N. Pozdnyshev, R.I. Masurov and R.M. Ruchkina, Chemical Technology
o f Fuel and O i l s ,

J.C. Suatoni and H.R.

E, 806 (1974).

Garber, J. Chromatog, Science, fi, 546 (1976).

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(5)
(6) U.S. Bureau o f Mines, API-RP-60 (1974).
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Time (rnin) Time (min)

FIGURE 1 Chromatogram o f FIGURE 2 Chromatogram o f an
Toluene Extracted Aromatics F r a c t i o n
B i tumen Separated on Silica-Alumina

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Time (min) Time (min),
FIGURE 3 Chromatogram o f a Resins FIGURE 4 Chromatogram o f an
F r a c t i o n Separated on Asphaltene F r a c t i o n
Attapulgus Clay P r e c i p i t a t e d by Pentane

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