Académique Documents
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by
G. A. Odoerfer, L . R. Rudnick and D. 0. W h i t e h u r s t
INTRODUCTION
i n t e r a c t i o n i n c o a l l i q u e f a c t i o n and t o e f f e c t i v e l y u t i l i z e a s o l v e n t f o r
t h i s process, d e t a i l e d i n f o r m a t i o n on t h e chemical c o m p o s i t i o n o f t h e
r e c y c l e s o l v e n t i s needed.
a c t as a hydrogen t r a n s f e r agent; ( 2 ) f u n c t i o n as a p h y s i c a l s o l v e n t ; ( 3 )
studies.
BACKGROUND
coal l i q u i d s .
89
I n i t i a l l y , one such method, t h e SESC chromatographic procedure (1,2)
s e q u e n t i a l e l u t i o n w i t h s p e c i f i c s o l v e n t s on s i l i c a gel columns, a l t h o u g h
by us, f o r t h e p a s t two y e a r s , i n t h e f r a c t i o n a t i o n o f c o a l d e r i v e d
s o l v e n t s p r i n c i p a l l y o f SRC o r i g i n .
I n t h e i n i t i a l p o r t i o n o f t h i s technique, s i m i l a r t o t h e SARA p r o -
as f o l l o w s :
*
These f r a c t i o n s are now b e i n g developed u s i n g heptane i n s t e a d
of petroleum ether.
90
Although t h i s sequence a l l o w s good s e p a r a t i o n o f hydrocarbons, and though
are g e n e r a l l y non-elutable.
as i n t h e SARA procedure.
Haas, a r e p o t e n t i a l l y u s e f u l f o r coal d e r i v e d s o l v e n t s e p a r a t i o n s o f t h i s
t h e y do n o t r e q u i r e s o l v e n t s w e l l i n g t o become e f f e c t i v e . The r e s i n ,
i n t r o d u c i n g an e l u t i o n s o l v e n t o f 5% EtOH i n THF, s e p a r a t i o n c o u l d be
possible.
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C o n s i d e r i n g a l l p a s t work, a procedure has been developed, u s i n g
i o n exchange r e s i n column f o r s e p a r a t i o n o f a c o a l d e r i v e d s o l v e n t .
EXPERIMENTAL
Sample
these s t u d i e s .
bla t e r ia 1
A. Reagents
S u r f a c e Area m2/g 28
k+ OH-
/I\
Exchange Capacity: c c c
meq/g 4.4
meqlml 1 .o
92
C . C hronia t o g rap hi c Supports
Silica
Preparative - Prep Pack - 500 c a r t r i d g e s ( 5 . 7 x 30 cm)
obtained from Waters Associates.
Analytical - LPS-2 37-53 um s i l i c a gel obtained from
Whatman I n c . , Clifton NJ.
A1 umi na
Basic Alumina Woelm Activity - 1 obtained from ICN.
PROCEDURE
The overall procedure i s shown schematically i n Figure 1 . The
i n i t i a l separation u t i l i z e d a modified version of our SESC ( 1 , 2 ) procedure
and was performed on a 10 g s c a l e .
The sample, Hydrogenated SRC-1, was dispersed on g l a s s beads
(Regular 170/230 mesh) a n d loaded in a pre-column. Chromatographic
separation was then accomplished, using a system s i m i l a r t o the Waters
LC/Prep 500 System containing two s i l i c a c a r t r i d g e s , a t a flow r a t e of
approximately 50 cc/min. The f r a c t i o n s obtained a r e presented in Table 1 .
Each f r a c t i o n i s o l a t e d in the i n i t i a l s t e p was analyzed by a n a l y t i c a l
S E X , u t i l i z i n g a s t a i n l e s s s t e e l column ( 3 x 1000 mm) and 1 cc/min flow
r a t e , t o determine the q u a l i t y of the separation. Vapor-phase chromatograms
of each f r a c t i o n were a l s o obtained on a Hewlett Packard 5750 Research
Chromatograph u t i l i z i n g a Dexsil 300 column (10% on Chromasorb; 1/8" x 10 f t )
and programmed a t 6°C per minute from 50°C t o 350°C.
The hydrocarbons a n d monofunctional compounds were f u r t h e r f r a c t i o n a t e d
by preparative chromatography over alumina. An Altex a n a l y t i c a l g l a s s
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column ( 1 5 x 1000 mm) equipped w i t h an a d j u s t a b l e p l u n g e r and a f l o w r a t e
f r a c t i o n s a r e p r e s e n t l y b e i n g examined by FIMS as w e l l as by o t h e r s p e c t r a l
methods and w i l l b e t h e s u b j e c t o f a f u t u r e p u b l i c a t i o n .
f r a c t i o n s i n d i c a t e t h a t t h e r e i s some o v e r l a p b u t t h a t i n general t h e
s e p a r a t i o n o b t a i n e d appears t o be q u i t e good.
by i o n exchange.
CONCLUSIONS
d e r i v e d coal l i q u e f a c t i o n r e c y c l e s o l v e n t s i n t o c h e m i c a l l y d i f f e r e n t
94
including s u l f u r containing heterocycles; furans; non basic N ; basic
nitrogen species; mono-phenols and polyfunctional compounds.
The combination of f r a c t i o n a t i o n w i t h additional study by elemental
analyses, FIMS as well a s by o t h e r spectral methods leads t o a good chemical
characterization o f each f r a c t i o n , and the t o t a l s o l v e n t .
The'developed method allows f o r t h e circumvention of any problems
normally encountered i n separating the desired f u n c t i o n a l i t i e s . The
u t i l i z a t i o n of such method coupled w i t h c h a r a c t e r i z a t i o n of t h e chemical
groups obtained allows f o r t h e gain of a more thorough understanding of
the chemistry of coal-solvent i n t e r a c t i o n and can lead t o a more d e t a i l e d
i d e n t i f i c a t i o n of t h e chemical composition of recycle s o l v e n t s .
The l a t t e r premise i s presently being investigated, f o r a v a r i e t y of
f u l l range process derived recycle solvents (400-800OF).
REFERENCES
1. 0. 0. Whitehurst, M. Farcasiu and T. 0. Mitchell, "The Nature and
95
ACKNOWLEDGEMENT
P r o j e c t Manager.
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Table 1
B S, 0, H e t e r o c y c l i c s and n o n b a s i c N Chloroform % 10
- Corn o s i t i o n
Weight
ResFonse Normal I=
I
-~ Factor x
Fraction A
Frac. 1-2 76.4 (1.81)* 90.61
" 3 1.2 (1.30) 1 .oo
I' 4 8.4 (0.52) 2.89
'I 5 8.4 (0.42) 2.83
'I 6 5.5 (0.07) 3.16
Fraction B
Frac. 3 59.4 (1.30) 78.2
4 28.1 (0.52) 14.8
" 5 8.7 (0.42) 3.7
IC 6 3.8 (0.87) 3.3
Fraction C
Frac. 3 2.1 11.30) 4.4
It 4 63.6 (0.5zj 53.4
'I 5 8.3 (0.42) 5.6
" 6-7 21.1 (0.07) 29.6
2.1 (0.78) 2.6
2.7 (0.97j 4.2
* Response f a c t o r s a s determined f o r solvent 6663. (1,3)
1 27.7
1A 8.6
2 10.2
3 11.4
4 15.0 7.0
4A 10.0 42.0
5 10.1 45.0
6 1 5.0*
.)
* Non-eluted by d i f f e r e n c e
99